A Textbook of

Physical Chemistry
Volume IV
A Textbook of Physical Chemistry

Volume I :
States of Matter and Ions in Solution
Volume II :
Thermodynamics and Chemical Equilibrium
Volume III :
Applications of Thermodynamics
Volume IV :
Quantum Chemistry and Molecular Spectroscopy
Volume V :
Dynamics of Chemical Reactions, Statistical Thermodynamics Macromolecules, and
Irreversible Processes
Volume VI : Computational Aspects in Physical Chemistry
 A Textbook of
Physical Chemistry
Volume IV
(SI Units)

Quantum Chemistry and Moucular Spectroscopy

Fifth Edition

k l kAPoor
Former Associate Professor
Hindu College
University of Delhi
New Delhi

McGraw Hill Education (India) Private Limited

New Delhi

McGraw Hill Education Offices

New Delhi New York St louis San Francisco Auckland Bogotá Caracas
Kuala lumpur lisbon london Madrid Mexico City Milan Montreal
San Juan Santiago Singapore Sydney Tokyo Toronto
Published by McGraw Hill Education (India) Private Limited,
P-24, Green Park Extension, New Delhi 110 016.
A Textbook of Physical Chemistry, Vol IV
Copyright © 2015 by McGraw Hill Education (India) Private Limited.
No part of this publication may be reproduced or distributed in any form or by any means, electronic, mechanical, pho-
tocopying, recording, or otherwise or stored in a database or retrieval system without the prior written permission of the
publishers. The program listings (if any) may be entered, stored and executed in a computer system, but they may not be
reproduced for publication.
This edition can be exported from India only by the publishers,
McGraw Hill Education (India) Private Limited.
Print Edition
ISBN (13): 978-93-39204-29-7
ISBN (10): 93-39204-29-8
E-book Edition
ISBN (13): 978-93-392-0430-3
ISBN (10): 93-392-0430-1

Managing Director: Kaushik Bellani

Head—Higher Education (Publishing and Marketing): Vibha Mahajan
Senior Publishing Manager (SEM & Tech. Ed.): Shalini Jha
Associate Sponsoring Editor: Smruti Snigdha
Senior Editorial Researcher: Amiya Mahapatra
Senior Development Editor: Renu Upadhyay
Manager—Production Systems: Satinder S Baveja
Assistant Manager—Editorial Services : Sohini Mukherjee
Assistant General Manager (Marketing)—Higher Education: Vijay Sarathi
Senior Graphic Designer—Cover: Meenu Raghav
General Manager—Production: Rajender P Ghansela
Manager—Production: Reji Kumar

Information contained in this work has been obtained by McGraw Hill Education (India), from sources believed to
be reliable. However, neither McGraw Hill Education (India) nor its authors guarantee the accuracy or completeness
of any information published herein, and neither McGraw Hill Education (India) nor its authors shall be responsible
for any errors, omissions, or damages arising out of use of this information. This work is published with the
understanding that McGraw Hill Education (India) and its authors are supplying information but are not attempting
to render engineering or other professional services. If such services are required, the assistance of an appropriate
professional should be sought.

Typeset at Script Makers, 19, A1-B, DDA Market, Paschim Vihar, New Delhi 110 063, and text printed at
To the Memory of My Parents
Preface
in recent years, the teaching curriculum of Physical Chemistry in many indian
universities has been restructured with a greater emphasis on a theoretical and
conceptual methodology and the applications of the underlying basic concepts and
principles. This shift in the emphasis, as i have observed, has unduly frightened
undergraduates whose performance in Physical Chemistry has been otherwise
generally far from satisfactory. This poor performance is partly because of the
non-availability of a comprehensive textbook which also lays adequate stress on
the logical deduction and solution of numericals and related problems. Naturally,
the students find themselves unduly constrained when they are forced to refer to
various books to collect the necessary reading material.

it is primarily to help these students that i have ventured to present a textbook

which provides a systematic and comprehensive coverage of the theory as well as
of the illustration of the applications thereof.
The present volumes grew out of more than a decade of classroom teaching
through lecture notes and assignments prepared for my students of BSc (General)
and BSc (honours). The schematic structure of the book is assigned to cover
the major topics of Physical Chemistry in six different volumes. Volume I
discusses the states of matter and ions in solutions. It comprises five chapters
on the gaseous state, physical properties of liquids, solid state, ionic equilibria
and conductance. Volume II describes the basic principles of thermodynamics
and chemical equilibrium in seven chapters, viz., introduction and mathematical
background, zeroth and first laws of thermodynamics, thermochemistry, second
law of thermodynamics, criteria for equilibrium and A and G functions, systems
of variable composition, and thermodynamics of chemical reactions. Volume III
seeks to present the applications of thermodynamics to the equilibria between
phases, colligative properties, phase rule, solutions, phase diagrams of one-,
two- and three-component systems, and electrochemical cells. Volume IV deals
with quantum chemistry, molecular spectroscopy and applications of molecular
symmetry. it focuses on atomic structure, chemical bonding, electrical and
magnetic properties, molecular spectroscopy and applications of molecular
symmetry. Volume V covers dynamics of chemical reactions, statistical and
irreversible thermodynamics, and macromolecules in six chapters, viz., adsorption,
chemical kinetics, photochemistry, statistical thermodynamics, macromolecules
and introduction to irreversible processes. Volume VI describes computational
aspects in physical chemistry in three chapters, viz., synopsis of commonly used
statements in BASiC language, list of programs, and projects.
The study of Physical Chemistry is incomplete if students confine themselves
to the ambit of theoretical discussions of the subject. They must grasp the practical
significance of the basic theory in all its ramifications and develop a clear
perspective to appreciate various problems and how they can be solved.
viii Preface

it is here that these volumes merit mention. Apart from having a lucid style
and simplicity of expression, each has a wealth of carefully selected examples and
solved illustrations. Further, three types of problems with different objectives in
view are listed at the end of each chapter: (1) Revisionary Problems, (2) Try Yourself
Problems, and (3) Numerical Problems. Under Revisionary Problems, only those
problems pertaining to the text are included which should afford an opportunity to
the students in self-evaluation. in Try Yourself Problems, the problems related to
the text but not highlighted therein are provided. Such problems will help students
extend their knowledge of the chapter to closely related problems. Finally, unsolved
Numerical Problems are pieced together for students to practice.
Though the volumes are written on the basis of the syllabi prescribed for
undergraduate courses of the University of Delhi, they will also prove useful to
students of other universities, since the content of physical chemistry remains the
same everywhere. in general, the Si units (Systeme International d’ unite’s), along
with some of the common non-Si units such as atm, mmhg, etc., have been used
in the books.

Salient Features

∑ Comprehensive coverage of wave mechanics, energy quantization and atomic

structure, theories of covalent bond, electrical and magnetic properties of
molecules, molecular spectroscopy, molecular symmetry and its applications
∑ emphasis given to applications and principles
∑ explanation of equations in the form of solved problems and numericals
∑ iUPAC recommendations and Si units have been adopted throughout
∑ Rich and illustrious pedagogy

Acknowledgements

i wish to acknowledge my greatest indebtedness to my teacher, late Prof. R P

Mitra, who instilled in me the spirit of scientific inquiry. I also record my sense
of appreciation to my students and colleagues at hindu College, University of
Delhi, for their comments, constructive criticism and valuable suggestions
towards improvement of the book. i am grateful to late Dr Mohan Katyal (St.
Stephen’s College), and late Prof. V R Shastri (Ujjain University) for the numerous
suggestions in improving the book. i would like to thank Sh. M M Jain, hans Raj
College, for his encouragement during the course of publication of the book.
i wish to extend my appreciation to the students and teachers of Delhi
University for the constructive suggestions in bringing out this edition of the book.
i also wish to thank my children, Saurabh-Urvashi and Surabhi-Jugnu, for many
useful suggestions in improving the presentation of the book.
Finally, my special thanks go to my wife, Pratima, for her encouragement,
patience and understanding.
Feedback request

The author takes the entire responsibility for any error or ambiguity, in fact or
opinion, that may have found its way into this book. Comments and criticism
from readers will, therefore, be highly appreciated and incorporated in subsequent
editions.
K L Kapoor

Publisher’s Note

McGraw-hill education (india) invites suggestions and comments from you, all
of which can be sent to [email protected] (kindly mention the title and
author name in the subject line).
Piracy-related issues may also be reported.
 Contents

Preface vii
Acknowledgements viii

1. WaVE MEcHaNIcs, ENErGy QuaNtIzatIoN aND atoMIc structurE 1

1.1 Towards Quantum Theory 1
1.2 Towards the wave Nature of the electron 22
1.3 Schrödinger wave Theory 30
1.4 Quantization of Translational energy 37
1.5 Quantization of Vibrational energy 58
1.6 Quantization of Rotational energy of Diatomic Molecules 69
1.7 Quantization of electronic energy: The hydrogen Atom 80
1.8 Pictorial Representations of wave Functions and Probability Density
Distributions for hydrogen-like Species 99
1.9 Angular Momentum and the Magnetic Moment 112
1.10 Zeeman and Anomalous Zeeman effects 116
1.11 Many-electron atoms 123
1.12 The indistinguishability of electrons and the Pauli exclusion
Principle 129
1.13 Atomic Term Symbols 134
1.14 hund’s Rule 139
1.15 The Aufbau Principle and The Electronic Configurations of Atoms 140
Annexure i Derivation of de Broglie Relation for a Photon 157
Annexure ii Solutions of Schrödinger equation for a harmonic Oscillator 159
Annexure iii Operators for the Components of Angular Momentum 170
Annexure iV Commutators of Angular Momentum Operators 177
Annexure V Transformation of laplacian Operator from Cartesian
Coordinates to Spherical Polar Coordinates 183
Annexure Vi Splitting of Schrödinger equation of hydrogen Atom 185
Annexure Vii Atomic Units 188
Annexure Viii The ladder-Operator Method Applied to Angular
Momentum 190
Annexure iX electronic Transitions in hydrogen Atom including
Spin-Orbit Coupling 202
Annexure X First-Order Perturbation Theory 204
Annexure Xi Proof of Variational Theorem 212
Annexure Xii The Variational Method 213

2. tHEorIEs of coVaLENt BoND 220

2.1 introduction 220
2.2 expression of Schrödinger equation 220
xii Contents

2.3 Born-Oppenheimer Approximation 221

2.4 Two Approaches For Approximate Solution of Schrödinger equation 222
2.5 lCAO-MO Treatment of h+2 228
2.6 lCAO-MO Treatment of a hydrogen Molecule 240
2.7 Valence-Bond Treatment of a hydrogen Molecule 242
2.8 Comparison Between MO and VB Treatments of a hydrogen Molecule 249
2.9 Mo Treatment of homonuclear Diatomic Molecules 252
2.10 Molecular Term Symbols 261
2.11 h eteronuclear Diatomic Molecules 263
2.12 United-Atom Concept and the Correlation Diagrams 268
2.13 hybrid Orbitals 272
2.14 Triatomic Molecules 282
2.15 Correlation of the Orbitals for Bent and linear Ah2 Molecules 306
2.16 Conjugated Organic Molecules 309
Annexure i localized Molecular Orbitals of CO and N2 Molecules 329
Annexure ii evaluation of integrals J, K and S in the lCAO-MO
Treatment of h+2 335
Annexure iii Conventional Representation of Sp3 hybrid Orbitals 338

3. ELEctrIcaL aND MaGNEtIc ProPErtIEs of MoLEcuLEs 341

3.1 introduction 341
3.2 e lectric Dipole Moment 341
3.3 effect of A Dielectric on the electrostatic Field of a Parallel Plate Capacitor 345
3.4 Clausius-Mosottii equation 346
3.5 Debye equation 348
3.6 e xperimental Method to Determine a and P 351
3.7 Variation of Molar Polarization with the Frequency of electric Field 353
3.8 lorentz-lorenz equation 354
3.9 Union of the Debye and the lorentz-lorenz equations 357
3.10 ionic Character of Diatomic Molecules 360
3.11 Bond Moments 360
3.12 Group Moments 367
3.13 Applications of Dipole Moments 370
3.14 Magnetic Field in a Substance 371
3.15 Molecular interpretation of Diamagnetism and Paramagnetism 371
3.16 Total Molar Magnetic Susceptibility 374
3.17 Calculation of the Number of Unpaired electrons 374
3.18 Gouy Balance Method to Measure Magnetic Susceptibility 375
Annexure i e lectrostatic and Magnetic Fields 383
Annexure ii expression of Orientation Polarizability 391

4. MoLEcuLar sPEctroscoPy 393

4.1 introduction 393
4.2 Nuclear Magnetic Resonance Spectroscopy 401
4.3 electron Spin Resonance Spectroscopy 430
 Contents xiii

4.4 Rotational Spectra of Diatomic Molecules 443

4.5 Vibrational Spectra of Diatomic Molecules 460
4.6 Vibration-Rotation Spectra of Diatomic Molecules 480
4.7 Vibration Spectra of Polyatomic Molecules 485
4.8 Raman Spectra 488
4.9 electronic Spectra of Diatomic Molecules 500
Annexure A Qualitative Study of Quantum Mechanical Treatment of
Spin Transitions in AX, A2 and AX2 Systems 527

5. MoLEcuLar syMMEtry aND Its aPLIcatIoNs 536

5.1 Symmetry elements and Associated Symmetry Operations 536
5.2 Classification of Molecules Based on Symmetry Elements 542
5.3 Matrix Representations of Geometrical Operations 548
5.4 Definition of a Group 551
5.5 Group consisting of Symmetry Operations on a Molecule 552
5.6 Classes of Symmetry Operations 559
5.7 A Few Representations of Symmetry Operations of a Point Group 560
5.8 Reducible and irreducible Representations 581
5.9 Characters of Matrices 583
5.10 The Great Orthogonality Theorem 584
5.11 Characteristics of irreducible Representations 586
5.12 worked out examples of irreducible Representations of a Group 588
5.13 Resolution of a Reducible Representation in Terms of irreducible
Representations 590
5.14 Description of a Character Table 592
5.15 Description of Mulliken Symbols 592
5.16 Reducible Representation Based on Translational Vectors and its Resolution
into irreducible Representations–Revisited 593
5.17 The Projection Operator 597
5.18 worked out examples of Salc’s and Mo’s 602
5.19 P-Molecular Orbitals of A Carbocyclic System 621
5.20 Formation of hybrid Orbitals 628
5.21 Predicting Zero Value of an integral 639
5.22 irreducible Representations of Vibrational Motions 656
5.23 Predicting Probability of a Spectral Transition 661
5.24 Correlation Diagrams For a D2 ion in an Octahedral and
Tetrahedral environments 670
Annexure Some Commonly Used Character Tables 689
Appendix I Units and Conversion Factors 697
Appendix II Some Mathematical expressions and Greek Alphabets 701
Index 703
 Wave Mechanics, Energy Quantization
1 and Atomic Structure

1.1 TOWARDS QUANTUM THEORY

Introduction During the latter of the nineteenth century, a number of experimental observations
were reported which could not be explained on the basis of the classical theory.
Among these were the spectral distribution of energy in black-body radiation,
photoelectric effect, variation of heat capacity of monatomic solids with temperature,
and the discrete spectra emitted by excited atoms. These observations established
that the classical theory was unable to account for the behaviour of small objects.

a new theory based on the quantum behaviour of energy. When applied to various
problems, it was able to account for the experimental observations and hence led
to the new theory, named, the quantum theory. In this section, we shall describe
how the quantum theory postulated by Planck could explain the experimental
observations listed above.
BLACK–BODY RADIATION

Classical Theory Prior to Max Planck (1901), light was considered to be electromagnetic wave
of Radiation whose energy was proportional to the square of the amplitude of the wave, and
was considered to be independent of the frequency of the radiation. This classical
theory of radiation was able to explain optical phenomena such as diffraction and
scattering. However, when applied to the black-body radiation, this theory could
not explain the relative intensities of radiations emitted from a black-body when
heated to a higher temperature.

Radiations A black-body is one which can absorb all types of radiation that falls upon it.
Emitted by a Experimentally, such a body is best represented by a hollow container with a
Black-Body very small hole in the wall. When such a body is heated, it emits radiations of
all types of wavelengths. The origin of radiations from a heated body is the rapid
vibrating particles (known as oscillators) composing the body. According to
Maxwell’s electromagnetic theory, these oscillators emit radiant energy in the form
of electromagnetic waves. The frequency of the wave emitted from an oscillator is
equal to the frequency of the latter. At low temperatures, the emission is mainly in
the infrared region, but as the temperature is raised, the wavelength at which most
of the light is emitted shifts towards the blue region of the spectrum. The intensity
of the emitted radiation depends on the temperature of the container as well as on
the wavelength of the radiation. Figure 1.1.1 shows the variation of the intensity
of radiation with the wavelength at three different temperatures.
2 A Textbook of Physical Chemistry

T1

T1 > T2 > T3

Intensity of radiation
T2

Fig. 1.1.1 Variation

of intensity of
radiation with the T3
wavelength of emitted
radiations at three
different temperatures 0 1 2 3 4 5 6
l / 10–6 m

Two Fundamental Based on the classical theory, attempts were made to explain qualitatively and
Laws of Black- quantitatively the nature of the curves depicted in Fig. 1.1.1. Two fundamental
Body Radiations laws regarding the nature of the curves were established. These are described below.

Stefan-Boltzman law This law was established experimentally by Stefan,

according to which, the intensity E of total radiation (the area under the curve) is
proportional to the fourth power of the kelvin temperature T, i.e.
E = s ¢T 4 = ÊÁ s ˆ˜ T 4
4
(1.1.1)
Ë ¯ c
where s is a constant, known as the Stefan’s constant. Its value is found to be
5.672 ¥ 10-8 J m-2 s-1 K-4. Subsequently, this law was derived by Boltzmann using
thermodynamic principles.

Wien's displacement law According to this law, the wavelength l at the

maximum of the spectral distribution is inversely proportional to the temperature
T. Thus
l max T = constant (1.1.2)
Various Attempts to Theoretical attempts were also made to construct the shape of the energy spectra
Construct the as a function of wavelength. We describe below the three important attempts in
Spectra this direction.

Wien's contribution Based on the classical electromagnetic theory and

assuming that the oscillators from which the radiations are emitted are of molecular
size, Wien was able to obtain the expression
a
E = 5 exp(– b/lT ) (1.1.3)
l
where E is the energy emitted between wavelengths l and l + dl and a and b are
constants.

curves in the low wavelength region, but fails to reproduce the results at the high
wavelength region (Fig. 1.1.2).
 Wave Mechanics, Energy Quantization and Atomic Structure 3

Fig. 1.1.2 Graph

of the experimental
curve by Wien’s law,
Rayleigh–Jeans’ law
and Planck’s law

Rayleigh–Jeans contribution Applying the classical law of equipartition of

energy (that each vibration mode possesses on an average energy E equal to kT )
to the oscillators of black-body, Rayleigh and Jeans derived Eq. (1.1.6) as follows.
It can be shown that the number dn of modes of oscillation in the wavelength
range l and l + dl per unit volume of the cavity is given by
8p
dn = dl (1.1.4)
l4
The energy density in this wavelength region is equal to (dn)( E ) and is also
equal to El dl, where El is the corresponding energy emitted. Thus, we have
El dl = (dn) E (1.1.5)
Substituting the expressions of dn and E , we get
8p ˆ
El dl = Ê dl (kT )
Ë l4 ¯
8pkT
Hence El = (1.1.6)
l4
According to Eq. (1.1.6), El is inversely proportional to the fourth power of the
wavelength. Hence, El continues to increase with decreasing l.

Equation (1.1.
region but fails completely at the low wavelength region and thus leads to what
is known as the ultraviolet catastrophe (Fig. 1.1.2).
Planck's contribution Keeping in view that the Wien’s relation was applicable
in the low wavelength region and that of Rayleigh-Jeans in the high wavelength
region, Planck sought an intermediate expression which could be reduced to the
above two laws in the proper range of values of l. He derived the expression:
a
El = (1.1.7)
l {exp(b/lT ) - 1}
5

Behaviour of Eq. (1.1.7) at low values of l The factor exp(b/lT) is very much
greater than one, and thus we may write
4 A Textbook of Physical Chemistry

exp(b/lT ) - 1 exp(b/lT )
With the above relation, Eq. (1.1.7) reduces to
a
El = 5 exp(-b/lT )
l
an expression identical to the Wien’s relation (Eq. 1.1.3).

Behaviour of Eq. (1.1.7) at high values of l If l is high, the term b/lT will
have a small value and thus the term exp(b/lT ) can be written as
b
exp(b/lT ) 1 +
lT
Substituting the above relation in Eq. (1.1.7), we get
a 1 a 1 a lT
El = = 5 = 5
l 5
exp(b / lT ) - 1 l 1 + (b / lT ) - 1 l b
aT
or El =
l 4b
which is identical to the Rayleigh-Jeans’ relation (Eq. 1.1.6) provided (a/b) = 8pk.

Theoretical Model After obtaining the expression for the energy distribution in black-body radiation,
of Planck Planck put forward a theoretical model in order to explain the results. He
completely rejected the classical principle of equipartition of energy since this
assumption led to the Rayleigh-Jeans expression. Instead, he used the bold
assumption that the oscillator of the black-body cannot have any amount of energy
but has a discrete energy equal to the integral multiple of some minimum energy
e , i.e.
e i = ne (1.1.8)
where ei is the energy of the ith oscillator and n is an integer.

Average Energy After this, he employed the Boltzmann expression to compute the average energy
of the Oscillator of the oscillator. According to the Boltzmann law, the number of oscillators having
energy ei at temperature T is given by
Ni = n0 exp(- ei /kT) (1.1.9)
where n0 is a constant. With this expression, the average energy of the oscillator
can be computed as follows.
Total number of oscillators, N = Â i Ni
Substituting Ni from Eq. (1.1.9), and by using Eq. (1.1.8), we get
N = n0 + n0 exp(- e /kT) + n0 exp(- 2e/kT ) +
= n0 (1 + x + x 2 + ) (1.1.10)
where x = exp(- e /kT) (1.1.11)
Equation (1.1.10) can be written as
n0
N= (1.1.12)
1- x
since the expansion of (1 - x)-1 gives (1 + x + x 2 + ).
 Wave Mechanics, Energy Quantization and Atomic Structure 5

Now, the average energy E is given by

 i ( Ni e i )
E =
N
Employing Eqs (1.1.8), (1.1.9) and (1.1.11), we get
1 1
[ N 0 (0) + N1 (e ) + N 2 (2e ) + ] = ÈÎn0e( x + 2 x + )˘˚
2
E =
N N
1 Èn e x(1 + 2 x + 3 x 2 + ) ˘
= Î 0 ˚ (1.1.13)
N
The expression within the bracket is equal to 1/(1 - x) 2. It can be proved as follows.
d d Ê 1 ˆ 1
(1 + 2x + 3x2 + ) = (1 + x + x2 + x3 + ) = Á ˜ =
dx dx Ë 1- x ¯ (1 - x) 2
With the above equality, Eq. (1.1.13) becomes
n0 e x / (1 - x )2
E =
N
which on using Eq. (1.1.12) becomes
n0 e x / (1 - x )2 ex
E = =
n0 / (1 - x ) 1- x
e exp(-e/kT ) e
i.e. E = = (1.1.14)
1 - exp(-e/kT ) exp(e/kT ) -1
Energy Emitted Substituting Eq. (1.1.14) and the expression of dn in Eq. (1.1.5), we get
at Wavelength l 8p dl ˆ Ê e ˆ
El dl = ÊÁ
Ë l 4 ˜¯ ÁË exp(e / kT ) - 1˜¯

8p Ê e ˆ
Hence El = Á ˜ (1.1.15)
l 4 Ë exp(e / kT ) - 1¯
Comparing Eqs (1.1.7) and (1.1.15), we have
a = 8pel
b e bk
and = or l =
l k e
Eliminating l in the above two expressions, we have

a = (8pe) ÊÁ ˆ˜
bk
Ë e ¯
or a = 8pbk
Reduction to In Eq. (1.1.15), e represents some minimum energy. If it be assumed that e is
Rayleigh–Jeans’ e Æ 0), it can be shown that the present
Relation approximation would lead to the classical expression of Rayleigh and Jeans. This
is to be expected since the actual energy of an oscillator which is an integral
6 A Textbook of Physical Chemistry

continuously—an assumption of the classical theory. In the above approximation,

we will have
e
exp(e /kT) 1+
kT
8p Ï e ¸ 8pkT
and thus El = Ì ˝ = (Eq. 1.1.6)
l4 Ó1 + (e kT ) - 1 ˛ l4
Reduction to In order that Eq. (1.1.15) could be reduced to the Wien’s relation in the low
Wien’s Relation wavelength region, Planck also took the bold step to state that the energy e is
directly proportional to the frequency of the radiation, i.e.
e μn
or e = hn (1.1.16)
where h is the Planck’s constant and has a value of 6.6252 ¥ 10-34 J s.
Since n = c/l, we have
hc
e = (1.1.17)
l
Substituting Eq. (1.1.17) in Eq. (1.1.15), we have
8p(hc / l )
El = (1.1.18)
l {exp(hc / l kT ) - 1}
4

Now for low values of l , we will have

exp(hc/lkT ) 1
With the above relation, the expression of El is reduced to
8phc
El = exp(- hc/lkT ) (1.1.19)
l5
Comparing the above expression with the Wien’s relation (Eq. 1.1.3), we have
a = 8phc
hc
b =
k
Wavelength of With Eq. (1.1.18), it is possible to reproduce the relative intensities of radiations
Radiation having from a black-body as a function of wavelength, both in the low and high
Maximum Spectral wavelength regions of the spectrum (Fig. 1.1.2). The wavelength at which the
Energy maximum in the spectral distribution of energy of Fig. 1.1.1 is observed can be
computed by differentiating Eq. (1.1.18) with respect to l and then setting the
resultant expression to zero. Starting with the simpler relation given by Eq. (1.1.19),
we have
dEl d
= 8phc [l-5 exp(-hc/lkT )] = 0
dl dl
È(-5)(l -6 ) + l -5 Ê hc ˆ ˘ exp(-hc/lkT ) = 0
or ÍÎ ÁË 2 ˜¯ ˙
l kT ˚
 Wave Mechanics, Energy Quantization and Atomic Structure 7

hc
Thus (- 5)(l-6) + =0
l 7 kT
hc
or lT = = constant
5k
This expression is, in fact, Wien’s displacement law (Eq. 1.1.2).

Summary of Planck’s contribution may be summarized as follows:

Planck’s
Contribution
∑ In order that the Planck’s equation (1.1.7) may be reduced to Rayleigh and
Jeans’equation (1.1.6) only in the longer wavelength region, Planck assumed
that the oscillator in a black-body can exchange energy only by discrete amounts,
i.e. the oscillator cannot radiate or absorb any amount of energy but can do so
only in small lumps or bundles called quanta.
∑ In order that the Planck’s equation may be reduced to the Wien’s equation
(1.1.3) only in the low wavelength region, Planck assumed that the energy of
the oscillator is directly proportional to its frequency with h as the constant of
proportionality. This constant is called Planck’s constant and it has to have a
h cannot be zero since this would lead to the classical
theory of continuous energy distribution.

Problem 1.1.1 Starting from Planck’s radiation law, obtain the Stefan–Boltzmann law E = s ¢T 4 where
E is the total radiation energy from l = 0 to l = •, i.e.
• •
x 3 dx p4
Ú El dl = s ¢T Ú (e x - 1)
4
E= Given: =
0 0 15
Solution The Planck’s equation is
8phc
El =
l {exp(hc l kT ) - 1}
5

Let x = hc/lk T. Therefore

l = hc/xkT and dl = - hc dx/x 2kT

Substituting the above relations in the Planck’s equation, we get
8phc
El =
(hc / xkT )5 (e x - 1)

8phc Ê - hc dx ˆ = E dx
Thus El dl =
(hc / xkT )5 (e x - 1) ÁË x 2 kT ˜¯
x

Integrating the above expression from 0 to •, we have

• 0 0
8phc Ê hc ˆ
E = Ú El dl = Ú Ex dx = Ú (hc / xkT )5 (e x - 1) ÁË - x 2 kT ˜¯
dx
0 • •
8 A Textbook of Physical Chemistry

0 0
8p x3k 4T 4 8pk 4T 4 x3
= –Ú dx = – Ú e x - 1 dx
•
(hc)3 (e x - 1) (hc)3 •

8pk 4T 4 Ê p 4 ˆ 8p5 k 4 4
=– - = T
(hc)3 ÁË 15 ˜¯ 15(hc)3

= s ¢T 4

where s ¢ = 8p 5k4/15(hc)3.

THE PHOTOELECTRIC EFFECT

The Planck’s statement that the oscillators in a black-body radiate energy in
elementary discrete units was extended by Einstein to the extent that the radiation
photons. Thus, Einstein
considered the light wave to be corpuscular in nature with each photon carrying
an energy equal to hn. With the corpuscular nature of light, he was successful in
interpreting the photoelectric effect.

Characteristics In the photoelectric effect, the electrons are emitted instantaneously from a clean
of Photoelectric metal plate in vacuum when a beam of light falls on it. The following characteristics
Effect are observed:

∑ The electrons are emitted instantaneously from a given metal plate when it is
irradiated with radiation of frequency equal to or greater than some minimum
frequency, called the threshold frequency.
∑ The kinetic energy of the emitted electrons depends on the frequency of the
incident radiation and not on its intensity. The kinetic energy of electrons
increases linearly with increase in the frequency of the incident radiation.
∑ The number of electrons emitted is proportional to the intensity of the incident
radiation.

Energy The electron in a metal possesses potential energy (PE) which must be supplied
Requirement for before an electron can be removed from the metal. This energy, known as the work
the Emission of function, is the ionization energy (IE) of the metal. If the emitted electron carries
Electrons some kinetic energy (KE), the total energy supplied to the electron is equal to the
sum of its potential energy and kinetic energy.

Failure of Classical In the classical theory, the energy of the light beam depends on its intensity. Thus,
Theory to Explain a continuous exposure of the metal with light causes the electron to gain more
Photoelectric Effect and more energy from the light and ultimately a stage would be reached when it

there might exist a time interval between the exposure of the metal and the
emission of electron. This time interval may be decreased by increasing the
intensity of the light. Thus, the classical theory of light cannot explain the
characteristics of photoelectric effect listed above, viz., the instantaneous emission
 Wave Mechanics, Energy Quantization and Atomic Structure 9

of electrons, existence of threshold frequency and the dependence of kinetic energy

of the emitted electron on the frequency of the light.

Einstein According to Einstein, the above characteristics can be explained by employing

Explanation of Planck’s idea of quantization of energy. Thus, light may be considered to be made
Photoelectric Effect up of discrete particles called photons. Each photon carries an energy equal to
hn. When this photon collides with the electron of the metal, the electron acquires
energy equal to the energy of the photon. Thus, the energy of the emitted electron
is given by
1
hn = KE + PE = mu 2 + IE (1.1.20)
2
If the incident radiation is of threshold frequency, the electron will be emitted
without any kinetic energy. In this case, we have
hn0 = IE (1.1.21)
It is obvious that if the frequency of the light is smaller than n0, the electron will

From Eq. (1.1.20), it follows that the kinetic energy of electrons depends on
the frequency of incident radiation and not on the intensity of light. By the term
intensity of light, we mean the number of quanta striking the metal per unit time.
This will have an effect only on the number of electrons emitted and not on their
kinetic energy. Thus, the number of electrons emitted increases with increase in
the intensity of light.

Kinetic Energy of Combining Eqs (1.1.20) and (1.1.21), we have

Emitted Electrons hn = KE + hn0 or KE = hn - hn 0 (1.1.22)

From Eq. (1.1.22), it may be concluded that the kinetic energy of the emitted
electrons varies linearly with the frequency of the incident radiation. A plot of
kinetic energy of the emitted electrons versus frequency of the incident radiation
yields a straight line with slope equal to the Planck’s constant h (Fig. 1.1.3). This
provides one of the methods to determine the value of Planck’s constant.

Fig. 1.1.3 Variation

of kinetic energy of the
emitted electrons with
the frequency of the
incident radiation
10 A Textbook of Physical Chemistry

Experimental The kinetic energy of emitted electrons can be determined with a device shown in
Determination of Fig. 1.1.4. In this method, a retarding voltage is applied and its value is steadily
Kinetic Energy of increased till no electrons from the metal plate reach the collector plate (Fig. 1.1.5).
Emitted Electrons
Light beam

+
Metal e–
plate –

Collector G

Fig. 1.1.4 Experimental

device to determine the
kinetic energy of the
emitted electrons

Photoelectric
current

Fig. 1.1.5 Decrease of

photoelectric current
with the retarding Vr 0 +V
potential Anode voltage

The electrical work done in the above process is Vr e, where Vr is the retarding
voltage and e is the electronic charge. The electrical work will be equal to the
kinetic energy of the electrons. Thus, we have
1
|Vr e| = mu2 = hn - hn0 (1.1.23)
2

Example 1.1.1 (a) Calculate the kinetic energy of a photoelectron emitted by a sodium surface when
light of wavelength 400 nm is incident on it. The work function of sodium is 2.28 eV.
(b) Calculate the value of the longest wavelength which can result in the emission of a
photoelectron from a sodium surface.
Solution (a) Energy of the incident photon is

hc (6.626 ¥ 10-34 J s)(3 ¥ 108 m s -1 )

E1 = = = 4.969 ¥ 10-19 J
l (400 ¥ 10-9 m)
 Wave Mechanics, Energy Quantization and Atomic Structure 11

The work function of sodium is

E2 = 2.28 eV ∫ (2.28 eV) (1.602 ¥ 10-19 J/1 eV)

= 3.653 ¥ 10-19 J
Energy carried by the electron is
E3 = E1 – E2 = 4.966 ¥ 10-19 J - 3.653 ¥ 10-19 J = 1.316 ¥ 10-19 J
(b)
hc (6.626 ¥ 10-34 J s)(3 ¥ 108 m s -1 )
l= =
work function (3.653 ¥ 10-19 J )
= 5.441 ¥ 10-7m = 544.1 nm

HEAT CAPACITY

Heat Capacity Einstein also showed that the problem of variation of heat capacity of monatomic
Based on the Law solids with temperature can be resolved by employing Planck’s idea of quantization.
of Equipartition of The monatomic solid may be considered a collection of oscillators with three
Energy vibrational degrees of freedom. On the basis of the classical law of equipartition
of energy, each oscillator of such a solid possesses an average energy equal to 3kT.
Thus, for one mole of oscillators, the molar energy is
E = NA (3kT ) = 3RT (1.1.24)
Since CV = (∂ E/∂T )V, we have
CV = 3R (1.1.25)
According to Eq. (1.1.25), monatomic solids have a constant heat capacity equal
to 3R (a value which was obtained empirically by Dulong and Petit). Experimentally,
it is found that this value of heat capacity is observed only at high temperatures.

Disagreement with According to the classical theory, the heat capacity of a monatomic solid should
Experimental Fact be independent of temperature. This conclusion, however, does not agree with

the decrease in temperature. Figure 1.1.6 depicts such variations for Pb, Cu,
Si and C.

Einstein By employing Planck’s idea of quantization, Einstein was able to explain the
Explanation of variation of heat capacity with temperature. He assumed that the oscillator can
Variation of Heat have vibrational energy which is an integral multiple of some minimum value, i.e.
Capacity E = ne
or n = nn0 (1.1.26)
where n is the frequency of the oscillator and n0 is the smallest allowed frequency.
Thus, all oscillators are not vibrating with the same frequency but have values
which are simply an integral multiple of the smallest frequency n 0. The number
of oscillators possessing the frequency n can be determined from Boltzmann
law (Eq. 1.1.9).
12 A Textbook of Physical Chemistry

Fig. 1.1.6 The

variation of molar
heat capacity with
temperature for Pb,
Cu, Si and C

The average energy of the oscillators as given by Eq. (1.1.14) is

e
E =
exp(e / kT ) -1
Substituting e = hn0 , we get
hn 0
E = (1.1.27)
exp(hn 0 / kT ) - 1
The molar energy of a solid is
Ï hn 0 ¸
E = NA (3 E ) = NA Ì3 ˝ (1.1.28)
Ó exp(hn 0 / kT ) - 1 ˛
and the corresponding value of molar heat capacity is
2
Ê ∂E ˆ Ê hn 0 ˆ exp(hn 0 / kT )
CV = ÁË ˜¯ = 3 NAk Á ˜ (1.1.29)
∂T V Ë kT ¯ {exp(hn / kT ) - 1}2
0

Equation (1.1.29) is known as Einstein equation.

Limiting Value of At low temperatures, we have

CV at Lower hn0 kT
Temperatures
and thus exp(hn0/kT) 1. Under these conditions, Eq. (1.1.29) will reduce to
2
Ê hn 0 ˆ
CV = 3NAk Á
Ë kT ˜¯
exp(- hn0 /kT ) (1.1.30)

On decreasing the temperature, the exponential factor decreases much faster than
the corresponding increase in the factor (hn0 /kT)2. Consequently, CV decreases
with decrease in temperature. Einstein suggested that the above decrease is
basically due to the lesser absorption of energy by the oscillators at low
temperatures. This is so because the oscillators can absorb energy in units of hn 0
and the value of kT is much smaller as compared to hn 0.
 Wave Mechanics, Energy Quantization and Atomic Structure 13

The value of n 0 is different for different solids. The temperature at which

the decrease in heat capacity becomes important depends upon the value of n 0 of
the solid. If we assume the oscillators to be harmonic, then
1 kf
n0 =
2p m
where k f is the Hooke’s law constant of the oscillator and m is its mass (see Section
1.5). It is obvious that the value of n 0 will be larger for more strongly bound atoms
in the solid (k f larger) and for the lighter atoms (m smaller). Thus, solid with
these characteristics will have a high temperature at which the heat capacity will
increase to the classical value of 3R.

Limiting Value of It can be shown that the Einstein equation (1.1.29) can be reduced to the classical
CV at Higher value of 3R at temperatures that are high enough so that the factor hn 0 is much
Temperatures less than kT. Equation (1.1.29) is
2
hn exp(hn 0 / kT )
CV = 3NAk ÊÁ 0 ˆ˜
Ë kT ¯ {exp(hn 0 / kT ) - 1}2
Expanding the exponential factor, we have

hn 2 È 1 + (kn 0 / kT ) + ˘
CV = 3NAk ÊÁ 0 ˆ˜ Í
{ }
Ë kT ¯ 2˙
Í 1 + (hn 0 / kT ) + 1 (hn 0 / kT ) 2 + -1 ˙
Î 2 ˚

(hn 0 / kT ) 2 + (hn 0 / kT )3 +
or CV = 3NAk
{ }
2
1
(hn 0 / kT ) + (hn 0 / kT ) 2 +
2
T, hn 0/kT is very small and the terms with
powers higher than two can be neglected. Thus, we have
CV = 3NAk = 3R

THE BOHR MODEL OF ATOM

Experimental Planck’s idea of quantization of energy was applied by Bohr to the problem of
Findings by hydrogen spectra. Experimentally, it was found by Balmer that the wavelengths of
Balmer about emitted radiations in the visible and near-ultraviolet spectrum of hydrogen could
Hydrogen Spectra be expressed as
Ê n22 ˆ
l /nm = 364.56 Á 2 (1.1.31)
Ë n - n 2 ˜¯
2 1

where n1 and n2 are integer constants. The constant n1

n2 has any integral value greater than 2, i.e. 3, 4, 5, º. For example, the observable
spectral lines in the Balmer series at 656.21 nm, 486.07 nm, 434.0 nm and
410.13 nm of the hydrogen spectra can be reproduced by the above formula as
14 A Textbook of Physical Chemistry

shown in the following.

Ê 32 ˆ
= 364.56 ÊÁ ˆ˜ = 656.21
9
l1 /nm = 656.21 = 364.56 Á 2
Ë 3 - 22 ˜¯ Ë 5¯

Ê 42 ˆ Ê 16 ˆ = 486.08
l2 /nm = 486.07 = 364.56 Á 2 2 ˜ = 364.56 Á
Ë4 -2 ¯ Ë 12 ˜¯

Ê 52 ˆ
= 364.56 ÊÁ ˆ˜ = 434.00
25
l 3 /nm = 434.00 = 364.56 Á 2
Ë 5 - 22 ˜¯ Ë 21¯

Ê 62 ˆ
= 364.56 ÊÁ ˆ˜ = 410.13
36
and l 4/nm = 410.13 = 364.56 Á 2
Ë 6 - 22 ˜¯ Ë 32 ¯
Expressing Eq. (1.1.31) in the frequency unit, we have
c c
n = = -9
l (364.56 ¥ 10 m)[n22 /(n22 - n12 )]

c n22 - n12 c Ê n12 ˆ

= = ÁË1 - n 2 ˜¯
(364.56 ¥ 10-9 m) n22 (364.56 ¥ 10-9 m) 2

c Ê 1 1ˆ
= -9
n12 Á 2 - 2 ˜
(364.56 ¥ 10 m) Ë n1 n2 ¯
Since n1 = 2, we have
4c Ê 1 1ˆ
n = Á
-9
- 2˜
(364.56 ¥ 10 m) Ë n1 n2 ¯
2

Ê 1 1ˆ
or n = RH Á 2 - 2 ˜ (1.1.32)
Ë n1 n2 ¯
Equation (1.1.32) was suggested by Ritz. The constant RH is known as the Rydberg
constant for hydrogen and has a value of 3.289 83 ¥ 1015 Hz. In wavenumber, Rydberg
constant is written as R• = 1.097 37 ¥ 105 cm–1.
Rutherford Model In the Rutherford model of the atom, electrons revolve around the nucleus in such
of Hydrogen Atom a way that the Coulombic attraction of the electron by the nucleus is balanced by
the centrifugal force which tends to pull the electron and nucleus apart, i.e.
|attractive (centripetal) force| = centrifugal force
( Ze)(e) mu 2
= (1.1.33)
(4pe 0 )r 2
r
where e is the elementary charge. All other symbols have their usual meanings.
According to Eq. (1.1.33), the electron can revolve in an orbit which can be at any
distance from the nucleus, i.e. r can have any value. For a given value of r, the
velocity with which an electron moves in the orbit can be calculated from
Eq. (1.1.33). Since r can vary in a continuous manner, the velocity of the electron
can also vary in a continuous manner.
 Wave Mechanics, Energy Quantization and Atomic Structure 15

Instability of The model of atom in which the electrons move in orbits around positively charged
Rutherford Model nucleus would have to be reconciled with the principles of classical electrodynamics,
of Hydrogen Atom according to which a negative charge revolving around a positive charge experiences
a continuous acceleration and thereby should radiate continuous energy. By losing
energy continuously, the electron would come nearer and nearer to the nucleus and
eventually would fall in the nucleus. Thus, it gives rise to an unstable atom—a
conclusion which contradicts the experimental observations (as atom is quite stable)
and moreover, such a model would give rise to continuous spectra instead of the
experimentally determined discrete spectra.

Bohr Model of Bohr resolved the above problem by introducing Planck’s idea of quantization of
Hydrogen Atom
did not adequately represent systems of atomic dimensions and, therefore, it has
to be set aside. His model of atomic structure involved the following postulates.

∑ The electron in an atom can revolve around the nucleus only in certain allowed
circular orbits without losing any energy.
∑ The electron can jump from one of the allowed orbits to another and can thereby
gain or lose energy equivalent to the difference in the energy of the two involved
orbits. Thus, when it jumps from a higher energy orbit to a state of lower energy,
the electron loses energy which appears in the form of radiation of frequency
n such that hn is equal to the difference in the energies of the two states.
Bohr showed that the allowed stationary orbits can be generated by imposing
the quantum restriction on the classical expression given by Eq. (1.1.33) of the
Rutherford’s model. The quantum restriction proposed by Bohr was that the angular
momentum of the revolving electron is an integral multiple of the basic unit of
(h/2p), i.e.

mu r = n Ê ˆ
h
(1.1.34)
Ë 2p ¯
where n is the number of quanta of angular momentum and is known as the quantum
number.† The number n can have only integral values 1, 2, 3, º.
†
This quantum restriction was derived by Bohr from his postulate that the binding energy of
an electron rotating in an orbit of an atom is given by the expression
W = nhw / 2
where n has integral values and w is the angular frequency of rotation of the electron in
an orbit of an atom. The angular momentum expression in terms of frequency of rotation
is given by
u ˆ
L = mu r = mu ÊÁ (since u = 2prw)
Ë 2pw ˜¯

= ÊÁ mu 2 ˆ˜ ÊÁ
1 1 ˆ T
¯ Ë pw ˜¯
=
Ë2 pw
Now since the kinetic energy T is equal to the binding energy W, we have
W 1 Ê nhw ˆ Ê hˆ
L = = Á ˜ = n ÁË ˜¯
pw pw Ë 2 ¯ 2p
16 A Textbook of Physical Chemistry

Radius of The allowed stationary orbits can be obtained by eliminating u from Eqs (1.1.33)
Stationary Orbits and (1.1.34). From Eq. (1.1.34), we have
nh
u=
2pmr
Substituting the above expression in Eq. (1.1.33), we get
Ze 2 m Ê nh ˆ
2
n2h2
2 = =
(4pe 0 )r r Ë 2pmr ¯ 4p 2 mr 3
Cancelling r 2, we have
Ze 2 n2h2
=
4pe 0 4p 2 mr
n 2 h 2 (4pe 0 ) n2
or r = = a0 (1.1.35)
4p 2 mZe 2 Z
h 2 (4pe 0 )
where a0 = (1.1.36)
4p 2 me 2
The quantity a0, known as Bohr radius, has a constant value since all the
quantities on the right side of Eq. (1.1.36) are constants. Its value may be calculated
as follows.
h 2 4pe 0
a0 =
4p 2 m e 2

(6.626 ¥ 10-34 J s) 2
=
4(3.1416) 2 (9.1095 ¥ 10-31 kg )
Ï (4) (3.141) (8.854 2 ¥ 10-12 C2 N -1 m -2 ) ¸
¥ Ì ˝
Ó (1.602 2 ¥ 10-19 C) 2 ˛
-10
= 0.529 ¥ 10 m = 52.9 pm
Comment on the From Eq. (1.1.35), it follows that only certain orbits are allowed since the quantum
Radii of Bohr number n can have only integral values 1, 2, 3, º. The smallest Bohr radius for a
Orbits hydrogen atom is equal to a 0, since n = 1 and Z = 1. The radii of other orbits are
simply n2 times the value of a0. Thus, the second orbit has a radius which is four

and so on (Fig. 1.1.7).

Energy of Electron The total energy of the electron in any orbit consists of two terms, viz., energy due
in a Stationary to its motion (kinetic energy, represented by the symbol T ) and energy by virtue of
Orbit its position relative to the nucleus (potential energy, represented as V). Thus, we
have
E =T+V
1 Ze 2
= mu 2 - (1.1.37)
2 (4pe 0 )r
 Wave Mechanics, Energy Quantization and Atomic Structure 17

n=4

n=3

16a0

9a0

n=2

4a0

n=1

a0

Fig. 1.1.7 Bohr’s

orbits in hydrogen atom

From Eq. (1.1.33), we have

Ze 2
mu 2 =
(4pe 0 )r
Substituting this in Eq. (1.1.37), we have
1 Ze 2 Ze 2 1 Ze 2
E= – =– (1.1.38)
2 (4pe 0 )r (4pe 0 )r 2 (4pe 0 )r
Substituting the expression of r from Eq. (1.1.35), we have
1 Ze 2
E=–
{
2 (4pe 0 ) n 2 h 2 (4pe 0 )/ 4p 2 mZe 2 }
1 Ê 2p 2 mZ 2e 4 ˆ
E=– (1.1.39)
n 2 ÁË h 2 (4pe 0 ) 2 ˜¯
Comment on Since n can have only integral values, it follows that the total energy of the electron
Energies is also quantized. The negative sign in Eq. (1.1.39) tells that the electron is bound
to the nucleus. The electron has a minimum energy when it occupies the lowest
allowed orbit (i.e. n = 1) and its energy increases as n becomes larger and larger.
The electron can have zero value of maximum energy when n = •. The zero energy
means that the electron is no longer bound to the nucleus.
18 A Textbook of Physical Chemistry

Energy Expression Now according to the Bohr postulate, the atom can emit radiations only when the
for the Spectral electron jumps from an orbit of higher energy to one of lower energy. This amounts
Lines to a jump from an orbit of higher quantum number (n2) to the orbit of lower quantum
number (n1). The energy difference would be
DE = En2 - En1
2p 2 mZ 2e 4 Ê 1 1ˆ 2p 2 mZ 2e 4 Ê 1 1ˆ
= 2 Á
- 2 + 2˜ = 2 Á - 2˜
h (4pe 0 ) Ë n2 n1 ¯ h (4pe 0 ) Ë n1 n2 ¯
2 2 2

For the hydrogen atom Z = 1, and thus

2p 2 me 4 Ê 1 1ˆ
DE = 2 Á
- 2˜
h (4pe 0 ) Ë n1 n2 ¯
2 2

Writing this in the frequency unit, we have

DE 2p 2 me 4 Ê 1 1ˆ
n= = 3 2 Á
- 2˜
h (4pe 0 ) Ë n1 n2 ¯
2
h
Ê 1 1ˆ
= RH Á 2 - 2 ˜ (1.1.40)
Ë n1 n2 ¯
where R H = 2p 2me 4/h 3(4pe 0) 2. This equation is, in fact, the Ritz equation
(Eq. 1.1.32).

Calculated Value
of Rydberg the value of which is calculated in the following.
Constant e4
RH = 2p m
2

h3 (4pe 0 )
2

2(3.1416) 2 (9.1095 ¥ 10-31 kg )

=
(6.626 ¥ 10-34 J s)3
È ˘
Í (1.602 2 ¥ 10-19 C) 4 ˙
¥ Í
{ }
-12 2 -1 -2 2˙
Î 4(3.1416)(8.854 2 ¥ 10 C N m ) ˚
= 3.2902 ¥ 10 s 15 –1

In terms of wavenumber, we have

3.2902 ¥ 1015 s -1
R• = -1
= 1.097 2 ¥ 107 m-1
2.997 9 ¥ 10 m s
8

The value of R• is very close to the experimental value of 1.097 37 ¥ 105 cm-1.
Spectral Series Five spectral series of atomic hydrogen are known. These are:
shown by Lyman series Lies in the ultraviolet spectral region.
Hydrogen Atom
Balmer series Lies in the visible region.
Paschen series Lies near infrared region.
Brackett series Lies in the infrared region.
Pfund series Lies in the far infrared region.
 Wave Mechanics, Energy Quantization and Atomic Structure 19

These spectral lines can be generated from Eq. (1.1.40) by giving different values
to n1 and n2. Thus, we have

Lyman series n1 = 1, n2 = 2, 3, 4, º
Balmer series n1 = 2, n2 = 3, 4, 5, º
Paschen series n1 = 3, n2 = 4, 5, 6, º
Brackett series n1 = 4, n 2 = 5, 6, 7, º
Pfund series n1 = 5, n2 = 6, 7, º
These are also shown in Fig. 1.1.8.

– (1/49)E n=7
– (1/36)E n=6
– (1/25)E Pfund n=5
– (1/16)E n=4
Brackett
– (1/9)E n=3
Paschen

– (1/4)E n=2
Balmer

Fig. 1.1.8 A
representation of the
observed spectral lines –E n=1
of the hydrogen atom Lyman

Limitations of At the end some remarks about the Bohr’s theory may be made. The Bohr’s theory
Bohr’s Theory was abandoned twelve years after its formulation in favour of the present quantum
theory of atomic structure. Bohr by introducing quantization of angular momentum
was able to explain the spectral lines of hydrogen atom. His theory can very well
account for the spectral lines for the hydrogenic species—species containing only
one electron such as He+ and Li 2+. Bohr’s theory, however, completely failed when
applied to atoms containing more than one electron. Besides these, Bohr’s theory
provides no explanation for the relative intensities of the various spectral lines and
about the splitting of spectral line into many lines in the presence of a magnetic
20 A Textbook of Physical Chemistry

Correction for the So far in the Bohr’s theory, we have assumed that the nucleus is at rest and the
Finite Mass of the electron is revolving around it. However, this assumption of the nucleus to be at
Nucleus

a common centre of mass which lies on the line connecting the two particles, as
shown in Fig. 1.1.9. In view of this, Bohr’s theory needs to be corrected.

me

r1
Fig. 1.1.9 Electron r2
and the nucleus
revolving around a mp
common centre of mass

It can be shown that the entire formalism of Bohr’s theory remains unaltered
even if the above feature of revolving nucleus and electron around the common
centre of mass is considered. The only change to be made is to replace the mass
of electron me
mp me
m=
mp + me
This may be proved as follows.
The linear velocity u of a particle revolving around a point can be expressed in
terms of its angular velocity w by an expression†
u = wr (1.1.41)
Now the orbital angular momentum of the electron
= mu r = mr 2w (1.1.42)
For the entire atom, the total orbital angular momentum is equal to the sum of the
orbital angular momenta for the electron of mass me and for the proton of mass
m p. Thus, we have
L = me r 12 w + mp r 22 w (1.1.43)
where the angular velocity w is the same for both electron and proton. The distances
r1 and r2 can be expressed in terms of the distance r between the proton and the

†
By definition, w is expressed in radians/second. In one revolution, the particle covers a
distance of 2pr and traverses an angle of 2p radians. If n is the frequency of rotation (number
of cycles/second), it follows that
u = (2pr)n and w = (2p)n
Hence u = wr
 Wave Mechanics, Energy Quantization and Atomic Structure 21

electron. From the location of centre of mass, we have

me r1 = mp r2
Combining this with the relation r = r1 + r2, we have
mp me
r1 = r and r2 = r
mp + me me + mp

2 2
Ê mp ˆ Ê me ˆ
L = me
Ám +m r ˜ w + mp Á r˜ w
Ë e p ¯ Ë me + mp ¯
Ê me mp ˆ 2
= Á ˜r w
Ë me + mp ¯
or L = mr 2w = Iw (1.1.44)
where I is the moment of inertia of the molecule. In a similar manner, it can be
shown that the expressions corresponding to the kinetic energy and centrifugal
force are
1 1
KE = m (rw)2 = Iw2 (1.1.45)
2 2
m (rw ) 2 Iw 2
Centrifugal force = = (1.1.46)
r r
Comparing Eq. (1.1.44) with Eq. (1.1.42), we observe that the orbital angular
momentum of a system involving the revolution of two particles (interparticle
distance r) can be obtained from the corresponding expression for a single revolving
particle by simply replacing the mass m by the reduced mass m and linear velocity
of the particle by r times its angular velocity. Comparison of Eqs (1.1.45) and
(1.1.46) with those for the single particle also leads to the same conclusion. In
other words, we can say that the system involving the revolution of two particles
may be replaced by a hypothetical, but mathematically equivalent, model in which
one of the particles (heavier one) is at rest and the other is revolving around it
with a mass of m instead of m.
Now the correction to Bohr’s theory can be made by simply replacing the mass
of electron me by the reduced mass m. Thus, the corrected expressions are
2p 2 m e 4
E = -
n h (4pe 0 ) 2
2 2

n 2 h 2 (4pe 0 )
r = = n2a0
4p 2 m e 2
h 2 (4pe 0 )
where a0 =
4p 2 m e 2

n = 2p 2 m e 4 Ê 1 1ˆ
and 2 Á
- 2˜
ch (4pe 0 ) Ë n1 n2 ¯
3 2
22 A Textbook of Physical Chemistry

Example 1.1.2
Given: a0
Solution We have
u =nÊ
hˆ 1
Ë 2p ¯ mr
n
(6.626 ¥ 10-34 J s)
u = (1)
(2) (3.1416) (9.1095 ¥ 10-31 kg) (52.9 ¥ 10-12 m)
-1
¥ 106
Example 1.1.3
Solution

n1 = 1 and n2 = •
2p 2 m Ê e4 ˆ Ê 1 1ˆ 2p 2 m Ê e 4 ˆ
DE =
h 2 ÁË ( 4pe ) 2 ˜¯ ÁË n 2 - n 2 ˜¯ = h 2 ÁË ( 4pe ) 2 ˜¯
0 1 2 0

2(3.1416) 2 (9.1095 ¥ 10-31 kg ) ÈÍ (1.602 2 ¥ 10-19 C) 4 ˘

˙
DE =
(6.626 ¥ 10-34 J s) 2 {
Í 4(3.1416)(8.854 2 ¥ 10-12 C2 N -1 m -2 ) }
2˙
Î ˚
¥ 10- J
Example 1.1.4
2+
Solution
2+
Æ 3+
+ e- Z
Ê 2p 2 m ˆ Ê e 4 ˆ
DE ÁË h 2 ˜¯ ÁË (4pe ) 2 ˜¯
0

DE ¥ ¥ 10 - ¥ 10 -17 J
¥ 10-
1.962 ¥ 10-17
D E/eV =
1.602 ¥ 10-19

1.2 TOWARDS THE WAVE NATURE OF THE ELECTRON

Wave-Particle
Duality
 Wave Mechanics, Energy Quantization and Atomic Structure 23

hc
Planck’s relation E = hn =
l
Einstein’s relation E = mc 2

hc h
mc 2 = or mc =
l l
m)
l c in
mc
p
h †
p =
l
c
u

Wavelength of l for an electron accelerated

an Electron–A V
Specific Example
1
mu 2 = eV
2

12
p = mu = m ÊÁ
2eV ˆ
= (2meV )1/ 2
Ë m ˜¯

h h h
l= = 1/ 2 = V -1/2
p (2meV ) (2me)1/ 2
h m and e
(6.626 ¥ 10-34 J s)
l = V -1/2
{2(9.109 ¥ 10 }
-31 -19 1/ 2
kg)(1.602 ¥ 10 C)
- -1/2
l ¥ 10 (V /volt)

l ¥ 10 - ¥ (300)-1/2 ¥ 10 -11
†
 A Textbook of Physical Chemistry

Experimental The appearanc

Verification of
Wave Nature of
Electron

are of the orde

Comment on the
Wave Nature of
Particles of Larger
Masses

Application of the
de Broglie
Relation to the
Hydrogen Atom

2p r = nl n …

l l

l
l
Fig. 1.2.1 A standing
electron wave in the
Bohr’s orbit
l
 Wave Mechanics, Energy Quantization and Atomic Structure 25

Ê hˆ
or pr = L = n Ê ˆ
h
2pr = n Á ˜
Ë p¯ Ë 2p ¯

Example 1.2.1
a potential difference of 500 V?
1
Solution Since mu 2 = eV
2
1/2
1/ 2
Ï 2(1.602 ¥ 10-19C)(500 V) ¸
u = ÊÁ
2eV ˆ
= Ì ˝
Ë m ˜¯ Ó 9.109 ¥ 10-31 kg ˛
-1
¥ 10 7
h (6.626 ¥ 10-34 J s)
l = =
(2meV )1 / 2 {2(9.109 ¥ 10-31 kg)(1.602 ¥ 10-19 C)(500 V)}
1/ 2

¥ 10 -10

Example 1.2.2

Solution (a)
h
u=
ml

(6.626 ¥ 10-34 J s) -1
u= ¥ 10 6
(9.109 ¥ 10-31 kg )(0.1 ¥ 10-9 m )
(b)
l ¥ 10- (V/volt)-1/2
2 2
Ê 1.227 ¥ 10-9 ˆ Ê 1.227 ¥ 10-9 ˆ
V/volt = Á ˜¯ = Á
Ë l m Ë 0.1 ¥ 10-9 ˜¯
(c)
1 1
= mu 2 = ¥ 10-31 ¥ 106 -1 2
)
2 2
¥ 10-17 J

hc
¥ 10-17 J
l
26 A Textbook of Physical Chemistry

hc (6.626 ¥ 10-34 J s)(3 ¥ 108 m s -1 )

or l = -17
=
2.414 ¥ 10 J (2.414 ¥ 10-17 J )
¥ 10 -

THE UNCERTAINTY PRINCIPLE

Statement of
the Uncertainty p l
Principle
p l
p

it is not possible to design an experiment with the help of which one can
determine simultaneously the precise values of both the position and the momentum
of subatomic particles

Qualitative
Explanation
of Uncertainty
Principle
a

2a
hv¢
Radiation hv q
Fig. 1.2.2 Location of x
electron b
the electron with the
help of a microscope
 Wave Mechanics, Energy Quantization and Atomic Structure 27

b x

h hv
p1 = =
l c

h hv ¢
p2 = =
l¢ c

1 p2
hv = hv¢ + mu2 = hv¢ +
2 2m
x- and
y-directions are
hv hv ¢
For x = cos q + p cos b
c c
hv ¢
For y sin q - p sin b
c
b
2
hv hv ¢ Ê hv ¢ ˆ
= cos q + p 1 - Á sinq ˜
c c Ë pc ¯
hn ¢
2
hv 1 Ê p2 ˆ Ê hv - p 2 / 2m ˆ
= hv - cos q + p 1+ Á sinq ˜
c c ÁË 2m ˜¯ Ë pc ¯

a q
a in order that it passes
Dq -a a
Dp

Approximate x and
Expression of p
Uncertainty Principle
A Textbook of Physical Chemistry

We have
hv hv ¢
= cos q + p cos b
c c
hv hv ¢ hv
or p cos b = – cos q (1 - cos q
c c c

x
a

hv hv
[1 - - a)] = (1 - sin a)
c c
hv hv
and [1 - + a)] = (1 + sin a)
c c
p is
2hv
|Dp| = sin a
c

l c
Dx =
sin a v sin a

Ê c ˆ
D p Dx = ÊÁ sin a ˆ˜ Á
2hv †
¯ Ë v sin a ˜¯
2h
Ë c

a a
†
The exact expression of uncertainty principle as given by Heisenberg is
h
D p Dx ≥
p
Dp and Dx

D p = ( · p2 Ò - · pÒ 2 )1/2 and Dx = ( ·x2 Ò - · x Ò 2 )1/2

· Ò

h
DE D t ≥
p
 Wave Mechanics, Energy Quantization and Atomic Structure

the value of Dp p
a
x
g
x
in p x and p

Consequence
of Uncertainty
Principle

the r
u
h
D x Dp = (Dx) (m Du) =
p

h 1
or Du =
p Dx
m

(6.626 ¥ 10-34 J s) -1
Du = ¥ 107
4(3.14)(9.109 ¥ 10-31 kg )(5 ¥ 10-12 m)

h 1 (6.626 ¥ 10-34 J s)
Du = = ¥ 10 -23 -1
p m Dx 4(3.14)(0.200 kg )(5 ¥ 10-12 m)
30 A Textbook of Physical Chemistry

1.3 SCHRÖDINGER WAVE THEORY

Necessity of Wave
Theory

Equation
Representing Ê ∂2Y ˆ 1 Ê∂ Yˆ
2
Standing Wave ÁË ∂x 2 ˜¯ = 2 ÁË ∂t 2 ˜¯
System t u x
Y x
t u u
Y
x
Y is
Y = y (x pvt
v -1

Ê ∂2y exp{i(2pvt )}ˆ 1 Ê ∂ y exp{i(2pvt )}ˆ

2

ÁË ˜¯ = Á ˜¯
∂x 2 t u2 Ë ∂t 2 x

d 2y 1
pvt )} 2
= 2
y(2pvi)2 pvt)}
dx u
d 2y 4p 2 v 2
or =– y
dx 2 u2
n u
u = lv
l

d 2y 4p 2
=– y
dx 2 l2
 Wave Mechanics, Energy Quantization and Atomic Structure 31

Eigenvalue pvt
Problem x
2
/dx2
function y y - p 2/l2
eigenvalue equation y is an
eigenfunction and the constant (- p 2/l2 eigenvalue

function y

∑ The function y
∑ The y single valued and x

y has a single value at x = x

y = 0 at
x=l
y = 0 at
x=0

Fig. 1.3.1 Vibrating

0 l
x

y (x y (x y z) and the operator d 2/dx2

∂2 ∂2 ∂2
+ +
∂x 2 ∂y 2
∂z 2

∂2y ∂2y ∂2y 4p 2

+ + =– y
∂x 2 ∂y 2
∂z 2 l2

4p 2
— 2y + y
l2
—2 ∂ 2/∂x2 ) + (∂2/∂y 2) + (∂ 2/∂z 2 Laplacian
operator del squared
Schrödinger
Equation
l
l = h/p

— 2y + 4p p y
2 2

h2
32 A Textbook of Physical Chemistry

E mu2 + V
p2
or E= +V
2m
or p = 2m (E - V
2

8p 2 m
— 2y + (E - V )y
h2

Quantum
Mechanical
Framework ∑ F y of the

∑ The function y

y
∑
†
The

xÆx

h ∂ h ∂ h ∂
px Æ py Æ pz Æ ‡
2pi ∂x 2pi ∂y 2pi ∂z
†

x and d 2/dx2

a (Cy) = C(a y)
C x
÷(Cy ) π C(÷y

‡
The form of operators given by Eq. (1.3.11) may be taken as such without any rigorous deri-
vation. However, these can be derived by combining the wave expression (Eq. 1.3.5) with de
Broglie relation as shown in the following.
d 2y 4p 2 4p 2 2p i ˆ 2 2
y =– y = ÊÁ px y
Ë h ˜¯
=–
dx 2 l2 (h px )2
2
Ê h dˆ 2 h d
or ÁË 2p i dx ˜¯ y = px y or
2p i dx
y = px y

h/2pi) (∂/∂x) is the operator for the x

 Wave Mechanics, Energy Quantization and Atomic Structure 33

∑ Â
Âop y = ay
 acts on the function y
y
a
y  and a

∑ Â
Â
· AÒ

· AÒ = Ú y * Â y dt
Ú y *y dt
y y

value of  a:

·AÒ = Ú y * Ây dt = Ú y * (ay ) dt =aÚ

y * y dt
=a
Ú y * y dt Ú y *y dt Ú y *y dt
·AÒ

variation theorem

Derivation of
Schrödinger
Equation
E
1 p2
E=T+V= mu 2 + V = +V
2 2m

px2 + p 2y + pz2
E= +V
2m
E

h ∂ h ∂ h ∂
px Æ py Æ pz Æ
2pi ∂x 2pi ∂y 2pi ∂z

and V ÆV
E is called the Hamiltonian operator
H
 A Textbook of Physical Chemistry

ÔÏÊ h ∂ ˆ Ê h ∂ ˆ Ê h ∂ ˆ Ô¸
2 2 2
1 +Á +
H = ÌË ˜ ˝+ V
2m ÔÓ 2pi ∂x ¯ Ë 2pi ∂y ¯ Ë 2pi ∂z ¯ Ô˛

h 2 Ê ∂2 ∂2 ∂2 ˆ
=– + + +V
8p 2 m ÁË ∂x 2 ∂y 2 ∂z 2 ˜¯

h2
or H =– 2
—2 + V
8p m

H y = Ey
E H

Ê h2 ˆ
ÁË - 8p 2 m — + V ˜¯ y = Ey
2

8p 2 m
or — 2y + (E - V )y
h2

Born
Interpretation of y y
the Wave Function

the
square of the function y at any point is proportional to the probability of

y
y2
y *y y y
(= -1 ) -

dxdydz situated at a point in space is proportional to

y *y dx dy dz or y *y dt
t = dx dy dz

Normalized Wave
Function

Ú y *y dt =N
 Wave Mechanics, Energy Quantization and Atomic Structure 35

1
N Ú y * y dt =1

Ê 1 ˆ Ê 1 ˆ
or Ú Ë N 1/ 2 y *¯ ÁË N 1/ 2 y ˜¯ dt
The factor 1/N 1 / 2 normalization constant
independent of the coordinates x y and z N 1/2)y
normalized function

Orthogonal Wave
Functions

Ú y i y j dt =0

Orthonormal Set
of Wave Functions d = 0 if i π j
È ij
Ú y i y j dt = d ij Í
Î dij = 1 if i = j

d is called

Problem 1.3.1 The operator Â

Ú y *n  y m dt = Ú y m Â* y n* dt
ym and yn Â

·ymynÒ

Solution (a) yn  and let a n

Âyn = an y n (1)
y *n

Ú y *n Ây n dt = a n Ú y *n yn dt (2)

Ú yn Â* y *n dt = a*n Ú yn y *n dt (3)
36 A Textbook of Physical Chemistry

Since Â

an Ú y *n y n dt = a n* Ú yn y *n dt or (a n - a*n ) Ú y *n yn dt
Since Ú y *n yn dt
a n = a*n (5)
a

(b) a m and a n y m and y n

Ây m = amym (6)
Â* y *n = a ny *n (7)
y *n

Ú y *n Âym dt = a m Ú y *n ym dt
ym

Ú y m Â* y*n dt = a n Ú y *n ym dt
Since Aop

am Ú y *n ym dt = an Ú y *n ym dt
or (a m - an) Ú y *n ym dt = 0
Since a m

Ú y *n ym dt = 0 (10)

Problem 1.3.2 y of an operator Â

ji
y= Â i ci j i
· AÒ for the function y
Â
Solution ·AÒ for the function y

· AÒ = Ú y Ây dt
Ú y y dt
y= Â i ci j i
 Wave Mechanics, Energy Quantization and Atomic Structure 37

· AÒ =
Ú {(Â i ci ji ) Â (Â i ci ji )} dt
Ú (Â i ci ji ) dt
2

=
Ú {(Â c j ) (Â c Âj )} dt
i i i i i i
=
Ú {(Â i ci ji ) (Â i ci ai ji )} dt
Ú (Â i ci ji ) Ú (Â i ci ji ) dt
2 2
dt

Ú j i j i dt = d ij

 i ci2 ai
·A Ò =
 i ci2
y  i ci2 c2i
ai
· AÒ = Â ci2 ai ai

1.4 QUANTIZATION OF TRANSLATIONAL ENERGY

Introduction

PRACTICE IN A ONE-DIMENSIONAL BOX

m
l
V

Fig. 1.4.1 The particle Vx = • Vx = 0 Vx = •

Vx = 0

Vx = •
0 l
 A Textbook of Physical Chemistry

Wave Function
of the Particle
Outside the Box d 2y 8p 2 m
+ (E - V )y
dx 2 h2
The function y x

d 2y 8p 2 m
+ (E - •)y = 0
dx2
h2
E •
d 2y 1 d 2y
=•¥y or y=
dx 2 • dx 2
y
x l
Form of
Schrödinger
Equation within
the Box d 2y 8p 2 m
+ Ey = 0
dx 2 h2

d 2y
+ a 2y
2
dx

8p 2 mE
a2 =
h2
Expression of
Wave Functions y = A sin (a x) + B cos (a x
A and B
A B and a

y = 0 at x = 0 and x = l

For y = 0 at x
0 = A sin (a ¥ 0) + B cos (a ¥ 0)

y = A sin (a x

For y = 0 at x = l

0 = A sin (a l )
 Wave Mechanics, Energy Quantization and Atomic Structure

al p
a l = np
n … n
since it leads to a = 0 or y (x a

np ˆ
y = A sin Ê x
Ë l ¯
Energies of the
Particle
8p 2 mE a 2h2
a2 = or E =
h2 8p 2 m
a

(n 2 p 2 / l 2 )h 2
E=
8p 2 m

Ê h2 ˆ
or E = n2 Á
Ë 8ml 2 ˜¯
Since the constant n

n represents the quantum number

Step Responsible
for Quantization of E
Energy a y = A sin (a x) + B
cos (a x a

E
E E
y x=0
and x = l a

p
a = nÊ ˆ
Ël¯
n …
 A Textbook of Physical Chemistry

Ê h2 ˆ
E = n2 Á
Ë 8ml 2 ˜¯
Factors
Governing the
Difference DE = En + 1 - En = (2n + 1)h 2 ml2
between the Two The e DE
Successive
Energy Levels
DE

DE

Normalization A
of the Wave
Functions
x = 0 to x = l

l l l
np 2 È
1 - cos (2np x / l ) ˘
1 = Ú y * y dx = A 2 Ú sin ÊË l xˆ¯ dx = A Ú0 ÍÎ ˙˚ d x
2
2
0 0

1 = A2 l A= 2
2 l

y= 2 sin Ê np ˆ
x
l Ë l ¯

Orthogonality of Fr
the Wave Functions
n
 Wave Mechanics, Energy Quantization and Atomic Structure 41

Ú y m* yn dt = 0
all space

where m and n are two different quantum numbers. For a particle in the one-
dimensional box, we have

y *m = ym = 2 sin Ê mpx ˆ
l Ë l ¯

yn = 2 sin Ê npx ˆ
l Ë l ¯

Thus, from the condition of orthogonality, we have

l
2 l mpx ˆ Ê npx ˆ
Ú y m* y ndx = sin Ê
l Ú Ë l ¯ Ë l ¯
sin dx
0 0

Following the trigonometric equation

(sin a) (sin b) = 1 cos (a - b) - 1 cos (a + b)

2 2
the right side of above expression becomes

{ } { }
l
1 È - cos (m + n)p ˘˙ dx
x x
l Ú ÍÎcos ( m - n) p
l l ˚
0

which on integration gives

{ } { }
t
1 È l x l x ˘
Í (m - n)p sin (m - n)p l - (m + n)p sin (m + n)p l ˙
l Î ˚0

Since m and n are integers, the above expression is numerically equal to zero.

The different wave functions generated by Eq. (1.4.11) are collectively

referred to as an orthogonal set. Furthermore, if each wave function in an
orthogonal set is also normalized, the set is known as orthonormal set (orthogonal
and normalized).

Plot of y and y 2 x is

npx ˆ
sin 2 Ê
2
y 2n = (1.4.12)
l Ë l ¯

Figure 1.4.2 illustrates the various wave functions, the corresponding energy
levels and the probability densities for a few lower quantum numbers n.
42 A Textbook of Physical Chemistry

Fig. 1.4.2 The

energies, wave
functions and
probability densities of
a particle in a box

A Few Features of The following features about the wave function and the probability distribution
a Particle in a Box may be pointed out.

∑ In order that the function y is zero at the walls, the length l of the box must
be an integral multiple of half-wavelengths, i.e.
l
l = n ÊÁ ˆ˜ (1.4.13)
Ë 2¯
Equation (1.4.13) can be derived starting from the relation
Ê h2 ˆ
E = n2 Á (Eq. 1.4.9)
Ë 8ml 2 ˜¯
 Wave Mechanics, Energy Quantization and Atomic Structure 43

1 p2
Now E= mu 2 =
2 2m
Using the de Broglie’s relation, we have
p2 (h / l )2 h2
E= = = (1.4.14)
2m 2m 2 ml 2
Equating Eqs (1.4.9) and (1.4.14), we get

h2 n2 h2 1 n2
= , i.e. =
2 ml 2 8ml 2 l2 4l 2
l
or l = n ÊÁ ˆ˜
Ë 2¯
Thus, the wave functions besides being zero at the walls of the box also have
zero values at various points within the box. The number of times the wave
function becomes zero, as may be seen from Fig. 1.4.2, is equal to (n - 1),
where n is the quantum number. The point at which wave function has a zero
value is known as the node of the wave function.
∑ The energy associated with a wave function increases with increase in the
number of nodes of the function.
∑ The symmetry of the wave functions with respect to the centre of the box may

Symmetric (or even) function where y (x) = y (- x)

Antisymmetric (or odd ) functions where y (x) = - y (- x)
From Fig. 1.4.2, it may be concluded that the functions y1, y 3, y5, …, etc.,
are symmetric functions whereas the functions y2, y4, y6, …, are antisymmetric
functions with respect to the centre of the box.
∑ The probability density is not uniform at all positions. This is more pronounced
when n is small. However, the distribution becomes more and more uniform as
n increases and will be completely uniform for very high value of n. According
to classical mechanics, the particle spends, on an average, equal amounts of
time at all points and this is achieved only when n attains a very large number.
Thus, the classical behaviour emerges when n becomes very large. This fact
is in agreement with the correspondence principle, according to which, the
predictions of quantum mechanics for a very large value of n are identical to
those predicted by classical mechanics.

Free-Electron An important application of particle in a one-dimensional box may be mentioned

Model here. The p
a one-dimensional box.† The length of the box may be taken as the end-to-end

†
Although a polyene is not a linear molecule it is assumed, for simplicity, that it is a
linear molecule.
44 A Textbook of Physical Chemistry

distance of the molecule.† Thus, knowing me and l, the electronic energy levels
in polyenes can be determined by using Eq. (1.4.9). The p-electrons of polyenes
are distributed over these levels following the Pauli exclusion (see Sections 1.12
and 1.14) and aufbau principles. The energy difference between the highest
occupied level (n) and the lowest unoccupied level (n
the electron transition energy.‡ The difference between these two levels is
D E = En + 1 - En
(n +1) 2 h 2 n2 h2 Ê h2 ˆ
= – = {(n + 1)2 - n2} Á 2 ˜
2
8l m 2
8l m Ë 8l m ¯

h2
= (2n + 1) (1.4.15)
8l 2 m
For example, in butadiene molecule we will have
l = 1(single bond-length) + 2(double bond-length) + 154 pm
= (154 pm) + 2(135 pm) + 154 pm
= 578 pm = 5.78 ¥ 10-10 m

Number of electrons 4
n= = =2
2 2

(6.626 ¥ 10-34 J s) 2
Hence D E = (2 ¥ 2 + 1)
8(5.78 ¥ 10-10 m) 2 (9.11 ¥ 10-31 kg )
= 9.02 ¥ 10-19 J
DE (9.02 ¥ 10-19 J )
DE = =
hc (6.626 ¥ 10-34 J s)(2.998 ¥ 108 m s -1 )

= 4.54 ¥ 106 m-1 = 4.54 ¥ 104 cm-1

The corresponding experimental value is 4.61 ¥ 104 cm-1.

Example 1.4.1 Consider a ball of mass 1 g moving with a speed 1 cm s-1 in a one-dimensional box of
edge-length equal to 10 cm. (i) Calculate its kinetic energy and the number n corresponding
to this kinetic energy. (ii) If the ball is to be promoted to the next higher quantum level, then
how much of energy is required? From the obtained value, justify that the kinetic energy of
a larger mass varies in a continuous manner.
Solution (i) Kinetic energy of the ball is

En = 1 mu 2 = ÊÁ ˆ˜ (10-3 kg) (10-2 m s-1)2

1
2 Ë ¯ 2
= 0.5 ¥ 10-7 J

†
In many cases, the end-to-end distance of the molecule is extended by a half C—C distance
on either side of the molecule, i.e. another 154 pm distance is considered.
‡
See Section 4.1 for the selection rule of particle in a box.
 Wave Mechanics, Energy Quantization and Atomic Structure 45

En = n 2 ÏÌ h ¸˝ , therefore
2
Since
2
Ó 8l m ˛
En E 8l 2 m (0.5 ¥ 10-7 J ) (8) (10-1 m) 2 (10-3 kg )
n2 = = n 2 =
(6.626 ¥ 10-34 J s) 2
2 2
(h / 8l m) h

= 9.11 ¥ 1054
or n 3.02 ¥ 10 27
D E = En + 1 - En = (2n + 1) Ê h ˆ
2
(ii) Now
ÁË 8l 2 m ˜¯

-34
= (2 ¥ 3.02 ¥ 1027 + 1) ÏÌ (6.626 ¥ 10 J s) ¸˝
2

-1 2 -3
Ó 8(10 m) (10 kg) ˛
= 3.32 ¥ 10 -35 J
It is impossible to observe such a small energy difference and thus E may be taken
to vary in a continuous manner—a characteristic of classical mechanics.

Example 1.4.2

x = 0 and
x = 0.2 nm?

h2 (6.26 ¥ 10-34 J s) 2
Solution (i) E1 = = = 6.025 ¥ 10-20 J
8mel 2
8(9.109 ¥ 10-31 kg )(10-9 m) 2

(ii) Now E2 = (4) E1 = 24.1 ¥ 10-20 J

Hence D E = E2 - E1 = 4E1 - E1 = 3E1 = 18.075 ¥ 10-20 J

(iii) x = 0 to x = 0.2 nm is
x = 0.2 nm x = 0.2 nm
2
Ú y 12 dx =
l Ú sin 2 (p x/l ) dx
x=0 x=0

x = 0.2 nm
2 Ê 1 ˆ [1 - cos (2px /l )] dx
=
l Ú ÁË ˜¯
2
x=0

0.2 nm
2 Èx sin (2p x / l ) ˘
= Í -
l Î2 2 (2p / l ) ˙˚0

=
2 È 0.2 nm - (1 nm) sin (0.4 p )˘
(l nm) ÍÎ 2 4p ˙˚

{ 1
Ë ¯ 4p }
= 2 0.1 - ÊÁ ˆ˜ (0.9511) = 2(0.1 - 0.075 7) = 0.048 6
46 A Textbook of Physical Chemistry

Problem 1.4.1 The quantum mechanical operator for the linear momentum in one direction is
(h/2 pi)/(d/dx). Apply this operator on the eigenfunctions of particle in a one-dimensional
box and thus show that these functions are not eigenfunctions of the momentum operator
and suggest a possible reason for this.
Solution The expression of eigenfunction for one-dimensional box is given by the expression
npx ˆ
sin ÊÁ
2
yn =
l Ë l ˜¯

h d h d Ê 2 sin npx ˆ
yn = Á l ˜¯
Therefore
2pi dx 2pi dx Ë l

h 2 np npx
= cos
2pi l l l

h d
Since y n π (constant) yn
2pi dx
it follows that y n is not an eigenfunction of the momentum operator.
The particle in the box has only kinetic energy, which is related to the momentum p by
E = p 2/2m. Thus p = ± 2mE . Thus for a given value of E, two directions of the momentum

Problem 1.4.2 Evaluate the expectation value of kinetic energy of a particle in a one-dimensional box by
making use of Eq. (1.3.13).
Solution The kinetic energy of the particle is given by

1 1 (mu ) 2 p2
T= mu 2 = =
2 2 m 2m
The corresponding quantum mechanical operator is

1 Ê h d ˆ2 h2 d 2
T = 2m ÁË 2pi dx ˜¯ = – 8p 2 m dx 2

The wave function for the particle in a one-dimensional box is given by

npx ˆ
sin ÊÁ
2
y =
l Ë l ¯˜

Since y is normalized function, the expression for the expectation value as given by
Eq. (1.3.13) becomes
l
· T Ò = Ú y ( T )y dt
0

Substituting the expression of y, we get

l
npx ˆ Ê h2 d 2 ˆ npx ˆ
sin ÊÁ sin ÊÁ
2 2
·T Ò = Ú l
˜ -
Ë l ¯ Ë 8p 2 m dx 2 ˜¯
Á l Ë l ˜¯
dx
0
 Wave Mechanics, Energy Quantization and Atomic Structure 47

2 Ê h ˆ 2 l
n p x ˆ È d2 Ê n p x ˆ ˘ dx
= ÊÁ ˆ˜ Á - 2 ˜ sin ÊÁ
Ë l ¯ Ë 8p m ¯ Ú ˜ Í 2 sin Á
Ë l ¯ Î dx ˜˙
Ë l ¯˚
0

2 Ê h2 ˆ Ï n p ¸
2 l
n p xˆ
= ÊÁ ˆ˜ Á - 2 ˜ Ì- ÊÁ ˆ˜ ˝ sin 2 ÊÁ
Ë l ¯ Ë 8p m ¯ ÓÔ Ë l ¯ ˛Ô Ú Ë l ¯ ˜ dx
0

2 Ê h ˆ np2 2 l
È1 - cos Ê 2n p x ˆ ˘ dx
= ÊÁ ˆ˜ Á 2 ˜ ÊÁ ˆ˜ 1
Ë l ¯ Ë 8p m ¯ Ë l ¯ Ú 2 ÍÎ ÁË ˜
l ¯ ˙˚
0

2
2 Ê h ˆ np2 2
= ÊÁ ˆ˜ Á 2 ˜ ÊÁ ˆ˜ ÊÁ ˆ˜ l
1
Ë l ¯ Ë 8p m ¯ Ë l ¯ Ë 2 ¯

2 2
= n h
8ml 2
Note: T y will give (n2h2/8ml2 )y indicating that n2h2/8ml 2 is an eigenvalue. This is due
to the fact that y is an eigenfunction of Top .

Problem 1.4.3 (a) Apply the variation functions (i) x, (ii) x2, (iii) x(l - x), (iv) x2(l - x)2 and (v) sin p x/ l
to the particle in a box (V = 0 for 0 < x < l and V = • elsewhere) and estimate the ground

state energy = h 2/8ml 2. (b) Explain why the functions (i) and (ii) cannot be used as varia-
tion function for the particle in a box. (c) Explain whether the functions (iii), (iv) and (v)
satisfy the variation principle or not.
Solution (a) The ground state energy can be computed from the relation
y | H |y
· EÒ =
y y
where H , the Hamiltonian operator, is given by the relation
2
H = – h2 d2
8p m dx 2
Thus, we have
h2 d 2
x- x
8p 2 m dx 2
(i) · EÒ = =0
x| x

0 - (h 2 / 8ml 2 )
Per cent error = ¥ 100 = - 100
(h 2 / 8ml 2 )

h2 d 2 2 Èl 2 ˘
x2 - x Í Ú x dx ˙
8p 2 m dx 2 h2 Í0 ˙
(ii) · EÒ = =- (2) Íl ˙
· x2 | x2 Ò 8p 2 m
Í x 4 dx ˙
ÍÎ Ú ˙˚
0

=-
h2
2
8p m
È l3 /3˘
(2) Í 5 ˙ = -
Îl /5˚
h2
8ml 2 { }
10
3p 2
48 A Textbook of Physical Chemistry

(h 2 / 8ml 2 )(-10 / 3p 2 ) - (h 2 / 8ml 2 )

Per cent error = ¥ 100
(h 2 / 8ml 2 )

- (10 / 3p 2 ) - 1
= ¥ 100 = – 133.75
1

h2 d 2
x (l - x) - x (l - x)
8p 2 m dx 2
(iii) · EÒ =
x (l - x) | x(l - x)

È l ˘
h 2
Í
Í
Ú x(l - x) dx ˙
˙ h2 È (l 3 / 2) - (l 3 / 3) ˘
= (2) Í l 0 ˙ = (2) Í 5 ˙
2
8p m 8p 2
m Î (l / 3) + (l 5
/ 5) - (l 5
/ 2 ) ˚
Í x 2 (l - x) 2 dx ˙
ÍÎ Ú ˙˚
0

h 2 Ê 10 ˆ
= Á ˜
8ml 2 Ë p 2 ¯

(h 2 / 8ml 2 )(10 / p 2 ) - (h 2 / 8ml 2 )

Per cent error = ¥ 100
(h 2 / 8ml 2 )
= + 1.24
h2 d 2 2
x 2 (l - x) 2 - x (l - x) 2
8 p 2 m dx 2
(iv) ·E Ò =
x 2 (l - x) 2 | x 2 (l - x) 2

Èl ˘

Ê h2 ˆ Í
Ú
Í x 2 (l - x) 2 (2l 2 + 12 x 2 - 12lx)dx ˙
˙
= Á- 2 ˜ Í 0 ˙
Ë 8p m ¯ Í l
˙
Ú x (l - x) dx
4 4
Í ˙
Í 0 ˙
Î ˚

Ê h 2 ˆ È - 2l 7 /105 ˘ Ê h 2 ˆ Ê 12 ˆ
= Á- Í ˙= Á 2˜
Ë 8p 2 m ˜¯ Î l 9 / 630 ˚ ÁË 8ml 2 ˜¯ Ë p ¯

(h 2 / 8ml 2 )(12 / p 2 ) - (h 2 / 8ml 2 )

Per cent error = ¥ 100
(h 2 / 8ml 2 )
= + 21.49
h2 d 2
sin (px / l ) - sin (px / l )
8 p 2 m dx 2 Ê h2 ˆ Ê p 2 ˆ
(v) ·E Ò = = Á- 2 ˜ Á- 2 ˜
sin (px / l ) | sin (px / l ) Ë 8p m ¯ Ë l ¯
h2
=
8ml 2
Per cent error = 0
 Wave Mechanics, Energy Quantization and Atomic Structure 49

(b) The functions x and x 2 cannot be used as the variation functions since they do not
satisfy the boundary conditions of y = 0 at x = 0 and x = l.
(c) The variation theorem may be stated as follows.
If a well-behaved approximate wave function is employed in evaluating the expectation
value of a system then the value so obtained will always be algebraically equal to or greater
than the true energy of the system.
Since the functions (i) and (ii) are not well-behaved functions (explained in
part b), the expectation values obtained by these functions are lower than the correct
value. Functions (iii), (iv) and (v) are well-behaved functions, the expectation values
obtained by these functions come out to be larger than (for functions iii and iv) and

by these functions.

Problem 1.4.4 Evaluate the expectation values of x, x 2, p and p 2 for a particle in a one-dimensional box
of length l and show that the product of root mean square uncertainties in p and x is greater
than h/4p.
Solution For a particle in a one-dimensional box, we have

n p xˆ
sin ÊÁ
2
yn =
l Ë l ˜¯
Since y n is the normalized wave function, we will have
l
·x Ò = Ú y | x| y dx
0

È 2np ˆ ˘
Í1 - cos Ê x ˙
l
2 Ê np
l
Ë l ¯˙
xˆ˜ dx = x ÍÍ
2 2
=
l Ú x sin ÁË
l ¯ l Ú 2 ˙ dx
0 0 Î ˚

2 Êl ˆ 2
= ÊÁ ˆ˜ Á ˜ =
l
Ë l¯ Ë 4¯ 2
l
np ˆ
sin2 ÊÁ
2
·x 2Ò = Úx
2
Ë l ˜¯
x dx
l 0

È 2np ˘
l Í1 - cos x˙
˙ d x = 1 Èl - l ˘
3 3
2 2Í l
=
l Ú x
Í 2 ˙ Í
lÎ3
˙
2n p 2 ˚
2
0 Î ˚

l
h d
·pÒ = Ú y y dx
0
2pi dx

l
h Ê 2 ˆ sin Ê n p x ˆ d sin Ê n p x ˆ dx
=
2pi Ú ÁË l ˜¯ ÁË ˜
l ¯ dx
ÁË
l ¯
˜
0
50 A Textbook of Physical Chemistry

l
h Ê n p ˆ Ê 2ˆ Ê n p x ˆ cos Ê n p x ˆ dx
2pi Ë l ¯ Ú0 Ë l ¯
= Á ˜ Á ˜ sin ÁË ˜ ÁË ˜
l ¯ l ¯
=0
l ÏÔ Ê h d ˆ 2 ¸Ô
· p2Ò = Ú Ìy Á ˜ y ˝ dx
ÔÓ Ë 2p i dx ¯ Ô˛
0

l
Ê h 2 ˆ ÏÊ 2 ˆ Ê n p x ˆ d 2 Ê n p x ˆ ¸ dx
2 ˜ Ú ÌÁ
= Á- ˜¯ sin ÁË ˜¯ 2 sin ÁË ˜˝
Ë 4p ¯ 0 Ó lË l dx l ¯˛

2 l
Ê h ˆ np
2
Ê 2 ˆ sin2 Ê n p x ˆ dx
= Á 2 ˜ ÊÁ ˆ˜ Ú
Ë 4p ¯ Ë l ¯ ËÁ l ¯˜ ÁË
l ¯
˜
0

2
Ê h2 ˆ Ê n p ˆ n2h2
= Á 2˜ Á (1) = = 2 mE
Ë 4p ¯ Ë l ¯˜ 4l 2

n2h2
Now (Dp)2 = · p 2 Ò - · pÒ2 = · p2 Ò =
4l 2

Ê l2 l2 ˆ 2 Ê l2 l2 ˆ
(Dx)2 = ·x2Ò - · xÒ2 = Á - 2 2 ˜ – ÊÁ ˆ˜ = Á - 2 2 ˜
l
Ë 3 2n p ¯ Ë 2¯ Ë 12 2n p ¯

Ê n2h2 ˆ Ê l 2 Ê - l2 ˆ ˆ Ê n2h2 ˆ 1 1
(Dp)2 (D x)2 = Á 2 ˜ Á - 2 2 ˜ = Á
Ë 4l ¯ Ë 12 2n p ¯ Ë 4 ˜¯ ÁË 12 2n 2 p 2 ˜¯

Ê h2 ˆ Ê n2p 2 ˆ
= Á - 2˜
Ë 16p 2 ˜¯ ÁË 3 ¯

h n2p 2 h
Hence Dp Dx = -2 > ; since n2p2/3 is always greater than 2.
4p 3 4p

Problem 1.4.5 Making use of the expression D pD x ≥ h/4p, show that for a free particle

h
dE D t ≥
4p
where dE and D t are the minimum uncertainties in energy and duration of measurement
of velocity, respectively.
Solution For a free particle, the energy expression is

1 p2
E= mu 2 =
2 2m
The uncertainty in energy will be given by
p
dE = dp
m
 Wave Mechanics, Energy Quantization and Atomic Structure 51

where d p is the uncertainty in p. Now p/m, which is velocity, may be measured by

determining the distance D x traversed in time Dt, such that
p Dx
=
m Dt
If Dx is the maximum uncertainty in position of the particle during the measurement of p,
then the minimum uncertainty in the value of p will be

d p ≥ ÊÁ ˆ˜
h 1
Ë 4p ¯ Dx
Dx
dp ≥ ÊÁ ˆ˜
p h 1
Hence d E = dp =
m Dt Ë 4p ¯ Dt

h
or d E Dt ≥
4p

Problem 1.4.6 A particle of mass m

the box. The box extends from - l /2 to + l/2. The potential energy is
Ï0; - l/2 < x < l/2
V(x) = Ì
Ó•; | x | ≥ l/2

inside and the outside of the box.

(b) Assume a solution (inside the box) of the form
y (x) = A sin (a x) + B cos (a x)

(c) Derive the energy expression of the particle.

Solution (a)
(i) Inside the box
h 2 d 2y
– = Ey (1)
8p 2 m dx 2
(ii) Outside the box
h 2 d 2y
– + •y = Ey (2)
8p 2 m dx 2
(b) Substituting the boundary conditions
y (+ l /2) = 0 and y (- l/2) = 0
in the expression
y (x) = A sin (a x) + B cos (a x)
we get
A sin (a l/2) + B cos (a l /2) = 0
and - A sin (a l/2) + B cos (a l /2) = 0
On adding and subtracting the above two equations, we get
A sin (a l/2) = 0 (3)
B cos (a l/2) = 0 (4)
52 A Textbook of Physical Chemistry

For Eq. (3), we must have either A = 0 or a l / 2 = n¢p with n¢ = 1, 2, 3, …, and for
Eq. (4), we must have either B = 0 or al / 2 = n≤p with n≤ = 1/2, 3/2, 5/2, ….

For A = 0, the wave function will be given by

y = B cos (a x) (5)
where a = 2n≤ p / l = np / l with n = 1, 3, 5, … (odd number only).
For B = 0, the wave function will be given by
y = A sin (a x) (6)
where a = 2n ¢p / l = np / l with n = 2, 4, 6, … (even number only).
Equations (5) and (6) may be combined to give

np ˆ
y = A sin ÊÁ x˜ ; n even
Ë l ¯

np
= B cos ÊÁ xˆ˜ ; n odd
Ë l ¯

(c) On substituting either Eq. (5) or Eq. (6) in Eq. (1), and carrying out the desired
differentiation, we get

n2h2
E= ; n = 1, 2, 3, …
8ml 2
[Note: Experimentally observable properties do not depend on the choice of the place of
origin, i.e. whether it is located at the wall or in between the one-dimensional box. This
is to be expected since the particle knows only the length of box where it has to move.]

transformation.
Let X = x + l /2 such that X = 0 at x = - l/2 and X = l at x = l/2.

= ÊÁ
d dX ˆ Ê d ˆ d
Since ˜ Á ˜ =
dx Ë dx ¯ Ë dX ¯ dX

h 2 d 2y
– = Ey
8p 2 m dX 2
The solutions of the equation is given by
y = A sin (a X) + B cos (aX)
Making use of boundary conditions ( y = 0 at X = 0 and X = l ), this reduces to

np
y = A sin ÊÁ X ˆ˜ ; n = 1, 2, 3, …
Ë l ¯

i.e. y = A sin { np
l }
( x + l/2) ; n = 1, 2, 3, …
 Wave Mechanics, Energy Quantization and Atomic Structure 53

THREE-DIMENSIONAL BOX

Ê ∂2 ∂2 ∂2 ˆ 8p 2 m
+ +
ÁË ∂x 2 ∂y 2 ∂z 2 ˜¯ y + Ey = 0 (1.4.16)
h2
where the function y will depend on the three independent variables x, y
and z. If an operator contains different terms each depending upon independent
coordinate, then the wave function can be written as the product of different wave
functions each involving individual independent coordinate. Guided by this, we
write the function as a product of three wave functions each involving only one
independent variable of x, y and z, respectively. Thus, we have
y (x, y, z) = X(x)Y(y)Z(z) (1.4.17)
where X(x), Y( y) and Z(z) are three functions.
Substituting Eq. (1.4.17) in Eq. (1.4.16), we get
8p 2 m
— 2(XYZ ) + EXYZ = 0
h2
Ê ∂2 ∂2 ∂2 ˆ 8p 2 m
or + +
ÁË ∂x 2 ∂y 2 ∂z 2 ˜¯ (XY Z) + E(XYZ) = 0
h2
Ê d2 ˆ Ê d2 ˆ Ê d2 ˆ 8p 2 m
or Y Z Á 2 X ˜ + X Z Á 2 Y ˜ + XY Á 2 Z ˜ + EXYZ = 0
Ë dx ¯ Ë dy ¯ Ë dz ¯ h2
(1.4.18)
Dividing by XYZ, we have
1 Ê d ˆ 1 Ê d Yˆ 1 Ê d ˆ
2 2 2
8p 2 m
X Z E = - a 2(1.4.19)
X ÁË dx 2 ˜¯ Á 2 ˜ Z ÁË dz 2 ˜¯
+ + = –
Y Ë dy ¯ h2
The term a 2 in the above equation is a constant quantity. Hence, the sum of
the three terms on the left side of Eq. (1.4.19) must also be a constant quantity.
If we change the value of x (or y or z) keeping the other two variables constants,

term is independent of the other terms and each is equal to a constant quantity so
that the sum of three constants is equal to a 2. Thus, we write
1 d2
X = - a x2 (1.4.20)
X dx 2
1 d2
Y = - a 2y (1.4.21)
Y dy 2
1 d2
Z = - a 2z (1.4.22)
Z dz 2
8p 2 m
where a x2 = Ex (1.4.23)
h2
54 A Textbook of Physical Chemistry

8p 2 m
a y2 = Ey (1.4.24)
h2

8p 2 m
a 2z = Ez (1.4.25)
h2
with a 2 = a 2x + a 2y + a 2z (1.4.26)

and E = Ex + Ey + Ez (1.4.27)
Now, we have three separate equations to be solved, each of them has a form of
one-dimensional box. Thus, the normalized wave function of a three-dimensional
box is
Ê 2 nx p ˆ Ê 2 ny p ˆÊ 2 np ˆ
y = XYZ = ÁË l sin l x˜¯ Á l sin l y˜ Á sin z z ˜
x x Ë y y ¯ Ë lz lz ¯

8 Ên p ˆ Ê ny p ˆ Ên p ˆ
= sin Á x x˜ sin Á y ˜ sin Á z z ˜ (1.4.28)
lx l y lz Ë lx ¯ Ë y ¯
l Ë lz ¯

The constants a x, a y and az will be given by

nx p ny p nz p
ax = , ay = and az = (1.4.29)
lx ly lz
and thus the total energy is

h 2 Ê nx n 2y nz2 ˆ
2
E = Ex + Ey + Ez = Á 2 + 2 + 2˜ (1.4.30)
8m Ë l x ly lz ¯

There are three quantum numbers, one each for every degree of freedom.

Example 1.4.3 The ground state translational energy of a particle in a one-dimensional box of 300 pm
length is about 4 eV. Suppose that the same particle is moving in a three-dimensional cubic
box of 100 pm on the side. Estimate the ground-state energy of the particle in the three-
dimesional box.
Solution The ground-state energy in one-dimensional box is

(1) 2 h 2
E1 =
8ml 2
Now l = 300 pm. Therefore

h2
E1 = = 4 eV
8m (300 pm) 2

h2
Hence = (4 eV) (300 pm) 2
8m
 Wave Mechanics, Energy Quantization and Atomic Structure 55

The energy expression in a three-dimensional box is

h 2 Ê nx n y n y ˆ
2 2 2

E¢1 = Á + + ˜
8m Ë l x2 l y2 l z2 ¯

For the ground state of particle in a three-dimensional box,

n x = ny = nz = 1
and it is given that
lx = l y = l z = 100 pm

h2 h2 3 2 Ï 3 ¸
Thus E¢1 = 2
(3) = ◊ 2 = {(4 eV) (300 pm) } Ì 2˝
8ml 8m (100 pm ) Ó (100 pm) ˛

= 4 ¥ 9 ¥ 3 eV = 108 eV

Example 1.4.4
energy corresponding to the radiation of wavelength about 70 nm. Benzene, as a rough
approximation, may be considered to be a two-dimensional box that encompasses the
regular hexagonal shape. The C — C bond length in benzene is 0.14 nm, so that side of the

excited state of benzene, assuming that it is p-bonding electrons that are involved.
Solution For the one-dimensional box,

h2
E= n2
8ml 2
Thus, the ground state energy E1 in a one-dimensional box of length 0.14 nm is
h2
E1 =
8m (0.14 nm) 2
For the two-dimensional square box,

h2
E2 = (n12 + n22 )
8ml 2
Now since l = 0.28 nm, we have

h2 E
E2 = (n21 + n22) = 1 (n12 + n22 )
8m(2 ¥ 0.14 nm) 2 4

The various energy levels are as follows.

n1 n2 E2
1 1 E1/2
2 1 (5/4) E1 ¸
˝ degenerate
1 2 (5/4) E1 ˛
2 2 2 E1
56 A Textbook of Physical Chemistry

n1 = 1, n2 = 2
state to n1 = 2, n2 = 2 state. Thus

5 3
D E = 2E1 - E1 = E1
4 4
Since the wavelength is inversely proportional to energy, the corresponding wavelength
would be (4/3)l, i.e.

4
¥ 70 nm = 93 nm
3

Example 1.4.5 A cubic box of edge-length 1.2 nm contains 10 electrons. Applying the simple particle-in-
a-box theory, calculate the value of D E
Solution The energy expression is given as

h2
E = (n12 + n22 + n23 )
8ml 2

(6.626 ¥ 10-34 J s) 2
= (n21 + n22 + n23 )
8(9.11 ¥ 10-31 kg )(1.2 ¥ 10-9 m) 2

= (4.183 4 ¥ 10-20 J) (n21 + n22 + n23 )

A few energy levels are shown in the following.

Quantum numbers E /J Distribution of 10

electrons in the
n1 n2 n3 energy levels

1 1 1 (4.183 4 ¥ 10-20 ) (3) ≠Ø

1 1 2 ¸
1 2 1 Ô (4.183 4 ¥ 10-20 ) (6) ≠Ø ≠Ø ≠Ø
˝
2 1 1 Ô
˛
1 2 2 ¸
2 1 2 Ô˝ (4.183 4 ¥ 10-20 ) (9) ≠ ≠
2 2 1 Ô˛ Ø DE
-20
3 1 1 (4.183 4 ¥ 10 ) (11)

The ten electrons can be distributed over the energy levels following the aufbau principle,

is promoted from the triply degenerate level of energy 9(4.183 4 ¥ 10-20 J) to the level of
energy 11(4.183 4 ¥ 10-20 J). Hence

D E = 2(4.183 4 ¥ 10-20 J) = 8.366 ¥ 10-20 J

 Wave Mechanics, Energy Quantization and Atomic Structure 57

Example 1.4.6 Determine the energy required for a transition from the nx = ny = nz = 1 to nx = ny = 1,
nz = 2 state for (a) an argon atom (molar mass = 39.95 g mol –1) in a cubic container with
a 1.0 cm side, (b) an electron (me = 9.11 ¥ 10-28 g) in a cubic hole of a crystal with
10-8 cm edge-length.
Solution (a) The mass of one argon atom is

(39.95 ¥ 10-3 kg mol-1 )

m= = 6.633 ¥ 10 -26 kg
(6.022 ¥ 1023 mol-1 )

h2 (6.626 ¥ 10-34 J s) 2
Now E1,1,1 = (n 2x + n 2y + n 2z ) = (12 + 12 + 12)
8ml 2 8(6.633 ¥ 10-26 kg )(10-2 m) 2

= (8.274 ¥ 10-39 J) (3)

= 2.482 ¥ 10-38 J
E1,1,2 = (8.274 ¥ 10-39 J) (12 + 12 + 22) = (8.274 ¥ 10-39 J) (6)
= 4.964 ¥ 10 -38 J
Hence D E = E1,1,2 - E1, 1,1 = (4.964 ¥ 10-38 J - 2.482 ¥ 10-38 J)

= 2.482 ¥ 10 -38 J
(b) In this case, we have

(6.626 ¥ 10-34 J s) 2
E1,1,1 = ¥ 3 = (6.024 ¥ 10-18 J) (3)
8(9.11 ¥ 10-31 kg )(10-10 m) 2

= 1.807 2 ¥ 10-17 J
and E1,1,2 = (6.024 ¥ 10-18 J) (6) = 3.614 4 ¥ 10-17 J
Thus D E = (3.614 4 ¥ 10-17 J - 1.807 2 ¥ 10-17 J)
= 1.807 2 ¥ 10 -17 J

Example 1.4.7 The average kinetic energy of a gas molecule is (3/2) kT, where k is the Boltzmann constant.
n2x + ny2 + n2z ) in order that an atom of He may

Solution The energy expression of a three-dimensional box is

h2
E= (n2x + n2y + n2z )
8ml 2
Since l = 10 nm, we have for He atom

(6.626 ¥ 10-34 J s) 2
E = (nx2 + ny2 + n2z )
{ }
(8) 0.0004 kg / (6.022 ¥ 1023 ) (10-8 m) 2

= (8.263 ¥ 10-26 J) (n2x + n2y + n2z )

58 A Textbook of Physical Chemistry

Now, the average kinetic energy at 300 K is

-1 -1
3 3 Ê R ˆ 3 Ê 8.314 J K mol ˆ
E = kT = Á ˜ T = Á -1 ˜ (300 K)
2 Ë NA ¯ 2 Ë 6.022 ¥ 10 mol ¯
22
2

= 6.211 7 ¥ 10 -21 J
Equating the above energy with E, we get

(8.263 ¥ 10 -26 J) (n2x + n2y + n2z ) = 6.211 7 ¥ 10 -21 J

6.2117 ¥ 10-21 J
nx2 + n2y + n2z = = 75 175
8.263 ¥ 10-26 J

1.5 QUANTIZATION OF VIBRATIONAL ENERGY

Harmonic For the sake of simplicity, we treat here only the simple harmonic motion of a
Oscillator single particle which oscillates to and fro about its equilibrium position. In harmonic
motion, the restoring force F acting on the particle is proportional to the displace-
ment x from the equilibrium position (Fig. 1.5.1).
Thus F μx
or F = - kf x (1.5.1)
where k f is a constant, called the force constant, and is a measure of the stiffness
kf and a weaker
spring will have a lesser value of kf. The negative sign in Eq. (1.5.1) indicates
that the restoring force always acts in the opposite direction of the displacement.

Fig. 1.5.1 Classical x

treatment of harmonic F
motion
At rest Stretched Compressed

Classical In classical mechanics, the above vibrational motion can be described in terms of
Treatment Newton’s second law of motion, according to which, we have
d2 x
F = ma = m (1.5.2)
dt 2
Equating Eqs (1.5.1) and (1.5.2), we get

d2 x
m = - kf x (1.5.3)
dt 2
 Wave Mechanics, Energy Quantization and Atomic Structure 59

The solution of the Eq. (1.5.3) has a form

x = A sin (2p n0t) (1.5.4a)
or x = A cos (2pn 0t) (1.5.4b)
where A is the maximum displacement of the vibration and n 0 is the frequency
of vibration.

Classical The value of n 0 depends on the mass of the particle and the force constant of the
Frequency of spring. The relation connecting these can be derived as follows.
Oscillation
Evaluating the second differential of Eq. (1.5.4a) and substituting in Eq. (1.5.3),
we get
m{- A (2pn 0)2 sin (2pn 0t)} = - kf A sin (2 pn0 t)
or m(2pn 0) 2 = kf
1 kf
or n0 = (1.5.5)
2p m
Potential Energy The potential energy of the particle at any instant can be evaluated from the
of the Oscillator expression
F = - dV/dx, i.e. dV = - F dx
Substituting F From Eq. (1.5.1), we have
dV = kf x dx
which on integrating gives
V x

Ú dV = kf Ú x d x
0 0

x2
i.e. V = kf (1.5.6)
2
The variation in potential energy with the displacement x is shown in Fig. 1.5.2.
V

Fig. 1.5.2 The

parabolic variation of
potential energy for the 0
harmonic oscillator x
60 A Textbook of Physical Chemistry

Total Energy of the The momentum of the particle at any instant is

Oscillator dx
p = mu = m = mA(2pn 0) cos(2pn0t) (1.5.7)
dt
The total energy of the particle at any instant is
E =T+V

1 p 2 kf x 2
= mu 2 + V = +
2 2m 2

=
{m A(2pn 0 ) cos(2pn 0t )}2 + kf { A sin(2pn t )}2
0
2m 2
m 2 A2 (kf/m)cos 2 (2pn 0t ) kf 2 2
= + A sin (2pn0 t)
2m 2
1 1
= k f A 2cos 2(2pn0t) + kf A2 sin2(2pn0t)
2 2
1
or E = k f A2 (1.5.8)
2
Classical The particle executing simple harmonic motion will have the following
Characteristics characteristics.
of a Harmonic
Oscillator ∑ The frequency of oscillation is a characteristic of the system which depends only
on k f and m, and not on the amplitude of vibration (Eq. 1.5.5). Thus, whatever
may be the amplitude the particle will oscillate with the same frequency.
∑ The potential energy of the particle, besides depending on k f , depends on the
square of the displacement (Eq. 1.5.6). Thus, the variation of potential energy
with displacement x is of parabolic in nature (Fig. 1.5.2).
∑ The total energy of the particle, besides depending upon k f , depends on the
square of the amplitude of the vibration (Eq. 1.5.8). Since the oscillating particle
can possess any amplitude, it is obvious that the total energy of the particle will
vary in a continuous manner.
∑ Classically speaking, the time spend at any position during vibration will depend
on the velocity of the particle at that instant; larger the velocity, lesser the time
spend and vice versa. Since, the total energy of an oscillator depends only on
the amplitude of the vibration (Eq. 1.5.8), it is obvious that the sum of kinetic
and potential energies remains the same at any instant of vibration. The potential
energy increases as the displacement x is increased (Eq. 1.5.6) and it attains a
maximum value equal to the total energy at the two extremes of the vibration.
Consequently, the kinetic energy of the particle decreases as the displacement
x is increased and it has a zero value at the two extremes of the vibration. At
equilibrium position (x = 0), the potential energy is zero and the particle carries
only kinetic energy equal to the total energy. Thus, we have
 Wave Mechanics, Energy Quantization and Atomic Structure 61

At x = 0; kinetic energy is maximum or velocity of the oscillator is maximum.

At x = A; kinetic energy is zero or velocity of the oscillator is zero.
Since the velocity of the oscillator at x = 0 is maximum and is zero at the
extremes of vibration, it is expected that the particle will spend maximum
time at the extremes and the minimum at the equilibrium position during
the course of its vibration.
Quantum
Mechanical given by
Treatment
d 2y 8p 2 m Ê 1 2ˆ
+ 2 ÁË E - kf x ˜¯ y = 0 (1.5.9)†
dx 2 h 2
The solution of this equation is described in Annexure II at the end of the

1. The energy of an oscillator is quantized and is given by the expression

Eu = ÊÁ u + ˆ˜ hn 0 = ÊÁ u + ˆ˜
1 1 h kf
(1.5.10)
Ë 2 ¯ Ë 2 ¯ 2p m
where n0 is the classical frequency of the oscillator and u is the vibrational quantum
number which can have only integral values including zero, i.e. u = 0, 1, 2, 3, … .
2. The acceptable normalized wave functions of Eq. (1.5.9) are given by the
expression

1/2
Ê a ˆ
Hu exp ÊÁ - y 2 ˆ˜
1
yu = Á u (1.5.11)
Ë 2 u ! p ˜¯ Ë 2 ¯

where y = a x. The symbol a in this expression is given by

mw
a= where w = kf m (1.5.12)
h 2p
Hu
polynomials are listed in Table 1.5.1.

Table 1.5.1 The First Few Hermite Polynomials

H0 = 1 H4 = 16y 4 – 48y 2 + 12

H1 = 2y H5 = 32y5 – 160y3 + 120y

H2 = 4y 2 – 2 H6 = 64y6 – 480y 4 + 720y 2 – 120

H3 = 8y3 – 12y

†
For a diatomic molecule, the mass m is replaced by reduced mass m [= m1m2/(m1 + m2)].
62 A Textbook of Physical Chemistry

Depiction of
Energies, Wave the probability densities of a harmonic oscillator.
Functions and
Probability
Densities

Fig. 1.5.3 The

energies, wave
functions and
probability densities of
a harmonic oscillator

Quantum A few important features shown in Fig. 1.5.3 may be highlighted here.
Characteristics
of a Harmonic ∑ The vibrational energies are quantized, and the separation between the successive
Oscillator energy levels is the same for all values of u, i.e.
D E = Eu + 1 - Eu = hn
∑ The particle is associated with the zero point energy of (1/2)hv (energy in the
lowest vibrational level, u = 0). This implies that the particle can never be
standstill. This is contrary to the classical picture where the particle has zero
potential energy at its equilibrium position, i.e. at x = 0.
∑ The wave functions fall of exponentially to zero as x Æ ± •. Hence the wave
function y and the probability density | y 2| are not zero even for a large value
of x
value of x. This is constrast to a classical harmonic oscillator which has a

quantum-mechanical energy expressions as given by Eqs (1.5.8) and (1.5.10),

respectively, such that
1/2
Ï (2u + 1)hv0 ¸
k f A 2 = ÊÁ u + ˆ˜ hv0 ,
1 1
i.e. A= Ì ˝ (1.5.13)
2 Ë 2¯ Ó kf ˛
 Wave Mechanics, Energy Quantization and Atomic Structure 63

∑
at the zero-displacement position (the so-called equilibrium position) and it
decreases sharply as the displacement from the equilibrium position is increased.
In other words, it can be stated that the particle spends much of its time at the
equilibrium position and the time spent at other positions becomes less and less
as x is increased. This fact is in contradiction with the classical picture where the
particle spends maximum time at the two extremes of vibration and minimum
time at the equilibrium position.
∑ On increasing the value of quantum number u, the maxima in the probability
density curve are shifted towards the two extremes of the vibration. At very high
quantum numbers, the probability density curve has two very large maxima very
near to the two extremes and the rest of the maxima have smaller values. This
means that only in the limit of very high quantum numbers, the particle spends
much of its time at the two extremes—a behaviour which was predicted by the
classical theory. This fact is in agreement with the correspondence principle
which states that the classical behaviour emerges when high quantum numbers
are reached.

Problem 1.5.1 Evaluate the expectation value of kinetic energy of the harmonic oscillator in the ground state.
Solution The ground-state normalized wave function for the harmonic oscillation is
12
Ê aˆ
y 0 = Á 1/2 ˜ exp(- a x 2/2)
Ëp ¯
Since y0 is normalized the expectation value of kinetic energy is given by

Hence · T Ò = Ú y 0 T y0 dt

+• 12
ÏÊ a ˆ Ê h2 d 2 ˆ Ê a ˆ
1/2
¸Ô
· TÒ = Ú ÌÁ 1/2 ˜ exp(- a x /2) Á - 2
2 exp(-a x 2/2 ) ˝
-• Ó
Ëp ¯ Ë 8p m dx 2 ˜¯ ÁË p1/2 ˜¯ ˛Ô
dx

+•
Ê aˆ Ê h2 ˆ Ï d2 2 ¸
Ú exp (- a x /2)
2
= Á 1/ 2 ˜ Á - 2 ˜ Ì 2 exp(-a x / 2 ˝ dx
Ë p ¯ Ë 8p m ¯ -• Ó d x ˛

+•
h2 ˆ È
+•
Ê aˆ Ê ˘
= Á 1 / 2 ˜ Á - 2 ˜ Í-a Ú exp(-a x )dx + a Úx
2 2 2
exp(-a x 2 ) dx ˙
Ë p ¯ Ë 8p m ¯ ÍÎ -• -• ˙˚

Ê aˆ Ê h2 ˆ È 1 1/ 2 ˘
= Á 1/ 2 ˜ Á - 2 ˜
ÍÎ- (p a ) + 2 (p a ) ˙˚
1/ 2
Ë p ¯ Ë 8p m ¯

=
a h2
16p 2m
Since a = 2pmw /h, and w = kf m , we get
64 A Textbook of Physical Chemistry

Ê 2pmw ˆ Ê h ˆ
2
hw h kf
·T Ò = ÁË ˜¯ Á = = = h n0
h Ë 16p 2 m ˜¯ 8p 8p m 4

Problem 1.5.2 Evaluate the expectation value of potential energy of the harmonic oscillator in the ground
state and show that it has the same value as that of kinetic energy.
Solution
· V Ò = Ú y 0V y 0dt

+• 1/ 2 1/ 2
Ê aˆ exp (- a x 2/2) ÊÁ kf x 2 ˆ˜ Ê a ˆ
1
= Ú ÁË p1 / 2 ˜¯ Ë2 ¯ ÁË p1 / 2 ˜¯
exp( –ax 2/2) dx
-•
+•
Ê aˆ
= Á 1/2 ˜ ÊÁ kf ˆ˜
Ëp ¯ Ë 2¯
Ú x 2 exp(- a x 2) dx
-•

1/ 2
Ê aˆ Êkfˆ Ê p
1/ 2
ˆ
= Á 1/ 2 ˜
Ëp ¯ ËÁ 2 ¯˜ ÁË 2a 3 / 2 ˜¯

kf Ê kf ˆ Ê h ˆ hk f m h kf h
= = Á ˜ = = = v
4a Ë 4 ¯ Ë 2pmw ¯ 8p m kf 8p m 4 0
On comparing · T Ò and ·V Ò

Problem 1.5.3 Determine the value of x at which the ground-state wave function of the harmonic oscillator
exhibits the maximum.
Solution The ground-state wave function is

Ê aˆ
y 0 = Á 1/ 2 ˜ exp(-a x2/2)
Ëp ¯
Making use of the mathematical criterion of maximum (i.e. dy 0 /dx = 0), we get

dy 0 Ê aˆ
= Á 1/ 2 ˜ {– a x exp(–ax2/2)} = 0
dx Ëp ¯
The above expression gives x = 0 and x = ± •.
2
y0 /dx2, which gives

d 2y 0 Ê aˆ
= Á 1/ 2 ˜ [– a + (ax)2] exp (–a x 2/2)
dx 2
Ëp ¯
Obviously, d 2y0 /dx2 is negative at x = 0. Hence, the function y0 exhibits a maximum at x = 0.
 Wave Mechanics, Energy Quantization and Atomic Structure 65

Problem 1.5.4 Determine the value of x

x

Solution We have

(2 )
1/ 2
Ê a ˆ ax
y1 =
ÁË 2p1 / 2 ˜¯ a x2

1/ 2
Ê a ˆ
Now
dy 1
dx
= Á 1/ 2 ˜
Ë 2p ¯
(2 a ) {exp(-a x / 2) - x a x exp(- a x / 2)}
2 2

1/ 2
= Á
Ê a ˆ
˜
Ë 2p1/ 2 ¯
(2 a ) a x2 a x2

y1
are x = 1/ a x 1/ a
Since a = 2 pmw /h w = kf / m
1/ 2 1/ 2
1 Ê h ˆ Ê h mˆ Ê h 1 ˆ
1/ 2
= ± Á
k f ˜¯
x=± =± Á =± Á
a Ë 2 p m w ˜¯ Ë 2p m Ë 2p kf m ˜¯

= ÊÁ u + ˆ˜
1 k x2 1 h kf
f
2 Ë 2 ¯ 2p m
u
1 3 h kf
k f x2 =
2 2 2p m
1/ 2 1/ 2
Ê h 1 ˆ Ê h 1 ˆ
= Á3
k f m ˜¯ Á 2p k f m ˜¯
or x
Ë 2p Ë
x x
1
x= x x
1.732

Problem 1.5.5 x x2 p p2
p x

Solution
1/ 2
Ê aˆ
y = Á ˜ a x2
Ë p¯

+• +•
a
· xÒ = Ú
-•
y | x| y x =
p Úx a x2 x
-•
66 A Textbook of Physical Chemistry

+• +•

Úx
a
Ú
2
· x 2Ò = y |x2| y x = a x2 x
-• p
-•

a Ï 1 Ê pˆ 1/ 2
¸ 1
= Ì Á ˜ ˝=
p ÔÓ 2a Ë a ¯ Ô˛ 2a
+•
Ê h dˆ
· pÒ =
-•
Ú y ÁË 2pi dx ˜¯ y x

+•
Ê h ˆ Ê aˆ Ïd ¸
= Á Á ˜
Ë 2pi ˜¯ Ë p ¯ Ú a x2
Ó dx
2
Ì exp(- a x / 2) ˝ x
˛
-•

+•
Ê h ˆ Ê aˆ
= Á Á ˜
Ë 2pi ˜¯ Ë p ¯
a Ú x a x2 x
-•

+•
h2 d 2
·p Ò =
2

-•
Ú y -
4p 2 dx 2
y x

+•
Ê h2 ˆ Ê a ˆ d2
= Á-
Ë
˜ Á ˜
4p 2 ¯ Ë p ¯ Ú
-•
a x2
dx 2
a x2 x

Ê h2 ˆ Ê a ˆ È Ê pˆ
1/ 2
Ï 1 Ê pˆ
1/ 2
¸˘
· p2Ò = Á - 2˜ Á ˜ Í(- a ) ÁË ˜¯ + a Ì 2 ÁË ˜¯ ˝˙
Ë 4p ¯ Ë p ¯ Î a ÓÔ 2a a ˛Ô˚

Ê h2 ˆ Ê a ˆ Ê a ˆ h 2a
= Á- - p˜ =
Ë 4 p 2 ˜¯ ÁË p ˜¯ ÁË 2 ¯ 8 p2

1
Now Dx ·x2 Ò ·xÒ2 1/2
=
2a
h a
Dp · p2Ò · p Ò2 1/2
(2 )
=
2p

Ê h a ˆ Ê 1 ˆ h
Dp D x = Á ˜ Á ˜ =
Ë 2 2p ¯ Ë 2a ¯ 4p

Problem 1.5.6 y=a bx2 m

h 2b k
E= + f
8p m 8b
2
 Wave Mechanics, Energy Quantization and Atomic Structure

Minimize E b
a
Solution
h2 d 2 1
H + kf x 2
8 p 2 m dx 2 2

a e - bx H a e - bx
2 2
y H y
E= =
a e - bx | a e - bx
2 2
y |y

h2 d 2 1
e - bx - + kf x 2 e - bx
2 2

= 8 p m dx
2 2
2
e -2bx
2

2 Ï h2 ¸
e - bx Ì- 2 ( - 2b + 4b 2 x 2 ) + kf x 2 ˝ e - bx
1 2

= Ó 8p m 2 ˛
e -2bx
2

+• +•
h 2b Ê h 2b 2 1 ˆÈ 2 -2bx 2 -2bx 2
˘
= + Á
Ë
- + k f¯ Ú x e
˜ Í dx Úe dx ˙
4p m
2
2p m
2
2 ÎÍ -• -• ˙˚

hb 2
Ê hb 1 ˆ Ê p / 2b 4b ˆ
2 2
h 2b k
= + Á - 2 + kf ˜ Á ˜ = 2 + f
4p m Ë 2p m
2
2 ¯Ë p / 2b ¯ 8p m 8b
∂E/∂b

h2 k p kf m
- f =0 fi b=
8p 2 m 8b 2 h

h 2 Ê p kf m ˆ kf Ê h ˆ
Emin = Á ˜+
8p 2 m Ë h ¯ 8 ÁË p kf m ˜¯

h kf h kf h kf
= + =
8p m 8p m 4 p m

+•

Úy dx = 1
2

-•
+•
p ˆ1 / 2
e -2bx dx = 1 a 2 ÊË
2
a2 Ú fi
2b ¯
=1
-•
1/ 4 1/ 4
2b 1 / 4 2 1 / 4 Ê p kf m ˆ Ê k mˆ
fi a 2 Ê ˆ = Ê ˆ ËÁ ˜ = ËÁ f ¯˜
Ë p¯ Ë p¯ h ¯ h/2

Problem 1.5.7
y2 = NH 2e - y
2
/2
where H2 = 4y2 ( a x )2 a x2

mw m kf /m 2pm kf 4p 2 m
a= = = = v0
h / 2p h / 2p h m h
68 A Textbook of Physical Chemistry

N
hv
Solution (a)
+• +•
(2a x 2 - 1) 2e -a x dx = 1
2

Ú y 2 dx = 1 Ú 4N
2 2

-• -•
+• +• +•
È ˘
4 N 2 Í4a 2 Ú x 4 e -a x dx + Ú e -a x dx - 4a Ú x 2 e -a x dx ˙ = 1
2 2 2

ÍÎ -• -• -• ˙˚
È Ï 3 p 1/ 2 ¸ Ï 1 p 1/ 2 ¸ Ï 1 Ê p ˆ1 / 2 ¸
4 N 2 Í4a 2 Ì2 ◊ 2 ÊË ˆ¯ ˝ + Ì2 ◊ ÊË ˆ¯ ˝ - 4a Ì2 ◊ ˝ =1
Î Ó 8a a ˛ Ó 2 a ˛ Ó 4a Ëa ¯ ˛
1 Ê a ˆ 1/ 4
N=
8 Ë p¯
(b) Since y2 E2 H y2 = E2 y2

h2 d 2 1
H = - + kf x 2
8 p 2 m dx 2 2
The vavefunction y2
2 Ê a ˆ 1/ 4
(2a x 2 - 1) e-a x / 2
2
y2 =
Ë
8 p ¯

d
(2a x 2 - 1) e-a x / 2 = [4a x + (2a x 2 - 1) (-a x)]e-a x / 2
2 2

dx
= (5a x - 2a 2 x3 ) e -a x
2
/2

d d
(2a x 2 - 1)e -a x / 2 = (5a x - 2a 2 x3 )e -a x / 2
3 2

dx 2 dx
= [(5a - 6a 2 x 2 ) + (5a x - 2a 2 x3 )(-a x)] e -a x
2
/2

= (5a - 11a 2 x 2 + 2a 3 x 4 ) e -a x = (5a - a 2 x 2 )(1 - 2a 2 x 2 )e -a x

2 2
/2 /2

h d2 h2 (
y2 -5a + a 2 x 2 )y 2
8p 2 m dx 2 8p 2 m
5h 2a 5h 2 Ê 4 p 2 m ˆ 5
Now = 2 Á Ë v0 ˜¯ = hv0
8p m 8p m
2
h 2
h 2a ( 2 2 ) h 2 ÏÊ 4p 2 m kf ˆ 2 ¸ 1
a x = ÌÁ ˜ x ˝ = kf x
2
8p m2
8p 2 m ÓË h 2 m ¯ ˛ 2

Ê h2 d 2 1 ˆ
H y2 = Á - 2 + kf x 2 ˜ y 2
Ë 8p m dx 2 2 ¯

(
ÎÍ 2 2 2 )
= È 5 hv0 - 1 kf x 2 + 1 kf x 2 ˘ y 2 = 5 hv0 y 2
˚˙ 2 ( )
E2 = Ê ˆ hv0
5
Ë2 ¯
 Wave Mechanics, Energy Quantization and Atomic Structure 69

1.6 QUANTIZATION OF ROTATIONAL ENERGY OF DIATOMIC MOLECULES

Classical
Treatment m1 m2
r

r1
r2

m1 u1
u2
m2

Fig. 1.6.1 The model

of a rigid rotator

u1 u2

1 1
T= m1u 21 + m 2u 22
2 2

u 1 = r1w
u 2 = r2w
where w r1 r2

1 1 1
T= m1 r1w 2 + m2 r2w 2 = m r 2 + m2r 22 w2
2 2 2 1 1
1
= Iw 2
2
where I

I = Â i mi ri
2

The moment of inertia I r

m1r1 = m2r2
 A Textbook of Physical Chemistry

Since r1 + r2 = r
m2 m1
r1 = r r2 = r
m1 + m2 m1 + m2

I = m1r 12 + m2r 22
2 2
Ê m2 ˆ Ê m1 ˆ Ê mm ˆ
I = m1 Á r ˜ + m2 Á r˜ = Á 1 2 ˜ r 2
Ë m1 + m2 ¯ Ë m1 + m2 ¯ Ë m1 + m2 ¯
= mr2
where m m 1m 2 m 1 + m 2

1 Ê 1 1 ˆ
= Á +
m Ë m1 m2 ˜¯
T= Iw2
2
T= mu with I m w
u

L = Iw

1 2 ( I w ) 2 L2
T= Iw = =
2 2I 2I

Quantum
Mechanical
Treatment 1 1 p2 p2
T= m1u 21 + m2u 22 = 1 + 2
2 2 2m1 2m2
where p1 p2

p12 p2
E= + 2
2m1 2m2

px21 + p 2y1 + pz21 px22 + p 2y2 + pz22

or E= +
2m1 2m2
where px py pz x - y-
z p
 Wave Mechanics, Energy Quantization and Atomic Structure

h 2 È ∂2 ∂2 ∂2 ˘ h 2 È ∂2 ∂2 ∂2 ˘
H = - Í + + ˙ - Í + + ˙
8p 2 m1 Î ∂x12 ∂y12 ∂z12 ˚ 8p 2 m2 Î ∂x22 ∂y22 ∂z22 ˚

Schrödinger
Equation in Terms
of Internal x = x2 x1 ; y = y2 y1 ; z = z2 z1
Coordinates

{ }
2 2
∂2 Ê ∂ ˆ Ï ∂x ∂ ¸ ∂ 2
∂2
Now = Á =Ì ˝ = (-1) =
∂x12 Ë ∂x1 ˜¯ ∂
Ó 1 x ∂ x ˛ ∂ x ∂x 2

h 2 Ê ∂2 ∂2 ∂2 ˆ h 2 Ê ∂2 ∂2 ∂2 ˆ
+ + - + +
8p 2 m1 Ë ∂x 2 ∂y 2 ∂z 2 ¯ 8p 2 m2 Ë ∂x 2 ∂y 2 ∂z 2 ˜¯
Á ˜ Á
H

h2 Ê 1 1 ˆ Ê ∂2 ∂2 ∂2 ˆ
= - Á + ˜ + +
8p 2 Ë m1 m2 ¯ ÁË ∂x 2 ∂y 2 ∂z 2 ˜¯

h 2 Ê ∂2 ∂2 ∂2 ˆ
= - + +
8p 2 m ÁË ∂x 2 ∂y 2 ∂z 2 ˜¯

h 2 Ê ∂2 ∂2 ∂2 ˆ
- + + y = Ey
8p 2 m ÁË ∂x 2 ∂y 2 ∂z 2 ˜¯
Transformation
of Schrödinger m1 m2 r q j a
Equation into
Spherical Polar x=r q j
Coordinates y=r q j
z=r q
z z

z m2 dr
r dq

θ r dq r

m1 y
y y
dj
j
x r sin q
r sinq dj
x (a) x (b)
Fig. 1.6.2 Cartesian Range of r is from 0 to • dt = (r dq) (dr) (r sinq dj)
and spherical Range of q is from 0 to p = (r2 dr) (sinq dq) (dj)
coordinates Range of j is from 0 to 2p
 A Textbook of Physical Chemistry
†

h2 È 1 ∂ Ê 2 ∂ ˆ 1 ∂ Ê ∂ˆ 1 ∂2 ˘
Í 2 r + 2 sin q + 2 2 ˙ y = Ey
8p m Î r ∂r Ë ∂r ¯ r sin q ∂q Ë
2
∂q ¯ r sin q ∂j 2 ˚

r
r

h2 È 1 ∂ Ê ∂ˆ 1 ∂2 ˘
2 Í ÁË sin q ˜ + ˙ Y q j EY q j
8p m r Î sin q ∂q
2
∂q ¯ sin 2 q ∂j 2 ˚
where the function y Yq j spherical
harmonics q j

È h2 ÔÏ 1 ∂ Ê ∂ˆ 1 ∂2 Ô¸˘
Í- 2 Ì Á sin q ˜ + ˝˙
ÍÎ 4p ÔÓ sin q ∂q Ë ∂q ¯ sin 2 q ∂j 2 Ô˛˙˚ Y EI Y

Splitting of
Eq. (1.6.20) into 2EI = L2
Two Separate
Equations ‡

Ÿ
L 2 Y = L2Y ††

L2
L2 = J J h/2p 2

where J

L2 1 Ê h ˆ2
E = =J J
2I 2 I Ë 2p ¯

2
È h2 Ï 1 ∂ Ê ∂ ∂ 2 ¸˘ Ê hˆ
sin q ˆ +
1
Í- 2 Ì ˝˙ Y = J J ÁË ˜¯ Y
Î 4p Ó sin q ∂q Ë ∂q ¯ sin 2 q ∂j 2 ˛˚ 2p

1 ∂ Ê ∂Y ˆ 1 ∂ 2Y
or ÁË sin q ˜¯ + 2 +J J Y
sin q ∂q ∂q sin q ∂j 2

†
Ÿ
‡
L2
Ÿ
††
L2
L̂z Y
 Wave Mechanics, Energy Quantization and Atomic Structure

2
q
∂ Ê ∂Y ˆ ∂2Y
2
q Á sin q ˜+J J Y q+
∂q Ë ∂q ¯ ∂j 2

q j
Yq j Q q F j

d Ê dQ ˆ 2
d 2F
F q sin q +J J QF q+Q
dq Ë dq ¯ dj 2

QF
1 d Ê dQ ˆ 2 1 d 2F
sin q sin q +J J q
Q dq Ë dq ¯ F dj 2
q
j
m2

1 d Ê dQ ˆ 2
sin q Á sin q ˜ +JJ q = m2
Q dq Ë dq ¯

1 d 2F
= m2
F dj 2
Solution of
Eq. (1.6.30) d 2F
m2 F
dj 2

F m= A mj
Boundary j j + 2p
Condition for the
Function F F j + 2p F j
Hence A m j + 2p A mj

m 2p
p im pm pm
m
m …
 A Textbook of Physical Chemistry

Normalization of The value of A F

the Function Fm
2p

Ú F *F
0
m m dj =1

2p

or A*A Ú exp
0
mj mj j=1

or | A |2 p
1
or A=
2p

1
Fm = mj m
2p
Fm
Table 1.6.1 Fm

m Fm

1 / 2p
+1 (1/ 2p ) j

(1/ 2p ) j

+2 (1/ 2p ) j

(1/ 2p ) j

Solution of
Eq. (1.6.29) x q
x
= · q
q q x x
2 2
q q x2
Q q ∫Px

1 d È dP ˘
ÈÎ- (1 - x ) 2 ˘˚ Í-(1 - x 2 ) ˙ + J J x2 m2
P dx Î dx ˚
x2 P
d È 2 dP ˘ È m2 ˘
(1 - x ) + Í J ( J + 1) - ˙P
dx ÍÎ dx ˙˚ Î (1 - x 2 ) ˚

d2 P dP È m2 ˘
x2 x + Í J ( J + 1) - ˙P
dx 2
dx Î 1- x2 ˚
 Wave Mechanics, Energy Quantization and Atomic Structure

associated Legendre equation

Px

J
J
P are the associated Legendre polynomials PJ| m| J
m
m
P ∫ PJ| m | x2 | m|/2
m PJ
x
where PJ Legendre polynomial J

1 dJ J
PJ = x2
2J J ! d x J
J P of the function Q
that the |m| £ J
| m|
PJ x| m| m J

J
m J
m J J
Expression of Q q
the Normalized Q
Functions
p

Ú Q*Q q q

1/ 2
È (2 J + 1) ( J - | m |)!˘
Q j, |m| = Í ˙ P |m|
Î 2 ( J + | m |)! ˚
J

The function Q J m
form of the function Q J |m| J m

Problem 1.6.1 Determine the form of the function Q for J m

Solution The Q
1/ 2
È (2 ¥ 2 + 1) 2!˘
Q = Í ◊ ˙ P2
Î 2 2! ˚
 A Textbook of Physical Chemistry

where P2
d0
P2 x2 P2 = P2
dx 0
P2

1 d2 1 d
P2 = x2 2
= x2 x
22 (2!) d x 2 2
2 (2!) dx

1
= x x x2
22 (2!)

1 3 2 1
= [12x 2 x
8 2 2

5 1/ 2 3 1ˆ Ê 2 ¥ 5 ˆ Ê 1 ˆ
Q = ÊÁ ˆ˜ ÊÁ x 2 - ˜= Á (3 x - 1)˜¯
2
Ë 2¯ Ë 2 2 ¯ ÁË 2 ¥ 2 ¯˜ Ë 2

10
= x2
4
Since x q
10 2
Q = q
4

Expressions of a
Few Qj,|m| J m
Functions
Table 1.6.2 QJ, | m |

J m QJ m

2/2

( 6 /2 ) q

1 ±1 ( 3 / 2) q

( 10 / 4) (3 cos2 q - 1)
2 ±1 ( 15 / 2) q q

2 ±2 ( 15 / 4) 2 q

Physical
Significance of the 2
Constant J Ê hˆ
L2 = J J ÁË ˜¯
2p
or L = J ( J + 1) h/2 p
 Wave Mechanics, Energy Quantization and Atomic Structure

L2 h2
E = = J ( J + 1) 2
2I 8p I
J L E
L

Physical m
Significance of the (1 / 2p ) mj z
Constant m

Ÿ h ∂ †
Lz =
2p i ∂j

Ÿ Ï 1 ¸ h ∂
L z Ì 2p exp(imj ) ˝ = 2pi ∂j
Ó ˛ { 1
2p
exp (imj ) }
h Ï 1 ¸
=m Ì exp (imj ) ˝
2p Ó 2p ˛
z

Lz = m ÊÁ ˆ˜
h
Ë 2p ¯

m z
m
º z
q z
j
Relation between J m
the Constants 2 2
J and m L Lz

Ÿ Ï 1 ¸ h Ï 1 ¸
We have Lz Ì exp(imj ) ˝ = m Ì exp(imj ) ˝
Ó 2p ˛ 2 p Ó 2p ˛

Ÿ
†
Lz
 A Textbook of Physical Chemistry

Ÿ Ï 1
L 2z Ì
Ó 2p
¸
˛
Ÿ
exp(imj ) ˝ = L z m h
2p { 1
2p }
exp(imj )

= m2 Ê ˆ
h 2
Ë 2p ¯ { 1
2p }
exp(imj )

2
z mh/2p

L2 = L2x + L2y + L2z

or L2 L2z = L2x + L2y
2
2 Ê hˆ 2 2
or [J J m ÁË ˜¯ = L x + L y
2p

J J m2 ≥
m| £ J
T m m J m can have
J m J are

Pictorial Since m J J J J J for

Representations J
of Angular
J ( J +1) h/2 p z
Momentum
Vectors mz h/2p mz J J
– J J

J space quantization of
angular momentum q
z
J ( J +1) q = mz
n
mz
q with the z

2 h / 2p
 Wave Mechanics, Energy Quantization and Atomic Structure

h/2p z

q j
L2 Lz Lx Ly †

h/2p

Fig.1.6.3 Possible
orientations of angular
momentum vectors for
J=1

Problem 1.6.2 Show that Q F +1

h2 È 1 ∂ Ê ∂ˆ 1 ∂2 ˘
2 Í ÁË sin q ˜¯ + 2 ˙
4p Î sin q ∂q ∂q sin q ∂j 2 ˚

Q = ( 15 / 2) q q F+ 1 = (1 2p ) j
Solution
h2 È 1 ∂ Ê ∂ˆ 1 ∂2 ˘
2 Í ÁË sin q ˜¯ + 2 ˙Q F+ 1
4 p Î sin q ∂q ∂q sin q ∂j 2 ˚

†
See Annexure IV at the end of the chapter for quantum mechanical explanation.
 A Textbook of Physical Chemistry

h 2 È F+1 d Ê Q 2, |±1| d 2 ˘
Q 2,|±1| ˆ˜ +
d
2 Í ÁË sin q ¯
F+1 ˙
4 p Î sin q dq dq 2
sin q dj 2
˚

Ê h 2 ˆ Ê 15 ˆ Ê 1 ˆ ÈÍ eij d Ê d ˆ + sin q cos q d eij ˘

2
= Á- Á ˜ Á sin q sin q cos q ˜ ˙
Ë 4p 2 ˜¯ ÁË 2 ˜¯ Ë 2p ¯ ÍÎ sin q dq Ë
Í
dq ¯ sin 2 q dj 2 ˚

Ê h 2 ˆ Ê 15 ˆ Ê 1 ˆ È eij d cos q ˘
= Á- ˜ Á ˜ Á ˜ Í (sin q cos 2q ) + (-1) eij ˙
Ë 4p 2 ¯ Ë 2 ¯ Ë 2p ¯ ÍÎ sin q dq sinn q ˙˚

Ê h 2 ˆ Ê 15 ˆ Ê eij ˆ Ê 1 ˆ
= Á- ˜Á ˜Á ˜Á ˜ q q q q q
Ë 4p 2 ¯ Ë 2 ¯ Ë 2p ¯ Ë sin q ¯

Ê h 2 ˆ Ê 15 ˆ Ê eij ˆ Ê 1 ˆ
= Á- ˜Á ˜Á ˜Á ˜
2
q q q 2
q q
Ë 4p 2 ¯ Ë 2 ¯ Ë 2p ¯ Ë sin q ¯

Ê h 2 ˆ Ê 15 ˆ Ê eij ˆ Ê 1 ˆ
= Á- ˜Á ˜Á ˜Á ˜
2
q q
Ë 4p 2 ¯ Ë 2 ¯ Ë 2p ¯ Ë sin q ¯

Ê h 2 ˆ Ê 15 ˆ Ê eij ˆ Ê h2 ˆ
Á 2˜Á sin q cos q ˜ Á ˜ = (6) Á 2 ˜ Q F+1
Ë 4p ¯ Ë 2 ¯ Ë 2p ¯ Ë 4p ¯

h2/4p2 h/2p 2

1.7 QUANTIZATION OF ELECTRONIC ENERGY: THE HYDROGEN ATOM

Necessity of
Replacing Bohr’s
Theory
+ 2+

Setting of
Schrödinger
Equation H Ytotal = EtotalYtotal

where H Etotal
Ytotal
 Wave Mechanics, Energy Quantization and Atomic Structure 81

function Ytotal
x e ye z e xn yn zn

H = T + V

Ê h2 h2 ˆ Ze 2
= Á- — e2 - 2 — n2 ˜ -
2
Ë 8p me 8p mn ¯ ( 4p e 0 ) r

È h 2 Ê ∂2 ∂2 ∂2 ˆ h 2 Ê ∂2 ∂2 ∂2 ˆ
Í - Á 2 + + 2˜
- Á 2 + + 2˜
Î 8p me Ë ∂xe ∂ye ∂ze ¯ 8p mn Ë ∂xn ∂yn ∂zn ¯
2 2 2 2

Ze 2 ˘
- ˙ Ytotal = Etotal Ytotal
(4pe 0 )r ˚

†
The

h2 Ê ∂2 ∂2 ∂2 ˆ
+ + yM = E yM
8p 2 (me + mn ) ÁË ∂xc2 ∂yc2 ∂zc2 ˜¯

È h 2 Ê ∂2 ∂2 ∂2 ˆ Ze2 ˘
Í- 2 Á 2 + 2 + 2 ˜ - ˙ ye = E ye
Î 8p m e Ë ∂ x ∂y ∂z ¯ ( 4 p e 0 ) r ˚

with E + E = Etotal

me + mn E

m
Z r
ye E

†
See Annexure VI at the end of the chapter for explanation.
82 A Textbook of Physical Chemistry

Schrödinger
Equation in Terms
of Spherical Polar V
Coordinates on r
r q j
x=r q j
y=r q j
z=r q

È h2 Ï ∂ Ê 2 ∂ ˆ 1 ∂ Ê ∂ ∂2 ¸ Ze 2 ˘
sin q ˆ + 2
1
Í- 2 2 Ì Ë r + ˝ - ˙ y = Ey
Î 8p m r Ó ∂r ∂r ¯ sin q ∂q Ë ∂q ¯ sin q ∂j 2 ˛ (4p e 0 )r ˚

where y r q j
Splitting of
Schrödinger
1 Ï∂ Ê 2 ∂ˆ 1 ∂ Ê ∂ˆ 1 ∂2 ¸
Equation Ì Á r ˜ + Á sin q ˜ + ˝y
r 2 Ó ∂r Ë ∂r ¯ sin q ∂q Ë ∂q ¯ sin 2 q ∂j 2 ˛

8p 2 m Ê Ze2 ˆ
+ 2 Á
+ E˜ y
h Ë ( 4 p e 0 ) r ¯
r2

È ∂ Ê 2 ∂ ˆ 8p 2 m r 2 Ï Ze2 ¸ 1 ∂ Ê ∂ ∂2 ˘
sin q ˆ + 2
1
Í Ër + Ì + E˝ + ˙y
Î ∂r ∂r ¯ h 2
Ó ( 4p e 0 ) r ˛ sin q ∂q Ë ∂q ¯ sin q ∂j 2 ˚

r
q j
y r q j

Yr q j = RrYq j

The function Y

dÊ 2 d 8p 2 m r 2 È Ze 2 ˘
Yq j r Rr ˆ + Í + E ˙ Rr Yq j
dr Ë d r ¯ h2 Î ( 4 p e 0 ) r ˚

È 1 ∂ Ê ∂ˆ 1 ∂2 ˘
+ Rr Í ÁË sin q ˜¯ + 2 ˙ Yq j
Î sin q ∂q ∂q sin q ∂j 2 ˚
 Wave Mechanics, Energy Quantization and Atomic Structure

Rr Yq j

È1 d Ê 2 d 8p 2 m r 2 Ï Ze 2 ¸˘
Í r Rr ˆ + Ì + E ˝˙
Î Rr dr Ë dr ¯ h2 Ó ( 4p e 0 ) r ˛˚

È 1 ÏÔ 1 ∂ Ê ∂ˆ 1 ∂2 ¸Ô ˘
Í Ì ÁË sin q ˜¯ + 2 ˝ q, j ˙
Y
ÓÔ sin q ∂q ∂q 2
ÍÎ Yq , j sin q ∂j Ô˛ ˙˚

l l
r q j

Equation involving the variable r

1 d Ê 2 dR ˆ 8p 2 m r 2 Ê Ze 2 ˆ
r + E + =l l
R d r Ë dr ¯ h 2 ÁË (4p e 0 )r ˜¯
Equation involving the angles q and j
1 Ï 1 ∂ Ê ∂ˆ 1 ∂2 ¸
Ì ÁË sin q ˜¯ + ˝Y l l
Yq , j Ó sin q ∂q ∂q sin 2 q ∂j 2 ˛ q j

2
q

È ∂ Ê ∂ˆ ∂2 ˘
˜¯ + l (l + 1) sin q +
2
Ísin q ÁË sin q ˙ Yq j
Î ∂q ∂q ∂j 2 ˚
q
the other on j Yq j
Yq j = Qq F j

d Ê dQq ˆ d2
2
Fj q Á sin q +l l q Qq Fj + Qq Fj
dq Ë dq ˜¯ dj 2
Qq Fj
2
sin q d Ê d Qq ˆ 2 1 d Fj
Á sin q q
dq ˜¯
+l l
Qq dq Ë Fj dj
2

m2
sin q d Ê d Qq ˆ 2
sin q +l l q = m2
Qq dq ÁË dq ˜¯
2
1 d Fj
m2
Fj dj 2
84 A Textbook of Physical Chemistry

Three Split
Expressions of
the Schrödinger ∑ Equation involving only r
Equation
1 Ê 2 dR ˆ 8p 2 m r 2 Ê Ze2 ˆ
Á r ˜ + Á E + =l l
R r Ë dr ¯ h2 Ë (4p e 0 )r ˜¯
∑ Equation involving only q
sin q d Ê dQ ˆ 2
ÁË sin q ˜ +l l q = m2
Q dq dq ¯
∑ Equation involving only j
1 d 2F
m2
F dj 2

Solutions of
j-Dependent
Equation 1
Fm = mj m …
2p
m magnetic quantum number
quantization of the z

Ÿ Ï 1 ¸ h ∂ Ï 1 ¸
Lz Ì exp(imj ) ˝ = Ì exp(imj ) ˝
Ó 2p ˛ 2pi ∂j Ó 2p ˛

h Ï 1 ¸
=m Ì exp(imj ) ˝
2p Ó 2p ˛
z
m h/2p
Solutions of
q -Dependent
1/ 2
Equation È (2l + 1) (l - | m |)!˘
Ql m| = Í ˙ Pl| m|
Î 2 (l + | m |)!˚

d| m | Pl
where Pl| m| x2 | m|/2

dx | m |
l
1 l
Pl = x2
2l l! x l
x q
 Wave Mechanics, Energy Quantization and Atomic Structure 85

l …
m … l
l azimuthal quantum number

Ÿ 2
2 Ê hˆ
L Ql m| =l l ÁË 2 p ˜¯ Ql m|

Solutions of
r-Dependent
Equation associated
Laguerre equation
d2 L L
r2 j r k j L
dr 2 r
where the function R L
r /2 r/2
Rr sr F r rl L r
r j k
r = 2a r
j = 2l
k=l+l

where a 2 8p 2 mE
h2
4p 2 m Z e 2
l=
(4pe 0 )h 2a

associated Laguerre polynomial k j j

j
L ∫ Lkj = Lk
rj
where Lk , the Laguerre polynomial of degree k
k
L k = er rk e r

rk
†

k … •
†
L r)
rƕ
86 A Textbook of Physical Chemistry

l k l
l n
k =n+l
Expression of R
the Normalized R
Functions R = rl e r/2
L2nl++l1

Ú R*R r 2
r=1

1/ 2
ÏÔÊ 2 Z ˆ 3 (n - l - 1)! ¸Ô
R ÌÁ ˝ rl e r/2
L2nl++l1
Ë na0 ˜¯ 2n [(n + l )!]3 Ô
ÓÔ ˛

Ê 4p 2 m Ze 2 ˆ Ê 2Z ˆ
where r ar Á 2 ˜ r = ÁË na ˜¯ r
Ë nh (4pe 0 ) ¯ 0

h 2 (4pe 0 )
a =
4p 2 m e 2
Allowed Values of n principal quantum number
n and its Relation
with l
j£k
Since j = 2l k=n+l
l £ n+l
or l + 1 £ n or l £ n
l
n n

n …
l … n
Expressions for the Rn l r n l
Function Rn, l
1/ 2
ÏÔÊ 2 Z ˆ 3 (n - l - 1)! ¸Ô
Rn l ÌÁ ˜ 3˝
rl e r/2
L2nl++l1
ÔÓË na0 ¯ 2n [(n + l )!] Ô˛

d 2l +1
L2nl++l1 = Ln+ l
dr 2l +1
 Wave Mechanics, Energy Quantization and Atomic Structure

n+l
Ln + l = er rn+ l e r
rn + l

Ê 2Z ˆ
where r= Á r
Ë na0 ˜¯

Problem 1.7.1 Determine the form of function R n l

Solution n l
1/ 2
ÏÔÊ 2Z ˆ 3 (2 - 0 - 1) ! ¸Ô
r /2
R ÌÁ ˝ r e L12
Ë 2a0 ˜¯ 2 ¥ 2[(2 + 0) !]3
ÓÔ ˛Ô
where L12

L12 = L2
r
where L2
d2
L2 = er r2 e r
dr 2

d Ïd 2 -r ¸ r d
L2 = er Ì (r e )˝ = e re r
r2 e r
dr Ó dr ˛ dr

= er r
re r
re r
+ r2 e r

r + r2

L12 = L2 = r + r2 r
r r

Ê 2Z ˆ Ê Zr ˆ
r= Á ˜ r= Á ˜
Ë na0 ¯ Ëa ¯

1/ 2
ÏÔÊ Z ˆ 3 1 ¸Ô
r/2
R ÌÁ ˜ ˝ e r
ÔÓË a0 ¯ 4 ¥ 8 Ô˛

3/ 2
Ê Z ˆ Ê Z rˆ
= Á
Ë 2a0 ˜¯ ÁË 2 - a ˜¯ e- Zr/2a0
0

Some of the
r-Dependent of n l
Solutions
88 A Textbook of Physical Chemistry

Table 1.7.1 Rn, l

n l Rn l

3/ 2
ÊZˆ
ÁË a ˜¯ Zr/a
0

3/ 2
Ê Z ˆ Ê Zr ˆ
2- ˜ Zr/2a
ËÁ 2a0 ¯˜ ËÁ a0 ¯
3/ 2
2 1 1 Ê Z ˆ Ê Zr ˆ Zr/2a
3 ÁË 2a0 ˜¯ ÁË a ˜¯
0

3/ 2
2Ê Z ˆ Ê 2 Zr 2 Z 2 r 2 ˆ Zr a
3 ÁË 3a0 ˜¯ ÁË 3 - a + 9a 2 ˜¯
0 0

3/ 2
2 2Ê Z ˆ Ê 2 Zr Z 2 r 2 ˆ
Á ˜ Á - ˜ Zr a
9 Ë 3a0 ¯ Ë a0 3a02 ¯
3/ 2
4 Ê Z ˆ Ê Z 2r 2 ˆ
Á ˜ Á 2 ˜ Zr a
27 10 Ë 3a0 ¯ Ë a0 ¯

h 2 (4pe 0 )
where a =
4p 2 m e 2

Energy of the
Electron
4p 2 m Ze 2
a = l=n
(4pe 0 )nh 2

2
È 4p 2 m Ze 2 ˘ 8p 2 mE
Í 2˙
ÍÎ (4pe 0 )nh ˙˚ h2

1 Ê 2p 2 m Z 2e 4 ˆ
E
n 2 ÁË h 2 (4pe 0 ) 2 ˜¯

n l m
n Rr
 Wave Mechanics, Energy Quantization and Atomic Structure 89

A Summary of the Quantum Mechanical Treatment of the Hydrogen-like Species

∑
Y

∑ Y
Y = yM ye
where yM ye on the internal

∑ ye
ye = R Q F
The function R r Q q F
j R
Q F

∑ R r
r
n l
Principal quantum number: n …
Azimuthal quantum number: l … n
R n l
∑ Q q
q
l m m …
±l Q m m
∑ F j
j m
∑ Q F
ye
n l m
ye n l m
90 A Textbook of Physical Chemistry

∑ n, l and m

1 È 2p 2 m Z 2 e 4 ˘ 1 È Z 2e2 ˘
E=– Í 2 2˙
=– 2Í ˙
n2 Î h (4pe 0 ) ˚ n Î 2(4pe 0 )a0 ˚
a0 = (4pe 0) h2/4p 2me 2
†

2
L 2 = l (l + 1) Ê ˆ
h
Ë 2p ¯
l
value of l: 0 1 2 3 4 5
designation: s p d f g h

z
n
Lz = m (h/2p)
∑ n l
and m ye n
l and m
n n2
Table 1.7.2

E = - 2p m Z e
2 2 4
(i) n = 1 l=0 m=0
(4pe 0 ) h
2 2
(ii) n = 2 l=0 m = 0
l=1 m = +1 1 È 2pm Z 2e 4 ˘
E=– Í ˙
m = 0 4 Î (4pe 0 ) 2 h 2 ˚
m = -1
(iii) n=3 l=0 m = 0
l=1 m = +1
m = 0
m = -1
1 È 2p 2 m Z 2 e 4 ˘
l=2 m = +2 E=– Í ˙
m = +1 9 Î (4pe 0 ) 2 h 2 ˚
m = 0
m = –1
m = -2

†
l
 Wave Mechanics, Energy Quantization and Atomic Structure 91

Spectra of
Hydrogen-like
Species
n, l and m l
and m

selection rules
n Dn
l Dl
and m Dm
n=2
n l l ¨ 2p is
¨ Dl

Fig. 1.7.1 The

allowed transitions of
the hydrogen atom
92 A Textbook of Physical Chemistry

Problem 1.7.2 y - ar

h2a 2 e 2 a0
E= –
8p 2 m 4pe 0
E a a

Solution
h2 e2
H =– — 2
–
8p 2 m (4pe 0 )r
—2

1 ∂ Ê 2 ∂ˆ 1 ∂ Ê ∂ˆ 1 Ê ∂2 ˆ
—2 = Á r ˜ + Á sin q ˜ +
r 2 ∂r Ë ∂r ¯ r 2 sin q ∂q Ë ∂q ¯ r 2 sin 2 q ÁË ∂j 2 ˜¯

·y | H | y Ò
E =
·y | y Ò

—2
1 d Ê 2 dˆ
—2 = Ár ˜
r2 dr Ë dr ¯

Ê h2 e2 ˆ
H y = Á- 2 — -
2
y
Ë 8p m (4pe 0 )r ˜¯

h 2 1 d Ï 2 d - ar ¸ e2
= - Ìr e ˝- e-a r
8p m r d r Ó d r
2 2
˛ ( 4 pe 0 ) r

Ï h2 1 e 2 ¸ –ar
= Ì- (
-2ar + a 2 r 2 - ) ˝e
( 4p e 0 ) r ˛
Ó 8p m r
2 2

·y | H | y Ò = Ú y | H | y dt t = r 2 dr sin q dq dj

• p 2p
Ï h2 e 2 ¸ -2ar
·y | H | y Ò = Ú Ì- 2 (-2ar + a r ) -
8p m
2 2
r˝ e
4pe 0 ˛
dr Ú sin q dq Ú dj
0Ó 0 0

È h2 Ï 1 2 ¸ e2 Ê 1 ˆ 2 ˘
= Í- - + -
2
Ì ( 2 a ) a ˝ ˙ (2)(2p)
Î 8p m Ó
2
( 2a ) 2 (2a )3 ˛ 4pe 0 Ë 2a ¯ ˚

p Ï h2 e2 ¸
= Ì 2 - ˝
a Ó 8p m (4pe 0 )a ˛
 Wave Mechanics, Energy Quantization and Atomic Structure 93

• p 2p
2 p
Ú r e- 2a r dr Ú sinq dq Ú dj
2
·y |y Ò = = (2) (2p) =
0 0 0 ( 2 a )3 a3

E=
y Hy
=
{
(p / a ) (h 2 / 8p 2 m) - (e 2 / 4pe 0 a ) }
y y (p / a3 )

h2 a 2 Ê e2 ˆ
= - a
8p 2 m ÁË 4pe 0 ˜¯
E a E/da

h2 e2
( 2 a ) - =0
8p 2 m (4pe 0 )

4p 2e 2 m
a=
h 2 (4pe 0 )
2
h2 Ï 4p 2e 2 m ¸ e2 4p 2e 2 m 2p 2e 4 m
E = Ì 2 ˝ – =– 2
Ó h (4pe 0 ) ˛ 4pe 0 h (4pe 0 ) h (4pe 0 ) 2
2
8p 2 m

Problem 1.7.3 F y - ar 2

3h 2 a e2 a
E= –
8p 2 m 2e 0 p 3 / 2
E a
4
e m
E =–
3pe 02 h 2
Solution
h2 e2
H =– — 2
–
8p 2 m (4pe 0 )r
—2

1 d Ê 2 dˆ
—2 = Ár ˜
r2 dr Ë dr ¯

È h2 1 d Ê 2 d ˆ e 2 ˘ -ar 2
H y = Í- Á r ˜ - ˙ e
Î 8p m r d r Ë d r ¯ (4pe 0 )r ˚
2 2

h2 1 d 3 -ar 2 e2 2
=– (- 2ar e ) – e-ar
8p 2 m r 2 d r (4pe 0 )r

h2 1 2 4 -ar
2 e2 2
=– (- 6ar 2
+ 4a r ) e – e-ar
8p m r
2 2 (4pe 0 )r
94 A Textbook of Physical Chemistry

• p 2p
È h2 e 2 ˘ -2ar 2
Ú ÍÎ 8p 2m (6a - 4a r Ú sinq Ú dj
2
·y | H | y Ò = 2 2
)- ˙ e r dr dq
0
(4pe 0 )r ˚ 0 0

• •
È h 2 ÔÏ ¸Ô
r 2e -2 ar d r - (4a 2 )
2
4 -2 ar 2
= Í Ì
ÍÎ 8p m ÓÔ
2
( 6 a ) Ú Úr e dr˝
Ô˛
0 0

•
e2 ˘
r e -2 ar d r ˙ (2) (2p)
2
– Ú
(4pe 0 ) 0 ˙˚

È h2 Ï 1 Ê p ˆ 1/ 2 3 Ê p ˆ 1/ 2 ¸
ÁË ˜¯ - (4a )
2
2 Ì Á ˜ ˝
= Í (6 a )
Î 8p m ÔÓ 4(2a ) 2a 8(2a ) 2 Ë 2a ¯ Ô˛

2 •
Ê e 2 ˆ 1 e -2 ar ˘
- Á ˙ (4 p)
Ë 4pe 0 ˜¯ 2 (-2a ) ˙
0˚

1/ 2
3h 2 Ê 1 ˆ Ê e2 ˆ Ê p ˆ
= Á ˜ –Á Á ˜
16 2m Ë pa ¯ Ë 4pe 0 ˜¯ Ë a ¯

• p 2p
2 -2 ar 2
·y |y Ò = Úr e dr Ú sinq dq Ú dj
0 0 0

1 Ê p ˆ 1/ 2 ( ) Ê p ˆ 3 / 2
= Á ˜ 4p = Á ˜
4( 2 a ) Ë 2 a ¯ Ë 2a ¯

3h 2 Ê 1 ˆ 1 / 2 Ê e 2 ˆ Ê p ˆ
-Á
y Hy 16 2m Ë pa ¯ Ë 4pe 0 ˜¯ Ë a ¯
E= =
y y ( p / 2 a )3 / 2

