SPECTROSCOPY

 Interaction of molecules with electromagnetic

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

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).

Spectroscopy is the combination of the following phenomena

1. Interaction of radiation with matter

2. Transition among different energy levels (exchange of energy

between light and matter)

3. Absorption and emission bands arising out of the transitions

 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
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( ͞n)

It is defined as the number of wavelengths which can be

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

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)

Quantum Theory of EMR
EMR is consisting of a stream of photons or quanta travelling in the
direction of propagation of the beam with the velocity of light.
Dual nature of light
hc 2
E  hn   hcn  mc

Electromagnetic Spectrum
Arrangement of EM radiations in order of their wavelengths or frequencies
 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.
For a molecule to interact with EMR and to absorb or emit a photon
of frequency n, it must exhibit an oscillating dipole at that frequency.
This condition imposes certain restrictions on the system and are
known as gross selection rules of a particular spectroscopy

Exactly how the radiation interacts with matter is directly dependent on

the energy of the radiation.
 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

͞n in cm-1 10-2 1 100 104 106 108

λ 10m 100cm 1cm 100μm 1μm 10nm 100pm

n 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
 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 = hn
Efinal
or DE = hn

If there are no available quantized energy

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

E2 E2
DE = hn DE = hn

E1 E1

Intensity
Intensity

n n
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 populated.
• At higher temperatures, higher energy states are also populated
kBT ~ 2.5 kJ mol-1 at 300 K.
 ROTATIONAL
SPECTROSCOPY
Discovered by Cleeton and Williams in 1934 (absorptions at
microwave frequencies by NH3)

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 (E = 10 – 103 joules/mole) matches

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

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

 = 1 cm – 100 m
n  1 100 cm 1
 The Gross Selection Rule for Rotational
Spectroscopy
A gross selection rule specifies the general features a molecule must have
if it is to have a spectrum of a given kind.

 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
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
Understanding Molecular Rotation
The rotation of a molecule can be described in terms of its angular
momentum (P = I) about the axis of rotation.
We need to know about the moment of inertia (I)
The moment of inertia I of a system about an axis passing through the
centre of mass is given by

I   mi ri 2
i

25
 1 2 1 2
Erot  m1 (.r1 )  m2 (.r2 ) v
2 2 
1 2 2 2 1 2 P 2 r
  (m1r1  m2 r2 )  I 
2 2 2I

P P  J ( J  1) 

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  2
J ( J  1) joules
8 I

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

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
42 B
J = 0, J=0 = 0  Molecule is not rotating
J = 1, J=1 = 2B
J = 2, J=2 = 6B J=5 30B
30 B

J=1  J=0 = 2B cm1 J=4 20B

20 B
J=2  J=1 = 4B cm1 J=3 12B
12 B

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
DJ  1
DJ  1 (absorption)
DJ  1 (emission)
The wavenumbers associated with
different transitions:
n J 0  J 1  2 B cm 1
n J 1  J  2  4 B cm 1
For a transition from J to (J+1)
n J  J 1  B (J  1 ) (J  2 ) - BJ(J  1 ) cm 1
1
n J  J 1  2 B (J  1 ) cm
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
  hcBJ ( J  1) 

(2J + 1) exp[BJ(J+1)hc //kT ]

N J  N 0 (2 J  1) exp B = 5 cm1

 kT 
The population rises to a maximum and then
diminishes.
dN J  2 hcB    hcBJ ( J  1) 
 2  (2 J  1)  exp 0 B = 10 cm1
dJ  kT   kT 

kT 1
J max  
2hcB 2 0 2 4 6 8 10 12
Rotational quantum number J
The line intensities are directly proportional to
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

The rotation spectrum of 12C16O at 40 K.

32
 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 2
=
8 Ic 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/II), so

( 1/
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
10B 12B
12 B
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.

B H 35Cl H 37
Cl
  1.0015
BH 37Cl H 35
Cl

35
The first line in the rotational spectrum of HBr is found to be at 16.90
cm1. Calculate the (i) moment of inertia and (ii) internuclear distance
of HBr.
The first line = 2B = 16.90 cm-1  B = 8.45 cm-1 = 8.45 x 102 m-1

I =  r2

36
Spectral line separation decreases with increased J
Bond length increases with increased J 37
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.

