Molecular Spectroscopy

in
Microwave to UV-visible range

Books:

1. Banwell & McCash, Fundamentals of Molecular Spectroscopy

2. J. M. Hollas, Basic Atomic and Molecular Spectroscopy
3. D. N. Sathyanarayana, Handbook of Molecular Spectroscopy
 Introduction
What is spectroscopy?
Interaction of matter with light (electromagnetic radiation).
Absorption, emission or scattering of electromagnetic radiation by
atoms or molecules

Purpose?
• It gives us structural information of molecules.
The number, position, band width and intensity of the absorption
or emission bands can be correlated with the electronic and
molecular structure and bonding.

• Helps to identify a molecule.

• Strongest analytical tool in chemistry.
Spectroscopy

Matter Light
 Introduction

Electromagnetic Radiation
Electromagnetic wave follows:
y = A sin(ωt)
At t = π/2ω, 5π/2ω, 9π/2ω ...etc, y = A (maximum value)

At t = π/ω, 2π/ω, 3π/ω ...etc, y = 0


And at θ = 3 π/2ω, 7 π/2ω, 11 π/2ω ...etc,
y
y = - A (minimum value) t
Velocity =  
 Is the frequency of the emr
 Is the wave length of the emr
 Introduction

Spread of EMR in terms of wave length or frequency is called as spectrum.

The process of getting a spectrum is called as spectroscopy.

Solar Spectrum contains Dark lines (Fraunhofer lines)

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
E  h   hc  mc 2

Electromagnetic Spectrum
Arrangement of EM radiations in order of their wavelengths or frequencies
 Introduction

Why molecules interact with electromagnetic radiation?

Molecule and its components

(electron cloud, proton) are
under constant periodic
motion. This motion creates a
local electric/magnetic field.

Two sinusoidal waves consist of oscillating electric and magnetic fields directed
perpendicular to each other and the direction of propagation of the wave.
 Interaction of radiation with matter
When a beam of light interacts with matter, numerous changes occur in
both light and matter. These changes are the basis for several research
tools
EMR is characterised by , , I and direction, so the change can be in
any of these characteristics

Change in direction: Reflection and Refraction, Diffraction

Scattering: Elastic (Rayleigh) and Inelastic (Raman)
If the beam is plane polarised and the direction is rotated by passing
through the compound: Optical rotation (Polarimetry)
Change in Intensity: Absorption
Emission of light (different  than the absorbed one)
 Interaction of radiation with matter

For a molecule to interact with EMR and to absorb or emit a photon

of frequency , 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.
 Rotational motion
Magnitude of dipole moment vector in y direction in each case is shown:

+
-

-
+
Y-axis - +
+ -

-
+
0 α 0 -α 0

Molecule rotates anti-clockwise manner

Dipole moment along y axis

α α

0 0
0 0
time
-α
-α

Periodic fluctuation or alteration of dipole moment

 Vibrational motion
y

δ-O

δ + +C

δ-O
Net dipole moment = 0
 Interaction of radiation with matter
Rotational motion
Fluctuating dipole moment of a (rotating) molecule interacts with periodically changing
electric field of electromagnetic radiation Rotational spectroscopy

Vibrational motion
Fluctuating dipole moment of a (vibrating) molecule interacts with periodically changing
electric field of electromagnetic radiation vibrational spectroscopy

….and similarly,

Electronic motion
The excitation of a valence electron involves the moving of electric charges in
a molecule creating changes in dipole moment, which interacts with undulatory
electric field of electromagnetic radiation electronic spectroscopy
 Region of spectrum