3h 2 a Ê e2 ˆ Ê a ˆ 1/ 2
=
8p 2 m
- 2 2 ( )
ÁË 4pe ˜¯ ÁË p ˜¯
0

E E/da

3h 2 Ê e2 ˆ Ê 1 ˆ Ê 1 ˆ 1/ 2
8p m
2 (
- 2 2 Á )
Á ˜Á ˜ = 0
Ë 4pe 0 ˜¯ Ë 2 ¯ Ë pa ¯

2 2
È 2 (e 2 / 4pe 0 )(1/ pa )1 / 2 ˘ Ê e 2 ˆ Ê 128p 3m 2 ˆ
a= Í ˙ = ÁË 4pe ˜¯ ÁË 9h 4 ˜¯
Î 3h / 8p m
2 2
˚ 0

2 1/ 2
Ê 3h 2 ˆ Ê e 2 ˆ Ê 128p 3m 2 ˆ Ê 2 ˆ Ê e ˆ Ê e ˆ Ê 128p m ˆ
1/ 2 2 2 3 2
E = Á 2 ˜Á - 2 ÁË ˜¯ Á
Ë 8p m ¯ Ë 4pe 0 ˜¯ ÁË 9h 4 ˜
¯ p Ë 4pe 0 ¯ Ë 4pe 0 ¯ Ë 9h 4 ˜¯
˜ Á ˜ Á
 Wave Mechanics, Energy Quantization and Atomic Structure 95

2 2
16p m Ê e 2 ˆ 2 ¥ 16 pm Ê e ˆ
2
= –
3h 2 ÁË 4pe 0 ˜¯ 3h 2
Á
Ë 4pe 0 ˜¯
2
16p m ˆ Ê e ˆ
2
e4m
= – ÊÁ ˜ Á ˜ =–
Ë 3h ¯ Ë 4pe 0 ¯
2 3pe 02 h 2

Problem 1.7.4 r
(Z
Solution n = 1, l = 0 and m

y 1, 0, 0 = R1, 0 Q0, 0 F0
È Ê 1 ˆ 3/ 2 ˘ 1 ˆ Ê 1 ˆ Ê 1 ˆ 1/ 2
= Í2 Á ˜ e - r / a0 ˙ ÊÁ ˜Á
- r/a
˜ = Á 3˜ e 0
ÍÎ Ë a0 ¯ ˙˚ Ë 2 ¯ Ë 2p ¯ Ë pa0 ¯

y1, 0,0 r
· rÒ = ·y 1,0,0 | r | y1,0,0Ò

ÈÊ 1 ˆ 1 / 2 - r / a Ê 1 ˆ
1/ 2
˘ Ê 1 ˆ
= Ú ÍÁË pa03 ˜¯
Í e 0
r ÁË p a 3 ˜¯ e
- r / a0
˙ dt = Á 3 ˜ Ú r e-2r/a0 dt
Î 0 ˙˚ Ë p a0 ¯

t = r 2 d r sinq dq dj
• p 2p
· rÒ = Ê 1 ˆ 3 -2 r / a0 dr
Ú sinq dq Ú dj
ÁË pa 3 ˜¯ Ú r e 0 0
0 0

Ê 1 ˆ È 3! ˘ 3
= Á 3˜ Í ˙ (2)(2p) = a0
Ë pa0 ¯ Î (2 / a0 ) 4 ˚ 2

Problem 1.7.5
Solution
y2, 0, 0 = R2,0 Q 0, 0 F 0
ÈÊ 1 ˆ 3 / 2 Ê rˆ ˘
Í
= Á ˜ Á 2 - ˜ e - r / 2 a0 ˙ ÊÁ 1 ˆ˜ ÊÁ 1 ˆ˜
ÍÎË 2a0 ¯ Ë a0 ¯ ˙˚ Ë 2 ¯ Ë 2p ¯
3/ 2
1 Ê 1ˆ Ê r ˆ -r/2a0
= Á ˜ ÁË 2 - a ˜¯ e
32p Ë a0 ¯ 0

r
· r Ò = ·y 2, 0, 0 |r | y2, 0,0 Ò

È 1 Ê 1 ˆ 3/ 2 Ê r ˆ - r / 2 a0 1 Ê 1ˆ
3/ 2
Ê r ˆ - r / 2 a0 ˘
= ÚÍ ÁË a ˜¯ ÁË 2 - a ˜¯ e r ÁË 2 - a ˜¯ e ˙ dt
ÍÎ 32 p 0 0 32p ÁË a0 ˜¯ 0 ˙˚
96 A Textbook of Physical Chemistry

2
1 Ê 1ˆ Ê r ˆ -r/a
32p ÁË a03 ˜¯ Ú ÁË
= r 2 - ˜ e 0 dt
a0 ¯

• 2 p 2p
1 Ê 1 ˆ 3Ê rˆ
= Á 3˜ Ú
32p Ë a0 ¯ 0
r Á 2 - ˜ e-r/a0 dr
Ë a0 ¯
Ú sinq dq Ú dj
0 0

•
1 Ê 1ˆ È Ê 3 r 4r 4 ˆ - r / a0 ˘
5
= Í ÚÁ
32p ÁË a03 ˜¯ ÍÎ 0 Ë
4 r + -
a02 a0 ˜¯
e dr ˙ (2) (2p)
˙˚

1 Ê 1 ˆÈ 3! 1 5! 4 4! ˘
= Á 3˜ Í
4 + 2 - ˙ (4p)
32p Ë a0 ¯ Î (1/ a0 ) 4
a0 (1/ a0 ) 6
a0 (1/ a0 )5 ˚

1 ˆÊ 1 ˆ 1 ˆÊ 1 ˆ
= ÊÁ [(24 + 120 - 96) a40 ] (4p) = ÊÁ (48a40 ) (4p)
Ë 32p ˜¯ ÁË a03 ˜¯ Ë 32p ˜¯ ÁË a03 ˜¯

= 6a0
Note:

Problem 1.7.6 V
·V Ò = 2· EÒ, (ii) ·V Ò = - 2 ·T Ò, and
(iii) · TÒ = - ·EÒ T
Solution n = 1, l = 0 and m

È Ê 1 ˆ 3/ 2 ˘ Ê 1 ˆ Ê 1 ˆ Ê 1 ˆ 1 / 2 -r/a
y1, 0, 0 = R1, 0 Q 0, 0F 0 = Í2 Á ˜ e - r /a0 ˙Á ˜Á ˜ = Á 3˜ e 0
ÍÎ Ë a0 ¯ ˙˚ Ë 2 ¯ Ë 2p ¯ Ë pa0 ¯

e2
V=–
(4pe 0 )r

y1, 0, 0

·V Ò = ·y1, 0,0 |V | y1, 0,0Ò

ÈÊ 1 ˆ 1 / 2 ˘ e2 ÈÊ 1 ˆ 1 / 2 - r / a ˘
= Ú ÍÍÁË pa03 ˜¯ e - r / a0 ˙ - ÍÁ 3 ˜ e 0 ˙ dt
Î ˙˚ (4pe 0 )r ÍÎË p a0 ¯ ˙˚

Ê 1 ˆ Ê e 2 ˆ 1 -2r/a
Ë pa0 ¯ Ë 4pe 0 ˜¯ Ú r
= Á 3˜ Á- e 0 dt
 Wave Mechanics, Energy Quantization and Atomic Structure

t = r 2 dr sin q dq dj

• p 2p
Ê 1 ˆ Ê e2 ˆ
Ë pa0 ¯ Ë 4pe 0 ˜¯ Ú0
·V Ò = Á 3 ˜ Á - r e-2r/a 0 dr Ú sinq dq Ú dj
0 0

Ê 1 ˆ Ê e2 ˆ Ê 1 ˆ
= Á 3˜ Á- (2) (2p )
Ë pa0 ¯ Ë 4pe 0 ˜¯ ÁË (2 / a0 ) 2 ˜¯

e2
=–
(4pe 0 )a0

·E Ò = - (e 2/4p e0) (1/2a0

·V Ò = 2 ·E Ò

·E Ò = ·T Ò + ·VÒ

1 1
·T Ò = ·E Ò - ·V Ò = ·V Ò - ·V Ò = – ·V Ò
2 2
·V Ò = - 2·TÒ

·E Ò = ·T Ò + ·VÒ

·T Ò = ·E Ò - ·V Ò = ·E Ò - 2·E Ò = - ·E Ò

Note: ·V Ò = 2·E Ò

Problem 1.7.7
Solution
d(r2 R21,0)/dr R1,0

d ( 2 -2r/a0 )
r e =0
dr

[2r + r 2 (-2 / a0 )]e-2r/a 0

=0

r = a0

Problem 1.7.8
a0

Solution
d(r2 R22,0)dr R2,0
98 A Textbook of Physical Chemistry

d 2
ÈÎr ( 2 - r / a0 )2 e - r/a0 ˘˚ = 0
dr

d ÈÊ 2 r 4 4r 3 ˆ - r/a0 ˘
Í 4r + 2 - e ˙=0
dr ÎÁË a0 a0 ˜¯ ˚

ÈÊ 4r 3 12r 2 ˆ Ê 2 r 4 4r 3 ˆ Ê 1 ˆ ˘ - r/a0
ÍÁ 8r + 2 - + 4r + 2 - - ˙e =0
ÎË a0 a0 ˜¯ ÁË a0 a0 ˜¯ ÁË a0 ˜¯ ˚

8r 3 16r 2 r 4
8r + - - 3 =0
a02 a0 a0

3 2
Ê r ˆ - 8 Ê r ˆ + 16 Ê r ˆ - 8 = 0
ËÁ a0 ¯˜ ÁË a ¯˜ ËÁ a0 ¯˜
0

ÈÊ r ˆ 2 Ê rˆ ˘Ê r ˆ
ÍÁ ˜ - 6 Á ˜ + 4˙ Á - 2˜ = 0
ÎË a0 ¯ Ë a0 ¯ ˚ Ë a0 ¯

r r 6 ± 36 - 16
= 2 and = = 3± 5
a0 a0 2

r/a0 R2,0
r2 R2 r r = (3 - 5 ) a0 and (3 + 5 ) a0

F = r2R2dr

2
È 1 ˆ 3/ 2 Ê r ˆ - r / 2 a0 ˘
F = r ÍÊÁ
2
˜¯ ÁË 2 - a ˜¯ e ˙ dr
Î Ë 2 a0 0 ˚

È 1 Ê r ˆ2Ê r 2 ˘
= Í Á ˜ Á 2 - ˆ˜ e - r / a0 ˙ dr
Î 0 0
8 a Ë a ¯ Ë a0 ¯ ˚
a0
1Ê r ˆ2Ê r ˆ 2 - r / a0
F= 2 - e
8 ÁË a0 ˜¯ ÁË a0 ˜¯

r/a0 = 3 – 5
1 2 2
F= e
8
 Wave Mechanics, Energy Quantization and Atomic Structure 99

1
=
8

r/a0 = 3 + 5

1 2 2
F= e
8

1
=
8

1.8 PICTORIAL REPRESENTATIONS OF WAVE FUNCTIONS AND PROBABILITY DENSITY

DISTRIBUTIONS FOR HYDROGEN-LIKE SPECIES

Expression of
Wave Function
yn, l, m = Rn, l Q l, | m | F m

Rn, l, Q l, | m| and Fm r, q and j dependences,

R n and l Q
l and |m F
m Q l, | m| and F m
R, Q and F

l and m
n
n l and m
p)1/2
q and j n y1s, y 2s,
y3s , … … r

Plots of Functions
of s-type
1
yn, 0, 0 = Rn, 0
4p

y n,0,0 r R r
100 A Textbook of Physical Chemistry

Plots of R1s and R2s R1s and R2s

r†

5.0 2.0

4.0 1.5

R20/1015 m–1.5
R10/1015 m–1.5

3.0 1.0
node
2.0 0.5

1.0 0 1 2 3 4 5 6 7 8 9
0

0 – 0.5 r/a0
Fig. 1.8.1 Plots of 0 1 2 3 4
functions (i) R1s and r/a0
(ii) R2s (i) (ii)

y1s r
2 (Z/a0)3/2 - Zr/a0
y 2s Z/2a0)3/2 and
- Zr/a0 - Zr/2a0
y1s
y2s y1s
(2 - Z r/a0 y2s
Zr/a 0 y2s
Zr
< 2, y 2s r
a0
Zr
> 2, y2s r
a0
Zr
and = 2, y2s r
a0
nodal point
nodal points Rn, l
(n - l -
2 2
Plots of R 1s and R 2s
y *y y
y -
y *y y2

†
 Wave Mechanics, Energy Quantization and Atomic Structure 101

5.0 0.5

4.0 0.4

/10 30 m –3

/10 30 m –3
3.0
R10 0.3

R20
2

2
2.0
0.2
node
1.0 0.1
Fig. 1.8.2 Probability
distribution for the 0
0
electron in (i) 1s and 0 1 2 3 4 0 1 2 3 4 5 6 7 8
r/a0 r/a0
(ii) 2s orbitals of the
hydrogen atom
(i) (ii)

Dot-Population y *y r
Diagrams

Spherical node

Fig. 1.8.3 The dot-

population pictures
(or the cloud density
patterns) for 1s and 2s
orbitals 1s 2s
102 A Textbook of Physical Chemistry

Equal-Probability
Contour Diagrams

Fig. 1.8.4 90%

probability contours
for 1s and 2s orbitals

Plots of Radial
Distribution
Functions

r and r + dr FR, as
FR
= (4p r 2dr) (R 2 †

the electron in a spherical shell of thickness dr located at the distance r from the
nucleus
Note: r and r + d r
r +d r p 2p

Ú R 2 r 2 dr Ú Q 2 sin q dq ÚF
2
r= dj
r 0 0
Q and F q and j

r +d r
r= Ú r 2 R 2 dr
r
r 2R2 r

†
r r
dV = (4/3)p (r + dr)3 - (4/3)pr 3 = (4/3)p (dr 3 + 3r 2dr + 3rdr 2
ing dr3 and dr2 V = 4pr 2 dr.
p 2p

2 2
R Ú
FR = R2 r2 dr sinq dq Ú dj = R2r2
dr (2) (2p) = 4pr R dr 0 0
 Wave Mechanics, Energy Quantization and Atomic Structure 103

r /a0

16
5
14
12 4
node

2 /1010 m–1
2 /1010 m–1

10
3
8

4 pr2 R20
4 pr 2 R10

6 2
4
Fig. 1.8.5 Radial 1
2
distribution function 0
0
for the electron in 1s 0 1 2 3 4 0 1 2 3 4 5 6 7 8 9
and 2s orbitals r/a0 r/a0

r
a0

r
r / a0 r = a0

Problem 1.8.1
a 0 /Z Z a0

Solution I r
r
r 2R1,0
2

d d ( 2 -2 Zr / a0 )
(r 2 R1,2 0 ) = r e
dr dr

-2 Zr / a0 Ê 2 Z ˆ -2 Zr / a0
= 2r e +r2 Á - e
Ë a0 ˜¯
104 A Textbook of Physical Chemistry

Ê Zr ˆ
-2 Zr / a0
= 2r Á 1 - ˜ e
Ë a0 ¯

Ê Zr ˆ -2 Zr / a0
2r Á 1 - ˜ e =0
Ë a0 ¯

r r = a0 /Z r=• R1,2 0
r = 0 and r = •
a0 /Z

Plot of Functions p l n
of 2p-type m r
n and l m n r

3/ 2
1 Ê Z ˆ Ê Zr ˆ
R2,1 = Á ˜ ÁË a ˜¯ - Z r/2a0
3 Ë 2a0 ¯ 0

∑ r
n-l-

∑ r
R2,1, R22,1 and 4pr 2R22,1 r†

0.5

0.4 0.3 6
5
0.3
0.2 4
21

4 p r R21
2 2

0.2 3
0.1 2
0.1
1
0 0
0
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7 8
r/a0 r/a0 r/a0

Fig. 1.8.6 Plots of R2, 1, R22, 1 and 4p r 2R2,

2
1 versus r/a0 for the hydrogen atom

The r

†
 Wave Mechanics, Energy Quantization and Atomic Structure 105

Shape of 2pz m
orbital 6 1
Q1,0 = q and F0 =
2 2p
F0 j
y 2,1, 0 0 q
Q1,0F0 q
xz yz xy
†

z QF
q
z q = 0 and
q=p xy q=p q

QF y2,1,0 z
z

q
z
q

+
QF (Q F)2
Fig. 1.8.7 (a) A
two-dimensional plot of
x (or y) x (or y)
Q1, 0F 0 in the xz-plane or
yz-plane against the angle q,
and (b) A two-dimensional –
plot of (Q1, 0F0)2 in the
xz-plane or yz-plane against
the angle q

Q F) 2
q
z
z
y2, 1,0 y 22, 1, 0

†
The number of nodal surfaces in the angular distribution function is equal to the value of
quantum number l.
106 A Textbook of Physical Chemistry

xy-nodal plane

Fig. 1.8.8 90%

x
probability contour
diagram of the orbital 2pz

Shapes of 2px and y2, 1,1 and y2, 1,-1

2py orbitals
3
Q = sin q
2
1
F+1 = j
2p
1
and F-1 = - ij
2p
y 2, 1, 1 and y2,1,-1 j
F

F+1 and F-1 F+ 1 and F-1

j

1
Fx = (F+1 + F-1
2
-i
and Fy = (F+1 - F-1
2
F+1 and F-1

1 Ê 1 ij 1 - ij ˆ
Fx = e + e
2 Ë 2p 2p ¯

- i Ê 1 ij 1 - ij ˆ
and Fy = e - e
2 Ë 2p 2p ¯
 Wave Mechanics, Energy Quantization and Atomic Structure

ei j j + i sin j
-ij
and e j - i sin j
ij -ij
+e j
- ij
and e -eij
= 2 i sin j
Fx and Fy

1 1 1
Fx = j= j
2 2p p

-i 1 1
and Fy = (2 i sin j) = sinj
2 2p p
x xy j p
j Fx x
x F
Fy y
j p p Fx and Fy
Q
x and 2py

Ê 3 ˆ 1
2px QFx = Á sinq ˜ Ê cosj ˆ
Ë 2 ¯ Ë p ¯

Ê 3 ˆ 1
2p y QFy = Á sinq ˜ Ê sinj ˆ
Ë 2 ¯ Ë p ¯

Q Fx q j angles
p q p j p),
x xz xy
z
Q Fy q j angles
p/2 and 3p q p j
p y
yz xy z and
2p x x x
yz y y
xz
y2px y 22 px) and y2py y 22 py) can

x and 2py
z
x y
108 A Textbook of Physical Chemistry

Fig. 1.8.9 90%

probability contour
of (i) 2px and (ii) 2py
orbitals
(i) (ii)
Plots of 3p Wave
Functions 2 2Ê Z ˆ
3/ 2
Ê 2 Zr Z 2 r 2 ˆ
R3, 1 = ÁË a - 3a 2 ˜¯ - Zr/3a0
9 ÁË 3a0 ˜¯ 0 0
r = 6a0/Z

x, 3py and 3pz x y

and z z

Fig. 1.8.10 90%

probability contour of
3pz orbital

Plots of Functions
of 3d Orbitals n-l-1=3-2-

10 1
q2, 0 = 2
q- F0 =
4 2p
 Wave Mechanics, Energy Quantization and Atomic Structure 109

15 1
q = sin q q F +1 = j)
2 2p
1
and F-1 = - ij
2p
15 1
q = sin2 q F+ 2 = j)
4 2p
1
and F- 2 = - 2ij
2p
Plot of Q2, 0 F 0 Q2, 0 F0
Q2, 0 2
q- q=
1 3 q ¢
q ¢ z
z z
0 z 2) is
2
q
2z2 – x2 – y2 z2
z
z
nodal
cone

y
q y

Fig. 1.8.11 (a) Nodal

surfaces forming two
cones about z-axis of x
x
3d z 2 orbital (b) 90%
probability contour
diagram of 3dz2 orbital q = 54.74°

Linear F+1, F-1, F+2 and F-2

Combinations of
the Remaining F
Functions
F +1 + F -1 1
Fx = = j
2 p
Ê F - F -1 ˆ 1
Fy = - i Á +1 ˜¯ = sin j
Ë 2 p
F + F -2 1
F x2 - y2 = +2 = j
2 p
Ê F - F -2 ˆ 1
and Fx y = - i Á +2 ˜¯ = sin 2j
Ë 2 p
110 A Textbook of Physical Chemistry

Expressions of
Total Angular 1/ 2
(Q2, ± 1Fx) = Ê ˆ
15
Functions sin q q j
Ë 4p ¯
1/ 2
= Ê ˆ
15
(Q2, ±1Fy ) sin q q sin j
Ë 4p ¯
1/ 2
(Q2, F ) = Ê 15 ˆ sin 2 q sin 2j
±2 x y
Ë 16p ¯
15 ˆ 1/ 2
and (Q2, ±2 Fx2 - y2) = Ê sin2 q j
Ë 16p ¯

Nodal Surfaces in q j
Q2, ± 1Fx q = 0 and j yz q
xy

1/ 2 sin 2q
= Ê ˆ
15
(Q2, ±1Fx ) j
Ë 4p ¯ 2
j = 1 and sin 2q = 1,
j q q
j q
x z
xz
Q Fx z
j
xz xz
q j q

yz-nodal plane
q = 0°, j = 90°
z z

y y
–
xy-nodal +
Fig. 1.8.12 (a) Two plane
q = 90° +
nodal surfaces yz –
x
and xy, (b) A two- x
dimensional plot of
function (Q2, ± 1, Fx z ) (a) (b)

Nodal Surfaces in q j
Q2, ±1Fy q j xz q
xy
 Wave Mechanics, Energy Quantization and Atomic Structure 111

1/ 2
Fy ) = Ê ˆ
15 sin 2q sin j
(Q
Ë 4p ¯ 2
j = 1 and sin 2q =
j q
j q
y z
yz- yz
yz q sin j q
z z

xz-nodal
plane
y
xy-nodal –
y
plane
+
+
–
x x
Fig. 1.8.13 (a) The
two nodal surfaces xy
and xz, (b) A two-
dimensional plot of
function (Q2, ±1 Fyz ) (a) (b)

Nodal Surfaces in q = 0, and j

Q2, ± 2Fx y q = 0 and j xz q = 0 and j
yz
q = 1 and sin 2j q and
j
q j x
and y xy
xy xy
dependence (sin q j) (sin q sin j
z yz-nodal z
plane

y
y
+
xz-nodal – –
Fig. 1.8.14 (a) The plane
+
two nodal surfaces
x x
xz and yz, (b) A two-
dimensional plot of
(Q2, ± 2F x y) (a) (b)
Nodal Surfaces in q = 0, and j j=-
Q2, ± 2Fx 2 - y 2 q = 0 and j q = 0 and
j=- x y z
112 A Textbook of Physical Chemistry

Fig. 1.8.15 (a) Two

nodal surfaces at angle
45° to x and y axes,
(b) A two-dimensional
plot of the function
(Q2, ±2 Fx 2 - y 2)

q j
q j
q j x
and y
(3dx2 – y2 x2 – y2 2
q 2
j
– sin2 q sin2 j
1.9 ANGULAR MOMENTUM AND THE MAGNETIC MOMENT

Classical
Expression of
Magnetic Moment

m = iA
i A

u r
i
i

= –Ê
u ˆ
e
Ë 2pr ¯

A
A = pr 2

Ê ue ˆ u re
m = Á- (pr 2) = –
Ë 2pr ˜¯ 2
 Wave Mechanics, Energy Quantization and Atomic Structure 113

me
Ê e ˆ Ê e ˆ
m = - (meur) Á =-L Á
Ë 2me ˜¯ Ë 2me ˜¯
L

m = - gL
g e /2me g
gyromagnetic ratio

Fig. 1.9.1 The

magnetic moment
vector associated with e
the orbital motion of
the electron mm

Quantum
Mechanical
Expression of
Magnetic Moment Ê hˆ
L= l (l +1) Á ˜
Ë 2p ¯
l

Ê eh ˆ
m = –Á
Ë 4pme ˜¯ ( l (l + 1) )

m =-m l (l +1)
m eh/4pme Bohr magneton
eh (1.6 ¥ 10-19C)(6.626 ¥ 10-34 J s)
m = =
4pme 4(3.14)(9.1 ¥ 10-31 kg)
¥ 10 -24 J T-1
z-Component of
Magnetic Moment
114 A Textbook of Physical Chemistry

Lz = mÊ ˆ
h
Ë 2p ¯
m m
… l q
z
Ê l (l + 1) h cos q ˆ = m Ê h ˆ
Ë 2p ¯ Ë 2p ¯
( l (l + 1) ) q=m

m q = mz
The z

z m
l (l +1) mz m

z l

Lz
+ (h/2p) L = 2 (h/2p)
mm mz
Fig. 1.9.2 The
allowed orientations mm L = 2 (h/2p)
of angular momentum
(solid arrows) and
the magnetic moment mm mz
(broken arrows) of an (h/2p) L= 2 (h/2p)
Lz
electron in l = 1 state

Larmor Precession Larmor

precession

q
 Wave Mechanics, Energy Quantization and Atomic Structure 115

Potential Energy The potential energy V B is given by

of an Electron in a V = - B mz
Magnetic Field
Substituting the expression of m z from Eq. (1.9.10), we get
Due to its Orbital
Motion V = - B (m m cos q )
which in view of Eq. (1.9.7) becomes
{
V = - B - m B l (l + 1) } cos q = B m B { l (l + 1) cos q }
Making use of Eq. (1.9.9) we get
V = B mB m (1.9.11)

E¢n = E n + BmB m (1.9.12)

where En is the corresponding quantum mechanical energy in the absence of a

Energy of Electron Since for s orbitals m = 0, it is obvious that the energy of s orbital remains
in s Orbital
that the angular momentum of electron in s orbital is zero and hence its magnetic
moment is also zero, i.e. the motion of electron in s orbital is such that it does not
produce any magnetic dipole and thus no interaction with the external magnetic

Energy of Electron The permitted values of m for p orbitals are +1, 0 and –1. Hence the energy of
in p Orbital
En(+ 1) = En + BmB (1.9.13)
En(0) = En (1.9.14)
En(– 1) = En – BmB (1.9.15)
Hence the degeneracy of the three p orbitals are removed in the presence of a

Degenerate
p orbitals + mB B
Energy

–mBB
Fig.1.9.3 Lifting of
degeneracy of p orbitals in
the presence of a magnetic
No field Magnetic
field

to the quantum number m

116 A Textbook of Physical Chemistry

nondegenerate with potential energies of 2Bm B, Bm B, 0, – Bm B and – 2Bm B,

respectively. Similarly, f orbitals split into seven orbitals all with different energies.
1.10 ZEEMAN AND ANOMALOUS ZEEMAN EFFECTS

Zeeman Effect Zeeman in 1986 observed that many of the spectral lines of an atom split into

Zeeman effect, has been explained on the basis of the removal of degeneracy of
orbitals having nonzero value of magnetic quantum number m in the presence of

since all three 2p orbitals are degenerate in energy. In the presence of a magnetic

the three transitions 1s ¨ 2p+ 1, 1s ¨ 2p0 and 1s ¨ 2p–1 are possible. These are

Magnetic
No field field
m = +1
2p m=0
m = –1

Fig. 1.10.1 Splitting

of a single 1s ¨ 2p
spectral line into three 1s
lines in the presence of
Spectrum Spectrum

Anomalous When the zeeman effect is examined under high resolution microscope, the spectrum
Zeeman Effect is found to be more complicated. In fact, a spectral line which appears to be a single

the three transitions 1s ¨ 2p+1, 1s ¨ 2p0 and 1s ¨ 2p–1

are actually made up of two closely packed lines. The existence of double lines
instead of a single line is also observed in the spectra for the alkali metals even in

Quantum Numbers In order to explain the existence of doublets in the spectra of alkali metals,
Describing Spinning Goudsmit and Uhlenbeck in 1925 proposed that the electron has an intrinsic
of Electron angular momentum due to spinning about its own axis. The value of the spin
angular momentum is quite independent of the orbital angular momentum and can
be described by two spin quantum numbers s and ms
these numbers is very similar to those of orbital quantum numbers l and m. The
quantum number s represents the total magnitude of the spin angular momentum S
and the quantum number ms represents the z-component of the angular momentum
Sz such that
 Wave Mechanics, Energy Quantization and Atomic Structure 117

h
S = s ( s + 1) (1.10.1)
2p
Sz = ms h (1.10.2)
2p
The relation between S and Sz is
Sz = S cos q (1.10.3)
where q is the angle which the angular momentum vector makes with z-axis.
Substituting Eqs (1.10.1) and (1.10.2) in Eq. (1.10.3), we get
ms = s ( s + 1) cos q (1.10.4)
The allowed values of ms are
– s, – (s – 1), , (s – 1), s (1.10.5)
It is found that the spin quantum number s has only one value of 1/2. Thus, the
magnitude of the spin angular momentum vector is
Ê hˆ 1 Ê1 ˆ Ê h ˆ Ê hˆ
S = s ( s + 1) Á ˜ = Á + 1˜ Á ˜ = 0866 ÁË ˜¯
Ë 2p ¯ 2 Ë 2 ¯ Ë 2p ¯ 2p
With s = (1/2), the permitted values of ms are + 1/2 and – 1/2. Thus, the z-components
of the spin angular momentum are given by
1Ê h ˆ
Sz = ± Á ˜
2 Ë 2p ¯
Only two orientations of the spin angular momentum are possible. These are shown

describable by classical mechanics. It is strictly a nonclassical concept.

z-axis

(1/2)(h/2p)

q F 3I F h I
GH 2 JK H 2p K
q
Fig. 1.10.2 Space
quantization of spin (1/2)(h/2p)
angular momentum

Magnetic Moment The spinning of the electron will be associated with the magnetic moment vector
Due to Spin of which will have its direction opposite to that of the angular momentum vector. The
Electron relation connecting the magnetic momentum m and the angular momentum S is
m = – 2gS (1.10.6)
where g is equal e/2me. The factor 2 in Eq. (1.10.6) has been added on the basis of
experimental evidence (e.g. the examination of the splitting of the spectral lines in

is twice as large as that of the orbital motion of the electron.

118 A Textbook of Physical Chemistry

Substituting the value of S from Eq. (1.10.1) in Eq. (1.10.6), we have

m = –2 Ê ˆ s ( s + 1)
gh
Ë 2p ¯
Substituting the expression of g, we have
Ê eh ˆ
m = – 2Á s ( s + 1) = – 2 m B s ( s + 1)
Ë 4pme ˜¯
(1.10.7)

where mB is the Bohr magneton.

Potential Energy
of a Spinning is given by
Electron in a V = – Bmz = – B (m cos q)
Magnetic Field
Substituting m from Eq. (1.10.7), we have

{ }
V = – B - 2 m B s ( s + 1) cos q
which on making use of Eq. (1.10.4) becomes
V = 2B mB ms (1.10.8)
According to Eq. (1.10.8), the potential energy of an electron depends on the
value of ms. Thus, we will have
(i) ms = + 1/2 ; V+1/2 = B mB (1.10.9)
(ii) ms = –1/2 ; V–1/2 = – B mB (1.10.10)
Spectral
Transitions in E≤n = En + BmBm + 2BmBms (1.10.11)
the Anomalous
where En BmBm is the
Zeeman Effect
potential energy due to the orbital motion, and 2BmBms is the potential energy due
to the spinning of the electron. Thus, we have
For s orbital Here m = 0. Therefore
E n≤ = En + 2BmB ms
and since ms
ms = + 1/2; E n,≤ 1/2 = En + BmB
ms = – 1/2; E≤n, –1/2 = En – BmB

For p orbitals Here, we can have the following combinations.

(i) m = + 1 ms = +1/2 ≤ = En + BmB + BmB = En + 2 BmB
E n1
(ii) m = + 1 ms = –1/2 ≤ = En + BmB – BmB = En
E n2
(iii) m = 0 ms = +1/2 ≤ = En + BmB
E n3
(iv) m = 0 ms = –1/2 ≤ = En – BmB
E n4
(v) m = – 1 ms = +1/2 ≤ = En – BmB + BmB = En
E n5
(vi) m = – 1 ms = –1/2 ≤ = En – BmB – BmB = En – 2BmB
E n6
 Wave Mechanics, Energy Quantization and Atomic Structure 119

2p orbitals, which also exhibits the allowed spectral transitions.

as those listed in Section 1.7 with one additional rule of Dms = 0. The allowed
transitions are listed in Table 1.10.1.
m ms
+1/2
+2BmB
+1 BmB +1/2 +1BmB
0 -1/2
2p 0
-BmB +1/2
1 BmB
-1 1/2
1/2 2 BmB

Fig. 1.10.3 Split

energy diagram and
the allowed transitions:
+1/2 +BmB
1s
0
BmB
with orbital and spin 1/2
motions
Spectrum Spectrum Spectrum
(a) (b) (c)

Table 1.10.1 The Allowed Electronic Transitions in the Presence of a

Transition Energy
Upper level Lower level

m = +1, ms = +1/2 ææ
Æ m = 0, ms = +1/2 D E = (E2p – E1s) + BmB

m = 0, ms = +1/2 ææ
Æ m = 0, ms = +1/2 D E = (E2p – E1s)

m = –1, ms = +1/2 ææ
Æ m = 0, ms = +1/2 D E = (E2p – E1s) – BmB

m = +1, ms = –1/2 ææ
Æ m = 0, ms = –1/2 D E = (E2p – E1s) + BmB

m = 0, ms = –1/2 ææ
Æ m = 0, ms = –1/2 D E = (E2p – E1s)

m = –1, ms = –1/2 ææ
Æ m = 0, ms = –1/2 D E = (E2p – E1s) – BmB
120 A Textbook of Physical Chemistry

Spin-Orbit
Coupling
account. The additional splitting of the lines cannot be explained unless we consider
the relativistic treatment of the hydrogen atom, given by Dirac in 1928. One of the
correction terms involves the interaction of orbital angular momentum and orbital
magnetic moment vectors with the correponding spin angular momentum and spin
magnetic moment vectors. This is known as spin-orbit coupling. In the latter, the two
vectors couple with each other and produce a resultant vector. The latter, like spin
and orbital angular momentum vector, is also quantized and can be characterized
by the total angular momentum quantum number, J. The magnitude of the resultant
vector is given by the relation

L = { J ( J + 1) }{ 2ph } (1.10.12)

The permitted values of J are

l + s, l + s – 1, …, l – s (1.10.13)†
The total angular momentum is also space quantized, i.e. the z-component
of the total angular momentum has only discrete values which are given by the
relation
h
Lz = L cos q = mJ
2p { } (1.10.14)

where mJ is known as the magnetic total angular momentum quantum number and

J, J – 1, …, – (J – 1), – J (1.10.15)
In a similar manner, the two magnetic moment vectors can be combined to give
a resultant total magnetic moment vector. This total magnetic moment vector does
not lie along the direction of total orbital momentum, since the magnitudes of the
two magnetic moment vectors do not bear the same relation with the corresponding

mm = – g L (Eq. 1.9.5)
whereas that for the spinning is
m m = – (2gS) (Eq. 1.10.6)
Thus, an electron with total angular momentum quantum number J with an
orientation given by mJ does not have an energy given simply by mJ mBB. In fact,
the energy can be expressed as
V = mJ (gJ mB B) (1.10.16)
where gJ is the Lande g-factor which takes into account the off-axis alignment of
the total angular momentum and the total magnetic moment and is given by
Ï J ( J + 1) - l (l + 1) + s ( s + 1) ¸
gJ = 1 + Ì ˝ (1.10.17)
Ó 2 J ( J + 1) ˛
†
This series is known as Clebsch-Gordan series.
 Wave Mechanics, Energy Quantization and Atomic Structure 121

Equation (1.10.17) is reduced to Eqs (1.9.5) and (1.10.6) in the two extreme
isolated cases. Thus, we have

(i) gJ = 1, when s = 0 and J = l — a value used while dealing with the orbital
motion only (Eq. 1.9.5).
(ii) gJ = 2, when l = 0 and J = s — a value used while dealing only with the
spin of the electron (Eq. 1.10.6).
Spectral
Transitions in the coupling is as follows.
Presence of Spin-
Orbit Coupling For 1s orbital Here l = 0 and s = 1/2. Thus J = 1/2 and the Lande g-factor =

≤ = (1/2) (2m BB) = mB B

V +1/2 (1.10.18)

and ≤ = – (1/2) (2m BB) = – mB B

V–1/2 (1.10.19)

For 2p orbitals Here l = 1 and s Jmax = 3/2, the permitted values of

mJ are 3/2, 1/2, – 1/2 and – 3/2.

The Lande g-factor for Jmax is given by

È 3 Ê 5ˆ 1 Ê 3ˆ ˘
Í 2 Ë 2 ¯ - 1 (2) + 2 Ë 2 ¯ ˙ 1 4
gJ = 1+ Í ˙ = 1+ =
2Ê ˆ Ê ˆ
Í 3 5 ˙ 3 3
ÍÎ Ë 2¯ Ë 2¯ ˙˚
The three degenerate 2p orbitals split into four of the following energies.
V3/2 = (3/2) (4/3) mB B (1.10.20)

V1/2 = (1/2) (4/3) mB B (1.10.21)

V–1/2 = (–1/2) (4/3) mB B (1.10.22)

and V–3/2 = (–3/2) (4/3) mB B (1.10.23)

The selection rules for the spectral transition in the framework of spin-orbit coupling
are
D mJ = 0, ± 1 (1.10.24)

possible. These are described in Table 1.10.2.

Paschen-Back
Effect are uncoupled and precess separately around their own axes. In such cases, the
anomalous Zeeman effect is reverted to the normal Zeeman effect with the spin
playing no role. This reversion is called the Paschen-Back effect.
122 A Textbook of Physical Chemistry

Table 1.10.2

Transition Energy
(1) V¢–1/2 ææ
Æ V +1/2
≤ DV1 = – (5/3) mB B

(2) V¢–3/2 ææ
Æ V≤–1/2 DV2 = – mB B

(3) V¢1/2 ææ
Æ V≤1/2 DV3 = – (1/3) mB B

(4) V¢–1/2 ææ
Æ V≤–1/2 DV4 = + (1/3) mB B

(5) V¢3/2 ææ
Æ V≤1/2 DV5 = + mB B

(6) V¢+1/2 ææ
Æ V≤–1/2 DV6 = + (5/3) mB B

mJ E
3 ( 4 m B)
3/2 B
2 3
1 4
1/2 ( m B B)
2 3
2p 1 4
1/2 ( m B)
l = 1, s = 1/2 2 3 B
J = 3/2
3 4
3/2 ( m B B)
2 3
Energy

1
+ 1/2 (2 mB B)
2
1s
l = 0, s = 1/2 1
1/2 (2 mB B)
J = 1/2 2
Fig. 1.10.4
The anomalous Spectrum Spectrum
Zeeman effect Field off Field on

Double Lines in The existence of double lines instead of one in the spectra of alkali metals can be
the Spectra of explained on the basis of spin-orbit coupling. Take, for example, the characteristic
Alkali Metals yellow line at 589 nm emission from sodium vapour when the latter is excited by
an electric discharge. This line is actually composed of two closely spaced lines,
one at 589.76 nm and the other at 589.16 nm. In the ground state of sodium, the
outer electron is in the s orbital and thus J≤ = 1/2. When this electron occupies
the next higher p orbital, the permitted values of J ¢ are 3/2 and 1/2. The energy
 Wave Mechanics, Energy Quantization and Atomic Structure 123

of the electron in J ¢ = 3/2 state is different from that in the J ¢ = 1/2 state. Thus,
two transitions J ¢ = 3/2 Æ J ≤ = 1/2 and J¢ = 1/2 Æ J ≤ = 1/2 are possible which
are observed as the two closely spaced lines.

The Stern-Gerlach The experimental demonstration for the existence of the electron spin is due to Stern
Experiment and Gerlach. They passed a beam of silver atoms through a strong inhomogeneous

magnet

N
1
ms = –
2

Ag
Beam atoms 1
source ms = +
Fig. 1.10.5 Stern- S 2
Gerlach experiment

The silver atom has a single s-electron outside a closed shell. The fact that for a
closed shell, the total orbital and spin magnetic moments are zero indicates that
the outer s-electron must have only two values of magnetic moments. The latter
can arise only when the electron is spinning around its own axis. Moreover, the
magnitude of the splitting is found to follow Eq. (1.10.6), i.e.
mm = – 2gS
where g is equal to e/2me in SI units.
1.11 MANY-ELECTRON ATOMS

Expression of The Hamiltonian operator for electrons in many-electron atoms can be written as
Hamiltonian
Ze2 n -1 e2
Operator h2 n n n
H =– Â — i2 – Â (4pe )r + Â Â (4pe )r (1.11.1)
8p 2 m i =1 i =1 0 i i = 1 j = i +1 0 ij

n electrons, the second

term represents the nuclear-electronic attractions and the last term represents the
electronic-electronic repulsions.
Expression of The Schrödinger equation as usual can be written as
Schrödinger
H y = Ey (1.11.2)
Equation
where the function y is a function of 3n independent variables.

Unfortunately, it has not been possible to solve Eq. (1.11.2) accurately and
124 A Textbook of Physical Chemistry

Eq. (1.11.2) comes from the electronic-electronic repulsion terms. In the absence
of these terms, Schrödinger equation can be solved by writing the wave function
y as the product of one electron wave functions (represented hereafter as y o). The
latter can be chosen from the hydrogen-like wave functions. When this product
function is substituted in Eq. (1.11.2), the latter splits into a number of equations,
each involving the coordinates of the individual electron. The form of the resultant
equations is identical to that of the hydrogen-like species. The total energy is equal
to the sum of the individual energies of various electrons.

The above results are very approximate and do not represent the quantitative
behaviour of electrons in the atom. However, the results can be improved by
following either the perturbation method or the variation method.
The Perturbation In the perturbation method†, the electronic repulsion terms are considered as small
Method perturbations on the Hamiltonian operator which neglects the electronic-electronic
repulsion terms, i.e.

h2 n n Ze 2
H° = – Â —i2 - Â (1.11.3)
8p 2 m i =1 i =1 (4pe 0 )ri

n n -1 e2
H = H° + Â Â (1.11.4)
i = 1 j = i +1 (4pe 0 )rij
Assuming that these small perturbations do not change the wave function y º
very much (wave function of the given state excluding the repulsion terms), we
can calculate an approximate average value of energy by employing the expectation
expression

E =
Ú y °* H y ∞ dt (1.11.5)
Ú y °* y ∞ dt
(Note that the function y ° is not an eigenfunction of the operator H and, therefore,
the operation of H on y° will not yield the exact energy eigenvalue.)
Equation (1.11.5) can be written as

Ê n-1 n e2 ˆ
Ú y ∞ * H ∞ y ∞ d t + Ú ÁË i =1 j = i+1 (4pe 0 )rij ˜¯ y ∞ dt
y ∞ * Â Â
E =
Ú y ∞*y ∞dt
Ê n-1 n e2 ˆ
Ú y ∞* Á Â
Ëi =1
 ˜ y ∞ dt
j = i +1 ( 4p e 0 ) rij ¯
or E = E° + (1.11.6)
Ú y ∞* y ∞ dt

†
See Annexure X for detail.
 Wave Mechanics, Energy Quantization and Atomic Structure 125

The second term of Eq. (1.11.6) is evaluated and adding this to E° gives the

helium atom which contains two electrons (n = 2) and has two positive charges
at the nucleus (Z = 2), the value of second term is found to be 5e2/{(4p e0)(4a0)}.
Now since EH = – e2/{(4p e 0)(2a0)} the value of the second term is equal to
– (5/2) EH, i.e. – (5/2) (– 13.6 eV) = 34.0 eV. Thus
E = E° + 34.0 eV
The numerical value of E° is
Z 2 EH Z 2 EH 4 EH 4 EH
E° = E°1 + E°2 = + = +
n12 n22 n12 n22
n1 and n2 are equal to one, thus
E° = 8 EH = 8 (– 13.6 eV) = – 108.8 eV
and hence
E = – 108.8 eV + 34.0 eV = – 74.8 eV
The experimental value is – 79.0 eV
The Variation In the variation method, the wave function is written containing a few adjustable
Method Z may
be taken as the adjustable parameter. This will take into account what is known as

of the positive nuclear charge for the second, vis-á-vis, the second electron does
not see two positive charges at the nucleus but sees a charge which is a little bit

functions so far widely used is due to Slater and thus are known as the Slater-
orbitals. The latter have angular distributions identical to those of hydrogen-like
orbitals but the radial distribution functions are given by the following expression.
n +1 / 2 1/ 2
Ê2 ˆ È 1 ˘
Rslater = Á Í (2n)!˙ rn –1 e–z r /a0 (1.11.7)
Ë a0 ˜¯ Î ˚
where the parameter z is called the orbital exponent.
The variation method is based on the variation theorem† which may be stated as
follows.
If one employs a well behaved approximate wave function in evaluating the
expectation value by using the expression

E =
Ú y * H y dt (1.11.8)
Ú y *y dt
then the value of E so obtained will always be algebraically equal to or greater
than the true energy E0 of the system, i.e. E ≥ E0.

†
See Annexure XII for the proof of variational theorem.
126 A Textbook of Physical Chemistry

In Eq. (1.11.8), the Hamiltonian operator H is the complete and correct operator
of the system under study.
Now the energy E can be written in terms of adjustable parameters. The best
choice of the values of adjustable parameters can be obtained by minimizing the
value of E, i.e. which brings E as close as possible to the true energy of the system.
E with respect to the adjustable
parameter and equating the resultant expression to zero. Take, for example, the
helium atom, the trial function could be chosen from the hydrogen-like orbitals
by replacing Z by Z¢, i.e.
3
1 Ê Z¢ˆ
y = y 1s(1) y 1s(2) = Ê ˆ Á ˜ exp (– Z ¢r1/a0) exp (– Z ¢r2/a0)
Ë p ¯ Ë a0 ¯

h2 Z e2 Z e2 e2
Now H =– ( —1
2
+ — 2
2 ) - - +
8p 2 m (4p e 0 ) r1 (4p e 0 ) r2 (4p e 0 ) r12

Ú y * H y dt = ÍÎÈ- 2Z ¢ 2 27 ˘
and E= + Z ¢ ˙ EH
4 ˚

Ê ∂E ˆ Ê 27 ˆ
Now ÁË ∂ Z ¢ ˜¯ = ÁË - 4 Z ¢ + 4 ˜¯ EH = 0

and hence
27
Z¢ =
16
Thus, the approximate energy E becomes

È Ê 27 ˆ Ê 27 ˆ ˘
2
Ê 27 ˆ
E = Í- 2 Á ˜ + Á ˜ Á ˜ ˙ EH
ÍÎ Ë 16 ¯ Ë 4 ¯ Ë 16 ¯ ˙
˚
= 5.70 EH = 5.70 (– 13.6 eV) = – 77.5 eV
This is to be compared with the experimental value of – 79.0 eV.†

Self-Consistent The above procedure of solving the Schrödinger equation cannot be extended if
Field Method the atom contains larger number of electrons. Another method, which is a more
practical one, was suggested by Hartree in 1928 and is known as the self-consistent

1. The total wave function of the system can be written as the product of one-
electron wave functions, i.e.
y = j 1(1)j2(2)j3(3) jn(n)
where j 1(1) is the wave function of the electron 1, and so on. These one-electron
wave functions can be any trial functions.
†
See Annexure XII for details.
 Wave Mechanics, Energy Quantization and Atomic Structure 127

2. Each electron is supposed to be moving in an average spherically symmetric

potential energy function Vi arises because of the nuclear attraction and the repulsion
from all other electrons. In order to evaluate the function Vi for the ith electron,
which is usually done by numerical integration, we require the knowledge of the
wave functions of all electrons except the one under study.
3. Once the function Vi is available, we can write the one-electron Schrödinger
equation as

h2
– — 2i j i + Viji = Ei j i (1.11.9)
8p 2 m
Solving this equation, we get the improved wave function j i and the corresponding
energy Ei .

V1 is evaluated by employing the trial

functions j 2(2), j3(3), , jn(n). This is substituted in Eq. (1.11.9) and is solved
j¢1(1) and the corresponding energy E¢1. We
now shift to the electron-2 and evaluate the function V2
improved wave function j ¢1(1) and the starting trial-functions j 3(3), j 4(4), ,
j n(n
function j¢2(2) and the corresponding energy E¢2. This process is repeated one by

V1
wave functions of all other electrons, viz., j ¢2(2), j ¢3(3), . On substituting V1 in
Eq. (1.11.9) and subsequently solving, we get the second-improved wave function
j ≤1 (1) and the corresponding energy E≤1. Similarly, the second-improved wave
functions for all the n-electrons are obtained one by one. We then again repeat
the process third time, this time using the second-improved j functions and thus
obtain the third-improved wave functions and third-improved energies. This iterative
process is repeated until the nth-improved wave functions agree within the limit
with the (n – 1)th-improved wave functions, i.e. they become self-consistent. The
energy of the atom is then given by
n
E = Â Ei (1.11.10)
i =1

The Schrödinger equation as given by Eq. (1.11.9) for the multi-electron atom
is identical to that of a single electron in the hydrogen-like species, with the only
difference of the form of the spherically symmetric potential-energy term Vi. Thus,
the mechanism of solution of Eq. (1.11.9) is very similar to that employed for
the hydrogen-like species. Since Vi appears only in the radial equations, the
solution for the angular dependence Q (q) and F (j ) are exactly the same as those
of hydrogen-like species. This means that the angular shapes and probability
distributions in the multi-electron atoms are exactly identical to those for the single
128 A Textbook of Physical Chemistry

electron in the hydrogen-like species. Thus the various orbitals may be designated
as usual by the symbol s, p, d and f and so on.

in the atom. Moreover, these distributions are obtained numerically in the form of
tables or plots rather than as the explicit equations as is in the case of hydrogen-
like species. This radial distribution again depends on the two quantum numbers,
viz., n and l. The energy associated with any radial distribution also depends on
these two quantum numbers unlike the case of hydrogen-like species where the
energy depends only on the principal quantum number n. The total wave function
of the electron can be obtained as usual by multiplying its radial distribution with
those of angular distribution. As stated earlier, the latter are identical to those for
the hydrogen-like species.

Description of Each electron will be described by the total wave function and hence by an orbital.
Quantum Numbers The latter, as usual, is designated by the three quantum numbers n, l and m. The
principal quantum number n represents the different shells of the atom and are
represented by the scheme shown in the following.
Value of n 1 2 3 4 º
Symbol used for
the shell K L M N º
The quantum number l represents the total angular momentum of the electron
and also the shape of the orbital. As is in the case of hydrogen-like species, the
various orbitals are represented by the symbols s, p, d, f depending upon the value
of l. The quantum number m represents the z-component of the angular momentum
and also the orientation of the orbital.
As usual, the principal quantum number n is the most important in deciding the
energy of the orbital. The actual energy of any particular orbital also depends on
the value of l
In third quantum shell, the increasing order of energy is 3s < 3p < 3d. In general,
the energy increases as the value of l increases within the same shell. This can
be explained on the basis of radial distribution. The electron with a larger value
of l virtually spends its time relatively far from the nucleus as compared to that
for the smaller value of l. Thus, the former experiences lesser attraction by the
nucleus and hence its energy is larger. However, it may be noted down that the
energy of an orbital does not depend upon the value of m. Thus, different orbitals
with the same value of l but different values of m are degenerate in nature, i.e.
their energies are identical.

Problem 1.11.1 Show that the electron distribution in the ground state of the neon atom has spherical
symmetry.
Solution The term spherical symmetry means the overall distribution of electrons is independent of
the angles q and j. In the present case, the overall probability distribution will be given
as (p2x + p2y + p2z ).
 Wave Mechanics, Energy Quantization and Atomic Structure 129

The angular expressions of px, py and pz are

Ê 3 ˆ Ê 1 ˆ
px = Á sin q ˜ Á cos j ˜
Ë 2 ¯ Ë p ¯

Ê 3 ˆÊ 1 ˆ
py = Á sin q ˜ Á sin j ˜
Ë 2 ¯Ë p ¯

Ê 6 ˆÊ 1 ˆ
pz = Á cos q ˜ Á ˜
Ë 2 ¯ Ë 2p ¯

3 3 3
Thus, p2x + p2y + p2z = sin2 q cos2j + sin2q sin2j + cos2q
4p 4p 4p
3 3
= sin2q (cos2j + sin2j) + cos2q
4p 4p

3 3
= (sin2q + cos2q ) =
4p 4p
Since p2x + p2y + p2z is independent of angles q and j, the ground state of the neon atom is
spherically symmetrical.
[In general, the sum of the probability distribution functions for a given value of the
azimuthal quantum number l and all the values of the magnetic quantum number m is
independent of angles q and j and is equal to (2l + 1)/4p
spherically symmetrical.]

1.12 THE INDISTINGUISHABILITY OF ELECTRONS AND THE PAULI EXCLUSION PRINCIPLE

Spatial Wave Let the total wave function of a system containing two electrons be written as the
Functions for product of one-electron spatial wave functions j 1 and j2. We can write this as
a Two-Electron
System y12 = j1(1)j 2(2) (1.12.1)
where j 1 and j 2 are occupied by the electrons 1 and 2, respectively. However, we
can equally write another product function where j 1 is occupied by the electron
2 and j 2 by the electron 1, i.e.
y21 = j 1(2)j2(1) (1.12.2)

This follows from the fact that the two electrons are indistinguishable in the
system and thus we cannot precisely label the individual electrons. The functions
y 12 and y 21 taken separately do not meet the requirement of indistinguishability of
the electron. However, if we take the linear combination of these two functions, we
can construct a wave function which besides being the solution of the appropriate

the resultant linear combination should represent the same probability distribution
as those represented by functions y12 or y21. This means that the square of the
resultant wave function should be equal to the square of either of the functions
130 A Textbook of Physical Chemistry

y 12 and y 21. The two such combinations are

1 1
ys = (y12 + y21) = [j 1(1)j 2(2) + j 1(2)j2(1)] (1.12.3)
2 2

1 1
and ya = (y12 – y21) = [j 1(1)j2(2) – j1(2)j2(1)] (1.12.4)
2 2
The subscripts ‘s’ and ‘a’ stand for symmetric and antisymmetric, respectively.
The function y s remains symmetric on interchanging the two electrons whereas
the function ya becomes –ya on interchanging the two electrons.
Spin Wave The electron in an atom is associated with the spin and thus the electron must
Functions for also be indistinguishable with respect to the orientation of intrinsic spin. We
a Two-Electron represent the spin of the electron by the spin functions. It is customary to write
System the spin with ms = +1/2 by the spin function which is written as a and that with
ms = – 1/2 with another function written as b. Experimentally, it is possible to
determine the total spin angular momentum of a system and not the spin of the
individual electrons. Thus, we cannot state that any particular electron has spin
a (or b ). Say, for example, in the above system the two electrons have opposite
spins, one is having a-spin (not known whether the electron 1 or electron 2) and
the other is having b-spin. Thus, we cannot say that the electron 1 has a a-spin
and the electron 2 has a b-spin. It is equally probable that the electron 2 has a
a-spin and the electron 1 has a b-spin. A complete description of the electron can
be described with the help of spin orbital which is simply the product of spatial
and spin functions. Thus, an electron in j 1 can be written as j 1a or j1 b depending
upon the spin of the electron.

Total Wave Function If the interaction between spin and orbital motion is neglected, the total wave
for a Two-Electron function of the system can be represented by the product of total spatial function
System
with the indistinguishability condition are
a (1)a (2) (1.12.5)

b(1)b (2) (1.12.6)

1
[a (1)b(2) + a (2)b(1)] (1.12.7)
2

1
[a (1)b(2) – a(2)b(1)] (1.12.8)
2

while the fourth one reverses the sign.

 Wave Mechanics, Energy Quantization and Atomic Structure 131

Now, when these four spin functions are combined with the two spatial functions
ys and ya , we get eight different combinations as shown below.
1
[j 1(1)j 2(2) + j 1(2)j2(1)] [a (1)a (2)] (symmetric)
2

1
[j 1(1)j2(2) + j 1(2)j 2(1)] [b(1)b(2)] (symmetric)
2

1 1
[j 1(1)j2(2) + j1(2)j2(1)] [a (1)b(2) + a (2)b (1)] (symmetric)
2 2

1 1
[j 1(1)j2(2) + j1(2)j2(1)] [a (1)b(2) – a (2)b (1)](antisymmetric)
2 2

1
[j 1(1)j2(2) – j1(2)j2(1)] [a (1)a (2)] (antisymmetric)
2

1
[j 1(1)j2(2) – j1(2)j2(1)] [b(1)b (2)] (antisymmetric)
2

1 1
[j 1(1)j2(2) – j1(2)j2(1)] [a (1)b (2) + a (2)b(1)] (antisymmetric)
2 2
1 1
[j 1(1)j2(2) – j1(2)j2(1)] [a (1)b(2) – a (2)b (1)] (symmetric)
2 2

Acceptable Wave The behaviour of the electron in an atom as suggested by the experimental evidences
Functions requires that the total wavefunction for a system of electrons must be antisymmetric
to the simultaneous exchange of coordinates and spins between any pair of electrons.
Thus, out of the above eight functions, only four antisymmetric functions represent

1 1
[j1(1)j2(2) + j1(2)j2(1)] [a (1)b(2) – a (2)b (1)] (1.12.9)
2 2
1
[j1(1)j2(2) – j1(2)j2(1)] [a (1)a (2)] (1.12.10)
2
1
[j1(1)j2(2) – j1(2)j2(1)] [b(1)b (2)] (1.12.11)
2
1 1
[j1(1)j2(2) – j1(2)j2(1)] [a (1)b (2) + a (2)b (1)] (1.12.12)
2 2
Pauli Exclusion
Principle and thus is known as the Pauli exclusion principle. It may be mentioned here that
the above antisymmetric principle is followed by all those particles which have a
132 A Textbook of Physical Chemistry

half-integral spin (i.e. s = 1/2) such as electrons, protons and neutrons. The various
nuclei, atoms, ions and molecules with an odd number of electrons, protons and
neutrons also have a half-integral spin and thus follow the above antisymmetric
principle. Such particles are known as fermions

follow the symmetric principle (i.e. their functions are symmetric on interchanging
the particles) and are known as bosons (after Satyendra Nath Bose). Such particles
follow Bose-Einstein statistics. Examples include photons and atoms, ions, nuclei,
and molecules with an even number of electrons, protons and neutrons.
A More Familiar Take, for example, the case in which both the spatial orbitals are identical, say
Form of Pauli 1s orbital. The two electrons thus have the same quantum numbers n, l and m.
Exclusion Principle Substituting 1s in place of both j 1 and j2 in Eqs (1.12.9) to (1.12.12), we get
1 1
[1s(1)1s(2) + 1s(2)1s(1)] [a (1)b(2) – a (2)b(1)] (1.12.13)
2 2
1
[1s(1)1s(2) – 1s(2)1s(1)] [a (1)a (2)] (1.12.14)
2
1
[1s(1)1s(2) – 1s(2)1s(1)] [b (1)b(2)] (1.12.15)
2
1 1
[1s(1)1s(2) – 1s(2)1s(1)] [a (1)b(2) + a (2)b (1)] (1.12.16)
2 2
Equations (1.12.14) to (1.12.16) are equal to zero, and hence we are left with
only one function in which the spin of the two electrons are different, i.e. the value
of the fourth quantum number is different for the two electrons. This leads to a
more familiar form of Pauli exclusion principle stated as follows.
No two electrons in a given atom may have all the four quantum numbers the
same.
When the two spatial orbitals are different, the value of at least one of the
quantum number n, l and m is different and thus the two electrons may have either
the same or different spins.
Number of Pauli exclusion principle involves the restriction on the number of electrons that can
Electrons in an be accommodated in one orbital. Taking an example of feeding the electrons in 1s
Orbital
n = 1, l = 0, m = 0 and ms
n = 1,
l = 0 and m = 0. Now according to the Pauli exclusion principle, the fourth one
(i.e. the spin quantum number) has to have a different value. Thus, ms = –1/2 (or

we will have spin quantum number either equal to +1/2 or –1/2 and thus all the four

or the second electron. This is in violation with the Pauli principle and thus we
cannot have more than two electrons in the same orbital.
The presence of two electrons in the same orbital with the opposite spins
 Wave Mechanics, Energy Quantization and Atomic Structure 133

electrons are present in the same region of the space and thus it is expected that
there occurs maximum electron-electron repulsion interaction. But because of the
opposite spins, the two tiny magnets generated because of the spinning of electrons
have unlike poles near to each other, i.e the north pole of the one of the magnets
is near to the south pole of the other and vice versa. This gives rise to the most
stable interaction with each other.
Determinant Wave The antisymmetric two-electron wave function as given by Eq. (1.12.13) can be
Function opened to give
1 1
y = [1s(1)1s(2) + 1s(2)1s(1)] [a (1)b(2) – a (2)b (1)]
2 2
1
= [1s(1)1s(2)a (1)b(2) – 1s(1)1s(2)a (2)b (1)
2 + 1s(2)1s(1)a (1)b(2) – 1s(2)1s(1)a(2)b (1)]
= 1s(1)a (1)1s(2)b (2) – 1s(1)b(1)1s(2)a (2)
The above expression can be written in a determinant form as
1s(1) a (1) 1s (1) b (1) 1s(1) 1s (1)
y = or simply as y = (1.12.17)
1s(2) a (2) 1s (2) b (2) 1s(2) 1s (2)
where the spatial function without overhead bar represents a-spin and that with
a overhead bar represents b-spin. The Pauli exclusion principle is automatically
explained by the properties of a determinant. If two electrons are placed into the
same spin orbital, then two columns of the determinant become identical, hence
the wave function becomes zero. The antisymmetric nature of the wave function
y on interchanging the coordinates and spins between any pair of electrons is also

electrons in the determinant form of wave function is equivalent to interchanging of

two rows of the determinant, which changes sign as a consequnce. There is another
property which may be highlighted here. If a row (or column) of a determinant
is replaced by the linear compination of this row (or column) with other rows
(or columns), the value of determinant ramains unchanged. A similar replacement
involving spin orbitals in the determinant form of the wave function does not cause
any change in the overall wave function.
The determinant form of writing a wave function can be easily extended to
a system containing more than two electrons. In the determinant form, columns
represent different spin orbitals (each of which is product of spatial wave function
and spin wave function) and the electrons to the wave functions are assigned

1s(1) a (1) 1s(1) b (1) 2s(1) a (1)

1
y = 1s(2) a (2) 1s(2) b (2) 2s(2) a (2)
3!
1s(3) a (3) 1s(3) b (3) 2s(3) a (3)
where the factor 1 / 3 ! represents the normalization constant of the wave
function y.
Note :

Slater determinant is possible and the total wave function is represented as linear combination
of these determinants.
134 A Textbook of Physical Chemistry

1.13 ATOMIC TERM SYMBOLS

L
L
L …

…
…
l …

S S
1 3 1 3
J S S
3 3
1

Basis of †
Determining the
Values of L, S
and J

L = Â i Li S = Â i Si

J
J=L +S
Quantum Numbers L S L
L, S and J S
ML MS
the z
z
z
z

Lz = Â i Lz i = (Â i mi ) h p ML h p

Sz = Â i S z i = (Â i ms i ) h p MS h p

†
j i = li +
si
J= Â i ji jj
 Wave Mechanics, Energy Quantization and Atomic Structure

The z
Jz = Lz + Sz ML + MS h p MJ h p
A Few Facts ∑ L ML L
about Angular
Momentum L L- … - L- -L
Quantum Numbers ∑ S MS S

S S- … - S- -S
∑ J MJ J

J J- … - J- -J
∑ J L S
J L+S
∑ J L S
J L–S
∑ J
J J - … J
L+S L+S- … |L - S|
∑
L S
∑

Term Symbol for

(ns )2 Configuration n l n n n n
a n
b

Orbital n n
≠ Ø
Value of ml
Value of ms +

ML = m1 + m
MS = m s + m s
ML L
MS S
S ¥
J=L+S
L
1
n S
 A Textbook of Physical Chemistry

Term Symbol n
for (ns)1 (n¢s)1 n n
Configuration n¢ n¢ ML
MS
Table 1.13.1 Four Configurations of (ns)1 (n¢s)1 System

n n n¢ n¢
No ml ML = Â i mi MS = Â i ms i
ms

1 1
≠ ≠ + + = +1
2 2
1 1
≠ Ø + - =0
2 2
1 1
Ø ≠ - + =0
2 2
1 1
Ø Ø - - = -1
2 2

Assignment of
Term Symbols
∑ ML
L
MS S
S ¥
MS MS MS = -
L
3
S1

∑
ML L
MS S
S ¥
J=L+S
L
1
S
3 1
n n¢ S1 S
Term Symbols for ML MS
(1s)2 (2s)2 (2p)2
Configuration
 Wave Mechanics, Energy Quantization and Atomic Structure 137

N
G
G! 6!
=
N !(G - N )! 2 ! 4!
ML MS

Table 1.13.2
Values of

+1 2p +1 2p 0 2p -1
ml +1 +1 ML = Â i mi MS = Â i ms i
ms
1 1
≠ Ø + - =0
2 2
1 1
≠ ≠ + + = +1
2 2
1 1
≠ Ø + - =0
2 2
1 1
≠ ≠ + + = +1
2 2
1 1
≠ Ø + - =0
2 2
1 1
Ø ≠ - + =0
2 2
1 1
Ø Ø - - = -1
2 2
1 1
Ø ≠ - + =0
2 2
1 1
Ø Ø - - = -1
2 2
1 1
≠ Ø + - =0
2 2
1 1
≠ ≠ + + = +1
2 2
1 1
≠ Ø + - =0
2 2
1 1
Ø ≠ - + =0
2 2
1 1
Ø Ø - - = -1
2 2
1 1
≠ Ø + - =0
2 2
138 A Textbook of Physical Chemistry

∑ ML L
MS S
L ML - -
L S

ML MS
ML MS
ML MS
ML = - MS
ML = - MS

S ¥
J=L+S
L
1

∑ ML
L ML -1.
ML MS
S MS -
ML MS
L S
MJ M L + MS
ML MS MJ
ML MS MJ = +1
ML MS = - MJ
ML MS MJ = +1
ML MS MJ
ML MS = - MJ = -1
ML = - MS MJ
ML = - MS MJ = -1
ML = - MS = - MJ = -

S ¥1+1=3
L
3
3
J in
MJ J
MJ - -
3
 Wave Mechanics, Energy Quantization and Atomic Structure 139

MJ -
MJ J
J MJ -
3
1
MJ J
3

Comment on the Values of J

J L+S L+S- … L-S J
L S

ML L
MS S
S ¥
J L+S
L
1
S
1 3
3 3 1
1 S
1.14 HUND’S RULE

∑ L S
S
∑ S L

∑ L S
J

J
3 1
Examples n n¢ S1 S
3
S1
1 3 3 3
S 1
1 3

Comment
S
S S
 A Textbook of Physical Chemistry

1.15 THE AUFBAU PRINCIPLE AND THE ELECTRONIC CONFIGURATIONS OF ATOMS

10
3p
2p 4s 4p
3s
2s

6s
5d
10 1s
5p
5s
4f
– eV

4d
-E

Increasing 3d
energy

100

Fig. 1.15.1 Energy

levels of atomic
orbitals in the multi- 1.0 10 100
electron atoms Z
 Wave Mechanics, Energy Quantization and Atomic Structure 141

1s

2s
2p

3s 3p 3d

4s 4p
4d
4f

5s 5p 5d
Fig. 1.15.2 Scheme to
arrange the orbitals in 6s
the increasing order of
energy

Table 1.15.1

1
x
1 1
x y
1 1 1 3
x y z
1 1 4
x y z
1
x y z
x y z
 A Textbook of Physical Chemistry

Electronic
Configurations
of Cr and Cu 1 1 4 9

DE = N ¥ K

N
K
n
N
n!
N=
2(n - 2)!

4
n DE K
1
n DE K
1
4

1
4 1
 Wave Mechanics, Energy Quantization and Atomic Structure 143

REVISIONARY PROBLEMS
Black-Body
Radiation

8p(hc / l )
El =
l 4{exp(hc / l kT ) - 1}

l T l El

E = s T4 E l l=•
•

E= Ú El d l = s T 4
Photoelectric
Effect
Bohr's Theory

de Broglie
Relation and
Uncertainty
Principle
144 A Textbook of Physical Chemistry

Schrödinger
Equation from Ê ∂ Yˆ 1 Ê ∂2 Y ˆ
Standing Waves
u 2 ÁË ∂t 2 ˜¯ x
ÁË ∂x ˜¯ =
t

Ê∂ yˆ 4p 2
ÁË ∂x ˜¯ y
l2
p= 2m( E - V )

8p 2 m
— y+ E-V y
h2

Postulates
of Quantum
Mechanics

Quantization of
Translational
Energy
Ê h2 ˆ
E=n Á
Ë 8ml 2 ˜¯
n

Quantization of
Vibrational Energy
n p k m
V k x
E= k A
 Wave Mechanics, Energy Quantization and Atomic Structure

y y

·xÒ

Quantization of
Rotational Energy E= Iw
I = mr
L = Iw

1 d 2F
=-m
F dj 2
1 d Ê dQ ˆ
q Á sinq ˜ +J J q=m
Q dq Ë dq ¯
Q

d2P dP È m2 ˘
-x x + Í J ( J + 1) - ˙P
dx 2 dx Î 1- x2 ˚
P x q
F
F j p F j
m

P | m| J m

|m| d | m|
P ∫ PJ -x |m
PJ
dx | m |
PJ
1 dJ
PJ = x - J
2 ( J )! dx J
J

m J
 A Textbook of Physical Chemistry

Q
1/ 2
È (2 J + 1)( J - | m |)!˘ | m|
QJ, | m| = Í ˙ PJ
Î 2( J + | m |)! ˚

Q
J m
J
m

J m

J ( J + 1) q = mz

Quantization of
Electronic Energy

h2 È ∂2 ∂2 ∂ ˘
Í 2 + 2 + 2 ˙ yM = E yM
8p (me + mn ) Î ∂xc ∂yc ∂xc ˚
2

È h 2 Ê ∂2 ∂2 ∂2 ˆ Ze 2 ˘
Í- 2 Á 2 + 2 + 2 ˜ - ˙ = Eye
Î 8p m e Ë ∂ x ∂y ∂z ¯ (4pe 0 )r ˚

1 d Ê 2 d R ˆ 8p 2 m r 2 Ê Ze 2 ˆ
Á r ˜ + Á E+ =l l
R dr Ë dr ¯ h 2
Ë (4pe 0 ) r ˜¯

sin q d Ê dQ ˆ
sin q q=m
Q dq ÁË dr ˜¯
+ll

1 d 2F
=-m
F dj 2

The Q F
q j Q
l m F m
 Wave Mechanics, Energy Quantization and Atomic Structure 147

l m
l m

l (l + 1) q=m

q z

d2L dL
r j+1-r k-j L
dr 2 dr
j l+1
k =l+l

4p 2 m Z e 2
l =
(4pe 0 )h 2a

a 8p 2 m E
h2
r ar
R r
L r
-r
Rr s r F r rl e-r L r

j
Lk k-j j
j
J d
L ∫ Lk = Lk
dr j
Lk k
k
d
Lk = e r rk e-r
dr k
R
1/ 2
ÏÔÊ 2 Z ˆ 3 n(n - l - 1)! ¸Ô
R ÌÁ r–l e-r L2nl++l1
˜ 3˝
ÓÔË na0 ¯ 2n[(n + l )!] ˛Ô

Ê 4p 2 m Z e 2 ˆ Ê 2Z ˆ
r ar ÁË (4pe )nh 2 ˜¯ r = ÁË na ˜¯ r
0 0

k
l n
148 A Textbook of Physical Chemistry

k
n
l£ n-

1 È 2p 2 m Z 2e 4 ˘
E Í ˙
n 2 Î (4pe 0 ) 2 h 2 ˚
R
R n l
n
l
n l
m
Probability
Distribution
Diagrams
R R

Q Q Q F Q F
q in the yz
Q F
z
F+1 F
Q Fx Q Fy

x y

Zeeman Effect
electron
m gL
m L
g e me

m m l (l + 1)
m eh/4p me

V = + Bm m
B
 Wave Mechanics, Energy Quantization and Atomic Structure 149

Many-Electron
Atom

Pauli’s Principle

Term Symbols
n n n¢
Electronic
Configuration
150 A Textbook of Physical Chemistry

TRY YOURSELF PROBLEMS

1.1 (a) Show that the function y = 8 exp(5x) is an eigenfunction of the operator d2/dx2.
What is the eigenvalue?
(b) Find the quantum-mechanical operator for p3x.
(c) Under what conditions is the function exp(- aq 2) an eigenfunction of the operator

d 2 - kq2
dq 2
where k is constant?
(Hint: Eigenvalue should not contain terms involving q, so equate the terms involving
q to zero.)
1.2 Laplacian operator

∂2 ∂2 ∂2
—2 = + 2+ 2
∂x 2
∂y ∂z

in spherical polar coordinates is given by

1 ∂ Ê 2 ∂ˆ 1 ∂ Ê ∂ˆ 1 ∂2
—2 = ÁË r ˜¯ + 2 ÁË sinq ˜¯ + 2 2
r ∂r
2
∂r r sinq ∂q ∂q r sin q ∂j 2

Show that the functions

(i) 1/r, (ii) cosq/r2, (iii) sinq sinj/r2, and (iv) sin2q sin 2j/r3 are the eigefunctions of

1.3 Show that 3 cos 2q - 1 is an eigenfunction of the operator

h 2 Ï ∂2 ∂ ¸
– ÊÁ ˆ˜ Ì 2 + cot q ˝
Ë 2 p ¯ Ó ∂q ∂q ˛
with the eigenvalue 6(h/2p)2.
1.4 Show that the functions:
(i) y1 = exp(- ax2) and (ii) y2 = x exp(- bx2) are the eigenfunctions of the Schrödinger
equation of a harmonic oscillator provided

p kf m
a=b=
h
Also show that the energy of the oscillator is equal to (h/4p) kf / m for the function

y1 and (3h/4p) kf / m for function y2.

(Hint: Evaluate H y and then put the terms other than constant equal to zero. The
constant term is equal to E.)
1.5 Show that the expectation value of momentum of a particle described by the wave
function exp (ik x) is h/2pk
(Hint: Employ the relation ·y* | p^ | y Ò/·y* y Ò.)
1.6 (a) The z-component of angular momentum in classical mechanics is given by
Lz = xpy – yp x
 Wave Mechanics, Energy Quantization and Atomic Structure 151

Write down its operator in Cartesian coordiantes and then convert it into spherical
polar coordiantes. Given:
x = r sin q cos j
y = r sin q sin j
z = r cos q
(Hint: Use the expression
∂ ∂r ∂ ∂q ∂ ∂j ∂
= ÊÁ ˆ˜ +Ê ˆ + ÊÁ ˆ˜
Ë ∂x ¯ ∂r ÁË ∂x ˜¯ ∂q
and similar expressions for
∂x Ë ∂x ¯ ∂j
∂/∂y and ∂/∂z.)
È h Ê ∂ ∂ˆ h ∂ ˘
Í Ans. 2pi ÁË x ∂ y - y ∂ x ˜¯ , 2pi ∂ j ˙
Î ˚
^ depends only the angle j, its eigenfunctions will be a function of angle
(b) Since Lz
j only. Let it be
^ F= LF
L z z
where Lz is the eigenvalue. By separating the variables, show that
F = exp (2piLzj /h)
(c) Since the function F has to be a single-valued, it should satisfy the relation:
F (j) = F (j + 2p)
Show that this condition leads to the expression:
Lz = m(h/2p), where m = 0, ± 1, ± 2, …
1.7 The particle in a box follows the relation
nl
l= , n = 1, 2, 3, …
2
where l is the length of the box and l is the wavelength of the particle. Invoking de
Broglie relation p = h /l in the above expression, show that the kinetic energy of the
particle is given by
n2h2
T=
8ml 2
1.8 Using the variation function x (l – x), calculate · x2 Ò for a particle in an one-dimensional
box and compare it with the true ground state · x2 Ò.
1.9 Show that n
wavelength or uncertainty in position.
(Hint: n = 0 means E = 0. Thus DE = 0 or D p = 0. Hence, D x
to uncertainty principle and l
1.10 The wave function for the lowest state of a harmonic oscillator has the form of a
Gaussian function exp(– a x2), where x is the displacement from equilibrium. Show
that this function on substituting in the appropriate Schrödinger equation (1.5.9) gives

a = (p/h) mkf and E = (1/2) (h/2p) kf / m

(Hint: After carrying out differentiation, put the terms involving x2 and constants
separately equal to zero and E, respectively.)
152 A Textbook of Physical Chemistry

(b) Verify that the function exp(– ax2) where a = mkf /2(h/2p) is an eigenfunction
of the one-dimensional simple harmonic oscillation with an eigenvalue of (1/2)hv.
1.11 For the ground state of a harmonic oscillator, calculate (a) · xÒ; (b) ·x2 Ò; and (c) · px Ò.
1.12 With the variation function axexp(– cx 2
oscillator. Explain why this energy is not equal to the correct energy (1/2)hv0.
[Ans. (3/2) hv0]
1.13 (a) Show that if l = 1 and |m| = 2, the associated Legendre polynomial vanishes, i.e.
Pl| m | = 0.
(b) The legendre polynomial is given as

1 dl
Pl = (x 2– 1)l
2l (l !) dx l

Show that the highest power of x in this expression is x l.

(c) Show that the associated Legendre polynomial Pl|m| vanishes whenever |m| > l.
(d) Show that the associated Legendre polynomial Pl|m| reduces to the Legendre
polynomial Pl when m = 0.
1.14 (a) Show that if n = 1 and l = 1, the associated Laguerre polynomial vanishes, i.e.

L2nl++l1 = 0

(b) Show that the highest power of r in the Laguerre polynomial is given by r k
and hence also show that the associated Laguerre polynomial vanishes whenever
j > k.

orbital angular momentum (L) vector of a p electron in the hydrogen atom.

(b) What is the length of the L vector?
(c) Which of the orientations has the greatest energy?
1.16 With the variation function a exp(– br
1.17 Calculate the velocity of 1s electron in an atom with nuclear charge Z. What value
of Z would make the 1s electron travel at the velocity of light? Comment upon the
implications of this result for the likelihood of producing an element with atomic
number of about 140.
1.18 If y1 and y2 are wave functions for a degenerate state of energy E, prove that any
linear combination c1y1 + c2y2 is also a wave function.

z electron in the xy-plane is zero.

1.20 Show that the radial distribution of 2s orbital of hydrogen atom exhibits two maxima
at r equal to 0.764a0 and 5.236a0, respectively.
(Hint: Put d 4p r2y220 /dr = 0 and simplify.)
1.21 Calculate the magnitude of the ground-state orbital angular momentum of the
electron in a hydrogen atom according to (a) quantum mechanics, and (b) the Bohr’s
theory.
 Wave Mechanics, Energy Quantization and Atomic Structure 153

1.22 Given below are the values of three wave functions involving r of hydrogen atom
for various values of r/a0. Plot R versus r/a0, R2 versus r/a0 and 4pr2R2 versus r/a0
and identify these wave functions. Compare your plots with those given in the text.

r/a0 R/1015 m–1.5

(i) (ii) (iii)
0 5.20 1.84 —
0.125 4.59 1.62 —
0.25 4.05 1.42 0.12
0.50 3.15 1.07 0.21
1.00 1.91 0.56 0.32
1.5 1.16 0.22 0.38
2.0 0.70 0 0.39
2.5 0.43 — —
3.0 0.26 – 0.21 0.36
3.5 0.16 — —
4.0 0.095 – 0.25 0.29
5.0 — – 0.23 0.22
6.0 — – 0.18 0.16
7.0 — – 0.14 0.11
[Ans. (i) R1, 0 , (ii) R2,0 and (iii) R2,1]
1.23 What is the degeneracy of the level of the hydrogen atom that has the energy:
(a) – RH, (b) – RH /9, and (c) – RH /25?
1.24 (a) According to the virial theorem, if the potential energy V is a homogeneous function
of the coordinates of degree r, then
Ê rˆ
·T Ò = Á ˜ ·V Ò
Ë 2¯
The potential energy of a system made up of charged particles that interact solely by
electrostatic forces is a homogeneous function of degree – 1. Thus
1
·T Ò = – ·V Ò
2

hydrogen atom for which the normalized wave function and energy operators in
atomic units (see Annexure VII) are
1
y = exp (– r)
p
Ê 1 ˆ ∂ Ê r2 ∂ ˆ
T = – ÁË ˜ Á ˜
2r 2 ¯ ∂ r Ë ∂ r ¯
154 A Textbook of Physical Chemistry

1
V =–
r
and the volume element is dt = 4p r2 dr.
(b) If · EÒ = · T Ò + · V Ò, what is the value of · EÒ in atomic unit?
1.25 Calculate the expectation value of r for the hydrogen atom in the ground state.
•

Given: Ú r2 exp (– 2r/a0) dr = 3!/(2/a0)4. [Ans. · rÒ = (3/2)a0]

0

1.26 Which of the following transitions are allowed in the normal electronic spectrum of
hydrogen atom?
(a) 2s Æ 1s, (b) 2p Æ 1s, (c) 3d Æ 2p, (d) 5d Æ 3s, (e) 5p Æ 3s.
1.27 The characteristic emission from potassium when heated is purple and lies at 770 nm.
On close inspection the line is seen to be composed of two closely spaced components,
one at 766.70 nm and the other at 770.11 nm. Account for this observation.
1.28 (a) Show that the hydrogen wave function for l = 1 have maxima along the directions
of the Cartesian axes.
(b) Show that the radial distribution function of 2p orbital of hydrogen atom exhibits
one maximum at r = 4a0.

d orbitals is spherically symmetrical. Which of the following species has spherical

symmetry? Na, Na+, Al, Zn, N, F, O2–, Cr
1.30 (a) The 3s orbital has two radial nodes. Calculate the value of r in terms of a0 at
which these two nodes are observed.
(b) The 3p orbital has one radial node. Calculate the value of r in terms of a0 at which
this node is observed.
(c) How many radial and angular nodes are present in the 3d orbital?
1.31 Find the value of r for which the radial distribution function for the 2s state of the
hydrogen atom has a maximum or a minimum.
1.32 Which of the following wave functions satisfy the principle of indistinguishability
of electrons and the Pauli principle?
(a) 1s(1)2s(2)a(1)b (2).
(b) (1/2) [1s(1)2s(2) – 2s(1)1s(2)] [a(1)b(2) + b (1)a(2)].
(c) (1 / 2 ) [1s(1)2s(2)a(1)b (2) – 2s(1)1s(2)b (1)a(2)].
(d) (1 / 2 ) [1s(1)2s(2) + 2s(1)1s(2)] a(1)a(2).
1.33 Give the magnitude of the angular momentum of an electron that occupies the
following orbitals:
(a) 1s, (b) 3s, (c) 3d, (d) 2p and (e) 3p.
Give the number of radial and angular nodes in each case.
1.34 The antisymmetric wave functions can be written in the form of determinant,
known as Slater determinant. For example, the wave function as given by
Eq. (1.12.10) is
1
[j1(1)j2(2) – j1(2)j2(1)] [a (1)a(2)]
2
 Wave Mechanics, Energy Quantization and Atomic Structure 155

1
i.e. [j 1(1)a(1)j2(2)a(2) – j1(2)a(2)j2(1)a(1)]
2
The above expression can be generated from the determinant
1 j1 (1) a (1) j 2 (1) a (1)
2 j1 (2) a (2) j 2 ( 2) a ( 2)

If in the above determinant j1 = j2, then the two rows of the determinant are identical
and hence its value is zero. This is, in fact, the Pauli exclusion principle according
to which the same orbital cannot hold two electrons of the same spin.
(a) Show that the wave function of Eq. (1.12.9) can be written as the sum of two
determinants
j1 (1) a (1) j 2 (1) b (1) j1 (1) b (1) j 2 (1) a (1)
-
j1 (2) a (2) j 2 (2) b (2) j1 (2) b (2) j 2 (2) a (2)
(b) Is the sum of the above two determinants zero for j1 = j2? Does the conclusion
agree with the Pauli exclusion principle?
1.35 The zero-point energies are a manifestation of the uncertainty principle. Discuss the
above statement in the light of the following facts.
‘The electron in a hydrogen atom and a harmonic oscillator have nonvanishing zero-
point energy whereas the zero-point energy of a rotator is zero.’

(a) (1s)1(2p)1, (b) (1s)1(2s)1, (c) (1s)2(2s)2(2p)1(3p)1, and (d) (1s)2(2s)2(2p)1(3d)1

[Ans. (a) 3P, 3P; (b) 3S, 1S; (c) 3S, 3P, 3D, 1S, 1P, 1D; (d) 1P 3P, 1D, 3D, 1F, 3F]
1.37 Show that y1s (H) and y2s(H) are orthogonal to each other.
1.38 Show that the most probable distance of an electron in the 2p orbital of hydrogen
atom is 4a0.
(Hint: Find r using the expression d(r2R2)/dr = 0.]

1.39 Computer ·rÒ for the 2s, 2p and 3s states of a hydrogen atom and compare the

results with the general expression ·rÒ =

a0
[3n2 - l (l + 1)]
2
1.40 Evaluate the commutators of each of the following.
(x, d/d x), ( y, d/d x) and (d/d x, d2/d x 2) [Ans. –1, 0, 0]
2
1.41 Show that the operators 3 x and d/dx do not commute with each other.

radius is 0.323.
1.43 Show that for 1s electron in a hydrogen atom · rÒ = (3/2)rmp.
1.44 Determine the minimum energy of a particle in a one-dimensional box (V = 0 for
0 < x < l and V = • elsewhare) by using the wave function
y = C1x(l – x) + C2x2 (l – x)2
[Hint: See Annexure XII.]
156 A Textbook of Physical Chemistry

NUMERICAL PROBLEMS

Black-Body 1.1 Given below are the wavelengths of emission maximum from a small pinhole of a
Radiation container at different temperatures.
T/K 1 273 1 773 2 273 2 723 3 273 3 773
l max/nm 2 180 1 600 1 240 1 035 878 763

Deduce graphically the value of Planck’s constant.

(Hint: Plot l max versus 1/T, slope = hc/5k, Eq. 1.1.19.)
Photoelectric 1.2 The following values for the retarding potentials at which the photoelectric current
Effect from a sodium surface was reduced to zero were obtained.

l /nm 312.5 365.0 404.7 433.9 546.1

Vr /V 2.128 1.595 1.215 1.025 0.467
Calculate (a) the threshold frequency, and (b) Planck’s constant.
(Hint: Plot V r versus 1/l , slope = hc/e, Eq. 1.1.23.)
Particle in a Box 1.3 Benzene may be regarded as a two-dimensional box of side about 0.35 nm and
containing six electrons. What wavelength of light should be required to promote an
Ans. 135 nm]
1.4 Naphthalene may be considered to be a rectangle of length and breadth equal to 0.7
nm and 0.4 nm, respectively. Derive the appropriate energy expression for a particle
in a rectangular box and calculate the expected wavenumber of radiation required to

1.5 The diameter of a typical small nucleus is about 10–13 cm. Suppose that a proton is
– 13
cm.

box, what would be the lowest energy level? From this result, conclude whether an
electron can exist within the nucleus or not.
Bohr’s Theory 1.6 A particle of charge equal to that of an electron and mass 208 times the mass of the
electron moves in a circular orbit around a nucleus of charge +3e. Assuming that the
Bohr model of the atom is applicable to this system, (a) derive the expression for
the radius of the nth Bohr orbit, (b) determine the value of n for which the radius of

atom, and (c) determine the wavelength of the radiation emitted when the revolving

[Ans. (a) r = n2(8.51 ¥ 10–14 m), (b) n = 25, (c) l = 55.2 pm]
1.7 The hypothetical element positronium consists of an electron moving in space around
a nucleus consisting of a positron (a subatomic particle similar to the electron except

orbit of the electron. [Ans. 106 pm, use m instead of me]

Magnetic Moment 1.8 Calculate the magnetic moment of a particle with charge 2.0 ¥ 10– 16 C moving in a
circle of radius 2.5 nm with speed 2.0 ¥ 105 m s–1. [Ans. 5.0 ¥ 10– 20 J T–1]
ANNEXURE I Derivation of de Broglie Relation for a Photon

According to theory of relativity, the mass of a particle varies with its velocity
according to the expression
m0
m= (AI.1)
{1- (u 2 / c 2 )}1/2
where m0, the mass as u Æ 0, is called the rest mass of the particle. The expression
of its momentum will be given by
m0u
p= (AI.2)
{1- (u 2 / c 2 )}1/2
For a photon, though m0 = 0, its momentum is not necessarily zero because for
u = c, Eq. (AI.2) gives
0
p=
0
an indeterminate quantity. To determine the value of p for a photon, we proceed
as follows.

u , i.e.
u =u u =u
T= Ú dw = Ú F dx
u =0 u =0

According to Newton’s second law, the above expression becomes

u =u u =u u =u u =u
du dx
T = Ú (ma) dx = Ú m
dt
dx = Ú d(mu) = Ú u d(mu)
dt u = 0
(AI.3)
u =0 u =0 u =0

For a nonrelativistic (or classical) mechanics, m is independent of u , hence we

get the classical expression of kinetic energy, i.e.
u
1
T = m Ú u du = mu 2
0
2
For a relativistic mechanics, m varies with velocity u according to Eq. (AI.1). Hence
u u
Ê m0u ˆ m0u
T= Ú ud Á 2 2 1/2 ˜
=Ú
Ë {1- (u / c )} ¯ 0 {1- (u 2 / c 2 )}3/2
du
0

È 1 ˘
= m 0 c2 Í -1˙ (AI.4)
Î {1 - (u 2 2 1/2
/ c )} ˚
158 A Textbook of Physical Chemistry

[Note that Eq. (AI.4) gives the classical result of T = (1/2) mu2 when (u/c) Æ
0. To prove this, we write {1 – (u2/c2)}– 1/2 as 1 + (1/2) (u2/c2) and substitute in
Eq. (AI.4) which gives T = (1/2) mu2.]

Invoking Eq. (AI.1) in Eq. (AI.4), we get

T = mc2 – m0c2 (AI.5)
2 2
The terms mc and m0c in Eq. (AI.5) represent the total energy and rest energy
of the particle, respectively. Hence, we write Eq. (AI.5) as
E = T + m0c2 (AI.6)

From Eq. (AI.2), it can be show that

u2 p2
=
c2 m02 c 2 + p 2
Substituting the above expression in Eq. (AI.4), we get

È 1 ˘
T = m0c2 Í - 1˙
ÍÎ {1 - p 2 /(m02 c 2 + p 2 )}1 / 2
˙˚

m0 c 2 (m02 c 2 + p 2 )1/ 2
or T + m0c2 = = c (m02 c2 + p2)1/2
(m02 c 2 )1/ 2
Squaring on both sides, we get
(T + m0c2)2 = c2(m02 c2 + p2)
which on substituting in Eq. (AI.6) gives
E2 = (pc)2 + (m0c2)2 (AI.7)
Using Planck’s equation E = hc/l in Eq. (AI.7), we get
2
Ê hc ˆ = (pc)2 + (m c2)2
ÁË ˜¯ 0 (AI.8)
l
For a photon, m0 = 0, hence
2
Ê hc ˆ = (pc)2
ÁË ˜¯
l
h
or p= (AI.9)
l
Equation (AI.9) is the required expression connecting particle nature (i.e. p)
with the wave nature (i.e. l) of a photon. According to de Broglie, Eq. (AI.9) is,
as well, applicable to all material particles.
ANNEXURE II Solutions of Schrödinger Equation for a Harmonic
Oscillator
THE POWER SERIES METHOD
Expression of The Schrödinger equation of a particle executing simple harmonic motion is
Schrödinger
d 2y 8p 2 m 1
Equation + 2
(E – kf x2 ) y = 0 (AII.1)
dx 2 h 2
Let we represent
8p 2 m
l = E (AII.2)
h2

8p 2 m Ê1k ˆ
and a2 = ÁË f ˜¯ (AII.3)
h2 2
With these, Eq. (AII.1) becomes

d 2y
+ (l – a2x2 ) y = 0
dx 2

y= ax (AII.4)
which gives

d 2y d 2y l
a + (l – a y2)y = 0, i.e. + ÊÁ - y 2 ˆ˜ y = 0 (AII.5)
dy 2 dy 2 Ëa ¯

Asymptotic y2 >> l /a , such that Eq. (AII.5)

Solution of is reduced to
Eq. (AII.5)
d 2y
– y2y = 0
dy 2
The solution of this equation is
2
y = e- y /2
(AII.6)
2
(Note: The solution e y /2 is rejected as y Æ • as y Æ •.)
2
Solution of y = e- y /2

Eq. (AII.5) expressed as

2
y = H e- y /2
(AII.7)

where H is a function of y
160 A Textbook of Physical Chemistry

Hermite’s From Eq. (AII.7), we have

Equation dy Ê dH ˆ - y 2 / 2 Ê 2yˆ Ê dH ˆ
- yH ˜ e - y / 2
2 2
= ÁË + H Ë - ¯ e - y / 2 = ÁË
dy ˜¯
e ¯
dy 2 dy

d 2y Ê d2 H dH ˆ - y 2 / 2 Ê dH ˆ -2 y ˆ - y 2 / 2
= Á 2 -H - y - yH ˜ ÊÁ
dy 2 Ë dy d y ˜
¯
e + ÁË
dy ¯ Ë 2 ˜¯ e

È d2 H dH ˘ 2
= Í 2 - 2y + ( y 2 - 1) H ˙ e - y / 2
Î dy dy ˚
With these, Eq. (AII.5) becomes
È d2 H ˘ 2 l
+ ( y 2 -1) H ˙ e - y / 2 + Ê - y 2 ˆ He - y / 2 = 0
dH 2
Í 2 - 2y Ë ¯
Î dy dy ˚ a

È d2 H dH Ê l ˆ ˘ - y 2 / 2
or Í 2 -2y + -1 H ˙ e =0
Î dy dy Ë a ¯ ˚

d2 H dH Ê l ˆ
or - 2y + -1 H = 0 (AII.8)
dy 2
dy Ë a ¯
Equation (AII.8) is known as Hermite’s equation.
Solution of In the series method, the function H is expressed as a power series in y.
Eq. (AII.8) by the H = a0 + a1 y + a2 y2 + a3 y3 + a4 y4 + (AII.9)
Power Series
From this series, we get
Method
dH
= a1 + 2a2 y + 3a3 y2 + 4a4 y3 + (AII.10)
dy

d2 H
and = (1 ¥ 2 )a2 + (2 ¥ 3)a3 y + (3 ¥ 4 )a4 y2 + (AII.11)
dy 2
Substituting Eqs (AII.9) to (AII.11) in Eq. (AII.8), we get
[(1 ¥ 2)a2 + (2 ¥ 3 ) a3 y + (3 ¥ 4 ) a4 y2 + ] – 2y[a1 + 2a2 y + 3a3 y2
l
+ 4a4 y3 + ] + ÊÁ - 1ˆ˜ [a0 + a1 y + a2 y2 + a3 y3 + ]=0
Ëa ¯
that is
È Êl ˆ ˘ È Êl ˆ ˘
ÍÎ(1 ¥ 2)a2 + ÁË a - 1˜¯ a0 ˙˚ + ÍÎ(2 ¥ 3)a3 + ÁË a - 1 - 2˜¯ a1 ˙˚ y

l
+ ÍÈ(3 ¥ 4)a4 + ÊÁ - 1 - 2 ¥ 2ˆ˜ a2 ˙˘ y2
Î Ëa ¯ ˚

l
+ ÍÈ(4 ¥ 5)a5 + ÊÁ - 1 - 2 ¥ 3ˆ˜ a3 ˙˘ y3 + =0
Î Ë a ¯ ˚
 Wave Mechanics, Energy Quantization and Atomic Structure 161

For the above expression to be true for all values of y

l
(1 ¥ 2)a2 + ÊÁ - 1ˆ˜ a0 = 0
Ëa ¯

l
(2 ¥ 3)a3 + Ê -1 - 2ˆ a1 = 0
Ëa ¯

l
(3 ¥ 4)a4 + Ê -1 - 2 ¥ 2ˆ a2 = 0
Ëa ¯

l
(4 ¥ 5)a5 + ÊÁ - 1 - 2 ¥ 3ˆ˜ a3 = 0
Ëa ¯
and so on.

Êl ˆ
(u + 1) (u + 2)au +2 + ÁË - 1 - 2u ˜¯ au = 0 ; u = 0, 1, 2, … (AII.12)
a
Equation (AII.12) is known as recursion formula. It permits the computation of
au + 2 au. If we set a1
can compute a2, a4, a6, etc., in terms of a0 a0
we can compute a3, a5, a7, etc., in terms of a1.
Restriction of H Æ • as the value of y Æ •.
Power Series to To avoid this, we choose values of l/a in Eq. (AII.12) such that the value of au
Finite Number of
Terms
l
- 1 - 2u = 0; u = 0, 1, 2, … (AII.13)
a
in Eq. (AII.12)
Explicit au.
Expression
of Hermite’s Case 1 When u has even values
Equation 1 Êl ˆ
For u = 0 a2 = – Á - 1˜ a0
1¥ 2 Ë a ¯
1 Êl ˆ
For u = 2 a4 = – Á - 1 - 2 ¥ 2˜¯ a2
3¥ 4 Ëa
1 Êl ˆ ˘ È 1 Ê l - 1ˆ a ˘
= ÈÍ- Á - 1 - 2 ¥ 2˜¯ ˙ Í- Á ˜ 0
Î 3¥ 4 Ëa ˚ Î 1 ¥ 2 Ë a ¯ ˙˚
1 Êl ˆÊl ˆ
= Á - 1˜ Á - 1 - 2 ¥ 2˜¯ a0
4! Ë a ¯ Ë a
162 A Textbook of Physical Chemistry

1 Êl ˆ
For u = 4 a6 = – Á - 1 - 2 ¥ 4˜¯ a4
5¥6Ëa
1 Êl ˆ˘È 1 Ê l ˆ Ê l
= ÈÍ- ˆ ˘
ÁË - 1 - 2 ¥ 4˜¯ ˙ Í ÁË - 1˜¯ ÁË - 1 - 2 ¥ 2˜¯ a0 ˙
Î 5 ¥ 6 a ˚Î 4 ! a a ˚

1 Êl ˆÊl ˆÊl ˆ
=– Á - 1˜ Á - 1 - 2 ¥ 2˜¯ ÁË - 1 - 2 ¥ 4˜¯ a0
6! Ë a ¯ Ë a a
and so on.
l
Substituting -1 = 2u (from Eq. AII.13) in the above expressions, we get
a
1 2u
a2 = – (2u ) a0 = – a0
1¥ 2 2!
1 22 u (u - 2)
a4 = (2u) (2u – 4)a0 = a0
4! 4!
1 23 u (u - 2) (u - 4)
a6 = – (2u ) (2u – 4) (2u – 8) a0 = – a0
6! 6!
and so on.
With these, the explicit expression of Hu for u even

È 2u 2 22 u (u - 2) 4 23u (u - 2) (u - 4) 6 ˘
Hu = a0 Í1 - y + y - y + ˙
Î 2! 4! 6! ˚
(AII.14)
It is custom a0 y,
that is yu, is 2u. With this, the above expression of Hu

u ! È 2u 2 22 u (u - 2) 4 23u (u - 2) (u - 4) 6 ˘
Hu = (– 1)u/2 Í1 - y + y - y + ˙
(u 2)! Î 2! 4! 6! ˚
(AII.15)
Case 2 When u has odd values
1 Êl ˆ
For u = 1 a3 = – Á - 1 - 2˜¯ a1
2¥3Ëa
1 Êl ˆ
For u = 3 a5 = – Á - 1 - 2 ¥ 3˜¯ a3
4¥5Ëa
1 Êl ˆ˘È 1 Ê l - - ˆ a ˘
= ÈÍ- ÁË - 1 - 2 ¥ 3˜¯ ˙ Í- Á 1 2˜ 0 ˙
Î 4¥5 a ˚Î 2¥3Ë a ¯ ˚
1Êl ˆÊl ˆ
= ÁË - 1 - 2˜¯ ÁË - 1 - 2 ¥ 3˜¯ a1
5! a a
 Wave Mechanics, Energy Quantization and Atomic Structure 163

1 Êl ˆ
For u = 5 a7 = – Á - 1 - 2 ¥ 5˜¯ a5
6¥7Ëa
1 Êl ˆ˘È 1 Ê l ˆÊl
= ÈÍ- ˆ ˘
ÁË - 1 - 2 ¥ 5˜¯ ˙ Í ÁË - 1 - 2˜¯ ÁË - 1 - 2 ¥ 3˜¯ a1 ˙
Î 6¥7 a ˚ Î 5! a a ˚
1 Êl ˆÊl ˆÊl ˆ
=– Á - 1 - 2˜¯ ÁË - 1 - 2 ¥ 3˜¯ ÁË - 1 - 2 ¥ 5˜¯ a1
7! Ë a a a
and so on.
l
Substituting – 1 = 2u (from Eq. AII.13) in the above expressions, we get
a
2(u - 1)
a3 = – a1
3!
22 (u - 1) (u - 3)
a5 = a1
5!
23 (u - 1) (u - 3) (u - 5)
a7 = – a1
7!
and so on.
Hence, the explicit expression of Hu for u odd
È 2(u - 1) 3 22 (u - 1) (u - 3) 5
Hu = a 1 Í y - y + y
Î 3! 5!
23 (u - 1) (u - 3) (u - 5) 7 ˘
– y + ˙ (A.II.16)
7! ˚
a1 y,
that is yu, is 2u. With this, the above expression of Hu
2(u !) È 2(u - 1) 3 22 (u - 1) (u - 3) 5
Hu = (– 1)(u – 1)/2 Íy - y + y
[(u - 1) 2]! Î 3! 5!
23 (u - 1) (u - 3) (u - 5) 7 ˘
- y + ˙ (AII.17)
7! ˚
Normalization y
Constant of the evaluating the integral
Function y +•
- y 2 /2 2
Ú ( NHu e ) dx = 1
-•

Since y = a x, we get
+•
N2 2

Ú H u2 e - y dy = 1
a -•

The value of integral is equal to 2uu ! p . Hence

N2
(2uu! p ) = 1
a
164 A Textbook of Physical Chemistry

1/ 2
Ê a ˆ
or N = Á (AII.18)
Ë 2 u ! p ˜¯
u

Energy Expression From Eq. (AII.13), we have

of Harmonic l
Oscillator – 1 – 2u = 0 ; u = 0, 1, 2, …
a
Substituting the expressions of l and a from Eqs (AII.2) and (AII.3), we get
8p 2 mE/h 2
– 1 – 2u = 0 ; u = 0, 1, 2, …
2p mkf /h
Rearranging this expression, we get
h kf Ê
u + ˆ = hn 0 Ê u + ˆ ; u = 0, 1, 2, …
1 1
E= Ë ¯ Ë (AII.19)
2p m 2 2¯
where n0

Alternative Way of
Defining Hermite the relation
Polynomials du
Hu = (– 1)u e
y2
u
(e - y )
2
(AII.20)
dy
For example, we have
2 d0 (e - y ) = e y
2 2 2
u=0 H0 = (– 1) 0 e
y
0
e- y = 1
dy

= -1 e ( -2 y e - y ) = 2y
2 d ( - y2 ) ( ) y2 2
u=1 H1 = (– 1)1 e y e
dy
d2
u=2 H2 = (– 1)2 e
y 2

2
(e- y ) = (-1)2 e y
2 2 d
(-2 y e- y2 )
dy dy

= (– 1)2 e
y 2
(-2e- y + 4 y 2 e- y ) 2
= 4y2 – 2
and so on.
Recursion
Formula u y 2 du (e - y )2
Hu = (– 1) e u (Eq. AII.20)
Involving Hermite dy
Polynomials
u +1
du
= ( -1)u ( 2 ye y ) u (e - y ) + ( -1)u e y (e - y 2 )
dH u 2 2 2 d
Hence u +1
dy dy dy
= 2y Hu – Hu + 1 (AII.21)
2
d Hu d d
2
= 2Hu + 2y Hu – Hu + 1
dy dy dy
= 2Hu + 2y (2yHu – Hu + 1) – (2y Hu +1 – H u + 2)
2
= 2 (1 + 2y ) Hu – 4y Hu +1 + Hu + 2 (AII.22)
 Wave Mechanics, Energy Quantization and Atomic Structure 165

The Hermite’s equation is

d 2 Hu l
+ ÊÁ - 1ˆ˜ Hu = 0
dH u
– 2y
dy 2 dy Ëa ¯
l
Substituting -1 = 2u, we get
a
d 2 Hu dH
- 2 y u + 2u Hu = 0
dy 2 dy
Substituting dHu /dy and d2Hu /dy2 from Eqs (AII.21) and (AII.22), we get
[2 (1 + 2y2 )Hu – 4y Hu + 1 + Hu + 2] – 2y [2yHu – Hu + 1] + 2u Hu = 0
or Hu + 2 – 2y Hu + 1 + 2(u + 1)Hu = 0
Replacing u u – 1, we get
Hu + 1 – 2y Hu + 2u Hu – 1 = 0 (AII.23)

known that H0 = 1 and H1 = 2y. For example, we have

For u = 1 H2 – 2yH1 + 2 ¥ 1 H0 = 0 or H2 = 2yH1 – 2H0 = 4y2 – 2
For u = 2 H3 – 2yH2 + 2 ¥ 2 H1 = 0 or H3 = 2yH2 – 4H1 = 2y (4y2– 2) – 4 (2y)
= 8y3 – 12y.

THE FACTORIZATION METHOD

oscillator.
Expression of The Hamiltonian operator of a diatomic molecule executing harmonic oscillation is
Hamiltonian
p2 kf x 2
Operator H = + (AII.24)
2m 2
hn (where n = (1 / 2p ) kf / m , a classical

H p2 k x2
H= = + f
hn 2 m hn 2hn

P2 X 2
= + (AII.25)
2 2
p2 kf x 2
where P2 = and X2 = = a x2 (AII.26)
m hn hn
The operator P
1 Ê h dˆ
P= Á ˜ (AII. 27)
m hn Ë 2p i dx ¯
166 A Textbook of Physical Chemistry

The differential dx is related to dX

hn
dx = dX (AII. 28)
kf
Replacing dx in terms of dX in Eq. (AII. 27), we get

1 Ê h kf d ˆ 1 d
P= ÁË ◊ ˜= (AII. 29)
m hn 2pi hn dX ¯ i dX
Definition of the
Ladder Operator
H + = P + iX and H - = P - iX (AII.30)

Commutator of We have
P and X [ P, X ] = PX - X P
1 d ˆ 1Ê
+ 1ˆ - X ÊË
1 d ˆ
X - X ÊË
1 d d
= = X
i dX i dX ¯ i Ë d X ¯ i dX ¯
1
= = -i (AII.31)†
i
Commutator of We have
H ± and X [ H ± , X ] = H ± X - X H ± = ( P ± i X ) X - X ( P ± iX )
= PX ± iX 2 - X P ∓ iX 2 = PX - X P
=–i (AII.32)
Commutator of We have
H ± and H [H ± , H ] = H ± H - H H±
Ê 2 2ˆ Ê 2 2ˆ
= ( P ± iX ) Á P + X ˜ - Á P + X ˜ ( P ± iX )
Ë 2 2 ¯ Ë 2 2 ¯
1
= ÈÎ( P + PX 2 ± iX P ± iX 3 ) - ( P ± i P X + X 2 P ± iX 3 ) ˘˚
3 2 3 2

Î( P X - X P ) ± i ( X P - P X )˚
1È 2 2 2 2
˘
= (AII.33)
2
1Ê 2 d ˆ 2 Ê1 d ˆ
Now PX 2 - X 2 P = Ê
1 d ˆ 2 2 Ê1 d ˆ
Ë i dX ¯ X - X Ë i d X ¯ = i Ë X d X + 2 X ¯ - X Ë i d X ¯
2X
= = -2iX (AII.34)††
i
† Ê d ˆ d df d
Ë dX ¯ X ∫ dX ( Xf ) = X dX + f ∫ X dX + 1

†† d 2
X ∫
d
( X 2 f ) = X 2 df + f ( 2 X ) ∫ X 2 d + 2 X
dX dX dX dX
 Wave Mechanics, Energy Quantization and Atomic Structure 167

1 d ˆ2 Ê1 d ˆ2
X P - P X = X ÊË
2 2
- X
i dX ¯ Ë i dX ¯

d2 Ê d2 d d ˆ
= -X +Á X + +
dX 2 Ë dX 2 dX dX ˜¯

= 2i ÊË
d 1 d ˆ
= 2 = 2i P (AII.35)†
dX i dX ¯
Substituting Eqs (AII.34) and (AII.35) in Eq. (AII.33), we get

[ H ± , H ] = 1 [-2iX ± 2i2 P ] = ∓ P - iX
2

= ∓ ( P ± iX ) = ∓ H ± (AII.36)

Successive The Schrödinger equation of the harmonic oscillator is

Operation of H ±
H y = E¢y
on the Eigenvalue
Equation hn, we get

H E¢ (AII.37)
y = y i.e. Hy = Ey
hn hn

H ± , we get

H ± ( Hy ) = H± ( E y )
which on using Eq. (AII.36) becomes
( H H± ∓ H ± )y = E ( H ± y )
i.e. H ( H ±y ) = ( E ± 1) ( H ± y ) (AII.38)

that is, the function H ±y is also an eigenfunction of H with an eigenvalue one

higher or lower than the eigenvalue of y.
H ± would give

H ± ( Hy ) = H ± ( Ey )
k k

i.e. ( k
)
H H ± y = ( E + k ) H ±y ( k
) k = 0, 1, 2, 3, ... (AII.39)

Lower Limit of Since both the kinetic and the potential energies are positive, no eigenvalue of H
the Eigenvalue
it be E0 y0.

d2 d Ê d d 2 f df d2
Xf ˆ¯ =
d Ê df
+ f ˆ¯ = X
† df d
2
X∫ Ë Ë X 2
+ + ∫X +2
dX dX dX dX dX dX dX dX dX 2 dX
168 A Textbook of Physical Chemistry

The application of H – on y0
lower than y0, i.e.

H –y0 = 0 (AII.40)
Operating H + on Eq. (AII.40), we get

H + H – y0 = 0
Substituting the expression of H + and H –, we get
( P + iX ) ( P - iX )y 0 = 0

or ( P 2 - i PX + iX P + X 2 )y 0 = 0
or ÈÎ( P 2 + X 2 ) - i ( PX - X P )˘˚ y 0 = 0 or [2 H - i (-i )]y 0 = 0

or 2 Hy 0 – (1) y0 = 0 or (2E0 – 1)y0 = 0

1
This gives E0 =
2
The eigenvalue corresponding to the Hamiltonian H will be

1
E0¢ = hn (AII.41)
2
Expression of The remaining eigenvalues of H
Energies
( )
Eu¢ = u +
1
2
hn ; u = 0, 1, 2, 3, ... (AII.42)

Expression of
Ground-State
Wave function H – y0 = 0 i.e. ( P – iX )y0 = 0

Substituting the expression of P from Eq. (AII.29), we get

Ê1 d - i X ˆ y = 0 dy 0
Ë i dX ¯ 0 or = - Xy 0
dX
dy 0
i.e. = - X dX
y0
which on integration gives

X2
ln y0 = – + constant or y0 = A exp(–X 2/2) (AII.43)
2
The constant A
which gives
 Wave Mechanics, Energy Quantization and Atomic Structure 169

()
+• • 1/ 2
p
Ú y 0 dX = 2 A Ú e dX = ( 2 A )
2
-X
A2 2 2 2
= A2 ( p )1/ 2 = 1
-• 0
4
1/4
i.e. A = (1/p) (AII.44)
Higher Wave y0
functions k
yk = H +y 0 (AII.45)

For example, for k = 1 we have

y1 = H + y0 = ( P + iX ) y0

Ê 1 d + iX ˆ y = Ê 1 d + iX ˆ ( Ae - X 2 / 2 )
=Ë ¯ 0 Ë i dX ¯
i dX

È d e - X 2 / 2 + Xe - X 2 / 2 ˘ = Ai [ - ( - X ) e - X 2 / 2 + Xe- X 2 / 2 ]
= Ai Í- ˙˚
Î dX

= i ( 2 X ) ( Ae - X )
2
/2
(AII.46)

For k = 2, we have

H +2 y0 = H + y1 = ( P + iX ) [ 2iXAe - X ]
2
/2

= È + iX ˘˙ [ 2iXAe - X / 2 ]
1 d 2

ÎÍ i dX ˚
d ( -X2 /2)
= -2 A ÍÈ- + X 2e - X / 2 ˘˙
2
Xe
Î dX ˚

= -2 A [ -e - X ]
2 2 2
/2
+ X 2 e- X /2
+ X 2 e- X /2

= - A [ 4 X 2 - 2] e - X
2
/2 (AII.47)

1/ 2
Ê a ˆ È Ê X 2ˆ˘
y u = Á u p1 / 2 ˜ ÍÎexp ÁË - ˜ ˙ Hu (AII.48)
Ë 2 u! ¯ 2 ¯˚
where a = kf/hn. The function Hu

H0 = 1; H1 = 2X; H2 = 4X 2 – 2;

H3 = 8X 3 – 12X; H4 = 16H 4 – 48X 2 + 12

and so on.
ANNEXURE III Operators for the Components of Angular Momentum

Definition of
Angular point is given by
Momentum L=r¥p (AIII.1)
where r p is its linear
momentum vector.
Expressions of In terms of Cartesian coordinates, we can write
Components of r =xi+yj+zk
Angular
Momentum and p = px i + py j + pz k

Hence, L = r ¥ p = (x i + y j + z k) ¥ (px i + py j + pz k)

= x px (i ¥ i) + x py (i ¥ j) + xpz (i ¥ k)

+ ypx ( j ¥ i) + ypy ( j ¥ j) + ypz ( j ¥ k)

+ zpx (k ¥ i) + zpy (k ¥ j) + zpz (k ¥ k)

Keeping in mind that

i¥i=0 ; j¥j=0 and k¥k=0

i¥j=k ; j¥k=i and k¥i=j

and j¥i=–k ; k¥j=–i and i¥k=–j

we get L = x py k – x pz j – y px k + y pz i + zpx j – zpy i
= (y pz – zpy) i + (z px – x pz) j + (x py – y px) k

Since L = Lx i + Ly j + Lz k, we get
Lx = y pz – z py (AIII.2)
Ly = z px – x pz (AIII.3)

Lz = x py – y px (AIII.4)

Note: The above expressions of components of angular momentum can be derived

by using the determinant notation
i j k
r¥p= x y z .
px p y pz
 Wave Mechanics, Energy Quantization and Atomic Structure 171

Angular Momentum Replacing px, py and pz in Eqs (AIII.2)–(AIII.4) by the corresponding operators we
Operators get the operators (represented by the symbol of physical quantity with overhead
in Cartesian cap) of Lx , Ly and Lz .
Coordinates
Ê h ∂ˆ Ê h ∂ˆ h Ê ∂ ∂ˆ
Lx = y Á - zÁ = y -z ˜ (AIII.5)
Ë 2p i ∂z ˜¯ Ë 2pi ∂y ˜¯ 2pi ÁË ∂z ∂y ¯

L y = z ÊÁ h ∂ ˆ˜ - x Ê h ∂ ˆ = h Ê z ∂ - x ∂ ˆ (AIII.6)
Ë 2 p i ∂x ¯ Ë 2pi ∂z ¯ 2pi Ë ∂x ∂z ¯
Ê h ∂ˆ h ∂ˆ h Ê ∂ ∂ˆ
Lz = xÁ ˜ - yÊ = Á x -y ˜ (AIII.7)
Ë 2 p i ∂y ¯ Ë 2pi ∂x ¯ 2pi Ë ∂y ∂x ¯
Angular Momentum The Cartesian coordinates (x, y, z) of a point are related to its spherical polar
Operators in coordinates (r, θ, j) by the expressions
Spherical Polar z = r cos q
Coordinates z
x = r sin q cos j
y = r sin q sin j
P(x, y, z)
z or
P(r, q, j)
q
r
y
y

j
x
Q
x

The transformations from Cartesian

coordinates to spherical polar coordinates can be carried over by using the
expressions
∂ Ê ∂ r ˆ ∂ Ê ∂ q ˆ ∂ + Ê ∂j ˆ ∂
= ÁË ˜¯ + ÁË ˜¯ Á ˜ (AIII.8)
∂x ∂x ∂r ∂ x ∂q Ë ∂x ¯ ∂j
∂ Ê ∂ r ˆ ∂ Ê ∂ q ˆ ∂ Ê ∂j ˆ ∂
= Á ˜ +Á ˜ +
Ë ∂y ¯ ∂r Ë ∂y ¯ ∂q ÁË ∂y ˜¯ ∂j
(AIII.9)
∂y
∂ Ê ∂ r ˆ ∂ Ê ∂q ˆ ∂ + Ê ∂j ˆ ∂
= ÁË ˜¯ + ÁË ˜¯ Á ˜ (AIII.10)
∂z ∂z ∂r ∂z ∂q Ë ∂z ¯ ∂j
Using the fact that r2 = x2 + y2 + z2, we get
∂r x r sin q cos j
(i) = = = sin q cos j
∂x r r
∂r y r sin q sin j
(ii) = = = sin q sin j
∂y r r
∂r z r cosq
(iii) = = = cos q
∂z r r
172 A Textbook of Physical Chemistry

z z
From the expression cos q = = 2 , we get
r ( x + y + z 2 )1 2
2

∂q 1 z
(iv) – sin q =- (2x)
∂x 2 ( x + y + z 2 )3 / 2
2 2

∂q zx (r cos q )(r sin q cos j ) cos q cos j

i.e. = = =
∂x sin q ( x + y + z )
2 2 2 3/ 2
(sin q ) r 3 r

∂q 1 z
(v) – sin q =- (2y)
∂y 2 ( x 2 + y 2 + z 2 )3 / 2

∂q zy (r cos q )(r sin q sin j ) cos q sin j

i.e. = = =
∂y sin q ( x 2 + y 2 + z 2 )3 / 2 (sin q ) r 3 r

∂q
+ ÊÁ - ˆ˜ 2
1 1 z
(vi) – sin q = 2
∂z ( x + y + z )
2 2 1/ 2 Ë 2 ¯ ( x + y + z 2 )3 / 2 (2z)
2

∂q Ê 1 ˆ Ê 1 r 2 cos 2 q ˆ Ê 1 ˆ Ê 1ˆ
i.e. = Á- ˜¯ Á - ˜ = Á- 2
˜ Á ˜ (1 – cos q)
∂z Ë sin q Ë r r 3
¯ Ë sin q ¯ Ë r ¯

sinq
=–
r
Finally, from the expression tan j = y/x, we get
∂j y
(vii) sec2 j =- 2
∂x x

∂j Ê 1 ˆ y Ê r sin q sin j ˆ
= - Á 2 ˜ ÊÁ 2 ˆ˜ = - (cos 2 j ) Á 2 2
sin j
i.e. ˜ =-
∂x Ë sec j ¯ Ë x ¯ Ë r sin q cos j ¯
2
r sin q

∂j 1
(ix) sec2 j =
∂y y

∂j Ê 1 ˆ Ê 1 ˆ Ê 1 ˆ cos j
= Á 2 ˜ Á ˜ = (cos2 j) Á =
Ë r sin q cos j ˜¯ r sin q
i.e. Ë ¯
∂y Ë sec j ¯ x

(x) ∂j = 0
∂z
With these derivatives, Eqs (AII.8) – (AII.10) become

∂ Ê ∂ r ˆ ∂ Ê ∂ q ˆ Ê ∂ ˆ Ê ∂j ˆ ∂
= Á ˜ +Á ˜ Á ˜ +Á ˜
∂ x Ë ∂ x ¯ ∂ r Ë ∂ x ¯ Ë ∂q ¯ Ë ∂x ¯ ∂ j

∂ Ê cos q cos j ˆ ∂ Ê sin j ˆ ∂

+Á ˜¯ + -
∂q ÁË r sin q ˜¯ ∂j
= (sin q cos j) (AIII.11)
∂r Ë r
 Wave Mechanics, Energy Quantization and Atomic Structure 173

∂ Ê ∂r ˆ Ê ∂ ˆ Ê ∂q ˆ Ê ∂ ˆ Ê ∂j ˆ Ê ∂ ˆ
= Á ˜+ Á ˜+
∂y ÁË ∂y ˜¯ Ë ∂r ¯ ÁË ∂y ˜¯ Ë ∂q ¯ ÁË ∂y ˜¯ ÁË ∂j ˜¯
∂ Ê cos q sin j ˆ ∂ Ê cos j ˆ ∂
= (sin q sin j) +Á ˜¯ +Á ˜ (AIII.12)
∂r Ë r ∂q Ë r sin q ¯ ∂j
∂ Ê ∂r ˆ ∂ Ê ∂q ˆ ∂ Ê ∂j ˆ ∂
= Á ˜ +Á ˜ +Á ˜
∂z Ë ∂z ¯ ∂r Ë ∂z ¯ ∂q Ë ∂z ¯ ∂j
∂ Ê sinq ˆ ∂
= (cos q) +Á- ˜ (AIII.13)
∂r Ë r ¯ ∂q
Expression of L x
We have

h Ê ∂ ∂ˆ
Lx = Á y -z ˜
Ë
2pi ∂z ∂y ¯
h È ∂ sin q ∂ ˆ
= Í (r sin q sin j ) Ê cos q -
2pi Î Ë ∂r r ∂q ¯

Ê ∂ cos q sin j ∂ cos j ∂ ˆ ˘

– (r cos q) Á sin q sin j + +
Ë ∂r r ∂q r sin q ∂j ˜¯ ˙˚
h È ∂ cos q cos j ∂ ˘
= Í (- sin 2 q sin j - cos 2 q sin j ) -
2pi Î ∂q sin q ∂j ˙˚
h Ê ∂ ∂ ˆ
=– sin j + cot q cos j (AIII.14)
2pi ÁË ∂q ∂j ˜¯
Expression of L y We have
h Ê ∂ ∂
Ly = z -x ˆ
Ë
2pi ∂x ∂z ¯
h È Ê ∂ cos q cos j ∂ sin j ∂ ˆ
= (r cos q ) Á sin q cos j + -
2pi ÍÎ Ë ∂r r ∂q r sin q ∂j ˜¯
∂ sin q ∂ ˆ ˘
– (r sin q cosj) ÊÁ cos q - ˜
Ë ∂r r ∂q ¯ ˙˚
h È ∂ cos q sin j ∂ ˘
= Í (cos 2 q cos j + sin 2 q cos j ) -
2pi Î ∂q sin q ∂j ˙˚
h Ê ∂ ∂ ˆ
= cos j - cot q sin j (AIII.15)
2pi ÁË ∂q ∂j ˜¯
Expression of L z
We know

h Ê ∂ ∂ ˆ
Lz = Á x -y ˜
Ë
2pi ∂y ∂x ¯
174 A Textbook of Physical Chemistry

h È Ê ∂ cos q sin j ∂ cos j ∂ ˆ

(r sin q cos j ) Á sin q sin j + +
∂q r sin q ∂j ˜¯
=
2pi ÍÎ Ë ∂r r
Ê ∂ cos q cos j ∂ sin j ∂ ˆ ˘
- (r sin q sin j) Á sin q cos j + -
Ë ∂r r ∂q r sin q ∂j ˜¯ ˙˚
h È ∂ ˘
= Í (cos 2 j + sin 2 j ) ˙
2pi Î ∂j ˚
h ∂
= (AIII.16)
2pi ∂j
Operator for the
Square of Angular momentum vector with itself, i.e.
Momentum L2 = L ◊ L
In terms of components, we have
L 2 = (Lx i + Ly j + L z k) . (L x i + Ly j + Lz k)
Using the fact that i ◊ j = d ij (where d i j = 1 if i = j and dij = 0 if i π j), we get
L 2 = L 2x + L2y + L2z (AIII.17)
2
The operator for L is
2 2 2 2 (AIII.18)
L = Lx + L y + Lz
2
Expression of Lx We have
Ÿ Ÿ Ÿ È h Ê ∂ ∂ ˆ˘
L2x = Lx Lx = Í- ÁË sin j ∂q + cot q cos j ∂j ˜¯ ˙
Î 2 pi ˚
È h Ê ∂ ∂ ˆ˘
Í- 2pi ÁË sin j ∂q + cot q cos j ∂j ˜¯ ˙
Î ˚

=–
h2 Èsin j ∂ Ê sin j ∂ ˆ + sin j ∂ Ê cot q cos j ∂ ˆ
4p 2 ÍÎ ∂q Ë ∂q ¯ ∂q ÁË ∂j ˜¯

∂ Ê ∂ˆ ∂ Ê ∂ ˆ˘
+ cot q cosj ÁË sin j ˜¯ + cot q cos j Á cot q cos j
∂j ∂q ∂j Ë ∂j ˜¯ ˙˚

h 2 È 2 ∂2 Ï ∂ ∂ ∂2 ¸
=– Ísin j 2 + sin j cosj Ì (cot q ) + cot q ˝
4p 2 Î ∂q Ó ∂q ∂j ∂q ∂j ˛

Ï ∂ ∂ ∂2 ¸
+ cot q cos j Ì (sin j ) + sin j ˝
Ó ∂j ∂q ∂j ∂q ˛

Ï ∂ ∂ ∂2 ¸
+ cot q cos j cot q Ì (cos j ) + cos j 2 ˝
Ó ∂j ∂j ∂j ˛
 Wave Mechanics, Energy Quantization and Atomic Structure 175

h2 È 2 ∂ ∂
2
=– Ísin j - sin j cos j cosec2 q
2
4p Î ∂q 2
∂ j
∂2 ∂
+ sinj cosj cot q + cot q cos2 j
∂q ∂j ∂q
∂2 ∂
+ cot q cos j sin j – cot2q cosj sin j
∂j ∂q ∂j
∂2 ˘
+ cot 2 q cos 2 j ˙ (AIII.19)
2 ∂j 2 ˚
Expression of Ly We have
2 È h Ê ∂ ∂ ˆ˘
Ly = Ly Ly = Í ÁË cos j ∂q - cot q sin j ∂j ˜¯ ˙
Î 2pi ˚
È h Ê ∂ ∂ ˆ˘
Í 2pi ÁË cos j ∂q - cot q sin j ∂j ˜¯ ˙
Î ˚
h2 È ∂ Ê ∂ˆ ∂ Ê ∂ ˆ
=– + cos j Á - cot q sin j
4p 2 ÍÎcos j ∂q Ë cos j ∂q ¯ ∂q Ë ∂j ˜¯
∂ Ê ∂ˆ ∂ Ê ∂ ˆ˘
- cot q sin j ÁË cos j ˜¯ - cot q sin j Á - cot q sin j
∂j ∂q ∂j Ë ∂j ˜¯ ˙˚

=–
h2
4p 2
È 2 ∂2
Ícos j 2 – cos j sin j
Î ∂q
∂
∂q {
(cot q )
∂
∂j
+ cot q
∂2 ¸
˝
∂q ∂j ˛
Ï ∂ ∂ ∂2 ¸
– cot q sin j Ì (cos j ) + cos j ˝
Ó ∂j ∂q ∂j ∂q ˛
Ï ∂ ∂ ∂ 2 ¸˘
+ cot 2q sin j Ì (sin j ) + sin j 2 ˝˙
Ó ∂j ∂j ∂j ˛ ˚
h 2 È 2 ∂2 ∂
= - 2 Í
cos j 2 + cos j sin j cosec2 q
4p Î ∂q ∂j

∂2
– cos j sin j cot q + cot q sin 2 j ∂
∂q ∂j ∂q
∂2 ∂
– cot q sin j cos j + cot 2 q sin j cos j
∂j∂q ∂j
∂2 ˘
+ cot 2 q sin 2 j ˙ (AIII.20)
Expression of L 2z ∂j 2 ˚
We have
2 Ê h ∂ ˆÊ h ∂ ˆ h 2 ∂2
Lz = Lz Lz = Á = -
Ë 2pi ∂j ˜¯ ÁË 2pi ∂j ˜¯
(AIII.21)
4 p 2 ∂j 2
176 A Textbook of Physical Chemistry

Ÿ
Expression of L2 We have
2 2 2 2
L = Lx + L y + Lz (AIII.22)
Ÿ Ÿ
Writing L2x and L2y together, we get

2 h2 È ∂2 ∂
L =– 2 Í
(sin 2 j + cos 2 j ) 2 + cot q (sin2 j + cos2 j)
4p Î ∂q ∂q

∂2 ˘ h 2 ∂2
+ cot 2 q (sin 2 j + cos2 j) ˙ –
∂j 2 ˚ 4p 2 ∂j 2

h 2 È ∂2 ∂ ∂2 ˘
=– 2 Í
+ cot q + (cot 2 q + 1) 2 ˙
4 p Î ∂q 2
∂q ∂j ˚

h2 È ∂2 cos q ∂ ∂2 ˘
=– Í 2 + + cosec 2
q ˙
4p 2 Î ∂q sin q ∂q ∂j 2 ˚

h2 È 1 Ê ∂2 ∂ˆ 1 ∂2 ˘
=– Í Á sin q 2 + cos q ˜ + 2 ˙
4p 2 Î sin q Ë ∂q ∂q ¯ sin q ∂j 2 ˚

h2 È 1 ∂ Ê ∂ˆ 1 ∂2 ˘
=– Í sin q + ˙ (AIII.23)
4p 2 Î sin q ∂q Ë ∂q ¯ sin 2 q ∂j 2 ˚
ANNEXURE IV Commutators of Angular Momentum Operators

Ÿ Ÿ Ÿ Ÿ Ÿ Ÿ
Definition of The commutator of two operators a and b ab – ba .
Commutator Ÿ Ÿ
This is usually written as [ a , b ].
Ÿ Ÿ
Commuting and The two operators a and b are said to commute each other if their commutator
Noncommuting is equal to zero, i.e.
Operators Ÿ Ÿ Ÿ Ÿ Ÿ Ÿ
[ a , b ] = ab – ba = 0 (AIV.1)
If the commutator is not equal to zero, the two operators are said to be non-
commuting, i.e.
Ÿ Ÿ Ÿ Ÿ Ÿ Ÿ
[ a , b ] = ab – ba π 0 (AIV.2)

that these operators operate on an arbitrary function, say f. If

Ÿ Ÿ Ÿ Ÿ
ab f = ba f for all functions f,
Ÿ Ÿ
then a and b commute with each other and if
Ÿ Ÿ Ÿ Ÿ
ab f π ba f for all function f,
Ÿ Ÿ
then a and b do not commutate with each other.
Ÿ Ÿ
a = d/dx and b = x. Then
Ÿ Ÿ Ê dˆ d df
a b f = Á ˜ (x)f = (x f ) = x +f
Ë dx¯ dx dx
Ÿ Ÿ Ê dˆ Êdf ˆ
b a f = (x) Á ˜ f = x Á
Ë dx¯ Ë d x ˜¯
Ÿ Ÿ Ÿ Ÿ Ÿ Ÿ Ÿ Ÿ
Hence ab f – ba f = f i.e. ( a b – b a ) f = I f; (where I = unit operator)

Thus, the operators x and d/dx do not commute with each other.
Ÿ Ÿ
Eigenfunction If two operators a and b commute, then there exists a set of functions which are
of Commuting simultaneously eigenfunctions of both the operators.
Operators
A simple proof of the above statement is as follows.
Ÿ
Let y i be an eigenfunction of the operator a . Hence, we can write
Ÿ
a y i = a i yi
178 A Textbook of Physical Chemistry

Ÿ Ÿ Ÿ Ÿ
Let the operator b commute with the operator a . Since a and b commute,
we can write
Ÿ Ÿ Ÿ Ÿ Ÿ Ÿ
a b y i = b a yi = b (a iyi ) = a i ( b y i )
Ÿ Ÿ Ÿ
i.e. a ( b y i ) = ai ( b y i)
Ÿ Ÿ
This means that b y i is also an eigenfunction of the operator a and its
eigenvalue ai is the same as that of the function y i. This is possible only when
Ÿ
b y i is a multiple of yi, say biy i , where b i is a constant, i.e.
Ÿ
b yi = biy i
Ÿ
This equation implies that yi is also an eigenfunction of b with eigenvalue bi.
The converse of the above fact may be stated as follows.
If there exists a set of functions y1, y2, y3 , …, y i which are eigenfunctions
Ÿ Ÿ
of two operators a and b , then these two operators commute.
This converse fact may be proved as follows.
Ÿ Ÿ
Let y i be an eigenfunction of the operators a and b with eigenvalues ai and bi,
respectively. We can write
Ÿ Ÿ
a y i = aiyi and b y i = bi y i
Ÿ Ÿ Ÿ Ÿ Ÿ Ÿ
Now a b y i = a ( b yi) = a (biyi) = bi ( a y i) = biai y i
Ÿ Ÿ Ÿ Ÿ Ÿ Ÿ
b a y i = b ( a y i ) = b (aiy i ) = ai ( b y i ) = aibiy i
From these expressions, it follows that
Ÿ Ÿ Ÿ Ÿ Ÿ Ÿ Ÿ Ÿ
ab y i – ba y i = 0 or ( a b – b a )y i = 0
Ÿ Ÿ Ÿ
that is the commutator of a and b is zero. This implies that the operators a and
Ÿ
b commute.

Physical We know that

Significance of (i) The eigenvalue of a Hermitian operator is real.
Commutation
Rules (ii) A real eigenvalue implies that the physical quantity for which the operator
stands for can be measured experimentally.
(iii) The eigenvalues of two commuting operators can be computed by using
the common set of eigenfunctions.
From these facts, it follows that
If the two operators commute, then it is possible to measure simultaneously the
precise values of both the physical quantities for which operators stand for.
 Commutators of Angular Momentum Operators 179

If the two operators do not commute, then it is not possible to measure

simultaneously the precise values of both the physical quantities for which operators
stand for.

Commutator of The operator of px is (h/2pi) (d/dx).

the Operators x
and px Hence
Ê h dˆ h df
x px f = (x) Á f= x
Ë 2pi d x ˜¯ 2pi d x
Ê h dˆ h d hx d f h
px x f = Á ˜ (x) f = (x f ) = + f
Ë 2pi d x ¯ 2pi d x 2pi d x 2pi
[ px , x ] f = px x f – x px f

Ê hx d f h ˆ Ê h dfˆ h
= Á + f˜ – Á x ˜ = f
Ë 2p i d x 2p i ¯ Ë 2pi d x ¯ 2pi
h
Hence [ px , x ] = I
2pi
where I is the unit operator. Since px and x do not commute, the linear
momentum of the particle along the x-axis and its position along the x-axis cannot
be determined simultaneously.

Commutation Rules Amongst the Components of Angular Momentum

Commutator of We have
Ÿ Ÿ
Lx and Ly Ÿ Ÿ È h Ê ∂ ∂ ˆ˘ È h Ê ∂ ∂ ˆ˘
Lx Ly = Í Á y - z ˜˙ Í Á z - x ˜˙
Î 2p i Ë ∂z ∂y ¯ ˚ Î 2p i Ë ∂ x ∂ z¯˚

h2 È ∂ Ê ∂ ˆ ∂ Ê ∂ˆ ∂ Ê ∂ˆ ∂ Ê ∂ ˆ˘
=– Íy
4p 2 Î ∂ z ÁË z ∂ x ˜¯ - y ∂ z ÁË x ∂z ˜¯ - z ∂y ÁË z ∂ x ˜¯ + z ∂ y ÁË x ∂z ˜¯ ˙
˚
h2 ÈÊ ∂2 ∂ˆ Ê ∂2 ˆ Ê ∂2 ˆ Ê ∂2 ˆ ˘
=– ÍÁ y z + y ˜ - Á y x 2 ˜ - Á z2 ˜ +Á z x ˜˙
4p 2 ÍÎË ∂z ∂x ∂ x¯ Ë ∂z ¯ Ë ∂y ∂x ¯ Ë ∂y ∂z ¯ ˙˚
Ÿ Ÿ È h Ê ∂ ∂ ˆ˘È h Ê ∂ ∂ ˆ˘
Ly Lx = Í Á z - x ˜˙Í Á y - z ˜˙
Î 2p i Ë ∂ x ∂ z ¯ ˚ Î 2p i Ë ∂ z ∂ y¯˚

h2 È ∂ Ê ∂ˆ ∂ Ê ∂ˆ ∂ Ê ∂ˆ ∂ Ê ∂ ˆ˘
=–
4p 2
Íz
∂ x ÁË y ∂ z ˜¯ - z ∂ x ÁË z ∂y ˜¯ - x ∂ z ÁË y ∂ z ˜¯ + x ∂ z ÁË z ∂ y ˜¯ ˙
Î ˚

h2 ÈÊ ∂2 ˆ Ê 2 ∂2 ˆ Ê ∂2 ˆ Ê ∂2 ∂ ˆ ˘
=– ÍÁ z y ˜ - Á z ˜ - Á x y 2˜
+ Á x z +x ˜ ˙
4p 2 ÍÎË ∂x ∂z ¯ Ë ∂x ∂y ¯ Ë ∂ z ¯ Ë ∂z ∂y ∂ y¯ ˙˚
Hence,
180 A Textbook of Physical Chemistry

[Lx , L y ] = L x L y – L y L x

h2 Ê ∂ ∂ ˆ h2 Ê ∂ ∂ˆ
=– 2Á
y - x ˜ = 2 Áx -y ˜
4p Ë ∂ x ∂ y ¯ 4p Ë ∂ y ∂ x¯

ih È h Ê ∂ ∂ ˆ ˘ ih Ÿ
= Í Á x - y ˜˙ = Lz (AIV.3)
2p Î 2p i Ë ∂ y ∂ x ¯ ˚ 2p
Commutator of Proceeding similarly, it can be shown that
ih
Ly and Lz , and [L y , Lz ] = L y Lz - Lz L y = Lx (AIV.4)
2p
Lz and Lx
ih (AIV.5)
[Lz , Lx ] = Lz Lx - Lx Lz = Ly
2p

Implication of Since the commutators [ L x , L y ] , [ L y , L z ] and [ L z , L x ] are not equal to zero, it

the Commutation follows that the simultaneously determination of Lx and Ly, Ly and Lz, and Lz and
Rules Lx are not possible. This, in turn, implies that if the value of any one component
(say, Lz) is determined precisely then the other two components (say, Lx and Ly)
cannot be determined precisely at the same time.
Commutation Rules Between the Square of Angular Momentum and
the Components of Angular Momentum

Commutator of L2 We have
and Lx 2 2
[L , Lx = L Lx - Lx L
2

Since L2 = L2x + L2y + L2z , we get

2
( 2 2 2
)
[L , L x ] = L x + L y + L z L x - L x L x + L y + L z ( 2 2 2
)
2 2 2 2 2 2
= Lx Lx + L y Lx + Lz Lx - Lx Lx - Lx L y - Lx Lz

( 2 2
) ( 2
= Lx Lx - Lx Lx + L y Lx - Lx L y + Lz Lx - Lx Lz
2
) ( 2 2
)
( 2 2
= L y Lx - Lx L y + Lz Lx - Lx Lz) ( 2 2
) (AIV.6)

To evaluate each of the two terms in the right side of Eq. (AIV.6), we proceed
as follows
2 2
L y Lx - Lx L y = L y L y Lx - Lx L y L y
 Commutators of Angular Momentum Operators 181

Adding and subtracting the term L y L x L y , we get

2 2
L y Lx - Lx L y = L y L y Lx - L y Lx L y + L y Lx L y - Lx L y L y

= L y (L y Lx - Lx L y ) + (L y Lx - Lx L y ) L y

Ê ih ˆ Ê ih ˆ
= Ly Á- Lz + - Lz L y
Ë 2p ˜¯ ÁË 2p ˜¯

(
= – i h L y Lz + Lz L y
2p
) (AIV.7)

Similarly,
2 2
Lz Lx - Lx Lz = Lz Lz Lx - Lx Lz Lz
Adding and subtracting the term L z L x L z , we get
2 2
Lz Lx - Lx Lz = Lz Lz Lx - Lz Lx Lz + Lz Lx Lz - Lx Lz Lz

= Lz (Lz Lx - Lx Lz ) + (Lz Lx - Lx Lz ) Lz
Ê ih ˆ Ê ih ˆ
= Lz Á Ly + L y Lz
Ë 2p ˜¯ ÁË 2p ˜¯
ih
= (
L L + L y Lz
2p z y
) (AIV.8)

Substituting Eqs (AIV.7) and (AIV.8) in Eq. (AIV.6), we get

2 È ih ˘ È ih ˘
[ L , L x ] = Í- ( L y L z + L z L y )˙ + Í ( L z L y + L y L z )˙ = 0
Î 2p ˚ Î 2p ˚
Commutator of L2 Proceeding similarly, we can prove that
2
[L , L y ] = 0 (AIV.9)
and Ly and L2
2
and Lz [L , L z ] = 0 (AIV.10)
Comment Equations (AIV.9) and (AIV.10) also follow from the fact that the
designation x-, y- and z-axes are matter of convenient only. All the three axes are
equivalent and can be designated in any manner.)
Physical We have the following commutation rules.
Significance of 2
Commutation (i) The operator L commute with each of the three components L x , L y and
Rules Lz .
(ii) No two components amongst L x , L y and L z commute with each other.
From these rules, it follows that
182 A Textbook of Physical Chemistry

(
The value of L2 or L = L2 ) and any one component (say, L x or Ly or Lz) can
Lz (i.e.
component of angular momentum along z-axis, which is the direction of magnetic
Lz L2, then the values of Lx
and Ly
principle. Had the values of all the three components Lx, Ly and Lz
precisely, this will lead to the precise location of the axis of rotation along which
the linear momentum (having zero value) is precisely known. This will violate the
uncertainty principle as the precise values of linear momentum in any direction
and location of this direction cannot be determined simultaneously.
ANNEXURE V Transformation of Laplacian Operator from Cartesian
Coordinates to Spherical Polar Coordinates

The Laplacian operator is

∂2 ∂2 ∂2
— 2
= + + (AV.1)
∂x 2 ∂y 2 ∂z 2

In Annexure III, we have derived the following expressions.

∂ ∂ Ê cos q cos j ˆ ∂ Ê sin j ˆ ∂

= (sin q cos j) +Á ˜¯ + -
∂x ∂r Ë r ∂ q ÁË r sin q ˜¯ ∂j

∂ ∂ Ê cos q cos j ˆ ∂ Ê cos j ˆ ∂

= (sin q sin j) +Á ˜¯ +
∂y ∂r Ë r ∂ q ÁË r sin q ˜¯ ∂j

∂ ∂ Ê sin q ˆ ∂
= (cos q ) +Á- ˜
∂z ∂ r Ë r ¯ ∂q

We now derive the expressions of ∂2/∂ x2, ∂2/∂y2 and ∂2/∂z2.

∂2 È ∂ cos q cos j ∂ sin j ∂ ˘

= Ísin q cos j + - ˙
∂x 2
Î ∂r r ∂ q r sin q ∂ j ˚

È ∂ cos q cos j ∂ sin j ∂ ˘

Ísin q cos j + - ˙
Î ∂ r r ∂ q r sin q ∂ j ˚

È ∂2 cos q cos j ∂
= sin q cos j Ísin q cos j 2 -
Î ∂r r2 ∂q

cos q cos j ∂2 sin j ∂ sin j ∂2 ˘

+ + 2 - ˙
r ∂ r ∂q r sin q ∂j r sin q ∂ r ∂j ˚

cos q cos j È ∂ ∂2 sin q cos j ∂

+ Ícos q cos j + sin q cos j -
r Î ∂ r ∂ q ∂ r r ∂q

cos q cos j ∂2 sin j cos q ∂ sin j ∂2 ˘

+ + - ˙
r ∂q 2 r sin 2 q ∂j r sin q ∂ q ∂ j ˚
184 A Textbook of Physical Chemistry

sin j È ∂ ∂2 cos q sin j ∂

– Í- sin q sin j + sin q cos j -
r sin q Î ∂r ∂j ∂ r r ∂q
cos q cos j ∂2 cos j ∂ sin j ∂2 ˘
+ - - ˙
r ∂ j ∂q r sin q ∂j r sin q ∂j 2 ˚

∂2 cos q Ê sin 2 j ˆ ∂
2
= sin q cos j 2 + 2 Á
- 2 sin q cos 2 j ˜
∂ r2 r Ë sin q ¯ ∂q

2 sin q cos q cos 2 j ∂2 sin j cos j È cos 2 q 1 ˘ ∂

+ + Í1 + + 2 ˙
r ∂ r ∂q r 2
Î sin q sin q ˚ ∂j
2

2 cos j sin j ∂2 1 ∂
– + (cos2q cos2j + sin2j)
r ∂ r ∂j r ∂r

2 cos q cos j sin j ∂2 cos 2 q cos 2 j ∂ 2 sin 2 j ∂ 2

– + +
r 2 sin q ∂q ∂j r2 ∂ q 2 r 2 sin 2 q ∂j 2
Similarly, we can proceed to show that
∂2 ∂2 cos q È cos 2 j ˘ ∂
= sin2q sin2j + 2 Í
- 2 sin q sin 2 j ˙
∂ y2 ∂ r2 r Î sin q ˚ ∂q

2 cos q sin q sin 2 j ∂2 sin j cos 2 j È cos 2 q 1 ˘ ∂

+ - Í1 + + 2 ˙
r ∂ r ∂q r 2
Î sin q sin q ˚ ∂j
2

2 cos j sin j ∂2 1
+ + (cos2j + sin2j cos2q ) ∂
r ∂ r ∂j r ∂r
2 cos q cos j sin j ∂2 cos 2 q sin 2 j ∂ 2 cos 2 j ∂2
+ + + 2 2
2
r sin q ∂q ∂j r 2
∂q 2
r sin q ∂ j 2

∂2 ∂2 2 sin q cos q ∂ 2 cos q sin q ∂2

= cos2q + -
∂ z2 ∂ r2 r2 ∂q r ∂ r ∂q

sin 2 q ∂ sin 2 q ∂2
+ + 2
r ∂r r ∂q 2
With these derivatives, Eq. (AV.1) becomes

Ê ∂2 2 ∂ ˆ Ê 1 ∂2 1 cos q ∂ ˆ 1 ∂2
—2 = Á 2 + ˜ +Á 2 + ˜ +
Ë ∂r r ∂ r ¯ Ë r ∂ q 2 r 2 sin q ∂ q ¯ r 2 sin 2 q ∂ j 2

1 ∂ Ê 2 ∂ˆ 1 ∂ Ê ∂ ˆ 1 ∂2
= r + sin q +
r 2 ∂ r ÁË ∂ r ˜¯ r 2 sin q ∂ q ÁË ∂ q ˜¯ r 2 sin 2 q ∂ j 2
ANNEXURE VI Splitting of Schrödinger Equation of Hydrogen Atom

The Schrödinger equation for hydrogen atom can be split into two equations
representing respectively the motion of centre of mass of atom and the motion of
electron relative to the nucleus within the atom.

The coordinates of centre of mass is

mn xn + me xe m y + me ye m z + me ze
xc = ; yc = n n ; zc = n n
mn + me mn + me mn + me
(AVI.1)

coordinates as
x = xn – xe ; y = yn – ye ; z = z n – ze (AVI.2)
By chain rule, we write

∂ ∂xc ∂ ∂x ∂
= +
∂xn ∂xn ∂xc ∂xn ∂x

∂2 Ê ∂ ˆ Ê ∂ ˆ È ∂xc ∂ ∂x ∂ ˘ È ∂xc ∂ ∂x ∂ ˘
= Á ˜ Á ˜ =Í + ˙Í + ˙
∂xn2 Ë ∂xn ¯ Ë ∂xn ¯ Î ∂xn ∂xc ∂xn ∂x ˚ Î ∂xn ∂xc ∂xn ∂x ˚

2 2
Ê ∂x ˆ ∂ 2 Ê ∂x ˆ ∂ 2 Ê ∂xc ˆ Ê ∂x ˆ ∂2
= Á c˜ + + 2 (AVI.3)
Ë ∂xn ¯ ∂xc2 ÁË ∂xn ˜¯ ∂x 2 ÁË ∂x ˜¯ ÁË ∂x ˜¯ ∂x ∂x
n n c

Now from Eqs (AVI.1) and (AVI.2), we get

∂xc mn ∂x
= and =1
∂xn mn + me ∂xn
With these, Eq. (AVI.3) becomes
2
∂2 Ê mn ˆ ∂2 ∂2 2 mn ∂2
=Á + + (AVI.4)
∂xn2 Ë mn + me ˜¯ ∂xc2 ∂x 2 mn + me ∂xc ∂x
Similar expressions for yn and zn components are
2
∂2 Ê mn ˆ ∂2 ∂2 2 mn ∂2
= Á + + (AVI.5)
∂yn2 Ë mn + me ˜¯ ∂yc2 ∂y 2 mn + me ∂yc ∂y

2
∂2 Ê mn ˆ ∂2 ∂2 2 mn ∂2
= Á ˜ + 2+ (AVI.6)
∂zn2 Ë mn + me ¯ ∂zc ∂z
2
mn + me ∂zc ∂z
186 A Textbook of Physical Chemistry

Similarly, we have
∂ ∂x ∂ ∂x ∂
= c +
∂xe ∂xe ∂xc ∂xe ∂x

∂2 Ê ∂ ˆ Ê ∂ ˆ È ∂xc ∂ ∂x ∂ ˘ È ∂xc ∂ ∂x ∂ ˘
=Á ˜ Á ˜ =Í + ˙Í + ˙
∂xe2 Ë ∂xe ¯ Ë ∂xe ¯ Î ∂xe ∂xc ∂xe ∂x ˚ Î ∂xe ∂xc ∂xe ∂x ˚

2 2
Ê ∂xc ˆ ∂2 Ê ∂x ˆ ∂2 Ê ∂x ˆ Ê ∂x ˆ ∂ 2
= Á ˜ +Á ˜ + 2Á c ˜ Á (AVI.7)
Ë ∂xe ¯ ∂xc Ë ∂xe ¯ ∂x
2 2
Ë ∂xe ¯ Ë ∂xe ˜¯ ∂xc ∂x

From Eqs (AVI.1) and (AVI.2), we get

Ê ∂xc ˆ me ∂x
ÁË ∂x ˜¯ = m + m and
∂xe
=–1
e n e

With these, Eq. (AVI.7) becomes

2
∂2 Ê me ˆ ∂2 ∂2 2 me ∂2
= Á ˜ + - (AVI.8)
∂xe2 Ë mn + me ¯ ∂xc2 ∂x 2 mn + me ∂xc ∂x
Similar expressions for ye and ze components are
2
∂2 Ê me ˆ ∂2 ∂2 2 me ∂2
= + - (AVI.9)
∂ye2 ÁË mn + me ˜¯ ∂yc2 ∂y 2 mn + me ∂yc ∂y
2
∂2 Ê me ˆ ∂2 ∂2 2 me ∂2
= + - (AVI.10)
∂ze2 ÁË mn + me ˜¯ ∂zc2 ∂z 2 mn + me ∂zc ∂z
The Schrödinger equations for hydrogen atom is
È h 2 Ê ∂2 ∂2 ∂2 ˆ h 2 Ê ∂2 ∂2 ∂2 ˆ
Í- 2 Á 2 + 2 + 2 ˜ - 2 Á 2 + 2 + 2 ˜
ÍÎ 8 p me Ë ∂xe ∂ye ∂ze ¯ 8 p mn Ë ∂xn ∂yn ∂zn ¯

Z e2 ˘
– ˙ Y = Etotal Ytotal
(4 p e 0 ) r ˚ total

Substituting Eqs (AVI.4) to (AVI.6) and Eqs (AVI.8) to (AVI.10), we get

È h2 Ê ∂2 ∂2 ∂2 ˆ
Í- 2 Á 2 + 2
+ 2˜
ÍÎ 8p (mn + me ) Ë ∂xc ∂yc ∂zc ¯

h2 Ê 1 1 ˆ Ê ∂2 ∂2 ∂2 ˆ Z e2 ˘
- + Á + + ˜ - ˙y
8p Ë me mn ˜¯ Ë ∂x
2 Á = Etotal ytotal
2
∂y 2
∂z ¯ (4p e 0 ) r ˙˚ total
2

(AVI.11)
 Wave Mechanics, Energy Quantization and Atomic Structure 187

If the distance r between electron and nucleus is expressed in the relative

coordinates, we see that the operator in Eq. (AVI.11) consists of two terms, each
depending on the two sets of independent coordinates. Hence, we can write
Ytotal = yc ye (AVI.12)
where yc describes the motion of centre of mass of hydrogen atom and ye describes
the motion of electron relative to the nucleus within the atom. Substituting
Eq. (AVI.12) in Eq. (AVI.11), we get

h2 Ê ∂2 ∂2 ∂2 ˆ
– ye Á 2 + 2
+ 2 ˜ yc
2
8p (mn + me ) Ë ∂ xc ∂ yc ∂ zc ¯

h2 Ê 1 1 ˆ Ê ∂2 ∂2 ∂2 ˆ
– + y Á + + ˜ ye
8 p Ë me mn ˜¯ Ë ∂ x
2Á c 2 2
∂y ∂ z2 ¯

Z e2
– yc ye = Etotal yc ye
(4 p e 0 ) r
Dividing throughout by ye yc, we get

h2 1 Ê ∂2 ∂2 ∂2 ˆ
– Á + + ˜ yc
8 p 2 (mn + me ) y c Ë ∂ xc2 ∂ yc2 ∂ zc2 ¯

h2 Ê 1 1 ˆ 1 Ê ∂2 ∂2 ∂2 ˆ
– + Á + + ˜y
8 p 2 ÁË me mn ˜¯ y e Ë ∂ x 2 ∂ y 2 ∂ z 2 ¯ e

Z e2
– = Etotal (AVI.13)
(4 p e 0 ) r
xc, yc and
zc and the second and third terms taken together on the coordinates x, y and z, and
the sum of these two terms is a constant. This is possible if each term is separately
constant. Writing
Etotal = Etrans + Eelec (AVI.14)
we can write
h2 Ê ∂2 ∂2 ∂2 ˆ
– 2 Á 2 + 2
+ 2 ˜ yc = Etrans yc (AVI.15)
8p (mn + me ) Ë ∂ xc ∂ yc ∂ zc ¯

È h 2 Ê ∂2 ∂2 ∂2 ˆ Z e2 ˘
and Í- 2 Á 2 + + 2˜ - ˙ ye = Eelec ye (AVI.16)
ÍÎ 8 p m Ë ∂ x ∂y 2
∂ z ¯ (4 p e 0 ) r ˙˚

1 1
where + has been replaced by 1/m , where m is the reduced mass of electron.
me mn
ANNEXURE VII Atomic Units

In the calculations of atomic and molecular quantities, the system of atomic units
is widely used. In this system, the electronic mass (me), the electronic charge (e),
the basic unit of angular momentum (h/2p) and the permittivity (4 pe0) are assigned
a value of unity. Thus
me = 1, e = 1, h/2p = 1 and 4pe0 = 1
All other physical quantities can be expressed in terms of the atomic units. The
following derived atomic units are also used.
1. Length The length is expressed in the atomic unit of length known as a Bohr.

( h / 2p ) 2
a0 = =1
me (e / 4pe 0 ) 2
2. Energy The energy is expressed in the atomic unit of energy known as a
hartree. This is twice of the ionization energy of atomic hydrogen. Thus

me (e / 4pe 0 ) 4 (e / 4p e 0 ) 2
Eh = = =1
( h / 2p ) 2 a0
3. Time The time is expressed in the atomic unit of time which is the period of

( h / 2 p )3
t0 = =1
me (e / 4p e 0 ) 4
4. Speed The speed is expressed in the atomic unit of speed which is the speed

(e / 4 p e 0 ) 2
c0 = =1
( h / 2p )
5. Electric potential This is expressed in atomic unit of potential which

i.e.
Potential energy of an electron in the first Bohr orbit
V0 =
Electronic chaarge

(e / 4pe 0 ) 2 / a0 e
= = =1
e (4p e 0 ) a0

6. Magnetic dipole moment This is expressed in the atomic unit of magnetic

 Wave Mechanics, Energy Quantization and Atomic Structure 189

e(h / 2p)
p0 = 2 m = =1
me
Table AVII.1 records the values of atomic units in terms of SI equivalents.
The Hamiltonian operator when written in terms of atomic units becomes
independent of any physical constants. For example, the Hamiltonian operator
( h 2p ) 2 2 ( h 2p ) 2 2 Ze 2 Ze 2 e2
H =– —1 - —2 - - +
2me 2me (4p e 0 ) r1 (4p e 0 ) r2 (4p e 0 ) r12

1 2 1 2 Z Z 1
H =– —1 - — 2 - - +
2 2 r1 r2 r12

Table AVII.1 Values of Atomic Units in SI Units

Atomic unit SI equivalent
me = 1 9.109 4 ¥ 10–31 kg
e=1 1.602 2 ¥ 10–19 C
h/2p = 1 1.054 6 ¥ 10–34 J s
4 p e0 = 1 1.112 6 ¥ 10–10 C2 J–1 m–1
a0 = 1 bohr 5.291 77 ¥ 10–11 m
Eh = 1 hartree 4.359 75 ¥ 10–18 J
t0 = 1 2.418 89 ¥ 10–17s
c0 = 1 2.18 77 ¥ 106 m s–1
V0 = 1 27.211 V
p0 = 1 1.854 64 ¥ 10–23 J T –1
ANNEXURE VIII The Ladder-Operator Method Applied to Angular
Momentum

The ladder-operator method can be used to determine the eigenvalues of square

and z-compouent of angular momentum arising due to orbital or spin motion of a
particle. We use symbol M instead of L to indicate that we may deal with either
type of angular momentum.
Definition of the
Ladder-Operators
M + = M x + i M y and M – = M x – i M y (AVIII.1)

Naming M + and M – as the ladder-operators will be described shortly. These are

also named as the raising operator and the lowering operator, respectively.

