Statistical Thermodynamics

Dr. Henry Curran

NUI Galway

1
Background
Thermodynamic parameters of stable
molecules can be found. However,
those for radicals and transition
state species cannot be readily
found. Need a way to calculate these
properties readily and accurately.

2
The Boltzmann Factor
fE E

Physical Quantity exp
const x fT T

Boltzmann law for the population of quantised

energy states:

ni i ni i j / kT
i j exp
nj j nj
3
Average basis of the behaviour of matter

Thermodynamic properties are concerned

with average behaviour.

ni
i j / kT
exp
nj

The instantaneous values of the occupation

numbers are never very different from
the averages.
4
Distinct, independent particles
Consider an assembly of particles at
constant temperature. These particles are
distinct and labelled (a, b, c, etc)
They are independent
interact with each other minimally
enough to interchange energy at collision
Weakly coupled
Sum of individual energies of labelled particles

E ...
a b c d i

i 5
 Statistical weights
At any instant the distribution of particles
among energy states involve n0 with energy 0, n1
with energy 1, n2 with energy 2 and so on. We
call the instantaneous distribution the
configuration of the system.
At the next moment the distribution will be
different, giving a different configuration with
the same total energy.
These configurations identify the way in which
the system can share out its energy among the
available energy states.
6
Statistical weights
A given configuration can be reached in a
number of different ways. We call the number
of ways the statistical weight of that
configuration. It represents the probability
that this configuration can be reached, from
among all other configurations, by totally
random means.
For N particles arriving at a configuration in
which there are n0 particles with energy 0, n1
with etc, the statistical weight is:
N!

n0 !n1!n2 !n3! ... 7
Principle of equal a priori probabilities
Each configuration will be visited exactly
proportional to its statistical weight
N ni E ni i
i i
We must find the most probable configuration
How likely is this to dominate the assembly?
For an Avogadro number of particles with an average change of
configuration of only 1 part in 10 10 reduces the probability by:

max A massive collapse

10 434
in probability!
8
 Maximisation subject to constraints
The predominant configuration among N
particles has energy states that are populated
according to:

ni i
e
N
where and are constants under the
conditions of constant temperature
9
 ni i
e
N
The lowest state has energy 0 = 0 and
occupation number n0
n0
e
N
which identifies the constant , and enables us
to write:
ni i n0 i
e e e
N N
ni i
e
n0 10
 ni i
e
n0
this is a temperature dependent ratio since
the occupation number of the states vary
with temperature

The constant can be stated as:

1

kT
where k is the Boltzmann constant 11
Molecular partition function
ni i j / kT
e
nj
i 0 / kT
ni n0 e
i
ni n0 e
Any state population (ni) is known if:
i, T, and n0 are known
12
Molecular partition function
If the total number of particles is N, then:
N n0 n1 n2 n3 ... n
all states
i

N n0 n0 e 1 n0 e 2 n0 e 3 ... n0 e i

all states

N
n0
e i

all states

Ne i
ni or writing q
e i

e i

all states
all states

Ne i
ni
q 13
Molecular partition function, q
Determines how particles distribute (or partition)
themselves over accessible quantum states.

1 2 3 1
q 1 e e e ... 0 0,
kT

An infinite series that converges more rapidly

the
larger both the energy spacing between quantum
states and the value of is. Convergence is
enhanced at lower temperatures since = 1/kT.
when >> 0, e- 14
Molecular partition function, q
If 1-0 () is large (kT)
q 1 (lowest value of q)

If 1-0 () kT (thermal energy)

q large number

magnitude of q shows how easily particles

spread over the available quantum states
and thus reflects the accessibility of the
quantum energy states of the particles
involved.
15
Energy states and energy levels
q e
all states
i

However, quantum states can be degenerate

with a number (g) of states all sharing the
same energy. States with the same energy
comprise an energy level and we use the symbol
gj to denote the degeneracy of the jth level

g e
j
q j
all levels
16
The partition function explored
The total number of particles in our
assembly is N or, expressed intensively, NA
per mole
N A ni g j n j n0 q
all states all levels

NA
q
n0

The partition function is a measure of the

extent to which particles are able to escape
from the ground state
17
The partition function explored
The partition function q is a pure number
which can range from a minimum value of 1
at 0 K (when n0 = NA and only the ground
state is accessible) to an indefinitely large
number as the temperature increases

Fewer and fewer particles are left in the

ground state and an indefinitely large
number of states become available to the
system
18
 The partition function explored
We can characterise the closeness of spacing
in the energy manifold by referring to the
density of states function, D(), which
represents the number of energy states in unit
energy level.

