Degeneracy

J=3 Energy only

J=2 determined by J

all mJ = -J,,+J
mJ = mJ = share the same
energy

mJ = J, J-1,, -J 2J+1 degeneracy

Selection rule: mJ = 0, 1
Nils Walter: Chem 260
 The allowed rotational transitions of a
rigid linear rotor and their intensity
Total relative
population
J = 1
2J + 1

2J + 1 B large B small
degenerate
states
increasingly
degenerate Boltzmann
distribution
N upper
E E = hBJ(J+1)
=e kT
N lower
Nils Walter: Chem 260
 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 + h
2
A B B 1 k spring
=
constant
2
m A mB zero point energy
effective =
(reduced) mass 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
= 300-3000 cm-1 = Infrared
2
Nils Walter: Chem 260
 Specific selection rules
harmonic oscillator In reality:
anharmonic oscillator
v = 1, 2, 3,...

h
D0

Deq

v = 1 xe = anharmonicity constant
2
1 1
Ev = Nils h Chem
v + Walter: v +260 hxe
2 2
 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 of these 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