 ROTATIONAL SPECTROSCOPY

(Microwave region)
 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

Polyatomics (>= 3)
3D-body rotation

Convention:
A-axis is the “unique” or
“figure” axis, along which
lies the molecule’s
defining symmetry

principal axes (orthogonal): A, B, C

3 principal moments of inertia: IA, IB, IC
Molecules are classified in terms of the relative values of IA,
IB, IC
 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

Symmetric Rotor

For symmetric rotor, the unique moment of inertia that about the principal
axis is denoted as 𝐼‖ and the other two as 𝐼⊥ .

• If 𝐼‖ > 𝐼⊥ , the rotor is classified as oblate (C6H6); if 𝐼‖ < 𝐼⊥ , it is

classified as prolate (CH3Cl).
 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
2
m1m2r
I  r 2

m1  m2
m1m2
  Reduced mass
m1  m2
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 2 Ic
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  2B 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= −
2ℎ𝑐𝐵 2
 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

Microwave Oven
Do you know what is the basic principle of
cooking in a microwave oven !!