Rotational Raman spectroscopy

Gross selection rule:

anisotropic polarization
(example: H-H)

Specific selection rules:

∆J = +2 (Stokes lines)
∆J = -2 (anti-Stokes lines)

Experimental
setup:

laser Nils Walter: Chem 260

 The vibration of molecules

Morse potential
1
V = k ( R − Re ) 2
2
Solution for the harmonic
oscillator:
 1
E v =  v +  hν
 2
A B B 1 k
ν=  
2π  µ 
m A mB
effective mass µ= zero point energy
m A + mB Nils Walter: Chem 260
 Vibrational transitions:
Infrared spectroscopy

Gross selection rule:

the electric dipole
moment of the
molecule must change
during the vibration

1 k
ν=   ⇒ 300-3000 cm-1 = Infrared
2π µ Nils Walter: Chem 260
 Specific selection rules
In reality: anharmonic oscillator

xe = anharmonicity
constant
∆v = ±1, ±2, ±3,...

D0
2
 1  1 Deq
Ev =  v + hν −  v +  hνxe
∆v = ±1  2  2

∆E
N upper −
=e kT
N lower
Nils Walter: Chem 260
 The vibrating rotor
∆J
∆ = -1 ∆J
∆ = +1

Born-Oppenheimer approximation:
The energies of rotations and vibrations are so
different that Etotal = Erot. + Evib. Nils Walter: Chem 260
Vibrations of polyatomic molecules:
How many are there?
Each atom can move along one of three axes:
⇒ 3N possible displacements (= degrees of freedom)
⇓
Three degrees of freedom correspond to translational motion:
⇒ 3N - 3 degrees of freedom left
⇓
Three (/two) degrees of freedom correspond to rotations:
⇒ 3N - 6 (3N - 5 for linear molecule) degrees of freedom left for vibrations

Nils Walter: Chem 260

 Vibrations of polyatomic molecules:
How can one describe them?
CO2: C-O stretch vibrations are NOT
independent (cannot be excited
independently)
Normal stretch modes (linear
combinations of C-O stretches) ARE
independent

inactive

active
antisymmetric:
symmetric
greenhouse gas
Nils Walter: Chem 260
 What is all this good for???

-NO2 group
C

Carboxylic acid
Benzene C-H stretch
C

O-H stretch
Conjugated
← low energy→
→

Identification of organic compounds!!!

Nils Walter: Chem 260