Course Title: Spectroscopy Third-Year Physics Salma

Mohammed Hassan Dr. Falh A. Mutlk

Course Syllabus

Spectroscopy
1. Introduction to Spectroscopy

Definition of spectroscopy and its importance in physics.

Types of spectra: absorption, emission, and scattering spectra.
Basic concepts: wavelength, frequency, and energy.
2. Electromagnetic Radiation

The electromagnetic spectrum.

Relationship between energy, wavelength, and frequency.
Interaction of electromagnetic radiation with matter.
3. Atomic Spectra

Atomic energy levels.

Hydrogen spectral lines (Balmer, Lyman, etc.).
Bohr’s model of the atom.
Atomic spectra of other elements.
4. Molecular Spectra

Introduction to molecules.
Rotational, vibrational, and electronic transitions.
Vibration-rotation spectra.
Selection rules in molecular spectroscopy.
5. UV-Visible Spectroscopy

Physical principles of UV-VIS spectroscopy.

Absorption and emission spectra in the UV-visible range.
Applications of UV-VIS spectroscopy.
6. Infrared Spectroscopy (IR)
Vibrational transitions.
Infrared spectra and chemical bond analysis.
Applications of IR spectroscopy in material identification.
7. Nuclear Magnetic Resonance Spectroscopy (NMR)
Physical principles of nuclear magnetic resonance.
Interaction of nuclei with radiofrequency radiation.
Applications of NMR in molecular structure determination.
1
 Course Title: Spectroscopy Third-Year Physics Salma
Mohammed Hassan Dr. Falh A. Mutlk

8. Raman Spectroscopy

The Raman effect.

Differences between Raman and IR spectroscopy.
Applications of Raman spectroscopy in material analysis.
9. X-Ray Spectroscopy

Continuous and characteristic X-ray spectra.

Applications of X-ray spectroscopy in physics and chemistry.
10. Laser Spectroscopy

Principles of laser-based spectroscopy.

Applications of laser spectroscopy.
Surface-Enhanced Raman Spectroscopy (SERS).
11. Nuclear Spectroscopy

Introduction to nuclear transitions.

Gamma-ray spectroscopy and its applications.
12. Applications of Spectroscopy
Use of spectroscopy in material science.
Industrial and medical applications.
Spectroscopy in space science and astrophysics.
13. Spectroscopic Instruments

Components of spectroscopic devices.

Analysis of spectra using devices such as spectrophotometers and mass
spectrometers.
14. Practical Exercises

Analysis of spectra for elements or compounds.

Comparing theoretical and experimental results.
The syllabus can be adjusted based on the students' level and the number of teaching
hours available.

2
 Course Title: Spectroscopy Third-Year Physics Salma
Mohammed Hassan Dr. Falh A. Mutlk

Spectroscopy - Lecture 1: Introduction to Spectroscopy

Objectives: By the end of this lecture, students will be able to define

spectroscopy and understand its importance. Identify the types of
spectra and their characteristics. Understand the basic concepts related
to spectroscopy: wavelength, frequency, and energy.

1. Definition of Spectroscopy:
Spectroscopy is the study of the interaction between electromagnetic radiation and
matter. It is a function of the wavelength or frequency of the radiation. It is a powerful
tool used to analyze the structure, composition, and properties of matter by observing
the emitted, absorbed, or scattered light. In these processes, the color changes
because some of the light is absorbed by the objects. How much and what spectral
regions are absorbed depends on the atoms and molecules in these objects. The light
not absorbed reaches our eyes. It carries the information of the molecular structure of
our surroundings with it. In our eyes its color is analyzed by 3 different types of
photoreceptors which absorb different light in spectral regions. In this way we
perform a spectroscopic experiment every time we look at things. There is a light
source, and object that reflects, transmits, scatters and absorbs light and a wavelength
dependent detector in our eyes. An apparatus for spectroscopic studies is called
spectrometer and a plot of a particular property of matter against wavelength,
frequency or energy of radiation is called spectrum. every element or compound has a
unique characteristic spectrum. Each compound absorbs and disperses light at a certain
range of wavelengths. Thereby, spectroscopy means the dispersion of light into
component colours. It is a method to measure how much light is absorbed by a substance
and at what is intensity light passes through it.
Spectroscopy can be used in physics, chemistry, biology, and even astronomy to

1. study atomic and molecular structures.