E = hν

ν = c/λ, or c = νλ,

E = hc/λ or, E = hcλ-1 = hc𝜈ҧ

[ where 𝜈ҧ stands for ‘nu bar’]
What happens after a molecule interacts with
electromagnetic wave?
Excited state
Excited state energy

hν hν ΔE

molecule
Ground state energy
Ground state
 Change in

structure
nuclear
in spin orientation of nuclei in molecule

vibrational motion in molecule

jump in molecular
Due to electronic
Energy gap created due to difference

electronic

in atomic
rotational motion in molecule

Energy gap created due to

orbital
Excited

jump
Energy gap created due to
state 6

orbital
Excited
state 5

Excited
state 4 ΔE6
ΔE5
Excited
state 3 C
Excited
Excited
state 2 ΔE3
state 1
ΔE2
ΔE1
Ground state
Radio Micro Infra red Visible & X-ray γ-ray
wave wave Ultra violet
Δ E 1 = hcλ1−1 Δ E 2 = hcλ2−1 Δ E 3 = hcλ3−1 Δ E 4 = hcλ4-1 Δ E 5 = hcλ5−1 Δ E 6 = hcλ6−1
λ1 =10 m – 1 λ2 = 1 cm - 100 λ3 = 100 μm – λ4 = 0.8 μm – 10 λ5 = 10 nm – 100 λ6 = 100 pm - -
cm μm 0.8 μm nm pm
 Interaction of EMR with matter
Change of spin Change of Change of Change of electron distribution Change of
orientation configuration nuclear
configuration
radiowave Microwave Infra-red Visible and UV X-ray - ray
NMR ESR

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

•NMR spectroscopy deals with nuclear spin motion

•Microwave spectroscopy deals with rotational motion
•IR spectroscopy deals with vibrational motion
•uv-visible spectroscopy deals with electronic motion (transition).
 Spectrum
What is a Spectrum
The data that is obtained from spectroscopy is called a spectrum.
A spectrum is a plot of the intensity detected versus energy (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 also 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).
 Spectrum

A spectrum is characterised by its position (, ), intensity (I), shape

and width
1. Spectral Position: Band position relates to the appropriate energy
levels and difference in energy thus it is the easiest parameter to
measure
2. Spectral Intensity: The intensity depends on three factors
(i) Transition Probability: allowed transitions generate intense
bands than the forbidden transitions
(ii) Population: Higher the population greater is the intensity
(iii) Concentration (and path-length): Beer-Lamberts’law can be used
to express the relationship between concentration, path-length
and intensity of radiation
 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.

Effect of temperature
• 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.
Examples of molecular spectra:

Rotational/microwave spectra
Examples of molecular spectra:

Vibrational/IR spectra

cm-1
 electronic/uv-visible spectra
Absorbance

Abs
What are common in the last 3 examples?

•There are peaks of curves as well as sharp lines.

•In the ‘y’ axis, either ‘absorbance’ or ‘transmittance’ is plotted

•in ‘x’ axis parameters of an electromagnetic radiation

(wave numbers or wavelength) have been plotted.
Summary:
Event Spectroscopy Range
Change in magnetic NMR/ESR Radiowave
dipole of
nucleus/electron
Change in dipole Rotational Microwave (mostly)/IR
moment due to rotation
Change in dipole Vibrational IR our study
moment due to vibration topics
Change in dipole Electronic UV-visible
moment due to
electronic transition
Change in electrical Raman IR (mostly)
polarizability due to
rotation/vibration
 ROTATIONAL SPECTROSCOPY
(Microwave region)
 Region of spectrum

E = hν

ν = c/λ, or c = νλ,

E = hc/λ or, E = hcλ-1 = hcഥ

𝝂
[ where 𝜈ҧ stands for ‘nu bar’]
 Rotational Spectroscopy

 Rotational spectroscopy: caused by the change of rotational state

of molecules. (Only observed in the gas phase molecules)

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

ranges of rotational states of molecules. Therefore it is also known
as Microwave Spectroscopy

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

 = 1 cm – 100 m
 1100 cm1
 Rotational Spectroscopy
Gross selection rule for observation of pure rotational spectrum:

 Molecules having a permanent dipole moment (polar

molecules) 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”

Q. Which of the molecules N2, CO2, OCS, H2O, CH2=CH2, C6H6

can have pure rotational spectrum?
 Rotational Spectroscopy
 During the rotational motion of a polar molecule the component of
dipole moment in a given direction fluctuates periodically, which is
similar in form to the fluctuating electric field of radiation.

