1

Rotational Spectroscopy
Outlines
- Rotation of diatomic molecules : rigid rotor model
- Classical physics for rigid rotor rotation
- Quantum mechanics of rigid rotor rotation
- Rotational operators
- Rigid rotor wavefunctions
- Rotational energy levels
- Energy levels, Transition & Rotational constant
- Rotational Spectra

Introduction
Some spectral lines in rotational spectrum of CO
A molecule with

permanent electric
dipole is microwave
active.

N. W. B. Stone, Applied Optics, 1978.

- Rational spectrum contains many peaks (many transitions).

-

Spectral lines are of almost equal spacing.

Slight changes in their relative intensities are observed.

The bond length can be determined from the spectrum.

Rotation of diatomic molecules : Rigid rotor model

Two atoms (mass m1 and m2) are connected with a fixed distance
and spin around the center of mass (CM).

Rigid implies the bond length

is fixed because no vibrational
motion of the bond.

CM

r2

r1

The molecule rotates with

rotational frequency of rot
CM : center of mass
r0: the bond length (fixed)
m1, m2 : mass

r0 (fixed)

v1, v2 : velocity (perpendicular

to r1 and r2, respectively)

Classical physics for rigid rotor rotation

Angular Momentum (L)

p
v

r
L

L rp
= 90o (r p)

Magnitude:

L rp
r p sin
r p mvr

p : linear momentum
r : radius of rotation
: angular velocity
L: angular momentum

Angular velocity () & Moment of inertia

Velocity

Momentum

Moment of inertia (I)

L m r 2
m r 2
I
I m r2

Linear

Angular

Relationship

rd
v
dt

dt

vr

p mv

L m r 2

Kinetic energy of rigid rotor rotation

1
1
2
T m1v1 m2 v 22
2
2
Rotation distance in
v 2 r0 rot

2 rot

1 cycle rot

The angular frequency

v r0
The molecule rotates at
fixed rotational frequency
rot

1
1
2 2
T m1 r1 m2 2 r22
2
2

1
1
2 2
T m1 r1 m2 2 r22
2
2
1 2
T m1 r12 m2 r22
2

Moment of inertia, I

I m1 r12 m2 r22

1 2
T I
2
1 ( I )
T
2 I
L2
T
2I

L = angular momentum

L I
The kinetic energy can be described in
terms of angular momentum and moment
of inertia.

Importance terms & Equations

Equations

Terms

I mr 2 r 2

Moment of inertia:
Angular velocity:

v r0 2 r0 rot

Angular momentum:

v
LI r
vr
r

m1m2

m1 m2

(Linear momentum, p =
mv)
Kinetic energy

2
1
1

r
KE v 2 v 2 2
2
2
r

1 ( v r)
1L

2
2 r
2 I
2

Reduced Mass

L2
KE
2I
In classical physics, the
direction or magnitude of L
can be any value.

Quantum mechanics of rigid rotor rotation

To solve the Schrdinger equation

H E
We need to set up the Hamiltonian:

H or H total T V
One need to define the kinetic and potential energy

10

ASSUMPTION
The potential energy of rigid rotor diatomic molecule is
zero:
IMPORTANCE ASSUMPTION
V 0
The Hamiltonian operator of rigid rotor diatomic
molecule corresponds to the kinetic energy operator:

H total

2
2

L
T
2
2
2I

11

Rotational operators: spherical polar coordinates

I m r m r r
2
1 1

2
2 2

2
0

m1m2

m1 m2

v 2 r0 rot r0
L I

V 0

H total T V
V
2

where 2 is the Laplacian Operator

In Cartesian coordinates

2
2
2

2 2 2 2
x y
z

12

Transformation to spherical polar coordinates

For rigid rotor model, we usually transform the 2 Cartesian coordinates

into spherical polar coordinates .
Cartesian
coordinates

Spherical polar
coordinates

( x, y , z )

(r , , )

x
y
z

0r
0
0 2
r x2 y2 z 2

z r cos
z
x r sin cos cos 1
r
y r sin sin
1 y
tan

13

Transform the 2 Cartesian coordinates into spherical polar coordinates

0
r
2
1

2
2 2
r
2
sin
2 2
r r
r r sin
r sin 2

1 1

1 2

2
sin

2
2
r0 sin
sin

Because of rigid bond

(fixed bond length)

r r0

2
2
2

H T

sin
2
2
2
2
2 r0 sin
sin

2 1

1 2

sin
2
2
2 I sin
sin

I r02

14

After transformation, we get:

