Science broadly defined as 'accumulated knowledge, based on observations,

suitably tested and verified, and properly or organized and classified'. The first step
in the development of any branch of science is to observe the facts or phenomena
as they take place in nature or laboratory. An attempt is then made to see if these
facts can be put in the form of a general statement or mathematical expression
which is known as the law. Therefore, a law is a mathematical statement of the
regularity of behavior. The second step consists in seeking an explanation for the
experimental facts by reasonable imagination or guess called Hypothesis. For
example, Dalton put forward the well-known atomic hypothesis to explain the law
of chemical combination. The third step is to put the hypothesis to test. If the
assumptions are found correct, the hypothesis is given the status of theory. The
actual or direct proof of the theory is impossible. For example, there is hardly any
doubt that the kinetic theory of gases is essentially correct but its direct proof has
never been fully established. Atoms are the smallest parts of an element that
chemically react. In 1808, John Dalton proposed the first atomic theory, i.e., an
individual particle of matter is known as an atom. At the end of the 19th century, it
was proved experimentally that atoms are divisible and consist of three
fundamental particles (electrons, protons and neutrons). This soon led to the
questions about the internal arrangement of these fundamental particles (atomic
structure).
Many atomic models such as J. J. Thomson's model, Rutherford's model,
Bohr's model, etc. were suggested from time to time.
ELECTROMAGNETIC RADIATIONS
In 1864, Clark Maxwell proved that an alternating current of high frequency is
capable of radiating continuous energy in the form of waves (electromagnetic
waves or electromagnetic radiations). They have both electric and magnetic
properties. The radiations such as visible, ultraviolet, infrared, X-rays, etc. are
called Electromagnetic Radiations. They consist of electric and magnetic fields
Oscillating perpendicular to other and both are perpendicular to the direction of
wave propagation. These waves do not require any medium for propagation.
Electromagnetic waves travel with the same speed of light
(3.0 x 1010 cm/s). All waves have the following five characteristics:
(i) Wavelength The distance between two consecutive crests or troughs of the
wave is known as wavelength (Fig. 1.1). It is denoted by λ (lambda)

Page 1 of 27
expressed in angstrom units (Å).
1 Å = 10−8 cm: 10−10 m
(ii) Frequency The number of times a wave passes through a fixed point per unit
time is known as frequency. It is denoted by 'υ' (nu) and expressed in cycles per
second or hertz (Hz).
(iii) Wavenumber The reciprocal of wavelength is called Wave Number. It is
denoted by 𝜐̅ and expressed in cm—I
(iv) Amplitude The depth of the trough or height of crest is known as amplitude.
It is denoted by 'a'.
(v) Velocity The distance traveled by a wave in one second is called velocity.
It is denoted by 'c' and expressed in m/sec or cm/sec. C = υλ (c: 3.0 x 108 m/sec
or 3.0 x 1010 cm/sec)
Electromagnetic Spectra
The arrangements of various types of electromagnetic radiations in terms of
increasing or decreasing wavelengths or frequency is called an electromagnetic
spectrum. The spectrum obtained by white light is a continuous spectrum. For
example, the visible light is the form of electromagnetic radiation that lies in the
wavelength range of 3800—7600 Å. The wavelengths of various waves
increase in the following order (Fig).

γ-rays < X-rays < UV rays < Visible rays < IR rays <Microwaves < Radio waves

Page 2 of 27
 PLANCK'S QUANTUM THEORY
Electromagnetic wave theory or radiations could not explain the phenomena of
black body radiations and photoelectric effect (When a beam of light of suitable
frequency is allowed to incident/fall on the surface of a metal, the electrons are
ejected from the surface of the metal). In 1900, Max Planck proposed a theory of
radiation to explain these phenomena. While analyzing the light emitted by heated
objects, he discovered that the emitted light is non-continuous and is in the form of
defined energy packets. These small packets of energy are known as quanta or
photons. The energy of the photon is directly proportional to the frequency of the
radiation.