When frequency of the electromagnetic radiation coincides with

that of the frequency of oscillation of dipole, then absorption of light
takes place and the molecule is excited to a higher rotational level.
 Rotational properties of molecule
Rotational properties of any molecule can be expressed in terms of the
moments of inertia about three perpendicular directions through the center
of gravity.

𝐼 = ෍ 𝑚𝑖𝑟𝑖2
𝑖 r1 m1
v

Axis of rotation
ri is the perpendicular distance of the atom i
from the axis of rotation.
mi is the mass of atom i.
How to consider I in a molecule?
This is a difficult equation to apply for molecules!

it is convenient to resolve the components

IB
of rotational motion into
3 mutually perpendicular axes
z

x
A real molecule y
may look like this IA
IC
3 components of molecule’s
IA IB IC
net moment of inertia

principal moments
of inertia

mutually orthogonal and pass through molecule’s centre of mass

 Classification of molecules based on the mutual relationship of IA, IB & IC

 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. F Cl

CH3F, BCl3, NH3
C B
H H H Cl Cl

 Spherical Tops: IB = IC = IA e.g.

CH4 (Microwave inactive)

 Asymmetric Tops: IB  IC  IA Majority of molecules belong to

this
class e.g. H2O, CH2-CHCl
H H
O C=C
H H H Cl

Each class of molecules has a distinct pattern of rotational spectra

 Rotational Spectra of Diatomic Molecules : Linear Rotors
Let’s consider molecules are rigid rotor, molecules that do not distort
under stress of rotation.

Rigid Rotor Model for linear molecule

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
 Rigid Rotor Model for Linear Molecule
The moment of inertia of the system about the center of mass (CM) is:

I  m1r12  m2 r22
As the system is balanced about its CM we can write m1r1  m2r2
Also we know r  r1  r2
 m2r m1r
On solving the equations we get r1  r2 
m1  m2 m1  m2
 Rigid Rotor Model for Linear Molecule
The moment of inertia of the system about the center of mass (CM) is:

I  m1r12  m2 r22



m1m2 r 2 
m1m2
 Reduced mass
I  r 2

m1  m2 m1  m2
 Rigid Rotor Model for Linear Molecule
Since the molecule is a rigid rotor, the potential energy is zero. And the energy of
the molecule is given by
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 ()
v

r
1 1
Erot  m1 (.r1 )  m2 (.r2 ) 2
2

2 2
2
1 2 1 P
  (m1r12  m2 r22 )  I 2 
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.
 Rigid Rotor Model for Linear Molecule

1 1
Erot  m1 (.r1 )  m2 (.r2 ) 2
2

2 2
2
1 2 1 P
  (m1r12  m2 r22 )  I 2 
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 it can be shown that the rotational
energy levels allowed to the rigid diatomic molecule are given by:

h2
EJ  J ( J  1) joules
8 I2

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

Solving the Schrodinger equation for a rigid rotor it can be shown that
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   2 J ( J  1) cm1 (J = 0, 1, 2, ... )
hc 8 Ic
  J  BJ ( J  1) cm1 (J = 0, 1, 2, ... )

h
B cm1
8 Ic2
J level Energy
B is the rotational constant J=6 42B

B contains information of I and

hence the mass and bond length J=5 30B
of the molecule
J=4 20B

Energy of rotational level: J=3 12B

J = 0, J=0 = 0 (Molecule is not rotating) J=2 6B
J = 1, J=1 = 2B J=1 2B
J = 2, J=2 = 6B J=0 0B
J = 3, J=3 = 12B Energy of rotational levels
(Not equally spaced)
 Rotational Spectrum of a Diatomic Rigid Rotor
Selection Rule
Transitions in which J changes by one unit are only possible, all
other transitions are spectroscopically forbidden
j  1
j  1 (absorption)
j  1 (emission)
The wave numbers/energy associated with
different transitions
 J 0  J 1  2 B cm1 First spectral line
 J 1  J 2  4B cm1 Second spectral line