2
2

T
sin
2
2
2 I sin
sin
2
L
Because
T
2I

The square of angular momentum operator becomes

2

L
sin
2
2
sin
sin

L2 is important operator in the solution for energy levels and

wavefunctions of rigid rotor in the Schrdinger equation.
Another importance of the angular momentum is Lz (the z-component)

L z i

15

Thus, the Hamiltonian operator in the Schrdinger equation

L2
H
2I
Another implication of the rigid rotor (fixed bond length) is the
wave function depends on and :

(r , , ) ( , )
H ( , ) E ( , )

16

Rigid rotor wavefunctions

H ( , ) E ( , )

0 : 0 2

2
2

H
sin
2
2
2 I sin
sin

The full wavefunctions

Reduce to

(r , , ) R (r )Y ( , )
( , ) Y ( , )

Consider only the

angular part of the
wavefunctions

2 1

1 2
Y ( , ) EY ( , )

sin
2
2
2 I sin
sin
Set the Schrdinger Equation equal to zero and

2 I sin 2 / 2

Y ( , ) 2Y ( , ) 2 I
2
sin

sin
EY ( , ) 0
sin

2
2

17

From the previous slide

Y ( , ) 2Y ( , ) 2 I
2
sin

sin
EY ( , ) 0
sin

2
2

Rearranging the differential equation separating the -dependent terms

from the -dependent terms:
2

2I

Y ( , )
2
sin sin 2 sin E Y ( , ) 2

Only

Only

the Schrdinger equation can be solved using separation of variables.

Y ( , ) ( ) ( )

18

From the previous slide

2

( ) ( )
2
sin sin sin ( ) ( )
2

2 IE
2

LHS operator does not operate on () and RHS operator does not
operate on ().
2

( )

( )
2
( ) sin
sin
sin ( ) ( ) ( )


2

Devide by () ()
2
sin d
d( )
1

( )
2
sin

sin

( ) d
d
( ) 2

Only
Only
Each side of the equation must be equal. Let give it to m2

19

From the previous slide

2
sin d
d( )
1

( )
2
2
sin

sin

( ) d
d
( ) 2

sin d
d( )
2
2
sin

sin

( ) d
d

1 2 ( )
2

m
( ) 2

(I)

(II)

20

Let solve Eq.(II)

1 2 ( )
2

m
( ) 2
2 ( )
1
2

m
2
( )
( ) Am e im or A m e im
Consider periodicity conditions

( 2 ) ( )

The solution for () is :

1 im
( )
e ; m 0, 1, 2,..
2
Normalization constant

21

The Legendre Equation

For solving Eq.(I),

sin d
d( )
2
2
sin

sin

( ) d
d
Change variables:
Since:

x cos , ( ) P( x),

dx
d
sin

1 x 1

sin 2 1 cos 2 1 x 2
The eq(I) is transformed into:
2
2

d
d
m
2
(1 x ) 2 P ( x) 2 P ( x)
P( x) 0
2
dx
dx
1 x

The Legendre Equation

22

Associated Legendre polynomials

The solutions of the Legendre Eq. are :

( ) Am PJ|m| (cos )
PJ|m| (cos )

The Associated Legendre polynomials

Normalization constant

2 J 1 J | m | !
Am

2 J | m | !

2 J 1 J | m | ! |m|
( )
PJ (cos )

2 J | m | !

23

The Associated Legendre polynomials

PJ|m| (cos )

; J 0, 1, 2,... and m 0, 1, 2,..

P00 (cos ) 1
P10 (cos ) cos
P11 (cos ) sin
1
P (cos ) (3 cos 2 1)
2
P21 (cos ) 3 sin cos
0
2

P2 2 (cos ) 3 sin 2

24

Spherical harmonic wavefunctions

Y ( , ) YJm ( , ) ( ) ( )
1 im
2 J 1 J | m | ! |m|
P
(cos

)
e

J
2 J | m | !
2

( )

( )

2 J 1 J | m | ! |m|
PJ (cos ) e im

4 J | m | !

YJm ( , )

; J 0, 1, 2,... and m 0, 1, 2,..