Mathematically,
ε = hυ
where ε= energy of the photon
υ = frequency of the radiation
h= Planck's constant (6.626 x 10—27 erg sec or 6.626 x 10—34 Joules sec)
Further, the total energy emitted or absorbed by a body is always in integer and
multiple of 'hυ', i.e.,
ε = nhυ where n = l, 2, 3, ..
For example, hυ, 2 hυ, 3 hυ, 4 hυ but never a fraction.
Similarly
ℎ𝑐 𝑐
ε= (⸫υ = )
𝜆 𝜆

The above equation says that a wave of higher frequency or lower wavelength will
be more energetic and vice versa. For example, the violet light of high frequency
has more energy whereas red light of low frequency will exhibit less energy.

Page 3 of 27
 DUAL NATURE OF MATTER
Bohr's model of the atom has the following two inherent defects:
(i) The simultaneous assignments of an exact position and definite momentum to a
given electron which is contradictory to Heisenberg uncertainty principle
(ii) Principle of quantization of angular momentum for which no justification was
made by Bohr. De-Broglie pointed out in 1924 that radiation including visible light,
infrared, ultraviolet and X-rays behave like waves in propagation experiments
based on interference and diffraction. These experiments conclusively proved the
wave nature of these radiations.
However, radiation behaves like a particle in interaction experiments which include
block body radiation, photoelectric effect and Crompton effect. Hence, radiations
have a dual nature/character, i.e., wave and particle. In other words, matter also
possesses particle as well as wave character. A wave is specified by its frequency,
wavelength, phase, amplitude, etc. while a particle is specified by its mass, velocity,
energy, etc. The concept of the dual character of matter gave birth to the wave
mechanical theory of matter, according to which electron, photon, and even atom
when in motion possess all wave properties. The new quantum mechanics which
take into account the particle, as well as the wave nature of matter, is termed as
wave mechanics.
De-Broglie’s Equation
According to de Broglie's hypothesis, all the matter particles like electrons,
protons, neutrons, atoms should have not only the particle nature but also the
wave properties. The wavelength of the matter particle (electron) in motion is
given by
ℎ ℎ
λ= or λ =
𝑚𝜐 𝑝

where λ= wavelength
m= mass of the
electron
h = Planck's constant
P=movement of
electron

Page 4 of 27
The above equation is known as de Broglie's wave equation, which is derived
from Planck's quantum theory and Einstein mass-energy relation.
According to Max Planck's Quantum theory
ε = hυ
ℎ𝑐 𝑐
= (⸫υ = ) …..(1)
𝜆 𝜆

According to Einstein mass energy relation

E = mc2 … (2)
Comparing the two equations 1&2
ℎ𝑐
= mc2
𝜆
ℎ
λ=
𝑚𝑐

If c' is replaced with the velocity of electrons 'υ', then

ℎ ℎ
λ= or λ =
𝑚𝜐 𝑝

de-Broglie's concept is significant for small (microscopic) particles like electrons

only. For macroscopic particle, the wavelength is so short and wave properties
cannot be observed. Thus, as per this theory, an electron is not a point mass
moving in an orbit but a standing wave extending around the nucleus in a circular
fashion.

Heisenberg Uncertainty Principle

One of the important consequences of dual nature of matter is the uncertainty
principle developed by Heisenberg in 1926. The Heisenberg Uncertainty principle
states that 'It is impossible to determine simultaneously both the position and
momentum of a microscopic particle like an electron with accuracy'.
Mathematically, the relation is
ℎ
Δx.Δp ≥
4𝜋
ℎ
Δx.mΔv ≥
4𝜋

Page 5 of 27
 Where Δx =uncertainty in position
Δp = uncertainty in momentum, i.e., mΔv
m= mass of electron
h =Planck's constant

If the position of the particle is known exactly (Δx= 0), then Δυ becomes infinity
and vice versa.
Case. I.
If the position of the particle known exactly (Δx= O), then
ℎ
Δx. Δυ =
4𝜋𝑚
ℎ
Δυ =
4𝜋𝑚𝛥𝑥
ℎ
Δυ =
4𝜋𝑚𝑥0