2. Determination of chemical compositions.
3. Material characterization.
4. Medical diagnostics (e.g., MRI uses NMR spectroscopy).

3
 Course Title: Spectroscopy Third-Year Physics Salma
Mohammed Hassan Dr. Falh A. Mutlk

Types of Spectroscopy
 Acoustic resonance

 Time-resolved

 Photoemission

 X-ray photoelectron

 Circular Dichroism

 Infrared spectroscopy

 Raman spectroscopy
In spectroscopy, the type of interaction between light and the material:

 Absorption spectroscopy

 Emission spectroscopy

 Elastic scattering

 reflection spectroscopy

 Impedance spectroscopy

 Inelastic scattering

 Coherent or resonance spectroscopy

Application of Spectroscopy
There are many applications to spectroscopy in many fields such as medicine, physics,
chemistry, and astronomy. Taking advantage of the properties of absorbance, it is in use
to identify certain states of nature. For instance, it includes:

 Cure monitoring of composites with the help of optical fibers.

 To estimate weathered wood exposure times with the help of near-infrared

spectroscopy.

4
 Course Title: Spectroscopy Third-Year Physics Salma
Mohammed Hassan Dr. Falh A. Mutlk

 Measurement of different compounds in food samples by absorption spectroscopy

in the visible and infrared spectrum.

 Measurement of toxic compounds in blood samples is done with the help of

spectroscopy

 Non-destructive elemental analysis by X-ray fluorescence.

 Electronic structure research with the use of various spectroscopes.

 Radar to determine the speed and velocity of a distant object is an important

application.

 Finding the physical properties of a distant star or nearby explant with the help of
the Relativistic Doppler effect.
2. Electromagnetic Radiation Overview

Electromagnetic radiation is a form of energy that exhibits wave-like behavior as it

travels through space. They are formed when an electric field couples with a
magnetic field . They can also be produced when high speed electrons enter into the
target metal which has high atomic weight. EM waves are also produced when a
radioactive nucleus de-excites.

The above figure shows the propagation of EM waves through a medium. The
electric field (E→) is directed along the x direction, magnetic field (B→) is directed
along y direction–hence they act perpendicular to each other, and also vary
sinusoidally. The direction in which the wave would propagate is given by
v→=E→×B→

5
 Course Title: Spectroscopy Third-Year Physics Salma
Mohammed Hassan Dr. Falh A. Mutlk

The speed of electromagnetic waves in vacuum or free space is given by,

1
C= ϵ μ
√ ° °

ϵ0 is permittivity of free space

μ0 is permeability of free space

In any other medium than air, the speed of an EM wave is given by,

1
v= μ,ϵ, indicate the permeability and permittivity of the medium respectively
√ ϵμ
Characteristics of EM waves
1) They do not require a medium for propagation.

2) They propagate in vacuum with a speed of 3.0 ×108ms.

3)EM waves are transverse in nature.

4) They are not deflected by electric and magnetic fields.

5)EM waves get polarized.

6)They carry energy and momentum

Properties of electromagnetic radiations

As waves, electromagnetic radiations are characterized by:

λ = wavelength (length of single wave), y = amplitude
C = speed of light in a vacuum
ϑ = frequency (number of cycles passing a certain point per second)
6
 Course Title: Spectroscopy Third-Year Physics Salma
Mohammed Hassan Dr. Falh A. Mutlk

in Hertz
Wavelength (λ): The distance between two consecutive peaks of a wave (measured in
meters).

Frequency (ϑ): The number of wave cycles that pass a point per second (measured in
Hertz, Hz).

Energy (E): The energy of a photon is proportional to its frequency.