For a transition from J to (J+1)

 J  J 1  B (J  1 ) (J  2 ) - BJ(J  1 ) cm1
 J  J 1  2B (J  1 ) cm1 cm1
0 4B 8B 12B

Spectrum consists of equidistant (2B) lines 2B 6B 10B 14B

 The expected rotational spectra:

Intensity (arbitrary unit)

ε4 20B
8 10 12 14 16 18 20

ΔE4 = 8B

ε3 12B
B cm-1

ΔE3 = 6B
0 2B 4B 6B 8B 10B
ε2 6B wave number (cm-1)
6

ΔE2 = 4B
0 2 4

ε1 2B
ΔE1 = 2B
ε0 0B
The actual rotational spectra:
J=4→5
high peaks

2B
2B 2B
2B

low peaks broadened peaks

2B
J=1→2
J=7→8 low peaks

J=0→1
The reason of the spectral pattern:
Height of the ‘spectral peak’ signifies the probability of a transition or intensity (I)

1. I ∝ Population of rotational levels, which depends on the thermal energy.

If population at J = 0 is denoted by N0, then the following distribution applies to
rotational spectroscopy:
𝐸𝐽
𝑁𝐽 −𝐾 𝑇 …eq. 1 [KB: Boltzmann const, T: Kelvin]
=𝑒 𝐵
𝑁0

According to eq. 1, NJ or the intensity would decrease with J values

J=0→1
expected according to Boltzmann distribution!
intensity

J=3→4

0 2B 4B 6B 8B
cm-1
The reason of the spectral pattern:
Height of the ‘spectral peak’ signifies the probability of a transition or intensity (I)

2. I ∝ population of molecules at a certain J level (NJ)

According to quantum physics, each J level is 2J+1 degenerate and NJ ∝ (2J+1)

…eq. 2
Thus, according to eq. 2, NJ or the intensity would increase with J values

J=3→4
intensity

expected according to quantum physics!

J=0→1

0 2B 4B 6B 8B
cm-1
The reason of the spectral pattern:
The two opposing effects as described, work at the same time in a molecule
during rotation! Thus, a compromise happens somewhere at the middle J values.

𝐸𝐽
−
The relative population (relative intensity) ∝ 2𝐽 + 1 𝑒 𝐾𝐵 𝑇

Maximum population,

𝑘𝑇 1
J= −2
2ℎ𝑐𝐵
 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 = 2
8 Ic 8 (  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 absorption 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
Application

• Are microwave spectroscopy and cooking in microwave oven related?

In microwave oven, food is excited with microwave radiation. The

biomolecules of food are far too large for rotation. It is the water
molecule only that absorbs the Microwave, reaches higher rotational
energy states and re-emits the excess rotational energy as heat.

• Estimation of bond lengths of polar molecules

• Remote sensing of planetary gaseous molecules and their temperatures

• Estimation of abundance of isotopes

Tutorial Problems
Q1. Calculate the moment of inertia of a diatomic molecule, HCl, with H―Cl bond
length is 1.27 Å.
[1 a.m.u = 1.66 x 10−27 kg]

I = μr2

Ans: 2.6 x 10−47 kg m2

Q2. Predict which of the following molecules will show rotational spectroscopy?

NH3, XeF4, SO2, CO2, HF, SF6, H2S, C2H2

Q3. Classify the following molecules in terms of linear, symmetric top, spherical top
and asymmetric top:

CF4, SO2, NF3, O2, PH3, CH3OH

Q4. In the year 1950, a group of scientist measured the first line in the rotation spectrum of CO as
3.842 cm-1. Hence they calculated the bond length of CO. What was the bond length of CO in Å?