=∞
Case. 2. If the velocity of the particle is known exactly (Δυ = O), then
ℎ
Δx. Δυ =
4𝜋𝑚
ℎ
Δx =
4𝜋𝑚𝛥𝜐
ℎ
Δx =
4𝜋𝑚𝑥0

=∞
The uncertainty principle has no significance for macromolecules. The uncertainty
principle which gives the wave nature of the electron only provides the probability
of finding the electron in a given space. Therefore, the classical concept of Bohr's
model of the atom has been replaced by probabilities approach.

Page 6 of 27
 SCHRODINGER EQUATION
In 1926, Erwin Schrodinger developed a new model of the atom. He incorporated
the idea of quantization and the conclusion of de Broglie's hypothesis and
Heisenberg's uncertainty principle in this model. In the Schrodinger wave
equation, electrons are treated as a wave motion in three- dimensional space
around the nucleus having nodes and quantized energies. From the classical wave
mechanics, if ψ(psi) is the amplitude or wave function of a wave moving in a
three-dimensional space with a velocity of 'υ' and frequency 'υ', the wave equation
is
2 2 2
𝑑 𝜓 𝑑 𝜓 𝑑 𝜓 4𝜋2
+ + + ψ =0 ….(3)
𝑑𝑥 2 𝑑𝑦 2 𝑑𝑧 2 𝜆2
de Broglie states that
ℎ
λ=
𝑚𝑣

ℎ2
λ2 = 2 2 …(4)
𝑚 𝑣
From equation 3&4
2 2 2
𝑑 𝜓 𝑑 𝜓 𝑑 𝜓 4𝜋2 𝑚2 𝑣 2
+ + + ψ=0
𝑑𝑥 2 𝑑𝑦 2 𝑑𝑧 2 ℎ2

The total energy (E) of system is given as

𝑬 = 𝑲. 𝑬. + 𝑽
K. E.= E-V
1
𝑚𝑣 2 = 𝑬 – V
2
𝑚2 𝑣 2 = 2m(E-V) …..(5)
From equation 4&5
2 2 2
𝑑 𝜓 𝑑 𝜓 𝑑 𝜓 8𝜋2 𝑚 (𝐸−𝑉)
+ + + ψ =0
𝑑𝑥 2 𝑑𝑦 2 𝑑𝑧 2 ℎ2
or
8𝜋2 𝑚 (𝐸−𝑉)
𝛻 2ψ + ψ =0
ℎ2

This is known as the Schrodinger equation, where

Page 7 of 27
 𝑑2 𝑑2 𝑑2
∇2 = ( 2
+ 2
+ )is called the Laplace operator.
𝑑𝑥 𝑑𝑦 𝑑𝑧 2

Here, m =mass of the electron

V= potential energy (P.E.)
E = total energy
h = Planck's constant
x, y, z are the Cartesian coordinates in the three-dimensional space.

Significance of ψ and ψ2
ψis the amplitude (maximum displacement) of the wave and is called the wave
function. It takes a positive value above the axis and negative value below the axis
and becomes zero while crossing/intercepting the axis. Ψ is a state function but it
has no physical significance, it only represents the amplitude of electron wave. The
square of ψ at a point gives the probability function, which describes the probability
of finding an electron around the nucleus, and the point where the value of ψ2 is
maximum is called the orbital. The value of is always positive. From the value of
at different points within the atom, it is possible to find out the orbital of the
electron. Evidently, ψ2 can be interpreted as a probability density. If dυ is definite
volume, then ψ2dυ gives the probability of finding the electron in the region having
a volume 'dυ'.

