Statistical Thermodynamics
Atkins, P. & de Paulo, J. (2009). Physical Chemistry. 9th edition.
Oxford: Oxford University Press. (Chapters 15, 16)
The Distribution of Molecular States
Configurations and Weights
The Dominating Configuration
Boltzmann Distribution
Molecular Partition Function & its
Partition Function for Independent Molecules
Perfect Gas
Translational, Electronic & Nuclear Partition Function
Partition Function for Diatomic Gas
Factorization
Vibrational Partition Function
Statistical Thermodynamics & Thermodynami Quantities
The Internal Energy
Heat Capacity
Entropy
2
Introduction
By solving the Shrodinger equation (H =E ), one can calculate the energy of
molecules & then related the result to their structures.
Thus, The next step is to see how this knowledge can be used to calculate the
properties of matter.
Statistical thermodynamics provides the link between the individual molecular
properties and its bulk thermodynamic properties.
It means that how the average behavior of large number of molecules will change.
For example, the pressure of the gas depends on the average force exerted by its
molecules & there is no need to specify which molecules happen to be striking the
wall at any instant.
Therefore, for a large number of molecules the change in any thermodynamic
properties can be negligible compared to the average values.
3
The Distribution of Molecular States
Consider a system composed of N molecules with a constant total energy, E.
These molecules are independent, i.e. no interactions exist among the molecules.
Countless collisions occur.
It is hopeless to keep a track of positions, momenta, and internal energies of all
molecules.
The Principle of equal a priori probabilities:
All possibilities for the distribution of energy are equally probable.
By this, the number of molecules and the total energy are kept the same.
Here, a Priori means as far as one knows.
Democracy among microscopic states !!!
4
For example, consider four molecules in a threelevel system. The following
two arrangements have the same probability.
ll 2
l
l 0
l 2
111
 0
Configurations and Weights
Imagine that there are N molecules in the system.
n0 molecules with energy 0; n1 molecules with energy 1; n2 molecules
with energy 2, and so on.
where 0 < 1 < 2 < ... are the energies of different states.
The average number of molecules occupying a state is called population. So,
the energy of the state is denoted as i .
The specific distribution of molecules is called configuration of the system,
denoted as { n0, n1, n2, ......}
5
For example, in the system below, there is 17 molecules, and each molecule has
four states. The above configuration is thus: { 4, 6, 4, 3 }
STATE
10
14
15
2
13
12
11
5
16
17
4
6
Now the question is how to determine the population ?
For example,
A configuration such as {N, 0, 0, ...} means that every molecule is in the
ground state, so there is only one way to achieve this configuration.
But a configuration such as {N2, 2, 0, ......} means that there are two
molecule is in the first excited state, and the rest in the ground state which can
be achieved in N(N1)/2 ways.
A configuration { n0, n1, n2, ......} can be achieved in W different ways.
W is called the weight of the configuration and can be evaluated as follows,
W = N! / (n0! n1! n2! ...)
1. It means that there is N! different ways to arrange N molecules.
2. ni! arrangements of ni molecules with energy i correspond to the same
configuration.
7
Question. Calculate the number of ways of distributing
20 objects into six boxes with the arrangement {1, 0, 3, 5,
10, 1}. Recall that; 0! = 1.
Answer:
20! / 1! 0! 3! 5! 10! 1! = 931,170,240
Question. Calculate the number of ways of distributing 3 objects a, b, and c
into two boxes with the arrangement {1, 2}.
Answer:
 a  b c ,  b  c a ,  c  a b .
Therefore, there are three ways 3! / 1! 2!
To eliminate overcounting
these configurations
of
 a  c b ,  b  a c ,  c  b a 
But what if the number of objects is so large ?!!
Stirlings Approximation:
When x is large: ln x! x ln x  x
x
ln x!
x ln x x
ln A
1
2
4
6
8
10
0.000
0.693
3.178
6.579
10.605
15.104
1.000
0.614
1.545
4.751
8.636
13.026
0.081
0.65
3.157
6.566
10.595
15.096
Note that : A = (2
)1/2 (x+1/2)x ex
10
Therefore:
ln W ( N ln N  N )  ( ni ln ni  ni ) = N ln N  ni ln ni
x
1
16
20
30
ln x!
