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Statistical Molecular Thermodynamics: Christopher J. Cramer

The document discusses the molecular partition function, which describes the probability distribution of possible energy states for a molecule. It can be written as the product of partition functions for different degrees of freedom like translation, rotation, vibration, and electronic states. Each partition function is a summation over energy states with a Boltzmann factor. Energy states that have the same energy are degenerate levels associated with different wave functions, and the degeneracy is included in the partition function expression. Examples are given for the vibrational and rotational partition functions.

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51 views6 pages

Statistical Molecular Thermodynamics: Christopher J. Cramer

The document discusses the molecular partition function, which describes the probability distribution of possible energy states for a molecule. It can be written as the product of partition functions for different degrees of freedom like translation, rotation, vibration, and electronic states. Each partition function is a summation over energy states with a Boltzmann factor. Energy states that have the same energy are degenerate levels associated with different wave functions, and the degeneracy is included in the partition function expression. Examples are given for the vibrational and rotational partition functions.

Uploaded by

Alvaro
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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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

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