38
 Solving the Schrodinger equation for a non-rigid rotor (harmonic
oscillator) 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 4 2 2
 2 cm
32 I r kc 
1 k
where  is the vibrational frequency of the bond 
2c 
k  force constant  4 2 2 c 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

39
 Selection rule remains same : DJ = ± 1
Wavenumber for a transition from J to (J+1) is given as

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

n 0  1  2 B ( 0  1 )  4 D(0  1)3 = (2 B  4 D) cm 1

n 1  2  2 B ( 1  1 )  4 D(1  1)3 = (4 B  32 D) cm 1

n 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
40
 • 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
10 B 12B
12 B

Non-rigid Rotor cm-1 spectrum

41
42
 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
 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.

Amino acids are also found!!

Microwave Oven
Do you know what is the basic principle of
cooking in a microwave oven !!
Vibrational Spectroscopy
 The bond between atoms is considered as a massless spring
The atoms are not static they vibrate about a mean position

m1 m2

The appropriate frequencies for molecular vibrations are in the

Infrared region of the electromagnetic spectrum therefore it is also
known as Infrared Spectroscopy

Spectral Frequency Wavenumber Wavelength

Region (Hz) (cm-1) (m)
Near IR 3.8 x 1014 - 1.2 x 1014 12800 - 4000 0.8 to 2.5
(NIR)
Mid IR 1.2 x 1014 - 6.0 x 1012 4000 - 200 2.5 to 50

Far IR 6.0 x 1012 - 3.0 x 1011 200 - 10 50 to 1000

 Gross Selection Rule for Vibrational Spectroscopy
 The molecule must undergo a change in dipole moment when the
vibration occurs
 If no change in dipole moment occurs, when the molecule vibrates,
there will be no interaction between the EMR and the molecule and
no absorption will take place regardless of energy compatibility –
Such a vibration is said to be IR-inactive.
 For diatomic molecules the molecule must be polar.
 Vibrational spectra are observed only for heteronuclear diatomic
molecules (HCl, CO etc.) and they are called IR active.
 Homonuclear diatomic molecules are IR Inactive (H2, O2 etc.) .
 The Vibrating Diatomic Molecule
A vibrating diatomic molecule can be envisaged as a
(1) Simple Harmonic Oscillator
(2) Anharmonic Oscillator
Simple Harmonic Oscillator : The atoms vibrate approximately like
an harmonic oscillator (behaving like a perfectly elastic spring) and
obeying Hooke’s Law:

f =  k (r – re)
EPE = ½ k (r – re)2
f : restoring force
k: force constant
r: inter-nuclear distance
re: equilibrium distance (bond length)
(rre) : displacement
EPE = Potential energy
Vibrational Energy of Diatomic Molecules
By solving Schrodinger equation for vibrational motion we get
Vibrational energy levels

1 
Ev  v   hosc joules


 2
(v  vibrational quantum number  0, 1, 2, ....)
osc  1 k Hz  classical oscillation frequency k = force constant
2  = reduced mass
Vibrational energy, like all other molecular energies, are quantized
Ev 
1 
osc  1 k cm-1
v    v   osc cm1

2 c
hc  2

Zero point energy  0  1 osc cm1 (v  0)

2
Molecule can never have zero vibrational energy
 Atoms can never be completely at rest relative to each other
 Ev
  v  1  osc cm1
 
v 
hc  2
 osc cm - 1
6
 0  1 osc cm1 (v  0)
2 5
cm - 1

Energy (cm-1)
 osc
4
1  3 osc cm1 (v  1)
2 3
 osc cm - 1
2
 2  5 osc cm1 (v  2)
2 1
v=0
 3  7 osc cm1 (v  3)
2 Internuclear distance (r)

Spacing between adjacent vibrational states:

D v osc cm-1 for any v
The vibrational levels of simple harmonic oscillator are equally spaced
 Specific Selection Rule for a Harmonic Oscillator

Dv =  1
Dv = + 1 (absorption)
Dv = 1 (emission)
 osc cm-1
6

v  v1 5

Energy (cm-1)
n  osc cm-1 4
spectroscopic 3

2
 Since all the vibrational levels are
1
equally spaced, transition between any two v=0
neighboring states will give rise to the
same energy change. Internuclear distance (r)

n  cm - 1
 Thus expect only one vibrational peak in spectroscopic osc

the IR spectrum of a diatomic simple

harmonic oscillator
 Anharmonic Oscillator Model
Real bonds, although elastic, do not exactly obey Hook’s law especially at
higher vibrational levels, when the restoring force is not proportional to the
displacement
If the bond between atoms is stretched, there comes a point at which it will
break – the molecule will dissociate into atoms
An empirical expression for this
curve was derived by P. M. Morse
and is called the Morse function


