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?

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 BornOppenheimer approximation

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.
3

Internal modes: separability of energies

Thus, the total energy of a molecule j:

j
tot

j
trs

j
rot

j
vib

j
el

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

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

Weak coupling: factorising the energy modes

The overall partition function, qtot:

qtot

( i r )

all states

expanding we would get:

qtot e ( 0 0 ) e ( 0 1 ) e ( 0 2 ) e ( 0 3 )
e

( 1 0 )

( 2 0 )

( 1 1 )

( 2 1 )

( 1 2 )

( 2 2 )

( 1 3 )

( 2 3 )

e ( 3 0 ) e ( 3 1 ) e ( 3 2 ) e ( 3 3 )
...

Weak coupling: factorising the energy modes

but e(a+b) = ea.eb, therefore:

qtot e
e

1
2

e
...

.e

.e

.e

e
e

.e

.e

.e

e
e

.e

.e

.e

...

...
...

each term in every row has a common factor of

first row,
in the
0
these factors row by row:

in the
second,
1 and so on. Extracting

Weak coupling: factorising the energy modes

qtot 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:

all

states

Weak coupling: factorising the energy modes

qtot e

all

states

x
all

...

all states

states

If energy modes are separable then we can

factorise the partition function and write:

qtot q x q
10

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:

qtrs

trs , tot

all states

qtrs

trs , x

all x states

( trs , x trs , y trs , z )

all states

trs , y

all y states

trs , z

all z states

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

11

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?

12

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
13

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.
14

Canonical partition function, Q

qtrs
N
N
N
qrot qvib qel
Qtot
N

and thus:

N!
1
N
Qtot qtrs .qrot .qvib .qel
N!

This conclusion assumes weak coupling. If

particles enjoy strong coupling (e.g. in liquids
and solutions) the argument becomes very
complicated!
15

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
1
J
2 J ( J 1) cm
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.

16

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
17

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:

18

Ideal diatomic gas: Rotational partition

function

qrot (2 J 1)e

J ( J 1) r / T dJ

qrot

T 8 2 IkT

r
h2

This equation works well for heteronuclear

diatomic molecules.
For homonuclear diatomics this equation
overcounts the rotational states by a factor of
two.

19

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

qrot

= 2 for homonuclear diatomics, = 1 for heteronuclear diatomics

= 2 for H2O, = 3 for NH3, = 12 for CH4 and C6H6
20

Rotational properties of molecules at 300 K

r/K

T/r

qrot

H2

88

3.4

1.7

CH4

15

12

20

1.7

HCl

9.4

32

32

HI

7.5

40

40

N2

2.9

100

50

CO

2.8

110

110

CO2

0.56

540

270

I2

0.054

5600

2800
21

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:

Qrot

hcB

8 IkT

2
h
2

22

Rotational Energy
ln Qrot

8 2 Ik

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
ln T
NkT
T V
T

U rot NkT (for diatomic molecules)

2

23

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)

24

Rotational entropy
S rot

ln Q
kT

U rot
k ln Q
k ln Q
T

8 IkT
NkT

k ln
2
T
h
2

S rot

8 2 k
IT

Nk 1 ln
ln
2

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

106.53

25

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

but qtrs 10

28

26

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:

qrot

r , x

r, y

r, z

1
2

27

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.
28

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

29

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:

osc

k
Hz

There is a quantum restriction on the available energies:

vib

1
v hosc
2

( v 0, 1, 2, ...)

30

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

31

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

32

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

2 h

3 h

...

a simple geometric series which yields q vib in closed

form:

qvib

1
1

vib / T
h
1 e
1 e

where vib = h/k = characteristic vibrational

33
temperature

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,
and with
1
hosc
exactly twice the zero-point energy,
.
2
34

Ideal diatomic gas: Vibrational

partition function
Vibrational energy level
spacings are much larger
than those for rotation, so Species
H2
typical vibrational
HD
temperatures in diatomic
molecules are of the order D2
of hundreds to thousands N2
of kelvins rather than the CO
Cl2
tens of hundreds
characteristic of rotation. I2

qvib
vib/K
5987

(@ 300 K)
1.000

5226

1.000

4307

1.000

3352

1.000

3084

1.000

798

1.075

307

1.556

35

Vibrational partition function, qvib

Light diatomic molecules have:
high force constants
low reduced masses

osc

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

36

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

37

Vibrational partition function, qvib

Situation in polyatomic
species is similar
complicated only by the
existence of 3N-5 or 3N-6
normal modes of vibration.