25

The wavefunctions for J =0, 1, 2

1
Y ,
4 1/ 2
0
0

Y10 ,

1/ 2

3
Y ,

cos
1/ 2

sin e i

1
1

16

Y20 ,

1/ 2

5
Y ,

16
1
2

Y2 2 ,

15

32

3 cos

1/ 2

sin cos e i
1/ 2

sin 2 e 2i

26

Rotational energy levels of rigid rotor

The Hamiltonian (Laplacian) operator:
2

H T
2I

1

1 2

sin
2
2
sin
sin

The spherical harmonic wavefunctions with Legendre functions :

2 1

1 2
Y ( , ) EY ( , )

sin

2
2
2 I sin
sin
2 J 1 J | m | ! | m|
Y ( , )
PJ (cos ) e im

4 J | m | !
m
J

Because YJm ( , ) are Eigenfunctions of H

solving for this Schrdinger gives the quantized J(J+1) result :

2

H YJm ( , )
J ( J 1) YJm ( , )
2I
2
E
J ( J 1)
2I

, J 0,1,2 ,...
J is Rotational
quantum number

27

Energy levels, Transition & Rotational constant

2
EJ
J J 1 BJ ( J 1) , J 0,1,2 ,...
Energy levels:
2I
2
h2
B
2
in Joule
2 I 8 I
Rotational constant :
B
B
in cm-1
hc
J = 0 there is no rotational energy at
ground state.
Energy levels
EJ
J
0
0
1
2B
2
6B
3
12B
4
20B

Energy levels are not equally

spaced.

28

States of the system (Degeneracy)

Because each J value has mJ = 2J+1 values
State of the system:

-mJ , mJ+1 ,, 0, 1, 2, ...+ mJ-1+ mJ

J
3

12B

mJ -3

-2

-1

2
1
0

3
6B

mJ
mJ
mJ

-2

-1
-1

0
0
0

1
1

2
2B
0

29

YJm ( , ) are also Eigenfunctions of L2 and L z

For L2 :

L2YJm ( , ) 2 J ( J 1) YJm ( , )
2

L
sin
2
2
sin
sin
2

L2 2 J ( J 1)

L J ( J 1)

For Lz :

L zYJm ( , ) mJ ( J 1) YJm ( , )

Lz i

Lz m

Lz mh

L J ( J 1)

30

In QM, rotational motion is quantized not continuous.

Only certain states of motion are allowed that are
determined by quantum numbers J and m.
J determines the length of the angular momentum
vector
L J ( J 1)
m indicates the orientation of the angular
momentum with respect to z-axis
Lz m

31

2
1
0

m
32

EJ
E J BJ ( J 1)

10
-1 -2
-3

10
-1 -2

1 0
-1
0

12B

L
L J ( J 1)

12h

6B

6h

2B

2h
h

Lz m
3h
2h
h
0
h
2h
2h
2h
h
0
h
2h
h
0
h
0

Lz mh

32

Rotational Transitions
Change in quantum number:
Selection rule:

J J final J initial

J 1

Absorption:
J 1
E J BJ ( J 1) , J 0,1,2 ,...
E E J 1 E J
B( J 1) J 2 BJ J 1
2 B( J 1)
E hvobs 2 B ( J 1)
In unit of Hz
In cm-1
wave number

vobs 2 B( J 1) / h

vobs
2 B ( J 1) / hc
c

2 B ( J 1)

2
h2
B
2
2 I 8 I
B
h
B
2
hc 8 Ic

33

(Pure) Rotational Spectra of Diatomic Molecule

Energy levels:

E J BJ ( J 1) , J 0,1,2 ,...

Transition energy :

E J J 1 2 B ( J 1)

J 1
J
01

EJJ+1

12

4B

23

6B

34

8B

45

10B

2B

2 B ( J 1)
Energy space between each transition levels: 2B

34

Energy levels for a rigid rotor.

The spectrum observed

through absorption of
microwave Radiation.

35

Why do we observe many

absorption peaks in
rotational microwave
spectrum? How many peaks
do we observe in vibrational
IR spectrum? Why ?
1)
2)

36

Ex. From the rotational microwave spectrum of 1H35Cl,

we find that the rotational constant
B 10.5934 cm -1
Determine the bond length of the 1H35Cl molecule.
Giving the masses of 1H and 35Cl are 1.008 and 34.969 amu

h
h
B 2 2 2
8 Ic 8 r0 c
h
r0
8 2 B c

8 2 (1.64 10-27

1.27 10 10 m

m1m2

1.64 10-27 kg
m1 m2
6.626 10 34 J s
kg)(10.5934 cm -1 )(2.998 1010 cm s -1 )