Expressions of We have
M+ M– and M+ M–
M + M – = ( M x + i M y)( M x – i M y)

= M 2x – i M x M y + i M y M x + M 2y

= ( M 2x + M 2y) – i( M x M y – M y M x)

= ( M 2 – M 2z – i Ê ˆ
ih
Ë 2p M z ¯
h
= M 2 – M 2z + Mz (AVIII.2a)
2p
Similarly, it can be worked out that
h
M – M + = M 2 – M 2z – Mz (AVIII.2b)
2p
Commutators of We have
M+ and M– with Mz [ M +, M z] = M + M z – M z M +
= ( M x + i M y) M z – M z ( M x + i M y)
= Mx Mz + i My Mz – Mz Mx – i Mz My
= ( M x M z – M z M x) + i( M y M z – M z M y)

My + i Ê M ˆ
ih ih
=–
2p Ë 2p x ¯
h h
=– ( M x + i M y) = – M+ (AVIII.3a)
2p 2p
Similarly, it can be worked out that
h
[ M – , M z] = M – M z – M z M – = M– (AVUL3b)
2p
 Wave Mechanics, Energy Quantization and Atomic Structure 191

Commutators of We have
M+ and M– [ M + , M 2] = M + M 2 – M 2 M +
2
with M
= ( M x + i M y ) M 2 – M 2 ( M x + i M y)
= Mx M2 + i My M2 – M2 Mx – i M2 My
= ( M x M 2 – M 2 M x) + i( M y M 2 – M 2 M y)
= [ M x, M 2] + i[ M y, M 2]
= 0 + i(0) = 0 (AVIII.4a)
Similarly, it can be worked out that
[ M _, M 2] = 0 (AVIII.4b)
2
Eigenvalue Since M and M z commute with each other, they will have the common set of
Expressions for eigenfunctions, we may write the eigenvalue expressions as
M2 and Mz M zY = bY (AVIII.5)
2
M Y = cY (AVIII.6)
Successive Operating M + on Eq. (AVIII.6), we get
Operations of M+ M +( M 2Y) = M + (cY)
and M– on
Eq. (AVIII.6) Since M + and M 2 commute with each other, we write the above expression as
M 2( M +Y) = c ( M +Y) (AVIII.7)
2
that is, the function M +Y is also an eigenfunction of M with the same eigenvalue
as that of the function Y.
Operating M + on Eq. (AVIII.7) would give

M + [ M 2( M +Y)] = M +[c( M +Y)}

or ( M + M 2)( M +Y) = c M +( M +Y) or ( M 2 M +)( M +Y) = c M 2+Y
or M 2( M 2+Y) = c( M 2+ Y)
that is, the function M 2+ Y is also an eigenfunction of M 2 with the same eigenvalue c.
The successive application of M + on Eq. (AVIII.6) would give
M 2 ( M k+ Y) = c( M k+ Y) (AVIII.8a)
Similarly, it can be worked out that
M 2 ( M k– Y) = c( M k– Y) (AVIII.8b)
Equations (AVIII.8a) and (AVIII.8b) may be written together as
M 2 ( M k+ Y) = c( M k+ Y) (AVIII.9)
Successive Operating M + on Eq. (AVIII.5), we get
Operations of M+ M + ( M z Y) = M +(bY) (AVIII.10)
and M– on
Eq. (AVIII.5)
192 A Textbook of Physical Chemistry

From Eq. (AVIII.3a), we get

h
[ M + , M z] = M + M z – M z M + = – M+
2p
h
i.e. M + M z = M z M +– M+ (AVIII.11)
2p
With this, Eq. (AVIII.10) becomes

Ê M M - h M ˆ Y = M (bY)
Ë z + 2p + ¯ +

or M z ( M + Y ) = (b + h/2p) ( M + Y ) (AVIII.12)
that is, the function M + Y is an eigenfunction of M z with eigenvalue b + h/2p. In
other words, operating on the eigenfunction Y with the raising operator M + converts
the function Y into M + Y with the eigenvalue h/2p higher than the eigenvalue of Y.
It is for this reason, the operator M + is known as the raising operator.
Operating M + on Eq. (AVIII. 12), we get

M + [ M z ( M + Y )] = M + [(b + h/2p)( M + Y )]
which on using Eq. (AVIII.11) becomes

Ê M M - h M ˆ ( M Y ) = (b + h/2p)( M 2 Y )
Ë z + 2p + ¯ + +

M z ( M +2Y ) = ÊË b + 2 ˆ¯ ( M +2Y )
h
or
2p
that is, the successive operation of M + on Eq. (AVIII.5) raises each time the
eigenvalue by h/2p. Thus, we can write

M z ( M +k Y ) = ÊË b + k ˆ¯ ( M +k Y )
h
(AVIII.13a)
2p
Similarly, we can worked out that
Ê hˆ
M z ( M –k Y ) = Ë b - k ¯ ( M –k Y ) (AVIII.13b)
2p
Equations (AVIII.13a) and (AVIII.13b) may be written together as

Ë 2p ¯
k
(
M z ( M k± Y ) = Ê b ± k ˆ M ± Y
h
) (AVIII.14)

Equation (AVIII.14) displays that the eigenvalues of M z are spaced at intervals

of h/2p.
Relation Between We have
the Constants
b and c M 2 ( M k± Y ) = c( M k± Y ) (Eq. AVIII.9)

M z ( M k±Y ) = Ê b ± k ˆ M ± Y
Ë
h
2p ¯
k
( ) (Eq. AVIII.14)
 Wave Mechanics, Energy Quantization and Atomic Structure 193

Operating M z on Eq. (AVIII.14), we get

k
Î 2p
(
M z [ M z( M ± Y )] = M z ÈÍÊË b ± k ˆ¯ M ± Y ˙˘
h k
˚
)
= ÊË b ± k ˆ¯ [ M z( M ± Y )]
h k
2p
2
= Êb ± k h ˆ ( M ± Y )
k
(AVIII.15)
Ë 2p ¯
Since M 2 = M 2x + M 2y + M 2z, we can write Eq. (AVIII.9) as
k k k
( M x2 + M 2y)( M ± Y)+ M 2z ( M ± Y ) = c( M ± Y )
which on using Eq. (AVIII.15) becomes

( M 2x + M 2y)( M ± Y ) = Íc - Ê b ± k ˆ ˙ ( M ±Y )
k È h 2˘ k

Î Ë ¯
2p ˚
2 2
The operators M x and M y correspond to non-negative physical quantities and
hence will have non-negative eigenvalues. Hence, we will have
h 2
c - ÊË b ± k ˆ¯ > 0 (AVIII.16)
2p
Upper Bounds of
the Values of b with increase in the value of k. In order that Eq. (AVIII.16) holds good, the value
of k will have upper bounds. Let these be represented as k¢ and k¢¢ for plus and
minus combinations, respectively. The corresponding functions may be written as
Ymax= M k+¢ Y and Ymin = M k-¢¢ Y

M z Ymin = ÊË b - k ¢¢ ˆ¯ Ymin
h
M z Ymax = Ê b + k ¢ ˆ Ymax
h
with and
Ë 2p ¯ 2p
For a value of k greater than k' or k",
accounted for by writing
M + Ymax = 0 and M – Ymin = 0 (AVIII.17)
Operating M – on M +Ymax, we get
M – ( M +Ymax) = 0
which on using Eq. (AVIII.2b) becomes
ÊM2 - M2 - h M ˆ Y = 0 (AVIII.18)
Ë z
2p
z
¯ max
h
This gives c – b2max – bmax= 0. (AVIII.l9a)
2p
Similarly operating M –Ymin by M + and then using Eq. (AVIII.2a), we get
h
c – b2min + bmin= 0 (AVIII.19b)
2p
194 A Textbook of Physical Chemistry

Eliminating c in Eqs (AVIII.19a) and (AVIII.19b), we get

h h
b2max + bmax = b2min – bmin
2p 2p

b + k ¢ ÊË ˆ¯ = - ÈÍb - k ¢¢ ÊË ˆ¯ ˙˘
or bmax = – bmin i.e. h h
2p Î 2p ˚

or b= ( 2 )
k ¢¢ - k ¢ Ê h ˆ
Ë 2p ¯ (AVIII.20)

The expressions of bmax and bmin become

bmax = b + k¢ Ê h ˆ =
Ë 2p ¯
k ¢¢ - k ¢ Ê h ˆ
2 Ë 2p ¯ (
+ k¢ Ê h ˆ)
Ë 2p ¯

= ( 2 )
k ¢¢ + k ¢ Ê h ˆ
Ë 2p ¯
(AVIII.21)

bmin = – bmax = – ( 2 )
k ¢¢ + k ¢ Ê h ˆ
Ë 2p ¯ (AVIII.22)

The expression of c is
k ¢¢ + k ¢ h ˆ 2
c = b2max + ÊË ˆ¯ bmax = ÊË ◊ ¯ + Ê ˆ Ê k ¢¢ + k ¢ ◊ h ˆ
h h
2p 2 2p Ë 2p ¯ Ë 2 2p ¯

= (
k ¢¢ - k ¢
2 ) Ê k ¢¢ + k ¢ ˆ Ê h ˆ 2
Ë 2 + 1¯ Ë 2p ¯
(AVIII.23)

Writing (k" + k')/2 by l, we get

bmax = l (h/2p) and bmin = – l (h/2p) (AVIII.24)
2
c = l(l + 1)(h/2p) (AVIII.25)
Since b changes in a step of h/2p (Eq. AVIII.14), we cover the entire range from
bmin to bmax by writing the expression
b = m (h/2p) (AVIII.26)
where m varies from –l to +l with a stepwise increase of one, i.e.
–l, – (l – 1), ..., (l – 1), l (AVIII.27)
The value of l may be integral or half-integral depending upon the even or odd
value of k" + k'.
Case 1 l has integral values In the case, k' = k", b = 0. (Eq. AVIII.20)
k ¢ + k ¢¢
Moreover, l= = integral value
2
For this case, we have
È Ê h ˆ˘
M z ( M m± Y ) = Ím Ë ¯ ˙ ( M m± Y ) m = 0, ± 1, ± 2, ..., ± l
Î 2p ˚
 Wave Mechanics, Energy Quantization and Atomic Structure 195

(M Y ) = l (l + 1) ÊË 2hp ˆ¯ (M Y );
2
2 l l
M ± ± l = 0, 1, 2, ...

Case 2 l has half-integral values For a case where k" = k' + 1, b = (1/2)(h/2p) and
the value of l will be
k ¢ + k ¢¢ k ¢ + k ¢ + 1 1
l= = = k ¢ + = half-integral values.
2 2 2
For this case, we have
m
( h
Î 2p ˚
)
M z M ± Y = ÈÍm ÊË ˆ¯ ˘˙ M ± Y ;
m
( ) m=±
1 3
,± , º ± l
2 2

(M Y ) = l (l + 1) ÊË 2hp ˆ¯ (M Y );
2
2 l l 1 3 5
M ± ± l= , , ,…
2 2 2
Explicit Form of The function Y depends on two numbers l and m and is written as Yl, m such that
the Functions Y
h 2
M 2Yl, m= l (l + 1) ÊË ˆ¯ Yl, m (AVIII.28)
2p

M zYl, m= m Ê ˆ Yl, m
h (AVIII.29)
Ë 2p ¯
The subscript l and m in Y l, m characterise the eigenvalues of M 2 and
M z respectively.
As stated above, the value of m varies from – l to + l with a stepwise increase
of one.

Expressions Since the z-component of angular momentum for the function M +Yl, m is h/2p
Relating Yl,m with higher than that of the function Yl, m , we may write the function M +Yl, m as
Yl,m + 1 and Yl,m – 1
M +Yl, m=K+ Yl, m + 1 (AVIII.30)
where K+ is a suitable multiplier. Similarly, we may write

M – Yl, m=K– Yl, m – 1 (AVIII.31)

Evaluation of Multiplier K+ Multiplying each side of Eq. (AVIII.30) by its

complex conjugate followed by integration, we get

Ú ( M +Yl, m)* ( M +Yl, m) dt = K 2+ Ú Y *l, m+1 Y l, m + 1 dt (AVIII.32)†

Assuming the function Yt, m's to constitute orthonormal set, we get

K 2+ = Ú ( M +Yl, m)* ( M +Yl, m)dt = Ú ( M +Yl, m)* ( M x + i M y)Yl, m dt

= Ú ( M +Yl, m)* M xYl, m dt + i Ú ( M +Yl, m)* M yYl, m dt (AVIII.33)

†
We assume that the multiplier K+ has a real value.
196 A Textbook of Physical Chemistry

Using the Hermitian property of M x and M y, Eq. (AVIII.33) can be written as

K 2+ = Ú Yl , m M *x ( M + Yl , m )* dt + i Ú Yl , m M *y ( M +Yl , m )* dt

Ú Yl , m (M x + i M y )(M + Yl , m ) dt
* * *
=

Ú Yl , m (M *x + i M *y )(M *x - i M y )Y *l , m dt
*
=

Taking the complex conjugate of the above expression, we get

Ú Yl , m (M x - i M y )(M x + i M y ) Yl , mdt
*
K +2 =

Ú Yl , m [M x + M y + i(M x M y - M y M x ]Yl , mdt

* 2 2
=

È - M z + i ÊË
ih
M z ˆ¯ ˙˘ Yl , m dt
Ú Yl , m ÍÎM
* 2 2
=
2p ˚

È h 2 h 2 h ˘
= Íl ( l + 1) Ê ˆ - m 2 Ê ˆ - Ê ˆ m Ê ˆ ˙ Ú Yl*, m Yl , m dt
h
Î Ë 2p ¯ Ë 2p ¯ Ë 2p ¯ Ë 2p ¯ ˚

h 2 h 2
= [l ( l + 1) - m 2 - m] Ê ˆ = [(l 2 - m 2 ) + (l - m) ]Ê ˆ
Ë 2p ¯ Ë 2p ¯

( l - m ) (l + m + 1) Ê
hˆ
i.e. K+ = (AVIII.34)
Ë 2p ¯
Evaluation of Multiplier K_ Proceeding similarly, it can be worked out that

( l + m ) (l - m + 1) Ê
K– = hˆ (AVIII.35)
Ë 2p ¯

Expression for the The function Yl,l can be determined by using the expression
Function Yl,l
M+ Yl, l = 0 (AVIII.36)

Expression of M+ The operator M + is

M+ = Mx + i My

h Ê ∂ ∂ ˆ h Ê ∂ ∂ ˆ
=– Á sin j + cot q cos j ˜ +i Á cos j - cot q sin j
2pi Ë ∂q ∂j ¯ 2pi Ë ∂q ∂j ˜¯

h È ∂ ∂
=
Í (cos j + i sin j ) + i cot q (cos j + i sin j ) ˘˙
2p Î ∂q ∂j ˚
 Wave Mechanics, Energy Quantization and Atomic Structure 197

∂ ∂ ˆ
= Ê ˆ (eij ) ÊÁ
h
+ i cot q (AVIII.37)
Ë 2p ¯ Ë ∂q ∂j ˜¯

Since the operator M + involves q and j variables, we write the funcition Y as

Yl, m = Qq Fj (AVIIL38)

Form of the Function Fj The form of the function Fj may be determined by

using the expression

M z Yl, m = m Ê ˆ Yl , m
h
(Eq. AVIII.29)
Ë 2p ¯
Since M z = (h/2pi) ∂/∂j, we have
h ∂
Qq Fj = m ÊË ˆ¯ Qq Fj
h
2pi ∂j 2p

Fj = m ÊË ˆ¯ Qq Fj
h d h
or Qq
2pi dj 2p

Cancelling (h/2p)Qq, we get

dF dF
= i mF or = i m dj
dj F

or In F = i m j + constant or F = Aeimj (AVIII.39)

From the boundary condition Fj = Fj+2p ,we get

Aeimj = Aeim (j + 2p) or l = e2p im

or cos(2p m) + i sin (2p/m) = 1

This will hold good if m = 0, ± 1, ± 2,....

The constant A is determined by the normalization of the function F, i.e.
2p

Ú F *F dj = 1
0

This gives
2p
A2 Ú e - i mj ei mj dj = 1
0
2p
or A2 Ú dj = 1 or A2(2p) = 1 or A=1 2p
0
198 A Textbook of Physical Chemistry

Hence, the function F is

1 - i mj
Fm= e ; m = 0 , ± l , ± 2 , ... (AVIII.40)
2p
With this, the function Yl, m becomes

Yl, m = Ê Qq
1 i mj ˆ
e (AVIII.41)
Ë 2p ¯

Form of the Function Q q Substituting Eqs (AVIII.37) and (AVIII.41) in

Eq. (AVIII.36), we get

Ê h ˆ ei j Ê ∂ + i cot q ∂ ˆ Ê 1 Q eil j ˆ = 0
Ë 2p ¯ ÁË ∂q ∂j ˜¯ Ë 2p
q ¯

Ê ∂ + i cot q ∂ ˆ Q ei l j = 0
or ÁË ∂q ∂j ˜¯
q

d d ilj
or ei l j Qq +i cot q Qq e =0
dq dj

d
or ei lj Qq +i cot q Qq (i lei l j ) = 0
dq

This gives

d
Q – l (cot q) Q = 0
dq

dQ cos q d ( sin q )
or = l cot q dq = l dq = l
Q sin q sin q
which on integration gives

ln Q = l ln (sin q) + constant

or Q = N sinlq (AVIII.42)

The constant N is determined via the normalization of the function Q by using

the expression
p

Ú Q Q sinq dq = 1
*
(AVIII.43)
0
 Wave Mechanics, Energy Quantization and Atomic Structure 199

Substituting the expression of Q and carrying out the integration†, we get

1/ 2
(2l + 1)!˘
N = ÈÍ
1
(AVIII.44)
Î 2 ˙˚ 2l l !
With this, the function Ql becomes
1/ 2
(2l + 1)!˘
Ql,l = È
1
sinlq (AVIII.45)
ÎÍ 2 ˚˙ 2 l!l

The function Yl, l becomes

Ê 1/ 2
ˆ 1 ilj ˆ
Yl, l = Ql,l Fl = Á È (2l + 1)!˘ 1
sin l q ˜ Ê e (AVIII.46)
Ë ÍÎ 2 ˙˚ 2l l ! ¯ Ë 2p ¯

Expression for the Using the lowering operator M _ on the function Yl, m, we get
Function Yl, l – 1
M _Yl , m = ( l + m ) ( l - m + 1) ÊË ˆ¯ Yl , m-1
h
2p
For m = l, we get

M _Yl , l = 2l ÊË ˆ¯ Yl , l -1
h (AVIII.47)
2p
The operator M– is

M _ = M x - iM y

Ê h ˆ Ê sin j ∂ + cot q cos j ∂ ˆ

= Ë-
2pi ¯ ÁË ∂q ∂j ˜¯
h Ê ∂ ∂ ˆ
-i cos j - cot q sin j
2pi ÁË ∂q ∂j ˜¯

p p p
1
= Q 2 sin q dq = Ú sin 2l +1 q dq = Ú sin 2l q d ( - cos q )
N 2 Ú0
†
0 0
p p
p
= sin 2l q ( - cos q ) Ú0 - Ú d (sin 2l q ) ( - cos q ) = 0 + Ú 2l sin 2l -1 q cos 2 q dq
0 0
p p p
È ˘
= ( 2l ) Í Ú sin 2l -1 q dq - Ú sin 2l +1q dq ˙ ∫ ÊË
2l ˆ
¯ Ú sin 2l -1q dq
ÍÎ 0 0 ˙˚ 2l + 1 0
p
Ê 2l ˆ Ê 2l - 2 ˆ 2( ( 2l )l ( l - 1) ( l - 2) 1 ( )
= Ë 2l + 1¯ Ë 2l - 1 ¯ - cos q ) = 2
3 0 (2l + 1) ( 2l - 1) 3

2 ( 2) ( 2l l !)
2
( 2) 2l l ! ( 2l ) ( 2l - 2)
= =
( 2l + 1) ( 2l - 1) 3 ( 2l ) ( 2l - 2) 2 (2l +1)!

(2l + 1)!˘1 / 2 1
Hence, N = ÈÍ
Î 2 ˙˚ 2l l !
200 A Textbook of Physical Chemistry

Ê h ˆÈ ∂ ∂
= Ë - ¯ Í(cos j - i sin j ) - i cot q (cos j - i sin j ) ˘˙ -
2p Î ∂q ∂j ˚
Ê h ˆ - ij Ê ∂ - i cot q ∂ ˆ
= Ë - ¯ (e ) Á
∂j ˜¯
(AVIII.48)
2p Ë ∂q

ÈÊ h ˆ - ij Ê ∂ - i cot q ∂ ˆ È( N sin l q ) Ê 1 e i lj ˆ ˘
Hence M – Yl, l = ÍË - ¯ (e ) Á
Î 2p Ë ∂q ∂j ˜¯ ÍÎ Ë 2p ¯ ˙˚

Ê 1 ˆ Ê - h ˆ (e - ij )(e i lj )
= NË [l sinl – 1q cos q – i(il) cot q sinl q]
2p ¯ Ë 2p ¯

= ÊË - ˆ¯ Ê
h 1 i(l -1)j ˆ
e (2 Nl sin l -1 q cos q ) (AVIII.49)
2p Ë 2p ¯
Substituting Eq. (AVIII.49) in Eq. (AVIII.47), we get
Ê - h ˆ Ê 1 ei(l -1)j ˆ ( 2 Nl sin l -1 q cos q ) = 2l Ê h ˆ Y
Ë 2p ¯ Ë 2p ¯ Ë 2p ¯ l , l -1
This gives Yl, l–1 = Ql, l–1 Fl–1
where Ql, l–1 = –N 2l sinl – 1q cos q (AVIII.50)
1 i(l-1)j
Fl –1 = e (AVIII.51)
2p
Substituting the expression of N from Eq.(AVIII.44) into Eq. (AVIII.50), we get
1/ 2
(2l + 1)!˘
Ql, l–1 = - ÈÍ
1
2l sin l -1 q cos q
Î 2 ˚˙ l
2 l!
1
= - [(l (2l + 1)!)]
1/ 2
sin l -1 q cos q (AVIII.52)
2l l !
Expression for the Using the expression
Function Yl, l – 2
M -Yl , m = ( l + m ) ( l - m + 1) ÊË ˆ¯ Yl ,m-1
h (AVIII.53)
2p
For m = l – 1, we get

M -Yl , l -1 = ( 2l - 1) 2 ÊË ˆ¯ Yl , l - 2
h (AVIII.54)
2p
∂ ∂ ˆ
M -Yl , l -1 = ÊË - ˆ¯ (e - ij ) ÊÁ
h
- i cot q
∂j ˜¯
Now
2p Ë ∂q

¥ È(- N 2l sin l -1 q cos q ) Ê

1 i(l -1)j ˆ ˘
ÍÎ e
Ë 2p ¯ ˙˚

= N 2l ÊË ˆ¯ (e - ij ) Ê
h 1 ˆ È i(l -1)j d
e (sin l -1 q cos q )
2p Ë 2p ¯ ÎÍ dq
d i(l -1)j ˘
-i cot q sin l -1 q cos q (e )˙
dj ˚
 Wave Mechanics, Energy Quantization and Atomic Structure 201

Ê h ˆ - ij Ê 1 ei(l -1)j ˆ l–2 2

= ( N ) 2l Ë ¯ (e ) Ë ¯ [(l – 1) sin q cos q
2p 2p
+ (sinl – 1 q)(– sin q) – i cot q sinl–1 q cos q{i(l – 1)}]

= ( N ) 2l ÊË ˆ¯ (e - ij ) Ê
h 1 i(l -1)j ˆ
e [2(l – 1) sinl – 2 q cos2q – sinlq ]
2p Ë 2p ¯

= ( N ) 2l ÊË ˆ¯ Ê
h 1 i(l - 2)j ˆ
e [sinl – 2 q {(2l – 1) cos2q – 1}]
2p Ë 2p ¯
Substituting the above expression in Eq. (AVIII.54), we get
Yl, l – 2 = Ql, l – 2 Fl – 2
where

Ql, l – 2 = N ( )
l 1/ 2
2l - 1
[sinl–2q {(2l – 1)cos2q – l}] (AVIII.55)

1 i(l- 2)j
Fl–2= e (AVIII.56)
2p
Substituting the expression of N in Eq. (AVIII.55), we get
1/ 2
È (2l + 1)!˘ 1 Ê l ˆ 1/ 2
Ql, l – 2 = Í [sinl–2q {(2l – 1)cos2q – l}]
Î 2 ˙˚ 2l 2 ! Ë 2l - 1¯
1/ 2
l (2l + 1)!˘
= ÍÈ
1
[sinl–2q {(2l – l) cos2q – l}] (AVIII.57)
Î 2(2l - 1) ˙˚ 2l +1
ANNEXURE IX Electronic Transitions in Hydrogen Atom including
Spin-Orbit Coupling

The electronic states along with their term symbols of hydrogen atom (see, Section
1.13) are as follows.

2
1s, 2s, 3s, ... S1/2
2
2p, 3p, 4p, ... P1/2, 2P3/2
2
3d, 4d, 5d, ... D3/2,2D5/2
2
4f, 5f, ... F5/2,2F7/2
According to Hund's rule (see, Section 1.14), the relative energies of states
follow the order:
2
2 P1/2 < 2S1/2 < 2P3/2
2
=3 P1/2 < 2Sl/2 < 2D3/2 � 2P3/2 < 2D5/2
2
n=4 P1/2 < 2Sl/2< 2D3/2 � 2P3/2 < 2F5/2 � 2D5/2 < 2F7/2

While discussing electronic spectrum of hydrogen atom including, spin-orbit

coupling, the selection rules to be followed are

DL = ±1 and D = 0, ±1
Some of the allowed electronic transitions in hydrogen atom are as follows.
2
S1/2(1s) ¨ 2P1/2(2p) 2
P1/2(2p) ¨ 2S1/2(3s)
2
Sl/2(1s) ¨ 2P3/2 (2p) 2
P3/2(3p) ¨ 2S1/2(3s)
2
S1/2(2s) ¨ 2P1/2(3p) 2
P3/2(2p) ¨ 2D3/2(3d)
2
S1/2(2s) ¨2P3/2(3p) 2
P3/2(2p) ¨ 2D5/2(3d)

These transitions are shown in Fig. AIX. 1. In the absence of spin-orbit coupling

In the presence of spin-orbit coupling, each absorption is found to be more than

one absorption (observable under high resolution).
The states S1/2 and P1/2 are two-fold degenerate corresponding to J +1/2
and –1/2. The states P3/2 and D3/2 are four-fold degenerate corresponding to J
= + 3/2, +1/2, –1/2 and –3/2. The state D5/2 is six-fold degenerate corresponding
to J = +5/2, +3/2, +1/2, –1/2, –3/2 and –5/2. These degeneracy are lifted up in
 coupling
spin-orbit coupling,
spectrum (a) with no

and (b) with spin-orbit

Fig. AIX.1 Hydrogen
Energy

1s
2s
3s

(a)
8225
8.20
cm -1
3p

1523
2p

2.98
cm -1
3d
S1/2

S1/2
D5/2

82258.92 cm-1

82259.27 cm-1
15233.26 cm-1
(b) 15233.29 cm-1

15232.94 cm-1
15232.36 cm-1
15233.39 cm-1
15233.03 cm-1

15233.07 cm-1
S1/2
P1/2
P3/2
P1/2
P3/2
D3/2
203
ANNEXURE X First-Order Perturbation Theory

The Method of The electronic Hamiltonian operator for the helium atom is
Perturbation
� Ê h2 Ze 2 ˆ Ê h 2 Ze2 ˆ e2
ÁË - 8p 2 m —1 - ( 4pe ) r ˜¯ + ÁË - 8p 2 m — 2 - ( 4pe ) r ˜¯ + ( 4pe ) r
2 2
H
0 1 0 2 0 12

� ( 0) + H
H � ( 0) + H
�¢ = H
� ( 0) + H
�¢ (AX.1)
1 2

� (0) and
� (0) is the unperturbed operator (which is sum of the operators H
where H 1
� (0) for electrons 1 and 2, respectively), and H
H � ¢ is the perturbation in the operator
2
� The Schrödinger equation
H

�y
H y (AX.2)
is not exactly solvable. However, if the perturbation is ignored, the problem is
solvable since we can write
� (0) y (0) =
H (0)
y (0) (AX.3)

where H � ( 0) + H
� (0) = H � ( 0) (AX.4)
1 2

y (0) = y1(0) y 2(0) (AX.5)

The solution of Eq. (AX.3) goes as follows.

y = (H � ( 0) ) (y ( 0) y ( 0) )
� (0) (0)
H � ( 0) + H
1 2 1 2

= y 2( 0) H 1 (
� ( 0)y ( 0) + y ( 0) H
1 1 2 )
� ( 0) y ( 0)
2 ( )
= y 20
( )
( ( 0)
1 y 10 ) + y 10
( ) ( )
( ( 0)
2 y2
( 0)
)
= ( ( 0)
1 +
( 0)
2 )(y 1(0) y 2(0) ) (AX.6)
that is, the energy of the system is sum of the energies of the two electrons.
The approximate solution of Eq. (AX.2) can be carried out by the perturbation
method. The Schrödinger equation for the perturbed system may be written as

( H� ( 0)
+ lH )
�¢ y = E y
n n n
(AX.7)
where l
(for l = 0, the perturbed system is reduced to unperturbed system with yn reducing
to y n(0) and for l 1, the problem is under full perturbation). The wave function
yn besides depending upon the electronic coordinates will also depend on the
parameter l Similarly, the energy n will depend on the parameter l The wave
function yn and energy n may be expanded as Taylor series in power of l:
 205

∂y n d 2y n
y = y n l =0 + l+ l2 +�
∂l l =0 ∂l 2 l =0
( 0) (1) ( 2)
= y n + ly n + l y n +�
2
(AX.8)
dEn d 2 En
n = En l =0 + l+ l2 +�
dl l =0 ∂l 2 l =0
( 0) (1) ( 2)
= En + l En + l En + �
2
(AX.9)
The term containing l
l2 as the second-order perturbation and so on. Substitution of Eq. (AX.8) and
Eq. (AX.9) in Eq. (AX.7), we get
�
(H
( 0) � ¢ )(y ( 0) + ly (1) + l 2y (2) + �)
+ lH n n n
( ) ( ) ( ) ( ) ( ) ( )
( En0 + l En1 + l 2 En2 + �) (y n0 + ly n1 + l 2y n2 + �)
This can be expressed as
( )
� ( 0)y ( 0) + l ( H
H � 0 y (1) ) + l 2 ( H
� ¢ y ( 0) + H � ( 0 ) y ( 2) + ( H
� ¢ y (1) ) + �
n n n n n
( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( )
= En y n + l ( En y n + En y n ) + l ( En y n + En y n ) + �
0 0 1 0 0 1 2 1 1 2 0

The above expression holds good for any value of l

l’s on either sides of the above expression, we get
� ( 0)y ( 0) = E ( 0)y ( 0) ;
H (Zero-order perturbation
n n n
equation)
� ¢ y ( 0) + H
H � ( 0) y (1) = E (1)y ( 0) + E ( 0)y (1) (First-order perturbation
n n n n n n
equation)
H � ¢ y (1) = E (1)y (1) + E (2)y ( 0)
� ( 0) y ( 2) + H (Second-orider perturbation
n n n n n n
equation)
and so on.
Correction due
to the First-order
� ( 0) y (1) = E (1)y ( 0) + E ( 0)y (1)
� ¢ y ( 0) + H
H
Perturbation n n n n n n

� ( 0) ( ) ( ) � ¢ )y 0 ( ) ( )
i.e. (H - En0 )y n1 = ( En1 - H n (AX.10)
The function yn(1)
can be written in terms of a complete set of unperturbed wave
functions as
y n1 = Â j a jy j0
( ) ( )
(AX.11)
Substituting Eq. (AX.11) in Eq. (AX.10), we get
�
(H
( 0)
- En0 )
( )
(Â j
( )
) � ¢ )y 0
a jy j0 = ( En1 - H n
( ) ( )

Multiplying the above expression by y (0)

space, we get

i.e. Úy m
( 0)* �
(H
( 0) ( )
- En0 ) (Â j
( )
) ( )
� ¢ )y 0 dtt
a jy j0 dt = Ú y m0 * ( En1 - H n
( ) ( )
206

 j a j ( E j0
( ) ( ) ( ) ( ) ( ) ( )
� ¢ y 0 dt( ) ( ) ( )
i.e. - En0 ) Ú y m0 *y j0 dt = En1 Ú y m0 *y n0 dt - Ú y m0 * H n

 j a j ( E j0
( ) ( ) ( )
� ¢ y 0 dt ( ) ( )
i.e. - En0 ) d mj = En1 d mn - Ú y m0 * H n

where d d = 1 for = and d = 0 for π ). The above

expression is equivalent to
( )
� ¢ y 0 dt ( )
( (0)
– (0)
n ) = (1)
d - Ú y m0 * H n (AX.12)
For = n, we get
( ) � ¢ y 0 dt( ) ( )
0 = En1 - Ú y n0 * H n

that is
( ) ( )
� ¢ y 0 dt ( )
En1 = Ú y n0 * H n (AX.13)

the unperturbed wave function y (0) and the perturbed part of the Hamiltonian.
with π in the perturbed wave function (Eq. AX.11) as
obtained from Eq. (AX.12) is given by
( 0)* � ( )

=
Úy m H ¢ y n0 dt
=
¢
H mn
(AX.14)
( 0) ( 0) ( 0) ( )
En - Em En - Em0
( ) ( )
provided En0 π Em0 . This amounts to the fact that the states to which the
n may
be determined by normalizing the perturbed wave function yn ( = y n + y n ) . The
( 0) (1)

convention is to set n = 1 as the choice of n does not affect the energy correction.
H¢
 E (0) -mnE (0) y m0
( ) ( )
Hence y n(1) y n0 + (AX.15)
mπ n n m

APPLICATION TO A HELIUM ATOM

For helium atom in the ground state, both the electrons are allocated to Is orbital,
for which, we have
Z 3/ 2 1 Ê Z ˆ 3 / 2 - Zr / a0
y 1s = R1,0Q 0,0F0 = 2 ÊÁ ˆ˜ e - Zr / a0 .
1 1
◊ = Á ˜ e
Ë a0 ¯ 2 2p p Ë a0 ¯
3
= y 10 y 20 = ÊÁ ˆ˜ e - Zr1 / a0 e - Zr2 / a0
( 0) ( ) ( ) 1 Z
Hence y (AX.16)
p Ë a0 ¯

Z2 È e2 ˘ Z2
En = - Í ˙ = - (13.6 eV )
n 2 Î 2(4pe 0 )a0 ˚ n2
 207
(0) (0) (0) (0)
Hence = 1 + 2 =2 1s

È 22 ˘
= -2 Í 2 (13.6 eV) ˙ = –108.8 eV (AX.17)
Î1 ˚
The perturbation energy is given by
(1) � ¢ | y(0)Ò
= ·y(0) | H

1 Ê Z ˆ 3 - Zr1 / a0 - Zr2 / a0 e2 1 Ê Z ˆ 3 - Zr1 / a0 -Zr2 / a0

= e e e e
p ÁË a0 ˜¯ (4p e 0 ) r12 p ÁË a0 ˜¯

1 Ê Z ˆ 6 Ê e 2 ˆ - Zr1 / a0 - Zr2 / a0 1 - Zr1 / a0 - Zr2 / a0

= Á ˜ Á ˜ e e e e (AX.18)
p 2 Ë a0 ¯ Ë 4p e 0 ¯ r12

2 2
dt = dt1 dt2 ( 1 d 1 sin q1 dq1dj1) ( 2 d 2 sin q2 dq2 dj2)

12 in terms
of spherical harmonics, which we write without deriving this expression.
• l
4p Ê r<l ˆ m
1
=Â
r12 l =0
 2l + 1 ÁË r>l +1 ˜¯
[Yl (q1,j1 )]* [Ylm (q 2 ,j 2 )] (AX.19)
m =- l

where < and > are smaller and larger of 1 and 2, respectivey. Using the fact
Y00 = 1 / 4p , we write the above expression as

• l
1 Ê r<l ˆ m
1 (
r12
= 16p 2 ) Â Â Á [Y (q1 , j1 )] Y00 (q1 , j1 ) [Y00 (q 2 , j 2 )] Yl m (q 2 , j 2 )
l +1 ˜ l
2l + 1 Ë r> ¯
* *

l =0 m =- l

Substitution of this expression in Eq. (AX.18), gives

Z 6 Ê e2 ˆ • l
E 1 = (16) ÊÁ ˆ˜ Á
1
 Â
( )

Ë a0 ¯ Ë 4pe 0 ˜¯ i =0 m =- l 2l + 1

• •
Ê rl ˆ
¥Ú Ú e -2 Zr1 / a0 e -2 Zr2 / a0 Á l<+1 ˜ r12 dr1r22 dr2
0 0
Ë r> ¯

2p p
¥Ú Ú [Yl m (q1 ,j1 )]*Y00 (q1 ,j1 )sin q1 dq1dj1
0 0

2p p
¥Ú Ú [Y00 (q 2 ,j 2 )]* Yl m (q 2 ,j 2 )sin q 2 dq 2dj 2 (AX.20)
0 0
208

Since the spherical harmonics constitute an orthogonal set, each of the two
integrals involving spherical harmonics will survive only for = 0 and = 0 for
which each integral will be equal to unity.

Hence, Eq. (AX.20) is reduced to

• •
Z ˆ 6 Ê e2 ˆ
= (16) Ê
(1) 1 2
E ÁË a ˜¯ ÁË 4pe ˜¯ Ú Ú e -2 Zr1 / a0 e -2 Zr2 / a0 r1 dr1r22dr2
0 0 0 0
r>

1 then in the range 0 < 1 < 2, we substitute > = 2;

in the range 2 < 1 < • we substitute > = 1. Also, let we write 2Z/ 0 = . Thus

• •
Z 6 Ê e 2 ˆ È - br2 ÏÔ 2 - br1 r12 ¸Ô ˘
r 2
E 1 = (16) ÊÁ ˆ˜ Á - br1 r1
( )
˜ Í Ú
Ë a0 ¯ Ë 4pe 0 ¯ Í 0
e ÌÚ e
r2
dr1 Ú e
+
r1
dr1 ˝ r22dr2 ˙
˙˚
Î ÔÓ 0 r2 Ô˛

Z 6 Ê e2 ˆ
= (16) ÊÁ ˆ˜ Á ( I + II ) (AX.21)
Ë a0 ¯ Ë 4pe 0 ˜¯

• Ê r2 ˆ
where I = Ú e - br2 Á Ú e - br1 r12 dr1 ˜ r2dr2 (AX.22)
0 Ë0 ¯

•
Ê• ˆ
II = Ú e - br2 Á Ú e - br1 r1dr1 ˜ r22 dr2 (AX.23)
0 Ë r2 ¯

r2 r2
2 - br1 È r12 2r1 2 ˘ - br1
Ú1r e dr1 = Í -
Î ( -b) ( -b ) 2
+ ˙e
( -b )3 ˚ 0
0

È r2 2r2 2 ˘ - br2 2
= Í 2 - + - (AX.24)
3˙
e
Î ( - b ) ( - b ) 2 ( - b ) ˚ ( - b )3
• •
- br È r 1 ˘ - br È r 1 ˘ - br2
Ú r1 e 1 dr = ÍÎ (-2b) - ( -b)2 ˙˚ e 1 r2
= Í- 2 +
Î ( - b ) (
˙e
-b )2 ˚
(AX.25)
r2

•
ÈÊ r23 2r22 2r2 ˆ -2br2 2r ˘
Hence, I = Ú ÍÁË - + ˜ e - 2 3 e -2br2 ˙ dr2 (AX.26)
Î ( -b) ( -b)
2 ( -b ) ¯
3
( -b) ˚
0

•
È r23 r22 ˘ -2br2
II = Ú Í - + 2˙
Î ( -b) ( -b) ˚
e dr2 (AX.27)
0
 209

Now using the standard integral

•
n!
Ú r n e - ar dr =
0
a n +1
we get
1 3! 2 2! 2 1 2 1
I= - + -
( -b ) ( 2b )4 ( -b )2 ( 2b )3 ( -b )3 ( 2b )2 ( -b )3 b2
6 4 2 2 10 5
=- 5
- 5
- 5
+ 5
= 5
= 5
(AX.28)
16 8 4 16 8
1 3! 1 2!
II = - +
(-b) (2b) 4
(-b) (2b)3

6 2 10 5
=
5
+ 5
= 5
= 5
(AX.29)
16 8 16 8
Since = 2Z/ 0, we get
5
5 5 5 5 Ê a0 ˆ 5a05
I + II = + = = = (AX.30)
8b5 8b5 4b5 4 Ë 2Z ¯ 128Z 5
Substituting Eq. (AX.30) on Eq. (AX.21), we get

Z 6 Ê e 2 ˆ Ê 5a05 ˆ 5 Z Ê e 2 ˆ
= (16) ÊÁ ˆ˜ Á
( 0)
E Á ˜=
Ë a0 ¯ Ë 4pe 0 ˜¯ Ë 128Z 5 ¯ 8 a0 ÁË 4pe 0 ˜¯

5Z È1 e2 ˘ 5¥ 2
= Í ˙= (13.6 eV ) = 34.0 eV (AX.31)
4 Î (
2 4 pe 0) 0 ˚
a 4
(0) (1)
Finally, = + = – 108.8 eV + 34.0 eV = – 74.8 eV
The experimental value is – 79.0 eV.

APPLICATION TO A PARTICLE IN A ONE-DIMENSIONAL BOX

For a particle in a one-dimensional box (V = 0 for 0 < < and V = • elsewhere),

we have

yn =
2
l
sin
np
l ( )
x with En =
n2h2
8ml 2
Suppose the particle in the box is subjected to potential energy given by the
expression
= for 0 < < and =• elsewhere.
In such a case, the perturbation is
H¢ =
210

l
( ) � ¢ | y dx
En1 = Ú y n | H n
0

( ) ( )
l
2 È np np ˘
l Ú0 ÍÎ
= sin x | kx |sin x ˙ dx
l l ˚

( ) Ú ( )
l l
2k np 2k x È 2 np ˘ dx
= Ú
l 0
x sin 2
l
x dx = Í
l 02Î
1 - cos
l
x ˙˚

2k È x 2 ˘ kl
l
= Í - ( zero )˙ =
l Î4 0 ˚ 2
The energy of the particle is given by

( ) ( ) n2 h2 kl
En = En0 + En1 = 2
+
8ml 2

APPLICATION TO A PERTURBED HARMONIC OSCILLATOR

For a harmonic oscillator, we have
1
V= kf x 2
2
1/ 4
a
y0 = Ê ˆ exp ( -a 2
/ 2) ; where a = kf m ( h / 2p )
Ë p¯

1 1 h kf
and E0 = hn 0 =
2 2 2p m

oscillator) be given by
1
V= kf x 2 + k ¢ x3 + k ¢¢x 4
2
where ¢ and ¢¢ are constants. In this case, the perturbation is
H' = ¢ 3 + ¢¢ 4

+•
( )
E01 = Ú y 0 | H� ¢ | y 0 dx
-•
+•
a 1/ 2
= ÊË ˆ¯ Ú (e-a x2 / 2 | k ¢ x3 + k ¢¢ x 4 | e-a x2 / 2 ) dx
p -•
+• +•
a 1/ 2 È ˘
= ÊË ˆ¯ Ík ¢ Ú x3e -a x dx + k ¢¢ Ú x 4e -a x dx ˙
2 2

p ÍÎ -• -• ˙˚
 211

+•
a 1/ 2 È ˘
= ÊË ˆ¯ Ík ¢ (zero) + 2k ¢¢ Ú x 4e -a x dx ˙
2

p ÍÎ -• ˙˚

a 1/ 2 È Ï 3 p
() ¸˘ 3k ¢¢ 3k ¢¢ ( h / 2p )2
1/ 2
= ÊË ˆ¯ Í2k ¢¢ Ì 2 ˝˙ = =
p Î Ó 8a a ˛˚ 4a 2 4 ( kf / m )
Hence, the energy of the perturbed oscillator is
( ) ( ) 1 h kf 3k ¢¢ ( h / 2p )2
E00 + E01 = +
2 2p m 4 ( kf / m )
ANNEXURE XI Proof of Variational Theorem

The proof of the variation theorem goes as follows.

The well-behaved approximate wave function y can be expanded in terms of a

� , that is
complete orthonormal set of eigenfunctions of the Hamiltonian operator. H
y = Â n Cnj n
With this, we have

E=
� |y
y*| H
=
(Â n Cn*j n* ) | H� | (Â n Cnj n )
y*|y (Â n Cn*j n* ) | (Â n Cnj n )
For an orthonormal set,
j n* | j n = 1 and j n* | j m = 0
With these, the above expression is reduced to

 n Cn*Cn En
E=
 n Cn*Cn
Subtracting 0 from both sides, we get

 n Cn*Cn En  n Cn*Cn ( En - E0 )
E - E0 = - E0 =
 n Cn*Cn  n Cn*Cn
Since n > 0 for all values of n and also C* Cn > 0, we will have
– 0 >0 or > 0

The variation function says that we can calculate the upper bound on 0 by using
the appropriate trial wave function. The closer the function to the exact wave
function, the closer the energy to the exact energy of the system.
ANNEXURE XII The Variational Method

ENERGY EVALUATION FOR A WAVE FUNCTION INVOLVING LINEARLY DEPENDENT VARIATION

PARAMETERS

For simplicity, let a wave function involve two linearly dependent variation
parameters, such that
y = C1y1+ C2y2
The energy expression is
�y
y H � (C y + C y )
(C1y 1 + C2y 2 ) H
E= = 1 2 2
y |y (C1y 1 + C2y 2 ) | (C1y 1 + C2y 2 )

C12 H11 + C22 H 22 + 2C1C2 H12

=
C12 S11 + C22 S22 + 2C1C2 S12
where � | y Ò and
H = H = ·y | H = = ·y | y Ò.

∂ /∂C = 0 leads to the following secular equations.

C1 ( H11 - ES11 ) + C2 ( H12 - ES12 ) = 0 ¸

˝ (AXII.1)
C1 ( H 21 - ES21 ) + C2 ( H 22 - ES22 ) = 0 ˛
These may be written in the determinant form as
H11 - ES11 H12 - ES12 C1
=0
H 21 - ES21 H 22 - ES22 C2
To have nontrivial roots of energy, we set the secular determinant equal to zero, i.e.
H11 - ES11 H12 - ES12
=0 (AXII.2)
H 21 - ES21 H 22 - ES22
which on opening gives

(H11 – 11)(H22 – 22) – (H12 – 12)(H21 – 21) =0

Since H12 = H21 and 12 = 21, we have
2
(H11 – 11)(H22 – 22) – (H12 – 12) =0
Knowing the values of H11, H22, H12, 11, 11 and 12, one can solve the above
quadratic expression in energy to get the two values of energy. Substituting these
one by one in secular equations along with the normalization expression of y (which
is 12 11 + 22 22 + 2C1C2 12 C1 and C2.
214

Note: For a wave function involving n linearly dependent variation parameters

(i.e. y = Â C y

H11 - ES11 H12 - ES12 � H1n - ES1n

H 21 - ES22 H 22 - ES22 � H 2 n - ES2 n
=0 (AXII.3)
� � �
H n1 - ESn1 H n 2 - ESn 2 � H nn - ESnn

For the orthonormal set of wave functions, for which = d , the above determinant
becomes

H11 - E H12 � H1n

H 21 H 22 - E � H 2n
=0 (AXII.4)
� � �
H n1 H n2 � H nn - E

APPLICATION TO A PARTICLE IN A ONE-DIMENSIONAL BOX

V = 0 for 0 < <

and V = • elsewhere) be given as

y = C1y1 + C2y2
2
where y1 = ( – ) and y2 = ( – )2. To evaluate the energies, we determine
the following integrals.
2
� | y Ò = x (l - x ) - h d2 (
H11 = ·y1 | H 1 x l - x)
8p m dx 2
2

l
h2 ( ) Ê h2 ˆ
= x (l - x ) - - = ÁË 2 ˜¯ Ú ( xl - x ) dx
2
2 2
8p 2 m 8p m 0

Ê h2 ˆ Ê l 3 ˆ
= Á 2 ˜ ÁË ˜¯
Ë 8p m ¯ 3

11 = ·y1 y1Ò = · ( – )| ( – )Ò

l5
Ú0 (l x + x 4 - 2lx3 ) dx =
l 2 2
30

Ê h2 ˆ Ê l 5 ˆ
H12 = H 21 = Á 2 ˜ ÁË ˜¯
Ë 8p m ¯ 15

l7
S12 = S21 =
140
 215

Ê h 2 ˆ Ê 2l 7 ˆ
H 22 = Á 2 ˜ ÁË
Ë 8p m ¯ 105 ˜¯

l9
S22 =
630
With these, the secular determinant (Eq. AXII.2) becomes

Ê h2 ˆ Ê l 3 ˆ Ê l5 ˆ Ê h2 ˆ Ê l 5 ˆ Ê l7 ˆ
ÁË 2 ˜¯ ÁË ˜¯ - E ÁË ˜¯ ÁË 2 ˜¯ ÁË ˜¯ - E ÁË ˜
8p m 3 30 8p m 15 140 ¯
=0
Ê h2 ˆ Ê l 5 ˆ Ê l7 ˆ Ê h 2 ˆ Ê 2l 7 ˆ Ê l9 ˆ
ÁË 2 ˜¯ ÁË ˜¯ - E ÁË ˜ ÁË 2 ˜¯ ÁË ˜¯ - E ÁË ˜
8p m 15 140 ¯ 8p m 105 630 ¯
2
K= /(8p 2 2
). With this, the above determinant becomes
1 E¢
-
Kl 5
3 30 ( ) Kl 7 (
1 E¢
-
15 140
=0
)
Kl 7 - (
1 E¢
15 140 ) Kl 9
2
( -
E¢
105 630 )
where ¢ = /K = 8p2 2 / 2.
Opening the determinant, we get

( )( ) ( )
2
1 E¢ 2 E¢ 1 E¢
K 2l14 - - - K 2l14 - =0
3 30 105 630 15 140
Multiplying throughout by (1 260)2/K2 14, we get
(420 – 42 ¢) (24 – 2 ¢) – (84 – 9 ¢)2 = 0
or 84(10 – ¢) (12 – ¢) – (84 – 9 ¢)2 = 0
or 84(120 – 22 ¢ + ¢2) – (84 ¥ 84 + 81 ¢2 – 84 ¥ 18 ¢) = 0
or ¢2(84 – 81) + ¢(84 ¥ 18 – 84 ¥ 22) + (84 ¥ 120 – 84 ¥ 84) = 0
or 3 ¢ – 336 ¢ + 3 024 = 0
2

or ¢2 – 112 ¢ + 1 008 = 0
The roots of energy are

112 ± 1122 - 4 ¥1 008 112 ± 8 512 112 ± 92.26

¢= = =
2 2 2
¢ = 102.13 and ¢ = 9.87
For the smaller root, we have
Ê 8p 2 ml 2 ˆ
ÁË ˜ E = 9.87
h2 ¯
9.87 Ê h 2 ˆ
or E= Á ˜
p 2 Ë 8ml 2 ¯
216

Substituting in secular equation (Eq. AXII.1), we get

C1(H11 – 11) + C2 (H12 – 12) =0

È h 2 l 3 Ê 9.87 h 2 ˆ Ê l 5 ˆ ˘
C1 Í 2 -Á ˜ Á ˜˙
Î 8p m 3 Ë l 2 8p 2 m ¯ Ë 30 ¯ ˚
È h 2 l 5 Ê 9.87 h 2 ˆ Ê l 7 ˆ ˘
+ C2 Í 2 -Á ˜Á ˜˙ = 0
Î 8p m 15 Ë l 2 8p 2 m ¯ Ë 140 ¯ ˚
This gives

C1 ÊË -
1 9.87 ˆ
+ C2 l 2 ÊË -
1 9.87 ˆ
¯ =0
3 30 15 140 ¯
i.e. C1 = C2 2 (0.885)
Substituting this in the normalization expression
C12 11 + C22 22 + 2C1C2 12 =1
we get
Ê l5 ˆ Ê l9 ˆ 2Ê l ˆ
7
C22l 4 ( 0.885)2 ÁË ˜¯ + C22 ÁË ˜¯ + 2C2 l ( 0.855) ÁË
2 2
˜ =1
30 630 140 ¯
2
2
9
(0.026 1 + 0.0159 + 0.012 6) = 1 fi 2
2
9
(0.040 3) = 1

1 ˆ 1/ 2 Ê 1 ˆ 4.98
C2 = ÊÁ =
Ë 0.040 3 ˜¯ ÁË l 9 ˜¯ l9

C1 = C2l 2 ( 0.885) = ÊÁ
4.98 ˆ ( 2 ) ( 4.41
l 0.885) =
Ë l 9 ˜¯ l5
Hence, the normalized wave function is
4.41 ( 4.98 2 (
y= x l - x) + x l - x )2
5
l l9

NUCLEAR CHARGE OF HELIUM ATOM AS A VARIATIONAL PARAMETER

The Hamiltonian operator of helium atom is

2 2 2
� = - h D 2 - h D 2 - Ze Ze 2 e2
H 1 2 - + (AXII.3)
8p 2 m 8p 2 m (4pe 0 )r1 (4pe 0 )r2 (4pe 0 )r12
The ground-state normalized wave function is
y = y1y2 = (R100 Q0,0 Q0)1 (R100 Q0,0 Q0)2
È Ê Z ˆ 3 / 2 - Zr1 / a0 1 1 ˘ È Ê Z ˆ 3 / 2 - Zr2 / a0 1 1 ˘
Í2 Á ˜ e ◊ ◊ ˙ Í2 Á ˜ e ◊ ◊ ˙
Î Ë a0 ¯ 2 2p ˚ Î Ë a0 ¯ 2 2p ˚
1 Ê Z ˆ 3 - Zr1 / a0 - Zr2 / a0
= e e
p ÁË a0 ˜¯
(AXII.4)
 217

Z as ¢
as effective nuclear charge). Thus
1 Ê Z ¢ ˆ 3 - Z ¢ r1 / a0 - Z ¢ r2 / a0
y = e e (AXII.5)
p ÁË a0 ˜¯
The Hamiltonian operator can be written as

� È h2 Z ¢e 2 ˘ È h 2 Z ¢e2 ˘
Í- 2 D1 - ˙ + Í- 2 D 2 -
2 2
H ˙
Î 8p m (4pe 0 )r1 ˚ Î 8p m (4pe 0 )r2 ˚

( Z ¢ - Z )e 2 ( Z ¢ - Z )e 2 e2
+ +
(4pe 0 )r1 (4pe 0 )r2 (4pe 0 )r12

� 2 + ( Z ¢ - Z )e + ( Z ¢ - Z )e +
2 2
�1 + H e2
=H (AXII.6)
(4pe 0 )r1 (4pe 0 )r2 (4pe 0 )r12
The electronic energy of the atom is given by
� |y Ò
= ·y | H

� 2 + ( Z ¢ - Z )e + ( Z ¢ - Z )e +
2 2
�1 + H e2
= y 1y 2 H y 1y 2
(4pe 0 )r1 (4pe 0 )r2 (4pe 0 )r12
�1 | y y | y + y | H
= y1 | H �2 |y y |y
1 2 2 2 2 1 1

( Z ¢ - Z )e 2 ( Z ¢ - Z )e 2
+ y1 y1 y 2 | y 2 + y 2 y 2 y1 | y1
(4pe 0 )r1 (4pe 0 )r2
e2
+ y 1y 2 y 1y 2
(4pe 0 ) 12
Since y1 and y2 are normalized, we get

� 2 y + y (Z ¢ - Z ) e y
2
�1 y + y H
E = y1 H 1 2 2 1 1
(4pe 0 )r12

( Z ¢ - Z ) e2 e2
+ y2 y 2 + y 1y 2 y 1y 2 (AXII.7)
(4pe 0 )r2 (4pe 0 )r12

�1 y = -Z ¢2 E
y1 H
Now 1 1s(H)

� 2 y = -Z ¢2 E
y2 H 2 1s(H)

•
( Z ¢ - Z ) e2 1 Ê Z ¢ ˆ 3 Ê - Z ¢ r1 / a0 ( Z ¢ - Z ) e 2 - Z ¢ r1 / a0 ˆ
p ÁË a0 ˜¯ Ú0 ÁË
y1 y1 = e e ˜¯
(4pe 0 )r1 (4pe 0 )r1
p 2p
¥ 12d 1 Ú sinq1dq1 Ú dj1
0 0
218

•
1 Ê Z ¢ ˆ 3 ( Z ¢ - Z ) e2 Ê -2 Z ¢ r1 / a0
ˆÊp ˆ Ê 2p ˆ
= Á ˜
p Ë a0 ¯ ( 4pe 0 ) Ë 0 Á Ú r1e dr1 ˜ Á
¯Ë0
Ú sin q1d q ˜ Á
¯Ë 0
Ú dj1 ˜
¯

1 Ê Z ¢ ˆ 3 ( Z ¢ - Z ) e2 È 1 ˘ [2][2p]
=
p ÁË a0 ˜¯ ( 4pe 0 ) ÍÎ ( 2Z ¢ / a0 )2 ˙˚

È1 e2 ˘
= 2Z ¢( Z ¢ - Z ) Í ˙ = 2 Z ¢ ( Z ¢ - Z ) E1s(H)
Î 2 ( 4pe 0 ) a0 ˚
Similarly,

( Z ¢ - Z )e 2
y2 y = 2 Z ¢ ( Z ¢ - Z ) E1s(H)
(4pe 0 ) r2 2
As derived in the perturbation theory, we will have

e2 5Z ¢
y 1y 2 yy = E1s(H) (Eq.AX.31)
(4pe 0 ) r12 1 2 4
With these integrals, Eq. (AXII.7) becomes

= – ¢2 1s(H) – ¢2 1s(H) + 2 ¢( ¢ – Z) 1s(H)

5Z ¢
+ 2Z¢(Z¢ – Z) 1s(H) + E1s(H)
4

È 5Z ¢ ˘ 5Z ¢ ˘
= Í-2 Z ¢ 2 + 4 Z ¢ ( Z ¢ - Z ) + E1s(H) = ÈÍ2 Z ¢ 2 - 4 Z ¢ Z + E1s(H))
Î 4 ˚˙ Î 4 ˚˙
Since Z = 2, we have
Ê 27 ˆ
E = Ë2 Z ¢ 2 - Z ¢ E1s(H)
4 ¯
To minimize ,we set d /d ¢ = 0. This gives
Ê 27 ˆ
Ë4 Z ¢ - 4 ¯ E1s(H) = 0

Hence ¢ = 27/16
Substituting ¢ = 27/16 in Eq. (AXII.8), we get

È 27 2 Ê 27 ˆ 27 ˘
= Í2 ÊË ˆ¯ - Ë ¯ÊË ˆ¯ ˙ = ÊË
27 ˆ Ê 27 27 ˆ
- ¯
16 ¯ Ë 8
min 1s(H) 1s(H)
Î 16 4 16 ˚ 4

= - ÊË ˆ¯ ÊË ˆ¯ (13.6 eV )
27 27
16 8
= –77.46 eV
The experimental value is –79.0 eV.
 219

SLATER RULES FOR EFFECTIVE NUCLEAR CHARGE

For helium atom, we have Z* = 27/16

This may be written as Z* = Z – 5/16

nuclear charge observed by electron 1 in Is orbital is 27/16 instead of 2 due to

the screening of nuclear charge by electron 2 in the same orbital, i.e. the electron
2 screens 5/16 of charge for electron 1 and vice versa. In general, we can write
Z i* = Z - Â j s ji
j πi

where the sum is over all the occupied spin orbitals other than the one considered.

effective nuclear charge as observed by an electron in an atom. The screening

contributions may be determined based on the following groups of orbitals.
(1s) (2s, 2p) (3s, 3p) (3d) (4s, 4p) (4d) (4f ) (5s, 5p)
The rules to be followed are as follows.
1. For the spin orbital from a group after that of the spin orbital , the value of
=0
2. For the spin orbital from the same group as that of the spin orbital , the
value of = 0.35
3. For the spin orbital from a group appearing before that of the spin orbital ,
the value of is:
(i) = 1 if is a d or f orbital
(ii) = 0.85 if is a s or p orbital when n = n – 1, otherwise = 1;
Examples
2
8 (2s)2 (2p)4
Grouping of the orbitals: (1s)2 (2s, 2p)6

S = Â j s ji = (2 ¥ 0.85) + (5 ¥ 0.35) = 3.45

j πi

Z* = Z –= 8 – 3.45 = 4.55
2
25 (2s)2 (2p)6 (3s)2 (3p)6 (3d)5 (4s)2
Grouping of the orbitals: (1s)2 (2s, 2p)8 (3s, 3p)8 (3d)5 (4s)2
4s
= (10 ¥ 1.0) + (13 ¥ 0.85) + (1 ¥ 0.35) = 21.40
Z* = Z – 5 = 25 – 21.4 = 3.6
3d
= (18 ¥ 1.0) + (4 ¥ 0.35) = 19.4
Z* = 25 – 19.4 = 5.6
 2 Theories of Covalent Bond

2.1 INTRODUCTION
The qualitative picture for the formation of a covalent bond was provided by G.N.
Lewis who described a covalent bond formation due to the sharing of electron
pairs between atoms. This sharing of electron pairs helps each atom acquire a

to the individual atoms can be understood qualitatively on the basis of electrostatic

interactions. The shared electron pair lies in the central region of the two atoms. This
arrangement besides decreasing the electrostatic repulsion between the two nuclei,
results in the maximum interaction between the nuclei and electrons. Consequently,
in a molecule the electrostatic attraction terms predominate over the repulsion terms
which results in the release of energy when a molecule is formed from the atoms.
Thus, a molecule is energetically more stable than the individual atoms.

The quantitative aspects for the formation of a covalent bond have been provided
by quantum machanics. According to the latter, a covalent molecule may be described
by means of a wave function which describes the behaviour of the electrons under

Thus, in principle, all that we have to do is to write the Schrödinger equation for
the molecule and then solve this equation for various allowed eigenvalues and
eigenfunctions. However, like many-electron atoms, only approximate methods can
be employed to solve the Schrödinger equation.
2.2 EXPRESSION OF SCHRÖDINGER EQUATION

The Schrödinger equation for a molecule containing N nuclei and n electrons is

H Y = EY (2.2.1)
where the Hamiltonian operator is given by

Ê N h2 n h2 ˆ
H = T + V =Á- Â 2 —i2 - Â — 2j ˜ + (Vne + Vee + Vnn)
Ë i =1 8 p M i j =1 8 p me
2
¯
(2.2.2)

The terms Vne, Vee and Vnn describe, respectively, the nucleus-electron, electron-
electron, and nucleus-nucleus interaction terms. These are given by

N n Zi e2
Vne = – Â Â (2.2.3a)
i =1 j =1 (4pe 0 ) ri j
 Theories of Covalent Bond 221

n -1
1 n n e2 n
e2
Vee = Â Â ≡ Â Â (2.2.3b)
2 i =1 j =1 (4pe 0 ) ri j i =1 j = i +1 ( 4p e 0 ) ri j
j πi

1 N N Zi Z j e2 N -1 N Zi Z j e2
Vnn = Â Â ≡ Â Â (2.2.3c)
2 i =1 j =1 (4pe 0 )ri j i =1 j = i +1 ( 4pe 0 ) ri j
j πi

where is e is equal to the elementary charge. The function Y depends on the

coordinates of both electrons and nuclei.
2.3 BORN-OPPENHEIMER APPROXIMATION

The term representing the nuclear motion in the Hamiltonian operator (Eq. 2.2.2)
can be removed with the help of Born-Oppenheimer approximation. This is based on
the fact that the electrons being much lighter than the nuclei, make many traverses
of the space available to them while the nuclei change their positions only slightly.
Hence, the translational energy of the molecule as a whole may be considered
separately and while evaluating the electronic energy, the various nuclei may be

The above approximation is achieved by writing the total wave function as the
product of electronic wave function and the nuclear wave function. The former
depends on the coordinates of the electrons as well as those of nuclei. The latter
depends only on the coordinates of nuclei. Thus, we have.
Y = yeyn (2.3.1)
The Hamiltonian operator of Eq. (2.2.2) may be written as
H = He + Hn (2.3.2)
n h2
where He = – Â —i2 + Vne + Vnn + Vee
i =1 8p 2 me
N h2
Hn = – Â 2
—i2
i =1 8p M i
The electronic wave function y e
H eye = Eeye (2.3.3)
and the nuclear wave function yn by
( H n + Ee)yn = E yn (2.3.4)
It may be mentioned here that Ee depends on the coordinates of nuclei. Since the
Ee represents the electronic

Eq. (2.3.4), the Hamiltonian operator for nuclear motion includes the nuclear
kinetic-energy operator and the electronic energy, so the symbol E represents the
total energy of the molecule, i.e. nuclear energy plus electronic energy.
222 A Textbook of Physical Chemistry

2.4 TWO APPROACHES FOR APPROXIMATE SOLUTION OF SCHRÖDINGER EQUATION

The electronic energy Ee for the given internuclear distances may be calculated by
solving the Schrödinger equation as given by Eq. (2.3.3):
H eye = Eeye (2.4.1)
However, the above equation cannot be solved exactly even if the internuclear
distances are held constant. This is due to the presence of electron-electron repulsion
terms in the Hamiltonian operator. Consequently, various approaches have been
developed for the approximate solution of Schrödinger equation. Of these, the
following two approaches have been widely used.

∑ The molecular orbital (MO) method developed by Hund, Mulliken, Lennard-

Jones and Hückel.
∑ The valence bond (VB) method developed by Heitler and London, Slater and
Pauling.

In the molecular orbital approach, we look at the molecule as a collection of

nuclei and electrons. We build up molecular orbitals for collection of nuclei and then
assign electrons to them. The valence orbital approach, which was developed prior
to the molecular orbital approach, is very similar to the classical chemical concept
of valence bond between two atoms and to the electron-pair bond postulated by
Lewis. In this method, the molecule is considered as a collection of atoms and then
the interactions between different atoms are considered. Hence, the two approaches
differ in the choice of trial wave functions whose parameters are then optimized by
the variation method. In their elementary forms, both these methods give results
that are crude from a quantitative point of view. However, both the methods can

Trial Wave The basic principles of MO method are very similar to those of the self-consistent
Function in MO
Method
∑ Each electron in a molecule is described by a wave function, known as the
molecular orbital. These molecular orbitals extend over the entire region of the
molecule, i.e. they are polycentric.
∑
y y *dt
element dt. Alternatively, y y*dt represents the relative charge density in the
volume element dt.
∑ Each MO may be represented by drawing contours of constant y or y 2 or by
drawing a boundary surface which includes the majority of charge cloud.
∑
solving the appropriate Schrödinger equation.
∑ The allocation of electrons to the various molecular orbitals of a molecule is
done following the aufbau and Pauli exclusion principles.
 Theories of Covalent Bond 223

Approximation of One of the most important ways of constructing molecular orbital is the scheme based
Linear Combination on the approximation of linear combination of atomic orbitals, abbreviated as LCAO
of Atomic Orbitals approximation. The choice of LCAO can be rationalized by taking an example of
a diatomic molecule AB. If the electron is in the neighbourhood of nucleus A, the

the ground-state MO, in this region should be similar to the ground-state atomic
orbital (AO) of atom A. Similarly, if the electron is in the neighbourhood of nucleus
B, the MO will look like very similar to the AO of the atom B. Thus, the form of
the MO should be such that it has characteristics possessed separately by yA and
yB, i.e. the MO should be reduceable to AOs in the extreme cases. The only choice is
to take MO as the linear combination of atomic orbitals. Mathematically, it is written as
y MO = C1yA + C2yB (2.4.2)
where C1 and C2
the functions yA and yB. In the extreme situations mentioned above, we will have
C1 = 1 and C2 = 0; when the electron is near to the nucleus A
and C1 = 0 and C2 = 1; when the electron is near to the nucleus B.

For any other situation C1 and C2 may have identical or different values depending
upon the nature of atoms and the associated wave functions yA and yB.
Physical Since the electron distribution is given by the square of the wave function, the
Significance of electron distribution for the function given by Eq. (2.4.2) is
Coefficients in a 2
y MO = C12y A2 + C22y B2 + 2C1C2yAyB
LCAO MO
The terms C12 and C22
orbitals yA and yB C1C2 describes the electron
probability density of orbitals yA and yB overlapping in the bond region.

The normalization criterion applied to y MO gives

Ú y MO dt = 1 = C12 Ú y A2 dt + C22 Ú y B2 dt + 2C1C2 Ú yAy Bdt

2

Assuming atomic orbitals to be normalized, we get

C12 + C22 + 2C1C2 SAB = 1
where SAB is the overlap integral between the orbitals yA and yB. In the zero-
overlap approximation (SAB = 0) the normalization condition is

C12 + C22 = 1

Mulliken Atomic In the zero-overlap approximation, C12 and C22 give directly the electronic charge
Population densities associated with the nuclei A and B, respectively. In the nonzero-overlap
Numbers C12 (or C22 ) and 2C1C2 are known as atomic-
orbital and overlap densities, respectively. To get the relative distribution of charge
on the two atoms, Mulliken gross atomic population numbers are evaluated by
adding the term (1/2)(2C1C2 SAB) to the atomic orbital densities. Thus, the gross
224 A Textbook of Physical Chemistry

atomic populations on atoms A and B due to one electron in the molecular orbital
y MO are C12 + C1C2SAB and C22 + C1C2 SAB, respectively.

The values of C1 and C2 are determined by the variation method, subjected to

the condition of normalization, written as

Ú y MO dt = 1
2
(2.4.3)

Comment on It is not necessary that we include only one atomic orbital from each atom. In
Molecular general, we can include any number of atomic orbitals belonging to the different
Orbitals atoms and thus write MO as
y MO = Â i Ciy i (2.4.4)
Larger the number of atomic orbitals included, better the molecular orbital. The

Ci. While evaluating Ci s, it may be found that for one combination, many of Ci
have zero values or small values and only a few (may be two or three or four)

equivalent to the combination of a few atomic orbitals.

Factors In general, the combination of AOs are determined by the following factors:
Determining the
Coefficients in a 1. The combination is better if the energies of yA and yB in their respective
Molecular Orbital atoms have comparable values. To illustrate the point, we may take an example
of H2 molecule, written as HA–HB. The combination of 1s(HA) and 1s(HB) or
2s(HA) and 2s(HB) or 2px(HA) and 2px(HB), and so on will be the most effective,
CA and CB are expected to have comparable values (in fact,
both of them will have the same value because atoms A and B are identical and
the orbital in combination have identical energies). The combination 1s(HA) +
2s(HB), 1s(HA) + 3s(HB), etc., may not be effective as the energies of involved
AOs have a large difference.
2. The combination is better if the charge clouds of yA and yB overlap each
other as much as possible.

3. Only those orbitals combine which have the same symmetry relative to the
molecular axis (taken to be z-axis). Thus, 1s(HA) and 2px (HB) orbitals will not
mix with each other as they have different symmetry.
The above factors can be easily explained by evaluating the trial function
y MO = C1yA + C2yB (2.4.5)
and the energy associated with this orbital. It will be shown in the next section that

of the two atomic orbitals yA and yB will be given by the following two simultane-
ous linear equations:
C1(aA — E ) + C2(bAB — ESAB) = 0 (2.4.6a)
C1(bAB — ESAB) + C2(aB — E) = 0 (2.4.6b)
 Theories of Covalent Bond 225

where aA and a B represent the energies of electron in the isolated atoms, bAB
is the resonance integral given by ÚyA| H |yB dt and SAB is the overlap integral
ÚyAyB dt ) which measures the extent of overlapping of the two orbitals.
It will also be shown that the energies of molecular orbitals will be given by the
following quadratic equation:
(aA – E)(aB – E) – (bAB – ESAB)2 = 0

i.e. (aA – E)(aB – E) = (bAB – ESAB)2 (2.4.7)

Proof of Condition (1) To prove condition (1), we assume that aA is very much smaller than a B. Since the
energy of an orbital depends on its size, it follows that the size of yA will be much
smaller than y B. Consequently both SAB and bAB will have low values and thus the

Eq. (2.4.7) also has a small value, it is expected that either aA – E or aB – E has
a small value. If we assume that aA – E is small, then the approximate solution of
Eq. (2.4.7) can be achieved by putting E = aA in the term aB – E. Thus, we get
(aA – E)(aB – aA) = (bAB – aASAB)2

(b AB - a A SAB ) 2
Hence E+ aA – aB - aA (2.4.8)

Similarly if we repeat the process for E aB, we get

(b AB - a B SAB ) 2
E– = aB + aB - aA (2.4.9)

Since aB aA, it follows that E+ and E– will have values very close to aA and
aB, respectively.

C1 b - E+ SAB
= – AB for y+ orbital
C2 a A - E+
C2 b - E- SAB
and = – AB for y– orbital
C1 a B - E-
Since E+ and E– are very close to aA and aB, respectively, it follows that
C1
will have a large value in y+ orbital
C2
C2
and will have a large value in y– orbital.
C1
The above facts imply that the mixing between yA and yB is very small. This
proves the condition (1) listed above.

Proof of Condition (2) The condition (2) follows directly from Eqs (2.4.8) and (2.4.9). If the two atomic
orbitals yA and yB do not overlap, then both SAB and bAB will have zero values.
226 A Textbook of Physical Chemistry

Thus E+ = aA and E– = a B, i.e. no effective combination between yA and yB

will occur. In other words, if we want an effective combination, the integrals SAB
and bAB must be nonzero. This conclusion is often referred to as the criterion of
maximum overlapping.

Proof of Condition (3) Proof of condition (3) follows directly from the fact that SAB has a zero value for
the orbitals having different symmetry about the molecular axis. For example, (1s)A
is completely symmetrical and (2px)B or (2py)B is antisymmetrical (positive lobe
on one side and negative lobe on the other side). Because of different signs of 2px
orbital, the integral SAB has a zero value even though the two orbitals overlap as
shown in Fig. 2.4.1.

Hence, no mixing between such orbitals can occur.

1

px
+
The area marked by 1 and 2 are
s + equal but carry different signs
and hence their sum is zero

–
Fig. 2.4.1 Overlapping
between s-type and
px-type orbitals
2

Example 2.4.1 Given that the electronic charge densities on the two hydrogen atoms of H +2 molecule are
equal, derive the values of C1 and C2 of the ground-state molecular orbital as given by
Eq. (2.4.2) in the zero- and nonzero overlap approximations.
Given: SAB = 0.458 4.

Solution The H +2 molecule contains 1 electron. Thus, in the zero-overlap approximation, we may write

C12 = C22 = 0.5

Thus C1 = C2 = 0.5 = 0.707

Hence, the form of molecular orbital is

yMO = 0.707 y 1s(H A ) + 0.707 y 1s(H B )

In the nonzero-overlap approximation, we will have

C12 + C1C2SAB = 0.5

C22 + C1C2SAB = 0.5

Since C1 and C2 will be identical in H +2 (because of symmetrical nature), we have

C12 + C12 (0.458 4) = 0.5

 Theories of Covalent Bond 227

0.5
or C12 = = 0.343
1 + 0.458 4
or C1 = 0.586
Thus, the y MO is given by
yMO = 0.586 y 1s(H A ) + 0.586 y 1s(H B )

Example 2.4.2 One of the molecular orbitals of a diatomic molecule is given by

yMO = C1y1s(A) + C2y2s(B) + C3y2p z(B)
Given that an electron spends 67.0, 21.6 and 11.4 per cents of its time in the orbitals y1s(A),
y2s(B) and y2pz(B) respectively, determine the form of the ground-state wave function yMO
in the zero-overlap approximation.
Solution We are given that
C12 = 0.670; C22 = 0.216 and C32 = 0.114

Taking the square roots, we get

C1 = 0.818; C2 = 0.465 and C3 = 0.337
Hence, the form of ground-state wave function is
yMO = 0.818y1s(A) + 0.465y2s(B) + 0.337y2p z(B)
(Note:

Trial Wave As indicated earlier, in the VB method, we consider a molecule as a collection

Function in VB of atoms. To know how a trial function in VB method is chosen, we consider
Method
very far apart with no interaction with each other, the total energy of the system
will be equal to the sum of the energies of the separate atoms. We may treat this
system separately as
( ) ( )
Etotal = EA1 + EB2
= ·yA(1)| H A|yA(1)Ò + ·yB (2)| H B|yB(2)Ò (2.4.10)
where yA(1) and H A are the wave function and the Hamiltonian operator for the
electron 1, respectively, associated with atom A and yB(2) and H B are those of
electron 2 associated with atom B.
The above assembly may equally be represented by writing the wave-function
and Hamiltonian operator as
y = yA(1) yB(2) (2.4.11)
H = HA + HB (2.4.12)
Thus Etotal = ·y | H | y Ò
= ·yA(1)yB(2) | H A + H B| yA(1)yB(2)Ò
= ·yA(1) | H A| yA(1)Ò ·yB(2) | yB(2)Ò
+ ·yB(2) | H B| yB(2)Ò ·yA(1) | yA(1)Ò
228 A Textbook of Physical Chemistry

Since the functions are normalized, the above expression becomes

Etotal = ·yA(1) | H A| yA(1)Ò + ·yB(2) | H B| yB(2)Ò
( ) ( )
= EA1 + EB2
Now consider that the two atoms are brought together to a distance rAB, where they
interact with each other. The Hamiltonian operator of the system will be given by
Ê h2 e2 ˆ Ê h2 e2 ˆ
H = Á - 2 —12 - ˜ + Á - 2 — 22 - ˜
Ë 8p m ( 4 pe 0 A1 ¯
) r Ë 8p m ( 4 pe 0 B2 ¯
) r

Ê e2 e2 e2 e2 ˆ
+ Á- - + + ˜
Ë ( 4 pe )
0 A2r ( 4 pe )
0 B1r ( 4 pe )
0 12r ( 4 pe 0 AB ¯
) r

= H A + H B + H (2.4.13)
In VB method, we say that the wave function of the above system has the form
as that of atoms very far apart (Eq. 2.4.10), i.e. y = yA(1)yB(2). But when the
two atoms are close together, we cannot distinguish electron 1 from electron 2.
We may have another combination where electron 1 is considered to be associated
with atom B and electron 2 with atom A, for which we write the wave function as
yA(2)yB (1). Hence the region where interaction occurs, Heitler and London
suggested that the wave function may be taken as the linear combination of the
two degenerate functions yA(1)yB(2) and yA(2)yB (1), i.e.
y VB = C1yA(1)yB(2) + C2yA(2)yB(1) (2.4.14)
The constants C1 and C2 are determined with help of variation method.
The wave functions in Eq. (2.4.14) represent covalent structures as each bonded
atom contains one electron. The wave function as given by Eq. (2.4.14) may be
improved upon by including the wave functions corresponding to the ionic structures
where both the electrons belong either to atom A or to atom B. Thus, we write
yVB = C1¢ ycovalent + C2¢ yionic (2.4.15)

where yionic = C1¢¢ yA(1)yA(2) + C2¢¢ yB(1)yB(2) (2.4.16)

2.5 LCAO-MO TREATMENT OF H+2

Expression of The hydrogen molecule ion which contains two protons and one electron is
Molecular Orbital the simplest molecule to be treated by LCAO-MO method. The lowest energy
atomic orbital of the hydrogen atom is the 1s orbital. It is expected that the linear
combination of 1s orbitals will yield molecular orbital of the lowest energy.
Referring to the two hydrogen atoms of H +2 as A and B, we may write the trial
function in the LCAO-MO framework as
yMO = C1y1s(A) + C2y1s(B) (2.5.1)
Expression of The Schrödinger equation is
Schrödinger Equation
H yMO = EyMO (2.5.2)
 Theories of Covalent Bond 229

where H , the Hamiltonian operator, is given by

h2 e2 e2 e2
H =– —2 – – + (2.5.3)
8p 2 m (4pe 0 ) rA (4pe 0 ) rB (4pe 0 ) R
The symbols rA, rB and R represent distances as shown in Fig. 2.5.1.
e

rA rB
Fig. 2.5.1 The
distances rA, rB and R
R
in the H2+ ion
HA HB

Expectation Value The energy E can be calculated by the expression

of Energy
·y MO | H | y MO Ò
E= (2.5.4)
·y MO | y MO Ò
Substituting the expression of yMO from Eq. (2.5.1), we get

·(C1y 1s(A) + C2 y 1s(B) ) | H | (C1y 1s(A) + C2y 1s(B) )Ò

E=
·(C1y 1s(A) + C2y 1s(B) ) | (C1y 1s(A) + C2y 1s(B) )Ò

C12 ·y 1s(A) | H |y 1s(A) Ò + C22 ·y 1s(B) | H |y 1s(B) Ò

+ C1C2 ·y 1s(A) | H |y 1s(B) Ò + C1C2 ·y 1s(B) | H |y 1s(A) Ò
= (2.5.5)
C1 ·y 1s(A) |y 1s(A) Ò + C22 ·y 1s(B) |y 1s(B) Ò + 2 C1C2 ·y 1s(A) |y 1s(B) Ò
2

The Hamiltonian operator belongs to the class of Hermitian operator for which
·y1s(A) | H |y1s(B) Ò = ·y1s(B)| H |y1s(A) Ò (2.5.6)
If the atomic orbitals are normalized, we will have
·y1s(A) |y1s(A) Ò = ·y1s(B)|y1s(B) Ò = 1 (2.5.7)
With Eqs (2.5.6) and (2.5.7), Eq. (2.5.5) becomes

C12 ·y 1s(A) | H |y 1s(A) Ò + C22 ·y 1s(B) | H |y 1s(B) Ò + 2 C1C2 ·y 1s(A) | H |y 1s(B) Ò

E= (2.5.8)
C12 + C22 + 2C1C2 ·y 1s(A) |y 1s(B) Ò
Following the notations
·y1s(A) | H |y1s(A)Ò = aA

·y1s(B) | H |y1s(B) Ò = aB

·y1s(A)| H |y1s(B) Ò = bAB

and ·y1s(A)|y1s(B)Ò = SAB
230 A Textbook of Physical Chemistry

We can write Eq. (2.5.8) as

C12a A + C22a B + 2C1C2 b AB

E= (2.5.9)
C12 + C22 + 2C1C2 SAB

The integrals aA and a B are known as Coulomb integrals. Their values are close
to E1s(A) and E1s(B), respectively, where E1s(A) and E1s(B) represent respectively the
energy of an electron in y1s(A) and y1s(B) in the isolated atoms.

The integral bAB is known as resonance integral, whose value is a measure of the
exchange of an electron from one atom to another. It always has a negative value.

The integral SAB is known as overlap integral, and is a measure of the extent
of overlapping of the two atomic orbitals.

Optimization of C1 and C2 in Eq. (2.5.9) are optimized by the variation method.

Coefficients C1 To make the energy minimum, we get
and C2
∂E ∂E
= 0 and =0
∂C1 ∂ C2
To determine ∂E/∂C1, we may write Eq. (2.5.9) as

E( C12 + C22 + 2C1C2 SAB) = C12 aA + C22 aB + 2C1C2bAB

and then differentiate it with respect to C1. Thus, we have

E(2C1 + 2C2 SAB) + ( C12 + C22 + 2C1C2 SAB)(∂E/∂C1) = 2C1aA + 2C2 bAB

Ê ∂E ˆ 2C1a A + 2C2 b AB - 2 E (C1 + C2 SAB )

or ÁË ∂C ˜¯ =
1 C12 + C22 + 2C1C2 SAB
On setting this expression to zero, we get
C1aA + C2bAB – E (C1 + C2SAB) = 0 (2.5.10)
Similarly, evaluating ∂E/∂C2, we get
C1bAB + C2aB – E (C1SAB + C2) = 0 (2.5.11)
Equations (2.5.10) and (2.5.11) may be written as
C1 (aA – E) + C2(bAB – ESAB) = 0 (2.5.12a)
C1 (bAB – ESAB) + C2 (aB – E) = 0 (2.5.12b)
or, in the matrix form, we have
aA - E b AB - ESAB C1
=0 (2.5.13)
b AB - ESAB aB - E C2
In order to have nontrivial solutions, we must set the determinant of the
 Theories of Covalent Bond 231

aA - E b AB - ESAB
=0 (2.5.14)
b AB - ESAB aB - E
Equations 2.5.12 are known as secular equations and the determinant of
Eq. (2.5.14) is known as the secular determinant.

Expressions of Expanding the determinant of Eq. (2.5.14), we get

Energy (aA – E)(a B – E) – (bAB – E SAB)2 = 0 (2.5.15)
Equation (2.5.15) is quadratic expression in E and, in principle, can be solved
for the two roots of E. These roots are then substituted in Eqs (2.5.12) to get the
expressions for C1 and C2 for each root separately. The numerical values of C1 and
C2 can be determined by making use of the normalization condition of molecular
C1 and C2 of the two molecular
orbitals (Eq. 2.5.1) and the energy associated with each of these molecular orbitals.
In general, we will get as many molecular orbitals as the number of atomic orbitals
of which we have taken the linear combination.

atomic orbitals which we have mixed are of identical nature. It follows that
aA = aB = a (2.5.16)
and thus Eq. (2.5.15) becomes
(a – E)2 – (bAB – ESAB)2 = 0
or a – E = ± (bAB – ESAB)
Hence the two roots are
a + b AB
E+ = (2.5.17a)
1 + SAB
a - b AB
E– = (2.5.17b)
1 - SAB
Expressions of These energies on substituting in Eqs (2.5.12) give
Coefficients C1 C1 = ± C2 (2.5.18)
and C2
Hence, we have
a + b AB
y+ MO = C+(y1s(A) + y1s(B)); E+ = (2.5.19a)
1 + SAB
a - b AB
y–MO = C– (y1s(A) – y1s(B)); E– = (2.5.19b)
1 - SAB
where the constants C+ and C– may be evaluated by applying the criterion that the
molecular orbitals are normalized. Thus, we have
·y+ MO |y+ MO Ò = 1
i.e. C+2 {·y1s(A) |y1s(A)Ò + ·y1s(B) |y1s(B)Ò + 2·y1s(A) |y1s(B)Ò}= 1

or C+2 (1 + 1 + 2SAB) = 1
232 A Textbook of Physical Chemistry

1
Thus C+ = (2.5.20a)
2 (1 + SAB )
Similarly, we can determine C–, for which, we have

1
C– = (2.5.20b)
2 (1 - SAB )

Analysis of the The term aA is given by

Term a A
aA = ·y1s(A) | H | y1s(A) Ò

h2 e2 e2 e2
Since H=– —2 – – +
2
8p m (4pe 0 ) rA (4pe 0 ) rB (4pe 0 ) R

h2 e2 e2 e2
we have aA = ·y1s(A) - — 2
- - + y1s(A) Ò
8p 2 m (4pe 0 ) rA (4pe 0 ) rB (4pe 0 ) R

h2 e2
= ·y1s(A) - — 2
- y1s(A)Ò
8p 2 m (4pe 0 ) rA

e2 e2
+ ·y1s(A) - y1s(A) Ò + ·y1s(A) y1s(A) Ò (2.5.21)
(4pe 0 ) rB (4pe 0 ) R

The first term is equal to the energy of 1s orbital of an isolated hydrogen atom. Since
the internuclear distance R is held constant (Born-Oppenheimer approximation), the
third term is simply equal to e2/(4pe0)R. The second term represents the electrostatic
attraction between proton B and an electron in a 1s orbital centred on proton A and
is known as Coulomb integral. Since the latter represents an attractive term, it has
a negative value. Writing the Coulomb integral as J, Eq. (2.5.21) may be written as

e2
aA = E1s(H) + J + (2.5.22)
(4pe 0 ) R

Analysis of the The term bAB is given by

Term bAB
bAB = ·y1s(A) | H |y1s(B) Ò

h2 e2
= ·y1s(A) - —2 - y1s(B) Ò
8p m 2
(4pe 0 ) rB

e2 e2
+ ·y1s(A) - y1s(B) Ò + ·y1s(A) y1s(B)Ò
(4pe 0 ) rA (4pe 0 ) R

Ê e2 ˆ
= E1s(H )SAB + K + Á S (2.5.23)
Ë (4pe 0 ) R ˜¯ AB
 Theories of Covalent Bond 233

where K is given by
e2
K = ·y1s(A) - y1s(B) Ò
(4pe 0 ) rA
and is known as exchange integral as roughly speaking it represents some sort
of exchange of electron between protons A and B and has a negative value. In
general, the value of K depends on the physical overlap of the orbitals in question.
Its magnitude also depends on the relative energies of the orbitals involved; the
value is maximum when the two orbitals have the same energy, and it decreases
as the difference of energies increases.

Energies in Terms With Eqs (2.5.22) and (2.5.23), the energies E+ and E– as given by Eqs (2.5.19) become
of J and K a + b AB e2 J+K
E+ = = E1s(H ) + + (2.5.24a)
1 + SAB (4pe 0 ) R 1 + SAB

a - b AB e2 J -K
E— = = E1s(H ) + + (2.5.24b)
1 - SAB (4pe 0 ) R 1 - SAB
Expressions of The hydrogen 1s orbital is given by the expression
Integrals J, K and S 3/2
1 Ê 1ˆ
y1s = Á ˜ exp (– r/a0)
p Ë a0 ¯
In atomic units†, we have
1
y1s = exp (– r)
p
Substituting this in the expressions of J, K and SAB and then evaluating the
integrals, we get
e2 1
J = ·y1s(A) - y1s(A)Ò = – {1 – (1 + R) exp(–2R)} (2.5.25)
(4pe 0 ) rB R

e2
K = ·y1s(A) - y1s(B) Ò = – (1 + R) exp(– R) (2.5.26)
(4pe 0 ) rA

Ê R2 ˆ
SAB = ·y1s(A) | y1s(B) Ò = Á1 + R + exp(– R) (2.5.27)
Ë 3 ˜¯
where R is expressed in atomic units.††
†
In atomic units, the energies are reported in hartree and distance in bohr. These

1 bohr ∫ a0 = 52 pm
e2
1 hartree ∫ = 27.112 eV = 2.617 MJ mol –1
(4pe 0 ) a0
See also Annexure VII at the end of Chapter 1.
††
See Annexure II for the evluation of integrals J, K and S.
234 A Textbook of Physical Chemistry

Comparison of Comparison of energies E+ and E– may be made by making use of either Eqs (2.5.19)
Energies E+ and E– or Eqs (2.5.24). For simplicity, we may assume, SAB = 0. From Eqs (2.5.19), we have
E+ = a + bAB
E– = a – bAB
Since both a and bAB are negative, it is obvious that
E+ < E– (2.5.28)
that is, the molecular orbital y+ MO has a lower energy than y–MO. On comparing
E+ and E–
E+ < a (2.5.29a)
E– > a (2.5.29b)
The above analysis is shown shematically in Fig. 2.5.2.

bAB
a
y1s(A) y1s(B)
Energy

bAB

E+ a+b
Fig. 2.5.2 Display of E+ y+MO
and E–

Even if we include the overlap integral SAB, the pattern shown in Fig. 2.5.2 is
maintained, but the deviation of energies of molecular orbitals from that of 1s
atomic orbital is uneven.
Coming to Eqs (2.5.24), the expressions after ignoring SAB are
e2
E+ = E1s(H) + + (J + K )
(4pe 0 ) R
e2
E— = E1s(H) + + (J – K )
(4pe 0 ) R
At larger internuclear distances, the terms J and K show the following
characteristics:
J varies as 1/R
K varies inverse exponentially with R.
Since the term J has a form of – 1/R, it is largely cancelled by the nuclear
repulsion term 1/R. Now since K has a negative value, we may conclude that
E+ < E1s(H)
E– > E1s(H)
the conclusions which are identical to those of Eqs (2.5.29).
 Theories of Covalent Bond 235

Bonding and A molecular orbital whose energy is lesser than those of the isolated atomic orbitals
Antibonding is called a bonding molecular orbital. Placing the electron in this orbital decreases
Orbitals the energy of the system, and hence contributes towards the formation of a chemical
bond. Conversely, if the energy of molecular orbital is larger than those of isolated
atomic orbitals, it is known as antibonding molecular orbital. Placing the electron
in this orbital contributes towards making the molecule less stable.
In H +2 , y+ MO is the bonding molecular orbital whereas y–MO is the antibonding
molecular orbital.

Potential Energy The potential energy curve depicts the variation of energy of a molecular orbital
Curves for H+2 with the internuclear distance. For the orbitals y+MO and y–MO, the plots of
E+ – E1s(H) versus R and E– – E1s(H) versus R are shown in Fig. 2.5.3.† The calculated
bond energy (the maximum depth in the E+ curve) is about 60% of the correct value.
The potential energy of y+ MO contains a minimum which will correspond to a
stable H +2 molecule. The minimum occurs at 132 pm (known as bond distance)
with the depth equal to 1.77 eV, i.e. 170.8 kJ mol –1 (known as bond energy).
The observed values are 106 pm and 2.79 eV, i.e. 269.2 kJ mol–1. The agreement
between the calculated and observed values is not very satisfactory. The calculated
values can be improved further by introducing additional parameters into the trial
function, such as including additional atomic orbitals and treating Z, the nuclear
charge, to be effective nuclear charge.

0.08

0.06
y–MO
0.04
(E – E1s(H))/hartree

0.02
1.0 2.0 3.0 4.0 5.0 6.0 7.0
0.0
R/a0
– 0.02 y+MO

Fig. 2.5.3 Variation – 0.04

of energies of y+MO and
y–MO with internuclear – 0.06
distance
– 0.08

The relative contribution of the various terms in Eqs (2.5.24) at the calculated bond
distance are shown in Fig. 2.5.4. Note that the bond energy is small difference
between large numbers.

†
For the data, see Try Yourself Problem 2.28.
236 A Textbook of Physical Chemistry

0
–257.6

–386
J
e2 1+S
+ R J –758.4

–1
–772 1– S

E / kJ mol
–961.0

K
–1158 1+S
–1312.2

–1483.0 (Calculated)
–1544
Fig. 2.5.4 Contribu- –1581.4 (Observed)
tions of various terms K
–
in the energy of y+ MO 1 +S
and y–MO –1930
–1909.5

Graphical The graphical representation of y+ MO and y–MO can be drawn by simply taking the
Representation of algebraic addition and subtraction of two atomic orbitals y1s(A) and y1s(B). These
2
yMO and y MO are shown in Fig. 2.5.5.

The terms y 2+MO and y 2– MO represent the electron probability distributions

associated with the molecular orbitals y+ MO and y–MO, respectively.

y+MO
y+2MO
y1s (A) y1s (B)
y 2 (A) y 2 (B)
1s 1s

A B A B
(i)

y–2 y 2 (B)
1s
y1s (A) MO
y 2 (A)
1s
y–MO

A B A B

y1s (B) (ii)

2
Fig. 2.5.5 Graphical representation of (i) y+MO and y +MO, and (ii) y–MO and y –2 MO
 Theories of Covalent Bond 237

We have
2
y 1s(A) + y 12s(B) + 2 y 1s( A ) y 1s(B)
y 2+ MO = (2.5.30)
2 + 2 SAB

2
2
y 1s(A) + y 12s(B) - 2 y 1s ( A )y 1s(B)
y –MO = (2.5.31)
2 - 2 SAB
In the region between the two nuclei, both y1s(A) and y1s(B) have appreciable
2
values, and so does their product. In y +MO , the term 2y1s(A)y1s(B) which appears

electron between the two nuclei is relatively high. The electrons in this region
interact with both the nuclei and hence the electrostatic attraction has a large
negative value. This attraction is larger than the nuclear repulsion. Thus, there
is a release of energy (or lowering of interpotential energy) when an electron is
placed in the bonding orbital.
The antibonding orbital has a zero value wherever y1s(A) and y1s(B) have the same
value. This occurs at r = R/2. Thus, the molecular orbital y–MO has a zero value
in a plane which is perpendicular to and bisects the axis between the two nuclei.
2
This plane is known as nodal plane. The value of y -MO is also zero on the nodal

is low in the region between the nuclei. In other words, the electron tends to avoid
the region where it can interact with both nuclei. Hence, the electrostatic repulsion
between the two nuclei is more than the net electrostatic attraction and thus there
occurs an increase in potential energy when an electron is placed in the antibonding
2 2
orbital. The representations of y +MO and y -MO are also shown in Fig. 2.5.5.

Problem 2.5.1 (a) Making use of LCAO and zero-overlap approximations, derive the various
molecular orbitals (involving only valence atomic orbitals) and the associated energies
for H 32+ molecule in the (i) linear, and (ii) equilateral triangle structures. Assume
bab = b for the next nearest neighbours and b ab = 0 for all other exchange integrals.
(b) Justify the fact that the geometry of H3 is linear whereas that of H3+ is an equilateral
triangle.

(c) Assuming that the energies of molecular orbitals of H32+ are applicable to H3+ and H3,
show that (i) H3 is stable with respect to 3H, (ii) H3+ is stable with respect to H + and 2H,
and (iii) H3+ is stable with respect to H + and H2.
Solution
(a) We write the molecular orbitals of H32+ as
y = C1y1s(Ha) + C2y1s(Hb) + C3y1s(Hc) (1)
The energy of y is given by
·y | H |y Ò
E = (2)
·y | y Ò
On substituting Eq. (1) in Eq. (2), we get

E = (C12 + C22 + C32 )a + 2C1C2 bab + 2C1C3 bac + 2C2C3 bbc (3)
C12 + C22 + C32 + 2C1C2 Sab + 2C1C3Sac + 2 C2C3Sbc
238 A Textbook of Physical Chemistry

where

a = ·y1s(Ha) | H | y1s(Ha)Ò = ·y1s(Hb) | H | y1s(Hb)Ò = ·y1s(Hc) | H | y1s(Hc)Ò

b ij = ·y1s(Hi) | H | y1s(Hj)Ò
Sij = ·y1s(Hi) | y1s(Hj)Ò
(i) For linear structure, we will have b ac = 0 and Sab = Sbc = Sac = 0. With these,
Eq. (3) becomes

E=
(C12 + C22 + C32 ) a + 2(C1C2 + C2C3 ) b
C12 + C22 + C32
Minimizing E with respect to C1, C2 and C 3 (i.e. substituting ∂E/ ∂C1 = ∂E/∂C2 =
∂E/∂C3 = 0), we get the three secular equations
C1(a - E) + C2b = 0 (4)

C1b + C2(a - E) + C3b = 0 (5)

C2 b + C3 (a - E) = 0 (6)

Writing Eqs (4)–(6) in the determinant from, we get

x 1 0 C1
1 x 1 C2 = 0
0 1 x C3

where x = (a - E )/b. In order to get nontrivial roots, we write

x 1 0
1 x 1 =0
0 1 x

Thus x (x 2 - 2)= 0
which gives x = - 2, 0 and 2 as the three roots.

Substituting x = - 2 in x = (a - E)/b, we get

E=a+ 2b
Substituting the above expression in the secular equations, we get

C1(- 2 b ) + C2b = 0

C1b + C2(- 2 b ) + C3 b = 0

C2b + C3(- 2 b) = 0

C1 = C3 and C2 = 2 C1
 Theories of Covalent Bond 239

Substituting these in the normalization condition

C12 + C22 + C32 = 1

1 1 1
we get C1 = , C2 = and C3 =
2 2 2
Thus, the molecular orbital y1,lin is given by

1 1 1
y1, lin = y1s(Ha) + y1s(Hb) + y1s(Hc); E1,lin = a + 2 b (7)
2 2 2
(bonding)

Proceeding similarly for other two roots, we get

1 1
y2, lin = y1s(Ha) – y1s(Hc); E2, lin =a (8)
2 2
(nonbonding)
1 1 1
y3, lin = y1s(Ha) - y1s(Hb) + y1s(Hc); E3, lin = a - 2b (9)
2 2 2
(antibonding)

(ii) For equilateral triangle structure, we will have Sab = Sbc = Sac= 0. With these,
Eq. (3) becomes
(C12 + C22 + C32 )a + 2(C1C2 + C2C3 + C1C3 )b
E=
C12 + C22 + C32

Minimizing E with respect to C1, C2 and C3, we get

C1(a - E) + C2 b + C3b = 0

C1b + C2(a - E) + C3 b = 0

C1b + C2b + C3(a - E) = 0

which will give
x 1 1
1 x 1 =0
1 1 x
or (x - 1) (x 2 + x - 2) = 0
The three roots are - 2, 1 and 1.
Substituting x = - 2 in x = (a - E) /b, we get
E = a + 2b
Substituting the above expression in secular equations, we get
C1(- 2 b) + C2 b + C3b = 0
C1b + C2(- 2b ) + C3b = 0
C1 b + C2b + C3(- 2b) = 0
240 A Textbook of Physical Chemistry

C1 = C2 = C3
which on substituting in the normalization condition give
1
C1 = C2 = C3 =
3
Hence, we have
1
y1, equil = {y1s(Ha) + y1s(Hb) + y1s(Hc)}; E1, equil = a + 2b
3
(bonding)
For root x
E=a-b
which on substituting in secular equations gives
C1 + C2 + C3 = 0
Making use of the fact that the orbital next to the ground state will have one node,
we may write
C2 = 0 and C1 = - C3.
From the normalization condition, we get
1 1
C1 = and C3 = –
2 2
1
Hence y2 (or 3), equil = {y1s(Ha) - y1s(H c)}; E2, equil = a - b
2
(antibonding)

(b) In equilateral triangle structure of H3, one electron is present in an orbital which is
antibonding with respect to atoms a and c (i.e. y2, equil). In order to get stable structure,
the electron in this orbital will try to keep the atoms a and c far apart from each other.
But in the equilateral triangle structure, these two atoms are close to each other. Hence
it is an unstable structure. The molecule will tend to attain a geometry in which atoms
a and c are far apart as in the case of linear structure. Hence, the linear structure is
preferred over the equilateral triangle structure. In H +3, the electron is not present in the
antibonding orbital. Consequently, the equilateral triangle is preferred. This is supported
by the fact that E1, equil < E1, lin.
(c) (i) E(H3) = 3a + 2 2 b and E(3H) = 3a. Since E(H3) < E(3H), it follows that
H3 is more stable than 3H.
(ii) E( H3+ ) = 2a + 4b and E(H + ) + E(2H) = 2a. Since the former is less than
the latter, H3+ is more stable than H + and 2H.

(iii) E ( H3+ ) = 2a + 4b and E (H + ) + E(H2) = 2a + 2b. Since the former is less

than the latter, H3+ is more stable than H + and H2.

2.6 LCAO-MO TREATMENT OF A HYDROGEN MOLECULE

The hydrogen molecule contains two protons and two electrons. The spinless
Hamiltonian operator is given by
 Theories of Covalent Bond 241

h2 h2 e2 e2 e2
H =– — 2
- — 2
- - -
(4pe 0 )r1a (4pe 0 )r2a (4pe 0 )r1b
1 2
8p 2 m 8p 2 m

e2 e2 e2
– + + (2.6.1)
(4pe 0 )r2 b (4p e 0 ) rab (4pe 0 )r12
where the various distances are shown in Fig. 2.6.1.
r12 e2
e1

r2b
r1a
Fig. 2.6.1 Various r1b
distances between r2a
electrons and nuclei in
hydrogen molecule Ha rab Hb

The two electrons will occupy the lowest bonding molecular orbital y + with
opposite spins. The total molecular wave function will include both the spatial
and spin functions and will be given by
ytotal = yspatial yspin (2.6.2)
where yspatial = y+ (1)y+ (2)

1
yspin = {a (1)b (2) – a(2)b(1)}
2
In the LCAO-MO framework, y+ will take the form of
y+ = C1 y1s(Ha) + C2 y1s(Hb) (2.6.3)

Since the two nuclei are identical, we will have

1
C1 = C2 = (2.6.4)
2(1 + S )
The energy of the system can be determined as usual by writing

·y + (1) y + (2) | H | y + (1)y + (2)Ò

E= (2.6.5)
·y + (1)y + (2) | y + (1)y + (2)Ò

From a quantitative point of view, the presence of two electrons in H2 produces

mathematical complications because of electron-electron repulsion term in the
Hamiltonian operator. Substitution of Eq. (2.6.3) in Eq. (2.6.5) produces a total
energy minimum of – 30.68 eV (– 2.96 MJ mol - 1 ) at the internuclear distance
of 73 pm. The respective observed values are – 31.95 eV (– 3.08 MJ mol–1)
and 74.1 pm. When the minimum is subtracted from the total energy of the two
hydrogen atoms, we get the bond energy of the hydrogen molecule equal to
3.48 eV, i.e. 335.78 kJ mol–1(calculated) and 4.75 eV, i.e. 458.32 kJ mol–1
(observed).
242 A Textbook of Physical Chemistry

The bond energy of H2 molecule is larger than that of H +2 . The bond distance
of H2 molecule is smaller than that of H +2 . These values may be interpreted in
terms of more electron density in between the two nuclei.

2.7 VALENCE-BOND TREATMENT OF A HYDROGEN MOLECULE

The simplest wave function in valence-bond framework is given by
y = y1s(Ha)(1)y1s(Hb)(2) (2.7.1)
Expression of The Hamiltonian operator of the hydrogen molecule (Eq. 2.6.1) may be written as
Hamiltonian
Operator H = Ha + Hb + H ¢ (2.7.2)

h2 e2 h2 e2
where Ha = – — 2
- ∫ - — 2
-
(4pe 0 )r1a (4pe 0 )r2a
1 2
8p 2 m 8p 2 m

h2 e2 h2 e2
Hb= – — 2
- ∫ - — 2
-
(4pe 0 )r2 b (4pe 0 )r1b
2 1
8p 2 m 8p 2 m

e2 e2 e2 e2
H¢= – - + +
(4pe 0 )r2a (4pe 0 )r1b (4pe 0 )r12 (4p e 0 )rab

e2 e2 e2 e2
∫ - + +
(4pe 0 )r1a (4pe 0 )r2 b (4pe 0 )r12 (4p e 0 ) rab

Expectation Value Assuming AOs are normalized, the energy of the wave function can be evaluated
of Energy by using the expression

E = ·y | H | y Ò (2.7.3)

On substituting Eq. (2.7.1) in Eq. (2.7.3), we get

E = · y 1s(Ha ) (1) y 1s(H b ) (2) Ω H a + H b + H ¢Ω y 1s(Ha ) (1) y 1s(H b ) (2)Ò

= · y 1s(Ha ) (1) Ω H aΩ y 1s(Ha ) (1)Ò · y 1s(H b ) (2)Ω y 1s(H b ) (2)Ò

+ · y 1s(H b ) (2) Ω H bΩ y 1s(H b ) (2)Ò · y 1s(Ha ) (1)Ωy 1s(Ha ) (1)Ò

+ · y 1s(Ha ) (1) y 1s(H b ) (2) Ω H ¢ Ω y 1s(Ha ) (1) y 1s(H b ) (2)Ò (2.7.4)

Since y 1s(Ha ) and y 1s(H b ) are the normalized functions, Eq. (2.7.4) reduces to

E = E1s(Ha ) + E1s(H b ) + Q = 2E1s(H) + Q (2.7.5)

where Q = · y 1s(Ha ) (1) y 1s(H b ) (2) Ω H ¢Ω y 1s(Ha ) (1) y 1s(H b ) (2)Ò

 Theories of Covalent Bond 243

On substituting the expression of H ¢, we will get

e2 e2
Q = – · y 1s(Ha ) (1) y 1s(Ha ) (1)Ò – · y 1s(H ) (2) y 1s(H ) (2)Ò
(4pe 0 )r1b b (4pe 0 )r2a b

e2 e2
+ · y 1s(Ha ) (1) y 1s(H b ) (2) y 1s(Ha ) (1) y 1s(H ) (2)Ò +
(4pe 0 )r12 b (4pe 0 )rab
The integral can be evaluated and is found to have a negative value.

The binding energy of the hydrogen molecule will be given by

Ebinding = E (H2) – 2E(H) = Q (2.7.6)

When Q is evaluated at different values of rab, it is found to have a minimum

of about 24 kJ mol –1 at a distance of about 90 pm. The experimental values of
binding energy and bond distance are 458 kJ mol–1 and 74 pm, respectively. The
agreement of calculated value of binding energy with the experimental value is
only about 5 per cent.
Heitler-London The above-mentioned poor agreement is due to the fact that it is not possible to
Wave Function label electrons since all electrons are indistinguishable from each other. Moreover,
even if this labelling is possible, one would not be sure that electron 1 is associated
with Ha and electron 2 with Hb. It might be possible that electron 1 is associated
with Hb and electron 2 with Ha. Heitler and London incorporated this fact by
writing the molecular wave function as
yVB = C1 y 1s(Ha ) (1) y 1s(Hb ) (2) + C2 y 1s(Ha ) (2) y 1s(Hb ) (1) (2.7.7)
We write Eq. (2.7.7) as
yVB = C1y1 + C2y2 (2.7.8)
where y1 = y 1s(Ha ) (1) y 1s(Hb ) (2) (2.7.9)

and y2 = y 1s(Ha ) (2) y 1s(Hb ) (1) (2.7.10)

Expectation Value The energy of H2 molecule is given by

of Energy
·y VB H y VB Ò ·(C1y 1 + C2y 2 ) H (C1y 1 + C2y 2 )Ò
E= =
·y VB | y VB Ò ·(C1y 1 + C2y 2 ) | (C1y 1 + C2y 2 )Ò

C12 y 1 | H | y 1 + C22 y 2 | H | y 2 + 2C1C2 y 1 | H | y 2

= (2.7.11)
C12 y 1 | y 1 + C22 y 2y 2 + 2C1C2 y 1y 2
We have
·y1y1Ò = · y 1s(Ha ) (1) y 1s(H b ) (2)Ω y 1s(Ha ) (1) y 1s(H b ) (2) Ò

= · y 1s(Ha ) (1)Ω y 1s(Ha ) (1) Ò · y 1s(H b ) (2)Ω y 1s(H b )(2) Ò

=1¥1=1
244 A Textbook of Physical Chemistry

·y2Ωy2Ò = · y 1s(Ha ) (2) y 1s(H b ) (1)Ω y 1s(Ha ) (2) y 1s(H b ) (1)Ò

= · y 1s(Ha ) (2)Ω y 1s(Ha ) (2) Ò · y 1s(H b ) (1)Ω y 1s(H b ) (1)Ò

=1¥1=1

·y1Ωy2Ò = · y 1s(Ha ) (1) y 1s(H b ) (2)Ω y 1s(Ha ) (2) y 1s( H b ) (1)Ò

= · y 1s(Ha ) (1)Ω y 1s(Hb ) (1) Ò · y 1s(H b ) (2)Ω y 1s(Ha ) (2)Ò

= S ¥ S = S2
where S is the overlap integral. Representing
·y1Ω H Ωy1Ò = a 1

·y2Ω H Ωy2Ò = a 2

·y1Ω H Ωy2Ò = b 12
we can write Eq. (2.7.11) as

C12a1 + C22a 2 + 2C1C2 b12

E= (2.7.12)
C12 + C22 + 2C1C2 S 2
Optimization of To minimize E with respect to C1 and C2, we get
Coefficients
∂E ∂E
=0 and =0
∂C1 ∂ C2

To evaluate ∂E/∂C1, we write Eq. (2.7.12) as

E ( C12 + C22 + 2C1C2S 2 ) = C12 a1 + C22 a 2 + 2C1C2 b12

and differentiate it with respect to C1 to give

Ê ∂E ˆ
E(2C1 + 2C2S2) + Á ( C 2 + C22 + 2C1C2S 2) = 2C1a1 + 2C2 b12
Ë ∂C1 ˜¯ 1
This gives

∂E 2C1a1 + 2C2 b12 - E (2C1 + 2C2 S 2 )

=
∂C1 C12 + C22 + 2C1C2 S 2

On setting the above expression equal to zero, we get

C1a1 + C2b12 – E (C1 + C2S2) = 0 (2.7.13)

Similarly, evaluating ∂ E/∂C2 = 0, we get

C1b12 + C2a 2 – E (C1S 2 + C2) = 0 (2.7.14)
Equations (2.7.13) and (2.7.14) may be written as
 Theories of Covalent Bond 245

C1(a1 – E) + C2 (b12 – ES2) = 0 (2.7.15)

C1 (b12 – ES 2) + C2 (a 2 – E) = 0 (2.7.16)
These equations are known as secular equations. In the matrix form, we get

a1 - E b12 - ES 2 C1
=0 (2.7.17)
b12 - ES 2 a2 - E C2

In order to have nontrivial solutions of secular equations, we get

a1 - E b12 - ES 2
=0 (2.7.18)
b12 - ES 2 a2 - E

This determinant is known as secular determinant. On opening the determinant,

we get
(a1 – E ) (a2 – E ) – (b12 – ES 2)2 = 0 (2.7.19)

Equation (2.7.19) is quadratic in E, and provides two roots of E. These roots

when substituted in the secular equations along with the normalization of the wave
function yVB C1 and C2.

For hydrogen molecule, the functions y1 and y2 in yVB involve the same type
of atomic orbitals with the exception of allocation of electrons 1 and 2 to atomic
orbitals. We may expect that
a 1 = a2
Writing it as a and b12 as b
(a – E) 2 – (b – ES 2) 2 = 0
this gives
a – E = ± (b – ES 2)
The two roots of E are
a+b a-b
E+ = and E– = (2.7.20)
1+ S 2
1 - S2
Expressions of Substituting the expression of E + in Eq. (2.7.15), we get
Coefficients C1
Ê a +bˆ Ê a + b 2ˆ
and C2 C1 Á a - 2˜
+ C2 Á b - S =0
Ë 1+ S ¯ Ë 1 + S 2 ˜¯
On simplifying this expression, we get
C1 = C2 (2.7.21)
Similarly, the substitution of the expression of E– in Eq. (2.7.15), we get
C1 = – C2 (2.7.22)
246 A Textbook of Physical Chemistry

Note: The fact that C1 = ± C2 follows directly from the symmetry consideration of
hydrogen molecule. Both the atoms will have identical charge densities and thus
C12 = C22 . From this it follows that C1 = ± C2.

The constants C1 (or C2) may be evaluated by using the normalization expression
of yVB:

Ú y VB dt = C12 + C22 + 2C1C2S 2 = 1

2

1
For C1 = C2, we get C1 = (2.7.23)
2(1 + S 2 )

1
For C1 = – C2, we get C1 = (2.7.24)
2(1 - S 2 )
Analysis of We have
Integral a
a = ·y 1s(Ha ) (1) y 1s(Hb ) (2)Ω H Ωy 1s(Ha ) (1) y 1s(Hb ) (2)Ò

= ·y 1s(Ha ) (1) y 1s(Hb ) (2)Ω H a + H b + H ¢Ωy 1s(Ha ) (1) y 1s(Hb ) (2)Ò

= ·y 1s(Ha ) (1)Ω H aΩy 1s(Ha ) (1)Ò · y 1s(Hb ) (2)Ω y 1s(Hb ) (2)Ò

+ · y 1s(Hb ) (2)Ω H bΩ y 1s(Hb )(2)Ò ·y 1s(Ha ) (1)Ωy 1s(Ha ) (1)Ò

+ ·y 1s(Ha ) (1) y 1s(Hb ) (2)Ω H ¢Ωy 1s(Ha ) (1) y 1s(Hb )(2)Ò

= E1s(Ha ) ·y 1s(Ha ) (1)Ωy 1s(Ha ) (1)Ò · y 1s(Hb ) (2)Ω y 1s(Hb ) (2)Ò

+ E1s(Hb ) · y 1s(Hb ) (2)Ω y 1s(Hb ) (2)Ò ·y 1s(Ha ) (1)Ωy 1s(Ha ) (1)Ò

+ ·y 1s(Ha )(1) y 1s(Hb )(2)Ω H ¢Ωy 1s(Ha ) (1) y 1s(Hb )(2)Ò

= E1s(Ha ) + E1s(Hb ) + Q
= 2E1s(H) + Q (2.7.25)
Analysis of We have
Integral b
b = ·y 1s(Ha ) (1) y 1s(Hb )(2)Ω H a + H b + H ¢Ωy 1s(Ha )(2) y 1s(Hb )(1)Ò

= ·y 1s(Ha ) (1)Ω H bΩ y 1s(Hb ) (1)Ò · y 1s(Hb ) (2)Ωy 1s(Ha ) (2)Ò

+ · y 1s(Hb ) (2)Ω H aΩy 1s(Ha ) (2)Ò ·y 1s(Ha ) (1)Ω y 1s(Hb ) (1)Ò

+ ·y 1s(Ha ) (1) y 1s(Hb ) (2)Ω H ¢Ωy 1s(Ha ) (2) y 1s(Hb ) (1)Ò

 Theories of Covalent Bond 247

= E1s(H ) ·y 1s(Ha ) (1)Ω y 1s(Hb ) (1)Ò · y 1s(Hb ) (2)Ωy 1s(Ha ) (2)Ò

b

+ E1s(Ha ) · y 1s(Hb ) (2)Ωy 1s(Ha ) (2)Ò ·y 1s(Ha ) (1)Ω y 1s(Hb ) (1)Ò

+ ·y 1s(Ha ) (1) y 1s(Hb ) (2) Ω H ¢Ωy 1s(Ha ) (2) y 1s(Hb ) (1)Ò

= E1s(Hb ) S 2 + E1s(Ha ) S 2 + A

= 2E1s(H) S 2 + A (2.7.26)

Expression of Substituting Eqs (2.7.25) and (2.7.26) in Eq. (2.7.20), we get

Energies
a+b (2 E1s(H) + Q) + (2 E1s(H) S 2 + A)
E+ = =
1 + S2 1 + S2

Q+A
= 2E1s(H) + (2.7.27)
1 + S2

a-b (2 E1s(H) + Q) - (2 E1s(H) S 2 + A)

E– = =
1 - S2 1 - S2

Q-A
= 2E1s(H) + (2.7.28)
1 - S2
Analysis of On substitution the expression of H ¢ in the expression of Q integral, we get
Integrals Q and A
e2 e2 e2
Q = ·y 1s(Ha ) (1) y 1s(Hb )(2) - – +
(4pe 0 )r1b (4pe 0 )r2a (4pe 0 )r12

e2
+ y 1s(Ha ) (1) y 1s(Hb ) (2)Ò
(4pe 0 )rab

e2
= ·y 1s(Ha ) (1) - y 1s(Ha ) (1)Ò · y 1s(Hb ) (2)Ω y 1s(Hb ) (2)Ò
(4pe 0 )r1b

e2
+ · y 1s(Hb ) (2) - y 1s(H )(2)Ò ·y 1s(H ) (1)Ωy 1s(H ) (1)Ò
(4pe 0 )r2a b a a

e2
+ ·y 1s(Ha ) (1)Ω y 1s(Hb ) (2) y 1s(Ha ) (1) y 1s(Hb ) (2)Ò
(4pe 0 )r12

e2
+ ·y 1s(Ha ) (1)Ωy 1s(Ha ) (1)Ò · y 1s(Hb ) (2)Ω y 1s(Hb ) (2)Ò
(4pe 0 )rab
248 A Textbook of Physical Chemistry

e2 e2
= – ·y 1s(Ha ) (1) y 1s(Ha ) (1)Ò – · y 1s(Hb ) (2) y 1s(H ) (2)Ò
(4pe 0 )r1b (4pe 0 )r2a b

e2 e2
+ ·y 1s(Ha ) (1) y 1s(Hb ) (2) y 1s(Ha ) (1) y 1s(Hb ) (2)Ò +
(4pe 0 )r12 (4pe 0 )rab
(2.7.29)
Similarly, the integral A can be analysed to give

e2 e2
A = – S ·y 1s(Ha ) (1) y 1s(H )(1)Ò – S · y 1s(H ) (2) y 1s(Ha ) (2)Ò
(4pe 0 )r1b b b (4pe 0 )r2a

e2 e2 S 2
+ ·y 1s(Ha ) (1) y 1s(Hb ) (2) y 1s(Ha ) (2) y 1s(Hb ) (1)Ò +
(4pe 0 )r12 (4pe 0 )rab
(2.7.30)

The integrals involved in Eq. (2.7.29) can be easily interpreted. For example, the

Ha with nucleus Hb via the Coulombic potential; the second term is the Coulombic
energy of interaction of the charge density of electron 2 around Hb with nucleus
Ha; the third term is the mutual Coulombic interaction energy of the two electronic
charge densities; and the fourth term is the nuclear-nuclear Coulombic interaction.
Since each term in Eq. (2.7.29) can be interpreted as a classical Coulombic
interaction, Q is referred to as the Coulomb integral. It is worth noticing that the
integrals involved in Eq. (2.7.30) cannot be likewise interpreted. Its presence in
the energy expressions is due to the form of the wave function (Eq. 2.7.7) which
explicitly recognizes the indistinguishability of the two electrons. Consequently, A
is a strictly quantum-mechanical quantity. Since A arises because of the exchange
of electrons between the two nuclei, it is referred to as the exchange integral.

The integrals Q and A can be evaluated. Near the observed internuclear distance,
both these integrals have negative values with A to be more negative than Q. With
this fact, it follows that E+ < E– .

Potential Energy The energy of hydrogen molecule relative to two hydrogen atoms is given by
Diagram
Q±A
DE± = (2.7.31)
1 ± S2
When D E± is plotted against the various values of rab, one gets the curves as shown
in Fig. 2.7.1. It is obvious that DE+ describes a stable chemical bond because the
energy is less than that of the two isolated hydrogen atoms, whereas D E– describes
a state that is unstable at all values of rab. The minimum of DE+ versus rab curve
occurs at 87 pm with ΩDE+Ω = 305 kJ mol –1. The observed values as stated above
are 74.1 pm and 458.32 kJ mol –1.
 Theories of Covalent Bond 249

3 D E–

0
D E+

2 Expt.

6
Fig. 2.7.1 Plot of DE± 0 1 2 3 4 5
versus rab/a0 rab/a0

Thus, the agreement of calculated binding energy with the experimental energy is
very much enhanced (about 66.6%). This is primarily due to the exchange integral.

The calculated binding energy can be improved further by including screening

parameter (i.e. treating Z
in the wave function. The value obtained is 365 kJ mol –1 at rmin = 74.3 pm. The
agreement is thus enhanced to about 80 per cent. If, in addition to the above
screening factor, the ionic structures are included, |DE+| and rmin become 388 kJ
mol–1 and 74.9 pm, respectively. The agreement in |DE+| becomes about 85 per cent.
2.8 COMPARISON BETWEEN MO AND VB TREATMENTS OF A HYDROGEN MOLECULE

Expression of In molecular orbital treatment of H2, two electrons with opposite spins are assigned
Molecular Orbital to the lowest molecular orbital y+. Thus, the spatial wave function of H2 is
yspatial = y+ (1)y+ (2)

=
1
2(1 + S )
{
y 1s(Ha ) (1) + y 1s(H ) (1)
b } {y 1s(Ha ) ( 2) }
+ y 1s(H ) (2)
b

Opening out the above expression, we get

1 Èy 1s(H ) (1) y 1s(H ) (2) + y 1s(H ) (1) y 1s(H ) (2)
yspatial =
2(1 + S ) Î a a a b

+ y 1s(H ) (1) y 1s(Ha ) (2) + y 1s(H ) (1)y 1s(H ) (2) ˘˚

b b b

In the above expression, the various terms represent the structures as described below.
First and fourth terms The terms are y 1s(Ha ) (1) y 1s(Ha ) (2) and y 1s(Hb ) (1)
y 1s(H ) (2) a or
b
atom Hb and hence they represent ionic structures.
250 A Textbook of Physical Chemistry

Second and third terms The terms are y 1s(Ha ) (1) y 1s(Hb ) (2) and y 1s(Hb ) (1) y 1s(Ha ) (2) .

represent covalent structures.

gives equal weightage to the ionic and covalent structures. It is expected that the
MO function will be poor at large internuclear separations since the dissociation
products will be an equal mixture of ions and atom. In actual practice we get two
hydrogen atoms. On the other hand, for very short internuclear distances one expects

orbital. Thus, MO treatment does take into account this fact, but perhaps gives
more weightage to this fact than what actually exists in the molecule.

The valence-bond treatment accounts for ionic structures by including the ionic
structures to the Heitler-London wave function which represents the covalent
structure. The amount of mixing is determined by the variation method which gives

Method of The MO can be improved by the method of . In this, the

Configuration wave function is taken as linear combination of functions arising from different
Interaction
functions are possible:
y1 = y+ (1)y+(2)
y2 = y+ (1)y–(2) + y+(2)y–(1)
y3 = y+(1)y–(2) – y+ (2)y- (1)
y4 = y–(1)y- (2)
In the wave function y1, both the electrons are assigned to the ground state
molecular orbital y+ , in y2 and y3, one electron is assigned to y+ and the other to
y–, and in y4, both the electrons are assigned to the antibonding molecular orbital
y–
y = C1y1 + C2y2 + C3y3 + C4y4 (2.8.1)

exchange of the two protons. Remembering that y+ and y– are symmetrical and
antisymmetrical wave functions, respectively, the symmetry nature of each of the

y1 = y+ (1) y+(2); (symmetrical)

(sym) (sym)
y2 = y+(1) y–(2) + y+(2) y–(1); (antisymmetrical)
(sym) (antisym) (sym) (antisym)
 Theories of Covalent Bond 251

y3 = y+(1) y–(2) – y+(2) y–(1); (antisymmetrical)

(sym) (antisym) (sym) (antisym)
y4 = y–(1) y–(2); (symmetrical)
(antisym) (antisym)
The functions y 1 and y 4 are symmetrical in nature whereas y 2 and y 3
are antisymmetrical. Hence, the configuration y 4 will only mix up with the
y1. thus, Eq. (2.8.1) reduces to†
y = C1y1 + C4y4 (2.8.2)
Substituting the expressions of y1 and y4, we get
y1 = C1y+ (1)y+(2) + C4y–(1)y–(2)
On substituting the LCAO expressions of y+ and y–, we get

{
y = C1 y 1s(Ha ) (1) + y 1s(H ) (1)
b } {y 1s(Ha ) ( 2) + y 1s(H ) (2)
b }
{
+ C4 y 1s(Ha ) (1) - y 1s(H ) (1)
b } {y 1s(Ha ) ( 2) }
- y 1s(H ) (2)
b
On opening the brackets and rearranging, we get
y = (C1 – C4) ycovalent + (C1 + C4) yionic (2.8.3)

where ycovalent = y 1s(Ha ) (1)y 1s(H ) (2) + y 1s(Ha ) (2)y 1s(H ) (1)
b b

and yionic = y 1s(Ha ) (1)y 1s(Ha ) (2) + y 1s(Hb ) (1)y 1s(Hb ) (2)

y1 and y4 in Eq. (2.8.2) will

C4 having positive and
negative values, respectively. From Eq. (2.8.3), it thus follows that the contributions

tion y1
y4.

interaction is exactly the same as valence-bond theory with ionic terms included.
Both methods approach each other when more and more of covalent and ionic terms

are included in the MO theory.

The MO theory is mathematically much simpler than the VB theory. The

MO theory can be applied to large molecules easily with the help of electronic
computers. By equating some of the cumbersome integrals to the experimental
quantities and empirical parameters, the MO treatment to larger molecules has

†
In fact, when the elements of secular determinant for the function y are evaluated, the
elements H12, H13, H24 and H34 will come out to be zero. This will lead to C2 = C3 = 0 in
one of the solutions of wave functions, i.e. it leads to wave function as given by Eq. (2.8.2).
252 A Textbook of Physical Chemistry

2.9 MO TREATMENT OF HOMONUCLEAR DIATOMIC MOLECULES

Shapes of In homonuclear diatomic molecules, we can form molecular orbitals by taking

Molecular Orbitals linear combinations of y1s(A) and y1s(B), y2s(A) and y2s(B), y 2p z ( A ) and y 2p z ( B) ,
y 2p x ( A ) and y 2p x ( B) , and y 2p y ( A ) and y 2p y ( B) , where z-axis is the internuclear
axis. The combinations y2s(A) and y 2p x ( B) (or y 2p y ( B) ), and y 2p z ( A ) and y 2p x ( B)
(or y 2p y ( B) ) do not produce any combination due to symmetry requirements. Each
combination produces two molecular orbitals, bonding and antibonding (Table
2.9.1). Their shapes are shown in Fig. 2.9.1.

Table 2.9.1 Molecular Orbitals of Homonuclear Diatomic Molecules

formed from the Orbitals of Principal Quantum Number 2
Molecular Bonding or Designation
wave function antibonding

N(y2s(A) – y2s(B)) antiboding s*2s or su 2s

N (y2s(A) + y2s(B)) bonding s 2s or sg 2s
N ( y 2p z ( A ) + y 2p z ( B) ) antibonding s*2p or su 2p

N ( y 2p z ( A ) – y 2p z ( B) ) bonding s 2p or sg 2p

N ( y 2p x or y ( A ) – y 2p x or y ( B) ) antibonding p*2p or pg 2p

N ( y 2p x or y ( A ) + y 2p x or y ( B) ) bonding p 2p or pu 2p

The molecular orbitals formed from the orbitals of principal quantum number 3
can be similarly worked out.

Designation of MO The designation shown in the last column of Table 2.9.1 is based on the following
facts.
(i) The value of component of the orbital angular momentum along the
internuclear axis.
The component of the orbital angular momentum along the internuclear distance
(z-axis) is ± ml h / 2p, where ml has integral values including zero, i.e. ml = 0, 1,
2, 3, . Except when ml = 0, the orbitals are all doubly degenerate corresponding
to the positive and negative angular momentum values along the z-axis. The
designation of orbitals based on the value of ml is given below:
ml 0 1 2 3
orbital type s p d j
(ii) The atomic orbitals into which they separate at large distances.
The nature of orbitals to which a molecular orbital degenerates is shown by
writing 1s, 2s, etc., after the s, p, d, , symbols.
(iii) The bonding-antibonding character or the symmetry of the orbital with
respect to its centre.
 Theories of Covalent Bond 253

The orbital designation with bonding and antibonding character or on the

symmetry of the orbitals with respect to its centre is done as described in the
following. The antibonding orbitals are designated by placing an asterisk on the
symbol listed above, the bonding orbitals do not carry any asterisk. Thus, s, p,
etc., are bonding orbitals and s *, p*. etc., are antibonding orbitals. Alternatively,
the symmetry of the orbitals with respect to its centre is shown by using the
symbols g (gerade, the German word for even or symmetrical) and u (ungerade,
the German word for odd or unsymmetrical) as the subscripts. From the contour
diagrams of molecular orbitals shown in Fig. 2.9.1, it follows that the bonding
orbitals s 2s and s 2p, and the antibonding orbital p*2p are gerade in nature and
thus are designated as sg2s, sg2p and pg2p, respectively. The antibonding orbitals
s *2s and s*2p and the bonding orbital p2p are ungerade in nature and thus are
designated as su2s, su2p and pu2p, respectively.

Fig. 2.9.1 Formation

of molecular orbitals
from the linear combi-
nations of two atomic
orbitals
254 A Textbook of Physical Chemistry

Relative Order The relative order of energies of various molecular orbitals is required for writing
of Energies of
Molecular Orbitals of a molecular orbital depends on the following two factors.
without s-p
(i) The type of atomic orbitals from which the molecular orbital is built up.
Interaction
(ii) The extent of overlap between the two involved orbitals.

Since the energy of 1s orbital is much lower than that of 2s orbital, it is obvious
that s 1s (or sg1s) and s *1s (or su1s) have energies lower than s 2s. In turn, as
2s orbitals has lower energy than 2p, it is expected that s 2s (or sg 2s) lies below
s 2p (or sg2p). Since the end to end overlap between two 2s orbitals or two 2pz
orbitals is larger than the sideway overlap between two 2px or 2py orbitals, it is
expected that the separation between the bonding and antibonding p orbitals is
lesser than the separation of those of s orbitals.

From the above facts, we may draw the molecular orbital energy diagram as
shown in Fig. 2.9.2.

s *2p

p*2p

2p 2p

p 2p
s2p

s *2s
Energy

2s 2s

s 2s

s*1s
1s 1s
Fig. 2.9.2 Molecular
atom s 1s
orbital energy diagram molecule atom
(A)
(B)

From Fig. 2.9.2, we may write

s 1s < s *1s < s 2s < s *2s < s 2p < p2p < p*2p < s *2p
 Theories of Covalent Bond 255

In terms of g and u representations, we have

sg1s < su1s < sg 2s < su2s < sg2p < pu2p < pg2p < su2p

Order of Energy In most cases, the orbitals 2s and 2p have energies close to each other. Because of
Levels with s-p this, the positive overlap between 2s(A) and 2pz(B) or vice versa will also contribute
Interaction to the formation of molecular orbitals. In other words, each of s and s * molecular
orbitals will be formed by mixing four atomic orbitals 2s(A), 2pz(A), 2s(B) and
2pz(B). Such mixing will also modify the molecular orbital energy diagram. The
s 2s and s 2p, and
s *2s and s *2p as described by the following wave functions:
y±1 = C1 (s 2s) ± C2 (s 2p) (2.9.1)

y±2 = C3 (s *2s) ± C4(s *2p) (2.9.2)

These interactions make s 2s and s *2s energetically more stable, and s 2p and
s *2p less stable, i.e. the energies of s 2s and s *2s are lowered whereas those of
s 2p and s

y–2

s *2p
y–1
Energy

s2p

s *2s
Fig. 2.9.3 Interaction y+2
between s 2s and s 2p,
and s *2s and s *2p s2s
orbitals y+1

For lighter molecules, the above interactions are important. Consequently, the
energy of s 2p orbital becomes larger than that of p 2p and thus the molecular

From Fig. 2.9.4, we may write

s 1s < s *1s < s 2s < s *2s < p2p < s 2p < p*2p < s *2p

In terms of g and u representations, we have

sg 1s < su1s < sg2s < su2s < pu2p < sg2p < pg2p < su2p

2
and F2.
256 A Textbook of Physical Chemistry

Energy

Fig. 2.9.4 Molecular

orbital diagram
where the interaction
between 2s and 2p is
observed

Electronic Following aufbau principle, Pauli exclusion principle and Hund’s rule, we can write
Configurations
of Homonuclear so, it is worth considering a very important conclusion that the electrons in the
Diatomic inner shells of atom play no effective part in molecular binding
Molecules for the above rule is given below.
s 1s)2(s *1s)2 of some heavier homonuclear diatomic
molecules (say, for example, C2 ). The charge distribution associated with the

2(y+1s)2 + 2(y–1s )2
Substituting the expressions of y+1s and y–1s, we get

+ y 1s(B) ˆ 2
Ê y ( ) - y 1s(B) ˆ
2
2 ¥ ÊÁ 1s(A)
y
+ 2 ¥ Á 1s A
Ë 2 (1 + S ) ˜¯ Ë 2 (1 - S ) ˜¯

or
2
{y 12s(A) + y 12s(B) - 2Sy 1s(A)y 1s(B) }
1- S2

Now for C2, S ª 10–5 for a normal C—C single bond. With this small value,
the above expression reduces to

2 (y 21s(A) + y 21s(B))
that is, it is simply equal to the sum of the electron densities of the 1s(A) and
1s(B) orbitals. This implies that in the formation of the diatomic molecules C2,
the electrons in the K-shells remain as they were in the isolated atoms. In other
 Theories of Covalent Bond 257

words, inner shells play no role in the molecular bonding. Thus, while writing

(s 1s)2(s *1s)2 by KK, meaning that both the K-shells are fully occupied.

molecules H2 to F2 and some of their positive ions. These are shown in Table 2.9.2.

Table 2.9.2
Molecule Electronic Dissociation energy Net excess of Bond Bond
kJ mol–1 bonding electrons order length / pm
H+2 (sg1s)1 255.7 1 0.5 106

H2 (sg1s)2 432.3 2 1 74

He+2 (sg1s)2(su1s)1 250.9 ± 48.2 1 0.5 108

He2 (sg1s)2(su1s)2 – 0 0
2
Li2 KK(sg2s) 110.0 2 1 267

Be2 KK(sg2s)2(su2s)2 – 0 0

B2 (Be2) (pu2p)2 289.5 ± 48.2 2 1 159

C2 (Be2)(pu2p)4 598.2 4 2 124

N+2 4
(Be2)(pu2p) (sg2p) 1
842.3 5 2.5 112

N2 (Be2) (pu2p)4 (sg2p)2 941.7 6 3 109

O+2 (Be2)(sg2p)2 (pu2p)4(pg2p)1 625.2 5 2.5 112

O2 (Be2)(sg2p)2 (pu2p)4 (pg2p)2 490.2 4 2 121

2 4 4
F2 (Be2) (sg2p) (pu2p) (pg2p) 154.4 ± 33.8 2 1 144

Ne2 (Be2)(sg2p)2(pu2p)4(pg2p)4(pu2p)2 – 0 0

A Few In general, we have

Characteristics of ∑ The strength of a bond depends on the net excess of electrons in bonding
Molecules orbitals over those of antibonding orbitals. Larger the bond strength, larger
the dissociation energy of the molecule.
∑ The number of bonds or bond order in a molecule is one half of the net excess
of bonding electrons.
∑ Addition of an electron in the bonding orbital makes the molecule more stable
whereas that in the antibonding orbital makes it less stable.
∑ Paramagnetism in a substance is due to the presence of unpaired electrons in
its molecules.
258 A Textbook of Physical Chemistry

Keeping in mind the above characteristics, we may derive the following conclusions
regarding some of the physical properties of diatomic molecules listed in Table 2.9.2.
1. The dissociation energy of H2 is almost twice that of H +2 . This follows from
the fact that H2 contains two bonding electrons in the sg1s whereas H +2 contains
only one. The decrease in bond length from H +2 to H2 is also due to the above fact.
2. The dissociation energy of H +2 is almost the same as that of He+2. The
presence of one electron in su1s in He+2 undo the effect of one electron in sg1s
and thus He+2 contains only one electron in sg1s.
3. The molecule He2 is not stable in the ground state as it contains equal
number of electrons in the bonding sg1s and antibonding su1s orbitals. Excited
state of He2, however, is observed. This is due to the promotion of electron from
antibonding orbital to the bonding orbital.
4. The Be2 molecule likewise is not a stable molecule.
5. N +2 is a paramagnetic substance as it contains one unpaired electron.
6. N2 has the maximum bond dissociation energy as it contains six net excess
of bonding electrons. The bond between N and N is a triple bond.
7. In going from N2 to N +2 , the bond energy weakens and bond length is increased.
This follows from the fact that the electron removed is from the bonding orbital.
8. O 2 molecule contains a double bond (one s and the other p). It is a
paramagnetic substance, which is due to the presence of two unpaired electrons
in the doubly degenerate pg2p orbitals.
9. In going from O2 to O+2, the bond dissociation energy is increased and the
bond length is shortened. This follows from the fact that the electron removed is
from the antibonding orbital.

Problem 2.9.1 (a) Show that the wave functions y±1 and y±2 as described by Eqs 2.9.1 and 2.9.2,
respectively, are equivalent to the molecular orbitals obtained by mixing the two hybrid
orbitals centred on atoms A and B, respectively.
(b) Draw schematic contour diagrams of y±1 and y±2 starting from those of involved
(i) molecular orbitals (i.e. s 2s, s*2s, etc.) and (ii) hybrid orbitals (i.e. sp1(A), sp1(B),
etc.). Also infer whether the orbitals y±1 and y±2 will be more or less stable than its
constituent orbitals.
Draw the correlation diagram for homonuclear diatomic molecules exhibiting s-p
mixing.
(a) The expression of the wave function y±1 is
Solution y±1 = C1 (s 2s) ± C2 (s 2p)
The function y+1 will include more contribution from s 2s (i.e. C1 > C2) and also will
be more stable than s2s orbital. On the other hand, the function y–1 will include more
contribution from s2p (i.e. C2 > C1) and will be less stable than this orbital.
Substituting the expressions of s2s and s2p (Table 2.9.1) in the wave function
y±1, we get
y+1 = C1 { N (y 2s(A) + y 2s(B) )} + C2 { N (y 2 pz (A) - y 2 pz (B) )}
= C 1¢ (y 2s(A) + ly 2 pz (A) ) + C1¢ (y 2s(B) - ly 2 pz (B) )
= C¢1 (y sp1(A) + y sp1(B) )
 Theories of Covalent Bond 259

where C1¢ = C1N, C2¢ = C2N and l = C2¢ / C1¢ . Since C1¢ is greater than C2¢ for the wave
function y+ 1, the term l will have a value less than one. Consequently, the hybrid
orbitals sp1(A) and sp1(B) will include more weightage from the orbitals 2s(A) and 2s(B),
respectively.
For the function y–1, we have
y –1 = C1 { N (y 2s(A) + y 2s(B) )} - C2 { N (y 2 pz (A) - y 2 pz (B) )}

= C2¢ {ly 2s(A) - y 2 pz (A) } + C2¢ {ly 2s(B) + y 2 pz (B) }

= = C2¢ {y sp2(A) + y sp2(B) }

where C2¢ = C2N, C1¢ = C1N and l = C1¢ / C2¢ . Since C2¢ is greater than C1¢ for the wave
function y– 1, the term l will have a value less than one. Consequently, the hybrid orbitals
sp2(A) and sp2(B) will include more weightage from the orbitals 2pz (A) and 2pz(B),
respectively.

For the function y+2 , we have

y+2 = C1 { N (y 2s ( A ) - y 2s ( B) )} + C2 { N (y 2 pz ( A ) + y 2 pz ( B) )}

= C1¢ {y 2s ( A ) + ly 2 pz ( A ) } - C1¢ {y 2s ( B) - ly 2 pz ( B) }

= C1¢ {y sp1 ( A ) - y sp1 ( B) }

The function y+2 will include more contribution from s *2s (i.e. C1 > C2) and also will
be more stable than s *2s orbital.
For the function y–2 , we have

y–2 = C1 { N (y 2s ( A ) - y 2s ( B) )} - C2 { N (y 2 pz ( A ) + y 2 pz ( B) )}

= C2¢ {ly 2s ( A ) - ly 2 pz ( A ) } - C2¢ {ly 2s ( B) + ly 2 pz ( B) }

= C2¢ {y sp2 ( A ) - y sp2 ( B) }

The function y–2 will include more contribution from s *2p (i.e. C2 > C1 ) and also
will be less stable than s *2p orbital.
(b) The following facts help constructing and understanding of the contour diagrams
and correlation diagram depicted in Fig. 2.9.5 and Fig. 2.9.6, respectively.
(i) The energies of hybrid orbitals sp1 and sp2 will lie in between those of 2s and 2pz
orbitals. Since sp1(A) and sp1(B) include more weightage from the 2s orbitals, their energies
will be nearer to 2s orbitals. On the other hand, the energies of sp2(A) and sp2(B) will be
nearer to 2pz orbitals as they include more weightage from these orbitals.
(ii) The wave function y+1 and y+2 are formed by ‘positive’ and ‘negative’ combinations
of y sp1 ( A ) and y sp1 ( B) , and thus y+1 will be more stable than y sp1 whereas y+2 will be
less stable than y sp1 . Similarly, the wave functions y–1 and y–2 are formed by ‘positive’
and ‘negative’ combinations of y sp2 ( A ) and y sp2 ( B) , and thus y–1 will be more stable than
y sp2 whereas y–2 will be less stable than y sp2 .
260 A Textbook of Physical Chemistry

(iii) As mentioned earlier, due to the s-p mixing, the function s2s and s*2s are more
stabilized whereas s2p and s*2p are less stabilized (or more destablized). This conclusion

function) in the bond region caused by s-p mixing as described in the following:
The function y+1 (or y+2) have more electron density in the bond region as compared
to that of its principal constituent s 2s (or s*2s). Hence y+1 and y+2 are more stable as
compared to s2s and s *2s, respectively.
The function y–1 (or y–2 ) have lesser electron density in the bond region as compared
to that of its principal constituent s 2p (or s*2p). Hence y–1 and y– 2 are less stable as
compared to s 2p and s *2p, respectively.

Fig. 2.9.5 Approxi-

mate contour
diagrams: (a) of
hybrid orbitals, (b)
of the molecular
orbitals obtained
via mixing of s 2s
and s 2p molecular
orbitals and via
mixing of sp-hybrid
orbitals
 Theories of Covalent Bond 261

No s-p mixing s-p mixing

s* 2p y–2

p*2p

2p 2p 2p 2p

p 2p sp2 y–1 sp2

s2p
y
+2
s*2s
sp1 sp1
2s 2s 2s 2s
y+ 1
s 2s

A B A A B B
(i) (ii)
Fig. 2.9.6 Correlation diagrams for homonuclear diatomic molecules exhibiting (i) no s-p mixing, and
(ii) s-p mixing viewed from the sp-hybrid orbitals centred on the two atoms

2.10 MOLECULAR TERM SYMBOLS

The electronic states of diatomic molecules, like atoms, may be designated by the
term symbols. The procedure to determine the term symbol is as follows:
(i) Determine the value of sum of z-component (i.e. along internuclear distance)
of orbital angular momentum quantum number.
The expression to be used is
ML = ml1 + ml + (2.10.1)
2

(ii) Determine the symbol corresponding to the value of M L

The symbol corresponding to the magnitude of M L , which is represented as L,
is the capital Greek letter as shown in the following:
ML 0 1 2 3 4
Symbol S P D F T
For each nonzero L value, there are two ML values; + L and –L; it is found that
the electronic energy depends on M L2, and there is a twofold degeneracy associated
with P, D, F, levels.
(iii) Determine the value of sum of z-component of spin angular momentum
quantum numbers.
The expression to be used is
MS = ms1 + ms2 + (2.10.2)
262 A Textbook of Physical Chemistry

(iv) Ascertain the value of total spin quantum number

From the values of MS , the value of S, which is equal to the maximum value
of MS , is ascertained.
(v) Designate the term symbol
The term symbol is represented as
2 S +1Ê symbolof ˆ
ÁË M ˜¯
L
1 3
A few examples are Â, Â and 2P.
A FEW WORKED OUT EXAMPLES

H2 molecule 2 is (sg1s)2. Thus, we have

ML = ml1 + ml2 = 0 + 0 = 0

MS = ms1 + ms2 = (+ 1/2 ) + (– 1/2) = 0

Symbol of ML equal to zero is Â.
Value of S is 0 (= 1/2 –1/2)
Multiplicity of spin, 2S + 1 = 2 ¥ 0 + 1 = 1
Hence, the term symbol is 1Â.
He+2 species He +2 is (sg1s)2 (su1s)1. Thus, we have
ML = ml1 + ml2 + ml3 = 0 + 0 + 0 = 0
MS = ms1 + ms2 + ms3 = (+ 1/2) + (– 1/2) + (± 1/2) = ± 1/2
Symbol of ML equal to zero is Â.
Value of S corresponding to MS = ± 1/2 is 1/2.
Multiplicity of spin, 2S + 1 = 2(1/2) + 1 = 2
Hence, the term symbol is 2Â.
B2 Molecule is
2
(sg1s)2(su1s)2(sg2s)2(su2s)2(pu2p)2.
T ML and
MS are separately equal to zero. For distributing two electrons amongst four spin
molecular orbitals of p-type, we proceed as follows:
ml = +1 ml = +1 ml = –1 ml = –1 Values of
ms = 1/2 ms = –1/2 ms = 1/2 ms = –1/2 ML MS
(i) ≠ Ø +2 0
(ii) ≠ ≠ 0 +1
(iii) ≠ Ø 0 0
(iv) Ø ≠ 0 0
(v) Ø Ø 0 –1
(vi) ≠ Ø –2 0
 Theories of Covalent Bond 263

∑ The symbol corresponding to |ML| = 2 is D.

The associated value of MS ( = 0 ) indicates that the value of S = 0. Thus, the
value of 2S + 1 = 1.
Hence, the term symbol for the enteries (i) and (vi) are 1D.
∑ The symbol corresponding to ML equal to 0 is Â.
The associated value of MS (= 1) indicates that the value of S = 1. Thus, the
value of 2S + 1 = 3.
The three spin projections associated with this are
MS = + 1, MS = 0 and MS = –1.
Hence, the enteries (ii), (iii) and (v) belong to the term symbol 3Â.
∑ The only left out entry is (iv) for which ML = 0 and MS = 0. Hence, its term
symbol is 1Â.
Thus, for B2, there are three possible molecular states. These are 1Â, 3Â and 1D.
Hund's rule is also applicable to molecular states. The ground state of B2 will
be 3Â as it has the largest spin multiplicity.

2.11 HETERONUCLEAR DIATOMIC MOLECULES

The LCAO-MO treatment of homonuclear diatomic molecules can be extended to

the heteronuclear diatomic molecules. For example, the molecular orbital of the
lowest energy may be constructed by the linear combination of 1s orbitals centred
on atoms A and B, respectively.
yMO = C1y1s(A) + C2y1s(B)
The energy of the orbital as usual can be determined by applying the variation
method to the expression:

y MO H y MO
E=
y MO | y MO
This will produce two secular equations:
C1 (aA – E ) + C2 (bAB – E SAB ) = 0
C1 (bAB – E SAB ) + C2 (aB – E) = 0

to zero, which on expanding will produce a quadratic expression in E. On solving

the latter, we get two roots of energy. These, in turn, can be substituted in the

general, the energy of one of the orbitals will be lesser than the smaller of the two
energies of atomic orbitals and the other will have larger value than the larger of
the two energies of atomic orbitals.

C1 and C2 are different and depend on the difference

in energies aA and aB (or difference of electronegativity of the two atoms). For

electronegative atom.
264 A Textbook of Physical Chemistry

In most cases, the difference of energies of 2s and 2p orbitals is not very large,
and hence the mixing of 2s and 2pz orbitals can also occur. This mixing will lower
the energies of s 2s and s *2s orbitals whereas those of s2p and s*2p are raised.

(i) One of the atoms is hydrogen and the other contains both s and p valence
orbitals. Examples include LiH, HCl, etc.
(ii) Both the atoms contain s and p valence orbitals. Examples include BN, BO,
CN, NO, etc.
The relative order of energies of various molecular orbitals for the above two

in the following.
ONE OF THE ATOMS IS HYDROGEN
In this category, we can have a molecule where H is more electronegative than the
other atom (example LiH) or vice versa (example HF). The hydrogen atom contains
only one valence orbital which can mix with 2s and 2pz orbitals of the other atom.

Lithium Hydride In LiH, 1s orbital of hydrogen mixes with both 2s and 2pz orbitals of Li, and thus
produces three molecular orbitals, s , s*s and s*z . The 2px and 2py orbitals do not
enter into any combination and thus their energies remain unaffected. Such orbitals
are known as nonbonding orbitals. The relative order of energies of various orbitals
is shown in Fig. 2.11.1. The lowest orbital s, which is more stable than 1s orbital
of hydrogen, is mainly composed of hydrogen 1s orbital with smaller fractions of
lithium 2s and 2pz orbitals.
sz*

ss*

2p {
p x, y

2s
Energy

ls
Fig. 2.11.1 Correla- s
tion diagram of LiH
Li LiH H

The s*s orbital has energy greater than px and py orbitals with much greater
weightage of lithium 2s orbital. The s*z orbital is less stable than that of 2pz orbital
of lithium and has considerable pz
Li(1s)2 (s)2
 Theories of Covalent Bond 265

Example 2.11.1 Determine the partial ionic character of LiH by evaluating the Mullikan gross atomic
population numbers. Given:
(i) The lowest bonding molecular orbital
s = 0.700 y1s(H) + 0.328 y2s(Li) + 0.204 y 2p z ( Li )
(ii) Overlap integrals: S (1s(H); 2s(Li)) = 0.469 and S(1s(H); 2pz (Li)) = 0.506
Solution The electron density in LiH is obtained by squaring the molecular orbital s and then
multiplying it by its occupancy number (i.e. 2). Thus we have
r = 2 (0.700y1s(H) + 0.328y2s(Li) + 0.204 y 2p z ( Li ) )2
2 2
= 0.98y 21s(H) + 0.215 y 2s ( Li ) + 0.083 y 2 p z ( Li )

+ 0.918y1s(H)y2s(Li) + 0.571y1s(H) y 2p z ( Li ) + 0.268y2s(Li) y 2p z ( Li )

The above density consists of atomic-orbital densities like y 21s(H), y 22s(Li) and y 22p z ( Li ) and
overlap densities like y1s(H)y2s(Li), y1s(H) y 2p z ( Li ) and y2s(Li) y 2p z ( Li ) . To get the relative

by the overlap integral involving the two orbitals and then it is divided by 2. The resultant

orbitals, i.e.
C
CyAyB = SAB{ y A2 + y B2 }
2
0.918
Hence, 0.918y1s(H)y2s(Li) = S(1s(H); 2s(Li))( y 12s(H) + y 22s(Li) )
2
0.918 ¥ 0.469
= ( y 12s(H) + y 22s(Li) )
2
2 2
= 0.215 y 1s(H) + 0.215 y 2s(Li)
0.571
0.571y1s(H) y 2p z ( Li ) = S(1s(H); 2pz(Li)) (y 21s(H) + y 22p z (Li) )
2
0.571 ¥ 0.506
= (y 21s(H) + y 22p z ( Li ) )
2
2
= 0.145 y 1s(H) + 0.145 y 22p z ( Li )
0.268
0.268y2s(Li) y 2p z ( Li ) = S(2s(Li); 2pz (Li))(y 22s(Li) + y 22p z ( Li ) )
2
= (zero)y 22s(Li) + (zero) y 22p z ( Li )
Thus, the gross-atomic population numbers are
n1s(H) = 0.98 + 0.215 + 0.145 = 1.340
n2s(Li) = 0.215 + 0.215 = 0.430
n2p z (Li) = 0.083 + 0.145 = 0.228
Total charge on Li atom = 0.430 + 0.228 0.66
Hence Li carries 1 – 0.66 = 0.34 positive charge
whereas H carries 1.34 – 1 = 0.34 negative charge
Thus, LiH may be written as Li + 0.34 H– 0.34.
266 A Textbook of Physical Chemistry

Hydrogen The energies of 1s(H), 2s(F) and 2p z(F) correspond to – 110 ¥ 10 3 cm –1,
Fluoride – 374 ¥ 103 cm–1 and –151 ¥ 103 cm–1, respectively. The 2s(F) orbital energy is
much lower than that of 1s(H) and that of 2pz(F) is closer to that of 1s(H). It may
be assumed that an effective combination takes place only between 1s(H) and 2pz(F)
orbitals. The orbitals 2s(F), 2px(F) and 2py(F) remain unaffected in the bonding
formation and thus are nonbonding orbitals. Since electrons are pulled toward
the atom that has the larger electronegativity, it is expected that in the bonding
orbital s y 2pz (F) will be much larger than that of y1s(H). In the
y1s(H) will be
larger than that y 2p z (F) .†

The relative order of energies of molecular orbitals in HF is shown in Fig. 2.11.2.

There are ten electrons in HF molecule, two of which are occupied by 1s(F) orbital.
The remaining eight valence electrons can be placed as follows:
(2s)2(s)2(2px)2(2py)2
There will be one sigma bond and three lone pairs in the three nonbonding orbitals.
This arrangement corresponds to the Lewis structure (H F ).

s*

1s
Energy

px, py
2p

s
Fig. 2.11.2 Correla- 2s
tion diagram of HF H HF F

BOTH ATOMS CONTAIN s AND p VALENCE ORBITALS

Correlation Let the atom B in the molecule AB be more electronegative than A. The energy of
Diagram for AB an atomic orbital of atom B will have a smaller value than that of the corresponding
Molecule orbital of atom A. The formation of s and p bonding and antibonding molecular
orbitals in AB molecule is similar to those of homonuclear diatomic molecule.
The shape of molecular orbitals is not symmetrical. This is due to fact that the

in the bonding orbital and lesser value in the antibonding orbital.

† In literature, the molecular orbitals s and s* are reported as s = 0.33 Y1s (H) + 0.94 Y2pz(F)
and s* = 0.94 Y1s(H) – 0.33 Y2pz(F).
 Theories of Covalent Bond 267

Figure 2.11.3 displays the relative orbital energies in AB molecule. Figure 2.11.4
displays the boundary surfaces of some of the molecular orbitals of an AB molecule.

Fig. 2.11.3 Relative

order of energies in an
AB molecule; atom B
is more electronegative
M
than A

Table 2.11.1
Molecules
Number Molecule Electronic Dissociation Bond Bond

electrons kJ mol–1 pm

8 BN (ss)2 (s*s)2 (px,y)3(spz)1 384.9 2 128

9 BO ¸ 774.0 2.5 120
Ô
Ô 1
CN ˝ (ss) (s*s) (px,y ) (spz )
2 2 4
786.6 117
Ô
CO+ Ô˛ 111.5

10 CO ¸ 1 070.3 3 112.8
+Ô
Ô 2
NO ˝ (ss) (s*2s) (p x, y) (spz)
2 2 4
106.2
Ô
CN– Ô˛ 114
(2) 1
11 NO (ss) (s*s) (p x, y ) s pz (p*x, y ) 667.8
2 2 4
2.5 115
268 A Textbook of Physical Chemistry

Atomic orbitals Combination Molecular orbitals

Fig. 2.11.4 Shapes of the molecular orbitals of an AB molecule; atom B is more electronegative than A. The
approximate representation involving only angular functions for 2p orbitals is used

2.12 UNITED-ATOM CONCEPT AND THE CORRELATION DIAGRAMS

Description of the So far, we have considered the formation of a diatomic molecule from the viewpoint
Concept of bringing two atoms close together from a large distance to the internuclear
distance of the molecule. The shapes and energies of various molecular orbitals
 Theories of Covalent Bond 269

have been derived following the LCAO scheme. There is another approach, known

molecular orbitals of a diatomic molecule. In this method, an united atom, formed

as a result of coalescence of two nuclei, is considered. Then the two nuclei are
imagined to be gradually separated. As the separation is increased from zero to

orbitals of the united atom will gradually change to the appropriate molecular

separated atoms. Consequently, it is expected that the energies of the united atomic
orbitals will change smoothly (not necessarily linear) to the energies of appropriate

the separated atoms. The above relationship between the orbitals of the three
different systems, viz., united atom, molecule and separated atoms, is exhibited
by the . In this, the energies of various united atomic orbitals
are displayed at one extreme and those of separated atoms at the other extreme
and then these energies are connected to exhibit the appropriate transformations.
Before we draw such diagrams, it is worth considering the example of H2
molecule. In the united atom concept, we consider He atom and then separate the
two protons along some axis, say, the z-axis. The behaviour of the orbitals of the

increased is shown in Fig. 2.12.1.

Classification of An examination of the orbitals in Fig. 2.12.1 reveals that the various orbitals may
Orbitals
1. United-atomic orbitals which on separation produce atomic orbitals of
the same principal quantum number. These are: 1s, 2s, 2px, 2py, 3d z 2 , 3dxy and
3 d x2 y 2 . The energy of this category of orbitals increases rapidly as the nuclei are
-
separated because the nuclear charge is halved in the separated atoms, and we are
dealing with the same principal quantum number. Conversely, we may state that
the energy of an orbital in this category decreases (not necessarily linearly) as the
nuclear separation decreases. Thus, these orbitals constitute the bonding orbitals.
2. United-atomic orbitals which on separation produce atomic orbitals of the
next inner principal quantum number. These are: 2pz, 3s, 3pz, 3dxz and 3dyz orbitals.
The energy of this category of orbitals decreases as the nuclei are separated, owing
to the change in the principal quantum number. If the energy of an orbital increases
as the nuclear separation is decreased, then it behaves as an antibonding orbital.
Since the energy difference between the united-atom orbitals of this category
and the separated atomic orbitals is relatively small, the prediction of the energy
of the orbitals at intermediate distances is not so simple. In fact, the energy of a
given orbital may exhibit a maximum or a minimum. For example, the energy
level of 3s united-atomic orbital exhibits a minimum at a normal bond distance
(not shown in Fig. 2.12.2). This minimum lies below the 2p orbital of separated
atom and hence behaves as the bonding orbital.
Figure 2.12.2 displays the correlation diagram for molecular orbitals in
homonuclear diatomic molecules. This diagram incorporates the variation in energies
270 A Textbook of Physical Chemistry

UNITED SLIGHT NORMAL COMPLETELY

ATOM SEPARATION BOND DISTANCE SEPARATED

Fig. 2.12.1 (continued)

 Theories of Covalent Bond 271

UNITED SLIGHT NORMAL COMPLETELY

ATOM SEPARATION BOND DISTANCE SEPARATED

Fig. 2.12.1 The change in the shapes of He+ orbitals with the separation of two nuclei

of the two types of orbitals discussed above. Consulting this diagram, we can write down
the relative order of energies of molecular orbitals at the given internuclear distance.
For example, at the two distances shown in Fig. 2.12.2, the relative orders are:
At r = rA sg1s < su1s < sg2s < su2s < sg2p > pu2p < pg2p < su2p
At r = rB sg1s < su1s < sg2s < su2s < pu2p < sg2p < pg2p < su2p
Thus knowing the internuclear distance of a diatomic molecule, we can write down

There is one universal rule which holds good in the correlation diagram and must
be highlighted here. This rule, which is known as the states that
plotted as functions of

cannot cross one another. This rule helps correlating the molecular orbital with
the united-atom orbital. For example, sg 2s must correlate with the united atom 2s
272 A Textbook of Physical Chemistry

su
u
pg
pu 3p
sg g

su
dg u
sg 3s
g pg g
3d
sg
su
pu u
3p u pg
su
2p
pu
g g
3s sg sg
su u
pu 2s
sg
Energy

u
2p su g

2s g sg

su
1s
sg

1s g
sg H2+ He2 N2 O2 F2
H2
United Separated
atom rB rA atoms

Fig. 2.12.2 Correlation diagram for homonuclear diatomic molecules (schematic)

orbital, and the sg2p with the united atom 3s orbital, and not the other way around
as it will violate the non-crossing rule.

Correlation Diagram The correlation diagram for the heteronuclear diatomic molecules is shown in
for the Heteronuclear
Diatomic Molecules diatomic molecules.

2.13 HYBRID ORBITALS

Explanation of Though the chemical bonding in a polyatomic molecule can be described under
Hybrid Orbitals the LCAO-MO framework, yet the very basic concept of chemistry of localized
bonds between particular atoms in the molecule is completely lost as the molecular
orbitals are delocalized over the entire molecule. However, Lennard-Jones and his
coworkers have shown that the delocalized molecular orbitals can be transformed
into the localized molecular orbitals (known as equivalent orbitals) through
mathematical transformations.
Alternatively, the formation of the localized bonds may be explained by the
overlapping between the hybrid orbitals of the one atom with the atomic orbitals
 Theories of Covalent Bond 273

s 3s (B)
3s (A)
4p s
s

d
3d p
s
p
p s 2p (B)
3p p
s 2p (A)
s
Energy

3s
s s
2s (B)
p 2s (A)
2p s
s
2s
s

s
1s (B)
s 1s (A)

1s
s CO NO Separated
United atom
atom

Fig. 2.12.3 Correlation diagram for heteronuclear diatomic molecules (only schematic)

or hybrid orbitals of the other atom (valence bond approach). The hybrid orbitals
are formed by the linear combination of atomic orbitals centred on the same atom.

(1s)2(2s) 2. Since the Be atom does not contain any unpaired electron, its combining
capacity with other atom should be zero. But invariably it is found to be divalent.
However, its divalent nature may be explained by promoting one of the 2s-electrons
to the 2p orbital. Such a situation may be described by the determinant
|(y2s a) (y 2p z a )| (2.13.1)

different types of bonds as the 2s orbital is nondirectional and 2p orbital has

directional characteristics. But in reality the two bonds formed are completely
identical in nature, and are oriented at an angle of 180º with each other.
It can be shown that the wave function as given by the determinant of Eq. (2.13.1)
remains unchanged when each column in the latter is replaced by the following
linear combinations of 2s and 2p orbitals:
1
y1 = (y2s + y 2p z ) (2.13.2)
2
274 A Textbook of Physical Chemistry

1
y2 = (y2s – y 2p z ) (2.13.3)
2
The functions y1 and y2 describe the hybrid orbitals of Be atom. (Note that
2s and 2pz orbitals in Eqs (2.13.2) and (2.13.3) belong to the same atom.) The
orbitals y1 and y2 are completely identical in size, shape, energy and directional
characteristics.

In general, the number of hybrid orbitals formed is equal to the number of atomic
orbitals that are being combined to form hybrid orbitals. Thus, by mixing one 2s and
two 2p orbitals, we get three equivalent sp2 hybrid atomic orbitals and mixing of one
2s and three 2p atomic orbitals produces four equivalent sp3 hybrid atomic orbitals.
In general, hybrid orbitals from s and p orbitals have two lobes, one of which is
highly enhanced and the other one is highly shortened. As a consequence, a better
overlapping between the hybrid orbital and the orbital of other atom is produced.
The orbital of the other atom may be simply an atomic orbital or a hybrid atomic
orbital. Thus, a hybrid orbital can form a better bond as compared to that formed
from the atomic orbital.