19.987
30.672
42.336
74.658
x ln x  x
17.819
28.361
39.915
72.036
ln A
19.980
30.666
42.332
74.656
Note that : A = (2
)1/2 (x+1/2)x ex
11
The Dominating Configuration
Imagine that there are N molecules distribute among two states. The
possible configurations are;
{N, 0}
{N1, 1},
{Nk, k},
{1, N1}
{0, N}
And their weights are 1; N; ... , N! / (Nk)! k!; ... ; N; 1, respectively.
For example, N=8,
the weight distribution is:
N=8
60
40
20
8
12
12000
N =16
10000
8000
6000
4000
2000
0
0
9 1 01 11 21 31 41 51 6
6 .0 0 E + 0 0 8
N = 32
5 .0 0 E + 0 0 8
4 .0 0 E + 0 0 8
3 .0 0 E + 0 0 8
2 .0 0 E + 0 0 8
1 .0 0 E + 0 0 8
0 .0 0 E + 0 0 0
0
12
16
20
24
28
32
k
13
When N is even, the weight is maximum at k = N/2, therefore;
Wk=N/2 = N! / [(N/2)!]2
When N is odd, the maximum is at k = N/2 1.
Therefore, as N increases, the maximum becomes sharper!
The weight for k = N/4 is Wk=N/4 = N! / [(N/4)! (3N/4)!]
The ratio of the two weights is equal to:
R(N) Wk=N/2 / Wk=N/4 =(N/4)! (3N/4)! / [(N/2)!]2
 N 4
 8  16  32  256
 6.0 x 1023
R(N)  1.5  2.5  7.1  57.1  3.5 x 1014  2.6 x 103e+22
14
Therefore, for a macroscopic molecular system ( N ~ 1023 ), there are
dominating configurations, so that the system is almost always found in
or near the dominating configurations, i.e. equilibrium.
What if the system has more states?
Constraints for the system
There are two constraints for the system:
1.
The total energy of a system is constant; ni i = E = constant
2.
The total number of molecules is conserved; ni = N = constant
How to maximize W or lnW under these constraints?
15
The Boltzmann Distribution
The Boltzmann distribution states;
ni / N = Pi = exp (
 i )
Pi is the probability.
is defined as; 1/
= kT ; Where k is the Boltzmann constant.
is a coefficient that makes the total probability equals ONE.
1 = i ni / N = i exp(

i)
exp(
) = 1 / i exp(
i)
=  ln [
i exp(
i)]
16
In summary, using the principle of equal a priori probabilities, the
probabilities of different configurations can be evaluated by simple counting.
Then, the dominating configuration whose population follows the Boltzmann
distribution can be found.
The Boltzmann distribution relates the macroscopic physical properties to the
microscopic molecular properties, and it is capable of explaining the equilibrium
properties of all materials.
To find the most important configuration, one need to vary { ni } to seek the
maximum value of W. But how?
For example, consider a onedimensional function such as F(x) = x2
dF/dx = 0
Is this enough?
17
How about a twodimensional case;
For example, finding the minimum point of the surface of a half
watermelon which is F(x,y).
F/
x = 0
F/
y = 0
If you have multidimensional function: F(x1, x2, , xn);
F/
xi = 0
i = 1,2,,n
To find the maximum value of W or lnW, we should have:
lnW / ni = 0
i=1,2,3,...
18
The method of Lagrange Multipliers
It is used to minimize or maximize a function F(x1, x2, , xn) under
constraints:
C1(x1, x2, , xn) = Constant1
C2(x1, x2, , xn) = Constant2
.
.
.
Cm(x1, x2, , xn) = Constantn
L = F(x1, x2, , xn)  i iCi(x1, x2, , xn)
L/
xi = 0
i=1,2, ...,
19
Lets see the water melons surface case. How to find the minimum
or maximum of F(x, y) under a constraint x = a ?
L = F(x, y)  x
L/x=0
L/y=0
Therefore;
dL = dF (x,y)  i i dCi
Under constraint of x=a, dCi = 0, thus dF = 0.
It means that F is at its maximum or minimum.
20
The method of Lagrangian Multiplier based on the Boltzmann
distribution function;
First, construct a new function, L.
L = lnW + i ni  i ni i
Next, we need to find the maximum of L by changing ni .