[given: absolute mass of H atom = 1.673 × 10-27 Kg, atomic wt of C = 12.00 and O = 15.99]

Ans.: dCO = 1.125 Å

Q5.

ℎ2 ℎ
B= (in energy scale) B= (in frequency scale)
8𝜋2 𝐼 8𝜋2 𝐼

For NaCl, NaBr and NaI, the bond distance = 2.36 Å, 2.50 Å, 2.71 Å respectively
Q6. Assume that the Mangalyaan launched by ISRO in 2013, has captured the
following first 3 lines of the absorption microwave spectrum of CO available in certain
atmospheric region of Mars, while orbiting the planet. Calculate the temperature (K)
of that particular atmospheric region on Mars’ surface from the spectrum below.

28
Intensity

10
0
0 3.8 7.6 11.4
cm-1

Given: KB (Boltzmann constant) = 1.38 × 10-23 JK-1

Q7. The first rotational absorption lines from 1H35Cl gas were found at 83.32 cm-1. Calculate
the moment of inertia and bond length of the molecule.

1.295 A
A space probe was designed to seek CO in the atmosphere of Saturn by looking for lines in
its rotational spectrum. If the bond length of CO is 112.8 pm, at which wavenumbers do
the first three rotational transitions appear?
 Molecular Spectroscopy
 Rotational Spectroscopy (Microwave Region)

 VIBRATIONAL SPECTROSCOPY
(IR region)
 Vibrational Spectroscopy
Vibrational spectroscopy: caused by the change of vibrational states of molecule.

The bond between atoms is considered as a massless spring. The atoms are not
static they vibrate about the 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 - 400 2.5 to 50

Far IR 6.0 x 1012 - 3.0 x 1011 400 - 100 50 to 1000

 Gross Selection Rule for Vibrational Spectroscopy

 The molecule must undergo a change in dipole moment when the vibration
occurs.
 The electric dipole moment depends on the charge separation and the inter-nuclear
distance. When a molecule vibrates the dipole moment changes as the inter-
nuclear separation changes.
 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 molecule the molecule must be
polar.

 Vibrational spectra are observed only in

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:
 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:
Energy

Cl H

Cl H
Simple Harmonic Oscillator : The atoms vibrate approximately like
an harmonic oscillator (behaving like a perfectly elastic spring) and
obeying Hooke’s Law:

The oscillation frequency k = force constant

μ = reduced mass
osc  1 k Hz
2

Energy
Cl H

Cl H
 Simple Harmonic Oscillator : The atoms vibrate approximately like
an harmonic oscillator (behaving like a perfectly elastic spring) and
obeying Hooke’s Law:

The oscillation frequency

Energy
Cl H
osc  1 k Hz
2
k = force constant Cl H
μ = reduced mass

Converting frequency into wave number

osc  1 k cm-1
2c
 Vibrational Energy of Diatomic Molecules

Vibrational energy, like all other molecular energies, are quantized

By solving Schrodinger equation for vibrational motion we get
Vibrational energy levels
Ev  (v  1) hosc joules
2
(v  vibrational quantum number  0, 1, 2, ....)
k = force constant
osc  1 k Hz  oscillation frequency
2  = reduced mass

Ev osc  1 k cm-1
v   (v  1) osc cm1
2c
hc 2
 Vibrational Energy of Diatomic Molecules
When v = 0, the potential energy of the molecule:

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

2

 Molecule can never have

vibrational energy = 0.
osc cm- 1
 Atoms can never be completely 6
at rest relative to each other. 5
osc cm- 1

Energy (cm-1)
4
 Violate Heisenberg’s Uncertainty
3
Principle. osc cm- 1
2

1
v=0

Internuclear distance (r)

 Vibrational Energy levels of Diatomic Molecules
Ev
v   (v  1) osc cm1
hc 2
0  1 osc cm1 (v  0) osc cm- 1
2 6