Guidelines for The wave functions of sp, sp2 and sp3 hybrid orbitals can be derived by following
Constructing the guidelines given below.
Hybrid Orbitals
∑ The charge density of s orbital will be equally distributed amongst the possible
hybrid orbitals. If there are n
s orbitals in all the n hybrid orbitals will have the same value of 1/n2.
∑ The atomic wave functions constitute the orthonormal set, such that
Ú yiyi dt = 1 (2.13.4)

Ú yiyj dt = 0 (2.13.5)
∑ The formed hybrid orbitals also constitute orthonormal set, i.e. for them also
the above expressions are applicable.
∑ For sp2
has its maximum on x-axis. Thus, this orbital will not include any contribution
from py or pz orbital.
∑ For sp3 hybridization, we may assume that the second orbital lies in a plane,
say, on xz-plane. Thus, this orbital will not include any contribution from py
orbital.
Following the guidelines given above, we now derive the wave functions and
their characteristics for sp, sp2 and sp3 hybrid orbitals.

sp HYBRID ORBITALS
Wave Functions of For the two hybrid orbitals, we may write
sp Hybrid Orbitals y1 = a1ys + b1yp
y2 = a2ys + b2yp
 Theories of Covalent Bond 275

(i) Since the charge density of s orbital is equally divided between the two hybrid
orbitals, we may write
1 1
a12 = a22 = i.e. a1 = a2 =
2 2
(ii) Since y1 is normalized, we may write

Ú y1 dt = a21 Ú y s2 dt + b12 Ú y p2 dt + 2a1b1 Úysyp dt = 1

2

Since atomic orbitals are orthogonal, we may write the above expression as
a21 + b21 = 1
Now since a21 = 1/2, we get
1
b1 =
2
(iii) Since y1 and y2 are orthogonal, we may write
a1a2 + b1b2 = 0
Substituting the values of a1, a2 and b1, we get
Ê 1 ˆ Ê 1 ˆ + Ê 1 ˆb=0
ÁË ˜ Á ˜ ÁË ˜ 2
2¯ Ë 2¯ 2¯
1
or b2 = –
2
Hence, the two functions are
1
y1 = (ys + yp ) (2.13.6)
2
1
y2 = (ys – yp ) (2.13.7)
2
Angle between the To derive angle and general shape of hybrid orbitals, we take the radius of
Two Orbitals spherical contour surface, representing the magnitude of the s-orbital, to be equal
to 1. Relative to this unit, the magnitudes of the p orbitals, which vary due to the
angular dependence, are
pz = 3 cos q (2.13.8)
px = 3 sin q cos j (2.13.9)
py = 3 sin q sin j (2.13.10)
where q is the angle of a vector with z-axis and j is the angle of the projection of
the vector on xy-plane with the x-axis.
Utilizing the above relations, Eqs (2.13.6) and (2.13.7) may be written as

y1 =
1
2
(1 + 3 cosq ) (2.13.11)

y2 =
1
2
(1 - 3 cosq ) (2.13.12)
276 A Textbook of Physical Chemistry

Since the above functions do not contain any j, it is obvious that both the functions
lie on z-axis and hence the angle between them must be 180º.
Shapes of the Two The function y1 will have its maximum when q = 0. This maximum relative to s
Orbitals orbital has a value of 1 + 3 (= 2.732). The corresponding value for pz orbital
is 3 (= 1.732).
Thus, it is obvious that the sp hybrid orbital will be better than pz orbital as far as
overlapping with the orbital of another atom is concerned, resulting in a better bond.
The functions y1 and y2 when plotted against different values of q give the
shapes as shown in Fig. 2.13.1.
Examples forming sp orbitals include Be and C (acetylene).

2s – 2p 2s + 2p
+ – – +
– +

Fig. 2.13.1 Schematic

representation of sp
hybridization 2p 2s 2p

sp2 HYBRID ORBITALS

Wave Functions of For the three hybrid orbitals, we may write
sp2 Hybrid Orbitals y1 = a1 ys + b1 y p + c1 y p y
x

y2 = a2ys + b2 y p x + c2 y p y

y3 = a3 ys + b3 y p x + c3 y p y

(i) Since the charge density of s orbital is equally divided among the three hybrid
orbitals, we get
1 1
a21 = a22 = a33 = i.e. a1 = a2 = a3 =
3 3
(ii) If we assume y1 to point towards x-axis, then the contribution of py orbital
in this will be zero, i.e.
c1 = 0
(iii) Normalization condition of y1 gives
a21 + b21 = 1

Since a1 = 1/ 3 , we get

2
b1 =
3
 Theories of Covalent Bond 277

(iv) Orthogonal conditions of y1 and y2, and y1 and y3 give

a1a2 + b1b2 = 0
a1a3 + b1b3 = 0

a1a2 1/ 3 1
Hence b2 = – =– =–
b1 2/3 6
a1a3 1/ 3 1
b3 = – =– =–
b1 2/3 6
(v) Normalization condition of y2 gives a22 + b22 + c22 = 1
1
c22 = 1 – (a22 + b22 ) = 1 – ÊÁ + ˆ˜ =
1 1 1
Hence or c2 =
Ë 3 6¯ 2 2
(vi) Normalization condition of y3 gives
a23 + b23 + c23 = 1

c23 = 1 – (a23 + b23 ) = 1 – ÊÁ + ˆ˜ =

1 1 1
Ë 3 6¯ 2
1
c3 = –
2
(For y2 and y3 to be different, we take the minus root of c3.)
Hence three functions are
1 2
y1 = ys + y px (2.13.13)
3 3
1 1 1
y2 = ys – y px + y py (2.13.14)
3 6 2
1 1 1
y3 = ys – y px – y py (2.13.15)
3 6 2
Angle between the Utilizing the expressions of Eqs (2.13.8) to (2.13.10), we get
Two Orbitals
1 2
y1 = + 3 sin q cos j
3 3
1 1 1
y2 = – 3 sin q cos j + 3 sinq sinj
3 6 2
1 1 1
y3 = – 3 sin q cos j – 3 sinq sinj
3 6 2
Since the pz orbital does not appear in Eqs (2.13.13) to (2.13.15), we may conclude
that all three orbitals lie in the xy-plane for which angle q is equal to 90º. Thus,
the above relations become
1
y1 = + 2 cos j (2.13.16)
3
1 1 3
y2 = – cos j + sinj (2.13.17)
3 2 2
278 A Textbook of Physical Chemistry

1 1 3
y3 = – cosj – sin j (2.13.18)
3 2 2
Let y1 have its maximum on x
y2, we equate dy2 /dj = 0. Thus, we have
dy 2 1 3
= sin j + cos j = 0
dj 2 2
3
or tan j = – 2 = – 3 = – 1.732
2
Hence j = 120º
Thus, the three hybrid orbitals are inclined at an angle of 120º with each other.

Shapes of the The function y1 will have its maximum, say on x-axis, for which j = 0. This
Orbitals maximum relative to s orbital has a value of 1 + 2 = 2.414. In comparison to px
orbital (q = 90º, j = 0, maximum = 1.732), the sp2 orbital is better in overlapping
with the orbital of another atom. The function y1, y2 and y3 when plotted against
different values of j give the orbitals (only schematic) as shown in Fig. 2.13.2.

Examples forming sp2 orbitals include B and C (ethylene).

Mixing
Fig. 2.13.2 Schematic
plots of sp2
hybridization. The
correct shape of sp2
hybrid orbital is shown
in Fig. 2.13.4

sp3 HYBRID ORBITALS

For the four hybrid orbitals, we may write
Wave Functions
y1 = a1ys + b1 y p x + c1 y p y + d1 y p z
of sp3 Hybrid
Orbitals y2 = a2ys + b2 y p x + c2 y p y + d2 y p z
y3 = a3ys + b3 y p x + c3 y p y + d3 y p z
y4 = a4ys + b4 y p x + c4 y p y + d4 y p z
(i) Since the charge density of s orbital is to be distributed equally over all the
four orbitals, we write
1 1
a21 = a22 = a23 = a42 = or a1 = a2 = a3 = a4 =
4 2
 Theories of Covalent Bond 279

(ii) Let us develop y1 on the x-axis. It is obvious that the contribution of y p y and
y p z in the function y1 will be zero and hence we may write
c1 = 0 and d1 = 0
(iii) Normalization of y1 gives
1 3
a21 + b21 = 1 or b12 = 1 – a21 = 1 – =
4 4
3
Hence b1 =
2
(iv) Orthogonal conditions of y1 and y2, y1 and y3, and y1 and y4 give
a1a2 + b1b2 = 0
a1a3 + b1b3 = 0
a1a4 + b1b4 = 0
a1a2 1/ 4 1
Hence b2 = b3 = b4 = – =– =–
b1 3/2 2 3
(v) We assume that y2 lies on xz-plane. Hence the contribution of py in y2 will
be zero, i.e.
c2 = 0
(vi) Normalization condition of y2 gives
a22 + b22 + d 22 = 1

d 22 = 1 – ( a22 + b22 ) = 1 – ÊÁ + ˆ˜ = 1 –
1 1 1 2
or =
Ë 4 12 ¯ 3 3
2
d2 =
3
(vii) Orthogonal condition of y2 and y3, and y2 and y4 gives
a2a3 + b2b3 + d2d3 = 0
a2a4 + b2b4 + d2d4 = 0
a2 a3 + b2b3 1 / 4 + 1 / 12 1
Hence d3 = d4 = – =– =–
d2 2/3 6
(viii) Normalization condition of y3 gives
a32 + b32 + c32 + d32 = 1
1 1 1
i.e. + + c32 + =1
4 12 6
1 1
or c32 = or c3 = +
2 2
(ix) For the normalization condition of y4, we take
1
c4 = –
2
280 A Textbook of Physical Chemistry

Hence the four functions are

1 3
y1 = ys + y px
2 2
1 1 2
y2 = ys – yp + y pz
2 2 3 x 3

1 1 1 1
y3 = ys – y px + y py – y pz
2 2 3 2 6

1 1 1 1
y4 = ys – y px – y py – y pz
2 2 3 2 6

Angle between the Utilizing the expression of Eqs (2.13.8) to (2.13.10), we get
Two Orbitals
1 3
y1 = + ( 3 sinq cosj )
2 2
1 1 2
y2 = – ( 3 sinq cos j ) + ( 3 cosq )
2 2 3 3

1 1 1 1
y3 = – ( 3 sinq cosj) + ( 3 sinq sinj ) – ( 3 cosq )
2 2 3 2 6

1 1 1 1
y4 = – ( 3 sinq cos j ) – ( 3 sinq sinj) – ( 3 cosq )
2 2 3 2 6
Let y1 have its maximum on x-axis, for q = 90º and j = 0º. Thus, the relative
magnitude of y1 on x-axis is

1 3
+ =2
2 2
This may be compared with the value of 1.732 of the pz orbital.

We have assumed the function y2 to lie on the xz-plane. We take j = 180º for
this plane. Substituting this value of j in y2, we get
1 1
y2 = + sin q + 2 cos q
2 2
Setting dy2/dq = 0, we get

1
cos q – 2 sin q = 0
2
1 1
or tan q = = = 0.354
2 2 2.828
Hence q = 19º28¢
 Theories of Covalent Bond 281

Since q is the angle between the axis of y2 and the z-axis, the angle between
the axes of y1 and y2 is 90º + 19º28¢ = 109º28¢.

The spatial arrangement of the four hybrid angles is tetrahedral. The appearance
of sp3 hybrid orbitals is very similar to those of sp and sp2 orbitals (Fig. 2.13.3).
z
sp3
pz
+
– px +
+ sp3
+
py –
–
– –

–
+ y mixing
+ +
Fig. 2.13.3 Schematic s sp3
plots of sp3 +
hybridization. The –
correct shape of sp3 sp3
hybrid orbital is shown
x
in Fig. 2.13.4
One of the most important examples exhibiting sp3 hybridization is carbon. The
Examples structures of H2O and NH +4 can also be explained on the basis of sp3 hybridization.

Figure 2.13.4 exhibits the comparison of the shapes of sp, sp2 and sp3 hybrid
Comparison of orbitals.
Hybrid Orbitals

sp

Fig. 2.13.4 Comparison

of sp, sp2 and sp3 hybrid
orbitals. The solid,
dashed and dotted
lines represent sp, sp2 sp3
and sp3 hybrid orbitals
sp 2
respectively

Hybrid Orbitals The hybrid orbitals involving d orbitals have been used in understanding the
Involving structure of transition metal complexes. The most common hybrid orbitals of the
d Orbitals above types along with their spatial arrangements are given below.
dsp2 Square plannar [Ni(CN)4]2–, [Cu(NH3)4]2+, PdCl2–
4

dsp3 Trigonal bipyramidal PF5, PCl5

d2sp3 Octahedral SF6, [Fe(CN)6]3–, [Fe(CN)6]4–
Numerous other types of hybridization are possible. Table 2.12.1 gives a brief
account of these orbitals.
282 A Textbook of Physical Chemistry

Table 2.12.1 Hybrid Orbitals

Coordination number Shape Hybridization
2 linear dp
bent p2, ds, d2
3 trigonal planar dp2,ds2, d3
unsymmetrical planar dsp
trigonal pyramidal p3,d2p
4 tetrahedral d3s
irregular tetrahedral d2sp, dp3, d3p
tetragonal pyramidal d4
5 bipyramidal dsp3, d3sp
tetragonal pyramidal d2sp2, d4s, d2p3, d4p
pentagonal planar d3p2
pentagonal pyramidal d5
6 trigonal prismatic d4sp, d5p
trigonal antiprismatic d3p3

2.14 TRIATOMIC MOLECULES

General Procedure In this section, we describe the approximate MO treatment of BeH2, CO2 and
of Building H2
Molecular Orbitals In general, we can take the linear combination of the valence orbitals of all

method. The number of molecular orbitals (n) formed will be equal to the number
of atomic orbitals (n) that are being mixed to form the molecular orbitals. The
energies of these molecular orbitals can be worked out by opening the n ¥ n
secular determinant, equating the resultant expression to zero, and then solving the
expression for E
the corresponding energy in the n simultaneous linear (secular) equations along
with the normalization equation of the molecular orbital. The above calculations
can be performed in a very short time with the help of electronic computers. In this
section as stated above, we will develop qualitatively the expressions of molecular
orbitals and their relative energies by following a few guidelines given below.

Qualitative ∑ Only those valence atomic orbitals belonging to different atoms will appear
Description of in the molecular orbital for which the overlapping is positive. For example,
Building Molecular in the linear molecule BeH2, 1s orbitals of hydrogen atoms will have positive
Orbitals overlap with the 2s and 2pz orbitals of berillium. Hence, the combination
involving either 1s(H) and 2s(Be) or 1s(H) and 2pz (Be) will appear in the
molecular orbital.
∑ The molecules to be dealt in this section have a general formula of AB2. The
positive and negative combinations of two higher energy atomic orbitals of B
 Theories of Covalent Bond 283

atoms. For example, in BeH2, we will take the combinations of two 1s orbitals
centred on the two hydrogen atoms, i.e.
y 1s(Ha ) + y 1s(H )
b
y 1s(Ha ) - y 1s(H
b)
Note
are symmetrically placed around the third atom.
In CO2, we will take the 2p orbitals and not the 2s orbitals as 2p orbital
has higher energy than 2s orbital. The latter thus acts as nonbonding orbital.
∑ The above two combinations are mixed one by one with the proper orbitals
of atom A. By the proper orbitals, we mean the matching of the symmetry
regarding the signs of lobes of orbital of atom A with that of the combination
given above. Thus, the function y 1s(Ha ) + y 1s(H ) which carries the same sign
b
in both the lobes will mix only with y2s(A) as the latter carries only one lobe
with the positive sign. The combination y 1s(Ha ) - y 1s(H ) which carries positive
b
and negative signs over the two lobes will combine only with y 2pz (A ) as the
latter also carries two lobes with positive and negative signs.
∑ While considering the signs of lobes in atomic orbitals, we have to consider a
coordinate system for the molecule. The lobe pointing towards the increasing
direction (shown by arrow) carries a positive sign and that away from the
arrow carries a negative sign.
∑ For each mixing discussed above, we will get two combinations, one by the
algebraic addition and the other by algebraic subtraction. For example, for
y 1s(Ha ) + y 1s(H ) combination with y2s(A), we will get two wave functions:
b

y1 = C1 y2s(A) + C2( y 1s(Ha ) + y 1s(H ) )

b
and y2 = C3 y2s(A) – C4 ( y 1s(Ha ) + y 1s(H ) )
b
To know whether y1 or y2 is bonding, the following procedure is adopted.
Put the points showing the locations of atoms in the molecule. Draw the
atomic orbitals involved in a given molecular orbital along with the correct
signs of lobes. Carry out the changes in the signs of lobes of atomic orbital
if it is being subtracted. Now if the atomic two lobes of nearby atoms carry
the same sign, the molecular orbital is bonding. If it carries opposite signs
the orbital is antibonding.
∑ The boundary surface of the molecular orbital may be derived very easily
C1 and C2 in

in the bonding molecular orbital has a larger value as compared to that of

the lesser electronegative atom. In the antibonding orbital the reverse is true,

atomic orbital is larger, then there occurs an enhancement in the electronic

cloud at the involved atom.
We now consider the MO treatment for the above mentioned molecules.
284 A Textbook of Physical Chemistry

Berillium Hydride
Geometry of the The berillium hydride is a linear molecule (Fig. 2.14.1). The coordinate system
Molecule adopted is also shown in Fig. 2.14.1.
x

Fig. 2.14.1 The Ha Be Hb

coordinate system of
BeH2
y
Formation In berillium hydride, the valance orbitals 1s(Ha), 1s(Hb), 2s(Be), 2px(Be), 2py(Be)
of Different and 2pz (Be) are involved in the formation of molecular orbitals. The various
Molecular Orbitals molecular orbitals may be formed as follows.

1. From the 1s(Ha) and 1s(Hb) orbitals, the following two group orbitals may
be formed.
y+ = y 1s(Ha ) + y 1s(H ; symmetrical
b)

y– = y 1s(Ha ) - y 1s(H ; antisymmetrical

b)
These two group orbitals are of s type.
2. Since the group orbital y+ is symmetrical, it may be combined linearly with
the symmetrical 2s orbital of berillium. Since the group orbital y– is antisymmetric,
it will combine with the antisymmetrical 2pz orbital of berillium. Hence, the four
molecular orbitals formed from these mixing are as follows.

y1 = C1y2s(Be) + C2(y 1s(Ha ) + y 1s(H ) ) (2.14.1)

b

y2 = C3y2s(Be) – C4(y 1s(Ha ) + y 1s(H ) ) (2.14.2)

b

y3 = C5 y 2p z (Be) + C6(y 1s(Ha ) - y 1s(H ) ) (2.14.3)

b

y4 = C7 y 2p z (Be) – C8(y 1s(Ha ) - y 1s(H ) ) (2.14.4)

b

3. The atomic orbitals 2px (Be) and 2py(Be) have zero overlap with 1s(Ha) and
1s(Hb). Thus, no mixing between these orbitals takes place. Thus, 2px(Be) and
2py(Be) orbitals will be nonbonding in nature.
Nature of The nature of a molecular orbital may be determined as usual from the signs of
Molecular Orbitals nearby lobes of its constituent atomic orbitals. From Fig. 2.14.2, the conclusions
drawn are shown in Table 2.14.1.
 Theories of Covalent Bond 285

+
y1 + + + + +

1s (Ha) 1s (Be) 1s (Hb)

Node Node

y2 - + + + - + - + -

1s (Ha) 2s (Be) 1s (Hb)

Node Node

y3 + + + - + - +
+ - + -
1s (Ha) 2s (Be) 1s (Hb)
Fig. 2.14.2 Contour
diagrams of molecular
orbitals (The approxi-
mate representation
involving only angular y4 - + + - + + +
function for 2p orbitals - +
is used) 1s (Ha) 2pz (Be) 1s (Hb)

Table 2.14.1 Nature of Molecular Orbitals of Berillium Hydride

Molecular Signs of the Nature of

orbital nearby lobes MO
y1 same bonding

y2 different antibonding

y3 different antibonding

y4 same bonding

Contour Diagrams A few characteristics of molecular orbitals are shown in Table 2.14.2. In the light
of MO of these characteristics, the contour diagrams of molecular orbitals can be drawn.
These are shown in Fig. 2.14.2.
286 A Textbook of Physical Chemistry

Table 2.14.2 A Few Characteristics of Molecular Orbitals

Molecular Nature Relative values of Characteristic
†
Mixing of Electron density
nearby lobes on‡
y1 bonding C2 > C1 Yes H > Be
y2 antibonding C3 > C4 No Be > H
y3 antibonding C5 > C6 No Be > H
y4 bonding C8 > C7 Yes H > Be
†

of less electronegative atom. In antibonding orbital, the reverse is true.

‡
The electron density on A > B implies that the function y will have larger value nearby
the atom A as compared to the atom B.

Relative Energies The following factors help deciding the relative orbital energies in berillium
of Molecular hydride (Fig. 2.14.3).
Orbitals
1. Since H is more electronegative than Be, the 1s orbitals of hydrogen atoms
are more stable than 2s and 2p orbitals of Be.
2. The group orbital y+ is of bonding nature. Hence, its energy will be smaller
than those of 1s(H) orbitals.
3. The group orbital y– is of antibonding nature. Hence, its energy will be
greater than that of 1s(H) orbital.
4. The bonding molecular orbital y1 will be more stable than the more stable
constituent orbital, i.e. y+.
5. The antibonding molecular orbital y2 will be less stable than the lesser stable
constituent orbital, i.e. 2s(Be).
6. The antibonding molecular orbital y3 will be less stable than the lesser stable
constituent orbital, i.e. 2pz(Be).
7. The bonding molecular orbital y4 will be more stable than the more stable
constituent orbital, i.e. y–.
8. The orbital y1 will be more stable than y4 as the overlapping of 1s(H) and
2s(Be) is more than that of 1s(H) and 2pz(Be).
9. The orbital y3 will be less stable than y2 as the energy of 2p(Be) orbital is
larger than that of 2s(Be).
10. The atomic orbitals 2px (Be) and 2py(Be) will act as nonbonding p molecular
orbitals. Their energies will remain unaffected.
Keeping in mind the above factors, the relative orbital energies in BeH2 is shown
in Fig. 2.14.3. Since there are four valence electrons (two from Be and one from
2 2
2 is (y 1 ) (y 4 )

The two lowest molecular orbitals of the molecule Ha—Be—Hb are given by
Example 2.14.1
y1 = C1 y 1s(Ha ) + C2 y2s(Be) + C3 y 1s(H )
b
y2 = C4 y 1s(Ha ) + C5 y 2p z (Be) + C6 y 1s(H
b)
with C1 = 0.59 and C4 = 0.63. Evaluate the charge densities of Be and H atoms.
 Theories of Covalent Bond 287

s *z
y3

s *s y2

2p{
2px, 2py

2s

Energy

y–
1s
y+

y4 sz

Fig. 2.14.3 Relative y1 ss

orbital energy of BeH2 Be BeH2 2H

Solution Based on the symmetry of BeH2, we expect that

C1 = C3 and C4 = C6
Under the zero-overlap approximation, we will have
C12 + C22 + C32 = 1 fi 2 C12 + C22 = 1 fi C2 = 1 - 2C12

fi C2 = 1 - 2 ¥ 0.592 = 0.55

and C42 + C52 + C62 = 1 fi 2 C42 + C52 = 1 fi C5 = 1 - 2C42

fi C5 = 1 - 2 ¥ 0.632 = 0.45

2 is (y 1 )2 (y 2 )2 , we will have
Charge on Ha (or Hb) = 2 ¥ 0.59 2 + 2 ¥ 0.632 = 1.49
Charge on Be = 2 ¥ 0.552 + 2 ¥ 0.452 = 1.01
Multiplication by 2 in each term in the above two expressions is due to the fact that
each of the two occupied molecular orbital contains 2 electrons.
It is customary to visualize the molecule of BeH2 in terms of the localized two-
electron bonds in between each of the two Be—H direction. Since the molecule is
Localized
linear, each of the Be—H bond is considered to be formed as a result of overlapping
Molecular Orbitals
between sp hybrid orbital of Be and 1s orbital of H as shown in Fig. 2.14.4. The
of BeH2 other two p orbitals of Be atoms, which lie perpendicular to the molecular axis,
are not involved in the bonding and hence they constitute a doubly degenerate
nonbonding orbitals of the molecule.
288 A Textbook of Physical Chemistry

+
+
Ha Be Hb

1s
sp2

Localized
electron-pair bonds

+
+

Ha Be Hb

Fig. 2.14.4 Localized 1s

bonds in BeH2 sp1

The two sp hybrid orbitals of Be atom are:

1
y sp = (y 2s(Be) + y 2 p z ( Be) )
1 (Be) 2

1
y sp = (y 2s(Be) - y 2 p z ( Be) )
2 (Be) 2
The molecular orbitals describing the localized Be—H bonds are:

y1, loc = C1¢y sp1 (Be) + C2¢ y 1s(Hb ) (2.14.5)

y2, loc = C1¢y sp2 (Be) + C2¢ y 1s(Ha ) (2.14.6)

where the subscript loc stands for the term localized. Substituting the expressions
of y sp (Be) and y sp (Be) , we get
1 2

y1, loc = C1¢¢(y 2s(Be) + y 2 p z (Be) ) + C2¢ y 1s(H b )

y2, loc = C1¢¢(y 2s(Be) - y 2 p z (Be) ) + C2¢ y 1s(Ha )

Conversion of While describing the excitation of an electron, the above treatment of localized
Localized MO into orbitals is not useful since it is not possible to associate the electron as coming
Nonlocalized MO from one Be—H link or the other. The two links are completely identical and are
and vice versa
molecular orbitals into nonlocalized orbitals. This is achieved by taking ‘positive’
and ‘negative’ combinations of y1, loc and y2, loc as shown in the following:
 Theories of Covalent Bond 289

y1 = y1, loc + y2, loc

y4 = y1, loc – y2, loc

Substituting the expression of y1, loc and y2, loc, we get

y1 = C1¢¢¢ y 2s(Be) + C2¢ (y 1s(Ha ) + y 1s(H ) )
b

y4 = C1¢¢¢ y 2 p z (Be) - C2¢ (y 1s(Ha ) - y 1s(H ) )

b

The functions y1 and y4 are, in fact, the same as described earlier (Eqs 2.14.1
and 2.14.4). Thus, from the two localized orbitals, we have got two nonlocalized
molecular orbitals.

The above treatment of constructing two nonlocalized molecular orbitals out

of two localized orbitals can be reversed, i.e. out of two nonlocalized orbitals, we
can construct two localized orbitals by simply taking the ‘positive’ and ‘negative’
combinations of y1 and y4. If we do so, we get back the functions y1, loc and
y2, loc.
The antibonding counterparts of localized bonding molecular orbitals are

y 1,¢ loc = C1¢ y sp - C2¢ y 1s(H

1 (Be) b)

y 2,¢ loc = C1¢ y sp - C2¢ y 1s(Ha )

2 (Be)

The ‘positive’ and ‘negative’ combinations of the above two localized molecular
orbitals generate the two nonlocalized antibonding orbitals y2 and y3, respectively.
y2 = C1¢ y 2s(Be) - C2¢ (y 1s(Ha ) + y 1s(H ) )
b

y3 = C1¢ y 2 p z (Be) + C2¢ (y 1s(Ha ) - y 1s(H ) )

b

Construction The schematic construction of correlation diagram may be carried out by following
of Correlation the steps given below.
Diagram 1. Depict the relative energies of atomic orbitals of Be and H atoms. Since H
is more electronegative than Be, the 1s orbitals of hydrogen atoms are more stable
than 2s and 2p orbitals of Be.
2. Depict the formation of sp hybrid orbitals of Be. The energies of hybrid
orbitals will be greater than that of 2s orbital but smaller than that of 2p orbital.
3. Depict the formation of localized molecular orbitals. There will be two
bonding (degenerate) and two antibonding (degenerate) orbitals.

Figure 2.14.5 exhibits the expected correlation diagram. Since BeH2 has four

(y 1, loc )2 (y 2, loc )2
Figure 2.14.5 also exhibits the change in energies of localized molecular orbitals
when they are converted into nonlocalized molecular orbitals.
290 A Textbook of Physical Chemistry

y¢1, loc ; y2,¢ loc y3

y2
2p 2p
2p{
2p
sp

2s

Energy

1s

y4
y1, loc;y2, loc; y1
Fig. 2.14.5 Correlation Be Be Ha, Hb
diagram for localized Localized Nonlocalized
orbitals of BeH2 MO MO

Comment on As described in Section 1.12, the eigenfunction of polyelectronic atom is

Hybridization antisymmetric with respect to the exchange of the coordinates of any two electrons,
and can be expressed as a Slater determinant whose elements are the various
occupied spin atomic orbitals. The same is applicable to a polyelectronic molecule
with the replacement of spin atomic orbitals by the spin molecular orbitals. For
example, the total molecular wave function of BeH2 which contains four valence
electrons can be written as
y 1(1) y 1(1) y 4 (1) y 4 (1)
1 y 1( 2 ) y 1( 2 ) y 4 ( 2 ) y 4 ( 2 )
y=
4! y 1( 3) y 1( 3) y 4 ( 3) y 4( 3)
y 1( 4) y 1( 4) y 4 ( 4) y 4 ( 4)
As described in Section 1.12, the replacement of wave function, say y1, by a
linear combination y1 ± y4 does not change the overall wave function, but such
a replacement in the present case helps visualizing BeH2 as its classical structural
formula representing the two bonds between Be and H atoms. It may be mentioned
here that the concept of hybrid orbitals follows from molecular geometry and not
vice-versa, since the choice of appropriate combination of molecular wave functions
representing the required hybrid orbitals from the large number of combinations can

geometry, one can identify the hybrid orbitals, by replacing the initial set of molecular
orbitals by a set of localized molecular orbitals. Since this mathematical substitution
does not change the overall molecular wave function, atomic orbital hybridization
cannot be regarded as a physical phenomenon.
WATER
The molecule of water is nonlinear with HOH bond angle equal to 105º. The
coordinate system of H2O is given in Fig. 2.14.6.
 Theories of Covalent Bond 291

Hb Ha y

Fig. 2.14.6 Coordinate

system of H2O. Points A
A and B are the x
projections of atoms Ha O
and Hb on the xy-plane
B

Formation The proper combinations of bonding and antibonding molecular orbitals of 2H atoms are
of Different y+ = y 1s(Ha ) + y 1s(H ) and y– = y 1s(Ha ) - y 1s(H )
b b
Molecular Orbitals
The valence orbitals of oxygen are 2s, 2px, 2py and 2pz. Their combinations with
y+ and y– are as follows.
1. From Fig. 2.14.7, where the overlapping of 1s(H) orbitals with 2pz(O) orbital
is shown, it may be concluded that the proper combination of two hydrogen atoms
that can combine with 2pz orbital of oxygen is 1s(Ha) + 1s(Hb). Besides this,
1s(Ha) + 1s(Hb) group orbital will also have positive overlap with 2s orbital of
oxygen. Thus, we may consider the formation of three nonlocalized molecular
orbitals by mixing three atomic orbitals, y2s(O),y 2p z (O) and y 1s(Ha ) + y 1s(Hb ) , i.e.

y1, 2, 3 = C1 y2s(O) + C2 y 2p z (O) + C3(y 1s(Ha ) + y 1s(H ) ) (2.14.7)

b
2. From Fig. 2.14.8, we may conclude that the proper combination of two
hydrogen atoms that can combine with 2px or/and 2py orbitals of oxygen is
1s(Ha ) – 1s(Hb
hybrid orbitals out of 2px(O) and 2py(O) orbitals. These are
y +¢ = y 2 p x (O) + y 2 p y (O) and y –¢ = y 2 p x (O) - y 2 p y (O)
z

Hb Ha
+ +
Fig. 2.14.7 Overlapping
+
of group orbital
y 1s ( Ha ) + y 1s ( H ) with
b
y 2p Hb Ha
z (O) – +
Fig. 2.14.8 Overlapp- –
2pz(O)
ing o f group orbital
y 1s ( Ha ) – y 1s ( H b) with – + x

y 2p ( O ) 2px(O)
x
292 A Textbook of Physical Chemistry

The schematic shapes of y +¢ and y –¢ are shown in Fig. 2.14.9.

y y

+ +

Fig. 2.14.9 x x
– –
y 2p x (O) + y 2p y (O ) and
y 2p x (O) - y 2p y (O)
orbitals
2px(O) + 2py(O) 2px(O) – 2py(O)

From Figs 2.14.6 and 2.14.9, it is obvious that y 1s(Ha ) - y 1s(H will have positive
b)
overlap with y 2p x (O) + y 2p y (O) , whereas the overlap with y 2p x (O) - y 2p y (O)
is zero. Thus, we construct two molecular orbitals out of the combinations of
{y 1s(Ha ) – y 1s(H b ) } and {y 2p x (O) + y 2p y (O) } as follows:

y4, 5 = C4 (y 2p x (O) + y 2p y (O) ) + C5 (y 1s(Ha ) - y 1s(H ) ) (2.14.8)

b

The orbital y 2p x (O) - y 2p y (O) will act as a nonbonding molecular orbital.

Relative Energies The following factors help deciding the relative orbital energies in H 2O.
of Different 1. Since oxygen is more electronegative than hydrogen, the 2s and 2p orbitals
Molecular Orbitals of oxygen are more stable than 1s hydrogen orbital.
2. Out of the three orbitals y1, y2 and y3, one will be strongly bonding (say,
y1), second will be bonding but near to nonbonding (say, y2) and the third will
be antibonding (say, y3).
3. Out of the orbitals y4 and y5, one will be bonding (say, y4) and the other
will be antibonding (say, y5 ).
4. The orbital y1 will be more stable than y4.
5. The orbital y4 will be more stable than y2.
6. In the antibonding orbitals, y3 is expected to be less stable than y5.
7. The orbital y –¢ = y 2p x (O ) – y 2p y (O ) is nonbonding. Hence, its energy is the
same as that of pure p orbital.
With the above facts, we may draw the correlation diagram depicting the relative
order of orbital energies as shown in Fig. 2.14.10. Since there are eight valence

ration of H2O is

(y 1 )2 (y 4 )2 (y 2 )2 (y -¢ )2
The molecule will be diamagnetic in nature.
 Theories of Covalent Bond 293

y3

y5

y–
1s
}
y+

y2pz y ¢–
2p { y +¢ {
y–¢ y2
Energy

2s y4

y1
O O Group Ha, Hb
H2O
Fig. 2.14.10 Correlation orbitals
diagram of H2O of hydrogen
atoms

Localized The formation of localized molecular orbitals in water is explained from the
Molecular Orbitals following two view points:
of H2O 1. The two OH bonds are formed as a result of overlapping between 2p oxygen
orbitals and 1s hydrogen orbitals (Fig. 2.14.11). Thus, we have
y 1¢ = C1¢ y 2 p x (O ) + C2¢ y 1s ( Ha ) and y 2¢ = C1¢ y 2 p y (O ) + C2¢ y 1s ( H )
b

Hb
+
py
+
Ha
– + + x
Fig. 2.14.11 px
Overlapping of 2px –
and 2py orbitals of
oxygen with 1s orbital
of hydrogen

The expected bond angle of 90º between the two OH bonds is expanded a little
due to the repulsion of two protons. This model of H2O neglects the two lone pairs
of electrons in 2s and one of the 2p orbitals of oxygen.
2. Since water molecule contains eight valence electrons, the most stable
structure would be the one where these electrons stay as far apart from each other
as possible. This is achieved by visualizing the valence orbitals of oxygen in the
294 A Textbook of Physical Chemistry

sp 3 hybrid state where the four equivalent orbitals point towards the corner of a
regular tetrahedron (Fig. 2.14.12).

+ H

H +
+
+
– –

–
–
+
+

z y
x
Fig. 2.14.12 Tetra-
hedral model of H2O Lone pairs

The two OH bonds in water are thus formed by overlapping between the two sp3
hybrid orbitals of oxygen and 1s orbitals of hydrogen atoms. For the ion O2–, the
arrangement of four lone pairs is expected to be perfectly tetrahedral, but when two
of these orbitals are utilized by two protons, this arrangement is slightly disturbed
due to the shifting of electron pairs away from oxygen. Consequently, the angle of
109º28¢ between the two orbitals of O2– is changed to 105º in water, owing to the
expansion of the electronic cloud by the two protons. The expansion of electronic
cloud means the OH bonds acquire a little more of 2p character.
Mathematically, the four sp3 hybrid orbitals of oxygen are given by the expressions
y
sp13 ( O )
= 1 y2s(O) + 1 y 2p x (O ) + 1 y 2p y (O ) + 1 y 2p z (O )
2 2 2 2
y 1 1 1 y 1
sp3
= y2s(O) – y 2p x ( O ) – 2p y ( O ) + y 2p z ( O )
2 (O) 2 2 2 2
y 1 1 1 y 1
sp3
= y2s(O) – y 2p x ( O ) + 2p y ( O ) – y 2p z ( O )
3 (O) 2 2 2 2
y
sp3
= 1 y2s(O) + 1
y 2p x ( O ) –
1 y
2p y ( O ) –
1
y 2p z ( O )
4 (O) 2 2 2 2
Considering the formation of the two localized molecular orbitals from y 3 and
sp1
y 3 , we have
sp 2
y1, loc = C¢1 y sp3 (O ) + C 2¢ y 1s(Ha ) (2.14.9)
1
y2, loc = C 1¢ y sp3 (O ) + C 2¢ y 1s(H (2.14.10)
2 b)

i.e. y1, loc = C 1¢ ÊÁ 1 y 2s(O) + 1 y 2 p x (O) + 1 y 2 p y (O) + 1 y 2 p z (O) ˆ˜ + C 2¢ y 1s(Ha )

Ë2 2 2 2 ¯

y2, loc = C 1¢ ÊÁ 1 y 2s(O) - 1 y 2 p x (O) - 1 y 2 p y (O) + 1 y 2 p z (O) ˆ˜ + C 2¢ y 1s(H )

Ë2 2 2 2 ¯ b

Conversion of While describing the excitation of an electron, the above treatment of localized
Localized MO into orbitals is not useful since it is not possible to associate the electron as coming
Nonlocalized MO from one OH link or the other. The two links are completely identical and are
and vice versa
molecular orbitals into nonlocalized orbitals. This is achieved by taking ‘positive’
and ‘negative’ combinations of y1, loc and y2, loc as follows.
 Theories of Covalent Bond 295

y1 = y1, loc + y2, loc and y4 = y1, loc – y2, loc

Substituting the expressions of y1, loc and y2, loc, we get
y1 = C1¢ (y 2s(O) + y 2 p z (O) ) + C2¢ (y 1s(Ha ) + y 1s(H ) )
b
y4 = C1¢ (y 2 p x (O) + y 2 p y (O) ) + C2¢ (y 1s(Ha ) - y 1s(H ) )
b
The functions y1 and y4 are, in fact, the same as described earlier (Eqs 2.14.7
and 2.14.8) provided, we have
C1 = C2 = C4 = C1¢ and C3 = C5 = C2¢
The above treatment of constructing two nonlocalized molecular orbitals out
of two localized orbitals can be reversed, i.e. out of two nonlocalized orbitals, we
can construct two localized orbitals by simply taking the ‘positive’ and ‘negative’
combinations of y1 and y4. If we do so, we get back the functions y1, loc and
y2, loc respectively.

Construction The schematic construction of correlation diagram may be carried out by following
of Correlation the steps given below.
Diagram 1. Depict the relative energies of atomic orbitals of O and H atoms. Since
oxygen is more electronegative than hydrogen, the 2s and 2p orbitals of oxygen
are more stable than 1s hydrogen orbital.
2. Depict the sp3 hybridization of oxygen orbitals. The energies of sp3 hybrid
orbitals will be greater than that of 2s orbital but smaller than those of 2p orbitals.
3. Depict the formation of localized molecular orbitals. There will be two
bonding (degenerate) and two antibonding (degenerate) orbitals.
Figure 2.14.13 exhibits the expected correlation diagram. Since H2O has eight
(y 1, loc )2 (y 2, loc )2 (y sp3 )2 (y sp3 )2 .
3 4

Figure 2.14.13 also exhibits the change in energies of localized molecular orbitals
when they are converted into nonlocalized molecular orbitals.
y 1¢ , loc; y 2¢ , loc y3

y5

1s

Ha, Hb

3 3
Energy

{ sp 2sp
{

2s y4

Fig. 2.14.13 Corre-

y 1, loc ;y 2, loc
lation diagram of H2O y1
O O Localized Nonlocalized
MO MO
296 A Textbook of Physical Chemistry

Carbon Dioxide
The carbon dioxide is a linear molecule (Fig. 2.14.14). The coordinate system
adopted is also shown in Fig. 2.14.14.

x x x

z z z
Oa C Ob

Fig. 2.14.14 The

coordinate system of CO2 y y y

Formation In carbon dioxide, all the three atoms have 2s and 2p valence orbitals and thus will
of Different be involved in the formation of molecular orbitals. The various molecular orbitals
Molecular Orbitals may be formed as follows.
1. Since the energies of 2s(Oa) and 2s(Ob) orbitals are far off from the energies
of other orbitals, the mixing of these two orbitals with other orbitals will be small
and thus may be treated as the nonbonding orbitals.
2. Of the six 2p orbitals of the two oxygen atoms, the following six group
orbitals may be formed.
y1– = y 2p z (Oa ) – y 2p z (Ob ) ; symmetrical

y1+ = y 2p z (Oa ) + y 2p z (O ) ; antisymmetrical

b

y2+ = y 2p (O ) + y 2p x (O ) ; antisymmetrical
x a b

y2– = y 2p (O ) – y 2p x (O ) ; symmetrical
x a b

y3+ =y 2p y (Oa ) + y 2p y (O ) ; antisymmetrical

b

y3– = y 2p y (Oa ) – y 2p y (O ) ; symmetrical

b

The group orbitals y1– and y1+ are of s type whereas y2+, y2–, y3+ and y3– are
of p type.
3. Since the group orbital y1– is symmetrical, it may be combined linearly with
the symmetrical 2s orbital of carbon. The group orbital y1+ is antisymmetrical, it
will combine with the antisymmetrical 2pz orbital of carbon.

Hence, the four molecular orbitals formed from these mixing are as follows.

y1 = C1y2s(C) + C2 (y 2 p z (Oa ) - y 2 p z (Ob ) ) (2.14.13)

 Theories of Covalent Bond 297

y2 = C3y2s(C ) – C4 (y 2 p z (oa ) - y 2 p z (ob ) ) (2.14.14)

y3 = C5 y 2p z (C) + C6 (y 2 p z (oa ) + y 2 p z (ob ) ) (2.14.15)

y4 = C7 y 2p z (C) – C8 (y 2 p z (oa ) + y 2 p z (ob ) ) (2.14.16)

4. The group orbitals y2+ and y3+ will have positive overlap with 2px and 2py
orbitals of carbon, respectively. Hence, their linear combinations will result into
the following four p-orbitals.

y5 = C9 y 2p x (C) + C10 (y 2 p x (Oa ) + y 2 p x (O ) ) (2.14.17)

b

y6 = C11 y 2p x (C) – C12 (y 2 p x (Oa ) + y 2 p x (O ) ) (2.14.18)

b

y7 = C13 y 2p y (C) + C14 (y 2 p y (Oa ) + y 2 p y ( O ) ) (2.14.19)

b

y8 = C15 y 2p y (C) – C16 (y 2 p y (Oa ) + y 2 p y ( O ) ) (2.14.20)

b

Since the designation of x- and y-directions is arbitrary, the molecular orbitals

y5 and y7, and y6 and y8 will constitute a degenerate set with the corresponding

5. The group orbitals y2– and y3– will have zero overlap with 2px and 2py
orbitals of carbon, and thus, will not enter into any combination.

Nature of The nature of a molecular orbital may be determined as usual from the signs of
Molecular Orbitals nearby lobes of its constituent atomic orbitals. From Fig. 2.14.15, the conclusions
drawn are shown in Table 2.14.3.

Table 2.14.3 Nature of Molecular Orbitals

Molecular Signs of the Nature of
orbital nearby lobes MO
y1 same bonding
y2 different antibonding
y3 different antibonding
y4 same bonding
y5, y7 same bonding
y6, y8 different antibonding

Contour Diagrams A few characteristics of molecular orbitals are shown in Table 2.14.4. In the light
of Molecular of these characteristics, the contour diagrams of molecular orbitals can be drawn
Orbitals and are shown in Fig. 2.14.15.
298 A Textbook of Physical Chemistry

Fig. 2.14.15 Contour

diagrams of
molecular orbitals
(The approximate
representation
involving angular
functions for 2p
orbitals is used)

Table 2.14.4 Characteristics of Molecular Orbitals of Carbon Dioxide

Molecular Nature Relative Characteristics
orbital values of
† Merging of Electron density
nearby lobes on‡
y1 bonding C2 > C1 Yes O>C
y2 antibonding C3 > C4 No C>O
y3 antibonding C5 > C6 No C>O
y4 bonding C8 > C7 Yes O>C
y5, 7 bonding C10 > C9 Yes O>C
C14 > C13
y6, 8 antibonding C11 > C12 No C>O
C15 > C16
†

the less electronegative atom. In antibonding orbital, the reverse is true.

‡
The electron density on A > B implies that the function y will have larger value nearby
the atom A as compared to that of the atom B.
 Theories of Covalent Bond 299

Relative Energies The following factors help deciding the relative orbital energies in carbon dioxide
of Molecular (Fig. 2.14.16).
Orbitals
1. Since oxygen is more electronegative than carbon, the orbitals 2s and 2p of
oxygen are expected to be more stable than the corresponding orbitals of carbon.
2. The 2p orbitals of oxygen atoms are less stable than 2s orbital of carbon
(orbital energies correspond to: 2s(C) = – 157 ¥ 103 cm–1; 2p(C) = – 86 ¥ 103cm–1;
2s(O) = – 261 ¥ 103 cm–1 and 2p(O) = – 128 ¥ 103 cm–1 ).
3. The group orbitals y1–, y2+ and y3+ are of bonding nature. Hence, their
energies will be smaller than those of 2p(O) orbitals. The orbital y1– is expected
to be more stable than the degenerate orbitals y2+ and y3+ as lateral overlapping
is larger than the side-way overlapping.
4. The group orbitals y1+, y2– and y3– are of antibonding nature. Hence, their
energies will be greater than those of 2p(O) orbitals. The orbital y1+ will be less
stable than the degenerate orbitals y2– and y3–.
5. The molecular orbital y1 being a bonding orbital will be more stable than
the more stable constituent atomic orbital, i.e. 2s(C).
6. The molecular orbital y2 being an antibonding orbital will be less stable than
the lesser stable constituent orbital, i.e. y1–.
7. The molecular orbital y3 being an antibonding orbital will be less stable than
the lesser stable constituent orbital, i.e. 2pz(C). The orbital y3 is expected to have
larger energy than the orbital y2 as 2 p(C) has much larger energy than that of 2s(C).
8. The molecular orbital y4 being a bonding orbital will be more stable than
the more stable constituent orbital, i.e. y1+.
9. The molecular orbital y4 will be even less stable than y1 as the overlapping
between 2pz (O) and 2pz (C) is smaller than between 2pz (O) and 2s(C).
10. The degenerate bonding p orbitals y5 and y7 will have lesser energies than
the more stable constituent orbitals, i.e. y2+ and y3+ , respectively.
11. The degenerate antibonding p orbitals y6 and y8 will have more energies
than the lesser stable constituent orbitals, i.e. 2px(C) and 2py (C), respectively.
12. The orbitals y5 and y7 will be less stable than y4 as side-way overlapping
between 2px(C) and 2px(O) or 2py(C) and 2py (O) will be smaller than the lateral
overlapping between 2pz (C) and 2pz (O). Similarly, the orbitals y6 and y8 will be
more stable than the orbitals y2 and y3.
13. The group orbitals y2– and y3– will be more or less nonbonding orbitals.

Keeping in mind the above factors, the relative orbital energies of carbon dioxide
can be drawn and is shown in Fig. 2.14.16. Since there are sixteen valence electrons
2 is

[2s(Oa)]2[2s(Ob)]2(y1)2(y4) 2(y5)2(y 7)2(y2–)2(y3–)2

There will be two s bonds (due to y 12 and y 42 ), two p bonds (due to y 52 and
y 72 ) and two lone pairs of electrons (due to y 22- and y 32- ).
300 A Textbook of Physical Chemistry

y3

y2
y6, y8

2p

y1+, y2–, y3–

Energy

y2–, y3–
Six
2p

y1–, y2+, y3+

2s y5, y7

y4

y1

Fig. 2.14.16 Relative

orbital energies for
2S
CO2 C CO2 2O

Localized The localized bond of carbon dioxide is shown in Fig. 2.14.17. There are: (i) two
Molecular Orbitals s bonds formed by the overlapping of sp1(C) with pz (Ob) and of sp2 (C) with
of Carbon Dioxide pz(Oa ); (ii) two p bonds formed by the overlapping of px (C) with px (Oa) and of
py (C) with py(Ob) or alternatively between px(C) and px(Ob) and between py(C)
and py(Oa); and two lone pairs of electrons (one pair in py(Oa) and the other in
px(Ob) or alternatively one pair in px(Oa) and the other in py(Ob). The localized
bonds will be described by the following expressions:
y¢1, loc= C1¢ y sp – C2¢ y 2p z (O
1 (C) b)

= C1¢ (y2s(C) + y 2p z (C) ) – C2¢ y 2p z (Ob ) (2.14.21)

y¢2, loc= C1¢ y sp + C¢ y 2p z (Oa )
2 (C)

= C1¢ ( y 2s (C) – y 2p z (C) ) + C2¢ y 2p z (Oa ) (2.14.22)

y¢3, loc = C3¢ y 2p x (C) + C4¢ y 2p x (Oa ) (2.14.23)

y¢4, loc = C3¢ y 2p y (C) + C4¢ y 2p y (O (2.14.24)

b)

y¢5, loc = y 2p y (Oa ) (2.14.25)

y 6,
¢ loc = y 2p x (O (2.14.26)
b)
 Theories of Covalent Bond 301

x x x

p y
y y

s s
sp2 –pz(b)
Oa C sp1 Ob z
pz(a)

x x x

p y
y y

s s
sp2 –pz(b)
Oa C sp1 Ob z
pz(a)

p
Fig. 2.14.17 Valence-
bond structures for CO2

Conversion of The localized molecular orbitals can be converted into nonlocalized molecular
Localized to orbitals by the following combinations.
Nonlocalized MOs y1 = y¢1,loc + y¢2,loc
= C≤1 y2s(C) + C≤2 (y 2p z (O a ) - y 2 p z (Ob ) )
y4 = y¢1,loc – y¢2, loc
= C≤1 y 2p z (C) – C≤2 (y 2p z (Oa ) + y 2 p z (Ob ) )
¢
y5 = y3, loc + C¢4 y 6,loc
= C¢3 y 2p x (C) + C¢4 (y 2p x (Oa ) + y 2 p x (Ob ) )
y7 = y¢4, loc + C¢4 y¢5,loc
= C¢3 y 2p y (C) + C¢4 (y 2p y (Oa ) + y 2 p y ( Ob ) )

The functions y1, y4, y5 and y7 are, in fact, the same as described earlier by Eqs
(2.14.13), (2.14.16), (2.14.17) and (2.14.19), respectively.
Correlation The schematic construction of correlation diagram may be carried out by following
Diagram the steps given below.
1. Depict the relative energies of atomic orbitals of O and C atoms: Since
oxygen is more electronegative than carbon, the 2s and 2p orbitals of oxygen are
more stable than the corresponding orbitals of carbon.
302 A Textbook of Physical Chemistry

2. Depict the sp hybridization of carbon orbitals: The energies of sp hybrid

orbitals will be greater than that of 2s orbitals but smaller than that of 2p orbital.
3. Depict the formation of localized molecular orbitals: There will be (i) two
degenerate s bonding orbitals y¢1, loc and y¢2, loc , (ii) two degenerate s antibonding
orbitals (the positive and negative combinations in Eqs 2.14.21 and 2.14.22,
respectively), (iii) two degenerate p bonding orbitals y¢3, loc and y¢4, loc , (iv) two
degenerate p antibonding orbitals (the negative combinations in Eqs 2.14.23 and
2.14.24), and (v) two degenerate 2p nonbonding orbitals y¢5, loc and y¢6, loc.
4. The energies of two s bonding orbitals will be smaller than those of p
bonding orbitals.
5. The energies of two s antibonding orbitals will be larger than those of p
antibonding orbitals.
Figure 2.14.18 exhibits the expected correlation diagram. Since CO2 has sixteen

(y 2s(Oa ) ) 2 (y 2s (O ) )2 (y1,¢ loc ) (y 2,¢ loc ) (y 3,¢ loc ) (y 4,¢ loc ) (y 5,¢ loc ) (y 6,¢ loc )
2 2 2 2 2 2
b

Figure 2.14.18 also exhibits the change in energies of localized molecular orbitals
when they are converted into nonlocalized molecular orbitals.

Fig. 2.14.18
Correlation diagram
of CO2. The localized
orbitals are simply
written as y 1¢ , y¢2, etc.
 Theories of Covalent Bond 303

Problem 2.14.1 (a) Construct the localized molecular orbitals of HCN molecule.
(b) Transform these localized molecular orbitals into nonlocalized molecular orbitals.
(c) Draw the contour diagrams of nonlocalized molecular orbital.
(d) Draw the energy level diagram correlating the energies of localized and nonlocalized
molecular orbitals. Assume 2s(N) orbital as the nonbonding orbital.
Solution (a) The HCN molecule has a linear structure with a single s bond between C and H and
three bonds (one s and two p) between C and N. The carbon atom is in the sp-hybrid
state. The two sp-hybrid orbitals of carbon are generated as follows.
(i) y sp1 = y2s(C) + y 2pz ( C)
(ii) y sp2 = y2s(C) – y 2pz ( C)
The shapes of these orbitals are shown in Fig. 2.14.19.
From Fig. 2.14.19, it follows that the two localized s bonds between N and C, and H and
C can be generated as follows.
(iii) y1, loc = C1 y sp1 (C) - C2 y 2pz ( N )
(iv) y2, loc = C3 y sp2 (C) + C4y1s(H)
The antibonding counterparts will be given by
(v) y 1,¢ loc= C1¢ y sp1 (C) + C2¢ y 2pz ( N)
(vi) y ¢2, loc = C3¢ y sp (C) – C4¢ y1s(H)
2

The two p bonds between C and N will be represented by the following combinations.
(vii) y3, loc = C5 y 2p x ( C) + C6 y 2p x ( N )

(viii) y4, loc = C7 y 2p y ( C) + C8 y 2p y ( N )

The orbitals y3, loc and y4, loc are degenerate with C5 = C7 and C6 = C8. The antibonding
counterparts will be given by
(ix) y 3,¢ loc = C5¢ y 2p x (C) – C6¢ y 2p x ( N )
(x) y ¢4, loc = C7¢ y 2 p y (C) - C8¢ y 2 p y ( N)

The two orbitals are also degenerate with C5¢ = C7¢ and C6¢ = C8¢ . There will be one
nonbonding orbital comprising of 2s(N) orbital, i.e.
(xi) y5, loc= y2s(N)
(b) The two nonlocalized s orbials can be obtained by taking ‘positive’ and ‘negative’
combinations of y1, loc and y2, loc. Thus, we have
y1, n1 = y1, loc + y2, loc
= (C1 + C3) y2s(C) + (C1 – C3) y 2 p z (C) - C2 y 2 p z ( N) + C4y 1s(H)
y2, n1 = y1, loc – y2, loc
y
= (C1 – C3 ) y2s(C) + (C1 + C3) y 2p z (C) – C2 2 p z ( N ) – C4y1s(H)

The two nonlocalized s* orbitals can be generated by taking ‘negative’ and ‘positive’
combinations of y 1,¢ loc and y 2¢, loc. Thus, we have
y ¢1, n1 = y 1,¢ loc – y 2,¢ loc
= ( C1¢ – C3¢ )y2s(C) + ( C1¢ + C3¢ ) y 2p z (C) + C2¢ y 2p z ( N) + C4¢ y1s(H)
y 2¢ , n1 = y 1,¢ loc + y 2,¢ loc
= ( C1¢ + C3¢ )y2s(C) + ( C1¢ – C3¢ ) y 2p (C) + C2¢ y 2p z ( N) – C4¢ y1s(H)
z
304 A Textbook of Physical Chemistry

H C∫ N z
y
+
(i) + – +
2pz(C)
2s(C) sp1 (C)

+
(ii) + – + –
–2pz(C)
2s(C) sp2 (C)

–
– + – +
(iii) – + –
2pz(N) y1, loc
sp1 (C)

– + –
(iv) + + +
1s(H) y2, loc
sp2(C)

+ + – + – + – +
(v) –

2pz(N) y¢
sp1(C) 1, loc

– –
– + + + – +
(vi)

1s(H) sp2(C) y¢2 , loc

(vii) +
+ +
and
(viii) +
– – –

y3, loc, y4, loc

2px(C) 2px(N)
or or
2py(C) 2py(N)

+ + + –
(ix)
and –
(x) – – – +

2px(C) 2px(N) y¢3, loc

or y¢4, loc
2py(C) 2py(N)

Fig. 2.14.19 The shapes of the two sp-hybrid orbitals of carbon and the formation of localized molecular orbitals
(schematic)
 Theories of Covalent Bond 305

If it is assumed that C1 – C3 << C1 + C3 and C1¢ – C3¢ << C1¢ + C3¢ the above four
nonlocalized orbitals may be written as
y1, n1 = (C1 + C3)y2s(C) – C2 y 2p z ( N) + C4y1s(H)
y2, n1 = (C1 + C3) y 2pz (C) – C2 y 2pz ( N) – C4y1s(H)
y ¢1, n1 = ( C1¢ + C3¢ ) y 2pz (C) + C2¢ y 2pz ( N) + C4¢ y1s(H)
y ¢2, n1 = ( C1¢ + C3¢ )y2s(C) + C2¢ y 2pz ( N) – C4¢ y1s(H)
The ‘positive’ and ‘negative’ combinations of y3, 1oc and y4, 1oc and y 3,¢ loc and y 4,¢ loc
create the molecular orbitals which are of the same type as represented by y3, 1oc,
y4, 1oc, y 3,¢ loc and y 4,¢ loc with the exception of change in the directions of molecular
orbitals. Thus, the orbitals y 3, 1oc,y 4, 1oc, y 3,¢ loc and y 4,¢ loc may be treated as
nonlocalized molecular orbitals. The nonbonding y5, loc will also remain unchanged.
(c) The contour diagrams of nonlocalized molecular orbitals are shown in Fig. 2.14.20.

Fig. 2.14.20 The contour diagrams of nonlocalized molecular orbitals

(d) The relative order of energies of localized molecular orbitals follows from the
following facts.

(i) The energy of nonbonding orbital y5, loc (= y2s(N) ) will have the smallest energy
as N is the most electronegative atom in HCN molecule.
(ii) The energy of y2, loc will be smaller than that of y1, loc as the overlapping
between 1s(H) and sp1(C) will be larger than that between y 2p z ( N ) and sp2(C).
306 A Textbook of Physical Chemistry

(iii) The energies of y3, loc and y4, loc, which represent p orbitals, will be larger than
y1, loc as the side-way overlapping between 2p(C) and 2p(N) will be smaller than that
between sp1(C) and 2p(N). The functions y3, loc and y4, loc will be degenerate.
(iv) The energies of antibonding y 3,loc¢ ¢
and y 4,loc orbitals will be larger than that
those of bonding y3, loc and y4, loc orbitals.
¢
(v) The energy of y 1,loc ¢
will be larger than y 2,loc since 2pz(N) orbital will lie
above 1s(H) orbital.
Keeping these facts in mind, the relative order of energies of orbitals is shown in
Fig. 2.14.21. The relative order of energies of nonlocalized molecular orbitals can be
derived from those of localized orbitals and is also shown in Fig. 2.14.21.

Fig. 2.14.21 The

relative order of
energies of (a)
localized, and (b)
nonlocalized orbitals in
HCN molecule

2.15 CORRELATION OF THE ORBITALS FOR BENT AND LINEAR AH2 MOLECULES

A.D. Walsh in 1953 correlated the molecular orbitals for bent and linear AH2
molecules and rationalized the following facts regarding the shapes of molecules
in the ground states.
AH2 molecules containing 4 valence electrons should be linear whereas those
containing 5–8 valence electrons should be bent.
The types of molecular orbitals involved in bent and linear AH2 molecules are
given in Table 2.15.1.
 Theories of Covalent Bond 307

Table 2.15.1 Types of Orbitals Involved in Bent and Linear AH2 Molecules
Bent molecules Linear molecules
1. Two bonding orbitals formed from: 1. Two bonding orbitals formed from:
(i) Group orbital 1s(Ha) + 1s(Hb) and (i) Group orbital 1s(Ha) + 1s(Hb)
2pz(A) when the bond angle is 90º or and 2s(A), e.g. Eq. (2.14.1).
1s(Ha ) + 1s(Hb ), 2s(A) and 2pz(A)
when the bond angle > 90º and
< 180º, e.g. Eq. (2.14.7).
(ii) Group orbital 1s(Ha) – 1s(Hb) and (ii) Group orbital 1s(Ha) – 1s(Hb)
2px (A) or 2px (A) + 2py(A), e.g. and 2pz (A), e.g. Eq. (2.14.4).
Eq. (2.14.8).
2. Two nonbonding orbitals: one is 2s(A) 2. Two nonbonding p orbitals
orbital and the other is 2py (A) or centred on A.
2px (A) – 2py(A) orbital.

When the bond angle of bent AH2 molecule is gradually increased from 90º to 180º
(linear structure), the following changes in energies of orbital occurs.
1. The bonding orbital
y1, b = C1¢ (y 1s(Ha ) + y 1s ( Hb ) ) + C2 y 2p z ( A )
is changed to
¢ = C1¢ (y 1s(Ha ) + y 1s ( Hb ) ) + C2¢ y 2p z ( A ) + C3¢ y2s(A)
y 1,b

y1, lin = C1¢ (y 1s(Ha ) + y 1s ( Hb ) ) + C2¢¢ y2s(A)

when the bond angle is 180º. The subscripts b and lin stand for bent and linear
structures, respectively. This means that the participation of 2s orbital centred on
A (which is nonbonding in the bent structure) in the molecular orbital increases
as the bond angle is increased from 90º to 180º. As a consequence of this, the
orbital energy decreases as the molecule is gradually changed from bent to the
linear structure. In the latter, 2p(A) orbital becomes nonbonding in place of 2s(A)
orbital in the bent structure.
2. The form of molecular orbital

y2, b or lin = C1 (y 1s ( Ha ) - y 1s ( Hb ) ) + C2 y 2p z ( A )

remains unchanged in converting bent structure to the linear structure. The group
orbital y 1s ( Ha ) – y 1s ( Hb ) of the end atoms of the molecule is antibonding and it
is known that the molecular orbital formed from such group orbital is stable when
the end atoms are as far apart as possible (i.e. in the linear molecule)†. Thus the
energy of orbital y2 decreases as the molecule is gradually changed from bent to
the linear structure.
†
If the orbital is bonding between the end atoms, it is most stable if the end atoms are
near to each other (i.e. in the bent structure).
308 A Textbook of Physical Chemistry

3. One of the two nonbonding orbitals is p orbital in both the structures and
hence its energy remains constant during the change of structure of the molecule.
The second nonbonding orbitals in bent structure is 2s(A) orbital whereas in the
linear structure, it is 2p(A) orbital. Since during the structural changes from bent
to linear, the 2p(A) orbital in the molecular orbital y1 is replaced by 2s(A) orbital,
it is obvious that the nonbonding 2s(A) orbital in the bent structure becomes 2p(A)
orbital in the linear structure. Thus, the energy of this nonbonding orbital increases
steeply until it becomes one of the degenerate p orbitals at 180º.
Figure 2.15.1 depicts the correlation diagram between the four orbitals described
above for bent and linear AH2 molecules. From Fig. 2.15.1, it may be concluded
that the AH2 molecules having 4-valence electrons will have the lowest energy if
its structure is linear, i.e. the stable structure for AH2 molecules having 4-valence
electrons is the linear structure. The molecules having 5, 6, 7 or 8 valence electrons
are not expected to have linear structure as it is possible to write down electronic

the molecules having 5, 6, 7 or 8 valence electrons are expected to be nonlinear. As

examples, the BeH2 and HgH2 molecules are expected to be linear in their ground
states whereas the CH2, OH2, SH2 molecules are expected to be nonlinear in their
of BeH2 or HgH2 is expected to be nonlinear.

y2p y4

y2, b
Energy

y2s

y1, b
Fig. 2.15.1 Qualita-
y2, lin
tive variation of
molecular orbital
y1, lin
energies with bond
angle HAH 90º Bond angle HAH 180º

The actual electro

to 180º cannot be predicted with certainty as the existence of electron repulsion
may offset the small energy difference between the two nonbonding orbitals.
For example, if the bond angle of CH2 molecule is close to 180º, the electronic

(y1, lin)2(y2, lin)2(y3, lin)1(y4, lin)1 (2.15.1)

 Theories of Covalent Bond 309

has lower energy than

(y1, b)2(y2, b)2(y2s)2 (2.15.2)
If, on the other hand, the apex angle is considerably less than 180º, the ground

A similar study on AB2 and BAC molecules by Walsh rationalized the following
facts regarding their shapes.
The molecules with not more than 16 valence electrons are linear in their
ground states; the molecules with 17, 18, 19 or 20 valence electrons are bent
in their ground states, the apex angle decreases markedly from 16- to 17- and
from 17- to 18- electron molecules and less markedly from 18- to 19- and 19- to
20-electron molecules; the molecules with 22 electrons are linear or very linear
in their ground states.
For molecules HAB, Walsh obtained the following facts:
The molecules having 10 and 16 valence electrons are linear whereas those
having 11–14 electrons are bent.
Examples of linear HAB, AB2 and BAC molecules are given in Table 2.15.2.

Table 2.15.2 Examples of Linear and Nonlinear Molecules

Valence electrons Structure Examples
10 linear HCN
11 nonlinear HCO
12 nonlinear HNO
13 nonlinear HO2
14 nonlinear HOCl
16 linear FHF–
12 linear C3
13 linear CCN
14 linear NCN
15 linear NCO
15 linear CO2+
16 linear NO+2, CO2, COS, CS2, N2O
ClCN, HgCl2, NCO–, N–3
AgCl2– and AuCl–2
17 nonlinear NO2
18 nonlinear NOCl, NOBr, NO–2, O3
19 nonlinear ClO2, NF2
20 nonlinear F2O, Cl2O, Cl2S
22 linear BrIBr–, CHCl–, I–3, KrF2, XeF2

2.16 CONJUGATED ORGANIC MOLECULES

A conjugated organic molecule involves an alternate arrangement of single and
double bonds between carbon atoms. The bonding in these molecules can be
310 A Textbook of Physical Chemistry

explained on the basis of sp2 hybrid orbitals of carbon atoms. The single bond
constitutes a s bond formed by the overlapping of the two sp2 hybrid orbitals of
neighbouring carbon atoms. The double bond contains one s and one p bond. The
former is formed again by overlapping of two sp2 hybrid carbon orbitals and the
latter is formed by the side-way overlapping of the pz orbitals.†
The entire molecule can be treated semiempirically by the molecular orbital
method.†† But because of the fact that various s bonds lie in the xy-plane and pz
orbitals perpendicular to this plane, we may expect that the latter’s do not take part
in the formation of s bonds. Thus, various pz orbitals and the other orbitals (s, px
and py) may be treated separately under the LCAO-MO framework.‡
In this section, we focus our attention on the p-electrons of conjugated organic
molecules. In the molecular orbital theory, these p-electrons are considered to
be distributed over the p-molecular orbitals extended over the entire molecule.
These molecular orbitals may be constructed by the linear combination of carbon
2pz orbitals, i.e.
n
jp = Â Cr c 2 p ( r )
z
(2.16.1)
r =1
where n represents the number of pz
Eq. (2.16.1) as usual can be determined by the variation method. The latter will
give us n simultaneous linear secular equations:

C1(H11 – ES11) + C2(H12 – ES12) + ◊ ◊ ◊ + Cn (H1n – ES1n ) = 0

C1(H21 – ES21 ) + C2(H22 – ES22) + ◊ ◊ ◊ + Cn(H2n – ES2n ) = 0

◊ ◊ ◊ ◊
◊ ◊ ◊ ◊
◊ ◊ ◊ ◊
C1(Hn1 – ESn1 ) + C2(Hn2 – ESn2) + ◊ ◊ ◊ + Cn(Hnn – ESnn) = 0 (2.16.2)

where Hrr = Ú c 2p z ( r ) | H | c 2p z ( r ) dt (2.16.3a)

Hrs = Ú c 2p z (r ) | H | c 2p z ( s )dt (2.16.3b)

Srr = Ú c 2p z ( r ) c 2p z ( r ) dt (2.16.3c)

Srs = Ú c 2p z ( r ) c 2p z ( s ) dt (2.16.3d)

†
The entire skeleton of a conjugated molecule lies in a plane (taken to be xy-plane). The
z-axis lies perpendicular to the plane of molecule.
††
One of the methods is the extended Hückel molecular orbital method where LCAO-MO
framework is applied to all valence orbitals of atoms in a molecule.
‡
This separation basically is due to the fact that the overlap integrals between s and pz, px
and pz, py and pz orbitals will be zero.
 Theories of Covalent Bond 311

For the nontrivial roots, we set n ¥ n secular determinant equal to zero, i.e.
H11 - ES11 H12 - ES12 � H1n - ES1n
H 21 - ES21 H 22 - ES22 � H 2 n - ES2 n
=0 (2.16.4)
� � �
H n1 - ESn1 H n 2 - ESn 2 � H nn - ESnn

Hückel In principle, the above determinant can be solved for the various energy values.
Approximations These when substituted one by one in secular equations (Eqs 2.16.2) along with
the normalization condition of the molecular orbital give the n
corresponding molecular orbitals.
In general, the evaluation of various integrals in Eq. (2.16.4) cannot be
carried out in a reasonably exact way. In order to make the calculations simple
enough to be useful to the average chemist, Hückel introduced the drastic
approximations regarding the values of integrals in Eq. (2.16.4). In spite of the
drastic approximations, the Hückel method has been found to be very useful
in understanding many important features of p bondings. The approximations
introduced by Hückel are:
∑ All overlap integrals Srs are assumed to be equal to zero. Since the atomic
orbitals are normalized, Srr = 1.
∑ Hrr is assumed to be the same for all the carbon atoms involved. It is usually
represented by the symbol a and is called the Coulomb integral. It is generally
treated as an unknown parameter.
∑ Hrs is assumed to have the constant value b if atoms r and s are bonded directly.
All other H¢rs are set equal to zero. The term b is called the resonance integral
and is again regarded as an adjustable parameter.
To illustrate the above approximations, we describe below the Hückel molecular
orbital calculations on ethylene, butadiene and benzene molecules.
ETHYLENE MOLECULE
Figure 2.16.1 illustrates the ethylene molecule.
p
H H

s s

C C
s
s s
Fig. 2.16.1 An
ethylene molecule H H

The secular determinant will take the form

a-E b
=0 (2.16.5)
b a-E
312 A Textbook of Physical Chemistry

Dividing each element of the above determinant by b and then setting (a – E )/b
= x, we get
x 1
=0
1 x
which on expanding gives
x2– 1 = 0
The two roots of the above equation are
x = – 1 and + 1
a-E a-E
Thus =–1 and =1
b b
which gives E+ = a + b (2.16.6a)
E– = a – b (2.16.6b)
Substituting these energies in the secular equations, we get
j+ = C ( c 2 p z (r ) + c 2 p z ( s ) ) ; E+ = a + b (2.16.7a)
j– = C ( c 2 p z ( r ) + c 2 p z ( s ) ) ; E– = a – b (2.16.7b)
The value of C as determined by normalizing the molecular orbital y+ or y– is
1
C= (2.16.8)
2
Thus for ethylene, we have two p-molecular orbitals. Since both a and b have
negative values, we may conclude that
E+ < E–
The function y+ is the bonding orbital and y– is the antibonding orbital. The
ground state p y+(1)y+(2). The ground state electronic
energy is
2(a + b ) (2.16.9)
Since b is a negative quantity, the above energy is less than the sum of energies
of electrons (= 2a) in the two pz orbitals.

Butadiene Molecule

Figure 2.16.2 illustrates the butadiene molecule.

1 p 2
H H
s s
p
3 p 4
C C H
s s s
s s
H C C

Fig. 2.16.2 A s s
butadiene molecule H H
 Theories of Covalent Bond 313

The scalar determinant will take the form

a-b b 0 0
b a -E b 0
=0 (2.16.10)
0 b a-E b
0 0 b a-E
Dividing each element of the above determinant by b and then setting (a – E )/b
= x, we get
x 1 0 0
1 x 1 0
=0
0 1 x 1
0 0 1 x
which on expanding gives
x4 – 3x2 + 1 = 0
The four roots of the above equation are
– 1.618, – 0.618, + 0.618 and + 1.618
The corresponding four values of energy are
E1 = a + 1.618 b (2.16.11a)
E2 = a + 0.618 b (2.16.11b)
E3 = a – 0.618 b (2.16.11c)
E4 = a – 1.618 b (2.16.11d)
Since b is negative, it follows that
E1 < E2 < E3 < E4

be obtained by substituting the above energies one by one in the secular equations,
which in the present case are
C1 (a - E ) + C2 b = 0 ¸
C1b + C2 (a - E ) + C3b = 0 ÔÔ (2.16.12)
˝
C2 b + C3 (a - E ) + C4 b = 0 Ô
C3 b + C4 (a - E ) = 0 Ô˛

For example, if we substitute E1 from Eq. (2.16.11a) in Eqs (2.16.12), we get

– 1.618 C1 b + C 2 b = 0
C1 b – 1.618 C 2 b + C3 b = 0 (2.16.13)
C2 b – 1.618 C 3 b + C4 b = 0
C3 b – 1.618 C 4 b = 0
Dividing by b and applying the normalizing condition
C12 + C22 + C32 + C42 = 1
314 A Textbook of Physical Chemistry

we get C1 = C4 = 0.372 (2.16.14a)

and C2 = C3 = 0.602 (2.16.14b)
Thus, the molecular orbital having energy E1 is
j1 = 0.372 c 2 p z (1) + 0.602 c 2 p z (2) + 0.602 c 2 p z (3) + 0.372 c 2 p z (4) (2.16.15a)
The molecular orbitals having the remaining energies can be determined in the
same way; they are
j2 = 0.6202 c 2 p z (1) + 0.372 c 2 p z (2) – 0.372 c 2 p z (3) – 0.602 c 2 p z (4) (2.16.15b)
j3 = 0.602 c 2 p z (1) – 0.372 c 2 p z (2) – 0.372 c 2 p z (3) + 0.602 c 2 p z (4) (2.16.15c)
j4 = 0.372 c 2 p z (1) – 0.602 c 2 p z (2) + 0.602 c 2 p z (3) – 0.372 c 2 p z (4) (2.16.15d)
These molecular orbitals are represented schematically in Fig. 2.16.3.
The number of nodes present in the wave functions j1, j2, j3 and j4 are also
shown in Fig. 2.16.3. The wave function j1 does not contain any node and is thus
a strongly bonding orbital. The function j2 has a node between second and third
carbon atoms. It has a partial bonding character as it accumulates charges between
atoms 1 and 2, and 3 and 4 (isolated double bonds). The functions j3 and j4 are
antibonding since their energies are greater than that of an isolated pz orbital.

Approximate Number of Energy

shape nodes

+ + + +
+
y1 a + 1.618 b
– – 0
– – –

+ – – + –
+
y2 + 1 a + 0.618 b
– – + – +

+ – – + + +
–
y3 2 a –1.618 b
– + + – – + –

Fig. 2.16.3 + – +
– +
Schematic graph of y4 a?–1.618 b
– 3
four p-molecular + – +
+
orbitals of butadiene
 Theories of Covalent Bond 315

The butadiene molecule contains four p-electrons and thus its ground state

(j1)2(j2)2
with the ground-state energy
E = 2 E1 + 2E2
= 2 (a + 1.618b ) + 2 (a + 0.618b )
= 4a + 4.472b (2.16.16)
Delocalization If we had considered a butadiene molecule to consist of two isolated double
Energy bonds, the total energy of the system would have been 4a + 4b. The difference
between the above energy and the energy of butadiene (Eq. 2.16.16) is 0.472 b.
This difference of energy is called the delocalization energy and has a negative
value as b is a negative quantity. Thus, delocalization of p-electrons over the entire
molecule has made it more stable by an amount 0.472b.

Benzene Molecule
Figure 2.16.4 displays the benzene molecule.

Fig. 2.16.4 Display of

benzene molecule

The secular determinant in the present case is

a-E b 0 0 0 b
b a-E b 0 0 0
0 b a-E b 0 0
= 0 (2.16.17)
0 0 b a-E b 0
0 0 0 b a-E b
b 0 0 0 b a -E

Dividing each element by b and replacing (a – E )/b by x, we get

316 A Textbook of Physical Chemistry

x 1 0 0 0 1
1 x 1 0 0 0
0 1 x 1 0 0
=0 (2.16.18)
0 0 1 x 1 0
0 0 0 1 x 1
1 0 0 0 1 x
The expansion of determinants such as this by an elementary method is a tedious
process.†
x6 – 6x4 + 9x2 – 4 = (x2 – 4 ) (x2 – 1)2 = 0
Thus, its roots are
±2, ±1 and ±1
Hence, the six energy expressions are
E1 = a + 2b
E2 ¸
˝= a + b
E3 ˛
E4 ¸
˝= a – b
E5 ˛
E6 = a – 2b

a, and the corresponding molecular

orbitals are bonding molecular orbitals. The other three molecular orbitals are
antibonding molecular orbitals. The energies E2 and E3, and E4 and E5 constitute
the degenerate levels.

below.
1
j1 =
6
( c 2 p (1) + c 2 p (2) + c 2 p (3) + c 2 p (4) + c 2 p (5) + c 2 p (6) )
z z z z z z

1
j2 =
2
( c 2 pz (2) + c 2 pz (3) - c 2 pz (5) - c 2 pz (6) )

j3 =
1
2 3
(2 c 2 p 1 + c 2 p
z
( ) z
( 2) - c 2 pz (3) - c 2 pz (4) - c 2 pz (5) + c 2 pz ( 6) )
1
j4 =
2
( c 2 pz (2) - c 2 pz (3) + c 2 pz (5) - c 2 pz (6) )

†
The roots can be determined by diagonalizing the matrix with the help of electronic

of the corresponding molecular orbitals. Thus, the solution of a tedius and lengthy secular
determinant can be done conveniently with the help of computers.
 Theories of Covalent Bond 317

1
j5 =
2 3
(2 c 2 p (1) - c 2 p (2) - c 2 p (3) + c 2 p (4) - c 2 p (5) - c 2 p (6) )
z z z z z z

1
j6 =
6
( c 2 pz (1) - c 2 pz (2) + c 2 pz (3) - c 2 pz (4) + c 2 pz (5) - c 2 pz (6) )
Schematic representations of these orbitals are shown in Fig. 2.16.5.
2 3 2 + 3 2 3
+ +
+ –
+ +
1 4 1 4 1 4

+ –
6 5+ 6 5 6 5

+ – –
+ –
Fig. 2.16.5 2 3 2 3 1 2
Schemation
1 4 + 1 4 + – 6 3 +
representation of 6
p-orbitals of benzene
6 5 6 5 5 4
(top view) – + – + –

There are six p

is
(j1)2(j2)2 (j3)2
with the ground-state energy equal to
E = 2E1 + 2E2 + 2E3 = 2(a + 2b ) + 4(a + b) = 6a + 8b (2.16.19)
The delocalization energy is
(6a + 8b ) – (6a + 6b ) = 2b
Some Useful Quantities

Electron Densities Some useful quantities pertaining to conjugated molecules are now described.
In general, we may write any molecular orbital as
n
jj = Â C jr c 2p z ( r )
r =1

where the subscript j refers to the jth molecular orbital and the subscript r refers
to the rth atom of the molecule. The quantity Cjr2 give the electron density on the
rth atom due to the jth molecular orbital. The total p-electron density on atom r
may be calculated from

qr = Â n j C 2jr
j ,occ

where the summation is carried over the occupied molecular orbitals and nj
represents the number of electrons occupying the jth molecular orbital.
318 A Textbook of Physical Chemistry

The sum of all the qs equals the total number of electrons in the system.
Examples: For butadiene, we have
2
q1 = 2C11 2
+ 2C21 = 2(0.372)2 + 2(0.602)2 = 2(0.140) + 2(0.360)
= 1.000
2
q2 = 2C12 2
+ 2C22 = 2(0.602)2 + 2(0.372)2 = 2(0.360) + 2(0.140)
= 1.000
Similarly, q3 = q4 = 1.000
In butadiene cation we have
2
q1 = 2 C21 2
+ C21 = 2.(0.372)2 + (0.602)2 = 0.640
2
q2 = 2 C12 2
+ C22 = 2(0.602)2 + (0.372)2 = 0.860
q3 = q2
q4 = q1
Bond Order The bond order between atoms r and s
prs = Â n j C jr C js
j,occ

The value of prs

length. One of the relations in use is
Rrs /pm = 151.7 – 18.0 prs

Examples: For butadiene, we have

p12 = 2C11C12 + 2C21C22 = 2(0.372) (0.602) + 2(0.602) (0.372)
= 0.894
p23 = 2C12C13 + 2C22C23 = 2(0.602) (0.602) + 2(0.372) (– 0.372)
= 0.447
Thus, the bond C1—C2 has more double bond character than C2—C3 bond.
Consequently, the bond length C1—C2 is smaller than that of C2—C3.

p12 = p23 = p34 = p45 = p56 = p16 = 0.667

that is, all the six bonds are identical in nature.
Free Valence The free valence index of atom r
Index Fr = 3 – Nr
where Nr is the sum of the bond order values for all bonds joining atom r. This
index has been used as a measure of ease of attack at atom r by free radicals.
Examples: For butadiene, we have
F1 = 3 – p12 = 1.732 – 0.894 = 0.838
F2 = 3 – p12 – p23 = 1.732 – 0.894 – 0.447 = 0.391
thus, the terminal atoms are more reactive than the central atoms.
 Theories of Covalent Bond 319

Longest Wave The electron on excitation from highest occupied molecular orbital (HOMO) to
Length of p Æ p* the lowest unoccupied molecular orbital (LUMO) absorbs radiation which may be
Transition correlated with the longest wavelength of p Æ p* transition. Thus, for ethylene
and butadiene we have
DEeth = (a – b ) – (a + b ) = – 2b
DEbuta = (a – 0.618 b ) – (a + 0.618 b ) = – 1.236 b

Thus, going from ethylene to butadiene, one observes bathochromic shift. In

general, conjugation leads to the red (bathochromic) shift. The above expressions
provide us one of the examples to estimate the value of b.†
General The general expression of the Hückel molecular orbital energy levels is available
Expressions of for linear and cyclic polyenes. These may be used to derive the energies of various
Energy molecular orbitals for a molecule and to compute p Æ p* transition. These are:
jp ˆ
Linear polyenes Ej = a + 2b cos ÊÁ
Ë n + 1˜¯
where j = 1, 2, , and n is the number of atoms in the molecule.
2 jp ˆ
Ej = a + 2b cos ÊÁ
Ë n ˜¯
Cyclic polyenes

where j = 0, ± 1, ± 2, , and n is the number of atoms in the molecule.

Extension to For an atom different from carbon, we will have different values of a and b. In
Molecules order to introduce these heteroatom values with the least possible disturbance of
Containing the secular determinant they are usually represented by the equation
Heteroatoms aX = aC + hX bCC
bCX = kCX bCC
where hX and kXC are constants, and are dependent on the heteroatoms.

Problem 2.16.1 (a) Using the Hückel approximations, show that for the allyl radical (CH
1
2 CH
2
CH2),
3
the wave functions and the corresponding energies are given by

1 1 1
j1 = c 2 p z (1) + c + c ; E1 = a + 2b
2 2 2 p z ( 2) 2 2 p z ( 3)

1 1
j2 = c 2 p z (1) – c ; E2 = a
2 2 2 p z ( 3)

1 1 1
j3 = c 2 p z (1) – c 2 p z ( 2) + c 2 p z ( 3) ; E3 = a – 2b
2 2 2
(b) Calculate the electron densities and bond orders for (i) allyl radical, (ii) allyl cation,
and (iii) allyl anion.

†
The other methods involve the data on heat of hydrogenation or resonance energies.
320 A Textbook of Physical Chemistry

Solution (a) The secular determinant for allyl radical is given by

a-E b 0
b a-E b =0
0 b a-E
Dividing each element of the above determinant by b and then setting (a – E )/b = x, we get
x 1 0
1 x 1 =0
0 1 x
which on expanding gives x3 – 2x = 0
The three roots of the above equation are – 2 , 0, 2
The corresponding three values of energies are
E1 = a + 2 b
E2 = a
E3 = a – 2 b
The secular equations are
C1x + C2 = 0
C1 + C2 x + C3 = 0
C2 + C3x = 0
For x = – 2 , we will have
– 2 C1 + C2 = 0 (1)
C1 – 2 C 2 + C3 = 0 (2)
C2 – 2 C3 = 0 (3)
Equations (1) and (2) suggest that
C2 C2
C1 = and C3 =
2 2
Using the normalization criterion
C12 + C22 + C32 = 1
2 2
we get Ê C2 ˆ + C22 + ÊÁ C2 ˆ˜ =1
ÁË ˜
2¯ Ë 2¯
1
or C2 = ±
2

1 1 1
j1 = c 2 pz (1) + c 2 pz (2) + c 2 p (3) (bonding)
2 2 2 z

Working out similarly with x = 0 and x = 2 , we get

1 1
j2 = c 2 pz (1) – c 2 pz (3) ; (nonbonding)
2 2
1
j3 = 1 c 2 p (1) – c 2 p z ( 2) +
1
c 2 pz (3) ; (antibonding)
z
2 2 2
 Theories of Covalent Bond 321

(b) Allyl radical

2 2
2 + 2 = 2 Ê 1ˆ Ê 1 ˆ =1
q1 = 2C11 C21 ÁË ˜¯ + ÁË ˜¯
2 2
2
2 + Ê 1 ˆ +0=1
q2 = 2 C12 C222 = 2 ÁË ˜¯
2
2
2 = 2 Ê 1ˆ -1 ˆ 2
2 +
ÁË ˜¯ + ÊÁ
Ë 2 ˜¯
q3 = 2 C13 C23 =1
2

p12 = 2C11C12 + C21C22 = 2 ÊÁ ˆ˜ ÊÁ

1 1 ˆ 1
Ë 2 ¯ Ë 2 ˜¯
+0=
2

1 ˆ Ê1 ˆ
p23 = 2C12C13 + C22C23 = 2 Ê
1
+0=
Ë 2 ¯ Ë2 ¯ 2

Note Cs represent molecular orbital and

atomic orbital, respectively.

Allyl cation

1 2
q1 = 2C 211 = 2 ÊÁ ˆ˜ =
1
Ë 2¯ 2

1 ˆ2
q2 = 2C212 = ÊÁ
Ë 2 ˜¯
=1

2
= 2 ÊÁ ˆ˜
2 1 1
q3 = 2C 13 =
Ë 2¯ 2

p12 = 2C11C12 = 2 ÊÁ ˆ˜ ÊÁ
1 1 ˆ 1
Ë 2 ¯ Ë 2 ˜¯
=
2

p23 = 2C12C13 = 2 ÊÁ
1 ˆ Ê 1ˆ 1
Ë 2 ˜¯ ÁË 2 ˜¯
=
2

Allyl anion
2
1 ˆ2
= 2 ÊÁ ˆ˜ + 2 ÊÁ
1
q1 = 2C 211 + 2C 21
2
Ë 2 ˜¯
= 1.5
Ë 2¯
1 ˆ2
q2 = 2C212 + 2C22
2
= 2 ÊÁ
Ë 2 ˜¯
+0=1

2
1 ˆ2
q3 = 2C 213 + 2C 223 = 2 ÊÁ ˆ˜ + 2 ÊÁ -
1
Ë ˜ = 1.5
Ë 2¯ 2¯

p12 = 2C11 C12 + 2C21 C22 = 2 ÊÁ ˆ˜ ÊÁ

1 1 ˆ 1
Ë 2 ¯ Ë 2 ˜¯
+0=
2

p23 = 2C12 C13 + 2C22 C23 = 2 ÊÁ

1 ˆ Ê 1ˆ 1
Ë 2 ˜¯ ÁË 2 ˜¯
+0=
2
322 A Textbook of Physical Chemistry

REVISIONARY PROBLEMS

2.1 Describe, in brief, the Lewis description of a covalent bond.

2.2 How does the Born-Oppenheimer approximation simplify the quantum
mechanical treatment of the covalent bond? Explain.
2.3 Explain, by setting the trial functions of H2, the difference between molecular
orbital and valence bond methods.
2.4 The mixing between two orbitals depends on the following factors:
(i) The difference between the energies of two orbitals.
(ii) The extent of overlapping between them.
(iii) The symmetry of orbitals relative to the molecular axis.
Justify the above factors by evaluating the energy expressions of molecular
orbitals of the molecule AB.
2.5 Justify the following statement.
It is often stated that the valence bond treatment of a covalent bond is very similar
to the electron-pair bond postulated by Lewis.
2.6 Give the statement of variation theorem.
2.7 Derive the expressions of wave functions and the associated energies of H+2
under the LCAO scheme of constructing molecular orbitals.
2.8 For H+2, the energies of the two wave functions are

1 J +K
E+ – EH = +
R 1 + Sab

J -K
E– – EH = 1 +
R 1 - Sab

1
where J=– [1 – (1 + R) exp (– 2R)]
R
K = – (1 + R) exp(– 2R)
Ê R2 ˆ
Sab = Á1 + R + exp(– 2R)
Ë 3 ˜¯
and R is expressed in atomic units. Evaluate the terms E+ – EH at the following
values of R and then draw the potential energy diagram. What do you conclude
from the latter?
R = 1.0, 1.50, 1.75, 2.00, 2.25, 2.50, 2.75, 3.00, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0
and 7.0.
2.9 What do you understand by (i) bonding, (ii) nonbonding, and (iii) antibonding
orbitals?
2.10 Justify the statement that the number of molecular orbitals obtained in the
LCAO is equal to the number of atomic orbitals involved in the summation.
2.11 Describe qualitatively the MO and VB treatments of hydrogen molecule. Compare
the merits and demerits of the above two methods.
 Theories of Covalent Bond 323

2.12 Draw the correlation diagram depicting the energies of various molecular orbitals
relative to those of atomic orbitals in a homonuclear diatomic molecule when
(i) s-p interaction is absent or small, and (ii) s-p interaction is strong. What are
the shapes of these orbitals?
2.13 Explain the following by using the molecular orbitals of homonuclear diatomic
molecules.
(i) The bond dissociation energy of H2 is almost double that of H+2.
(ii) The bond length of H2 is smaller than that of H+2.
(iii) He2 is not stable but He+2 has been observed.
(iv) B2 and O2 are paramagnetic in nature.
(v) The dissociation energy decreases in going from N2 to N+2 whereas it
increases in going from O2 to O+2.
(vi) The dissociation energy of N2 is maximum amongst the homonuclear
diatomic molecules.
(vii) The bond length increases in going from N2 to N+2 whereas it decreases
in going from O2 to O+2.
2.14 Derive the molecular term symbol for H2, He+2 and B2.
2.15 (a) Draw the correlation diagram relating molecular orbitals of heteronuclear
diatomic molecules AH relative to those of isolated atoms when (i) H is more
electronegative than A (example LiH), and (ii) A is more electronegative than H
(example HF).
(b) How will you determine theoretically the partial ionic character in LiH
bond?
2.16 (a) Draw the correlation diagram relating molecular orbitals of a heteronuclear
diatomic molecule AB (atom B is more electronegative than A) relative to those
of isolated atoms.

BN, BO, CN, CO+, CO, NO+, CN– and NO.

2.17 What is an united-atom concept? Describe how does it lead to the correlation
diagrams for homonuclear and heteronuclear diatomic molecules? What are the
utilities of correlation diagrams?
2.18 Under the LCAO scheme, construct qualitatively the expressions and shapes
of molecular orbitals involving the valence orbitals of BeH2, H2O and CO2
molecules. Draw the appropriate energy diagrams and write down the electronic

2.19 (a) What are hybrid orbitals? Construct the wave functions for sp, sp2 and sp3
hybrid orbitals. Derive the angle between the two hybrid orbitals belonging to
the above categories.
(b) Justify the statement that hybrid orbitals are better than pz orbitals in forming
the covalent bond.
(c) Describe how the geometries of H2O, NH+4, NH3, HC ∫∫ CH, H2C == CH2
and, H3C—CH3 can be explained on the basis of hybrid orbitals.
2.20 (a) Describe the Hückel approximations and show how these help simplifying
the LCAO-MO framework of p-electrons of conjugated hydrocarbons.

energy for each of the following molecules: (i) ethylene, (ii) butadiene, and
(iii) benzene.
324 A Textbook of Physical Chemistry

(c) Justify the statement that in the conjugated molecules, double bonds are not
localized in the true sense but they are delocalized over the entire molecule.

(i) Delocalization energy

(ii) Electron density on an atom of a molecule
(iii) Bond order
(iv) Free valence.
(e) Explain, how the Hückel method of conjugated hydrocarbons can be
extended to heteromolecules.
2.21 Construct qualitatively the expressions of localized molecular orbitals of BeH2,
H2O and CO2 molecules. Show that the nonlocalized bonding orbitals of these
molecules can be obtained by taking ‘positive’ and ‘negative’ combinations of
the appropriate localized molecular orbitals.
2.22 Construct schematically the correlation diagram depicting the change in orbital
energies of the bent AH2 molecule when its bond angle is gradually increased from
90º to 180º. Derive the Walsh’s rule regarding the structure of AH2 molecules.
2.23 (a) Using the Hückel approximations, show that for the allyl radical
(CH2 CH CH2), the wave functions and the corresponding energies are
1 2 3
given by

1 1 1
j1 = c 2 pz (1) + c 2 p z ( 2) + c 2 pz (3) ; E1 = a + 2b
2 2 2

1 1
j2 = c 2 pz (1) – c 2 pz (3) ; E2 = a
2 2

1 1 1
j3 = c 2 pz (1) – c 2 p z ( 2) + c 2 pz (3) ; E3 = a – 2b
2 2 2
(b) Show that j1, j2 and j3 are bonding, nonbonding and antibonding orbitals,
respectively.
(c) Calculate the electron densities and bond orders for (i) allyl radical,
(ii) allyl cation, and (iii) allyl anion.

TRY YOURSELF PROBLEMS

2.1 Write down the expression of H for the H –2 molecular ion.
+
and NF–. Describe how
bond energy and bond length vary in these species.
2.3 Discuss the bond properties of Cl2 and Cl+2 using molecular orbital theory.
2.4 Explain, why the dissociation energy and bond length for B2 are greater than
those for F2?
+
2?
2.6 Draw the potential energy curves for the valence bond functions of H2 from the
following data expressed in atomic units:
 Theories of Covalent Bond 325

R/atomic units 0 1 2 3 4
S 1.0 0.86 0.59 0.35 0.19

Ú 1sa 1/ rb 1sa dt 1.0 0.73 0.47 0.33 0.25

Ú 1sa 1/ rb 1sb dt 1.0 0.74 0.41 0.20 0.09

Ú 1sa(1)1sb(2) 1r12 1sa(1)1sb (2)dt 0.63 0.55 0.43 0.32 0.25

1/R 1.0 0.50 0.33 0.25
2.7 Draw the potential energy curves of sg and su molecular orbitals of H2 molecule
from the following data:
rAB/bohr 1.00 1.50 2.00 2.50 3.00
E(sg )/hartree – 0.985 9 – 1.097 2 – 1.080 8 –1.033 8 – 0.982 9
E(su)/hartree + 0.705 2 + 0.057 9 – 0.274 6 – 0.462 8 – 0.575 0
3.50 5.00 7.00
– 0.935 8 – 0.834 3 – 0.770 8
– 0.643 8 – 0.729 1 – 0.746 4
Compute the values of bond distance and bond energy.
2.8 Describe the molecular orbital treatment of the molecular ion HeH+ relative to
that H2.
2.9 Is the allene molecule HC2 == C == CH2 belong to conjugated molecule?
2.10 The molecule CH2 is nonlinear with bond angle near to 180º. Experimentally,
this molecule is found to be triplet and not the singlet as is expected from the
correlation diagram of bent AH2 molecule. How will you explain this behaviour?
2.11 Calculate the delocalization energy of the following:

(i) HC CH (ii) CH (iii) H2C HC CH2

HC CH HC CH
[Ans. (i) zero (ii) b and (iii) 0.828b ]
2.12 Explain why O–2 has a longer bond than O2 (0.121 nm versus 0.112 nm) whereas
CN– has a shorter bond than CN (0.109 nm versus 0.118 nm).
2.13 Which of the following species would you expect to be paramagnetic?
(a) He+2 (b) NO (c) NO+ (d) N22+

(e) O–2 (f) O2–

2 (g) C2 (h) C2–
2

2.14 Show that for a linear polyene containing 2N carbon atoms, the longest p Æ p*
transition is given by the expression

p
DE = – 4b sin ÊÁ ˆ
Ë 2 ( 2 N + 1) ˜¯
326 A Textbook of Physical Chemistry

2.15 Using the Hückel parameters hO = 1 and kC=O = 1.1, derive the ground-state

energy for the system C O and compare it with that of C C .

2.16 Explain why:

(a) N2 and I2 are diamagnetic.
(b) C2 is paramagnetic.
(c) The bond energy increases regularly from Li2, Na2, K2, Rb2 and Cs2.
2.17 Which of the species N2, NO, O2, C2, F2, CN would you expect to be stabilized
by the (a) addition of an electron, (b) removal of an electron?
[Ans. (a) C2, CN; (b) NO, O2, F2]
2.18 Arrange the following molecules in order of increasing bond length: O2, O+2,
O–2 and O2–
2. Which molecule will have the greater dissociation energy: O2 or
O+2 ? [Ans. O+2 < O2 < O–2 < O2– +
2 ; O2 > O2.]

2.19 Rationalize the empirical facts that the ionization energy of H2 is greater than
that of atomic H, whereas that of O2 is less than that of atomic O.
2.20 Would you expect Cl–2 to exist as a stable species? Why?
2.21 Explain whether the molecules PH2, PF2, SO2 and MgH2 should be bent or linear.
2.22 (a) Construct molecular orbitals of MgF2 (linear structure) starting from 3s
and 3p orbitals of Mg and 2s and 2p orbitals of F. Write down its electronic

–
2.
2.23 Draw the molecular orbital diagram for (a) CO and (b) XeF and write their
+
is more stable than XeF.
2.24 For linear H3 molecule, three molecular orbitals formed from three 1s orbitals
are given by
y1 = C1 y 1s ( Ha ) + C2 y 1s ( H + C3 y 1s ( Hc )
b)

y2 = C4 y 1s ( Ha ) – C5 y 1s ( Hc )

y3 = C6 y 1s ( Ha ) – C7 y 1s ( Hb ) + C8 y 1s ( Hc )

The orbital y1 is strongly bonding, y2 is weakly antibonding between the

end atoms and nonbonding between the outer and centre atoms and y3 is strongly
antibonding. Justify the following facts.
(i) H3 is stable with respect to 3H.
(ii) H3 is slightly unstable with respect to H2 and H and thus H3 is a transient
species and cannot be isolated in large amount.
(iii) The geometry of H3 is linear because of the presence of one electron in
y2 which is antibonding between the two end atoms.
(iv) H+3 is stable with respect to (i) H+ + 2H and (ii) H+ and H2.
(v) The geometry of H+3 is not linear but an equilateral triangle.
(vi) Consider the H+3 molecule in both the linear (H—H—H)+ and triangular
+
H
states. Utilizing simple Hückel approximations with the
H H
 Theories of Covalent Bond 327

hydrogen 1s orbitals as a basis set, set up the secular determinant and

compute the energies of the molecular orbitals for each geometry. Predict
which geometry would be more stable for H+3 and H–3.
[Ans. (i) Because of two electrons in strongly bonding orbital, (ii) because of
one electron in weakly antibonding orbital, (iii) any bending of the molecule
brings two end atoms together which is opposed by the electron in the weakly
antibonding orbital, (iv) no electron in antibonding orbital, and (v) electrons are
present only in bonding orbital between the end atoms and is formed by mutual
overlap of three 1s atomic orbitals.]
2.25 Justify the following facts by making use of Fig. 2.15.1.
(a) BH2
state.
(b) NH2
(c) H2O molecule is bent in the ground state.
2.26 Using Walsh’ rules, predict the geometries of the following molecules: (a) CCO,
(b) FCO, (c) NCO, (d) FOO, (e) FCN, (f) FNO, (g) OBO, (h) CNC, (i) O–3, (j) O+3
and (k) F+3.
2.27 HCN is a linear molecule. Construct the two localized MOs and then transform
them into nonlocalized MOs. Draw the correlation diagram and write the

2.28 Given below are the computed values of J, K, SAB, E+ – EH and E – – EH at the
various values of R of H+2 molecule. Plot E+ – EH versus R and E– – EH versus R
and compare them with those given in Fig. 2.5.3.
R J/hartree K/hartree SAB (E+ – EH )/ (E– – EH )/
atomic hartree hartree
unit (Eq. 2.5.25) (Eq. 2.5.26) (Eq. 2.5.27) (Eq. 2.5.24a) (Eq. 2.5.24b)
1.0 – 0.729 – 0.736 0.858 0.212 1.045
1.25 – 0.652 – 0.645 0.794 0.077 0.763
1.5 – 0.584 – 0.558 0.725 0.005 0.573
1.75 – 0.524 – 0.478 0.655 – 0.034 0.438
2.0 – 0.473 – 0.406 0.586 – 0.054 0.339
2.5 – 0.391 – 0.287 0.458 – 0.065 0.210
3.0 – 0.330 – 0.199 0.349 – 0.059 0.133
3.5 – 0.285 – 0.136 0.244 – 0.052 0.089
4.0 – 0.250 – 0.092 0.189 – 0.037 0.055
4.5 – 0.222 – 0.061 0.136 – 0.027 0.036
5.0 – 0.199 – 0.040 0.096 – 0.019 0.024
5.5 – 0.182 – 0.027 0.068 – 0.013 0.015
6.0 – 0.167 – 0.015 0.053 – 0.006 0.006
7.0 – 0.143 – 0.006 0.028 – 0.002 0.003
2.29 The N–3 molecule has a linear structure. Construct the localized and nonlocalized
orbitals and draw their contour diagrams. Is it diamagnetic or paramagnetic?
328 A Textbook of Physical Chemistry

2.30 The molecule CO is written as : C ∫∫ O : with C as as the negative end of the

dipole. Explain this structure on the basis of MO theory and also explain the fact
that CO is a better electron pair donor through carbon.
(Hint: See Annexure I at the end of the chapter for MO treatment of CO.)
2.31 Derive the molecular term symbols for the ground state of H+2, C2, N+2, N2, O+2,
O2 and F2.
[Ans. 2S, 1S, 2S,1S,2P,3S and 1S]
2.32 (a) The four lowest molecular orbitals of water molecule are as follows.
y 1 = 0.820 y 2s(O) + 0.132y p x (O) + 0.152 [y 1s(Ha ) + y 1s(H b ) ]

y 2 = 0.441 ÈÎy 2 p s (O) + y 2p y (O) ˘˚ + 0.424 [y 1s(Ha ) - y 1s(H b ) ]

y 3 = 0.502 y 2s(O) - 0.787y 2 p z (O) - 0.264 [y 1s(Ha ) + y 1s(H b ) ]

y 4 = 0.707 ÈÎy 2 p x (O) - y 2 p y (O) ˘˚

If S[1s(Ha), 2s(O)] = S[1s(Hb), 2s(O)] = 0.471

S [1s(H a ), 2p x (O)] = - S [1s(H b ), 2p x (O)] = 0.225

S [1s(H a ), 2p y (O)] = - S [1s(H b ), 2p y (O)] = 0.225

S [1s(H a ),2p z (O)] = S [1s(H b ), 2p z (O)] = 0.247

S[1s(H a ),1s(H b )] = 0.238

Calculate Mulliken gross atomic population numbers of atoms.

(b) What would be the molecular orbitals if the charge densities on atoms
under zero-overlap approximation are equal to the corresponding
atomic population numbers calculated in part (a) of the question?
[Ans. (a) 6.446 on oxygen and 0.777 on each hydrogen.]
(b) y 1 = 0.889[y 2s(O) + 0.165 y 2 p z (O) ] + 0.303[y 1s(Ha ) + y 1s(H b ) ]
y 2 = 0.528[y 2 p x (O) + y 2 p y (O) ] + 0.470 [y 1s(Ha ) - y 1s(H b ) ]
y 3 = 0.357y 2s(O) - 0.849 y 2 pz (O) - 0.274 [y 1s(Ha ) + y 1s(H b ) ]
y 4 = 0.707[y 2 p x(O) - y 2 p y (O) ]
ANNEXURE I

Localized Molecular Orbitals of CO and N2 Molecules

INTRODUCTION A large number of complex compounds of carbon monoxide with the transition
metals are known. In these molecules, the linkage between the two is through
the carbon end of the CO molecule. This is due to the presence of a lone pair of
electrons on carbon which can be easily shared between its orbital and the empty
d orbital of the transition metal. Though the oxygen end of the CO molecule also
contains a lone pair of electrons, yet no compound is known where this lone pair
of electrons is involved. Similarly, the molecule N2, which is isoelectronic to
CO, is essentially behaves like an inert molecule. In order to understand these
characteristics, it is worth considering the electronic structures of these two
molecules from the view-point of their molecular orbitals and their associated
directional characteristics.

The general appearances of the correlation diagrams of N2 and CO molecules

will be very similar to those described by Figs 2.9.4, and 2.11.3, respectively. The
contour diagrams of the associated molecular orbitals will also be very similar
to those described by Figs 2.9.1 and 2.11.4, respectively. The great difference in

molecular orbitals. However, these characteristics are better understood from the

Jaffe and Orchin. Before describing these diagrams, it is desirable to understand

qualitatively the classical description of the chemical bonds existing in the above
two molecules.

NITROGEN MOLECULE
2 2 1 1 1
Description of x y . It contains
z
Bonding three unpaired electrons. The N2 molecule is diamagnetic indicating the absence
of any unpaired electrons. This indicates the presence of a triple bond between the
two N atoms. This triple bond will include one s
of 2pz p
2px A x B y A y B
Each atom is expected to possess a lone pair of 2s electrons with no directional

s bond may be
considered to involve sp1 A 1 B
involves the larger contribution from the 2pz orbital and lesser from the 2s orbital.
The lone pairs will be present in sp2 A 2 B
major contribution from the respective 2s orbital and lesser from the 2pz orbital
and thus are essentially nondirectional.
330 A Textbook of Physical Chemistry

CARBON MONOXIDE
2 2 1 1
Description of and
x y
2 2 2 1 1
Bonding x y , respectively. In order to understand the directional
z
characteristics of a lone pair of electrons on C atom, the arrangement of its valence
electrons may be assumed to be as follows.
2 0
1 2 2px1 2p1y
where sp1 and sp2 are the two hybrid orbitals formed from the 2s and 2pz orbitals

energy. In the CO molecule, the presence of two p bonds may be proposed due to
the side-way overlapping of 2px x y y
respectively. Besides these, a third bond may exist due to the overlapping of the
sp2 z
exclusively from the O atom. In classical view-point, this bond is known as the
coordinate bond. Hence, we may write the molecule CO as
C O
where the lone pairs on C and O will be present in sp1
respectively. The electrons on the C atom are expected to possess directional
characteristics whereas those present on the O atom are expected to be non-
z

the 2pz

The dipole moment of CO is 0.118 D, a small value with carbon as the negative

above proposed structure of carbon monoxide. Since the oxygen atom is more
electronegative than the carbon atom, the electrons in the p-bonds will be more
near to the oxygen atom. Consequently, the oxygen atom will acquire a net d –
charge and carbon a net d + charge. This drift of electronic charge is more than
counteracted by the mutual sharing of the two electrons of oxygen atom in the
coordinate bond resulting in the net d– overall charge on carbon and d+ overall
charge on oxygen.

The proposed structures of N2 and CO can also be explained from the correlation

and Orchin and are described below.

Correlation As usual, the energy of valence orbitals of isolated atoms are depicted at the extreme
Diagram of z orbitals on
Nitrogen
y sp 1 ( N ) = y A
– l y 2pz A

y sp2 ( N ) = ly A
+ y 2pz A
 Theories of Covalent Bond 331

y sp2 B
=y B
– l y 2pz B

y sp2 B
= ly B
+ y 2pz B

†
where l is the weighing factor .

The hybrid orbitals sp1 A 1 B

††

orbitals do not possess much of the directional characteristics and thus will act as
nonbonding orbitals.

The hybrid orbitals sp2 A 2 B

respective 2pz
2pz z
orbitals will possess directional characteristics along the N—N axis. From these

formed according to the expressions‡.

y1 = C (y sp2 ( N A ) – y sp2 ( N B ) )

y¢1 = C (y sp2 ( N A ) + y sp2 ( N B ) )

The 2px and 2py orbitals centred on each of the two nitrogen atoms will form
doubly degenerate p and p* molecular orbitals according to the expressions given
below.
y2 = C (y 2p x (NA ) + y 2p x (NB ) )

(
y3 = C y 2p y (NA ) + y 2p y (NB ) )
y 2¢ = C (y 2p x (NA ) – y 2p x (NB ) )

y 3¢ (
= C y 2p y (NA ) – y 2p y (NB ) )
The energies of bonding orbitals y2 and y3 A
B y 2¢ and y 3¢ will be larger than
the energies of these orbitals. Similarly, the bonding molecular orbitals y1 will be
more stable than sp2 A 2 B y 1¢ will be less
stable than these hybrid atomic orbitals. Since end to end overlap is larger than
side way overlap, the bonding s orbital y1 will be more stable than the bonding
†
The weighing factor would be unnecessary if the hybrid orbitals were made up of equal
1 2
£l£
††
According to the advanced calculations by Scherr’s, the 2s contribution is about 71 per
cent.
‡
The symmetry of the molecule requires that each molecular orbital will be made up of
equal contributions from the two atoms.
332 A Textbook of Physical Chemistry

p orbitals y2 and y3. On the other hand, the antibonding s orbital y 1¢ will be less
stable than the antibonding p orbitals y 2¢ and y 3¢.

Figure AI.1a depicts the expected energy level diagram for the N2 molecule.

(y 1 ) 2 , (y sp1 ( N A ) ) 2 , (y sp1 ( N B ) ) 2 , (y 2 ) 2 , (y 3 ) 2
The molecule will have a triple bond; one s bond due to the two electrons in
y1; and two p bonds due to the two electrons in each of y2 and y3 molecular
orbitals. The two electrons in each of y sp1 ( N A ) and y sp1 ( N B ) will constitute two
lone pairs of electrons, essentially of 2s character with not much of the directional
characteristics. It is because of this fact that the N2 molecule does not exhibit any
complex-compound formation with the transition metals.

Correlation
Diagram of Carbon E ª – 1.88 MJ mol–1
Monoxide
E ª – 1.03 MJ mol–1
E ª – 3.13 MJ mol–1
E ª – 1.53 MJ mol–1
The placing of these energies at the extreme right and left of the correlation diagram

effective mixing of 2s and 2pz orbitals to form sp hybrid orbitals. The mixing in
case of C is expected to be more as the difference in energy levels of the involved

y sp (C) =y C + l y 2p z (C)
1

y sp (C) = ly C – y 2p z (C)
2

y sp
1
(O) = y O + l¢ y 2p z (O )
y sp2 (O ) = l¢ y O – y 2p z (O )

with l¢ < l.† Energy of sp1

2
atomic orbital, i.e. 2pz 1 2
z

†
According to the advanced calculations by Sahni, sp1 1
22 per cents p character, respectively. On the other hand, sp2 2
32 and 22 per cents s character, respectively.
 Theories of Covalent Bond 333

Fig. AI.l Correlation diagram of the (a) nitrogen, and (b) carbon monoxide molecules

2
to that of the sp1 2
that the s bond formation between C and O is due to the involvement of sp1
and sp2
†
y1 = C1 y sp1 (C) + C2 y sp2 (O ) C2 > C1

y 1¢ = C1¢ y sp1 (C) – C2¢ y sp2 (O ) †

C1¢ > C2¢
The 2px and 2py orbitals centred on each of the two atoms will form doubly
degenerate p and p* molecular orbitals as in the case of nitrogen molecule according
to the expressions given below.
y2 = C3 y 2 p x ( C) + C4y 2 p x ( O) ; C4 > C3
y3 = C5 y 2 p y ( C) + C6y 2 p y ( O) ; C6 > C5
†
The terms C2 > C1 and C1¢ > C2¢ follow from the fact that the electron density in the
bonding orbital will be more on the more electronegative atom whereas in the antibonding
orbital, it is more on the lesser electronegative atom.
334 A Textbook of Physical Chemistry

y 2¢ = C3¢ y 2p x ( C) – C4¢ y 2p x ( O) C3¢ > C4¢

y 3¢ = C5¢ y 2p y ( C) – C6¢ y 2p y ( O) C5¢ > C6¢

The orbitals y2 y3
orbital 2py x y 2¢ y 3¢ ) will be less stable than
its lesser stable constituent atomic orbital 2px y

The antibonding s orbital y ¢1 , as usual, is expected to be less stable than the

antibonding p orbitals y 2¢ and y 3¢ .

The sp2 1
act as nonbonding orbitals.

Figure AI.1b depicts the expected correlation diagram of the CO molecule. Since

(y sp1 (O ) ) 2 (y 1 ) 2 (y 2 ) 2 (y 3 ) 2 (y sp2 (C) ) 2

Ligand The correlation diagram of the CO molecule explains nicely the ability of this
Characteristics of molecule to form transition metal complexes through the carbon end of the
Carbon Monoxide molecule. The highest occupied molecular orbital is the nonbonding orbital with the
predominant 2p character of the carbon. This orbital is mainly concentrated on the
side of the carbon remote from the oxygen. This orbital can overlap with a metal
orbital to form a sigma bond. The attachment of carbonyl groups with the central
metal places substantial negative charge on the metal. This charge on the metal
can be relieved by donation of electrons from dxy, dxz and dyz orbitals of the central
metal to the lowest unoccupied antibonding p orbital of the CO molecule. This
happens because of the fact that dxy xz or dyz
as that of the lowest unoccupied orbital and thus results into a positive overlap.
This is known as back bonding. The sharing of two electrons of sp2
molecule with the metal atom and the back-bonding in the antibonding orbital of
the CO molecule result into the weakening of the C—O bond. Consequently, the
force constant of C—O bond decreases which, in turn, results into a decrease in
the bond stretching frequency as is evident from infrared spectra of the unbounded
and bounded CO molecules.
ANNEXURE II

Evaluation of Integrals J, K and S in the LCAO-MO

treatment of H+2

The integrals J, K and S in the LCAO-MO treatment of H+2 are:

e2
J = y 1s(A ) - y ( ) (AII.1)
(4p e 0 ) rB 1s A

e2
K = y 1s(A ) - y ( ) (AII.2)
(4p e 0 ) rA 1s B
S = y 1s(A ) | y 1s(B) (AII.3)
Definition
of Elliptical
Coordinates
rA + rB
m= (AII.4)
R

rA - rB
n= (AII.5)
R
and the angle f
xz

1£m£• (AII.6)

–1£n£+1 (AII.7)

0 £ f £ 2p (AII.8)

R3
dt = (m2 – n 2) dm dn df (AII.9)
8
Atomic Orbitals y1s(A) and y1s(B) are
Expressed in
Atomic Units 1 Ê Z ˆ 3 / 2 - ZrA / a0
y1s(A) = Á ˜ e (AII.10)
p Ë a0 ¯

1 Ê Z ˆ 3 / 2 - ZrB / a0
y1s(B) = Á ˜ e (AII.11)
p Ë a0 ¯
336 A Textbook of Physical Chemistry

1 -rA
y1s(A) = e (where Z = 1) (AII.12)
p
1 -rB
y1s(B) = e (where Z = 1) (AII.13)
p
Evaluation of The integral J
Integral J 1 - rA 1 1 - rA 1 1
J= e - e = - Ú e -2 rA . dt (AII.14)
p rB p p rB
m = (rA + rB)/R and n = (rA – rB)/R, we get

m + n = 2rA/R and m – n = 2rB/R

1 1
e - R( m + n ) .
p Ú
J=– dt
R (m - n ) / 2
t from Eq. (AII.9), we get

R 2 - R( m + n ) 1 R3
p Ú
J=– e . . (m2 – n 2) dm dn df
R (m - n ) / 2 8

R 2 - R( m + n )
( m + n ) dm dn df
4p Ú
=– e

• +1 2p • +1 2p
R2 È - Rm - Rn - Rm - Rn
˘
4p ÍÎ Ú1 Ú e dn Ú
=– Í m e d m df + Ú e dm Ú n e d n Ú df ˙˙
-1 0 1 -1 0 ˚

R2 È• - Rm +1 - Rn •
- Rm
+1
- Rn
˘
=– Í Ú m e dm Ú e dn + Ú e dm Ú ne dn ˙
2 ÍÎ 1 -1 1 -1 ˙˚

• •
È e - Rm e - Rm ˘
= Ê + 2 ˆ e- R
- Rm 1 1
Ú me dm = Í m
Î - R
-
( - R ˚1
) 2˙ Ë R R ¯
1
+1 +1
e - Rn e- R e R 1 R - R
= (e - e )
- Rn
Ú e dn = - R -1
=-
R
+
R R
-1
• - Rn +1
- Rm e e- R
Úe dm =
-R -1
=
R
1
+1 +1
È e - Rn e - Rn ˘
= - Ê + 2 ˆ e- R + Ê - + 2 ˆ e R
- Rn 1 1 1 1
Ú ne dn = Ín -
Î - R ( - R ) ˚ -1
2 ˙ Ë R R ¯ Ë R R ¯
-1
 Theories of Covalent Bond 337

1
J=– [1 – (1 + R)e– 2R] (AII.16)
R
Evaluation of The integral K
Integral K 1 - rA 1 1 - rB
K= e - e
p rA p
1 -(rA + rB ) 1
pÚ
=– e . dt
rA

1 - Rm 2 R3 2
( m - n 2 ) dm dn df
pÚ
=– e . .
R (m + n ) 8

R 2 - Rm
( m - n ) dm dn df
4p Ú
=– e

• +1 2p • +1 2p
R2 È - Rm
˘
df - Ú e - Rm dm
4p ÍÎ Ú1 Ú dn Ú Ú n dn Ú df ˙˙
=– Í m e dm
-1 0 1 -1 0 ˚

R2 ÈÊ 1 1 ˆ - R ( ) ( ) Ê e - R ˆ ( ) ( )˘
=– ÍÎË + e 2 2p - ÁË ˜ 0 2p ˙
4p R R2 ¯ R ¯ ˚
= – (1 + R)e–R

Evaluation of The integral S

Integral S
1 - rA 1 - rB 1
S= e e = Ú e -(rA + rB )dt
p p p
1 - Rm R 3 2
( m - n 2 ) dm d n d f
pÚ
= e .
8
• +1 2p • +1 2p
R 3 È 2 - Rm - Rm
˘
ÍÚ Ú Ú - Ú Ú Ú
2
= m e d m d n df e d m v d n df ˙
8p ÍÎ 1 -1 0 1 -1 0 ˙˚
• •
2 - Rm È e - Rm e - Rm e - Rm ˘
Now Úm e dm = Í m 2
Î (- R )
- 2m +
( - R )2 ( - R )3 ˙˚1
1

= Ê + 2 + 3 ˆ e- R
1 2 2
ËR R R ¯

Hence, S = ÍÎ{
R3 È 1
8p R R
2
R
2
} Ê e- R ˆ 2
+ 2 + 3 e - R ( 2) ( 2p ) - ÁË
R
˜¯
3
˘
( 2 p )˙
˚()
Ê R2 ˆ - R
= ÁË1 + R + ˜e (AII.18)
3 ¯
ANNEXURE III Conventional Representation of sp3 Hybrid Orbitals

3
y1, y2, y3 and y4

( 3 / 2, 0, 0) , Q ( -1 / 2 3 , 0, 2 / 3 ) , R ( -1/2 3 ,1 / 2 , -1 / 6 )
and S(–1/2 3 , –1/2, –1/ 6
The length of each vector is 3/2
x y z

q = 35.27° (= 180° – 109.46°/2)

y f
the z see

È X ˘ Ècos j - sin j 0˘ Ècos j 0 - sin q ˘ È x ˘

Í Y ˙ = Í sin j cos j 0˙ Í 0 1 0 ˙ Í y˙
Í ˙ Í ˙Í ˙Í ˙
ÍÎ Z ˙˚ ÍÎ 0 0 1 ˙˚ ÍÎ sin q 0 cos q ˙˚ ÍÎ z ˙˚
This gives

X = x cos j cos q – y sin j – z cos j sin q

Y = x sin j cos q + y cos f – z sin j sin q

Z = x sin q + z cos q

Ê 3ˆ 1 ˆ Ê 2ˆ
X = ÁË ˜¯ Ê
1
Á ˜ -0+0=
2 Ë 2¯ Ë 3¯ 2

Ê 3ˆ 1 ˆ Ê 2ˆ
Y = ÁË ˜¯ Ê
1
Á ˜ +0-0=
2 Ë 2¯ Ë 3¯ 2
Ê 3ˆ 1
Z = ÁË ˜¯ ÊÁ ˆ˜ =
1
2 Ë 3¯ 2
 Theories of Covalent Bond 339

)- 21 , - 21 , 21 )C B
y 2¢

A
D ) 21 , 21 , 21 )
O y 1¢
y

y 3¢
y1 G
P F
)
- 1, 1,- 1
2 2 2 )
Fig.AIII. 1 y 4¢
x
A tetrahedron
arrangement E H
within a cube ) 21 , - 21 , - 21 )
Point Q ( -1 / 2 3 , 0, 2 / 3 )
1 1 2 2 1 1 1 1 1
X= - -0- =- - =-
2 3 2 3 3 2 3 6 3 2
1 1 2 2 1 1 1 1 1
Y= - -0- =- - =-
2 3 2 3 3 2 3 6 3 2
1 1 2 2 1 2 1
Z= - + =- + =
2 3 3 3 3 6 3 2

Point R ( -1 / 2 3 , 1 / 2 , - 1 / 6 )
11 2 1 1 1 1 1 1 1 1 1
X= - - + =- - + =-
2 3 2 3 2 2 6 2 3 6 2 6 2

1 1 2 1 1 1 1 1 1 1 1 1
Y= - + + =- + + =
2 3 2 3 2 2 6 2 3 6 2 6 2

1 1 1 2 1 1 1
Z= - - =- - =-
2 3 3 6 3 6 3 2

Point S ( - 1 / 2 3 , - 1 / 2 , - 1 / 6 )

11 2 1 1 1 1 1 1 1 1 1
X= - + + =- + + =
2 3 2 3 2 2 6 2 3 6 2 6 2
340 A Textbook of Physical Chemistry

1 1 2 1 1 1 1 1 1 1 1 1
Y=– - + =- - + =-
2 3 2 3 2 2 6 2 3 6 2 6 2
1 1 1 2 1 1 1
Z= - - =- - =-
2 3 3 6 3 6 3 2

1 1 1 1
y 1¢ = y s + y px + y p y + y pz
2 2 2 2
1 1 1 1
y 2¢ = y s - y p x - y p y + y p z
2 2 2 2
1 1 1 1
y 3¢ = y s - y p x + y p y - y p z
2 2 2 2
1 1 1 1
y 4¢ = y s + y p x - y p y - y p z
2 2 2 2
 3 Electrical and Magnetic Properties
of Molecules

3.1 INTRODUCTION

This chapter deals with the structural information that can be derived when a
substance is placed in an electrostatic or a magnetic field. The basic electrical
property of a molecule is its dipole moment which helps understanding the
relative location of various bonds in the molecule. The study of a substance
in a magnetic field helps knowing whether the substance is paramagnetic or
diamagnetic. Paramagnetism in a molecule is due to the presence of one or
more than one unpaired electron whereas in diamagnetism, no such unpaired
electron is present. Thus, this helps understanding the electronic configurations
of atoms and molecules.

3.2 ELECTRIC DIPOLE MOMENT

Definition of The spatial distribution of bonding electrons between the two nuclei of a diatomic
Dipole Moment molecule depends on the nature of the two involved atoms. For homonuclear
diatomic molecules such as H2, N2, etc., the distribution of electronic cloud is
symmetrical around the two nuclei of the molecule. In heteronuclear diatomic
molecules such as HCl, HBr, etc., the charge distribution is not symmetrical,
the bonding electrons are more near to the more of electronegative atom.
Consequently, the molecule acquires separation of charges at the two ends; the
more electronegative atom serves as the negative end and the positive end is the
lesser electronegative atom. The distribution of charges in a molecule can be
described by a physical quantity, known as the dipole moment. It is represented by
the symbol p
of the charge Q at either end of the molecule and the distance r between the two

p=Qr (3.2.1)
The dipole moment is a vector quantity, i.e. it has both magnitude as well as
direction. It can be represented by an arrow which indicates the direction from
negative to positive end of the molecule. The length of the arrow is directly
proportional to the magnitude of the dipole moment (Fig. 3.2.1a).

vector additions, i.e.

p= Â Qi ri (3.2.2)
i
342 A Textbook of Physical Chemistry

where Q i is the charge of the ith species and ri is the vector length of this charge

p = (+ Q) r1 + (- Q) r 2 = Q(r1 - r2) = Q r (3.2.3)

r –Q –Q
r

+Q +Q
p = Qr

r2
r1 q

Fig. 3.2.1
Representation of q1 q2
dipole moment x
O
(a) (b)

Component The vector addition shown in Fig. 3.2.1b can be conveniently carried out by making
Method of Adding
Vectors p = (p2x + p2y )1/2
where p x and py are the x- and y-components of the dipole moment. From
Fig. 3.2.1b, we have
px = (+ Q)r1 cos q1 + (- Q)r2 cos q2
py = (+ Q)r1 sin q1 + (- Q)r2 sin q2

Thus p2 = {(+ Q)r1 cos q1 + (- Q)r2 cos q2}2

+ {(+ Q)r1 sin q1 + (- Q)r2 sin q2} 2
= Q2 r12 + Q2 r 22 - 2Q2 r1r2 cos q1 cos q2 - 2Q 2 r1r2 sin q1 sin q2
= Q 2 {r 12 + r 22 - 2r1r2(cos q1 cos q2 + sin q1 sin q2)}
= Q2 {r12 + r 22 - 2r1r2 cos(q1 - q2 )}
= Q 2 r2
Dipole Moment
of More than Two
Charges

p= Ú r r(r ) dt (3.2.4)
where r (r r and dt is the
volume element.
 Electrical and Magnetic Properties of Molecules 343

Example 3.2.1
moment. Given: The angle between the dashed lines is 30°.

r2 = 4 ¥ 10 –10 m

3Q 2Q

Fig. 3.2.2 The given

assembly of charges r1 = 6 ¥ 10 –10 m

Solution Let us have the origin at 3Q charge as shown in Fig. 3.2.2.

Thus, we have
p= Â Qi ri = (3Q)(0) + (2Q)r1 + (Q)r2
i
= (2Q)r1 + (Q) r2
Now px = px, 2Q + px, Q
= (2Q) (6 ¥ 10- 10 m) cos 0° + Q(4 ¥ 10-10 m) cos 30°
= (2Q) (6 ¥ 10–10 m) + Q(4 ¥ 10-10 m) ( 3 /2)
= Q (15.464 ¥ 10-10 m)
py = py, 2Q + py, Q
= (2Q) (6 ¥ 10-10 m) sin 0° + Q(4 ¥ 10-10 m) sin 30°
= Q (2 ¥ 10-10 m)
Now p = (p2x + p2y )1/2
= {Q 2 (15.464 ¥ 10-10 m)2 + Q 2(2 ¥ 10-10 m) 2}1/2
= Q (15.593 ¥ 10-10 m)
py Q(2 ¥ 10-10 m)
tan f = = = 0.128
px Q(15.464 ¥ 10-10 m)
f = 7.3°

Unit of Dipole Since p = (charge) (distance), we will have

Moment CGS-esu units The unit of p is esu cm.
SI units The unit of p is C m.

If one electronic charge is separated from an equal positive charge by a distance

of 0.1 nm, its dipole moment would be
CGS-esu units
p = (4.8 ¥ 10-10 esu) (1.0 ¥ 10-8 cm) = 4.8 ¥ 10 - 18 esu cm
344 A Textbook of Physical Chemistry

SI units
p = (1.602 ¥ 10- 19 C) (1.0 ¥ 10-10 m) = 1.602 ¥ 10 - 29 C m
Most of molecules possess dipole moment of the order of 10-18 esu cm. In
-18
esu cm
unit of dipole moment is named as the Debye unit and is represented by the symbol
D. It is obvious that
4.8 D = 1.602 ¥ 10- 29 C m
1.602 ¥ 10-29 C m
Hence 1D= = 3.3356 ¥ 10-30 C m (3.2.5)
4.8

Induced Dipole The electronic distribution of a molecule is distorted in the presence of a static
Moment
symmetric or nonsymmetric charge distribution are polarizable in the presence

induced dipole moment in a molecule is directly proportional to the strength of

pind μ E
or pind = a E (3.2.6)
where a is the constant of proportionality and is a measure of easiness with which
a molecule can be polarized, and is known as the polarizability of the molecule.
a is equal to the induced dipole moment generated by a unit strength

Different Kinds of
Polarization ways as follows.
Electronic polarization In this, the electronic cloud of the molecule is distorted

is represented as a e.

Atomic polarization In this, the nuclei (atoms) are distorted towards the
a a.

Orientation polarization This is operative only when the molecule carries

as a o.

The total polarizability a of the molecule is an algebraic sum of the above

three polarizabilities, i.e.
a = a e + a a + ao (3.2.7)
The electronic and atomic polarizations taken together is referred to as distortion
polarization. Thus, distortion polarizability ad is given as
a d = ae + aa (3.2.8)
 Electrical and Magnetic Properties of Molecules 345

Unit of Since a = pind /E, we have

Polarizability CGS-esu units The unit is
esu cm
-2
= cm 3
esu cm
that is, the unit of a is the unit of volume.
SI units Here we have
Cm
-1
= C 2 m N -1
NC
In the SI system, a /4pe 0 has the unit of volume as shown below.
a C2 m N -1
= 2 -1 -2 = m 3
4pe 0 C N m

3.3 EFFECT OF A DIELECTRIC ON THE ELECTROSTATIC FIELD OF A PARALLEL

PLATE CAPACITOR

Let s

s
E0 without dielectric = (3.3.1)
e0
s
E with dielectric = (3.3.2)
e
where e0 and e are the permittivities of vacuum and medium, respectively.
Since e is greater than e 0 for most of dielectric, we have
E < E0 (3.3.3)
that is, the presence of a dielectric in a parallel plate capacitor decreases its electrical

The charge density s on the plates polarizes the molecules of the dielectric
and thereby generates induced dipole moment in the molecules. These induced

negatively charged plate and negative ends towards the positively charged plates
as shown in Fig. 3.3.1.

Fig. 3.3.1 Distortion

and orientation of
molecules in an electro-
346 A Textbook of Physical Chemistry

This arrangement of molecules adjacent to the plates decreases the net charges on
the plates. If sind is the induced charge per unit area on each plate, we will have
Net charge per unit area on each plate = s – s ind (3.3.4)
The term sind is known as polarization. The factor sind will also be equal to the
induced dipole moment per unit volume of the dielectric. This may be understood
as follows.
sind = Induced positive or negative charge per unit area of the plate
Induced charge
i.e. s ind =
Unit of area
Multiplying and dividing by a unit of length, we have
(Induced charge)( Unit of length )
sind =
( Unit of area )( Unit of length )
Induced dipole moment
=
Unit of volume
E in the presence
of a dielectric as
s - s ind
E= (3.3.5)
e0

s ind
E = E0 - (3.3.6)
e0
E er =
e/e0 = E0/E, where er stands for relative permittivity), we get a relation which on
rearranging gives
(s ind /e 0 )
E= (3.3.7)
(e / e 0 ) - 1

the relative permittivity (or the dielectric constant) of the dielectric in the capacitor.

3.4 CLAUSIUS-MOSOTTII EQUATION

The Clausius-Mosottii equation relates the distortion polarizability of the molecule
with the dielectric constant of the substance. The required relationship may be
derived as follows.

Expression of Let N * be the number of molecules per unit volume of the dielectric material and let
Polarizability pind be the induced dipole moment on each of the molecule. Since the polarization
Without Induced sind represents induced dipole moment per unit volume of the dielectric, we have
Dipole Interactions sind = N * pind (3.4.1)
If a d is the distortion polarizability of the molecule, we have
pind = a d E
 Electrical and Magnetic Properties of Molecules 347

Substituting pind
s ind = N*ad E (3.4.2)
If Vm is the molar volume of the dielectric, we will have
NA N ÊN ˆ
= Á
Ë M ˜¯
N* = = r (3.4.3)
Vm M r
where r

ÊN ˆ Ê s ind / e 0 ˆ
s ind = Á
Ë M ˜¯
r (ad) Á
Ë (e / e 0 ) - 1˜¯

1 ÊMˆ
or ad = (e - e 0) Á ˜ (3.4.4)
NA Ë r¯
Expression of Since ad
Polarizability with
Induced Dipole (e - e0)/r is independent of the density of the medium. However, this is found
Interactions to be so only when the molecules do not posses any permanent dipole moment
and for which the pressure is low so that the interaction between neighbouring
induced dipoles is negligible because of the relatively larger distance between

phases because of the considerable interaction between the neighbouring induced

s - s ind + s ind /3 s ind

Eint = =E+ (3.4.5)
e0 3e 0
where s ind /3e 0
(3.4.2) in the present case becomes
s ind = N*ad Eint (3.4.6)
Substituting Eint E
Ê s ind ˆ s ind / e 0 s ind
ÁË N*a ˜¯ = (e / e ) - 1 + 3e
d 0 0

Ê 1 ˆ 1/ e 0 1
or ÁË N*a ˜¯ = (e / e ) - 1 + 3e (3.4.7)
d 0 0

(e / e 0 ) - 1 Ê 1 ˆ Ê 1 ˆ ÊN ˆ
(a d ) Á
Ë M ˜¯
= Á ˜ ad N * = Á
Ë 3e 0 ˜¯
r
(e / e 0 ) + 2 Ë 3e 0 ¯

(e / e 0 ) - 1 M 1
or = N ad (3.4.8)
(e / e 0 ) + 2 r 3e 0
348 A Textbook of Physical Chemistry

Clausius-Mosottii equation. The left side of

molar polarization and is represented as Pm. From
Pm is independent of temperature as the right side of
this equation is independent of temperature.
Clausius-Mosottii equation is found to be applicable only for nonpolar molecules
2, CH4 and
CO2. For molecules such as HCl, CH3Cl, H2O, NH3, etc., which have permanent
dipole moment, the Clausius-Mosottii equation fails very badly. Moreover, the

temperature.
3.5 DEBYE EQUATION
The reason why the Clausius-Mosottii equation is not applicable to polar molecules

factor which opposes the orientation polarization is the thermal energy of molecules.
Larger the thermal energy, greater will be randomness and hence lesser will be
the orientation polarization. Since thermal energy of gaseous system depends on
temperature, it follows that the value of orientation polarization depends on the
temperature of the system.
In general, the orientation polarizability depends on the following two factors.
∑ Directly proportional to the average value of component of permanent dipole
moment p
∑ Inversely proportional to the temperature of the system.
Detailed calculations have shown that the orientation polarizability is given by
p2
ao = (3.5.1)†
3kT
Since total polarizability is the sum of distortion and orientation polarizabilities

a total = ad + ao (3.5.2)

(e / e 0 ) - 1 M 1
= N a total (3.5.3)
(e / e 0 ) + 2 r 3e 0
Debye equation

(e / e 0 ) - 1 M 1 1 Ï p2 ¸
= N (a d + ao) = N Ìa d + ˝
(e / e 0 ) + 2 r 3e 0 3e 0 Ó 3kT ˛

1 Ï p2 ¸
that is, Pm = N Ìa d + ˝ (3.5.4)
3e 0 Ó 3kT ˛
†
see
 Electrical and Magnetic Properties of Molecules 349

Graphical Display Pm varies linearly with inverse of temperature. The slope

of Debye Equation and intercept of linear plots are (1/9)N p 2/ke0, and (1/3)N ad / e 0, respectively.
From slope and intercept, p and ad of the molecule may be determined.
Figure 3.5.1 illustrates the linear plots for the two gaseous systems. For nonpolar
molecules, since p = 0, the plot of Pm versus 1/T would yield a straight line parallel
to 1/T

Fig. 3.5.1 Plots of Pm

versus 1/T for the two
gaseous systems

Example 3.5.1 For SO2(g) at 273 K and 1 atm pressure, the dielectric constant (or relative permittivity)
2
behaves as an ideal gas, calculate per mol of (a) total, (b) orientation, and (c) induced
polarizations, and (d) distortion polarizability.
Solution We have
e
er = = 1.009 93
e0
p = 1.63 D = 1.63 (3.335 6 ¥ 10 -30 C m)
Vm = 22 414 cm3 mol-1 at 1 atm and 273 K
(a) Total polarization,
e r - 1 M 1.00993 - 1
Ptotal = = ¥ 22 414 cm3 mol -1
e r + 2 r 1.00993 + 2

= 73.95 cm3 mol-1

(b) Orientation polarization,
NA Ê p2 ˆ
Po =
3e 0 ÁË 3 kT ˜¯

Ï {6.022 ¥ 1023 mol-1} ¸ Ï (1.63 ¥ 3.335 6 ¥ 10-30 C m) 2 ¸

= Ì -12 2 -1 -2 ˝ Ì -23 -1 ˝
Ó 3(8.854 ¥ 10 C N m ) ˛ Ó 3(1.38 ¥ 10 J K )(273 K ) ˛
= 59.31 ¥ 10 -6 m3 mol–1 = 59.31 cm3 mol-1
350 A Textbook of Physical Chemistry

(c) Induced polarization,

Pind = Ptotal - Po = 73.95 cm3 mol -1 - 59.31 cm3 mol-1
= 14.64 cm3 mol -1
(d) Distortion polarizability,

Pind 14.64 ¥ 10-6 m3 mol-1

ad = =
(1/ 3e 0 ) N A {1/(3 ¥ 8.854 ¥ 10-12 C2 N -1 m -2 )}(6.022 ¥ 1023 mol-1 )

= 6.46 ¥ 10 -40 C2 N -1 m

Example 3.5.2 3 is reported to be 1.44 D and the atomic and electronic

polarization total about 6.0 cm3 mol-1. Calculate the dielectric constant or permittivity of
NH3 at 1 atm and 273 K if NH3 is a perfect gas.

Solution We have p = 1.44 D = 1.44 (3.335 6 ¥ 10 -30 C m)

Pd = Pe + Pa = 6.0 cm3 mol -1

Vm = 22 414 cm3 mol-1 at 1 atm and 273 K

The Debye equation is
er - 1 M 1 Ê p2 ˆ 1 1 p2
= N Áad + ˜ = N ad + N
e r + 2 r 3e 0 Ë 3kT ¯ 3e 0 3e 0 3kT

1
Now N ad = (6.0 ¥ 10–6) m3 mol–1
3e 0

NA p2 Ï {6.022 ¥ 1023 mol-1} ¸ Ï (1.44 ¥ 3.3356 ¥ 10-30 C m) 2 ¸

= Ì -12 2 -1 -2 ˝ Ì -23 -1 ˝
3e 0 3kT Ó 3(8.854 ¥ 10 C N m ) ˛ Ó 3(1.38 ¥ 10 J K )( 273 K ) ˛

= 46.29 ¥ 10–6 m3 mol–1

er - 1
(22 414 ¥ 10 -6 m3 mol-1) = (6.0 ¥ 10-6 + 46.29 ¥ 10-6) m3 mol-1
er + 2

= 52.29 ¥ 10 - 6 m3 mol -1

er - 1 52.29 ¥ 10-6 m3 mol-1

Hence = = 0.002 33
er + 2 22 414 ¥ 10-6 m3 mol-1

Solving for e r, we get

e r = 1.007
Now e r = e /e 0 , therefore

e = er e0 = (1.007) (8.854 ¥ 10-12 C2 N-1 m-2)

= 8.916 ¥ 10-12 C2 N -1 m -2
 Electrical and Magnetic Properties of Molecules 351

3.6 EXPERIMENTAL METHOD TO DETERMINE a AND p

Application for For a substance in the gaseous phase, a and p may be determined from the slope
Gaseous System and intercept of linear plot of Pm versus 1/T (Debye equation). We have
NA Ê p2 ˆ
Slope, b =
3e 0 ÁË 3k ˜¯
9e 0 k b
Hence p = (3.6.1)
NA
NA
Intercept, a = distortion polarization = a (3.6.2)
3e 0 d
Hence
Ê 3e 0 ˆ
Distortion polarizability, a d = Á
Ë N A ˜¯
a (3.6.3)

p2
Orientation polarizability, a o = 3 kT (3.6.4)

b
Orientation polarization = (3.6.5)
T
Application for The above method of determining a and p is applicable only for gaseous systems.
Condensed For condensed systems, the Debye equation cannot be applied as such because
System of stronger interactions among the closely packed polar molecules. The Debye
equation can, however, be applied for dilute solutions of a polar substance in a
nonpolar solvent. Though the polar molecules are relatively far apart, yet there

Pm versus
x2 to zero amount fraction of solute in solution. The procedure to be adopted is
now summarized.
Let the measurement of dielectric constants D12 (i.e. relative permittivities) and
densities r12 of dilute solutions of the polar substance in a nonpolar solvent be
P12

D12 - 1 M av
P12 = (3.6.6)
D12 + 2 r12
where
Mav = x1 M1 + x2M2 (3.6.7)
where x1 and x2 are amount fractions of solvent and solute, respectively. The molar
polarization P12 of the solution includes contributions from both solute and solvent
polarizations. If it be assumed that these polarizations are directly proportional to
the respective amount fractions, we have
P12 = x1P1 + x2P2 = (1 - x2)P1 + x2P2
= P1 + (P2 - P1) x2 (3.6.8)
352 A Textbook of Physical Chemistry

The molar polarization P1 of the pure solvent can be determined from the values
of dielectric constant and density of pure solvent. Knowing P12, P1 and x2, the
apparent molar polarization of the solute P2
The values of P2 thus obtained are found to vary with amount fraction of solute
in solution. This variation is attributed to the solute-solute interactions and can
P2 versus x2 to zero value of x 2. This
gives the value of P2 P2•. Knowing P2•
at different temperatures, the dipole moment p of the solute can be obtained by
using the Debye equation. This method, however, does not eliminate the solute-
solvent interactions.

Example 3.6.1 The following data have been reported for NH3(g).

Temperature/K 250 275 300 350

Dielectric constant 1.008 5 1.007 1 1.006 1 1.004 5
3 –1
g 1 180 1 305 1 420 1 670

Calculate the dipole moment of the NH3 molecule.

Solution Table 3.6.1 includes the given data along with the calculated values of Pm.

Table 3.6.1 Calculation of Pm from the Given Data

T K Relative Molar Molar polarization, Pm

volume
K T permittivity, e r Vm /cm3 mol -1 Ê er - 1ˆ 3 -1
ÁË e + 2 ˜¯ Vm /cm mol
r

250 0.004 00 1.008 5 1 180 ¥ 17 56.8

275 0.003 64 1.007 1 1 305 ¥ 17 52.5

300 0.003 33 1.006 1 1 420 ¥ 17 49.1

350 0.002 86 1.004 5 1 670 ¥ 17 42.6

In Fig. 3.6.1, the calculated values of Pm have been plotted against 1/ T. The slope of
the straight-line plot is 12 200 cm3 K mol–1. Hence
1/ 2
Ê 9e 0 k ¥ slope ˆ
p= Á ˜¯
Ë NA
1/ 2
Ï 9(8.854 ¥ 10-12 C2 N -1 m 2 )(1.38 ¥ 10-23 J K -1 )(12 200 ¥ 10-6 m3 K mol-1 ) ¸
= Ì ˝
Ó 6.022 ¥ 1023 mol-1 ˛
= 4.72 ¥ 10-30 C m
Ê 1D ˆ
= (4.72 ¥ 10- 30 C m) Á = 1.415 D
Ë 3.3356 ¥ 10-30 C m ˜¯
 Electrical and Magnetic Properties of Molecules 353

Fig. 3.6.1 The plot of

Pm versus 1/T

3.7 VARIATION OF MOLAR POLARIZATION WITH THE FREQUENCY OF ELECTRIC FIELD

The molar polarization of polar molecules as described by the Debye equation is
er -1 M NA
Pm = = (a d + ao) (3.7.1)
er + 2 r 3e 0
The value of dielectric constant is determined by placing the substance between
the plates of a capacitor connected to an alternating current of frequency about
1 MHz (n = 106 s-1). It is found that the value of relative permittivity e r (or molar
polarization Pm) does not remain constant as the frequency of alternating electric
er is due to the fact that the polar molecules

as described in the following.

partial alignment and to reach the random distribution of orientations. This time
is known as the relaxation time

constant. When, however, the period of alternations (= 1/n) becomes comparable

orientation polarization decreases. The frequency range at which this change occurs
is usually 1010 - 1012 Hz.

and only the distortion contribution remains. The latter results from the distortion
354 A Textbook of Physical Chemistry

polarization further drops. This happens when the frequency of the alternating

electromagnetic spectrum to the visible region (� 1015 Hz). The only remaining
polarization is due to the electronic polarization which persists even at higher
frequencies. The variation of molar polarization with the frequency of the alternating

R — Radio
I — Infrared
V — Visible
U — Ultra violet

Pm
Po

Pa

Pd R I V U
Pe
Fig. 3.7.1 Variation of
Pm with frequency of 109 1011 1013 1015 1017
Frequency/Hz

3.8 LORENTZ-LORENZ EQUATION

It was seen in the previous section that the molar polarization induces only the
electronic polarization when the substance under study is subjected to alternating
15

be written as

er - 1 M NA
Pe = = a (3.8.1)
e r + 2 r 3e 0 e

as the data of relative permittivity are measured by employing alternating current

of low frequency of the order of 106

e r = n2 (3.8.2)
where n
both relative permittivity er n be measured at the same
frequency. In actual practice, the relative permittivity, as stated above, is determined
by electrical method using the alternating current of frequency £ 106 Hz while

frequencies (> 1014

these quantities are measured at different frequencies. The reason being that
 Electrical and Magnetic Properties of Molecules 355

the orientation polarizability is altogether absent in such type of molecules and

that the nuclei distortion polarizability has a negligible value in comparison to
the electronic distortion polarizability. In other words, the measurements of e r
and n at different frequencies include only electronic polarization and hence,

will be applicable provided both er and n are measured at the same frequency.

molecules. The dielectric constant measurement includes all three polarizabilities,

only the electronic polarizability. The major contribution to the total polarizability is
from the orientation polarizability. Consequently, the value of relative permittivity

For benzene e r = 2.27 and n = 1.50 : Hence er � n 2

(nonpolar)
For water e r = 80 and n = 1.33 : Hence er π n 2
(polar)
Thus, electronic polarization of a molecule (polar or nonpolar) may be
determined by replacing e r by n 2
n2 - 1 M N A
= a (3.8.3)
n 2 + 2 r 3e 0 e
Lorentz-Lorenz equation. The quantity
n -1 M
2

n2 + 2 r
is known as molar refraction and is represented by the symbol R m.
Both molar polarization and molar refraction are additive quantities, i.e. the
molar values of these properties for a molecule can be obtained by adding the
appropriate atomic values.

Example 3.8.1 2 molecule at 273 K and 760 mmHg is

1.000 516 and its dielectric constant is 1.001. (a) Calculate its dipole moment. (b) How are
the atoms arranged in the molecule?
Solution D � n2 2 is nonpolar (i.e. its
2

Example 3.8.2 Calculate the value of molar refraction for CH2BrI, given the same for the following
compounds.
CH3I 19.5 cm3 mol-1; CH3Br 14.5 cm3 mol-1; HBr 9.9 cm3 mol-1 and CH 4 6.8 cm3 mol-1.

Solution Since molar refraction of a molecule can be obtained by the addition of appropriate molar
refractions of atoms, we have
RCH 3 I = RC + 3RH + RI = 19.5 cm3 mol-1 (i)
3 -1
RCH3 Br = RC + 3RH + RBr = 14.5 cm mol (ii)
356 A Textbook of Physical Chemistry

RHBr = RH + RBr = 9.9 cm3 mol -1 (iii)

RCH4 = RC + 4RH = 6.8 cm3 mol-1 (iv)

RC + 2RH + RBr + RI = (19.5 + 14.5 - 6.8) cm3 mol -1 = 27.2 cm3 mol -1
Thus RCH 2BrI = 27.2 cm3 mol-1
Molar refractions of atoms can be calculated as follows.

RC + 2RH = 4.6 cm3 mol -1 (v)

2RH = 2.2 cm3 mol -1

or RH = 1.1 cm3 mol-1 (vi)

RBr = 9.9 cm3 mol-1 - RH = 9.9. cm3 mol-1 - 1.1 cm3 mol -1
= 8.8 cm3 mol-1 (vii)

RC = 14.5 cm3 mol-1 - 3RH - RBr = (14.5 - 3.3 - 8.8) cm3 mol-1
= 2.4 cm3 mol-1 (viii)

RI = 19.5 cm3 mol-1 - RC - 3RH = (19.5 - 2.4 - 3.3) cm3 mol-1

= 13.8 cm3 mol-1

Example 3.8.3 nH2n + 2 is found to be 1.001 39 when the gas

is at STP. Given the molar refractions as 1.1 and 2.42 cm3 mol-1 for H and C, respectively,
determine the formula for the hydrocarbon.
Solution Molar refraction of the molecule,
Ê 1.001 392 - 1 ˆ
Rm = Á (22 414 cm 3) = 20.75 cm3 mol -1
Ë 1.001 392 + 2 ˜¯
This will also be given by
Rm = nRC + (2n + 2) RH
Substituting the values, we get
20.75 cm3 mol-1 = n(2.42 cm3 mol-1) + (2n + 2) (1.1 cm3 mol -1)

or n(2.42 cm3 mol-1 + 2.2 cm3 mol-1) = 20.75 cm3 mol-1 - 2.2 cm3 mol-1
= 18.55 cm3 mol-1
18.55 cm3 mol-1
or n= = 4.02 = 4
4.62 cm3 mol-1
Hence, the compound is C4H10
 Electrical and Magnetic Properties of Molecules 357

3.9 UNION OF THE DEBYE AND THE LORENTZ-LORENZ EQUATIONS

It is possible to determine the dipole moment of polar molecules by taking

measurements at one temperature as compared to the Debye method where
measurements at various temperatures are required. This is possible by the union
of Debye and Lorentz-Lorenz equation. This can be done as follows.
N
Debye equation Pm = A (a e + aa + ao) (3.9.1)
3e 0
NA
Lorentz-Lorenz equation Rm = ae (3.9.2)
3e 0

NA
Pm - R m = (a a + ao) (3.9.3)
3e 0
Since a a is much smaller than ao
NA N Ê p2 ˆ
Pm - Rm � ao = A ÁË 3kT ˜¯ (3.9.4)
3e 0 3e 0
1/ 2
Ê 9e k ˆ
Hence p = Á 0 ˜ {(Pm - Rm)T }1/2
Ë NA ¯
1/ 2
Ê 9(8.854 ¥ 10-12 C2 N -1 m -2 )(1.38 ¥ 10-23 J K -1 ) ˆ
=Á ˜¯ {(Pm - Rm)T}1/2
Ë 6.022 ¥ 1023 mol-1
i.e. p/C m = (4.273 ¥ 10-29){(Pm - Rm)/m3 mol–1}1/2(T/K)1/2 (3.9.5)
Pm and R m

in a nonpolar solvent, P2• is used in place of Pm. The value of Rm can be calculated

as those obtained by the temperature variation method owing to the uncertainty in

the value of molar polarization of atoms. For a polar liquid in a nonpolar solvent,
P2• and R2• may be employed in place to Pm and Rm, respectively, in order to
get more reliable results as these values eliminate the solute-solute interactions.

Example 3.9.1 The following data refer to dilute solutions of benzal chloride (C6H5CHCl2) in benzene at
298 K.
Amount fraction of Density Refractive Relative
C6H5CHCl2 g cm–3 index permittivity

0.000 00 0.874 0 1.502 00 2.272 7

0.013 14 0.880 6 1.502 94 2.353 4
0.018 43 0.883 6 1.503 37 2.386 1
0.026 04 0.888 1 1.503 87 2.433 0
Calculate the dipole moment of benzal chloride.
358 A Textbook of Physical Chemistry

Solution (i) Evaluation of P2•

First of all, the values of P12 at different concentrations were calculated. From the obtained
values of P12, the molar polarization contribution P2 of the solute at different concen-
trations are calculated. Finally, a plot of P2 versus x2
x2 Æ 0 to obtain the value of P2•. Table 3.9.1 includes the data of calculations.
Table 3.9.1 Calculation of P2

Ê e - 1 M av ˆ Ê P - Px ˆ
P12 = Á r P2 Á = 12 1 1 ˜
x2 r er - 1 M av (=  xi M i ) Ë e r + 2 r ˜¯ P1x1 Ë x2 ¯
g cm -3 er + 2 g mol-1 cm3 mol-1 cm3 mol-1 cm3 mol-1
0.0000 0 0.874 0 0.297 87 78.108 26.620 26.620 —
0.013 14 0.880 6 0.310 86 79.196 27.959 26.270 128.54
0.018 43 0.883 6 0.316 02 79.630 28.480 26.129 127.56
0.026 04 0.888 1 0.323 26 80.267 29.217 25.927 126.34

Figure 3.9.1 shows the plot of P2 versus x2 P2• is found to be

131.0 cm3 mol-1.

131

130
P2/cm3 mol–1

129

128

127

126
Fig. 3.9.1 The plot of 0.0 0.01 0.02 0.03
x
P2 versus x2 2

(ii) Evaluation of R2•

In a similar way, the value of R2• was determined. Table 3.9.2 includes the data
of calculations.
Table 3.9.2 Calculation of R2

n2 - 1 M av
x2 R12/cm3 mol–1 R1x1/cm3 mol–1 R2/cm3mol–1
n2 + 2 g mol-1
0.000 00 0.295 11 78.108 26.373 26.373 —
0.013 14 0.295 58 79.196 26.583 26.026 42.390
0.018 43 0.295 79 79.630 26.657 25.887 41.780
0.0260 4 0.296 04 80.267 26.756 25.686 41.091
 Electrical and Magnetic Properties of Molecules 359

Figure 3.9.2 illustrates the plot of R2 versus x2. The value of R2• is found to be 44.0 cm3
mol -1.

44

43

P2/cm3 mol–1
42

41

40
Fig. 3.9.2 The plot of 0.0 0.01 0.02 0.03
R2 versus x2 x
2

Now P2• = Po, 2• + Pd, 2•

where Pd, 2• and Po, 2•
respectively.
Since atomic polarization contribution is usually less that 10%, we have
Pd, 2• = R2•

Hence Po, 2• = P2 • - R2• = 131 cm3 mol-1 - 44 cm3 mol-1 = 87 cm3 mol-1
From Po, 2•, the dipole moment p of the solute is determined as follows.
NA Ê p2 ˆ
Since Po, 2• =
3e 0 ÁË 3kT ˜¯

1/ 2
ÏÊ 9e kT ˆ ¸
we get p = ÌÁ 0 ˜ Po, 2• ˝
ÓË N A ¯ ˛
Substituting the data, we have

ÈÏ 9(8.854 ¥ 10-12 C2 N -1 m -2 )(1.38 ¥ 10-23 J K -1 )(298 K ) ¸

p = ÍÌ ˝
ÎÓ 6.022 ¥ 1023 mol-1 ˛
1/ 2
˘
¥ (87 ¥ 10 -6 m3 mol-1) ˙
˚
= 6.880 ¥ 10-30 C m

Ê 1D ˆ
= (6.880 ¥ 10-30 C m) Á = 2.06 D
Ë 3.338 ¥ 10-30 C m ˜¯
360 A Textbook of Physical Chemistry

3.10 IONIC CHARACTER OF DIATOMIC MOLECULES

The value of dipole moment of a diatomic molecule provides an insight into the
sharing of valence electrons between the two atoms. If the electrons are equally
shared, the centre of positive charge coincides with the centre of negative charge
and hence the dipole moment of the molecule is zero. If the sharing is unequal the
molecule has a net dipole moment. If it is assumed that the bonding electrons lie in
the bond between the two atoms, the ionic character of the bond may be determined

bonding electrons were completely held by chlorine, we would have a situation

of 100 per cent ionic bond where chlorine and hydrogen carry uninegative and
unipositive charges, respectively. Since the bond distance is 127.5 pm, the dipole
moment of such a completely ionic structure (100%) would be

pionic = (1.60 ¥ 10-19 C) (127.5 ¥ 10-12 m)

= 20.4 ¥ 10-30 C m = 6.12 D
On the other hand, if the bonding electrons are equally shared by H and Cl
atoms, the HCl molecule would have carried zero per cent ionic character. The
actual value of dipole moment is 1.03 D, suggesting that it is neither 100% ionic
nor 0%, but in between. The amount of ionic character can be calculated by using

pobs
Per cent ionic character = p ¥ 100 (3.10.1)
ionic

Thus, for HCl, we have

Ê 1.03 D ˆ
Per cent ionic character = Á
Ë 6.12 D ˜¯
(100) � 17

3.11 BOND MOMENTS

It was seen in Section 3.2 that the bond connecting the two atoms of different

each bond is associated with its own dipole moment value and net dipole moment

angle of 105° (Fig. 3.11.1). Let pOH be the bond moment of O—H bond. From
Fig. 3.11.1, it is obvious that
pH2O = 2 pOH cos (q/2) (3.11.1)
where q = 105°. The dipole moment of water is 1.85 D. Thus, we have
pH 1.85 D 1.85 D
2O
pOH = = = = 1.52 D
2 cos(q/2) 2cos (52.5°) 2 ¥ 0.6085
Note the vector addition of bond moments along the line perpendicular to the
dashed line is zero.
 Electrical and Magnetic Properties of Molecules 361

assumed that the contribution of nonbonding electrons (if any) towards the total
dipole moment is included within the bond moments of the molecule.

Fig. 3.11.1 Vector

addition of bond
moments in water
molecules

If the molecule has a centre of symmetry, its dipole moment is zero. In

such molecules, though the individual bonds may have bond moments, but the
arrangement of the bonds is such that the resultant dipole moment is zero. For
C == O bonds constitute a linear
C == O bond carries bond moment, but the vector addition of the
two bond moments is zero, as shown in the following.

O C O

carries a bond moment, but the arrangement of four C—H bonds in CH4 is such
that their vector addition is zero. The geometry of CH4 is tetrahedral. Obviously,
the bond moment of any one C—H bond is equal and opposite to the sum of
components of vectors of the rest of the three C—H bonds along the direction of
the C—H bond understudy, and, their sum along the line perpendicular to the
C—H bond is zero.
Note that for molecules having net dipole moment equal to zero, it is not possible
to derive the values of individual bond moments.
The bond moment of C—H bond, as found by Meyer, is 0.4 D with the hydrogen
atom being the positive end of the dipole. With this information it is possible
to evaluate the bond moment of C—X bond from the dipole moment of CH3X
3
of the components of three C—H bond moments along the C—Cl direction is equal
to the bond moment of C—H, acting in the same direction of the Cl—C bond
moment. The vector addition of components of the three C—H bond moments
along the line perpendicular to the Cl—C direction is zero. Hence
p(CH3Cl) = p(Cl—C) + p(C—H)
or p(Cl—C) = p(CH3Cl) – p(C—H)
p(CH3Cl) is 1.87 D. Hence
p(Cl—C) = 1.87 D – 0.4 D = 1.47 D
362 A Textbook of Physical Chemistry

Cl

1.47 D 1.87 D

Sum is
C zero
Fig. 3.11.2 Vector
addition of bond
moments in CH3Cl 0.40 D
(a) along, and H H H
(b) perpendicular to p = 1.87 D
the Cl—C bond (a) (b)

Example 3.11.1 The bond angle in H2S is 97º and its dipole moment is 1.47 D. Find the S—H bond moment.
2S. The S—H bond distance is 133.4 pm.

Solution
p
p = 2pSH cos (q/2) or pSH =
2 cos(q 2)
Substituting the values, we get
1.47 D 1.47 D
pSH = = = 1.11 D
2 cos (48.5º ) 1.325
Per cent ionic character
p 1.11 ¥ 3.335 6 ¥ 10-30 C m
= p SH ¥ 100 = ¥ 100
ionic (1.60 ¥ 10-19 C)(133.4 ¥ 10-12 m)
� 17
Note that the sum of components of bond moments along the line perpendicular to the
dashed line is zero.

Example 3.11.2 3Cl, CH2Cl2 and CHCl3 molecules. Given: p(C—Cl) =

1.47 D with Cl as the negative end and p (C—H) = 0.4 D with C as the negative end.
Solution CH3Cl Molecule We consider the atoms Ha b
and Hc
We resolve each of the two bond moments in a plane along the two mutually perpendicular
x
 Electrical and Magnetic Properties of Molecules 363

Fig. 3.11.3 Orientation

of CH3Cl molecule
Component along x-axis
px = ( pCHa – pCCl – pCH b – pCHc ) cos (109.48∞/2)
= (– pCCl – pCH) cos (54.74°) = – (1.47 D + 0.4 D)(0.577) = – 1.08 D
Components along y
p y = (–pCCl – pCH ) sin (54.74°) = – (1.47 D + 0.4 D)(0.817) = – 1.53 D
a
Components along yB
p yB = ( pCH – pCH ) sin (54.74°) = 0
b c

The dipole moment of CH3Cl will be

p = px2 + p 2y + p 2y = (-1.08 D) 2 + (-1.53 D) 2 + 02 = 1.87 D
A B

CH2Cl2 Molecule We consider the atoms Cla and Clb a

and Hb
We resolve each of the two bond moments in a plane along the two mutually perpendicular
x

Fig. 3.11.4 Orientation

of CH2Cl2 molecule
364 A Textbook of Physical Chemistry

Components along x-axis

px = (– pCCla – pCClb – pCHa – pCH b ) cos (54.74°)
= (–1.47 D – 1.47 D – 0.4 D – 0.4 D)(0.577)
= – 2.16 D
p y = (+ pCCla – pCClb ) sin (54.74°) = 0

p yB = ( pCHa – pCH b ) sin (54.74°) = 0

Hence, the dipole mement of CH2Cl2 is 2.16 D.

