SPECTROSCOPY

 Interaction of molecules with electromagnetic

radiation
 Rotational, vibrational and electronic spectroscopy
 Basic concepts of emission, absorption and LASER.

Suggested Books
 Banwell & McCash, Fundamentals of Molecular Spectroscopy, 4th edition, 1996
 Atkins, Physical Chemistry, 9th edition, 2009
What is Spectroscopy?

Spectroscopy is the study of the interaction between

matter and electromagnetic radiation.

What is a Spectrum?

The data that is obtained from spectroscopy is called a

spectrum. A spectrum is a plot of the intensity of energy
detected versus the wavelength (frequency, wavenumber
etc.).
What information is Obtained?

• A spectrum can be used to obtain information about atomic and

molecular energy levels, molecular geometries, chemical bonds,
interactions of molecules, and related processes.

• Often, spectra are used to identify the components of a sample

(qualitative analysis). Spectra may also be used to measure the
amount of material in a sample (quantitative analysis).

• Compared to chemical analysis, spectroscopic methods are

faster and more accurate, require less sample, and are usually
nondestructive.
What Instruments Are Needed?

There are several instruments that are used to perform a

spectroscopic analysis. In simplest terms, spectroscopy
requires an energy source and a device for measuring
the change in the energy source after it has interacted
with the sample (often a spectrometer).
 What is electromagnetic radiation?
Maxwell Suggestion: An alternating current of high frequency is
capable of radiating energy in the form of waves, which travel in
space with the speed of light called as electromagnetic waves or
electromagnetic radiations.
They are named so as consist of
oscillating electric and magnetic
fields directed perpendicular to the
direction of propagation of the
wave.

Ex: Radio waves,

Visible light, IR ,
UV light, X-rays
and γ-rays
 Characteristics of EM radiations
The electromagnetic radiation is looked at as sinusoidal
waves which are composed of a combination of two fields.
An electric field (which we will use, in this course, to
explain absorption and emission of radiation by matter)
and
A magnetic field at right angle to the electric field (which
is used to explain phenomena like NMR, EPR
spectroscopy).
Characteristics of EM radiations
All the electromagnetic radiations have the same speed in vacuum
(i.e. speed of light).
But their speeds are reduced in material media and to different extent.
Thus mixture of electromagnetic radiations can be separated out into
components.

Material Speed (km/s)

Vacuum 300,000
Air < 300,000
Water 226,000
Glass 200,000
Wavelength ()

The wavelength of a wave is the distance between two consecutive

maxima or two consecutive minima on the wave. It can also be
defined as the distance between two equivalent points on two
successive maxima or minima.
Wavenumber( 
͞ )

It is defined as the number of wavelengths which can be

accommodated in 1 cm length along the direction of propagation.
Hence
1
͞  
It is generally expressed in unit of cm-1
This is an important property especially in the study of infrared
spectroscopy.
Frequency ()

The frequency of the wave is directly proportional to the energy of the

wave and is defined as the number of wavelengths passing a fixed
point in space in one second.

It is expressed in hertz (Hz), kilohertz( kHz), megahertz (MHz)

 Electromagnetic Spectrum
Arrangement of EM radiations in order of their wavelengths or frequencies
The Sun produces full spectrum of electromagnetic radiations

EMR is divided into different regions based on the type of atomic or molecular
transition that gives rise to the absorption or emission of photons.

The boundaries describing the electromagnetic spectrum are not rigid, and an
overlap between spectral regions is possible.
 Different parts of the EM spectrum interact with matter in different ways.
Change of spin Change of Change of Change of electron distribution Change of
orientation configuration nuclear
configuration

Nmr Esr Microwave Infra-red Visible and UV X-ray - ray

Or

͞ in cm-1 10-2 1 100 104 106 108

λ 10m 100cm 1cm 100μm 1μm 10nm 100pm

 in Hz 3 x 106 3 x108 3x 1010 3 x 1012 3x 1014 3 x 1016 3 x 1018

E in J/mol 10-3 10-1 10 103 105 107 109

The different properties of the various types of electromagnetic radiation are

due to differences in their wavelengths, and the corresponding differences in
their energies: shorter wavelengths correspond to higher energy.
Thus different parts of the EM spectrum interact with matter in different
ways.
 Interaction of radiation with matter
In order that there shall be some mechanism for interaction
between the incident radiation and the nuclear, molecular or
electronic changes, there must be some electric or magnetic effect
produced by the change, which can be influenced by the electric
or magnetic fields associated with the radiation.