Relationship Between λ, ν, and E:C =λϑ

E = hν
Planck’s constant ( h).=6.63x10-34 J.s

What are the seven electromagnetic spectrum regions? Electromagnetic radiation in

the electromagnetic spectrum can be classified into seven different types. In order
from highest frequency to lowest, they are

Type of Radiation Frequency Range (Hz) Wavelength Range

Gamma-rays 1020 – 1024 < 10-12 m

X-rays 1017 – 1020 1 nm – 1 pm

Ultraviolet 1015 – 1017 400 nm – 1 nm

Visible 4 x 1014 – 7.5 x 1014 750 nm – 400 nm

Near-infrared 1 x 1014 – 4 x1014 2.5 μm – 750 nm

Infrared 1013 – 1014 25 μm – 2.5 μm

Microwaves 3 x 1011 – 1013 1 mm – 25 μm

Radio waves < 3 x 1011 > 1 mm

7
 Course Title: Spectroscopy Third-Year Physics Salma
Mohammed Hassan Dr. Falh A. Mutlk

Types of Spectra
If white light falls on a prism, mounted in a spectrometer, the prism deviates the
waves of varying wavelengths to different directions. The picture obtained in the
telescope field of view is composed of a variety of colored slit images. That kind of
picture is called a spectrum.

For example, if the slit is illuminated with light from a sodium vapor lamp, two
images of the slit are obtained in the yellow region of the spectrum. These images are
the emission lines of sodium having wave lengths (5896 A o) and (5890 Ao). This is
known as the spectrum of sodium.

8
 Course Title: Spectroscopy Third-Year Physics Salma
Mohammed Hassan Dr. Falh A. Mutlk

Spectra are the fingerprints of matter and can be classified into three main types:

Emission Spectrum: Produced when excited atoms or molecules release energy

as light.Appears as bright lines or bands against a dark background

The emission spectrum is of three types.

1. Continuous spectrum. It consists of undivided, bright white bands of all

wavelengths (from violet to red).
2. Line spectrum
It sharp lines of wavelengths specific. It is used to detect the gas. Arise from atom

Band spectrum. Is a spectrum consisting of tightly spaced lines or bands. Arise from
molecule

9
 Course Title: Spectroscopy Third-Year Physics Salma
Mohammed Hassan Dr. Falh A. Mutlk

Absorption Spectrum: Produced when a material absorbs specific wavelengths of

light. Appears as dark lines or bands in a continuous spectrum. Used to identify
elements or compounds in a sample.

Absorption spectra is also of three types

1. Continuous absorption spectrum

2. Line absorption spectrum and
3. Band absorption spectrum
Line spectra: Electron transitions between energy levels result in emission or
absorption lines. So it divided to Emission spectra and Absorption spectra.

Different elements produce different spectra due to differing atomic structure

(discovered by Kirchhoff and Bunsen).
10
 Course Title: Spectroscopy Third-Year Physics Salma
Mohammed Hassan Dr. Falh A. Mutlk

Continuous Spectrum: Contains all wavelengths within a given range.

Produced by incandescent solids, liquids, or dense gases. Example: The spectrum of

sunlight.

3- Atomic Spectra
11
 Course Title: Spectroscopy Third-Year Physics Salma
Mohammed Hassan Dr. Falh A. Mutlk

Atomic spectra are defined as. The spectrum of the electromagnetic radiation emitted
or absorbed by an electron during transitions between different energy levels within
an atom. When an electron gets excited from one energy level to another, it either
emits or absorbs light of a specific wavelength We know that in an atom, electrons
have discrete and specific energies. There are more energy states in an atom than
there are electrons. When an electron transitions from one energy level to another, it
emits light or photon with a specific wavelength. In any given set of conditions, the
collection of all these specific wavelengths is what constitutes the atomic spectrum.
Hence, atomic spectra are the spectra of atoms.

Bohr’s Theory of The Atomic Spectrum of Hydrogen

12
 Course Title: Spectroscopy Third-Year Physics Salma
Mohammed Hassan Dr. Falh A. Mutlk

In1913, Niels Bohr combined elements of quantum theory and

classical physics in a treatment of the hydrogen atom. He stated four
postulates for an electron in an atom:

1- There were certain “allowed” orbits in which the electron could

move without radiating electromagnetic energy.

2- Each orbital has certain radius and energy.