CHCl3 Molecule We consider the atoms Cla and Clb
Clc
We resolve each of the two bond moments in a plane along the two mutually perpendicular
x

Fig. 3.11.5 Orientation

of CHCl3 molecule

Components along x-axis

px = (– pCCla – pCClb + pCClc – pCH) cos (54.74°)

= (– pCCla – pCH) cos (54.74°) = (–1.47 D – 0.4 D) (0.577)

= – 1.08 D
p y = ( + pCCl – pCClb ) sin (54.74°) = 0
a

p yB = (– pCCl – pCH) sin (54.74°) = (–1.47 D – 0.40 D) (0.817)

c

= – 1.53 D
The dipole moment of CHCl3 will be

p= px2 + p 2yB + p 2yA = (-1.08 D) 2 + (-1.53 D) 2 + 02 = 1.87 D

 Electrical and Magnetic Properties of Molecules 365

Alternative
Procedure CH3Cl Molecule Let the bond moments be resolved into the Cartesian x-, y- and
z
z

Cl

Hc

Ha
Fig. 3.11.6 Orientation Hb
of CH3Cl molecule x

We have
(
pz = – pCCl – pCHa + pCH + pCHc
b ) cos (180° – 109.48°)
= – 1.47 D – (0.40 D + 0.40 D + 0.40 D) cos (70.52°)
= – 1.47 D – (1.20 D) (0.333)
= – 1.47 D – 0.40 D = – 1.87 D

( )
py = – pCHa cos (109.48∞ – 90°) + pCH b + pCHc sin (180°–109.48∞) cos 60°
= – (0.40 D) cos (19.48 ∞) + 2 pCH sin (70.52°) cos 60°
= – (0.40 D) (0.943) + (2 ¥ 0.40 D) (0.943) (0.5)
= – 0.377 D) + 0.3777 D = 0
( )
px = pCH b - pCHc sin (180° – 109.48 ∞) sin 60°
=0
The dipole moment of CH3Cl will be

p2 = px2 + p 2y + pz2 = 1.87 D

CH2Cl2 Molecule Let the bond moments be resolved into the cartesion x-, y- and
z

Fig. 3.11.7 Orientation

of CH2Cl2 molecule
366 A Textbook of Physical Chemistry

We have
pz = – pCCla + ( pCClb + pCHa - pCH b ) cos (70.52°)
= – 1.47 D + (1.47 D – 0.40 D – 0.40 D) (0.333)
= – 1.47 D + 0.22 D
= – 1.25 D
py = pCClb cos (19.48°) + ( pCHa + pCH b ) sin (70.52°) cos 60°
= (1.47 D) (0.943) + (0.40 D + 0.40 D) (0.943) (0.5)
= 1.39 D + 0.38 D = 1.76 D
px = ( pCH b – pCHa ) sin (70.52°) sin 60°
=0
The dipole moment of CH2Cl2 will be

p= px2 + p 2y + pz2 = (-1.25 D) 2 + (1.76 D) 2 + 0

= 2.16 D
CHCl3 Molecule Let the bond moments be resolved into the Cartesion x-, y- and
z

Clc

Fig. 3.11.8 Orientation Cla

of CHCl3 molecule x Clb

We have
pz = pCH + ( pCCla + pCClb + pCClc ) cos (70.52°)
= 0.40 + (3 ¥ 1.47 D) (0.333)
= 1.87 D
py = pCCla cos (19.48°) – ( pCCl + pCCl ) sin (70.52°) cos 60°
b c

= (1.47 D) (0.943) – (2 ¥ 1.47 D) (0.943) (0.5)

=0
px = ( - pCCl + pCCl ) sin (70.52°) sin 60°
b c

=0
The dipole mement of CHCl3 molecule is

p= px2 + p 2y + pz2 = 1.87 D

 Electrical and Magnetic Properties of Molecules 367

3.12 GROUP MOMENTS

In evaluating the dipole moment of benzene derivatives, the study of group

moment is of greater importance than the concept of bond moment. For example,
in chlorobenzene, if it is assumed that all C—H linkages in benzene have zero
bond moments, then the observed dipole moment of 1.55 D of chlorobenzene may
be assumed to arise from the C—Cl linkage. Thus, the group moment of chlorine
atom is –1.55 D. The sign of group moment indicates the direction in which the
group moment acts; positive sign implies that the group moment acts away from
the benzene ring whereas negative sign implies that it acts towards the ring. Table
3.12.1 includes the group moments of a few groups.

Table 3.12.1 Group Moments of a Few Groups

Group NO2 CN OH Cl H CH3 NH2

Group moment/
Debye – 3.98 –3.8 –1.6 – 1.58 0 + 0.4 – 1.53

The dipole moment of any substituted benzene can be derived from the following
expression of vector addition of group moments. Consider, for example, the
arrangement of two bond moments p1 and p2 inclined at an angle q with respect
to each other. The addition of these two may be carried out by adding separately
the two x- and y-components of p1 and p2 so as to give px and py, respectively,
and then by employing the expression
p = (p2x + py2 )1/2
we get the resultant moment of the two moments. If q1 and q2 are the respective
angles of p1 and p2 with x-axis, we have
px = p1, x + p2, x = p1 cos q1 + p2 cos q2
py = p1, y + p2, y = p1 sin q1 + p2 sin q2
Hence p = {(p1 cos q1 + p2 cos q2)2 + (p1 sin q1 + p2 sin q2)2}1/2
= {p21 + p22 + 2p1 p2 (cos q1 cos q2 + sin q1 sin q2}}1/2
p = {p21 + p22 + 2p1 p2 cos (q1 – q2)}1/2
or p = (p21 + p22 + 2p1 p2 cos q)1/2 (3.12.1)

Example 3.12.1 Show that the dipole moment of 1,2-disubstituted benzene (C6H4X2 ) and 1,3-disubstituted
benzene (C6H4X2 ) are 1.732p and p, respectively, where p is the dipole moment of
monosubstituted benzene (C6H5X).
Solution For 1,2-disubstituted benzene, the angle q between the two vectors is 60º. Substituting this
value in the expression
ptotal = ( p21 + p22 + 2p1 p2 cos q )1/2
we get
ptotal = (p2 + p2 + 2 pp cos 60º)1/2 = 3 p = 1.732 p
368 A Textbook of Physical Chemistry

For 1,3-disubstituted benzene, the angle q between the two vectors is 120º. Substituting
this value of angle, we get
ptotal = ( p2 + p2 + 2p p cos 120°)1/2 = (p2 + p2 – 2p p sin 30°)1/2
=p

Example 3.12.2 The dipole moment of chlorobenzene is 1.70 D. Calculate the corresponding values for 1,2-
and 1,3-dichlorosubstituted benzenes. Compare these values with the experimental values
of 2.53 D and 1.68 D, respectively.
Solution From Example 3.12.1, we have
p1, 2– = 1.732 pmono
p1, 3– = pmono
Substituting the value of pmono, we have
p1, 2– = 1.732 ¥ 1.70 D = 2.94 D
p1, 3– = 1.70 D

for 1,3-dichlorobenzene whereas for 1,2-dichlorobenzene, the agreement is not satisfactory.

This may be due to either or both of the following reasons.
(i) The angle between C—Cl bond vectors may be larger than 60º because of mutual
repulsion of the relatively negative chlorine atoms.

Example 3.12.3 The dipole moments of nitrobenzene, toluene and chlorobenzene are 3.93 D, 0.46 D, and
1.55 D, respectively. Calculate the dipole moments of the following compounds.
(i) o-, m-, p-dinitrobenzenes (ii) o-, m-, p-dimethylbenzenes
(iii) o-, m-, p-dichlorobenzenes (iv) o-, m-, p-nitrotoluenes
(v) o-, m-, p-chlorotoluenes (vi) 1,3- and 1,4-chloronitrobenzenes
Solution From Example 3.12.1, we have
portho = 3p
pmeta = p
Hence, we have
(i) o-, m-, p-dinitrobenzenes
o-dinitrobenzene : p = 1.732 ¥ 3.93 D = 6.81 D
m-dinitrobenzene : p = 3.93 D
p-dinitrobenzene : p = 0
(ii) o-, m-, p-dimethylbenzenes
o-dimethylbenzene : p = 1.732 ¥ 0.46 D = 0.797 D
m-dimethylbenzene : p = 0.46 D
p-dimethylbenzene : p = 0
(iii) o- m-, p-dichlorobenzenes
o-dichlorobenzene : p = 1.732 ¥ 1.55 D = 2.68 D
m-dichlorobenzene : p = 1.55 D
p-dichlorobenzene : p = 0
 Electrical and Magnetic Properties of Molecules 369

(iv) o-, m-, p-nitrotoluenes

We have

pNO2 = – 3.93 D and pCH3 = 0.46 D

o-nitrotoluene: Angle q is 60º. Hence
p/D = (p21 + p22 + 2p1 p2 cos q )1/2
= {(– 3.93)2 + (0.46)2 + 2(– 3.93) (0.46) (1/2)}1/2
= (15.445 + 0.212 – 1.808)1/2 = 3.72
m-nitrotoluene: Angle q is 120º. Thus
p/D = {(– 3.93) 2 + (0.46)2 + 2(– 3.93) (0.46) cos 120°}1/2
= (15.445 + 0.212 + 1.808)1/2 = (17.465)1/2 = 4.18
p-nitrotoluene: Angle q is 180º. Thus
p/D = {(– 3.93)2 + (0.46)2 + 2(– 3.93) (0.46) cos 180º}1/2
= (15.445 + 0.212 + 3.616)1/2 = 4.39
Alternatively, for p-nitrotoluene, the dipole moment may be derived directly by simple
algebraic addition of the two dipole moments as the two vectors point in the same direction.
Hence p = pNO2 + pCH3 = 3.93 D + 0.46 D = 4.39 D

(v) o-, m-, p-chlorotoluenes

Here pC1 = – 1.55 D and pCH3 = 0.46 D
Hence,
o-chlorotoluene: p/D = {(– 1.55)2 + (0.46)2 + 2(– 1.55) (0.46) cos 60°}1/2
= (2.402 + 0.212 – 0.713)1/2 = (1.901)1/2 = 1.379
m-chlorotoluene: p/D = {(– 1.55)2 + (0.46)2 + 2(– 1.55) (0.46) cos 120°}1/2
= (2.402 + 0.212 + 0.713)1/2 = (3.327)1/2 = 1.824
p-chlorotoluene: p = 0.46 D + 1.55 D = 2.01 D
(vi) 1,3 and 1,4-chloronitrobenzenes
pC1 = – 1.55 D and pNO2 = – 3.93 D
1,3-chloronitrobenzene
p/D = {(– 3.93)2 + (– 1.55)2 + 2(– 3.93) (– 1.55) cos 120°}1/2
= (15.445 + 2.402 – 6.092)1/2 = 3.43
1,4-chloronitrobenzene
The two vectors point in the opposite directions, and hence the magnitude of dipole moment
is
p = 3.93 D – 1.55 D = 2.38 D
370 A Textbook of Physical Chemistry

3.13 APPLICATIONS OF DIPOLE MOMENTS

For example, if a molecule has a centre of symmetry, its dipole moment is zero. In
general, if the various identical groups are symmetrically placed around the centre
of symmetry, the molecule has a zero dipole moment. A few examples illustrating
the structural application of dipole moment values are now described.
Shapes of The dipole measurements have been used to determine the shapes of simple
Molecules molecules. For example, the triatomic molecules like BeCl2, CO2, CS2, HgCl2,
etc., have zero dipole moment whereas molecules like H2O, H2S, SO2, etc., have
non-zero dipole moments. Thus, it may be concluded that the former molecules are
linear molecules with centre of symmetry, and the latter are nonlinear molecules.
Hence, the structures are

Compounds of the type AX4 (CH4, TiCl4, CCl4, SnCl4, Ni(CO)4, etc.) have
been found to possess zero moment. Thus, their structures are either tetrahedral
or square planar. Some of AX5 (PF5, PCl5, Fe(CO)5, etc.) and AX6 (SF6, WF6)
molecules have zero moments. Thus, these molecules also have symmetrical
structures. Their structures are

Geometrical It is possible to distinguish between the cis- and trans-forms of a molecule from
Isomers
zero dipole moment.
p-Substituted Dipole moment values have been used to show whether the linkages C—X in
Benzene p-substituted benzenes are coplanar with the benzene ring or not. 1,4-dichlorobenzene
Molecules has zero dipole moment whereas 1,4-dihydroxybenzene (hydroquinone) has a dipole
moment of 1.64 D. Assuming planar structure, hydroquinone has two conformations
as shown in the following.
H
O O and O O
H H H
(I) (II)
 Electrical and Magnetic Properties of Molecules 371

The structure (I) is expected to have zero dipole moment whereas the structure
(II) is expected to have dipolemoment. This may be concluded from the vector
addition of the two O—H bond moments.
3.14 MAGNETIC FIELD IN A SUBSTANCE
I B
H by the relation
B = m0 H (Eq. A.31b of Annexure I)
Within a substance B is, in general, not given by the above relation. It may be
greater or less than m0 H and is given by
B = m0 (H + M ) (3.14.1)
where M is the magnetic moment per unit volume and is known as the magnetization.
It is a measure of the capacity of a substance to develop magnetization when placed
–1
.

and is thus given by

M = cB (B/m0) (3.14.2)
where cB is the dimensionless quantity known as the magnetic susceptibility.
The following types of substances are of interest depending upon the sign of
magnetic susceptibility.
Paramagnetic substance For such a substance, cB is positive and has a value
of the order of +104. The magnetization of the substance has a positive value and
thus B > H.
Diamagnetic substance For such a substance, cB is negative and has a value of
the order of –10–6. The magnetization of the substance is negative and thus B < H.
Experimentally, the more useful quantity is the product of magnetic susceptibility

cm = (Molar volume) (magnetic susceptibility)

ÊMˆ
= Á ˜ cB (3.14.3)
Ë r¯
Since cB has no unit, the unit of cm is that of molar volume, i.e. m3 mol–1.
3.15 MOLECULAR INTERPRETATION OF DIAMAGNETISM AND PARAMAGNETISM

the sign of intensity of magnetization. In this section, we describe the molecular

interpretations of diamagnetism and paramagnetism.
Diamagnetism The diamagnetism in atoms, ions or molecules is due to the orbital motion of
electrons. A simple interpretation of diamagnetism is obtained if we imagine the
372 A Textbook of Physical Chemistry

to the atomic resistance. Inside the atom, there is no resistance to the electronic

Diamagnetism is exhibited by all types of substances, whether the substance

is diamagnetic or paramagnetic. If the substance is paramagnetic, the underlying
diamagnetism is entirely concealed by the large value of magnetic moment of the
substance.
Since the orbital motion of electrons is independent of the thermal energy, it
follows that diamagnetism is independent of temperature of substance. Besides this,
the substance has the same value of magnetic susceptibility whether it is present
in the gaseous or liquid state.
If am is the induced diamagnetic susceptibility per atom (or magnetizability),
the magnetic susceptibility per mole of the substance is given by
cm = NA am (3.15.1)
As in the electrical case, a m

P. Pascal observed that the diamagnetic susceptibilities are approximately

additive and thus the diamagnetic susceptibility of a substance can be obtained by
adding the appropriate atomic and bond contributions. Table 3.15.1 includes the
molar diamagnetic susceptibilities for some of the atoms and bonds.

Table 3.15.1 Molar Diamagnetic Susceptibilities for a Few Atoms and Bonds

Atom or Diamagnetic Atom or Diamagnetic

bond susceptibility bond susceptibility
10–12 m3 mol–1 10–12 m3 mol–1
H – 2.93 Cl – 20.1
C – 6.00 Br – 30.6
O (in alcohols
and ethers) – 4.61 C == C bond 5.5
O (in ketones) + 1.73 C == N bond 8.2

O in C == O – 3.36
N (in open – 5.57 N == N bond 1.9
chain)
N (in ring) – 4.61 C ∫∫ C bond 0.8
N (in amines) – 1.54 C == C C == C 10.6
bond
F – 11.5 Benzene ring – 1.4
 Electrical and Magnetic Properties of Molecules 373

Paramagnetism The phenomenon of paramagnetism is due to the presence of unpaired electron(s)

in the atom or molecule. In Section 1.8, we have seen that the orbital motion of an
electron and the spinning of electron around its own axis produces tiny magnets.

itself, and thus produces a net positive magnetization on the microscopic level.
The magnetic moments of tiny magnets are given by
Orbital motion mm = mB l (l +1) (3.15.2)
Spinning of electron mm = 2 mB s ( s +1) (3.15.3)
where l and s are the azimuthal and spin quantum numbers, respectively, and mB
is the basic unit of magnetic moment called the Bohr magneton and is given by
the expression
eh
mB = (3.15.4)
4pme
Its value is
(1.602 ¥ 10-19 C)(6.626 ¥ 10-34 J s)
mB =
4(3.14)(9.1 ¥ 10-31 kg)
= 9.274 ¥ 10–24 J T–1 (3.15.5)
If an atom has more than one unpaired electron, the magnetic moment due to
the spins of electrons is given by
mm = (2mB) S ( S +1) (3.15.6)
where S is given as
Ê 1ˆ
S = nÁ ˜ (3.15.7)
Ë 2¯
where n is the number of unpaired electrons.
In case of molecules, the only contribution which is important is due to the
spinning of electrons. The orbital contribution is found to be ineffective because

for ions in solution. Here the interaction of orbitals of ions with the solvating

is generally quite small and the majority of contribution comes from the spinning
of unpaired electrons.

It may be emphasized here that the paramagnetic susceptibility is entirely due to

the unpaired electrons. If all the electrons are paired, the value of S is zero and thus
mm is also zero. This is due to the fact that the magnetic moment generated by the
spinning of one electron in one direction (say, a-spin) is completely balanced by
the opposite spinning electron (i.e. b-spin). In other words, the generated dipoles
have opposite polarities and are placed adjacent to each other. Thus, their effects
are mutually cancelled.
374 A Textbook of Physical Chemistry

The paramagnetic susceptibility contribution towards the molar magnetic

susceptibility can be worked out and is found to be given by
Ê m m2 ˆ
cm = NA Á 0 m ˜ (3.15.8)
Ë 3kT ¯
The value of cm varies inversely with temperature. This is to be expected since
the only factor which opposes the perfect alignment of dipoles is the thermal
energy. Larger the thermal energy (i.e. larger temperature), lesser the alignment.

3.16 TOTAL MOLAR MAGNETIC SUSCEPTIBILITY

The total molar magnetic susceptibility is the algebraic sum of molar diamagnetic
susceptibility and molar paramagnetic susceptibility, i.e. sum of Eqs (3.15.1) and
(3.15.8). Thus, we have
Ê m0 m m2 ˆ
cm = NA Á a m +
Ë 3kT ˜¯
For diamagnetic substances, mm = 0 and hence
cm = NA am (Eq. 3.15.1)
Thus, diamagnetic susceptibility is independent of temperature.

For paramagnetic substances, both the contributions are present. For such a
substance, cm is usually of the order of 10–3 –10– 4 per gram and thus the small
diamagnetic contribution (10–6 per gram) is overwhelmed. Thus, we may write
Ê mo m m2 ˆ
cm = NA Á ˜ (Eq. 3.15.8)
Ë 3kT ¯

3.17 CALCULATION OF THE NUMBER OF UNPAIRED ELECTRONS

The number of unpaired electrons in an atom, molecule or ion can be worked out
by combining Eqs (3.15.6) and (3.15.8). Thus, we have
N A m0 2 N m
{ }
2
cm = m m = A 0 2 m B S ( S + 1)
3kT 3kT

4 m B2 m0 N A
= S (S + 1)
3kT

È 4(9.274 ¥ 10-24 J T -1 ) 2 (4p ¥ 10-7 N C-2 s 2 )(6.022 ¥ 1023 mol-1 ) ˘

=Í ˙ S(S + 1)
Î 3(1.38 ¥ 10-23 J K -1 )(298 K ) ˚
= 4p (1.68 ¥ 10–9 m3 mol–1 ) S(S + 1) (3.17.1)

The molar magnetic susceptibility c m can be determined experimentally.

Knowing cm, the value of S can be obtained from Eq. (3.17.1). The value of S
thus obtained can be interpreted in terms of the number of unpaired electrons by
using Eq. (3.15.7).
 Electrical and Magnetic Properties of Molecules 375

Table 3.17.1 shows the results to be expected for cm at 298 K for various number
of unpaired electrons.

Table 3.17.1 The Values of Molar Magnetic Susceptibility at 298 K

Number of Total electron Spin magnetic Molar magnetic

unpaired spin quantum moment,mm/mB susceptibility
electrons number, S =2 S ( S + 1) cm/m3 mol–1
1 1/2 1.732 15.84 ¥ 10–9
2 2/2 2.828 42.12 ¥ 10–9
3 3/2 3.873 79.09 ¥ 10–9
4 4/2 4.899 126.61 ¥ 10–9
5 5/2 5.916 184.53 ¥ 10–9
6 6/2 6.928 252.9 0 ¥ 10–9

3.18 GOUY BALANCE METHOD TO MEASURE MAGNETIC SUSCEPTIBILITY

In the Gouy balance method, the sample whose magnetic susceptibility is required,
is taken in a tube. The tube is suspended from one arm of a balance in such a way

magnet is turned on the following two alternatives are observed.

attraction is due to the alignment of the tiny magnets generated in the magnetic

Fig. 3.18.1 Experi-

mental set up of the
Gouy balance method

experienced by the sample by considering the force experienced by the small

segment of the sample and then integrating the resultant expression from B = 0
376 A Textbook of Physical Chemistry

to B = Bmax. This force is related to the magnetic susceptibility and can be worked
out as follows.
From Eq. (3.14.2), we have
Ê Bˆ
M=c Á ˜
B Ëm ¯
0
Since M represents the magnetic moment per unit volume, we may write
Magnetic moment per unit volume of the sample
Ê Bˆ
=c Á ˜ (3.18.1)
B Ëm ¯
0
Consider a small segment of the length dz of the tube (Fig. 3.18.1). Let A be
area of cross-section of the tube. We have
Magnetic moment of the material within the volume A dz
Ê Bˆ
= c Á ˜ A dz (3.18.2)
B Ëm ¯
0

induction changes by a value of dB over the length dz, the change in potential
energy of the sample is given by
dV = – (Magnetic moment) (change in magnetic induction)
Ï Ê Bˆ ¸Ô
= – ÔÌ c ( A dz ) ˝ dB (3.18.3)
BÁ ˜
ÔÓ Ë m0 ¯ Ô˛
The force experienced by the sample is the rate of change of potential energy
with respect to z, i.e.
dV
dF = –
dz
Thus, we have
B
dF = c A dB (3.18.4)
B m0
The total force experienced by the sample when it moves from outside the

a maximum value) can be obtained by integration of Eq. (3.18.4). Thus, we have

F B = Bmax
B
F=
Ú
0
dF = Ú
B=0
cB A
m0
dB

1 B2
= c A max (3.18.5)
2 B m0
If the buoyancy correction is included, Eq. (3.18.5) becomes
2
1 Bmax
F= (c – c0 ) A (3.18.6)
2 B B m0
where c B0 is the susceptibility of air.
 Electrical and Magnetic Properties of Molecules 377

The force F is measured in terms of the masses that are added or removed
from the balance pan in order to keep the position of the sample unshifted. Thus
F = (Dm)g
Thus, knowing F, the magnetic susceptibility can be calculated by using
Eq. (3.18.5). In practice, however, one frequently compares the force of a standard
sample with that of a known sample instead of evaluating the cross-section of the

Example 3.18.1 The ion Co( NH3 )3+ has been shown from magnetic measurements to have no unpaired
6

electrons, whereas CoF63- has four unpaired electrons. Considering only the effect of unpaired
electrons, calculate the change in apparent mass of a 0.1 mol dm–3 solution of salts of these

5 000 gauss is turned on.

6 , Dm = 0 since it contains no unpaired electron. For CoF6 , we have

For Co( NH3 )3+
Solution 3-

cm = 4p(10.08 ¥ 10–9 m3 mol–1) for four unpaired electrons

Vm = 1 dm3/0.1 mol = 10–2 m3 mol–1
m0 = 4p ¥ 10–7 N C–2 s2
g = 9.806 7 m s–2
A = pr2 = 3.14 ¥ 0.0052 m2
B = 5 000 G = 0.5 T ∫ 0.5 N C–1 m–1 s
1 Ê cm ˆ ( )Ê B2 ˆ
Hence Dm = AÁ ˜
2 g ÁË Vm ˜¯ Ë m0 ¯

Ï 1 ¸ Ï 4p (10.08 ¥ 10-9 m3 mol-1 ) ¸

˝ (3.14 ¥ 0.005 m )
2 2
= Ì -2 ˝ Ì
Ó 2(9.806 7 m s ) ˛ Ó 10-2 m3 mol-1 ˛

Ï (0.5 N C-1 m -1 s) 2 ¸
¥ Ì -7 -2 2 ˝
Ó 4p ¥ 10 N C s ˛
= 1.01 ¥ 10–5 kg

Example 3.18.2 A sample of an organometallic compound was placed in a susceptibility balance. The
following data were obtained.
F = 2.47 ¥ 10–4 N; A = 1.8 ¥ 10–5 m2; B = 4 000 G
Solution Find the susceptibility of the compound.
We have
F = 2.47 ¥ 10–4 N
A = 1.8 ¥ 10–5 m2
B = 4 000 G = 0.4 T ∫ 0.4 N C–1 m–1 s
Rearranging the expression

1 Ê B2 ˆ
F= cB A Á ˜
2 Ë m0 ¯
378 A Textbook of Physical Chemistry

for cB, we get

2 F m0
cB =
AB 2
which on substituting the data gives
2(2.47 ¥ 10-4 N)(4p ¥ 10-7 N C-2 s 2 )
cB =
(1.8 ¥ 10-5 m 2 )(0.4 N C-1 m -1 s) 2
= 2.156 ¥ 10–4

REVISIONARY PROBLEMS

3.1 terms:
(i) Coulomb’s law. (ii) Dielectric constant. (iii) Permittivity of the space. (iv) Intensity

capacitor. (vii) Induced dipole moment. (viii) Polarization of the molecule in the

polarizabilities.
(Hint: See Annexure at the end of the chapter.)
3.2 Deduce the following:
(i) 1 esu (or stat coulomb) = 1 dyn1/2 cm = 1 g1/2 cm3/2 s–1
(ii) 1 C = 1 A s
(iii) D = e/e0
(iv) 1 C = 2.997 9 ¥ 109 stat C
(v) The unit of volt is erg (esu)–1 or J C–1
(vi) 1 V = 1 kg m2 s–2 C–1
(vii) 1 stat V = 1 g1/2 cm–1/2 s–1
(viii) 1 unit of E = dyn (esu)–1 ∫ 1 erg cm–1 esu–1 ∫ 1 (stat V) cm–1
or 1 unit of E = 1 N C –1 = 1 N J–1 V = 1 V m–1
(ix) 1 stat V = 300 V
(x) The unit of dipole moment is esu cm or C m
(xi) 1 D = 3.338 ¥ 10–30 C m
(xii) The unit of polarizability is cm3 or C2 m N–1
(xiii) The unit of a / 4 pe0 is m3
(Hint: See Annexure I at the end of this chapter.)
3.3 Derive the Clausius-Mosottii equation:
(e / e 0 ) - 1 M 1
= N a
(e / e 0 ) + 2 r 3e 0 A d
Explain, why the above equation is applicable for nonpolar molecules and not for
polar molecules.
3.4 (a)Debye equation is
(e / e 0 ) - 1 M 1 Ê p2 ˆ
Pm = = NA Á a d +
(e / e 0 ) + 2 r 3e 0 Ë 3kT ˜¯
Explain, the nature of plots of P m versus 1/T for (i) polar molecules and
(ii) nonpolar molecules.
 Electrical and Magnetic Properties of Molecules 379

(b) Debye equation can be used to determine the dipole moment for molecules
in gaseous system, whereas it cannot be used as such for molecules in condensed
system. Explain.
(c) To determine dipole moment of molecules in condensed system, it is preferable
to plot P2• versus 1/ T, where P2•
dilution.
(d) The molar polarization of a polar molecule varies with temperature whereas
that of a nonpolar molecules is independent of temperature. Explain, why it is so.
3.5 Explain, how the molar polarization varies with the frequency of an electrostatic

3.6 Under what conditions, does the Maxwell relation D = n2 hold good? Explain why
for polar molecules D π n2.
3.7 What is molar refraction? Show that it is given by

n2 - 1 M NA
Rm = = a
n2 + 2 r 3e 0 e
3.8 Derive the relation
p/C m = 4.273 ¥ 10–29 {(Pm – Rm)/m3 mol–1}1/2 (T /K)1/2
3.9 Explain, how the dipole moment of a diatomic molecule determines its per cent
ionic character.
3.10 What do you understand by the terms bond moments and group moments? How
does the dipole moment of a diatomic molecule or bond moment determine its per
cent ionic character?
3.11 Show that the vector addition of two moments p1 and p2 inclined at an angle q is
given by the relation
p2 = p21 + p22 + 2p1 p2 cos q
3.12 The dipole moment of the following molecules is zero. What do you conclude about
their geometry?
CO2, CS2, HgCl2, CH4, SF6, Ni(CO)4
3.13 (a) The magnetic force on a moving charged particle is known as the Lorentz force
and is given by
F = Qu B
Show that the unit of magnetic induction B is given by
1 T = 1 kg s–1 C –1
(b) Show that 1 T = 104 G
(c)Show that 1 oersted = 1 A m–1/4p ¥ 10–3
(Hint: See Annexure I)
d produced by an electric current I
a long straight wire is

B = ÊÁ 0 ˆ˜
m I
Ë 2p ¯ d
Show that m0, the permeability of vacuum, has the unit of N C –2 s2.
380 A Textbook of Physical Chemistry

(b) Making use of the expression of B given in Part (a) show that the force between
two electric currents in two parallel rectilinear conductor of length l separated by
a distance d in vacuum is given by

F = ÊÁ 0 ˆ˜ 1 2
m II l
Ë 2p ¯ d
F given in
Part (b).
(d) Show that m0 = 4p ¥ 10–7 T m A–1
(e) Show that product of e0 and m0 is equal to 1/c2.
H and magnetic induction
B? How are they related to each other? What are the units of H in Gaussian and
SI systems?
B affected in a substance? Show that the magnetic
susceptibility is unitless.

magnetic susceptibility and intensity of magnetization.

(Hint: See Annexure I)
3.18 Show that the value of Bohr magneton is given by 9.274 1 ¥ 10–24 J T–1.
3.19 How are paramagnetism and diamagnetism explained from the molecular point of
view?
3.20 The paramagnetic susceptibility contribution towards the molar magnetic
susceptibility is given by
Ê m0 m m2 ˆ
cm = NA Á
Ë 3kT ˜¯
How does the above relation help in computing the number of unpaired electrons
in a molecule of a substance?

NUMERICAL PROBLEMS

nH2n+2 was found to be 1.38 and its

density is 0.66 g cm–3. Given are the molar refractions of H and C as 1.1 and 2.42
cm3 mol–1, respectively. Calculate the molecular formula of the compound.
[Ans. C5H12]
3.2 Given the following data
CH3CH2CH2CH3 Rm = 20.6 cm3 mol–1
CH3CH2OH Rm = 12.9 cm3 mol–1
CH3OH Rm = 8.3 cm3 mol–1
Calculate Rm for CH3CH2CH2CH2OH. [Ans. 22.1 cm3 mol–1]
3.3 Given the molar refractions: CH4 = 6.82 cm3 mol–1; C2H6 = 11.44 cm3 mol–1, C3H8 =
16.06 cm3 mol–1, CH3CH2CH2OH = 17.58 cm3 mol–1, calculate the molar refraction
of glycol,HOCH2CH2OH, and its index of refraction. The density of glycol is
1.115 g cm–3. [Ans. 14.48 cm3 mol–1, 1.43]
 Electrical and Magnetic Properties of Molecules 381

3.4 Calculate the dipole moment of water in the vapour state and estimate the dipole
moment of each OH bond if the angle between these bonds is 105º. The values of
the molar polarization P with temperature are tabulated below.
T/K 384.3 420.1 444.7 484.1 522.0
Pm/cm3 mol–1 57.4 53.6 50.7 46.8 43.4
[Ans. pH 2 O = 1.85 D, pOH = 1.52 D]

3.5 The dipole moment of SO2 is 1.61 D, the length of each S—O bond is 0.145 nm
and the bonds have approximately 25% ionic character. Calculate the bond angle
in SO2 molecule. [Ans. q = 124.88º]
3.6 The molar refraction for oxygen in an ether group (ROR) is 1.643 cm3 mol–1. It is
6.818 cm3 mol–1 for methane and 13.279 cm3 mol–1 for dimethyl ether. Calculate
the value for diethyl ether. [Ans. 22.915 cm3 mol–1]
3.7 A liquid of molar mass 112.0 g mol–1 has a refractive index 1.347, dielectric constant
4.285 and density 1.108 g cm–3 at 25°C. What are the values of its molar refraction
and molar polarization? [Ans. 21.6 cm3 mol–1, 52.85 cm3 mol–1]
3.8 The density of ethyl alcohol at 20 ºC is 0.789 g cm–3 while that of methyl alcohol
is 0.792 g cm–3. Assuming ideal behaviour, calculate the index of refraction of a
solution containing 50% by mass of each component.
Given are the molar refraction contributions: C; 2.418 cm3 mol–1: H; 1.100 cm3
mol–1: O in OH group; 1.525 cm3 mol–1. [Ans. 1.349]
3.9 The molar polarization of a certain vapour is found to obey the equation
P/cm3 mol–1 = 60 + 20.5 K/T
Assuming ideal behaviour, calculate (i) molar polarization, (ii) dipole moment, (iii)
index of refraction, and (iv) dielectric constant of the vapour at STP.
[Ans. 60.08 cm3 mol–1, 0.058 D, 1.004, 1.008]
3.10 Calculate the dipole moment of diethyl ether from the following data for its solution
in cyclohexane at 20 ºC.
x2 0.123 25 0.088 54 0.047 2 0.000 0
er 2.246 2.178 2.109 2.033
r/g cm–3 0.769 1 0.772 0 0.775 1 0.778 4
The index of refraction and density of pure diethyl ether are 1.352 and 0.710 g
cm–3, respectively.
3.11 Calculate the dipole moment and the distortion polarizability of BrF5 from the
following data for the dielectric constant of the vapour. Assume ideal behaviour for
the calculation of molar volume. Given: Vm = 22 414 cm3 mol–1 at 273.15 K and
1 atm.
T/K 345.6 374.9 402.4 430.8
er 1.006 32 1.005 52 1.004 91 1.004 38

[Hint: V m (273 K, 1 atm) = 22 414 cm 3 mol –1 , calculate V m (T, 1 atm) =

(22 414 cm3 mol–1) ¥ (T/273 K).]
3.12 The magnetic susceptibility c for a sample at 275 K is found to be 4.26 ¥ 10–4. If
the magnetic moment is 1.91 ¥ 10–23 m2 A, the molar mass is 2.055 kg mol–1, and
the density is 0.971 kg dm–3, estimate the value of magnetic susceptibility, am.
382 A Textbook of Physical Chemistry

3.13 A 0.1 mol dm–3 solution of an iron coordination compound was placed in a tube of
area of cross-section 1 cm2 and suspended in a Gouy balance at 25 ºC. A magnetic

the solvent was 18.4 mg. The diamagnetic correction for the compound itself was
– 2.5 ¥ 10–9 m3. Calculate the number of unpaired electrons per Fe atom. Assume
complete orbital moment quenching. [Ans. 5 electrons]
(Hint: Evaluate cB using Eq. (3.18.6), add |cdia | and then consult Table 3.17.1.)
3.14 Calculate cm for benzene and benzoic acid by adding the appropriate atomic
and bond diamagnetic susceptibilities, and compare with the observed values of
– 54.8 ¥ 10–12 m3 mol–1 and – 70.3 ¥ 10–12 m3 mol–1, respectively.
3.15 A 0.010 27 mol dm–3 solution of KMnO4 had an apparent mass of 9.805 9 g in a

Calculate the number of unpaired electrons for Mn(VII). [Ans. n = 0]

3.16 Explain qualitatively the following facts.
(a) At very high temperatures Pm(HCl) > Pm (HBr) > Pm (HI)
(b) At low temperatures Pm (HCl) < Pm (HBr) < Pm (HI)
(Hint:
3.17 The permittivity of gaseous sulphur dioxide at 1 atm as a function of temperature
are as follows.
T/K 267.6 297.2 336.9 443.8
1012e/C 2 N–1 m–2 8.942 0 8.926 1 8.902 7 8.882 5
Estimate the dipole moment of SO2. Assume ideal behaviour. Given: e0 = 8.854 2
¥ 10–12 C2 N–1 m–2. [Ans. 1.91 D]
3.18 The permittivity of gaseous sulphur dioxide at 1 atm as a function of temperature
are as follows.
T/K 384.3 420.1 444.7 484.1 522.0
1012e/C 2 N –1m–2 8.902 5 8.895 4 8.895 4 8.885 5 8.881 0

Estimate the dipole moment of H2O. Assume ideal behaviour. Given: e0 = 8.8542
¥ 10–12 C2 N–1 m–2. [Ans. 1.96 D]
3.19 The permittivity of gaseous BrF5 at 1 atm as a function of temperature are as follows.
T/K 345.6 374.2 402.4 430.8
1012e/C2 N–1m–2 8.910 2 8.903 1 8.897 7 8.893 0
Estimate the dipole moment of BrF5. Assume ideal behaviour. Given: e0 = 8.854 2
¥ 10–12 C2 N–1 m–2. [Ans. 1.50 D]
ANNEXURE I Electrostatic and Magnetic Fields

A FEW DEFINITIONS REGARDING THE ELECTROSTATIC FIELD

Coulomb’s Law CGS-esu units

Q1 Q2 r

Q1Q2
F=
Dr 2
D
D Q1 Q2 F

Q1 Q2 F

(1 esu ) 2
1 cm 2
1/2 1/2 1/2 3/2

SI system

ampere

2 ¥ 10

I = dQ/dt
Q = I dt
coulomb

¥
 A Textbook of Physical Chemistry

Q1Q2
F=K
r2
K
1
K=
4pe
e e0
¥ 10 2
N
¥ 10 2 2

Relationship
between (1 C2 )
stat Coulomb F=
4p(8.854 ¥ 10 C2 N -1 m -2 )(1 m) 2
-12
and Coulomb
¥ 10 N

F ¥ 10
F r
2
(1 C )
¥ 10
(100 cm) 2
¥ 10 1/2

¥ 10 ¥ 10
Relationship
between D and e Fvacuum Q1Q2 / r 2
CGS-esu units = =D
Fmedium Q1Q2 / Dr 2
Fvacuum Q Q /(4pe 0 )r 2 e
SI units = 1 2 =
Fmedium Q1Q2 /(4pe )r 2 e0

e
D= =e
e0
e
Intensity of
Electric Field The intensity of electric

F
E=
Q
Q r
Q
CGS-esu units E=
Dr 2
 Q
SI units E=
(4pe )r 2
F E

E
Q Q
Q r

Ê Electrical field intensityˆ Ê The total area of ˆ

Á at a point at a distance ˜ Á cross -section at ˜
ÁË r from the charge ˜¯ ÁË the distance r ˜¯

Ê Q ˆ pQ
CGS-esu units ÁË 2 ˜¯ pr2
Dr D
Ê Q ˆ Q
SI units ÁË (4pe ) r 2 ˜¯ pr2
e
D
e /e0
e Electric field in vacuum
D= =
e0 Electric field in the given medium

Electrical Potential
the amount

V we Ú F dr
•
r Q
r
Q
Ú Dr
Q
CGS-esu units V 2 dr =
•
Dr
r
Q Q
SI units V Ú
•
(4pe)r 2 dr =
(4pe)r

CGS-esu units dV Q dr E dr
Dr 2
Q
SI units dV dr E dr
(4pe )r 2
 A Textbook of Physical Chemistry

dV
E
dr

Units of E and V
F
E =
Q
V E dr

CGS-esu units
E
V

1/2 3/2
1/2 1/2

E
E∫ ∫ ∫
SI units
E
V

E
E∫ ∫ ∫ ∫
The Relationship
between stat V 1J
and V 1C

107 ergs
{(4.803 ¥ 10-10 )/(1.602 ¥ 10-19 )}esu

1 erg Ê 4.803 ¥ 10-10 ˆ Ê 1 ˆ

= Á ˜Á ˜
1 esu Ë 1.602 ¥ 10-19 ¯ Ë 107 ¯

Capacitance of
the Parallel Plate A
Capacitor V
Q Q
 d

Fig. AI.1 A capacitor

Q
s=
A

CGS-esu units
E
pQ ps
E= =
DA D
V

= ÊÁ
Q Q ˆ
V= =
Dd Ë Dd 2 ˜¯
C

= DÊ
Q Q Q A ˆ
C= = =
V Ed (4pQ / DA)d Ë 4pd ¯

A
C0 =
pd
SI units
Q s
E= =
eA e
Q È Q ˘
V= =Í ˙ =
(4pe )d Î (4pe )d 2 ˚

= e ÊÁ ˆ˜
Q Q A
C= =
Ed (Q / e A)d Ë d¯

C0 = e0 ÊÁ ˆ˜
A
Ëd¯

e C
D= =
e 0 C0

1C 2 2
1 kg m 2 s -2 C-1
388 A Textbook of Physical Chemistry

A FEW DEFINITIONS REGARDING MAGNETIC FIELD

The Magnetic
Field

Lorentz
force Q u
B F
Qu B
Gaussian system F=
c
SI units F = QuB
Q u c
F B

∫ ∫ 1/2 3/2
∫ 1/2

Q u F
2
B

∫ ∫
B
B
x y
z
u B F
Relationship
between Tesla and
Guass Units F

F = 1 N ∫ 10

(2.997 9 ¥ 109 esu )(102 cm s -1 ) ( B)

10
(2.997 9 ¥ 1010 cm s -1 )
B = 10 = 10

Magnetic Field
Produced by an I I
Electric Current
 I
B=k
d
k k

2 m0
Gaussian system k=
c
m0
SI units k=
2p
m0 m0
B cd Bcd
Gaussian system 2m0 = =
I Q /t

(g1/ 2 cm -1/ 2 s -1 )(cm s -1 )(cm)

=
(g1/ 2 cm3 / 2 s -1 ) (s)

m0
m0 Bd (kg s -1 C-1 ) (m)
SI system = =
2p I C s -1
2

2
Henry per metre
A

Force between I1 I2
Two Electric l
Currents

Gaussian system
Ê Q2u ˆ
F= Á
Ë c ˜¯ 1
B =
Q2 (l t )
c {B1 =
c } {
(Q2 t ) l
B1 }
Ê I 2l ˆ
= Á ˜ B1
Ë c ¯
B1
Ê I 2l ˆ 2 I
F = Á ˜ ÊÁ 1 ˆ˜ = 12 2
2I I l
Ë c ¯ Ëc d¯ c d
SI units F Q 2 u B1 Q2 l /t B1 Q2 /t l B1
= I 2 l B1
B1

I2 l Á 0 1 ˆ˜ = Á 0 ˆ˜ 1 2
Êm I Êm II l
F
Ë 2p d ¯ Ë 2p ¯ d
 A Textbook of Physical Chemistry

¥ 10

m0
m0 = 2p ¥ 10 p ¥ 10 2

p ¥ 10
Product of e0 and
m0
e0 ¥ 10 2
N
m0 p ¥ 10 2

e 0 m0 ¥ 10 2
N p ¥ 10 2

¥ 10 2

1 1
= = 2
(2.9979 ¥ 108 m s -1 ) 2 c
c

The Magnetic Field B

Strength H

Gaussian system B = H
H
SI Units B = m0H
m0 H

unit of B N C-1 m -1 s
H= =
unit of m0 N C-2 s 2
Relationship
between Oersted H
and A m–1
B 10-4 T 1
= =
m0 4p ¥ 10-7 T m A -1 4p ¥ 10-3
1
4p ¥ 10-3
ANNEXURE II Expression of Orientation Polarizability

p q
E
V pE q
†
dw q dq dj

V/kT
dN = Ae dw = Ae pE q /kT
q dq dj

w
dp p q N

p q AepE q /kT
q dq dj

p 2p

Ú dpcontribution = Ap Ú e cos q sin q dq Ú dj

pE cos q / kt

0 0

p = Ú dpcontribution Ú dN
p 2p
Ap Ú cos q e pE cosq / kT sin q dq Ú dj
0 0
= p 2p
A Ú e pE cosq / kT sin q dq Ú dj
0 0

dq
sin q dj
† y
q q dj

x
A Textbook of Physical Chemistry

x = pE/kT y q y q dq

+1
p Ú ye xy dy
-1
pav = +1

Úe
xy
dy
-1

+1 +1 +1 xy +1 +1
e xy e e xy e xy
Ú ye xy dy = y
x -1
- Ú x dy = y x -1
-
x2 -1
-1 -1

1 ( x -x ) 1 ( x -x )
= e +e - 2 e -e
x x
+1 +1
e xy 1
Ú e dy =
xy
= (e x - e - x )
-1
x -1 x

Ê e x + e- x 1 ˆ
p = p Á x - x - ˜ = p coth x -
Ëe -e x¯
1
x ( )
1
L x x-
x
x pE/kT

1 1 1 1
x= � = (1 - x 2 / 3) -1 � (1 + x 2 / 3)
tanh x x - x / 3 x
3
x

È 1 Ê x2 ˆ 1 ˘
pav = p Í ÁË1 + ˜¯ - ˙ = p
Îx 3 x˚
x
=
p2
3 3kT
E ()
p2/3kT p E
 4 Molecular Spectroscopy

4.1 INTRODUCTION

Absorption and The subject of molecular spectroscopy deals with the interaction of electromagnetic
Emission Spectra radiations with the matter. The absorption (or emission) of electromagnetic
radiations by a molecule is highly selective and follows the relation
D E = hn = E2 - E1 (4.1.1)
where n is the frequency of radiation absorbed, and E1 and E2 are the lower and
higher energies of molecular levels, respectively. Thus, the molecule is excited
from a lower molecular energy level to the higher one when it absorbs radiation.
In emission of radiation, the reverse of the above is observed.

It is possible to correlate the experimentally observed data on absorption or

emission with the nature of molecular changes which are responsible for the
absorption or emission. With the help of these correlations, much useful information

molecule can be deduced. Before considering such correlations, a brief discussion

on different types of molecular energies is in order.

Different Types A molecule possesses many forms of energies. These are:

of Molecular
Energies ∑ Translational energy ; by virtue of its translatory motion.
∑ Rotational energy ; by virtue of bodily rotation of the molecule about its
centre of gravity.
∑ Vibrational energy ; by virtue of the periodic displacement of its atoms
from their equilibrium positions.
∑ Electronic energy ; by virtue of different electronic arrangements in the
molecule.
It was seen in Chapters 1 and 2 that the energies listed above are all quantized,
i.e. a molecule cannot have any arbitrary energies of rotation, vibration or electronic,
but can exist only in the allowed energy levels. According to the Born-Oppenheimer
approximation, the energies listed above can be treated separately and we can write
the total energy of the molecule as
Etotal = Etrans + Erot + Evib + Ee1
where Etrans, Erot, Evib and Ee1 represent translational, rotational, vibrational and
electronic energies, respectively. In general
Ee1 Evib Erot Etrans
394 A Textbook of Physical Chemistry

The approximate difference between the two levels of any one of these energies
may be worked out from the following expressions.
Ê h2 ˆ
Etrans = n2 Á
Ë 8ml 2 ˜¯
where n is the translational quantum number and has integral values 1, 2, 3, 4, ….
h2
Erot = J (J + 1)
8p 2 I
where J is the rotational quantum number. The permitted values of J are 0, 1, 2, 3, ….

Evib = Ê u + ˆ
1 h kf
Ë 2 ¯ 2p m
where u is the vibrational quantum number and possesses values of 0, 1, 2, 3, ….

2p 2 e 4 Z 2
Ee1 = –
(4pe 0 ) 2 n 2 h 2
where n is the electronic quantum number and has values 1, 2, 3, 4, ….
Exclusion of At the very outset, an important conclusion regarding the energy difference between
Translational the two translational levels may be stated. The energy difference between the
Spectroscopy two successive translational levels is of the order of 10 – 60 J mol-1 for a normal
molecule moving in a container of ordinary size. This separation is too small to
be determined experimentally. It is for this reason that the translational energy is
considered to be continuous and thus the corresponding translational spectroscopy
to be observed is completely excluded.

Order of Energy The order of energy difference between the two successive energy levels for other
Difference motions along with the approximate wavelengths of radiation to be employed for
the required transitions are shown in Table 4.1.1.

Table 4.1.1 Energy Difference between the Two Successive Energy Levels
Motion D E/ J l /m
molecule- 1
Rotation 10- 23 10-2
Vibration 10-21 10- 4
Electronic 10- 19 10 - 6

From Table 4.1.1, it follows that the separation between the two electronic
energy levels are larger than that between the two vibrational energy levels, which
in turn, is larger than that between the two rotational levels.
Diagrammatic It is customary to show the different energy separations in a diatomic molecule by
Representation of a diagram shown in Fig. 4.1.1. Each stable electronic level exhibits a minimum
Energy Levels in the potential energy diagram. The upper level relative to the ground level has a
smaller depth which lies at a larger internuclear distance. In the minimum valley,
the different vibrational and rotational levels are shown by straight lines. The
vibrational energy levels are almost equidistant (strictly true only for a harmonic
 Molecular Spectroscopy 395

vibration) and the energy separation between the two successive rotational levels

Fig. 4.1.1 A schematic

representation of
various energy levels

In Fig. 4.1.1 only a few energy levels have been shown. In fact, a very large
number of vibrational levels going up to the dissociation limit exist for each
electronic level. Similarly, a series of rotational levels exist with each of the
vibrational level.
Different Types of Transitions between rotational levels belonging to a particular vibration level are
Spectroscopy observed in the microwave region of the electromagnetic spectrum (l 10 -2 to
10- 4 m); these are called pure rotational spectra. Transitions between vibrational
levels within the same electronic state lie in the infrared region (l 10-4 to 10-6 m)
and are responsible to exhibit pure vibrational and vibrational-rotational spectra.
Finally, transitions between electronic levels give rise to the spectra in the visible
or ultraviolet region (l 10 - 6 to 10 -9 m) and are called electronic spectra.

In addition to the various spectra listed above, there exist two other important
spectra which lie in the radiofrequency region of the spectrum (10 m to 1 cm
wavelength). These are connected with the reversal of spin of a nucleus and that of
an electron, and are known as nuclear magnetic resonance spectrum and electron-
spin resonance spectrum, respectively.
396 A Textbook of Physical Chemistry

Lastly, we may mention another type of spectroscopy which is known as Raman

spectroscopy. This yields information similar to that obtained in microwave and
infrared regions. The incident light used in this spectroscopy lies in the visible
region. Figure 4.1.2 depicts a schematic diagram of the various electromagnetic
spectra listed.
In the following sections, we describe the different types of spectroscopy in the
increasing magnitude of energy of absorbed or emitted electromagnetic radiations.

6
n/s 10 108 1010 1012 1014 1016 1018
micro- ultra-
radio wave

visible
violet
far near
X-rays

infrared
l/m
102 1 10–2 10–4 10–6 10–8 10–10

( )
NMR ESR Raman
( ) ( )
Fig. 4.1.2 Schematic rotation electronic
diagram of ( )
vibration
electromagnetic spectra

The Absorption The absorption of microwave, infrared, visible, and ultra-violet radiations by a
of Radiation gaseous or liquid sample is often expressed by the Beer-Lambert law:
I
log = - e lc (4.1.2)
I0
where c and l are the concentration and path length of the sample, I0 and I are the
intensities of incident and transmitted light, and e
which has a characteristic value for a particular absorption of a molecule.

The Probability of The absorption of a photon of frequency n by a molecule causes a transition

Transition from the lower energy state m to the higher energy state n provided the following
and Selection
Rule(s) En - Em = hn
The above transition is caused by the interaction of the oscillating electric

mechanical treatment shows that the probability of absorption or emission between

the two stationary states m and n is proportional to the square of transition moment
integral
pmn = Ú y m* p yn dt (4.1.3)
 Molecular Spectroscopy 397

where p is the electric dipole-moment operator and is given by

p = Â i Qi ri (4.1.4)
The integration in Eq. (4.1.3) is carried over the full range of electronic and
nuclear coordinates. Of many possible transitions, only those transitions are allowed
for which pmn is nonzero. The transitions having pmn = 0 are forbidden. The condi-
tion(s) stating the difference of quantum numbers of involved stationary states in
a transition is (are) known as selection rule(s).

Einstein Absorption The actual expression of the probability of absorption of radiation is known as
Coefficient and is given by
8p 2
Bmn = pmn (4.1.5)
h2
Bmn e . Since an
actual absorption is spread over a region of wavelength, the Bmn is related to the
∼
integral intensity Ú e dv through the expression

∼
∼ hN A n 0
Ú e dv = (2.303)(103 )c 2
B mn (4.1.6)

∼
where c is the speed of radiation and v0 is the wavenumber of a band maximum.

Oscillator Strength It is conventional to take as the ideal case of the transition of electronic mass
between u = 0 to u = 1 states of a harmonic oscillator. For this, Bmn is given by
pe 2
B mn = (4.1.7)
(hmv0 )
and the transition probability is given by

(Ú e dv) ∼
ideal
=
p(e 2 / 4pe 0 ) N A
(2.303)(103 )mc 2
= 2.31 ¥ 106 m mol–1 (4.1.8)

The oscillator strength f

and ideal transition probabilities, such that

Ê ∼ˆ
∼
( Ú e dv)actual
f= ∼
( Ú e dv)ideal
Ú
= (4.33 ¥ 10 - 7 mol m–1) Ë e dv¯
actual
(4.1.9)

The area under an absorption band gives either Bmn through Eq. (4.1.6) or f
through Eq. (4.1.9).
Qualitative From the expression of transition moment (Eq. 4.1.3) often some very important
Derivation of statements can be deduced qualitatively regarding the possibility of an induced
Selection Rule for transition by the radiation. For an illustration, the system of particle in a box is
Particle in a Box considered here. Let the particle be an electron and let the balancing positive charge
398 A Textbook of Physical Chemistry

be located at the mid-point of the box. A few wave functions of the present system
are shown in Fig. 4.1.3. The symmetry of the wave functions with respect to the
centre of the box are also depicted in Fig. 4.1.3. These wave functions may be

Symmetric (or even) functions where y (y) = y (- y)

Antisymmetric (or odd) functions where y ( y) = - y (- y)
From Fig. 4.1.3, it may be concluded that the functions y1, y3, y5, …, etc., are
symmetric functions whereas the functions y2, y4, y6, …, etc., are antisymmetric
functions.
5py Symmetric
n = 5; y5 = cos
l (even)

4py
n = 4; y4 = sin Antisymmetric
l (odd)

3py
n = 3; y3 = cos Symmetric
l (even)

Fig. 4.1.3 Symmetric

2py
and antisymmetric n = 2; y2 = sin Antisymmetric
l (odd)
wave functions of
particle in a box and 1py
n = 1; y1 = cos Symmetric
some of the allowed –y +y (even)
l
transitions –l /2 0 l/2

The dipole moment of the system is given by

p = ey
where y is the distance of the electron from the centre of the box. For an observable
transition from a state n to a state m, we must have
+l / 2
pmn = Ú y n (ey) ym dy π 0 (4.1.10)
-l / 2
Without actually carrying out the above integration, we can derive the
selection rules by studying the symmetry of the three functions yn, ym and (ey).
If the product of these three functions is an odd function, the result of the integral
from - l/2 to 0 will exactly cancel the contribution from 0 to l/2, and thus pnm
will be equal to zero. The dipole moment operator is an odd function and thus a
transition from an odd function to an odd function or from an even function to an
even function will lead to pnm equal to zero and hence such transitions will not be
 Molecular Spectroscopy 399

permissible. However, for a transition from an even function to an odd function

or vice versa, the expression y n(ey)ym will be even and thus pnm will be nonzero.
Consequently, such a transition will be allowed.
The above guidelines may be summarized as follows.
yeven Æ yodd
allowed
yodd Æ yeven
yeven Æ yeven
forbidden
yodd Æ yodd
Hence, the selection rule for a particle in a box is D n = ±1, ±3, ± 5, …. Some
of the allowed transitions are shown in Fig. 4.1.3.
Quantitative The coordinate system of particle in a box discussed in Section 1.4 is related to
Derivation of that shown in Fig. 4.1.3 by the relation
Selection Rule for l
Particle in a Box y=x–
2
Hence, the dipole moment operator is

p = ey = e ÊÁ x - ˆ˜
l
Ë 2¯
The wave functions are given by the expression
2 np x
yn = sin
l l
The expression of transition moment is
l
2e Ê np x ˆ Ê mp x ˆ Ê
x - ˆ dx
l
pnm = Ú
l 0 Ë
sin
l ¯ Ë
sin
l ¯ Ë 2¯
Since the functions are orthogonal, the integral arising from the l/2 term will be
zero and thus we may write pnm as
l
2e Ê np x ˆ Ê mp x ˆ
l Ú0 Ë
pnm = sin sin (x)dx
l ¯Ë l ¯
Making use of relations
1
sin q sin j = [cos (q - j) - cos (q + j)]
2
1 x
and Úx cos ax dx =
a2
cos ax +
a
sin ax

el È cos[(n - m)p] - 1 cos[(n + m)p] - 1˘

we get pnm = Í - ˙
p2 Î ( n - m) 2 ( n + m) 2 ˚
where the sine terms have been ignored since n - m and n + m are integers. If
n and m are both even numbers or both odd numbers, then n - m and n + m are
400 A Textbook of Physical Chemistry

even numbers and hence these will lead to pnm = 0; consequently, such transitions
will be forbidden, If n is even and m is odd or vice versa, then n - m and n + m
are odd and thus pnm is nonzero; consequently, such transitions are allowed. Thus,
the selection rule in the present case is that n - m should be an odd number, i.e.
Dn = ±1, ±3, ±5, ….

Selection Rule The harmonic-oscillator wave functions are given by

for a Harmonic 1/ 2
Ê a ˆ
Oscillator yn = Á n exp(- y 2/2) Hn; where y = ax (Eq. 1.5.11)
Ë 2 n! p ˜¯
From this, we can write
1/ 2
Ê a ˆ
yy n = Á n exp(- y 2/2) ( yH n)
Ë 2 n! p ˜¯
Since yHn = nHn - 1 + (1/2) Hn + 1,we get
1/ 2
Ê a ˆ
exp(- y 2/2) ÈÍnH n -1 + H n +1 ˙˘
1
yy n = Á n
Ë 2 n! p ˜¯ Î 2 ˚
Since y = a x, we can write the above expression as
1/ 2
n 1/ 2 Ê a ˆ
xyn = Ê ˆ Á n-1 exp(- y 2/2) Hn - 1
Ë 2a ¯ Ë 2 (n - 1)! p ˜¯
1/ 2
n + 1ˆ 1/ 2
Ê a ˆ
+ Ê ÁË 2n+1 (n + 1)! p ˜¯ exp(- y 2/2)Hn + 1
Ë 2a ¯
1/ 2 1/ 2
= ÊÁ n ˆ˜ y n - 1 + ÊÁ n + 1ˆ˜ y n + 1
Ë 2a ¯ Ë 2a ¯
With this, the expression of transition moment integral ·y m |qx| yn Ò becomes
n 1/ 2 n + 1ˆ 1/ 2
q · ym | x| yn Ò = q y m Ê ˆ y n -1 + Ê y n +1
Ë 2a ¯ Ë 2a ¯

ÈÊ n ˆ 1/ 2 Ê n + 1ˆ ·y | y Ò ˘
1/ 2
= q ÍÁË ˜¯ ·y m | y n -1 Ò + ÁË ˜ n +1 ˙
2a ¯
m
Î 2a ˚
Using the orthonormality of Hermite polynomials, we can write
1/ 2 1/ 2
·ym | x| ynÒ = ÊÁ n ˆ˜ dm, n - 1 + ÊÁ n + 1ˆ˜ dm, n + 1
Ë 2a ¯ Ë 2a ¯
where d stands for Kronecker delta (d mn = 1 if m = n otherwise zero).
Thus, the allowed electric-dipole transitions for the harmonic oscillator involve
a change of ± 1 in the quantum number.
The selection rule for a rigid rotator can be derived similarly and are found
to be DJ = ± 1, respectively, (See page 450).
 Molecular Spectroscopy 401

4.2 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY

The nuclear magnetic resonance spectroscopy (NMR) which lies in the radiofre-
quency region of electromagnetic radiation is found to be very useful for the
structural elucidation of molecules, especially in the domain of organic molecules.
We now discuss the various aspects of NMR spectroscopy.
Nature of the The nuclear magnetic resonance spectroscopy basically deals with the interaction
Nucleus
protons and neutrons. A proton carries a unit positive charge whereas the neutron
is an uncharged entity. Both these particles spin around their own axis with the
same spin quantum number 1/2.
The value of angular momentum associated with each of these spins is
1Ê1 ˆ Ê h ˆ 3Ê h ˆ
+1 =
Ë
2 2 ¯ Ë 2p ¯ 2 Ë 2p ¯
Each nucleus possesses a total spin quantum number which results simply
from the vector addition of the spins of its protons and neutrons. Some empirical
rules based on experimental facts regarding the total spin quantum number are
available. These are:
∑ Nuclei having both charge number and mass number even (i.e. having both
protons and neutrons even in number) have zero spin quantum number.
Examples include 42 He , 126 C and 168 O .
∑ Nuclei having odd charge number and even mass number (i.e. both protons
and neutrons are odd in nature) have integral spin quantum number. Examples
include 2H, 14N (spin = 1) and 10B (spin = 3).
∑ Nuclei with odd mass number have half-integral spin. Examples include 1H,
15
N (spin = 1/2), 17O (spin = 5/2), 19F (spin = 1/2) and 35C1 (spin = 3/2).
Angular The magnitude of angular momentum vector L associated with the spinning of a
Momentum of the nucleus having total spin quantum number I is given by
Nucleus h
L= I ( I +1) (4.2.1)
2p
According to quantum mechanics, the angular momentum vector cannot have any
arbitrary direction but can point only along certain directions (space quantization
of the angular momentum vector). These directions are such that the component
of angular momentum vector along a certain reference axis, known as the z-axis,
has only quantized values. This reference axis is usually taken to be the direction

momentum along the z-axis are given by the expression mI (h/2p), where mI can
take the following values:
mI = I, (I - 1), …, - (I - 1), - I (4.2.2)
There are a total of (2I + 1) components in each case. These components are
normally degenerate (i.e. all of them have same energy). This degeneracy is lifted

basically due to the lifting up of degeneracy of these energy levels.

402 A Textbook of Physical Chemistry

Magnetic Moment The spinning of a nucleus is equivalent to the circulation of a positive charge
of the Nucleus around the axis of spinning. This, in turn, produces a tiny magnet placed along
the spin axis. The magnetic moment of the generated magnet can be calculated
with the help of Ampere’s law:
mm = i A (4.2.3)
where i is the current circulating in the coil per unit time, A is the area of cross-
section of the coil.
If r is the radius of the coil and u is the velocity with which charge is spinning,
then
i = (Number of revolutions per unit time) ¥ (Positive charge on the
nucleus)
u
= (e)
2pr
and A = pr 2
Substituting these expressions in Eq. (4.2.3), we get
ue ˆ
mm = i A = Ê (pr 2)
Ë 2pr ¯

= L ÊÁ
e ˆ
= (mpu r) ÊÁ
e e ˆ
= (ur) ˜ (4.2.4)
2 Ë p¯
2 m Ë p ˜¯
2 m
Thus, the value of the magnetic momentum vector is (e/2mp) times the value
of the angular momentum vector. Since the charge on the nucleus is positive, it
follows from Eq. (4.2.4) that both angular and magnetic momentum vectors point
towards the same direction.
Experimentally, it is found that Eq. (4.2.4) is not applicable as such but requires
the addition of one more factor, g. This factor is known as the nuclear splitting
factor or simply the nuclear g value. The numerical value of g cannot be calculated
theoretically and thus is determined from the experimental data. With this,
Eq. (4.2.4) becomes

m m = g ÊÁ
e ˆ
L (4.2.5)
Ë 2mp ˜¯
Substituting the expression of L from Eq. (4.2.1) in Eq. (4.2.5), we get

mm = g ÊÁ
eh ˆ
I ( I + 1) (4.2.6)
Ë 4p mp ˜¯

Ê eh ˆ
mN = Á (4.2.7)
Ë 4p mp ˜¯
The basic unit mN is called the nuclear magneton. Its value for the hydrogen
nucleus is
eh (1.602 ¥ 10-19 C)(6.626 ¥ 10-34 J s)
mN = =
4p mp 4(22 / 7) (1.673 ¥ 10-27 kg )
= 5.047 ¥ 10 -27 J T -1 (4.2.8)
 Molecular Spectroscopy 403

Potential Energy Potential energy V B is given by the relation

of a Nucleus in a
V = - B mz (4.2.9)
Magnetic Field
where m z is the z-component of the magnetic momentum vector. Let q be the angle
between the magnetic momentum vector and the z-axis, then
mz = mm cos q (4.2.10)
Substituting Eq. (4.2.6) in Eq. (4.2.10), we get

( )
m z = g m N I ( I + 1) cos q (4.2.11)
The angle q cannot have any arbitrary value, but only a few allowed discrete
values which satisfy the condition of quantization of the component of angular

Ê I ( I + 1) h ˆ cos q = m h
Ë 2p ¯
I
2p

or I ( I +1) cos q = mI (4.2.12)

Substituting Eq. (4.2.12) in Eq. (4.2.11), we get
mz = g mN mI
Substituting the above relation in Eq. (4.2.9), we have
V = - B(m N g mI ) (4.2.13a)

depends on the value of mI. Equation (4.2.13a) is usually written as

h
V=–g B mI (4.2.13b)
2p
where g = 2p mN g/h and is known as gyromagnetic ratio (see Eq. 4.2.18).

Three cases may be distinguished.

value of mI. This is due to the fact that the orientation of the poles of tiny magnet
generated due to the spinning of the nucleus is in the unfavourable position, i.e.
the north pole of the tiny magnet is near to the north pole of external magnet and
the south pole is near to the south pole. This arrangement leads to more and more

value of mI. Here the orientation of tiny magnet is in the favourable direction, i.e.
the north pole of the tiny magnet is near to the south pole of the external magnetic

3. The potential energy remains unchanged for a zero value of mI. Here the
orientation of tiny magnet is in the perpendicular direction of the external magnetic
404 A Textbook of Physical Chemistry

Potential Energy The value of spin quantum number for protons is +1/2. Thus, mI can have two
of a Proton in a values of +1/2 and - 1/2. The schematic variations of potential energies of a and
Magnetic Field b protons are shown in Fig. 4.2.1.

mI = –1/2, b-spin

Energy

Fig. 4.2.1 Variations

of potential energies of
a and b protons in the mI = +1/2, a-spin
presence of increasing
B

The value of g for protons is found to be 5.585 4. Substituting the values of m I

and g along with m N from Eq. (4.2.8), we get
V+1/2 = - (5.047 ¥ 10 - 27 J T - 1) (5.585 4) (1/2) B
= - (1.410 ¥ 10 - 26 J T - 1) B
V-1/2 = - (5.047 ¥ 10 -27 J T -1) (5.585 4) (- 1/2) B
= + (1.410 ¥ 10 - 26 J T - 1) B
Transition The energy difference between the two levels as given by Eq. (4.2.13a) is
Involving the DV = m N g B (4.2.14)
Reversal of Spins
of Protons = (2.820 ¥ 10 - 26 J T - 1) B (4.2.15)
In terms of frequency unit, we have
(2.820 ¥ 10-26 J T -1 ) B
n= = (4.26 ¥ 107 T –1 s–1) B (4.2.16)
6.626 ¥ 10-34 J s
Thus, a proton in the lower energy level (m I = 1/2) can be promoted to the
higher energy level (mI = -
the necessary energy in the form of electromagnetic radiation of frequency equal to
{4.26 ¥ 107 Hz (B/T)}. Such type of transitions is the subject of NMR spectroscopy
and if protons are involved, it may be called proton magnetic resonance (PMR)
spectroscopy. The frequency associated with such a transition depends on the
 Molecular Spectroscopy 405

the frequency of radiation required for the reversal of the spin of proton is
n = (4.26 ¥ 107 T –1 s–1)(1 T) = 42.6 ¥ 106 Hz = 42.6 MHz (4.2.17)
The above frequency lies in the radiofrequency region of the electromagnetic
spectrum (3 ¥ 106 -3 ¥ 1010 Hz).
The energy difference between the two nuclear levels can also be expressed in the
unit of angular frequency w (expressed as radians/second). Since w = 2pn, we have
m g
w = 2pn = 2p ÊÁ N ˆ 2p m N g ˆ
B˜ = ÊÁ B=gB (4.2.18)
Ë h ¯ Ë h ˜¯
where g is the nuclear constant and is known as the gyromagnetic ratio or the
magnetogyric ratio.
Magnetic Active It may be mentioned here that the absorption of radiation of a suitable wavelength
and Inactive
Nuclei have nonzero spin angular momentum. Such types of nuclei are known as magnetic
active nuclei. Magnetic inactive nuclei have zero spin quantum number, vis-à-
vis, zero magnetic moment. Such type of nuclei cannot interact with the external
12 16
C and O.
Intensity of NMR The excitation of a nucleus from the lower energy level to the higher one can
Signals occur only if the lower level is more populated than the higher one. The relative
populations of nuclei over the available energy levels can be calculated from the
Boltzmann equation
n2
= exp(- DV/kT) (4.2.19)
n1
when n1 and n2 are the number of nuclei in the lower and higher energy levels,
respectively, DV is the energy difference between these two levels and k is the
Botlzmann constant (k = R/NA).
A given system with the minimum potential energy is the most stable one. Thus,
it may be expected that the most stable arrangement of nuclei in the magnetic

example, the system consisting of protons only. Energetically, the system would
have been most stable where all the protons occupy the lowest energy level (i.e.
all protons have a-spins). The only factor which opposes this arrangement is the
value of thermal energy relative to that of energy difference between the two levels.
If DV is much larger than kT, then the lowest energy level is densely populated.

This number decreases rapidly as DV becomes larger and larger. On the other
hand, if DV is much smaller than kT, the upper levels are also equally populated;
nevertheless, the population in the lowest level is still larger than those in the upper
levels. The two levels will have the same population only when the term DV/kT in
Eq. (4.2.19) has a zero value. This is possible only when the temperature of the
406 A Textbook of Physical Chemistry

lowest level is always more populated than the upper level.

Let us calculate the relative population of protons in the two available energy

DV = (2.820 ¥ 10 -26 J T –1) (1 T) = 2.820 ¥ 10 -26 J (Eq. 4.2.15)

- 23 -1 -21
kT = (1.38 ¥ 10 J K ) (300 K) = 4.14 ¥ 10 J
n2
= exp(- DV/kT ) = exp{(- 2.820 ¥ 10 - 26 J)/(4.14 ¥ 10 - 21 J)}
n1
= exp(- 6.81 ¥ 10 - 6) 0.999 993
Thus if ground level, for example, contains 106 molecules, then the upper level
will contain 0.999 993 ¥ 106 molecules. Hence, there exists a population difference
of about 7 molecules out of a total of 106 + 0.999 993 ¥ 106 molecules (i.e. 2
million molecules).
Transition from one level to another can take place in either directions, i.e. the
nucleus can be promoted from the lower energy level to the upper one (upward
transition) with the absorption of radiation and also it can come back from the
upper level to the lower level (downward transition) with the emission of radiation.
Statistically, it may be expected that the rate at which transitions from a level takes
place depends on the population of the level. Thus, it may be concluded that the
upper transitions are more than the downward transitions and hence there occurs
a net absorption.
The intensity of net absorption depends on the difference between the populations
of particles in the two involved levels. In the case of NMR, this difference is
small and thus the intensity of absorption is also small. However, the intensity of
absorption can be enhanced either by carrying NMR at low temperatures and/or by

difference between the two levels in accordance with the Boltzmann distribution
law (Eq. 4.2.19).

Diagrammatic The expressions of magnetic moment and its z-component are

Representation of m m = g mN I ( I +1) (Eq. 4.2.6)
Magnetic Moment
m z = g mN mI (Eq. 4.2.11)
where I is the spin quantum number and m I is the component spin quantum number.
The permitted values of mI are I, I - 1, …, - (I - 1), - I.
Since mI can never be equal to I ( I +1) , it follows from Eq. (4.2.11) that m z
can never be equal to mm, i.e. the magnitude of the magnetic moment vector and
its z-component can never be the same. This means that the magnetic moment
vector can never be directed along the magnetic axis and will always be oriented
with respect to z-axis. The angle of orientation is given by
mz mI
cos q = m = (4.2.20)
m I ( I +1)
 Molecular Spectroscopy 407

For protons, the two directions of magnetic moment vector are shown in Fig. 4.2.2.
z-axis

1 3
g mN g mN
2 2
q
1/ 2
cos q = = 0.5774
3 /2
q = 54.72∞
Fig. 4.2.2 The
two orientations of
magnetic moment 1 3
vectors of a proton – g mN g mN
2 2
along the z-axis

Larmor Precession

is not possible because of the above quantum mechanical restriction. The only

direction keeping all the while its orientation angle q constant, i.e. the magnetic

precession is known as the Larmor precession.

S

z-axis

Fig. 4.2.3 The

Larmor precession N

The Larmor frequency in radians per second is given by

2p m N g ˆ
w = g B = ÊÁ B
Ë h ˜¯

g m N I ( I + 1) Ê Magnetic moment ˆ
B= Á
Ë Angular momentum ˜¯
= B (4.2.21)
I ( I + 1)(h / 2p)
Equation (4.2.21) is identical with Eq. (4.2.18) implying that the Larmor
frequency is equal to the angular frequency separation between the two nuclear
magnetic energy levels.
408 A Textbook of Physical Chemistry

remains constant in this precession. This potential energy can be changed by

changing the orientation angle of the magnetic moment vector to the other permitted

giving rise to either absorption or emission of energy.

Experimental Set Up
sending the output of a radiofrequency oscillator through a helical coil (solenoid)

The latter is generated with the help of an electromagnet. The sample under study
is placed in a glass tube positioned along the axis of the coil. An electric current

same frequency (Fig. 4.2.4). One of these directions is the same as that of the

quency of separation between the two levels, a condition of resonance exists and
thereby the nucleus can either absorb or emit energy from the secondary magnetic

is more populated than the excited level.

The above resonance phenomenon can be achieved by either of the following ways:
1. By varying the frequency of the oscillator keeping the external magnetic

constant.

Radio- Radio- (b)

frequency frequency Detector
transmitter amplifier

Audio-
amplifier
recorder

Sweep (a) resultant

generator
 Molecular Spectroscopy 409

In the former, we are keeping the Larmor frequency at a constant value and

precessional frequency. However, in the latter, we keep the frequency of the external

to the sample by an electromagnet.

Example 4.2.1
Given: The factor g for proton is 5.585.
Solution Since DV = mN gB, we have
DV (220 ¥ 106 s -1 )(6.626 ¥ 10-34 J s)
B= =
mN g (5.047 ¥ 10-27 J T -1 )(5.585)
= 5.171 5 T
Example 4.2.2
Solution The precessional frequency is
m N gB (5.047 ¥ 10-27 J T -1 )(5.585)(1.5 T )
n= =
h (6.626 ¥ 10-34 J s)
= 6.38 ¥ 107 s -1.

Example 4.2.3 Calculate the value of gyromagnetic ratio g .

Solution The value of gyromagnetic ratio is
2p m N g 2(3.14)(5.047 ¥ 10-27 J T -1 )(5.584)
g = =
h (6.626 ¥ 10-34 J s)

= 2.671 ¥ 108 T -1 s-1.

Example 4.2.4 Calculate the angular momentum and magnetic moment values for a proton. Given:
g = 5.585.
Solution We have

I ( I + 1) Ê ˆ
h
L = and m m = g m N I ( I +1)
Ë 2p ¯
For a proton, I = 1/2. Thus, we have

1Ê1 ˆ Ê h ˆ Ê 6.626 ¥ 10-34 J s ˆ

= 0.866 Ê ˆ = 0.866 Á
h
L = +1 ˜¯
2 Ë 2 ¯ Ë 2p ¯ Ë 2p ¯ Ë 2 ¥ 3.14
= 0.913 7 ¥ 10 -34 J s
1Ê1 ˆ
and m m = (5.585) (mN) Á + 1˜ = 4.837 mN
2Ë2 ¯
= 4.837 (5.047 ¥ 10 -27 J T -1) = 2.441 ¥ 10-26 J T -1.
410 A Textbook of Physical Chemistry

PMR of Organic The NMR signal of a nucleus is highly characteristic of the nucleus under study.†
Compounds Moreover, the area under the NMR signal is directly proportional to the number
of such resonating nuclei. Thus, NMR technique has been widely employed in
determining the nature and number of resonating nuclei. The widest application

structural elucidation of organic compounds. It is a great blessing that 12C and 16O
are the magnetic inactive atoms and thus do not exhibit any NMR signals. The only
widest distributed magnetic active nucleus in organic compounds is the hydrogen
atom, and hereafter, we shall focus attention only on the PMR spectroscopy.
The structure elucidation of organic compounds is based on two principles.
These are the chemical shift and the spin-spin interaction.

THE CHEMICAL SHIFT

Proton Signals in
a Compound been shown in Fig. 4.2.1. However, while dealing with atoms or molecules,
the various nuclei are not present as the bare nuclei but are associated with the
electronic clouds. The density of electronic cloud around any particular nucleus

electronic cloud associated with any particular nucleus tends to circulate around

known as diamagnetic circulation

Bobserved = Bapplied - Binduced (4.2.22)

Binduced μ Bapplied

or Binduced = s Bapplied (4.2.23)

where s is a constant, called the shielding constant. Its value depends on the
electron density around the nucleus in a molecule. If the electron density around
any particular nucleus is larger than the other, it has a larger value of s and is

it follows that the nucleus with larger value of shielding constant will observe a

a nucleus will be smaller than that seen by a less shielded nucleus (Eq. 4.2.22).

Substituting Eq. (4.2.23) in Eq. (4.2.22), we get

Bobserved = Bapplied (1 - s) (4.2.24)

†
See Annexure at the end of the chapter for the qualitative quantum mechanical study of
NMR signals for simple molecules.
 Molecular Spectroscopy 411

For a bare proton, s = 0 and hence

Bobserved = Bapplied

For a proton in a molecule, s is positive and hence

Bobserved < Bapplied

PMR Spectrum of The extent of shielding will be constant for a given atom in isolation, but will
CH3OH vary in a molecule because of different chemical environments. Consider, for an
example, the molecule CH3

bond are different. Since oxygen is more electronegative than carbon, the electron

s CH > s OH

Thus, from Eq. (4.2.24) it follows that

Bapplied (1 - s CH ) < Bapplied (1 - sOH)

or (Bobserved )CH < (Bobserved) OH

the hydroxyl proton.

as given by Eq. (4.2.14) is

h
DV = V-1/2 - V1/2 = g m N Bobserved = g Bobserved
2p
h
=g (1 - s ) Bapplied (4.2.25)
2p
Since
(Bobserved)OH > (Bobserved)CH (4.2.26)

ma 3
Fig. 4.2.5.

Since most of NMR spectrometers are operated by using a constant frequency

from Fig. 4.2.5 that the hydroxyl proton will be thrown into resonance earlier than
the methyl protons
412 A Textbook of Physical Chemistry

of methyl protons will be three times larger than that under the hydroxyl proton,
since in the former we have three identical protons. It may be recalled that neither
oxygen nor carbon will exhibit any absorption as both of these are magnetic
inactive nuclei.

OH
mI = –1/2; b - spin

CH3
mI = –1/2; b - spin

60 MHz
V

mI = 1/2; a -spin
CH3

Fig. 4.2.5 Variation CH3

of potential energy of
methyl and hydroxyl mI = 1/2; a -spin
OH
protons of CH3OH
in the presence of OH
varying external
No Relative ratio 1 3
field B

PMR Spectrum of In ethyl alcohol, we have three different types of protons: (1) the hydroxyl proton,
CH3CH2OH (2) the methylene protons, and (3) the methyl protons. Of these, the hydroxyl proton
is expected to be the least shielded as it is attached to the more electronegative

than those of methylene and methyl protons. Of the methylene and methyl groups,
the hydrogen atoms attached to the former are expected to be less shielded as the
CH2 group is directly attached to the oxygen atom. Thus, the methylene protons
will come into resonance earlier than those of the methyl protons. The expected
spectrum of ethyl alcohol is shown in Fig. 4.2.6. It has three absorption signals.

is due to the methyl protons and at the centre is due to the methylene protons.
The area under these peaks will follow the ratio 1 : 2 : 3 as they represent one
proton of the OH group, two protons of the CH2 group and three protons of the
CH3 group, respectively.

The spectrum shown in Fig. 4.2.6, which shows only the effects of chemical
shift, is known as the low-resolution spectrum.
 Molecular Spectroscopy 413

CH3

CH2

OH
Fig. 4.2.6 Low-
resolution spectrum of
ethyl alcohol B

Expressing The spacing between the two signals of the same type of nuclei (say protons
Chemical Shift under different chemical environments) is known as the chemical shift. The
numerical values of chemical shifts are very small as compared to the external
Binduced is much smaller than Bapplied. The magnitude

spectrum is recorded at constant radiation frequency and by varying the external

hertz as if the spectrum has been recorded by varying the applied frequency at a

DE g mN
Dn = = DB (4.2.27)
h h
The conversion factor is as follows.
(5.585)(5.047 ¥ 10-27 J T -1 )
Dn = (DB)
(6.626 ¥ 10-34 J s)
= (42.54 ¥ 106 T –1 s–1) (DB)
If D B is 1 mT, i.e. 10–6 T, we have
Dn = 42.54 s–1
Thus, 1 microtesla ∫ 42.54 s–1
If s1 and s2 are the shielding constants of two protons under different chemical
environments, then the chemical shift between them as given by Eq. (4.2.27)
becomes
DE g mN
Dn = = (B2 - B1)
h h
g mN
= {Bapplied (1 - s2) - Bapplied (1 - s1)}
h
g mN
= Bapplied (s1 - s2) (4.2.28)
h
Since s
it is obvious from Eq. (4.2.28) that the chemical shift varies linearly with the

experimental conditions. However, this dependency can be removed if the chemical

414 A Textbook of Physical Chemistry

quantity, which is dimensionless, is multiplied by a factor of 106 to express it as

parts per million (ppm). Thus, we have
Bref - Bsamp
d = ¥ 106 (4.2.29)
Bref
where Bref and Bsamp
resonances occur of the protons of the reference compound and that of the given
compound, respectively.†

Reference The reference compound is dissolved in the same solution as the sample so that both
Compound in PMR
Spectra which is universally selected for hydrogen resonances in non-aqueous solvents is
tetramethylsilane (CH3 )4Si or TMS in short. It has the following characteristics:
∑ It gives a single intense peak, since all the twelve hydrogen nuclei are
equivalent.
∑ The hydrogen nuclei in TMS are highly shielded as compared to those in the

(1.409 2 T for 60 MHz radiation) which can easily be recognized.

∑ It has a low boiling point (27 ºC) and hence can be readily removed after the
spectrum has been recorded.
In view of the limited solubility of TMS in water, the salt (CH3)3SiCD2CD2CO -2
is commonly used in the solvent.

d- and t-Scales Two scales are commonly employed to represent the various signals. These are: (i)
the d-scale, and (ii) the t -scale. On the d-scale, d is set equal to zero at the reference

that a larger value of d

removed in the t-scale where TMS signal is assigned a value of 10 and it decreases
t means that the nucleus is less shielded and a
higher value means the nucleus is more shielded. The two scales are related to
each other by the expression
t = 10 - d

t-Values of For most organic compounds, the t-value lies between 0 and 10 and is highly
Hydrogens characteristic of the chemical environment. It is for this reason, they can be used
to detect the type of proton that is present in a given organic molecule. Table 4.2.1
records some of the t -values of protons under different chemical environments.

†
Alternatively, in terms of frequency, we have

Dn
d= ¥ 106
Fixed frequency of the probe
 Molecular Spectroscopy 415

Table 4.2.1 t-Values of Hydrogens in Some of the Organic Compounds

Compound t-value Compound t-value

Tetramethylsilane 10 Methyl alcohol
Cyclopropane 9.78 Methyl protons 6.62
Methane 9.77 Dioxane 6.2
Tetramethylmethane 9.08 Nitromethane 5.72
Ethyl alcohol
Methyl protons 8.83 Water 4.8
Methylene protons 6.41 Methylene chloride 4.2
Cyclohexane 8.56 Ethylene 4.16
Methyl cyanide 8.03 2.73
Acetone 7.91 Chloroform 2.3
Acetaldehyde
Methyl protons 7.85 Naphthalene 2.27
Aldehydic proton 0.28 Sulphuric acid – 1.6

Comment t = 2.73) as compared to

those of aliphatic protons. This is attributed to the circulating current in benzene due
to the six p

H H Bext
Fig. 4.2.7 Ring current
due to the circulation of
p electrons

Problem 4.2.1 Figure displays a PMR-spectrum (without the intensity factor) at 60 MHz of a
solution containing the following components in deuteriochloroform.

CH3COCH3, CHCl3, , CH2Cl2,

(I) (II) (III) (IV)

, (CH3)4Si and Cl3CCH3

(V) (VI) (VII)

(a) Match each of the components with the corresponding peak (say, for example, the
peak 7 represents the compound VI).
416 A Textbook of Physical Chemistry

6
4
5 7
2 3
1

440 318 217 165 125 86 0

Dn/Hz

(b) What would be the position (in Hz) of the chloroform peak at 60 MHz with
reference to the cylohexane peak?
(c) Express the separation of each line with reference to TMS line in each of the three
scales (Hz, d - and t-scales). What would be the separation of these peaks at 100
MHz? Give the answer in each of three scales.
Solution (a) The position of absorption of a proton depends on its electronic environment. A

and hence will exhibit only one absorption. The shielding constants of protons in given
molecules are expected to follow the following order:
s (TMS) > s(C6H12) > s(C3H6O) > s(C4H8O2) > s(Cl3CCH3)
>s (CH2Cl2) > s(CHCl3)
Thus, the assignment of peaks is as follows.
Molecule VI III I V VII IV II
Peak 7 6 5 4 3 2 1

(b) Chloroform peak is at 440 Hz and that of cyclohexane is at 86 Hz. Thus, chloroform
peak lies 354 Hz (= 440 Hz - 86 Hz) away from the cyclohexane peak towards the low-

(c) The separation of each line with reference to TMS line in terms of Hz, d- and t-scales
are described below.

Molecule Hz d -value t-value

TMS 0 0 10
Cyclohexane 86 86/60 = 1.43 8.57
Acetone 125 125/60 = 2.08 7.92
Dioxane 165 165/60 = 2.75 7.25
1, 1, 1 -Trichloroethane 217 217/60 = 3.61 6.39
Dichloromethane 318 318/60 = 5.30 4.70
Trichloromethane 440 440/60 = 7.33 2.67
 Molecular Spectroscopy 417

The separation of lines in Hz will increase by employing high frequency of

radiation. Since the separation is directly proportional to the frequency of radiation,
the separation of each line will increase by a factor of (100/60). The d- and t-values,
however, will remain unaltered.
THE SPIN-SPIN INTERACTIONS

Effect of a
Neighbouring
Proton This is due to the spin-spin interactions. A proton can have either a-spin (mI =
+1/2) or b-spin (mI = -1/2). These spins are represented by arrows; a -spin is
represented by an arrow pointing upwards and b-spin by an arrow pointing
downwards. Consider a situation in which the proton A is present in the

following two alternatives:

(i) Proton has a-spin a -spin, then it creates a

Bobserved = Bapplied – Binteraction (4.2.30)

where Binteraction
(ii) Proton has b-spin b -spin, it creates a magnetic

Bobserved = Bapplied + Binteraction (4.2.31)

where Binteraction

B (a- or (b-spin)
(a - or
Bapplied

A b -spin) A B
b-spin)
(a-spin)

Fig. 4.2.8 The spin-

spin coupling between
the two protons

Effect on Potential The potential energy of proton A will now be given by the relations
Energy Va = – mN g (Bapplied – Binteraction) mI
and Vb = – mN g (Bapplied + Binteraction) mI

where the subscripts a and b represent, respectively, the spins a and b of the
 418 A Textbook of Physical Chemistry

bb

ba

b
60 MHz
a
V
Fig. 4.2.9 Variation
of potential energy of a
proton in the presence aa
and absence of a
neighbouring proton. ab
The levels aa and bb
are destabilized and
those ab and ba are
stabilized
B

PMR Spectrum If the system is irradiated with a radiation of 60 MHz (or of any other frequency),
then it can be concluded from Fig. 4.2.9 that the single absorption which is expected
to occur in the absence of spin-spin interaction (shown by broken line) splits
into two symmetrically placed absorptions, one with a-spin of the neighbouring
proton and the other b-spin of the neighbouring proton (shown by solid line).† The
absorption corresponding to the a-spin of the neighbouring proton lies towards
b
under these two peaks will be identical to that under the one peak observed in
the absence of spin-spin coupling. The spin-spin splitting separation between the
component lines usually has a small value as compared to the chemical shift of the
involved protons and can be observed only if the spectrometers of high resolution

recorded with the minimum precision of one part in 107. It is for this reason, the
recorded spectrum is known as the high-resolution spectrum.
The spin-spin interaction decreases very rapidly as the distance between the
protons is increased and this interaction is transmitted through the bonds. In
molecules, it operates only between the next nearest neighbours. Moreover, the
interaction is always mutual, i.e. if the splitting of A occurs due to the interaction

intramolecular behaviour, i.e. the PMR signals of one molecule

will not be affected by the protons of the other molecule. The spin-spin splitting
separation between the component lines is also found to be independent of the

Effect of More Than In organic molecules, the spin-spin interaction may involve more than one
One Neighbouring neighbouring proton. Take, for example, the methyl alcohol in which the hydroxyl
Proton proton interacts with the three identical protons of methyl group. We consider now
the scheme for this type of interactions. We restrict overselves to the simple type
†
During the transition, the spin of neighbouring proton does not change. This is, in fact,
the selection rule for the nuclear spin transitions.
 Molecular Spectroscopy 419

of molecules in which the chemical shift between the involved protons is much
larger than the coupling constant (the separation between the two splitted lines
of the same signal). Such types of molecules are abbreviated as AnXm, where A
and X represent the two different neighbouring protons in a molecule. We discuss
below the scheme of spin-spin interactions with the typical examples of methyl
alcohol and ethyl alcohol.
High-Resolution The three hydrogen atoms of methyl group have the same chemical environment and
Spectrum of thus have the same shielding constant. Consequently, the chemical shifts of all the three
Methyl Alcohol hydrogen atoms are identical. The rotation of methyl group around the C—O bond
makes all the three protons of methyl group magnetically equivalent to the hydroxyl
proton, and thus the interactions of methyl protons with the hydroxyl proton are all
equal. It is known that the couplings within a group of magnetically and chemically
equivalent nuclei do not affect the spectrum and can be ignored. Thus in methyl
alcohol, we need not consider the couplings amongst the protons of methyl group
and should consider only the coupling of methyl protons with the hydroxyl proton
and vice versa (see Annexture at the end of the chapter). These are considered below:
Coupling of methyl protons with the hydroxyl proton The methyl protons will
observe two possible arrangements of the hydroxyl proton, viz., a and b, and hence

a-spin acts in the opposite direction and that generated

by b

b-spin and it will be slightly less when

the hydroxyl proton has a-spin. Accordingly, the variation of potential energy of

(Bapplied - Binteraction Bapplied + Binteraction). These are

shown in Fig. 4.2.10.
Coupling of hydroxyl proton with methyl protons The hydroxyl proton couples
with the neighbouring three methyl protons. Each proton can have either a-spin or
b-spin. The total number of possible arrangements which the hydroxyl proton
observes when each proton of methyl group has either a-spin or b-spin are as
follows.
Proton 1 b a

Proton 2 bb ba ab aa

Proton 3 bbb bba ba b ba a abb aba aab aaa

There are eight arrangements in all. These fall into the following categories:
1. All the three protons have a-spins.
2. Two of them have a-spin and the third has b-spin.
3. Two of them have b-spins and the third has a-spin.
4. All the three protons have b-spins.
420 A Textbook of Physical Chemistry

bbb
bb a ; b ab ; abb
baa ; aba; aab
aaa

OH b
CH3
b a b

60 MHz
V

a a
CH3
OH b a
aaa

baa ; aa b ;a b a
bba; a b b;bab
3
bbb

Relative area 1 3 3 1 1 1
hydroxyl proton methyl protons

Fig. 4.2.10 High-resolution spectrum of methyl alcohol

The number of such combinations in each of the above four categories are
1, 3, 3, 1, respectively. It means that the number of hydroxyl protons observing
either 2a and 1b or 2b and 1a arrangement of methyl protons will be three times
larger than those observing either 3a or 3b arrangement. Each of these arrangements

a b-spin

(Bobserved) 3a < (Bobserved)2a and 1b < (Bobserved) 0a and 0b

< (Bobserved) 2b and 1a < (Bobserved)3b

where the subscripts represent the arrangements of the neighbouring methyl protons
Bobserved) 0a and 0b
interaction. Thus, the variation of potential energy of the hydroxyl proton will
be represented by four different lines corresponding to each of the four different
arrangements of methyl protons. These are shown in Fig. 4.2.10.
 Molecular Spectroscopy 421

absorption lines are observed for methyl protons and four absorption lines for
hydroxyl proton as shown at the foot of Fig. 4.2.10. The two absorption lines
of methyl protons will have identical intensities whereas those of hydroxyl
proton will have the intensity ratio of 1 : 3 : 3 : 1. The ratio 1 : 3 : 3 : 1 arises
because of the fact that the number of arrangements of 2a and 1b, and 2b and
1a are three times larger than those of 3a and 3b. The total area under the two
absorption lines of methyl protons will be identical to the corresponding single
absorption observed in the absence of spin-spin coupling (shown by broken line).
Similarly the area under the four peaks of hydroxyl proton will be identical to
the corresponding single absorption in the absence of spin-spin coupling.

Characteristics of In general, if a proton is coupled with the neighbouring n equivalent (magnetically

High-Resolution and chemically) protons, the number of absorptions observed is (n + 1). Their
Spectrum relative intensities are given by†

n n!
Cm =
m!(n - m)!
where m goes from 0 to n. The above general rule will be applicable only in
case of AnXm molecules where the chemical shift between the involved protons
is much larger than the spin-spin coupling constant. If these two are comparable,
complex patterns are obtained, which can, however, be analysed by the quantum
mechanical method.
It may once again be recalled that the spin-spin couplings are intramolecular

not the spin-spin couplings. In general, recording a NMR spectrum at a very

the low frequency (say, 40 MHz). This is due to the fact that at high frequency,
the spin-spin couplings, which are comparable with the chemical shifts at low
†
An easy way to determine the relative intensities is to use Pascal’s triangle, given by

n relative intensities
0 1
1 1 1
2 1 2 1
3 1 3 3 1
4 1 4 6 4 1
5 1 5 10 10 5 1
6 1 6 15 20 15 6 1
422 A Textbook of Physical Chemistry

frequency, become negligible in comparison to the latter. This arises because

of the fact that the spin-spin couplings remain unaltered whereas the chemical

General Remarks In general, the chemically equivalent protons do not exhibit spin-spin splitting
about Spin-Spin in the NMR spectrum in spite of the fact that there exist spin-spin interactions
Coupling amongst them (See Annexure). Thus, only single proton resonance line is observed
for the molecules H2, CH4, C6H6, etc. The effect of one proton on the resonance of
another proton or group of equivalent protons depends on the number and kind of
intervening chemical bonds. Normally, the splitting for nonequivalent protons in
saturated molecules are of the order of 15 Hz when located on the same carbon, 5
to 8 Hz when located on the next neighbouring carbons and essentially zero when
separated by more than two carbons.
High-Resolution The low-resolution spectrum of ethyl alcohol was described earlier. We get three
Spectrum of Ethyl
Alcohol
In high-resolution spectrum, the absorption peak of methyl protons will split into
three peaks with relative intensities as 1, 2, 1 since it is attached to the methylene
group. The absorption peak of methylene protons will primarily split into four
peaks with intensities 1, 3, 3, 1 due to the interaction with the methyl protons. Each
of these four peaks will further split into two peaks of equal intensity due to
the coupling with the hydroxyl proton. Thus, in a very high resolution spectrum,
the methylene protons will exhibit an octet with relative intensities 1, 1, 3, 3, 3,

4, 6, 4, 1, as if it has coupled with four protons (three from methyl and one from
hydroxyl). The hydroxyl proton will split into three peaks of intensities 1, 2, 1 due
to the coupling with methylene protons.

The expected high-resolution spectrum of ethyl alcohol is shown in Fig. 4.2.11a.

Ethyl Alcohol The hydroxyl proton of ethyl alcohol is not immutably locked in any particular
Spectrum in the ethyl alcohol molecule. It is, in fact, being continuously exchanged from one
Presence of Trace molecule to the other molecule. The rate of this exchange is relatively slow in
of Acid or Alkali pure ethyl alcohol. The time spent by the proton on any ethyl alcohol molecule is

and thus causing spin-spin splitting. In the presence of acid or alkali, the rate of
transfer of hydroxyl proton from one molecule to the other is very much enhanced
and thus the time spend by the hydroxyl proton with any particular molecule is
too small to allow the interaction with the methylene protons. Thus, the splitting
of hydroxyl and methylene protons due to each other is completely prevented and
thus one observes a single peak of the hydroxyl proton. Likewise, the methylene
protons show only splitting due to the neighbouring methyl protons and hence the
quintet is replaced by the quartet. The resultant spectrum is shown in Fig. 4.2.11b.
 Molecular Spectroscopy 423

CH3

(a) CH2
OH

(III) (II) (I)

B
CH3

(b) CH2

OH

(III) (II) (I)

B
(c) CH3

CH2

Fig. 4.2.11 High-

resolution spectra of
(II) (I)
ethyl alcohol
B
Ethyl Alcohol On adding D2O in ethyl alcohol, the hydroxyl proton of the latter is replaced by
Spectrum in the deuterium nucleus. It is thus expected that under such conditions, the absorption
Presence of D2O peak of hydroxyl proton will disappear (Fig. 4.2.11c). Though deuterium nucleus is
also magnetic active (I = 1), no absorption peak corresponding to this is observed

the fact that the NMR-frequency of deuterium nucleus occurs at a very small
frequency as compared to the hydrogen nucleus; 9.21 MHz as compared to 60

the deuterium nucleus may be observed, one has to employ a very large magnetic
¥ 60/9.1 (= 9.1) tesla if the frequency of radiation is kept at 60 MHz.
Since the magnetic moment of deuterium is much smaller than proton, the spin-spin
interactions of deuterium with neighbouring protons may be neglected.

Problem 4.2.2 The PMR spectrum of dimethylformamide at 40 MHz and at room temperature is shown

H O
C

N
H3C CH3 A B C
B
424 A Textbook of Physical Chemistry

The doublet B, C might arise either from chemically different groups or from spin-spin
coupling. (i) What feature of the spectrum immediately rules out one of these explanations
in this case? (ii) What experimental operation offers a general method for distinguishing
between chemical shift and spin-spin splitting? (iii) Explain the origin of the lines A, B and
C. (iv) What will be the effect of temperature on the given spectrum?
Solution (i) The doublet B and C arise due to the chemically different methyl groups. This results
because of the restricted rotation around C—N axis. The possibility of spin-spin splitting
may be excluded since it is on the mutual basis, i.e. if the peak of methyl protons is split
into two, the CH peak would have split into seven peaks.
(ii) The chemical shift and the spin-spin splitting can be distinguished on the basis of

remains unchanged.

(iii) Peak A is due to the proton of CH group as it is least shielded. Peak B is due to the
protons of methyl group near to the CO group (i.e. in the cis position) and the peak C is
due to the trans methyl group.

(iv) On increasing temperature, the restricted rotation around CN axis is decreased. At very
high temperatures, the rotation speed becomes very large and hence both the methyl groups
become identical. This will result in the collapse of the two given signals into a single peak.

Problem 4.2.3 Write down all possible structural formulae having molecular formula C3H6Cl2. Is it possible
to identify them on the basis of low or/and high PMR spectra? Ignore the interactions of
Cl atoms with H.
Solution The structural formulae of C3H6Cl2 along with their low and high resolution spectra are
given below.

(I)
3 2 1
CH3 CH 2CHCl2

1 2 3 1:2:1 1:4:6:4:1 1:2:1

B B
(II)
3 1 2
CH3CHClCH 2 Cl
(Secondary proton
shows absorption

the primary
1 2 3 sixtet 1:1 1:1
protons.)
B B
 Molecular Spectroscopy 425

(III)

CH3CCl2CH3
Identical protons

B B

(IV)

ClCH2CH2CH2Cl

4 2 1:2:1 1:4:6:4:1

B B

resolution spectra. The only exception is the identical low resolution spectra of compounds
(I) and (II). However, they may be distinguished from the following points.
1. The t

two chlorine atoms while the latter represents a proton attached to the one chlorine atom.

to be larger than the corresponding chemical shift of compound (II).

Problem 4.2.4 Predict whether it is possible to distinguish the following two compounds on the basis of
their low or/and high resolution PMR spectra.

and

(a) (b)
Solution Low-Resolution PMR Spectra The expected order of shielding constants of protons in the
given compounds are

(a) (b)

s2 < s1 < s3 s1 < s2 < s3

Thus, their low-resolution PMR spectra would look like as shown in the following
426 A Textbook of Physical Chemistry

1 3 1 3

2 2

relative area 2 3 3 3 2 3
B B
(a) (b)
Since the two spectra are not identical, the two compounds are distinguishable from their
low-resolution spectra.
High-Resolution PMR Spectra Peak 2 in both the low-resolution spectra will split into four
as the methylene group is attached to the methyl group. Similarly, peak 3 in both the spectra
will split into three. Peak 1 will remain unaffected. Thus, the high-resolution PMR spectra
would look like as shown in the follo
1 1

3 3
2 2

Relative area 1:3:3:1 1:2:1 1:3:3:1 1:2:1

B B

Problem 4.2.5 6H10O2. Suggest its structure.

Solution Analysis of the spectrum

(i) The relative areas of different peaks suggest the presence of two methylene groups
(peaks 1 and 2) and two methyl groups (peaks 3 and 4).
(ii) If we subtract two methylene and two methyl groups from C6H10O2, we get C2O2.
The latter may represent two CO groups.
 Molecular Spectroscopy 427

The probable structure consistent with the above facts is

3 1 2 4
CH3CO CH 2CO CH 2CH3

Problem 4.2.6 5H10O2. Suggest its structure.

3

4.0 3.0 2.0 1.0 0 d -scale

relative area 1 3 6
B
Solution Analysis of the spectrum
The relative areas of different groups suggest that
(i) Peak 1 must be due to a CH group. The latter must be attached with a stronger
electron withdrawal group.
(ii) Peak 2 must represent a methyl group.
(iii) Peak 3 must represent two identical methyl groups. Protons of these methyl groups
are more shielded than the protons of the other methyl group (peak 2).
If we subtract CH, CH3 and two CH3 groups from C5H10O2, we get CO2 as the remaining
fragment. we may conclude that the molecule is a derivative of a carboxylic acid. The two
identical methyl groups and one CH group may arise from the isopropyl group. Since CH
group shows peak at the high d -value, we may conclude that it is attached directly to the
carboxylate group. The probable structure consistent with the above facts is

Problem 4.2.7 8H14O4. Suggest its structure.

Solution Analysis of the spectrum

(i) The hydrogen atoms represented by the peak 1 must be attached to a methyl group.
(ii) The hydrogen atoms represented by the peak 3 must be attached to a methylene group.
428 A Textbook of Physical Chemistry

The above two points taken together suggests the presence of ethyl group. The relative
intensities of peaks 1 and 3 suggest the presence of two such ethyl groups placed in a
symmetrical manner with respect to each other.
(iii) The peak 2 has a relative intensity of 4 which is identical with that of peak 1. We
may conclude the presence of two other identical methylene groups. Since the peak 2 shows
no splitting, the two identical methylene groups are not attached to the neighbouring groups
containing hydrogen atoms.
(iv) If we subtract two CH3CH2— groups and the two CH2— groups from C8H14O4, we
get C2O4 as the remaining fragment. These may represent two groups.

(v) The two methylene groups of ethyl fragments must be attached to the electron
withdrawal groups as the peak 1 has the highest d -value.
(vi) The two bare methylene groups must be attached to the carbons of two carboxylate
groups.
The probable structure consistent with the above facts is

Problem 4.2.8 The PMR spectrum of an aromatic compound C12H14O4 shows the following characteristics:
(i) Triplet at t = 8.62; Integral trace = 16 units; relative intensities 1 : 2 : 1
(ii) Quartet at t = 5.65; Integral trace = 11 units; relative intensities 1 : 3 : 3 : 1
(iii) Singlet at t = 1.98; Integral trace = 11 units
Suggest the probable structure of the compound.
Solution Analysis of the spectrum
1. Triplet at t = 8.62 with relative intensities 1 : 2 : 1 suggests that the protons representing
this peak are attached to a methylene group.
2. Quartet at t = 5.65 with relative intensities 1 : 3 : 3 : 1 suggests that the protons
representing this peak are attached to a methyl group.
The above two points taken together suggest the presence of ethyl group in the molecule.
3. The peak at t =1.98 suggests that the protons representing this peak are not attached
to a group containing any hydrogen atoms. A very low value of t indicates that the protons
of peak 1 must be attached to a strong electron withdrawal group.
4. The ratio of integral trace is 16 : 11 : 11. Thus, a total of 38 units (16 + 11 + 11)
represents 14 protons of the molecule. It means that a step of 38/14 (= 2.7) units represents
one proton.
Thus, the number of protons represented by the peaks at t = 1.98, 5.65 and 6.82 are 4, 4
and 6, respectively. From this information, we may conclude that peaks 2 and 3 represent
two identical ethyl groups which are placed symmetrically with each other.
5. Since the compound is an aromatic one, we must be having at least a benzenoid group.
 Molecular Spectroscopy 429

Total number of carbon atoms Ï(4 carbon atoms from the ethyl groupings
accounted so far = 10 Ì
Ó + 6 carbon atoms from the benzenoid group)
Total number of hydrogen atoms Ï(10 hydrogen atoms from the ethyl groupings
Ì
accounted so far = 14 Ó + 4 hydrogen atoms of peak 1)
Thus, so far we have accounted for 10 carbon atoms and 14 hydrogen atoms, i.e. C10H14.
If we subtract this from C12H14O4, we get C2O4 as the remaining fragment indicating the
presence of two groups.

The probable structure consistent with the above fact is

Problem 4.2.9 3H5ON in an acidic medium. Suggest

its structure. Given that the peak 1 disappears in the presence of D2O.

13
units
2 3

13
units

1
6 units

5.78 6.17 7.37

5.0 6.0 7.0 8.0 9.0 10.0
B

Solution Analysis of the spectrum

1. Since the peak 1 disappears in the presence of D2O, it may represent a group containing
an active hydrogen. This group may be a hydroxyl group.
2. The peaks 2 and 3 must represent the hydrogen atoms attached to the methylene group.
3. The analysis of integral trace indicates the presence of 1, 2 and 2 protons within the
peaks 1, 2 and 3, respectively.
The point 3 suggests the presence of two methylene groups. These must be attached to each
other (point 2).
The only structure consistent with the above fact is
HOCH2CH2CN
430 A Textbook of Physical Chemistry

Problem 4.2.10 5 H 9 O 4 N. Suggest its

structure.

4 9 units

3
9 units

2 6 units
3 units
1

4.78 5.71 8.22 8.67

4.0 5.0 6.0 7.0 8.0 9.0 10.0
B

Solution Analysis of the spectrum

1. The integral trace analysis indicates the presence of 1, 2, 3 and 3 protons in the peaks
1, 2, 3 and 4, respectively.
2. The peak 1 which represents one proton must be attached to a methyl group. This
suggests the presence of group.

3. The quartet of peak 2 also indicates the coupling of two protons with the three protons.
Thus, the presence of —CH2CH3 group is indicated.
4. The points 2 and 3 discussed above account for all protons of the given molecule. The
remaining fragment still to be accounted for is CO4N. This may be present as
and —NO2 groups.

Structures consistent with the above fragments are

(A) (B)
However, the structure A may be ruled out on the basis that the expected t-value of CH
group will be far away from that of CH2 group, since the former is attached the two strong
electron withdrawing groups.

4.3 ELECTRON SPIN RESONANCE SPECTROSCOPY

Another spectroscopy which requires the use of radiation in the radiofrequency
region of electromagnetic radiation is the electron spin resonance (ESR) or electron
paramagnetic resonance (EPR). The theory of ESR is developed on the same line
as that of PMR. In the latter, we deal with the interaction of a positively charged
 Molecular Spectroscopy 431

below, in brief, the theory of ESR.

Magnetic The spinning of an electron is characterized by its spin quantum number which
Characteristics has a value of 1/2. The magnitude of angular momentum is s ( s +1 (h/2p) (i.e.
Associated with 3 h /4p). The z-component of the intrinsic angular momentum is m s (h/2p),
Spin of Electron where ms has a value of either +1/2 (a-spin) or –1/2 (b -spin). Thus, the angular

(Fig. 4.3.1). The orientation angle q is given by the relation

Ê s ( s + 1) h ˆ cos q = m h (4.3.1)
Ë 2p ¯
s
2p

or s ( s +1) cos q = ms (4.3.2)

Fig. 4.3.1 The two

orientations of spin
angular momentum
vector

The spinning of the electron around its own axis generates a magnetic dipole, the
magnetic moment of which is given by
Ê eh ˆ
mm = – g Á s ( s + 1)
Ë 4pme ˜¯

= – g mB s ( s +1) (4.3.3)

where g is known as the Lande splitting factor and mB is the basic unit of the
magnetic moment for the electron, known as the Bohr magneton. The direction of
the vector is that of the linear motion of a right-handed screw turned in the same
sense as the current and pointing perpendicular to the plane of the coil. The unit
of mm in SI unit is A m2.
The value of g for a free electron is found to be 2.002 3. The value of mB as
calculated in Eq. (3.15.5) is
mB = 9.274 1 ¥ 10 –24 J T–1 (4.3.4)
432 A Textbook of Physical Chemistry

The negative sign in Eq. (4.3.3) indicates that the direction of the magnetic
moment vector is opposite to that of the angular momentum as shown in Fig. 4.3.2.
z-axis

angular
momentum
vector
Fig. 4.3.2 The
orientation of magnetic
moment vector relative Magnetic
to that of angular moment
vector
momentum vector

Potential Energy The potential energy V B is given

of Electron in a by the expression
Magnetic Field V = – B mz = – B( mm cos q ) (4.3.5)
Substituting the expression of mm from Eq. (4.3.3), we get
( )
V = – B - g m B s ( s + 1) cos q (4.3.6)
= Bg mB ms
Since ms has only two values, we have
V+1/2 = (1/2) g mB B ; ms = 1/2 (4.3.7a)
V–1/2 = – (1/2) g mB B ; ms = – 1/2 (4.3.7b)
Variation of The variations of V+1/2 and V–1/2
Potential Energy energy of a-spin increases linearly whereas that of b-spin decreases with the
with Magnetic
Field direction of tiny magnet that is generated as a result of spinning of the electron. In
a-spin, the generated magnet has an unfavourable orientation, i.e. the north pole
of the tiny magnet is nearer to the north pole of the external magnet, thus causing
b-spin, the
generated tiny magnet has a favourable direction so as to give rise to a net attraction.

1 , a-spin
ms = +
2

Fig. 4.3.3 The

V

variation of potential 1 , b-spin

ms = –
energy of an electron 2
in the presence of an
No
field B
 Molecular Spectroscopy 433

Potential Energy The difference in energy between the two levels of electron at a given magnetic
Difference at a
Given Magnetic DV = (1.854 ¥ 10–23 J T –1) B
Field (1.854 ¥ 10-23 J T -1 ) B
n = = (2.86 ¥ 1010 s–1 T –1) B
(6.26 ¥ 10-34 J s)

strength, the energy difference is

n = (2.86 ¥ 1010 s–1 T –1) (0.3 T) = 8.58 ¥ 109 Hz
which falls in the radiofrequency region of the electromagnetic spectrum
(3 ¥ 106 – 3 ¥ 1010 Hz). On comparing the above energy difference between the
two levels of an electron with that involved in the two levels of a proton in NMR

this is the smaller mass of the electron relative to that of a proton.

Intensity of ESR The relative distribution of electrons over the two levels as governed by the
Signal Boltzman distribution law is
n1/ 2
n-1/ 2 = exp(– DV/ kT ) (4.3.8)

Thus, the lower level is more populated than the upper level. The difference of
population in the present case will be larger than the population difference between
the two PMR levels because of the larger value of DV. Consequently, the ESR
signals are expected to be more intense than those of PMR.
The mechanism of transition from the lower level to the upper level is similar

with a frequency equal to the angular frequency separation between the electronic
spin energy levels. Thus, the transition of electron from one level to another can

The ESR signals like PMR signals can be achieved in two ways: (i) varying

revert from the excited level to the ground level).† In order to improve accuracy,
†
One of the reasons of observing wide signal is the Heisenberg uncertainty principle,
according to which, DE◊Dt ≥ h/4p
DE does not have a single value but exhibits wide range.
The linewidth of the signal is the width at half height of the absorption signal. The other
factors causing line broadening are the Doppler effect (change in radiation frequency due to
different component velocity of molecules in the direction of radiation), pressure broadening
or collision broadening (change in stationary-state energy levels due to the varying
intermolecular forces, also shortening of the lifetimes of excited states due to molecular
collisions) and saturation broadening (change in population due to the intensity of radiation).
434 A Textbook of Physical Chemistry

the signals are recorded as the derivative of the absorption curve with respect to
the magnetic

absorption

Derivative of absorption
B B

Fig. 4.3.4 ESR signal

Hyperfine The interaction of the magnetic moment of an electron with those of surrounding
Structures
i.e. a single absorption signal splits into more than one signal. The interaction
energy depends on the relative direction of the magnetic moment of the electron
relative to that of the proton. This interaction energy is expressed as amsmI where
a is a constant term, known as the or the
splitting constant. It represents the extent of interaction between the electron and
the interacting nucleus.
The electronic energy including the above interaction energy becomes
V = g mBmsB + amsmI
Thus, for a given value ms, the potential energy also depends on the value of
mI. For a proton, we have
V+1/2, +1/2 = (1/2) gmBB + (1/4)a
V+1/2, –1/2 = (1/2) gmBB – (1/4)a
V–1/2, –1/2 = – (1/2) gmBB + (1/4)a
V–1/2, +1/2 = – (1/2) gmBB – (1/4)a
ms and the second that of mI. The

in Fig. 4.3.5. The broken lines represent energies in the absence of interactions.
The value of B at which adsorptions are expected (only schematic) are shown at

The selection rules for the electron magnetic transitions are Dms = 1 and
DmI = 0, i.e. during the transition from ms = – 1/2 to ms = 1/2, the directions of
the associated nuclear spins remain unchanged. Thus, if the system as shown in

of energies
E1 = g mBB – (1/2) a ; mI = – 1/2
E2 = g mBB + (1/2) a ; mI = + 1/2
 Molecular Spectroscopy 435

Fig. 4.3.5 Variation of

potential energy of an
electron in a varying

The separation between these two absorptions is a. Thus, the constant a

In terms of frequency unit, we have

g mB B 1 a
n1 = - ; mI = – 1/2
h 2h
g mB B 1 a
and n2 = + ; mI = + 1/2
h 2h

hn a
B1 = - ; mI = + 1/2
g mB 2 g mB
hn a
and B2 = + ; mI = – 1/2
g mB 2 g mB
For example, the ESR spectrum of the hydrogen atom produced by electric

of about 0.05 T.
Interactions with The energy of an unpaired electron coupled with two nuclei is given by
Two Nuclei
V = gmBmsB + a1ms mI1 + a2 ms mI 2
where a1 and a2 are the coupling constants of the electron interacting with nuclei 1
and 2, and mI1 and mI 2 are the quantum numbers of the component of the nuclear
spins 1 and 2, respectively.
For the coupling with the two protons, each electronic level will split into a
quartet. These are
436 A Textbook of Physical Chemistry

V–1/2, +1/2, +1/2 = – (1/2) g mBB – (1/4)a1 – (1/4)a2

V–1/2, +1/2, –1/2 = – (1/2) gmBB – (1/4)a1 + (1/4)a2

V–1/2, –1/2, +1/2 = – (1/2) gmBB + (1/4)a1 – (1/4)a2

V–1/2, –1/2, –1/2 = – (1/2) gmBB + (1/4)a1 + (1/4)a2

V+1/2, –1/2, –1/2 = (1/2) gmBB – (1/4)a1 – (1/4)a2

V+1/2, –1/2, +1/2 = (1/2) gmBB – (1/4)a1 + (1/4)a2

V+1/2, +1/2, –1/2 = (1/2) gmBB + (1/4)a1 – (1/4)a2

V+1/2, +1/2, +1/2 = (1/2) gmBB + (1/4)a1 + (1/4)a2

ms and the second and third those

of mI1 and mI2, respectively (Fig. 4.3.6).

ms mI mI
1 2 V
+ 1/2 1 gm 1 1
BB+ a1 + a2
2 4 4
+ 1/2

1 gm 1 1
BB+ a1 – a2
– 1/2 2 4 4
+ 1/2

+ 1/2 1 gm 1 1
BB– a1 + a2
2 4 4

– 1/2
1 gm 1 1
BB– a1 – a2
– 1/2 2 4 4
E1 E2 E3 E4
V

– 1/2 1 gm 1 1
– BB + a + a2
2 4 1 4
– 1/2

1 gm 1 1
– BB + a – a2
+ 1/2 2 4 1 4

– 1/2
– 1/2 1 gm 1 1
– BB– a + a2
2 4 1 4

+ 1/2
1 gm 1 1
– BB– a – a2
+ 1/2 2 4 1 4
Fig. 4.3.6 Interaction
of the electron with two No Field Coupling
protons with a1 > a2 field
 Molecular Spectroscopy 437

Following the selection rules (Dms = 1 and DmI = 0), the energies of four
absorption lines observed will be
E1 = gmB B – (1/2)a1 – (1/2)a2 ; mI1 = – 1/2, mI2 = –1/2
E2 = gmB B – (1/2)a1 + (1/2)a2 ; mI1 = – 1/2, mI2 = +1/2
E3 = gmB B + (1/2)a1 – (1/2) a2 ; mI1 = +1/2, mI2 = –1/2
E4 = gmB B + (1/2)a1 + (1/2)a2 ; mI1 = + 1/2, mI2 = +1/2
If the frequency is held constant, the four signals will be observed at the

hn a1 a2
B1 = - - ; mI1 = + 1/2, mI2 = +1/2
g mB 2 g mB 2 g mB
hn a1 a2
B2 = – + ; mI1 = + 1/2, mI2 = –1/2
g mB 2 g mB 2 g mB
hn a1 a2
B3 = + – ; mI1 = – 1/2, mI2 = +1/2
g mB 2 g mB 2 g mB
hn a1 a2
B4 = + + ; mI1 = – 1/2, mI2 = –1/2
g mB 2 g mB 2 g mB
Three Subcases Three cases may be distinguished on the basis of the relative magnitudes of a1
and a2
(i) a1 > a2
(ii) a1 a2 a2 has a negligible value, then the interaction with the nucleus
2 may be neglected. The two lines which are observed due to the interaction with
the nucleus 1 are
hn a1
B1 = – ; mI1 = 1/2
g mB 2 g mB

hn a1
B2 = + ; mI1 = – 1/2
g mB 2 g mB
Each line will be twice as intense as the corresponding line in the case (i) discussed
above.
(iii) a1 = a2. Three lines will be observed at
hn a
B1 = – ; mI1 = + 1/2, mI2 = +1/2
g mB g mB

hn ÔÏmI1 = +1/ 2, mI 2 = -1/ 2

B2 = ; Ì
g mB ÔÓmI1 = -1/ 2, mI 2 = +1/ 2
hn a
and B3 = + ; mI1 = – 1/2, mI2 = – 1/2
g mB g mB
The second line will be twice as intense as the other two, i.e. their relative ratio
438 A Textbook of Physical Chemistry

ms mI mI
1 2
+1/2 1gm B+ 1 a
B 2
2
+1/2

+1/2 –1/2 1 gm B
B
+1/2 2

–1/2
1 g 1
mB B – a
–1/2 2 2
V

–1/2 1 1
– gmB B + a
2 2
–1/2

+1/2 1 gm B
– B
+1/2 –1/2 –1/2 2

+1/2
1 1
– gmB B – a
+1/2 2 2

No Coupling Energy
Field
field

Fig. 4.3.7 Interaction

of an electron with two B1 B2 B3
identical protons B

Interaction with n The energy expression will be given by

Nuclei V = g mBms B + a1ms mI1 + a2ms mI2 + + anms mIn
and the resonance condition is given by
hn = g mB B + a1 mI1 + a2 mI2 + + an mIn (4.3.9)
The number of mI is given by the relation 2I + 1, where I is the spin quantum
number of the nucleus. Thus, the interaction of an electron with n nuclei gives rise
to N transitions, where
N = (2I1 + 1) (2I2 + 1) (2In + 1) (4.3.10)
A special case of interest is worth mentioning here. This is when all the n protons
are identical, i.e. a1 = a2 = = an. The resonance condition is
 Molecular Spectroscopy 439

hn = gmB B + a(mI1 + mI2 + + mIn) (4.3.11)

If n is held constant, the values of B at which absorptions are expected are given
by the expression
B = B0 – a¢ (mI1 + mI2 + + mIn)
Since for a proton the permitted values of mI are + 1/2 and – 1/2, the sum in the
above parenthesis can have (n + 1) different values as given by
, – ÊÁ - 1ˆ˜ , -
n n n n
, – 1,
2 2 Ë 2 ¯ 2
Thus, the expected number of lines are (n + 1). All of them will be equidistant
from each other. The intensity of an absorption line will be directly proportional
to the degree of degeneracy of the involved levels. The relative intensities may
be computed from
n n!
Cm =
m !(n - m)!
where m = 0, 1, …, n. The above scheme may be illustrated with the example of
p-benzosemiquinone radical anion.

relative intensities as 4C0 4C1 4C2 4C3 4C4

shown in Fig. 4.3.8.
ESR Spectrum of The benzene anion radical may be prepared by the chemical reduction of benzene
Benzene Anion with alkali metal in an inert solvent such as 1, 2-dimethoxyethane or tetrahydrofuran.
Radical

¥ 10–4 T.
The unpaired electron in benzene anion radical is present in the antibonding
p-molecular orbital which has a node in the plane of the molecule. Due to this, the
carbon atoms have zero-electron densities. However, this p-electron can polarize
electron pairs of C—H bond, causing hydrogen atom to have a some unpaired spin

a) and the unpaired spin density (r)

aH = Q rp,C
where Q is called the spin-polarization parameter. For p radicals, its value is

For methyl radical, the value of rp,C

440 A Textbook of Physical Chemistry
ØØØØ
ØØ Ø Ø Ø ØØ
≠ Ø, ≠Ø , Ø≠≠, Ø ≠
Ø Ø≠ Ø ≠ØØ Ø
≠ ØØ, Ø , ØØ ≠≠, Ø , Ø Ø≠
≠ØØØ, Ø≠ØØ, ØØ≠Ø, ØØØ≠
ØØØØ

ØØØØ
≠ Ø ≠Ø ≠ Ø ≠≠Ø
ØØ , Ø Ø, Ø , ØØ
≠ ØØ Ø Ø ≠Ø Ø ≠Ø
Ø , Ø≠ Ø, Ø ≠ Ø , ØØ≠
≠ØØØ Ø≠ØØ ≠ØØØ Ø≠ØØ
, , ,
ØØØØ
No Field Coupling Description
field

absorption
Fig. 4.3.8 ESR
spectrum of
p-benzosemiquinone derivative
radical anion

Example 4.3.1
unoccupied molecular orbital of naphthalene is of the form

y [y 2 p z (1) + y 2 p z ( 4) - y 2 p z (5) - y 2 p z (8) ]

[ - y 2 p z ( 2 ) - y 2 p z ( 3) + y 2 p z ( 6 ) + y 2 p z ( 7 ) ]
where numbering of carbon atoms in naphthalene goes as follows.

a and b carbon atoms.

 Molecular Spectroscopy 441

Solution

McConnell relation, aH = Q rp,C.

The p 2
which is
0.1809. Hence,
a = Q rp,C ¥ 10–4 T) (0.180 9)
¥ 10–4 T
The p 2
which is

Hence a = Qrp,C ¥ 10–4 ¥ 10–4 T.

The observed values are 4.94 ¥ 10 T and 1.83 ¥ 10 T, respectively.
–4 –4

Example 4.3.2 The benzene radical anion C H – has a g

Solution We have
n = 9.302 GHz = 9.302 ¥ 109 s–1
DV = hn ¥ 10–34 J s) (9.302 ¥ 109 s–1 ¥ 10–24 J
Now since, DV = g mB B, we have
DV (6.164 ¥ 10-24 J )
B= = = 0.332 T
g mB (2.002 5)(9.2741 ¥ 10-24 J T -1 )

Example 4.3.3

Solution

B = B0 + a1 mI1 + a2 mI 2 (Eq.4.3.9)
where we can identify a1 = 2.0 mT, and a2 mI and mI ,
1 2

B1
B2
B3
B4
All the four lines will be equally intense.

Example 4.3.4 Predict the form of spectrum of a radical containing one 14N nucleus (I = 1, a = 1.03
mT) and two equivalent protons (I = 1/2, a
Solution Due to 14N, the line will split into three lines (2I + 1 = 3) of equal intensities with
the separation of 1.03 mT. Each line will further split into three lines due to the presence
442 A Textbook of Physical Chemistry

Example 4.3.5 spectrum of the radical

∑
CD3 (I = 1 for D).
Solution Each of the two energy levels of electron will show the splitting as shown in Fig. 4.3.9. Thus,
the

Fig. 4.3.9

Example 4.3.6 Predict the appearance of the a(CH 2) =

0.224 mT and a(CH3
Solution The ethyl radical contains two types of protons, viz., methylene and methyl protons. Due
to the methylene protons, the line will split into three lines of relative intensities

For identical protons, the lines are observed at

hn
= B0 + a(mI + mI + ) (4.3.11)
g mB 1 2

For methylene protons SmI have the values of + 1, 0 and –1. Hence, the lines with relative

B1 = B0 + 0.224 mT
B2 = B0
B3 = B0 – 0.224 mT
 Molecular Spectroscopy 443

For methyl protons S mI have the values of 3/2, 1/2, – 1/2 and –3/2. Thus, each of the above

B11 = B0 B0
B12 = B0 B0
B13 = B0 B0 + (0.09 mT)
B14 = B0 B0 – (0.178 mT)

B21 = B0 B0 + (0.402 mT)

B22 = B0 B0 + (0.134 mT)
B23 = B0 B0 – (0.134 mT)
B24 = B0 B0 – (0.402 mT)

B31 = B0 B0 + (0.178 mT)

B32 = B0 B0 – (0.09 mT)
B33 = B0 B0
B34 = B0 B0

arranged in the increasing order of B

Relative intensities 1 2 1 methylene

protons

methyl
protons

1 2 3 1 6 3 3 6 1 32 1 Relative
intensities

Fig. 4.3.10 –0.6 –0.4 –0.2 B0 +0.2 +0.4 +0.6

4.4 ROTATIONAL SPECTRA OF DIATOMIC MOLECULES

Introduction The absorption spectrum in the microwave region corresponds to the promotion
of a molecule from its lower rotational level to the higher ones. The correlation
of experimental absorption with the theoretical difference in energy levels yields
information regarding the interatomic distances of gaseous diatomic molecules.
444 A Textbook of Physical Chemistry

Expression
of Rotational we have replaced a diatomic molecule by a rigid rotator model. In this model, a
Energies gaseous molecule is represented by a dumb-bell having two balls of masses m1
and m2 (representing the masses of the atoms) which are connected to each other
by a rigid rod of length r (representing the distance between the two atoms in
the molecule). It was seen that the rotational energies of diatomic molecules are
quantized and are given by the expression
h2
E= J (J + 1) (4.4.1)
8p 2 I
where I is the moment of inertia of the molecule and J is the rotational quantum
number which can have integral values of 0, 1, 2, 3, …. The moment of inertia
is given by
I = m r2 (4.4.2)
here m, the reduced mass, is given by
1 1 1 m1m2
= + , i.e. m = m +m (4.4.3)
m m1 m2 1 2

It may be noticed that the energy expression (Eq. 4.4.1) may be obtained by
introducing the quantization condition of angular momentum in the classical
expression of rotational energy, i.e.
1 1 ( I w ) 2 1 L2
E= Iw 2 = = (4.4.4)
2 2 I 2 I
where L is the angular momentum whose quantized values are given by

J ( J + 1) Ê ˆ ;
L= h J = 0, 1, 2, 3, …
Ë 2p ¯

given by Eq. (4.4.1).

Degeneracy of The condition of quantization of angular momentum means that a diatomic molecule
Rotational Levels cannot rotate with any arbitrary angular velocity but with a velocity that leads to
any of the quantized values of angular momentum of 0, 2 (h/2p), (h/2p), …,
and so on. The angular momentum, being a vector quantity, also has a direction
which acts along the axis of rotation. The latter lies perpendicular to the plane of

quantization of angular momentum vector, i.e. the angular momentum vector

cannot have any arbitrary direction in space but can have only a few selective
orientations as dictated by the quantization condition of the component of angular
momentum vector along a given reference direction. The latter is conveniently
z-axis.
These orientations are characterized by the magnetic quantum number mJ which
determines the allowed values of z-component of angular momentum, i.e. mJ (h/2p).
For a given value of J, the allowed values of mJ are
J, (J – 1), …, 0, …, – (J – 1), – J
 Molecular Spectroscopy

Thus, a molecule can have (2J + 1) orientations of its angular momentum vector
or in other words, it can have (2J + 1) orientations in space and thus (2J + 1)
different axes of rotation. The energy of the rotator depends only on the quantum
number J and thus all these (2J + 1) orientations are degenerate. Figure 4.4.1
depicts the orientations of angular momentum vectors for J = 1 and J = 2. For
J = 1, we have three different directions of angular momentum and thus three
different axes of rotation. The rotations around these three axes carry the same
amount of rotational energy. Similarly for J

+2 (h/2p)
6 (h/2p)
2 (h/2 p)
+1 (h/2p) +1 (h/2p)
6 (h/2p)

0 (h/2p) 2 (h/2p) 6 (h/2p)

0 (h/2p)

6 (h/2p)
–1 (h/2p)
–1 (h/2p)
2 (h/2p)

Refrence 6 (h/2p)
Fig. 4.4.1 Orientations direction –2 (h/2p)
of angular momentum
vectors for J = 1 and J = 2 J=1 J=2

Energy Level The allowed rotational energies are given by the expression
Diagram
h2
E= J(J + 1); J = 0, 1, 2, 3, … (Eq. 4.4.1)
8p 2 I
In spectroscopy, the rotational energies is expressed in wavenumber and is known
F). These are obtained by dividing rotational energy
with hc. Hence

E ( h 2 / 8p 2 I ) J ( J + 1) h
F= = = 2 J ( J + 1)
hc hc 8p I c

= B J (J + 1) ; J = 0, 1, 2, 3, …
2
where B = h/8p Ic and is known as the rotational constant. In trems of rotational
constant B, the expression of rotational energy is

E = B h c J (J + 1); J = 0, 1, 2, 3, … (4.4.7)

The approximate order of the value of B may be seen from the following calculations
on CO and HBr.
 A Textbook of Physical Chemistry

Carbon monoxide For CO, r CO = 113 pm. The reduced mass is

mC mO {(0.012 kg ) / (6.022 ¥ 1023 )}{(0.016 kg ) / (6.022 ¥ 1023 )}
mCO = =
mC + mO {(0.012 kg ) / (6.022 ¥ 1023 )} + {(0.016 kg ) / (6.022 ¥ 1023 )}
= 1.14 ¥ 10 kg
Thus, its moment of inertia is
I = m r2 = (1.14 ¥ 10 kg) (113 ¥ 10–12 m)2
¥ 10–47 kg m2
h (6.626 ¥ 10-34 J s)
Hence B= =
8p 2 Ic 8 (3.14) 2 (14.5 ¥ 10-47 kg m 2 ) (2.998 ¥ 108 m s -1 )
= 1.932 ¥ 102 m–1
The value of rotational constant in joule is
Bhc = (1.932 ¥ 102 m–1 ¥ 10–34 J s) (2.998 ¥ 108 m s–1 )
= 3.838 ¥ 10–23 J
Hydrogen bromide For HBr, rHBr = 141 pm. Thus, we have
mH mBr {(0.001 kg ) / (6.022 ¥ 1023 )}{(0.079 9 kg ) / (6.022 ¥ 1023 )}
mHBr = =
mH + mBr {(0.001 kg ) / (6.022 ¥ 1023 )} + {(0.079 9 kg ) / (6.022 ¥ 1023 )}
¥ 10–27 kg
IHBr = m r2 ¥ 10–27 kg) (141 ¥ 10–12 m)2
¥ 10–47 kg m2
h (6.626 ¥ 10-34 J s)
B= =
8p Ic
2
8 (3.14) (3.26 ¥ 10-47 kg m 2 ) (2.99 8 ¥ 108 m s -1 )
2

¥ 102 m–1
The value of rotational constant in joule is
Bhc ¥ 102 m–1 ¥ 10–34 J s) (2.998 ¥ 108 m s–1)
= 1.707 ¥ 10–22 J.
The various allowed rotational energy levels for these two molecules are shown
in Fig. 4.4.2.

Relative The relative populations of energy levels can be computed by the Boltzmann
Populations of equation
Energy Levels n2
n1 = exp(– D E/kT) (4.4.8)
where n1 and n2 are the number of molecules in the lower and upper levels,
respectively, and D E is the energy difference between the two levels. The population
in each level is given by the expression
nJ μ exp(– EJ /kT ) (4.4.9)
 Molecular Spectroscopy 447

Fig. 4.4.2 The

allowed rotational
energy levels for CO
and HBr

Since the molecule can rotate in 2J + 1 different planes with the same rotational
energy, the various rotational energy states are degenerate by a factor of 2J + 1.
This factor is known as the multiplicity of energy level and is written as gJ . The
probability of occupancy of these degenerate states are completely identical and
thus all the degenerate states are equally populated. Incorporating this multiplicity
factor in Eq. (4.4.9), we get
nJ μ gJ exp(– EJ /kT ) (4.4.10)
From Eq. (4.4.10), we may write
nJ ¢ (2 J ¢ + 1) exp (- EJ ¢ / kT ) (2 J ¢ + 1)
= = exp( – D E/kT ) (4.4.11)
nJ ¢¢ (2 J ¢¢ + 1) exp (- EJ ≤ / kT ) (2 J ¢¢ + 1)
where J ¢ and J≤ are the rotational quantum numbers of the higher and lower energy
levels, respectively.
448 A Textbook of Physical Chemistry

A qualitative discussion regarding the relative populations of various energy

levels may be made here. At the very outset, it may be concluded that many of
the lower rotational levels are expected to be thickly populated since D EJ < kT.
This also follows immediately from the fact that the thermal energy (= kT = 4.1 ¥
10–21 J at 298 K), which is much larger than the energy difference of many lower
levels with respect to J
energetically most stable level (i.e. J = 0 for which EJ = 0) to the higher ones
(Fig. 4.4.2).
Now according to Eq. (4.4.10), the number of molecules in any level depends
on two factors, viz., the multiplicity factor 2J + 1 and the exponential term
exp(– EJ /kT ). These two factors have altogether different characteristics. As J
increases, the multiplicity factor increases steadily whereas the exponential factor
decreases slowly in the beginning and more rapidly with the higher values of J.
As a consequence of these two factors, the number of molecules (or the relative
population with respect to J = 0 level) in the various levels increases in the beginning
and after passing through the maximum, it decreases.
Table 4.4.1 depicts the results of calculation on CO, for which the rotational
constant B = 3.838 ¥ 10–23 J. Figure 4.4.3 shows the corresponding plots of relative
populations against the value of J.

Table 4.4.1 The Value of gJ exp(– EJ /kT) for CO at 298 K for Different Values of

EJ {= Bhc J ( J + 1)}

J gJ = ( 2J + 1) 10–23 J exp (– EJ / kT) gJ exp (– EJ / kT )

0 1 0
1 3 2B hc
B hc
3 7 12B hc
4 9 20B hc
B hc
B hc
B hc
8 17 72B hc
9 19 90B hc
10 21 110B hc
11 23 132 B hc
B hc
13 27 182 B hc
14 29 210B hc
B hc
 Molecular Spectroscopy 449

Fig. 4.4.3 The

relative populations
in various rotational
levels of CO at 298 K
Maximum The value of J (nearest integral) having maximum number of molecules can be
Populated determined by differentiating Eq. (4.4.10) with respect to J and then setting the
Rotational Level resultant expression to zero.
Thus, we have
dnJ d { g J exp(- EJ / kT }
= =0
dJ dJ
This gives
d
{(2J + 1) exp(– BhcJ(J + 1)/kT)} = 0
dJ
or 2 exp(–BhcJ(J + 1)/kT)
Bhc
– (2J + 1) (2J + 1) exp(– Bhc J (J + 1)/kT ) = 0
kT
Bhc
or 2 – (2J + 1)2 =0
kT
kT 1
or J= – (4.4.12)
2 Bhc 2
For CO at 298 K, the value of J is equal to
1/2
Ï 1 (1.38 ¥ 10-23 J K -1 ) (298 K ) ¸ 1
Ì -23 ˝ – 7
Ó 2 (3.83 ¥ 10 J ) ˛ 2
This value is also in agreement with the data recorded in Table 4.4.1.
Mechanism The interaction between the radiation and the rotating molecule is through the
of Interaction
between the rotation of the molecule. The electrical component of the radiation oscillates in
Radiation and the a plane perpendicular to the direction of propagation of the wave. The frequency
Rotating Molecule of this oscillating electrical component is equal to the frequency of the radiation.

molecule which has a permanent dipole moment. On rotation, the positive and
negative ends of the molecule change places periodically and thus the component
of dipole moment in a given direction such as the vertical component in the

rotation of the molecule.

 A Textbook of Physical Chemistry

+ QB A B A
A B B A A B
– QA
B A B

Fig. 4.4.4 Fluctuation

Direction
in the vertical of
component of the dipole
dipole moment during
the rotation of the
molecule having a Vertical Time
permanent dipole component
of dipole
moment moment

frequency of rotation of the molecule) becomes equal to that of the electric

component of the radiation (i.e. the frequency of radiation itself), there occurs the
phenomenon of resonance and hence energy can be transferred from the radiation
to the molecule and vice versa. If the energy is absorbed by the molecule, it is
promoted from a lower rotational level to a higher level. On the other hand, if the
energy is given out, the molecule comes back from a higher level to a lower level.
A molecule having no permanent dipole moment does not generate the oscillating

molecule does not exhibit the rotational spectrum. Thus, the essential criterion for
a molecule to exhibit rotational spectrum is that it must have a permanent dipole
moment. The molecules with permanent dipole moment are known as microwave
active molecules and those with no permanent dipole moment are known as
microwave inactive molecules.
The homonuclear molecules such as H2, N2, O2, Cl2, etc., have no permanent
dipole moment and hence do not exhibit the rotational spectra. Molecules having
centre of symmetry do not possess permanent dipole moment and hence also fall
in the category of microwave inactive molecules. Examples include
, etc. Molecules such as CH 4 also do not have
permanent dipole moment and thus are microwave inactive molecules.
Selection Rule The quantum mechanical calculations show that for a rigid rotator, the transition
from one rotational level to another occurs with the condition of
DJ = ± 1 (4.4.13)
that is, the change in the rotational quantum number is unity.† Equation (4.4.13) is,
†
In deriving the selection rule for rotational changes, the transition moment integral involves
the term
p 2p

Ú Ú [Y mJ ]*Y mJ¢¢ cosq sinq dq dj

0 0

ÈÏ ( 2 J + 1)( J - | m |)! ¸1/ 2 |m| ˘ È 1

where YmJ = QJ,|m| Fm= Í Ì ˝ PJ ˙ Í eimj ˘˙
ÍÎÓ 2( J + | m |)! ˛ ˙˚ Î 2p ˚
Integration over j requires that m = m¢ for a nonzero value of the integral. Hence,
the selection rule is Dm = 0. Integration over q requires that for m = m¢, we must have
DJ = ± 1 for a nonzero value of the integral.
 Molecular Spectroscopy

in fact, the selection rule for the rotational transitions. The probability of transition
from any quantum level to the next higher level is the same and all other transitions
are forbidden. For example, if a molecule is in the J = 0 level, it can be promoted
only to J = 1 level and if it exists in J = 1 level, it can be promoted with equal
probability to J = 2 level and so on.

Appearance The difference between the two rotational terms is

of Rotational
D F = BJ ¢(J¢ + 1) – BJ≤(J ≤ + 1) (4.4.14)
Spectrum
where J ¢ and J≤ are the rotational quantum numbers of higher and lower levels
respectively. According to the selection rule, we have
J¢ = J≤
Subsituting the above relation in Eq. (4.4.14), we get
D F= B (J≤ + 1) (J ≤ + 2) – BJ≤(J≤ + 1)
= B(J ≤ + 1) (J≤ + 2 – J ≤ )
†
= 2B (J≤
Since many of the lower rotational levels are populated, it is expected that the
pure rotational spectrum would consist of more than one absorption line. In fact,
a series of absorption lines at the wave numbers listed in Table 4.4.2 are observed.

Table 4.4.2
Transition D F = 2B(J" + 1)

J ¢ = 1 ¨ J≤ = 0 2B
J¢ = 2 ¨ J ≤ = 1 4B
J¢ = 3 ¨ J ≤ B
J¢ = 4 ¨ J ≤ = 3 8B
J¢ ¨ J≤ = 4 10B
— — —
— — —
— — —

The spacing between any two nearest absorption signals is constant and is equal
to 2B. The intensities of all these transitions are not equal. It may be expected that
the number of molecules promoted from a given level depends on its population, i.e.
larger the population, larger the number of molecules that can be promoted to the
next higher level, and hence larger the intensity of absorption. Thus, the expected
relative intensities of various transitions follow the curve as shown at the foot of

after passing through a maximum, it diminishes.

† For transition J ¢ = J≤ + 1, D F is labeled as D FJ ¢¢ + 1

2
 A Textbook of Physical Chemistry

12 156 B

11 132 B

10 110 B

9 90 B

8 72 B

7 56 B
6 42 B

5 30 B
4 20 B
3 12 B
2 6B
1 2B
0 2B 4B 6B 8B 10B 12B 14B 16B 18B 20B 22B 24B D E 0B

0 1
1 2

2 3
11 12
3 4 10 11

4 5 9 10
5 6 7 8 8 9
6 7
Fig. 4.4.5 A typical
rotational spectrum 2B 2B 2B 2B 2B 2B 2B 2B 2B 2B 2B

Application of The rotational spectrum can be used to determine the bond distance of a diatomic
the Spectrum to
Determine Bond is found to be at 3.842 4 cm–1. This is equal to 2B. Thus, we have
Distance
= 2B = 3.842 4 cm–1
∼
n J¢ = 1¨ J≤ = 0

Thus B = 1.921 2 cm–1 = 1.921 2 ¥ 102 m–1

h h
Since B= therefore I =
8p Ic
2
8p 2 Bc
Substituting the values, we have
(6.626 ¥ 10-34 J s)
I=
8(3.14) 2 (1.921 2 ¥ 102 m -1 ) (2.998 ¥ 108 m s -1 )
¥ 10 kg m2
Now I = m r2 therefore r = (I/m)1/2
 Molecular Spectroscopy

The values of m for CO molecule is

m1m2 {(0.012 kg )/(6.022 ¥ 1023 )}{(0.016 kg )/(6.022 ¥ 1023 )}

m= =
m1 + m2 {(0.012 kg ) / (6.022 ¥ 1023 )} + {(0.016 kg ) / 6.022 ¥ 1023 )}

0.012 ¥ 0.016
= kg = 1.14 ¥ 10 kg
0.028 ¥ 6.022 ¥ 1023

1/ 2
Ê 1.458 ¥ 10-46 kg m 2 ˆ
1/ 2
ÊIˆ
Hence r= Á ˜ = Á
Ë m¯ Ë 1.14 ¥ 10-26 kg ˜¯

= 1.13 ¥ 10–10 m = 1.13 ¥ 10–8 cm = 113 pm

Effect of Isotopic When a particular atom in a molecule is replaced by its isotope, the resultant
Substitution molecule is found to be chemically identical to the original molecule. The
internuclear distance and the electron distribution of the molecule do not change by
the isotopic substitution and thus its dipole moment remains unaltered. However,
there occurs an increase in the moment of inertia of the molecule. Since I appears
in the denominator of the expression of B(= h/8p2Ic), it follows that an increase
in the value of I leads to a decrease in the value of B. This, in turn, decreases the
energies of various rotational levels with the result that the energy levels become
closer to one another. As a consequence of this, the spacing between the two
absorption signals, which is equal to 2B, is also decreased.

A closer examination of the rotational spectrum of gaseous molecules obtained

by isotopic substitution helps not only to determine the atomic masses of isotopes
but also their relative abundance from the comparison of absorption intensities.

Example 4.4.1 12
C O is found to occur at 3.842 4 cm–1 while that of
13
C 3 4 cm . Assuming the molar masses of O and 12
–1 –1

and 12.0000 g mol–1 respectively, calculate the molar mass of 13C.

Solution We are given that
2 B12 = 3.842 4 cm–1 and 2 B13 –1
C16O C16O

Thus B12 = 1.921 2 cm–1 and B13 –1

C16O C16O
Taking the ratio of the two Bs, we have
B12 h / 8p 2 I12 c I13 m13
C16O C16O C16O C16O
= 2
= =
B13 h / 8p I13 c I12 m12
C16O C16O C16O C16O

m13 m16 (m12 + m16 )

C O C O
= ¥
(m13 + m16 ) m12 m16
C O C O

m13 (m12 + m16 ) M13 ( M12 + M16 )

C C O C C O
= =
m12 (m13 + m16 ) M12 ( M13 + M16 )
C C O C C O
454 A Textbook of Physical Chemistry

M13 (12.000 0 + 15.999 4)

1.921 2 cm -1 C
Thus =
1.836 7 cm -1 (12.000 0)( M13 + 15.999 4 g mol-1 )
C

Solving for M13 , we get

C

M13 = 13.000 7 g mol–1

C

Example 4.4.2 The wavenumbers of pure rotational lines of HBr are represented by the equation
∼
n = (16.90 J ) cm-1, where J has integral values. Calculate: (a) The moment of inertia.
(b) The internuclear distance of HBr. (c) Rotational frequency and the period of rotation
for the rotational quantum number 1. (d) Which rotational energy level has the highest
population at 298 K? (e) What is the change in rotational constant when H is replaced by D?
Solution (a) The difference between the two successive rotational trems as given by Eq. (4.4.16) is

DF = 2B(J ≤ + 1) = 2BJ ¢
Equating this to the given value, we get
2B = 16.90 cm- 1
or B = 8.45 cm -1 = 8.45 ¥ 102 m-1
Now B is given by

h
B=
8p 2 Ic

h (6.626 ¥ 10-34 J s)
Hence I= =
8p 2 Bc 8(3.14) 2 (8.45 ¥ 102 m -1 )(2.998 ¥ 108 m s -1 )

= 3.316 ¥ 10- 47 J s2 ∫ 3.316 ¥ 10-47 kg m2

(b) Now
I = m r2
where m for HBr is

mH mBr {(0.001 kg) / (6.022 ¥ 1023 )}{(0.079 9 kg ) / (6.022 ¥ 1023 )}

m HBr = =
mH + mBr {(0.001 kg ) / (6.022 ¥ 1023 )} + {(0.079 9 kg ) / (6.022 ¥ 1023 )}

= 1.64 ¥ 10 -27 kg
-47 1/ 2
I = Ê 3.316 ¥ 10 kg m ˆ
2
Thus r= ÁË 1.64 ¥ 10-27 kg ˜¯
m

= 1.42 ¥ 10 -10 m = 142 pm

(c) The rotational term for J = 1 will be

F1 = 16.90 cm-1 = 16.90 ¥ 102 m-1

Converting this to the joule unit, we have

E = hcF1= (6.626 ¥ 10 -34 J s) (2.998 ¥ 108 m s -1) (16.90 ¥ 102 m -1)

= 3.357 ¥ 10 -22 J
 Molecular Spectroscopy 455

From classical mechanics, the rotational energy E of the molecule is given by

1
E= Iw 2
2
where w is the angular velocity in radians per second.
Hence
1/ 2
2 E Ê 2 ¥ 3.357 ¥ 10-22 J ˆ
w= =Á
I Ë 3.316 ¥ 10-47 kg m 2 ˜¯
= 4.50 ¥ 1012 s-1
Now w = 2pn, where n is the frequency of rotation. Hence
w 4.50 ¥ 1012 s -1
n= = = 7.169 ¥ 1011 s -1
2p 2 ¥ 3.14
Period of rotation, t = 1/n = 1.395 ¥ 10 -12 s
(d) The rotational level having maximum population is given by the quantum number
1 kT 1
J= -
2 Bhc 2
1/ 2
Ï1 (1.38 ¥ 10-23 J K -1 )(298 K ) ¸ 1
= Ì 2 -1 -34 -1 ˝
-
Ó 2 (8.45 ¥ 10 m )(6.626 ¥ 10 J s)(2.998 ¥ 10 m s ˛
8
2
= 3.5 - 0.5 = 3
(e) The substitution of H by D does not affect the internuclear distance of HBr but changes
only its reduced mass. Since B is inversely related to I, we may write

BDBr m HBr
=
BHBr m DBr

mD mBr {(0.002 kg) / (6.022 ¥ 1023 )}{(0.079 9 kg ) / (6.022 ¥ 1023 )}

But m DBr = =
mD + mBr {(0.002 kg ) / (6.022 ¥ 1023 )} + {(0.079 9 kg ) / (6.022 ¥ 1023 )}
= 3.239 ¥ 10 -27 kg
Ê 1.64 ¥ 10-27 kg ˆ
Hence BDBr = Á (8.45 cm -1)
Ë 3.239 ¥ 10-27 kg ˜¯
= 4.278 cm-1

Example 4.4.3 (a) Show that the frequency of rotation (s-1) of a rigid rotator increases with increase in
rotational quantum number J according to the expression
h
n= J ( J + 1)
4p 2 I
(b) The increase in the frequency of rotation increases the centrifugal force which tends
to move the atoms apart. Consequently, the bond length of a diatomic molecule increases
with increase in the value of J, i.e. the molecule does not behave as a rigid rotator but as
a nonrigid rotator. For a molecule executing simple harmonic motion and behaving like a
nonrigid rotator, the rotational trems is given by the expression

FJ = BJ(J + 1) - DJ 2(J + 1) 2
456 A Textbook of Physical Chemistry

where D is known as centrifugal distortion constant and is given by the expression

h3 16 B 3p 2 m c 2
D= =
32p I r kf c
4 2 2
kf
where kf is the force constant of the bond (see Section 4.5). Show that for such a molecule,
the difference between two nearest rotational terms is given by the relation

D FJ = n J = 2(J + 1) {B - 2D(J + 1) 2}
∼
+1¨ J

and hence conclude that D FJ +1¨ J

decreases with increase in the value of J.
(c) Three consecutive lines in the rotational spectrum of H79 Br are observed at 84.544,
101.355 and 118.112 cm-1. Assign the lines to their appropriate J ¢ ¨ J ≤ transitions, then
deduce values for B and D and hence evaluate the bond length and approximate values of
force constant and vibrational frequency of the molecule.
Solution (a) The energy expression for the rotational levels of a rigid rotator is given by
h2
E= J(J + 1) (1)
8p 2 I
According to classical mechanics, the rotational energy of the molecule is given by
1
E= Iw 2
2
where w is the angular velocity in radians per second. Since
w = 2pn (where v is the frequency of rotation)
we have
1
E= I (2pn)2 = 2 I p 2n 2 (2)
2
Equating Eqs (1) and (2), we get
h2
2Ip2n 2 = J (J + 1)
8p 2 I
h
or n= J ( J + 1)
4p 2 I

(b) D FJ +1¨ J
= FJ +1
- FJ

= {B(J + 1) (J + 2) - D(J + 1) 2 (J + 2) 2} - {BJ(J + 1) - DJ 2(J + 1) 2}

= 2B(J + 1) - 4D(J + 1)3
= 2(J + 1) {B - 2D(J + 1) 2 }

As J increases, the factor B - 2D(J + 1) 2 decreases and hence D FJ +1¨ J

decreases with
increase in the value of J.
(c) The difference between the given transitions is of the order of 17 cm-1. For a rigid
-1
rotator, this difference is 2B will be of the order
of 10B. The latter value corresponds to J¢ = 5 ¨ J≤ = 4 transition for a rigid rotator and
hence we conclude the following rotational transitions in H79Br molecule.
 Molecular Spectroscopy 457

DFJ ¢ = 5 ¨ J ¢¢ = 4 = 84.544 cm-1

DFJ ¢ = 6 ¨ J ¢¢ = 5 = 101.355 cm-1

DFJ ¢ = 7 ¨ J ¢¢ = 6 = 118.112 cm-1

Employing the relation given in Part (b), we get

84.544 cm-1 = 2(5) {B - 2D(25)}
101.355 cm-1 = 2(6) {B - 2D(36)}
Solving for B and D, we get
B = 8.473 cm - 1 and D = 3.704 ¥ 10 -4 cm-1
h h
Now since B = , we get I =
8p 2 I c 8p 2 B c
Substituting the values, we get

(6.626 ¥ 10-34 J s)
I=
8(22 / 7) (8.473 ¥ 102 m -1 )(2.998 ¥ 108 m s -1 )
2

= 3.301 ¥ 10 - 47 kg m2

Now I = m r2

mH mBr
where m=
mH + mBr

{(0.001 kg ) / (6.022 ¥ 1023 )}{(0.079 9 kg ) / (6.022 ¥ 1023 )}

=
{(0.001 kg ) / (6.022 ¥ 1023 )} + {(0.079 9 kg ) / (6.022 ¥ 1023 )}
= 1.64 ¥ 10 -27 kg
1/ 2
I Ê 3.301 ¥ 10-47 kg m 2 ˆ
Hence r = = = 1.419 ¥ 10- 10 m = 141.9 pm
m ÁË 1.64 ¥ 10-27 kg ˜¯

16 B 3p 2 m c 2
Since D= , we have
kf

kf = 16 B p m c
3 2 2

16(8.473 ¥ 102 m -1 )3 (22 / 7) 2 (1.64 ¥ 10-27 kg )(2.998 ¥ 108 m s -1 ) 2

=
(3.704 ¥ 10-2 m -1 )
= 3.825 ¥ 102 N m-1
Now, frequency of vibration is

1 kf 1 3.825 ¥ 102 N m -1
n= = (See Eq. 4.5.10)
2p m 2(22 / 7) 1.64 ¥ 10-27 kg

= 7.68 ¥ 1013 s-1

458 A Textbook of Physical Chemistry

Example 4.4.4 The energy expression for various rotational levels of a linear triatomic molecule is the
same as that of a diatomic molecule. For H12C14N and D12C14N, the rotational constants in
frequency unit are 44 315.97 MHz and 36 207.40 MHz, respectively. Assuming that the bond
lengths are independent of isotopic substitution, calculate the C—H and C—N bond lengths.
Solution From the following facts about HCN molecule
H C N
rCH rCN
´ rN
rC
rH Centre of gravity
we may write
rCH = rH - rC (1)
rCN = rC + rN (2)
Balancing the moments about the centre of gravity, we get
mH rH + mC r C = mN rN
Expressing rH and rN in terms of rC with the help of Eqs (1) and (2), we get
mH(rCH + rC) + mC rC= mN (rCN - rC )
mN rCN - mH rCH mN rCN - mH rCH
or rC = = (3)
mH + mC + mN mHCN
where mHCN = mH + mC + mN.
The expression of moment of inertia is
IHCN = mH rH2 + mC r C2 + mN r 2N
Expressing rH and rN in terms of rC with the help of Eqs (1) and (2), we get
IHCN = mH(rCH + rC) 2 + mC rC2 + mN(rCN - rC) 2
2
= mH r CH 2
+ mN r CN + r C2 (mH + mC + mN) + 2rC (mH rCH - mN rCN )
2
= mH r CH 2
+ mN r CN + r C2 mHCN + 2rC(mH rCH - mN rCN)
Substituting rC from Eq. (3), we get

2 2 (mN rCN - mH rCH ) 2

IHCN = mH r CH + mN r CN +
mHCN

Ê m r - mH rCH ˆ
+ 2 Á N CN
Ë mHCN ˜¯ (mH rCH - mN rCN)

1
2
= mH rCH 2
+ mN r CN - (mH rCH - mN rCN )2 (4)
mHCN
Equation (4) is the required expression of moment of inertia for HCN molecule. For
DCN molecule, the corresponding expression is
1
2
IDCN = mD r CD 2
+ mN r CN - (mD rCD - mN rCN)2 (5)
mDCN
For calculating rCH and rCN IHCN and IDCN from the
given values of BHCN and BDCN, respectively. The rotational constant in frequency unit is
given by B¢ = h /8p2I. Hence, we have
 Molecular Spectroscopy 459

h 1
IHCN =
8p 2 B ¢ HCN
h 1
and IDCN =
8p 2 B ¢ DCN
Substituting the given data, we get
(6.6 ¥ 10-34 J s) Ê 1 ˆ
IHCN = ÁË 44 315.97 ¥ 106 s -1 ˜¯
8(3.14) 2
= 1.895 ¥ 10-46 J s2 ∫ 1.895 ¥ 10- 46 kg m2 (6)
-34
(6.6 ¥ 10 J s) Ê 1 ˆ
IDCN = ÁË 36 207.40 ¥ 106 s -1 ˜¯
8(3.14) 2
= 2.315 ¥ 10- 46 J s2 ∫ 2.315 ¥ 10 - 46 kg m2 (7)

10-3 kg mol-1
Now mH = = 0.166 ¥ 10 -26 kg (8)
6.022 ¥ 1023 mol-1
2 ¥ 10-3 kg mol-1
mD = = 0.332 ¥ 10-26 kg (9)
6.022 ¥ 1023 mol-1
12 ¥ 10-3 kg mol-1
mC = = 1.993 ¥ 10 -26 kg (10)
6.022 ¥ 1023 mol-1
14 ¥ 10-3 kg mol-1
mN = = 2.325 ¥ 10- 26 kg (11)
6.022 ¥ 1023 mol-1
Substituting Eqs (6)–(11) in Eqs (4) and (5), we get
1.895 ¥ 10- 46 kg m2 = (0.166 ¥ 10-26 kg) rCH
2
+ (2.325 ¥ 10 -26 kg) r CN
2

{(0.166 ¥ 10-26 kg ) rCH - (2.325 ¥ 10-26 kg) rCN }2

-
(0.166 + 1.993 + 2.325) ¥ 10-26 kg

(0.166 rCH - 2.325 rCN ) 2

1.895 ¥ 10-20 m2 = 0.166 rCH
2 2
+ 2.325 rCN -
4.484
or 8.5 ¥ 10- 20 m 2 = 0.715 rCH
2 2
+ 5.02 r CN + 0.77 rCH rCN (12)
Similarly for DCN molecule after using rCH = rCD, we have
10.76 ¥ 10-20 m 2 = 1.43 r CH
2 2
+ 5.41 rCN + 1.54 rCH rCN (13)
Multiplying Eq. (12) by 2 and subtracting from it Eq. (13), we get
6.24 ¥ 10-20 m2 = 4.63 rCN
2

1/ 2
Ê 6.24 ¥ 10-20 m 2 ˆ
or rCN = Á ˜¯ = 1.16 ¥ 10-10 m
Ë 4.63
Now substituting rCN value in Eq. (13), we get
2
1.43 rCH + (1.79 ¥ 10-10 m) rCH - 3.48 ¥ 10 -20 m2 = 0
Solving the quadratic expression, we get
rCH = 1 ¥ 10-10 m
460 A Textbook of Physical Chemistry

4.5 VIBRATIONAL SPECTRA OF DIATOMIC MOLECULES

Introduction The absorption spectrum in the infrared region corresponds to the promotion of a
molecule from its lowest vibrational level to the next higher one. The correlation
of experimental absorption with the theoretical difference in energy levels yields

Classical Figure 4.5.1 illustrates the typical vibration exhibited by a diatomic molecule.
Frequency 1 2
of Harmonic (i) Equilibrium position
Oscillator x1 x2

(ii) Extension of the spring

F1 F2

(iii) Equilibrium position

(iv) Compression of the spring

(v) Equilibrium position

Fig. 4.5.1 Symmetrical

stretching vibration of (vi) Extension of the spring
a diatomic molecule
Positive direction of
displacement and force
Solid arrows indicate the directions of motion of atoms and dotted arrows indicate
the directions of restoring forces.
The vibration shown in Fig. 4.5.1 is known as the symmetrical stretching
vibration. In classical mechanics, this vibration may be represented by a model in
which two balls of masses m1 and m2 are connected with each other by a spring.
To determine the displacement of the ball from its equilibrium position and the
force acting on it, we choose the axis system as shown in Fig. 4.5.1. Thus, the
displacement to the right of the equilibrium position will have a positive value
whereas that to the left has a negative value.