If D() is high (translational motion in gas):

particles find it easy to leave ground state
q will rise rapidly as T increases
If D() is low (vibrations of light diatomic molecules)
small value of q ( 1)
19
 The partition function explored
If q/NA (the number of accessible states per
particle) is small
few particles venture out of the ground state

If q/NA is large
there are many accessible states and molecules are
well spread over the energy states of the system

q/NA >> 1 for the valid application of the

Boltzmann law in gaseous systems

20
Canonical partition function
ln q
Em L
Molecular molar level V

assume value of an extensive function for N

particles is just N times that for a single
particle
true for energy of non-interacting particles but not so
for other properties (e.g. entropy)
Particles do interact! Thus we consider:
every system has a set of system energy states
which molecules can populate
these states are not restricted by the need for
additivity but can adjust to any inter-particle
interactions that may exist
21
 Canonical partition function
Molar sum over states
each possible state of the whole system
involves a description of the conditions
experienced by all the particles that make
up a mole
Suppose N identical particles each with
the set of individual molecular states
available to them.
Particle labels 1, 2, 3, 4, , N
Molecular states a, b, c, d,
22
 Canonical partition function
Any given molar state can be described by a
suitable combination of individual molecular
states occupied by individual molecules. If
we call the ith state i, we can begin to give a
description of this molar state by writing:
i 1a 2b 3h 4 f 5c 6 k 7 c 8t ...
with energy: Ei ...
1
a
2
b
3
h
4
f
5
c
6
k
7
c
8
t

there is no restriction on the number of particles

that can be in the same molecular state
(e.g. particles 5 & 7 are both in molecular state c)
23
Canonical partition function (QN)
State i, with energy Ei is just one of many
states of the whole system. The predominant
molecular configuration is called the canonical
distribution
applies to states of an N-particle system
at constant amount, volume, and Temperature
QN e
system
i

states

ln QN
with energy: Em Ei
V 24
The Molar energy
ln QN
Em Ei
V

The canonical partition function (QN) is much

more general than the product of N molecular
partition functions q since there is no need to
consider only independent molecules

N q ln q
E N
q V V
25
 The Molar energy
If we are able to calculate thermodynamic
properties for assemblies of N
independent particles using q and for N
non-independent particles using QN, then,
in the limit of the particles of QN,
becoming less and less strongly
interdependent, the two methods should
eventually converge.

26
The Molar energy
Note that the expressions:

ln q ln QN
N and
V V

are compatible if we assume that the two

different partition functions are related
simply by: N
Qq
where Q is a function of an N-particle
assembly at constant T and V
27
Distinguishable and indistinguishable
particles
Ei a b h f c k c t ...
1 2 3 4 5 6 7 8

for the canonical partition function we can write:

Q exp ...
1
a
2
b
3
h
4
f
5
c
6
k
7
c
8
t
i

In every one of the i system states, each particle (1, 2,

3, ) will be in one of its possible j molecular states
(a,b, c, d ) just once in each system state. If we
factorise out each particle in turn from the summation
over the system states and then gather together all
the terms that refer to a given particle, we get: 28
Distinguishable and indistinguishable
particles


e e e
j j j
Q ...
molecular molecular molecular
states 1 states 2 states 3

If all molecules are of the same type and

indistinguishable by position they do not need labelling
N

e
j
Q

q N

j
29
Distinguishable and indistinguishable
particles
If particles are indistinguishable the number of
accessible system states is lower than it is for
distinguishable ones. A system i
i 1a 2b 3h ...
differs from a state j
j 1a 2 h 3b ...
if particles are distinguishable, because of the
interchange of particles 2 and 3 between states b
and h. However, i is identical to j if particles are
indistinguishable
30
Distinguishable and indistinguishable
particles
In systems which are not at too high a density and
are also well above 0 K, the correction factor for
this over-counting of configurations is 1/N!

Q q N
( for distinguishable particles)

qN
Q ( for indistinguishable particles)
N!

31
Two-level systems
The simplest type of system is one which
comprises particles with only two
accessible states in the form of two non-
degenerate levels separated by a narrow
energy gap :
nu 0

nl 0
At temperatures that are comparable to /k only
the ground state and first excited state are
appreciably populated
32
Effect of increasing Temperature
The average population ratio of the two
levels is an assembly of such two-level (or
two-state) particles is given by:
nu 2 L / T
e e
nl
where the two-level temperature (2L) is defined as:

2L
k
33
Temperature Dependence of the populations
Comparing energy gap 2 L Comparing characteristic T
with background thermal (2L) with Temperature (T)
energy kT T

if T 5 2 L (high T )
nu
then e e 2 L / T e 1/ 5 0.82 (1)
nl

if T 0.5 2 L (low T )
nu
then e 1/ 0.5 0.14 ( 0)
nl
34
 T dependence of populations

nl e nu
but total number of particles is constant nl nu N
1 e n

u N
1 e

nu
N
N
1 e e 1
e 1
nl
N
N
1 e e 1
35
T dependence of populations (Fig. 6.2)
1.0

nl
number of particles / N

0.5

nu

0 T T
0.0
0.1 1 10
Reduced temperature T/ 2L 36
 Two-level Molecular partition function
The effect of q2 L e i
e 0
e ( 0 )

increasing T both
states
only two energy
states to consider e 0 (1 e )

if 0 0 q2 L (1 e )
High T Low T
T = 52L T = 0.52L
q2L = 1 + 0.82 q2L = 1 + 0.14
q2L 2 q2L 1
Both states equally only lower state
accessible accessible 37
The energy of a two-level system
E2 L ni ei nl x 0 nu x nu
i

