Purdue University

ME 501: Statistical Thermodynamics

Lecture 18: Population Distributions
for Diatomic Molecules
Prof. Robert P. Lucht
Room 2204, Mechanical Engineering Building
School of Mechanical Engineering
Purdue University
West Lafayette, Indiana
Lucht@purdue.edu, 765-494-5623 (Phone)
October 17, 2011
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Lecture Topics
The nuclear partition function.
Rotational distributions for heteronuclear molecules.
Vibrational distributions.
Electronic distributions.
Rotational distributions for homonuclear molecules.

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The Nuclear Partition Function

Let IA and IB be the spins of the ground states of nuclei A and B (don't have
to consider excited nuclear states very often):

go, A 2 I A 1

go, B 2 I B 1

Z nuc g o , A g o, B 2 I A 1 2 I B 1

The nuclear partition function is often grouped with the rotational partition
function because of the strong influence of nuclear spin on the relative
intensities of even and odd J lines for homonuclear molecules,

Z rot Z nuc

2 I A 1 2 I B 1
rot

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Rotational Distribution for a Heteronuclear

Molecule
Boltzmann distribution law is applied separately to each mode: for the
translational mode this leads to the Maxwell velocity distribution that will be
discussed in detail later.
Rotational distribution: Assume that T >> rot, heteronuclear molecule,
electronic level with electronic degeneracy =1. Then:

g exp J / k BT
N l vJ
J

N lv
Z rot

2 J 1 exp J J 1 rot / T
T / rot

Note that the level population is proportional to (2J+1).

Determination of the rotational level with the maximum population. Assume
that J varies continuously:

dNlvJ
T
14
Template
for JBorder
0Patterned

max
dJ
2 rot
2
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Rotational Distribution for the OH Molecule

For OH in the ground electronic state, Be = 18.911 cm-1, rot = 27.2 K.
T (K)

Jmax

500

2.5

1000

3.5

1500

4.5

2000

5.5

2500

6.5

3000

7.5

Jmax rounded to
nearest halfinteger

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Vibrational Distribution
Include zero-point energy (ZPE):

g vib exp vib / k BT

1 exp vib / T
N lv
1

exp v 2 vib / T
Nl
Z vib
exp vib / 2T
N lv
exp v vib / T 1 exp vib / T
Nl
Note: ZPE contribution divides out.
Do not include zero-point energy (ZPE):

g vib exp vib / k BT

N lv

exp v vib / T 1 exp vib / T

Nl
Z vib
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Note: You get the same answer as long as you are consistent in your
treatment of ZPE.
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Electronic Distribution
Not much simplification because we dont have an analytical expression for
the energy of different electronic levels in a diatomic molecule:

gl exp lelec / k BT
Nl

N
Z elec

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Rotational Distributions for Homonuclear

Molecules: Hydrogen
For nuclei of odd mass number (fermions) the total wavefunction tot = rot
vib elec nuc must be antisymmetric with respect to exchange of nuclei:

tot x , y, z tot x , y, z
rot x , y, z rot x , y, z

odd

rot x , y, z rot x , y, z

even

vib x , y, z vib x , y, z

all v

Diatomic Hydrogen: Diatomic hydrogen has a symmetric ground

electronic level. We construct the following table:
1H
2

rot

J even

+
-

J odd

vib

elec

nuc

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+
+

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+
+

tot

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Rotational Distributions for Homonuclear

Molecules: Hydrogen
For H2 molecules with a symmetric nuclear spin wavefunction, only
rotational states with odd J are possible. For H2 molecules with an
antisymmetric nuclear spin wavefunction, only rotational states with even J
are possible.
There are a total of (2I + 1)2 = (go)2 nuclear spin states, and of the nuclear
spin states are go (go+1)/2 are symmetric, and go (go-1)/2 are
antisymmetric.
The population of the rotational levels is thus given by:
g g 1 2 J 1
NJ
o o
exp J J 1 rot / T
N
Z ( rot ,nuc )
2

odd

g g 1 2 J Patterned
1
NJ
9
exp JBorder
o o
J 1 Template
rot / T

N
Z ( rot ,nuc )
2

even

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Rotational Distributions for Homonuclear