37

Ex. Spectral line spacing of rotational microwave spectrum

of a diatomic molecule is 3.8626 cm-1 . Determine the bond
length of this molecule.
Spectral line spacing (E) = 2B
Spectrum (cm-1)

3.8626 cm-1

vobs 3.8626 (cm -1 )

Wave number

CO

vobs 3.8626 (cm -1 ) c 1.16 1011 Hz

B hvobs / 2 3.84 10-23 J

hvobs 2 B

h2
B 2
8 I

h2
I 2 1.45 10-46
8 B

I r

m1m2

1.15 10-26 kg
m1 m2

2
0

r0 I / 1.12 10 10

Example: Using the following total energy eigenfunctions for

the three-dimensional rigid rotor, show that the J=0 J=1
transition is allowed, and that the J=0 J=2 transition is
forbidden:
M

Providing the notation

1
Y00 ,
4 1/ 2
5
0
Y2 ,

16

1/ 2

Y j jis used for the preceding functions.

3
Y10 ,

3 cos

1/ 2

cos

Assuming the electromagnetic field to lie along the z-axis,

the transition dipole moment takes the form
2

zJ 0 d YJ0 , cos Y00 , sin d

z cos

For the J=0 J=1 transition,

Y00 ,
2

1
4 1/ 2

Y10 ,

1/ 2

cos

0
0

10

cos

Y
z
J 0 , sin d
J 1

4
0

d
0

1/ 2

cos cos

3
2

cos
sin d

4 0 0

(2 ) cos 2 sin d
4
0

1
sin d
1/ 2
4

3
2

cos
sin d

2 0

d 0 2 0
0

For the J=0 J=1

transition,

Now consider

2
cos
sin d
0

Use reduction or substitution method

dz
1
sin x, dx
dz
dx
sin x

x , z cos x,

1
2
cos
x
sin
xdx

z
sin
xdx

z
sin
x

dz

z
dz

sin x
1
1
z 3 cos 3 x
3
3
2

Replace the result into the original integration

cos
0

sin d

cos 3
3

1
2
3
3
(1 1 )
3
3

From the previous derivation:

3
2

cos
sin d

2 0

10
z

For the J=0 J=1

transition,

10
z

3 2
3

2 3
3

Thus:
10
z

3
0
3

The J=0 J=1 transition is allowed.

2
cos
sin d
0

2
3

For the J=0 J=2 transition,

1
0
Y0 ,
4 1/ 2
2

16

Y20 ,

1/ 2

3 cos 1

z20 d YJ0 2 , cos YJ00 , sin d

16

d
0

1/ 2

3 cos

1 cos

1
sin d
1/ 2
4

3
d

(
3
cos
sin cos sin )d

5
3

(
3
cos
sin cos sin )d

4 0

d 0 2 0
0

Let consider by dividing into two separate

terms:
3
3
cos
sin d

cos sin d
0

Consider

For the J=0 J=2

transition,

cos sin d

3
3
cos
sin d

Use the substitution method (similar to the previous one)

dz
1
x , z cos x,
sin x, dx
dz
dx
sin x
1
3 4
3

3
3
3
4
3
cos
x
sin
xdx

3
z
sin
xdx

3
z
sin
x

dz

cos
x

4
4
sin x

Replace x with and integrate from 0 to , we get:

3
4
3
cos

sin

cos

0
4
3

3
((1) 4 14 ) 0
4

Do the same for

cos sin d
0

1
1 2
1
2
cos
x
sin
xdx

z
sin
x

dz

cos
x0

2
2
sin x

For the J=0 J=2

transition,

Thus:

3
3
cos
sin d 0

cos sin d 0

From the previous derivation:

20
z

5
3

(
3
cos
sin cos sin )d 0

4 0

Therefore:

z20 0

Thus, the J=0 J=2 transition is forbidden.

