Statistical Molecular

Thermodynamics
Christopher J. Cramer
Video 3.7
The Molecular Partition Function

Relationship between Q and q

The probability that a member
of an ensemble is in quantum
state j is:

pj =

E j

E j
ensemble energy

Similarly the probability (j) that a

molecule is in its jth molecular
energy state is:

j =

By analogy, the probability that a

molecule is in some vibrational
state can be written as:

vib
j

We can write the

same types of
expressions for elec, trans, and
rot degrees of freedom

molecular energy

vib
j

e
j

vib
j

Further Analogies

vib

vib vib
j
j

vib
j

vib
j

vib
j

=
j

vib
j

vib
j

qvib

lnqvib
2 lnqvib
=
= k BT

elec

rot

lnqelec
= k BT
T

lnqrot
= k BT
T

trans

vib

lnqvib
= k BT
T
2 lnqtrans
= k BT
T
2

The Molecular Partition Function

The energy of a molecule is composed of translational,
rotational, vibrational, and electronic components according to:

= trans + rot + vib + elec

Leading to a molecular partition function:

q(V,T) = e

( trans + rot + vib + elec ) j

= e
i

trans,i

e
j

= qtransqrot qvibqelec

rot, j

e
k

vib,k

e
l

elec,l

Degeneracy
Partition functions can be written as summations over states.
Each state is associated with a wave function having a
corresonding energy. States that have the same energy are
called levels. The number of different wave functions that have
the same energy for a given level is called the degeneracy g.

q(V,T ) = e

j (states)

q(V,T ) = g j e
j (levels)

terms representing a degenerate

level are repeated gj times
terms representing a degenerate
level are written once and multiplied
by gj

This expression is more convenient to use in

future manipulations.

E.g., Rotational Partition Function

For allowed rotational energies for a linear molecular we have:
h2
J = J ( J + 1)
2I

J = 0,1,2,K

g J = 2J +1

So,

qrot (V,T) = e

= e J =0 / kBT + e J =1 / kBT + e J =1 / kBT + e J =1 / kBT +K

j(states)

qrot (V,T) =

g je

= 1e J =0 / kBT + 3e J =1 / kBT +K

j(levels)

more convenient to denote explicitly the degeneracy