EMorse  De 1  e 
 a ( r  re ) 2

De is the dissociation energy

a is a constant for a particular molecule
and controls the width of the potential
(smaller the a, larger is the well)
ke ke = force constant at the
a
2 De minimum of the well
The curve is called the Morse Curve
By solving Schrodinger equation for an anharmonic oscillator we get the
allowed vibrational energy levels:
2
v  v  1 e - v  1 e xe cm1
   
   

2 
2   (v = 0, 1, 2, ….)
   

e  equilibrium oscillation (vibration) frequency of the anharmonic system

xe = anharmonicity constant. It has small positive magnitude

  1 
osc  e 1  xe  v   
 2
 
e
xe  osc  1 k cm-1
4 De 2 c
Zero point energy
1 
 0  e 1- 1 
xe cm1 (v  0)
2  2 
 2
v  v  1 e - v  1 e xe cm1 (v = 0, 1, 2, ….)
   
   

2 
 2 




 0  1 e  1 e xe cm1 (v  0)
2 4

1  3 e  9 e xe cm1 (v  1)
2 4

Energy (cm-11)
 2  5 e  25
e xe cm1 (v  2)
2 4

3  7 e  49
e xe cm1 (v  3)
2 4
Internuclear distance (r)

The vibrational levels crowd more closely together with increasing v

55
 Specific Selection Rule for the Anharmonic Oscillator
Dv =  1,  2,  3, …
Dv = + 1, + 2, + 3… (absorption)
Dv = 1, 2, 3 … (emission)
Boltzmann distribution says the population
of the v =1 state is around 1% of the
ground state population.
Consider only the transitions from v=0
state at room temperature
Transitions from v=1 can be seen at high
temperatures (Hot bands, less intense)
Only the lines of Dv = 1, 2, 3 have
observable intensity; transition probability
rapidly diminishes for higher jumps
 2
v  v  1 e - v  1 e xe cm1 (v = 0, 1, 2, ….)
   
   

 2 
 2





 0  1  e (1 - 2xe) cm-1 v  0  v  1 (Dv 1)

 0  2  2e (1 - 3xe) cm-1 v  0  v  2 (Dv 2)

 0  3  3e (1 - 4xe) cm-1 v  0  v  3 (Dv 3)

v =0  v = +1 : fundamental absorption
(Intense band)
v =0  v = +2 : first overtone band
(less intense band)
v =0  v = +3 : second overtone band
(negligible intensity)
Hot Band
1  2  e (1 - 4xe) cm-1 v 1  v  2 (Dv 1)57
Hot Band

 e cm -1  2e cm -1  3e cm -1 58
Normal vibrational modes of a molecule containing N atoms
• Number of possible normal vibrational modes
• Nonlinear molecule: 3N – 6
• Linear molecule: 3N – 5
• Total degrees of freedom: 3N i.e. 3 coordinates in space for N=1
• 3 translational and 3 rotational account for 6 degrees of freedom
• A linear molecule can be placed along one Cartesian coordinate and
rotation about this axis cannot be recognized as a spatial movement
 only 2 rotational degrees of freedom
• Remaining degrees of freedom represent vibrational motion. Out of
3N-6 vibrational modes, (N-1) will be stretching and rest will be
bending.
• Each normal vibration is associated with a characteristic frequency
• Only those vibrations in which there is a change in the molecular
dipole moment are IR active and show IR spectrum
 Vibrations of Polyatomic Molecules
The fundamental vibrations of a molecule are
1. Stretching vibration: The stretching vibration in which the distance
between two atoms around a bond varies with time.
 Symmetrical stretching : bonds are alternately stretched and compressed in a
symmetrical manner
 Asymmetrical stretching: One bond is stretched while the other is compressed
and vice versa