45

Home Work 2
1. Spectral line spacing of rotational microwave spectrum
of OH radical is 37.8 cm-1 . Determine the OH bond
length (in pm unit) and moment of inertia (in kg m 2)
mO = 15.994 amu
Spectrum (cm-1)

mH = 1.008 amu

37.8 cm-1

2. Use the bond length of diatomic molecules in Table to

predict line spacing (in cm-1 unit) of rotational microwave
spectrum.
molecule bond length (pm)
HF

91.7

HI

161

HCl

128

HBr

141

46

3. Determine the bond length of these diatomic gases in

Table and arrange them in order of increasing the bond
length.
Bond length (pm)
B (cm -1 )
OH

37.80

ICl

0.11

ClF

1.03

AlH

12.60

4. Using the information in the Table to calculate the ratio

between the transition energy of rotation from J=0 to J =1
and vibration from n=0 to n=1 for H2
Atomic mass

1.008 amu

Bond length of H2

74.14 pm

Erotation , J 0 J 1

Force constant of H2

575 N/m

Evibration ,n 0n 1

47

Why do we observe many

absorption peaks in
rotational microwave
spectrum? How many peaks
do we observe in vibrational
IR spectrum? Why ?
1)
2)

48

Reason 1) Vibration spectrum has only one peak because

Based on harmonic oscillator model of diatomic molecule,
energy-level spacing between adjacent levels is the same for
all values of the vibrational quantum number. With the
selection rule (n=1) , all transitions have the same
frequency. So we expect only one intense peak for
vibrational spectrum.
1
Vibrational energy level: En (n ) hv
2
n

Evib
(harmonic)

En-En-1

1/2 h

3/2 h

5/2 h

2
3

7/2 h

4
3

2
h

49

Rotational microwave spectrum has many peaks

because the rotational energy levels are not equally
spaced in energy. Different transitions give rise to
separate peaks.
Rotational energy level
2
EJ
J J 1 BJ ( J 1) , J 0,1,2 ,...
2I
Energy levels
EJ
J
0
0
1
2B
2
6B
3
12B
4
20B

Energy levels are not equally

50

Reason 2)
Nearly all the molecules in a macroscopic sample are in
their ground vibrational state (n=0) at room temperature
(even at 1000K). Only the n = 0 n = 1 transition is
observed in vibrational spectroscopy.
N1 g1 hv / k BT

e
Boltzmann population
N0 g0

N1/N0 is very low.

HCl, 1<J<5; 10-22- 10-21 J

51

In case of rotational transition, Erotation < kBT,

many rotational energy levels can be populated.
4.14X10-21 J
Boltzmann distribution

N J 1 g J 1 E / k BT

e
NJ
gJ

52

Questions
1) In the microwave spectroscopy, is the photon energy
sufficient to excite vibrational transitions?
2) In the IR spectroscopy, is the photon energy sufficient to
excite rotational transitions?

53

Vibrational transitions usually also involve

rotational transitions.

54

Ex. Consider (Cl2) adsorbed on a platinum surface. The ClCl bond length is 2.00 . Assuming Cl-Cl can be modeld by
a rigid rotor. Calculate the wave number of rotational
transition of Cl2 from ml= 3 to ml= 6, how many rotational
spectral lines do we observe?

m1m2

m1 m2

= 2.94X10-26 kg

h2
h2
B 2 2 2
8 I 8 r0
B
B
hc

= 4.72X10-24 J

= 0.238 cm-1

E J B J ( J 1)

ml= 3 J = 3 and ml= 6 6

Selection rule:

55

J 1

E 2 B ( J 1)

J
34
45
56

E (cm-1)
1.90
2.38
2.85

For the rotational transition from m l= 3 to ml= 6, we

expect to observe three rotational spectral lines.
Calculate energy gap or spacing between spectral lines in
cm-1 unit?
energy spacing between spectral lines
2 B 2 0.238 0.476 cm -1

56

57

58

Centrifugal Distortion

59

Rigid rotor wavefunctions

H ( , ) E ( , )

0 : 0 2

2
2

H
sin
2
2
2 I sin
sin

Consider only the angular part of the wavefunctions

( , ) Y ( , )
Let

( , ) ( ) ( )

2
EJ
JJ
2I

(r , , ) R(r )Y ( , )

Set the Schrdinger Equation equal to zero:

sin d
d 2 IE 2
sin
2 sin
d
d

the Schrdinger equation can be solved using separation of variables.

Solution Assuming the electromagnetic field

z the
cos zaxis,
to lie along
, and the
transition dipole moment takes the form
2

zJ 0 d YJ0 , cos , Y00 cos sin d

For the J=0 J=1 transition,

Y00 ,

10
z

1
4 1/ 2

Y10 ,

1/ 2

3
3 cos
2
d

cos

sin

4 0
2
3

0
3

cos

3
0
3

61

The Hamiltonian Operator can now be written:

2

2r02

1
Y ( , )
1 2Y ( , )
sin

EY ( , )
2
2
sin

sin

62

63

64

65