A harmonic oscillator follows Hooke’s law, according to which, the restoring

force F acting on the ball is directly proportional to the displacement D x, i.e.
F = - kf (D x) (4.5.1)
 Molecular Spectroscopy 461

where kf is a constant, known as the force constant. This constant is a characteristic

constant of the spring and is a measure of the stiffness of the spring (or the bond).
The negative sign in Eq. (4.5.1) indicates that the force is a restoring force and
thus has a direction opposite to that of the displacement.
Let x1 and x2 be the displacements of the two balls as shown in Fig. 4.5.1.
Then, we have
Extension of the spring = x2 - x1 (4.5.2)
According to the Newton’s second law, we have
d 2 x1
Restoring force acting on the ball 1 = m1 (4.5.3)
dt 2
d 2 x2
Restoring force acting on the ball 2 = m2 (4.5.4)
dt 2
Now, according to Hooke’s law and the sign convention shown in Fig. 4.5.1,
we have
Restoring force acting on the ball 1 = k f (x2 - x1) (4.5.5)
Restoring force acting on the ball 2 = - k f (x2 - x1) (4.5.6)
From Eqs (4.5.3) and (4.5.5), and Eqs (4.5.4) and (4.5.6), we get
d 2 x1
m1 = kf (x2 - x1) (4.5.7a)
dt 2
d 2 x2
m2 = - kf (x2 - x1 ) (4.5.7b)
dt 2
The coordinates x1 and x2 follow either the cosine or sine relation given below.
x1 = A1 cos (2pn t) or x1 = A1 sin (2pnt) (4.5.8)
x2 = A2 cos (2pn t) or x2 = A2 sin (2pnt) (4.5.9)
where A1 and A2 are the amplitudes of the vibrations of balls 1 and 2, respectively,
and n is the frequency of vibration. The term 1/n gives the time interval required
for the balls to complete one vibration. Note that A1 and A2 may have different
values but the frequency n has the same value for both the balls.

Substituting the cosine relations (we can equally use the sine functions) in
Eqs (4.5.7a) and (4.5.7b), we get
d 2 A1 cos( 2pn t )
m1 = kf (A2 - A1) cos (2 pnt)
dt 2
d 2 A2 cos( 2pn t )
m2 = - kf (A2 - A1) cos (2 pnt)
dt 2
On carrying out the differentiations and cancelling the common terms, we get
- m1A1(2pn) 2 = kf (A2 - A1)
- m2A2(2pn)2 = - kf (A2 - A1)
462 A Textbook of Physical Chemistry

Writing the above equations in the determinant form, we get

m1 (2pn ) 2 - kf kf A1
=0
kf m2 (2pn ) - k f A2
2

In order to have nontrivial roots of A1 and A2, we must have

m1 (2pn ) 2 - kf kf
=0
kf m2 (2pn ) 2 - k f
Opening this determinant, we get
m1m2(2pn) 4 - k f m1(2pn) 2 - kf m2(2pn) 2 + kf 2 - kf2 = 0
or m1m2(2pn)2 – kf (m1 + m2) = 0
1 kf 1 kf
or n= = (4.5.10)
2p m1m2 (m1 + m2 ) 2p m
where m = m1m2/(m1 + m2) and is known as the reduced mass of the molecule.
Equation (4.5.10) is the required characteristic frequency at which atoms of a
diatomic molecule undergo harmonic vibration.

Classical The potential energy of a system at any instant can be evaluated from the expression
Potential Energy dV
of Harmonic F=– (4.5.11)
dx
Vibration of a In the present case, we have
Diatomic Molecule
dV
- kf D x = –
d ( Dx)
or dV = kf D x d(Dx)
On integrating, we get
( Dx) 2
V = kf +I
2
where I is the constant of integration whose value may be determined from the
fact that at Dx = 0, V = 0. Thus I = 0 and the potential energy expression becomes
1
V= kf (D x)2 (4.5.12)
2
The variation of potential energy with displacement is shown in Fig. 4.5.2.
Classically speaking, the molecule can vibrate with any amount of potential energy,
i.e. the potential energy of the molecule is a continuous function of the displacement
from the equilibrium position.
The vibration motion of a real diatomic molecule is approximately harmonic for

Thus, from Eq. (4.5.12) it follows that for a real diatomic molecule
Ê ∂2V ˆ
kf = Á
Ë ∂( D x) 2 ˜¯ DxÆ0
 Molecular Spectroscopy 463

V
Fig. 4.5.2 Potential
energy diagram for a
–ve +ve
classical oscillator (x2 – x1)

that is, the force constant is equal to the value of second derivative of potential
energy V with respect to the displacement D x evaluated when Dx approaches zero.
In other words, it is a measure of rate of change of the slope of V versus Dx graph

Quantum Since the classical laws do not hold good for particles of very small masses,
Expression of Eq. (4.5.12) will not be applicable to diatomic molecules. The potential energy
Potential Energy expression for such a case has to be derived quantum mechanically by solving the
appropriate Schrödinger equation. In the present case the solution of Schrödinger
equation yields the following expression of energy:
Evib = (u + 1/2) hnclassical (4.5.13)
where nclassical is the classical frequency of vibration (Eq. 4.5.10) and u is the
vibrational quantum number. The allowed values of the latter are 0, 1, 2, …, etc.
Thus, the vibrational energies are quantized, i.e. the molecule cannot vibrate with
any arbitrary amount of energy but with only certain discrete vibrational energies
as given by Eq. (4.5.13).
In spectroscopy, the vibrational energies is expressed in wavenumber and is
known as vibrational term (symbol: G). These are obtained by dividing vibration
energy with hc Hence
E
( )
G = vib = u + w e
hc
1
2
(4.5.14)

where we (n classical/c) is harmonic vibration wavenumber

Energy Level The allowed vibrational energy levels of a diatomic molecule are shown by the
Diagram horizontal lines within the classical potential energy diagram (Fig. 4.5.2). The
following two characteristics may be noted down.
∑ The energy levels are equally spaced, i.e. the difference between the two nearest
levels is the same throughout and has a value of hnclassical.
If u and (u + 1) are the vibrational quantum numbers of the two nearest energy
levels, we have
464 A Textbook of Physical Chemistry

DE = {(u + 1) + 1/2)} hnclassical - (u + 1/2) hnclassical

= hnclassical (4.5.15)
∑ The lowest vibrational energy (u = 0) is not zero as in the case of classical
vibrator but has a value of (1/2)hnclassical.
This lowest energy is known as zero-point energy. This means that the atoms
in a molecule can never be completely at rest relative to each other. This fact is in
agreement with the Heisenberg uncertainty principle. If the atoms were standstill,
the uncertainty in the position would be zero and hence, according to the uncertainty

avoid this, the atoms ought to have certain uncertainty in position, i.e. the atoms
will have to have some vibrational energy.
In classical mechanics, the minimum vibrational energy which a diatomic
molecule can possess is zero, i.e. the atoms can be at rest relative to each other.
The zero-point energy is just half of the energy difference between the two
nearest vibrational energy levels. It may be noted that both these quantities depend
on the classical vibration frequency and hence on the strength of the chemical bond
and the atomic masses (Eq. 4.5.10).
Relative The relative populations of energy levels as given by Boltzmann equation is
Population of Ni = N0 exp(- DEi /kT)
Energy Levels
where D Ei the energy difference between the ith level and the zeroeth level. The
relative population, i.e. the term Ni/N0, depends on the ratio D Ei /kT. From the
experimental data on the vibrational spectra, it is found that in most diatomic
molecules D E1 ¨ 0 is much higher than the thermal energy kT. For example, for
CO and Cl2 molecules we have
Carbon monoxide D E1¨ 0 = 42 ¥ 10 -21 J
Chlorine D E1¨ 0 = 11 ¥ 10- 21 J
These values may be compared with the thermal energy 4.1 ¥ 10-21 J at 298 K.
On computing the ratios N1/N0, N2/N0
For carbon monoxide
N1
= exp{(- 42 ¥ 10 -21 J)/(4.1 ¥ 10 -21 J)} = exp(-10.244) = 3.6 ¥ 10 -5
N0
N2
= exp{(- 84 ¥ 10 - 21 J)/(4.1 ¥ 10-21 J)} = exp(-20.488) = 3.1 ¥ 10- 9
N0
For chlorine
N1
= exp{(- 11 ¥ 10 -21 J)/(4.1 ¥ 10–21 J)} = exp(-2.683) = 6.8 ¥ 10 - 2
N0
N2
= exp{(- 22 ¥ 10 - 21 J)/(4.1 ¥ 10 - 21 J)} = exp(-5.366) = 4.7 ¥ 10- 3
N0
From the above calculated values, we observe that the populations in the higher
vibrational levels are negligible in comparison to the population in the ground level.
 Molecular Spectroscopy 465

Thus, we may conclude that the excitation of molecules from u = 0 level will be
much more intense than from any of the higher levels.
Mechanism of The interaction between the radiation and the vibrating molecule is through the
Interaction with
Radiation vibration of the molecule. The electrical component of the radiation oscillates in
a plane perpendicular to the direction of propagation of the wave. The frequency
of this oscillating electrical component is equal to the frequency of the radiation.

when there occurs a change in dipole moment during the vibration of the molecule.
In diatomic molecules, we have only one type of vibration, i.e. symmetrical
stretching vibration, where the molecule is alternatively stretched and compressed.
It is expected that the change in dipole moment during the vibration of a diatomic
molecule will occur only if the molecule has a permanent dipole moment. This is
shown in Fig. 4.5.3.

Fig. 4.5.3 The

vibration of dipole
moment during the
stretching vibration of
a diatomic molecule
having permanent
dipole moment

Homonuclear diatomic molecules have zero dipole moment and also there occurs
no change in dipole moment during the symmetrical stretching vibration, and hence
such molecules are infrared inactive, i.e. they do not show any vibrational spectra.
Heteronuclear diatomic molecules do have a permanent dipole moment and they also
exhibit a change in dipole moment during the vibration and hence are infrared active.
The active and inactive vibration modes of linear and nonlinear triatomic
molecules may be illustrated here. We take the examples of CO2 (linear) and H2O
(nonlinear). It will be shown in Section 4.7 that the linear triatomic molecules have
four fundamental vibration modes and nonlinear molecules have three fundamental
vibration modes as described in Table 4.5.1.
Table 4.5.1 Vibrational Modes in a Triatomic Molecule

Vibrational mode Description

1. Symmetrical stretch mode Bonds are alternately stretched and
compressed in a symmetrical manner
2. Antisymmetrical stretch mode One bond is stretched while the other is
compressed and vice versa
3. Bending mode (doubly degenerate for Bond angle changes periodically within
linear molecules) a plane

The changes in dipole moment during the three vibrational modes of CO2 are
shown in Fig. 4.5.4.
466 A Textbook of Physical Chemistry

From Fig. 4.5.4, it is obvious that the symmetrical stretching vibration will be
infrared inactive whereas antisymmetrical and bending modes will be infrared active.
For water molecule, all the three vibrational modes will be infrared active as
they are accompanied by the change in the dipole moment.
Symmetrical stretching
O O O O
O O O O O
O O
No Change in dipole C C C C C C C C C C
C
moment (IR inactive)
O O
O O O O O O
O O O

Dipole 0 0 0 0 0 0 0 0 0 0 0
moment

Antisymmetrical stretching
O O O
O O O O O O
Dipole moment O O
Changes parallel to the C C C C C C C C C C C
symmetry axis. This
O O O
vibration is known as O O O O O O O
O
parallel vibration and
is shown by the sign (||) Dipole
moment 0 0 0 0 0 0

Component
of
dipole
moment

Bending

O C O O O O C O C O C O O O
Dipole moment C O O C
Changes perpendicular Dipole
moment 0
to the symmetry axis. 0 0
This vibration is known
Vertical
as perpendicular component
vibration and is shown of
by the sign (^) dipole
moment

Fig. 4.5.4 The variations of dipole moment during the three vibrational motions of CO2

Selection Rule The quantum mechanical calculations show that for harmonic vibration of a
heteronuclear diatomic molecule, the transition from one vibrational level to another
occurs with the condition of
Du = ± 1 (4.5.16)
that is, the change in the vibrational quantum number is unity. Equation (4.5.16)
is, in fact, the selection rule for the vibrational transitions (see Section 4.1).
 Molecular Spectroscopy 467

Vibrational Since the vibrational levels are equally spaced (Eq. 4.5.15), transitions between
Spectrum any two neighbouring levels will give rise to the same energy change. Thus, only
one absorption line is observed in the vibrational spectrum of a diatomic molecule.
Determination of Substituting Eq. (4.5.10) in Eq. (4.5.15), we get
Force Constant
h kf
DE = (4.5.17a)
2p m
which on rearranging gives
4p 2 m( DE ) 2
kf = (4.5.17b)
h2
Expressing D E in the wavenumber unit, we have
DE 1 kf
DG = = (4.5.17c)
hc 2p c m
On rearranging the above expression, we get

kf = 4p2c 2 m (DG)2 (4.5.17d)

Equations (4.5.17b) and (4.5.17d) may be used to determine the force constant
of a diatomic molecule.
For HCl and CO, the values of kf have been calculated in the following.
Hydrogen Chloride
DG = 2 890 cm- 1 = 2 890 ¥ 102 m-1
The value of m is
mH mCl {(0.001kg ) / (6.022 ¥ 1023 )}{(0.0355 kg ) / (6.022 ¥ 1023 )}
m= =
mH + mCl {(0.001kg ) /(6.022 ¥ 1023 )} + {(0.0355 kg )/(6.022 ¥ 1023 )}
= 1.615 ¥ 10 - 27 kg

Hence kf = 4p 2c 2 m (DG )2
= 4(3.14)2 (2.998 ¥ 108 m s-1 )2 (1.615 ¥ 10-27 kg) (2 890 ¥ 102 m-1)2
= 4.781 ¥ 102 kg s-2 ∫ 4.781 ¥ 102 N m- 1
Carbon Monoxide
D E = 4.24 ¥ 10 - 20 J
The value of m is
mC mO {(0.012 kg ) / (6.022 ¥ 1023 )}{(0.016 kg ) / (6.022 ¥ 1023 )}
m= =
mC + mO {(0.012 kg ) / (6.022 ¥ 1023 )} + {(0.016 kg ) / (6.022 ¥ 1023 )}
= 1.138 ¥ 10 - 26 kg

4p 2 m( D E ) 2 4(3.14) 2 (1.138 ¥ 10-26 kg )(4.24 ¥ 10-20 J ) 2

Hence kf = =
h2 (6.626 ¥ 10-34 J s) 2
= 1.838 ¥ 103 kg s - 2 ∫ 1.838 ¥ 103 N m-1
468 A Textbook of Physical Chemistry

Amplitude of
Vibration the extremes of vibration, whole of the energy is present in the form of potential
energy. Equating the classical expression of potential energy (1/2)kx 2max with the
xmax from the equilibrium
bond length. Thus, we have
1 h kf Ê 1ˆ
ÁË u + ˜¯
2
kf x max =
2 2p m 2
1/ 2
Ïh 1 Ê 1 ¸
Hence x max = Ì u + ˆ˝ (4.5.18)
Ó p kf m Ë 2¯ ˛
Let us now compute the vibrational amplitude of HCl molecule in the lowest
vibrational level, i.e. u = 0. From Eq. (4.5.18), we get
1/ 2
Ê h 1 ˆ
x max = Á ˜
Ë 2 p k fm¯

For HCl, m = 1.615 ¥ 10- 27 kg and kf = 4.781 ¥ 102 kg s - 2, hence

1/ 2
È (6.626 ¥ 10-34 J s) Ï 1 ¸ ˘
1/ 2

x max = Í Ì ˝ ˙
ÍÎ (2 ¥ 3.14) ÔÓ (4.781 ¥ 102 kg s -2 )(1.615 ¥ 10-27 kg ) ˛Ô ˙˚
= 1.096 ¥ 10- 11 m = 10.96 pm

amplitude is about 10 per cent of the bond length. With such a small displacement,
the vibration may be considered harmonic in nature.
Anharmonic The vibrational quantum number in the energy expression of a harmonic oscillator
Vibration (Eq. 4.5.13) can have any value starting from the minimum value of zero to any
larger integral value. This means that a diatomic molecule which is considered
to execute harmonic oscillations can have any higher allowed energy without
exhibiting any sign of breaking into two atoms. This fact is contrary to the
experimental behaviour that the molecule breaks into atoms if it is stretched beyond
a certain limit. Figure 4.5.5 compares the classical potential energy diagram of a
harmonic oscillator with the actual energy diagram of a typical diatomic molecule.
The two curves differ very widely in the lower and higher internuclear distances.
The actual energy diagram rises more steeply than the harmonic parabola energy
diagram in the lower internuclear distance. In the higher internuclear distance, the
energy of harmonic oscillator goes on increasing without any limit whereas that
in the actual energy diagram, the rise is less steep and it approaches the limiting

equilibrium internuclear distance, the two curves do not show appreciable departure
from each other. This fact is in agreement with the statement made earlier that in
the lowest vibrational level, the oscillation may be considered to be harmonic since
the maximum displacement from the equilibrium bond length, which is about 10
per cent, is not very large. Within this displacement, the bond may be considered
to be elastic so as to obey Hooke’s law.
 Molecular Spectroscopy 469

Energy

Fig. 4.5.5 Potential

energy diagram of a
real diatomic molecule 0.05 0.10 0.15 0.20 0.25
(solid curve) Internuclear distance, req / nm

The maximum displacement from the equilibrium bond length increases with
increase in vibrational quantum number (Eq. 4.5.18). For larger displacements, the
bonds are no larger elastic and hence deviation from the harmonic vibration energy
is expected for the larger vibrational quantum numbers.
Morse Potential Many empirical expressions have been suggested for the correlation of energy of
a diatomic molecule with the internuclear distance. One of the expressions which

is known as Morse potential. The energy expression is

V = D [1 - exp{a(req - r)}]2 (4.5.19)
where a is a constant for a particular molecule and D is the dissociation energy.
The constant a is given by kf /2 D (see Example 4.5.5).

Vibrational Energy Substitution of the Morse potential energy expression in Schrödinger equation
of a Diatomic and the approximate solution of the resultant equation gives the following energy
Molecule following expression for the various allowed vibrational energy levels.
the Morse
Potential E = (u + 1/2) hne [1 + (u + 1/2) xe] (4.5.20a)
where n e is known as equilibrium oscillation frequency of the anharmonic
oscillator, xe is the corresponding anharmonicity constant and u is the vibrational
quantum number which has integral values including zero, i.e. u = 0, 1, 2, …. The
anharmonicity constant xe is approximately given by hne /4D (see Eq. 4.5.25) and
has a small positive value of the order of 0.01.
Expressing Eq. (4.5.20a) in vibrational trem, we have
Gv= (u + 1/2) we [1 + (u + 1/2) xe] (4.5.20b)
470 A Textbook of Physical Chemistry

The energy as given by Eq. (4.5.20a) may be written in the form similar to that
of a harmonic oscillator (i.e. Eq. 4.5.13), if we write Eq. (4.5.20a) as

E = ÊÁ u + ˆ˜ hn
1
n = n e È1 - ÊÁ u + ˆ˜ xe ˘
1
where
Ë 2¯ ÍÎ Ë 2 ¯ ˙˚
The above expressions suggest that anharmonic oscillator may be treated like an
oscillator whose oscillation frequency decreases steadily with increasing u.
Energy Level The energy of a few low vibrational levels are given below.
Diagram
hne ÊÁ1 - xe ˆ˜
1 1
u=0 E0 =
2 Ë 2 ¯

hne ÊÁ1 - xe ˆ˜
3 3
u=1 E1 =
2 Ë 2 ¯

hne ÊÁ1 - xe ˆ˜
5 5
u=2 E2 =
2 Ë 2 ¯

hn e ÊÁ1 - xe ˆ˜
7 7
u=3 E3 = (4.5.21)
2 Ë 2 ¯
The difference between the two vibrational energy levels is

Ê 1ˆ
2 { Ê
Ë
1ˆ
2¯ }
Ê 1ˆ
{ Ê 1ˆ
D E = ÁË u ¢ + ˜¯ hne 1 - Á u ¢ + ˜ xe – ÁË u ¢¢ + ˜¯ hne 1 - ÁË u ¢¢ + ˜¯ xe
2 2 }
(4.5.22)
where u ¢ and u ≤ are the vibrational quantum numbers of the higher and lower
levels, respectively.
For the two nearest levels, we will have
u ¢ = u≤ + 1
Hence, the energy difference between the two nearest levels is

ÎË
3
2 ¯ { Ë
3
2 ¯ }˚ Î Ë
1
2 ¯ { Ë
1
2¯ }
D E = ÈÍÊ u ¢¢ + ˆ h ve 1 - Ê u ¢¢ + ˆ xe ˘˙ - ÈÍÊ u ¢¢ + ˆ h ve 1 - Ê u ¢¢ + ˆ xe ˙˘
˚
= hne{1 - 2xe (1 + u ≤)} (4.5.23a)
In terms of vibrational term, Eq. (4.5.23a) is expressed as
DGu ¢¢ + 1 = we [1 – 2xe (1 + u ¢¢)] (4.5.23b)
2

Since the anharmonicity constant has a small positive value, it follows from
Eq. (4.5.23) that the difference DV between the two closest levels decreases with
increasing value of vibrational quantum number. Thus, the vibrational levels are
no more equally spaced as in the case of a harmonic oscillator but becomes closer
to each other with increasing value of u (Fig. 4.5.6).
 Molecular Spectroscopy 471

u= 8
7
6
5

Energy
4
Fig. 4.5.6 The 3
allowed energy 2
levels (schematic of 1
a diatomic molecule
executing anharmonic 0
oscillations) Internuclear distance

Vibrational The selection rules for an anharmonic oscillator are

Transitions Du = ± 1, ± 2, ± 3, …
Hence, all types of transitions from any lower vibrational level to any of the higher
vibrational levels are allowed. Since only the lowest level is thickly populated
and because the population decreases very rapidly with increasing u, only a few
transitions from the lowest vibrational level (u = 0) to the next nearest vibrational
levels are actually observed at room temperature. The transition u¢ = 1 ¨ u≤ = 0
is found to be the most intense and is known as the fundamental absorption. The
transition u¢ = 2 ¨ u≤ = 0, is found to have a poor intensity and is known as the
. The transition u ¢ = 3 ¨ u≤ = 0 is found to have negligible intensity
and is known as the second overtone. The higher overtones are too weak to be
realized experimentally. The energies of the observed transitions may be worked
out from Eq. (4.5.22) and are as follows:
(1) u ¢ = 1 ¨ u≤ = 0; D E = hne (1 - 2xe)
(2) u ¢ = 2 ¨ u ≤ = 0; D E = 2hne (1 - 3xe)
(3) u ¢ = 3 ¨ u ≤ = 0; D E = 3hne (1 - 4xe)
In the wave number unit, we have
(1) u ¢ = 1 ¨ u≤ = 0; D G = we(1 - 2xe)
(2) u ¢ = 2 ¨ u≤ = 0; D G = 2 we(1 - 3xe)
(3) u ¢ = 3 ¨ u≤ = 0; D G = 3 we(1 - 4xe )
The transitions from u = 1 to the higher levels are not observed unless the
temperature of the sample is high. This is due to the fact that the population in
u = 1 level is negligible at room temperature and it becomes appreciable at higher
temperatures. These transitions are known as hot bands as they appear only at higher
temperatures. The intensities of hot bands are usually very weak and become more
intense on increasing temperature of the sample.
472 A Textbook of Physical Chemistry

Dissociation The vibrational energy of a molecule increases with increase in the vibrational
Energy of quantum number. Eventually, a stage is reached where vibrational energy is quite
a Diatomic nto atoms. This energy is known as the dissociation
Molecule energy of the diatomic molecule. Thus at the dissociation stage of the molecule, the
vibrational energy has a maximum value. The value of vibrational quantum number
at this stage may be determined from Eq. (4.5.20a) by applying the mathematical
criterion of maximum, i.e. ∂E/∂u = 0. Thus, we have
∂E
= 0 = hn e {1 - (u max + 1/ 2) xe } + (u max + 1/ 2) hne (- xe)
∂u
or 1 - 2 (u max + 1/ 2) xe= 0
h ne 1
or u max = – (4.5.24)
4 xe 2
Substituting umax in Eq. (4.5.20a), we get
h ne
Emax = (4.5.25)
4 xe
This will represent the dissociation energy of the molecule with respect to the
bottom of the potential energy diagram. The true dissociation energy, however,
will be given by
D = Emax - E0

- hn e ÊÁ1 - xe ˆ˜
h ne 1 1
= (4.5.26)
4 xe 2 Ë 2 ¯
The obtained value of dissociation energy will not be an accurate one since
the energy expression (Eq. 4.5.20) is obtained as an approximate solution of the
Schrödinger equation. More precise solution, in fact, includes the cubic, quartic,
etc., terms in (u + 1/2) with anharmonicity constants ye, ze, etc. The magnitudes
of ye, ze, etc., diminish very rapidly. Though these higher terms are negligible for
the small values of u, they become important at large u.

Example 4.5.1 The fundamental vibration frequency and rotational constant of CO molecule are
6.5 ¥ 1013 s-1 and 1.743 ¥ 1011 s-1, respectively. Find the rotational quantum number for

state with no rotational energy.

Solution Since the rotational constant in terms of frequency unit is h/8p2I, we have
h
= 1.743 ¥ 1011 s-1
8p 2 I
Thus, the expression of energy of various rotational levels is
E h
= J(J + 1) = (1.743 ¥ 1011 s-1) J (J + 1)
h 8p 2 I
We have to calculate the value of J for which E/h is equal to the fundamental vibration
frequency, i.e. 6.5 ¥ 1013 s-1. Hence, we have
6.5 ¥ 1013 Hz = (1.743 ¥ 1011 Hz) J (J + 1)
6.5 ¥ 1013
or J(J + 1) = = 372.9
1.743 ¥ 1011
 Molecular Spectroscopy 473

Solving for J, we get

-1 + 1 + 4 ¥ 372.9
J= = 18.82 19
2

Example 4.5.2 N16O are centred at 1 876.06 cm-1 and

14
-1
3 724.20 cm , respectively. Evaluate the equilibrium vibration frequency, the anharmonicity
constant, the zero-point energy, the force constant and the dissociation energy of the molecule.
Solution We have
Fundamental absorption we (1 - 2xe) = 1 876.06 cm-1 (i)
-1
First overtone 2 we (1 - 3xe) = 3 724.20 cm (ii)

Dividing Eq. (ii) by Eq. (i), we get

2(1 - 3 xe ) 3 724.20
= = 1.985 117
1 - 2 xe 1 876.06
Solving for xe, we get
xe = 0.007 332
Substituting the value of xe in the expression

we(1 - 2xe) = 1 876.06 cm-1

and solving for we, we get

we = 1 903.98 cm-1
The vibrational term corresponding to the lowest vibrational level for an anharmonic
oscillator is given by
1 Ê 1 ˆ
G0 = w e Á1 - xe ˜
2 Ë 2 ¯

(1 903.98 cm -1 ) ÊÁ1 - ¥ 0.007 332ˆ˜

1 1
=
2 Ë 2 ¯
= 948.5 cm–1
The force constant can be calculated from the expression
1 kf
we = (Eq. 4.5.17)
2pc m
i.e. kf = 4p2c2 m w e2
14
The reduced mass m for N16O is
{(0.014 kg ) / (6.022 ¥ 1023 )}{(0.016 kg) / (6.022 ¥ 1023 )}
m=
{(0.014 kg ) / (6.022 ¥ 1023 )} + {(0.016 kg ) / (6.022 ¥ 1023 )}
= 1.239 7 ¥ 10-26 kg
Hence
kf = 4(3.14)2 (2.998 ¥ 108 m s-1)2 (1.239 7 ¥ 10-26 kg) (1 903.98 ¥ 102 m-1)2
= 1.593 ¥ 103 kg s-2 ∫ 1.593 ¥ 103 N m-1
474 A Textbook of Physical Chemistry

The umax corresponding to the dissociation energy is given by

1 1
umax = - (Eq. 4.5.24)
2 xe 2
Substituting the value of xe, we get
1 1
umax = - = 67.694 67.7 68
2 ¥ 0.007332 2
Ê 1ˆ Ï Ê 1ˆ ¸
Hence GD = Gmax = Á u max + ˜ w e Ì1 - Á u max + ˜ xe ˝
Ë 2 ¯ Ó Ë 2¯ ˛
= (68.5) (1 903.98 cm-1) (1 - 68.5 ¥ 0.007 332)
= 64 918.9 cm-1 = 64 918.9 ¥ 10 2 m-1
In the unit of joule, we have
ED = (64 918.9 ¥ 102 m –1) (6.626 ¥ 10 –34 J s) (2.998 ¥ 108 m s–1)
= 1.29 ¥ 10 –18 J
The wavenumber corresponding to the true dissociation energy with respect to that of zero-
point energy will be given by

G D¢ = GD – G0 = 64 918.9 cm–1 – 948.5 cm–1 = 63 970.4 cm–1

In the unit of joule, we get
E¢D = (63 970.4 ¥ 10 2 m–1) (6.626 ¥ 10–34 J s) (2.998 ¥ 108 m s–1)
= 1.27 ¥ 10–18 J

Example 4.5.3 The vibrational energy levels of CO molecule is given by expression

2
Eu /J mol –1 = 25 940 ÊÁ u + ˆ˜ - 152 ÊÁ u + ˆ˜
1 1
Ë 2¯ Ë 2¯
where u is the vibrational quantum number. Calculate: (a) The force constant of the
molecule. (b) The anharmonicity constant. (c) Zero-point energy. (d) Fundamental vibrational

of vibration in the lowest vibration level. (g) The number of molecules in the level u = 1
relative to u = 0 level at 500 K. (h) The value of vibrational quantum number which leads
to the dissociation of the molecule. (i) The dissociation energy of the CO molecule. Do you
expect it to be overestimated?
Solution The energy expression for an anharmonic oscillator is
Eu = hne (u + 1/2) – hnexe (u + 1/2)2
The given energy expression per mol is
Eu = (25 940 J mol–1) (u + 1/2) – (152 J mol–1) (u + 1/2)2
Hence, the energy per molecule is
Eu = (4.307 ¥ 10 – 20 J) (u + 1/2) – (2.524 ¥ 10 –22 J) (u + 1/2)2
Comparing this with the theoretical expression, we get
hne = 4.307 ¥ 10 –20 J
hne xe = 2.524 ¥ 10 –22 J
 Molecular Spectroscopy 475

4.307 ¥ 10-20 J
Hence ve = = 6.500 ¥ 1013 s -1
6.626 ¥ 10-34 J s
2.524 ¥ 10-22 J
xe = = 5.860 ¥ 10–3
4.307 ¥ 10-22 J
(a) The force constant of the molecule can be calculated from the expression

1 kf
ne =
2p m
Hence kf = (2pne)2 m
Now m for CO is

m=
mC mO
=
{(0.012 kg ) / (6.022 ¥ 1023 )}{(0.016 kg ) / (6.022 ¥ 1023 )}
mC + mO {(0.012 kg ) / (6.022 ¥ 1023 )} + {(0.016 kg ) / (6.022 ¥ 1023 )}
= 1.138 ¥ 10–26 kg
Thus kf = (2pne)2 m
= {2(3.14) (6.500 ¥ 1013 s –1)}2 (1.138 ¥ 10–26 kg)
= 1.896 ¥ 103 kg s–2 ∫ 1.896 ¥ 103 N m–1
(b) The anharmonicity constant xe = 5.860 ¥ 10–3
(c) For zero-point energy, u = 0. Hence
2
E = (4.307 ¥ 10–20J) ÊË ˆ¯ – (2.524 ¥ 10–22J) ÊË ˆ¯
1 1
2 2
= 2.153 5 ¥ 10 –20
J – 0.631 ¥ 10 –22
J
= 2.147 2 ¥ 10 –20
J
(d) The fundamental vibrational frequency
ne = 6.500 ¥ 1013 s–1
(e) u = 0 to u = 2. The energy difference
between these two levels is
DE = 2(hne ) (1 – 3xe) = 2(4.307 ¥ 10–20J) (1 – 3 ¥ 5.860 ¥ 10–3)
= 8.463 ¥ 10–20 J
(f) The period of vibration is

1 1
t= = = 1.538 ¥ 10 –14 s
n 6.502 ¥ 10-13 s -1
Equating zero-point energy with the classical expression of potential energy, we get

1 2
k f x max = 2.147 2 ¥ 10–20J
2
12 12
Ê 2 ¥ 2.147 2 ¥ 10-20 J ˆ Ê 2 ¥ 2.147 2 ¥ 10-20 J ˆ
x max = Á ˜ = Á
Ë kf ¯ Ë 1.896 ¥ 103 N m -1 ˜¯

= 4.754 ¥ 10 –12 m = 4.754 pm

476 A Textbook of Physical Chemistry

(g) We have
N1
= exp(– DE1/kT )
N0
Now DE1 = E1 – E0 = (hne)(1 – 2xe) = (4.307 ¥ 10–20 J)(1 – 2 ¥ 0.005 86)
= 4.256 ¥ 10 –20 J
N1
Thus = exp[– (4.256 ¥ 10 –20 J)/{(1.38 ¥ 10 –23 J K–1) (500 K)}]
N0
= exp(– 6.168) = 2.95 ¥ 10–3
(h) The quantum number of the vibrational level leading to the dissociation of the molecule
is given by
1 1 1 1
umax = – = – = 85.32 – 0.5 = 84.82 = 85
2xe 2 2 ¥ 0.005 86 2
(i) Substituting umax in the given energy expression, we get
2
E/J mol –1 = 25 940 ÊÁ u max + ˆ˜ – 152 ÊÁ u max + ˆ˜
1 1
Ë 2¯ Ë 2¯
= 25 940 (85.5) – 152 (85.5)2 = 1.107 ¥ 106
2
E0 /J mol –1 = 25 940 ÊË ˆ¯ – 152 ÊË ˆ¯ = 12 932
1 1
Now
2 2
DEdiss = E – E0 = 1.094 ¥ 106 J mol–1
The above value of dissociation energy is overestimated as the energy expression does not
include higher anharmonicity constants.

Example 4.5.4 The value of we is 4 395 cm–1 for H2 molecule. Calculate the approximate zero-point energy
per mole of H2. If w e xe is 118 cm –1, what is the exact zero-point energy?
Solution Approximate zero-point energy
1 1
hcwe = (6.626 ¥ 10–34 J s) (3 ¥ 108 m s–1) (4 395 ¥ 102 m–1)
2 2

= 4.368 ¥ 10–20 J

Hence, approximate zero-point energy per mole

= (4.368 ¥ 10 –20 J) (6.022 ¥ 1023 mol–1)
= 2.631 ¥ 10 4 J mol–1 = 26.31 kJ mol–1
Exact zero-point energy per mole
1 1
= NAhcwe– hc(we xe ) NA
2 4
1
= 26.31 ¥ 10 3 J mol –1 – (6.626 ¥ 10–34 J s) (3 ¥ 108 m s–1)
4
 Molecular Spectroscopy 477

Example 4.5.5 ¥ (118 ¥ 102 m–1 ) (6.022 ¥ 1023 mol–1)

= 25.96 ¥ 103 J mol –1 = 25.96 kJ mol–1
The vibrational potential energy of a diatomic molecule can be represented approximately
by the Morse function
V = b [1 – exp{a (req – r)}]2
where b and a are positive characteristic constants of a molecule, r is internuclear distance
and req is the equilibrium of r.
(a) Show that V has a minimum value at r = req.
(b) Show that for a small displacement from the equilibrium position, the above function
is approximated by a simple harmonic potential. Also show that at r = req
(d 2V/dr 2) = kf.
(c) Derive the expression of frequency of oscillation, n, in terms of b, a and req. Also
show that a = 4.445 n m b .
(d) Derive the expression of the dissociation energy in terms of b, a and req.
Solution (e) For HBr b = 6.280 ¥ 10–19 J, a = 18.11 nm–1 and req = 0.141 4 nm, calculate (i) kf ,
(ii) n, (iii) zero-point energy, and (iv) dissociation energy of HBr.
(a) For showing minimum at r = req, we set (dV/dr)req = 0 and proceed to show that
(d2V/dr2)req > 0. Thus, we have
dV
= 2b[1 – exp{a (req – r)}] [a exp{a(req – r)}]
dr
= 2ba exp{a (req – r)} – 2ba exp{2a(req– r)}
At r = req, we have
Ê dV ˆ = 0
Ë dr ¯

d 2V
Now = – 2ba2 exp{a (req – r)} + 4ba2 exp{2a(req – r)}
d 2r
At r = req, we have
dV 2
= 2ba2 > 0
dr 2
Hence at r = req, V exhibits a minimum value.
(b) For a small displacement, we can write
exp{a (req – r)} = 1 + a(req – r) +
Thus V = b[1 – {1 + a(req – r) + }]2
= b[– a(req – r) – ]2

V = ba2 (req – r)2

which is the same as that of the harmonic oscillator (Eq. 4.5.12) provided, we have
1
kf = ba2
2
or kf = 2ba2
478 A Textbook of Physical Chemistry

Ê d 2V ˆ 2
Since ÁË 2 ˜¯ = 2ba (derived in part a)
dr
Ê d 2V ˆ
we have kf = Á 2 ˜
Ë dr ¯ r = r
eq

(c) The frequency of oscillation n is given by

1 kf
n =
2p m
Substituting kf = 2ba2, we get

1 2ba 2 a b
n = =
2p m ( 2)p m
Rearranging, we get

m m
a = ( 2 ) pv = 4.45 n
b b
(d) The dissociation energy of the molecule is given by
D = V(r = •) – V(r = req )
From the given expression of Morse function, we have
D=b–0=b
Since the minimum potential energy is not equal to zero but (1/2)hn, we have
1 1 ha 2b
D=b– hn = b –
2 2 2p m
(e) We have
(i) kf = 2ba2
= 2 (6.280 ¥ 10 –19J) (18.11 ¥ 109 m–1)2 = 4.119 ¥ 102 N m–1
a 2b
(ii) n=
2p m
m1m2
Now m=
m1 + m2

=
{(1 ¥ 10-3 kg ) / (6.022 ¥ 1023 )}{(79.9 ¥ 10-3 kg ) / (6.022 ¥ 1023 )}
{(1 ¥ 10-3 kg ) / (6.022 ¥ 1023 )} + {(79.9 ¥ 10-3 kg ) / (6.022 ¥ 1023 )}
79.9 ¥ 10-3
= kg = 1.64 ¥ 10 –27 kg
80.9 ¥ 6.022 ¥ 1023
1/ 2
Ê 18.11 ¥ 109 m -1 ˆ Ê 2 ¥ 6.28 ¥ 10-19 J ˆ
Thus n= Á = 7.98 ¥ 1013 s–1
Ë 2 ¥ 3.14 ¯˜ ÁË 1.64 ¥ 10-27 kg ˜¯
(iii) Zero-point energy
1 1
= hn = (6.626 ¥ 10 –34 J s) (7.98 ¥ 1012 s–1)
2 2
= 2.64 ¥ 10–21J
 Molecular Spectroscopy 479

1
(iv) D=b– hn = 6.280 ¥ 10 –19J – 2.64 ¥ 10–21J
2
= 6.254 ¥ 10 –19J

Example 4.5.6 The wavenumber corresponding to the equilibrium vibrational frequency of iodine molecule
is 215 cm–1, and the anharmonicity constant is 0.003. At 300 K, what is the intensity of the
hot band relative to that of the fundamental absorption?
Solution
populations in u = 0, 1 and 2 vibrational levels. The energies of these levels are as follows.
1 Ê 1 ˆ
u = 0; G0 = w e Á1 - xe ˜ = 107.339 cm–1
2 Ë 2 ¯

3 Ê 3 ˆ
u = 1; G1 = w e Á1 - xe ˜ = 321.094 cm–1
2 Ë 2 ¯

5 Ê 5 ˆ
u = 2; G2 = w e Á1 - xe ˜ = 533.469 cm–1
2 Ë 2 ¯

Now DGu ¢ = 1 ¨ u ¢¢ = 0 = DG1 = 321.049 cm–1 – 107.339 cm–1 = 213.71 cm–1

= 213.71 ¥ 102 m–1

DE1 = DG1 hc0

= (213.71 ¥ 102 m–1) (6.626 ¥ 10 –34 J s) (2.998 ¥ 108 m s–1)

= 4 245.295 ¥ 10–24 J
N1
= exp(– DE1/kT )
N0

= exp[– (4 245.295 ¥ 10 –24J)/{(1.38 ¥ 10–23J K–1)(300 K)}]

= exp(– 1.025 4) = 0.358 1
DGu ¢ = 2 ¨u ¢¢ = 0 = DG2 = 533.469 cm–1 – 107.339 cm–1 = 426.13 cm–1

= 426.13 ¥ 102 m–1

DE2 = (426.13 ¥ 102 m–1) (6.626 ¥ 10–34J s) (2.998 ¥ 108 m s–1)
= 8 464.965 ¥ 10–24J
N2
= exp(– DE2/kT)
N0
= exp[– (8 464.965 ¥ 10–24J)/{(1.38 ¥ 10–23J K–1) (300 K)}]
= exp(– 2.044 6) = 0.129 5
If the intensity of transition is assumed to be proportional to the number of molecules in
the state from which the transition occurs, then the intensity of hot band will be about 0.36
of that of the fundamental transition. If we assume it to be proportional to the difference in
populations of involved levels, then the ratio of intensities would be given by
480 A Textbook of Physical Chemistry

Difference of population in n = 1 and n = 2 levels

Difference of population in n = 0 and n = 1 levels

0.3581 - 0.129 5 ˆ 0.228 6

= ÊÁ ˜=
Ë 1.0 - 0.3581 ¯ 0.641 9
= 0.356 0.36

4.6 VIBRATION-ROTATION SPECTRA OF DIATOMIC MOLECULES

Energy Level Under the Born-Oppenheimer approximation, the molecule may be considered
Diagram to execute rotation and vibration motions quite independently of each other. This
follows from the fact that the vibrational energy is much larger than the rotational
energy. The total energy of a molecule executing both vibration and rotation motions
may be taken as the sum of the separate energies, i.e.
Etotal = Erot + Evib (4.6.1)
Thus, the energies of molecules belonging to the same vibrational level may
differ depending upon their rotational energies.
The energy of a molecule executing both vibrational and rotational motions
may be represented as shown in Fig. 4.6.1.

u = 0, J = 9

u = 0, J = 8

u = 0, J = 7
Energy

u = 0, J = 6

u = 0, J = 5
u = 0, J = 4
u = 0, J = 3
u = 0, J = 2
Fig. 4.6.1 Different u = 0, J = 1
rotational levels u = 0, J = 0
r0
associated with the
lowest vibrational level Displacement

The lines shown in Fig. 4.6.1 represent the different rotational levels in the lowest
vibrational level, i.e. u = 0. Similarly the energies of rotational levels associated
with the excited vibrational state can be displayed (Fig. 4.1.1). The energy may be
presented by the symbol Eu, J
vibrational and rotational quantum numbers, respectively. For example, E0, 1 and
E1, 0

At room temperature, most of molecules are associated with the lowest

vibrational level and with many of the associated rotational levels. In fact, the
 Molecular Spectroscopy 481

distribution of molecules in the rotational levels associated with the lowest

vibrational level is the same as that of pure rotational levels as shown in Fig. 4.4.3.

If we consider a molecule to execute anharmonic oscillations and rigid rotations,

its energy in the wavenumber unit will be given by the expression
E total = FJ + Gu

( ) { ( )}
E total = BJ(J + 1) + u + 1 w e 1 - xe u + 1
2 2
(4.6.2)

where the various symbols have their usual meanings.

Selection Rules of A molecule on absorbing the radiation corresponding to the vibrational excitation
Vibration-Rotation may simultaneously be accompanied by the change in the rotational level. The
Spectra spectrum exhibiting such transitions is known as vibration-rotation spectrum. It
can be shown that the selection rules for such transitions are the same as those for
each separately. Thus, we have
Du = ± 1, ± 2, etc.
DJ = ± 1 (4.6.3)
Since D J equal to zero is not allowed, it follows that a vibrational change will
always be accompanied by a simultaneous rotational change.
Expression Let u≤, J≤ and u¢, J¢ be the vibrational and rotational quantum numbers of the
of Transition lower and upper energy levels, respectively. The difference between these two
Energies levels in the unit of wavenumber will be
D E = [BJ¢ (J¢ + 1) – BJ≤ (J≤ + 1)]

Î( 2 ) { (
+ ÈÍ u ¢ + w e 1 - xe u ¢ +
1 1
2 )} (- u ¢¢ +
1
2) { (
w e 1 - xe u ¢¢ + )}
1 ˘
2 ˙˚
(4.6.4)
If we restrict to u¢ = 1 ¨ u≤ = 0 transition, we will have
DE = B(J¢ – J≤ ) (J¢ + J≤ + 1) + we (1 – 2xe ) (4.6.5)
Since D J = ± 1, we will have

Transitions with D J = + 1, i.e.

J¢ = J≤ + 1
Hence D E = 2B(J≤ + 1) + we (1 – 2xe ) (4.6.6)
where J≤ can have values 0, 1, 2, , and so on.

Transitions with D J = – 1, i.e.

J¢ = J≤ – 1 or J≤ = J¢ + 1
Hence DE = – 2B(J¢ + 1) + we (1 – 2xe ) (4.6.7)
482 A Textbook of Physical Chemistry

where J¢ can have the values 0, 1, 2, , and so on.

Equations (4.6.6) and (4.6.7) may be combined into one expression as

DE = 2 Bm + we (1 – 2xe ) (4.6.8)
where m can have values ±1, ±2, , and so on. The symbol m represents (J≤ + 1)
in case of D J = + 1 and (J¢ + 1) in case of D J = –1. Positive and negative values
of m correspond to D J = +1, and D J = –1, respectively.

Vibration-Rotation Equation (4.6.8) describes the combined vibration-rotation spectrum. Since m can
Spectrum have values ±1, ±2, , it follows that the spectrum will consist of equally spaced
lines (spacing 2B) on each side of the wave number we (1 – 2xe) as shown in
Fig. 4.6.2.

7
6
u=1
5
4
3
2
J¢ 1
0
8

7
6
u=0
5
4
3
J≤ 21
0

Fig. 4.6.2 A typical

vibration-rotation
spectrum

2B 2B 2B 2B 2B 2B 2B 4B 2B 2B 2B 2B 2B 2B 2B

The absorption line corresponding to we (1 – 2xe) will not appear as m cannot be

equal to zero. This wavenumber is referred to as band centre or band origin or
Q branch of the spectrum. The lines to the low wavenumber side of band centre
correspond to the negative values of m and represent transitions corresponding
to the negative value of DJ, i.e. these transitions correspond to J¢ = 0 ¨ J≤ = 1,
J ¢ = 1 ¨ J≤ = 2, and so on. These lines are referred to as P branch of the spectrum.
 Molecular Spectroscopy 483

The lines corresponding to the high wavenumber side of band centre correspond
to the positive values of m and hence represent transitions corresponding to
the positive values of D J, i.e. these transitions correspond to J¢ = 1 ¨ J≤ = 0,
J¢ = 2 ¨ J≤ = 1, and so on. These lines are referred to R branch of the spectrum.
(The labelling as P, Q, and R branches can be extended if in addition to DJ = ±1,
the values 0 and ± 2 are also allowed. The labelling of branches goes as follows.

lines arising from DJ =–2 –1 0 +1 +2

labelling of the branch O P Q R S.)
The intensities of lines in P and R branches will be of the type exhibited by the
pure rotation spectrum. The spectrum shown in Fig. 4.6.2 will be observed only
by the high resolving spectrometer. If the resolving power is not high, one will
observe the spectrum as shown in Fig. 4.6.3.

~
x

Fig. 4.6.3 Vibration-

rotation spectrum under
very low resolution

Wavenumber

Application of The vibration-rotation spectrum can be utilized to determine all those molecular
Vibration-Rotation parameters which can be determined separately from the pure vibration and
Spectrum pure rotation spectra. The location of band centre corresponding to the transition
u¢ = 1 ¨ u≤ = 0 (the fundamental transition) and u¢ = 2 ¨ u≤
overtone) helps in providing the values we and xe, and hence the value of force
constant. The separation of lines in either P branch or R branch provides the value
of 2B and hence the values of moment of inertia and the bond length.

The approximate value of parameter B can even be evaluated if the rotational

lines are not resolved, i.e. from the spectrum shown in Fig. 4.6.3.

The quantum number of the rotational level having maximum population is given by

kT 1
J= – (Eq. 4.4.12)
2 Bhc 2
This quantum level will produce the maximum intensity of the rotational transition.
Now since m = ± (J + 1), we have

Ê kT 1ˆ
mmax = ± Á + ˜
Ë 2 Bhc 2 ¯
484 A Textbook of Physical Chemistry

and hence the maxima of P and R branches will be located at

Ê kT 1ˆ
D E = ± 2B ÁË + ˜¯ + w e (1 – 2xe ) (Eq. 4.6.8)
2 Bhc 2
and hence the separation between them is
Ê kT 1ˆ 8kTB
x = 4B Á
Ë + ˜¯ = + 2B
2 Bhc 2 hc
The factor 2B is much smaller than the factor 8kTB / hc and hence the above
relationship can be approximated to
∼ 8kTB
x
hc
hc x 2
or B (4.6.9)
8kT
Problem 4.6.1 (a) Show that the expression of wavenumber for the transitions u¢ = 1 ¨ u≤ = 0 and D J =
±2 (i.e. O and S branches of vibrational-rotational spectrum) is given by
DG = ± 2Bm + we (1 – 2xe)
where m = 2J≤ + 3 for D J = + 2 transitions and m = 2J¢ + 3 for D J = – 2 transitions.
(b) Show that the separation between the maxima of O and S branches is given by

32BkT
DG = + 8B
hc
(c) Calculate the rotational constants for HgCl2 at 555 K if the separation between the
maxima of O and S branches is 23.8 cm–1.
Solution (a) From Eq. (4.6.5), we have
DG (u¢ = 1 ¨ u≤ = 0; J¢ ¨ J≤ ) = B(J¢ – J≤ ) (J¢ + J≤ + 1) + we(1 – 2xe )
For O branch (D J = – 2), we have

J¢ = J≤ – 2 or J≤ = J¢ + 2; J¢ = 0, 1, 2,

Hence DG = – 2B (2J¢ + 3) + we (1 – 2 xe) (1)

For S branch (D J = + 2), we have

J¢ = J≤ + 2; J≤ = 0, 1, 2,
Hence DG = 2B (2J≤ + 3) + we (1 – 2 x e) (2)
Writing Eqs (1) and (2) together, we have
DG = ± 2Bm + we (1 – 2xe) (3)
where m = 2 J + 3 and can have values 3, 5, 7,

kT 1
(b) Now Jmax = – (Eq. 4.4.12)
2 Bhc 2
 Molecular Spectroscopy 485

kT
Hence mmax = 2 +2
2 Bhc
Thus, DG at m = mmax is given by
Ï kT ¸
DG = ± 2B Ì2 + 2 ˝ + we (1 – 2xe )
Ó 2 Bhc ˛
The separation between the maxima of O and S branches is given by
Ï kT ¸ 32BkT
DG = 4 B Ì2 + 2˝ = + 8B
Ó 2 Bhc ˛ hc

(c) Since 8B is smaller than 32 BkT / hc , we may write

32BkT
B = ÊÁ
hc ˆ
DG = or ( DG )2
hc Ë 32 kT ˜¯
Substituting the values, we get

(6.626 ¥ 10-34 J s)(3 ¥ 1010 cm s -1 )

B= (23.8 cm–1)2
(32)(1.38 ¥ 10-23 J K -1 )(555 K)
= 0.045 95 cm–1

4.7 VIBRATION SPECTRA OF POLYATOMIC MOLECULES

Number of A system consisting of N particles can be described by specifying three coordinates
Fundamental for each particle, i.e. a total of 3N coordinates. Even when these particles are
Vibrations undergoing motions, howsoever complicated they may be, the system at any
instant can be described by stating these 3N coordinates. Since any one of these
components can vary by any amount, the system is said to possess 3N independent
components of motion or degrees of freedom. If N particles are bound to form
a molecule, then the 3N degrees of freedom are conveniently chosen as follows.
Translational Motion The translational motion of a molecule as a whole can be
described by the motion of its centre of mass. Since three coordinates are required
to describe the position of centre of mass, three degrees of freedom are utilized in
describing the translational motion of the molecule.
Rotational Motion A linear molecule can rotate about two mutually perpendicular
axes whereas a nonlinear molecule can rotate about three axes. Thus, two degrees
of freedom are utilized in describing the rotational motion of a linear molecule
and three for those of a nonlinear molecule.
Vibrational Motion The remaining (3N – 5) degrees of freedom for a linear
molecule and (3N – 6) for a nonlinear molecule are utilized in describing the
internal vibrations (stretching and bending motions) of the molecule. In other
words, a linear molecule has (3N – 5) fundamental vibrations (or normal modes
of vibration) whereas a nonlinear molecule has (3N – 6) fundamental vibrations.
Since a molecule consisting of N atoms contains a total of (N – 1) bonds between
its atoms, (N – 1) vibrations out of (3N – 5) or (3N – 6) modes of vibrations are
those of bond stretching motions and the remaining (2N – 4) or (2N – 5) are those
of bending motions. The former motions involve the change in bond lengths whereas
the latter involve the change in bond angles of the molecule.
486 A Textbook of Physical Chemistry

Table 4.7.1 describes the normal modes of vibrations of di-, tri- and tetra-atomic
molecules.
Table 4.7.1 Normal Modes of Vibrations of Di-, Tri- and Tetra-Atomic Molecules
Molecule Number of Total degrees Number of Number of motions of
atoms N of freedom modes of
vibrations Bond Bending
stretching
(3N – 5) (N – 1) (2N – 4)
or or
(3N – 6) (2N – 5)
Diatomic; 2 6 1 1 0
H2, O2, HCl, etc.
Symmetric H H
stretching

Nonlinear triatomic; 3 9 3 2 1
SO2, H2O, etc. Symmetric Antisymmetric Symmetric
stretching stretching bending
O O O
H H H H H H

Linear triatomic; 3 9 4 2 2
CO2, N2O, etc. Symmetric Antisymmetric Symmetric bending
stretching1 stretching2 (doubly degenerate3)

O C O O C O O C O

Linear tetra-atomic; 4 12 7 3 4
Acetylene Symmetric Symmetric Antisymmetric Bending Bending
stretching stretching stretching (doubly (doubly
degenerate) degenerate)

H C C H H C C H H C C H H C C H H C C H

1. Two outer atoms move in opposite directions, the central one is stationary.
2. Two outer atoms move in one direction, the central one in opposite direction.
3. The outer atoms move in opposite directions approximately at right angles to the molecular axis and the valence
angle at the central atom changes.

Infrared Spectrum A polyatomic molecule exhibits (3N – 5) or (3N – 6) normal modes of vibrations.
of a Polyatomic These vibrations fall into two categories, viz., skeletal vibration and group
Molecule vibrations. The former involves more or less all atoms of the molecule and in the
latter vibrations of a small group of atoms are more vigorous than those of the
remaining atoms.
 Molecular Spectroscopy 487

Skeletal vibrations exhibit absorptions below 1 500 cm–1 which are characteristics
of the molecule as a whole. These may be utilized to establish the general structure
of the molecule such as the linear structure, branched structure, benzenoid structure
and so on.
Since the bands observed in the region below 1 500 cm–1 are characteristic of
the compound in question, this region is known as the . The use

sample is considered to be one of the most reliable methods.

Group vibrations involve the vibrations of the various functional groups or
other characteristic groups present in the molecule. Such vibrations are usually
independent of the structure of the molecule as a whole and exhibit absorptions
in the region above 1 500 cm–1. A few functional groups exhibit the absorption in

Some commonly encountered group absorption wavenumbers are listed in Table

4.7.2.
Table 4.7.2 Characteristic Group Absorption Wavenumbers
Bond Group Description Approximate
wavenumber
cm–1
C—H CH3, alkane stretching 2 960, 2 870
C—H CH2, alkane stretching 2 920, 2 850
C—H — CH==CH— stretching 3 095 — 3 010
C—H ∫∫ C—H stretching 3 300
C—H — C—H, aromatic stretching 3 100 — 3 030
C—H — CH2— bending 1 470 — 1 400
C—H — C — CH3 bending 1 380 — 1 360
C—H — CH==CH—, trans bending 1 300, 970
C—H — CH==CH—, cis bending 690
C—C (CH3)3C— skeletal 1 250
C—C — (CH2 )n (n > 3) skeletal 725
C—C — CH==CH— stretching 1 680 — 1 620
C—C — C∫C— stretching 2 230
C—H C6H5— CH wag 1 600, 1 500
(monosubstituted aromatic)

O—C C O stretching 1 760 — 1 690

O—C C O stretching 1 250 — 1 000

C—N C N stretching 1 690 — 1 630

O—H O—H (free) stretching 3 620
O—H O—H stretching 3 600 — 3 300
(hydrogen bonded, alcohols)
N—H N—Hx (x = 1, 2, 3) stretching 3 500 — 3000
S—H S—H stretching 2 600
Cl — C Cl — C stretching 800 — 700
488 A Textbook of Physical Chemistry

The group frequencies follow approximately the equation

kf
n= 1 (Eq. 4.5.17a)
2p m
Thus for one type of group, the group frequency increases with increase in
force constant of the bond and decreases with increase in the reduced mass of
the group. For example, in the group —C—X, where X may be H, F, Cl, Br, the
group frequencies follow the relation
CH > CF > CCl > CBr
since the reduced mass of the group follows the order
mCH < mCF < mCCl < mCBr
The triple bond shows absorption at higher frequency than double bonds and
double bonds higher than single bonds, since the bond strength or the force constant
follows the relation
kC ∫∫ C > kC==C > kC—C
In general, the infrared spectrum of a polyatomic molecule may be complex
owing to the appearance of overtones, and combination and difference bands
corresponding to n1 + n2 and n1 – n2, respectively, where n1 and n2 are the
frequencies of the two fundamental modes of vibrations. Besides this, the two
close frequencies of vibrations undergo changes due to the mutual interactions.
For example, one of the fundamental transition of CO2 is at 1330 cm–1 and one of
the overtone transition is at 1334 cm–1. This close by transitions are referred to as
accidental degeneracy. Due to mutual interactions, these are shifted to 1285 cm–1
and 1388 cm–1, respectively. Also the intensity of the overtone transition is very
much enhanced at the expense of the fundamental transition. This type of shifting
of intensities is known as Fermi resonance. Nevertheless, the infrared spectrum
is very helpful in detecting the functional groups and the general structure of the
molecule. Moreover, shifts of observed group frequencies can often be used to
infer the nature of the bonding of adjacent groups in the molecule.
4.8 RAMAN SPECTRA

Introduction Let a beam of monochromatic light from the visible portion of the spectrum be
chosen such that it is not absorbed by the substance under study. If such a light
is passed through the substance, nearly all of it is transmitted and a very small
fraction of it is scattered in all directions (Fig. 4.8.1). If the scattered light in a
direction perpendicular to the incident beam is spectrographed, it is found not
only to contain a line corresponding to the frequency of incident light, but also
a pattern of relatively weak lines on the low-frequency side of the incident light
and a similar pattern of still more weak lines on the high-frequency side (Fig. 4.8.2).
Scattered light Rayleigh
Fig. 4.8.1 Scattering Raman lines line Raman lines
of light by nonabsorbing Dn < 0 Dn > 0
substance
Incident Transmitted
light light
Fig. 4.8.2 Schematic
representation of a
Raman spectrum
Scattered light Frequency
 Molecular Spectroscopy 489

The line at the incident frequency is known as Rayleigh line (after Lord Rayleigh

are called the Raman lines (after C.V. Raman who was the discoverer of these
lines). The difference between the frequencies (or wavenumbers) of the Rayleigh
line and a Raman line is known as the Raman shift, and may be expressed as
Dn = |n0 – nR| (4.8.1a)

Dn = |n 0 - n R | (4.8.1b)
where the subscripts 0 and R stand for incident and Raman lines, respectively.
For a given substance, the Raman shift is found to be independent of the
frequency of the incident radiation, i.e. it has the same value for different frequency
of the incident light. The difference is a characteristic of the substance and is found
to be equal to its vibrational or rotational transition.
Classical The Raman spectroscopy is observed only when there occurs a periodic change in
Explanation of the polarizability of molecule due to its vibrational or rotational oscillation. From
Raman Lines the classical point of view the above fact may be understood as follows.

charged nuclei and the negatively charged electronic cloud is attracted towards the

acquires an induced dipole moment which is given by†

pind = a E (4.8.2)
where a is the polarizability of the molecule.
In the presence of a beam of radiation, the molecule also acquires an induced
dipole moment due to the electrical component of the incident light. This electrical
component is not static but varies as the sine (or cosine) wave according to the
equation
E = E0 sin (2pnt) (4.8.3)
where n is the frequency of radiation and t is the time. This variation is illustrated
in Fig. 4.8.3. Consequently, the induced dipole moment also oscillates according
to the equation
p = aE = a E0 sin (2pn t) (4.8.4)

Direction of
Fig. 4.8.3 The propagation
H
variation of electric-
component of the
radiation with time

†
See Section 3.2.
490 A Textbook of Physical Chemistry

According to the electromagnetic theory, an oscillating dipole emits radiation

of its own frequency. This explains the occurrence of Rayleigh line in the light
scattered by the substance. The presence of Raman lines is due to the periodic
change in the value of a due to the internal vibrational or rotational motion†
according to the equation
∂a
a = a0 + ÊÁ ˆ˜ x 0 sin (2pnit) (4.8.5)
Ë ∂x ¯
where ∂a /∂x is the change in polarizability with the displacement coordinate x,
ni the frequency of internal motion, and a 0 is the polarizability in the equilibrium
position x 0.

The periodic change in the polarizability will also change periodically the
induced dipole moment (Eq. 4.8.2). When this periodic change is superimposed
upon the periodic oscillation due to the electrical component of light (Eq. 4.8.4),
we get

{ Ê ∂a ˆ x sin 2pn t
pind = a 0 + Á
Ë ∂x ˜¯ 0 i } E0 sin 2pnt

Ê ∂a ˆ
= a0 E0 sin (2pnt) + Á x E sin (2pnit) sin (2pn t)
Ë ∂x ˜¯ 0 0
(4.8.6)

Since 2sin q sin j = cos (q – j) – cos (q + j), we get

1 Ê ∂a ˆ
pind = a0 E0 sin (2pnt) + x E cos {2p(n – ni)t}
2 ÁË ∂x ˜¯ 0 0

1 Ê ∂a ˆ
x E cos {2p (n + ni )t}
2 ÁË ∂x ˜¯ 0 0
– (4.8.7)

that is, induced dipole moment of the molecule not only oscillates with frequency
n, but also with frequencies n – ni and n + ni. It is thus expected that besides the
frequency n, the oscillating dipole will also emit radiations of frequencies n – ni
and n + ni. These radiations appear as the Raman lines in the light scattered by
the substance.

Criterion of Note that if ∂a / ∂x is zero, i.e. there occurs no change in the polarizability during
Observing Raman the small displacement from the equilibrium position of the internal motion, then
Lines the induced dipole moment of the molecule will oscillate with only one frequency
corresponding to the frequency of incident light. In such a case, the molecule emits
only Rayleigh line and hence Raman lines are not observed, i.e. the molecule is
Raman inactive. Thus, the essential criterion for a molecule to be Raman active is
that a molecular vibration or rotation must cause a change in the component of
molecular polarizability. This criterion may be compared with those of rotational
†

internuclear distance also depends on the orientation of the molecule with respect to the
 Molecular Spectroscopy 491

and vibrational spectroscopy which respectively are: (1) the molecule must have a
permanent dipole moment, and (2) there should occur a change in dipole moment
during the vibration motion.

Since the polarizability has the dimension of volume in gaussian units (see,
Section 3.3) it may be concluded that only those vibrations which are associated
with the change in the volume will be Raman active.

Quantum The Raman lines are, in general, of very weak intensities as compared to the
Explanation of Rayleigh line. From the qualitative quantum viewpoint, the occurrence of Raman
Raman Lines lines may be understood as follows.
The photon on colliding with a molecule will constitute either an elastic or
inelastic collision. We may consider the molecule to form a complex with the
photon during the extremely short time of collision ( 10–15 s). The energy of the
complex will not correspond to a molecular electronic energy level (Fig. 4.8.4a).
Now if the collision is elastic, the complex will dissociate to give the molecule
and photon of the same energy which it had before the collision. This gives rise
to the Rayleigh scattering. On the other hand, if the collision is inelastic, there
can occur an exchange of energy between molecule and photon. This exchange
of energy can be of two types.

∑ The molecule before the collision occupies a lower vibrational or rotational

energy level and after the emission of the photon, it may be present in any
one of the higher energy levels as permitted by the selection rule. In this case,
the molecule gains energy equivalent to the energy difference between the two
involved levels. This energy is provided by the photon and hence its energy
is decreased and thus a Raman line on the low frequency side is observed
(Fig. 4.8.4b).
∑ The molecule before the collision occupies one of the higher vibrational or
rotational energy level and after the emission of the photon may be present
in any one of the lower energy levels as permitted by the selection rule. In
this case, the molecule loses an energy equivalent to the energy difference
between the two involved levels. This energy is gained by the photon and
hence its energy is increased and thus a Raman line on the high frequency
side is observed (Fig. 4.8.4c).
n=1

Fig. 4.8.4 Schematic

representation of
(a) Rayleigh scattering
with Dn = 0.
(b) Raman scattering n=0
u=1
with Dn < 0, and
(c) Raman scattering n=0
u=0 (a) (b) (c)
with Dn > 0
492 A Textbook of Physical Chemistry

Pure Rotational The selection rules for the pure rotational Raman spectra of diatomic molecules are
Raman Spectra D J = 0 and ± 2
of Diatomic The selection rule D J = 0 gives rise to the Rayleigh scattering only. The selection
Molecules rule D J = ± 2 gives rise to the Raman lines. The factor 2 is due to the fact that
the polarizability ellipsoid rotates twice as fast as the rotation of the molecule.
The rotational energy expression in wavenumber unit is
FJ = BJ(J + 1) (Eq. 4.4.7)
The difference in wavenumber between two levels is
D F = BJ¢(J ¢ + 1) – BJ ≤(J ≤+ 1) (Eq. 4.4.14)
For the selection rule DJ = J ¢ – J ≤ = 2, we have
D F = B(J≤ + 2) (J ≤ + 3) – BJ ≤(J ≤ + 1)
= B (4J ≤ + 6); J≤ = 0, 1, 2, (4.8.8)
Similarly for the selection rule DJ = J ¢– J≤ = – 2, we have
D F = – B(4J¢+ 6); J¢ = 0, 1, 2,
Thus, Raman lines will appear at wave numbers given by the expression
F = F0 ± B(4J + 6); J = 0, 1, 2, 3, (4.8.9)
where F0 is the wavenumber of Rayleigh line. The lines at wavenumbers less
than F0 are known as Stokes’ lines and those having wavenumbers greater than F0
are known as anti-Stokes’ lines. The expected pure rotational Raman spectrum is
shown in Fig. 4.8.5.
B from the
Rayleigh line. The remaining lines will lie at a constant spacing of 4B.

Stokes lines Anti-Stokes lines

Fig. 4.8.5 An expected

pure rotational Raman
spectrum for a diatomic
molecule
4B 4B 4B 4B 4B 4B 6B 6B 4B 4B 4B 4B 4B 4B
The intensities of Raman lines will, as usual, depend on the population of the initial
Intensities of Pure
Rotational Raman Jinitial < J Jinitial > J (Fig. 4.8.5).
Spectra Since the population in the rotational levels is as shown in Fig. 4.4.3, it is expected

For molecules having a centre of symmetry, the nuclear spins also affect the
population in the rotational levels. For molecules having nuclear spin zero (e.g. O2
†
Since the polarizability a is even function, the transition moment integral pmn = y m a y n
will be nonzero if the product of ym and yn is an even function, i.e. both ym and yn are
either even or odd functions. This leads to the selection rule DJ = ± 2.
 Molecular Spectroscopy 493

and CO2), every alternate rotational level is unoccupied. For example, the levels
J ≤ = 0, 2, 4, … in case of O2 and J ≤ = 1, 3, 5, … in case of CO2 are unoccupied.

spectrum of O2 occur at F0 – 10B and F0 + 10B, respectively, and those of CO2

occur at F0 – 6B and F0 + 6B, respectively, with the remaining absorptions in both
cases occur at the interval of 8B. For molecules having nonzero nuclear spin (e.g.
H2 and N2), the rotational levels show alternation in population as given by the
following expression.†
J : odd J :: I(2I + 1) : (I + 1) (2I + 1) :: I : (I + 1)
Integral spin even J : odd J :: (I + 1) (2I + 1) : I (2I + 1) :: (I + 1) : I
where I
rotational spectra. For H2(I = 1/2), the alternation in intensities is 1 : 3 while for
N2(I = 1), it is 2 : 1
Application of The pure rotational Raman spectra provides the value B. Thus, the moment of inertia
Pure Rotational and bond length of the molecule can be determined. The usefulness of Raman
Raman Spectra spectroscopy may be emphasized here. Homonuclear diatomic molecules do not
exhibit pure vibrational or rotational spectra as they possess no dipole moment.
But they do exhibit rotational Raman spectra and hence structural parameters
which cannot be determined by pure rotational spectra can be determined from
the Raman spectra.
Vibrational Raman The selection rules for the vibrational Raman spectra are the same as those for
Spectra pure vibrational spectra, i.e.
Du = ± 1, ± 2,
For a vibrational mode, the vibrational energy expression is
{
Gu = (u + 1 2) w e 1 - (u + 1 / 2) xe } (Eq. 4.5.20)
The differences in energy levels are
u¢ = 1 ¨ u≤ = 0 ; DGfundamental = we (1 – 2xe )
u¢ = 2 ¨ u≤ = 0 ; DGovertone = 2we (1 – 3xe )
u¢ = 2 ¨ u≤ = 1 ; DGhot = we (1 – 4xe )
Since the population in u = 1, u = 2, etc., levels are very small, the overtones
and hot lines are of very weak intensities as compared to the fundamental line.
Restricting only to the fundamental transition, we will observe Raman lines at the
following wave numbers:
Gfundamental = G0 ± Ge(1 – 2xe)

u¢ = 0 ¨ u≤ = 1, it is
expected to be very weak as very few molecules exit in the u≤ = 1 state at normal
temperature. On increasing temperature, the population of u = 0 state is decreased
whereas that of u = 1 state is increased. it is, thus, expected that the intensity of

†
The given expressions represent the ratio of nuclear wave functions associated with the
corresponding rotational levels. See, Annexure II of the Chapter 4 of Volume 5.
494 A Textbook of Physical Chemistry

the temperature of the sample.

As mentioned earlier, only those vibrational modes will be Raman active for
which ∂a/∂ x is nonzero. A molecule with little or no symmetry, all of its vibrational
modes are usually Raman active. But a molecule with a considerable symmetry,
it is not so. Moreover, the symmetric vibrations produce a large value of da/dx
near the equilibrium position of vibration and hence produce intense Raman lines.
For antisymmetric vibrations, da /dx is either zero or usually very small and hence
they produce either no line or weak (and sometimes unobservable) Raman lines.
Rotational Fine
Structure spectrum of a large molecule is ignored as it is beyond resolution. Only in case

E u, J = BJ(J + 1) + (u + 1 2) we {1 + (u + 1 / 2) xe }
The selection rules are
Du = ± 1, ± 2,
D J = 0, ± 2
Restricting to the fundamental vibration transition, we have
D J = 0; D E Q = we (1 – 2xe ) ; (for all J )
D J = +2; D E S = we (1 – 2xe ) + B(4J ≤+ 6); (J ≤ = 0, 1, 2, )
DJ = – 2; D E O = we(1 – 2xe ) – B(4J¢ + 6); (J ¢ = 0, 1, 2, )
where the subscripts Q, S and O refer to the Q, S and O branches, respectively.
If E 0 i
at the following wavenumbers.
EQ = E0 – D EQ
ES = E0 – D ES
EO = E0 – D EO
E 0 towards
the high wavenumber side.

Example 4.8.1 For acetone a normal mode of vibration that involves the stretching of the carbonyl bond is
active in both Raman and infrared spectra. The Raman line associated with this normal mode
is found at 547 nm when excited by incident light whose wavelength is 500 nm. Calculate
the wavelength of the centre of the corresponding infrared absorption band.
Frequency of the Raman line at wavelength 547 nm is
c c
n1 = =
Solution l 547 ¥ 10-9 m
Frequency of the incident light of wavelength 500 nm is
c c
n2 = =
l 500 ¥ 10-9 m
Change in frequency of the light is
c c c ( 47 ¥ 10-9 m )
Dn = – =
-9
500 ¥ 10 m -9
547 ¥ 10 m (500 ¥ 10-9 m) (547 ¥ 10-9 m)
The change in frequency of the light is related to the energy difference between the
two vibrational levels. Hence, the wavelength of the centre of the corresponding infrared
 Molecular Spectroscopy 495

absorption band is

(500 ¥ 10-9 m) (547 ¥ 10-9 m) 500 ¥ 547 ˆ

= ÊÁ
c
˜¯ ¥ 10 m
–9
l = =
Dn -9
(47 ¥ 10 m) Ë 47

= 5.819 ¥ 10–6 m = 5.819 mm

Rule of Mutual A general rule, known as the rule of mutual exclusion, for molecules having centre
Exclusion of symmetry has been established. This rule states that:
If a molecule has a centre of symmetry, then Raman active vibrational modes
are infrared inactive, and vice versa.
Thus by comparing Raman and infrared spectra of a substance, it is possible
to establish whether the molecule has a centre of symmetry or not and hence
its structure can be established. If the two spectra do not include the common
absorptions, it implies that the molecule has a centre of symmetry. On the other
hand, if the two spectra include common lines, it implies that the molecule has
no centre of symmetry.

2
and SO2 molecules. The structure of CO2 is linear and thus it possesses the centre
of symmetry. The molecule of SO2 is nonlinear and thus it does not possess the
centre of symmetry. The CO2 molecule has four vibrational modes, whereas the
SO2 molecule has three vibrational modes. These modes along with the associated
change in the dipole moment and polarizability are described in the following.
1. Symmetrical Stretch ¨ O == C == O Æ
During this vibration, the dipole moment of the molecule remains zero throughout
the vibration, i.e. the dipole moment does not alter periodically, and hence this
vibrational mode will be infrared inactive. Since during the vibration, volume
of the molecule changes, it may be concluded that there occurs a change in the
polarizability of the molecule and hence this vibrational mode will be Raman
active. More precisely, the slope of the a versus x curve will be nonzero near the
equilibrium position of the vibrational motion, i.e. the small displacement near the
equilibrium position produces a change in the polarizability.
2. Antisymmetric Stretch O == C == O
Æ ¨ Æ
Since during the vibration, one of the bond undergoes stretching whereas the other
bond undergoes shortening of the bond length it is expected that there will occur a
change in dipole moment of the molecule and hence this vibrational mode will be
infrared active. Since the lengthening and shortening of bonds occur by the same
amounts, it is expected that the polarizability (or volume) of the molecule does not
change during the vibration. More precisely, da/dx = 0 near the equilibrium position
of the vibrational motion. Thus, this vibrational mode will be Raman inactive.

3. Bending Mode (doubly degenerate) O C O

During the bending motion, the dipole moment of the molecule changes but not its
496 A Textbook of Physical Chemistry

polarizability and hence this vibrational mode will be infrared active and Raman
inactive.

Thus, we see that if a vibrational mode of CO2 is infrared active, it is necessarily

Raman inactive, on the other hand, if it is infrared inactive, then it is Raman active.
This is due to the fact that the CO2 molecule has a centre of symmetry.

Coming to the SO2

infrared and Raman active. The analysis of symmetric stretch is described below.

The sulphur dioxide molecule has a permanent dipole moment and its value
changes periodically during the symmetrical stretch vibrational mode. Since the
volume of the molecule changes during the vibration, it is expected that there will
also occur a change in polarizability of the molecule. Hence, this vibrational mode
will be infrared as well as Raman active.

Infrared and Raman spectra supplement each other in the determination of

molecular structure. Both types of spectra are needed to determine the structure
of the molecule. One of the rules which helps establishing the centre of symmetry
in the molecule has been described above. Besides this rule, the following rules
Application of are also helpful.
Infrared and
Raman Spectra ∑ If the molecule is linear, then all those vibrational modes in which linearity
rotation spectrum.The vibrational modes in which linearity is destroyed will
include PQR contours. Thus, if one or more bands in the infrared spectrum
contains only PR contour we can conclude that the molecule is linear.
∑ In general, a symmetric vibration gives rise to a polarized or partially polarized

plane) while an antisymmetric vibration gives a depolarized line. In general,

tion decreases with increasing molecular symmetry.

∑ In most cases the absorption lines follow the order:
nbending < nstretch
nsym stretch< nantisym stretch

With these additional rules, one can often assign the structure of simple
molecules and also the nature of fundamental modes of vibration associated with
the observed infrared or Raman lines. The following problems illustrate the use
of above rules in establishing the structure of simple molecules.

Problem 4.8.1 For CO2, the following spectroscopic data are available. Predict the geometry of CO2
molecule.

Wavenumber Infrared Raman

 Molecular Spectroscopy 497

cm–1

1 330 Inactive Active

2 349 Active Inactive

(PR)

667.3 Active Inactive

(PQR)

Solution The analysis of data is given below.

1. Since transition at 2 349 cm–1 includes PR contour, we may conclude that the
molecule CO2 is linear.

2. The infrared and Raman spectra do not include any common line and hence the
molecule of CO2 contains the centre of symmetry.

Hence, the structure of CO2 is O == C == O.

The CO2 molecule exhibits 4(= 3 ¥ 3 – 5) fundamental vibration modes. These are
symmetric stretch, antisymmetric stretch and doubly degenerate bending vibration. Since
during symmetric stretch vibration, the dipole moment of CO2 does not change whereas its
polarizability does change, the transition at 1 330 cm–1 may be assigned to the symmetric
stretch. The transition at 2 349 cm–1 which include only PR contour may be assigned to
antisymmetric stretch, since during this mode the linearity of the molecule is not changed.
Lastly, the transition at 667.3 cm–1 may be assigned to the bending vibrational mode. This
assignment also follows from the fact that (i) the transition includes PQR contour (linearity
is lost during vibration), and (ii) bending vibration is easy to carry out than the stretching
as in the latter, changes in the bond length occur whereas in the former only bond angle is
changed. The above assignment is also shown in Table 4.8.1.

Table 4.8.1 Assignment of Vibrational Modes

Wavenumber
cm–1 Assignment

1 330 Symmetric stretch O C O

2 349 Antisymmetric stretch O C O

667.3 Bending O C O

Problem 4.8.2 For N2O, the following spectroscopic data are available. predict the geometry of N2O
molecule.
Wavenumber Infrared Raman
498 A Textbook of Physical Chemistry

cm–1
589 Active Inactive
(PQR)
1 285 Active Active (polarized)
(PR)
2 224 Active Active (depolarized)
(PR)
Solution The analysis of data is given below.
1. Since the transition at 1 285 cm–1 includes PR contour, we may conclude that the
molecule of N2O is linear.
2. The infrared and Raman spectra contain some common lines. Thus, we may conclude
the absence of centre of symmetry in the N2O molecule.
Hence, the structure of N2O is N ∫∫ N == O
The assignment of modes of vibration along with the reasons is given in Table 4.8.2.
Table 4.8.2 Assignment of Vibrational Modes
Wavenumber Assignment Reasons
cm–1
1 285 Symmetric stretch Linearity of the molecule is
N N O maintained (PR contour in
infrared spectrum).
Raman line is polarized.
2 224 Antisymmetric stretch Linearity of the molecule is
N N O maintained (PR contour in
infrared spectrum).
Raman line is depolarized.
589 Bending Linearity of the molecule is
lost (PQR contour in infrared
N N O spectrum). Minimum energy
is required for bond bending.

For SO2, the following spectroscopic data are available. Predict the geometry of SO2
molecule.
Wavenumber Infrared Raman
cm–1
Problem 4.8.3
519 Active ( ) Active
(PQR) (polarized)]
1 151 Active ( ) Active
(PQR) (polarized)
1 361 Active (^) Active
(PQR) (depolarized)
The analysis of the data is given below.
1. Since all transitions include PQR contour, it may be concluded that the molecule is
nonlinear.
2. The infrared and Raman spectra involve common lines and hence the absence of
 Molecular Spectroscopy 499

Solution centre of symmetry is concluded. This also follows from the fact that a nonlinear triatomic
molecule cannot have a centre of symmetry.
3. Since some Raman lines are polarized, it indicates that the symmetry of the molecule
is preserved during the vibration. This gives an indication that the two oxygen atoms are
placed symmetrically with respect to sulphur atom.

Hence, the structure of SO2 is

S The assignment of modes of vibration along with
O O
the reasons is given in Table 4.8.3. The assignment is also supported by the information on
parallel and perpendicular vibrations shown in the given data.

Table 4.8.3 Assignment of Vibrational Modes

Wavenumber Assignment Reasons
cm–1
1 151 Symmetric stretch Raman line is polarized.
S (Parallel vibration )
O O

1 361 Antisymmetric stretch Raman line is depolarized.

S (Perpendicular vibration )
O O
519 Bending Raman line is polarized.
S Minimum energy for bond
O O deformation.
(Parallel vibration )

Problem 4.8.4 For acetylene, the following spectroscopic data are available. Deduce its structure.
Wavenumber Infrared Raman
cm–1
3 374 Inactive Active
(polarized)
1 974 Inactive Active
(polarized)
3 287 Active Inactive
(PR)
612 Inactive Active
(weak)
729 Active Inactive
(PQR)

The analysis of the given data is given below.

1. Since the line at 3 287 cm–1 includes PR contour, it may be concluded that the
molecule is linear.
Solution 2. Since infrared and Raman spectra do not contain any common line, the presence of
centre of symmetry may be concluded.
Hence, the structure of acetylene is H — C ∫∫ C — H.
500 A Textbook of Physical Chemistry

The assignment of modes of vibration along with the reasons is given in Table 4.8.4.

Table 4.8.4 Assignment of Vibrational Modes

Wavenumber Assignment Reasons

cm–1
3 374 Symmetric stretch No change in dipole moment during the vibration (infrared
H C C H inactive), polarizability changes during the vibration (Raman
active). Raman line is polarized.

1 974 Symmetric stretch No change in dipole moment during the vibration (infrared
H C C H inactive). Polarizability changes during the vibration (Raman
active). Raman line is polarized.

3 287 Antisymmetric stretch Dipole moment changes during the vibration (infrared active).
H C C H No change in polarizability during the vibration (Raman
inactive). Linearity of the molecule is maintained (PR contour).

612 Bending No change in the dipole moment during the vibration

doubly (infrared inactive.)
degenerate H C C H

729 Bending Change in dipole moment during the vibration.

doubly Linearity of the molecule is lost during the vibration
degenerate H C C H (infrared active)

The electron in a diatomic molecule can be excited from an occupied molecular orbital to an empty or

4.9 ELECTRONIC SPECTRA OF DIATOMIC MOLECULES

Introduction electronic
transition. The radiation required for the electronic transition lies in the visible or
ultraviolet region. A molecule in each stable electronic level can execute vibrational

write the total energy of the molecule as

Etotal = Eelec + Evib + Erot (4.9.1)
The various vibrational and rotational levels associated with each stable
electronic level have been shown schematically in Fig. 4.1.1.
The electronic transitions are accompanied by changes in vibrational and
rotational energy levels. The vibrational transitions appear as the coarse structure
whereas rotational transitions as the .
For a transition of the vibrational coarse structure of spectra, we may write
D E = DEelec + DEvib (4.9.2)
For a given electronic transition, there is no quantum mechanical restriction (i.e.
 Molecular Spectroscopy 501

Franck-Condon the selection rules) on the change in the vibrational quantum number. Since in
Principle the gro
types of transitions from this lowest vibrational level to any of vibrational levels
of the higher electronic state are possible. Experimentally, it is known that all
such transitions are not equally intense. This fact can be explained with the help
of Franck-Condon principle, which may be stated as follows.

The electronic transition occurs so quickly that the internuclear separation

during the transition remains unchanged.

Thus, the instantaneous internuclear separation in the excited electronic state

is the same as it was in the initial ground state at the time of electronic transition.
Since the internuclear separation remains the same, the transition in the energy
diagram will be shown by a vertical line as shown in Fig. 4.9.1 The probability
or intensity of transition at a particular internuclear separation depends on the

given internuclear separation. A transition involving the largest probabilities in

the lower and excited vibrational levels will be the most intense. Other transitions
will have lesser probabilities and thus will have lesser intensities. Figure 4.9.1

principle. Transition labelled as b in Fig. 4.9.1 will be more intense than the other
two shown transitions.
First
excited
state
Energy

Ground
a b c state

Transition b will be more

intense than transitions a and c

Fig. 4.9.1 A schematic

illustration of Franck- ro r
Condon principle
The exact nature of electronic spectrum depends on the internuclear separation of
502 A Textbook of Physical Chemistry

the molecule in the excited state relative to that in the ground state. In general, the
internuclear separation in the excited state is slightly larger and the force constant
is slightly smaller than those in the ground state. This follows from the fact that the
excited state usually corresponds to a weak bond in the molecule. Consequently,
the depth in the potential energy diagram of the excited state is slightly displaced
towards the larger internuclear distance and the spacing between the associated
vibrational levels is smaller than those of the lower electronic state.

Figure 4.9.2 displays typical electronic spectra when there occurs (a) no change,
(b) a little change, and (c) a larger change in internuclear distance of the excited
state relative to the ground state. In 4.9.2c continuum indicates that all radiations
are absorbed causing the molecule to dissociate. The energy excess of dissociation
limit is utilized in imparting kinetic energies to the dissociated atoms.

If the internuclear separation in the excited state is much larger than in the
Dissociation of lower level, the electronic transition may lead to the dissociation of the molecule
Molecule (Fig. 4.9.2c). This happens when the vertical transition ends at a point where the

Excited Excited
Excited state state
state

Ground
state Ground
state Ground
state

r r r
Intensity

(0,0) Continuum
(0,2)
dissociation
limit
(a) (b) (c)

Fig. 4.9.2 Typical electronic spectra, (a) with no change, (b) a little change, and (c) a larger change in internuclear
separation in the excited state relative to the ground state
 Molecular Spectroscopy 503

electronic energy of the molecule in the excited state is larger than the corresponding
dissociation energy. In the present case, electronic spectrum generally consists of
the coarse structure (corresponding to the different changes in vibrational quantum
number) which ends at a continuum representing the dissociation limit of the
spectrum. This continuum is observed because of the fact that the kinetic energy

state above that needed just for the dissociation of the molecule) is not quantized.
Thus, in the continuum region, we may write
Eabsorbed photon = Ed1 + Eextra (4.9.3)
where Ed1 and Eextra represent the energy of dissociation limit and the extra energy,
respectively. In most cases, only one of the dissociation atoms produced as a result
of absorption of energy Ed1 is in its electronic excited state and the other one is in
its ground electronic state. Thus, the energy Ed1 may be written as
Ed1 = ED¢¢ + Eex (4.9.4)
where ED¢¢ is the dissociation energy of the molecule in the ground electronic
state and Eex is the excitation energy of one of the atoms produced on dissociation
(Fig. 4.9.3). From Fig. 4.9.3, we can also write
E0,0 + E¢D = ED¢¢ + Eex
Hence E¢D = ED¢¢ + Eex – E0,0 (4.9.5)†

Fig. 4.9.3 A schematic

representation of
dissociation on
excitation

†
The value of E¢D can also be determined with the help of Birge and Sponer extrapolation
method where DE involving the neighbouring vibrational absorptions (e.g., DE (u¢ = 1 ¨
u≤ = 0) – D E(u¢ = 2 ¨ u≤ = 0) is plotted against the vibrational quantum number u¢. A
smooth curve passing through these points is drawn and is extrapolated up to the u¢
Since the dissociation energy of the molecule is equivalent to the sum of all DE plotted
above, the area under the curve of D E versus u¢ directly gives the required dissociation
energy of the molecule in the excited state.
504 A Textbook of Physical Chemistry

Alternatively, the molecule (e.g. H2 molecule) is dissociated if the electron is excited

to the unstable electronic state (no minimum energy in the energy curve). This is
shown in Fig. 4.9.4. The electronic spectrum in this case consists of only continuum.

Unstable
excited
state

Energy
Stable
ground
state

Fig. 4.9.4 Dissociation

of the molecule
on excitation to the req
unstable excited state

Predissociation of
Molecule spectrum are quite distinct for small and large changes in the vibrational quantum
number, but in the central region a continuum is observed. This behaviour, which
is known as predissociation, can be explained by the energy diagram shown in Fig.
4.9.5. This diagram is observed when for a particular geometry near to the end of
the molecular vibration, the energy of the molecule in the stable electronic excited
state is identical with that in t
First excited
singlet state

h
g
f
e

d
c Nonbonding
b
Singlet
a ground state

Fig. 4.9.5 A schematic

illustration of
predissociation
 Molecular Spectroscopy 505

energy curves intersect each other at this geometry. There is high probability
(since the molecule spends larger time near the extreme ends of vibrational motion
for larger value of vibrational quantum number) that the molecule during vibration

distance smaller and larger than this geometry, the probability of crossing over
decrease
small.

Now if the electronic excitation ends with the low and high vibrational quantum
levels in the excited state (e.g. levels a, b, g and h in Fig. 4.9.5), it is expected

electronic state when the molecule is at the extreme of vibration leading to the
dissociation of the molecule and hence a continuum.

Fine Structure
of Electronic-
Vibration in the gaseous phase. In the liquid or dissolved states, the perturbing effect of
Transitions

approximation and with the help of the energy expressions for the various energy
levels of a diatomic molecule.

Application Finally, a few application of electronic spectra of diatomic molecules may be

of Electronic described. The electronic spectrum is often helpful in establishing the electronic
Spectra structure of a molecule. It can also provide data on the dissociation energy of the
molecule. Homonuclear molecules (e.g. H2, N2 ) separately do not exhibit pure
rotational (as they do not have permanent dipole moment) and pure vibrational
(as component of dipole moment does not change during vibration) spectra, but
because of the necessary change in dipole moment during electronic transition, they

about the molecule may be obtained.

Electronic A few lines about the electronic transitions in polyatomic molecules may be added
Transitions in here. At the outset it may be stated that the spectrum is usually very complex and
Polyatomic in few cases, correlation between the absorption band and the type of transition
Molecules
range in which it occurs may be made. These are:

(i) s Æ s* transition l lies in ultraviolet or far ultraviolet region as s electrons

(ii) p Æ p* transition l lies in the near ultraviolet region and visible regions.
(iii) n Æ p* transition l lies in the visible region of light. Normally they have very
weak intensities as their excitation involves different region of the molecule.
506 A Textbook of Physical Chemistry

Fluorescence A photon which is absorbed by the molecule may be emitted as such and can be
displayed in the emission spectrum. In this case, absorption and emission spectra
are identical. In many cases, these two spectra are not identical especially when the
excitation ends at a higher vibrational level. Generally, the emission spectrum is
slightly shifted to the longer wavelength (red shift). This fact has been attributed to
the radiationless decay (or thermal degradation) of the energy. What happens that
the excess vibrational energy is transferred to the neighbouring molecules during
the intermolecular collisions. This transference appears as the kinetic energy and
hence heating effects are produced. When the excited molecule reaches the lowest
vibrational level of the excited electronic state, the electron comes back to the
ground electronic state and hence emits radiation which is of higher wavelength
(low frequency) than that of the absorbed photon. The above mechanism is
and the emission spectrum is called the
spectrum (Fig. 4.9.6). The time between initial absorption and emission is of the
order of 10–8 s.

Radiation less
decay
Energy

Absorption
Fluorescence

Fig. 4.9.6 Schematic

representation of
req

Phosphorescence In some cases, the emission of radiation is delayed (may be by seconds, minutes or
more) and this results into what is known as phosphorescence. This phenomenon
has been explained by the energy diagram shown in Fig. 4.9.7. This diagram is

curves intersect each other at this point. There is some probability that the molecule
undergoes intersystem crossing where during the vibration it shifts over from the
singlet to triplet state.
 Molecular Spectroscopy 507

First excited
singlet state

Radiationless
decay
Triplet
state

Intersystem
crossing

Absorption Singlet
ground state

Phosphorescence

Fig. 4.9.7 Schematic

representation of
phosphorescence

Explanation of Before describing the mechanism of phosphorescence, it is worth explaining the

Singlet and Triplet terms singlet and triplet states. These two terms represent the multiplicity of the
States spin vector and is equal to 2S + 1, where S is the total spin quantum number. For
an arrangement of two opposite spins (s1 = 1/2 and s2 = – 1/2), the value of S,
which is equal to s1 + s2, is zero. Hence multiplicity is one. Such an arrangement
will be represented by a single wave function and thus gives rise to a singlet
state. For an arrangement of two parallel spins (may be a and a or b and b), the
value of S is 1 and hence the multiplicity is three. This corresponds to the three
different orientations of the total spin angular momentum vector with z
equal to +1(h/2p), 0(h/2p) and –1(h/2p). Thus, the arrangement of two parallel
spins can be represented by the three degenerate wave functions (one for each
value of ms) and gives rise to a triplet state. In general, the energy of the triplet
state is slightly smaller than the corresponding singlet state. Physically, this can
be explained from the fact that each electron is associated with a tiny magnet.
In an arrangement of parallel spins, the electrons will be farther apart in space
(because of repulsion between the similar orientations of tiny magnets) than in the
arrangement of opposite spins. Hence, the electronic repulsion in the triplet state
is smaller than that in the singlet state. Consequently, the triplet state has smaller
energy than the singlet state.

Quantum mechanically, the allowed electronic transitions are those in which

spin of electron is preserved. A transition in which spin is reversed is a forbidden

heavy atoms of a molecule can reverse the relative orientation of pair of electrons.
508 A Textbook of Physical Chemistry

Phosphorescent Now the mechanism of phosphorescence may be explained. The absorption of a

Spectrum photon induces the singlet to singlet transition. In the excited singlet state some
of the vibrational energy is lost as the thermal energy due to the intermolecular
collisions. When the excited molecule attains the vibrational quantum number where

molecule is large) the geometry of the molecule corresponds to the crossing point
of the two energy curves (singlet and triplet), the molecule can cross over from
the singlet to triplet state. In triplet state, it continues to exhibit radiationless decay
till it has reached the ground vibrational level. Now the molecule cannot radiate
its energy because a return to the ground electronic state involves a forbidden
transition. But because of spin-orbit coupling, this selection rule is slightly relaxed
and thus emission may last long after the original excited state is formed. The
above mechanism is in accord with the experimental facts, viz., phosphorescence

over from singlet to triplet due to less effective collisions between the molecules
and the environment), amount of phosphorescence depends on the presence of
heavy atoms (which helps breaking the selection rule) and acquiring the magnetic
properties by the excited state (due to the presence of the unpaired electron spins).

with the Raman effect. In both cases, red shift is observed. In the former, an
electronic excitation is induced whereas in the latter no such excitation is induced.

Raman effect, the energy is merely transferred from the radiation to molecule and
only instantaneous complex is formed.

Dissipation of In the end, a few facts regarding the molecular spectra and the dissipation of energy
Energy from the from the electronically excited state may be mentioned. In general, we have
Excited States Period of rotation 10–11 s or 10–12 s
Period of vibration 10–13 s or 10–14 s
Average time between two molecular collisions in the gaseous state
(p 1 atm) = 10–10 s
Average time between two molecular collisions in the liquid
phase = 10–13 s
The following conclusions may be drawn from the above data.
∑ In the gaseous phase, a molecule can execute many rotations and vibrations
between two successive molecular collisions. It is because of this reason, the
electronic spectra in the gaseous phase is usually accompanied by the coarse

rotational transitions).
∑ In the liquid phase, a molecule does not complete its one complete rotation
between the two successive molecular collisions. In other words, the molecule

structure in the vibrational or electronic spectrum is usually absent when the

spectrum is recorded in the liquid phase.
 Molecular Spectroscopy 509

∑ The dissipation of rotational energy by the nonradiative process is relatively

easy. Most of molecular collisions are in fact effective in exchange of such
energy.
∑ The dissipation of vibrational energy by the nonradiative process is not so easy.
On an average, 104 collisions are required for the transfer of excess vibrational
energy as the rotational and translational energy. The life time of a vibration-
ally excited molecule is thus of the order of 10–9 s (104 collisions ¥ 10–13 s
collision–1). This time is much larger than the period of vibration (10 –13 s), and
hence, a molecule completes many vibrational cycles before it is deactivated.
∑ When during the vibrational deactivation, the molecule is reached to the lowest
vibrational level of the excited electronic state, it is highly improbable that the
electronic deactivation, whereby the molecule comes back to the ground-state

via a radiative process, i.e. the emission of energy as radiation (phenomenon

∑ During the vibrational deactivation, the molecule may cross over from one
potential-energy curve to another if the two curves cross each other. Two
types of crossing are possible; (i) where the number of paired or unpaired
electrons remain the same, e.g. singlet to singlet or triplet to triplet, and (ii)
the number of paired or unpaired electrons differ, e.g. singlet to triplet or
vice versa. The transitions involving singlet to singlet or triplet to triplet are
quantum mechanically allowed whereas those involving singlet to triplet or
vice versa are forbidden. In some molecules, the singlet-triplet transition is
weakly allowed due to the spin-orbit interaction between the heavy atoms of
the molecules. The crossing over of the molecule from singlet to singlet or
triplet to triplet is known as internal conversion whereas that from singlet to
triplet or vice versa is known as intersystem crossing.
∑ A molecule may dissipate its entire excited electronic and vibrational energy
by the nonradiative process if there exists a number of electronic arrangements
whose potential energy curves cross one another and also the potential energy
curve of the lowest excited electronic state crosses that of the ground electronic
state. In the excited electronic state, the vibrational energy is dissipated and in
the region where two potential energy curves intersect, an internal conversion
takes place where the molecule is moved to the new electronic excited state.
In this new state, vibrational deactivation is continued till another crossing
of two electronic states is reached. Here again internal conversion occurs
followed by the vibrational deactivation. This process of internal conversion
and vibrational deactivation is continued till the molecule is reached to the
ground electronic state.
∑ The energy dissipation by nonradiative process is very much affected by the
factors which change the frequency of molecular collisions. One of the factors
is the temperature of the system. In fact, the energy dissipation by nonradiative
process may be replaced by the radiative process if the temperature of the
system is very much lowered.
510 A Textbook of Physical Chemistry

Example 4.9.1 The absorption spectrum of I2 vapour consists of a series of bands which terminate in
continuous absorption at 499.5 nm. I2 molecule in the upper state dissociates into an
atom in its ground state and one with an excitation energy of 90.79 kJ mol–1. (a) Calculate
the dissociation energy of I2 in its ground electronic state. (b) If the difference between
the minima of excited and ground states is 180.46 kJ mol –1, what is the dissociation
energy in the excited state?
Solution (a) Energy of a photon of wavelength 499.5 nm

hc (6.626 ¥ 10-34 J s)(2.998 ¥ 108 m s -1 )

= = = 3.977 ¥ 10–19 J
l (499.5 ¥ 10-9 m)
Excitation energy of I atom

90.79 ¥ 103 J mol-1

= = 1.507 ¥ 10–19 J
6.022 ¥ 1023 J mol-1

Dissociation energy of I2 molecule in its ground electronic state

= 3.977 ¥ 10–19 J – 1.507 ¥ 10–19J = 2.47 ¥ 10–19 J
Dissociation energy of 1 mol of I2
=(2.47 ¥ 10–19 J) (6.022 ¥ 1023 mol–1) = 1.488 ¥ 10 5 J mol–1
= 148.8 kJ mol–1
(b) Dissociation energy per mol in the excited state
= Energy of 1 mol of 499.5 nm photons – Energy difference between the
minima of excited and ground states
= (3.977 ¥ 10 –19 J) (6.022 ¥ 1023mol–1) – 180.46 ¥ 103 J mol–1
= 59.08 ¥ 103 J mol–1 = 59.08 kJ mol–1

Example 4.9.2 Find the kinetic energy of the hydrogen atom produced by photo-dissociation of hydrogen
bromide with light of 253.7 nm wavelength. The bond dissociation energy of HBr is
equal to 364 kJ mol–1. Assume the bromine atom to be in its ground electronic state.
Solution Energy carried by a photon of wavelength 253.7 nm

hc (6.626 ¥ 10-34 J s)(2.998 ¥ 108 m s -1 )

= = = 7.830 ¥ 10 –19 J mol–1
l (253.7 ¥ 10-9 m)
Energy required to break one bond of HBr

(364 ¥ 103 J mol-1 )

= = 6.044 ¥ 10 –19 J
6.022 ¥ 1023 mol-1

Kinetic energy of H atom

= 7.830 ¥ 10–19 J – 6.044 ¥ 10–19J = 1.786 ¥ 10–19 J
Example 4.9.3 (i) The values of we in the ground and one of the electronically excited states of a
diatomic molecule are 1 641.4 cm–1 and 1 788.2 cm–1, respectively, and those of xe are
7.11 ¥ 10–3 and 9.19 ¥ 10–3, respectively. Determine the values of vibrational quantum
 Molecular Spectroscopy 511

numbers which will lead to the dissociation of the molecule in the ground and excited
states. What are the values of dissociation energies?
(ii) The electronic spectrum of this diatomic molecule involving the above two
electronic states includes n 00 line at 19 378 cm–1 and a convergence limit at 39 231
cm–1. The dissociation is into one ground state atom and one excited atom with the
excitation energy corresponding to 10 308 cm–1. Calculate the dissociation energies of
the two states and compare with those obtained in part (i). Explain any discrepancy.
(iii) Do you expect the molecule to exhibit radiationless decay when it comes back
from the excited state to the ground state?
Solution (i) The expression for the vibrational quantum number leading to the dissociation of
the molecule is
1 1
umax = -
2 xe 2
Hence
1 1
umax (ground state) = - = 70.32 – 0.5 70
2 ¥ 7.11 ¥ 10-3 2
1 1
umax (excited state) = - = 54.41 – 0.5 54
2 ¥ 9.19 ¥ 10-3 2
The expression for Emax is
hn e hc we
Emax = = (Eq.4.5.25)
4 xe 4 xe
Hence
(6.626 ¥ 10-34 J s)(3 ¥ 108 m s -1 )(1 641.4 ¥ 102 m -1 )
Emax (ground state) =
4(7.11 ¥ 10-3 )
= 1.147 ¥ 10–18 J
(6.626 ¥ 10-34 J s) (3 ¥ 108 m s -1 )(1788.2 ¥ 102 m -1 )
Emax(excited state) =
4(9.19 ¥ 10-3 )
= 9.670 ¥ 10–19 J
The expression for E0 is

hne ÊÁ1 - e ˆ˜ = hc we ÊÁ1 - e ˆ˜

1 x 1 x
E0 =
2 Ë 2¯ 2 Ë 2¯
Thus
1
E0 (ground state) = (6.626 ¥ 10–34J s) (3 ¥ 108 m s–1)
2
1
¥ (1 641.4 ¥ 102 m–1) (1 - ¥ 7.11 ¥ 10-3 )
2
= 1.628 ¥ 10–20 J
1
E0 (excited state) = (6.626 ¥ 10 –34J s)(3 ¥ 108 m s–1 )
2
1
¥ (1 788.2 ¥ 102 m–1) (1 - ¥ 9.19 ¥ 10-3 )
2
= 1.765 ¥ 10 –20
J
512 A Textbook of Physical Chemistry

Now D = Emax – E0
Thus D (ground state) = 1.147 ¥ 10–18J – 1.628 ¥ 10 –20 J = 1.131 ¥ 10–18 J
D (excited state) = 9.670 ¥ 10–19J – 1.765 ¥ 10–20 J = 9.496 ¥ 10–19 J
For one mole of the substance, we will have
D (ground state) = (6.022 ¥ 10 23 mol –1) (1.131 ¥ 10–18 J)
= 6.811 ¥ 10 3 J mol–1 = 681.1 kJ mol –1
D (excited state) = (6.022 ¥ 10 23 mol–1) (9.496 ¥ 10 –19 J)
= 5.719 ¥ 105 J mol–1 = 571.9 kJ mol–1
(ii) D (ground state) = n (continuum) – n (excitation energy of the atom)
= 39 231 cm–1 – 10 308 cm–1
= 28 923 cm–1
D (ground state) per mole of the substance is

NA(hc D ) = (6.022 ¥ 10 23 mol–1) (6.626 ¥ 10–34 J s)

¥ (3 ¥ 108 m s–1) (28 923 ¥ 102 m–1)
= 3.463 ¥ 105 J mol–1 = 346.3 kJ mol–1

D (excited state) = n (continuum) – n 00

= 39 231 cm–1 – 19 378 cm–1

= 19 853 cm–1
D (excited state) per mole of the substance is

NA(hc D ) = (6.022 ¥ 10 23 mol–1) (6.626 ¥ 10 –34J s)

¥ (3 ¥ 108 m s–1) (19 378 ¥ 102 m–1)

= 2.320 ¥ 105 J mol–1 = 237.2 kJ mol–1

Comparison of these values with those obtained in Part (i) reveals that the former
are much less than the latter. This is due to the fact that the energy expression is not
exact as it does not include higher anharmonicity constants.

(iii) We have D (ground state) = 28 923 cm–1

n 00 = 19 378 cm–1

Since n 00 < D (ground state), it is expected that many of the vibrational levels of the
excited state will overlap with those of the ground state. Thus, during the vibrational
deactivation in the excited state, the molecule can switch over to the vibrational levels
of the ground state. Hence, the molecule can come back from the excited state to the
ground state via radiationless decay.
 Molecular Spectroscopy 513

REVISIONARY PROBLEMS

Nuclear Magnetic 4.1 (a)What do you mean by magnetic active and inactive nuclei?
Resonance (b) State whether the spin quantum number is zero, integral or half integral
Spectroscopy for nuclei having the following characteristics.
(i) Both charge and mass even.
(ii) Odd charge and even mass.
(iii) Even charge and odd mass.
(iv) Odd charge and odd mass.
(c) What do you mean by the space quantization of angular momentum vector?
4.2 (a) Ampere’s law is
m = iA
Making use of the above law, derive the relation
Ê e ˆ
m= Á ˜L
Ë 2mp ¯

where the various symbols have their usual meaning.

(b) Quantum mechanical expression of magnetic moment vector is
m = g mN I ( I + 1)

Derive the above expression from the expression of m given in Part (a). What
is the value of m N for a proton?
4.3 (a) Show that the potential energy of a proton in the presence of a magnetic

V = – BmN g mI

(c) The value of g for proton is 5.585 4. Calculate the energy difference between

radiation does the above energy difference lie?

of 10 000 gauss and using the Boltzmann distribution

n–1/2/n+1/2 = exp(– DV/kT)
(i) Calculate the relative population of protons at 300 K.
(ii) At what temperature will the upper level be more populated than the lower

(iii) Do you expect any NMR signal when both levels are equally populated?
4.5 Why does the magnetic moment vector execute Larmor precession instead of
alignm
4.6 (a) Explain the following terms with adequate illustrations.
(i) Chemical shift
(ii) Spin-spin interaction
(b) Explain, how chemical shift and spin-spin interaction vary with (i) temperature,
514 A Textbook of Physical Chemistry

(c) The PMR signal of a proton depends upon its environments. A less shielded
proton shows the sign
2CCl2CH3.

(d) Explain why TMS, (CH3)4Si, is used as one of the internal references in the
measurement of chemical shifts of protons.
(e) What are the d- and t-scales?
4.7 (a) Describe the expected low resolution and high resolution spectra of CH3OH
and CH3CH2OH.
(b) Discuss the spectrum of CH3CH2OH in acidic medium.
(c) Describe the spectrum of CH3CH2OH in the presence of D2O.
4.8 Comment upon the following:
(a) Though the NMR spectrum is recorded at constant radiation frequency and

often reported in the unit of frequency, i.e. Hz.

(b) The spin-spin interactions are intramolecular interactions.

(d) Chemical shifts are dependent whereas spin-spin interactions are independent of

12 16
(e) C and O do not exhibit NMR spectra.
Electron Spin
Resonance V = g mBBms
Spectroscopy Derive the above relation.
(b) Calculate: (i) The value of Bohr magneton. (ii) Energy difference between the

electromagnetic radiation does this energy difference lie?

(c) Using the Boltzmann distribution and the above energy difference between
the two levels of electron, calculate the relative distribution of electrons in the two
levels.
4.10 The interaction of the unpaired electron with the magnetic active protons of molecule
n protons in a
molecule and if they are equally coupled with the electron, then:
(i) How many lines will be observed in the ESR spectrum?
(ii) How are the relative intensities of these lines related to each other?
Rotational 4.11 (a) Quantum mechanical expression of rotational energy levels is
Spectroscopy h 2 J(J + 1)
E=
8p 2 I
where the various terms have their usual meanings. Show that the above expression
can be derived by introducing the appropriate quantum mechanical restriction to
the corresponding classical expression of energy.
(b) Show that the degeneracy of various rotational levels is given by the factor
(2J + 1).
 Molecular Spectroscopy 515

4.12 (a) Explain, why many of the lower rotational levels are thickly populated.
(b) Show that the rotational level whose quantum number is given by the expression

1 Ê kT ˆ 1
J= -
2 Ë Bhc ¯ 2
has a maximum population.
(c) Show that the rotational frequency is equal to (h/4p2I) J ( J + 1) .
4.13 Explain, why only molecules having permanent dipole moment exhibit rotational
spectra.
4.14 (a) What are the selection rules for the rotational transitions of a diatomic molecule?
(b) Describe the general appearance of rotational spectrum of a diatomic molecule.
(c) What information can be derived from a rotational spectrum?
Vibrational 4.15 Derive the following classical expression for the frequency of harmonic vibration
Spectroscopy of a diatomic molecule.

1 kf
n=
2p m
where the symbols have their usual meanings.
4.16 (a) Show that the classical expression of potential energy of harmonic vibration
of a diatomic molecule is given by
V = (1/2) k f (x2 – x1)2
where x2 and x1 are the displacements of the two atoms from their equilibrium
positions.
(b) Since x2 – x1 can have any value, the potential energy is a continuous function
of displacement. Does this statement hold good for a diatomic molecule? Explain.
4.17 (a) Quantum mechanical expression of the energy of a harmonic vibration of a
diatomic molecule is
E = (u + 1/2)hnclassical
where u is the vibrational quantum number. What are the permitted values of u?
(b) What is zero-point energy? Is it consistent with the uncertainty principle?
(c) Explain, why only the lowest vibrational level is thickly populated.
(d) Explain, why only those molecules for which dipole moment varies during the
vibration exhibit vibrational spectra.
4.18 (a) What are the selection rules for the vibrational transitions of a diatomic molecule
executing harmonic vibrations?
(b) What is the general appearance of vibrational spectrum of a diatomic molecule?
(c) What information can be derived from a vibrational spectrum?
4.19 (a) The vibration of a diatomic molecule is anharmonic in nature. One of the
potential energy expressions in use is the Morse potential expression:
V = Deq [1 – exp{a (req – r)}]2
516 A Textbook of Physical Chemistry

Draw the typical diagram of potential energy of a diatomic molecule and compare
it with that of a classical vibrator.
(b) The energy expression of a molecule exhibiting anharmonic potential of Morse
is given by

E= u+( ) { ( )}
1
2
1
hne 1 + u + xe
2
where ne is known as equilibrium oscillation frequency of the anharmonic oscillator
and xe is the corresponding anharmonic constant. Show that the energy difference
between the two nearest levels is given by
DE = hne{1 – 2xe (1 + u≤ )}
and hence show that the difference DE decreases with increasing value of vibrational
quantum number.
(c) What are the selection rules for an anharmonic vibrator?
(d) Explain, what do you understand by (i) fundamental transition, (ii) overtone
transitions, and (iii) hot-bands.
(e) Show that a diatomic molecule dissociates into atoms if it is present in the
vibration state of vibrational quantum number
1 1
u= –
2xe 2
Vibration-Rotation 4.20 (a) What is the vibration-rotation spectrum of a molecule?
Spectroscopy (b) Explain, why the vibrational and rotational energies can be simply added to
give the total energy of a molecule executing simultaneously vibration and rotation
motions.
(c) What are selection rules for the vibration-rotation transitions of a diatomic
molecule?
(d) Show that the wavenumber for the transitions u¢ = 1 ¨ u≤ = 0 and D J = ±1
is given by
DE = ± 2Bm + we(1 – 2xe )
where m can have values, 1, 2, , and is given by
m = J≤ + 1 ; for D J = + 1 transitions
m = J¢ + 1 ; for D J = – 1 transitions
(e) Draw a typical vibration-rotation spectrum of a diatomic molecule with proper
labelling of its P, Q, and R branches.
(f) What are the essential requirements for a diatomic molecule to exhibit vibration-
rotation spectrum? What information can be derived from a vibration-rotation
spectrum?
Vibrational 4.21 (a) What do you understand by the degrees of freedom of a molecule? How many
Spectrum of fundamental vibrations are possessed by a linear and a nonlinear molecule
a Polyatomic consisting of N atoms?
Molecule (b) Taking the examples of CO2 (linear molecule) and H2O (nonlinear molecule),
illustrate the following vibrational modes: (i) symmetrical stretch. (ii) antisymmetric
stretch, (iii) bending.
 Molecular Spectroscopy 517

(c) Each vibrational mode exhibits its own vibrational spectrum. State how many
vibrational lines are expected for CO2 and H2O molecules.
(d) What do you understand by the group vibrations and skeletal vibrations?
(e) In general, n (antisymmetric stretch) > n(symmetric stretch) > n (bending)
Explain, the probable reasons for the above fact.
(f) Explain the following order of group frequencies.

n (CH) > n (CF) > n (CCl) > n (CBr)

n (C∫∫ C) > n(C == C) > n (C—C)

Raman 4.22 (a) What is a Raman spectrum? What is the essential criterion for a molecule to
Spectroscopy be Raman active?
(b) How does classical mechanics account for the existence of Raman spectrum?
(c) What is the explanation of Raman lines from the quantum view point?
4.23 (a) What are the selection rules for the pure rotational Raman spectra of diatomic
molecules? Hence, show that the Raman lines appear at wavenumbers:

n = n 0 ± B (4 J≤ + 6)

where n 0 is the wave number of Rayleigh line.

(b) What are the Rayleigh, Stokes and anti-Stokes lines? How do the intensities
of Stokes and anti-Stokes lines vary in a pure rotational Raman spectrum?

4.24 (a) What are the selection rules for the vibrational Raman spectrum of a diatomic
molecule? Show that the fundamental transitions in the Raman spectrum is observed
at wave numbers:

n = n 0 ± n e (1 – 2xe)
(b) How do the intensities of Stokes and anti-Stokes lines compare with each other
in the vibration Raman spectrum?
4.25 State the rule of mutual exclusion. Illustrate this by taking typical examples of CO2
and H2O.
Electronic 4.26 Discuss the following:
Spectroscopy (i) Franck-Condon principle
(ii) Dissociation and pre-dissociation

(iv) s Æ s *, p Æ p* transitions
(v) Singlet-to-singlet and triplet-to-triplet transitions.
(vi) Singlet-to-triplet transitions are forbidden.
518 A Textbook of Physical Chemistry

TRY YOURSELF PROBLEMS

NMR Spectra 4.1 Given below are a few PMR spectra. The molecular structure of the compound is
given along with the spectrum. Identify the various peaks in a spectrum with the
corresponding hydrogen atoms.

CH2N (CH2CN)2

439 226 215

n/HZ

(C6H5)2CHCCH3

434 305 132

n/HZ
 Molecular Spectroscopy 519

4.2 Given below are a few PMR spectra. Identify the structure of the compound whose
molecular formula is shown along with the diagram.
520 A Textbook of Physical Chemistry

C3H6Cl2

3 4 5 6 7 8 9 10
t -Value

C2 H3Cl3

3 4 5 6 7 8 9 10
t -Value

C3H7NO2

3 4 5 6 7 8 9 10
t -Value

4.3 The infrared spectrum of a compound having the formula C3H9N has no peak at
3 300 cm–1. Predict the NMR spectrum of this compound in terms of the number
of peaks expected and their relative intensities.
4.4 The NMR spectrum of a compound of molecular formula C4H9NO has two singlet
with an intensity ratio of 2 : 1. Identify the compound.
4.5 Explain, how to distinguish between the molecules CH3COCH3 and CH3CH2CHO
on the basis of NMR spectroscopy alone.
 Molecular Spectroscopy 521

4.6 Predict the NMR spectrum of diethyl ether.

4.7 (a) A compound contains 54.55 mass % carbon, 9.09 mass % hydrogen and 36.36

a quartet and is one third as intense as the second peak, which is doublet. Propose
a structure for the compound.
(b) Draw a schematic NMR spectrum of the aromatic compound C6H5OCH2CH3.
4.8 (a) Explain, why chloroethylene CH2 == CHCI has three distinct peaks in its NMR
spectrum, all of equal intensity.
(b) Sketch the NMR spectrum for HD molecule.
4.9 The NMR spectrum of a compound containing 63.9% carbon, 14.5% hydrogen, and
21.6% oxygen consists of a quartet and a triplet, the latter is 1.5 times as intense
as the former. What is the structure of the compound?
4.10 (a) The low-resolution spectrum of the compound C4H8O2 exhibits three peaks
at 8.1,5.2 and 1.3 ppm with relative ratio 1, 1 and 6, respectively. Deduce the
structure and also draw its expected high-resolution spectrum.
CH3 O
[Ans. CH C , the peaks at 5.2 and 1.3 ppm split into seven and
CH3 OH
two, respectively.]
(b) The low-resolution NMR spectrum of the compound C5H10O exhibits two
peaks with relative intensities of 2 and 3, respectively. Deduce the structure and
also draw its expected high-resolution spectrum.
[Ans. CH3 CH2 COCH2CH3

ESR Spectroscopy 4.11 (a) How many lines will be observed in the ESR spectrum of benzene anion
radical. What will be their relative intensities?
(b) The ESR spectrum of C3H7 radical showed 14 absorption peaks with relative
intensities of 1, 1, 6, 6, 15, 15, 20, 20, 15, 15, 6, 6, 1 and 1. Is this n-propyl or an
isopropyl radical?
[Hint: Use Eq. 4.3.10; n-propyl: 36 peaks (3 ¥ 3 ¥ 4); isopropyl: 14 peaks
(2 ¥ 7)]
(c) How many ESR peaks are expected for ethyl radical?
[Ans. 12 peaks]
4.12 Sketch the ESR spectrum of cyclopentadienyl radical C5H5.

|a1| = 2.7 G, |a2| = 1.5 G and |a9| = 5.3 G

where numbering goes as follows.
8 9 1
7 2
6 3
5 10 4
Predict the ESR spectrum of this ion.
4.14 How many ESR absorption lines do you expect for triphenylmethyl radical.
[Ans. 196 lines]
522 A Textbook of Physical Chemistry

Rotational Spectra 4.15 Explain with examples the effect of thermal energy on the general appearance of
the (i) rotational spectra, (ii) vibrational spectra, and (iii) Raman spectra.
4.16 Derive the expression of moment of inertia for OCS molecule.
2 2
[Ans. I = mOrCO + mSrCS – (mOrCO – mSrCS)2/M, where M = mO + mC + mS.]
4.17 Is it possible to distinguish between linear and nonlinear molecules from the
vibration-rotation spectra?
Vibrational Spectra 4.18 How will you distinguish between the overtones and hot bands of a spectrum?
4.19 Classify the following molecules into different categories exhibiting pure rotational,
pure vibrational, vibrational-rotational, rotational Raman and vibrational Raman
spectra.
H2, HCl, CH4, H2O, CO2, N2, NO2, N2O.
4.20 Tabulated below are the stretching frequencies in cm–1 of some of the bonds.
OH 3 700 : NH 3500 : CH 3 000 : SH 2 600 : PH 2 400
Explain the relative frequencies in terms of bond characteristics.
4.21 Figure 4.5.2 depicts the plot of V versus Dx. What type of graph do you expect
between dV/d(Dx) and Dx? What is its slope?
4.22 Why is the stretching vibration frequency of a hydrogen bonded O—H bond lower
than that of a free O—H bond?
[Hint: Lengthening of O—H bond due to hydrogen bonding reduces the force
constant.]
Electronic Spectra 4.23 Justify the following statements:
(a) The vibration structure of the electronic absorption spectrum is characteristic of

of the lower electronic state.

(b) Fluorescence or phosphorescence radiation has a lower frequency than the
incident radiation.
(c) Phosphorescence is intense from solid samples.
(d) The amount of phosphorescence depends on the presence of a heavy atom.
(e) Fluorescence is favoured in very low pressure.

[Ans. (a) Absorption (emission) involves the transfer of electron from the lowest
vibrational level of the lower (upper) electronic state to the various vibration levels
of the higher (lower) electronic state. (b) Loss of vibrational energy in the upper
electronic state as radiationless decay due to the molecular collisions. (c) Less

(d) Heavy atom helps breaking the selection rule of not allowing singlet-to-triplet
transition. (e) Less collisions at low pressure decreases the chances of radiationless
decay. (f) During the time required for intersystem crossing, a large number of
collisions that take place increases the chances of radiationless decay and decreases
the chances of intersystem crossing.]
4.24 The energy of n, p and p* orbitals of ab-unsaturated carbonyl compounds are
lowered in a more polar solvent due to the solvation effects. The effects produced
are
(DE)n (D E)p* > (DE)p
Predict, what effects on n Æ p* and p Æ p* transitions are produced if the spectra
of these compounds are recorded in the solvents of increasing polarity.
[Ans. Blue shift (wavelength decreases) for n Æ p* transitions and red shift
(wavelength increases) for p – p* transition.]
 Molecular Spectroscopy 523

NUMERICAL PROBLEMS

Proton Magnetic 4.1 (a) A particular isotope absorbs energy at the radiofrequency of 17.3 ¥ 106 Hz
Resonance g factor for this
isotope.

TMS peak using a spectrometer operating at 60 MHz. Calculate its chemical shift
in ppm relative to TMS.
[Ans. (a) 2.310 6; (b) 4 ppm]
(c) A particular NMR
are required to bring a hydrogen nucleus and a 13C nucleus to resonance at this
frequency. Given: g(H) = 5.584 and g(13C) = 1.1404
[Ans. H; 0710 T; 13C; 2.8274 T]
4.2 (a) The nucleus 11B has mI = 3/2 and gN = 1.792. Calculate the energy levels of
a 11
frequency of 11
Electron Spin 4.3 (a) Calculate the relative population difference, i.e. (nb – na )/(nb + na ) for electron
Resonance
[Hint: Evaluate na /nb using Boltzmann equation, add and subtract this quantity
in one and then take the ratio.] [Ans. 0.000 675]
(b) Repeat the problem 4.3a for protons. [Ans. 10–6]
(c) The ESR spectrum of atomic hydrogen was recorded on a spectrometer working

Find the value of B at which the two lines of atomic hydrogen will be observed.
[Ans. 306.85 mT and 357.55 mT]
(d) Predict the appearance of the ESR spectrum of (a) CD2 and (b) CH3CD2.
[Ans. (a) Quintet of relative intensities 1 : 2 : 3 : 2 : 1 and (b) Quartet
(1 : 3 : 3 : 1) of quintets (1 : 2 : 3 : 2 : 1).]
(e) An unpaired electron in the presence of two protons gives the following four
line ESR spectrum: DB = 0, 1, 3, 4 G. What are the two coupling constants in G
and MHz?
[Ans. a1 = 3 G or 8.40 MHz, a2 = 1 G or 2.80 MHz]
Rotational Spectrum 4.4 The separation between successive lines of the rotational spectrum of a diatomic
molecule is 20 cm–1. Calculate:
(a) The moment of inertia of the molecule.
(b) Rotational frequency and the period of rotation for the rotational quantum
number 1.
(c) Relative population of molecules in the rotational states J = 0, 3 and 6 at
300 K with respect to that of J = 0.
(d) Which rotational energy level has the highest population.
Vibrational Spectrum 4.5 The vibrational spectrum of a linear molecule shows two strong absorptions at
727 cm–1 and 3 270 cm–1, two absorptions of medium intensity at 1 433 cm–1 and
2 085 cm–1 and two weak absorptions at 1 370 cm–1 and 2 800 cm–1. Suggest
assignment of these absorptions.
524 A Textbook of Physical Chemistry

4.6 The vibrational energy levels of I2 molecule is given by the expression

E u / cm -1 = 215 u + ( ){ 1
2 ( )}
1 - 0.003 u +
1
2
where u is the vibrational quantum number.
Calculate: (a) The force constant of the molecule. (b) The anharmonicity
constant. (c) Zero-point energy. (d) Fundamental vibrational frequency.
(e) The frequency of first overtone. (f) The period of vibration in the lowest
vibrational level. (g) The number of molecules in the level u = 1 relative to
u = 0 level at 500 K. (h) The value of vibrational quantum number which leads to
the dissociation of the molecule. (i) The dissociation energy of the I2 molecule. Do
you expect it to be overestimated?
4.7 The vibrational wavenumbers of the following molecules in their u = 0 are
HCl: 2 885 cm–1; DCl: 1 990 cm–1; D2: 2 990 cm–1; and HD: 3 637 cm–1. Calculate
the energy change, in kJ mol–1 of the reaction.
HCl + D2 Æ DCl + HD
[Hint: D E = n0, DCl + n0, HD – n0, HCl – n0, D2] [Ans. – 2.967 kJ mol–1]
4.8 Compare the force constants for the bond strengths in CN and CN+ if we = 2 068.61
cm–1 and 1 580 cm–1, respectively. Interpret the results on the basis of electronic

4.9 To what temperature must we heat a diatomic gas at 298 K to excite one per cent

vibrational frequency of the gas is 1 545 cm–1. [Ans. 482.4 K]

4.10 The first four vibrational energy levels of HCl were found to lie at 2 885.9,
5 668.0, 8 346.9, 10 923.1 cm–1 with respect to the ground-state level. With the
help of these data, calculate the anharmonicity constant, zero-point energy and the
dissociation energy of the molecule. [Ans. DE = 5.14 eV]
4.11 The force constant for 2D35Cl is 4.903 ¥ 105 dyn cm–1. Calculate we of u = 0 state.
What is the frequency of vibration of DCl in u = 0 state? Is this dependent on u ?
[Ans. 2 091 cm–1, 6.27 ¥ 10 13 s–1, no]
4.12 The constant a in the Morse potential (Eq. 4.5.19) is given by the relation
a = 4.445 ne m / D
The values of we and we xe for H2 are 4 395.24 and 118.0 cm–1. Its dissociation energy
is 38 278 cm–1. Plot the Morse curve for H2 and show the spacing of vibrational
levels on the graph.
4.13 The Morse potential (Eq. 4.5.19) generates
2
Ê 1ˆ Ê 1ˆ
E n = w e Á u + ˜ - w e xe Á u + ˜
Ë 2¯ Ë 2¯
1/ 2
ha 2
if we= 10 –1 a ÊÁ 2 e ˆ˜
hD
and we xe = 10–2
Ë 2p cm ¯ 8p 2 cm
 Molecular Spectroscopy 525

where De, we and we xe are in cm–1 while the other quantities are in normal SI units.
If re = 74.17 pm, De = 38 318 cm–1, we = 4 405.3 cm–1 and we xe = 125.325 cm–1
for H2, plot U(r) = E (r) – De against r
[Ans. Minimum at 74.17 pm and – 38 318 cm–1 vibrational lines at
– 36 147, – 31 922 – 28 088 and – 24 435 cm–1 ]
Vibration-Rotation 4.14 In the vibration-rotation spectrum of 1H35Cl, the following absorptions occur.
Spectrum Label the lines and calculate B, r, we and k of the molecule.
n /cm–1 2 906.3 2 927.5 2 948.7 2 969.9 30 12.23 3 033.4
3 054.6 3 075.8
Which of the absorption will have maximum intensity?
[Ans. B = 10◊6 cm–1, r = 127 pm, we = 2 991 cm–1, k = 5.14 ¥ 105 dyn cm–1]
Raman Spectrum 4.15 A molecule AB2 has the following infrared and Raman spectra:

cm–1 Infrared Raman

3 756 Very strong –
3 652 Strong Strong, polarized.
1 595 Very strong –

Comment upon the geometry of the molecule and assign the observed lines to the
corresponding vibrations.
4.16 If one of the Raman lines appears as at 460 nm when excited by light of wavelength
435.8 nm, at what frequency will it show absorption in the infrared region?
4.17 The vibrational Raman spectrum of 35Cl2 shows a series of Stokes lines separated
by 0.975 2 cm–1. What is the bond length of Cl2?
[Ans. 0.198 8 nm]
Electronic 4.18 The band spectrum of Br2 terminates at a wavelength of 510.7 nm. The energy of
Spectrum the excited atoms formed in the dissociation is 43.51 kJ mol–1 in excess of that
possessed by the neutral atoms. What is the spectroscopic dissociation energy of
Br2? [Ans. 190.37 kJ mol–1]
4.19 The dissociation energy of ground electronic state of a diatomic molecule is 326.35
kJ mol–1
the other in excited state. The energy of excitation of the excited atom is 209.2 kJ
mol–1. What is the maximum wavelength of radiation which will cause the molecule
in the ground state to cause dissociation in the excited state? If the difference in
the potential energy minima for the two molecular levels is 2.95 ¥ 106 m–1, what
is the dissociation energy of the excited state of the molecule?
[Ans. 223.4 nm, 182.42 kJ mol–1]
4.20 The zero-point energy of the ground state of a molecule is 1.176 ¥ 105 m–1 and that
of its lowest excited state is 7.27 ¥ 104 m–1. The energy difference between the two
minima of molecular electronic levels is 5.020 6 ¥ 106 m–1. What is the energy of
the electronic excitation from u≤ = 0 level to u¢ = 0 level?
[Ans. 4.975 7 ¥ 106 m–1]
526 A Textbook of Physical Chemistry

4.21 The values of we and we xe for upper and lower electronic states of a molecule are
151 561, 1 725 and 217 021 and 1 346 m–1, respectively. If the difference between
the minima of two molecular levels is 6.507 48 ¥ 106 m–1, calculate the energy of
(0, 0)-transition. [Ans. 6.474 655 ¥ 106 m–1]
4.22 The absorption spectrum of O2 shows vibrational structure which ends with
a continuum at 56 876 cm–1; the upper electronic state dissociates into one
ground state atom and the other at excited state with the excitation energy of
15 875 cm–1. Estimate the dissociation energy in the ground state.
[Ans. 4.906 ¥ 105 J mol–1]
Vibration-Rotation 4.23 Which of the vibrational modes of CO2 are IR active? What is the line spacing in
Spectrum the P and R branches of the vibration-rotation spectrum of these vibrational modes
[Ans. Antisummetric stretch and bending
vibrations. Line spacing is 4B as alternative
rotational levels are unoccupied.]
4.24 Which of the vibrations modes of acetylene are IR active? What is the line spacing
in the P and R branches of the vibrations-rotation spectrum of these vibrations
modes?
[Ans. Antisymmetric strectch and one of
the bending modes. Line spacing
is 2B with intensity wariations in the
ratio of 3 : 1 due to hydrogen atoms.]
 ANNEXURE A Qualitative Study of Quantum Mechanical Treatment
of Spin Transitions in AX, A2 and AX2 Systems

The spins of protons in a molecule can be described by the nuclear spin wave
functions. For the protons in AX, A2 and AX2 systems, the nuclear spin wave
functions along with their energies and the possible spin transitions amongst them
are described below.

The System AX Since the proton can have two nuclear spins (mI = 1/2 designated as a spin and
mI = - 1/2 designated as b spin), there are four possible magnetic states that
correspond to the four possible combinations of the spin quantum numbers of A
and X protons. These are shown in Table A.1.

Table A.1 Nuclear Spin Wave Functions for AX System

mI (A) mI (X ) mI (A) + mI(X) Wave function†

1 1
1 y +1 = a (A) a (X)
2 2
1 1
– 0 y 0 = a(A) b (X)
2 2
1 1
- 0 y¢0 = b(A) a (X)
2 2
1 1
- – -1 y -1 = b (A) b (X)
2 2
†
Subscript of wave function y is the value of total magnetic quantum number. The symbol
a and b represent spin wave functions.

The energies of the states shown in Table A.1 can be evaluated as usual by
employing the expression

y Hy
E= (A.1)
y |y
If the two protons in the AX system do not interact with each other, then
the energy operator H is simply the sum of energy operators for the individual
protons, i.e.
H = H (A) + H (X)

It can be shown that with the form of wave functions given in Table A.1, the
energy of a system is simply the sum of individual energies of protons.
528 A Textbook of Physical Chemistry

For example, for the function y+ 1, we have

a ( A )a ( X ) | H ( A ) + H ( X ) | a ( A )a ( X )
E1 =
a ( A )a ( X ) | a ( A )a ( X )
a (A ) | H (A ) | a (A ) a (X ) | a (X ) + a (X ) | H (X ) | a (X ) a (A ) | a (A )
=
a (A ) | a (A ) a (X ) | a (X )
Since the spin functions constitute an orthogonal set, we have
E1 = ·a(A) | H (A)| a(A) Ò + ·a(X) | H (X)| a(X) Ò
= EA + EX (A.2)
The potential energy of a hydrogen atom in a molecule in the presence of a

h
EmI = - m1g (1 - s )B
2p
where s is the shielding constant of the hydrogen atom and g is gyromagnetic ratio.
The Hamiltonian operator is given by
Ÿ
H = - g B(1 - s ) L z
Ÿ
where L z is the operator corresponding to the z-component of angular momentum.
Ÿ
The operation of L z on the proton spin wave function is represented as

{ }
Ÿ
L z a = mI ÊÁ h ˆ˜ a where mI = +1/2
Ë 2p ¯

L b= { }b
Ÿ
mI ÊÁ ˆ˜
h
z where mI = -1/2
Ë 2p ¯
Thus, the Schrödinger equation for the proton spins can be written as

Ha= - g {
1 h
2 2p
(1 - s ) B a } (A.3a)

Hb= + g {
1 h
2 2p
(1 - s ) B b } (A.3b)

Following Eqs (A.2) and (A.3), the energies of the wave functions given in
Table A.1 can be derived and are given in Table A.2.
Table A.2 Energies of Wave Functions for AX System
Wave function Energy

1 h 1 h
y+1 = a(A)a(X) E+1 = – g B (1 - s A) - g B(1 - s X)
2 2p 2 2p
1 h 1 h
y0 = a(A)b(X) E0 = – g B(1 - sA ) + g B (1 - sX)
2 2p 2 2p
1 h 1 h
y 0¢ = b (A)a(X) E 0¢ = + g B (1 - sA ) - g B (1 - s X)
2 2p 2 2p
1 h 1 h
y-1 = b (A)b (X) E-1 = + g B(1 - sA ) + g B(1 - s X )
2 2p 2 2p
 Molecular Spectroscopy 529

Assuming s A to be smaller than s X , the relative order of energies are

E+1 < E0 < E 0¢ < E-1
Figure A.1a displays schematically the relative order of energies of the four
magnetic states.
The selection rules as derived from quantum mechanics are as follows.
DmI = ± 1 for the nucleus undergoing spin transition
DmI = 0 for the other nuclei
+ J/4
E–1
y–1 = b (A) b (X)
X A X A

E¢0
y¢0 = b (A) a (X) – J/4
A
A
E0
y0 = a (A) b (X) – J/4
X X
+ J/4
E+1
y+1 = a (A) a (X)

J/2 J/2

Fig. A.1 Energies of X E A X E A

wave functions and
allowed spin transitions
for system A2 (a) in the
absence of spin-spin
interactions, and (b) in
the presence of spin-spin A B X A B X
interactions (n constant) (n constant)
(a) (b)
The allowed spin transitions and the associated energy changes are described
in Table A.3. These are also shown in Fig. A.1.
Table A.3 Allowed Spin Transitions for the System AX

Proton Transition Energy change

undergoing transition transition
h
A y 0¢ ¨ y+1 ¸ g B (1 - s A)
2p
A y-1 ¨ y0 ˝˛
h
X y0 ¨ y+1 ¸ g B (1 - sX)
X y-1 ¨ y ¢0 ˝ 2p
˛
530 A Textbook of Physical Chemistry

Thus, two transitions at the indicated energy changes are observed as shown at
the foot of Fig. A.1a. The chemical shift between the two is
h
g B(s X - sA) (A.4)
2p
If the spins of protons A and X interact with each other, it is expected that the
system of parallel spins (a and a or b and b ) will repel each other and that of
opposite spins will attract each other. Thus, the systems of parallel spins (i.e. of
wave functions y-1 and y+1) will be destabilized whereas those of paired spins
(i.e. of wave functions y 0 and y 0¢ ) will be stabilized. If we write the change in
energy for each state as ± J/4 (= JmA mX ), then the energy diagram is changed
as shown in Fig. A.1b. From Fig. A.1b, it also follows that the energies of
transitions y0 ¨ y+1 and y ¢0 ¨ y+1 are decreased by J/2 whereas those of
y-1 ¨ y 0¢ and y- 1 ¨ y0 are increased by J/2. The spectrum thus will modify
as shown at the foot of Fig. A.1b. Hence, the single resonance lines of A and X
protons observed in the absence of spin-spin interactions will each be replaced by
two lines. The intensities of the two lines of either A proton or X proton will be
half of the parent line observed in the absence of spin-spin interactions.

The System A2 The best example of A2 molecule is H2. The nuclei in H2 molecule can have either
the same spin (aa or bb ) or different spins (ab). The different magnetic states of H2

1. Total magnetic quantum number equal to - 1 In this state, both the nuclei
have b spin. The nuclear wave function describing this state is
y-1 = b (1) b (2)
2. Total magnetic quantum number equal to + 1 In this stage, both the
nuclei have a spin which is described by the wave function
y+ 1 = a (1)a (2)
3. Total magnetic quantum number equal to zero In this state, one nucleus
has a spin and the other has b spin. Since the two nuclei are indistinguishable,
such a situation is described with the linear combinations of spin wave functions
a(1)b (2) and b (1)a(2). Thus, we have
1
Symmetric wave function: y0, s = [a (1)b (2) + b (1)a (2)]
2
1
Antisymmetric wave function: y0, a = [a(1)b (2) - b (1)a (2)]
2
where the subscripts s and a stand for the symmetric and antisymmetric nature of

all the above four wave functions have the same energies. In the presence of a
removed. The respective energies of the four
functions y+1, y0, s, y0, a and y-1, as derived by the method describe above, are
h h
–g (1 - s) B ; 0 ; 0 ; + g (1 - s)B;
2p 2p
These are shown schematically in Fig. A.2a.
 Molecular Spectroscopy 531

Quantum mechanically, the spin transitions are allowed only amongst either
symmetric or antisymmetric wave functions. The spin transitions from symmetric
to antisymmetric wave functions or vice versa are forbidden. Besides the above
restriction, the selection rule permits only those transitions for which D mI = ± 1
for the proton undergoing transition. Thus, two transitions y 0, s ¨ y +1 and
y-1 ¨ y0, s are allowed and both of them have the same energy. Hence, the system
A2 produces only one resonance line.
In the presence of spin-spin interactions, the energies of symmetric wave
functions are destabilized by the same amount +J /4 whereas that of antisymmetric
wave function is stabilized by the amount - 3J/4.† The energy diagram shown in

Since the transitions only amongst symmetric wave functions are allowed, it
is obvious from Fig. A.2b that the energies of allowed transitions y0, s ¨ y+1 and
y-1 ¨ y0, s remain the same as those observed in the absence of spin-spin
interaction. Thus, the single resonance line observed in the absence of spin-spin
interaction remains unaffected in the presence of spin-spin interaction. The above
characteristic of destabilization of all symmetric wave functions due to the spin-spin
interactions is maintained for any number of chemically equivalent protons. Thus,
we conclude that the chemical equivalent protons do not show spin-spin splitting
in spite of the fact that they do involve spin-spin interactions.

The System AX2 For the system AX2, we have eight magnetic states as described in Table A.4. Let
sA and sX be the shielding constants for protons A and X, respectively, and let
we write
1 h
EA = (1 - sA) B (A.5)
2 2p

1 h
EX = (1 - s X) B (A.6)
2 2p
†
The spin-spin interaction energy is proportional to the scalar product of nuclear spin
angular momenta of the two protons, i.e. E μ L1◊L2. Since the square of the total nuclear
spin angular momenta is
L2 = (L1 + L2) ◊(L1 + L2) = L21 + L22 + 2L1◊L2
we can write
L1◊L2 = (1/2) (L2 – L21 – L22) = (1/2) [I(I + 1) –I1(I1 + 1) – I2(I2 + 1)](h/2p)2
For protons, I1 = I2 = 1/2. Hence
L1◊L2 = (1/2) [I (I + 1) – 3/2] (h/2p)2
For the two parallel spins of protons, I = 1. Hence
L1◊L2 = (1/2)(2 – 3/2)(h/2p)2 = (1/4) (h/2p)2
and thus E μ (1/4) (h/2p)2 = (1/4) J
For the two antiparallel spins of protons, I = 0. Hence
L1◊L2 = (1/2) (0 – 3/2) (h/2p)2 = – (3/4) (h/2p)2
and thus E μ – (3/4) (h/2p)2 = – (3/4) J
532 A Textbook of Physical Chemistry

Fig. A.2 Energies

of wave functions
and allowed spin
transitions for the
system A2 (a) in the
absence of spin-spin
interactions, and (b) in
the presence of spin-
spin interactions
(a) (b)
For the eight magnetic states shown in Table A.4, the energy expressions in the
absence of spin-spin interactions can be worked out as usual. These are also
included in Table A.4.

Table A.4 Wave Functions and the Corresponding Energies for the System AX2

Magnetic state Total magnetic Function Energy

quantum number
3
1 + aaa - EA - 2EX
2

2 +
1
2
a { 1
2
(ab + ba ) } - EA

3 +
1
2
a { 1
2
(ab - ba ) } - EA
1
4 + baa EA - 2EX
2
1
5 – ab b - EA + 2EX
2
6 –
1
2
b { 1
2 }
(ab + ba ) EA

7 –
1
2
b { 1
2 }
(ab - ba ) EA

3
8 – bbb EA + 2EX
2
 Molecular Spectroscopy 533

Assuming EA to be smaller than 2EX, the relative order of energies are as follows:
(EA + 2EX) > EA > (- EA + 2EX) > (EA - 2 EX) > - EA > (- EA - 2EX)

Figure A.3a displays the energy diagram for AX2 molecule in the absence of
spin-spin interactions. Following the selection rule, four A-transitions of equal
energy 2EA and four X-transitions of equal energy 2 EX are observed (Table A.5).
Quantum mechanically it can be shown that the probability of each of X-transition
is twice as large as that of each of A-transition. Thus, the intensity of the single
line of X-transitions is twice as large as that of the single line of A-transitions.
JAX/2 + JXX/4
EA + 2EX
y8

A X A
X

JXX/4
EA
y6 y7 – 3/4 JXX
X
– EA + 2 EX
y5 –JAX/2 + JXX/4

X X A
A A
X
EA – 2 EX A
y4 –JAX/2 + JXX/4
JXX/4
– EA – 3 /4 JXX
y2 y3

A A
X
X

JAX/2 + JXX/4
– EA – 2 EX
y1

JAX/2
JAX

X E A X E A
Fig. A.3 Energies
of wave functions
and allowed spin
transitions for the
system AX2, (a) in the
absence of spin-spin
A B X A B X
interactions, and (b) in
the presence of spin- (n constant) (n constant)
spin ineractions (a) (b)
534 A Textbook of Physical Chemistry

Table A.5 Allowed Spin Transitions in AX2 System

Proton undergoing Transition Energy change

transition
A y4 ¨ y1 2EA
A y6 ¨ y2 2EA
A y8 ¨ y5 2EA
A y 7 ¨ y3 2EA
X y 2 ¨ y1 2EX
X y5 ¨ y2 2EX
X y6 ¨ y4 2EX
X y8 ¨ y6 2EX

out following the principles given below.

1. Interactions for chemically nonequivalent protons A pair of parallel spins
will repel each other (hence energy increases by an amount JAX mAmX =JAX/4)
whereas that of opposite spins attract each other (hence energy decreases by an
amount JAX/4).
2. Interactions for chemically equivalent protons The interaction between the
two protons causes an increase in energy of JXX /4 for a symmetric wave function
and a decrease of 3JXX/4 for an antisymmetric wave function. As mentioned earlier,
these changes do not affect the overall spectrum.
Table A.6 gives the types of interactions and the corresponding energy changes
for the eight magnetic states described in Table A.4.
Figure A.3b depicts the above energy changes. Table A.7 gives the energies of
the allowed transitions in the presence of spin-spin interactions.

Table A.6 Energies of Wave Functions in the Presence of Spin-Spin Interactions

State Types of interactions Energy

1 2 {a (A)a (X)} + a (X)a (X) - EA - 2EX + JAX/2 + JXX/4
2 a (A)a (X) + a (A)b (X)
+ symmetric X2 wave function - EA + JXX/4
3 a (A)a (X) + a (A)b (X)
+ antisymmetric X2 wave function - EA - 3JXX/4
4 2{b (A)a (X)}
+ symmetric X2 wave function EA - 2EX - JAX/2 + JXX/4
5 2{a (A)b (X)}
+ symmetric X2 wave function - EA + 2EX - JAX/2 + JXX/4
6 b (A)a (X) + b (A)b (X)
+ symmetric X2 wave function EA + JXX/4
7 b (A)a (X) + b (A)b (X)
+ antisymmetric X2 wave function EA - 3JXX/4
8 2(b (A)b (X)}
+ symmetric X2 wave function EA + 2EX + JAX/2 + JXX/4
 Molecular Spectroscopy 535

Table A.7 Spin Transitions for System AX2 in the Presence of Spin-Spin Interactions

Proton undergoing Transition Energy change

transition

A y4 ¨ y1 2EA - JAX
A y6 ¨ y2 2EA
A y8 ¨ y5 2EA + JAX
A y7 ¨ y3 2EA
X y2 ¨ y1 2EX - JAX/2
X y5 ¨ y2 2EX - JAX/2
X y6 ¨ y4 2EX + JAX/2
X y8 ¨ y6 2EX + JAX/2

From Table A.7, we conclude that (i) two of the X transitions have the energy
2EX + JAX/2 while the other two have the energy 2EX - JAX/2, and (ii) one A
transition has the energy 2EA + JAX, two have the energy 2 EA and one has the
energy 2EA - JAX. Thus, the single transition for the proton X observed in the
absence of spin-spin interactions splits into two transitions whereas the single
transition of A proton splits into three transitions (Fig. A.3b). The intensities of
X-transitions are equal while that of A-transition at 2EA is twice as intense as the
other two transitions.
 5 Molecular Symmetry and Its
Applications

5.1 SYMMETRY ELEMENTS AND ASSOCIATED SYMMETRY OPERATIONS

Introduction The study of symmetry of a molecule is often useful in making its theoretical
and experimental treatments simpler. A point in the molecule is chosen and the
symmetry with respect to lines and planes passing through this point is studied.
Before studying these in detail, it is worthwhile to make distinction between the
symmetry element and the associated symmetry operation.
The symmetry element is a geometrical entity such as a line, a plane or a point with
respect to which the symmetry operation is carried out. The associated symmetry
operation is actually carrying out the operation on the object. If on carrying out some

which is completely indistinguishable from the previous one, the object is said to
possess the above symmetry operation and the corresponding symmetry element.

Four types of symmetry elements are used to describe the symmetry of a molecule.
A brief description of these symmetry elements and the corresponding symmetry
operations is in order.

Rotations: Axes of An axis of symmetry is a line around which the rotation operation is carried
Symmetry out. The order of rotation axis (symbol: n
equal to 360º/n axis

S
by the symbol Cn.

C2 Axis of Rotation An example of a molecule possessing the C2 axis of rotation

is water. The symmetry operation corresponding to this axis of rotation is the
a and
b , the effect of rotating water molecule clockwise by an angle 180º about the

O p/2 O p/2 O
1 1
C2 C2

Ha Hb Hb Ha Ha Hb
Fig. 5.1.1 The
operations C2 and C 22
on water molecule C 22 (= E)
 Molecular Symmetry and Its Applications

is represented as C22 (the subscript 2 represents order of axis of rotation and the
†
.
2
Since the operation C 2
identity operation (symbol:
E C2 axis of rotation are C12 ann C22 (= E

Problem 5.1.1
Solution A molecule of ethylene has three twofold axes of rotation. These are depicted in

C2
H H

C C C2
Fig. 5.1.2 Three
C2 axes in ethylene H H
molecule C2

C2 axis is collinear with the C—C axis.

C 2 axis is perpendicular to the plane of the molecule and bisects the
C—C line.
C2 axis is in the plane of the molecule and bisects the C—C line.

C3 Axis of Rotation An example of a molecule possessing the C3 axis of rotation

a, F b and F c , respectively, the

successive rotations are represented as C13, C23, and C33, respectively. Note that the
operations C13 and C23

Fig. 5.1.3 The three C3

†
In general, the notation C m
n represents n-fold axis of rotation and the angle through which
the molecule is rotated clockwise is given by m ¥ 2p/n.
 A Textbook of Physical Chemistry

C33
operation C33 is also the identity operation. Thus, the sequence of operations for a
C3 axis are C13 , C23 and C33 (= E
Simultaneous
Existence of C2
and C3 Axes threefold axis of rotation. The existence of the C3 axis and one C2 axis perpendicular
to the C3 axis implies the presence of two more C2 axes at angles 2p p/3 to
C2 axis, since the rotations of molecule by 2p p/3 about the C3 axis
C2
The three C2 axes are said to constitute a set of equivalent symmetry elements.

C2
C3
F

B F C2
Fig. 5.1.4 Three C2
axes perpendicular to
F
the C3 axis in boron
C2

Problem 5.1.2
Solution

C3 C2
H H

C3
H H
C C C2
Fig. 5.1.5 A
tetrahedron drawn H H
within a cube and C3
depiction of (a) C3 H C2
H
axes and (b) C2 axes in
C3
methane (a) (b) .

Methane has four threefold rotation axes, each passing through one of the hydrogen atoms

Methane has three twofold rotation axes, each bisecting the bond angles between the two
pairs of bonds pointing opposite to each other. These axes also pass through the centre of two
opposite faces of the cube in which tetrahedron structure of

Reflections: A
Symmetry Planes
 Molecular Symmetry and Its Applications

symmetry plane.†
a plane must pass through the skeleton of the molecule.
Example An example of a molecule having a symmetry plane is water, which
in fact, contains two symmetry planes: a molecular plane and a plane bisecting

C2 C2

sV
O O sV

H H H H
planes in water
molecule

i.e. s2 = E. A plane are represented

by the symbol s. This is further subscripted by the symbols v, d and h, which respectively
stand for vertical, diagonal and horizontal.
sv Plane If the symmetry plane contains the highest-order axis of rotation (known

s v. If there are more than one such

planes, they are labelled as sv, s¢v, s¢¢v or [sv sv sv
sh Plane If the symmetry plane is perpendicular to the principal axis, it is
labelled as sh.
sd Plane If the symmetry plane bisects the two s v planes, it is labelled as sd.
These planes are illustrated in Fg.
C4 C4 C4 C4
A
sv sd

F F F F F F F
F
Xe Xe Xe Xe sh
F F F F F F F F

sv

(a) sv plane (b) sv plane (c) sd plane (d) sh plane

other atoms lying outside the plane must occur twice in number.
 A Textbook of Physical Chemistry

Inversion: Centre In the operation of centre of symmetry, a point in the molecule is chosen as the
of Symmetry origin of coordinates and each atom of the molecule is shifted to a point whose
or Centre of
Inversion
a centre of symmetry (or
The symbol for the centre of inversion and for the corresponding operation is i.
The operation in = i if n is odd and in = E if n is even.
Examples Examples of molecules having centre of symmetry are XeF , benzene
and acetylene.
The operation of inversion can be regarded as composite movement comprising

Fig. 5.1.8 Equivalence between inversion operation and the composite operation involving rotation by 180º

Improper Rotation: The operation corresponding to the improper rotation axis is to rotate a molecule
Rotation- clockwise by an angle 2p/n (where n
Reflection Axes

an improper rotation axis.

The symbol of improper rotation axis is Sn, where n decides the angle 2p/n through
which molecule is rotated. The successive improper-rotation operation (rotation
S mn . It can be shown that the rotation

er rotation need not specify the order.

Examples Examples of improper rotation axis are shown by

The sequence of operation shown by the improper axis of rotation of order n

depends whether n is even or odd. These can be worked out keeping in mind that
 Molecular Symmetry and Its Applications

Ha Hd
Ha

Hb
Hb Hc
rotation by reflection
C C C
90°
Hc Hd Ha

Hd Hc Hb
(i)

Ha Hd
Hc

Hd
Hb Hc
reflection rotation by
C C C
90°
Ha
Hc Ha

Hd Hb Hb

(ii)

Fig. 5.1.9 The operation S4

rotation by 60° reflection in a plane

about the C—C axis ^ to the C—C bond

Fig. 5.1.10 Effect of S6

operation in staggered
ethane S16

Sequence of The sequence of operations for n = 6 is as follows.

Operations for
S6 = s hC6 = S6
Even Value of n
S62 = (s hC6 shC6 ∫ (shsh C6 C6 ∫ (E C62 ∫ C62 ∫ C31
S63 = (s hC6 shC6 shC6 ∫ (shs hsh C6C6C6 ∫ (sh C63 ∫ (s h C21 ∫ i
S6 = (s hC6 shC6 shC6 shC6 ∫ (sh C6 ∫ (E C6 ∫ C6 ∫ C32
S6 = (s hC6 s hC6 s hC6 shC6 s hC6 ∫ (sh C6 ∫ (s h C6 ∫ S6
S66 = (shC6 s hC6 shC6 shC6 shC6 sh C6 ∫ (sh6 C66 E E ∫ (E
Thus, sequence of operations generated by the element S6 are S6, C3, i, C32, S6
and E. This set contains C3, C32, and E, which are the operations generated by a
 A Textbook of Physical Chemistry

C3 S6 axis automatically implies the existence of

the C3 axis. Generalization of this statement requires the existence of Cn/2 axis if
there exists an improper rotation axis of even order.
The repetition of sequence occurs from Snn+1 onwards.
Sequence of The sequence of operations for n
Operations for
S = s h C1 = S 1
Odd Value of n
C 2 = (s hC s hC ∫ (shsh C C ∫ (E C2 ∫ C2
C 3 = (s hC s hC shC ∫ (shshsh C C C s h C3 S3

C = (s hC ∫ (s h C E C C
C = (s hC ∫ (s h C ∫ (sh E sh

C 6 = (shC 6
∫ (s 6h C 6 ∫ (E C1 C1

C ∫ (s hC ∫ (s h C ∫ (sh C 2 S2

C 8 ∫ (s hC 8
∫ (s 8h C 8 E C3 C3

C ∫ (s hC ∫ (s h C ∫ (sh C S
C 10 ∫ (s hC 10
= (s 10 C 10 ∫ (E C E E E
The sequence of operations generated by Sn with n odd are 2n in numbers. For S ,
these are S1 , C 2 , S 3 , C , sh, C 1 , S 2 , C 3 , S , and E. The repetition of sequence
occurs from Sn2 n +1 onwards.

It may be noted that an S1

S2 operation is equivalent to an inversion operation.
A molecule having no improper rotation axis is dissymmetric. This implies that
such a molecule is not superimposable on its mirror image and thus shows optical
isomerism.

5.2 CLASSIFICATION OF MOLECULES BASED ON SYMMETRY ELEMENTS

point groups
based on its symmetry elements. We start with the minimum symmetry element

n, s, i and Sn
different point groups.

Point Group C1 This group includes molecules having only identity element or C1 axis of rotation.
An example of this group is a carbon atom attached to four different atoms, e.g.
 Molecular Symmetry and Its Applications

F
C

Cl
Fig. 5.2.1 An example
of the point group C1
Br

Point Group Cn This group includes molecules having only one axis of symmetry of order n (more
Cn is C1n, C2n, º,
n–1 n
C n , C n (= E

Point Group Cs This group includes molecules having only one symmetry plane. The sequence
of operations associated with the Cs group is s and s2 (= E
2

Point Group Ci This group includes molecules having only a centre of symmetry. The sequence of
operations associated with this group is i and i2 (= E

Cl
F
Br
C
Fig. 5.2.2 An example
Br
of the point group Cs
S C
Br
O Cl
Centre of
symmetry
Fig. 5.2.3 An example O H
of the point group Ci

Point Group Cnv This group includes molecules having an axis of symmetry, Cn, along with n
vertical planes. The sequence of operations associated with the group Cnv are Cn,
C2n, C3n, º, C nn, sv, s¢v º (a total n
in the following.
Point group C2v Example is C2, sv and s¢v.
The operations are C2, C 22 (= E sv and s¢v.
 A Textbook of Physical Chemistry

C2 sv

O sv¢

H H

Fig. 5.2.4 An example

of the point group C2v

Point group C 3v 3 and PCl 3 . The operations are C 3 ,

C3 , C3 = E ) , s v , s ¢v and s v¢¢. The axis C3 passes through N atom and centre of
2 3(

sv includes

H H H

C3 C3 C3

N N N
H H H

H H H

Fig. 5.2.5 C3 axis and three vertical planes in NH3 molecule

Point group C4v Example is BrF C axis passes through the
apex F and the central Br atoms. There are four s v symmetrical planes (in fact,
two are labelled as sv and two are labelled as sd

C4 C4

F sv F

s v¢ sd¢
F F
F Br F F Br F
F F sd

Fig. 5.2.6 An
example of the point
group C4v
(a) (b)

Point Group Cnh This point group includes molecules having an axis of symmetry, Cn, along with
one horizontal plane of symmetry. Examples of this group are trans-N2F2 and
3 3
 Molecular Symmetry and Its Applications

C3

C2
H
O

F H
sh N N B
O O
F

Fig. 5.2.7 Examples H

of (a) C2h and (b) C3h
groups (a) (b)

Point Group S2n This point group includes molecules having an S2n axis coincident with a C2n
axis. The group S2 is the same as the group Ci, as a rotation by 180º followed by
i.
Point Group Dn This point group includes molecules having a Cn axis along with n twofold axes
right angles to the Cn 3 group is the gauche conformation of
ethane.
Point Group Dnh This point group includes molecules having an axis of symmetry, Cn, along with
n twofold axes right angle to the Cn axis and a horizontal symmetrical plane.
Examples of this group are as follows.

2h ; C2 axis, two twofold axes perpendicular to the C2 axis and sh

plane.

3h CO32- ; C3 axis, three twofold axes perpendicular to the C3 axis

and sh plane.
XeF ; C axis, four twofold axes perpendicular to the C axis and
sh plane.

6h C6 6 ; C6 axis, six twofold axes perpendicular to the C6 axis and sh

plane.

Point Group Dnd This point group includes molecules having a Cn axis of symmetry along with n
twofold axes of symmetry perpendicular to the Cn axis and n vertical symmetry
planes bisecting the angles between axes (these planes are known as dihedral
planes of symmetry, sd 2d is allene (C3
C2 axis, two twofold axes perpendicular to
the C2 axis and two sd planes.
Point Group C•v The point group C•v includes linear molecules without a centre of symmetry.
O C S. These molecules contain a C• axis of
sv planes.
 A Textbook of Physical Chemistry

C2¢
H
sd
H

C C C C2
sd¢
H
Fig. 5.2.8 An
example of the point H
group D2d C 2²

Point Group D•h T includes linear molecules with a centre of symmetry. Examples
•h
— C ∫∫ C—
contain a C• axis of rotation coinciding with internuclear axis, a sh plane and an
C¢2 axes perpendicular to the C• axis.

Point Group Td The point group Td includes symmetry elements possessed by a tetrahedron. These

A tetrahedron has the following symmetry elements.

∑ Four C3 axes of rotation; each passing through two opposite apices of the cube

these axes generates C3 and C 23 operations—a total of eight operations.

∑ Three S axis of rotation; each passing through the centres of an opposite pairs
of faces of the cube. Each of these generates the operations S , S 2 (= C2
S 3 — a total of six operations excluding the operations C2.

∑ Three C2 axes of rotation; each passing through the centres of an opposite

pairs of faces of the cube. Each of these axes generates an operation C2 which
are already included in S operations.

∑ Six sd planes of symmetry; each passing through two vertices and bisecting
the line joining the other two vertices of the cube. These generate six operations
sd.
Thus, we have the following set of symmetry operations in the point group Td.
E, 8C3, 3C2, 6S , 6sd

Point Group Oh h includes symmetry elements possessed by an octahedron.

 Molecular Symmetry and Its Applications

C4, C2, S4
C3, S6
C2, S4
C3

C 2¢

Fig. 5.2.9 A tetrahedron drawn within a cube Fig. 5.2.10 An octahedron drawn within a cube
An octahedron has the following symmetry elements.
∑ Three S axes of rotation; each passing through opposite apices. Each generates
the operations S , S 2 (= C2 S 3 —a total of six operations excluding the
operations C2.
∑ Three C2 axes of rotation coinciding with the S axes, respectively. Each of
these generates the operation C2 which are already included in the S operations.
∑ Three C axes of operations coinciding with the S¢ s and C¢2s axes. Each of these
generates the operations C , C2 (= 2C2 C3. These generate six operations
excluding the operations C¢2 s.
∑ Four S6 axes of rotation; each passing through the centres of a pair of opposite
triangular faces. Each of these generates the operations S6, S 62 (= C3 S 63 (= i
S 6 (= C 32 S 6—a total of eight operations excluding S 62, S 63 and S 6.
∑ Six C¢2 axes; each passing through the centre of opposite edges. These generate
six C2 operations.
∑ For C3 axes coinciding with the S¢6 s. Each generates C3 and C32 operations
which are also generated by the S6 axes.
∑ An inversion centre; this generates the operation of inversion. This is also
generated by each of the S 63 operations.
∑ Three horizontal planes sh; each passing through four of the six apices.
∑ Six vertical planes sd; each passing through two apices and bisecting two
opposite edges. Each of these generates an operation sd.
Thus, we have the following set of h.
E, 8C3, 6C , 6C2, 3C2 (= C2 i, 6S , 8S6, 3sh, 6sd

Point Group Ih This is highy symmetrical group with h = 120. These are E, 12C , 12C 2, 20C3,
C2, i, 12S10, 12S103, 20S6 s. Examples include regular icosahedron and
dodecahedron and Buckminster fullerence (C60
 A Textbook of Physical Chemistry

Systematic A systematic procedure for classifying a molecule in its point group is shown in
Classification of
Molecules
Start
Special group
yes no
Cn
yes no
sh
S2n or S2n and i only
collinear with principal yes no
axis Cn i
C¥v D¥v Td Oh Ih yes no yes no
Cs
nC2¢ s ^ to Cn
yes no
S2n Ci Cl
sh sh
yes no yes no
nsd¢ s ns v¢ s
yes no yes no
Dnh Cnh

Dnd Dn Cnv Cn

Fig. 5.2.11 A systematic way of classifying a molecule in its point group

5.3 MATRIX REPRESENTATIONS OF GEOMETRICAL OPERATIONS

expressed mathematically by using the matrix notations.

