Chapter 2:

Ensemble and Partition Functions

References:
1. “A Modern Course in Statistical Physics”, L. Reichl, 2ed, Ch.
7.A on Ensembles; 7.B on microcanonical ensemble; 7.G on
grand canonical ensemble.
2. On molecular quantum mechanics and spectroscopy:
“Molecular Quantum Mechanics”, Peter W. Atkins and
Ronald S. Friedman;
“Quantum Chemistry”, Ira N. Levine;
“Spectra of Atoms and Molecules”, Peter F. Bernath.
3. Nuclear Spin Statistics:
“Molecular spectra and molecular structure: v1: Spectra of
diatomic molecules”, Gerhard Herzberg, Chpater III.2.f, for
diatomic molecules;
“Molecular Symmetry and Spectroscopy”, Philip R. Bunker
and Per Jensen, 2ed. Chapter 8, for polyatomic molecules.
 Ensembles
Ensemble: A large collection of identical unites or replicas of a system, represents all
possible configurations of the system and the probability of realizing each
configuration. Properties of ensemble members depend on a few observable
parameters. They are usually in statistical equilibrium.

A mathematical expression for ensemble: ρ(XN, t), where XN, is the state vector for N
particles, t is time, and ρ is density function – first proposed by W. Gibbs. [Reichl,
P296].

Ensemble provides a theoretical concept by

which the microscopic properties of matter
can be related to the corresponding
macroscopic (thermodynamic) system
properties: The averaged value for a property
of the ensemble corresponds to the time-
averaged value for the corresponding
macroscopic property of the system.
 Ensembles
Three general types of ensembles, in order of increasing complexity:
Summary of Ensembles
ensembles Microcanonical Canonical Grand canonical
Variables
(suppressed
E, N, V T, N, V T, μ, V
constant for
ensemble)
Number of Canonical partition Grand canonical partition
microstates function function
Microscopic
features W Q

Macroscopic
function W Q
 Ensembles
The averaged value for a property of the ensemble corresponds to the time-
averaged value for the corresponding macroscopic property of the system. For
instance, the total energy of the ensemble:

where a(c)i are the occupation numbers corresponding to the number of ensemble
members having energy Ei.

The weight of associated with a specific configuration of energy among the Nc

members of the ensemble is: (modified from E&R)
Nc !
W( c )i 
 a(c )i !
i
The probability of finding an ensemble member at energy Ei is:
W( c )i e   Ei
P( Ei ) 
Q

where Q is the conical partition function: and the summation is

over all the energy levels.
 Canonical Ensemble and Q
The probability of finding an ensemble member at energy Ei is:
W( c )i e   Ei
P( Ei ) 
Q

P(Ei) peaks around the average energy <E>:

 Q v.s. q
Canonical partition function Q of a system with N particles can be related to
molecular partition function q. For distinguishable units/particles:
Q   e   En En, with n=1,2…n: energy of
n
ensemble members;levels
 n , N
 e N
with  n,N  En 1,2…N: particles;
n N

  e
  n , N

n N εn: energy levels.

  e
  n , N

N n

  qN
N

 qN
The last step uses the factor that all ensemble members have the same energy levels
and hence the same partition function.

Note that the ensemble members can be individual atoms/molecules.

 Q v.s. q
Canonical partition function Q can be related to molecular partition function q:

The second equation above applies to quantum system under two conditions:
1. The particles are not interacting with each other (“ideal quantum gases”);
2. The temperature is so that that the number of available energy levels (n) is
significantly greater than the number of particles (N).

We will be discussing ideal quantum gases (Bose-Einstein gases and Fermi-Dirac

gases) if time allows. (Reichl Ch. 7.H).
 Molecular q
Molecular motions and energies:
Three most important quantities: Separation of molecular motions:
1. Fine structure constant 1. Electronic
e2 Wel ~  Ry n 2 ~ 104  105 cm-1
  ~ 102
c
2. Vibrational
2. Born-Oppenheimer constant
1
Wvib ~  2 Ry ~ 102  103 cm-1
m  4
   e  ~ 101 3. Rotational
M  Wrot ~  4 Ry ~ 1  10 cm -1
3. Rydberg constant:
Ry ~ 105 cm-1 4. Translational
Wtrans ~ 1015 cm -1
1cm-1~30GHz~10-4eV~10-2 kJ/mol~1.4K

[1] T. Oka, "Orders of

Magnitude and Symmetry
in Molecular Spectroscopy“,
in "Handbook of High-
resolution
Spectroscopy“ (2011)
 Molecular q
Molecular motions and energies:

 T   R  V   E
 Translational qT

Because ΔεT<<kT: (Δ for “energy level spacing)

with

Another way to express qT:

where Note that the momentum of a 1D gas

h
 particle is:
p
p  mkT
is the thermal de Broglie wavelength.
Translational qT
 Rotational qR
Diatomic molecules and linear
polyatomic molecules

B is rotational constants: I is moment of inertia.