5
1  3 osc cm1 (v  1)

Energy (cm-1)
osc cm- 1
2 4
3
 2  5 osc cm1 (v  2) osc cm- 1
2
2
1

 4  7 osc cm1 (v  3) v=0

2
Internuclear distance (r)
Spacing between adjacent vibrational sates:
 v osc cm-1 for any v osc  1 k cm-1
2c
The vibrational levels of simple harmonic oscillator are equidistant.
 Specific Selection Rule for a Harmonic Oscillator

v =  1
v = + 1 (absorption)
v = 1 (emission)
  osc cm-1 6

v  v1 5

Energy (cm-1)
 spectroscopic  osc cm-1 4

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)

  cm- 1
 Thus only one vibrational peak is spectroscopic osc

observed in the IR spectrum of a diatomic

simple harmonic oscillator.
Actual spectra of gas phase HCl looks like: 35Cl

37Cl

ഥ ± 2B(J+1) cm−1
ε=𝜔
 Anharmonic Oscillator Model
Real bonds, although elastic, do not exactly obey Hook’s law especially at
higher vibrational levels.
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

E Morse  Deq (1  e  a ( r  re ) ) 2
Deq is the dissociation energy
a is a constant for a particular molecule

The curve is called the Morse Curve

By solving Schrodinger equation for an anharmonic oscillator we get the
allowed vibrational energy levels:

v  (v  1) e - (v  1)2 exe cm1 (v = 0, 1, 2, ….)

2 2
e  equilibrium oscillation frequencyof the anharmonicsystem
xe = anharmonicity constant. It has small positive magnitude

εv = 0 = ½ e − ¼ e xe
εv = 1 = 3/2 e − 9/4e xe
e
εv = 2 = 5/2 e − 25/4 e xe
Energy (cm-1)

The vibrational levels crowd more

closely together with increasing v.

Internuclear distance (r)

Selection rule for the anharmonic oscillator
v =  1,  2,  3, …
v  (v  1) e - (v  1)2 exe cm1
v = + 1, + 2, + 3… (absorption) 2 2
v = 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
Only the lines of v =  1,  2,  3 have
observable intensity; transition probability
rapidly diminishes for higher jumps
 0  1  e (1 - 2xe) cm-1 v  0  v  1 (v 1)
 0  2  2e (1 - 3xe) cm-1 v  0  v  2 (v 2)
 0  3  3e (1 - 4xe) cm-1 v  0  v  3 (v 3)

v =0  v = +1 : fundamental absorption
v =0  v = +2 : first overtone band
v =0  v = +3 : second overtone band
 Vibrations of Polyatomic Molecules
Normal vibrational modes of a molecule containing N atoms is

• Total degrees of freedom: 3N (N = No. of atoms in a molecule)

Number of parameters Each atom can be specified using three coordinates (e.g. x, y, and z)
of a system that may
vary independently.

• Translational motion uses 3 degrees of freedom.

• Rotation of nonlinear molecule can occur along three axial direction,

which counts 3 degrees of freedom.

• For nonlinear molecule the remaining degrees of freedom, 3N−6, is

due to internal vibration.

For nonlinear N atomic molecule: 3N – 6 fundamental vibrations.

 Vibrations of Polyatomic Molecules

• A linear molecule there is no rotation about the bond axis.