1

N x
1 e
N

1 e

N 1 e
1

At high T, half the particles occupy the
upper state and the total energy takes the
value N 38
Two-level heat capacity, CV
The spacing of energy levels in discussing
two-level systems is not affected by
changes in volume, so the relevant heat
capacity is CV not CP

U U
CV
T V T
Variation of CV with T is a measure of how
accessible the upper states becomes as T
increases.
39
 Two-level heat capacity, CV
Low T
kT is small
small T has little tendency to excite particles
overall energy remains constant => CV low
Intermediate T
kT is comparable to
small T has larger effect in exciting particles
CV is somewhat larger
High T
Almost half particles in excited state
small T causes very few particles excited to upper
Overall energy remains constant => CV low
40
Two-level heat capacity, CV

E2 L N 1 e
1

dE
dT

N 1 e
2
e 2

kT
2 e
CV Nk ( )

e 1
2

41
 0.5 1.0
0.44Nk

0.4 0.8

CV/Nk 0.3 0.6

E/Emax
0.2 0.4

0.1 0.2

0.0 0.0
0.1 0.42 1 10
Reduced temperature (T/ )

Variation of CV and Energy of a two-level

system as a function of reduced Temperature
42
The effect of degeneracy
Consider a two-level system with degenerate
energy levels. If the degeneracy of the lower
level is g0 and that of the upper level is g1 then
the two-level molecular partition function is:

q2 L ( g 0 g1e )

43
The effect of degeneracy
Energy of the degenerate two-level system:
g1
N
g0
E
g1

e
g 0
and the heat capacity: g1
e
CV 2
g0
Nk 2
g1 e
g 0

44
 Toolkit equations
1. Massieu bridge :
A A(0)
k ln Q
T
ln Q
2. Internal energy : U U (0) kT 2

T V

ln Q
3. Equation of state : p kT
V T

ln Q 2 2 ln Q
4. Heat capacity : CV 2kT kT
T V T
2
V

ln Q
5. Entropy : S k ln Q kT
T V
45
Toolkit equations
ln Q ln Q
6. Enthalpy : H H (0) kT 2
kTV
T V V T

ln Q
7. Gibbs free energy : G G (0) kT ln Q kTV
V T

In order to relate the partition function to

classical thermodynamic quantities, the equations
for internal energy and entropy are needed. Once
these have been expressed in terms of the
canonical partition function, Q, the Massieu bridge
can be derived. This in turn provides the most
compact link to classical thermodynamics.
46
Ideal monatomic gas

Consider an assembly of particles constrained to

move in a fixed volume. This system consists of
many, non-interacting, monatomic gas particles in
ceaseless translational motion. The only energy
that these particles can possess is translational
kinetic energy.

47
Translational partition function, qtrs

In classical mechanics, all kinetic energies are

allowed in a system of monatomic gas particles at a
fixed volume V and temperature T. Quantum
restrictions place limits on the actual kinetic
energies that are found.
To determine the partition function for such a
system to need to establish values for the allowed
kinetic energies.
We consider a particle constrained to move in a
cubic box with dimensional box with dimensions lx,
ly, and lz.
48
Particle in a one-dimensional box
The permitted energy levels, x, for a particle of
mass m that is constrained by infinite boundary
potentials at x = 0, and x = lx to exist in a one-
dimensional box of length lx are given by:
2 2
nh
x x
2
8mlx
and similarly for the y- and z-directions. The
translational quantum number, nx, is a positive
integer and the quantum numbers in the y- and z-
directions are ny and nz, respectively.
49
One-dimensional partition function
The one-dimensional partition function, q trs,x, is
obtained by summing over all the accessible energy
states. Thus:

qtrs , x e n x2 h 2 / 8 ml x2

all n

an expression that is exact but cannot be

evaluated except by direct and tedious numerical
summation.
50
 One-dimensional partition function
For all values of lx in any normal vessel, these
energy levels are very densely packed and lie
extremely close to each other. They form a virtual
continuum, so the summation can be replaced by an
integration with the running variable nx

qtrs , x e n x2 h 2 / 8 ml x2
dnx
0
resulting in the expression: 1
2m 2 lx
qtrs , x
h 51
Extension to three dimensions
We can factorise the translational partition
function: 3
2m 2 lx ly lz
qtrs qtrs , x x qtrs , y x qtrs , z
h3

product of three dimensions gives the volume, V:

