Rotational (microwave) spectroscopy

Moment of inertia (I) defines rotational motion

For a body consists of N point masses

𝑁
𝐼 =∑ 𝑚𝑖 𝑟 2
𝑖
r1
v
m1

𝑖=1

Axis of rotation
For a molecule I defines the energy gap
between ground & excited states of rotational energy

(Axis of rotation passing through center of gravity)

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
mutually orthogonal and pass through
principal moments molecule’s centre of mass
of inertia
Classification of molecules based on the mutual
relationship of IA, IB & IC

H---Cl O=C=O H--CΞC—H

i) Linear
IA = 0, IB = IC

ii) Spherical top SF6

IA = IB = IC ≠ 0
iii) Symmetric top
F Cl
ammonia benzene
C B
H H H Cl Cl

IB = IC ≠ IA, IA ≠ 0

iv) Assymetric top O H

C=C
H
H H H Cl

IA ≠ IB ≠ IC

Each class of molecules has a distinct pattern of rotational spectra

Expression of I in a diatomic molecule:
Assumption: rigid rotor Molecule: diatomic Type: Linear (IA = 0, IB = IC = I)

m1 m2
ro ro = r1 + r2 ...............................eq. 1
m1r1 = m2r2 ..........................eq. 2
F H

C The moment of inertia around point C is defined by:

I = m1r12 + m2r22 .............................eq. 3
r1 r2

I = m1m2ro2/(m1+m2) = μ ro2 μ is called the reduced mass of the system

Since HF is linear molecule, IA = 0 and IB = IC = I = μ ro2

I contains the information of mass of the diatomic molecule and bond length!
Effect of I on rotational spectra:
εJ
Rotational energy
energy states of molecules
ε2
ε1
ε0 ground level
Continuous Discrete
(classical physics) (quantum physics)

With the help of Schrodinger equation, the expression of any such quantized
energy
level εJ2can be given as:
εJ = h J(J+1)/8π2I joules where J = 0, 1, 2, 3 ..... etc
εJ = hJ(J+1)/8π2Ic cm-1 ........................eq. 4 J= rotational quantum number
Alternatively, eq. 4 can be expressed as:
εJ = BJ(J+1) cm-1 where B = h/8π2Ic cm-1 & I = IB = IC = μro2 .................eq. 5

B is called rotational constant B contains information of I and hence the mass

and bond length of the molecule
Values of rotational energy levels (εJ ):

εJ = BJ(J+1) cm-1 J= rotational quantum number B = rotational constant

Value of J Value of εJ (cm-1)

0 0
1 2B
2 6B
3 12B
4 20B
5 30B
-- --
etc so on
 Spacings of rotational energy levels (εJ ):
8 10 12 14 16 18 20 ε4 20B
Selection rule for rotational spectroscopy:
Allowed ΔJ = ± 1 (any other ΔJ is forbidden)
ΔE4 = 8B

ε3 12B
B cm-1

Δ ε ( from J to J+1)
ΔE3 = 6B
= εJ+1 – εJ cm-1
ε2 6B
6

ΔE2 = 4B = B(J+1) (J+1+1) – BJ(J+1) cm -1

0 2 4

ε1 2B = 2B(J + 1) cm -1
ΔE1 = 2B
ε0 0B

putting J = 0, 1, 2, 3, 4, 5 …. etc we get Δε = 2B, 4B, 6B, 8B, 10B, 12B…….etc

 The expected rotational spectra:

ε4 20B
8 10 12 14 16 18 20

Intensity (arbitrary
ΔE4 = 8B

ε3 12B
B cm-1

unit)
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

s ity
n

de
e
nt

cre
g i 2B
sin

asin
e a 2B 2B
r

g
inc

int
2B

en
sit
y
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)

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

If population at J = 0 is denoted by N0, then the following distribution applies to

=
rotational spectroscopy:

…eq. 1 [KB: Boltzmann const, T: Kelvin]

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)

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

and NJ ∝ (2J+1) …eq. 2

According to quantum physics, each J level is 2J+1 degenerate

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.

The relative population (relative intensity) ∝ …eq. 3

Equation 3 makes it possible to estimate atmospheric temperatures of planets through

remote sensing*!

*Ref: Vibrational-rotational spectroscopy for planetary atmosphere, NASA Conference Publication 2223, Volume-1, March 17-19, 1980, USA
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
1. Predict which of the following molecules will show rotational spectroscopy?

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

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

cyclobutane, CF4, SO2, NF3, O2, PH3

3. In the year 1950, a group of scientist measured the first line in the rotation

What was their calculation in Å?

spectrum of CO as 3.842 cm-1. Hence they calculated the bond length of CO.

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

and O = 15.99]
4. Assume that the Mangalyaan launched by ISRO in 2013, has captured the
following first 3 lines of the 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