8.

2 Energy level and its degeneracy

1
0

3
3

Energy levels are said to be degenerate, if the same energy

level is obtained by more than one quantum mechanical state. They
are then called degenerate energy levels.
The number of quantum states at the same energy level is called
the degree of degeneracy.

N ni
i

U ni i
i

A molecular energy state is the sum of

an electronic (e), nuclear (n), vibrational
(v), rotational (r) and translational (t)
component, such that:

t r v e n

The degree of freedom of movement

Translation: x,y,z F=3

Rotation
For linear molecules, F=2
For non-linear molecules, F=3

Vibration
A polyatomic molecule containing n
atoms has 3n degrees of freedom
totally. Three of these degrees of
freedom can be assigned to
translational motion of the center of
mass, two or three to rotational motion.
3n-5 for a linear molecule;
3n-6 for a nonlinear molecule

 CO2 has 33-5 = 4 degrees of freedom of

vibration; nonlinear molecule of H2O has 33-6 =
3 degrees of freedom of vibration.

8.2.1 Translational particle

The expression for the allowed translational energy levels of a
particle of mass m confined within a 3-dimensional box with
sides of length a, b, c is
2

2
x
2

2
y
2

2
z
2

n
h n
t
( )
8m a b
c
Where h 6.62610-34Js nx, ny, nz are integrals called
quantum numbers. The number of them is 1,2, .
2

If a=b=c,
equation becomes

h
2
2
2
t
(
n

n
)
x
y
z
3/ 2
8mV

all energy levels except ground energy level

are degenerate.
Example At 300K, 101.325 kPa, 1 mol
of H2 was added into a cubic box. Calculate
the energy level t,0 at ground state, and the
energy difference between the first excited
state and ground state.

Solution Take the H2 at the condition as an ideal gas,

then the volume of it is
nRT 1 8.3145 300
V

0.02462 m3
p
101325

The mass of hydrogen molecule is

m M / L 2.0158 103 / 6.022 10 23 3.347 10 27 kg

 t,0

h2
3 (6.626 1034 ) 2
40

5.811

10
J
2/3
27
2/3
8mV
8 3.347 10 0.02462

h2
40
t,1

11.622

10
J
2/3
8mV

t,1 t,0 (11.622 5.811) 1040 5.811 1040 J

the energy difference is so small that the translational particles
are excited easily to populate on different excited states, and
that the energy changes of different energy levels can be think
of as a continuous change approximately.

8.2.2 Rigid rotator (diatomic)

The equation for rotational energy level of diatomic molecules is

h2
r
J ( J 1)
2
8 I

J 0
1
2

where J is rotational quantum number, I is the moment of

inertia ( )

m1m2
2
2
I (
) R0 R0
m1 m2
is the reduced mass ( ), The degree of degeneracy is

g r,J 2 J 1

8.2.3 One-dimensional harmonic oscillator

1
v ( v )h
2

v 0,1, 2,

Where v quantum number when v=0 the

energy is called zero point energy.

v,0
v,2

1
h
2
5
h
2

3
v,1 h
2
7
v,3 h
2

One dimensional harmonic vibration is non-degenerate.

8.2.4 Electron and atomic nucleus

The differences between energy levels of electron
motion and nucleus motion are big enough to keep the
electrons and nuclei stay at their ground states.
Both degree of degeneracy, ge,0, for electron motion
at ground state and degree of degeneracy, gn,0, for
nucleus motion at ground state are different for
different substances, but they are constant for a given
substance.