Particle in a Box
As shown in Fig. a particle of mass 'm', which is free to move along x-direction
between x =0 and x=d is inside a box bounded by infinity rigid walls. As per the
quantum mechanics, the potential energy (V) of the particle infinite on both sides
of the box and inside the box V is constant (V= O). ψ function has to be zero at
x=0 and all negative values of x, since the particle is not allowed over the walls of
the box. Similarly, ψ function must be zero for all values x=d. Therefore, it can be
stated that the particle is combined with the box and cannot exist outside the box.
Inside the box, the Schrodinger's wave equation is
2
𝑑 𝜓 8𝜋2
+ m (E−V)ψ =0
𝑑𝑥 2 ℎ2

Page 8 of 27
 2
𝑑 𝜓 8𝜋2
+ m (Eψ) =0 since V =0 ….(6)
𝑑𝑥 2 ℎ2
(or)
2
𝑑 𝜓
+ k2 ψ =0 ….(6)
𝑑𝑥 2
8𝜋2 𝑚𝐸
Here k2 = …7
ℎ2

Ψ must be zero outside the region x = 0 and x= d, so that ψ must be continuous

in the region between x= 0 and x =d. A general solution of Schrodinger's equation
is
ψ = A sin 𝑘 𝑥 + B cos 𝑘 𝑥

where A and B constant.

In order to satisfy the condition of ψ=0 at x=0,
0 = A sin 𝑘 (0) + B cos 𝑘 (0)
0= Asin(0) + B cos (0)
0= A(0) + B (1)

i.e., B=0
So wave function is ψ = A sin 𝑘 𝑥

Case (ii)
At the other boundary conditions ψ = 0 at at x=d, then
0 = A sin 𝑘 (𝑑)
0 = sin 𝑘 (𝑑)
Sin nπ = sin 𝑘 (𝑑)
nπ =kd

Page 9 of 27
 k2 = (nπ/d )2
=
(n2π2/d2) ….(8)

From equation 7&8

4𝜋2 𝑚𝐸
= (n2π2/d2)
ℎ2
𝑛2 ℎ 2
En =
8𝑚𝑑 2

where n= l, 2, 3, 4, ……∞
Thus, a particle in a box does not possess any arbitrary amount of energy, rather it
possesses a discrete set of energy values, i.e., its energy is quantized.
Some of the energy levels are
ℎ2
E1 =
8𝑚𝑑 2
4ℎ2
E2 =
8𝑚𝑑 2

9ℎ2
E3 =
8𝑚𝑑 2

Therefore, according to the above equation, a particle in a box (bound particle)

possess quantized energy but a free particle does not.

Page 10 of 27
Atomic Orbitals Molecular Orbital (MO)
The wave function of an electron in The wave function of an electron in a
an atom is called atomic orbitals molecule is called molecular orbital
Atomic orbitals is mono centric Molecular orbital is polycentric
No bonding and anti-bonding atomic There are bonding anti-bonding
orbitals molecular orbitals.
It is less stable. It is more stable.
It has a simple It has a complex shape.
Atomic orbitals are designated as Molecular orbitals designated as
s, p, d, f etc., , *, , *, , *

Bonding Molecular Orbitals Anti-bonding Molecular Orbitals

The bonding molecular orbital is Anti-bonding molecular orbital is
formed by a linear combination of two formed by a linear combination of two
atomic orbitals when their wave atomic orbitals when their wave
functions are added functions are subtracted.
It has lower energy and greater It has higher energy and lower
stability compared to that of the stability compared to that of the
combining atomic orbitals. combining atomic orbitals.
Probability of finding the electrons The probability of finding the
within the inter-nuclear region is electrons within the inter-nuclear
greater than that of the overlapping region decreases and becomes zero.
atomic orbitals.
It has no nodal plane It has a nodal plane.
(plane where the electron density is zero).
The energy difference between the The energy difference between the
bonding molecular orbital and the anti-bonding molecular orbital and
combining atomic orbitals is as the combining atomic orbitals is
stabilization energy known as de-stabilization energy.
The linear combination of atomic The linear Combination of atomic
orbitals with the same sign on their orbitals with opposite signs on their
lobes takes place. lobes takes place.
Designated by , , , etc. Designated by *, *, *etc.