3 3
2m 2mkT
2 2
qtrs 2 V V
h
2
h
52
Extension to three dimensions

For the canonical partition function

for N indistinguishable particles

N N
3
3

N
q 1 2m 2 1 2mkT
2 V
2
Qtrs trs
V
N! N! h N! h2

53
Testing the continuum approximation
At its boiling temperature of 4.22 K, one mole of He
occupies 3.46 x 10-4 m3. How many translational
energy states are accessible at this very low
temperature, and determine whether the virtual
continuum approximation is valid.
3
2k
2 3
qtrs 2 ( MT ) 2 V
h NA
5 3 5 3

(5.942 x 1030 / mol m 3 kg K
2 2 2
) ( MT ) V
2

3
(5.942 x 1030 )(4.003 x 10 3 x 4.22) (3.46 x 10 4 )
2

4.5 x 10 24 (unitless) 54
 Ideal monatomic gas: thermodynamic
functions

Since all classical thermodynamic functions are

related to the logarithm of the canonical
partition function, we start by taking the
logarithm of Qtrs:

3 3
ln Qtrs N ln(2m) N ln T N ln V 3 N ln h ln N !
2 2

55
Ideal monatomic gas: thermodynamic
functions
ln Qtrs 3N

T V 2T
ln Qtrs
2
3N
2
T
2
V
2T
ln Qtrs N

V T V
56
 The translational energy, Etrs
For a monatomic gas, the translational kinetic
energy, Etrs, is the only form of energy that the
monatomic particles possess, so we can equate
it directly to the internal energy, U, and
substitute the value of the derivative:
ln Qtrs 3
Etrs U kT 2
NkT
T V 2
(for one mole N = NA, NAk = R)
3
U m RT
2
57
 The equation of state
This can be derived using:

ln Qtrs NkT
p kT
V T V
(for one mole N = NA, NAk = R)

RT
p or pVm RT
Vm
58
 The heat capacity, CV
This can be derived using:

ln Qtrs ln Qtrs
2
CV 2kT kT 2

T T
2
V V

3 3
3 Nk Nk Nk
2 2
(for one mole N = NA, NAk = R)
3
CV , m R
2
59
Entropy of an ideal monatomic gas
All of the simplifying factors that result from
taking partial derivatives of ln Qtrs no longer hold
ln Qtrs
S k ln Qtrs kT
T V

3 3
ln Qtrs N ln(2m) N ln T N ln V 3 N ln h ln N !
2 2
lnQtrs is a direct term and so all variables appear
1 N
k ln Qtrs k ln q
N!
1 N
k ln ln q k ( N ln q ln N !)
N! 60
Entropy of an ideal monatomic gas
Next, using Stirlings approximation (lnN! NlnN N)
q
k ln Qtrs k ( N ln q N ln N N ) Nk 1 ln
N
q 3 5 q
S Nk 1 ln Nk Nk ln
N 2 2 N
3

5 2mkT 2 V
S Nk ln
2 h 2
N

One mole: (N = NA, NAk = R, NAm = M and V = RT/p
3

5 2MkT 2 RT
S m R ln
2
NA p
2 h NA
61
 Entropy of an ideal monatomic gas
gathering together all experimental variables (M. T, p)

3 5
3

M T
2 2 2 2 5

S m R ln R ln (ek )
2
2
p N Ah

The Sackur-Tetrode Equation

The first term contains all of the experimental

variables, the second consists of constants 62
 Using the Sackur-Tetrode equation
The second term has a value of 172.29 J K -1 mol-1
or 20.723 R. Thus we can write:

3


3
1 2 1
S m / R ln M / kg mol (T / K ) ( p / Pa) 20.723
2

Some calculated and measured entropies
Argon Krypton
Tb / K 87.4 120.2
Scalc / R 15.542 17.451
Scalor / R 15.60 17.43
63
Using the Sackur-Tetrode equation
The Sachur-Tetrode equation can also be written
as using ln p-1 = ln V ln R ln T

3 3
S m R ln V R ln T R ln M 18.605 R
2 2
where the variables are expressed in SI units (V/m 3, T/K, and M/kg
mol-1)

64
Significance of Sackur-Tetrode equation
3 3
S m R ln V R ln T R ln M 18.605 R
2 2
volume temperature
dependence dependence
V2 3 T2
ST R ln SV R ln the first two terms are
V1 2 T1
known from classical
T2 thermodynamics
CV ln
T1
the last two terms (3/2 R lnM and 18.605 R) could not
have been foreseen from classical thermodynamics 65
Change in conditions
Effect of increase in T, V, or M on:

D() Q U p CV S

T nil nil

V nil nil nil

M nil nil nil

66
Ideal diatomic gas: internal degrees
of freedom
Polyatomic species can store energy in
a variety of ways:
translational motion
rotational motion
vibrational motion
electronic excitation
Each of these modes has its own manifold
of energy states, how do we cope? 67
Internal modes: separability of energies
Assume molecular modes are separable
treat each mode independent of all others
i.e. translational independent of vibrational,
rotational, electronic, etc, etc

Entirely true for translational modes

Vibrational modes are independent of:
rotational modes under the rigid rotor
assumption
electronic modes under the Born-
Oppenheimer approximation 68
Internal modes: separability of energies
Thus, a molecule that is moving at high speed is
not forced to vibrate rapidly or rotate very fast.