8.5 Computations of the partition function

8.5.1 Some features of partition functions
(1) at T=0, the partition function is equal to the
degeneracy of the ground state.

q gi e

i
kT

lim q g 0
T 0

(2) When T is so high that for each term i/kT=0,

lim q

(3) factorization property If the energy is a sum

of those from independent modes of motion, then

q qt qr qv qe qn
i t , i r ,i v ,i e ,i n ,i
g i g t , i g r , i gv , i g e , i g n , i
The partition functions for 5 mode motions are expressed as

qt gt ,i e

t ,i
kT

qe g e,i e
i

qr g r ,i e

r ,i
kT

e ,i
kT

qe g e ,i e
i

qv g v ,i e
i

e ,i
kT

v ,i
kT

 t ,i
r,i
q [ g t,i exp( )] [ g r,i exp( )]
kT
kT
i
i
v,i
e,i
[ g v,i exp( )] [ g e,i exp( )]
kT
kT
i
i
n,i
[ g n.i exp( )]
kT
i

qt qr qv qe qn

8.5.2 Zero-point energy

zero-point energy is the energy at ground state or
the energy as the temperature is lowered to
absolute zero.
Suppose some energy level of ground state is 0,
and the value of energy at level i is i, the energy
value of level i relative to ground state is

i 0
0
i

Taking the energy value at ground state as zero,

we can denote the partition function as q0.

q gi e
0

i0

kT

q e q
0

q e

t ,0 / kT

q e

e ,0 / kT

0
t
0
e

r ,0 / kT

qt ;

q e

qe ;

q e

0
r

0
n

qr ; q e

n ,0 / kT

0
v

qn

Since t,00, r,0=0, at ordinary temperatures.

q qt , q qr
0
t

0
kT

0
r

v ,0 / kT

qv

 The vibrational energy at ground state is

v ,0 h
1
2

therefore

q e
0
v

h /2 kT

qv

the number of distribution in any levels does not

depend on the selection of zero-point energy.
N
N
N
i / kT
( i0 0 )/ kT
i0 / kT
ni gi e
0 0 / kT g i e
0 gie
q
q e
q

8.5.3 Translational partition function

Energy level for translation
2

2
x
2

2
y
2

2
z
2

h n
n
i ,t
( )
8m a b
c
The partition function

t ,i
qt gt ,i exp( )
kT
i

2
2
2

n
n
n
h
y
x
z
qt exp
/ kT
2 2 2

c
nx 1 n y 1 nz 1
8m a b

h2
h2 2
h2 2
2
exp
n exp
n y exp
n
2 x
2
2 z
8mkTb
8mkTc
nx 1
nz 1
8mkTa ny 1

qt , x qt , y qt , z

h
qt , x exp
2
8
mkTa
nx 1

h2
qt , z exp
2
8
mkTc
nz 1

2
nx

2
z

qt , y

h2
exp
2
8
mkTb
n y 1

2
y

Take qt,x as an example

qt, x

2
x
2

n
h
exp(
)
8mkT a
nx 1

h
2
(

2
8mkTa

exp( n )
2

nx 1

2
x

For a gas
2 at ordinary temperature 2<<1, the summation
converts into an integral.

qt,x exp( n )dnx

0

2
x

From mathematic relations in Appendix

x 2

1 12
dx ( )
2

1
1
1
2

mkT
2
qt,x
( ) 2 (
)
a
2
2
h

qt,y In like
qt,z manner,

2 mkT 3 2
qt (
) a bc
2
h
2 mkT 3 2
(
) V
2
h

 Example Calculate the molecular partition

function q for He in a cubical box with sides 10cm
at 298K.
Solution The volume of the box is V=0.001m3.
The mass of the He molecule is 0.004/
(6.0221023)=6.646610-27kg. Substituting these
numbers and the proper natural constants, we have
2 6.6466 10 1.38 10
q
34 2
(6.626

10
)

27

23

298

3/2

0.001 7.820 1027

For ideal gas,

M
m
L

nRT NkT
V

p
p

8.2052 107 N M
1
kg

mol

qt
p
Pa

T K

5
2

8.5.4 Rotational partition function

The rotational energy of a linear molecule is given by
r = J(J+1)h2/82I and each J level is 2J+1 degenerate.
h2
r J ( J 1) 2
8 I
qr g r ,i e
i

r ,i
kT

J 0
1
2

h2
(2 J 1) exp J ( J 1) 2
8 IkT
J 0

define the characteristic rotational temperature

h2
r 2
8 Ik

J ( J 1) r
qr (2 J 1) exp(
)
T
J 0

r<<T at ordinary temperature, The summation can be

approximated by an integral

qr (2 J 1) exp J ( J 1) r / T dJ
0

Let J(J+1)=x, hence J(2J+1)dJ=dx, then

qr exp( x r / T )dx T r 8 IkT h

0

For a homonuclear diatomic molecule, such as O2, it comes back

to the same state after only 180o rotation.