3- Electron could move around nucleus only in orbitals which have

angular momentum of the electron is a multiple of (h/2π). Where
for a rotating object angular momentum is expressed as (mvr), so
(mvr = nh/2π); m=mass of electron, v=velocity of electron,
r=radius of shell, n= integer, n is known as a quantum number
or, more specifically, the principal quantum number.

4- Electromagnetic energy emitted as the electron moved from a

higher orbital (larger n value) to a lower one and absorbed in the
reverse process.

 In order for the electron to move in a stable orbit, the electrostatic

attraction between it and the proton must be balanced by the
centrifugal force that results from its circular motion. As shown in
Figure below, the forces are actually in opposite directions, and equal in
its magnitudes.

The electrostatic force is (e2/r2), while the centrifugal force on the *

electron is (mv2/r). Therefore, we can write eq.(1)

13
Course Title: Spectroscopy Third-Year Physics Salma
Mohammed Hassan Dr. Falh A. Mutlk

..............................(1)

 From eq. (14) we can calculate the velocity of the electron as

follow, eq.(2).

..............................(2)

 Since ( mvr= nh/2π ), we can write eq.(3)

..............................(3)

 Because the moving electron has only one velocity, the values for v
given in Eqs. (2) and (3) must be written as eq. (4).

..............................(4)

 We can now solve for r to obtain, eq.(5)

..............................(5)

14
Course Title: Spectroscopy Third-Year Physics Salma
Mohammed Hassan Dr. Falh A. Mutlk

* In Eq. (5), only r and n are variables. From the nature of this equation,
we see that the value of r, the radius of the orbit, increases as the square
of n. For the orbit with n=2, the radius is four times that when n=1, etc.
 From eq.(1), we can write eq.(6):-

......................................(6)

 Multiplying both sides of the eq.(6), by 1/2 we obtain eq.(7):-

......................................(7)

 Where the left-hand side is simply the kinetic energy of the

electron. The total energy of the electron is the sum of the kinetic
energy and the electrostatic potential energy, (-e2/r), eq.(8):-

......................................(8)

 Substituting the value for r from Eq. (5) into Eq. (8) we
obtain eq.(9)

......................................(9)

15
Course Title: Spectroscopy Third-Year Physics Salma
Mohammed Hassan Dr. Falh A. Mutlk

 From eq.(9), we see that there is an inverse relationship between the

energy and the square of the value n. The lowest value of E (and it is
negative!) is for n =1 while E=0 when n has an infinitely large value
that corresponds to complete removal of the electron. If the constants
are assigned values in the cm-g-s system of units, the energy calculated
will be in erqs. Of course 1 J = 107 erq and 1 cal = 4.184 J.

 By assigning various values to n, we can evaluate the corresponding

energy of the electron in the orbits of the hydrogen atom. When this is
done, we find the energies of several orbits as follows:

 Although the Bohr model successfully accounted for the line

spectrum of the hydrogen atom, it could not explain the line spectrum
of any other atom. It could be used to predict the wavelengths of
spectral lines of other species that had only one electron such as He+,
Li+2, and Be+3.
 Energy is absorbed or emitted only when an electron moves from
one energy level to another and the energy change is given by eq.(10),
where n1 and n2 are the principal quantum numbers referring to the
energy levels En1 and En2 respectively.

16
Course Title: Spectroscopy Third-Year Physics Salma Mohammed
Hassan Dr. Falh A. Mutlk

.................(10)

 Emitted radiation is expressed in terms of frequency (γ) or

wave number (γ-). Eqs. (11) and (12), respectively :-

........................(11)

........................(12)

 The eq.(12), similar to that of Rydberg eq. where:-

 We can calculate the value of Rydberg constant from values of (m), (e),
(c) and (h). So for hydrogen atom , where Z=1
While for ions similar to hydrogen atom, where Z larger than 1.

Spectral Series of Hydrogen Atom

When a high potential is applied to hydrogen gas at low pressure in a discharge tube, it
starts emitting a bright light. It is separated into several radiations and forms a spectrum

17
Course Title: Spectroscopy Third-Year Physics Salma Mohammed
Hassan Dr. Falh A. Mutlk

upon passing through a prism or grating. The spectrum consists of separate lines
corresponding to different wavelengths. This is called Hydrogen atomic spectrum.
The spectral lines are formed due to electronic transitions from one energy level to
another. These lines are divided into five series according to the range of wavelengths as
follows.