Page 11 of 27
Salient Features of Molecular Orbital Theory
The main of the molecular orbital theory are as follows:
1. The number of molecular orbitals produced is equal to the number of atomic
orbitals combined
2. When two atomic orbitals combine, they form two molecular orbitals.
One of which is called bonding molecular orbital and other is called anti-
bonding molecular orbital. These are formed by addition and subtraction of
wave functions, respectively.
3. The electrons normally seek the lowest energy molecular orbitals, i.e.,
bonding molecular orbitals available to them in a molecule.
4. Bonding molecular orbitals have energy lower than the combining atomic
orbitals while anti-bonding molecular orbitals have higher energy than
combining atomic orbitals.
5. Obeying Pauli Exclusion Principle, each molecular orbital accommodates a
maximum of two electrons in it.
6. Obeying Hund's rule, electrons enter in the molecular orbitals of identical
energies singly before they pair up.
7. Molecular orbitals are filled to increase energies starting with the orbital of
minimum energy (Aufbau principle).
8. Shapes of molecular orbitals formed depend on the type of combining
orbitals.

Liner Combination of Atomic Orbitals (LCAO)

Molecular orbitals of a molecule are obtained by the Liner combination of atomic
Orbitals of bonded atoms. According to the LCAO method, the linear
combination of atomic orbitals can take place either by adding (constructive) or
subtracting (destructive) the wave functions of the atomic orbitals involved.
If the two identical waves are added, the combine constructively to produce the
wave with double the amplitude and same wave length. Whereas, if they
combine destructively to produce the wave with zero amplitude.

Page 12 of 27
Fig. Formation of bonding and anti-boding molecular orbitals

The molecular orbital formed as a result of constructive interference is known

as Bonding Molecular Orbitals and the molecular orbital formed as a result of
destructive interference is called Anti-bonding Molecular Orbital.
This can be shown mathematically, if ΨA and ΨB represent wave functions
(amplitude) of the electron waves of the atomic orbitals of two atoms A and B,
respectively.
Case l. When two waves are in phase, i.e., constructive interference occurs, the
waves are added so that the wave function of the new wave, i.e., bonding
molecular orbital (Ψb) is
Ψb= ΨA+ ΨB

Case 2. When the two waves are out of phase, i.e., destructive interference
occurs, the waves are subtracted from each other so that the wave function of
the new wave, i.e., anti-bonding molecular orbital (Ψa) is
Ψa= ΨA- ΨB

Page 13 of 27
The probable electron density is given by the square of the wave function,
therefore
Ψ2b= (ΨA+ ΨB)2
Ψ2b= Ψ2A+ Ψ2B+2ΨAΨB
i.e., Ψ2b> Ψ2A+ Ψ2B

Ψ2a= (ΨA-ΨB)2
Ψ2a= Ψ2A+ Ψ2B-2ΨAΨB
i.e., Ψ2a< Ψ2A+ Ψ2B

Types of Combinations of Atomic Orbitals

When two atomic orbitals combine along the internuclear axis, the molecular
orbitals formed are called and * molecular orbitals and when overlap
sideways (lateral), the molecular orbitals formed are known as and *
molecular orbitals. As s-orbitals are spherical symmetrical, their wave functions
have the same sign in all directions. While in the case of p-orbitals, one lobe is
given '+' sign and another lobe as a ‘-’ sign. Combining of positive (+) lobes or
negative (-) lobes of two p-orbitals forming bonding molecular orbital and
combining Of one '+' ‘lobe’ of one orbital and ‘-’ lobe of Other orbital forms anti-
bonding molecular orbital. Positive (+) lobe interaction with positive (+) lobe
means the addition of wave functions, while positive (+) lobe interaction with
negative (-) lobe subtraction of wave functions.

(1) S-S combination of orbitals: On the linear combination of 1s atomic

orbitals of two atoms formed two molecular orbitals (Fig. 1.8).

