Vibrational-Rotational Spectroscopy

Vibrational-Rotational Spectrum of Heteronuclear Diatomic

Absorption of mid-infrared light (~300-4000 cm
-1
):
Molecules can change vibrational and rotational states
Typically at room temperature, only ground vibrational state populated but
several rotational levels may be populated.
Treating as harmonic oscillator and rigid rotor: subject to selection rules
v = 1 and J = 1


= +
field vib rot
E E E
( ) ( ) , ,
f i
E E E v J E v J = = =
( ) ( ) ( ) ( )
1 1
0 0 2 2
1 1
2
( ( = = + + + + + +

v v v BJ J v v BJ J
c

At room temperature, typically v =0 and v = +1:

( ) ( )
0
1 1 v v B J J J J = + + + (



Now, since higher lying rotational levels can be populated, we can have:


1
1
J
J
= +
=

1
1
= +
=
J J
J J

( )
0
0
2 1
2
v v B J
v v BJ
= + +
=

R branch
P branch

5.33 Lecture Notes: Vibrational-Rotational Spectroscopy Page 2


v=0
v=1
J=0
J=1
J=2
J=3
J=0
J=1
J=3
J=4

+4B +2B +8B

4B 2B 2B 2B 2B 2B
-4B -2B -6B
0

P branch Q branch
E =0
2B
6B
12B
J



By measuring absorption splittings, we can get B. From that, the bond length!

In polyatomics, we can also have a Q branch, where J 0 = and all transitions lie at
0
= . This transition is allowed for perpendicular bands: q to molecular
symmetry axis.


Intensity of Vibrational-Rotational Transitions

There is generally no thermal population in upper (final) state (v,J) so intensity should
scale as population of lower J state (J).

( , ) ( , ) ( ) = N N v J N v J N J

( ) ( )
( ) ( ) exp( / )
2 1 exp( 1 / )

= + +
J
N J g J E kT
J hcBJ J kT


5.33 Lecture Notes: Vibrational-Rotational Spectroscopy Page 3


J''
N
J''
g
J''
thermal population
0 5 10 15 20
Rotational Quantum Number
Rotational Populations at Room Temperature for B = 5 cm
-1



So, the vibrational-rotational spectrum should look like equally spaced lines about
0

with sidebands peaked at J>0.

0


Overall amplitude from vibrational transition dipole moment
Relative amplitude of rotational lines from rotational populations


In reality, what we observe in spectra is a bit different.

0




Vibration and rotation arent really independent!

5.33 Lecture Notes: Vibrational-Rotational Spectroscopy Page 4


J
J J-1 =
J=J+1
R P
Two effects:

1) Vibration-Rotation Coupling:
For a diatomic: As the molecule vibrates more, bond stretches
I changes B dependent on v.

( )
1
2
v
e e
B B = +


Vibrational-rotational coupling constant!

2) Centrifugal distortion: As a molecule spins faster, the bond is pulled apart
I larger B dependent on J

( ) 1 = +
e e
B B D J J

Centrifugal distortion term


So the energy of a rotational-vibrational state is:

( ) ( ) ( ) ( ) ( )
2
1 1
0 2 2
v 1 v 1 1
e e e
E
v B J J J J D J J
hc
= + + + + + + (




Analysis in lab:
Combination differences Measure E for two transitions with common state



Common J
( ) ( )
( )
R P
e
E E E v 1, J J 1 E v 1, J J 1
3
B 4J 2
2
= = = + = =
| |
= +
|
\ .

B

Common J ( )
R P e
1
E E B 4J 2
2
| |
= +
|
\ .

B
BB =
J
J=J-1
J=J+1
R P

5.33 Lecture Notes: Vibrational-Rotational Spectroscopy Page 5


Vibrations of Polyatomic Molecules Normal Modes

Remember that most of the nuclear degrees of freedom are the vibrations!

It was clear what this motion was for diatomic (only one!).

For a polyatomic, we often like to think in terms of the stretching or bending of a
bond. This local mode picture isnt always the best for spectroscopy.

The local modes arent generally independent of others! The motion of one usually
influences others.

EXAMPLE: CO
2
linear: 3n5 = 4 normal modes of vib.

O O C
O O C
O O C
O O C
O O C
O O C
O O C
O O C
local modes
stretch
bend
symmetric stretch
asymmetric stretch
bend
(+) () (+)
normal modes
g
+

u
+

Molecules with linear symmetry: : motion axially symmetric
: motion breaks axial symmetry
g/u : maintain/break center of symmetry

Which normal modes are IR active?

symmetric stretch
O O C
O O C
0
Q
=

asymmetric stretch
O O C
Q

not IR active IR active
O O
C
bend
Q

IR active

3n6 nonlinear
3n5 linear
C.O.M.
fixed
Not
independent!
C.O.M.
translates.
Doubly
degenerate
Perpendicular to
symmetry axis
(J = 1,0,+1)