Spectral series Spectral region n1 n2

1. Lyman series Ultra-violet 1 2,3,4,5,6,7,_
__
2. Balmer series Visible 2 3,4,5,6,7,_ _
__
3. Paschen series near infra-red 3 4,5,6,7,_ _ _
_
4. Brackett series infra-red 4 5,6,7,_ _ _ _
5. Pfund series far infra-red 5 6,7

The wave numbers of spectral lines in each series can be calculated using Rydberg's
equation as follows.
ϑ' =RH ¿)
RH is the Rydberg constant (1.09737*107 m-1)
Z is the atomic number
n2is the upper energy level
n1is the lower energy level
ϑ' is the reciprocal wavelength of light =1/λ
Spectral series of single-electron atoms like hydrogen have Z = 1.

18
Course Title: Spectroscopy Third-Year Physics Salma Mohammed
Hassan Dr. Falh A. Mutlk

Ex: Calculate the wave length of forth line (n=6), in Balmer series of
hydrogen atom.
.Ans

= 1.097*105 cm-1 *[(1/22) – (1/62)]

cm-1 24372.88 =

λ=1/γ
-

λ = (1/24372.88 cm-1) = 4.103*10-5 cm

 Ex: Calculate the radius of first, second and third Bohr orbitals of
hydrogen atom. Ans:

r=[(1)2 *(6.626*10-27 erq.seq)2] / [4*(3.14)2 * (9.1072*10-28 g) *

(4.8032*10-10 erq. cm)2]
r= 0.529 *10-8 cm r=

0.529 A0

19
 Course Title: Spectroscopy Third-Year Physics Salma Mohammed
Hassan Dr. Falh A. Mutlk

*This constant value of first Bohr orbital of hydrogen atom and referred as
(a0).
*For second orbital r=0.529
r= a0 * n2
* 10-8 cm * 22

r= 2.116 * 10-8 cm

*For third orbital r=0.529 *

10-8 cm * 32

r= 4.761 * 10-8 cm

 Ex: Find the velocity of electron for first Bohr orbital of hydrogen
atom.

.Ans

V=nh / 2πmr

V= [(1) * (6.626*10-27 erq. sec) / 2*(3.14)*(9.1072*10-28 g)*(0.529*10-8

cm)]

V= 2.188 * 108 cm.sec-1

 Ex: Calculate the electron's energy in the first and second orbits of the
hydrogen atom.

-:Ans
From eq.(9), E= - e2 / 2r

As r=a0 * n2

E = - e2 / (2 a0 * n2)

20
Course Title: Spectroscopy Third-Year Physics Salma Mohammed
Hassan Dr. Falh A. Mutlk

So, The energy of electron at first orbital;

En=1 = - (4.8032 * 10-10 e.s.u) / (2*(0.529 * 10-8 cm) * (1)2

= -2.17987 * 10-11 erq

*To calculate the energy in Joule unit

En=1 = -2.17987 * 10-11 erq * (1 J / 1*107 erq)

= -2.17987 * 10-18 J

*To calculate the energy in e.v unit

En=1 = -2.17987 * 10-18 J * (1 e.v/1.602 * 10-19 J)

e.v 13.6- =

*The energy of electron at second orbital;

En=2 = - (En=1 / n2)

= -(13.6 e.v / 22)

e.v 3.4- =

electrostatic unit of charge (e.s.u) , 1e.s.u= erq1/2 * cm1/2*

The e.s.u of charge, also called the franklin or statcoulomb, is the charge such
that two equal q=1 stat charges at a distance of 1cm from each other exert an
electrostatic force of 1dyn on each other.