Exactly how the radiation interacts with matter is directly

dependent on the energy of the radiation.
 Interaction of radiation with matter
 Atoms, ions, and molecules can exist in certain discrete energy
states only. Only certain energy states are allowed (energy is
quantized).
 Thus, Electromagnetic radiation is absorbed only when the
energy of photon corresponds to difference in
energy between two states and is related to the frequency of
radiation absorbed or emitted by the relation:

Efinal – Einitial = h
Efinal
or E = h

If there are no available quantized energy

 E = h
levels matching the quantum energy of the
incident radiation, then the material will be
transparent to that radiation Einitial
 Absorption Emission

E2 E2
E = h E = h

E1 E1

Intensity
Intensity

 
Frequency Frequency
 Types of Energy States
Three types of energy states are usually identified and used for the
explanation of atomic and molecular spectra:
1.Electronic Energy States: These are present in all chemical species
as a consequence of rotation of electrons, in certain orbits, around
the positively charged nucleus of each atom or ion. Atoms exhibit
this type of energy levels only.
2.Vibrational Energy Levels: These are associated with molecular
species only and are a consequence of interatomic vibrations.
Vibrational energies are also quantized, that is, only certain
vibrations are allowed.
3.Rotational Energy Levels: These are associated with the rotations
of molecules around their center of gravities and are quantized. Only
molecules have vibrational and rotational energy levels.
 Molecular Energy Levels
Molecules can have the following types of energy
Kinetic (due to motion)
Electronic (PE and KE of electrons)
Vibrational (oscillation of atoms in bonds)
Rotational

All except the KE are quantized

Emolecule = Erotational + Evibrational + Eelectronic

Rotational Vibrational Electronic

Transition << Transition
<< Transition

1-20 cm-1 2000-4000 cm-1 10000-50000 cm-1

 Molecular Energy Levels

Excited
Electronic
State

Electronic Transition
Vibrational
Rotational Energy Levels
Energy Levels

Ground
Vibrational Transition Electronic
State
Rotational Transition
 Population of energy states
• The continuous thermal agitation that molecules experience at any temperature
ensures that they are distributed over all possible energy levels.
• Population of a state = the average number of molecules in a state at any given
time.

The mathematical formulation of how to calculate the

population of a state was provided by Ludwig Boltzmann in
the late 19th century.
The Boltzmann distribution
The Boltzmann distribution defines the relative population of energy states
(usually the ratio of excited states to ground state).

There is always a higher

population in a state of lower
energy than in one of higher
energy.

kB = Boltzmann constant (= R / NA) = 1.381x10-23 J K-1

T = temperatre (Kelvin)

Effect of temperature
• The Boltzmann distribution is a continuous function.
• At lower temperatures, the lower energy states are more greatly populated.
• At higher temperatures, higher energy states are also populated
kBT ~ 2.5 kJ mol-1 at 300 K.
 ROTATIONAL
SPECTROSCOPY
• Translational energy: by virtue of its translatory motion
• Rotational energy: by virtue of bodily rotation of a 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 arrangement in
the molecule
Etotal = Etrans + Erot + Evib + Eel

Motion  E (J molecule1)   (m)

Rotation 1023 102
Vibration 1021 104
Electronic 1019 106
 Rotational spectroscopy: caused by the rotations of molecules

 When frequency of the electromagnetic radiation coincides with

that of the molecular rotation then absorption of light takes place and
the molecule is pushed to a higher rotational level

 Energy of microwave photons (0.00001-0.001 eV) matches the

ranges of energies separating quantum states of molecular rotations
therefore it is also known as Microwave Spectoscopy

 Microwave region:  = 3 x 1010 – 3 x 1012 Hz

 = 1 cm – 100 m
 1100 cm1
 The Gross Selection Rule for Rotational
Spectroscopy

 Molecules having a permanent dipole moment only show

rotational spectra and are called “microwave active” : HCl,
CO etc.
 Homonuclear molecules such as H2, Cl2, N2 etc. do not
show rotational spectra and are called “microwave inactive”
 During the rotational motion in a polar molecule, the direction of
the dipole undergoes periodic change resulting in fluctuations in the
magnitude of a component of the dipole, which is similar in form to the
fluctuating electric field of radiation
Thus interaction can occur, energy can be absorbed or emitted, and
the rotation gives rise to a spectrum
 The rotation of a three-dimensional body is quite complex
 For convenience the molecular rotation is resolved into
rotational components about three mutually perpendicular
directions through the center of gravity – the principal axes
of rotation
 Thus a molecule has three principal moments of inertia,
one about each axis, designated as IA, IB and IC
 Molecules are classified into groups according to the
relative values of these three principal moment of inertia:
depends mostly on their shapes
 Linear Rotor (Linear Molecules): IB = IC , IA = 0 (about the bond axis)
e.g. HCl, OCS
 Symmetric Tops: IB = IC  IA , IA  0 e.g. CH3F, BCl3, NH3
 Spherical Tops: IB = IC = IA e.g. CH4 (Microwave inactive)
 Assymetric Tops: IB  IC  IA Majority of molecules belong to this
class e.g. H2O
Rotational Spectra of Diatomic Molecules : Linear Rotors
1. Rigid Rotor
2. Non-rigid Rotor
1. Rigid Rotor Model
The molecule is supposed to consist of two
atoms of masses m1 and m2 connected by a
massless rigid rod of length r (bond length)
and their distance from the center of mass are
r1 and r2 , respectively
The moment of inertia of the system about the CM is: Imr m r
11
2
2 2
2