2
h2 For diatomic molecules:
Or: B  
2I 8 2 I
Or:
I is reduced mass.
For diatomic molecules:

In general: I   mi r ,i ,   x, y, z in principal axis

2

system. i
 Rotational qR
Diatomic molecules and linear polyatomic molecules
For heteronuclear diatomic molecules:

If ΔεR<<kT: (Δ for “energy level spacing), which is NOT always a good approximation:
 Most populated rotational energy level
Most populated rotational energy level:
N
aJ   (2 J  1)e   hcBJ ( J 1)
qR
 N   hcB  (2 J  1)e   hcBJ ( J 1)

da J
 N   hcB   2e   hcBJ ( J 1)  (2 J  1)   hcB  (2 J  1)  e   hcBJ ( J 1) 
dJ
 N   hcB  e   hcBJ ( J 1)   2   hcB  (2 J  1) 2 

For the most populated rotational energy level Jmax:

da J
0 , i.e.,
dJ
 hcB  (2 J  1) 2  2

Finally:
kT 1
J max  
2hcB 2
Corrections to Rotational qR: Nuclear Spin Statistics
Nuclear Spin Statistics (Using H2 as an example):
H is fermion, so upon exchange of the two nuclei, i.e., the two protons:
where, 
E * total   total total   el  vib  rot  nuclear  spin

For H2 in its lowest electronic (1Σg+) and vibrational (v=1) state, both the electronic
and vibratioanl wavefunctions are symmetric. From the properties of the rotational
wavefunctions, i.e., a spheric harmonics, we know that for even (odd) J, the
rotational wavefunction is symmetric (antisymmetric). Therefore, the spin
wavefunction of even (odd) J is antisymmetric (symmetric).
 spin   S , M S .
1,1   (1) (2) 

 (1) (2)   (1) (2) symmetric, triplet, 2S +1=3
1
1,0 
2 
1,1   (1)  (2) 

 (1) (2)   (1) (2) antisymmetric, singlet, 2S +1=1

1
 0,0 
2 
where α (β) stands for spin up (down), i.e., |↑> (|↓>).
Spin Multiplicity
Rotational qR
Nuclear Spin Statistics
As a result, the nuclear spin statistics of
the even v.s. odd J rotational energy
levels is: 1:3.

The H2 molecules on even (odd) J

rotational energy levels are called para-
(ortho-) hydrogen. Usually they don’t
interconvert.

In general, the nuclear spin statistics for

homonuclear diatomic molecules is:
I 1
R
I
where I is nuclear spin. R has to be
considered in calculating qR. For H2:
 Corrections to Rotational qR: Symmetry Number
Symmetry Number: number of equivalent rotational configurations.

σ=1 σ=3

σ=2
σ=3×4=12
 Corrections to Rotational qR: Symmetry Number
At high temperature, the value of qR determined using symmetry
number will, to good approximation, equal that obtained using
nuclear spin statistics.

Text reading: Ex 14.5, Page 352.

 Rotational qR
Rotational Temperature:

1 kT T
qR   
 hcB  hcB  R
High-temperature limit.
 Rotational qR
Nonlinear polyatomic molecules:
EJ  hcAJ A ( J A  1)  hcBJ B ( J B  1)  hcCJ C ( J C  1)
with rotational constants:
A BC
Partition function:
 Vibrational qV
Diatomic molecules (harmonic approximation):

The last steps uses the Taylor expansion:

 Vibrational qV
Diatomic molecules (harmonic approximation):
If v=0 level is used as reference for vibrational energy:

Note that although expression for qV is different, thermodynamic quantities will

not be affected as long as the reference for energy is self-consistent in calculating
the partition function and other quantities. For example, the probability of
occupying a vibrational energy level is, using the qV expressing with ZPE:

The same as calculated using qV expressing without ZPE.

 Vibrational qV
Vibrational degree of freedom:
Diatomic and

Generate expression of vibrational partition function:

When degeneracy is considered:

where n’ is the total number of unique vibrational frequencies and gi

is vibrational degeneracy.
 Vibrational qV
Vibrational Temperature:

If T>>ΘV, because

Comparing to:
1 kT T
qR   
 hcB  hcB  R
 qR and qv
Examples: E&R 14.5, P352; 14.8, P356.

• Notes:
(1) On the unit of B;
(2) On different “temperatures”;
(3) Can temperature be “negative”?
 Electronic qE
Electronic energy levels of H atom:

Note that Rydberg Constant:

Electronic partition function:

Usually we have: En>>kT. And hence:

Similar to ΘR and ΘV , the electronic

temperature is defined as:
 Partition Function - Summary
For one mole of diatomic molecules (not a quantum
system):
Ensemble partition function:
1 NA
Q qtotal
NA !
Molecular partition function:
qtotal  qT qV qR qE
 V  1  1 
  3     hc  ( g0 )
     hcB   1  e 
 V  T  T 
  3    ( g 0 ) (high T -limit)
     R   V 
Each terms of molecular partition function increases as temperature
increases.
 Classic q and the Law of Equipartition
Classic partition function for ideal gases:

where the Hamiltonian can be expresses as function of position (x or

q) and momentum (p) and angular momentum (l or J-for rotational
angular momentum):

p2 Degrees of Freedom:
HT =
2m -3
HR =
l2 - 3 for nonlinear molecules and 2 for linear
2I molecules (including diatomic molecules.)
p2 1 2 - 3N-6 for nonlinear molecules and 3N-5 for
H V = T +V = + kx
2m 2
linear molecules (including diatomic molecules.)
First (second) term for kinetic (potential) energy,
T and V, respectively.
Total DOF: 3N, where N is number of atoms.
 Classic q and the Law of Equipartition
In quantum mechanics, the quantities, x/q, p, and l/J, becomes
operators:
x  xˆ  x  or rˆ  r  for 3D cases,

p  pˆ  i or  i  for 3D cases,
x
 
l  lˆ  xˆ  pˆ with lˆx  ypˆ z  zpˆ y  i ( y  z ) , etc.
z y
For rotational angular momentum, it is easier to use spherical coordinates:
 1  2
1   1  
Jˆ    2
2
  
 sin   2
sin    sin   

And the eigenfunction for J is spherical harmonics Yl,m(θ,φ).

Law of Equipartition:
Any term in the classic Hamiltonian that is quadratic with respect to either position
or momentum will contribute kT/2 to the average energy.
Translational: kT/2 for each DOF;
Rotational: kT/2 for each DOF;
vibrational: kT for each DOF (kT/2 from T, kT/2 from V);