Page 14 of 27
Fig. Molecular orbital formation by the combination of 1s atomic orbitals

As shown in Fig. 1.8, when the addition of wave functions occur (both wave
same sign), 1s molecular orbital is formed while subtraction of wave functions
occur (both wave opposite sign), * 1s molecular of is formed. The dotted line
between two lobes indicates a nodal orbital where the probability of finding the
electron density is zero. Similaraly, the combination of two 2s orbitals forms
two molecular orbitals 2s and *2s

(2) P-P combination of orbitals: There are two possibilities for the
combination of two 'p' orbitals, i.e., either end-to-end combination or a side-
by-side combination.
(a) End-to-end or axial combination of P-P orbitals: If the Inter nuclear axis
is assumed to fall with the x-axis, then the combinations of two px atomic
orbitals will yield a bonding or anti-bonding sigma ( ) molecular orbitals

Fig. Sigma bond resulting from P-P orbital combination

Page 15 of 27
(b) Side by side or lateral combination of P-P orbitals: overlapping of two
orbitalssituated perpendicular to the intemuclear axis (Py, Pz) gives rise -
bonding molecular orbital and also *-anti- bonding molecular orbital.

C) Non-bonding combination of orbitals: When the combination of two atomic

orbitals brings no change in overall energy, then the situation is called no-
bonding. For example, let us consider a lateral combination of s and p orbitals

Fig. Non-Bonding combination of S and P orbitals

In this overlap, the stabilization accruing from positive (+) and positive (+) above
inter-nuclear axis is destabilized by positive (+) or negative (-) overlap below the
inter nuclear axis, thus leading to non-bonding. Similarly, other non-bonding
combinations of atomic orbitals are given in Fig.

Fig: Some other non-bonding combinations

Page 16 of 27
Bond Order of a Molecule
The number of covalent bonds between the constituent atoms in a molecule is
called its bond order. Bond order is defined as one half of the difference between
the number of electrons present in the bonding and the anti-bonding orbitals.
Mathematically,
Bond order (BO) = 1/2(Number of electrons in bonding orbitals-Number of
electrons in anti-bonding orbitals)

=1/2(Nb-Na)
The bond order provides the following information:
l. The value of bond order refers to the existence and stability of the molecule
If the value of the bond order is zero or less than zero which indicates the
species does not exist or unstable, such as He2. In case the values l, 2 and 3
indicate that the molecule is stable and the two atoms are held together by a
single, double and triple bond respectively. +1/2 indicates that species exists
but is unstable, such as He2+, H2+
2. Bond order is inversely proportional to bond length
3. Higher the bond order, the larger is the bond dissociation energy, i.e. bond
order is directly proportional to the bond dissociation energy.

Page 17 of 27
 Bonding in Homo-Nuclear Diatomic Molecules
H2 molecule
It is formed by the combination of two 1s atomic orbitals.
Molecular orbital configuration of hydrogen molecule = (1s)2
Bond order = ½(2-0) = 1
Thus, the hydrogen atoms in the hydrogen molecule are bonded through a
single covalent bond. It is a stable and diamagnetic molecule.

Molecular orbital energy-level diagram For H2 molecule

2. Hydrogen molecule ion (H2+): This ion has one hydrogen atom and one
H + ion. It contains only one electron.
Molecular configuration of H2+ = (1s)1
Bond order = ½ (1-0) = 1/2
From the above data, H2+ ion is weaker than that of hydrogen (H2) molecule. It
is unstable and paramagnetic in nature

Molecular orbital energy-level diagram For H2+ molecule

Page 18 of 27
3. Helium molecule (He2)
The electronic configuration of helium (He) is 1s2.
The molecular orbitals of the helium molecule are formed by 1s2 orbitals of
two helium atoms.
Molecular orbital configuration of He molecule = (1s)2 *(1s)2
Bond order: ½ (2-2) = 0
So that the molecule does not exist

Fig. Molecular orbital energy-level diagram for He2 molecule

Page 19 of 27
Nitrogen molecule (N2) The electronic configuration of nitrogen is 1s22s22p3.
There are five valence electrons in each nitrogen atom.
Therefore, the molecular orbitals of nitrogen molecules have ten electrons.
Molecular orbital configuration of nitrogen molecule (N2)
KK (2s)2 *(2s)2 (2px)2 (2py)2 (2Pz2)
Bond order =1/2(8-2) = 3
Nitrogen molecule is diamagnetic because there are no unpaired electrons
The molecular orbital energy-level diagram for N2 molecule is presented in Fig.