21
Course Title: Spectroscopy Third-Year Physics Salma Mohammed
Hassan Dr. Falh A. Mutlk

Uses of Atomic Spectroscopy

1. It is used for identifying the spectral lines of materials used in metallurgy.
2. It is used in pharmaceutical industries to find the traces of materials used.
3. It can be used to study multidimensional elements.
Homework :1 determine the wave length, frequency and energy of the fifth line of
Lyman series and the third line of Balmmer series.
2:The Pfund series of lines in the emission spectrum of hydrogen corresponds to
transitions from higher excited states to the n = 5 orbit. Calculate the wavelength of
the second line in the Pfund series to three significant figures. In which region of the
spectrum does it lie?
Answer: 4.65 × 103 nm; infrared
Boltzmann Distribution
Consider two energy of a system of particle Eo and Ei of corresponding occupation no. No
and Ni and degeneracy go and gi
Applying (M.B) statics for these two levels:
For Ei
− Ei/ KT
gi N e
Ni= -----------(1)
z̀

For Eo
−Eo/ KT
go N e
N0= -----------(2)
z̀
By divided eq(1) on eq.(2) we get:

Ei N i gi e−Ei / KT
= =
Eo N o g o e−Eo / KT
(‫وتعطينا هذه المعادلة التركيز النسبي للجزيئات‬
‫)اي عدد الجسيمات في المستوي المتهيج‬ulation pop
‫المستوي االرضي‬ ‫الى‬

gi −(Ei−Eo)/ KT
N i= N e
go o
‫اما هذه المعادلة فتمكننا من ايجاد تركيز الجسيمات في المستوي العلوي او‬
‫المتهيج‬
This is the general form of M.B. for thermal distribution low
In special case when gi=go(‫)ال يوجد تهيج او انتقال بالجسيمات اي عند التوازن الحراري‬,
then
N i = N o e−(Ei−Eo)/ KT
22
Course Title: Spectroscopy Third-Year Physics Salma Mohammed
Hassan Dr. Falh A. Mutlk

Boltzmann distribution Low is applicable for thermal equilibrium condition only

‫هناك انواع عديدة من الحاالت الطاقية للجزيئات تشمل مستويات الطاقة الدورانية‬
‫ومستويات الطاقة االهتزازية ومستويات الطاقة االلكترونية‬
‫ بالنسبة للمستويات االلكترونية واالهتزازية ثابتة اي ال‬g( (‫وتقريبا درجة انحالل كل مستوي‬
‫ لكن يوجد انحالل بالمستويات الدورانية ناتجة عن الحركة الدورانية‬,g=1 ‫يوجد انحالل اي انه‬
‫ ليست ثابتة ويمكن حساب درجة االنحالل او التعددية من‬g ‫اي عدد الحاالت او التعددية‬
:‫المعادلة التالية‬
g= (2J +1)
‫ لذلك يمكن ايجاد التركيز النسبي للجزيئات باتباع قانون‬, ‫ العدد الكمي الدوراني‬J ‫حيث‬
. g ‫التوزيع الحراري لماكسويل بولتزمان من بعد تعيين قيمة‬

Examples of the law of thermal equilibrium:

Example(1):
What happens if we apply thermal energy (kT) on a mole of
molecules can find in a jar at constant temperatures? Suppose
KT ≫¿∆Eij , ∆ E ij =25 kJ /mole at 25oC,
KT=2.5KJ/mole
Answer:
The molecule takes up the energy and
distribute it among the available energy
levels, this distribution studied by Boltzmann who showed
that:
− Ei/ KT −Ej / KT
gi N e gj N e
Ni= -----(1), Nj= -------(2) Divide equation (1) on (2)
z̀ z̀

23

KT=1.38x10-23J/Kx298Kx10-
 Course Title: Spectroscopy Third-Year Physics Salma Mohammed
Hassan Dr. Falh A. Mutlk

gi −(Ei− Ej)/ KT
N i= N je ------(1) This is the general form of M.B thermal distribution Low, In
gj
special case when gi=gj(at thermal equilibrium)
N i= N j e−(E − E )/ KT --------(2)
i j

If you have the ground state ( N o) then eq.(2) becomes

N i −∆ E / KT
N i= N o e−∆ E / KT → =e
No
At Room Temp.
N i st
(1 excited state)=e−25 ¿¿
No

N i −10
∴ =e =4.5x10-5=5x10-5=0.005%
No

i.e only 0.005% of molecules are in the first excited state

at high temperatures KT ≫¿ ∆Eij

∴ ∆ Eij →0

N i −0
∴ =e =1
No

at Low temperatures ∆ E ij ≫TK

N i −∞
∴ =e =0
No

i.e the ground state is felled by electrons and the excited states are empty.

