Statistical Molecular

Thermodynamics
Christopher J. Cramer
Video 1.6
Diatomic Molecular Energy Levels

How is energy stored in a Molecule?

Electronic energy. Changes in the kinetic and
potential energy of one or more electrons associated
with the molecule. Same as many-electron atoms.
Kinetic Energy:
Translational energy. The molecule can move
(translate) in space. Same particle-in-a-box solutions
as for atoms.
Rotational energy. The entire molecule can rotate in
space. Schrdinger equation: Rigid-rotator.
Vibrational energy. The nuclei can move relative to
one another in space. Schrdinger equation:
Quantum-mechanical harmonic oscillator.

Rotational Energy LevelsDiatomics

moment of inertia: I = m1R12 + m 2 R22

The Schrdinger equation for the rigid

rotator provides energy levels:

h2
J = J ( J + 1)
2I

J = 0,1,2,K

The degeneracy of a given level, gJ, is:

g J = 2J +1

6h 2
3 =
I
3h 2
2 =
I
h2
1 =
I
0 = 0

J=4

J=3
J=2
J=1
J=0

rotational energy

10h 2
4 =
I

Vibrational Energy Levels

m1

m2

Vibrational motion is modeled as a harmonic oscillator, with

two masses attached by a spring

careful, nu and vee

R
Solving the Schrdinger equation for the QM
harmonic oscillator yields the energy levels:

v = h v +
2

v = 0,1,2, K
The levels are non-degenerate,
that is gv=1 for all values of v.

energy

The energy levels

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

Re

The energy levels are equally

spaced by h.
The energy of the lowest state
is NOT zero. The difference is
called zero-point energy.
1
R

0 = h
2

Bond Dissociation energy

m1

V(R)

Energy

The dissociation energy and the

electronic energy of a diatomic
molecule are related by the zero
point energy,

m2

negative of the ground-state electronic energy

D0

h
De = D0 +
2

De

dissociation energy

=0

De

For example, for H2(g):

R
Re

De = 458 kJ mol1

The zero-point vibrational energy: h/2

D0 = 432 kJ mol1

= 4401 cm1 = 52 kJ mol1