As the system is balanced about its CM we can write m1r1  m2r2

Also we know r  r1  r2
 m2 r m1r
On solving the equations we get r1  r2 
m1  m2 m1  m2
2
m1m2 r
I   r 2
m1  m2

m1m2
  Reduced mass
m1  m2
Since the molecule is a rigid rotor, the potential energy is zero. And the energy of
rotation is all kinetic energy given as
1 1
E rot  m1 v1  m2 v 22
2

2 2
Where v1 and v2 are linear velocities of masses m1 and m2, respectively.
Since r1 and r2 are assumed to remain unchanged during rotation, the above
equation can be written in terms of the angular velocity () by using the relation
v

r
1 1
Erot  m1 (.r1 )  m2 (.r2 ) 2
2

2 2
1 2 1 2 P2
  (m1r1  m2 r2 )  I 
2 2
P  J ( J  1) 
2 2 2I
Where P is the angular momentum = I
P is a vector and has magnitude as well as direction. The direction of the angular
momentum vector is conventionally taken to be along the axis about which rotation
occurs.
Solving the Schrodinger equation for a rigid rotor
h2   2 2 2 
 2  2  2  2   E
8   x y z 
the rotational energy levels allowed to the rigid diatomic molecule are
given by:
h2
EJ  J ( J  1) joules
8 I
2

J = rotational quantum number = 0, 1, 2, ... (integral values)

I can be either IB or IC since both are equal.
The rotational energy is quantized, the molecule can have only certain
permitted values of rotational energy.
In the rotational region, spectra are usually discussed in terms of
wavenumber in cm1
EJ h
J   J ( J  1) cm1 (J = 0, 1, 2, ... )
hc 8 2 Ic
  J  BJ ( J  1) cm 1 (J = 0, 1, 2, ... )

B is the rotational constant

h
B cm 1 J level
8 2 Ic Energy
J=6 42B
J = 0, J=0 = 0  Molecule is not rotating
J = 1, J=1 = 2B
J = 2, J=2 = 6B J=5 30B

J=1  J=0 = 2B cm1 J=4 20B

J=2  J=1 = 4B cm1 J=3 12B

In general the energy difference between J = 2 6B

two rotational levels J and (J +1) is J=1 2B
J=0 0B
Energy of rotational energy
J+1  J = 2B (J + 1) cm1 levels: (Not equally spaced)
 Rotational Spectrum of a Diatomic Rigid Rotor
Transitions in which J changes by one unit
Specific Selection Rule are only possible, all other transitions are
spectroscopically forbidden
 J  1
J  1 (absorption )
J  1 (emission )

The wavenumbers associated with

different transitions:
 J 0  J 1  2 B cm 1
 J 1  J  2  4 B cm 1
For a transition from J to (J+1)
 J  J 1  B (J  1 ) (J  2 ) - BJ(J  1 ) cm 1

 J  J 1  2 B (J  1 ) cm 1
0 4B 8B 12B cm1
Spectrum consists of equidistant (2B) lines
2B 6B 10B 14B
 Intensities of Spectral Lines
All spectral lines are not equally intense.
Intensity depends on the population in each state.
Population of a state is governed by two factors:
1. Boltzmann distribution
2. Degeneracy in the energy state
Boltzmann distribution

NJ  EJ   Bhc J(J  1 ) 
 exp     exp  
N0  kT   kT 

The population thus depends upon J and temperature T.

Population is smaller for higher J states.
Rapid decrease of NJ/N0 takes place with increasing J
and with larger B
Greater initial state population gives stronger (intense) spectral lines
Degeneracy in the energy states
Degeneracy : existence of two or more energy states having exactly the same energy
Each level J is (2J+1) degenerate  population is greater for higher J states
Boltzmann distribution suggests an exponential decrease in the molecular
population in each level
but the number of degenerate levels available increases rapidly with J.