Homework :

A comparison of population density between temperatures (25-1000oC) calculate the

ratio of molecule in excite rotation vibration and electronic energy level to that in the
lower energy level?

Assume J=4
∴ g=( 2 x 4+1 ) =9

4. Molecular Spectra
Properties of molecules depend on:
24
Course Title: Spectroscopy Third-Year Physics Salma Mohammed
Hassan Dr. Falh A. Mutlk

1 The specific kind of atoms they are composed of.

2 The spatial structure of the molecules – the way in which the atoms are arranged within
the molecule
3 The binding energy of atoms or atomic groups in the molecule.
TYPES OF MOLECULES q
1 MONOATOMIC MOLECULES The elements that do not have tendency to form
molecules. § Elements which are stable single atom molecules are the noble gases :
helium, neon, argon, krypton, xenon and radon.
2 DIATOMIC MOLECULES Diatomic molecules are composed of only two atoms - of
the same or different elements. Examples: hydrogen (H2), oxygen (O2), carbon
monoxide (CO), nitric oxide (NO)
3 POLYATOMIC MOLECULES Polyatomic molecules consist of a stable system
comprising three or more atoms
Introduction to molecular spectra:
Apart from the ground state, a molecule can be in a higher energy state, and transitions
between the various energy levels give rise to the observed molecular spectra. The energy
of a diatomic molecule arises from three modes:
(i) the electronic configuration of the electrons in the molecule,
(ii) the vibration of the atoms about the equilibrium position, and
(iii) the rotation of the molecule as a whole about its center of mass.
The total energy of a molecule can be expressed as the sum of three independent terms:
E = Ee+ Ev + Er ...(1)
Ee , Ev , Er are quantized and Ev > Er .
If the molecule remains in its ground state level of electronic and vibrational energies,
and if it suffers transitions between different rotational energies, we get the pure
rotational spectrum of the molecule. These spectra are in the microwave and far infrared
regions. If the molecule remains in its ground state level of electronic energy, and if
transitions occur between different vibrational and rotational energies we get the
vibration-rotation spectrum of the molecule. These spectra are in the near infrared region

Consider a diatomic molecule as consisting of atoms of masses m1 and m2 a distance R

apart. The diatomic molecule can rotate about its center of mass as shown in Fig
The moment of inertia of this molecule about an axis passing through its center of mass
and perpendicular to a line joining the atoms is

25
 Course Title: Spectroscopy Third-Year Physics Salma Mohammed
Hassan Dr. Falh A. Mutlk

26
Course Title: Spectroscopy Third-Year Physics Salma Mohammed
Hassan Dr. Falh A. Mutlk

Selection Rules of Rotational Spectroscopy

There are three rules for rotational spectra out of which two holds very firm role:

1. The molecule must have a permanent dipole moment i.e. 𝜇 ≠ 0.

2. ∆𝐽 = ±1

3. ∆𝑀𝐽 = 0, ±1 this rule only holds for the cases when the molecules is in electric or
magnetic field.

Structure of rotational spectra Spherical top molecules have no net dipole moment. A
pure rotational spectrum cannot be observed by absorption or emission spectroscopy
because there is no permanent dipole moment whose rotation can be accelerated by the
electric field of an incident photon

Under the rigid rotor model, the rotational energy levels, F(J), of the molecule can be
expressed as,

𝐹 𝐽 = 𝐵(𝐽 + 1) where B is the rotational constant of the molecule and is related to the
moment of inertia of the molecule and J=0,1,2,3 and the value of B is given by

𝐵 = ℎ 2/ 8𝜋2 I

27
Course Title: Spectroscopy Third-Year Physics Salma Mohammed
Hassan Dr. Falh A. Mutlk

For J= 0, F(0) = BJ(J+1) = B X 0 (1)= 0

For J=1, F(1) = BJ(J+1) = B X 1 (1+1)= 2B

For J=2, F(2) = BJ(J+1) = B X 2 (2+1)= 6B

For J=3, F(3)= BJ(J+1)= B X 3(3+1)= 12B

Therefore for transition from 0 1 the difference is 2B and for transition from 1 2 the
energy difference is 4B. The above equation can be summarized as