Molecules: Hydrogen
For H2 molecules, I = 1/2 because the proton has a spin of 1/2. The
nuclear degeneracy is thus g0 = (2I+1) = 2. For H2:

Z ( rot ,nuc )

1 2 T
1
2 T
g0

2 I 1
2
2
rot
rot

2 J 1

NJ
3
exp J J 1 rot / T
N
Z ( rot ,nuc )

J 1,3,5,...

ortho H 2

NJ
2 J 1 exp J J 1 / T
1

rot

N
Z ( rot ,nuc )

J 0, 2, 4,...

para H 2

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Rotational Distributions for Homonuclear

Molecules: Hydrogen
CARS spectrum of diatomic hydrogen clearly shows the effect of nuclear
spin on the rotational level populations:

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Rotational Distributions for Homonuclear

Molecules: Nitrogen
Diatomic nitrogen also has a symmetric ground electronic level

g .

However, the nuclear spin of the 14N nucleus is I = 1, and therefore

diatomic nitrogen obeys boson statistics. Nuclei of even mass number are
bosons because the nuclear spin will be integral and the total wavefunction
tot = rot vib elec nuc must be symmetric with respect to exchange of
nuclei :

tot x , y, z tot x , y, z
rot x , y, z rot x , y, z

odd

rot x , y, z rot x , y, z

even

vib x , y, z Patterned
vib x , Border
y, z Template
all 12v

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Rotational Distributions for Homonuclear

Molecules: Nitrogen
Therefore we develop the following table:
14N
2

rot

vib

elec

nuc

tot

J even

+
-

+
+

+
+

+
-

+
+

J odd

For N2 molecules with a symmetric nuclear spin wavefunction, only

rotational states with even J are possible. For N2 molecules with an
antisymmetric nuclear spin wavefunction, only rotational states with odd J
are possible.
For N2 molecules, the nuclear spin I = 1 and the nuclear degeneracy is thus
g0 = (2I+1) = 3.
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Rotational Distributions for Homonuclear

Molecules: Nitrogen
For N2 therefore:

g g 1 2 J 1
J J 1 rot
NJ
o o
exp

N
2
Z ( rot ,nuc )
T

2 J 1
Z ( rot ,nuc )

J J 1 rot
exp

even J 0, 2, 4,

g g 1 2 J 1
J J 1 rot
NJ
exp
o o

N
2
Z ( rot ,nuc )
T

2 J 1
Z ( rot ,nuc )

J J 1 rot
exp
odd J 1,3,5,

T
Patterned

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Template 14

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Rotational Distributions for Homonuclear

Molecules: Nitrogen
The N2 CARS spectrum also shows the effects of nuclear spin coupling
with the rotational levels:

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Rotational Distributions for Homonuclear

Molecules: Oxygen

Diatomic oxygen also has an antisymmetric ground electronic level g .

For diatomic oxygen the nuclei are bosons and the total wavefunction must
be symmetric with respect to exchange of nuclei.
3

We develop the following table:

16O
2

rot

vib

elec

nuc

tot

J even

+
-

+
+

+
+

J odd

For O2 molecules with a symmetric nuclear spin wavefunction, only

rotational states with odd J are possible. For O2 molecules with an
antisymmetric nuclear spin wavefunction, only rotational states with even J
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are possible.
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Rotational Distributions for Homonuclear

Molecules: Oxygen
For 16O, I = 0, go = 1. The populations of the rotational levels are given by

g g 1 2 J 1
J J 1 rot
NJ
o o
exp

N
2
Z ( rot ,nuc )
T

2 J 1
Z ( rot ,nuc )

J J 1 rot
exp

odd J 1,3,5,

g g 1 2 J 1
J J 1 rot
NJ
exp
o o

N
2
Z ( rot ,nuc )
T

2 J 1
Z ( rot ,nuc )

J J 1 rot
exp
even J 0, 2, 4,
0
T
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Template 17
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Rotational Distributions for Homonuclear

Molecules: Oxygen
The even rotational levels are missing for the oxygen molecules, at least for
the most common isotopic species 16O2. The isotope 16O18O has both even
and odd rotational levels, however; this was how the isotope was first
discovered.

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