An isolated molecule which has an excess of any

one energy mode cannot divest itself of this
surplus except at collision with another molecule.

The number of collisions needed to equilibrate

modes varies from a few (ten or so) for rotation,
to many (hundreds) for vibration.

69
Internal modes: separability of energies

Thus, the total energy of a molecule j:

j
tot
j
trs
j
rot j
vib j
el

70
Weak coupling: factorising the energy modes
Admits there is some energy interchange
in order to establish and maintain thermal equilibrium
But allows us to assess each energy mode as if it
were the only form of energy present in the
molecule
Molecular partition function can be formulated
separately for each energy mode (degree of
freedom)
Decide later how individual partition functions
should be combined together to form the overall
molecular partition function
71
Weak coupling: factorising the energy modes
Imagine an assembly of N particles that can store
energy in just two weakly coupled modes and
Each mode has its own manifold of energy states
and associated quantum numbers
A given particle can have:
- -mode energy associated with quantum number k
- -mode energy associated with quantum number r

tot k r
72
Weak coupling: factorising the energy modes
The overall partition function, qtot:

e
( i r )
qtot
all states
expanding we would get:

qtot e ( 0 0 ) e ( 0 1 ) e ( 0 2 ) e ( 0 3 )
( 1 0 ) ( 1 1 ) ( 1 2 ) ( 1 3 )
e e e e
( 2 0 ) ( 2 1 ) ( 2 2 ) ( 2 3 )
e e e e
e ( 3 0 ) e ( 3 1 ) e ( 3 2 ) e ( 3 3 )
... 73
Weak coupling: factorising the energy modes
but e(a+b) = ea.eb, therefore:
0 0 0 1 0 2
qtot e .e e .e e .e ...
1 0 1 1 1 2
e .e e .e e .e ...
2 0 2 1 2 2
e .e e .e e .e ...
...
each term in every row has a common factor of
in the first row, in the
second,
1 and so on. Extracting
e 0
these factors row by row: e
74
Weak coupling: factorising the energy modes
0 0 1 2 3
qtot e (e e e e ...)
1 0 1 2 3
e (e e e e ...)
2 0 1 2 3
e (e e e e ...)
e 3 (e 0 e 1 e 2 e 3 ...)
...
the terms in parentheses in each row are
identical and form the summation:

j
e
all states 75
Weak coupling: factorising the energy modes


qtot e 0
e 1
e 2
e 3
e
...
j


all states

j j
e x e
all states all states

If energy modes are separable then we can

factorise the partition function and write:

qtot q x q
76
Factorising translational energy modes
Total translational energy of molecule j:
j
trs , tot j
trs , x j
trs , y j
trs , z
which allows us to write:

e e
trs , tot ( trs , x trs , y trs , z )
qtrs
all states all states

e e e
trs , x trs , y trs , z
qtrs x x
all x states all y states all z states

qtrs qtrs , x x qtrs , y x qtrs , z

77
Factorising internal energy modes
Total translational energy of molecule j:

qtot qtrs . qrot .qvib .qel

using identical arguments the canonical partition
function can be expressed:

Qtot Qtrs . Qrot . Qvib .Qel

but how do we obtain the canonical from the
molecular partition function Qtot from qtot? How
does indistinguishability exert its influence?
78
 Factorising internal energy modes
When are particles distinguishable (having
distinct configurations, and when are they
indistinguishable?
Localised particles (unique addresses) are always
distinguishable
Particles that are not localised are indistinguishable
Swapping translational energy states between such
particles does not create distinct new configurations
However, localisation within a molecule can also
confer distinguishability
79
 Factorising internal energy modes
When molecules i and j, each in distinct rotational and
vibrational states, swap these internal states with
each other a new configuration is created and both
configurations have to be counted into the final sum
of states for the whole system. By being identified
specifically with individual molecules, the internal
states are recognised as being intrinsically
distinguishable.

Translational states are intrinsically indistinguishable.