Let P(x, y, z
point P¢(x¢, y¢, z¢ symmetry operations listed earlier.
The coordinates (x¢, y¢, z¢ x, y, z
notations.
z

P¢(x¢, y¢, z¢) P (x, y, z)

Fig. 5.3.1 Cartesian

axes
x

Identity Operation In an identity operation, the new coordinates (x¢, y¢, z¢

ones, i.e. (x, y, z
Ê x¢ ˆ Ê 1 0 0ˆ Ê xˆ
Á y ¢ ˜ = Á 0 1 0 ˜ Á y˜
Á ˜ Á ˜Á ˜
Ë z¢ ¯ Ë 0 0 1¯ Ë z ¯
The 3 ¥ 3 unit matrix represents the identity operation.
 Molecular Symmetry and Its Applications

Reflection xy xz yz
Operation respectively.

(yz)

(xz)
y

(xy)

planes
x

we have
Ê x¢ ˆ Ê 1 0 0 ˆ Ê xˆ
sx y; (x, y, z Æ (x, y, – z Á y ¢ ˜ = Á 0 1 0 ˜ Á y˜
Á ˜ Á ˜Á ˜
Ë z¢ ¯ Ë 0 0 -1¯ Ë z ¯

Ê x¢ ˆ Ê 1 0 0ˆ Ê xˆ
sx z; (x, y, z Æ (x, – y, z Á y ¢ ˜ = Á 0 -1 0 ˜ Á y ˜
Á ˜ Á ˜Á ˜
Ë z¢ ¯ Ë 0 0 1¯ Ë z ¯

Ê x¢ ˆ Ê -1 0 0 ˆ Ê x ˆ
sy z; (x, y, z Æ (– x, y, z Á y¢ ˜ = Á 0 1 0 ˜ Á y˜
Á ˜ Á ˜Á ˜
Ë z¢ ¯ Ë 0 0 1¯ Ë z ¯
Inversion In the inverse operation, all the three coordinates of a point change sign, i.e.
Operation
Ê x¢ ˆ Ê -1 0 0 ˆ Ê x ˆ
i; (x, y, z Æ (– x, – y, – z Á y ¢ ˜ = Á 0 -1 0 ˜ Á y ˜
Á ˜ Á ˜Á ˜
Ë z¢ ¯ Ë 0 0 -1¯ Ë z ¯
Proper Rotation Let the rotation be carried out clockwise by an angle q about the z
Operation After the rotation, the coordinate z remains unaffected, i.e. z¢ = z. The expressions of
(x¢, y¢ x, y x-component
and y-component vectors clockwise by an angle q. The x- and y-components of
the rotated vectors are as follows.
x-component vector x1 = x cos q and y1 = – x sinq
y-component vector x2 = y sin q and y2 = y cosq
x¢ = x1 + x2 = x cos q + y sin q
y¢ = y1 + y2 = – x sin q + y cos q
 A Textbook of Physical Chemistry

P(x, y)
y
y2
y
y¢ q
P¢(x¢, y¢)
x2 x1
x
q x x¢
x
Fig. 5.3.3 Effect of
rotation about z y1
axis on a point

Alternative ¢
Procedure when the former is rotated clockwise by an angle q about the z-axis.
z z

z P z¢ P¢

y y¢
O y O y
Fig. 5.3.4 Rotation d
f f–q d
of OP clockwise by an
x x¢
angle q about the x x
z-axis
(a) (b)

x = d cos f and y = d sin f

x¢ = d cos (f – q d cos f cosq + d sin f sin q

= d(x/d q + d ( y/d q = x cosq + y sin q
y¢ = d sin (f – q d sin f cos q – d cosf sin q
= d (y/d q – d (x/d q = y cosq – x sin q
In the matrix notation, we have
Ê x¢ ˆ Ê cos q sin q 0ˆ Ê xˆ
Á y ¢ ˜ = Á - sin q cos q 0˜ Á y˜
Á ˜ Á ˜Á ˜
Ë z¢ ¯ Ë 0 0 1¯ Ë z¯
Improper Rotation
Operations perpendicular to the axis of rotation. If the rotation is carried out about z-axis, then
xy plane. The latter operation causes the
reversal of sign of z z¢ = – z. Thus, the matrix representing
improper rotation is obtained from that of proper rotation by changing 1 to –1.
The obtained matrix is
 Molecular Symmetry and Its Applications

Ê cos q sin q 0ˆ
Á - sin q cos q 0˜
Á ˜
Ë 0 0 -1¯

Utility of Matrix If an object is subjected to more than one symmetry operation in succession, the
Notation net result can be obtained by left multiplying the corresponding matrices in the
syz and sxz in
succession, we will have
Ê 1 0 0 ˆ Ê -1 0 0 ˆ Ê -1 0 0 ˆ
sxz syz ∫ Á 0 -1 0 ˜ Á 0 1 0 ˜ = Á 0 -1 0 ˜
Á ˜Á ˜ Á ˜
Ë 0 0 1¯ Ë 0 0 1¯ Ë 0 0 1¯

Ê cos 180∞ sin 180∞ 0 ˆ

∫ Á - sin 180∞ cos 180∞ 0 ˜ ∫ C2(z
Á ˜
Ë 0 0 1¯
that is, the net result is to carry out the clockwise rotation by 180º about the
z-axis [i.e. C2(z
5.4 DEFINITION OF A GROUP

In the mathematical sense, a group is a collection of elements satisfying the

following four characteristics.
Combination of Any combination of two or more elements of the collection must be equivalent to
Elements one element which is also a member of the collection.
The combination of two elements, say A and B, is written either as AB (spelled as
B left-multiplied by A BA (spelled as B right-multiplied by A
this combination is one of the elements of the same group.
The combination is said to be commutative if AB = BA, i.e. the result is the same.
A group satisfying this condition is said to be Abelian group.
The combination is said to be noncommutative if AB π BA, i.e. the order in which
the combination is carried out yields different elements of the same group.
Commutation of
Elements them unchanged. This element is called the identity element and is designated by
the symbol E. If A and B are other elements, then we have
AE = EA = A and BE = EB = B
Associative Law
of Multiplication multiplication. This implies that
A(BC AB C
that is, the combination BC when left-multiplied by A yields the same result as
the combination AB right-multiplied by C.
 A Textbook of Physical Chemistry

Reciprocal of Every member of a group has a reciprocal, which is also an element of the group.
Elements A is X such that AX = XA = E
The reciprocal X in the above expression is also written as A–1.
Problem 5.4.1
to the combination of the reciprocals in the reverse order.
Solution Let AB = D
Right multiplication on both sides by B –1A–1, we get
AB B –1A–1 = DB–1A–1
i.e. A(BB –1 A –1 = DB–1A–1
or AE A–1 = DB–1A–1 (since BB–1 = E
i.e. (AE A –1 = DB–1A–1
or AA–1 = DB–1A–1 (since AE = A
–1 –1
or E = DB A
–1 –1
This implies that B A is the reciprocal of D AB.

5.5 GROUP CONSISTING OF SYMMETRY OPERATIONS ON A MOLECULE

Point Group All symmetry operations of a molecule taken together constitute a group, known as
Consisting point group
of Symmerty these characteristics, it is worth considering the group-multiplication table of
Operations operations of a point group.
The binary products of symmetry operations of a point group are shown in the form
of a group multiplication table. The table includes as many rows and columns as
the number of symmetry operations of a molecule. Each row and each column are
headed by a symmetry operation. Their product is shown under the given column
¥ (row
2 2v
3 molecules (point group C3v
Transformation The symmetry elements in water are E, C2, sv and s¢v sv
Matrices for the s¢v coincides with the molecular plane. Since water
Point Group C2v molecule is a planar molecule, the geometric operations may be described by
2¥

O y

Fig. 5.5.1
Ha Hb
Orientation of (x, –y) (x, y)
water molecule x
 Molecular Symmetry and Its Applications

E operation The coordinates of a point remain unchanged in the E operation.

Ê x¢ ˆ Ê 1 0ˆ Ê xˆ
ÁË y ¢ ˜¯ = ÁË 0 1 ˜¯ ÁË y ˜¯

C2 operation The rotation about x-axis by 180º changes the y component of a

Ê x¢ ˆ Ê 1 0 ˆ Ê xˆ
ÁË y ¢ ˜¯ = ÁË 0 -1˜¯ ÁË y ˜¯

sv operation sv changes the y

Ê x¢ ˆ Ê 1 0 ˆ Ê xˆ
ÁË y ¢ ˜¯ = ÁË 0 -1˜¯ ÁË y ˜¯

s¢v operation s¢v does not change the coordinates of a point.

Ê x¢ ˆ Ê 1 0ˆ Ê xˆ
ÁË y ¢ ˜¯ = ÁË 0 1 ˜¯ ÁË y ˜¯

Group The group multiplication table of the point group C2v

Multiplication
Table of the Point
Group C2v
C2 C2 (= C 22 svsv (= s2v s¢vs¢v (= s¢v2

Table 5.5.1 Group Multiplication Table of the Point Group C2v

C2v E C2 sv s v¢
E E C2 sv s v¢
C2 C2 E s v¢ sv
sv sv s v¢ E C2
s v¢ s v¢ sv C2 E

The rest of the combinations can be worked out either by carrying out the
operations in succession in the order shown (starting from the operation written

the corresponding matrices. The six remaining combinations to be worked out in

†

†
a b as their positions get affected in the symmetry operations. The
position of oxygen remains unaffected.
 A Textbook of Physical Chemistry

∑ s vC2 a b Æ sv b a Æ a b ∫ s¢v a b svC2 ∫ s¢v

Ê1 0 ˆ Ê 1 0 ˆ Ê 1 0ˆ
Using the matrix notations, we have ÁË 0 -1˜¯ ÁË 0 -1˜¯ = ÁË 0 1 ˜¯
sv C2 s¢v
∑ s¢v C2 a b Æ s¢v b a Æ b a ∫ sv a b s¢v C2 = s v.

Ê 1 0ˆ Ê1 0 ˆ Ê1 0 ˆ
Using the matrix notations, we have ÁË 0 1 ˜¯ ÁË 0 -1˜¯ = ÁË 0 -1˜¯
s¢v C2 sv
∑ C2 sv a b Æ C2 b a Æ a b ∫ s¢v a b C2 sv ∫ s¢v

Ê1 0 ˆ Ê1 0 ˆ Ê 1 0ˆ
Using the matrix notations, we have ÁË 0 -1˜¯ ÁË 0 -1˜¯ = ÁË 0 1 ˜¯
C2 sv s¢v
∑ C2 s¢v a b Æ C2 a b Æ b a ∫ sv a b C2 s¢v ∫ sv

Ê1 0 ˆ Ê 1 0ˆ Ê1 0 ˆ
Using the matrix notations, we have ÁË 0 -1˜¯ ÁË 0 1 ˜¯ = ÁË 0 -1˜¯
C2 s¢v sv
∑ sv s¢v a b Æ sv a b Æ b a ∫ C2 a b sv s¢v ∫ C2

Ê 1 0 ˆ Ê 1 0ˆ Ê1 0 ˆ
Using the matrix notations, we have ÁË 0 -1˜¯ ÁË 0 1 ˜¯ = ÁË 0 -1˜¯
sv s¢v C2
∑ s¢v sv a b Æs¢v b a Æ b a ∫ C2 a b s¢v sv ∫ C2

Ê 1 0ˆ Ê1 0 ˆ Ê1 0 ˆ
Using the matrix notations, we have ÁË 0 1 ˜¯ ÁË 0 -1˜¯ = ÁË 0 -1˜¯
s¢v sv C2
Comments on
Table 5.5.1
∑ Each row and each column includes each symmetry operation once and
only once.
∑ Each row and each column is a rearranged list of the symmetry operations.
∑
Transformation The symmetry elements in ammonia are E, C3, sv sv sv
Matrices for the corresponding symmetry operations are E, C3, C 23, sv sv sv
Point Group C3v
 Molecular Symmetry and Its Applications

Fig. 5.5.2 Ammonia

molecule within a cube

The matrices for the operations E, C3, C 23, sv sv sv

as shown in the following.
Operation E The operation E
Ê x¢ ˆ Ê 1 0 0ˆ Ê xˆ
Á y ¢ ˜ = Á 0 1 0 ˜ Á y˜
Á ˜ Á ˜Á ˜
Ë z¢ ¯ Ë 0 0 1¯ Ë z ¯
New E
coordinates coordinates
Operation C3 The C3
The rotation by 2p/3 about the C3 a b b c c a. This
rotation also sends the axis x into z, y into x and z into y. Thus, the coordinates of
a
x¢ = y,
y¢ = z and z¢ = x
Ê x¢ ˆ Ê 0 1 0 ˆ Ê x ˆ
In matrix notation, this change is expressed as Á y¢ ˜ = Á 0 0 1 ˜ Á y˜
Á ˜ Á ˜Á ˜
Ë z¢ ¯ Ë 1 0 0 ¯ Ë z ¯
z

(x ², y ², z ²) Hc C3

N y

Ha (x, y, z)

Fig. 5.5.3 C3 axis of (x¢, y¢, z¢ ) Hb

rotation in NH3 x

Operation C 32 a c b a c b. This rotation

also sends the axis x into y, y into z and z into x. Thus, the coordinates of a point
a
x¢ = z, y¢ = x and z¢ = y
 A Textbook of Physical Chemistry

Ê x¢ ˆ Ê 0 0 1ˆ Ê xˆ
In the matrix notation, this change is expressed as Á y¢ ˜ = Á 1 0 0 ˜ Á y˜
Á ˜ Á ˜ Á ˜
Ë z¢ ¯ Ë 0 1 0¯ Ë z¯
Operation sv(1) sv
sv a b b a
the axis x into y and y into x a

x¢ = y, y¢ = x and
z¢ = z
Ê x¢ ˆ Ê 0 1 0ˆ Ê xˆ
In matrix rotation, this change is expressed as Á y¢ = Á 1 0 0 ˜ Á
˜ y˜
Á ˜ Á ˜ Á ˜
Ë z¢ ¯ Ë 0 0 1¯ Ë z¯
Operation sv(2) sv
sv b c c b
the axis x into z and z into x b

x¢ = z, y¢ = y z¢ = x
and
Ê x¢ ˆ Ê 0 0 1ˆ Ê x ˆ
In the matrix notation, this change is expressed as Á y¢ = Á 0 1 0 ˜ Á y ˜
˜
Á ˜ Á ˜ Á ˜
Ë z¢ ¯ Ë 1 0 0¯ Ë z ¯
Operation sv(3) sv
sv a c c a
sends the axis y into z and z into y a

x¢ = x, y¢ = z and
z¢ = y
Ê x¢ ˆ Ê 1 0 0ˆ Ê xˆ
In the matix notation, this change is expressed as Á y ¢ ˜ = Á 0 0 1 ˜ Á y˜
Á ˜ Á ˜ Á ˜
Ë z¢ ¯ Ë 0 1 0¯ Ë z¯

z z z

Hc Hc Hc
sv(3)

sv(1)
N y N y N y

Ha Ha Ha
sv(2)

Hb Hb Hb
x x x
(a) (b) (c)

sv sv s v (3) plane
 Molecular Symmetry and Its Applications

Group The group multiplication table for the point group C3v
Multiplication
Table of the Point multiplication of an operation with an identity operation leaves it unchanged, and
Group C3v
C3 C23(= C33 C23 C3 (= C33 sv sv sv 2 sv sv
2 2
[= sv sv sv sv
remaining 18 combinations can be worked out either by carrying out the operations
in the order shown (starting from the operation written at the extreme right and

matrices.

Table 5.5.2 Group Multiplication Table for the Point Group C3v

C3v E C3 C32 sv(1) sv(2) sv(3)

2
E E C3 C3 sv(1) sv(2) sv(3)
2
C3 C3 C3 E sv(2) sv(3) sv(1)
2
C3 C 32 E C3 sv(3) sv(1) sv(2)
sv(1) sv(1) sv(3) sv(2) E C3
2
C3
2
sv(2) sv(2) sv(1) sv(3) C3 E C3
2
sv(3) sv(3) sv(2) sv(1) C3 C3 E

a b c as their positions are changed in the operations. The

position of N does not change in any operation.
∑ sv C3 a b c Æ sv c a b Æ a c b ∫ sv a b c

Ê 0 1 0ˆ Ê 0 1 0ˆ Ê 0 0 1ˆ
In the matrix notation, we have Á 1 0 0˜ Á 0 0 1˜ = Á 0 1 0˜
Á ˜ Á ˜ Á ˜
Ë 0 0 1¯ Ë 1 0 0¯ Ë 1 0 0¯
sv C3 sv

∑ sv C3 a b c Æ sv c a b Æ c b a ∫ sv a b c
∑ sv C3 a b c Æ sv c a b Æ b a c ∫ sv a b c
∑ sv C23 a b c Æ sv b c a Æ c b a ∫ sv a b c
∑ sv C23 a b c Æ sv b c a Æ b a c ∫ sv a b c
∑ sv C23 a b c Æ sv b c a Æ a c b ∫ sv a b c
∑ C3 sv a b c Æ C3 b a c Æ c b a ∫ sv a b c
∑ C23 sv a b c Æ C23 b a c Æ a c b ∫ sv a b c
 A Textbook of Physical Chemistry

∑ sv sv a b c Æ sv b a c Æ b c a ∫ C23 a b c
∑ sv sv a b c Æ sv b a c Æ c a b ∫ C3 a b c
∑ C3 sv a b c Æ C3 a c b Æ b a c ∫ sv a b c
∑ C23 sv a b c Æ C23 a c b Æ c b a ∫ sv a b c
∑ sv sv a b c Æ sv a c b Æ c a b ∫ C3 a b c
∑ sv sv a b c Æ sv a c b Æ b c a ∫ C23 a b c
∑ C3 sv a b c Æ C3 c b a Æ a c b ∫ sv a b c
∑ C23 sv a b c Æ C23 c b a Æ b a c ∫ sv a b c
∑ sv sv a b c Æ sv c b a Æ b c a ∫ C23 a b c
∑ sv sv a b c Æ sv c b a Æ c a b ∫ C3 a b c

Characteristics of The entries in a group multiplication table are in agreement with the four
a Point Group characteristics of a group. These are highlighted in the following.
∑ Any combination of two or more elements of the collection must be equivalent
to one element which is also a member of the collection.
group multiplication
2 3
∑
them unchanged.

∑ Every member of a group has a reciprocal, which is also an element of the

group.
For example, C23 is a reciprocal operation of C3 in a point group C3v. The

∑ The associative law of multiplication holds good.

C3sv sv
C3v.
C3{sv sv
Ê 0 1 0ˆ Ï Ê 0 1 0ˆ Ê 1 0 0ˆ ¸ Ê 0 1 0ˆ Ê 0 0 1ˆ Ê 1 0 0ˆ
Á 0 0 1 ˜ ÔÌ Á 1 0 0 ˜ Á 0 0 1 ˜ Ô˝ = Á 0 0 1 ˜ Á 1 0 0 ˜ = Á 0 1 0 ˜
Á ˜ Á ˜Á ˜ Á ˜Á ˜ Á ˜
Ë 1 0 0 ¯ ÔÓ Ë 0 0 1 ¯ Ë 0 1 0 ¯ Ô˛ Ë 1 0 0 ¯ Ë 0 1 0 ¯ Ë 0 0 1 ¯
E
C3sv sv
Ï Ê 0 1 0ˆ Ê 0 1 0ˆ ¸Ê 1 0 0ˆ Ê 1 0 0ˆ Ê 1 0 0ˆ Ê 1 0 0ˆ
ÔÁ Ô
Ì 0 0 1˜ Á 1 0 0˜ ˝Á 0 0 1˜ = Á 0 0 1˜ Á 0 0 1˜ = Á 0 1 0˜
Ô Ë 1 0 0 ¯ Ë 0 0 1 ¯ Ô ÁË 0 1 0 ˜¯ ÁË 0 1 0 ˜¯ ÁË 0 1 0 ˜¯ ÁË 0 0 1 ˜¯
Á ˜ Á ˜
Ó ˛
E
C3{sv sv C3sv sv E
This may be extended to any number of combinations of members of a group.
 Molecular Symmetry and Its Applications

5.6 CLASSES OF SYMMETRY OPERATIONS

The elements of a group can be separated into smaller sets, known as classes. This
is based on the similarity
B = X–1AX
where A, B and X are the elements of the group. This expression is stated as: ‘B is
the similarity transform of A by X’. The elements A and B are said to be conjugate
to each other.
If each element of a group is subjected to similarity transformation by each
element of the group, then the elements are divided into several classes such that
no element belongs to more than one class. Thus, a complete set of elements which
are conjugate to one another is called a class of the group. Also, if n and m are
the elements of a group and one of its classes, respectively, then n/m is always an
integer. For example, if a group contains 10 elements, then the classes can have

Illustration We work out the classes in the point group C3v. Its members are E, C3, C32, sv
sv sv E –1 = E; C3–1 = C32; C3–2 = C31; sv –1
–1 –1
= sv sv = sv sv = sv group multiplication
table, we carry out the similarity transformation on each element by each of the
elements listed above.
Similarity Transformation of E We have
–1 –1 –1 –1
E EE = E E = E sv E sv sv sv E
C3–1EC31 = C3–1 C31 =E sv –1
E sv sv sv E
C3–2EC32 = C3–2 C32 = E sv –1
E sv sv sv E
Since E is similarity transform to E itself, the element E belongs to a class of the
group.
Similarity Transformation of C31 We have
–1
E C31 E = E C31 = C31
–1
sv C31 sv sv sv C32
C3–1 C31 C31 = C3–1C32 = C31 sv C31 sv sv sv C32
C3–2 C31 C32 = C3–2E = C31E = C31 sv C13sv sv sv C32
The similarity transformation of C31 always give C31 or C32. Thus, the operations
C31 and C32 belong to one class of the group C3v.
Similarity Transformation of C 23 We have
E–1C32 E = EC32 = C32 sv C32 sv sv sv C31
C3–1 C32 C31 = C32E = C32 sv C32sv sv sv C31
C3–2 C32 C32 = C3–2C31 = C32 sv C32sv = sv sv C31
The similarity transformation of C32 always give C31 or C32.
 A Textbook of Physical Chemistry

Similarity Transformation of sv We have

E –1sv E = Esv sv sv sv sv sv E = sv
–1 1
C3 sv C3 = C3 sv 2
sv sv sv sv sv C31= sv
C3–2sv C32 = C31sv sv sv sv sv sv C32 = sv
The similarity transformation of sv sv sv sv
the operations sv sv sv C3v.
Similarly, it can be worked out that the similarity transformation of sv sv
results into either sv sv sv
Simple Rules The determination of classes in a group may be time consuming especially when
for Determining the group contains larger number of elements. The following simple rules help
Classes of a deciding the classes in a group.
Group ∑ The symmetry operations E, i and sh are each in a class by themselves.
∑ The rotation operations C nk and C nn– k (= C n– k
(a different class for each value of k
symmetry containing the Cnk axis or a C2 axis perpendicular to the C nk axis. If
not, they belong to different classes.
∑ s and s ¢ belong to the same class provided a
symmetry operation in the group throws all points on the s¢ plane into
corresponding points in the s plane.
A similar rule holds good for two rotational operations C nk and C nk ¢ (or S nk and
S n–k ¢
Characteristics of A few characteristics shown by classes may be highlighted here.
a Class ∑ Every element is conjugate with itself, i.e. A = X –1AX. The element X may
always be E or any other element which commute with A. This follows from
the expression
E = A–1A = A–1(X–1AX A–1X –1 AX XA –1(AX
∑ If A is conjugate with B, then, B is conjugate with A. This follows from the
fact Let A = X –1BX
Y –1AY = Y –1 (X –1BX Y = Y –1 X –1B XY = B if Y –1 = X and Y = X –1.
∑ If A is conjugate with B and C, then B and C are conjugate with each other.
∑
the order of the group.
5.7 A FEW REPRESENTATIONS OF SYMMETRY OPERATIONS OF A POINT GROUP

symmetry operations of a molecule can

be expressed mathematically in the matrix notations. In this section, a few
representations of symmetry operations in a point group are described.

TRANSLATIONAL VECTORS AS A BASIS OF REPRESENTATION

The translational vectors attached to one or more atoms of a molecule may be taken
as a basis for representation of symmetry operations in a point group. This is being
illustrated by taking the examples of water and ammonia molecules.
 Molecular Symmetry and Its Applications

Example of H2O Let a translational vector in y-direction be attached to each atom of a water molecule
Molecule Ty. The behaviour of
this set of vectors on applying the symmetry operations of the point group C2v is

z x z z
O O O
E C2

Ha Hb Ha Hb Ha Hb
E(Ty) = (+1)Ty C2(Ty) = (–1)Ty
sxz syz
z z
O O

Ha Ha Ha Hb
sxy(Ty) = (–1)Ty syz(Ty) = (+1)Ty

Fig. 5.7.1 Translational vectors Ty in H2O molecule which lie in the yz-plane

It is found that the directions of the vectors either remain unchanged or show
reversal of directions. This fact is expressed as follows.
E(Ty Ty sxz(Ty Ty
C2(Ty Ty syz(Ty Ty
where +1 and –1 represent ‘direction unchanged’ and ‘direction reversed’,
respectively. The above facts are shown in the following.
C2v E C2 s xz syz

+1 –1 –1 +1 Ty
The above facts display one-dimensional representation of the point group C2v
for which translational vectors Ty form the basis. Similarly, one can obtain one-
dimensional representations based on translational vectors Tx Tz.
These along with Ty
water molecule.

Table 5.7.1 Tx, Ty and Tz

C2v E C2 sxz syz

+1 –1 +1 –1 Tx
+1 –1 –1 +1 Ty
+1 +1 +1 +1 Tz
 A Textbook of Physical Chemistry

y
x

z z z

O E O C2 O

Ha Hb Ha Hb Ha Hb

E(Tx) = (+1)Tx C2(Tx) = (–1)Tx

s (xz) s (yz)

z z

O O

Ha Hb Ha Hb

s (xz)(Tx) = (+1)Tx s (yz)(Tx) = (–1)Tx

Fig. 5.7.2 Translational vectors Tx in water molecule

Example of Ammonia molecule belongs to the point group C3v. A set of Cartesian axes is located
Ammonia on nitrogen atom with the rotational axis C3 coinciding with the z
Molecule
z
y

N x

Fig. 5.7.3 Cartesian

H
axes on N atom in NH3
H H

Let the translational vectors Tx, Ty and Tz be placed on the nitrogen atom along
the x-, y- and z-axes, respectively. The behaviour of these vectors is studied when
the molecule is subjected to the symmetry operations of the point group C3v.
Let the molecule be rotated clockwise about the z
the main symmetry axis (i.e. z translational vectors T¢x
and T¢y
translational vectors Tx and Ty as described in the following.
 Molecular Symmetry and Its Applications

Fig. 5.7.4 Effect

of rotation on
translational vectors

The vector T¢x is obtained by the vector subtraction of Ty sin q from Tx cos q, i.e.
= Tx cos q – Ty sin q
The vector T¢y is obtained by the vector addition of Tx sin q and Ty cos q, i.e.
= Tx sin q + Ty cos q

Ê Tx¢ ˆ Ê cos q - sin q ˆ Ê Tx ˆ

ÁË T ¢ ˜¯ = ÁË sin q cos q ˜¯ ÁË Ty ˜¯
y

3 molecule is represented by a 2 ¥ 2 transformation

matrix†
Transformation Now, we describe the transformation matrices for the symmetry operations of the
Matrices point group C3v.
Identity Operation Since the vectors Tx and Ty remain unshifted, the transformation matrix of this
Ê 1 0ˆ
operation is Á .
Ë 0 1 ˜¯
C3 Operation The angle q
Ê cos 120∞ - sin 120∞ ˆ Ê -1/2 - 3 2 ˆ
ÁË sin 120∞ cos 120∞ ˜¯ i.e. Á ˜.
Ë 3 2 -1/2 ¯

†
3 molecule about z-axis, the translation vector Tz remains
unshifted. We may include this effect by writing 3 ¥ 3 transformation matrix as
Ê cos q - sin q 0ˆ
Ê cos q - sin q ˆ
Á sin q 0 ˜ . This matrix may be factored as ÁË sin q cos q ˜¯
cos q
Á ˜
Ë 0 0 1¯
Since the translational vector Tz is not mixed up with Tx and Ty under any symmetry
operation and the fact that Tx and Ty mix each other, we describe only 2 ¥ 2 transformation
matrices for the various symmetry operations of the point group C3v.
 A Textbook of Physical Chemistry

C 32 Operation The angle q

Ê cos 240∞ - sin 240∞ ˆ Ê -1 2 3 2ˆ

ÁË sin 240∞ cos 240∞ ˜¯ i.e. Á ˜
Ë- 3 2 -1 2 ¯
sv(1) Operation sv 3 molecule, when viewed down the z-axis, is

Tx remains unaffected while the vector Ty shows

†
is
Ê 1 0 ˆ
ÁË 0 -1˜¯
sv(2) Operation sv 3 molecule, when viewed down the z-axis, is

Tx is equivalent to rotating it by an angle 120º clockwise

and that of Ty

Ê -1 2 - 3 2 ˆ
Ê cos 120∞ - sin 120∞ ˆ
ÁË sin 300∞ cos 300∞ ˜¯ i.e. ÁË - 3 2 12 ¯
˜.

sv(3) Operation sv 3 molecule, when viewed down the z-axis, is

Tx is equivalent to rotating it by an angle 120º

Ty is equivalent to rotating it by

Ê cos 240∞ - sin 240∞ ˆ Ê -1 2 3 2ˆ

ÁË sin 60∞ i.e. . Á
cos 60∞ ˜¯ Ë 3 2
˜
12 ¯

sv sv sv(3)

Note: sv T x by 0º, and

Ty
Ê cos 0∞ - sin 0∞ ˆ Ê +1 0 ˆ
ÁË sin 180∞ cos 180∞ ˜¯ i.e. ÁË 0 -1˜¯ .
 Molecular Symmetry and Its Applications

3v based on the
translational vectors located on the N atom.
Note:
3 molecule.

Table 5.7.2 Representation of the Point Group C3v

C3v E C3 C32 sv sv sv
1 1 1 1 1 1 Tz

Ê 1 0ˆ Ê -1 2 - 3 2ˆ Ê -1 2 3 2ˆ Ê 1 0 ˆ Ê -1 2 - 3 2ˆ Ê -1 2 3 2ˆ
ÁË 0 1˜¯ Á ˜ Á ˜ Á ˜ Á ˜ Á ˜ (Tx, Ty)
Ë 3 2 -1 2 ¯ Ë - 3 2 -1 2 ¯ Ë 0 -1¯ Ë - 3 2 12 ¯ Ë 3 2 12 ¯

ROTATIONAL VECTORS AS A BASIS OF REPRESENTATION

Example of H2O Let the water molecule s z-axis. The
Molecule a b lie in xy plane. Their behaviour
under symmetry operations of the point group C2v
z

x
z z z

O O xy plane O

Ha Hb E Ha Hb C2 Hb Ha

E(Rz) = (+1) Rz C2(Rz) = (+1) Rz

s (xz) s ( yz)

z z

O O

Hb Ha Ha Hb

s(xz)(Rz) = (–1) Rz s(yz)(Rz) = (–1) Rz

Fig. 5.7.8 Rotational vectors Rz in H2O molecule

It is found that the rotational vectors either remain unchanged or show reversal of
directions. These facts are expressed as
E(Rz Rz sxz(Rz Rz
C2(Rz Rz syz(Rz Rz
 A Textbook of Physical Chemistry

where +1 and –1 represent ‘direction unchanged’ and ‘direction reversed’,

respectively. The above facts are shown in the following.

C2v E C2 sxz syz

1 1 –1 –1 Rz

The above facts display one-dimensional representation of the point group C2v. This
is based on the rotational vectors Rz. Similarly, one can work out one-dimensional
representations based on Rx Ry
The rotational vectors Rx lie in the yz a
b
– y direction. Consequently, the rotational vectors Rx and the translational vectors
Ty behave in identical manner under the symmetry operations and thus produce
exactly identical one-dimensional representations.

x
z z z

O O O

E C2
Ha Hb Ha Hb Hb Ha

yz plane yz plane yz plane yz plane yz plane yz plane

E(Rx) = (+1)Rx C2(Rx) = (–1)Rx
s (xz) s (yz)
z z

O O

Ha Hb Ha Hb

yz plane yz plane yz plane yz plane

s(xz)(Rx) = (–1)Rx s(yz)(Rx) = (+1)Rx

Fig. 5.7.9 Behaviour of Rx under symmetry operations

 Molecular Symmetry and Its Applications

x
z z z

O O O

E C2
Ha Hb Ha Hb Hb Ha

xz plane xz plane xz plane xz plane xz plane xz plane

E(Ry) = (+1)Ry C2(Ry) = (–1)Ry
s (xz) s ( yz)

z z

O O

Hb Ha Ha Hb

xz plane xz plane xz plane xz plane

s(yz)(Ry) = (+1)Ry s(yz)(Ry) = (–1)Ry

5.7.10 Behaviour of Ry under symmetry operations

The rotational vectors Ry lie in the xz a

b
+ x direction. Consequently, the rotational vectors Ry and the translational vectors
Tx behave in identical manner under the symmetry operation and thus produce
exactly identical one-dimensional representations.

2v based
on the Rx and Ry vectors along with that of the Rz vectors.

Table 5.7.3
C2v E C2 sxz syz
1 –1 –1 1 Rx (behaves like Ty
1 –1 1 –1 Ry (behaves like Tx
1 1 –1 –1 Rz
 A Textbook of Physical Chemistry

Example of NH3 The top view of ammonia molecule when look down the + z axis is shown in
Molecule rotational vectors Rz attached to the three hydrogen atoms, when the
molecule is rotated about the z
under symmetry operations of the point group C3v is shown in the following.

C3v E C3 C 23 sv sv sv
1 1 1 –1 –1 –1 Rz

When the molecule is rotated about the x-axis, the three hydrogen atoms rotate in
their respective yz plane and the rotation vectors originate tangentially from their
respective y-direction. Consequently, the rotational vectors Rx and the translational
vectors Ty behave in identical manner under the symmetry operations and produce
exactly identical two-dimensional representations.

Fig. 5.7.11 Top view

of ammonia H H

When the ammonia molecule is rotated about the y-axis, the rotational vectors Ry
attached to each of the three hydrogen atoms lie in their respective xz planes and
originate tangentially from the respective x-direction, respectively. Consequently,
the rotational vectors Ry and the translational vectors Tx behave in identical manner
under the symmetry operations and produce exactly identical two-dimensional
representations.

3v based on the Rx and

Ry vectors along with that of the Rz vectors.

Table 5.7.4 Representations of the Point Group C3v

C3v E C3 C32 sv sv sv
1 1 1 –1 –1 –1 Rz

Ê 1 0 ˆ Ê -1 2 - 3 2 ˆ Ê -1 2 3 2ˆ Ê -1 0 ˆ Ê -1 2 - 3 2 ˆ Ê -1 2 3 2ˆ
ÁË 0 1 ˜¯ ÁË 3 2 -1 2 ˜¯ ÁË - 3 2 ˜
-1 2 ¯ ÁË 0 1 ˜¯ ÁË - 3 2 ˜
12 ¯
Á
Ë 3 2
˜ (Rx, Ry
12 ¯
 Molecular Symmetry and Its Applications 569

BOND VECTORS AS A BASIS OF REPRESENTATIONS

The set of bond vectors may be taken as the basis of representations of symmetry
operations of a point group. This is being illustrated by taking the examples of
water and ammonia molecules.

Example of Water Figure 5.7.12 displays the bond vectors of H2O molecul
Molecule
z

z z z

O O O
r1¢ = r1 r2¢ = r2 E r1 r2 C2 r1¢ = r2 r2¢ = r1

Ha Hb Ha Hb Hb Ha

s (xz) s (yz)

z z

O O
r1¢ = r2 r2¢ = r1 r1¢ = r1 r2¢ = r2

Hb Ha Ha Hb

Fig. 5.7.12 Behaviour of bond vectors under symmetry operations applied to H2O

If we carry out the symmetry operations of C2v on these two vectors, we obtain
the following facts.
Identity operation We have s (xz) operation We have

Ê r1¢ ˆ Ê 1 0 ˆ Ê r1 ˆ Ê r1¢ ˆ Ê 0 1 ˆ Ê r1 ˆ
ÁË r ¢ ˜¯ = ÁË 0 1 ˜¯ ÁË r ˜¯ ÁË r ¢ ˜¯ = ÁË 1 0 ˜¯ ÁË r ˜¯
2 2 2 2

C2 operation We have s ¢yz operation We have

Ê r1¢ ˆ Ê 0 1 ˆ Ê r1 ˆ Ê r1¢ ˆ Ê 1 0 ˆ Ê r1 ˆ
ÁË r ¢ ˜¯ = ÁË 1 0 ˜¯ ÁË r ˜¯ ÁË r ¢ ˜¯ = ÁË 0 1 ˜¯ ÁË r ˜¯
2 2 2 2
Transformation Hence, the transformation matrices of the point group C2v are as follows.
Matrices
C2v E C2 s (xz) s (yz)

Ê 1 0ˆ Ê 0 1ˆ Ê 0 1ˆ Ê 1 0ˆ
ÁË 0 1 ˜¯ ÁË 1 0 ˜¯ ÁË 1 0 ˜¯ ÁË 0 1 ˜¯
570 A Textbook of Physical Chemistry

Example of Figure 5.7.13 displays the bond vectors in NH3 molecule as viewed from the top
Ammonia of the molecule.
Molecule
sv(2)

Fig. 5.7.13 Bond

vectors in NH3 (viewed r3
from top, C3 axis N
lies perpendicular to r2 r1
plane of paper passing
sv(3) sv(1)
through N atom)

If we carry out the symmetry operations of C3v on these three vectors, we obtain
the following facts.
Identity operation We have C 31 operation We have
Ê r1¢ ˆ Ê 1 0 0 ˆ Ê r1 ˆ Ê r1¢ ˆ Ê0 0 1 ˆ Ê r1 ˆ
Á r2¢ ˜ = Á 0 1 0 ˜ Á r2 ˜ Á r2¢ ˜ = Á 1 0 0 ˜ Á r2 ˜
Á ˜ Á ˜Á ˜ Á ˜ Á ˜Á ˜
Ë r3¢ ¯ Ë 0 0 1 ¯ Ë r3 ¯ Ë r3¢ ¯ Ë0 1 0 ¯ Ë r3 ¯
2
C 3 operations We have s v(1) operation We have

Ê r1¢ ˆ Ê0 1 0 ˆ Ê r1 ˆ Ê r1¢ ˆ Ê1 0 0 ˆ Ê r1 ˆ
Á r2¢ ˜ = Á 0 0 1 ˜ Á r2 ˜ Á r2¢ ˜ = Á 0 0 1 ˜ Á r2 ˜
Á ˜ Á ˜Á ˜ Á ˜ Á ˜Á ˜
Ë r3¢ ¯ Ë1 0 0 ¯ Ë r3 ¯ Ë r3¢ ¯ Ë0 1 0 ¯ Ë r3 ¯
s v (2) operation We have s v (3) operation We have

Ê r1¢ ˆ Ê 0 0 1 ˆ Ê r1 ˆ Ê r1¢ ˆ Ê 0 1 0 ˆ Ê r1 ˆ
Á r2¢ ˜ = Á 0 1 0 ˜ Á r2 ˜ Á r2¢ ˜ = Á 1 0 0 ˜ Á r2 ˜
Á ˜ Á ˜Á ˜ Á ˜ Á ˜Á ˜
Ë r3¢ ¯ Ë 1 0 0 ¯ Ë r3 ¯ Ë r3¢ ¯ Ë 0 0 1 ¯ Ë r3 ¯
Transformation The transformation matrices of the point group C3v are as follows.
Matrices

C3v E C 31 C 32 sv(1) sv(2) sv(3)

Ê 1 0 0ˆ Ê 0 0 1ˆ Ê 0 1 0ˆ Ê 1 0 0ˆ Ê 0 0 1ˆ Ê 0 1 0ˆ
Á 0 1 0˜ Á 1 0 0˜ Á 0 0 1˜ Á 0 0 1˜ Á 0 1 0˜ Á 1 0 0˜
Á ˜ Á ˜ Á ˜ Á ˜ Á ˜ Á ˜
Ë 0 0 1¯ Ë 0 1 0¯ Ë 1 0 0¯ Ë 0 1 0¯ Ë 1 0 0¯ Ë 0 0 1¯

ATOMIC WAVE FUNCTIONS AS A BASIS OF REPRESENTATIONS

Atomic wave functions (i.e. atomic orbitals) may be taken as the basis of
representations of symmetry operations of a point group. One can write out
the atomic functions explicitly (or the angular part only since the radial part is
unaltered by all symmetry operations) and determine the effect of performing
 Molecular Symmetry and Its Applications 571

symmetry operation on it. Alternatively, the effects may be visualized by carrying

out the symmetry operation on the orbital diagrams. We illustrate these by taking
the examples H2O and SO2 for the point group C2v and NH3 and PCl3 from the
point group C3v.

POINT GROUP C2V

EXAMPLE OF p ORBITALS (WATER MOLECULE)

Considering the p orbitals of oxygen, we write their angular wave functions as
px = sin q cos j; py = sin q sin j and pz = cos q
Note: The subscript to the orbital p corresponds to the respective angular
dependence.
Effects on The various operations of the point group C2v have the following effects on angle
Angles q and j q and j (see Fig. 5.7.14).
by Symmetry
Operations z

Ha Hb y
Fig. 5.7.14 q = 90°, j = 270° q = 90°, j = 90°
Orientation of
water molecule x

Identity operation No effect on q and j.

Rotation (clockwise) operation If the rotation axis coincides with the z-axis
(Fig. 5.7.14), then q remain unaltered and j changes to j – 360º/n, where n is the
order of rotational axis.

sxz plane: q remains the same, j changes to – j

syz plane: q remains the same, j changes to 180º – j
sxy plane: q changes to 180º – q, j remains the same

Effects on cos j The effect on cos j and sin j are as follows.

and sin j C2 Operation C2 cos j = cos (j – 180º) = – cos j
C2 sin j = sin (j – 180º) = – sin j

sxz Operation sxz cos j = cos (– j) = cos j

sxz sin j = sin (– j) = – sin j
syz Operation syz cos j = cos (180º – j) = – cos j
syz sin j = sin (180º – j) = sin j
572 A Textbook of Physical Chemistry

Effect on px The effect on px orbitals are as follows.

Orbital E(px) = (+ 1)px
C2(px) = C2(sin q cos j) = – sinq cos j = (–1)px
sxz(px) = sxz(sin q cos j) = sinq cos j = (+1)px
syz(px) = syz(sin q cos j) = – sinq cos j = (–1)px
Effect on py E(py) = (+ 1)py
Orbital C2(py) = C2(sin q sin j) = – sin q sin j = (– 1)py
sxz(py) = sxz(sin q sin j) = – sin q sin j = (– 1)py
syz(py) = syz(sin q sin j) = sin q sin j = (+ 1)py
Effect on pz Since pz orbital does not include angle j, we will have
Orbital E(pz) = (+ 1)pz ; C2(pz) = (+ 1)pz
sxz(pz) = (+ 1)pz; syz (pz) = (+ 1)pz
The above facts can also be visualized by carrying out the symmetry operations
on the orbital diagrams of px, py and pz orbital. Figure 5.7.15 displays these effects
for px and py orbitals.
px z

– + – + x + –
E C2

Ha Hb Ha Hb Hb Ha
(+1) px px (–1) px
s (xz) s (yz)

– + + –

Hb Ha Ha Hb
(+1) px (–1) px

py z

+ + –
x
– E – C2 +

Ha Hb Ha Hb Hb Ha
(+1) py py (–1) py
s (xz) s (yz)

– +

+ –

Ha Hb Ha Hb
(–1) py (+1) py

Fig. 5.7.15 Effect of symmetry operations on px and py orbitals of oxygen in water

 Molecular Symmetry and Its Applications 573

Transformation The transformation matrices (which is 1 ¥ 1) of the point group C2v based on p
Matrices orbitals are as follows
C2v E C2 sxz syz
+1 +1 +1 +1 pz
+1 –1 +1 –1 px
+1 –1 –1 +1 py

EXAMPLES OF d ORBITALS (SULPHUR DIOXIDE MOLECULE)

Considering the d orbitals of sulphur in SO2, we write the angular portions of
these orbitals.
d 2 z 2 - x 2 - y 2 d z 2 = 3 cos2 q – 1 dxz = sin q cos q cos j

d x2 - y 2 = sin2 q cos 2j dyz = sin q cos q sin j

2
dxy = sin q sin 2j
Note: The subscripts to the d orbitals correspond to the respective angular
dependence. Exception is d 2 which actually corresponds to d 2 z 2 - x 2 - y 2 .
z
Effect on sin 2j The effects on cos 2j and sin 2j are as follows.
and cos 2j C2 Operation C2 (cos 2j) = cos 2(j – 180º) = cos 2j
C2 (sin 2j) = sin 2(j – 180º) = sin 2j
s xz Operation sxz (cos 2j) = cos {2(– j)} = cos 2j
sxz (sin 2j) = sin {2(– j)} = – sin 2j
syz Operation syz (cos 2j) = cos 2(180º – j) = cos 2j
syz (sin 2j) = sin 2(180º – j) = – sin 2j
With these, the effect on d orbitals are as follows.
Effect on Since d z 2 orbital does not include j-dependent term, we will have
d 2 Orbital
z E( d z 2 ) = (+ 1) d z 2 C2( d z 2 ) = (+ 1) d z 2
sxz( d z 2 ) = (+ 1) d z 2 syz( d z 2 ) = (+ 1) d z 2

Effect on d x 2 - y 2 E (d x2 - y 2 ) = E(sin q cos 2j) = sin2 q cos 2j = (+ 1) d x2 - y 2

2

Orbital C2 (d x2 - y 2 ) = C2(sin2 q cos 2j) = sin2 q cos 2j = (+ 1) d x2 - y 2

sxz (d x2 - y 2 ) = sxz(sin2 q cos 2j) = sin2 q cos 2j = (+ 1) d x2 - y 2
syz (d x2 - y 2 ) = syz (sin2 q cos 2j) = sin2 q cos 2j = (+ 1) d x2 - y 2
Effect on dxy E(dxy) = E(sin2 q sin 2j) = sin2 q sin 2j = (+ 1)dxy
Orbital
C2(dxy) = C2(sin2 q sin 2j) = sin2 q sin 2j = (+ 1)dxy
sxz(dxy) = sxz (sin2 q sin 2j) = – sin2 q sin 2j = (– 1)dxy
syz(dxy) = syz (sin2 q sin 2j) = – sin2 q sin 2j = (– 1)dxy

Effect on dxz E(dxz) = E(sin q cos q cos j) = sin q cos q cos j = (+ 1)dxz
Orbital C2(dxz) = C2(sin q cos q cos j) = – sin q cos q cos j = (– 1)dxz
574 A Textbook of Physical Chemistry

sxz(dxz) = sxz (sin q cos q cos j) = sin q cos q cos j = (+ 1) dxz

syz(dxz) = syz (sin q cos q cos j) = – sin q cos q cos j = (– 1) dxz
Effect on dyz E(dyz) = E(sin q cos q sin j) = sin q cos q sin j = (+ 1) dyz
Orbital C2(dyz) = C2(sin q cos q sin j) = – sin q cos q sin j = (– 1) dyz
sxz(dyz) = sxz (sin q cos q sin j) = – sin q cos q sin j = (– 1) dyz
syz(dyz) = syz (sin q cos q sin j) = sin q cos q sin j = (+ 1) dyz
Display of The above facts can also be visualized by carrying out the symmetry operations
Operations on the d-orbital diagrams. Figure 5.7.16 displays these effects for d x 2 - y 2 , dxy, dxz
on d orbitals and dyz obitals.

dxy y y y

– + – + – +
E C2
x x x
+ – + – + –

(+1) s (xz) s (yz) (+1)

y y

+ – + –
x x
– + – +

(–1) (–1)
Fig. 5.7.16 (continued)
 Molecular Symmetry and Its Applications 575

dyz z z z

– + – + + –
E C2
y y y
+ – + – – +

(+1) s (xz) s (yz) (–1)

z z

+ – – +
y y
– + + –

(–1) (+1)

dxz z z z

+ –
Effect on dyz + E C2
Orbital – – +
– – +
–
+ +
x x x
s (xz) s (yz) (–1)
(+1)
z z

+ –
– +
– +
Fig. 5.7.16 Effect of
+ –
symmetry operations
on d orbital of sulphur x x
in SO2 (+1) (–1)

Transformation The transformation matrices (each one is 1 ¥ 1) of the point group C2v based on
Matrices d orbitals are as follows.

C2v E C2v sxz syz

+1 +1 +1 +1 d z 2 , d x2 - y 2
+1 +1 –1 –1 dxy
+1 –1 +1 –1 dxz
+1 –1 –1 +1 dyz
576 A Textbook of Physical Chemistry

POINT GROUP C3V

EXAMPLE OF p ORBITALS (AMMONIA MOLECULE)
Considering the p orbitals of nitrogen, we have
px = sin q cos j ; py = sin q sin j; pz = cos q
Effect on q and j For the various operations of the point group C3v, we have the following effects
on angle q and j.
Identity operation No effect on q and j.
Rotation operation If the rotation axis coincides with the z-axis, (see,
Fig. 5.7.17), then
q remains constant
j changes to j – m ¥ 360º/n, where n is the order of rotation axis, m is
the number of times the rotation applies
Thus, For C3, j changes to j – 120º and for C 32, j changes to j – 240º.
z

Hc N
q = 90°, j = 210°

Fig. 5.7.17 Hb Ha y
q = 90°, j = 330° q = 90°, j = 90°
Orientation of NH3
molecule
x
Let the bond N—Ha lies in the yz-plane (Fig. 5.7.17).
q remains the same while the angle j undergoes the
following changes.
syz = s NHa j changes to 180º – j
s NH b j changes to 660º – j, i.e. 300º – j
s NHc j changes to 420º – j, i.e. 60º – j
Effect on cos j The effect on cos j and sin j are as follows.
and sin j C3 Operation
1 3
cos (j – 120º) = – sin (30º – j) = – cos j + sin j
2 2
3 1
sin (j – 120º) = – sin (60º + j) = – cos j – sin j
2 2
C32 Operation
1 3
cos (j – 240º) = – cos (60º – j) = – cos j – sin j
2 2
3 1
sin (j – 240º) = sin (60º – j) = cos j – sin j
2 2
s NHa Operation
cos (180° – j) = – cos j
sin (180°) – j) = sin j
 Molecular Symmetry and Its Applications 577

s NHb Operation
1 3
cos (300º – j) = cos (60º + j) = cos j – sin j
2 2
3 1
sin (300º – j) = – sin (60º + j) = – cos j – sin j
2 2
s NHc Operation
1 3
cos (60º – j) = cos j + sin j
2 2
3 1
sin (60º – j) = cos j – sin j
2 2

Effect on px The effects on px orbital are shown in Table 5.7.5.

Orbital
Table 5.7.5 Effects on px Orbital
E(px) = px
Ê 1 3 ˆ 1 3
C3(px) = C3(sin q cos j) = sin q ÁË - cos j + sin j ˜¯ = - p x + py
2 2 2 2

Ê 1 3 ˆ 1 3
C32 (px) = C32 (sin q cos j) = sin q ÁË - cos j - sin j ˜¯ = - p x - py
2 2 2 2
s NHa (px) = s NHa (sin q cos j) = – sin q cos j = – px
Ê1 3 ˆ 1 3
s NH b (px) = s NH b (sin q cos j) = sin q ÁË cos j - sin j ˜¯ = p x - py
2 2 2 2

s NHc (px) = s NHc (sin q cos j) = sin q ÊÁ 1 cos j + 3 sin j ˆ˜ = 1 p x + 3 p y

Ë2 2 ¯ 2 2

Effect on py The effects on py orbital are shown in Table 5.7.6.

Orbital
Table 5.7.6 Effects on py orbital

E(py) = py

Ê 3 1 ˆ 3 1
Ë 2 cos j - 2 sin j ˜¯ = - 2 p y - 2 p y
C3(py) = C3(sin q sin j) = sin q Á -

Ê 3 1 ˆ 3 1
C32 (py) = C32 (sin q sin j) = sin q Á
Ë 2 cos j - 2 sin j ˜¯ = 2 p x - 2 p y

s NHa (py) = s NHa (sin q sin j) = sin q sin j = py

Ê 3 1 ˆ 3 1
s NH b (py) = s NH b (sin q sin j) = sin q ÁË - cos j - sin j ˜¯ = - px - p y
2 2 2 2

s NHc (py) = s NHc (sin q sin j) = sin q ÊÁ 3 cos j - 1 sin j ˆ˜ = 3 1

px - p y
Ë 2 2 ¯ 2 2
578 A Textbook of Physical Chemistry

Effect on pz Since pz orbital does not involve angle j, we will have

Orbital E(pz) = pz C3(pz) = pz C32 (pz) = pz
s NHa (pz) = pz s NH b (pz) = pz s NHc (pz ) = pz

Transformation The transformation matrices based on p orbitals for the point group C3v are as
Matrices follows.

C3v E C3
C32 s NHa s NH b s NHc

1 1 1 1 1 1 pz

Ê 1 3ˆ Ê 1 3ˆ Ê 1 3ˆ Ê 1 3ˆ
Ê 1 0ˆ Á -2 2 ˜ Á-2 -
2 ˜ Ê -1 0 ˆ Á 2 -
2 ˜ Á 2 2 ˜
ÁË 0 1 ˜¯ Á ˜ Á ˜ ÁË 0 1 ˜¯ Á ˜ Á ˜ (px, py)
Á 3 1˜ Á 3 1 ˜ Á 3 1 ˜ Á 3 1˜
ÁË - - ˜¯ ÁË - ˜¯ ÁË - - ˜¯ ÁË - ˜¯
2 2 2 2 2 2 2 2

EXAMPLE OF d ORBITALS (PHOSPHORUS TRICHLORIDE)

Considering the 3d orbitals of phosphorus, we have

dxy = sin2 q sin 2j 2

d z 2 = 3 cos q – 1

dxz = sin q cos q cos j d x 2 - y 2 = sin2 q cos 2j

dyz = sin q cos q sin j

Effect on cos 2j The effect on cos 2j and sin 2j are as follows.
and sin 2j
C3 Operation
1 3
cos 2(j – 120º) = – cos (60º – 2j) = – cos 2j – sin 2j
2 2
3 1
sin 2(j – 120º) = sin (60º – 2j) = cos 2j – sin 2j
2 2
C32 Operation
1 3
cos 2(j – 240º) = – cos (60º + 2j) = – cos 2j + sin 2j
2 2

3 1
sin 2(j – 240º) = – sin (60º + 2j) = – cos 2j – sin 2j
2 2
s NHa Operation
cos 2 (180° – j) = cos 2j
sin 2 (180º – j) = – sin 2j
 Molecular Symmetry and Its Applications 579

s NHb Operation
1 3
cos 2(300º – j) = – cos (60° – 2j) = – cos 2j – sin 2j
2 2
3 1
sin 2(300º – j) = – sin (60° – 2j) = – cos 2j + sin 2j
2 2
s NHa Operation

1 3
cos 2(60º – j) = – cos (60° – 2j) = – cos 2j + sin 2j
2 2

3 1
sin 2(60º – j) = sin (60° – 2j) = cos 2j + sin 2j
2 2
With these, the effect on d orbitals are as follows.
Effect on dz 2 Since d 2 orbital does not involve angle j, we will have
z
Orbital
E( d z 2 ) = d z 2 C3( d z 2 ) = d z 2 C23( d z 2 ) = d z 2

s NHa ( d z 2 ) = d z 2 s NH b ( d z 2 ) = d z 2 s NHc ( d z 2 ) = d z 2

Effect on d 2 2 The effects on d x2 - y 2 orbital are shown in Table 5.7.5.

x -y
Orbital

Table 5.7.7 Effects on d 2 2 orbital

x -y

E d x2 - y 2 = E(sin2 q cos 2j) = sin2 q cos 2j = d x2 - y 2

Ê 1 3 ˆ 1 3
C3 (d x2 - y 2 ) = C3(sin2 q cos 2j) = sin2 q ÁË - cos 2j - sin 2j ˜¯ = - d x2 - y 2 - d xy
2 2 2 2

Ê 1 3 ˆ 1 3
C32 (d x2 - y 2 ) = C32 (sin2 q cos 2j) = sin2 q Á - cos 2j + sin 2j ˜¯ = - d x2 - y 2 + d xy
Ë 2 2 2 2

s NHa (d x2 - y 2 ) = s NH (sin2 q cos 2j) = sin2 q cos 2j = d x2 - y 2

a

Ê 1 3 ˆ 1 3
s NH b (d x2 - y 2 ) = s NH (sin2 q cos 2j) = sin2 q ÁË - cos 2j - sin 2j ˜¯ = - d x2 - y 2 - d xy
b 2 2 2 2

Ê 1 3 ˆ 1 3
s NHc (d x2 - y 2 ) = s NH (sin2 q cos 2j) = sin2 q ÁË - cos 2j + sin 2j ˜¯ = - d x2 - y 2 + d xy
c 2 2 2 2
580 A Textbook of Physical Chemistry

Effect on dxy The effects on dxy are shown in Table 5.7.8.

Orbital

Table 5.7.8 Effects on dxy orbital

E(dxy) = E(sin2 q sin 2j) = sin2 q sin 2j = dxy

Ê 3 1 ˆ 3 1
C3(dxy) = C3(sin2 q sin 2j) = sin2 q Á
Ë 2 cos 2j - 2 sin 2j ˜¯ = 2
d x2 - y 2 - d xy
2

Ê 3 1 ˆ 3 1
C32 (dxy) = C32 (sin2 q sin 2j) = sin2 q Á -
Ë 2 cos 2j - 2 sin 2j ˜¯ = - 2 d x2 - y 2 - 2 d xy

2 2
s NHa (dxy) = s NHa (sin q sin 2j) = – sin q sin 2j = – dxy

2 2 Ê 3 1 ˆ 3 1
s NH b (dxy) = s NH b (sin q sin 2j) = sin q ÁË - cos j + sin 2j ˜¯ = - d x2 - y 2 + d xy
2 2 2 2

2 2 Ê 3 1 ˆ 3 1
s NHc (dxy) = s NHc (sin q sin 2j) = sin q ÁË + cos 2j + sin 2j ˜¯ = + d x2 - y 2 + d xy
2 2 2 2

Effect on dxz The effects on dxz are shown in Table 5.7.9.

Orbital

Table 5.7.9 Effects on dxz orbital

E(dxz) = E(sin q cos q sin j) = sin q cos q sin j = dxz

Ê 1 3 ˆ 1 3
C3(dxz) = C3(sin q cos q cos j) = sin q cos q Á - cos j + sin j ˜¯ = - d xz + d yz
Ë 2 2 2 2

Ê 1 3 ˆ 1 3
C32 (dxz) = C32 (sin q cos q cos j) = sin q cos q Á - cos j - sin j ˜¯ = - d xz - d yz
Ë 2 2 2 2

s NHa (dxz) = s NHa (sin q cos q cos j) = – sin q cos q cos j = – dxz

Ê1 3 ˆ 1 3
s NH b (dxz) = s NH b (sin q cos q cos j) = + sin q cos q ÁË cos j - sin j ˜¯ = d xz - d yz
2 2 2 2

Ê1 3 ˆ 1 3
s NHc (dxz) = s NHc (sin q cosq cos j) = sin q cosq ÁË cos j + sin j ˜¯ = d xz + d yz
2 2 2 2
 Molecular Symmetry and Its Applications 581

Effect on dyz The effects on dyz are shown in Fig. 5.7.10.

Orbital
Table 5.7.10 Effects on dyz orbital

E(dyz) = E(sin q cos q sin j) = sin q cos q sin j = dyz

Ê 3 1 ˆ 3 1
C3(dyz) = C3(sin q cos q sin j) = sin q cos q Á -
Ë 2 cos j - 2 sin j ˜¯ = - 2 d xz - 2 d yz

Ê 3 1 ˆ 3 1
C32 (dyz) = C32 (sin q cos q sin j) = sin q cos q Á
Ë 2 cos j - 2 sin j ˜¯ = 2
d xz - d yz
2
s NHa (dyz) = s NHa (sin q cos q sin j) = sin q cos q sin j = dyz
Ê 3 1 ˆ 3 1
s NH b (dyz) = s NH b (sin q cosq sin j) = sin q cosq Á -
Ë 2 cos j - 2 sin j ˜¯ = - 2 d xz - 2 d yz

Ê 3 1 ˆ 3 1
Ë 2 cosj - 2 d yz ˜¯ = d xz - d yz
s NHc (dyz) = s NHc (sin q cos q sin j) = sin q cos q Á
2 2

Transformation The transformation matrices based on d orbitals for the point group C3v are as follows.
Matrices

C3v E C3 C32 s NHa s NH b s NHc

1 1 1 1 1 1 d z2

Ê 1 3ˆ Ê 1 3ˆ Ê 1 3ˆ Ê 1 3ˆ
- - Á -2 - - Á-2
Ê 1 0ˆ Á 2 2 ˜ 2 ˜ Ê1 0 ˆ Á 2 2 ˜ 2 ˜
ÁË 0 1 ˜¯ Á
Á 3
˜
1 ˜
Á
Á 3 1˜
˜ ÁË 0 -1˜¯ Á
Á 3 1 ˜
˜ Á
Á 3
˜
1 ˜
(d x2 - y 2
, d xy )
ÁË - ˜¯ ÁË - - ˜¯ ÁË - ˜ ÁË ˜
2 2 2 2 2 2 ¯ 2 2 ¯

Ê 1 3ˆ Ê 1 3ˆ Ê 1 3ˆ Ê 1 3ˆ
- Á-2 - -
Ê 1 0 ˆ Á 2 2 ˜ 2 ˜ Ê -1 0 ˆ Á 2 2 ˜ Á 2 ˜
ÁË 0 1 ˜¯ Á ˜ Á ˜ ÁË 0 1 ˜¯ Á ˜ Á
2
˜ (d xz , d yz )
Á 3 1˜ Á 3 1 ˜ Á 3 1 ˜ Á 3 1˜
ÁË - - ˜¯ ÁË - ˜¯ ÁË - - ˜¯ ÁË - ˜¯
2 2 2 2 2 2 2 2

5.8 REDUCIBLE AND IRREDUCIBLE REPRESENTATIONS

Section 5.7 describes a few bases of representations of symmetry operations of a

and irreducible representations.

The C31 representation of the point group C3v based on the bond vectors of NH3
molecule is
Ê0 0 1ˆ
A = Á1 0 0˜
Á ˜
Ë0 1 0¯
582 A Textbook of Physical Chemistry

Let this matrix be subjected to a similarity transformation X – 1AX where the matrix
X is given by
Ê -2 3 x 0 -1 3 y ˆ
Á
X = 1 3 x -1 3 x -1 3 y ˜
Á ˜
ÁË -1 3 x 1 3 x -1 3 y ˜¯

where x = 2/3 and y = 1/3 . The matrix X –1 is the inverse of matrix X (by
XX – 1 = E) and is given by
Ê -x x 2 x 2 ˆ
X –1
= Á 0 - 3x 2 3x 2 ˜
Á ˜
Ë -y -y -y ¯
Thus
Ê 0 0 1 ˆ Ê -2 3 x 0 -1 3 y ˆ Ê 1 3 x 1 3x -1 3 y ˆ
Á
AX = 1 0 0 ˜ Á ˜ Á
1 3 x -1 3 x -1 3 y = -2 3 x 0 -1 3 y ˜
Á ˜Á ˜ Á ˜
Ë 0 1 0 ¯ ÁË 1 3 x 1 3 x -1 3 y ˜¯ ÁË 1 3 x -1 3 x -1 3 y ˜¯
Ê -x x 2 x 2 ˆ Ê 1 3x 1 3 x -1 3 y ˆ
–1 Á
S = X (AX) = 0 - 3 x 2 ˜ Á
3 x 2 -2 3 x 0 -1 3 y ˜
Á ˜Á ˜
Ë -y -y - y ¯ ÁË 1 3 x -1 3 x -1 3 y ˜¯

Ê -1 2 - 3 2 0 ˆ
Á ˜
= Á 3 2 -1 2 0 ˜
ÁË 0 0 1 ˜¯
A (which involves zeros along the diagonal and at the
other places distributed unsymmetrically about the diagonal) is transformed into
the matrix S (which involves zeros distributed symmetrically about the diagonal).
Moreover, the nonzero elements in the matrix S are distributed along the diagonal
into two blocks of the order 2 ¥ 2 and 1 ¥ 1, respectively.
If now the above similarity transformation involving the same matrices X and
X –1 is extended to the corresponding matrices of the remaining symmetry operations
of the point group C3v, we get

Ê0 1 0ˆ Ê -1 2 3 2 0ˆ
-1 Á ˜ Á ˜ Ê -1 2 3 2ˆ
X –1
C32
X= X 0 0 1 X =Á- 3 2 -1 2 0 ˜ ∫ Á ˜ and (1)
Á ˜ ÁË 0 Ë- 3 2 -1 2 ¯
Ë1 0 0¯ 0 1 ˜¯
Ê1 0 0ˆ Ê 1 0 0ˆ
Ê1 0 ˆ
X –1sv(1)X = X -1 Á 0 0 1 ˜ X = Á 0 -1 0 ˜ ∫ Á and (1)
Á ˜ Á ˜ Ë 0 -1˜¯
Ë0 1 0¯ Ë 0 0 1¯

Ê 0 0 1ˆ Ê -1 2 - 3 2 0 ˆ
Á ˜ Ê -1 2 - 3 2 ˆ
X –1sv(2)X = X -1 Á 0 1 0 ˜ X = Á - 3 2 1 2 0 ˜ ∫ Á ˜ and (1)
Á ˜ ÁË 0 ˜ Ë- 3 2 1 2 ¯
Ë 1 0 0¯ 0 1 ¯
 Molecular Symmetry and Its Applications 583

Ê 0 1 0ˆ Ê -1 2 3 2 0ˆ
-1 Á Á ˜ Ê -1 2 3 2ˆ
X–1
sv(3)X = X 1 0 0˜ X = Á 3 2 1 2 0˜ ∫ Á ˜ and (1)
Á ˜ ÁË 0 Ë 3 2 12 ¯
Ë 0 0 1¯ 0 1 ˜¯

involving nonzero elements along the diagonal and each one is factored into two
identically situated 2 ¥ 2 and 1 ¥
matrices are identical to the matrix representations based on the translational
vectors Tx and Ty (taken together) and Tz, respectively. Thus, the above similarity
transformation is equivalent to changing the basis of representation from bond
vectors to translational vectors.
Since the matrix A can be converted into two matrices of the lower orders by a
suitable similarity transformation, the representation depicted by the matrix A is
said to be reducible representation. If the resultant matrices cannot be reduced
further by a similarity transformation, the corresponding representation is said to
represent irreducible representation.
The irreducible representations play fundamental role in the application of symmetry
to molecular problems.
5.9 CHARACTERS OF MATRICES
c) of a square matrix of dimension n is the sum
of its diagonal elements, i.e.
n
c= Â aii (5.9.1)
i =1
It is found that the informations conveyed by the transformation matrices of any
representation is contained in the character of these matrices.
There are two theorems concerning the behaviour of characters. These are as
follows.
Theorem 1 If C = AB and D = BA, then the characters of C and D are identical.

n n
Ê n
ˆ
Character of C =  Cii =  ÁË Â aik bki ˜¯
i =1 i =1 k =1

n
Ê n
ˆ
=  ÁË Â bki aik ˜¯ (Product of two numbers is commutative)
i =1 k =1

n
Ê n
ˆ
=  ÁË Â bki aik ˜¯ (Order of summation is immaterial)
k =1 i =1

n
= Â dkk = Character of D (5.9.2)
k =1
584 A Textbook of Physical Chemistry

Theorem 2 Conjugate matrices have identical characters.

The conjugate matrices A and B are related to each other by the expression
B = X – 1AX
where X is a square matrix such that the product of X – 1 and X yields a unit matrix
E, i.e. X–1X = E. Let we represent C = AX and Y = X –1. Hence B = YC. Now
n n
Ê n ˆ n n
Ê n ˆ
Character of B =  ii  Á  ik ki ˜   ik Á  akj x ji ˜
b = y c = y
i =1 i =1 Ë k =1 ¯ i =1 k =1 Ë j =1 ¯

n n n n n
Ê n
ˆ
=    yik akj x ji =   akj ÁË Â x ji yik ˜¯
i =1 k =1 j =1 k =1 j =1 i =1

n n
= Â Â akj e jk (5.9.3)
k =1 j =1

Since E is a unit matrix, we will have

ejk = djk djk = 1 when j = k
djk = 0 when j π k (5.9.4)
With this, we can write the above expression as
n
Character of B = Â akk = character of A (5.9.5)
k =1

Since reducible representation and irreducible representation are related to each

other through similarity transformation, their characters are identical.

5.10 THE GREAT ORTHOGONALITY THEOREM

The elements of the matrices which constitute the irreducible representations of a

group follow ‘the great orthogonality theorem’ which is stated as follows.

h
 R [G i ( R )mn ][G j ( R )m¢n¢ ]
*
=
I i I j dij dmm¢ dnn¢ (5.10.1)

where
(i) The summation R represents the summation of various operations in a group.
(ii) Gi (R)mn represents the matrix element Rmn of the matrix R representing Rth
symmetry operation of the ith representation of a group.

(iii) [G j ( R )m ¢ n ¢ ]* represents the complex conjugate of the matrix element Rm¢n¢ of

the matrix R representing Rth symmetry operation of the jth representation
of a group.
 Molecular Symmetry and Its Applications 585

(iv) h is the order of a group which is equal to the number of symmetry operations
in a group.
(v) Ii and Ij are the dimensions of the ith and jth representations (which respectively
are equal to the order of the corresponding matrices) of a group.
(vi) dij stands for Kronecker delta. Its value is 1 if i = j, and is zero if i π j.
Simpler Forms of In the simpler forms, Eq. (5.10.1) may be written as
Eq. (5.10.1)
(i) Â R Gi ( R )mn G j ( R )mn = 0 if i π j
This implies that the sum of the products of the corresponding elements of
matrices of the various symmetry operations belonging to two different irreducible
representations is zero.
Illustration The irreducible representations of water based on the translational
vectors are
C2v E C2 s (xz) s (yz)
+1 –1 +1 –1 Tx
+1 –1 –1 +1 Ty
+1 +1 +1 +1 Tz

Taking Gx and Gy representations, we have

Gx(E) Gy(E) + Gx(C2) Gy(C2) + Gx(sxz) Gy(sxz) + Gx(syz) Gy(syz)

= (+ 1) (+1) + (–1) (–1) + (+1) (– 1) + (– 1) (+1) = 0

Similarly, it can be shown that sum is zero for each of the two representations
(Gx and Gz ), and (Gy and Gz ).

(ii) Â R Gi ( R )mn Gi ( R )m¢ n¢ = 0 if m π m¢ and/or n π n¢.

This implies that the sum of the products of two corresponding different elements
of matrices of the various symmetry operations belonging to the same irreducible
representation is zero.
Illustration The irreducible representation of the point group C3v based on the
translational vectors (Tx and Ty) is

C3v E C31 C32 sv ¢ sv≤ sv¢≤

Ê 1 0 ˆ Ê -1 2 - 3 2 ˆ Ê -1 2 3 2 ˆ Ê 1 0 ˆ Ê -1 2 - 3 2 ˆ Ê -1 2 3 2ˆ
ÁË 0 1 ˜¯ Á ˜ Á ˜ Á ˜ Á ˜ Á ˜ (Tx, Ty)
Ë 3 2 -1 2 ¯ Ë - 3 2 -1 2 ¯ Ë 0 -1¯ Ë - 3 2 1 2 ¯ Ë 3 2 12 ¯
586 A Textbook of Physical Chemistry

Taking matrix elements (1, 1) and (1, 2), we have

E(1, 1) E(1, 2) + C31 (1, 1) C31 (1, 2) + C32 (1, 1) C32(1, 2)
+ sv¢(1, 1)sv¢(1, 2) + sv≤(1, 1)sv≤ (1, 2) + sv¢≤ (1, 1)sv¢≤ (1, 2)

= 1 ¥ 0 + (–1/2)(– 3 /2) + (–1/2)( 3 /2) + 1 ¥ 0 + (–1/2)(– 3 /2)

+ (–1/2)( 3 /2) = 0
Similarly working for other pairs (1, 1) and (2, 1), and (1, 1) and (2, 2), and

(iii) Â R G i( R )mn G i( R )mn = hi/Ii

This implies that the sum of square of the corresponding element of matrices
of the various symmetry operations belonging to the same irreducible
representation is equal to order of the point group divided by the dimension
of matrices of the irreducible representation.
Illustration Taking the element (1, 1) of the matrices of irreducible representations
of the point group C3v
{E(1, 1)}2 + {C31 (1, 1)}2 + {C32 (1, 1)}2 + {sv¢(1, 1)}2 + [sv≤(1, 1)}2
+ {sv¢≤ (1, 1)}2 = h/I
i.e. 12 + (– 1/2)2 + (– 1/2)2 + 12 + (– 1/2)2 + (–1/2)2 = 3 = 6/2

is equal to 3.

5.11 CHARACTERISTICS OF IRREDUCIBLE REPRESENTATIONS

Rule 1 The following characteristics hold good for irreducible representations.

The sum of the squares of characters of identity operations of the irreducible
representations of a group is equal to the order of the group, that is

 i [ ci( E )]2 =h (5.11.1)

The irreducible representation of an identity operation involves + 1 in one-
dimensional representation or +1 along the diagonal of its matrix representation.
Thus, the character of identity operation will be equal to the order of its
representation. Hence, this rule may be stated as follows.
The sum of squares of the dimensions of the irreducible representations of a group
is equal to the order of the group, that is

 i Ii2 =h (5.11.2)
Rule 2 The sum of the squares of the characters of symmetry operations in any irreducible
representations equals h, that is

 R [ ci( R )]2 = hi (5.11.3)

 Molecular Symmetry and Its Applications 587

Explanation This rule follows from ‘The Great Orthogonality Theorem’:

h
 R [G i( R )mn ][G j ( R )m¢ n¢ ] = Ii I j
dij dmm¢ dnn¢ (Eq. 5.11.1)

For the same representation i = j

For the diagonal elements m = n and m¢ = n¢
For the above conditions, Eq. (5.11.1) is reduced to
h
 R [G i( R )mm ] [G i( R )m¢ m¢ ] = I dmm¢
i

Carrying out the summation over m and m¢ gives

h
 R ÈΠm G i( R )mm ˘˚ ÈΠm¢ G i( R )m¢ m¢ ˘˚ = I i ( m  m¢ δ mm¢ )
i

h
or  R c i ( R ) c i ( R ) = I i Ii
i

 R [ c i ( R )]
2
or = hi

Rule 3 The sum of products of corresponding characters of two different irreducible

representations is equal to zero, that is

 R ci( R ) c j ( R ) = 0 when i π j. (5.11.4)

Explanation This rule follows from ‘The Great Orthogonality Theorem’.
For two different representations i π j.
For the corresponding elements in two different representations
m = m¢ and n = n¢

For the diagonal elements m = n and m¢ = n¢.

For these facts, Eq. (5.10.1) is reduced to

 R [G i( R )mm ][G j ( R )mm ] = 0 for i π j.

Carrying summation of m for the two representations, we get

 R ÈΠm G i( R )mm ˘˚ ÈΠm G j ( R )mm ˘˚ =0 for i π j.

 R ci( R ) c j ( R ) =0 for i π j.
Note: Rules 2 and 3 can be written together by the expression

 R ci( R ) c j ( R ) = hi dij (5.11.5)

Rule 4 In a given representation (reducible or irreducible) the characters of all matrices
belonging to the symmetry operations in the same class are identical.
588 A Textbook of Physical Chemistry

Explanation This follows from the fact that the representations of the operations
in the same class are conjugate to one another through similarity transformations.
Moreover, the characters of the representations remain unaltered in a similarity
transformation.
Rule 5 The number of irreducible representations of a group is equal to the number of
classes in the group.
5.12 WORKED OUT EXAMPLES OF IRREDUCIBLE REPRESENTATIONS OF A GROUP

Irreducible ∑ The group C2v includes four symmetry operations, namely, E, C2, s (xz) and
Representations s(yz), and each one constitutes a separate class.
of the Point According to Rule 5, the group C2v will have four irreducible representations.
Group C2v
∑ According to Rule 1, we will have
 i Ii2 =h (Eq. 5.11.1)
Since h = 4, we have
I12 + I22 + I32 + I42 = 4
Obviously, we will have
I1 = I2 = I3 = I4 = 1
that is, each of the four irreducible representations of the point group C2v is
one-dimensional.
∑ Rule 2 states that

 R [ ci( R )]2 =h (Eq. 5.11.3)

Hence, the characters of representations in any one irreducible representation
will be either equal to + 1 or – 1, i.e.
ci (R) = ± 1.
∑ Let one of the representations has c (R) = +1 for each operation R, i.e.
E C2 s (xz) s(yz)
G1 1 1 1 1

Rule 3 states that

 R c i ( R ) c j( R )
=0 (Eq. 5.11.4)
This implies that each of the remaining three irreducible operations has two
+ 1’s and two – 1’s as the characters. Since the character of identity operation
is always + 1, we have to distribute one + 1 and two –1’s in the remaining three
operations, namely, C2, s (xz) and s(yz). Hence, we will have
C2v E C2 s(xz) s(yz)
G1 1 1 1 1
G2 1 1 –1 –1
G3 1 –1 1 –1
G4 1 –1 –1 1
 Molecular Symmetry and Its Applications 589

This is often stated as that the two irreducible representations of a group are
orthogonal to each other.
Irreducible ∑ The elements of the point group C3v are E, C31, C32, sv (1), sv(2) and sv(3).
Representations These belong to three classes, elements of which are E, 2C3 and 3sv.
of the Point ∑ Rule 5 states that the point group C3v will have three irreducible representations.
Group C3v
∑ Rule 1 states that
I12 + I22 + I32 = h = 6
The only possibility satisfying the above expression is 1, 1 and 2, i.e. there are
two one-dimensional representations and one two-dimensional representation.
∑ Rule 2 states that

 R [ ci( R )]2 =h
One of the irreducible representations will have + 1 as the character for each of
six symmetry operations, i.e.
E 2C3 3sv
G1 1 1 1

such that [ c (E)]2 + 2[ c (C3)]2 + 3[ c (s v)]2 = 12 + 2 ¥ 12 + 3 ¥ 12 = 6

∑ Rule 3 states that

 R ci( R ) c j ( R ) =0 when iπj

We are looking for two other representations, each one of which is orthogonal
to the representation G1 listed above. One of the possibilities that there are three
+ 1’s and three – 1’s as the characters. Since all the symmetry operations in a
class has the same character, we will have
E 2C3 3sv
G2 1 1 –1
∑ We are left with only one more representation of dimension 2. Since the matrix
corresponding to identity operation has + 1 in each of its diagonal elements,
we will have
c(E) = 2
∑ The characters of the classes C3 and sv can be worked out by using Rule 3

(Â R c i ( R ) c j ( R ) = 0) .
For the representations 1 and 3, we get
c1(E) c3(E) + 2c1(C3) c3(C3) + 3c1(s ) c3(s) = 0
i.e. (1) (2) + 2(1) c3(C3) + 3(1) c3(s) = 0 (5.12.1)
590 A Textbook of Physical Chemistry

For the representations 2 and 3, we get

c2(E) c3(E) + 2c2(C3)c3(C3) + 3c2(s) c3(s) = 0
i.e. (1)(2) + 2(1) c3(C3) + 3(– 1) c3(s) = 0 (5.12.2)
Equations (5.12.1) and (5.12.2) may be solved for c3(C3) and c3(s), which gives
c3(C3) = – 1 and c3(s) = 0
Thus, the third representation is
E 2C3 3sv
G3 2 –1 0

The complete set of characters of irreducible representations of the group C3v is

C3v E 2C3 3sv

G1 1 1 1
G2 1 1 –1
G3 2 –1 0

5.13 RESOLUTION OF A REDUCIBLE REPRESENTATION IN TERMS OF IRREDUCIBLE

REPRESENTATIONS

As described earlier, a reducible representation of a group can be converted into

irreducible representations by a suitable similarity transformation. However, without
going into such a mathematical exercise, it is possible to determine nature and
number of irreducible representations by using the expression
1
ai =
hi
 R c( R ) ci( R ) (5.13.1)

where ai is the number of times the ith irreducible representation present in the
reducible representation. The summation is carried over all the symmetry operations
of the group of order h and c (R) and ci (R) are the characters of the operation R
in reducible and irreducible representations, respectively.
Derivation of Since the character of a matrix is not changed during a similarity transformation,
Eq. (5.13.1) we can write

c(R) = Â j a j c j(R) (5.13.2)

where c (R) is the character of the matrix corresponding to operation R in

the reducible representation, and aj is the number of times the jth irreducible
representation appear in the reducible matrix of operation R and cj (R) is the character
of the matrix corresponding to operation in the jth irreducible representation.
Multiplying Eq. (5.13.2) by ci (R) and carrying out the summation over R’s of the
group, we get
 Molecular Symmetry and Its Applications 591

 R c( R ) ci( R ) =  j a j { R ci( R ) c j ( R )}
= Â j a j hi dij (using Eq. 5.11.5)

= ai hi (only the term having i = j survives)

1
Hence ai =
hi
 R c ( R ) ci( R )
Since the characters of operations within a class are identical, we can write the
above expression as
1
ai =
hi
 C nC c (C ) ci (C ) (5.13.3)

where the summation is over the classes of a group.

Illustration One of the reducible representations of H2O molecule obtained by placing three
vectors on each atom along the Cartesian axes with atom as an origin (see, Section
5.16) is
C2v E C2 s (xz) s(yz)
G3N 9 –1 1 3
We can work out the nature and number of irreducible representations in the above
reducible representation by using Eq. (5.13.1). The irreducible representations of
the point group C2v are
C2v E C2 s (xz) s(yz)
G1 1 1 1 1
G2 1 1 –1 –1
G3 1 –1 1 –1
G4 1 –1 –1 1

Numbers of representations

1
a1 = [ c (E) ci (E) + c (C2) ci (C2) + c (sxz) ci (sxz) + c (syz) ci (syz)]
4
1
= [ 9 ¥ 1 + (– 1)(1) + (1)(1) + (3)(1)] = 3
4
1
a2 = [9 ¥ 1 + (– 1)(1) + (1)(– 1) + (3) (– 1)] = 1
4
1
a3 = [9 ¥ 1 + (– 1)(– 1) + (1)(1) + (3)(– 1)] = 2
4
1
a4 = [9 ¥ 1 + (– 1)(– 1) + (1)(– 1) + (3)(1)] = 3
4
Hence, the occurrence of G1, G2, G3 and G4 in the reducible representation G3N are
3, 1, 2 and 3, respectively. We can verify the above conclusion by writing explicitly
592 A Textbook of Physical Chemistry

C2v E C2 s (xz) s (yz)

Three times G1 3(1) 3(1) 3(1) 3(1)
One time G2 1(1) 1(1) 1(– 1) 1(–1)
Two times G3 2(1) 2(–1) 2(1) 2(–1)
Three times G4 3(1) 3(– 1) 3(–1) 3(1)
Sum 9 –1 1 3

5.14 DESCRIPTION OF A CHARACTER TABLE

A character table lists all irreducible representations of a group. The general layout
of such a table is as follows
I II
III IV V VI
where the sections I to VI are as follows.
Section I
Section II This place lists the classwise symmetry operations of the point group.
Section III This place lists the Mulliken’s symbols of the irreducible
representations. These are described in Section 5.15.
Section IV This place lists row-wise the characters of symmetry operations
(classwise) against the irreducible representations listed in Section III.
Section V This place lists the translational vectors (x, y, z) and rotational vectors
(Rx, Ry, Rz) which form the bases of irreducible representations.
Section VI This place provides information about the binary combinations of x,
y and z which form the bases of certain irreducible representations.
5.15 DESCRIPTION OF MULLIKEN SYMBOLS

∑ A one-dimensional representation is designated as A if the character of rotation

about the principal axis (rotation axis of highest order) is + 1.
If the character is –1, the representation is designed as B.
∑ The symbol A or B is subscripted by ‘1’ if the character of rotation about C2
axis perpendicular to the principal axis is +1. If C2 axis does not exist, the
s v plane should be +1.
If the character is – 1, the symbol A or B carries the subscript ‘2’.
∑ If there exists a centre of symmetry, the subscript ‘1’ or ‘2’ is appended with
‘g’ (from gerade) if the character of inversion operation is +1. It is appended
with ‘u’ (from ungerade) if the character of inversion is –1.
∑ The symbol A or B is superscripted by a single prime (¢) if the character of
sh plane is +1. If it is –1, the symbol is superscripted by a
double prime (≤ ).
 Molecular Symmetry and Its Applications 593

∑ Designation of higher-dimensional representation goes as follows.

Two-dimensional by E
Three-dimensional by T or F
Four-dimensional by G
Five-dimensional by H, and so on.
∑ A different notation is usually used for the linear groups C•v and D•h. The
symbols used here are S, P, D, F, etc., depending upon the unit 0, ± 1, ± 2,
± 3, etc., respectively, of angular momentum component about the linear
axis. Such a symbolism corresponds to the s, p d, f notation for the azimuthal
quantum number l for atoms.
The above symbols are used to represent the symmetry behaviour of normal
modes of vibration, molecular orbitals, and electronic and vibrational wave
functions.
5.16 REDUCIBLE REPRESENTATION BASED ON TRANSLATIONAL VECTORS AND ITS
RESOLUTION INTO IRREDUCIBLE REPRESENTATIONS–REVISITED

In this section, we consider an important reducible representation which is useful

in the study of molecular structure.
Three Mutually Taken each atom as the origin, we can position three vectors along the Cartesian
Perpendicular coordinates. For water molecule, it is shown in Fig. 5.16.1.
Vectors on Each z z x
Atom
O y C2 y O
Fig. 5.16.1 Three z x z z
x
z
x
mutally perpendicular
vectors on each atom of Ha y Hb y y Hb y Ha
H2O x x
The operation C2 causes the following changes.
x¢(Ha) = – x(Hb) x¢(Hb) = – x(Ha) x¢(O) = – x(O)
y¢(Ha) = – y(Hb) y¢(Hb) = – y(Ha) y¢(O) = – y(O)
z¢(Ha) = z(Hb) z¢(Hb) = z(Ha) z¢(O) = z(O)
the matrix representation of the above changes is
È x ¢(Ha ) ˘ È0 0 0 -1 0 0 0 0 0˘ È x(Ha ) ˘
Í y ¢(H ) ˙ Í0 0 0 0 -1 0 0 0 0˙ Í y (H ) ˙
Í a ˙ Í ˙Í a ˙
Í z ¢(Ha ) ˙ Í0 0 0 0 0 1 0 0 0˙ Í z (Ha ) ˙
Í ˙ Í ˙Í ˙
Í x ¢ ( H )
b ˙ Í -1 0 0 0 0 0 0 0 0˙ Í x(H b ) ˙
Í y ¢(H b ) ˙ = Í 0 -1 0 0 0 0 0 0 0˙ Í y (H b ) ˙
Í ˙ Í ˙Í ˙
Í z ¢(H b ) ˙ Í0 0 1 0 0 0 0 0 0˙ Í z (H b ) ˙
Í x ¢( O ) ˙ Í0 0 0 0 0 0 -1 0 0˙ Í x( O ) ˙
Í ˙ Í ˙Í ˙
Í y ¢( O ) ˙ Í0 0 0 0 0 0 0 -1 0˙ Í y( O) ˙
Í z ¢( O ) ˙ Í0 1 ˙˚Í z( O) ˙
Î ˚ Î 0 0 0 0 0 0 0 Î ˚
new coordinates transformation matrix original coordinates
594 A Textbook of Physical Chemistry

The character of the above transformation matrix is – 1.

Instead of writing explicitly the transformation matrix of each operation, one can
determine its character by the following observations.
∑ If an atom and its associated vectors are shifted to a different position in
space by any symmetry operation, then the corresponding diagonal positions
include only zeros and thus their contributions towards the character of the
transformation matrix is zero.
∑ If an atom remains unshifted in a symmetry operation, the corresponding
diagonal positions include nonzeros and their contributions towards the
character of the transformation matrix is nonzero.
Thus, the working procedure to determine the character of transformation of
an operation ( ) is to count the number of unshifted
atoms and determine the corresponding affects on the vectors following the rules
given below.
Guidelines We now list the guidelines to determine character for a given symmetry operation
to Determine on a molecule.
Characters Identity Operation All atoms and also their vectors remain unshifted. For each
atom, there will be +1 for each of the three vectors along the diagonal of the
transformation matrix and hence its contribution towards character is +3 for each
atom.
Inversion Operation The effect of inversion is the reversal of direction of vectors
on each atom. Hence, for each unshifted atom, the contribution towards the character
is – 1 for each vector and a total of –3 for all the three vectors.

remain unaltered. Hence, the contribution per atom towards character is +1(= +1
+1 –1).
Rotation Operation The effect of clockwise rotation about the z-axis by an angle
q is expressed as
Ê x¢ ˆ Ê cos q sin q 0 ˆ Ê x ˆ
Á y ¢ ˜ = Á - sin q cos q 0 ˜ Á y ˜
Á ˜ Á ˜Á ˜
Ë z¢ ¯ Ë 0 0 1¯ Ë z ¯
Hence, the contribution towards character of an unshifted atom is 1 + 2 cos q.
Improper Rotation The effect of clockwise rotation about the z-axis followed by
z-axis is expressed as
Ê x¢ ˆ Ê cos q sin q 0 ˆ Ê xˆ
Á y ¢ ˜ = Á - sin q cos q 0 ˜ Á y˜
Á ˜ Á ˜Á ˜
Ë z¢ ¯ Ë 0 0 -1¯ Ë z¯
Hence, the contribution towards character of an unshifted atom is – 1 + 2 cos q.
With the above guidelines, we can tabulate the reducible representation of a group.
 Molecular Symmetry and Its Applications 595

Example of Water For water (point group C2v), we have

C2v E C2 s xz syz
Unshifted atom 3 1 1 3
(all the three atoms) (oxygen atom) (oxygen atom) (all the three atoms)
G3N 3(+ 3) = 9 1(1 + 2 cos 180º ) = – 1 1(+ 1) = + 1 3(+ 1) = + 3

Example of NH3 For NH3 (point group C3v) we have

C3v E 2C3 3s v
Unshifted atoms 4 1 2
Ê all the ˆ Ê nitrogen ˆ Ê nitrogen atom andˆ
ÁË four atoms˜¯ ÁË atom ˜¯ ÁË one of H atoms ˜¯

G3N 4(+ 3) = 12 1(1 + 2 cos 120º) = 0 2(+ 1) = + 2

Reduction into
Irreducible representations contained in it by using the expression
Representations 1
ai =
hi
 C nC c (C ) ci (C ) (Eq. 5.13.3)

Irreducible For H2O (point group C2v), we have

Representations of Reducible representation Irreducible Representations
Water
E C2 s v(1) s v(2) E C2 sv(1) sv(2)
G3N 9 –1 1 3 A1 1 1 1 1
A2 1 1 –1 –1
B1 1 –1 1 –1
B2 1 –1 –1 1

1
a (A1) = [1(9) (1) + 1(–1)(1) + 1(1)(1) + 1(3)(1)] = 3
4
1
a (A2) = [1(9) (1) + 1(–1)(1) + 1(1)(–1) + 1(3)(–1)] = 1
4
1
a (B1) = [1(9)(1) + 1(–1)(–1) + 1(1)(1) + 1(3)(–1)] = 2
4
1
a (B2) = [1(9)(1) + 1(–1)(–1) + 1(1)(–1) + 1(3)(1)] = 3
4
Hence G3N = 3A1 + A2 + 2B1 + 3B2 (5.16.1)
Irreducible For NH3 (point group C3v), we have
Representations of Reducible representation Irreducible representations
Ammonia
C3v E 2C3 3s v C3v E 2C3 3sv
Unshifted 4 1 2 A1 1 1 1
atoms
A2 1 1 –1
G3N 12 (1+2cos 120º) = 0 2 E 2 –1 0
596 A Textbook of Physical Chemistry

1
a (A1) = [(1) (12)(1) + (2) (0) (1) + 3(2)(1)] = 3
6
1
a (A2) = [(1) (12)(1) + 2(0) (1) + 3(2) (– 1)] = 1
6
1
a (E) = [(1) (12)(2) + 2(0)(– 1) + 3(2)(0)] = 4
6
Hence G3N = 3A1 + A2 + 4E (5.16.2)
Problem 5.16.1 Work out the reducible representation of methane based on the three translational vectors
on each atom and resolved into irreducible representations.
Solution For CH4(point group Td), we have
Reducible representation
Td E 8C 3 3C2 6S4 6sd
No. of unshifted
atoms 5 2 1 1 3

Ê carbon atom ˆ Ê carbon atomˆ

Ê all the ˆ Á and one ˜ Ê carbon ˆ Ê carbon ˆ Á and two ˜
ÁË five atoms˜¯ Á ˜ ÁË atom ˜¯ ÁË atom ˜¯ Á ˜
Ë of H atoms ¯ Ë H atoms ¯
G3N 15 0 –1 –1 3
Irreducible representations from the character table
E 8C3 3C2 6S4 6s d
A1 1 1 1 1 1
A2 1 1 1 –1 –1
E 2 –1 2 0 0
T1 3 0 –1 1 –1
T2 3 0 –1 –1 1
Thus, we have
1
a (A1) = [1(15) (1) + 8(0)(1) + 3(–1)(1) + 6(–1)(1) + 6(3)(1)] = 1
24
1
a (A2) = [1(15) (1) + 8(0)(1) + 3(–1) (1) + 6(–1) (– 1) + 6(3)(–1)] = 0
24
1
a (E) = [1(15) (2) + 8(0)(– 1) + 3(– 1)(2) + 6(–1) (0) + 6(3)(0)] = 1
24
1
a (T1) = [1(15)(3) + 8(0)(0) + 3(–1)(–1) + 6(–1) (1) + 6(3)(–1) = 1
24
1
a (T2) = [1(15) (3) + 8(0)(0 ) + 3(–1)(–1) + 6(–1)(–1) + 6(3)(1)] = 3
24
Hence, G3N = A1 + E + T1 + 3T2 (5.16.3)
Problem 5.16.2 Work out the reducible representation of trans-N2F2 on the basis of three translational vectors
on each atom and resolve them in irreducible representations.
Solution The structure of N2F2 is
 Molecular Symmetry and Its Applications 597

It belongs to the point group C2h. For this molecule, we have

Reducible representation
C2h E C2 i sh
Unshifted atoms 4 0 0 4
G3N 12 0 0 4
Irreducible representations from the character table
C2h E C2 i sh
Ag 1 1 1 1
Bg 1 –1 1 –1
Au 1 1 –1 –1
Bu 1 –1 –1 1
1
a (Ag) = [1(12) (1) + 1(0)(1) + 1(0)(1) + 1(4)(1)] = 4
4
1
a (Bg) = [1(12)(1) + 1(0)(–1) + 1(0)(1) + 1(4)(–1)] = 2
4
1
a (Au) = [1(12)(1) + 1(0)(1) + 1(0)(–1) + 1(4)(–1)] = 2
4
1
a (Bu) = [1(12)(1) + 1(0)(–1) + 1(0)(–1) + 1(4)(1)] = 4
4
Hence G3N = 4Ag + 2Bg + 2Au + 4Bu (5.16.4)

5.17 THE PROJECTION OPERATOR

The application of group theory to simplify molecular problems involves the

construction of molecular wave functions which form the bases of irreducible
representations of the symmetry group of the molecule. Such a function is built by
the appropriate combination of atomic wave functions and is known as symmetry-
adapted linear combination (abbreviation: SALC).
The SALC’s of a molecule is built by using the
Ii Ÿ

h
Â
Pi =R
c i ( R) R (5.17.1)
where Ii is the dimension of matrices of ith irreducible representation,
h is the order of the group,
ci is the character of the matrix representing to the Rth operation in the ith
irreducible representation,

and R is the operator for the symmetry operation R.

Establishing Suppose we have an orthonormal set of functions f1(i ) , f2(i ) ,… , which form a basis
the Projection for the ith irreducible representation (of dimension Ii) of a group of order h. By
Operator
Rf s(i ) = Â t G i ( R )st ft(i ) (5.17.2)
598 A Textbook of Physical Chemistry

� on one of the functions f (i )

which implies that the result of symmetry operation R s
is obtained by carrying out the summation of the product of the elements of sth row
of the matrix representing of the operation R in the ith irreducible representation
with the corresponding basis functions.†
*
Multiplying both sides of Eq. (5.17.2) by ÈÎG i ( R )s¢t ¢ ˘˚ and summing over all
operations in the group, we get

 R ÈÎG i ( R )s¢t ¢ ˘˚  R  t ÈÎG i ( R )s¢t ¢ ˘˚ G i ( R )st ft(i )

*� *
R f s(i ) =

Since the functions fs(i)’s are independent of the operation, we can rewrite the right
side of the above expression as

 R ÈÎG i( R )s¢t ¢ ˘˚  t ft(i ) ( R ÈÎG i ( R )s¢t ¢ ˘˚ )

*� *
R f s(i ) = G i ( R )st

which on using ‘The Great Orthogonality theorem’ becomes

(i ) È ˘
Ât f
h
 R ÈÎG i ( R )s¢t ¢ ˘˚
* � f (i ) =
R s t Í δ ss¢ δ tt ¢ ˙
I
Î i ˚
On carrying out the summation over t, only the term for which t = t¢ survives.
Hence, we get
Ii
 R ÈÎG i( R )s¢t ¢ ˘˚
* � (i )
Rf s = ft(¢i ) δ ss¢ (5.17.3)
h

Â
(i ) I *
P� s¢t ¢ = i ÈÎGi ( R )s¢t ¢ ˘˚ R� (5.17.4)
h R

we can write Eq. (5.17.3) as

(i )
P� s ¢t ¢f s(i ) = ft(¢i ) δ ss ¢ (5.17.5)

For s = s¢, the above expression becomes

(i )
P� s ¢t ¢f s(i¢ ) = ft(¢i ) (5.17.6)

†
For example, the C3 operation of the point group C3v over the coordinates x(= j 1),
y (= j2) and z (= j3) is represented as
È x¢ ˘ È - 1 2 - 3 2 0˘ È x ˘
Í y¢ ˙ = Í ˙Í ˙
Í ˙ Í 3 2 - 1 2 0˙ Í y ˙
ÍÎ z ¢ ˙˚ Í 0 1˙˚ ÍÎ z ˙˚
Î 0

In Eq. (5.17.2), if s = 1, then � 3f (i ) = G (C ) f (i ) + G (C ) f (i ) + G (C ) f (i )

C 1 i 3 11 1 i 3 12 2 i 3 13 3

which in the present case becomes

� = - 1 x - 3 y + 0( z )
Rx i.e. x¢ =
1
(- x - 3 y )
2 2 2
 Molecular Symmetry and Its Applications 599

� (si¢)t ¢ over the function

Equation (5.17.6) implies that the application of the operator P
f s(i¢ ) ft(¢i ) .
Illustration of Equation (5.17.6) may be illustrated by taking an example of the group C3v. If x
Eq. (5.17.6) and y coordinates form the basis of E representation, then the matrices representing
different symmetry operations (see Table 5.7.2) are as follows.

C3; -1 2 - 3 2 C32 ; -1 2
1 0 3 2
E;
0 1 3 2 -1 2 - 3 2 -1 2

-1 2 - 3 2
s v¢≤; -1 2
1 0 3 2
s v¢; s v≤;
0 -1 - 3 2 12 3 2 12

The effects of symmetry operations on x, y and z are as follows.

x y z
E x y z
C3 - (1 2) x - ( 3 2) y ( 3 2) x - (1 2) y z

C32 - (1 2) x + ( 3 2) y - ( 3 2) x - (1 2) y z
s¢v x –y z
sv - (1 2) x - ( 3 2) y - ( 3 2) x + (1 2) y z

s ¢v - (1 2) x + ( 3 2) y ( 3 2) x + (1 2) y z

In the present case, f1 = x and f2 = y.

In Eq. (5.17.6) if s¢ = 1 and t¢ = 1, we will ge
(E)
P� f = f
11 1 i.e 1 P� 11 x = x

È Ii
 R G ( R )11 R� ˘˚˙ x
(E)
P� 11 x = Í
Îh
Ii È Ÿ
= G ( E )11 E x + G (C3 )11 C � 3 x + G (C 2 ) C �2
Î 3 11 3 x
h
+ G (s v¢ )11 s�v¢ x + G (s v¢¢)11 s�v¢¢ x + G (s v¢¢¢)11 s�v¢¢¢ x ˘˚
2 È Ê 1 ˆÊ 1 3 ˆ Ê 1 ˆÊ 1 3 ˆ
= ÍÎ(1) x + Ë- ¯ÁË - x - y˜ + - Á - x + y˜
6 2 2 2 ¯ Ë 2 ¯Ë 2 2 ¯
Ê 1 ˆÊ 1 3 ˆ Ê 1 ˆÊ 1 3 ˆ˘
+ (1) x + Ë- ¯ÁË - x - y ˜¯ + Ë- ¯ÁË - x + y˜ ˙
2 2 2 2 2 2 ¯˚
2È 1 3 1 3 1 3 1 3 ˘
= ÍÎ x + x + y+ x- y+ x+ x+ y+ x- y˙
6 4 4 4 4 4 4 4 4 ˚
2
= (3x) = x
6
600 A Textbook of Physical Chemistry

Similarly, it can be shown that

P� 12 f = f
1 2 i.e P� 12 x = y
P� 21 f2 = f1 i.e P� 21 y = x
P� 22 f = f
2 2 i.e P� 22 y = y

The expressions P� 12 f2, P� 21 f1, P� 11 f2 and P� 22 f1 will each be equal to zero as the
condition of s = s¢
as shown for the one typical case of P� 11 f2.
I
P� 11f2 = P� 11 y = i
h
 R G ( R )11 R� y
Ii ( ) � � 3 y + G (C 2 ) C �2
= ÈÎG E 11 Ey + G (C3 )11 C 3 11 3 y + G (s v¢ )11 s v¢ y
�
h
+ G (s v¢¢)11 s�v¢¢y + G(s v¢¢¢)11 s� ˘
v¢¢¢ y ˚

2È Ê 1ˆ Ê 3 1 ˆ Ê 1ˆ Ê 3 1 ˆ
= ÍÎ(1) y + Ë- ¯ ÁË x - y ˜¯ + Ë- ¯ ÁË - x - y ˜¯
6 2 2 2 2 2 2
Ê 1ˆ Ê 3 1 ˆ Ê 1ˆ Ê 3 1 ˆ
= + (1) ( - y ) + Ë- ¯ ÁË - x + y ˜¯ + Ë- ¯ ÁË x + y ˜¯
2 2 2 2 2 2
2È 3 1 3 1 3 1 3 1 ˘
ÍÎ y -
= x+ y+ x+ y- y+ x- y- x - y˙
6 4 4 4 4 4 4 4 4 ˚
=0
Note: Had we taken the function x + y, even then we will have
P� 11 (x + y) = P� 11 x + P� 11 y = x + 0 = x
P� 22 (x + y) = P� 22 x + P� 22 y = 0 + y = y
This implies that f s(i¢ ) in Eq. (5.17.6) may be any arbitrary function. The effect of
ft(¢i ) if present in the
function, otherwise the result will be zero.
Projection In Eq. (5.17.4), the
Operator in Terms the matrices of symmetry operations. It is advantageous to express the
of Characters operator in terms of characters, since these are normally available in a character
table. For one-dimensional representations, Eq. (5.17.4), in fact, involves characters
as the matrices are of 1 ¥ 1 dimensions.
For two- and three-dimensional representations, we can write
(i ) I
P�i =  s¢ P� s¢ ,s¢ = i  s¢  R [G i ( R )s¢s¢ ]* R
�
h
I
{
= i  R  s¢ [G i ( R )s¢s¢ ]* R
h
�
}
which on using Eq. (5.17.1) becomes
I
P�i = i
h
 R ci ( R) R� (5.17.7)
 Molecular Symmetry and Its Applications 601

Illustration Equation (5.17.7) may be illustrated by applying the

irreducible representations of the point group C3v to the function x + y + z.
∑ For the A1 representation, we have c (E) = 1, c(C3) = 1 and c(sv) = 1. Thus
� I � (x + y + z) + c(C ) C � (x + y + z)
PA1 (x + y + z) = A1 [c (E) E 3 3
h
� 2 (x + y + z) + c (s¢ ) s�¢ (x + y + z)
+ c (C 32) C 3 v v
� �
+c (s≤ ) s ¢¢ (x + y + z) + (s≤¢ ) s ¢¢¢ (x + y +z)]
v v v v

1È ÏÊ 1 3 ˆ Ê 3 1 ˆ ¸
= ÍÎ(1)( x + y + z ) + (1) ÌÓÁË - x - y ˜¯ + ÁË x - y ˜¯ + z ˝
6 2 2 2 2 ˛

{ Ê 1
+ (1) ÁË - x +
2
3 ˆ Ê
y˜ + Á -
2 ¯ Ë 2
3 1 ˆ
}
x - y ˜¯ + z + (1) ( x - y + z )
2

ÏÊ 1 3 ˆ Ê 3 1 ˆ ¸
+ (1) ÌÁË - x - y ˜¯ + ÁË - x + y˜¯ + z ˝
Ó 2 2 2 2 ˛
ÏÊ 1 3 ˆ Ê 3 1 ˆ ¸˘
+ (1) ÌÁË - x + y˜ + Á x + y˜¯ + z ˝˙
Ó 2 2 ¯ Ë 2 2 ˛˚
1
= (6z) = z
6
Hence, the 1 z
(and not x and y). Hence, the coordinate z forms the basis of A1 representation.
∑ For the E representation, we have c (E) = 2, c (C3) = – 1 and c (sv) = 0. Thus
I
P�E (x + y + z) = E ÈÎ c ( E ) E
� ( x + y + z ) + c (C ) C
3
� 3 (x + y + z)
h

+ c (C32 ) C
� 32 ( x + y + z ) + c (s¢v) s�v¢ (x + y + z)

+ c (s≤v ) s�v¢¢ (x + y + z) + c (s≤¢ �

v ) s v¢¢¢ (x + y + z)]

2È ÏÊ 1 3 ˆ Ê 3 1 ˆ ¸
= Í( 2) ( x + y + z ) + ( -1) ÌÁË - x - y ˜¯ + ÁË x - y ˜¯ + z ˝
6Î Ó 2 2 2 2 ˛
ÏÊ 1 3 ˆ Ê 3 1 ˆ ¸˘
+ ( -1) ÌÁË - x + y ˜¯ + ÁË - x - y ˜¯ + z ˝˙
Ó 2 2 2 2 ˛˚
2
= (3x + 3y) = x + y
6
Thus, the x
and y (and not z). Thus, x and y taken together form the bases of E representation.
From the above two illustrations, it is obvious that the
applied to a function annihilates the element that does not contribute to a given
irreducible representation.
602 A Textbook of Physical Chemistry

5.18 WORKED OUT EXAMPLES OF SALC’s AND MO’s

A BENT AX2 MOLECULE (EXAMPLE: H2O)
A bent AX2 molecule belongs to the point group C2v. The common example is
H2O molecule (Fig. 5.18.1).
z

O y
Fig. 5.18.1 H2O
molecule with x
cartesian axes on
oxygen atom Ha Hb

Nature of ∑ From the character table of the group C2v

Irreducible (i) 2s(O) and 2pz(O) orbitals belong to a1 irreducible representation†
Representations
(ii) 2px (O) orbital belongs to b1 irreducible representation
(iii) 2py(O) orbital belongs to b2 irreducible representation
∑ The symmetries of possible combinations of 1s orbitals of hydrogen atoms are
determined as follows.
The reducible representation obtained on the basis of 1s(Ha) and 1s(Hb) is
C2v E C2 s (xz) s (yz)
G 2 0 0 2
Ê both the orbitals ˆ Ê orbitals exchangeˆ Ê orbitals exchangeˆ Ê both the orbitals ˆ
ÁË remain unshifted ˜¯ ÁË positions ˜¯ ÁË positions ˜¯ ÁË remain unshifted ˜¯

1
The use of reduction formula ai =
hi
 R c ( R) c i( R ) gives

1
a(a1) = [(2) (1) + (0)(1) + (0)(1) + (2)(1)] = 1
4
1
a(a2) = [(2)(1) + (0)(1) + (0)(– 1) + (2)(– 1)] = 0
4
1
a(b1) = [(2)(1) + (0)(– 1) + (0)(1) + 2(– 1)] = 0
4
1
a(b2) = [(2)(1) + (0) (– 1) + (0)(– 1) + 2(1)] = 1
4
Hence G = a1 + b2 (5.18.1)
SALC from The symmetry-adapted linear combinations of 1s(Ha) and 1s(Hb) orbitals can be
1s Orbitals of constructed by using the
Hydrogen Atoms I
P�j = j
h
 R c j ( R ) R� (5.18.2)

†
Lower case Mulliken symbols are used to represent irreducible representations for
one-electron atomic orbitals.
 Molecular Symmetry and Its Applications 603

on the generating function y 1s(Ha ) , we have

P� a1y 1s(H ) = 1 È c a ( E ) E
a
4Î 1
�y { } {
1s ( H a ) + c a1 (C2 ) C 2y 1s ( H a )
� }
+ c a1(s xz ) s� { } {
xzy 1s( H a ) + c a1(s yz ) s yzy 1s( H a ) ˚
� ˘ }
1
=
4
[(1)y 1s(Ha ) + (1)y 1s(Hb ) + (1)y 1s(Hb ) + (1)y 1s(Ha ) ]
1
i.e. j1¢ =
2
[y 1s(H ) + y 1s(H ) ]
a b

The factor 1/2 in the above expression may be ignored as it provides the relative
values resulting from the operators. The absolute values may be determined by
the normalization of the wavefunction. The expression of normalized function is
1
j1 =
2
[y 1s(H ) + y 1s(H ) ]
a b
(5.18.3)

Similarly, we have
1
P� b2 y 1s ( Ha ) = [(1)y 1s(H ) + (-1)y 1s(H ) + (-1)y 1s(H ) + (-1)y 1s(H ) ]
4 a b b a

1
i.e. j2 =
2
[y 1s(Ha ) - y 1s(Hb ) ]
The expression of normalized function is
1
j2 =
2
[y 1s(Ha ) - y 1s(Hb ) ] (5.18.4)

Molecular Orbitals The molecular orbitals of H2O can be constructed by mixing atomic orbitals of
of Water oxygen with the correct symmetry-adapted linear combination of 1s orbitals of
hydrogen atoms.

Mixing of orbitals of a1 irreducible representation

y1, 2, 3 = C1y2s(O) + C2 y 2p y ( O) + C3j1
= C1y2s(O) + C2 y 2p z ( O) + C3 [y 1s(Ha ) + y 1s(H b ) ] (5.18.5)
This combination yields three molecular orbitals, one strongly bonding, one slightly
bonding and one strongly antibonding.

Mixing of orbitals of b2 irreducible representation

y4 = C4 y 2p y ( O) + C5j2 = C4 y 2p y ( O) + C5 [y 1s(Ha ) + y 1s(H b ) ] (5.18.6)

y5 = C6 y 2p y ( O) – C7 [y 1s(Ha ) + y 1s(H b ) ] (5.18.7)

The plus combination with C4 > C5 yields bonding molecular orbital and negative
combination with C7 > C6 yields antibonding molecular orbital.

The atomic orbital y 2p x ( O) acts as nonbonding orbital.

604 A Textbook of Physical Chemistry

Correlation The correlation diagram of water is shown in Fig. 5.18.2.

Diagram of H2O
b2*

a1* b2
1s(H)
b2 a1
b1
b1
E a1 2p

a1

b2
a1
2s
Fig. 5.18.2 a1
Correlation diagram
of water O H2 O 2H

A LINEAR AX2 MOLECULE (EXAMPLE: BeH2)

A linear AX2 molecule belongs to the D•h point group. The common example is
BeH2 molecule (Fig. 5.18.3).

Fig. 5.18.3 Geometry z axis

of BeH2 Ha Be Hb

From the character table of the D•h

(i) 2s(Be) belongs to S g+ irreducible representation.
(ii) 2pz(Be) belongs to S +u irreducible representation.

(iii) 2px(Be) and 2py(Be) belong to Pu irreducible representation.

Nature of ∑ The reducible representation obtained on the basis of 1s(Ha) and 1s(Hb) is
Irreducible
Representations D•h E 2C• � •s v i 2S• � •C2
G 2 2 2 0 0 0

It is not possible to resolve the above reducible representation into irreducible

representations of the group D•h because h = •. It is, therefore, necessary to carry
out the resolution by inspection of the
+
G = s g + s u+ (5.18.8)
 Molecular Symmetry and Its Applications 605

†
SALC from that
1s Orbitals of 1
Hydrogen Atoms s g+ symmetry: j1 = [y 1s(H ) + y 1s(H ) ] (5.18.9)
a b
2
1
s u+ symmetry:
2
[y 1s(Ha ) - y 1s(Hb ) ]
j2 = (5.18.10)

where the factor 1 / 2 in each of the above two expressions is normalization

constant.
Molecular Orbitals The molecular orbitals of BeH2 can be constructed by mixing atomic orbitals of
of BeH2 beryllium with the correct symmetry-adapted linear combination of 1s orbitals of
hydrogen atoms.
+
Mixing of orbitals of s g irreducible representation We have

y1 = C1y2s(O) + C2j1 = C1y2s(O) + C2 [y 1s(Ha ) + y 1s(H b ) ] (5.18.11)

y2 = C3y2s(O) – C4j1 = C3y2s(O) – C4 [y 1s(Ha ) + y 1s(H b ) ] (5.18.12)

Mixing of orbitals of s u+ irreducible representation We have

y3 = C5 y 2p z ( Be) + C6j2 = C5 y 2p z ( Be) + C6 [y 1s(Ha ) - y 1s(H b ) ] (5.18.13)

y4 = C7 y 2p z ( Be) – C8j2 = C7 y 2p z ( Be) – C8 [y 1s(Ha ) - y 1s(H b ) ] (5.18.14)

The atomic orbitals y 2p x ( Be) and y 2p y ( Be) act as nonbonding orbitals.

Correlation The correlation diagram of BeH2 is shown in Fig. 5.18.4.

Diagram of BeH2
s u+ *

s g+ *
su+ , pu
pu

sg+
E

su+

sg+
su+
Fig. 5.18.4
sg+
Correlation diagram
of BeH2 Be BeH2 2H
†
See example of H2O.
606 A Textbook of Physical Chemistry

A PLANAR AX3 MOLECULE (EXAMPLE: BH3)

A planar AX3 molecule belongs to the D3h point group. The common example is
BH3 molecule (Fig. 5.18.5).
Hc

B Ha
Fig. 5.18.5 Geometry
of BH3
Hb

Nature of ∑ From the character table of the D3h

Irreducible (i) s(B) orbital belongs to a 1¢ irreducible representation.
Representations (ii) pz(B) orbital belongs to a 2¢¢ irreducible representation.
(iii) px(B) and py(B) orbitals belong to e¢ irreducible representation.
∑ The symmetries of possible combinations of 1s orbitals of hydrogen atoms are
determined as follows.
The reducible representation obtained on the basis of 1s(Ha), 1s(Hb) and 1s(Hc) is

D3h E 2C3 3C2 sh 2S3 3s v

G 3 0 1 3 0 1 (= number of
unshifted orbitals)
Ê One of theˆ Ê The threeˆ Ê One of the ˆ
Ê The three ˆ Ê All the threeˆ Á orbitals ˜ Á orbitals ˜ Ê All the three ˆ Á orbitals ˜
Á orbitals remain ˜ Á orbitals are ˜ Á ˜ Á ˜ Á orbitals are ˜ Á ˜
Á ˜ Á ˜ Á remains ˜ Á remain ˜ Á ˜ Á remains ˜
Ë unshifted ¯ Ë shifted ¯ ÁË unshifted ˜¯ ÁË unshifted ˜¯ Ë shifted ¯ ÁË unshifted ˜¯

1
The use of reduction formula ai = Â nC c (C ) ci (C ) gives
hi C
1
a( a1¢ ) = [1(3)(1) + 2(0)(1) + 3(1) (1) + 1(3)(1) + 2(0)(1) + 3(1)(1)] = 1
12
1
a(e¢) = [1(3)(2) + 2(0)(–1) + 3(1)(0) + 1(3)(2) + 2(0)(–1) + 3(1)(0)] = 1
12
This also follows by inspection of character table since the addition of corresponding
characters of a1¢ and e¢ gives the characters of reducible representation. Hence
G = a1¢ + e¢ (5.18.15)
SALC from The symmetry-adapted linear combinations of 1s(Ha), 1s(Hb) and 1s(Hc) orbitals
1s Orbitals of can be constructed by using the expression
Hydrogen Atoms Ij
P� jf =
h
 R c j ( R ) {R� f }
or simply by the expression
P� jf = Â c j ( R ) {R
R
� f}

normalization procedure. Taking f as y 1s(Ha ) , we get

 Molecular Symmetry and Its Applications 607

P� a1¢ y 1s(Ha ) = ÈÎ c a1 ( E ) E{
�y } È� �2 ˘
1s( H a ) + c a1 (C3 ) ÎC 3 y 1s( H a ) + C 3 y 1s( H a ) ˚

+ c a1(C2 ) ÈÎC � 2y � � ˘
1s( H a ) + C2¢ y 1s( H a ) + C2¢¢ y 1s( H a ) ˚

{ }
+ c a1(s h ) s� hy 1s(Ha ) + c a1( S3 ) ÈÎ S� 3y 1s(Ha ) + S� 3y 1s(Ha ) ˘˚
2

+ c a1 (s v ) ÈÎs�v y 1s(Ha ) + s�v¢ y 1s(Ha ) + s�v¢¢y 1s(Ha ) ˘˚

= (1)y 1s(Ha ) + (1) {y 1s(H b ) + y 1s(Hc ) }
+ (1) {y 1s(Ha ) + y 1s(H b ) + y 1s(Hc ) } + (1) y 1s(Ha )

{ }
+ (1) y 1s(H b ) + y 1s(Hc ) + (1) {y 1s(Ha ) + y 1s(H b ) + y 1s(Hc ) }
= 4 [y 1s(Ha ) + y 1s(H b ) + y 1s(Hc ) ]
The expression of normalized SALC is
1
j1 =
3
[y 1s(Ha ) + y 1s(Hb ) + y 1s(Hc ) ] (5.18.16)

The operation of P� e¢ on y 1s(Ha ) gives

P� e¢ y 1s(Ha ) = [( 2)y 1s(Ha ) + ( -1) {y 1s(H b ) + y 1s(Hc ) }

+(0) {y 1s(Ha ) + y 1s(H b ) + y 1s(Hc ) } + ( 2)y 1s(Ha )

+ (–1) {y 1s(H b ) + y 1s(Hc ) } + ( 0) {y 1s(Ha ) + y 1s(H b ) + y 1s(Hc ) }

= 4 y 1s(Ha ) - 2 y 1s(H b ) - 2 y 1s(Hc )
The expression of normalized SALC is
1
j2 =
6
[2y 1s(Ha ) - y 1s(Hb ) - y 1s(Hc ) ] (5.18.17)

Note that the SALC j 2 is orthogonal to the SALC j 1.

Since e¢ representation contains doubly generate orbitals, we may generate the
second SALC by using either of the orbitals y 1s(H b ) and y 1s(Hc ) . The operation
P� e¢ on these orbitals would give
1
j 3¢ =
6
[2y 1s(Hb ) - y 1s(Hc ) - y 1s(Ha ) ]
1
j 3¢¢ =
6
[2y 1s(H ) - y 1s(H ) - y 1s(H ) ]
c a b

But neither j 3¢ nor j 3¢¢ is orthogonal to j2. However, if we take linear combination
j 3¢ – j 3¢¢ , the resultant expression is orthogonal to j2. The expression of normalized
second orbital in e¢ representation is
1
j3 =
2
[y 1s(H ) - y 1s(H ) ]
b c
(5.18.18)
608 A Textbook of Physical Chemistry

Note: The combination j 3¢ + j 3¢¢ results into the function j 2, which may thus
be excluded.

Alternative Instead of using full symmetry of the point group C3v, the SALC’s may be derived
Procedure by using only the pure rotational symmetry, i.e. rotation about the principal axis.
In the present case, we have

{ � } � { } {
P� a y 1s(Ha ) = c a ( E ) E y 1s(Ha ) + c a (C3 ) C 3y 1s(Ha ) + c a (C3 ) C3 y 1s ( Ha )
2 � 2
}
i.e. j1¢ = (1)y 1s(Ha ) + (1)y 1s(H b ) + (1)y 1s(Hc )

j 2¢¢ = P� e¢ y 1s(Ha ) = (1)y 1s(Ha ) + ( e )y 1s(H b ) + (e *)y 1s(Hc )

j 3¢¢ = P� e¢ y 1s(Ha ) = (1)y 1s(Ha ) + (e *)y 1s(H b ) + ( e )y 1s(Hc )

where e = cos (2p/3) + i sin (2p/3) and e*= cos (2p/3) – i sin (2p/3)
The imaginary quantities in j 2¢¢ and j 3¢¢ can be removed as follows.

{
j 2¢ = j 2¢¢ + j 3¢¢ = 2y 1s(Ha ) + 2cos (2p/3) y 1s(H ) + y 1s(H )
b c
}
= 2y 1s(Ha ) - y 1s(H b ) - y 1s(Hc )

j 3¢ = j 2¢¢ - j 3¢¢ = 2 sin ( 2p / 3) {y 1s(H ) - y 1s(H ) }

i b c

= 3 {y 1s(H b ) - y 1s (Hc ) }

Molecular Orbitals The molecular orbitals of BH3 can be constructed by mixing of atomic orbitals of
of BH3 B with the correct symmetry-adapted linear combination of 1s orbitals of hydrogen
atoms.
Mixing of orbitals of a1 irreducible representations
y1 = C1y2s(B) + C2 [y 1s(Ha ) + y 1s(H b ) + y 1s(Hc ) ] (5.18.19)

y 2* = C3y2s(B) – C4 [y 1s(Ha ) + y 1s(H b ) + y 1s(Hc ) ] (5.18.20)

Mixing of orbitals of e¢ irreducible representitions

y3 = C5 ÈÎy 2 p x(B) + y 2 p y (B) ˘˚ + C6 [ 2y 1s(Ha ) - y 1s(H b ) - y 1s(Hc ) ] (5.18.21)

y4 = C5 ÈÎy 2 p x (B) - y 2 p y (B) ˘˚ + C6 [y 1s(H b ) - y 1s(Hc ) ] (5.18.22)

y *5 = C7 ÈÎy 2 p x (B) + y 2 p y (B) ˘˚ – C8 [ 2y 1s(Ha ) - y 1s(H b ) - y 1s(Hc ) ] (5.18.23)

y *6 = C7 ÈÎy 2 p x (B) - y 2 p y (B) ˘˚ – C8 [y 1s(H ) - y 1s(H ) ] (5.18.24)

b c

The orbital j 2p z ( B) acts as nonbonding molecular orbital.

 Molecular Symmetry and Its Applications 609

Correlation The correlation diagram of BH3 is shown in Fig. 5.18.6.

Diagram of BH3

Fig. 5.18.6
Correlation diagram
of BH3

A POLAR AX3 MOLECULE (EXAMPLE: NH3)

Nature of The point group of NH3 is C3v
Irreducible (i) s(N) and pz orbitals belong to a1 irreducible representation.
Representations (ii) px and py orbitals belong to e irreducible representation.
∑ The reducible representation obtained on the basis of 1s(Ha), 1s(Hb) and 1s(Hc) is
C3v E 2C3 3s v

G 3 0 1 (= number of unshifted orbitals)

Ê All the three orbitalsˆ Ê All the three orbitalsˆ Ê Oneof the 1s(H) orbitalˆ
ÁË remain unshifted ˜¯ ÁË are shifted ˜¯ ÁË remains unshifted ˜¯

∑ The use of reduction formula gives

1
a(a1) = [(3) (1) + 2(0)(1) + 3(1)(1)] = 1 (5.18.25)
6
1
a(e) = [(3) (2) + 2(0)(– 1) + 3(1)(0)] = 1 (5.18.26)
6
Thus G = a1 + e
SALC from The symmetry-adapted linear combinations of 1s(Ha), 1s(Hb) and 1s(Hc) orbitals
1s Orbitals of can be worked out and are found to be identical to those of BH3. These are:
Hydrogen Atoms 1
a1 symmetry j1 =
3
[y 1s(Ha ) + y 1s(Hb ) + y 1s(Hc ) ] (5.18.27)

1
e symmetry j2 =
6
[2y 1s(Ha ) - y 1s(Hb ) - y 1s(Hc ) ] (5.18.28)
610 A Textbook of Physical Chemistry

1
j3 =
2
[y 1s(Hb ) - y 1s(Hc ) ] (5.18.29)

Molecular Orbitals The molecular orbitals of NH3 can be constructed by mixing of atomic orbitals of
of NH3 N with the correct symmetry-adapted linear combination of 1s orbitals of hydrogen
atoms.
Mixing of orbitals of a1 symmetry Mixing of 2s(N) and 2pz(N) with the group
orbital j1 leads to the formation of three molecular orbitals.

y1 = C1y2s(N) + C2 y 2p ( N ) + C3 [y 1s(H ) + y 1s(H ) + y 1s(H ) ] (5.18.30)

z a b c

y2 = C1¢ y2s(N) – C2¢y 2 p ( N ) + C3¢ [y 1s(H ) + y 1s(H ) + y 1s(H ) ] (5.18.31)

z a b c

y3 = C1¢¢ y2s(N) – C2¢¢y 2 p (N) - C3¢¢[y 1s(H ) + y 1s(H ) + y 1s(H ) ] (5.18.32)

z a b c

Mixing of orbitals of e symmetry

y4 = C4 y 2 p x ( N ) + C5 [ 2y 1s(Ha ) - y 1s(H b ) - y 1s(Hc ) ] (5.18.33)

y5 = C4¢ y 2 p x ( N ) - C5¢ [ 2y 1s(Ha ) - y 1s(H b ) - y 1s(Hc ) ] (5.18.34)

y6 = C6 y 2 p y ( N ) + C7 [y 1s(H b ) - y 1s(Hc ) ] (5.18.35)

y7 = C6¢ y 2 p y ( N ) - C7¢ [y 1s(H b ) - y 1s(Hc ) ] (5.18.36)

Localized A molecule of ammonia may be depicted within a cube (Fig. 5.18.7). The nitrogen
Molecular atom lies at the centre of the cube which is considered to be the origin of the
Orbitals of NH3 Cartesian axes pointing towards the centres of the faces of the cube. If the edge
length of the cube is unity, the three hydrogen atoms may be considered to occupy
the positions (1/2, 1/2, 1/2), (– 1/2, 1/2, – 1/2) and (– 1/2, – 1/2, 1/2), respectively.

Hc

z
Ha

y N

Hb
Fig. 5.18.7 Ammonia x
molecule within a cube

Each of the three localized molecular orbitals in ammonia may be considered to

involve the sp3 hybrid orbital of nitrogen and 1s orbital of hydrogen atom. These
combinations may be obtained by the linear combinations of nonlocalized molecular
orbitals as shown in the following.
 Molecular Symmetry and Its Applications 611

y N - Ha = y1 + y4 + y6

= C1 y 2s( N ) + C2 y 2p z ( N ) + C4 y 2p x ( N ) + C6 y 2p y ( N )

+ (C3 + 2C5) y 1s(Ha ) + (C3 – C5 + C7) y 1s(H b )

+ (C3 – C5 – C7) y 1s(Hc )

Assuming C3 – C5 + C7 and C3 – C5 – C7 to be negligible in comparison to
C3 + 2C5, we get

y N - Ha = C1 y 2s( N ) + C2 y 2p ( N ) + C4 y 2p ( N ) + C6 y 2p y ( N ) + (C3 + 2C5) y 1s(H )

z x a

(5.18.37)
Similarly, we get
y N - H b = y1 – y4 + y6
= C1¢y 2s( N ) - C2¢ y 2 p z ( N ) - C4 y 2 p x ( N ) + C6 y 2 p y ( N )

+ ( C3¢ + C5 + C7)y 1s(H b ) (5.18.38)

y N - Hc = y1 – y4 – y6
= C1 y 2s( N ) + C2 y 2 p z ( N ) - C4 y 2 p x ( N ) - C6y 2 p y ( N )

+ (C3 + C5 + C7)y 1s(Hc ) (5.18.39)

Correlation The correlation diagrams of nonlocalized and localized molecular orbitals of NH3
Diagrams of NH3 are shown in Fig. 5.18.8.

e
y5,y7
a1
y3

2p e e
a1 2p
a1 1s
y2 a1 1s
e sp3
y4,y6
E

2s 2s
a1

a1
y1

N Ha, Hb, Hc N Ha, Hb, Hc

(a) (b)

Fig. 5.18.8 Correlation diagrams depicting (a) nonlocalized and (b) localized molecular orbitals of NH3
612 A Textbook of Physical Chemistry

MOLECULAR ORBITAL TREATMENT OF METHANE

Dipction of CH4 A molecule of methane may be depicted within a cube (Fig. 5.18.9). The carbon
Molecule atom lies at the centre of the cube which is considered to be the origin of the
Cartesian axes pointing towards the centres of the faces of the cube. If the edge
length of the cube is unity, the hydrogen atoms lie at (1/2, 1/2, 1/2), (1/2, – 1/2,
– 1/2), (– 1/2, 1/2, – 1/2) and (– 1/2, – 1/2, 1/2), respectively.

Hd

Ha

C y

Hc

Fig. 5.18.9 Methane x

molecule Hb

Valence Orbitals of The valence orbitals of carbon and hydrogen atoms to be considered for the
Molecule treatment of molecular orbitals are 2s(C), 2px(C), 2py(C), 2pz(C), 1s(Ha), 1s(Hb),
1s(Hc) and 1s(Hd), respectively.
The point group of methane is Td. The atomic orbital 2s(C) belongs to the
representation a1. The atomic orbitals 2px(C), 2py(C) and 2pz(C) belong to the
representation, t2; each of these orbitals is sent into some linear combination of
the three orbitals by each symmetry operation of the point group.

Formation of To describe the mixing of carbon orbitals with 1s orbitals of hydrogen atom, we
Molecular Orbitals form the following four group orbitals.
y ¢ = y 1s(Ha ) + y 1s(H b ) + y 1s(Hc ) + y 1s(Hd ) (5.18.40)

yx = y 1s(Ha ) + y 1s(H b ) - y 1s(Hc ) - y 1s(Hd ) (5.18.41)

yy = y 1s(Ha ) - y 1s(H b ) + y 1s(Hc ) - y 1s(Hd ) (5.18.42)

yz = y 1s(Ha ) - y 1s(H b ) - y 1s(Hc ) + y 1s(Hd ) (5.18.43)

The group orbital y ¢ behaves as A1 representation whereas yx, yy and yz behave
at T2 representations. The subscripts x, y and z indicate that the functions yx, yy
and yz have the same symmetry behaviour as x-, y- and z-coordinates, respectively,
 Molecular Symmetry and Its Applications 613

and each of the four functions is sent into some linear combinations with carbon
orbitals.
Combining the carbon orbitals with the group orbitals involving hydrogen atoms
of the appropriate symmetry results into the following eight molecular orbitals.

Molecular orbitals of A1 symmetry

y1 = C1 y 2s( C) + C2y ¢ (bonding)

= C1 y 2s( C) + C2 [y 1s(Ha ) + y 1s(H b ) + y 1s(Hc ) + y 1s(Hd ) ] (5.18.44)†

y2 = C1¢y 2s( C) – C2¢y ¢ (antibonding)

= C1¢y 2s( C) – C2¢ [y 1s(Ha ) + y 1s(H b ) + y 1s(Hc ) + y 1s(Hd ) ] (5.18.45)

Molecular orbitals of T2 symmetry

y3 = C3 y 2p x ( C) + C4yx (bonding)

= C3 y 2p x ( C) + C4 [y 1s(Ha ) + y 1s(H b ) - y 1s(Hc ) - y 1s(Hd ) ] (5.18.46)†

y4 = C3¢ y 2 p x - C4¢y x (antibonding)

= C3¢y 2 p x - C4¢ [y 1s(Ha ) + y 1s(H b ) - y 1s(Hc ) - y 1s(Hd ) ] (5.18.47)

y5 = C3 y 2p y ( C) + C4yy (bonding)

= C3 y 2p y ( C) + C4 [y 1s(Ha ) - y 1s(H b ) + y 1s(Hc ) - y 1s(Hd ) ] (5.18.48)

y6 = C3¢ y 2 p y ( C) - C4¢ yy (antibonding)

= C3¢ y 2 p y ( C) - C4¢ [y 1s(Ha ) - y 1s(H b ) + y 1s(Hc ) - y 1s(Hd ) ] (5.18.49)

y7 = C3 y 2p z ( C) + C4yz (bonding)

= C3 y 2p z ( C) + C4 [y 1s(Ha ) - y 1s(H b ) - y 1s(Hc ) + y 1s(Hd ) ] (5.18.50)

y8 = C3¢ y 2 p z ( C) - C4¢ yz (antibonding)

= C3¢ y 2 p z ( C) - C4¢ [y 1s(Ha ) - y 1s(H b ) - y 1s(Hc ) + y 1s(Hd ) ] (5.18.51)

The molecular orbital y1 is bonding and builds the charge between the carbon atom
and each of the four hydrogen atoms. The molecular orbitals y3, y5 and y7 are
bonding and build the charge in the regions about the x-, y- and z-axes, respectively.
†
The values of C1, C2, C3 and C4 reported in literature are 0.58, 0.19, 0.55 and 0.32,
respectively.
614 A Textbook of Physical Chemistry

Localized Bonding Because of the tetrahedral symmetry, each of the bonding molecular orbitals must
Molecular Orbitals point along a CH bond. The four localized bonding molecular orbitals may be
of Methane obtained by the linear combination of four nonlocalized molecular orbitals y1, y3,
y5 and y7. We may write it as
y = ay1 + by3 + cy5 + dy7 (5.18.52)
The molecular orbital y1 is directed equally to all four hydrogen atoms, the variation
in the value of a does not direct y preferentially to any one hydrogen. The molecular
orbitals y3, y5 and y7 are directed along the x-, y- and z-axes, respectively, and
thus the variations in b, c and d help directing y towards the hydrogen atoms.
Since y3, y5 and y 7 have directional characteristics along x-, y- and z-axes,
respectively, the linear combination of these orbitals in Eq. (5.18.52) will have
directional characteristics of
bx + cy + dz (5.18.53)
Let l1, m1 and n1 be the direction cosines of the CHa line (taken as the x¢ axis) with
the original x-, y- and z b, c and d are chosen
as proportional to these direction cosines (i.e. b = el1, c = em1 and d = en1, where
e is a constant of proportionality), then the direction as given by Eq. (5.18.53) is
along the CHa bond. We will have
bx + cy + dz = e(l1x + m1y + n1z) = ex¢ (5.18.54)
Since the above expression involves x¢, the direction as given by Eq. (5.18.54)
will directed towards x¢-axis (that is, CHa line). With this, Eq. (5.18.52) becomes
y CHa = ay1 + el1 y3 + em1y5 + en1y7 (5.18.55)

From Fig. (5.18.9), it follows that

l1 = m1 = n1 = cos (109º 48¢/2) = 1 3

Hence y CHa = ay1 + (e 3 ) (y3 + y5 + y7) (5.18.56)

Proceeding similarly, it can be shown that
y CH b = ay1 + (e 3 ) (y3 – y5 – y7) (5.18.57)

y CHc = ay1 + (e 3 ) (– y3 + y5 – y7) (5.18.58)

y CHd = ay1 + (e 3 ) (– y3 – y5 + y7) (5.18.59)

Orthonormality of the localized bonding molecular orbitals requires that

e2 e2 e2
a2 + + + =1 i.e. a2 + e2 = 1
3 3 3
e2 e2 e2 e2
a2 - - + =0 i.e. a2 – =0
3 3 3 3
 Molecular Symmetry and Its Applications 615

These give a = 1/2 and e = 3 2 . (5.18.60)

With these, the expressions of localized molecular orbitals become

1 1
y CHa = y1 + (y3 + y5 + y7) (5.18.61)
2 2
1 1
y CH b = y1 + (y3 – y5 – y7) (5.18.62)
2 2
1 1
y CHc = y1 + (– y3 + y5 – y7) (5.18.63)
2 2
1 1
y CHd = y1 + (– y3 – y5 + y7) (5.18.64)
2 2

Explicit Substituting the expressions of y1, y3, y5 and y7, we get

Expressions
of Localized C C ÊC 3 ˆ
y CHa = 1 y 2s( C) + 3 ÈÎy 2 p x ( C) + y 2 p y ( C) + y 2 p z ( C) ˘˚ + Ë 2 + C4 ¯ y 1s(Ha )
Molecular Orbitals 2 2 2 2

+ ( C2 C4
2
-
2 )
[y 1s(Hb ) + y 1s(Hc ) + y 1s(Hd ) ]

C1 � C3 and C2 � C4
Setting C1 = C3 and C2 = C4, the function y CHa becomes

C1
y CHa = Èy 2s( C) + y 2 p x ( C) + y 2 p y ( C) + y 2 p z ( C) ˘˚ + 2C2y 1s(Ha ) (5.18.65)
2 Î
Proceeding similarly, it can be shown that
C1
y CH b = Èy 2s( C) + y 2 p x ( C) - y 2 p y ( C) - y 2 p z ( C) ˘˚ + 2C2y 1s(H b )
2 Î
(5.18.66)
C1
y CHc = Èy 2s( C) - y 2 p x ( C) + y 2 p y ( C) - y 2 p z ( C) ˘˚ + 2C2y 1s(Hc )
2 Î (5.18.67)
C1
y CHd = Èy 2s( C) - y 2 p x ( C) - y 2 p y ( C) + y 2 p z ( C) ˘˚ + 2C2y 1s(Hd )
2 Î
(5.18.68)
The localized molecular orbitals include equal contributions from 2s(C), 2px(C),
2py(C) and 2pz(C) orbitals, that is, the localized molecular orbitals include sp3
hybrid orbitals of carbon atom.

Correlation The correlation diagrams depicting nonlocalized and localized molecular orbitals
Diagram of CH4 of CH4 are shown in Fig. 5.18.10.
616 A Textbook of Physical Chemistry

Fig. 5.18.10 Correlation diagrams depicting (a) nonlocalized and (b) localized molecular orbitals of CH4.

SALC’s AND p-MOLECULAR ORBITALS OF trans–BUTADIENE

The point group of trans-butadiene (Fig. 5.18.8) is C2h.

4
+ +

2 –
Fig. 5.18.8 Four 3
+
2pz orbitals of trans-
– –
butadiene 1
–

Nature of The reducible representation based on the four 2pz orbitals (which point in the
Irreducible direction perpendicular to molecular plane) is
Representations
C2h E C2 i sh
Gp 4 0 0 –4
���������
Ê All the four ˆ
Ê All the four ˆ
Ê All the four ˆ Á ˜ Á orbitals are ˜
Á orbitals remain ˜ Á orbitals are ˜ Á ˜
Á ˜
Á ˜ Á ˜ Á reversed ˜
Ë unshifted ¯ Ë shifted ¯
ÁË without shifting˜¯
 Molecular Symmetry and Its Applications 617

The use of reduction formula ai = (1/hi) Â R c( R) ci(R) gives

1
a(Ag) =
[(4) (1) + (0)(1) + (0)(1) + (– 4)(1)] = 0
4
1
a(Bg) = [(4)(1) + (0)(– 1) + (0)(1) + (– 4)(– 1)] = 2
4
1
a(Au) = [(4)(1) + (0)(1) + (0)(– 1) + (– 4)(– 1)] = 2
4
1
a(Bu) = [4(1) + (0)(– 1) + (0)(– 1) + (– 4)(1)] = 0
4
Hence, Gp = 2Bg + 2Au (5.18.69)

SALC from 2pz The four 2pz orbitals form two subsets, f1 and f4, and f2 and f3, respectively. The
Orbitals of Carbon members of each are symmetry equivalent to each other but not to those in other
Atoms sets. We construct molecular orbitals taking one from each subset,
(
∑ The use of projection operator P� j = Â c j ( R ) R
R )
� on the 2pz orbitals of
carbons 1 and 2 (represented respectively by f1 and f2), we get

P� Bg f1 = c Bg( E ) {E
�f } + c (C ) {C
1 Bg 2
� 2f } + c (i ){�i f } + c (s ) {s� h f }
1 Bg 1 Bg h 1

= (1)(f1) + (– 1) f4 + (1)(– f4) + (– 1)(– f1)

= 2(f1 – f4) (5.18.70)
Similarly, we will have

P� Bg f2 = 2(f2 – f3) (5.18.71)

P� A u f1 = 2(f1 + f4) (5.18.72)

P� A u f2 = 2(f2 + f3) (5.18.73)

MO’s of trans- The interactions between the two Bg combinations and the two Au combinations
Butadiene give the following four molecular orbitals of trans-butadiene

Bg: y1 = a1(f1 – f4) + a2 (f2 – f3) (5.18.74)

y2 = a2(f1 – f4) – a1 (f2 – f3) (5.18.75)
A u: y3 = a3(f1 + f4) + a4 (f2 + f3) (5.18.76)
y4 = a4(f1 + f4) – a3(f2 + f3) (5.18.77)
where a1, a2, a3 and a4 are constants. The detail quantum-mechanical calculations†
result into
a1 = a4 = 0.602 and a2 = a3 = 0.372.

†
See Section 5.21.
618 A Textbook of Physical Chemistry

p-MOLECULAR ORBITALS OF NAPHTHALENE

Nature of The point group of naphthalene (Fig. 5.18.9) is D2h.

Irreducible
y
Representations

8 1
Fig. 18.9 7 2
Naphthalene molecule. 9
x
The z-direction is 10
perpendicular to the 6 3
plane of molecule 5 4

The reducible representation obtained on the basis of ten 2pz orbitals (which point
in the direction perpendicular to molecular plane) is
D2h E C2(z) C2(y) C2(x) i s (xy) s(xz) s(yz)
Gp 10 0 –2 0 0 – 10 0 2
All the ten All orbitals Eight orbitals All the ten All the ten All the ten Eight orbitals
orbitals are shifted are shifted. orbitals are orbitals orbitals are are shifted.
remain Two orbitals of shifted undergo reversal shifted Two orbitals
unshifted C9 and C10 in direction of C9 and C10
undergo reversal remain unshifted
in direction

The use of reduction formula [ai = (1/hi) Â R c (R) ci(R)] gives

1
a (Ag) = [(10) (1) + (– 2)(1) + (– 10)(1) + (2)(1)] = 0
8
1
a (B1g) = [(10)(1) + (– 2)(– 1) + (– 10)(1) + (2)(–1)] = 0
8
1
a(B2g) = [(10)(1) + (– 2)(1) + (– 10)(– 1) + (2)(– 1)] = 2
8
1
a(B3g) = [(10)(1) + (– 2)(– 1) + (– 10)(– 1) + (2)(1)] = 3
8
1
a(Au) = [(10)(1) + (– 2)(1) + (– 10)(– 1) + (2)(– 1)] = 2
8
1
a(B1u) = [(10)(1) + (– 2)(– 1) + (– 10)(– 1) + (2)(1)] = 3
8
1
a(B2u) = [(10)(1) + (– 2)(1) + (– 10)(1) + (2)(1)] = 0
8
1
a(B3u) = [(10) (1) + (– 2)(– 1) + (– 10)(1) + (2)(– 1)] = 0
8
 Molecular Symmetry and Its Applications 619

Hence Gp = 2B2g + 3B3g + 2Au + 3B1u (5.18.78)

SALC from 2pz The ten 2pz orbitals form three subsets:
Orbitals of Carbon Sebset 1: f 1, f4, f5, f8
Atoms
Subset 2: f 2, f3, f6, f7
Subset 3: f9 and f10
The members in each subset are symmetry-equivalent to each other but not to
those in other sets. We construct the required number of symmetry-adapted linear
combination of given symmetry taking one orbital from each subset. For example,
for two B2g molecular orbitals, and we apply projection operator on the orbital
j 1(subset 1) and j2(subset 2), respectively, and so on.

P� B2g j 1 = ÈÎ c ( E ) {E j1 } + c (C2 z ) {C 2 z j1 } + c (C2 y ) {C 2 y j1 }

B2g: � � �

� 2 xj } + c ( ) {�ij } + c s {s� xyj }

+ c (C2 x ) {C 1 i 1 ( xy ) 1

{ Ÿ
} {
+ c (s xz ) s xz j1 + c (s yz ) s yz j1
Ÿ
}
= [(1)j1 + (-1)j 5 + (1) ( -j8 ) + (-1) ( -j 4 )
+ (1)(– j5) + (– 1)(– j1) + (1)(j4) + (– 1)(j8)]
i.e. y ¢1 = 2[j 1 – j5 – j8 + j4]
1
The normalized SALC is y ¢1 = [j 1 – j5 – j8 + j4] (5.18.79)
2
P� B2g j 2 = [(1) j2 + (– 1)j6 + (1) (– j7) + (– 1)(– j3)
+ (1)(– j 6) + (– 1)(– j2) + ( 1) (j3) + (– 1)(j7)]
i.e. y¢3 = 2[j 2 – j6 – j7 + j3]
1
The normalized SALC is y¢2 = [j 2 – j6 – j7 + j3] (5.18.80)
2
B3g: P� B3g j 1 = [(1)j1 + (–1)j5 + (– 1)(– j8) + (1)(– j4)
+ (1) (– j5) + (– 1)(– j1) + (– 1)(j4) + ( 1)(j8)]
i.e. y¢3 = 2[j 1 – j5 + j8 – j4]
1
The normalized SALC is y ¢3 = (j 1 – j5 + j 8 – j 4) (5.18.81)
2
P� B3g j 2 = [(1)j2 + (– 1)j6 + (–1)(–j7) + (1)(– j 3)
+ (1) (– j6) + (– 1)(– j2) + (– 1)(j3) + (1)(j7)]
i.e. y ¢4 = 2[j 2 – j6 + j7 – j 3]
620 A Textbook of Physical Chemistry

1
The normalized SALC is y ¢4 = (j 2 – j6 + j7 – j 3) (5.18.82)
2
P� B3g j 9 = [(1)j9 + (– 1)(j10) + (– 1)(– j9) + (1)(– j10)
+ (1) (–j10) + (–1)(– j9) + (–1)(j 10) + (1)j9]
i.e. y¢5 = 4[j 9 – j10]
1
The normalized SALC is y ¢5 = (j 9 – j10) (5.18.83)
2
Au: P� A u j 1 = [(1) j1 + (1)j5 + (1)(– j8) + (1)(– j4)
+ (– 1)(– j 5) + (– 1)(– j1) + (– 1)j4 + (– 1)j8]
i.e. y¢6 = 2[j 1 + j5 – j8 – j4]

1
The normalized SALC is y¢6 = (j1 + j5 – j8 – j4) (5.18.84)
2
P� A u j 2 = [(1) j2 + (1)j6 + (1) (– j7) + (1)(– j3)
+ (– 1) (– j6) + (– 1)(– j2) + (– 1)j3 + (– 1)j7]
i.e. y¢7 = 2 [j 2 + j6 – j7 – j3]

1
The normalized SALC is y¢7 = (j 2 + j6 – j7 – j3) (5.18.85)
2
B1u: P� B1u j 1 = [(1) j1 + (1) j5 + (– 1)(– j8) + (– 1)(– j4)
+ (– 1)(– j 5) + (– 1)(– j 1) + (1) j4 + (1)j8]
i.e. y¢8 = 2[j 1 + j5 + j8 + j4]

1
The normalized SALC is y ¢8 = (j 1 + j5 + j8 + j4) (5.18.86)
2
P� B1u (j 2) = [(1)j2 + (1) j6 + (– 1)(– j7) + (– 1) (– j3)
+ (– 1)(– j 6) + (– 1)(– j2) + (1)j3 + (1)j7]
i.e. y¢9 = 2[j 2 + j6 + j7 + j3]
1
The normalized SALC is y ¢9 = (j 2 + j6 + j7 + j3) (5.18.87)
2
P� B1u (j 9) = [(1) j9 + (1)j10 + (– 1)(– j9) + (– 1)(– j10)
+ (– 1)(– j 10) + (– 1)(– j9) + (1)j10 + (1)j9]
i.e. y¢10 = 4[j 9 + j10]
1
The normalized SALC is y¢10 = (j 9 + j10) (5.18.88)
2
MO’s of The SALC’s y ¢1, y ¢2, ..., y 10
¢ may be combined to give molecular orbitals of
Naphthalene naphthalene. Since the combinations of the same symmetry combine, we form
molecular orbitals as listed in the following.
 Molecular Symmetry and Its Applications 621

B2g symmetry: y 1,2 = C1y ¢1 + C2y ¢2 (5.18.89)

B3g symmetry: y 3,4,5 = C3y ¢3 + C4y ¢4 + C5y ¢5 (5.18.90)
Au symmetry: y 6,7 = C6y ¢6 + C7y ¢7 (5.18.91)
B1u symmetry: y 8,9,10 = C8y ¢8 + C9y ¢9 + C10y ¢10 (5.18.92)

the secular determinant of one symmetry equal to zero; solving it for energies and
then substituting these energies one by one in the corresponding secular equations
along with the normalization expression of the molecular orbitals (see, Section 5.21).

5.19 p-MOLECULAR ORBITALS OF A CARBOCYCLIC SYSTEM

Carbocyclic The molecular formula of carbocyclic systems is C nHn. Each carbon atom of
System a carbocyclic molecule carries a p-electron in its pz orbital which is in the
perpendicular direction of the molecular plane. Examples include C3H3, C4H4, C5H5,
C6H6 and so on. The SALC involving pz orbitals of carbon atoms of a carbocyclic
molecule can be easily constructed by using the pure rotational symmetry about
the principal axis of the molecule and by using the characters from the character
table of the cyclic group.
A cyclic group of order h Xn, where n = 1, 2, ..., h with Xh =
E. Each of its h elements constitutes a separate class. Thus, it has h one-dimensional
irreducible representations. Since XmXn = Xn Xm, a cyclic group is an Abelian group.
Irreducible A general scheme to write irreducible representations of a cyclic group is available.
Representations This is based on the use of exponential
of a Cyclic Group eh = exp(2pi/h) (5.19.1)
Obviously,
ehh = [exp(2pi/h)]h = exp(2p ih/h) = exp(2pi)
= cos 2p + i sin 2p = 1 + 0 = 1
In terms of eh, the irreducible representations of a cyclic group of h = 5 are shown
in Table 5.19.1.

Table 5.19.1 Irreducible Representations of Cyclic Group of Order 5

C5 C52 C53 C54 C55

G1 e5 e 52 e 53 e 54 e 55

G2 = (G1)2 e 52 e 54 e 56 e 58 e 10
5

G3 = (G1)3 e 53 e 56 e 59 e 12
5 e 15
5

G4 = (G1)4 e 54 e 58 e 12
5 e 16
5 e 520

G5 = (G1)5 e 55 e 10
5 e 15
5 e 520 e 525
622 A Textbook of Physical Chemistry

Rewriting The representations given in Table 5.19.1 constitute a orthonormal set satisfyingte
Table 5.19.1 expression
h
 ÈÎG p (Chn )˘˚ ÈÎG q (Chn )˘˚ = dpq h
*
(5.19.2)
n =1
The representations shown in Table 5.19.1 can be written with smaller exponents
using the following facts.
Chh = E
Chnh = Chh Chh º n times = (1) (1) º = 1
and Chm = Chn+ h = Chn Chh = Chn with m > h and n < h. (5.19.3)
The resultant representations are shown in Table 5.19.2.
Table 5.19.2 Representations of the Cyclic Group of Order Five

C5 C52 C53 C54 C55

G1 e5 e 52 e 53 e 54 1

G2 e 52 e 54 e5 e 53 1

G3 e 53 e5 e 54 e 52 1

G4 e 54 e 53 e 52 e5 1

G5 1 1 1 1 1
Rewriting Also from the fact that
Table 5.19.2 *
[e hm ]* 2pm 2pm ˘ 2pm 2pm
= ÈÍcos + i sin ˙ = cos - i sin
Î h h ˚ h h

= cos 2p - { 2pm
h } {
+ i sin 2 π -
2pm
h }
2p ( h - m ) 2p ( h - m )
= cos + i sin
h h
( )
= e hh - m (5.19.4)
we can write the representations of Table 5.19.2 as shown in Table 5.19.3.
Table 5.19.3 Representations of Cyclic Group of Order Five

C5 C52 C53 C54 C55

G1 e5 e 52 e 52* e*5 1

G2 e 52 e*5 e5 e 52* 1

G3 e 52* e5 e*5 e 52 1

G4 e*5 e 52* e 52 e5 1

G5 1 1 1 1 1
 Molecular Symmetry and Its Applications 623

Rearrangement The representations shown in Table 5.19.3 are rearranged as shown in Table 5.19.4.†
Table 5.19.3
Table 5.19.4 Character Table of Cyclic Group of Order Five

E C5 C52 C53 C54

A 1 1 1 1 1
ÏÔ1 e5 e 52 e 25* e*5
E1 Ì
ÓÔ1 e*5 e 52* e 52 e5
ÏÔ1 e 52 e*5 e5 e 52*
E2 Ì
ÓÔ1 e 25* e5 e*5 e 52

In Table 5.19.4, the E representations appear in the form of two associated one-
dimensional representations. The use of corresponding projection operator provide
the two symmetry-adapted linear combinations belonging to the E representation.
This is advantage of using only the principal axis rotational symmetry for
constructing molecular orbitals.
A General Rule The rule states that
for Constructing In a cyclic (CH)n molecule with rotational symmetry Cn, there will always be n
Molecular Orbitals p molecular orbitals, one-belonging to each irreducible representation of the group
Cn.
The above rule may be illustrated by taking an example of benzene (C6H6).
The reducible representation of benzene based on six pz orbitals is as follows.

E C6 C62 = C3 C63 = C2 C64 = C62 C65

Gp 6 0 0 0 0 0
Note that c(E) = 6 and all other characters are zero. This follows from the fact
that only the identity operation leaves each of pz orbital unshifted while all other
operations shift each of pz orbitals.
The character table of C6 group is as follows.
C6 E C6 C3 C2 C32 C5
A 1 1 1 1 1 1
B 1 –1 1 –1 1 –1
Ï1 e – e* –1 –e e*
E1 Ì
Ó1 e* –e –1 – e* e

Ï1 – e* –e 1 – e* –e
E2 Ì
Ó1 –e – e* 1 –e – e*

†
In the new rearrangement, we have
∑ The total symmetric representation is written at the top. It is represented by the symbol A.
∑ The remaining representations are written in pairs, such that the elements of one row
in each pair are complex conjugate of the other.
624 A Textbook of Physical Chemistry

If the reducible representation listed above is resolved into irreducible

Gp = A + B + E1 + E2
The above result follows from the fact that the only way to get c (E) = 6 and all other
characters zero is that the sum of characters of various irreducible representations
in a symmetry operation is always zero except that of E operation.
Thus, each of the six molecular orbitals of C6H6 molecule belongs to each of the
six irreducible representations of the group C6.
General Way of Since each of the six linear combinations belongs to separate one-dimensional
Constructing representation, the projection operator technique is extremely simple to apply. The
LCAO Expressions result is the expression which includes the sum of six terms involving the product
of the MOs pz orbital taken in numerical order with the character for one of the six operations
in the conventional order (for example, E, C6, C62, C63, º ). Hence, the sets of

To illustrate the above fact, we built molecular orbital of C6H6 molecule belonging
to E1 representation. The use of projection operator gives

P� E1 f1 = c(E) E � f + c (C 2) C
� f 1 + c (C6) C � 2 f + c (C 3) C
� 3f
6 1 6 6 6 1 6 6 6 1

� 4f + c(C 5) C
+ c (C64) C �5 f
6 1 6 6 1
= c (E)f1 + c(C6)f2 + c(C62)f3 + c(C63)f4 + c(C64)f5 + c(C65)f6

p-MOLECULAR ORBITALS OF THE CYCLOPROPENYL

The cyclopropenyl has a molecular formula C3H3. Each carbon has one p-electron
in the respective pz orbital (Fig. 5.19.1)

+ +

– –
+

Fig. 5.19.1 p-Orbitals

of cyclopropenyl –

The symmetry-adapted linear combination of the three pz orbitals can be constructed

by using the character table for the cyclic system of order h = 3 (Table 5.19.5).
Table 5.19.5 Character Table of Cyclic System of Order h = 3

C3 E C3 C32
A 1 1 1
Ï1 e3 e*3 {where e 3 = exp (2pi/3)}
E Ì
Ó1 e*3 e3
 Molecular Symmetry and Its Applications 625

Application of the projection operators P�A, P�E(1) and P�E(2) to the orbital f (neglecting
constant numerical factors) gives the following molecular orbitals.

P� Af 1 = {cA(E)} E � f + {c (C 2)} C
� f1 + {cA(C3)} C3 1 A 3
�2 f
3 1

= (1)f 1 + (1)f2 + (1)f3

i.e. y1 = f 1 + f2 + f3 (5.19.5)
P� E(1) f 1 = {cE1(E)} E � f + {c (C 2)} C
� f1 + {c E1(C3)} C3 1 E1 3
�2 f
3 1

= (1)f1 + (e3) f2 + (e*3) f3

i.e. y¢2 = f 1 + e3f2 + e*3 f3 (5.19.6)

P� E(2) f 1 = {cE2(E)} E � f + {c (C 2)} C

� f1 + {cE2(C3)} C3 1 E2 3
�2 f
3 1

= (1)f1 +(e*3)f2 + (e3)f3

i.e. y¢3 = f 1 + e*3 f 2 + e 3 f3 (5.19.7)

The combinations y ¢2 and y ¢3

y 2 = y¢1 + y¢3 (5.19.8)

1
y3 = [y¢2 – y¢3] (5.19.9)
i
Thus, we get
y 2 = [f1 + e3 f2 + e *3 f 3] + [f1 + e*3 f 2 + e3 f3]
= 2f 1 + (e3 + e*3 )f 2 + (e3 + e*3)f3
Since e 3 = exp(2pi/3) = cos (2p/3) + i sin (2p/3)
and e *3 = exp(– 2p i/3) = cos (2p/3) – i sin (2p/3)
we get y 2 = 2f1 + {2 cos (2p/3)}f2 + {2 cos (2p/3)}f3

= 2f1 – f2 – f3 (5.19.10)

1 1
y3 = [y¢2 – y¢3] = [(f1 + e3f2 + e*3f 3) – (f 1 + e *3f 2 + e3f3)]
i i
1
= [(e3 – e *3)f2 + (e*3 – e 3)f 3]
i
1
= [{2i sin (2p /3)}f2 + {– 2i sin (2p/3)}f3
i
= 3 (f2 – f3) (5.19.11)
626 A Textbook of Physical Chemistry

The three normalized combinations are

(A) 1
y 1 = (f 1 + f 2 + f3) (5.19.12)
3
1
y 2(E) = (2f 1 – f2 – f 3) (5.19.13)
6
1
y 3(E) = (f 2 – f3) (5.19.14)
2

p-MOLECULAR ORBITALS OF BENZENE

Benzene is a carbocyclic system. The cyclic group of order h = 6 (see, page 623)
can be used to built six p-molecular orbitals (Fig. 5.19.2).