Fig. Molecular orbital energy-level diagram for N 2 molecule

7. Oxygen molecule (O2): The electronic configuration of oxygen atom is
1s22s22p4. There are twelve valence electrons to be accommodated in the
molecular orbitals of O2 molecule.
Molecular orbital configuration of oxygen molecule (O2)
KK (2s)2 *(2s)2 (2Pz2) (2px)2 (2py)2 *(2px)l *(2py)l
Bond order= ½[8-4] = 2
The last two molecular orbitals are singly occupied; hence, the molecule is
paramagnetic in nature. The molecular orbital energy-level diagram for

Page 20 of 27
O2 molecule is shown in Fig.

Molecular orbital energy-level diagram for O2 molecule

Nitric oxide molecule (NO): The electronic configuration of nitrogen is

1s22s22p3 (five valence electrons) and oxygen is 1s22s22p4 (six valence
electrons). It shows that all put together, they have eleven valency electrons.
Molecular orbital configuration of nitric oxide molecule (NO)=
KK (2s)2 *(2s)2 (2Pz2) (2px)2 (2py)2 *(2px)l
Bond order=1/2 (8-3) = 2.5
The presence of one unpaired electron makes the molecule unstable and
paramagnetic in nature.
The molecular orbital energy-level diagram for NO molecule is shown in Fig.

Page 21 of 27
Fig. Molecular orbital energy-level diagram for NO molecule

Carbon monooxide molecule (CO): The electronic configuration of Carbon is

1s22s22p2 (four valence electrons) and oxygen is 1s22s22p4 (six valence
electrons). It shows that all put together, they have eleven valency electrons.
Molecular orbital configuration of Carbon monooxide molecule (CO)=
KK (2s)2 *(2s)2 (2Pz2) (2px)2 (2py)2 *(2px)

Bond order=1/2 (8-2) = 3

The presence of no unpaired electron makes the molecule stable and

diamagnetic in nature.
The molecular orbital energy-level diagram for CO molecule is shown in Fig.

Page 22 of 27
CRYSTAL FIELD THEORY (CFT)
Bethe and Vanvleck proposed Crystal Field Theory (CET) which was later
extended by Orgel. This theory is mainly applicable to transition metals.
According to this theory, the central metal ion of the complex is regarded as a
point charge. Similarly, surrounding ligands are considered as point masses.
Bonding between the central metal ion and the surrounding ligands are
assumed to be ionic, i.e., bonding between a central metal ion and its ligands
simply arises from the purely electrostatic force of attraction (an attraction
between a positively charged metal ion and negative charge of the ligand or
partial negative charge of ligand). If the ligand is a neutral molecule, the
negative end of the dipole is attracted towards the central positive metal ion.
The five d-orbitals (dxy, dyz, dzx, dX2-y2 and dz2) in a metal atom or ion have the
same energy (degenerate orbitals). This degeneracy is maintained if a
Page 23 of 27
spherically symmetrical field of negative charges surrounds the metal atom or
ion. If the negative filed is due to ligands in a complex, it becomes asymmetrical
and the degeneracy of the orbitals is changed and results in the splitting of the
d-orbitals. The pattern of splitting depends upon the nature of the crystal field.
Crystal Filled Splitting in Octahedral Geometry
In the octahedral complex, six ligands occupy the six corners of an
octahedron. There will be repulsion between the electrons in metal d-orbitals
and the electrons of the ligands. However, not all the d-electrons will be affected
equally. Those in the dX2-y2 and dz2and orbitals (eg orbitals) which are directed
along the x, y and z axes will be repelled more than those in the dxy, dyz and dzx
orbitals (t2g orbitals) which are directed between these axes. Hence, under the
influence of the approaching ligands, the electrons in the orbitals dX2-y2 and dz2
and exist in the higher energy levels compared to dxy, dyz and dzx. This splitting
of the degenerate levels due to the presence of a definite geometry is known as
Crystal Field Splitting.
The difference between the eg and t2g orbitals is designated by ∆o
(subscript 'o' denotes an octahedral environment) or 10Dq. This is called crystal
field stabilization energy (CFSE). The two eg orbitals are raised by 3/5 ∆o or 0.6
∆o or 6Dq and three orbitals are lowered by 2/5 ∆o or 0.4 ∆o or 4Dq. in octahedral
field. The splitting of the d-orbitals in an octahedral field is given in Fig.