Finding and is equivalent to finding the maximum of W under the
two constraints defined before, i.e.;
L/
ni = lnW/
ni + 
i = 0
Assignment 1. Prove this equation is correct.
21
ln W ( N ln N  N )  i ( ni ln ni  ni )
Since,
= N ln N  i ni ln ni
lnW/
ni = (N ln N)/
ni  (ni ln ni)/ ni
=  ln (ni/N)
Therefore,
ln (ni / N) + 
i = 0
ni / N = exp(

i)
By this,
E = N < > = 3N/2
 where < > is the average kinetic energy of a molecule.
Therefore,
< > = <mv2/2> = 3/2
22
On the other hand, according to the Maxwell distribution of speed,
the average kinetic energy of a molecule at an equilibrium is:
<mv2>/2 = 3kT/2
This is actually the definition of the temperature where k is the
Boltzmann constant.
Thus, 1 / = kT. This is the physical meaning of , the reciprocal
temperature.
23
Q. Consider a molecule whose ground state energy is 10.0 eV, the first excited
state energy 9.5 eV, the second excited state energy 1.0 eV. Calculate the
probability of finding the molecule in its first excited state at T = 300, 1000,
and 5000 K.
Hint;
The energies of second, third and higher excited states are much higher than those of
ground and first excited states, for instance, at T = 5,000 K, the probability of finding
the first excited state is,
p2 = exp(

2)
with 2 = 9.5 eV
And, the probability of finding the second excited state is,
p3 = exp(

3)
with 3 = 1.0 eV
If you calculate the ratio of probabilities between second & first excited states at this
temperature and then compared that to the first excited state, you will see the chance
that the molecule is in second excited state is exceedingly slim. Thus, we consider
only the ground and first excited states, a twostate problem.
Note that: [ 1 eV = 1.60 x 1019 J; k = 1.38 x 1023 J.K1]
24
Therefore, the probability of finding the molecule in the first excited state is:
p = exp(
2) / [exp(
1) + exp(
2)]; where, 1 = 10.0 eV, and 2 = 9.5 eV
(1) T = 300 K
p =
(2) T = 1000 K
p =
0.5 11600
exp
300
0.5 11600
+ exp
300
0.5 11600
exp
1000
0.5 11600
+ exp
1000
0.5 11600
exp
5000
0.5 11600
+ exp
5000
(3) T= 5000 K
p =
25
The Molecular Partition Function
The Boltzmann distribution function can be written as;
pi = exp (
i) / q
where pi is the probability of a molecule being found in a state i with
energy i.
q is called the molecular partition function;
q = i exp (
i)
The summation is over all possible states (not just the energy levels).
For example, if the energy level is gifold degenerate, then the molecular
partition function can be re written as;
q = i gi exp(
i)
26
It means that:
As T 0,
q g0
Meaning at T = 0, the partition function is equal to the degeneracy of
the ground state.
As T ,
q the total number of states.
Therefore, the molecular partition function gives an indication of the
average number of states that are thermally accessible to a molecule at
the temperature of the system.
The larger the value of the partition function is, the more the number
of thermally accessible states is.
Thus, The relationship between q and : exp(
) = q1
27
28
2
q=e +e
=q1
3
+e
+ ......
Therefore,

q=1/(1e
)
29
Partition Function for Independent Molecules
Consider a system which is composed of N identical & indistinguishable
molecules with no interaction between them.
We may generalize the molecular partition function q to the partition
function of the system Q (=1/kT);
Q = i exp(
Ei)
where Ei is the energy of a state i of the system, and summation is over
all the states.
Since there is no interaction among molecules, Ei can be expressed as;
Ei = i(1) + i(2) +i(3) + + i(N)
where i( j) is the energy of molecule j in its molecular state.
30
The partition function Q:
Q = i exp[
i(1)  i(2)  i(3)  
i(N)]
= {
i exp[
i(1)]}{
i exp[
i(2)]} {
i exp[
i(N)]}
= {
i exp(
i)}N
= qN
where q i exp(
i) is the molecular partition function.
This equality (Q= qN) is satisfied because the molecules are
independent of each other.
31
Perfect Gas
Perfect gas is an idealized gas where an individual molecule is treated as a point
mass which randomly moving and no interaction exists among molecules (PV=nRT).