+ +
1 2

– –
+ +
6 3
– –
+ +

Fig. 5.19.2 Benzene 5 4

Molecule – –

P� A f1 = {cA(E) E � f + [c (C 2)} C
� f 1 + [cA(C6)} C6 1 A 6
�2 f
6 1

� 3 f + {c (C 4)} C
+ {cA(C 63)} C � 4 f + {c (C 5)} C
�5 f
6 1 A 6 6 1 A 6 6 1

= (1)f1 + (1)f2 + (1)f3 + (1)f4 + (1)f5 + (1)f6

Hence, y 1 = f1 + f2 + f3 + f4 + f 5 + f 6 (5.19.15)

P� B f1 = (1)f1 + (– 1)f2 + (1)f3 + (– 1)f4 + (1)f5 + (– 1)f6

Hence, y2 = f1 – f2 + f3 – f4 + f5 – f6 (5.19.16)

P� E1 (1) f1 = (1)f 1 + (e6)f2 + (– e*6 )f3 + (– 1)f4 + (– e6)f5 + (e*6 )(f6)

Hence y ¢3 = f1 + e 6f2 – e*6 f 3 – f4 – e6f5 + e *6f 6 (5.19.17)

P� E1 (2) f1 = (1)f 1 + (e*6 )f 2 + (– e6)f3 + (– 1)f4 + (– e*6 )f5 + (e 6)f6

Hence, y ¢4 = f1 + e*6 f 2 – e6f3 – f4 – e*6 f 5 + e6f6 (5.19.18)

P� E 2 (1) f 1 = (1)f1 + (– e *6)f 2 + (– e6)f3 + (1)f4 + (– e*6 )f5 + (– e6)f6

Hence y ¢5 = f 1 – e*6 f 2 – e6 f3 + f4 – e*6 f 5 – e6f6 (5.19.19)
 Molecular Symmetry and Its Applications 627

P� E 2 (2) f 1 = (1)f1 + (– e 6 )f2 + (– e*6 )f3 + 1(f4) + (– e6)f5 + (– e*6 )f6

Hence y ¢6 = f 1 – e6f2 – e*6 f 3 + f4 – e6f5 – e*6 f 6 (5.19.20)

y3 = y ¢3 + y¢4 = 2f 1 + (e 6 + e*6 )f2 – (e*6 + e 6)f 3 – 2f 4 – (e6 + e*6 )f5

+ (e 6 + e*6 ) f6

= 2f 1 + 2cos (2p/6)f2 – 2cos (2p/6)f 3 – 2f4 – 2cos (2p/6)f 5 + 2cos (2p/6)f6

= 2f 1 + f2 – f3 – 2f4 – f5 + f6 (5.19.21)

y 3¢ - y 4¢ 1
y4 = = [(e 6 – e*6 )f2 + (e6 – e*6 )f 3 – (e 6 – e*6 )f 5 – (e6 – e*6 )f 6 ]
i i
1
= [2i sin (2p /6)f 2 + 2i sin (2p/6)f 3 – 2i sin (2p/6)f5 – 2i sin (2p/6)f 6]
i
= 3 [f 2 + f 3 – f5 – f6] (5.19.22)
y5 = y ¢5 + y ¢6 = 2f1 –(e6 + e*6 )f2 –(e6 + e*6 )f3 + 2f4 –(e6 + e*6 )f5 –(e6 + e*6 )f6

= 2f1 – f 2 – f3 + 2f4 – f5 – f 6 (5.19.23)

y 5¢ - y 6¢ 1
y6 = = [(e 6 – e*6 )f 2 – (e6 – e*6 )f3 + (e 6 – e*6 )f 5 – (e6 – e*6 ) f6 ]
i i
= f 2 – f3 + f5 – f6 (5.19.24)
Finally, the molecular orbitals are normalized to give
1
y1 (A) = [ f1 + f2 + f3 + f4 + f5 + f6] (5.19.25)
6
1
y2 (B) = [f1 – f2 + f3 – f4 + f5 – f6] (5.19.26)
6
1
y3 (E2) = [2f1 + f2 – f3 – 2f4 – f5 + f6] (5.19.27)
12
1
y4 (E1) = [f2 + f3 – f5 – f6] (5.19.28)
2
1
y5 (E2) = [2f1 – f2 – f3 + 2f4 – f5 – f6] (5.19.29)
12
1
y6 (E2) = [f2 – f3 + f5 – f6] (5.19.30)
2
From the characters of the operations C6, C 62 (= C3), C 63 (= C2), C 64 (= C 32) and C 56
associated with the group D6h (to which benzene belongs), it is obvious that the
representations A, B, E1 and E2 correspond to A2u, B2g, E1g and E2u, respectively.
628 A Textbook of Physical Chemistry

5.20 FORMATION OF HYBRID ORBITALS

HYBRIDIZATION INVOLVING s -ORBITALS

The hybrid orbitals of an atom is obtained by mixing atomic orbitals of the same
atom. The bonding in a molecule ABn may be described in terms of hybrid orbitals
of the central atom A. The constituent atomic orbitals in a hybrid orbital can be
predicted from the reducible representation of the molecule of which bond vectors
form its basis. The following example illustrates the procedure.

Example of Planar The planar AB3 molecule (assume to lie in the xy plane) belongs to the point
AB3 group D3h. The bond vectors coincide with the three hybrid orbitals of the atom
A. These orbitals point towards the atoms B with each bond angle equal to 120º.
The character of reducible representation based on bond vectors may be worked
out by following the guideline stated as follows.
The character of reducible representation of a symmetry operation is equal to the
number of unshifted bond vectors.
The set of characters for the symmetry operations of the point group D3h is shown
in Table 5.20.1.

Table 5.20.1 Reducible representation based on bond vectors of AB3 molecule belonging
to the point group D3h

Operation Number of unshifted vectors Character

E Each of the three bond vectors remains unshifted 3

2C3 All the three bond vectors are shifted 0
3C2 One bond vector coinciding with rotation axis 1
remains unshifted
sh All the three bond vectors remain unshifted 3
2S3 All the three bond vectors are shifted 0
3sv One bond vector lying in the symmetry plane 1
remains unshifted

The resolution of reducible representation in terms of irreducible representations

of the point group D3h can be carried by using the expression
1
ai =
hi
 nC c(C)ci(C)
C
For the molecule AB3, we have
1
a(A¢1) = [1(3)(1) + 2(0)(1) + 3(1)(1) + 1(3)(1) + 2(0)(1) + 3(1)(1)] = 1
12
1
a(A¢2) = [1(3)(1) + 2(0)(1) + 3(1)(– 1) + 1(3)(1) + 2(0)(1) + 3(1)(– 1)] = 0
12
 Molecular Symmetry and Its Applications 629

1
a(E¢) = [1(3)(2) + 2(0)(– 1) + 3(1)(0) + 1(3)(2) + 2(0)(– 1) + 3(1)(0)] = 1
12
Similarly, it can be shown that
a(A≤1 ) = 0; a(A≤2 ) = 0 and a(E≤) = 0
Hence,
G = A¢1 + E¢ (5.20.1)
From the character table of the point group D3h atomic orbitals
which form the bases of A¢1 and E¢ are as follows
A¢1 s (5.20.2)
E¢ (px, py) or/and (d ,d xy ) (5.20.3)
x2 - y 2
Hence, the hybrid orbitals of the central atom A involve either s + px + py (i.e. sp2
hybridization) or s + d x2 - y 2 + d xy (i.e. sd2 hybridization). However, the scheme sd2
for molecules BH3, BCl3 and CH3 may be excluded since the 3d orbitals have
much larger energy as compared to 2s orbital.
The three equivalent sp2 hybrid orbitals may be represented as follows.
y sp2 = C11 y2s + C12 y 2p + C13 y 2p y (5.20.4)
1 x

y sp2 = C21 y2s + C22 y 2p + C23 y 2p y (5.20.5)

2 x

y sp2 = C31 y2s + C32 y 2p + C33 y 2p y (5.20.6)

3 x

In the matrix notations, we have

Èy sp2 ˘
Í 1 ˙ È C11 C12 C13 ˘ È y 2 s ˘
Í ˙
Íy sp2 ˙ = ÍC C22 C23 ˙ Íy 2 p x ˙ (5.20.7)
Í 2 ˙ Í 21 ˙Í ˙
Í
Í sp2 ˙ ÎC31 C32
y C33 ˙˚ Íy 2 p ˙
Î 3˚ Î y ˚

From this, it follows that

È y 2s ˘ -1 Èy 2 ˘
È C11 C12 C13 ˘ Í sp1 ˙
Í ˙ Í ˙
Íy 2 p x ˙ = ÍC21 C22 C23 ˙ Íy sp22 ˙ (5.20.8)
Í ˙ Í ˙
Í ˙
ÎC31 C32 C33 ˚ Íy sp2 ˙
ÍÎy 2 p y ˙˚ Î 3˚
The inverse of matrix C can be obtained by transposing the matrix if the latter
represents an orthogonal matrix.
The projection operator technique is used to transform a set of equivalent orbitals

s orbitals of the pendent atoms B) into symmetry-adapted linear combinations

(see
with the matrix C –1. The inverse of this matrix (which is C) is obtained by taking
its transpose, which on substitution in Eq. (5.20.7) gives the expressions of set of
hybrid orbitals on the contral atom A.
630 A Textbook of Physical Chemistry

B s3

sp32
s1
sv A x
B
sp12
Fig. 5.20.1 The sp22
equivalent orbitals of
atom A and atoms B s2
B

For the planar AB3 atomic

orbitals of atoms B are as follows.
(A1¢ ) 1
y1 = [s1 + s2 + s3] (Eq. 5.18.16)
3
1
y 2(E ¢) = [2s1 – s2 – s3] (Eq. 5.18.17)
6
1
y 3(E ¢) = [s2 – s3] (Eq. 5.18.18)
2
In terms of hybrid orbitals centred on atom A, we will get
(A1¢ ) 1
y1 = Èy 2 + y sp22 + y sp32 ˘˚ (5.20.7)
3 Î sp1
1
y 2(E ¢) = È2y 2 - y sp22 - y sp32 ˘˚ (5.20.8)
6 Î sp1
1
y 3(E ¢) = Èy 2 - y sp32 ˘˚ (5.20.9)
2 Î sp2
y1 y2s(A) as both belong to the A1¢ representation.
y2 y 2 px (A) as both remain unchanged on
applying the operator s�v .
y3 y 2 p y (A) as both change sign on applying
the operator s�v .
Hence, we write
1
y 2 s(A) = Èy 2 + y sp2 + y sp2 ˘ (5.20.10)
3 Î sp1 2 3 ˚

1
y 2 p x (A) = È2y 2 - y sp2 - y sp3 ˘ (5.20.11)
6 Î sp1 2 2 ˚

1
y 2 p y (A) = Èy 2 - y sp2 ˘ (5.20.12)
2 Î sp2 3 ˚
 Molecular Symmetry and Its Applications 631

In the matrix notation, we write

È y 2s ˘ È 1 1 1 ˘ Èy sp2 ˘
Í 3 ˙Í
1
Í ˙ 3 3 ˙
Í ˙
Í ˙ 2 1 1 ˙ y 2˙
Í
Íy 2 p x ˙ = Í - - Í sp2 ˙
Í ˙ Í 6 6 6˙Í ˙
Íy ˙ Í 1 1 ˙Í ˙
ÍÎ 2 p y ˙˚ Í 0 - ˙ Íy sp2 ˙
Î 2 2˚Î 3 ˚
From this, we get
Èy sp12 ˘ È 1 ˘ -1 È y 2 s ˘ È
0 ˙˘ È 2 s ˘
1 1 1 2 y
Í ˙ Í 3 3 3 ˙ Í ˙ Í 3 6 Í ˙
Í ˙ Í 2 1
˙ Í
1 ˙ y ˙ Í
Í
1 1
˙
1 ˙ Íy ˙
Íy sp22 ˙ = Í - - Í 2px ˙ = - Í 2px ˙
Í ˙ Í 6 6 6˙ Í ˙ Í 3 6 2 ˙Í ˙
Í ˙ Í 1 1 ˙ Í ˙ Í 1 1 1 ˙ Íy ˙
Íy sp32 ˙ Í 0 - ˙ ÍÎy 2 p y ˙˚ Í - - ˙ Í 2 p y ˚˙
Î ˚ Î 2 2˚ Î 3 6 2˚Î
1 1
that is y sp2 = y 2s + y 2px (5.20.13)
1 3 6
1 1 1
y sp2 = y 2s - y 2p x + y 2p y (5.20.14)
2 3 6 2
1 1 1
y sp2 = y 2s - y 2p x - y 2p y (5.20.15)
3
3 6 2
Example of The structure of methane can be drawn within a cube as shown in Fig. 5.20.2. It is
Methane a tetrahedral molecule and belongs to the point group Td. The bond vectors coincide
with the four hybrid orbitals of carbon and point towards hydrogen atoms. The
set of characters of the reducible representation based on these vectors is shown
in Table 5.20.2.
C3b C2z, S4z

Hb
C3a

Ha
yb ya

C C2y, S4y

yd

yc Hd
C2x, S4x
C3d
Hc
Fig. 5.20.2 Methane
molecule C3c
632 A Textbook of Physical Chemistry

Table 5.20.2 Reducible representation based on the bond

vectors of CH4 molecule

Operation Number of unshifted vectors Character

E Each of the four bonds remains unshifted 4

8C3 Bond vector coinciding with the rotational 1
axis remains unshifted
3C2 All the four bonds are shifted 0
6S4 All the four bonds are shifted 0
6sd
remain unshifted

The irreducible representations contained in the reducible representation are as

follows.
1
a(A1) = [1(4) (1) + 8(1) (1) + 3(0) (1) + 6(0) (1) + 6(2) (1)] = 1
24
1
a(A2) = [1(4) (1) + 8(1) (1) + 3(0) (1) + 6(0) (– 1) + 6(2) (– 1)] = 0
24
1
a(E) = [1(4) (2) + 8(1) (– 1) + 3(0) (2) + 6(0) (0) + 6(2) (0)] = 0
24
1
a(T1) = [1(4) (3) + 8(1) (0) + 3(0) (– 1) + 6(0) (1) + 6(2) (– 1)] = 0
24
1
a(T2) = [1(4) (3) + 8(1) (0) + 3(0) (– 1) + 6(0) (– 1) + 6(2) (1)] = 1
24
Hence, Gbond vector = A1 + T2

From the character table of the point group Td atomic orbitals

which form the bases of A1 and T2 representations are as follows.
A1 s
T2 (px, py, pz) or/and (dxy, dxz, dyz)
Hence, the hybrid orbitals of carbon atom involves either s + px + py + pz (i.e. sp3
hybridization) or s + dxy + dxz + dyz (i.e. sd3 hybridization). However, the scheme
sd3 may be excluded since the 3d orbitals of carbon have much larger energy as
compared to its 2s orbitals.
Table 5.20.3 includes the results of applying the symmetry operations of the
point group Td to the hybrid orbitals (represented as ya, yb, yc and yd) of carbon
atom.
 Molecular Symmetry and Its Applications 633

Table 5.20.3 Transformation of hybrid orbitals of carbon under the

symmetry operations of the point group Td
2
E C3a C3a C3b C23b C3c 2
C3c C3d C23d C2x C2y C2z
ya ya ya ya yc yd yd yb yc yb yc yd yb
yb yb yd yc yb yb ya yd ya yc yd yc ya
yc yc yb yd ya yd yc yc yb ya ya yb yd

S4x S 34x S4y 3

S 4y S4z 2
S 4z sab scd sac sbd sbc sad
ya yd yb yb yc yc yd ya yb ya yc yd ya
yb ya yc yd ya yd yc yb ya yd yb yb yc
yc yb yd ya yd yb ya yd yc yc ya yc yb

∑ The application of P� A1 on ya results into

A1 symmetry y 1¢ = 6ya + 6yb + 6yc + 6yd

∑ The application of P� T2 on ya results into

T2 symmetry y ¢2 = 6ya – 2yb – 2yc – 2yd
∑ The application of P� T2 on yb results into
T2 symmetry y 3¢ = – 2ya + 6yb – 2yc – 2yd
∑ The application of P� T2 on yc results into
T2 symmetry y 4¢ = – 2ya – 2yb + 6yc – 2yd
The wavefunction y 1¢ is orthogonal to y 2¢ , y 3¢ and y 4¢ . But the functions y 2¢ , y 3¢
and y 4¢ are not orthogonal to each other. However, the orthogonal set can be
constructed as follows.
A1 representation y ≤1 = y 1¢ = 6ya + 6yb + 6yc + 6yd
È y ≤2 = y 2¢ + y 3¢ = 4ya + 4yb – 4yc – 4yd
T2 representation Í y ≤3 = y 2¢ + y 4¢ = 4ya – 4yb + 4yc – 4yd
Í
ÍÎ y ≤4 = – (y 3¢ + y 4¢ ) = 4ya – 4yb – 4yc + 4yd
The orthonormal set of these hybrid orbitals are as follows.
1
A1 representation y1 = (ya + yb + yc + yd)
2
1
È y2 = (ya + yb – yc – yd)
Í 2
Í 1
T2 representation Í y3 = (ya – yb + yc – yd)
Í 2
Í 1
ÍÎ y4 = (ya – yb – yc + yd)
2
634 A Textbook of Physical Chemistry

The wavefunction y1 y2s(C) as bond belong to the A1

representation.

The wavefunction y2 y 2pz (C) as ya and yb have positive

components along the + z axis and yc and yd have negative components along
the + z axis.

The wavefunction y3 y 2p x (C) as ya and yc have positive

components along the + x axis and yb and yd have negative components along
the + x axis.

The wavefunction y4 y 2p y (C) as ya and yd have positive

components along the + y axis and yb and yc have negative components along
the + y axis.

Hence, we can write

È1 1 1 1˘
È y 2s ˘ Í2 2 2 2˙ Èy a ˘
Í ˙ Í ˙ Í ˙
Íy ˙ Í1 1 1 1 Íy ˙
Í x ˙
- - ˙
2 p
Í2 2 2 2˙ Í b˙
Í ˙ = Í Í ˙
Íy 2 p ˙ Í1 1 1 1 ˙˙ Íy c ˙
- -
Í y
˙ Í2 2 2 2˙ Í ˙
Í ˙ Í1 1 1 1˙ Í ˙
ÍÎy 2 p z ˙˚ Í - - ˙ Îy d ˚
Î2 2 2 2˚
Thus

Èy a ˘ È1 1 1 1˘
È y 2s ˘
Í ˙ Í2 2 2 2˙ Í ˙
Íy ˙ Í1 1 1 1˙ Íy ˙
Í b˙ Í - - ˙ Í 2px ˙
Í ˙ = Í2 2 2 2˙ Í ˙
Íy c ˙ Í1 1 1 1˙ Íy 2 p ˙
Í - - ˙
Í ˙ Í y
˙
Í ˙ Í2 2 2 2˙
Í ˙
Îy d ˚ Í1 -
1 1
-
1˙
ÍÎy 2 p z ˙˚
ÍÎ 2 2 2 2 ˙˚
This gives

y sp3 =
1
1
2
(
y 2s +y 2 p x +y 2 p y +y 2 p z )
y sp3 =
2
1
2
(
y 2s - y 2 p x - y 2 p y +y 2 p z )
y sp3 =
3
1
2
(
y 2s + y 2 p x - y 2 p y - y 2 p z )
y sp3 =
4
1
2
(
y 2s - y 2 p x + y 2 p y - y 2 p z )
 Molecular Symmetry and Its Applications 635

HYBRIDIZATION INVOLVING p - ORBITALS

EXAMPLE OF AB3 MOLECULE
Ap
For each B atom in the planar AB3, there are two 2p orbitals (namely, 2px and 2py)
of p-nature. Of these, one is in the molecular plane perpendicular to A—B bond
and the second one is perpendicular to the molecular plane (Fig. 5.20.3). These may
be represented by vectors pointing in the appropriate directions and are referred to
as p(| |) and p(^) orbitals, respectively.

B
C3

B
A
Fig. 5.20.3 Vectors
representing p-orbitals
of B atoms in the
planar AB3 molecule B

The two sets of p-orbitals may be treated separately as no vector of one set is
interchanged with the vector of the second set under the symmetry operations of
the group D3h. Thus, each of the two sets may be considered separately as a basis
for a reducible representation.
Reducible The character of a symmetry operation may be determined based on the following
Representations facts.
(i) A displaced vector contributes zero.
(ii) An undisplaced vector without changing direction contributes + 1.
(iii) An undisplaced vector with changing direction in the opposite contributes – 1.
The following are the characters of reducible representations based on all the six
p-orbitals and those based on the two sets of p-orbitals.
E 2C3 3C2 sh 2S3 3sv
Gp 6 0 –2 0 0 0
Gp(| |) 3 0 –1 3 0 –1
Gp(^) 3 0 –1 –3 0 1
Irreducible The resolution of two reducible representations in terms of irreducible representations
Representations of the point group D3h are as follows.
Gp(| |) = A¢2 + E¢
Gp(^) = A≤2 + E≤
Formation of The orbitals belonging to the above irreducible representations (see character table)
p- Orbitals are as follows.
A¢2 : none
E¢ : (px, py) and (d x2 - y 2 , d xy )
A≤2 : pz
E≤ : (dxz, d yz)
 636 A Textbook of Physical Chemistry

From these, the following conclusions can be drawn.

∑ The orbitals p(^) can form bonds with atom A involving pd2 hybridization
which includes pz, d xz and dyz orbitals.
∑ The orbitals p(| |) can form two bonds with atom A involving px and py (or
d x2 - y 2 and d xy) orbitals. These two bonds are shared equally among the three
B atoms.
EXAMPLE OF AB6 MOLECULE
The molecule AB6 has octahedral structure (Fig. 5.20.4). The two p-orbitals
associated with each B atom are also shown in Fig. 5.20.4.

B
B
z
y
B A B
Fig. 5.20.4 Twelve x
p-orbitals of the B B
atoms in AB6 molecule B

Reducible Each vector is exchanged with each of the other eleven by one symmetry operation
Representations or another of the point group Oh. This implies that all the twelve orbitals of atoms
B (and also those of atom A) have to be considered together as a basis of reducible
representation. The characters of symmetry operations of the reducible represn-
tation are as follows.
Oh E 8C3 6C2 6C4 3C2 (= C24 ) i 6S4 8S6 3sh 6sd
Gp 12 0 0 0 –4 0 0 0 0 0
Irreducible From the character table of Oh
Representations Gp = G1g + G2g + G1u + G2u
Also the orbitals belonging to above irreducible representations are as follows.
G1g : none
G2g : (dxy, dxz, dyz)
G1u : (px, py, pz )
G2u : none
Formation of The following conclusion can be drawn for p-bondings in AB6 molecule.
p-Orbitals ∑ Since six atomic orbitals of atom A are used in forming six s bonds with B
atoms, it is not possible to form the entire set of twelve A—B p-bonds.
∑ The p¢s orbitals of A must have been used in forming s bonds with the
appropriate orbitals of atoms B. Thus, p orbitals of atom A cannot form any
p-bond with B atoms.
∑ Only the three d orbitals of atom A can be used in the p-bonds formation. It
can be said that the three p-bonds shared equally among the six A—B pairs
are formed in AB6 molecule.
 Molecular Symmetry and Its Applications 637

Problem 5.20.1 Form the hybrid orbitals of atom A involved in the s bondings with the four B atoms in a
planar AB4 molecule. Also analyse the hybridization in p-bondings.
Solution The planar molecule AB4 (Fig. 5.20.5) belongs to the group D4h. The reducible representation
based on its for bond vectors is as follows.

E 2C4 C2 2C¢2 2C≤2 i 2S4 sh 2sv 2sd

Gbond 4 0 0 2 0 0 0 4 2 0

The irreducible representations in the above reducible representation are as follows.

1
a(A1g) = [1(4)(1) + 2(2)(1) + 1(4)(1) + 2(2)(1)] = 1
16
1
a(B1g) = [1(4)(1) + 2(2)(1) + 1(4)(1) + 2(2)(1)] = 1
16
1
a(Eu) = [1(4)(2) + 2(2)(0) + 1(4)(2) + 2(2)(0)] = 1
16
Hence Gbond = G A + G B + G E
1g 1g u

From the character table of D4h

G A1g : s, d 2
z
G B1g : d 2 2
x -y
G E u : px, py
z
y
B B
y3
y4
A
y2 y1
Fig. 5.20.5 The B B
planar AB4 molecule
x

Formation of Hence, the atom A involves dsp2 hybridization (or d2p2). We consider here dsp2
Hybrid Orbitals
C4 symmetry.
�4 3 �
P� A1g y 1 = c A1g ( E ){E
� y } + c (C ){C
1 A1g 4
� y } + c (C 2 ){C
4 1 A1g 4 2 y 1} + c A1g (C4 ){C4 y 1}
3

= (1)y1 + (1)y2 + (1)y3 + (1)y4

1
The normalized function is j1 = (y1 + y2 + y3 + y4)
2
P� B1g y1 = (1)y1 + (– 1)y2 + (1)y3 + (– 1)y4
1
The normalized function is j2 =
(y1 – y2 + y3 – y4)
2
P� E u y1 = (2)y1 + (0)y2 + (– 2)y3 + (0)y4
638 A Textbook of Physical Chemistry

1
The normalized function is j3 = (y1 – y3)
2
P� E u y2 = (2)y2 + (0)y3 + (– 2)y4 + (0)y1
1
The normalized function is j4 =
(y2 – y4)
2
j1 to j4 with atomic orbitals is as follows.
A1g representation j1 = y2s
B representation j = y d 2 2
1g 2 x -y

j = y p x ; y1 and y3 lie along x axis

Ï 3
Eu representation Ì
Ó j4 = y p y ; and y4 lie along y axis
Hence
Èy 2 s ˘ È 1 1 1 1˘
Í 2˙ Èy 1 ˘
Í ˙ Í
2 2 2
˙ Í ˙
Íy ˙ Í
1 1 1 1
˙ Íy ˙
Í x2 - y 2 ˙
d - -
Í 2˙
˙ = ÍÍ
2 2 2 2˙
Í ˙ Í ˙
Íy p ˙ 1 1
Í 0 - 0˙ Íy 3 ˙
Í x
˙ Í 2 2 ˙ Í ˙
Í ˙ Í 1 1 ˙ Í ˙
y
ÍÎ p y ˙˚ 0 0 - Îy 4 ˚
ÍÎ 2 2 ˙˚
This gives
È 1 1 1 1 ˘ -1 y
È 1˘
y È 2s ˘
Í 2 2 2 2˙ Í ˙
Í ˙ Í 1 ˙ Í
Íy ˙ 1 1 1 ˙
Í - - ˙ Íy d x2 - y2 ˙
Í 2˙ Í 2 2 2 2 ˙
Í ˙ = Í 1 Í ˙
1 ˙ Íy ˙
Íy 3 ˙ Í 0 - 0˙ p
Í ˙ Í x ˙
Í 2 2 ˙ Í ˙
Í ˙ Í 0 1 1 ˙ y p y ˙˚
y
Î 4˚ 0 - Í
Î
ÍÎ 2 2 ˙˚
È1 1 1
0 ˘˙ Èy 2 s ˘
Í2 2 2 Í ˙
Í1 1 ˙ Íy
˙ Í d 2 2 ˙˙
1
Í - 0
= Í 2 2 2 ˙ Í x -y ˙
Í1 1 1 ˙
Í - 0 ˙ Íy p x ˙
Í2 2 2 ˙ ÍÍ ˙
˙
Í 1 1 1 ˙ Íy p
- 0 - Î ˙˚
ÍÎ 2 2 2 ˙˚
y

This gives
1 1 1
y1 = y 2s + y d 2 2 + yp
2 2 x -y 2 x
1 1 1
y2 = y 2s - y d 2 2 + yp
2 2 x -y 2 y
 Molecular Symmetry and Its Applications 639

1 1 1
y3 = y 2s + y d 2 2 - yp
2 2 x -y 2 x
1 1 1
y4 = y 2s - y d 2 2 - yp
2 2 x -y 2 y
Analysis of Figure 5.20.6 displays the eight p-orbitals of the for B atoms in a planar AB4
p-Hybridization molecule.
p(^) p(^)
p(||)
B B
p(||)
p(^) A p(^)
p(||)
Fig. 5.20.6 p-orbitals
of B atoms in a planar B B
molecule AB4 p(||)

The p(| |) orbitals are not interchanged with any of p(^) orbital under the symmetry
operations of the group D4h. Hence, these may be treated separately as far as the
bases of reducible representations are concerned. Hence, we have
E 2C4 C2 2C¢2 2C≤2 i 2S4 sh 2sv 2sd
Gp(| |) 4 0 0 –2 0 0 0 4 –2 0
Gp(^) 4 0 0 –2 0 0 0 –4 2 0
Their resolution in the irreducible representations gives
Gp(| |) = G A 2g + G B2g + G E u
Gp(^) = G A 2u + G B2u + G Eg
The orbitals involved in these irreducible representations are
A2g : none B2g : dxy Eu : (px, py)
A2u : pz B2u : none Eg : (dxz, dyz)
The conclusions regarding p-bonds are as follows.
∑ Neither of the two sets will form complete bonding as the orbitals (among s, p
and d) do not exist under the representation A2g and B2u, respectively.
∑ Among parallel p-orbitals, only dxy orbital is available since px and py orbitals
are already involved in s bondings. Hence, only one p-bond in molecular plane
shared equally among all four A—B pairs is possible.
∑ Among perpendicular orbitals, only pz, dxz and dyz orbitals are available. Hence
three p-bonds perpendicular to the molecular plane shared equally among all
four A—B pairs are possible.

5.21 PREDICTING ZERO VALUE OF AN INTEGRAL

Introduction Consider the integrals
+a +a
x2 a 2 (- a)2
Ú x d x =
2
=
2
-
2
=0
-a -a
640 A Textbook of Physical Chemistry

+a +a
x3 a 3 ( - a )3 2 3
Ú x2 d x =
3
=
3
-
3
= a
3
-a -a

In general, if the integrand is odd, i.e. f (x) = – f (– x), then the integral of the above
type results into a zero value. If the integrand is even, i.e. f (x) = f (– x), then the
integral results into a nonzero value. The above generalization can be extended to
more involved integrals which appear in many applications of quantum chemistry.
Integrals Involved In the evaluation of electronic energies in an atom or a molecule, one encounters
in Secular integrals of the type
Equations
Hij = Ú yi H
� y dt
j (5.21.1)
�
where H is Hamiltonian operator and yi and yj are the orbitals.
The Hamiltonian operator is an energy operator. Since the latter is no way affected
by the symmetry operations, it belongs to the totally symmetric representation. The
symmetry of the integrand in the above integral depends on the representations
contained in the direct product of the representations of yi and yj. This direct
product will yield totally symmetric representation only when both y i and yj
belong to the same irreducible representation. Hence, the criterion of the integral
Hij having a nonzero value is as follows.
Both yi and yj must belong to the same irreducible representation of the molecular
point group.
ILLUSTRATION OF trans-BUTADIENE
If we adopt 2pz orbitals (represented as j1, j2, j3 and j4) as the basis of constructing
molecular orbitals of trans-butadiene (Fig. 5.21.1), we would write the molecular
orbitals as
yM0 = C1j1 + C2j2 + C3j3 + C4j4 (5.21.2)

+ +
2
1C C

– – + +
3
4
C C
Fig. 5.21.1 Trans-
Butadiene – –

The energies of molecular orbitals, under Hückel approximations, are given by

the secular determinant,
a-E b 0 0
b a-E b 0
=0 (5.21.3)
0 b a-E b
0 0 b a-E
 Molecular Symmetry and Its Applications 641

On opening this determinant, we get an expression of fourth power in E which can

be solved to give the following roots.
E = a + 1.618 b E¢ = a + 0.618 b
E≤ = a – 0.618 b E≤¢ = a – 1.618 b (5.21.4)
Substituting these energies one by one in secular equations along with the

C1, C2, C3 and C4.

Simplification by
using SALCs adapted linear combinations (Eqs 5.18.70 to 5.18.74).
1 1
Bg : y1 = (j1 – j4) and y2 = (j2 – j3) (5.21.5)
2 2
1 1
Au : y3 = (j1 + j4) and y4 =
(j2 + j3) (5.21.6)
2 2
� |y Ò is zero unless y and y
Knowing the fact that the matrix element ·yi | H j i j
belong to the same irreducible representation, the secular determinant for the
molecular orbital
yMO = C1y1 + C2y2 + C3y3 + C4y4 (5.21.7)
takes the following form.
H11 - E H12 0 0
H 21 H 22 - E 0 0
=0 (5.21.8)
0 0 H 33 - E H 34
0 0 H 43 H 44 - E

This determinant is factored into two determinants:

H11 - E H12 H 33 - E H 34
=0 and =0 (5.21.9)
H 21 H 22 - E H 43 H 44 - E
Thus, we get all the four energies by solving two determinants of the order 2 ¥
2 instead of one determinant of the order 4 ¥ 4. This way, the symmetry of the
molecule helps simplifying the molecular calculations.
In the present case, we have
1 � |(j – j )Ò
H11 = ·(j1 – j4)| H 1 4
2
1 � |j Ò – ·j | H
� |j Ò – ·j | H
� |j Ò + ·j | H
� |j Ò]
= [·j1| H 1 1 4 4 1 4 4
2
Under the Hückel approximations, this reduces to
1
H11 = [a – 0 – 0 + a] = a
2
642 A Textbook of Physical Chemistry

H22 = a – b
H12 = H21 = b

a-E b x 1
= 0 or = 0 where x = (a – E )/b
b (a - b ) - E 1 x -1
This gives x(x – 1) – 1 = 0 i.e. x2 – x – 1 = 0

1- 1+ 4 1+ 1+ 4
Its roots are x1 = and x2 =
2 2
a - E1 1- 5
Hence = fi E1 = a + 0.618b (5.21.10)
b 2

a - E2 1+ 5
and = fi E2 = a – 1.618b (5.21.11)
b 2
Similarly working with the second determinant, we will get
E3 = a + 1.618b and E4 = a – 0.618b (5.21.12)

Substitution of these energies one by one in the corresponding secular equations

along with the normalization expression of molecular orbitals provides the
C1, C2, C3 and C4 in Eq. (5.21.7). For example, for E1 = a + 0.618b,
we get
C1(a – E) + C2b + C3(0) + C4(0) = 0
or C1[a – (a + 0.618b )] + C2b = 0
or C1 = C2/0.618

Substituting this in the expression C21 + C22 = 1, we get

2
Ê C2 ˆ 2
Ë 0.618 ¯ + C2 = 1 fi C22 = 0.276 fi C2 = 0.526

C2 0.526
C1 = = = 0.851
0.618 0.618
Hence
(B )
g
E1 = a + 0.618b y 1,MO = 0.851y1 + 0.526y2

È 1 (j - j ) ˘
= 0.851 ÍÈ (j1 - j 4 ) ˘˙ + 0.526 Í
1
2 3 ˙
Î 2 ˚ Î 2 ˚
= 0.602(j1 – j4) + 0.372(j2 – j3) (5.21.13)
 Molecular Symmetry and Its Applications 643

Similarly, working with other energies, we will get

(B )
g
E2 = a – 1.618b y 2,MO = 0.372(j1 – j4) – 0.602(j2 – j3) (5.21.14)
(A u )
E3 = a + 1.618b y 3,MO = 0.372(j1 + j4) + 0.602(j2 + j3) (5.21.15)
(A u )
E4 = a – 0.618b y 4,MO = 0.602(j1 + j4) – 0.372(j2 + j3) (5.21.16)
ILLUSTRATION OF NAPHTHALENE
I
naphthalene (Eqs. 5.18.79 to 5.18.88). In the molecular orbital treatment, the secular
determinant of naphthalene will be factored into the following four determinants
(see, Eqs 5.18.89 to 5.18.92).
H11 - E H12
B2g symmetry: =0 (5.21.17)
H 21 H 22 - E
H 33 - E H 34 H 35
B3g symmetry: H 43 H 44 - E H 45 =0 (5.21.18)
H 53 H 54 H 55 - E
H 66 - E H 67
Au symmetry: =0 (5.21.19)
H 76 H 77 - E
H 88 - E H 89 H 8,10
B1u symmetry: H 98 H 99 - E H 9,10 =0 (5.21.20)
H10,8 H10,9 H10,10 - E
Working for Here, we work out the molecular orbitals y1 and y2. The remaining molecular
Molecular Orbitals orbitals can be worked out following the same procedure. We follow Hückel
Y1 and Y2 approximations while examining the elements of secular determinants. These are
� |j
ji | H i =a

and � |j
ji | H =b if i and j are neigbouring atoms
j

=0 if i and j are non-neighbouring atoms

We have
� | y ¢ = 1 (j - j - j + j ) | H
H11 = y 1¢ | H � | (j - j - j + j )
1 1 5 8 4 1 5 8 4
4
1 � |j + j | H � |j + j | H � |j + j | H � |j ]
= È j1 | H
4Î
1 5 5 8 8 4 4

=a
� | y¢ Ò = 1 ·(j – j – j + j ) | H
H12 = ·y¢1 | H � | (j – j – j + j )Ò
2 1 5 8 4 2 6 7 3
4
1 � | j Ò + ·j | H � | j Ò + ·j | H � | j Ò + (j | H � | j )]
= [·j1 | H 2 5 6 8 7 4 3
4
=b
H21 = H12
644 A Textbook of Physical Chemistry

1
H22 = ·y¢1 | H | y¢2Ò = (j2 – j6 – j7 + j3) | H | ·j2 – j6 – j7 + j3)Ò
4
1
=[·j2 | H | j2Ò + ·j2 | H | j3Ò + ·j6 | H | j6Ò + ·j6 | H | j7Ò
4
+ ·j7 | H | j6Ò + ·j7 | H | j7Ò + ·j3 | H | j2Ò + ·j3 | H | j3Ò]
=a+b
With these, the secular determinant as given by Eq. (5.21.17) becomes
a-E b x 1
= 0 or =0 [where x = (a – E)/b ]
b a +b -E 1 x +1
Opening the determinant, we get
x(x + 1) – 1 = 0 or x2 + x – 1 = 0
Its roots are
-1 - 1 + 4 -1 + 1 + 4
x1 = = – 1.618 and x2 = = 0.618
2 2
a - E1
Hence = – 1.618 fi E1 = a + 1.618b
b
a - E2
= 0.618 fi E2 = a – 0.618b
b
The secular equations are
C1(H11 – E) + C2 H12 = 0 i.e. C1(a – E) + C2 b = 0
C1 H21 + C2 (H22 – E) = 0 i.e. C1b + C2(a + b – E) = 0
∑ For E1 = a + 1.618b, we get
C1(– 1.618b ) + C2 b = 0 i.e. C1/C2 = 1/1.618 = 0.618
From the normalization of y 1, we get
C12 + C22 = 1 fi (0.618 C2)2 + C22 = 1
fi C2 = 1/(1 + 0.6182 ) = 0.850
Hence C1 = (0.618)C2 = (0.618)(0.850) = 0.526
Thus y 1 = C1y¢1 + C2y¢2 = 0.526y¢1 + 0.850y¢2

= 0.526 È (j1 - j 5 - j8 + j 4 ) ˘ + 0.850 È (j 2 - j 6 - j 7 + j 3 ) ˘

1 1
ÎÍ 2 ˚˙ ÍÎ 2 ˚˙
= 0.263(j1 – j5 – j8 + j4) + 0.425 (j2 – j6 – j7 + j3)
∑ For E2 = a – 0.168b, we get
C1(0.618b) + C2 = 0 i.e. C1/C2 = – 1/0.618 = – 1.618
From the normalization of y 2, we get
C12 + C22 = 1 fi (– 1.618C2)2 + C22 = 1
fi C2 = 1/(1 + 1.6182 ) = 0.526
Hence C1 = (– 1.618)C2 = (– 1.618) (0.526) = – 0.850
 Molecular Symmetry and Its Applications 645

Thus y 2 = C1y¢1 + C2y¢2 = – 0.850y¢1 + 0.526y¢2

= – 0.850 È (j1 - j 5 - j8 + j 4 ) ˘ + 0.526 È (j 2 - j 6 - j 7 + j 3 ) ˘

1 1
ÎÍ 2 ˚˙ ÎÍ 2 ˚˙
= – 0.425(j1 – j5 – j8 + j4) + 0.263 (j2 – j6 – j7 + j3)
Energies of Working similarly, it can be shown that the energies and wavefunctions of the
Remaining MOs remaining symmetries are as follows.
B3g Symmetry
E3 = a + 1.303b
y3 = 0.400(j1– j4 – j5 + j8) + 0.174(j2 – j3 – j6 + j7) + 0.347(j9 – j10)
E4 = a–b
y4 = 0.408(j2 – j3 - j6 + j7) – 0.408(j9 – j10)
E5 = a – 2.303b
y5 = 0.301(j1 – j4 – j5 + j8) – 0.231(j2 – j3 – j6 + j7) – 0.461(j9 –j10)
Au Symmetry
E6 = a + 0.168b
y6 = 0.425(j1 – j4 + j5 – j8) + 0.263(j2 – j3 + j6 – j7)
E7 = a – 1.618b
y7 = 0.263(j1 – j4 + j5 – j8) – 0.425(j2 – j3 + j6 – j7)
B1u Symmetry
E8 = a + 2.303b
y8 = 0.301(j1 + j4 + j5 + j8) + 0.231(j2 + j3 + j6 + j7) + 0.461 (j9 + j10)
E9 = a + b
y9 = 0.408(j2 + j3 + j6 + j7) – 0.408(j9 + j10)
E10 = a – 1.303b
y10 = 0.400(j1 + j4 + j5 + j8) – 0.174(j2 + j3 + j6 + j7) – 0.347(j9 + j10)

Problem 5.21.1 Work out the Hückel p-molecular orbitals along with their energies for the molecule
tetramethylenecyclobutane (assume it to be planar).
Solution The molecule tetramethylenecyclobutane belongs to the point group D4h. The numbering
of atoms is shown in Fig. 5.21.2.

1 4
H2C CH2

2 3

Fig. 5.21.2 A molecule 7 6

of tetramethylene-
cyclobutane H2C CH2
8 5
646 A Textbook of Physical Chemistry

Two sets of 2pz Each of the eight carbon atoms contributes one 2pz orbital towards p-molecular
Orbitals orbitals. These orbitals may be divided into two sets since the orbitals in one set
(2pz orbitals of carbon atoms 1, 4, 5 and 8) are not interchanged with any of the
orbitals in the second set (2pz orbitals of carbon atoms 2, 3, 6 and 7) under the
symmetry operations of the point group D4h. The two sets may be treated separately
to work out SALC’s.
Reducible Based on the two sets of 2pz orbitals the reducible representations are as follows.
Representations
D4h E 2C4 C2 2C¢2 2C≤2 i 2S4 sh 2sv 2sd
Gset1 4 0 0 0 –2 0 0 –4 0 2
Gset2 4 0 0 0 –2 0 0 –4 0 2
Irreducible Both representations being identical will contain the same type and numbers of
representations irreducible representations. Based on the expression
1
ai = Â C nC c (C ) c i (C )
h
we get the following representations.
1
a(A2u) = [1(4)(1) + 2(–2)(–1) + 1(–4)(–1) + 2(2)(1)] = 1
16
1
a(B1u) = [1(4)(1) + 2(–2)(–1) + 1(–4)(–1) + 2(2)(1)] = 1
16
1
a(Eg) = [1(4)(2) + 2(–2)(0) + 1(–4)(–2) + 2(2)(0)] = 1
16
Hence Gset1 = A2u + B1u + Eg and Gset2 = A2u + B1u + Eg
These may be generated by considering the symmetries of the group C4. We ignore
multiplication factors as these are ascertained by the normalization of SALC’s.
Formation of A2u Symmetry
SALC’s Ÿ
2 2 3 3
P A f1 = c (E)E f1 + c (C4) C 4 f1 + c(C4) C 4 f1 + c (C4) C 4 f1
= (1)f1 + (1)f4 + (1)f5 + (1)f8
1
The normalized SALC is y1 = (f1 + f4 + f5 + f8)
2
The operation of P A on f2 (orbital of second set) would give
1
y2 = (f2 + f3 + f6 + f7)
2
B1u Symmetry
P B f1 = (1)f1 + (–1)f4 + (1)f5 + (–1)f8
1
The normalized SALC is y3 = (f1 – f4 + f5 – f8)
2
For the set 2, we have
1
y4 = (f2 – f3 + f6 – f7)
2
 Molecular Symmetry and Its Applications 647

Eg Symmetry
P E f1 = (1)f1 + (i)f4 + (–1)f5 + (–i)f8
i.e. y 5¢ = f1 + if4 – f5 – if8
P E f1 = (1)f1 + (–i)f4 + (–1)f5 + (i)f8
i.e. y 6¢ = f1 – if4 – f5 + if8
The SALC’s y 3¢ and y 4¢
y5 = y 5¢ + y 6¢ = 2f1 – 2f5
y 5¢ - y 6¢
y6 = = 2f4 – 2f8
i
The normalized SALC’s are
1 1
y5 = (f1 – f5) y6 = (f4 – f8)
2 2
For the set 2, we have
1 1
y7 = (f2 – f6) y8 =(f3 – f7)
2 2
Formation of The molecular orbitals are obtained by mixing SALC’s of appropriate symmetries.
Molecular Orbitals
A2u Symmetry Y1,2 = C1y1 + C2y2
B1u Symmetry Y3,4 = C3y3 + C4y4
Eg Symmetry Y5,6,7,8 = C5y5 + C6y6 + C7y7 + C8y8
Molecular Orbitals For the molecular orbitals Y1,2, we have
Y1,2
H11 - E H12
=0
H 21 H 22 - E

1
where H11 = ·y1 H y1Ò = [·(f1 + f4 + f5 + f8) H (f1 + f4 + f5 + f8)Ò]
4
1
= [·f1 H f1Ò + ·f4 H f4Ò + ·f5 H f5Ò + ·f8 H f8Ò]
4
1
= (a + a + a + a) = a
4
1
H12 = ·y1 H y2Ò = [·(f1 + f4 + f5 + f8) H (f2 + f3 + f6 + f7)Ò]
4
1
= [·f1 H f2Ò + ·f4 H f3Ò + ·f5 H f6Ò + ·f8 H f7Ò]
4
1
= (b + b + b + b ) = b
4
H21 = H12
648 A Textbook of Physical Chemistry

1
H22 = ·y2 H y2Ò [·(f2 + f3 + f6 + f7) H (f2 + f3 + f6 + f7)Ò]
4
1
= [·f2 H f2Ò + ·f2 H f3Ò + ·f2 H f7Ò + ·f3 H f2Ò
4
+ ·f3 H f3Ò + ·f3 H f6Ò + ·f6 H f3Ò + ·f6 H f6Ò
+ ·f6 H f7Ò + ·f7 H f2Ò + ·f7 H f6Ò + ·f7 H f7Ò]
1
= [a + b + b + b + a + b + b + a + b + b + b + a]
4
= a + 2b
With these, the secular determinant becomes
a-E b x 1 x-E
=0 fi where x=
b a + 2b - E 1 x+2 b
which gives
x(x + 2) –1 = 0 i.e. x2 + 2x – 1 = 0 fi x = –1 ± 2
a - E1
Hence = –1 – 2 fi E1 = a + 2.414b
b
a - E2
= –1 + 2 fi E2 = a – 0.414b
b

For E1 = a + 2.414b, the secular equation C1(H11 – E) + C2H12 = 0, gives

C1(–2.414)b + C2b = 0 fi C1/C2 = 1/2.414 = 0.414
From the normalization of MO, we get
C 12 + C 22 = 1 fi (0.414C2)2 + C 22 = 1 fi C2 = 0.924
C1 = (0.414)C2 fi (0.414)(0.924) = 0.382
The MO becomes
Y1 = C1y1 + C2y2

= (0.382) ÈÍ (f1 + f4 + f5 + f8 ) ˙˘ + (0.924) ÈÍ (f2 + f3 + f6 + f7 ) ˙˘

1 1
Î2 ˚ Î2 ˚
= 0.191(f1 + f4 + f5 + f8) + 0.462(f2 + f3 + f6 + f7)

For E2 = a – 0.414b, we will get

Y2 = 0.289(f1 + f4 + f5 + f8) – 0.408(f2 + f3 + f6 + f7)
Molecular Orbitals For the functions Y3,4, we will have
Y3,4
H 33 - E H 34 a-E b x 1
=0 fi =0 fi =0
H 43 H 44 - E b a - 2b - E 1 x-2
 Molecular Symmetry and Its Applications 649

This gives x(x – 2) –1 = 0 i.e. x2 –2x –1 = 0 fi x=1± 2

a - E3
Hence, =1– 2 fi E3 = a + 0.414b
b

a - E4
=1+ 2 fi E4 = a – 2.414b
b
For E3 = a + 0.414b, the secular equation C3(H33 – E) + C4 H12 = 0, gives
C3(– 0.414b) + C4b = 0 fi C3/C4 = 1/0.414 = 2.414
From the normalization condition, we get
C 32 + C 42 = 1 fi (2.414C4)2 + C 42 = 1 fi C4 = 0.383
C3 = 2.414C4 = (2.414)(0.383) = 0.924

Hence, Y3 = 0.924 ÈÍ (f1 - f4 + f5 - f8 ) ˘˙ + 0.383 ÍÈ (f2 - f3 + f6 - f7 ) ˘˙

1 1
Î2 ˚ Î2 ˚
= 0.462(f1 – f4 + f5 – f8) + 0.191(f2 – f3 + f6 – f7)

For E4 = a – 2.414b, we will get

y4 = 0.191(f1 – f4 + f5 – f6) – 0.462(f2 – f3 + f6 – f7)

Molecular Orbitals For the molecular orbitals Y5,6,7,8, we have

Y5,6,7,8
H 55 - E H 56 H 57 H 58
H 65 H 66 - E H 67 H 68
=0
H 75 H 76 H 77 - E H 78
H 85 H 86 H 87 H 88 - E

a-E 0 b 0
0 a-E 0 b
fi =0
b 0 a-E 0
0 b 0 a-E
Carrying out the change R2 ´ R3 and then C2 ´ C3, we get
a-E b 0 0
b a-E 0 0
=0
0 0 a-E b
0 0 b a-E
This factors into
Y5,7 = C5y 5 + C7y 7 ¸ a-E b x 1
˝ with =0fi =0
Y6,8 = C6y 6 + C8y 8 Ô˛ b a-E 1 x
650 A Textbook of Physical Chemistry

This gives x2 – 1 = 0 fi x=±1

Substituting in secular equation along with normalization of MO, we get
For x = –1, E5 = a + b ; C5 = C7 = 1/ 2
For x = 1, E7 = a – b ; C5 = – C7 = 1/ 2
Hence, the molecular orbitals are
1
For E5 = a + b Y5 = (f1 – f5 + f2 – f6)
2
1
For E6 = a – b Y7 = (f1 – f5 – f2 + f6)
2
1
For E7 = a + b Y6 = (f4 – f8 + f3 – f7)
2
1
For E8 = a – b Y8 = (f4 – f8 – f3 + f7)
2
Problem 5.21.2 Work out the Hückel p-molecular orbitals along with their energies for trivinylmethyl
radical, ∑C(CH == CH2)3.
Solution The radical trivinylmethyl belongs to the point group D3h. The numbering of atoms is
shown in Fig. 5.21.3.
1
CH2

4
CH
Fig. 5.21.3 Numbering
in trivinylmethyl radical C 5
6 7
HC CH
3 2
H 2C CH2

Three Sets of 2pz Each of the seven carbon atoms contributes one 2pz orbital towards p-molecular
Orbitals
are not interchanged with any of the orbital in the other sets under the symmetry
operations of the point group D3h. The three sets are as follows.
Set 1 Carbon atoms 1, 2 and 3
Set 2 Carbon atoms 4, 5 and 6
Set 3 Carbon atom 7
These three sets may be considered separately for the formation of SALC’s.
Reducible Based on the 2pz orbitals in each set, the reducible representations are as follows.
Representations
D3h E 2C3 3C2 sh 2S3 3sv
Gset1 3 0 –1 –3 0 1
Gset2 3 0 –1 –3 0 1
Gset3 1 1 –1 –1 –1 1
 Molecular Symmetry and Its Applications 651

Irreducible The sets 1 and 2 have identical reducible representations and thus will include
Representations the same type and number of irreducible representations. Based on the expression
1
ai = Â nC c(C) ci (C)
h C
the irreducible representations are as follows.
1
a(A≤2) = [1(3)(1) + 2(0)(1) + 3(–1)(–1) + 1(–3)(–1) + 2(0)(–1) + 3(1)(1)] = 1
12
1
a(E≤) = [1(3)(2) + 2(0)(–1) + 3(–1)(0) + 1(–3)(–2) + 2(0)(1) + 3(0)(1)] = 1
12
For the rest of representations, a = 0.
Hence, Gset1 = A≤2 + E≤
Gset2 = A≤2 + E≤
Gset3 = A≤2
Generation of The SALC’s involving 2pz orbitals which form the bases of above irreducible
SALC’s representations may be generated by considering the symmetry operations of the
group C3. We ignore multiplication factors as these are ascertained by normalization
of SALC’s.
2
A Symmetry Set 1 P A f1 = c (E) E f1 + c(C3) C 3 f1 + c (C 32) C 3 f1
= (1)f1 + 1(f2) + 1(f3)
The normalized SALC is
1
y1 = (f1 + f2 + f3)
3
1
Set 2 y2 = (f4 + f5 + f6)
3
Set 3 y3 = f7
E≤ Symmetry Set 1 P E f1 = (1)f1 + ef2 + e*f3; where e = exp(2pi/3)
i.e. y 4¢ = f1 + ef2 + e*f3
P E ¢ f1 = (1)f1 + e*f2 + ef3
i.e. y 5¢ = f1 + e*f2 + ef3

The SALC’s y 4¢ and y 5¢ may be combined so as to give SALC’s involving real

y4 = y 4¢ + y 5¢ = 2f1 + (e + e*)f2 + (e + e*)f3

= 2f1 + 2 cos (2p/3) {f 2 + f3}

= 2f1 – f2 – f3
y 4¢ - y 5¢
y5 = = 2 sin(2p/3) {f2 – f3} = 3 (f2 – f3)
i
652 A Textbook of Physical Chemistry

The normalized SALC’s are

1 1
y4 = (2f1 – f2 – f3) and y5 = (f2 – f3)
6 2
1 1
Set 2 y6 = (2f4 – f5 – f6) and y7 = (f5 – f6)
6 2
Formation of The molecular orbitals are obtained by mixing SALC’s of appropriate symmetries.
Molecular Orbitals Y1,2,3 = C1y1 + C2y2 + C3y3
Y4,5,6,7 = C4y4 + C5y5 + C6y6 + C7y7
Molecular Orbitals For the molecular orbitals Y1,2,3, we have
Y1,2,3 H11 - E H12 H13
H 21 H 22 - E H 23 =0
H 31 H 32 H 33 - E
1
where H11 = ·y1 | H | y1Ò = [·(f1 + f2 + f3) | H | (f1 + f2 + f3)Ò]
3
1
= [·f1 | H | f1Ò + ·f2 | H | f2Ò + ·f3 | H | f3Ò]
3
1
= (a + a + a) = a
3
1
H12 = ·y1 | H | y2Ò = [·(f1 + f2 + f3) | H | (f4 + f5 + f6)Ò]
3
1
= [·f1 | H | f4Ò + ·f2 | H | f5Ò + ·f3 | H | f6Ò]
3
1
= (b + b + b) = b
3
1
H13 = ·y1 | H | y3Ò = [·(f1 + f2 + f3) | H | f7Ò]
3
=0
H21 = H12 = b
1
H22= [·y2 | H | y2Ò = [·(f4 + f5 + f6) | H | (f4 + f5 + f6)Ò]
3
1
= [·f4 | H | f4Ò + ·f5 | H | f5Ò + ·f6 | H | f6Ò]
3
1
= (a + a + a) = a
3
1
H23 = [·y2 | H | y3Ò = [·(f4 + f5 + f6) | H | f7Ò]
3
1
= [·f4 | H | f7Ò + ·f5 | H | f7Ò + ·f6 | H | f7Ò]
3
1
= (b + b + b) = 3 b
3
 Molecular Symmetry and Its Applications 653

H31 = H13 = 0
H32 = H23 = 3b
H33 = ·y3 | H | y3Ò = ·f7 | H | f7Ò = a
With these, the secular determinant becomes
a-E b 0 x 1 0
a-E
b a-E 3b =0 fi 1 x 3 = 0 where x =
b
0 3b a-E 0 3 x
2
which gives x(x – 3) – x = 0 i.e. x = 0, x = –2 and x = 2
These give E1 = a ; E2 = a + 2b and E3 = a – 2b
The secular equations are
C1(a – E) + C2b = 0
C1b + C2(a – E) + C3 ( 3b = 0)
C2 ( )
3b + C3(a – E) = 0
These along with normalization expression
C 12 + C 22 + C 32 = 1
give the following MOs.
1 1
Y1 = (f1 + f2 + f3) – f7; E1 = a
2 2
1 1 3
Y2 = (f1 + f2 + f3) + (f4 + f5 + f6) + f7; E2 = a + 2b
2 6 6 2 6
1 1 3
Y3 = (f1 + f2 + f3) – (f4 + f5 + f6) + f7; E3 = a – 2b
2 6 6 2 6
Molecular Orbitals For molecular orbitals Y4,5,6,7, we will have
Y4,5,6,7 H 44 - E H 45 H 46 H 47
H 54 H 55 - E H 56 H 57
=0
H 64 H 65 H 66 - E H 67
H 74 H 75 H 76 H 77 - E
a-E 0 b 0
0 a-E 0 b
fi =0
b 0 a-E 0
0 b 0 a-E
Carrying out the change R2 ´ R3 follwoed by C2 ´ C3, we get
a-E b 0 0
b a-E 0 0
= =0
0 0 a-E b
0 0 b a-E
 654 A Textbook of Physical Chemistry

The above secular determinant leads to the following combinations.

Y4,6 = C4y4 + C6y6
Y5,7 = C5y5 + C7y7
For both these combinations, the secular determinant is
a-E b x 1
= 0 i.e. =0
b a-E 1 x
Opening the secular determinant, we get
x2 – 1 = 0 fi x = – 1 and x = 1
These give
E4 = a + b and E6 = a – b
E5 = a + b and E7 = a – b
Substituting these in the secular equation C4(a – E) + C6b = 0 [or C5(a – E)
+ C7b = 0] along with the normalization expression C 42 + C 62 = 1 (or C 25 + C 27 = 1)
give the following results.
1 1
Y4 = (2f1 – f2 – f3) + (2f4 – f5 – f6); E4 = a + b
12 12
1 1
Y5 = (f2 – f3) + (f5 – f6); E5 = a + b
2 2
1 1
Y6 = (2f1 – f2 – f3) – (2f4 – f5 – f6); E6 = a – b
12 12
1 1
Y7 = (f2 – f3) – (f5 – f6); E7 = a – b
2 2

Problem 5.21.3 Work out p-molecular orbitals of an allyl radical along with their energies.
Solution The allyl redical is shown in Fig. 5.21.4. All the three carbon atoms lie in the xy plane. The
pz orbital on each carbon atom lies along the z-direction. The molecule belongs to the group
C2v with C2 axis coinciding with y-direction.

Fig. 5.21.4 An allyl

radical

Irreducible The reducible representation based on the three pz orbital is

Representations
C2v E C2 syz sxy
Gp 3 –1 1 –3
The reduction of reducible representation gives
1
a(A2) = [c (E) ci(E) + c(C2) ci(C2) + c(syz) ci(syz) + c(sxy) ci(sxy)]
h
 Molecular Symmetry and Its Applications 655

1
=
[(1)(3) + (1)(–1) + (–1)(1) + (–1)(–3)] = 1
4
1
a(B1) = [(1)(3) + (–1)(–1) + (1)(1) + (–1)(–3)] = 2
4
Hence Gp = A2 + 2B1
Formation of The use of projection operator gives the following SALC’s.
SALC’s P B1 f1 = c B1( E ){Ef1} + c B1(C2 ){C 2f1} + c B1(s yz ){s yzf1} + c B1(s xy ){s xyf1}
= (1)f1 + (–1)(–f3) + (1)(f3) + (–1)(–f1)
= 2f1 + 2f3
1
The normalized function is y 1¢( B1 ) = (f1 + f3)
2
P B1 f2 = (1)(f2) + (–1)(–f2) + (1)(f2) + (–1)(–f2) = 4f2

that is y 2¢ ( B1 ) = f2
P A 2 f1 = (1)f1 + (1)(–f3) + (–1)(f3) + (–1)(–f1)
= 2f1 – 2f3
(A ) 1
The normalized function is y 3¢ 2 = (f1 – f3)
2
Formation of Since y 1¢ and y 2¢ are of same symmetry, we may write
Molecular Orbitals y1,2 = C1y 1¢ + C2y 2¢
The secular determinant is
H11 - E H12
=0
H 21 H 22 - E
1
where H11 = ·y 1¢ | H | y¢1Ò = [·(f1 + f3) | H | (f1 + f3)Ò]
2
1
= [·f1 | H | f1Ò + ·f1 | H | f3Ò + ·f3 | H | f1Ò + ·f3 | H | f3Ò]
2
1
= [a + 0 + 0 + a] = a
2
1
H12 = ·y 1¢ | H | y¢3Ò = [·(f1 + f3) | H | f2Ò]
2
1
= [·f1 | H | f2Ò + ·f3 | H | f2Ò]
2
1
= (b + b) = 2 b
2
a-E 2b x 2
Hence =0 i.e. =0 where x = (a – E)/b
2b a-E 2 x
This gives x2 – 2 = 0 or x=± 2
For x=– 2 , E1 = a + 2 b
and for x= 2, E2 = a – 2 b
656 A Textbook of Physical Chemistry

The secular equations are

C1 (H11 – E) + C2 H12 = 0
C1 H21 + C2 (H22 – E) = 0
For E1 = a + 2 b, we get C1 = C2
E2 = a – 2 b; we get C1 = – C2
From the normalization expression (C 12 + C 22 = 1) of molecular orbital, we get
E1 = a + 2 b ; C1 = C2 = 1/ 2
E2 = a – 2 b; C1 = – C2 = 1/ 2
1 1 1
Hence y1 = y 1¢ + y 2¢ =
(f1 + 2 f2 + f3); E1 = a + 2 b
2 2 2
1 1 1
y2 = y 1¢ – y 2¢ = (f1 – 2 f2 + f3); E2 = a – 2 b
2 2 2
The energy of y3 is
1
E3 = ·y3 | H | y3Ò = [·(f1 – f3) | H | (f1 – f3)Ò]
2
1
= [·f1 | H | f1Ò – ·f1 | H | f3Ò – ·f3 | H | f1Ò + ·f3 | H | f3Ò]
2
1
= [a – 0 – 0 + a] = a
2

5.22 IRREDUCIBLE REPRESENTATIONS OF VIBRATIONAL MOTIONS

Degrees of A system consisting of N atoms can be described by specifying three coordinates

Freedom for each atom, i.e. a total of 3N coordinates. Since any one of these components
can vary by any amount, the system is said to possess 3N independent components
of motion or degrees of freedom. If N atoms are bound to form a molecule, the 3N
degrees of freedom can be reallocated as described in the following.
Translational Motion The translational motion can be described by stating x-,
y- and z-coordinates of the centre of mass of the molecule. Thus, 3 degrees of
freedom are used to describe the translational motion of a molecule.
Rotational Motion The rotational motion can be described by stating two angles
along the two axes (excluding molecular axis) for a linear molecule and three
angles along the three axes for a nonlinear molecule. Thus, 2 degrees of freedom
for a linear molecule and 3 degrees of freedom for a nonlinear molecule are used
to describe the rotational motion of a molecule.
Vibrational Motion The remaining degrees of freedom (3N –5 for a linear
molecule and 3N–6 for a nonlinear molecule) are used to describe the vibrational
motion of a molecule. In other words, a molecule has 3N–5 (for a linear molecule)
or 3N–6 (for a nonlinear molecule) independent modes of vibrations. These can be
described in terms of internal displacement vectors representing changes in bond
lengths and bond angles of a molecule.
 Molecular Symmetry and Its Applications 657

Irreducible The irreducible representations for which vibrational motions form the bases are
Representations of determined indirectly as described in the following.
Vibrational Motions
Reducible representations based on the three mutually perpendicular vectors attached
to each atom is determined. This is resolved into irreducible representations.
From these, irreducible representations of translational and rotational motions
as determined from the character table are deleted. The remaining irreducible
representations correspond to the vibrational motions of the molecule.

Example of Water Molecule

Water molecule (point group C2v) has a total of nine (= 3N) degrees of freedom
of which three (= 3N –6) belongs to vibrational motions. As deduced earlier
(Eq. 5.16.1), we have
G3N = 3A1 + A2 + 2B1 + 3B2 (a total of 9 representations)
From the character table of C2v
Gtrans = B1 + B2 + A1 (a total of 3 representations)

Grot = B2 + B1 + A2 (a total of 3 representations)

Hence Gvib = G3N – Gtrans – Grot
= 2A1 + B2 (a total of 3 representations)
The above representations may be attributed to different modes of vibration
involving changes in the internal coordinates, namely, bond lengths and bond angles.
Bond-Stretching Bond-stretching vibrations may be analysed by associating each bond with the
Vibrations change in bond-stretching vector. Reducible representation based on these vectors
is established and is resolved into irreducible representations of the point group.
The results are is follows.

O C2v E C2 sv(1) sv(2) Comments

r1 r2 Gstretch 2 0 0 2 C2 and sv(1) interchange
the two vectors, while E and
H H sv(2) leave both unshifted

1
a(A1) = [1(2)(1) + 1(0)(1) + 1(0)(1) + 1(2)(1)] = 1
2
1
a(B2) = [1(2)(1) + 1(0)(–1) + 1(0)(–1) + 1(2)(1)] = 1
2
Hence Gstretch = A 1 + B2
Thus, two modes of vibration belong to bond-stretching vibrations with irreducible
representations A1 and B2, respectively.
Angle-Deforming Angle-deforming vibrations may be analysed in terms of change in bond angles as
Vibrations the bases. The vector used is the change in angle Dq which undergoes deformation.
Reducible representation with this vector as a basis is
658 A Textbook of Physical Chemistry

O C2v E C2 sv(1) sv(2) Comments

Gangle 1 1 1 1 In each operation, bond
q angle remains unshifted.
H H

These characters are those of the A1 irreducible representation. This also follows
from the expression Gvib – Gstretch.

Example of NH3 Molecule

Ammonia (point group C3v) has a total of twelve (= 3N, N = 4) degrees of
freedom of which six (= 3N –6) belongs to vibrational motions. As deduced earlier
(Eq. 5.16.2), we have
G3N = 3A1 + A2 + 4E (a total of 12 representations)
From the character table of C3v
Gtrans = E + A1 (a total of 3 representations)
Grot = E + A2 (a total of 3 representations)
Hence Gvib = G3N – Gtrans – Grot
= 2A1 + 2E (a total of 6 representations)
Bond-Stretching Reducible representation for which changes in bond-stretching vectors form the
Vibrations bases is
N C3v E 3C3 3sv Comments

3 0 1 E interchanges no bond vector, C3 and

H
C 23 change all the three vectors and
H H
each of three sv operation leaves one
bond unshifted..
This is resolved as
Gstretch = A1 + E (a total of 3 representations)
Angle-Deforming There are three angle-deforming vectors Dq1, Dq2 and Dq3. Based on these, the
Vibrations reducible repesentation is
C3v E 2C3 3sv Comments

Gangle 3 0 1 E interchanges no bond angle, C3 and

C 23 shift all the three angles and each
of three sv operation leaves one angle
unshifted.
This is resolved as
Gangle = A1 + E (a total of 3 representations)

Example of CH4 Molecule

Methane (point group Td N) degrees of freedom of which
nine (= 3N–6) belong to vibrational motions. As deduced earlier (Eq. 5.16.3), we have
G3N = A1 + E + T1 + 3T2 (a total of 15 representations)
 Molecular Symmetry and Its Applications 659

From the character table of Td, we have

Gtrans = T2 (a total of 3 representations)
Grot = T1 (a total of 3 representations)
Hence Gvib = G3N – Gtrans – Grot
= A1 + E + 2T2 (a total of 9 representations)
Bond-Stretching Reducible representation for which changes in bond-stretching vectors form the
Vibrations bases is
Td E 8C3 3C2 6S4 6sd

Gstretch 4 1 0 0 2
This is resolved as
Gstretch = A1 + T2 (a total of four representations)

Angle-Deforming There are six angle-deforming vectors (HaCHb, HaCHc, HaCHd, HbCHc, HbCHd,
Vibrations HcCHd). Based on these, the reducible representation is

Gd E 8C 3C2 6S4 6sd

Gangle 6 0 2 0 2

This is resolved as
Gangle = A1 + E + T2 (a total of six representations)
Redundant Representation If we count the number of representations in Gstretch
and Gangle

Gstretch + Gangle = (A1 + T2) + (A1 + E + T2)

= 2A1 + E + 2T2 (Eqs.)
Comparing this with
Gvib = A1 + E + 2T2 (Eq.)
1 is extra. This is called the spurious or redundant
representation. Which of the two A1 representations (whether in Gstretch of Gangle)

There are four bonds in CH4 molecule and each of these can undergo a change
in bond length independently of the others. But the six angles in CH4 cannot be

1 representation of Gangle, all the six angles

have to be changed in identical manner (either increase or decrease) at the same
time which is not possible. Hence, the A1 representation in Gangle is redundant.
Thus, the correct list of representations is
Gstretch = A1 + T2
Gangle = E + G2
660 A Textbook of Physical Chemistry

From this, it may be concluded that

(i) The representation A1 consists of purely bond stretching, i.e. only bond
distances are changed.
(ii) The representation E consists of purely bond-angles deformation.
(iii) The representations T2 which occur in both Gstretch and Gangle involve both
bond stretching and angles deformation.
Example of CH3D
The molecule CH3D belongs to the point group C3v. It has a total of 15 (= 3 N,
N = 5) degrees of freedom of which 9 (= 3N –6) belongs to the vibrational motions.
The reducible representation based on the three vectors on each atom is
C3v E 2C3 3sv
G3N 15 0 3
The resolution of this representation gives
G3N = 4A1 + A2 + 5E

Gtrans = A1 + E
Grot = A2 + E
Hence Gvib = G3N – Gtrans – Grot = 3A1 + 3E
Bond-Stretching The reducible representation based on the changes in bond-stretching vectors is
Vibrations C3v E 2C3 3sv
Gstretch 4 1 2
Its resolution gives
Gstretch = 2A1 + E
Angle-Deforming The reducible representation based on angle-deforming vectors is
Vibrations C3v E 2C3 3sv
Gangle 6 0 2

Its resolution is Gangle = 2A1 + 2E

The A1 representation in Gangle is redundant since it is not possible to change all
the six angles in identical manner.

Example of trans-N2F2
Trans-N2F2 (point group C2h) has a total of twelve (= 3N) degrees of freedom of
which six (= 3N –6) belong to vibrational motions. As deduced earlier (Eq. 5.16.4),
we have
G3N = 4Ag + 2Bg + 2Au + 4Bu
From the character table of C2h
Gtrans = Bu + Bu + Au
Grot = Bg + Bg + Ag
 Molecular Symmetry and Its Applications 661

Bond-Stretching Hence Gvib = G3N – Gtrans – Grot = 3Ag + Au + 2Bu

Vibrations Reducible representation for which changes in bond-stretching vectors form the
bases is
C2h E C2 i sh
Gstretch 3 1 1 3
This is reduced to
Gstretch = 2Ag + Bu
Angle-Deforming There are two angle-deformation vectors in the molecular plane. Reducible
Vibrations representation for which these vectors form the bases is
C2h E C2 i sh
Gangle 2 0 0 2

This is reduced to
Gangle = Ag + Bu
The only left-out representation is Au. Inspection of this irreducible representation

representation represents out-of-plane deformation.

5.23 PREDICTING PROBABILITY OF A SPECTRAL TRANSITION

Criterion of The intensity of a spectral transition from a state yi to a state yj is directly

Feasibility of a
Transition
T = Ú y i m y j dt (5.23.1)

where m is the operator for the electric-dipole of a molecule. Since the electric
dipole is a vector quantity, the above integral may be expressed in terms of the
following integrals.

Tx = Ú y i m xy j dt ; Ty = Ú y i m yy j dt and Ú y i m z y j dt (5.23.2)

The transition is said to be one-dimensionally polarized if any one of the three

above integrals has a nonzero value while the other two have zero values.

In a molecule, if both x and y jointly form the bases of irreducible representation,

the transition is said to be xy polarized provided Tx π 0, Ty π 0 and Tz = 0.

No polarization effect is observed if all the three coordinates form the bases of
irreducible representation of a molecule.

The problem of predicting whether a certain transition is allowed or not depends

on the nonzero value(s) of the above three integrals. The guiding principle for this
fact may be understood from the following analysis.
662 A Textbook of Physical Chemistry

Each transition moment integral, i.e. ·yi | m | yjÒ, is a number and is therefore invariant
under all the operations of the group to which the molecule belongs. Hence, all
operations on the transition moment integral should leave it unchanged, i.e.
R ·yi | m | yjÒ = (+1)·yi | m | yjÒ

transforms as the totally symmetric representation of the group concerned. In other

words, for the transition yi Æ yj to be allowed, the direct product of representations
of yi, yj and m (which implies the multiplication of the corresponding characters
of operations of the involved representations) should correspond to the totally
symmetric representation.
Alternatively, it may be stated as follows. The direct product of the representations
of the two states yi and yj should correspond to the irreducible representation to
which x, y, or z, respectively, belongs.
Symmetry For the fundamental transition in the ith normal mode of vibration, Eq. (5.23.2)
Selection Rules takes the form
for Infrared
Spectra Ú y 0 | m x | y 1 dt
Ú y 0 | m y | y 1 dt
Ú y 0 | m z | y 1dt
where y0 is the vibrational ground wave function and y1
excited wave function. It is known that
(i) The vibrational ground wave function is totally symmetric.
(ii) The symmetry properties of the component of the dipole moment are the same
as those of a translational vector along the same axis.

same as those of irreducible representation of the normal mode of vibration.

In order that the direct product of y0, m k and y1 belongs to the totally symmetric
representation, both m k and y1(1) should belong the same representation.
Thus the essential criterion for observing fundamental transition in the infrared
spectroscopy is
A fundamental transition will be infrared active if the normal mode which is
excited belongs to the same representation as any one or several of the Cartesian
coordinates.
Symmetry The symmetry selection rule for Raman spectra is derived from the integral
Selection Rule for Ÿ
Raman Spectra Ú y 0 | a | y 1dt (5.23.3)

where a is the polarizability of the molecule. The polarizability a is a tensor, it

has a 3 ¥ 3 array of components
 Molecular Symmetry and Its Applications 663

a x2 a xy a xz
a yx a y2 a yz (5.23.4)
a zx a zy a z2
For vibrational transitions aij = aji (where i, j = x, y or z), and thus there are six
distinct components, namely, a x2 , a y 2 , a z 2 axy, axz and ayz. These are transformed
by the symmetry operations in the same way as x2, y2, z2, xy, xz and yz, respectively.
The six polarizability functions generate a reducible representation which can
be resolved into irreducible representations involving the above combination of
coordinates.
In order that Eq. (5.23.3) is nonzero with any of the six components, we must have
A fundamental transition will be Raman active if the normal mode involved belongs
to the same irreducible representation as one or more of the components of the
polarizability tensor of the molecule.

ILLUSTRATIONS OF IR AND RAMAN SPECTRA

Water Molecule Water belongs to the point group C2v
Stretching vibration A1 includes z, x2, y2 and z2. Thus it is active in both infrared
and Raman spectra.
Stretching vibration B2 includes y and yz. Thus, it is active in both infrared and
Raman spectra.
Bond-deformation vibration A1 is also active in both infrared and Raman spectra.
Ammonia Ammonia belongs to the point group C3v
Molecule Stretching vibration A includes z, x2 + y2 and z2. Thus, it is active in both infrared
and Raman spectra
Stretching vibration E includes x, y, xz and yz. Thus, it is active in both infrared
and Raman spectra.
Bond-deformation vibrations also belong to A and E representations and thus both
will be active in both infrared and Raman spectra.
Trans N2F2 Trans N2F2 belongs to the point group C2h
Stretching vibrations Ag includes x2, y2 and xy. Thus, these modes are infrared
inactive and Raman active.
Stretching vibration Bu involves x and y. Thus, this mode is infrared active and
Raman inactive.
Likewise bending modes Ag and Bu are respectively, infrared inactive and Raman
active.
Bending mode Au involves only z. Thus, this mode is infrared active and Raman
inactive.
664 A Textbook of Physical Chemistry

Methane Molecule Methane belongs to the group Td

stretching vibration of A1 representation is IR inactive and Raman active.
Bond deformation vibration of E representation is also IR inactive and Raman active.
The stretching and bond deformation vibrations of T2 representation are active in
both IR and Raman spectra.
Example of CH3D The representation A1 includes z, x2 + y2 and z2. Thus, the three non-degenerate
Molecule fundamental vibrations are both infrared and Raman active.
The representation E includes (x, y), (x2 – y2, xy) and (xz, yz). Thus, the doubly
degenerate fundamental vibrations are also both infrared and Raman active.
Rule of Mutual For a molecule having centre of symmetry, we have the following facts.
Exclusion
∑ The representations generated by the Cartesian coordinates x, y or z belong to
u representations as the values of x, y and z change sign on inversion through
the centre of symmetry. Since the dipole moment is ungerade and involves
Cartesian coordinates, it follows that all vibrational modes belonging to u
representations will be infrared active.
∑ The representations generated by binary products of two Cartesian coordinates
(say, xy, xz, yz, x2, y2 and z2) belong to g representations as these do not change
sign on inversion through the centre of symmetry. Since the polarizability
tensor involves binary products of Cartesian coordinates, it follows that all
vibrational modes belonging to g representations will be Raman active.

The above fact, known in the form exclusion rule, is stated as follows.
In a centrosymmetric molecule no Raman-active vibration is infrared active and
vice versa.
ANALYSIS OF VIBRATIONAL MODES OF A LINEAR MOLECULE
A linear molecule (point groups C•v and D•h
symmetry operations. It is not possible to resolve a reducible representation into
irreducible representations as h = •. It is, therefore, necessary to carry out the
resolution by inspection.

Taking an example of CO2 (point group D•h) with the molecular axis as the
z-axis, the reducible representation based on rotating the molecule about the z-axis
by an angle j is

D•h E 2C•(j) •sv i 2S•(j) •C2

No. of unshifted 3 3 3 1 1 1
atoms
G 9 3(1 + 2 cos j)† 3 –3 (–1 + 2 cos j) –1

†
The z-vector contributes 1 as it remains unshifted. Each of x- and y-vectors contributes
cos j as the component of displaced vector along the original vector is cos j.
 Molecular Symmetry and Its Applications 665

From the character table of D•h

D•h E 2C•(j) •sv i 2S•(j) •C2
S +u 1 1 1 –1 –1 –1 Tz
Pu 2 2 cos j 0 –2 2 cos j 0 (Tx, Ty)
Pg 2 2 cos j 0 2 –2 cos j 0 (Rx, Ry)
Hence, the characters Gtrans + Grot are
E 2C•(j) •sv i 2S•(j) •C2
Gtrans + Grot 5 1 + 4 cos j 1 –1 –1 –1
= S +u + Pu + Pg
The characters Gvib are
E 2C•(j) •sv i 2S•(j) •C2
Gvib = G – (Gtrans 4 2 + 2 cos j 2 –2 2 cos j 0
+ Grot)
Inspection of the character table of D•h reveals that Gvib is obtained by adding the
following representations.
E 2C•(j) •sv i 2S•(j) •C2
S+g 1 1 1 1 1 1 x2 + y2, z2
S+u 1 1 1 –1 –1 –1 z
Pu 2 2 cos j 0 –2 2 cos j 0 (x, y)

Hence Gvib = S +g + S +u + Pu
that is, there are two non-degenerate vibrations, one of which is totally symmetric
and two doubly-degenerate vibrations.
r1 r2
Reducible representation based on the bond-stretching vectors (O C O) is

E 2C•(j) •sv i 2S•(j) •C2

2 2 2 0 0 0
which is obtained by adding irreducible representations S +g and S +u.
The bending vibrations correspond to the remaining representation Pu.
The CO2 molecule a centrosymmetric molecule. The rule of mutual exclusion is
followed by this molecule. The vibration S +g is IR inactive and Raman active. The
vibrations S u+ and Pu are IR active and Raman inactive.

Problem 5.23.1 Work out the irreducible representations of acetylene. Indicate which one is IR or Raman
active.
Solution ∫∫ centre of symmetry. It
belongs to the group D•h.
Taking the molecular axis as the z-axis, the reducible representation based on
rotating the molecule about the z-axis by an angle j is
666 A Textbook of Physical Chemistry

D•h E 2C•(j) º •sv i 2S•(j) º •C2

No. of unshifted atoms 4 4 4 0 0 0

G 12 4(1 + 2 cos j) 4 0 0 0

From the character table of D •h

representing translational and rotational motion is
E 2C•(j) º •sv i 2S•(j) º •C2
Gtrans + Grot 5 1 + 4 cos j 1 –1 –1 –1
= S +u + Pu + Pg
The characters of Gvib are
E 2C•(j) º •sv i 2S•(j) º •C2
Gvib = G– (Gtrans + 7 3 + 4 cos j 3 1 1 1
Grot)

Inspection of the character table of D•h reveals that Gvib is obtained by adding the
following representations.
E 2C•(j) º •sv i 2S•(j) º •C2
S+g 1 1 1 1 1 1 x2 + y2, z2 (Raman active)
S+g 1 1 1 1 1 1 x2 + y2, z2 (Raman active)
S+u 1 1 1 –1 –1 –1 z (IR active)
Pu 2 2 cos j 0 –2 2 cos j 0 (x, y) (IR active)
Pg 2 2 cos j 0 2 –2 cos j 0 (xz, yz) (Raman active)
There are three non-degenerate vibrations, two of which are totally symmetric and
a pair of two doubly-degenerate vibrations.
Reducible representation based on the bond-stretching vectors is
E 2C•(j) º •sv i 2S•(j) º •C2
3 3 3 1 1 1
which is obtained by adding irreducible representations
S g+, S g+ and S +u
The bending vibrations correspond to the remaining representations Pu and Pg.
The vibration modes S g+ are IR inactive and Raman active. These correspond to
symmetrical stretching modes which do not involve change in dipole moment.
The vibration mode S +u is IR active and Raman inactive. This corresponds to
unsymmetrical stretching mode which involves change in dipole moment.
The vibration modes Pg involve symmetrical bending which do no involve change
in dipole moment. These are IR inactive and Raman active. The vibration modes
Pu involve unsymmetrical bending which involve change in dipole moment and
is IR active and Raman inactive.
 Molecular Symmetry and Its Applications 667

ILLUSTRATIONS OF ELECTRONIC TRANSITIONS

Electronic The electronic transitions in an atom follow the following two selection rules.
Transitions in an
LaPorte’s rule Each component of dipole moment operator has odd (ungerade)
Atom
parity. In order to obtain an even (gerade) parity, the direct product of the
¥
odd = even. This is possible if one of the wave functions is odd and the other even.
This fact is known as LaPorte’s rule which may be stated as follows.
The electronic transition between states of the same parity are forbidden.
For example, s-s, p-p, or d-d transitions are forbidden while s-p, p-d, or
d-f transitions are allowed. LaPorte’s rule expressed in the form of selection rule
is Dl = ± 1, where l is azimuthal quantum number.
Spin selection rule Since the dipole moment operator does not involve spin, we
can integrate spin components of wave functions separately, in order to have nonzero

same spin. Thus, the spin selection rule is DS = 0.

Electronic While predicting the feasibility of electronic transitions in a molecule, it is desirable
Transitions in a to work out with the symmetries of ground and excited electronic states of the
Moecule molecule instead of involved orbitals in the electronic transition. The symmetry
of electronic state of a molecule is determined by evaluating direct product of
representations (which involves the multiplication of corresponding characters)
of the involved molecular orbitals. For a singly-occupied molecular orbital, the
symmetry is that of the molecular orbital itself. For a doubly-occupied molecular
orbital, the direct product of the same two representations always yields a totally
symmetric representation and thus may be ignored in evaluating the direct product
of the state of the molecule.
Electronic The ground electronic state of water† (point group: C2v) is
Transitions in (a1)2 (b2)2 (a1)2 (b1)2
Water
Its symmetry is A1 as it involves doubly occupied molecular orbitals.
The two electronic excited states of the molecules are as follows.
(i) (a1)2 (b2)2 (a1)2 (b1) (a 1*) Symmetry: (b1)(a1) = B1
2
(ii) (a1) (b2) (a1)2 2
(b1) (b *2) Symmetry: (b1)(b2) = A2
The symmetries of components of transition moment integrals (·yi | m x| yj Ò,
·yi | m y| yjÒ and ·yi | m z| yjÒ) for these transitions are as follows.
∑ a1 ¨ b1 transition
x-component: A1 ¥ B1 ¥ B1 = A1 ˘ Since the x-components includes
y-component: A1 ¥ B2 ¥ B1 = A2 ˙ a totally symmetric A1 representa-
˙
z-component: A1 ¥ A1 ¥ B1 = B1 ˙˚ tion, the transition is allowed.

†
For a single-electron orbital, a lower case Mulliken symbol is used. The symmetry of
electronic state of the molecule is represented by a capital letter.
668 A Textbook of Physical Chemistry

∑ b2 ¨ b1 transition
x-component: A1 ¥ B1 ¥ A2 = B2 ˘ Since a totally symmetric
˙
y-component: A1 ¥ B2 ¥ A2 = B1 ˙ representation is absent, the
z-component: A1 ¥ A1 ¥ A2 = A2 ˙˚ transition is forbidden.
Electronic The ground electronic state of butadiene (point group: C2h) is
Transitions in (au)2 (bg)2 Symmetry: ag ¥ ag = Ag
trans-Butadiene The four electronic excited states of the molecule are as follows.
(au)2 (bg) (a*u) Symmetry: b g ¥ a u = Bu
(au)2 (bg) (b*g) Symmetry: bg ¥ b g = A g
(au) (bg)2 (a*u) Symmetry: au ¥ a u = A g
(au) (bg)2 (b*g) Symmetry: au ¥ bg = Bu
The components of transition moment integrals for these transitions are as follows.
(i) a*u ¨ bg and b*g ¨ au transitions
x-component Ag ¥ Bu ¥ Bu = Ag ˘ Since the x- and y-components involve
y-component Ag ¥ Bu ¥ Bu = Ag ˙ a totally symmetric representation Ag,
˙
z-component Ag ¥ Au ¥ Bu = Bg ˙ the transitions are allowed.
˚
(ii) b*g ¨ bg transition a*u ¨ au transitions
x-component Ag ¥ Bu ¥ Ag = Bu ˘ Since a totally symmetric representa-
y-component Ag ¥ Bu ¥ Ag = Bu ˙ tion is absent, the transitions are
˙
z-component Ag ¥ Au ¥ Ag = Au ˙˚ forbidden.
Comment From the above transitions, it follows that
g´u transitions are allowed
g ´ g¸
˝ transitions are forbidden
u ´ u˛
Electronic In Sec. 5.19, we have worked out the p-molecular orbitals of benzene. These are
Transitions in as follows.
Benzene 1
Y1(a2u) = (f1 + f2 + f3 + f4 + f5 + f6)
6
1
Y2(e1g) = (2f1 + f2 – f3 – 2f4 – f5 + f6)
12
1
Y3(e1g) = (f2 + f3 – f5 – f6)
2
1
Y4(e2u) = (2f1 – f2 – f3 + 2f4 – f5 – f6)
12
1
Y5(e2u) = (f2 – f3 + f5 – f6)
2
1
Y6(b2g) = (f1 – f2 + f3 – f4 + f5 – f6)
6
Under Hückel approximations, the energies of the above molecular orbitals can
be worked out by using the expression ·y | H | y Ò. Their energies are as follows.
E1 = a + 2b, E2 = E3 = a + b, E4 = E5 = a – b and E6 = a – 2b.
Since the benzene contains 6 p-electrons, the ground state of benzene is
 Molecular Symmetry and Its Applications 669

(a2u)2 (e1g)4 Symmetry: A1g

The electronic spectrum of benzene will involve transitions from the e1g level to
the e2u and b2g levels. However, the transition e1g Æ b2g involves g ´ g transition
and thus is a forbidden transition.
The promotion of one electron from e1g level to e2u will lead to the excited state
(a2u)2 (e1g)3 (e2u)
To work out the symmetry of the excited state, we require the symmetry of (e1g)3.
The direct product E1g ¥ E1g ¥ E1g does not give the correct result for the orbital
symmetry. From quantum mechanics, it is found that the symmetry properties of
(e1g)3 state is identical with that of (e1g).† Hence, the symmetry of the above excited
state can be obtained by direct product of E1g and E2u which gives
E1g ¥ E2u Æ B1u + B2u + E1u
Hence, the transition moment integrals involve the following direct product.
z-components A1g ¥ A2u ¥ B1u = B2g ˘ Symmetry
A1g ¥ A2u ¥ B2u = B1g ˙ forbidden
˙
A1g ¥ A2u ¥ E1u = E1g ˙˚ transition
x and y components A1g ¥ E1u ¥ B1u = E2g
A1g ¥ E1u ¥ B2u = E2g
A1g ¥ E1u ¥ E1u = A1g ¥ (A1g + A2g + E2g)
= A1g ¥ A1g + A1g ¥ A2g + A1g ¥ E2g
= A1g + A2g + E2g
Since A1g ¥ E1u ¥ E1u contains A1g as one of the representations, the transition
E1u ¨ A1g is a symmetry allowed transition.
The spin selection rule states that the spin of electron during electronic transition
remains the same, the spin multiplicity of the excited state will remain the same
as that of ground state. Since the orbitals in the ground state are fully occupied,
the spin multiplicity of the ground state is one. This will be preserved during the
transition and hence the electronic spectrum of benzene will include one absorption
due to the transition 1E1u ¨ 1A1g.‡

†
In general, if a shell has a total capacity of n electrons, then the symmetry properties
n – m) electrons are exactly identical to that
containing m electrons. This behaviour is explained on the basis that there exists m holes
n – m electrons and these holes have the same properties
as m electrons in an empty shell.
‡
Besides 1E1u state, the other states of the arrangement (a2u)2 (e1g)3 (e2u)1 are 1B1u, 1B2u,
3
B1u, 3B2u and 3E1u, since the single electron in each of e1g and e2u orbitals may have
parallel (S = 1) and antiparallel (S = 0) spins.
670 A Textbook of Physical Chemistry

5.24 CORRELATION DIAGRAMS FOR A d2 ION IN AN OCTAHEDRAL AND TETRAHEDRAL

ENVIRONMENTS

Term Symbols for The number of ways of assigning two electrons (N = 2) amongst ten spin orbitals
d2 Configuration (G = 10) involving d orbitals is given by
of a Free Ion
G! 10 !
= = 45 (5.24.1)
N !(G - N )! 2 !8!
T ML and MS values are listed in
Table 5.24.1.
The assignment of terms symbols goes as follows.
∑ The largest value of ML is + 4. This implies L = 4 and the nine permitted
values of ML are + 4, + 3, + 2, + 1, 0, – 1, – 2, – 3 and – 4.
The maximum value of MS associated with ML = 4 is 0. This implies that S = 0.
Thus the spin multiplicity is 2S + 1 = 2 ¥ 0 + 1 = 1.
L = 4 and S = 0 state. These may be

The value of J = L + S = 4 + 0 = 4.
The symbol for L = 4 is G.
Hence, the L = 4 and S = 0
state is 1G4.
∑ ML = 3. This implies
that L = 3 and the seven permitted values of ML are + 3, + 2, + 1, 0, – 1, – 2 and
– 3.
Associated with ML = + 3, the maximum value of MS = + 1. This implies S = 1
and the permitted values of MS are + 1, 0 and – 1. (i.e. the spin multiplicity
is 2S + 1 = 2 ¥ 1 + 1 = 3.)
Thus, with each of seven values of ML, there are three values of MS. Hence,
L = 3 and S = 1

The symbol for L = 3 is F.

Hence, the term symbol for L = 3 and S = 1 is 3F. The permitted values of
J are L + S, L + S – 1, …, |L – S|. This gives J = 4, 3 and 2. Thus, the term
symbols for L = 3 and S = 1 state are 3F4, 3F3 and 3F2.
∑ The next maximum value of ML = + 2. This implies L = 2 and the permitted
values of ML are + 2, + 1, 0, – 1 and – 2.
 Molecular Symmetry and Its Applications 671

Table 5.24.1 Forty Five 2 Ion

S.N. ML MS S.N. ML MS S.N. ML MS

1 d+2 d+2 +4 0 16 d+2 d–2 0 0 31 d0 d0 0 0

2 d+2 d+1 +3 1 17 d+2 d-2 0 –1 32 d0 d–1 –1 1

3 d+2 d+1 +3 0 d+1 d+1 +2 0 33 d0 d-1 –1 0

4 d+2 d0 +2 1 d+1 d0 +1 1 34 d0 d–2 –2 1
5 d+2 d0 +2 0 20 d+1 d0 +1 0 35 d0 d-2 –2 0

6 d+2 d–1 +1 1 21 d+1 d–1 0 1 36 d0 d–1 –1 0

7 d+2 d-1 +1 0 22 d+1 d-1 0 0 37 d0 d-1 –1 –1

d+2 d–2 0 1 23 d+1 d–2 –1 1 d0 d–2 –2 0

d+2 d-2 0 0 24 d+1 d-2 –1 0 d0 d-2 –2 –1

10 d+2 d+1 +3 0 25 d+1 d0 +1 0 40 d–1 d-1 –2 0

11 d+2 d+1 +3 –1 26 d+1 d0 +1 –1 41 d–1 d–2 –3 1

12 d+2 d0 +2 0 27 d+1 d–1 0 0 42 d–1 d-2 –3 0

13 d+2 d0 +2 –1 d+1 d-1 0 –1 43 d-1 d–2 –3 0

14 d+2 d–1 +1 0 d+1 d–2 –1 0 44 d-1 d-2 –3 –1

15 d+2 d-1 +1 –1 30 d+1 d-2 –1 –1 45 d–2 d-2 –4 0

The maximum value of MS associated with ML = + 2 is 0. The spin multiplicity

is 2S + 1 = 2 ¥ 0 + 1 = 1.

L = 2 and S = 0 state. These may be

represented as 12, 14, 16, 36 and 40.
The term symbol of L = 2 is D. The permitted value of J is L + S = 2.
Hence, the term symbol for L = 2 and S = 0 state is 1D2.
∑ The next maximum value of ML = + 1. This implies L = 1 and the permitted
values of ML are + 1, 0 and – 1.
The maximum value of MS associated with ML = + 1 is 1. Thus, the permitted
values of MS are + 1, 0 and – 1 (i.e. the spin multiplicity is 2S + 1 = 2 ¥ 1 +
1 = 3).
For each of the three values of ML, there are three values of MS. Hence,
L = 1 and S = 1. These may be
672 A Textbook of Physical Chemistry

The term symbol for L = 1 is P. The permitted values of J are L + S, L + S – 1,

…, |L – S|, i.e. 2, 1 and 0. Hence, the term symbols for L = 1 and S = 1 are
3
P2, 3P1 and 3P0.
∑ ML = 0 and MS = 0. This
implies L = 0 and S = 0.
The spin multiplicity is 2S + 1 = 2 ¥ 0 + 1 = 1
The term symbol for L = 0 is S.
The value of J = 0 (= L + S)
Thus, the term symbol for L = 0 and S = 0 is 1S0.
∑ Thus, the term symbols for d2
1
G4, 3F4, 3F3, 3F2, 1D2, 3P2, 3P1, 3P0 and 1S0 (5.24.2)

Splitting of d The wave functions of d orbitals may be chosen as the basis for a reducible
Orbitals in an representation of the point group Oh. Since the d orbitals are even to inversion, the
Octahedral characters of reducible representation can be obtained by using the pure rotational
Environment subgroup O and then adding the subscript ‘g’ to each of them.
In general, an orbital is represented as
Y = Rr Qq Fj

where (i) the function R is invariant to all operations in a point group,

(ii) the function Q is also invariant if rotation is carried out about the
z-axis with respect to which the angle q is measured (since the angle q
remains constant during the rotation),
and (iii) the function F varies since the angle j is varied during the rotation
about the z-axis.
Hence, the function F needs only to be considered to determine the character of
reducible representation for the point group O.
Leaving aside the normalization constant, the function F is given by
F = eimj
For d orbital, m = + 2, + 1, 0, – 1 and – 2.
If a rotation about the z-axis is carried out by an angle a, its effect on d orbitals
is represented as
e 2i (j +a ) e 2 ia 0 0 0 0 e 2 ij
ei (j +a ) 0 e ia 0 0 0 e ij
e0 = 0 0 e0 0 0 e0
e- i (j +a ) 0 0 0 e - ia 0 e - ij
e -2i (j +a ) 0 0 0 0 e -2ia e-2ij
 Molecular Symmetry and Its Applications 673

The character of the transformation matrix is

c(a) = e2ia + eia + e0 + e– ia + e– 2ia

=
( )
sin 2 +
1
2
a
; (a π 0) (5.24.3)†
sin(a / 2)

sin 5p / 2 1
Hence, c(C2) = = =1
sin p / 2 1

c(C3) = sin 5p / 3 = - sin p / 3 = -1

sin p / 3 sin p / 3

and c(C4) = sin 5p / 4 = – sin p / 4 = -1

sin p / 4 sin p / 4

O E 6C4 3C2(= C42 ) C3 6C2

c(R) 5 –1 1 –1 1

Using the reduction formula

1
ai =
hi
 C nc c (C ) ci (C )
we get
1
ae =
24
1
at 2 =
24
Hence, G = e + t2
Since d orbitals are even to inversion, we can add subscript g in the above
representations to give
G = eg + t2g (5.24.4)

Diagrammatic
Representation of symmetry. These split into a triply degenerate set, t2g, and a doubly degenerate
Splitting set, eg.
From the character table Oh

†
In general, the sum
elia + e(l – 1)ia + + e– lia

{ ( )}
is given by c(a) = sin l +
1
2
a {sin(a / 2)} provided a π 0 (5.24.5)
674 A Textbook of Physical Chemistry

eg orbitals are d 2 z 2 - x2 - y 2 , d x2 - y 2 , i.e d z 2 , d x2 - y 2 .

t2g orbitals are dxy, dyz, dxz
The d 2 and d x2 - y 2 have lobes along the axes and dxy, dyz and dxz have lobes mid-
z
way between the two involved axes, respectively. When a negatively charged ligand
approaches the central ion along the axes, it raises the energies of d orbitals along
the axes (i.e. d 2 and d x2 - y 2 ) more than it does for the orbitals lying in between
z
the axes (i.e. dxy, dyz and dxz). Consequently, in the octahedral environments, the
energies of d orbitals get affected as shown in Fig. 5.24.1. The splitting is the
weighted average such that the total energy of d orbitals in the octahedral envi-
ronment remains constant.

eg (dz2, dx2 – y2)

0.6 ho = 6 Dq
E
D
– 0.4 ho = – 4 Dq

} t2g (dxy, dxz, dyz)

Configuration of In the limit of an extremely large splitting of d orbitals (which occurs when the
d2 Ion in Large interactions between central ion and the surrounding ligands are strong), the
Splitting

∑ 2
Both the electrons occupy the stable t2g orbitals. The
direct product of t2g ¥ t2g and the irreducible representations contained in it
are shown in Table 5.24.2.

Table 5.24.2 Irreducible representations contained in t22g

Oh E C3 6C2 6C4 3C2(= C42) i 6S4 S6 3sh 6sd

I t2g 3 0 1 –1 –1 3 –1 0 –1 1
II t2g ¥ t2g
A 1 1 1 1 1 1 1 1 1 1
Ï 1g
Ô Eg 2 –1 0 0 2 2 0 –1 2 0
III Ì T1g 3 0 –1 1 –1 3 1 0 –1 –1
Ô
Ó T2g 3 0 1 –1 –1 3 –1 0 –1 1
The entry I represents irreducible representation t2g, II represents direct product and III
represents irreducible representations in the direct product.

∑ e Each of the orbitals t2g and eg contains one electron.

The direct product t2g ¥ eg and the irreducible representations contained in it
are shown in Table 5.24.3.
 Molecular Symmetry and Its Applications 675

Table 5.24.3 Irreducible representations contained in t2geg

Oh E C3 6C2 6C4 3C2(= C42) i 6S4 S6 3sh 6sd

I t2g 3 0 1 –1 –1 3 –1 0 –1 1
eg 2 –1 0 0 2 2 0 –1 2 0
II t2g ¥ eg 6 0 0 0 –2 6 0 0 –2 0

Ï T1g 3 0 –1 1 –1 3 1 0 –1 –1
III Ì
T
Ó 2g 3 0 1 – 1 – 1 3 – 1 0 –1 1
The entry I represents the irreducible representations, II represents direct product and III
represents the irreducible representations in the direct product.

∑ 2
Both the electrons are excited to eg orbitals. The direct
product of eg ¥ eg and the irreducible representations contained in it are shown
in Table 5.24.4.

Table 5.24.4 Irreducible representations contained in e2g

Oh E C3 6C2 6C4 3C2(= C42) i 6S4 S6 3sh 6sd

I eg 2 –1 0 0 2 2 0 –1 2 0
II e2g 4 1 0 0 4 4 0 1 4 0
A 1 1 1 1 1 1 1 1 1 1
Ï 1g
III Ì A2g 1 1 –1 –1 1 1 –1 1 1 –1
Ó Eg 2 –1 0 0 2 2 0 –1 2 0
The entry I represents the irreducible representation, II represents direct product and III
represents the irreducible representations in the direct product.

Splitting of the The splitting of S, P, D, … terms of an ion involving more than one electron under
Terms of an Ion octahedral environment (or any other environment) follows the
Under Weak same pattern as those of one-electron s, p, d, ... orbitals, respectively. This is based
Interactions on the fact that both involve the same type of j-dependent function. It is exp(iMj)
for a term and exp(imj) for an orbital.
The splitting of one-electron d orbitals has been worked out earlier (Eq. 5.24.4).
The same pattern is followed by the term D and thus it splits into Eg and T2g
representations under the octahedral environment. Following the same procedure,
the splitting of other orbitals can be worked out. For s, p, f and g orbitals, split-
tings are as follows.

Splitting of S Term Since s orbital has a spherical symmetry with no q and j-dependence terms, the
representation based on s orbital will include one as the character in all the rotational
operations. Hence, the term S belongs to A1g representation.

Splitting of P Term For p orbitals l = 1. The character of rotational operation as given by Eq. (5.24.5) is

c(R) =
( )
sin l +
1
2
a
=
sin(3a / 2)
sin(a / 2) sin(a / 2)
676 A Textbook of Physical Chemistry

Hence, we have
sin 270∞ sin 90∞
C2 rotation a cR = =- =–1
sin 90∞ sin 90∞
sin 180∞
C3 rotation a cR = =0
sin 60∞
sin 135∞ sin 45∞
C4 rotation a cR = = =1
sin 45∞ sin 45∞
The reducible representation of which p orbitals form the basis is given by

O E 6C4 3C2 (= C42 C3 6C2

c(R) 3 1 –1 0 –1

From the
corresponds to the irreducible representation t1. Hence, the term P of d2
belongs to T1g representation under octahedral environment.

Splitting of F Term For f orbitals, l = 3. The character of rotational operations is given by

sin (7a / 2)
c(R) =
sin (a / 2)

Hence, we have
sin 630∞ sin 90∞
C2 rotation a cR = =- = -1
sin 90∞ sin 90∞
sin 420∞ sin 60∞
C3 rotation a cR = = =1
sin 60∞ sin 60∞

sin 315∞ sin 45∞

C4 rotation a cR = =- = -1
sin 45∞ sin 45∞
The reducible representation for which f orbitals form the basis is

O E 6C4 3C2 (= C42 C3 6C2

7 –1 –1 1 –1

From the character table of the group O, this is equivalent to a2 + t1 + t2. Since
orbitals are odd to inversion, the f orbitals split into a2u, t1u and t2u.
The term F under octahedral symmetry will split into A2g, T1g and T2g.

Splitting of G Term For g orbitals, l = 4. The character of rotational operation is given by

sin (9a / 2)
c(R) =
sin (a / 2)
 Molecular Symmetry and Its Applications 677

Hence, we have
sin 810∞ sin 90∞
C2 rotation a c(R) = = =1
sin 90∞ sin 90∞
sin 540∞ sin 180∞
C3 rotation a c(R) = = =0
sin 60∞ sin 60∞

sin 405∞ sin 45∞

C4 rotation a c(R) = = =1
sin 45∞ sin 45∞
The reducible representation for which g orbitals form the basis is
O E 6C4 3C2 (= C42 C3 6C2

From the character table of the group O, this is equivalent to a1, e, t1 and t2. Since
g orbitals are even to inversion, the g orbitals split into a1g, eg, t1g and t2g.
The term G splits into A1g, Eg, T1g and T2g representations in an octahedral
environment.

Assigning Spin The chemical environment does not interact directly with the electron spins and
Multiplicity thus the states splitted from a particular term have the same spin multiplicity as
that of the involved terms. Table 5.24.5 correlates terms with states along with spin
multiplicity and their numbers.

Table 5.24.5 Correlation between Terms and the Corresponding States

†

S(2L + 1) Sa¥b
1
S (1)(2 ¥ 0 + 1) = 1 1
A1g 1¥1=1
3
P (3)(2 ¥ 3
T1g 3¥
1
D (1)(2 ¥ 2 + 1) = 5 1
Eg and T2g1
1¥2+1¥3=5
3
F (3)(2 ¥ 3 + 1) = 21 3 3
A2g, T1g and T2g 3
3 ¥ 1 + 3 ¥ 3 + 3 ¥ 3 = 21
1
G (1)(2 ¥ 1
A1g, Eg, T1g and T2g 1 ¥ 1 + 1 ¥ 2 + 1 ¥ 3 + 1 ¥
1 1 1

†
a ¥ b involves spin-multiplicity a and dimension b of the state.

Construction The correlation diagram for a d2 ion in an octahedral environment may be drawn
of Correlation as described in the following.
Diagram
∑ On the extreme left, the free-ion terms (Eq. 5.24.2) in the increasing order of
energies are depicted. Experimentally, it is found that

E(3F) < E(1D) < E(3P) < E(1G) < E(1S)

 A Textbook of Physical Chemistry

Immediately right to the above energies, the states into which these free-

environment are depicted. The spin multiplicities of these states are the same
as that of the corresponding free-ion terms.
∑ 2
2g, t2geg
2
and e g in the increasing order are depicted. The energy difference between the
two successive levels is D0
the limit of an extremely large splitting of the d orbitals which occurs in the
presence of strong interaction between the ion and the octahedral environment.
Immediately left to these levels, the states involved in these levels are shown
which arise due to the relaxation of strong interaction between the ion and the
environment. However, the spin multiplicity of these states are not known as
the distribution of two electrons may lead to singlets or triplets.

Two Basic ∑ In constructing the correlation diagram, the following two principles hold good.
Principles 1. In going from weak to strong interactions with the environment, the symmetry
followed in properties as well as their spin multiplicity are preserved. Thus, there must
Constructing exit a one-to-one correspondence between the states on the either sides of
Correlation the correlation diagram.
Diagram 2. In going from weak to strong interactions with the environment, the states
of the same spin multiplicity and symmetry do not cross each other. This is
known as non-crossing rule.

Description Guided by these principles, we can correlate states on either sides as described in
of Correlation the following.
Diagram
∑ There is only one A2g state on either side of the diagram—3A2g in the term
3
F and A2g in the energy level e 2g. We joint these two states. Since the spin
multiplicity is preserved, the A2g state in e 2g level must also be triplet.
∑ There are two A1g states on either side of the diagram—1A1g in 1S1 and 1A1g
in 1G, and A1g in e2g and A1g in t 22g. In accordance with the non-crossing rule,
we joint 1A1g of 1S1 with A1g of e 2g and 1A1g of 1G with A1g of t 22g. This also
establishes that A1g in each of e 2g and t 22g is singlet.
∑ There are two Eg states on either side of the diagram—1Eg in 1G and 1Eg in
1
D, and Eg in e2g and E g in t 22g. In accordance with the non-crossing rule, we
joint 1E g of 1G with Eg of e 2g and 1Eg of 1D with Eg of t 22g. This also establishes
that Eg in each of e 2g and t 22g is singlet.
∑ We are left with three T1g and three T2g states. On left side, we have 3T1g, 3T1g,
1
T1g and 3T2g, 1T2g, 1T2g. Since on right side, there are two T1g and two T2g
states in t2g eg, we propose that each of the two involves one singlet and one
triplet, i.e. 1T1g, 3T1g and 1T2g, 3T2g. We are left with one 3T1g and 1T2g on the
left side, we associate these states to the t 22g level.
∑ We joint single 3T2g in 3F with 3T2g of t2g eg and single 1T1g in 1G with 1T1g
of t2geg.
 Molecular Symmetry and Its Applications

∑ In accordance with the non-crossing rule, we join 3T1g of 3F with 3T1g of t 22g
and 3T1g of 3P with 3T1g of t2geg. For the same reason, we join 1T2g of 1D with
1
T2g of t 22g and 1T2g of 1G with 1T2g of t2geg.
This completes the correlation diagram and is shown in Fig. 5.24.2. This diagram
is known as Tanabe and Sugano diagram. While interpreting electronic spectra,
Orgel diagram is more useful at it depicts only those terms that have the same
multiplicity as the ground state.

(1) 1A1g
(2) 1Eg e2g
1A +12 Dq
1S 1g (3) 3A2g (6)
(1)
(1)
1E
g
(2)
1T
1g
1G (3)
1T
2g
(9) (3)
1A
1g
(1)

3P 3T
1g
(9) (9)
(3) 1T1g
1E
g (3) 1T2g
(2) t2geg
1D
1T (9) 3T1g (24)
+2 Dq
(5) 2g
(3)
(9) 3T2g

3A
2g
(3)
3T
3F 2g
(9)
(21)
3T
1g
(9)
(1) 1A1g
1E
(2) g 2
t 2g
1T – 8 Dq
(3) 2g (15)
(9) 3T
1g

(a) (b) (e) (d) (c)

2
 A Textbook of Physical Chemistry

The Method of The spin multiplicity of the states arising from the energy levels t 22g and eg2 when
Descending the strong interactions of the ion with the environment is relaxed can be ascertain
Symmetry by the method of descending symmetry. This method is based on the principle
that the spin multiplicity of a state is not changed on descending the symmetry.
States arising from the 2
The level t 22g leads to A1g, Eg, T1g and
T2g representations. We look the transformation table† where each of the above
representations in the group Oh are changed or decomposed into one-dimensional
representation or sum of one-dimensional representations in its subgroup of lower
symmetry. The subgroup satisfying this condition is C2h or C2v.
Selecting the subgroup C2h
O C
A1g Ag
Eg A g + Bg
T1g A g + Bg + Bg
T2g A g + A g + Bg

Since t2g in Oh goes over to ag + ag + bg in C2h. We write two ag as ag(1) and ag(2).
The direct product t2g ¥ t2g goes into sum of the six direct products listed below.
ag(1) ¥ ag(1) = 1Ag Both the electrons belong to the same orbital ag(1)
ag(1) ¥ ag(2) = Ag and Ag
1 3
Each of the two electrons belongs to different ag
orbitals
ag(1) ¥ bg = 1Bg and 3Bg Each of the two electrons belongs to different orbitals
ag(1) and bg
ag(2) ¥ ag(2) = 1Ag Both the electrons belong to the same orbital ag(2)
ag(2) ¥ bg = Bg and Bg
1 3
Each of the two electrons belongs to different orbit-
als ag(2) and bg
bg ¥ bg = 1Ag Both the electrons belong to the same orbital bg

* The transformation table is as follows.

Oh Td D4h D2d D2 C4v C2h C2v

A1g A1 A1g A1 A1 A1 Ag A1
A2g A2 B1g B1 A2 B1 Bg A2
Eg E A1g + B1g A1 + B1 E A1 + B1 Ag + Bg A1 + A2
T1g T1 A2g + Eg A2 + E A2 + E A2 + E Ag + 2Bg A2 + B1 + B2
T2g T2 B2g + Eg B2 + E A1 + E B2 + E 2Ag + Bg A1 + B1 + B2
A1u A2 A1u B1 A1 A2 Au A2
A2u A1 B1u A1 A2 B2 Bu A1
Eu E A1u + B1u A1 + B1 E A2 + B2 Au + Bu A1 + A2
T1u T2 A2u + Eu B2 + E A2 + E A1 + E Au + 2Bu A1 + B1 + B2
T2u T1 B2u + Eu A2 + E A1 + E B1 + E 2Au + Bu A2 + B1 + B2
 Molecular Symmetry and Its Applications

Hence, it leads to 41Ag + 3Ag + 21Bg + 23Bg, a total of nine representations. With
degeneracy equal to 15 [= 4 (1 ¥ 1) + 1(3 ¥ 1) + 2(1 ¥ 1) + 2(3 ¥
Since there is only one 3Ag state and two 3Bg states, and these are the states obtained
from T1g on descending from Oh to C2h, we assign triple spin-multiplicity to the state
T1g. All remaining states are singlet and can be assigned without any ambiguity.
Hence, the designation of spin-multiplicity goes as follows.
O ¨æ
æ C
1
A1g ¨æ
æ 1Ag
1
Eg ¨æ
æ 1Ag + 1Bg
3
T1g ¨æ
æ 3Ag + 3Bg + 3Bg
1
T2g ¨æ
æ 1Ag + 1Ag + 1Bg
States arising from e 2 The level e 2g leads to A 1g, A 2g and
Eg representations. On lowering the symmetry to D4h
transformations.
Oh D4h
A1g A1g
A2g B1g
Eg A1g + B1g
Since eg in Oh goes over to a1g + b1g in D4h, the direct product e2g goes into sum
of the three direct products listed below.
a1g ¥ a1g = 1A1g Both the electrons belong to the same orbital a1g
a1g ¥ b1g = 1B1g and 3B1g Each of the two electrons belongs to different orbitals
b1g ¥ b1g = 1A1g Both the electrons belong to the same orbital b1g.
Hence, e2g leads to 2 A1g + B1g + 3B1g, a total of four representations with
1 1

degeneracy equal to six [= 2 (1 ¥ 1) + 1(1 ¥ 1) + 1(3 ¥

Since there is only one 3B1g state and this state is obtained from A2g on descending
from Oh to D4h, we assign triple spin-multiplicity to the state A2g. All remaining
states are single and can be assigned without any ambiguity. Hence, the designation
of spin-multiplicity goes as follows.

O ¨æ
æ D
1
A1g ¨æ
æ 1A1g
3
A2g ¨æ
æ 3B1g
1
Eg ¨æ
æ 1A1g + 1B1g

CORRELATION DIAGRAM FOR A d2 ION IN A TETRAHEDRAL ENVIRONMENT

Following the procedure for the octahedral environment, the correlation diagram
for a d2 ion in a tetrahedral environment can be constructed.
The terms for d2 tetrahedral environment split as follows.
3
F ææ
Æ 3A2 + 3T1 + 3T2
 A Textbook of Physical Chemistry

1
D ææ
Æ 1E + 1T2
3
P ææ
Æ 3T1
1
G ææ
Æ 1A1 + 1E + 1T1 + 1T2
1
S ææ
Æ 1A1

They split into a doubly degenerate set e and a triple degenerate set t as shown
in Fig. 5.24.3.
t2

0.4 ht
E
D

0.6 ht

the tetrahedral environment in the increasing order of energy are e2, et2 and t 22.

irreducible representations:
e2 Æ A 1 + A 2 + E
et2 Æ 2T1 + 2T2
t 22 Æ A1 + E + T1 + T2
Correlation The correlation (Fig. 5.24.4) diagram can be completed by joining the states on
Diagram left side (weak interaction) with those of right side (strong interaction) as described
in the following.
∑ 3A2 state in 3F is joined with A2 state in e2, this also establishes the triple spin
multiplicity for A2 state in e2.
∑ 1A1 state in 1S is joined with A1 state in t 22 and 1A1 in 1G is joined with A1
state in e2. These also generate single spin multiplicity in both A1 states on
the right side.
∑ 1E state in 1G is joined with E state in t 22 and 1E state in 1D is joined with E
state in e2, again generating single spin multiplicity in both E state on the right
side.
∑ Assigning T1 states in et2 as 1T1 and 3T1, we join the states 1T1 in et2 with 1T1 in
1
G and 3T1 in et2 with 3T1 in 3F. Similarly assigning T2 states in et2 as 1T2 and
3
T2, we join the states 1T2 in et2 with 1T2 in 1D and 3T2 in et2 with 3T2 in 3F.
∑ We are left with 3T1 in P and 1T2 in 1G on the left side and T1 and T2 in t 22
on the right side. Thus, we joint 3T1 in P with T1 in t 22 (establishing triple
spin degeneracy in T1) and 1T2 in 1G with T2 in t 22 (establishing singlet spin
degeneracy in T2).
This completes the correlation diagram (Fig. 5.24.4).
 Molecular Symmetry and Its Applications

EXERCISES

1. Distinguish between the terms symmetry element and symmetry operation.

2. Explain with suitable examples the following symmetry elements and the associated
symmetry operations. (a) Axis of rotation. (b) Symmetry planes. (c) Centre of inversion.
(d) Improper axis of rotation.
3. (a) Describe the sequence of operations in S5 and S6 symmetry elements.
(b) Show that the presence of Sn with n = odd implies the existence of Cn and
s perpendicular to Cn.
(c) Show that the presence of Sn with n = even implies the existence of Cn/2 and centre
of inversion.
(d) Show that Sn with n = odd generates 2n operations.
4. If there is C2 axis perpendicular to the principal axis C3, show that there will be three
such C2 axis.
5. Distinguish amongst the symmetry elements sv, sh and sd.

this axis is equivalent to the centre of inversion.

z, y and
x axes is equivalent to an identity operation.
(c) Show geometrically by taking a point in three-dimensional space, the following
facts.
A Textbook of Physical Chemistry

(i) If there are two C2 axes perpendicular to each other, there must be a third
C2 axis perpendicular to both.
(ii) If there is a C4 axis and a plane containing this, there must also a plane
containing C4
(iii) If there are C4(z) and C2( y) axes, a C2 axis lying in the 1st and 3rd quadrants
of the xy C2( y) must exist.
j
is equivalent to a rotation by an angle 2j
intersection of the two planes.
7. (a) What is a point group? Describe the main symmetry elements present in each of
the following point groups.
C1, Cn, Cs, Ci, Cnv, Cnh, S2n, Dn, Dnh, Dnd, C•v, D•v, Td and Oh
(b) A molecule contains a C3 axis and a sh. Assign the point group to this molecule.
Write down all the symmetry operations and indicate which could be grouped to
the same class.
point groups.
C4, D4, C4v, C4h, D2h, D2d, Td and Oh
point groups.
H2O, NH3, CH4, BeH2, BCl3, staggered ethane, allene, H3BO3, PtCl 2–
4

naphthalene, Cl2FSO, NO–3, PF5, CO, CO2, C5H–5, B2H6, SF6

(b) In NiBr 2–
4 (Td ), if one Ni—Br is stretched relative to other without bending, what
are the symmetry elements lost and what is the point group? If two of Ni—Br are
stretched what is the answer?
10. (a) Indicate which operation is equivalent to the following products of the operations
of the point group Td.
(i) S4 ¥ S4 (ii) C3 ¥ C2 (iii) sd ¥ C2
(b) Indicate which operator is equivalent to the following products of operations in
PF5 molecule.
(i) C2 ¥ sh (ii) C32 ¥ C2 (iii) C3 ¥ C2 ¥ sh
(Take any one of the C2 axes)

groups.
12. Explain the term Abelian group.

1, – 1, i and – i with ordinary multiplication form a group.

14. Show that the reciprocal of a combination of two (or more) elements of a group is
equal to the combination of the reciprocals in the reverse order.
15. Construct the group multiplication table for the point group C2v.
16. (a) Explain the term classes in a point group. How many classes are present in the
point group C3v?
(b) A molecule contains a Cn axis. Do the symmetry operations C m n–m
n and C n belong
to the same class. Another molecule has Cn axis and a C2 axis perpendicular to Cn
axis. How many more C2 axis perpendicular to Cn are present? Will the symmetry
operations around these C2 axes belong to the same class?
 Molecular Symmetry and Its Applications

17. Construct the group multiplication table for the point group C3v.
2O molecule, set up one-dimensional representations of the
point group C2v based on the translational vectors Tx, Ty and Tz.
2O molecule, set up one-dimensional representations of the
point group C2v based on the rotational vectors Rx, Ry and Rz.
20. Taking an example of NH3 molecule, set up one-dimensional representation of the point
group C3v based on the translational vector Tz attached to the nitrogen atom.
21. Taking an example of NH3 molecule, set up two-dimensional representations of the
point group C3v based on the translational vectors Tx and Ty attached to the nitrogen
atom.
22. Taking an example of NH3, set up one-dimensional representation of the point group
C3v based on rotational vectors Rz attached to the three hydrogen atoms.
23. Set up a two-dimensional representation of the point group C2v based on the bond
vectors associated with the two O—H bonds of water molecule.
24. Set up a three-dimensional representation of the point group C3v based on the bond
vectors associated with the three N—H bonds of NH3 molecule.
25. Based on px, py and pz orbitals of oxygen atom in H2O molecule, set up the one-
dimensional representations of the point group C2v.
2S molecule, set up the one-dimensional
representations of the point group C2v.
Set up the one-dimensional representations of s, p and d orbitals in the group D2h.
E C2x C2y C2z i sxy sxz syz
d x 2 - y 2 ,d z 2 , s 1 1 1 1 1 1 1 1
dxy 1 1 –1 –1 1 1 –1 –1
dxz 1 – 1 1 –1 1 –1 1 –1
dyz 1 – 1 –1 1 1 –1 –1 1
px 1 – 1 –1 1 –1 1 1 –1
py 1 – 1 1 –1 –1 1 –1 1
pz 1 1 –1 –1 –1 –1 1 1
27. Explain the terms ‘reducible and irreducible representations’.

(i) If C = AB and D = BA, then the characters of matrices C and D are identical.
(ii) Conjugate matrices have identical characters.
Great Orthogonality Theorem’.
30. (a) Explain the following characteristics followed by irreducible representations of a
group.
(i) The sum of the squares of the dimensions of the irreducible representations
of a group is equal to the order of the group.
(ii) The sum of the squares of the characters of symmetry operations in any
irreducible representations is equal to h.
(iii) The sum of products of corresponding vectors of two different irreducible
representations is equal to zero.
A Textbook of Physical Chemistry

(iv) In a given representation (reducible or irreducible) the characters of all matrices

belonging to the symmetry operations in the same class are identical.
(b) Show that the characters of the group C4v obey the orthogonality rules.
(c) Determine irreducible representations contained in the direct product of the
following irreducible representations.
(i) A1 ¥ A1; A1 ¥ A2 for C3v
(ii) E¢ ¥ E¢, A≤1 ¥ A≤2 for D3h.
31. Based on the characteristics of irreducible representation, set up the irreducible
representations of the point groups C2v and C3v.
32. (a) Derive the expression for determining the number of times the ith irreducible
representation present in a reducible representation, i.e. derive the expression
1
ai = Â c( R) ci(R)
h R
(b) Given are the characters of reducible representations for the indicated groups for
the various classes in the order. Determine irreducible representations.
(i) C2v; 4, – 2, 0, – 2
(ii) C3h; 4, 1, 1, 2, – 1, – 1
(iii) Oh; 15, 0, – 1, 1, 1, – 3, 0, 5, – 1, 3
33. Set up the reducible representation based on the three translational vectors attached to
each atom in H2O molecule and resolve it into the irreducible representations.
34. Set up the reducible representation based on the three translational vectors attached to
each atom of CH4 molecule and resolve it into irreducible representations.
35. Set up the reducible representation based on the three translational vectors attached to
each atom of trans-N2F2 and resolve it into irreducible representations.
36. (a) Explain the following general layout of a character table
I II
III IV V VI
(b) Determine from character tables, the representations to which s, p and d orbitals
of an atom in a molecule belonging to (i) Oh, (ii) Td, (iii) D4h, (iv) D3 groups, (v)
C2v, and (vi) C3v groups.
37. Describe the Mülliken symbols used to designate irreducible representations.
4h, show that the orbitals
s and d z 2 belong to a1g ; d x 2 - y 2 belongs to b1g

dxy belong to b2g ; pz belong to a2u

and dxz, dyz belongs to eg px, py belong to eu
( Work out the symmetries using the operations of the group D4 and then add
the subscript g and u as the case may be.)
(b) In the group D3h, show that the orbitals
s and d z 2 belong to a¢1 ; pz belongs to a≤2
px, py belong to e¢ ; dxz, dyz belong to e≤
and d x 2 - y 2 belongs to e¢

Ii
projection operator Pi =
h R
 c i ( R) R
 Molecular Symmetry and Its Applications

40. Using the projection operator on the function x + y + z, show that for the point group
C3v (i) z forms the basis for A1 representation, and (ii) x and y together form the bases
of E representation
41. Work out the SALC’s of H2O molecule involving 1s orbitals of hydrogen atoms and
also form molecular orbitals of H2O molecule.
42. Work out the SALC’s of BeH2 molecule involving 1s orbitals of hydrogen atoms and
also form molecular orbitals of BeH2 molecule.
43. Work out the SALC’s of BH3 molecule involving 1s orbitals of hydrogen atoms and
also form molecular orbitals of BH3 molecule.
44. Work out the SALC’s of NH3 molecule involving 1s orbitals of hydrogen atoms and
also form molecular orbitals of NH3 molecule.
45. Work out the localized and nonlocalized molecular orbitals of CH4 molecule.
46. Work out SALC’s and p-molecular orbitals of trans-butadiene.
47. Work out SALC’s and p-molecular orbitals of naphthalene.
cyclic group of order from two to six involving the
element eh = exp(2pi/h).
[ For C6, use e2 = – e* and e2* = – e.)
allyl radical ( H2C CH CH2, point group
C2v). Find out their energies and compare with those of cyclopropenyl.
[ y1(A2) = (1/ 2 ) (f1 – f3); E1 = a
y2(B2) = (1/2) (f1 + 2 f2 + f3); E2 = a + 2b
y2(B2) = (1/2) (f1 – 2 f2 + f3); E3 = a – 2b
(b) Work out p-molecular orbitals of cyclopropenyl and their energies.
[ y1(A) = (1 3 ) (f1 + f2 + f3); E1 = a

y2(E) = (1 6 ) (2f1 – f2 – f3); E2 = a – b

y3(E) = (1 2 ) (f2 – f3); E3 = a – b

(c) Work out p-molecular orbitals of benzene.

50. Work out the hybrid orbitals of atom A in the molecule AB3.
51. Work out the hybrid orbitals of atom C in the molecule CH4.
52. Work out the hybrid orbitals of atom A in a planar molecule AB4.
53. Discuss the hybrid orbitals in p bonding in the planar AB3 and AB4 molecules.
54. Using SALC’s of butadiene, calculate the energies of its molecular orbitals. Also work
out its molecular orbitals.
55. Using SALC’s of naphthalene, calculate the energies of its molecular orbitals. Also
work out its molecular orbitals.
56. Work out the molecular orbitals of tetraethylenecyclobutane. Determine its delocalization
energy, charge densities and bond orders.
57. Work out the molecular orbitals of trivinylmethyl radical.
A Textbook of Physical Chemistry

water,
(b) ammonia, (c) methane, and (d) trans-N2F2.
60. State the essential criteria for a fundamental mode of vibration to be infrared and
Raman active. Illustrate these with the fundamental modes of vibration in (a) water,
(b) ammonia and (c) trans-N2F2.
61. Discuss the feasibility of electronic transitions in water, butadiene and benzene.
62. State the rule of mutual exclusion.
63. Determine the terms symbols for the d2
64. Explain how d orbitals split in energy in (a) an octahedral, and (b) tetrahedral
environments.
2
65. (a) Work out the irreducible representations in (a) t2g, (b) t2geg and (c) e 2g
(b) Work out the splitting of the atomic terms of d2
environment.
(c) Draw qualitatively the correlation diagram of d2 ion in an octahedral environment.
66. Explain the method of descending symmetry to ascertain the spin multiplicity of the
2
states arising from the energy levels t2g and eg2 when the strong interactions of the ion
with the octahedral environment is relaxed.
67. Draw qualitatively the correlation diagram of d2 ion in a tetrahedral environment.
p-molecular orbitals and their energies for the molecule C4H4.
1
[ y (A) = (j1 + j2 + j3 + j4); E = a + 2b
2
1 1
y (Ea) = (j1 – j3); y(Ea) = (j2 – j4); E = a
2 2
1
y (B) = (j1 – j2 + j3 – j4 E = a – 2b
2
p-molecular orbitals and their energies of the molecule C H .
1
[ y (A) = (j1 + j2 + j3 + j4 + j5 + j6 + j7 + j ); E = a + 2b
8
1
y(B) = (j1 – j2 + j3 – j4 + j5 – j6 + j 7 – j ); E = a – 2b
8
1
y(E1a) = ( 2 j1 + j2 – j4 – 2 j5 – j6 + j ); E = a + 2 b
8
1
y(E1b) = (j2 + 2 j3 + j4 – j6 – 2 j7 – j ); E = a + 2b
8
1
y(E2a) = (j1 – j3 + j5 – j7); E = a
2
1
y(E2b) = (j2 – j4 + j6 – j ); E = a
2
1
y(E3a) = ( 2 j1 – j2 + j4 – 2 j5 + j6 – j ); E = a – 2 b
8
1
y(E3b) = (j2 – 2 j3 + j4 – j6 + 2 j7 – j E=a– 2b
8
70. Work out the irreducible representations for the vibrational modes of CO2 and acetylene
molecules. Also identify which ones of these are IR or/and Raman active.
ANNEXURE Some Commonly Used Character Tables

1. The Cn Groups

C2 E C2
A 1 1 z, Rz x2, y2, z2, xy
B 1 –1 x, y, Rx, Ry yz, xz

C3 E C3 C32 e = exp(2pi/3)
A 1 1 1 z, Rz x2 + y2, z2
Ï1 e e *¸
E Ì ˝ (x, y), (Rx, Ry) (x2 – y2, xy), (yz, xz)
Ó1 e* e˛

C4 E C4 C2 C43
A 1 1 1 1 z, Rz x2 + y2, z2
B 1 –1 1 –1 x2 – y2, xy
Ï1 i -1 - i¸
E Ì ˝ (x, y), (Rx, Ry) (yz, xz)
Ó1 -i -1 i˛

C5 E C5 C52 C53 C54 e = exp(2pi/5)

A 1 1 1 1 1 z, Rz x2 + y2, z2
ÏÔ1 e e2 e 2* e *¸Ô
E1 Ì 2*
˝ (x, y), (Rx, Ry) (yz, xz)
ÔÓ1 e* e e 2
e Ô˛

ÏÔ1 e2 e* e e 2*¸Ô
E2 Ì ˝ (x2 – y2, xy)
ÔÓ1 e 2* e e* e 2 Ô˛

C6 E C6 C3 C2 C32 C65 e = exp(2pi/6)

A 1 1 1 1 1 1 z, Rz x2 + y2, z2
B 1 –1 1 –1 1 –1

Ï1 e -e * -1 e e *¸
E1 Ì ˝ (x, y) (Rx Ry) (yz, xz)
Ó1 e* -e -1 -e * e˛

Ï1 -e * -e 1 -e * -e ¸
E2 Ì ˝ (x2 – y2, xy)
Ó1 -e -e * 1 -e -e *˛
690 A Textbook of Physical Chemistry

2. The Dn Groups

D2 E C2(z) C2(y) C2(x)

A 1 1 1 1 x2, y2, z2
B1 1 1 –1 –1 z, Rz xy
B2 1 –1 1 –1 y, Ry xz
B3 1 –1 –1 1 x, Rx yz

D3 E 2C3 3C2
A1 1 1 1 x2 + y2, z2
A2 1 1 –1 z, Rz
E 2 –1 0 (x, y), (Rx, Ry) (x2 – y2, xy), (xz, yz)

D4 E2 2C4 C2(= C42) 2C2¢ 2C2¢¢

A1 1 1 1 1 1 (x2 + y2, z2)
A2 1 1 1 –1 –1 z, Rz
B1 1 –1 1 1 –1 x2 – y2
B2 1 –1 1 –1 1 xy
E 2 0 –2 0 0 (x, y), (Rx, Ry) (xz, yz)

D6 E 2C6 2C3 C2 3C2¢ 3C2¢¢

A1 1 1 1 1 1 1 x2 + y2, z2
A2 1 1 1 1 –1 –1 z, Rz
B1 1 –1 1 –1 1 –1
B2 1 –1 1 –1 –1 1
E1 2 1 –1 –2 0 0 (x, y) (Rx, Ry) (xz, yz)
E2 2 –1 –1 2 0 0 (x2 – y2, xy)

3. The Cnv Groups

C2v E C2 sv(xz) s v¢ (yz)
A1 1 1 1 1 z x2, y2, z2
A2 1 1 –1 –1 Rz xy
B1 1 –1 1 –1 x, Ry xz
B2 1 –1 –1 1 y, Rx yz

C3v E 2C3 3sv

A1 1 1 1 z x2 + y2, z2
A2 1 1 –1 Rz
E 2 –1 0 (x, y), (Rx, Ry) (x2 – y2, xy), (xz, yz)
 Molecular Symmetry and Its Applications 691

C4v E 2C4 C2 2sv 2sd

A1 1 1 1 1 1 z x2 + y2, z2
A2 1 1 1 –1 –1 Rz
B1 1 –1 1 1 –1 x2 – y2
B2 1 –1 1 –1 1 xy
E 2 0 –2 0 0 (x, y), (Rx, Ry) (xz, yz)

C6v E 2C6 2C3 C2 3sv 3sd

A1 1 1 1 1 1 1 z x2 + y2, z2
A2 1 1 1 1 –1 –1 Rz
B1 1 –1 1 –1 1 –1
B2 1 –1 1 –1 –1 1
E1 2 1 –1 –2 0 0 (x, y) (Rx, Ry) (xz, yz)
E2 2 –1 –1 2 0 0 (x2 – y2, xy)

4. The Cnh Group

C2h E C2 i sh
Ag 1 1 1 1 Rz x2, y2, z2, xy
Bg 1 –1 1 –1 Rx, Ry xz, yz
Au 1 1 –1 –1 z
Bu 1 –1 –1 1 x, y

C3h E C3 C23 sh S3 S32 e = exp (2p i/3)

A¢ 1 1 1 1 1 1 Rz x2 + y2, z2
Ï1 e e* 1 e e *¸
E¢ Ì ˝ (x, y) (x2 – y2, xy)
Ó1 e* e 1 e* e˛
A≤ 1 1 1 –1 –1 –1 z
Ï1 e e* -1 -e -e *¸
E≤ Ì ˝ (Rx, Ry) (xz, yz)
Ó1 e* e -1 -e * -e ˛

C4h E C4 C2 C43 i S43 sh S4

Ag 1 1 1 1 1 1 1 1 Rz x2 + y2, z2
Bg 1 –1 1 –1 1 –1 1 –1 x2 – y2, xy
Ï1 i -1 -i 1 i -1 -i ¸
Eg Ì ˝ (Rx, Ry) (xz, yz)
Ó1 -i -1 i 1 -i -1 i˛
Au 1 1 1 1 –1 –1 –1 –1 z
Bu 1 –1 1 –1 –1 1 –1 1
Ï1 i -1 -i -1 -i 1 i¸
Eu Ì ˝ (x, y)
Ó1 -i -1 i -1 i 1 -i ˛
692 A Textbook of Physical Chemistry

5. The Dnh Groups

D2h E C2(z) C2(y) C2(x) i s (xy) s (xz) s (yz)

Ag 1 1 1 1 1 1 1 1 x2, y2, z2
B1g 1 1 –1 –1 1 1 –1 –1 Rz xy
B2g 1 –1 1 –1 1 –1 1 –1 Ry xz
B3g 1 –1 –1 1 1 –1 –1 1 Rx yz
Au 1 1 1 1 –1 –1 –1 –1
B1u 1 1 –1 –1 –1 –1 1 1 z
B2u 1 –1 1 –1 –1 1 –1 1 y
B3u 1 –1 –1 1 –1 1 1 –1 x

D3h E 2C3 3C2 sh 2S3 3sv

A¢1 1 1 1 1 1 1 x2 + y2, z2
A¢2 1 1 –1 1 1 –1 Rz
E¢ 2 –1 0 2 –1 0 (x, y) (x2 – y2, xy)
A≤1 1 1 1 –1 –1 –1
A≤2 1 1 –1 –1 –1 1 z
E≤ 2 –1 0 –2 1 0 (Rx, Ry) (xz, yz)
 Molecular Symmetry and Its Applications 693

D4h E 2C4 C2 2C¢2 2C≤2 i 2S4 sh 2sv 2sd

A1g 1 1 1 1 1 1 1 1 1 1 x2 + y2, z2
A2g 1 1 1 –1 –1 1 1 1 –1 –1 Rz
B1g 1 –1 1 1 –1 1 –1 1 1 –1 x2 – y2
B2g 1 –1 1 –1 1 1 –1 1 –1 1 xy
Eg 2 0 –2 0 0 2 0 –2 0 0 (Rx, Ry) (xz, yz)
A1u 1 1 1 1 1 –1 –1 –1 –1 –1
A2u 1 1 1 –1 –1 –1 –1 –1 1 1 z
B1u 1 –1 1 1 –1 –1 1 –1 –1 1
B2u 1 –1 1 –1 1 –1 1 –1 1 –1
Eu 2 0 –2 0 0 –2 0 2 0 0 (x, y)

D6h E 2C6 2C3 C2 3C ¢2 3C≤2 i 2S3 2S6 sh 3sd 3sv

A1g 1 1 1 1 1 1 1 1 1 1 1 1 x2 + y2, z2
A2g 1 1 1 1 –1 –1 1 1 1 1 –1 –1 Rz
B1g 1 –1 1 –1 1 –1 1 –1 1 –1 1 –1
B2g 1 –1 1 –1 –1 1 1 –1 1 –1 –1 1
E1g 2 1 –1 –2 0 0 2 1 –1 –2 0 0 (Rx, Ry) (xz, yz)
E2g 2 –1 –1 2 0 0 2 –1 –1 2 0 0 (x2 – y2, xy)
A1u 1 1 1 1 1 1 –1 –1 –1 –1 –1 –1
A2u 1 1 1 1 –1 –1 –1 –1 –1 –1 1 1 z
B1u 1 –1 1 –1 1 –1 –1 1 –1 1 –1 1
B2u 1 –1 1 –1 –1 1 –1 1 –1 1 1 –1
E1u 2 1 –1 –2 0 0 –2 –1 1 2 0 0 (x, y)
E2u 2 –1 –1 2 0 0 –2 1 1 –2 0 0

6. The Dnd Groups

D2d E 2S4 C2 2C¢2 2sd

A1 1 1 1 1 1 x2 + y2, z2
A2 1 1 1 –1 –1 Rz
B1 1 –1 1 1 –1 x2 – y 2
B2 1 –1 1 –1 1 z xy
E 2 0 –2 0 0 (x, y), (Rx, Ry) (xz, yz)

D3d E 2C3 3C2 i 2S6 3sd

A1g 1 1 1 1 1 1 x2 + y2, z2
A2g 1 1 –1 1 1 –1 Rz
Eg 2 –1 0 2 –1 0 (Rx, Ry) (x2 – y2, xy), (xz, yz)
A1u 1 1 1 –1 –1 –1
A2u 1 1 –1 –1 –1 1 z
Eu 2 –1 0 –2 1 0 (x, y)
694 A Textbook of Physical Chemistry

D4d E 2S8 2C4 2S 83 C2 4C 2¢ 4sd

A1 1 1 1 1 1 1 1 x2 + y2, z2
A2 1 1 1 1 1 –1 –1 Rz
B1 1 –1 1 –1 1 1 –1
B2 1 –1 1 –1 1 –1 1 z
E1 2 2 0 – 2 –2 0 0 (x, y)
E2 2 0 –2 0 2 0 0 (x2 – y2, xy)
E3 2 – 2 0 2 –2 0 0 (Rx, Ry) (xz, yz)

D6d E 2S12 2C6 2S4 5

2C3 2S 12 C2 6C2¢ 6sd

A1 1 1 1 1 1 1 1 1 1 x2 + y2, z2
A2 1 1 1 1 1 1 1 –1 –1 Rz
B1 1 –1 1 –1 1 –1 1 1 –1
B2 1 –1 1 –1 1 –1 1 –1 1 z
E1 2 3 1 0 –1 – 3 –2 0 0 (x, y)
E2 2 1 –1 –2 –1 1 2 0 0 (x2 – y2, xy)
E3 2 0 –2 0 2 0 –2 0 0
E4 2 –1 –1 2 –1 –1 2 0 0
E5 2 – 3 1 0 –1 3 –2 0 0 (Rx,Ry) (xz, yz)

7. The S2n Groups

S4 E S4 C2 S 34

A 1 1 1 1 Rz (x2 + y2, z2)

B 1 –1 1 –1 z (x2 – y2, xy)
Ï1 i -1 -i¸
E Ì ˝ (x, y), (Rx, Ry) (xz, yz)
Ó1 -i -1 i˛

S6 E C3 C32 i S 56 S6 e = exp(2pi/3)
Ag 1 1 1 1 1 1 Rz (x2 + y2, z2)

Eg Ï1 e e* 1 e e *¸
(Rx, Ry) (x2 – y2, xy); (xz, yz)
Ì ˝
Ó1 e* e 1 e* e˛
Au 1 1 1 –1 –1 –1 z

Ï1 e e* -1 -e - e *¸
Eu Ì ˝ (x y)
Ó1 e* e -1 -e * -e ˛
 Molecular Symmetry and Its Applications 695

8. The Cubic Groups

T E 4C3 4C23 3C2 e = exp(2pi/3)

A 1 1 1 1 x2 + y2 + z2
Ï1 e e* 1 (2z2 – x2 – y2,
E Ì
Ó1 e* e 1 x2 – y2)
T 3 0 0 –1 (Rx, Ry, Rz), (x, y, z) (xy, xy, yz)

Td E 8C3 3C2 6S4 6sd

A1 1 1 1 1 –1 x2 + y2 + z2
A2 1 1 1 –1 –1
E 2 –1 2 0 0 (2z2 – x2 – y2, x2 – y2)
T1 3 0 –1 1 –1 (Rx, Ry, Rz)
T2 3 0 –1 –1 1 (x, y, z) (xy, xz, yz)

O E 8C3 3C2(= C 42) 6C4 6C2

A1 1 1 1 1 1 x2 + y2 + z2
A2 1 1 1 –1 –1
E 2 –1 2 0 0 (2z2 – x2 – y2, x2 – y2)
T1 3 0 –1 1 –1 (Rx, Ry, Rz), (x, y, z)
T2 3 0 –1 –1 1 (xy, xz, yz)

Oh E 8C3 6C2 6C4 3C2(= C 24) i 6S4 8S6 3sh 6sd

A1g 1 1 1 1 1 1 1 1 1 1 x2 + y2 + z2
A2g 1 1 –1 –1 1 1 –1 1 1 –1
Eg 2 –1 0 0 2 2 0 –1 2 0 (2z2 – x2 – y2, x2 – y2)
T1g 3 0 –1 1 –1 3 1 0 –1 –1 (Rx, Ry,Rz)
T2g 3 0 1 –1 –1 3 –1 0 –1 1 (xz, yz, xy)
A1u 1 1 1 1 1 –1 –1 –1 –1 –1
A2u 1 1 –1 –1 1 –1 1 –1 –1 1
Eu 2 –1 0 0 2 –2 0 1 –2 0
T1u 3 0 –1 1 –1 –3 –1 0 1 1 (x, y, z)
T2u 3 0 1 –1 –1 –3 1 0 1 –1
696 A Textbook of Physical Chemistry

9. The Groups C•v and D•h for Liner Molecules

C•v E 2C •j º •sv

A1 ∫ S+ 1 1 º 1 z x2 + y2,z2
A2 ∫ S – 1 1 º –1 Rz
E1 ∫ P 2 2cos j º 0 (x, y), (Rx, Ry) (xz, yz)
E2 ∫ D 2 2 cos 2j º 0 (x2 – y2, xy)
E3 ∫ F 2 2 cos 3j º 0
º º º º º

D• h E 2C •j • sv i 2S•j • C2

S +g 1 1 1 1 1 1 x2 + y2, z2
S –g 1 1 –1 1 1 –1 Rz
Pg 2 2 cos j 0 2 –2 cos j 0 (Rx, Ry) (xz, yz)
Dg 2 2 cos 2j 0 2 2 cos 2j 0 (x2 – y2, xy)

S +u 1 1 1 –1 –1 –1 z
S –u 1 1 –1 –1 –1 1
Pu 2 2 cos j 0 –2 2 cos j 0 (x, y)
Du 2 2 cos 2j 0 –2 –2 cos 2j 0
APPENDIX I Units and Conversion Factors

SI Units
There are seven base quantities in SI units. These are described in Table AI.1.

Table AI.1 Seven Basic Quantities in SI Units

quantity unit
Length meter m The meter is the length of path travelled
by light in vacuum during a time interval
of 1/299 792 458 of a second.
Mass kilogram kg A cylinder of platinum-irridium alloy
kept by the International Bureau of
Weights and Measures in Paris
Time second s The duration of 9 192 631 770 periods of
the radiation associated with the transition

ground caesium–133 atom

Electric current ampere A The magnitude of the current that, when

parallel wires of negligible circular cross-

section and separated by one 1 m in free
space, results in a force between the two
wires of 2 ¥ 10–7 N for each meter of length

Thermodynamic kelvin K The kelvin, unit of thermodynamic

temperature temperature, is the fraction of 1/273.16
of the thermodynamic temperature of the
triple point of water.
Amount of mole mol Amount of substance that contains
substance as many elementary entities (atoms,
molecules, ions, etc.) as there are carbon
atoms in 0.012 kg of carbon–12

Luminous candela cd The candela is the luminous intensity, in

a given direction of a source that emits
monochromatic radiation of frequency
540 ¥ 1012 hertz and that has a radiant
intensity in that direction of (1/683) watt
per steradian
698 A Textbook of Physical Chemistry

Units Derived from the Base SI Units

Force newton N = kg m s–2 or J m–1

Energy joule J = kg m2 s–2 or N m
Electric charge coulomb C=A s
Potential difference volt V = kg m2 s–3 A–1 or J A–1 s–1
Resistance ohm W = kg m2 s–3 A–2 or V A–1
Frequency hertz = cycle per second Hz = s–1
Area square metre m2
Volume cubic metre m3
Density kilogram per cubic metre kg m–3
Velocity metre per second m s–1
Angular velocity radian per second rad s–1
Acceleration metre per square second m s–2
Pressure newton per square metre N m–2 or Pa
or pascal
Conductivity siemen S = W–1
–2
= V s m–2
Electric capacitance farad F = C V –1

Inductance henry H = Wb A–1

CGS Units vis-á-vis SI Units

Physical quantity CGS units SI units

Name Symbol Name Symbol
Length centimetre cm metre m
–8
Angstron (10 cm) Å
Mass gram g kilogram kg
Time second sec second s
celsius °C
Temperature kelvin °K kelvin K
Energy calorie cal joule J
kilocalorie kcal kilojoule kJ
litre-atmosphere lit-atm
ergs erg
Electric current ampere A ampere A
 Molecular Symmetry and Its Applications 699

Conversion of CGS Units to SI Units

Quantity Units Equivalent†

Length Angstron, Å 10–10 m = 10–1 nm = 102 pm

micron, m 10–6 m

Volume litre 10–3 m3 = dm3

Force dyne 10–5 N

Energy erg 10–7 J

cal 4.184 J
eV 1.602 1 ¥ 10–19 J
eV/mole 98.484 kJ mol–1
Pressure atmosphere 101.325 kN m–2
mmHg (or Torr) 133.322 N m–2
bar (106 dyn/cm2) 105 N m–2

Viscosity poise 10–1 kg m–1 s–1

–4
T
(magnetic induction)

10–1 deci d 10 deca da

–2 2
10 centi c 10 hecto h

10–3 milli m 103 kilo k

10–6 micro m 106 mega M

10–9 nano n 109 giga G

–12 12
10 pico p 10 tera T

10–15 femto f 1015 peta P

700 A Textbook of Physical Chemistry

Values of Some Physico-Chemical Constants

Constant CGS units SI units
–2
Acceleration of gravity, g 980.66 cm sec 9.806 65 m s–2
Avogadro’s constant, NA 6.022 05 ¥ 1023 molecules mole–1 6.022 05 ¥ 1023 mol–1
Bohr magneton, mB 9.2741 ¥ 10–21 erg gauss–1 9.27408 ¥ 10–24 A m2
Bohr radius, a0 0.529 177 Å 5.291 77 ¥ 10–11 m
Boltzmann constant, k 1.380 66 ¥ 10–16erg (degree K)–1 1.380 60 ¥ 10–22 J K –1
molecule–1
Debye 10–18 esu◊cm 3.335 6 ¥ 10–30 C m
Elementary charge, e 4.802 98 ¥ 10–10esu 1.602 16 ¥ 10–19 C
Electronic rest mass, me 9.109 53 ¥ 10–28g 9.109 53 ¥ 10–31 kg
Faraday constant, F 96 487 coulomb equiv–1 9.648 46 ¥ 104 C mol–1
Ï 8.31.441 ¥ 107 ergs (degree K)–1 Ï 8.314 41 J K–1 mol–1
Ô mole–1 Ô 8.314 41 N m K –1 mol–1
Ô 8.31441 Joules (degree K)–1 Ô 8.314 41 Pa m3 K –1
Ô –1 Ô
Gas constant, R Ì mole Ì mol–1
Ô 0.082 054 litre-atm (degree K)–1 Ô 8.314 41 kPa dm K –1
3
Ô Ô
Ô mole–1 Ô mol–1
Ó 1.987 cal (degree K)–1 mole–1 Ó 8.314 41 MPa cm3 K–1
mol–1
Molar volume of ideal gas
at 0 °C and 1 atm, Vm 22.414 litres 2.241 4 ¥ 10–2 m3 mol–1
Permittivity of
vacuum, e0 = m0–1 c–2 8.854 188 ¥ 10–12 C2 s2
Permeability of kg–1 m–3
–7 –1
vacuum, m0 4p ¥ 10 H m
Planck’s constant, h 6.626 18 ¥ 10–27 erg sec 6.626 18 ¥ 10–34 J s
Proton rest mass, mp 1.67265 ¥ 10–24 g 1.672 65 ¥ 10–27 kg
Vacuum speed of light, c0 2.997 925 ¥ 1010 cm sec–1 2.997 925 ¥ 108 m s–1
Standard atmospheric 76 cmHg
pressure 760 mmHg (or Torr) 101.325 kPa
1.1032 ¥ 106 dynes/cm2 1.0132 5 bar

Valence-Orbital Ionization Energies

Atom E1s /MJ mol–1 E2s / MJ mol–1 E2p /MJ mol–1
H 1.317
He 2.371
Li 0.527
Be 0.898
B 1.353 0.802
C 1.880 1.030
N 2.466 1.269
O 3.125 1.533
F 4.478 1.808
Ne 4.681 2.083
 Molecular Symmetry and Its Applications 701

APPENDIX II

1 1
sin a sin b = cos (a – b ) – cos (a + b )
2 2
1 1
cos a cos b = sin (a – b) + cos (a + b )
2 2
1 1
sin a cos b = sin (a + b ) + sin (a – b )
2 2
sin (a ± b ) = sin a cos b ± cos a sin b
cos (a ± b) = cos a cos b sin a sin b
e±iq = cos q ± i sin q
e iq + e - iq
cos q =
2
e iq - e - iq
sin q =
2i

x2 x3 x 4
ex = 1 + x + + + +
2 ! 3! 4 !
x2 x 4 x6
cos x = 1 – + - +
2! 4! 6!
x3 x5 x7
sin x = x – + - +
3! 5! 7!
1
= 1 + x + x 2 + x 3 + x4 + ; x2 < 1
1- x

n ( n - 1) 2 n ( n - 1) ( n - 2 ) 3
(1 ± x ) n = 1 ± n x + x ± x + ; x2 < 1
2! 3!
•
n - ax n!
Úx e dx =
a n +1
; (n positive integer)
0

( )
• 1/ 2
- ax 2 p
Úe dx =
4a
0

()
•
2 n - ax 2 1 ◊ 3 ◊ 5 ( 2 n - 1) p 1/ 2

Úx e dx =
2 n+1 a n a
; (n positive integer)
0
702 A Textbook of Physical Chemistry

•
2 n +1 - ax 2 n!
Úx e dx =
2a n +1
; (n positive integer)
0

npx mpx npx mpx

a a
a
Ú sin a
sin
a
dx = Ú cos
a
cos
a
dx = d nm
2
0 0

npx mpx
a

Ú cos a
sin
a
dx = 0 ; (m and n integers)
0

Ê du ˆ
Ú uu dx = uÚ u dx - Ú Ë dx ¯ Ú (u dx) dx

Symbol Symbol
Name Roman Italic Roman Italic Name Roman Italic Roman Italic
Alpha A A a a Nu N N n n
Beta B B b b Xi X X x x
Gamma G G g g Omicron O o o o
Delta D D d d Pi P P p p
Epsilon E E e e Rho R R r r
Zeta Z Z z z Sigma S S s s
Eta H H h h Tau T T t t
Theta Q Q q q Upsilon U U u u
Iota I I i i Phi F F f f
Kappa K K k k Chi C C c c
Lambda L L l l Psi Y Y y y
Mu M M m m Omega W W w w
 Index

Allyl radical, 281 Bosons, 128

Ampere’s law, 108 Boundary conditions, 38
Angular momentum, 162 Brackett series, 19
Angular momentum quantum
number, 88 Chemical shift, 364
Anharmonicity constant, 423 Clausius-Mossottii equation, 302
Anharmonic vibration, 422 Cloud density pattern, 97
Anomalous Zeeman effect, 112 Commutator, 169
Antibonding molecular orbital, 197 Comparison between MO and
Anti-Stokes Lines, 446 VB, 211
Antisymmetric wave function, 43 Compton shift, 27
Antisymmetric stetching Configuration interaction, 212
vibration, 420 Conjugated molecules, 271
Associated Laguerre equation, 83 Contour plots, 97
Associated Laguerre polynomial, 83 Correlation diagram, 230
Associated Legendre equation, 73 Correspondence principle, 43
Associated Legendre polynomials, 73 Criterion of maximum overlap, 188
Atomic orbitals, 89 Coulomb integral, 192
Atomic-orbital density, 185 de Broglie relation, 23, 153
Atomic term symbols, 130
Atomic units, 180 Debye equation, 304
Aufbau principle, 136 Degenerate functions, 88
Azimuthal quantum number, 88 Degrees of freedom, 439
Del squared, 31
Balmer series, 19 Delocalization energy, 277
Black-body radiation, Density,
Planck’s contribution, 3 atomic orbital, 185
Rayleigh-Jeans contribution, 3 overlap, 185
Wein’s contribution, 2 Diamagnetic susceptibility, 328
Bohr magneton, 109 Diamagnetism, 327
Bohr model of atom, 13 Diatomic molecules,
Bohr orbits, 16 dissociation energy of, 426
Bohr theory of hydrogen atom, 15 heteronuclear, 225
Boltzmann constant, 493 homonuclear, 214
Boltzmann equation, 359 Dielectric constant, 305
Bond moment, 316 Different types of spectroscopy, 349
Bond order, 219, 280 Dipole moment,
Bonding molecular orbital, 197 application of, 326
Born interpretation, 34 definition of, 297
Born-Oppenheimer Dot population picture, 97
approximation, 183 Dulong-Petit law, 11
704 Index

Eigen-function, 31 Group vibrations, 440

Eigenvalue problem, 31 Gyromagnetic ratio, 109
Einstein absorption coefficient, 351
Electric dipole moment, 297 Hamiltonian operator, 34
Electronic configurations, Harmonic oscillator, 58
of atoms, 136 Heat capacity, 11
of homonuclear diatomic effect of temperature, 12
molecules, 219 Hermitian operator, 35
Electron density, 279 Heisenberg uncertainty principle, 26
Electron spin resonance, 384 Heitler-London treatment of H2, 205
Electron volt, 492 Hermite equation, 156
Electronic radical wavefunction, 98 Hermite polynomials, 61
Energy expressions of, Homonuclear diatomic
bohr orbits, 16 molecules, 214
rotational levels, 70 Hooke’s law, 414
translational levels, 39, 54 Hückel MO method, 272
vibrational (anharmonic) Hund’s rule, 135
levels, 424 Hybrid orbitals, 234
vibrational (harmonic) levels, 61 sp, 236
Energy levels of, sp2, 238
a particle in a box, 42 sp3, 240
electron in a hydrogen atom, 89 Hydrogen fluoride, 228
harmonic oscillator, 62 Hydrogen molecule, 202
ESR spectroscopy, 384 Hydrogen molecule ion, 190
Even function, 43 Hyperfine coupling constant, 388
Exchange integral, 195
Expectation value, 33 Index of refraction, 310
Extended Hückel method, 272 Infrared-active species, 419
Infrared-inactive species, 419
Far-infrared radiation, 350 Infrared radiation, 350
Fermions, 128 Intensity of NMR signals, 359
Finger print region, 441 Internal conversion, 463
Fluorescence, 460 Internal coordinates, 69
Forbidden transition, 351 Intersystem crossing, 463
Force constant, 58 Ionic character of diatomic
Franck-Condon principle, 455 molecules, 316
Free-electron model, 43 Isotopic substitution, 407
Free-valence index, 280
Fundamental absorption, 425 Kronecker delta, 35

Gerade, 215 Laguerre polynomial, 83

Gouy-balance method, 331 Lande g-factor, 116
Gross atomic population Leplacian operator, 31
number, 185 Larmor precession, 110
Grotrian diagram, 89 LCAO MO treatment of,
Group moment, 323 H +2 , 190
 Index 705

H2, 202 nitrogen, 291

H32+ , 199 triatomic molecules, 244
Legendre polynomial, 73 water, 252
Linear operator, 32 Molecular spectroscopy, 347
Localized molecular orbitals Moment of inertia, 67
of beryllium hydride, 249 Morse potential, 423
Mulliken gross atomic population
of carbon dioxide, 262
of water, 255 number, 185
Lorentz-Lorenz equation, 310
Lymann series, 19 Nodal point, 43
Normal modes of vibration, 439
Magnetic field intensity, 346 Normalization constant, 35
Magnetic flux density, 346 Nonrigid rotator, 409
Nuclear g factor, 356
Magnetic moment, 108
Nuclear magnetic resonance
Magnetic moment of nucleus, 356
Magnetic quantum number, 88 spectroscopy, 355
Nuclear magneton, 356
Magnetic resonance
spectroscopy, 355
Magnetic susceptibility, 327 Odd function, 43
Operators,
Magnetization, 327
definition, 32
Many-electron atoms, 119
Maxwell relation, 310 Hamiltonian, 34
Measurement of magnetic Hermitian, 35
linear, 32
susceptibility, 331
Modes of vibration, 439 of components of angular
Molar polarization, 304 momentum, 162
square of angular momentum, 70
Molar refraction, 311
Molecular orbital theory, 184 One-dimensional box, 37
Molecular orbital treatment of, Orbital,
atomic, 89
allyl radical, 281
benzene, 277 exponent, 121
hybrid, 234
beryllium hydride, 246
butadiene, 274 localized, 249
carbon dioxide, 258 nonlocalized, 250
molecular, 184
carbon monoxide, 291
ethylene molecule, 273 slater, 121
Orthogonal, 35
H +2 , 190 Orthonormal, 35
H2, 202 Overlap density, 185
H32+ , 199 Overlap integral, 192
heteronuclear diatomic Overtones, 425
molecules, 225
hydrocyanic acid, 265 P-branch, 437
hydrogen fluoride, 228 Paramagnetism, 329
homonuclear diatomic Particle in a,
molecules, 214 one-dimensional box, 37
lithium hydride 226 three-dimensional box, 53
706 Index

Pascal triangle, 375 rotational energies, 67

Paschen-Back effect, 118 translational energies, 37
Paschen series, 19 vibrational energies, 58
Pauli exclusion principle, 125 Quantum numbers, 87
Permittivity, 301
Perturbation method, 120 R-branch, 437
Pfund series, 19 Radial distribution function, 98
Phosphorescence, 460 Raman shift, 443
Photoelectric effect, 8 Raman spectroscopy, 442
Photon, 9 Rayleigh-Jeans contribution, 3
Physical constants, table of, 493 Reduced mass, 20
Planck’s constant, 9 Resonance integral, 192
Plot of wave functions of, Rigid rotator, 67
d-orbitals, 104 Rotational constant, 399
p-orbitals, 100 Rotational energy,
s-orbitals, 95 for nonrigid rotator, 409
translational levels, 42 for rigid rotator, 70, 399
vibrational levels, 62 Rotational levels, 401
Polarizability, 300 Rotational spectrum, 406
Polarization, Rutherford model of atom, 14
atomic, 300 Rydberg constant, 14
electronic, 300
molar, 304 Schrödinger equation, 31
orientation, 300 Schrödinger wave theory, 30
Power series method, 155 Second overtone, 425
Postulates of quantum mechanics, 32 Secular determinant, 193
Potential energy curve of, Secular equations, 193
hydrogen molecule, 211 Selection rules for,
hydrogen molecular ion, 197 anharmonic oscillator, 425
Predissociation, 458 atomic hydrogen, 89
Principal quantum number, 88 harmonic oscillator, 354, 420
Probability density distributions, 95 particle in a box, 353
Probability of transition, 350 rigid rotator, 404
Proton magnetic resonance spectrum vibrational-rotational
of, spectrum, 435
dichloropropane, 378 Self-consistent field method, 122
dimethyl formamide, 377 Shielding constant, 364
ethyl acetate, 379 SI units, 490
ethyl alcohol, 376 Singlet state, 461
isopropyl acetate, 381 Slater determinant, 129
methyl alcohol, 365 Slater orbitals, 121
methyl propionate, 376 sp hybrid orbitals, 236
sp2 hybrid orbitals, 238
Q-branch, 437 sp3 hybrid orbitals, 240
Quantization of, Space quantization of angular
electronic energies, 78 momentum, 76
 Index 707

Spectral series of atomic Valence bond,

hydrogen, 18 method, 189
Spherical harmonics, 70 treatment of H2, 204
Spherical polar coordinates, 69
Spin function, 126 Variation principle, 33, 121
Spin multiplicity, 135 Vibrational energy, 417
Spin-orbit coupling, 116 Vibrational modes, 439
Spin quantum number, 112 Vibrational-rotational spectrum, 434
Spin-spin interactions, 371 Vibrational spectra of
Standing wave system, 3 polyatomic molecules, 439
Stefan-Boltzmann constant, 2 Virial theorem, 95
Stefan-Boltzmann law, 2
Stern-Gerlach experiment, 119 Walsh rule, 268
Stokes lines, 446 Wave function,
Symmetric functions, 43 Born interpretation of, 34
Symmetrical stretching vibration,
419 radial distribution, 98
Wave function for,
Term symbol, harmonic oscillator, 61
atomic, 130 hydrogen atom, 84
molecular, 223 particle in a box, 40
Tesla, 344 rigid rotator, 72-73
Theories of covalent bond, 182 Wave nature of electron, 23
Three-dimensional box, 53 Wavelength of an electron, 23
Threshold frequency, 8 Wave-particle duality, 22
Transition moment integral, 350 Wein’s displacement law, 2
Triplet state, 461 Work function, 8

Ultraviolet catastrophe, 3 Zeeman effect, 112

Uncertainty principle, 26 Zero-point energy, 418
United-atom concept, 230