Fig. Splitting old-orbitals in an octahedral field

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Crystal Field Splitting in Tetrahedral Geometry
In a tetrahedral complex, the splitting is the reverse of octahedral splitting. The
direction of approach of the four ligands does not coincide exactly with the eg or
t2g orbitals. Now, the approach of ligands raises the energy for both eg and t2g
sets of orbitals. However, the energy of t2g sets of orbitals is raised maximum,
since they are closest to the ligands. Therefore, crystal splitting is opposite of
that takes place in octahedral complexes. For the same metal, same ligands and
metal-ligand distance, the relation between tetrahedral splitting energy (∆t) and
octahedral splitting energy (∆o) is

∆t = 2/3 x 2/3 = 4/9 ∆o

Thus, the tetrahedral splitting (∆t) is always much smaller than the octahedral
splitting (∆o). The splitting of the d-orbitals is given in Fig. in a tetrahedral field.

Fig. Splitting old-orbitals in a tetrahedral field

The orbital splitting energies are not sufficiently large for force paring and
therefore, low spin configurations are rarely observed in tetrahedral complexes.

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 Pi molecular orbitals of Butadiene
• Butadiene is a conjugated diene consisting of two adjacent pi-bonds and
comprised of 4 p-orbitals and 4 pi-electrons.
• To draw the molecular orbital diagram of butadiene, start by drawing 4
p-orbitals all aligned with the same phase. This has zero nodes and is
the lowest energy pi-orbital (π1 )
• As the number of nodes in an orbital increases, so does its energy. The
highest-energy molecular orbital has three nodes and has all p-orbitals
with opposite phases (π4)
• Intermediate orbitals (π2 ) and (π3 ) have one and two nodes, respectively.
• Once the molecular orbital diagram is built, the next step is to add the
4 pi-electrons. This will fill up the lowest-energy orbital (π1 ) and the
second-lowest-energy orbital (π2 )
• The highest-occupied molecular orbital (HOMO) of butadiene is the
highest-energy orbital that contains pi-electrons. This is π2
• The lowest-unoccupied molecular orbital (LUMO) of butadiene is the
lowest-energy orbital that has zero pi-electrons. This is π3

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Pi molecular orbitals of Benzene
A molecular orbital description of benzene provides a more satisfying and
more general treatment of "aromaticity". We know that benzene has a planar
hexagonal structure in which all the carbon atoms are sp2 hybridized, and all
the carbon-carbon bonds are equal in length. As shown below, the remaining
cyclic array of six p-orbitals ( one on each carbon) overlap to generate six
molecular orbitals, three bonding and three antibonding. The plus and minus
signs shown in the diagram do not represent electrostatic charge, but refer to
phase signs in the equations that describe these orbitals (in the diagram the
phases are also color coded).
When the phases correspond, the orbitals overlap to generate a common
region of like phase, with those orbitals having the greatest overlap (e.g. π1)
being lowest in energy. The remaining carbon valence electrons then occupy
these molecular orbitals in pairs, resulting in a fully occupied (6 electrons) set
of bonding molecular orbitals. It is this completely filled set of bonding orbitals,
or closed shell, that gives the benzene ring its thermodynamic and chemical
stability, just as a filled valence shell octet confers stability on the inert gases.

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