Methylene Group Stretching Vibrations

2. Bending vibrations: The angle between two atoms varies with time.
• Wagging: the structural unit swings back and forth
• Twisting: the structural unit swings back and forth out of the plane of the molecule
• Rocking: the structural unit rotates about the bond which joins it to the rest of the
molecule
• Scissoring: scissors like movement

rocking scissoring twisting wagging

R R
H H
R H R H In - plane Out -of - plane
scissoring rocking
R R
H H
R H R H
wagging twisting
 CO2: Linear molecule with 3 atoms,
there are 3(3) – 5 = 4 fundamental vibrations

n = 1340 cm1

n = 667 cm1
Degenerate

n = 2349 cm1
 Carbon Dioxide

This stretching mode results in no peak because the dipole moment is

zero does not change during vibration
 Carbon Dioxide
Asymmetric stretching results in a change in dipole moment during
vibration and produces a peak in the IR spectrum.
 Carbon Dioxide
The bending mode of vibration gives a peak in the IR spectrum
66
 IR Spectrum of Polyatomic Molecules
1. Skeletal vibrations where all the atoms in the molecule move about to some
extent.
These vibrations give rise to absorption peaks in the range 400 – 1600 cm-1 which
is called the fingerprint region. These may be utilized to establish the general
structure of the molecule (linear, branched etc.)

2. Functional group vibrations in which only the atoms in that functional group
vibrate appreciably.
Each functional group gives rise to an absorption peak at a characteristic
frequency, no matter what the rest of the molecule contains. These peaks can be
used to identify the functional groups present in the molecules.

4000 cm-1 1600 cm-1: “functional group” region.

Most of the stretching bands, specific functional groups
(specific atom pairs).
1600 cm-1  400 cm-1: “fingerprint” region.
Many bands of mixed origin. Some prominent bands are reliable.
Characteristic Stretching Frequencies of Some Molecular Groups
 Four Primary Regions of IR Spectrum

n  osc = 1  k cm-1
spectroscopic 2 c
Larger k  higher frequency
Larger  (large atomic mass)
 lower frequency
The x-axis of the IR spectrum is in units of wavenumbers (cm-1):
directly proportional to the energy of transition being observed
The y-axis on an IR spectrum is generally in % transmittance
 1. The fundamental vibrational frequency of HCl is 2890 cm-1.
Calculate the force constant of HCl. Atomic masses of 1H =
1.673 x 10-27 kg and 35Cl = 58.06 x 10-27 kg
osc  1 k cm-1
2 c
2. CO shows an intense band at 2142 cm-1 and a weak band at 4260
cm-1. Calculate the fundamental frequency, force constant and the
anharmonicity constant for CO molecule.   1 
osc  e 1  xe  v   
  2 
 0  1  e (1 - 2xe) cm-1 v  0  v  1 (Dv 1)
3. The vibrational spectrum of HCl shows an intense band at 2886
cm-1 and a weak band at 5668 cm-1. Calculate the following:
(i) Fundamental absorption frequency
(ii)The anharmonicity constant
 Electronic Spectroscopy
UV--Vis spectroscopy
UV

200-400 nm
• UV-Vis spectroscopy corresponds to electronic
transitions between energy levels of molecular orbitals
(UV = 200 nm - 400 nm, Visible = 400 nm - 800 nm)
• Responsible for the colour of many objects
• Unlike in vibrational and rotational spectroscopies, all
molecules give electronic spectra
 When electromagnetic radiation in the UV-Vis range falls on a molecule,
the electric field of the radiation tends to disturb the charge cloud around
the molecule and generates a dipole in the particle in the direction of the
electric vector of the field.

 The oscillating electric field of EMR thus creates an oscillating dipole

(transient dipole) in the matter with which it is interacting.

+  + 
 +  +
+
+  + 
 +  +
74
 Origin of electronic spectra

Absorptions of UV-Vis light photons by molecule results in

electronic excitation of molecule.