• So, only 2 rotational degrees of freedom (and 3

translational degrees of freedom).
• Hence there are 3N – 5 degrees of vibrational freedom for
linear molecule.
Fundamental modes of vibration in water molecule
O
O symmetric stretching O
H H
H H
ν1 = 3652 cm-1 H H

anti-symmetric
stretching O O
O
H H
H H
ν3 = 3756 cm-1
H H

Bending O
O (symmetric) O
H H
H H H H
ν2 = 1595 cm-1
Fundamental modes of vibration in CO2 molecule

O CH O O CH O O CH O

Symmetric stretch
ν1 = 1330 cm-1

O CH O O CH O O CH O

Assymmetric stretch
ν3 = 2349 cm-1

O CH O

Two degenerate bending modes

ν2 = 667 cm-1
 Vibrational modes of H2O and CO2 Molecules
H2O (nonlinear molecule)
Number of vibration modes: 3N−6 = 3

CO2 (linear molecule)

Number of vibration modes: 3N−5 = 4

IR inactive mode
 Vibrations of Polyatomic Molecules

For nonlinear N atomic molecule: 3N – 6 fundamental vibrations.

For a linear N atomic molecule: 3N – 5 fundamental vibrations

For both cases, since and N-atomic molecule has N−1 bonds (for
acyclic molecules), so N−1 vibrations are bond-stretching vibrations.

2N−5 (for non linear) or 2N−4 (linear) are bending motions.

• Occasionally more absorption bands than would be predicted are
found.
The number of observed absorption bands may be increased by the
presence of bands which are not fundamentals but combination
bands, overtones, or difference bands.
hot band is a band centred on a hot transition, which is a transition between
two excited vibrational states
More often fewer absorption bands are identified.
• It may happen to have frequencies of some vibrations so nearly
alike that they are not separated by the spectrometer
• Some fundamental bands may be so weak that they are not
observed or are overlooked.
 IR Spectrum of Complex Organic Molecules
Two types of vibrational modes are possible:
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.

1600 cm-1  400 cm-1: “fingerprint” region.

Many bands of mixed origin. Some prominent bands are reliable.

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).
Characteristic Stretching Frequencies of some Molecular Groups
 Four Primary Regions of IR Spectrum

  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 in % transmittance
Few specific examples
 Predicting the trend of stretching frequency
 Effect of bond order (directly proportional)

 Effect of reduced mass (inversly proportional)

 Effect of Hybridisation
 Predicting the trend of stretching frequency

 Effect of resonance

 Intensity of the bands depends upon the magnitude of dipole moment associated with the concerned
bond

 Bending vibrations involve lower energy than stretching vibrations

 Asymmetric stretching involves a larger dipole moment, hence absorbs strongly at higher frequency
than symmetric stretching
 Effect of ring size on
endocyclic double bonds:
With increase in ring strain,
the p-character of the
endocyclic bonds increase
to partly compensate the
ring strain, and thus the p-
character of the exocyclic
bonds decrease to
compensate for the
endocyclic bonds.
Effect of ring size: Smaller the ring, higher is the absorption frequency

Conjugation lowers the absorption frequency:

Q1. 𝜈ҧ0→1 = 1500 cm −1 and 𝜈ҧ0→2 = 2900 cm −1 are appeared in the IR spectrum
of a diatomic molecule. What is the anharmonicity constant of the molecule?

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

 0  2  2e (1 - 3xe) cm-1 v  0  v  2 (v 2)
 0  3  3e (1 - 4xe) cm-1 v  0  v  3 (v 3)

Ans.: 0.03

Q2. What are the total number of vibrational modes and stretching vibrations in
methanol?

Ans. 12 and 5
Q3. What is the sum of Δε for a molecule in the ground state electronic state?

E Morse  Deq (1  e  a ( r  re ) ) 2
Q4. The fundamental and first overtone transitions of 14N16O are centered at
1876.06 cm−1 and 3724.20 cm−1, respectively. Calculate the equilibrium
vibration frequency, anharmonicity constant and the exact zero point energy.

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

 0  2  2e (1 - 3xe) cm-1 v  0  v  2 (v 2)
 0  3  3e (1 - 4xe) cm-1 v  0  v  3 (v 3)

Ans. ωe = 1903.98 cm−1

χe = 7.3 x 10 −3

Zero point energy = 948.5 cm −1

v  (v  1) e - (v  1)2 exe cm1

2 2
IR Spectroscopy: Home Assignment