ΔF(J)= 2B(J+1) and for J=0, ΔF(0)= 2B,

for J=1, ΔF(1)= 2B(J+1)=4B

J=2, ΔF(2)=2B(J+1)=6B J=3, ΔF(3)=2B(J+1)= 8B

Beer-Lambert’s law

If material bodies are exposed to radiation, part of the incident radiation is absorbed, a
part is scattered and a part is transmitted. As a result of absorption the intensity of light
passing through material bodies, i.e. the intensity of transmitted light, decreases. The

28
Course Title: Spectroscopy Third-Year Physics Salma Mohammed
Hassan Dr. Falh A. Mutlk

fraction of incident light absorbed depends on the thickness of the absorbing medium.
Lambert derived a quantitative relationship between the decrease in intensity of a
monochromatic light due to the passage through a homogeneous medium of thickness dx
and the intensity of light I. This law is known as Lamberts law, and may be stated as The
decrease in intensity of light with thickness of the absorbing medium at any point is
directly proportional to the intensity of light. Monochromatic light x Incident beam
Intensity Io Absorbing solution concentration, c Emergent beam Intensity I Thickness
Mathematically it can be expressed as

- 𝑑𝐼 /𝑑𝑥 ∝ 𝐼 --- --- --- --- --- --- (1)

Where dI is a small decrease in intensity of light upon passing through a small distance
dx and I is the intensity of the monochromatic light just before entering the medium.
Equation (1) may be written as

- 𝑑𝐼 𝑑𝑥 = 𝑎𝐼 --- --- --- --- --- --- (2)

Where - 𝑑𝐼 𝑑𝑥 is the rate of decrease of intensity with thickness dx , a is called the

absorption co-efficient. Integration of equation (2) after rearrangement gives,

- ln I = ax+C --- --- --- --- --- --- (3)

Where C is a constant of integration. At x=0, I=Io. So, C = - ln Io. Introducing this in

equation (3) we get,

ln I/ Io = - ax --- --- --- --- --- --- (4) Equation (4) can also be written as,

I = Io 𝑒 −𝑎𝑥 --- --- --- --- --- --- (5) Equation (5) can also be written as,

29
 Course Title: Spectroscopy Third-Year Physics Salma Mohammed
Hassan Dr. Falh A. Mutlk

log I/ Io = − a 2.303 x --- --- --- --- --- (6) or, log I/ Io = -a` x --- --- --- --- --- (7) Where a`
(= a 2.303 ) is called extinction co-efficient and -ln I Io is termed absorbance of the
medium. Absorbance is represented by A. Lambert’s law was extended by beer who
showed that when light passes through a solution of a given thickness the fraction of
incident light absorbed is dependent not only on the intensity I of light but also on the
concentration c of the solution. This is known as the Beer’s law.

- 𝑑𝐼/ 𝑑𝑥 ∝ 𝑐 --- --- --- --- --- --- (8) The two laws may be combined to write

– 𝑑𝐼/ 𝑑𝑥 ∝ 𝐼 × 𝑐 Or, - 𝑑𝐼/ 𝑑𝑥 = 𝑏 × 𝐼 × 𝑐 --- --- --- --- --- (9)

When the concentration, c, is expressed in mol /L, b is called the molar absorption co-
efficient. As in the case of Lambert’s law equation (9) may be transformed into,

log I /Io = − 𝑏 2.303 × 𝑐 × 𝑥 --- --- --- --- --- (10)

log I /Io = - ∈× 𝑐 × 𝑥 --- --- --- --- --- (11)

Where ∈ (= 𝑏 2.303 ) is called the molar extinction co-efficient which is expressed in

L/mol/cm. The molar extinction co-efficient ∈ is dependent on the nature of the
absorbing solute as well as on the wave length of the incident light used. The expression
(equation 11) is commonly known as Beer-Lambert’s law.

Limitation of Beer-Lamber’s law:

• The electromagnetic radiation should be monochromatic.

• The light beam should not be scattered.

• The solution should be diluted.

30