80
 Canonical partition function, Q

Qtot
qtrs
N
qrot qvib qel
N N N

N!
and thus: 1
Qtot qtrs .qrot .qvib .qel
N

N!
This conclusion assumes weak coupling. If
particles enjoy strong coupling (e.g. in liquids
and solutions) the argument becomes very
complicated!
81
Ideal diatomic gas: Rotational
partition function
Assume rigid rotor for which we can write
successive rotational energy levels, J, in terms
of the rotational quantum number, J.
h2
E J 2 J ( J 1) joules
8 I
EJ h
J 2 J ( J 1) cm 1

hc 8 Ic
BJ ( J 1) cm 1
where I is the moment of inertia of the
molecule, is the reduced mass, and B the
rotational constant. 82
Ideal diatomic gas: Rotational
partition function
Another expression results from using the
characteristic rotational temperature, r,

h2 hcB
r 2 k r hcB
8 Ik k
E J J ( J 1)k r ( joules )

1st energy increment = 2kr

2nd energy increment = 4kr
83
Ideal diatomic gas: Rotational
partition function
Rotational energy levels are degenerate and
each level has a degeneracy gJ = (2J+1). So:

qrot g J e J / kT
(2 J 1)e J ( J 1) r / T

If no atoms in the atom are too light (i.e. if the

moment of inertia is not too small) and if the
temperature is not too low (close to 0 K), allowing
appreciable numbers of rotational states to be
occupied, the rotational energy levels lie
sufficiently close to one another to write:
84
 Ideal diatomic gas: Rotational partition
function

qrot (2 J 1)e J ( J 1) r / T dJ

T 8 2 IkT
qrot
r h2
This equation works well for heteronuclear
diatomic molecules.
For homonuclear diatomics this equation
overcounts the rotational states by a factor of
two.
85
Ideal diatomic gas: Rotational partition
function
When a symmetrical linear molecule rotates through
180o it produces a configuration which is
indistinguishable from the one from which it started.
all homonuclear diatomics
symmetrical linear molecules (e.g. CO2, C2H2)
Include all molecules using a symmetry factor

T
qrot
r
= 2 for homonuclear diatomics, = 1 for heteronuclear diatomics
= 2 for H2O, = 3 for NH3, = 12 for CH4 and C6H6 86
Rotational properties of molecules at 300 K
r/K T/r qrot

H2 88 2 3.4 1.7
CH4 15 12 20 1.7
HCl 9.4 1 32 32
HI 7.5 1 40 40
N2 2.9 2 100 50
CO 2.8 1 110 110
CO2 0.56 2 540 270
I2 0.054 2 5600 2800
87
Rotational canonical partition function

Qrot q N
rot

relates the canonical partition function to the

molecular partition function. Consequently, for the
rotational canonical partition function we have:

N N N
T T 8 IkT
2
Qrot
r h
2
hcB
88
 Rotational Energy
8 2 Ik
ln Qrot N ln T N ln 2

h
this can differentiated wrt temperature, since the
second term is a constant with no T dependence

ln Qrot 2
U rot kT 2
NkT ln T
T V T
U rot NkT (for diatomic molecules)
89
 Rotational heat capacity
U rot NkT (for diatomic molecules)

this equation applies equally to all linear molecules

which have only two degrees of freedom in rotation.
Recast for one mole of substance and taking the T
derivative yields the molar rotational heat capacity,
Crot, m. Thus, when N = NA, the molar rotational energy
is Urot,m

U rot , m RT
Crot ,m R (linear molecules)
90
 Rotational entropy
ln Q U rot
S rot kT k ln Q k ln Q
T V T
N
NkT 8 IkT 2
k ln
h
2
T
IT 8 2 k
S rot Nk 1 ln ln 2

h
Srot is dependent on (reduced) mass (I = r2), and there
is also a constant in the final term, leading to:

S rot / R ln I / kg m T / K
2
1
106.53
91
Rotational entropy
Typically, qrot at room T is of the order of hundreds
for diatomics such as CO and Cl2. Compare this with
the almost immeasurably larger value that the
translational partition function reaches.

qrot 10 2
but qtrs 10 28

92
 Extension to polyatomic molecules
In the most general case, that of a non-linear
polyatomic molecule, there are three independent
moments of inertia.
Qrot must take account of these three moments
Achieved by recognising three independent characteristic
rotational temperatures r, x, r, y, r, z corresponding to the
three principal moments of inertia Ix, Iy, Iz
With resulting partition function:
1

T T T 2
qrot


r, y

r, z

r , x
93
Conclusions
Rotational energy levels, although more widely
spaced than translational energy levels, are still
close enough at most temperatures to allow us to
use the continuum approximation and to replace
the summation of qrot with an integration.

Providing proper regard is then paid to rotational

indistinguishability, by considering symmetry,
rotational thermodynamic functions can be
calculated.
94
Ideal diatomic gas: Vibrational partition
function
Vibrational modes have energy level spacings that
are larger by at least an order of magnitude than
those in rotational modes, which in turn, are 25
30 orders of magnitude larger than translational
modes.
cannot be simplified using the continuum approximation
do not undergo appreciable excitation at room Temp.
at 300 K Qvib 1 for light molecules

95
 The diatomic SHO model
We start by modelling a diatomic molecule on a
simple ball and spring basis with two atoms, mass
m1 and m2, joined by a spring which has a force
constant k.
The classical vibrational frequency, oscis given
by:
1 k
osc Hz
2
There is a quantum restriction on the available energies:
1
vib v hosc ( v 0, 1, 2, ...)
2 96
The diatomic SHO model
1
The value hosc is know as the zero point energy
2

Vibrational energy levels in diatomic molecules

are always non-degenerate.