Molecular energy; the total energy of each molecule is defined as the sum of the
translational (kinetic) and internal energies;
= trans + int
The internal energies include rotational, vibrational, electronic, and nuclear
energies
int = rot + vib + elect + nucl
electronic
vibrational
rotational
translational
32
Translational Partition Function (qT) of a monoatomic gas
A molecule moves in a threedimensional space, but first consider onedimensional case.
Imagine a molecule of mass m moves along the x direction between x= 0 &
x= X, but it has been confined in the y and z direction. What is its partition
function qx?
From particle in a box calculation, the energy levels are;
En = n2h2 / (8mX2)
n = 1, 2, 3,
If the lowest energy equals to zero point energy, the relative energies can
then be expressed as;
n = (n21)
with
= h2 / (8mX2)
qx = n exp [ (n21)
]
33
is very small, thus;
qx = dn exp [ (n21)
]
= dn exp [ n2 ] = (2
m/h22)1/2 X
Now consider a molecule of mass m, free to move in a container of volume,
V=XYZ.
Its partition function qT can be expressed as;
qT = qx qy qz
= (2
m/h22)1/2 X (2
m/h22)1/2 Y (2
m/h22)1/2 Z
= (2
m/h22)3/2 XYZ = (2
m/h22)3/2 V
= V/
3
where, = h(
/2
m)1/2 or (h2/2
mkT)1/2, the thermal wavelength. The thermal
wavelength is small compared with the linear dimension of the container.
Partition function of a perfect gas (N molecules);
Q = (qT) N = V N / 3N
34
For example, calculate the molecular partition function q for He in a cubical
box with sides 10 cm at 298 K.
Answer;
The volume of the box is V=0.001m3. The molar mass of the He molecule is
0.004/(6.0221023)=6.64661027kg. Substituting these numbers and the proper
natural constants, we have;
27
2 6.6466 10 1.38 10
q=
(6.626 10 34 ) 2
23
298
3/ 2
0.001 = 7.820 10 27
N
n =
NA
nRT NkT
V=
=
p
p
8.2052 107 N M
1
kg
mol
qt =
p
Pa
(T K )
5
2
35
Electronic Partition Function
The electronic partition function is usually written as a sum over
energy levels rather than a sum over states (Where gi is the
degeneracy of the ith electronic level);
qelect = gi e i
Recall that the first electronic level is the ground state & the
remaining energy levels are expressed in terms of their spacing
relative to that.
qelect = g1 + g 2 e 12 + L
At ordinary temperatures, usually only the ground state and perhaps
the first excited state need to be considered.
36
Nuclear Partition Function
The nuclear partition function has a form similar to that of the
electronic partition function.
qelect = gi e i
Nuclear energy levels are separated by millions of electron volts.
It means that temperatures on the order of 1010 K need to be
reached before the first excited state becomes populated to any
significant degree.
qelect = g1 + g 2 e 12 + L
Therefore, at ordinary temperatures we can simply express the
nuclear partition function in terms of the degeneracy of the ground
state.
37
Table below shows the electronic energies for a number of atoms
38
Diatomic Gas
Consider a diatomic gas made of two atoms A and B with N identical
molecules. A and B may be the same (homonuclear) or different
(heteronuclear).
The mass of a diatomic molecule is M. These molecules are
indistinguishable. Thus, the partition function Q of the gas can be
expressed in terms of the molecular partition function q;
Q = q / N!
N
The molecular partition q;
q = exp(i )
i
where, i is the energy of a molecular state i, =1/kT, and is the
summation over all the molecular states.
39
Modes of motions; translation, vibration, rotation
40
Molecular Partition Function; Factorization
The energy of a molecule j is the sum of contributions from its different
modes of motion; T (translation), R (rotation), V (vibration), E, (electronic)
( j) = T ( j) + R ( j) + V ( j) + E ( j)
The separation of the electronic and vibrational motions is justified by
different time scales of electronic and atomic dynamics.
Rotational motion is approximated based on rigid rotor in QM. It
means rotary motion is about the center of mass.
Vibrational motion is approximated based on harmonic oscillator. It
means relative vibratory motion of the two atoms.
q = i exp( i ) = i exp[ ( iT + iR + iV + iE )]
= [ i exp( iT )][ i exp( iR )][ i exp( iV )][ i exp( iE )]
= q T q R qV q E
41
The translational partition function of a molecule
T
exp(
i
i )
qT
sums over all the translational states of a molecule.