The electronic transition involves promotion of electron from an

electronic ground state to higher energy state, usually from HOMO
to LUMO.
HOMO: Highest Occupied Molecular Orbital
LUMO: Lowest Unoccupied Molecular Orbital
Electronic transition usually originates from the ground state in a
chromophore.
 UV-Vis Spectral Origin
Excited state

v= 2
v= 1
v= 0 LUMO
E
hn
Energy

Ground state
HOMO

Ground state Excited state

v= 2
v= 1
v= 0

Internuclear distance

Transition of an electron from HOMO to LUMO by UV-Vis photon

 Singlet state and Triplet state
Singlet state: the state in Triplet state: the state in
which the spins are opposed which the spins are parallel

*
*
Spin multiplicity = S = 2s+1 = 1 Spin multiplicity = S = 2s+1 = 3
In general T state is of lower energy than the corresponding S state

E S2
T2
S1
T1

S0

Singlet States Triplet States

 Selection Rule for Electronic Transition

Spin selection rule:: DS = 0

allowed transitions: singlet  singlet or triplet  triplet
forbidden transitions: singlet  triplet or triplet  singlet

Changes in spin multiplicity are forbidden

S→S, T→T, are allowed,

S→T, T→S, are forbidden
 Quantitative Analysis
Measurement of Absorbance
Beer – Lamberts’ Law

A =   c l
A : Absorbance (optical density) at wavelength 
 : molar absorptivity (molar absorption coefficient)
at  (unit of : L mol-1 cm-1)
l: path length (cm) (generally taken as 1 cm)
c : concentration of the compound in solution,
expressed in mol L-1

Absorbance (A)
Beer’s Law is always wavelength-specific 
Using the calibration plot one can determine the
concentration of unknown sample by monitoring
the absorbance
Concentration (M)
 Beer – Lamberts’ Law I: Intensity of light
dI passing through the
  kcdl
I sample

IT dI l When l = 0, I = I0
I0 IT   kc  dl When l = l, I = IT
Ia I0 I 0

 IT 
  ln   kcl
 I0 
l: pathlength  IT 
I0= Ia + IT  2.303 log   kcl
 I0 
I0 : Intensity of incident light
Ia : Intensity of absorbed light  I0   k 
log   A  cl   
IT : Intensity of transmitted light  IT   2.303 
k: Absorption coefficient
: Molar absorption coefficient
 IT 
  log T  A  T  
T: Transmittance (IT / I0)  I0 
 Absorption Spectra of Mixtures
Containing n components
Absorbance is additive for mixtures
Amixture  A1  A2  ...  An
Amixture  1lc1   2 lc2  ...   n lcn
Amixture  1c1   2 c2  ...   n cn (If l = 1 cm)

Absorbance of a mixture, at a certain wavelength, is the sum of each

component absorbance at the considered wavelength

Transmittance (T) is not additive

 IT 
A = log (1/T)  T  
 I0 
 Internal Energy of Molecules

Etotal = Eelec + Evib + Erot

Eelec: electronic energy
Evib: vibrational energy
Erot: rotational energy
DEtotal = DEelec + DEvib + DErot

Only the ground state electronic level is populated and virtually all
molecules exist in the lowest vibrational level (v=0)
•When a molecule absorbs light having sufficient energy to cause an
electronic transition, changes in the vibrational and rotational states
can occur as well.

•The reason why electronic absorption bands of molecules (unlike

atomic spectra) are usually very broad is that many different
vibrational and rotational levels are available at slightly different
energies.

•Therefore, a molecule could absorb photons with a fairly wide

range of energies and still be promoted from the ground electronic
state to one particular excited electronic state.

• Vibrational changes produce a “coarse structure” and rotational

changes a “fine structure” on the electronic transitions.
Absorption spectra from the ground state are more
likely: virtually all the molecules are in their lowest
vibrational state (v = 0), so that the only transitions we v=2
v=1
observe are (0, 1), (0, 2), (0, 3) etc. S2 v=0

First Excited State

v=2
v=1
v= 3 S1 v=0
v= 2
v= 1
v= 0
v=2
S0
Energy

Ground State v=1

v=0

S2S0

Absorbance
v= 2
v= 1 S1S0
v= 0

84
Internuclear distance Wavelength (nm)
 Frank-Condon Principle
• Electronic transitions are so fast (10-15 s) in comparison to
the nuclear motion (10-13 s) that immediately after the
transition, the nuclei have nearly same relative position and
momentum as they did just before the transition.

