Applied

Spectroscopy

Rotational Spectroscopy

Recommended Reading:
1. Banwell and McCash: Chapter 2
2. Atkins: Chapter 16, sections 4 - 8
 Aims
In this section you will be introduced to
1) Rotational Energy Levels (term values) for diatomic molecules and
linear polyatomic molecules
2) The rigid rotor approximation
3) The effects of centrifugal distortion on the energy levels
4) The Principle Moments of Inertia of a molecule.
5) Definitions of symmetric , spherical and asymmetric top
molecules.
6) Experimental methods for measuring the pure rotational spectrum
of a molecule
Microwave Spectroscopy - Rotation of Molecules
Microwave Spectroscopy is concerned with transitions between
rotational energy levels in molecules.

Definition d
Electric Dipole: p = q.d +q -q
p

Most heteronuclear molecules possess

Cl H a permanent dipole moment
-q +q e.g HCl, NO, CO, H2O...
p

Molecules can interact with electromagnetic radiation, absorbing or

emitting a photon of frequency ω, if they possess an electric dipole
moment p, oscillating at the same frequency
Gross Selection Rule:
A molecule has a rotational spectrum only if it has a permanent
dipole moment.

Rotating molecule

_ _
dipole moment p

+ +

_ _
+ +

Homonuclear molecules (e.g. O2, H2, Cl2, Br2…. do not have a

permanent dipole moment and therefore do not have a microwave
spectrum!
 General features of rotating systems
m
Linear velocity v angular velocity
v = distance ω = radians
time O r
time

v = ω ×r
Moment of Inertia I = mr2.
A molecule can have three different moments of
inertia IA, IB and IC about orthogonal axes a, b and c.

I = ∑ miri2
i
R
Note how ri is defined, it is
the perpendicular distance
from axis of rotation
ri
 Rigid Diatomic Rotors
ro
IB = Ic, and IA = 0.
m1 m2 C = centre of gravity.
C
Express I in terms of m1,
r1 r2
m2 and r0.

r1 + r2 = r0 (1)
(2 ) m1 ⋅ m2 2
from m1 ⋅ r1 = m2 ⋅ r2 I= r0 = μ ⋅ r02
m1 + m2
I = m1 ⋅ r12 + m2 ⋅ r22 (3)
Derive this expression
NOTE:
Units of I = kg.m2.
μ = reduced or effective mass of the molecule
 Energy and Angular Momentum
Angular momentum about axis a is JA = IAωA
Energy of a body rotating about an axis a with
constant angular velocity !1 a is 2
Ea = IA ωA
2

A body free to rotate about all three axes has a total

rotational energy
1 2 1 2 1
E = IA ωA + IBωB + ICω2C
2 2 2
And a total angular momentum given by

J2 = J2A + JB
2
+ J2C
Recall that J is
= (IA ωA )2 + (IBωB )2 + (ICωC )2 a vector
 Energy Levels of a Rigid Diatomic Rotor
For diatomic molecule IB = Ic = I and IA = 0 so:

2 2 2
1 2 1 J J J
E = IBωB + ICω2C = B + c =
2 2 2IB 2Ic 2I

Can find quantum energy levels using Correspondence

Principle:
J2 → J(J + 1)⋅  2 =
J(J + 1) ⋅ h2

4 π2
1. Rotational energy for a rigid diatomic rotor is quantised

J(J + 1)⋅ h2 Units: Joules

EJ =
8 π 2I J = 0, 1, 2, 3, …
= rotational quantum number
 Energy Levels of a Rigid Diatomic Rotor
2. Rotational energy is usually expressed in units of cm-1.
E
Recall E = hν = h ⋅ c ⋅ ~
ν therefore ~ν = ε = then
h⋅c
EJ h2 J(J + 1) h
εJ = = = J(J + 1) cm-1
h ⋅ c 4 π 2 ⋅ 2I ⋅ hc 8π 2Ic

B - Rotational Constant, units cm-1

h 
ε J = B ⋅ J(J + 1) where B=
2
=
8π Ic 4 πIc

εJ gives the allowed energy levels of the rigid rotor

(in cm-1).
B can be determined experimentally by spectroscopy
 Notation: Rotational Term F(J)
The energy of a rotational state is normally reported as
the Rotational Term, F(J), a wavenumber divided by hc
"E
F(J) ! ! J = = B # J ( J +1)
hc
Ritz Combination Principle
The wavenumber of any spectral line is the difference
between two terms. Two terms T1 and T2 combine to
produce a spectral line of wavenumber.