(qvib)
Species
CO2

vib/K
3360

(@ 300 K)
1.091

1890
954(2)
NH3

4880(2)

1.001

4780

Some of these normal modes

are degenerate

2330(2)
1360

tot
(n)
qvib
qvib
qvib(1) x qvib( 2) x q
(1), (2), (3), denoting individual normal
modes 1, 2, 3, etc.

CHCl3
( 3)
vib

x ...

4330

2.650

1745(2)
1090(2)
938
523
374(2)

38

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:

qvib

1
10
1 e

in contrast with qrot ( 10) and qtrs ( 1030)

For most molecules only the ground state is
accessible for vibration

39

High T limiting behaviour of qvib

1

1 e vib / T

At high temperature the equation qvib

gives a linear dependence of qvib with temperature.
vib / T
1

e
If we expand
, we get:

qvib

1 1 ( vib / T ) ... vib

High T limit

40

T dependence of vibrational partition

function
2.0
1.8

As T increases, the
linear dependence of
qvib upon T becomes
increasingly obvious

qvib

1.6
1.4
1.2
1.0
0.0

0.2

0.4

0.6

0.8

1.0

1.2

Reduced Temperature T/

1.4

41

The canonical partition function, Q vib

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:

U vib

ln Q
kT

T
2

Nk vib
vib / T
e
1

42

The vibrational energy, Uvib

U vib , m

R vib
vib / T
(e
1)

This is not nearly as simple as:

3
U trs , m kT
2
U rot , m RT linear molecules
43

The vibrational energy, Uvib

U vib , m

R vib
vib / T
(e
1)

This does reduce to the simple form at

equipartition (at very high temperatures) to:

U vib , m RT
Normally, at
room T:

U vib , m

(equipartition)

3000 R 1
10
R
(e 1) 7

44

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

U vib , m

R vib
vib / T
U (0) vib , m
(e
1)
R vib
1
vib / T
N A h
(e
1) 2

45

Vibrational heat capacity, Cvib

The vibrational heat capacity can be found using:

Cvib , m

U vib , m

vib
R

vib / T

vib / T

(e

1)

The Einstein Equation

This equation can be written in a more compact
form as:

Cvib , m

vib
RF E

46

Vibrational heat capacity, Cvib

FE with the argument vib/T is the Einstein function
2 u

u e
FE u
2
(e 1)

vib
u

The Einstein function

47

The Einstein heat capacity

1.0

FE

0.5

low T

0.0

High T
0.1

10

Reduced temperature T/

48

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

49

The vibrational entropy, Svib

S vib

U vib U vib (0) Avib Avib (0)

T
T
U vib U vib (0)

k ln Qvib
T

Nand N = N for one mole, thus:

We know Qvib qvib
A

ln Qvib N A k ln qvib R ln qvib

vib / T
vib / T

vib / T
ln 1 e
R
(e
1)
S vib , m

50

Variation of vibrational entropy with

reduced temperature
3.0
2.5

Svib/R

2.0
1.5
1.0
0.5
0.0

0 T
0.1

10

Reduced temperature T/

51

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.
52

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

e 0 (higher terms ) 1

To do so would be unwise!
One must consider degeneracy of the ground
electronic state.
53

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

Most molecules and stable ions have nondegenerate ground states.

A notable exception is molecular oxygen, O2,
which has a ground state degeneracy of 3.
54

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 =

(2S+1)

55

Electronic partition function

spectroscopic atom ground state =

(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)

56

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.
57

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)

58

Electronic partition function

Species
Li

Term
Symbol

gn

S1/2

g0 = 2

P0

g0 = 1

S3/2

g0 = 4

P2

g0 = 5

P3/2

g0 = 4

P1/2

g1 = 2

1/2

g0 = 2

3/2

g1 = 2

-g

g0 = 3

g1 = 1

C
N

3
4

O
F

3
2

NO

2
2

O2

el/K

590
178
11650

59

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:

qel g 0 g1e

el / T

60

Electronic partition function

For F atom at 1000 K we have:

qel g 0 g1e

el / T

4 2e 590 /1000 5.109

For NO molecule at 1000 K we have:

qel g 0 g1e

el / T

2 2e 178 /1000 3.674

61