•Since the nuclei do not move during the excitation, the

internuclear distance remains the same, and “the electronic
transitions involve only the vertical transitions”.
 Excited state Excited state

v= 3 v= 3
v= 2 v= 2
v= 1 v= 1
v= 0 v= 0
Energy

Energy
Ground state Ground state

v= 2 v= 2
v= 1 v= 1
v= 0 v= 0

Internuclear distance
Internuclear distance
 The probability of finding the molecule
at the centre of v=0 state is maximum
Excited state
 The intensity of the transition
v= 4 originating from the centre of v=0 is
v= 3
v= 2 maximum (02 transition in the figure)
v= 1
v= 0
02
Energy

Ground state

Absorbance
03 01
04 00

v= 2
v= 1
v= 0 Wavelength (nm)

Internuclear distance 00, 01, 02, 03, 04 etc. are the
vibrational bands in the absorption spectrum
 Excited state

v= 4
v= 3
v= 2
v= 1
v= 0
Energy

Ground state

00

Absorbance
01
v= 2 02
v= 1
v= 0

Internuclear distance
Wavelength (nm)
 Excited state
Dissociative State
v= 4
v= 3
v= 2
v= 1
v= 0
Energy

Ground state

Absorbance
v= 2
Continuum
v= 1
v= 0
Wavelength (nm)
Internuclear distance
 Electronic Transitions

There are three types of electronic transition

• Transitions involving ,  and n electrons
• Transitions involving d and f electrons
• Transitions involving charge-transfer
Absorbing species containing , , and n electrons
n <  < n     

UV/Vis Vacuum UV or Far UV

(λ<190 nm )
 n  * and   * Transitions
• Most absorption spectroscopy of organic compounds is based on
transitions of n or  electrons to the * excited state

• These transitions fall in an experimentally convenient region of the

spectrum (200 - 700 nm)

• n→ π* is observed at longer wavelength (lower energy, red shifted)

than π → π*

n → π* transitions have low molar absorptivity

(poor overlap of orbitals)(ε ~ 10 - 100 L/mol·cm)

π → π* transitions have high molar absorptivity

(ε ~ 1000 - 10000 L/mol·cm)
 Example of Electronic Transitions: Absorptions

O Contains both π and

Formaldehyde
nonbonding electrons (n)

C 

Absorbance
H H

n

200 Wavelength (nm) 700

Inorganics: d-d transition
• Transitions between d orbitals, split by presence of ligand field
• Usually in visible region
• These transitions have low molar absorptivity ()
Charge Transfer Transition
• These electronic transitions usually appear in light absorption of
inorganic molecules (Metal-ligand complexes)
• Electron moves between ligand and metal orbitals
• One must act as donor and other as acceptor.
• The absorption of radiation involves an electron transfer from an
orbital of a donor to an orbital associated with an acceptor.
• Charge-transfer transitions have high molar absorptivity (ε > 10000
l/mol·cm).
• Typical metal-ligand transition: an electron from an orbital of the
metal is transferred to a π * orbital of the ligand.
• If the metal has an empty d orbital, it is possible a transfer from
ligand to metal.
 Fate of Excited Molecule
A molecule excited to a higher energy state must return to the ground
state, unless it gets involved in a photochemical reaction.

v=2
First Excited state
v=1
E1 v=0
v= 3
Absorption Emission v= 2
hna v= 1
v=2 v= 0
v=1
E0 v=0

Energy
Ground state
hne
• Absorption can be to any higher
energy level (Sn)
• Emission will always be from v= 2
the 1st excited state (S1 or T1) v= 1

S1  S0 : Fluorescence v= 0
T1  S0 : Phosphorescence
Internuclear distance
 Fate of Excited Molecule
A + hn  A’ Excitation(Absorption) S0  Sn
A’ : an electronically excited molecule with excess vibrational energy in
S1 state or a molecule excited to a higher singlet state S2, S3 etc.
The various photophysical processes that can occur are:

A’  A + heat Internal Conversion(IC) Sn  S1

A  A + heat Internal Conversion(IC) S1  S0
A  A + hnf Fluorescence S1  S0
A  3A + heat Intersystem Crossing (ISC) S1  T1
3A  A + hn Phosphorescence T1  S0
p
3A  A + heat Reverse Intersystem Crossing (ISC)
T1  S0
IC & ISC : Non-radiative Transition
Fluorescence & Phosphorescence : Radiative Transitions
Jablonski Diagram
Radiative: De-excitation by photon emission.
Fluorescence: Emission ceases ‘soon’ after exciting light is
switched off.
Phosphorescence: Emission persists for ‘relatively longer’
times.