The total relative population at an energy EJ

(2J + 1) exp[BJ(J+1)hc /kT ]

B = 5 cm1
 (2J + 1) exp(EJ /kT )

The population rises to a maximum and then

diminishes.
B = 10 cm1

𝑘𝑇 1
Maximum population: 𝐽 = 
2ℎ𝑐𝐵 2

0 2 4 6 8 10 12
The line intensities are directly proportional to Rotational quantum number J
the population
Transition between levels with very low and very high J values will
have small intensities while the intensity will be maximum near the J
value where population is maximum
 Effect of Isotope Substitution on the Rotational Spectra
Diatomic molecules having different isotopes of the same element show different
rotational spectra e.g. HCl and DCl; 12C16O and 13C16O etc.
Mass of the isotopic atoms are different  the reduced mass (µ), moment of inertia (I),
rotational constant (B) are different
h h
B =
8 Ic
2
8 2 (  r 2 )c
Since there is no appreciable change in the internuclear distance (r) on
isotopic substitution  B  1/µ
Spectrum of heavier species will show smaller value of B and hence smaller
separation between the spectral lines.
Comparison of rotational spectra of molecules with isotope substitution
can determine:
(i) isotopic masses accurately, to within 0.02% of other methods for atoms in
gaseous molecules
(ii) isotopic abundances from the relative intensities.
Effect of isotopes

From 12C16O  13C16O, mass increases, B decreases ( 1/I), so

energy levels lower and smaller separation between the spectral
lines is observed

12CO
J=6 13CO

Energy
5 levels

4
3
2
1
0
2B’ 4B’ 6B’ 8B’ 10B’ 12B’
cm-1 spectrum

2B 4B 6B 8B 10B 12B
2. Non-Rigid Rotor Model
We know the molecules vibrate  can not be strictly rigid rotors

J is high  rotational energy high  a tendency for the bond to stretch

because of the centrifugal distortion  moment of inertia increases  B
decreases and the spectral line separation decreases

Therefore a better model for representing the rotations of the molecule is to

consider the diatomic molecule to consist of two atoms connected by a
massless spring and this is known as non-rigid rotor model.
 Solving the Schrodinger equation for a non-rigid rotor we can get

 J  BJ ( J  1)  DJ 2 ( J  1) 2 cm 1
D is the centrifugal distortion constant: a small value compared to B

h3 4 B 3 1
D  2 cm
32 I r kc 
4 2 2

where  is the vibration al frequency of the bond

k  force constant  4 2 2c 2 

The energy difference between two rotational levels J and (J +1) is

J+1  J = 2B (J + 1) – 4D (J+1)3 cm1

 Selection rule remains same : J = ± 1
Wavenumber for a transition from J to (J+1) is given as

J  J 1  2 B (J  1 )  4 D ( J  1) 3
cm 1
(J = 0, 1, 2, ... )

 0  1  2 B ( 0  1 )  4 D(0  1)3 = (2 B  4 D) cm 1
 1  2  2 B ( 1  1 )  4 D(1  1)3 = (4 B  32 D) cm 1
 2  3  2 B ( 2  1 )  4 D(2  1)3 = (6 B  108D) cm 1

Separation between 1st and 2nd line = (4B - 32D) – (2B - 4D) = (2B – 28D) cm1
Between 2nd and 3rd line = (6B - 108D) – (4B - 32D) = (2B – 76D) cm1

• The spectral lines are no longer equidistant

• The separation decreases with increasing J value
 • The spectral lines are no longer equidistant
• The separation decreases with increasing J value

Rigid Rotor
J=6 Non-rigid Rotor
Energy
5 levels

4
3
2
1
0

cm-1 spectrum
Rigid Rotor
2B 4B 6B 8B 10B 12B

Non-rigid Rotor cm-1 spectrum

 Application of Microwave Spectroscopy
At lower energy levels of rotation the spectral lines are
equidistant. This is utilized in the determination of the bond-
distance in diatomic molecules.
Is also useful in determining the moment of inertia and
reduced mass of diatomic molecules

Comparison of rotational spectra of molecules with isotope

substitution can determine
 (i) isotopic masses accurately, to within 0.02% of other
methods for atoms in gaseous molecules
 (ii) isotopic abundances from the relative intensities
 Application of Microwave Spectroscopy

From three consecutive lines accurate values of B, D

and J can be determined.
Knowledge of D enables to determine the
approximate vibrational frequency of a diatomic
molecule.
One fascinating area where microwave analysis is
being used is in the chemical examination of
interstellar space.
Nearly 130 molecules/ions have been identified using
rotational emission spectra.
Microwave Oven
Do you know what is the basic principle of
cooking in a microwave oven !!