T
8 2 IkT
qr

2
r
h
where is called the symmetry number. is the number of
indistinguishable orientations that a molecule can exhibit by
being rotated around symmetry axis. It is equal to unity for
heteronuclear diatomic molecules and is equal to 2 for
mononuclear diatomic molecules.
For HCl, = 1; and for Cl2, = 2.

8.5.5 Vibrational partition function

Vibrational energies for one dimensional oscillator are

1
v (v )h
2

v 0,1, 2,

Vibration is non-degenerate, g=1. The partition function is

qv gv ,i e
i

v ,i

kT

exp v h / kT
2
v 0

Define the characteristic vibrational temperature

h
v , v
k
v
3 v
5 v
qv exp( ) exp(
) exp(
)
2T
2T
2T

v
v
2 v
exp( ) [1 exp( ) exp(
) ]
2T
T
T

 Characteristic vibrational temperatures are usually

several thousands of Kelvins except for very low
frequency vibrational modes.

v,H2 5986 K
v,CO 3084 K

v,O2 2239 K
we cannot use integral instead of summation in the
calculation of vibrational partition function.

At low T v 1 exp( v ) 1
T
T
according to mathematics

when x 1 1 x x
1 x
2

v / 2T
1
e
1
v /2T
qv e

v / 2T
v / T
v /2T
1 x 1 e
e
e

take the ground energy level as zero,

qv0

1
exp v,0 / kT qv
h

1 exp( )
kT

For NO, the characteristic vibrational temperature is

2690K. At room temperature v/T is about 9; the
, indicating
qv0 1 that the vibration is almost in the ground
state.

8.5.6 Electronic and nuclear partition function

e,0
e,1
qe g e,0 exp(
) g e,1 exp(
)
kT
kT

e,0
g e,1
e,1 e,0
g e,0 exp(
)[1
exp(
) ]
kT
g e,0
kT

( e,1 e,0 ) 400 kJ mol ,

-1

Energy difference is large, so electrons are generally at ground

state, all terms except first one in the summation expression is
negligible.

e,0
qe g e,0 exp(
)
kT

q e
0
e

e ,0 / kT

qe g e ,0

 If the quantum number of total angular momentum

for electronic motion is j, the degeneracy is (2j+1).
Then the electronic partition function can be
written as

q 2 j 1
0
e

A rare exception is halide atoms and NO molecule.

The difference between the ground state and the
first excited state of them are not so large, the
second term in the summation has to be
considered.

Nuclear motion
Nuclear motion is always in the ground state at ordinary
chemical and physical process because of large energy
difference between ground and first excited state. Its
partition function has the form of

n,0
qn g n,0 exp(
)
kT

q g n ,0 2 I 1
0
n

where I is a quantum number of nuclear spin.

8.6 Thermodynamic energy and partition function

Independent particle system:

U ni i
i

N
i / kT
ni gi e
;
q
N
i / kT
U gi e
i
i q

(8.48)

8.6 Thermodynamic energy and partition function

T V T
gi e
i

g e
i

i / kT

i / kT

i 1
2
k T

1
2 gi e i / kT i
kT i
q
kT gi e i / kT i
T V i
Substitute this equation into equation (8.48), we have
2

N 2 q
2 ln q
U kT
NkT

Substitute the factorization of partition function for q

ln qt qr qv qe qn
U NkT

V
2

Only qt is the function of volume, therefore

 ln qt
2 d ln qr
2 d ln qv
U NkT
NkT
NkT
dT
dT
T V
2 d ln qe
2 d ln qn
NkT
NkT
dT
dT
Ut U r Uv Ue U n
2