The vibrational partition function of a molecule
qV
sums over all the vibrational states of a molecule.
The rotational partition function of a molecule
qR
sums over all the rotational states of a molecule.
The electronic partition function of a molecule
qE
sums over all the electronic states of a molecule.
V
exp(
i
i )
R
exp(
i
i )
E
exp(
i
i )
42
A polyatomic molecule containing N atoms has 3N degrees of freedom
totally.
Three of these degrees of freedom can be assigned to translational
motion.
Two (linear molecules) or three (for nonlinear molecules) are for
rotational motion.
Thus, there are (3N5) (linear molecule) and 3N6 (nonlinear molecule)
for vibrational motion.
43
For example, CO2 has 335 = 4 degrees of freedom of vibration;
nonlinear molecule of H2O has 336 = 3 degrees of freedom of
vibration.
44
Recall rigid rotor & harmonic oscillator energy levels and degeneracy's
for rotational and vibrational motion.
Rigid Rotor
h 2 J ( J + 1)
J =
8
I
Harmonic Oscillator
J = 0,1, 2,K
I = re2
B rotational const.
12
v frequency
re bond length
m reduced mass
n = 0,1, 2,K
n = 1
J = 2 J + 1
I moment of inertia
v = h ( n + 12 )
m1m2
=
m1 + m2
1 k
v=
2
k force constant
B = h 8 2 Ic wave number
v
=
c
45
Vibrational Partition Function
Two atoms vibrate along an axis connecting the two atoms. The
vibrational energy levels; n= 0, 1, 2, .
nV = (n +1/ 2)hv
If we set the ground state energy to zero or measure energy from the
ground state energy level, the relative energy levels can be expressed as;
nV = nhv
55hv
44hv
33hv
22hv
1hv
00
= hv
46
Then, the molecular partition function can be evaluated;
e q v = e + e 2 + e 3 + .... = q v 1
q v = 1 + e + e 2 + e 3 ...
q v = n exp( n ) = n exp(nhv) = 1 /[1 exp( hv)]
Assignment 2;
q = 1 /( 1 e
v
1
)=
1 e hv
At very high temperature where kT >>hv, i.e.,
hv << 1, q 1
v
e hv 1 h
The vibrational temperature, v hv/k,
is often used instead of the vibrational
frequencies.
v/K
v/cm1
2
309
215
F2
HCl
H2
1280 4300 6330
892 2990 4400
47
Q. Calculate the proportion of I2 molecules in their ground, first excited,
and second excited vibrational states at 25oC. The vibrational
wavenumber is 214.6 cm1.
n = (n+1/2) h
q = n exp(
n) = exp (
h
/2) n exp (n
h
)
= exp (
h
/2) / [1 exp (
h
)]
Portion of I2 is in nth vibrational state is
n) / q = exp (n
h
) [1 exp (
h
)]
pn = exp (
Therefore, at T = 25oC = 298.15 oK,
h
= 1.036
p0 =0.645
p1 = 0.229
p2 = 0.081
48
For Example, evaluate the vibrational partition functions at 1500 K. We
know that there are three normal modes of H2O vibrational partition
function.
kT hc = 1042.6 cm 1
At 1500 K:
1594.8 cm1
3656.7 cm1
3755.8 cm1
Mode
~ cm 1
hc~ kT
3656.7
1594.8
3755.8
3.507
1.530
3.602
qV
1.031
1.276
1.028
qV = 1.0311.276 1.028 = 1.353
49
Table below shows the molecular constants for several diatomic
molecules.
50
Connection between Thermodynamic & Statistical Quantities
Thermodynamics is the science of energy conversion involving heat and
other forms of energy.
A thermodynamic system is defined by a macroscopic region of the universe,
often called a physical system studied by using the principles of
thermodynamics.
Statistical thermodynamics, or statistical mechanics, is the study of the
microscopic behaviors of thermodynamic systems using statistical methods and
probability.
The essential problem in statistical thermodynamics is to determine the
distribution of a given amount of energy E over N particles in a system.
The macroscopic properties such as internal energy, heat capacity, & can
be calculated in terms of partition functions.
By this, statistical thermodynamics is a bridge between macroscopic and
microscopic properties of a system.
51