Degeneracy has to be considered for polyatomic

species
Linear: 3N-5 normal modes of vibration
Non-linear: 3N-6 normal modes of vibration

97
 Vibrational partition function, qvib

Set 0 = 0, the ground vibrational state as the

reference zero for vibrational energy.

Measure all other energies relative to reference

ignoring the zero-point energy.

in calculating values of some vibrational thermodynamic

functions (e.g. the vibrational contribution to the internal
energy, U) the sum of the individual zero-point energies of
all normal modes present must be added

98
Vibrational partition function, qvib
The assumption (0 = 0) allows us to write:
1 h , 2 2h , 3 3h , 4 4h , ...
Under this assumption, qvib may be written as:

qvib e vib
1 e h
e 2 h
e 3 h
...
a simple geometric series which yields q vib in closed
form:
1 1
qvib h
vib / T
1 e 1 e
where vib = h/k = characteristic vibrational
temperature 99
 Vibrational partition function, qvib
Unlike the situation for rotation, vib, can be
identified with an actual separation between
quantised energy levels.

To a very good approximation, since the

anharmonicity correction can be neglected for low
quantum numbers, the characteristic temperature
is characteristic of the gap between the lowest
and first excited vibrational states,
1 and with
hosc
exactly twice the zero-point energy, .
2
100
 Ideal diatomic gas: Vibrational
partition function
Vibrational energy level qvib
spacings are much larger
vib/K
than those for rotation, so Species (@ 300 K)
H2 5987 1.000
typical vibrational
temperatures in diatomic HD 5226 1.000
molecules are of the order D2 4307 1.000
of hundreds to thousands N2 3352 1.000
of kelvins rather than the CO 3084 1.000
tens of hundreds Cl2 798 1.075
characteristic of rotation. I2 307 1.556

101
 Vibrational partition function, qvib
Light diatomic molecules have:

high force constants 1 k

low reduced masses
osc
2
Thus:
vibrational frequencies (osc) and characteristic vibrational
temperatures (vib) are high
just one vibrational state (the ground state) accessible at room T
the vibrational partition function qvib 1

102
 Vibrational partition function, qvib

Heavy diatomic molecules have:

rather loose vibrations
Lower characteristic temperature

Thus:
appreciable vibrational excitation resulting in:
population of the first (and to a slight extent higher)
excited vibrational energy state
qvib > 1

103
 Vibrational partition function, qvib
Situation in polyatomic (qvib)
species is similar Species vib/K (@ 300 K)
complicated only by the CO2 3360 1.091
existence of 3N-5 or 3N-6 1890
normal modes of vibration. 954(2)
NH3 4880(2) 1.001

Some of these normal modes 4780

are degenerate 2330(2)

1360
CHCl3 4330 2.650
tot
qvib qvib
(n)
qvib(1) x qvib( 2) x q ( 3)
vibx ... 1745(2)
1090(2)

(1), (2), (3), denoting individual normal 938

modes 1, 2, 3, etc. 523 104
374(2)
Vibrational partition function, qvib
As with diatomics, only the heavier species show
values of qvib appreciably different from unity.

Typically, vib is of the order of ~3000 K in many

molecules. Consequently, at 300 K we have:
1
qvib 10
1
1 e
in contrast with qrot ( 10) and qtrs ( 1030)

For most molecules only the ground state is

accessible for vibration 105
High T limiting behaviour of qvib

1
At high temperature the equation qvib
1 e vib / T
gives a linear dependence of qvib with temperature.

vib / T
If we expand 1 e , we get:

1 T
qvib High T limit
1 1 ( vib / T ) ... vib

106
T dependence of vibrational partition
function
As T increases, the
2.0 linear dependence of
qvib upon T becomes
1.8 increasingly obvious

1.6
qvib

1.4

1.2

1.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
Reduced Temperature T/ 107
The canonical partition function, Q vib
N
1
Qvib q N
vib vib / T
1 e
Using U kT 2 ln Q we can find the first
T V
differential of lnQ with respect to temperature
to give:

ln Q Nk vib
U vib kT 2
vib / T
T V e 1
108
The vibrational energy, Uvib
R vib
U vib , m vib / T
(e 1)

This is not nearly as simple as:

3
U trs , m kT
2
U rot , m RT linear molecules
109
The vibrational energy, Uvib
R vib
U vib , m vib / T
(e 1)
This does reduce to the simple form at
equipartition (at very high temperatures) to:

U vib , m RT (equipartition)