If the ground energy is specified to be zero, then

0

0
2 ln q
U NkT

T V

Substitute q =qe

0 / kT

into this equation, it follows that

U U N 0
0

It tells us that the thermodynamic energy depends

on the zero point energy. N0 is the total energy of
system when all particles are localized in ground
state. It (denoted as U0) can also be thought of as the
energy of system at 0K. Then,

U U U0
0

 U0 can be expressed as the sum of different

energies

U U U U U U
0

0
t

0
r

0
v

U Ut

U Ur

U 0

U 0

0
t
0
e

0
r

0
n

0
e

0
n

Nhv
U Uv
2
0
v

The calculation of U t0 , U r0 , U v0
(1) The calculation of

0
t

ln qt
U U t NkT

T V
0
t

2 mkT
ln

2
h

2
NkT

3/2

3
NkT
2
V

The calculation of

U r0

ln qr
U U r NkT

T V
T
d ln
r
2
NkT
NkT
dT
The degree of freedom of rotation for diatomic or
0
r

linear molecules is 2, the contribution to the energy of

every degree is also RT for a mole substance.

The calculation of U

0
v

1
d ln
0
v / T
0
2 d ln qv
2
1

e
U v NkT
NkT
U
dT
dT U
1
Nk v v /T
e
1
0
v

0
v

Usually, v is far greater than T, the quantum effect

of vibration is very obvious. When v/T>>1, U v0 0
Showing that the vibration does not have contribution
to thermodynamic energy relative to ground state.

 If the temperature is very high or thev is very

small, thenv/T<<1, the exponential function can
be expressed as
v /T

e
U Nk v
0
v

1
ev /T

v
1
T

1
Nk v
NkT
v
1
1
1
T

 For monatomic gaseous molecules we do

not need to consider the rotation and
vibration, and the electronic and nuclear
motions are supposed to be in their ground
states. The molar thermodynamic energy is

3
U m RT U 0,m
2

 For diatomic gaseous molecules vibration and

rotation must be considered. If only lowest
vibrational levels are occupied, the molar
thermodynamic energy is

5
U m RT U 0,m
2

(U 0)
0
v

 If all vibrational energies are equally accessible,

the molar thermodynamic energy for vibration is

U RT
0
v

The molar thermodynamic energy for diatomic

molecules is then

7
U m RT U 0,m
2

(U RT )
0
v

8.7 Heat capacity and partition function

The molar heat capacity, CV,m, can be derived
from the partition function.
U m

ln q

2
CV ,m
CV ,m
RT

T V V
T V
T
Replace q with

0 0 / kT

qq e

CV ,m

ln q0

RT 2
T

We can see from above equations that heat capacity does not
depends on the selection of zero point of energy.

 Electrons and nucleus are in ground state

ln q0
2
t
RT
CV ,m

V V

CV ,t CV ,r CV ,v

ln qr0
RT

V
2

ln qv0
RT

V
2

The calculation of CV,t, CV,r and CV,v

(1) The calculation of CV,t

2 mkT 3 2
qt (
)
V
2
h

CV ,m

ln q0
t
RT 2
T

3
R
2

 (2) The calculation of CV,r

8 2 IkT
T
qr

2
h
r
CV ,r

(linear molecules)

2 ln qr

RT
R
T
T V

If the temperature is very low, only the lowest rotation state is

occupied and then rotation does not contribute to the heat
capacity.

The calculation of CV,v

q e
0
v

CV ,v

v,0

kT

qv

1 e

d
2 ln qv

RT

dT
T V

CV , v

v
R
e
T

Generally, v/T>>1, equation becomes

2

CV ,v

v
R
e
T

v
T e T
R
e

v
v
T
R
e
0

It shows that under general conditions, the contribution to heat

capacity of vibration is approximately zero.