~ ΔE
ν = T1 − T2 =
hc
Energy Levels of a Rigid Diatomic Rotor
ε J = B ⋅ J(J + 1) J = 0, 1, 2, 3 .....
6 42B

F(J) (= εJ)
J
5 30B

4 20B

3 12B

2 6B
1 2B
0 0
Can we predict nature of a microwave rotational spectrum?
 Rotational Transitions in Rigid Diatomic Molecules
Selection Rules: J=
1. A molecule has a rotational spectrum 5
only if it has a permanent dipole moment.
2. ΔJ = ± 1 +1 = adsorption of photon,
-1 = emission of photon. 4

Transitions observed in absorption spectrum. 3

J = 0 è J=1
2
ν = Δε J = ε J=1 − ε J=0 = 2B − 0 = 2B cm-1
~
1
J = 1è J = 2 0
ν = Δε J = ε J=2 − ε J=1 = 6B − 2B = 4B cm-1
~ 6B
4B 8B
2B 10 B
In general νJ→ J+1 = 2B(J + 1) cm-1
~

Spacing between lines in spectrum = 2B cm-1

 Rotational Spectra of Rigid Diatomic Molecules

Line separation in the rotational spectrum of HCl is ≈ h

B=
21.2 cm-1 è B = 10.6 cm-1; IHCl can be found from
8 π 2Ic
m1 ⋅ m2 2
Once IHCl is known, then rHCl (the bond I= r0 = µ ⋅ r02
length) can be determined from m1 + m2

Need to know mH and mCl, but these are known and tabulated.
 Summary so far:
1.Microwave spectroscopy is concerned with transitions
between rotational energy levels of molecules
2. General features of rotational systems: I, ω, μ

I = ∑ miri2 m1 ⋅ m2 2
I= r0 = μ ⋅ r02
i m1 + m2
3. Energy Levels of a rigid diatomic rotor
h
F(J) ≡ ε J = B ⋅ J(J + 1) B=
8π 2Ic
J = 0, 1, 2, ….; B = rotational constant, units cm-1

4. Selection rules: (1) permanent dipole moment,

(2) ΔJ = ± 1 only
5. Spacing between lines of in rotational spectra of rigid
diatomic molecules is constant and equal to 2B cm-1.
 Why is Rotational Spectroscopy important?

1. bond lengths
From pure rotational 2. atomic masses
spectra of molecules we
3. isotopic abundances
can obtain:
4. temperature

Important in Astrophysics: Temperature and

composition of interstellar medium

Diatomic molecules found in interstellar gas:

H2, OH, SO, SiO, SiS, NO, NS,

HCl, PN, NH, CH+, CH, CN, CO,
CS, C2.
S.Taylor, D. Williams, Chemistry in Britain, 1993 pg 680 - 683
 Population of Rotational Energy Levels
N J +1 # "E & # ! J hc &
= exp % ! ( = % !
$ kT ('
Boltzmann distribution: exp
N J =0 $ kT '

Orientation of the angular momentum L is quantised. This results

in a (2J+1) degeneracy of the energy level
 Population J $ #E ' $ BJ ( J +1) hc '
! ( 2J +1) exp & " = ( +1) &% "
% kT )(
2J exp )(
Population J =0 kT

Spectral Line Intensity ∝ Population

 Example: Rotational Spectrum of HCl
ro

m1 m2
C
r1 r2

B = 10.6 cm-1,
T = 300K
 Maximum Value of J
At what value of J will the
intensity be a maximum,
at a given temperature?

We can find the value of Jmax by finding the value of J that

maximises the population:
$ #E ' $ BJ ( J +1) hc '
Population ! ( 2J +1) exp & " = ( 2J +1) exp & "
% kT )( % kT )(

Differentiate w.r.t. J and set equal to zero for a maximum. This gives
kT 1
Jmax = −
2hcB 2
must round this value to the nearest integer (J can only be an integer)
Bond lengths and Rotational Constants of some
Diatomic Molecules

Note effect of r0 and m on the rotational constant B.

I ∝ r0 and m and B ∝ 1/I
 Effect of Isotope Substitution

From spectra we can obtain:

bond length or atomic weights
and Isotopic Abundances
 Effect of Isotope Substitution on Spectra
For 12C16O B = 1.92118 cm-1.
13C16O B = 1. 83669 cm-1.

B=
h B' h 8 π 2I' ' c I' ' µ' '
= = = = 1.046001
8π 2Ic 2
B' ' 8 π I' c h I' µ'
Atomic weight 12C = 12.0000, 16O = 15.9994 13C = 13.0007,
12C16O
5 13C16O
J=

2
1
0
 Non-Rigid Rotor
For a non-rigid rotor the bond-length increases as the angular
velocity increases Centrifugal Distortion
h 1 B decreases as J
B= B∝
8π 2Ic r2 increases

For a non-rigid rotor

ε J = B ⋅ J(J + 1) − D ⋅ J2 (J + 1)2

D - Centrifugal Distortion constant

(stiffness constant)
units: cm-1.

Like B, D depends on the molecule

 rigid rotor non-rigid rotor
ε J = B ⋅ J(J + 1) ε J = B ⋅ J(J + 1) − D ⋅ J2 (J + 1)2
J= 5

2
1
0

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

ε J = B ⋅ J(J + 1) − D ⋅ J2 (J + 1)2

~
ν = ε J +1 − ε J = 2B ⋅ (J + 1) − 4 D ⋅ (J + 1)3
The rigid rotor selection rules still apply, i.e. ΔJ = ±1
Typical values: B ~ 1 - 10 cm -1 and D ~ 10-3 – 10-2 cm-1.

D can be related to the 4B3

D=
vibrational frequency of the molecule ν2
~
vib
 Summary
1. Population of energy levels:
Boltzmann Distribution
degeneracy of rotational states

2. Efect of bond length and mass

on rotational constant of diatomic
molecule

3. Efect of isotopic substitution

atomic weights and
isotopic abundances

4. Non-rigid rotor
D - centrifugal distortion constant