Normally, at
room T:
3000 R 1
U vib , m 10 R
(e 1) 7 110
The zero-point energy
So far we have chosen the zero-point energy
(1/2h) as the zero reference of our energy scale
Thus we must add 1/2h to each term in the
energy ladder
For each particle we must add this same amount
Thus, for N particles we must add U(0)vib, m = 1/2Nh
R vib
U vib , m vib / T U (0) vib , m
(e 1)
R vib 1
vib / T N A h
(e 1) 2 111
Vibrational heat capacity, Cvib
The vibrational heat capacity can be found using:

U vib , m
2 vib / T
vib e
Cvib , m R vib / T
T 1) 2
V T (e
The Einstein Equation

This equation can be written in a more compact

form as:
vib
Cvib , m RF E
T 112
 Vibrational heat capacity, Cvib

FE with the argument vib/T is the Einstein function

u e 2 u
vib
FE u u
(e 1) 2
T
The Einstein function

113
The Einstein heat capacity

1.0

FE
0.5

low T High T
0.0
0.1 1 10
Reduced temperature T/
114
The Einstein function
The Einstein function has applications beyond
normal modes of vibration in gas molecules.
It has an important place in the understanding
of lattice vibrations on the thermal behaviour
of solids
It is central to one of the earliest models for
the heat capacity of solids

115
The vibrational entropy, Svib
U vib U vib (0) Avib Avib (0)
S vib
T T
U vib U vib (0)
k ln Qvib
T
We know Qvib qvib
Nand N = N for one mole, thus:
A

ln Qvib N A k ln qvib R ln qvib

vib / T
ln 1 e
S vib , m vib / T
vib / T
R (e 1) 116
Variation of vibrational entropy with
reduced temperature
3.0

2.5

2.0
Svib/R

1.5

1.0

0.5
0 T T
0.0
0.1 1 10
Reduced temperature T/
117
Electronic partition function
Characteristic electronic temperatures, el,
are of the order of several tens of thousands
of kelvins.
Excited electronic states remain unpopulated
unless the temperature reaches several
thousands of kelvins.
Only the first (ground state) term of the
electronic partition function need ever be
considered at temperatures in the range
from ambient to moderately high.
118
Electronic partition function
It is tempting to decide that qel will not be a
significant factor. Once we assign 0 = 0, we
might conclude that:

qel e
el , i / kT 0
e 0 (higher terms ) 1
i

To do so would be unwise!
One must consider degeneracy of the ground
electronic state.

119
Electronic partition function
The correct expression to use in place of the
previous expression is of course:

qel g i e
el , i / kT
g 0 e 0 0 (higher terms) g 0
i

Most molecules and stable ions have non-

degenerate ground states.
A notable exception is molecular oxygen, O2,
which has a ground state degeneracy of 3.
120
Electronic partition function
Atoms frequently have ground states that are
degenerate.
Degeneracy of electronic states determined
by the value of the total angular momentum
quantum number, J.
Taking the symbol as the general term in the
RussellSaunders spin-orbit coupling
approximation, we denote the spectroscopic
state of the ground state of an atom as:
spectroscopic atom ground state = J
(2S+1)

121
Electronic partition function
spectroscopic atom ground state = J
(2S+1)

where S is the total spin angular momentum

quantum number which gives rise to the term
multiplicity (2S+1). The degeneracy, g0, of the
electronic ground states in atoms is related to
J through:
g0 = 2J+1 (atoms)

122
 Electronic partition function
For diatomic molecules the term symbols are
made up in much the same way as for atoms.
Total orbital angular momentum about the
inter-nuclear axis.
Determines the term symbol used for the
molecule ( etc. corresponding to S, P, D,
etc. in atoms).
As with atoms, the term multiplicity (2S+1) is
added as a superscript to denote the
multiplicity of the molecular term.

123
Electronic partition function
In the case of molecules it is this term
multiplicity that represents the degeneracy of
the electronic state.
For diatomic molecules we have:
spectroscopic molecular ground state = (2S+1)

for which the ground-state degeneracy is:

g0 = 2S + 1 (molecules)

124
Electronic partition function
Term
Species Symbol gn el/K
Li 2
S1/2 g0 = 2
C 3
P0 g0 = 1
N 4
S3/2 g0 = 4
O 3
P2 g0 = 5
F 2
P3/2 g0 = 4
2
P1/2 g1 = 2 590
NO 2
1/2 g0 = 2
2
3/2 g1 = 2 178
O2 3
-g g0 = 3
1
g g1 = 1 11650 125
Electronic partition function
Where the energy gap between the ground and
the first excited electronic state is large the
electronic partition function simply takes the
value g0.
When the ground-state to first excited state
gap is not negligible compared with kT (el/T is
not very much less than unity) it is necessary
to consider the first excited state.
The electronic partition function becomes:
el / T
qel g 0 g1e
126
Electronic partition function
For F atom at 1000 K we have:
el / T
qel g 0 g1e 4 2e 590 /1000 5.109

For NO molecule at 1000 K we have:

el / T
qel g 0 g1e 2 2e 178 /1000 3.674

127