When temperature is high enough,

v
1
T

CV ,v

v
T
v
R
e

T
v

Re

In gases, all three translational modes are active and their

contribution to molar heat capacity is

3
CV R
2

The number of active rotational modes for most linear

molecules at normal temperature is 2

CV 2 12 R R
In most cases, vibration has no contribution to the heat capacity,

CV CV ,t

5
CV ,v 0 R
2

8.8 Entropy and partition function

8.8.1 Entropy and microstate
Boltzmann formula

S k ln

k = 1.3806210-23 J K-1
As the temperature is lowered, the , and hence the S of the
system decreases. In the limit T0, =1, so ln=0, because
only one configuration is compatible with E=0. It follows
that S0 as T0, which is compatible with the third law of
thermodynamics.

ln ln WD ln Wmax
D

S k ln Wmax
For example
48

10
0.01
50
10

ln1048
0.96 1
50
ln10

When N approaches infinity,

ln Wmax
1
ln

8.8.2 Entropy and partition function

For a non-localized system, the most probable
ni
distribution number is
g

WD
i

ni !

ln WD (ni ln gi ln ni !)
i

Using Stirling equation ln N!=N ln N - N and Boltzmann

distribution expression

N
ni gi e i / kT
q

 We have,
ln WB (ni ln gi ni ln ni ni )
i

ni i
N
(ni ln g i ni ln ni ln gi
ni )
q
kT
i
q U
N ln
N
N kT
q U
S k ln WB Nk ln Nk
(non-localised system)
N T
or
q0 U 0
S Nk ln
Nk
N T

(non-localised system)

 For localized system

S k ln WB Nk ln q

U
T

(localised system)

or
U0
S Nk ln q
T
0

(localised system)

Entropy does not depend on the selection of zero point

energy .

 Factorizing the partition function into different

modes of motions and using

U U U U U U
0

0
t

0
r

0
v

0
e

We can give

S St S r S v S e S n

0
n

For identical particle system, entropies for every mode of

motion can be expressed as

qt0 U t0
St Nk ln
Nk
N T
0
r

0
r

q U
S r Nk ln
N T

qe0 U e0
Se Nk ln
N T

0
v

0
v

0
e

0
e

q U
Sv Nk ln
N T

q U
St Nk ln
N T

8.8.3 Calculation of statistical entropy

At normal condition electronic and nuclear
motions are in ground state, and in general
physical and chemical process the contribution to
the entropy by two modes of motion keeps
constant. Therefore only translational, rotational
and vibrational entropies are involved in
computation of statistical entropy.

S St S r S v

8.8.3 Calculation of statistical entropy

(1) Calculation of St

2 mkT 3 2
q qt (
) V
2
h

3
U NkT
2

0
t

0
t

qt0 U t0
St Nk ln
Nk
N T
St

2 mkT

Nk ln
Nh3

3/2

5
Nk
2

 For ideal gases, the SackurTetrode equation is

used to calculate the molar translational entropy.
S m ,t

5
3

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

(2) Calculation of Sr
For linear molecules

qr0 qr T / r

U r0 NkT

When all rotational energy levels are accessible

qr0 U r0
S r Nk ln
N T
We obtain

S r Nk ln(T / r ) Nk
Sm,r

T
R ln
R
r

(3) Calculation of Sv
Substitute

q 1 e
0
v

v / T

and U Nk r e
0
v

v / T

Into the following equation

S v Nk ln qv0 U v0 / T

v / T

v / T

Nk ln 1 e

S m,v R ln 1 e

Nk vT
R vT

v / T

v /T

residual entropy
in some the experimental entropy is less than the
calculated value. One explanation to this
discrepancy is that the experimental system does
not reach a real state of equilibrium. In other
words, some disorder is present in the solid even
at T = 0 K. In this case, the entropy at T = 0 is then
greater than zero. This difference in entropy is
called the residual entropy.

8.9 Other thermodynamic functions and partition

functions
1

A, G, H and q

q U

A U TS U T Nk ln Nk
N T

q
NkT ln NkT kT N ln q N ln N N
N
kT N ln q N ln N N kT N ln q ln N !
qN
A kT ln
N!
A kT ln q N

(for identical particles)

(localized system)

 A
ln q
G A pV
p
NkT

T
ln q
N
G kT ln q / N ! NkTV
(non-localized system)
V T
ln q
G kT ln q NkTV
(localized system)
V T
H U pV
N

ln q
ln q
NkT
NkTV

V
T V