Statistical Thermodynamics: Molecules to Machines

Venkat Viswanathan
May 5, 2015

Module 4: Non-interacting systems:

two- level systems and ideal
gases
Learning Objectives:
Discuss the statistical mechanics of non-interacting particles/molecules

Introduce distinguishability and indistinguishability of molecules

Analyze the statistical thermodynamics of a system of 2-state particles

Develop the statistical thermodynamics of a diatomic molecule

Key Concepts:
Non-interacting particles, distinguishable versus indistinguishable, singleparticle partition function, 2-state model, diatomic molecule, quantummode partition function, de Broglie wavelength, symmetry factor, electronic degeneracy, ideal gas equation of state, equipartition theorem.

statistical thermodynamics: molecules to machines

Non-interacting particles
Distinguishable particles
Consider a system of 2 distinguishable particles, meaning that they
can be uniquely identified according to some criterion (e.g. fixed
spatial position of particles on a surface or in space). The two particles
contain energy levels sA (with i = 1, 2, ..., a) and sB (with i = 1, 2,
..., b). In the i
i
canonical ensemble, the partition function Q is given by:

Q=

E .

.
.

exp
k T

exp

i=1 j=1

b
A

.
.

i
kBT

a
b
.
.

exp

exp

i=1

j=1

i + j
k BT

j
kBT

.
=
q

A qB

where qA and qB are the single-particle partition functions for the two
particles.
Generally, for a system with N non-interacting, distinguishable
par- ticles, each with a single-particle partition function q, the
partition func- tion is given by Q = qN .

Indistinguishable particles
Many systems are composed of particles that cannot be distinguished
from each other; for example, particles in the gas phase cannot be distinguished from each other.
For a system of N non-interacting, indistinguishable particles, the
partition function summation contains instances where particles exist
in different states but cannot be distinguished. On one extreme, if all
particles exist in different states, the over-counting factor is N !
(number of ways of reassigning N particle labels). On the opposite
extreme, if all particles are in the same state, the
indistinguishability and the degeneracy are the same, so there is no
over-counting factor.
At finite temperature, the particles are more likely to exist in a diversity of states that are over-counted by the factor N !. Thus to correct
for the indistinguishability at finite temperature, the partition
function
is given by Q =

1
N
!

qN .

Two-state, non-interacting particles

Consider a collection of non-interacting, distinguishable particles that
can exist in two states: the ground state (with zero energy) and the
excited state (with energy 0). We will analyze this system using two of

statistical thermodynamics: molecules to machines

the ensembles derived in the previously to show equivalence.

Microcanonical Ensemble
For a system of N particles, we consider a state with a fixed energy
E = 0n, where n is the number of particles in the excited state. The
degeneracy in the number of states with this fixed energy E is given
by:
N!
n! (N n)!
which is the number of permutations of n in N (N choose
n).
Therefore, the entropy of the system is given by:
.
.
N
S = kB log
n)!
!
n!(N

(1)

(2)

To approximate the entropy for large number of particles N (thermodynamic limit), we use Stirlings approximation:
.N
The logarithm of N ! is first written as log N ! = i= log i

The summation is then converted to an integral to give:

N
N
.
log n dn log n = N log N N + 1 N log N N (3)
1

n=1

Stirlings approximation is written as log N ! N log

N N . The entropy is now written as:
S = kB
log

n)!
!
n! (N

kB [N log N N n log n + n (N n) log(N n) + (N

n)]
= kBN [(1 x) log(1 x) + x log x]
(4)

where x = n/N = E/ (0N ) is the fraction in the excited state.

Using
. thermodynamic relations, the temperature is found to be:
1
S
.
.
.
x
[log(1 x) log x]
S
.
=
.
V
,N
V
,N
V
,N
=
=
kB N
T
E
E
0N
. x .
x

0
thus
= exp
= or x =

1x
1+
kBT
The Helmholtz free energy per particle f = F /N is given by:
f = e Ts = 0x +
kBT

= kBT

1 log
1+

1 1+

+ log
1 +

1+

..

log + kBT log(1 + ) + kBT

log
1 +.
1+
.
..
0
= kBT
1+
= kBT log q
(5)
kBT
log
exp

.
where we define q = 1 + exp
k

singleparticle canonical partition function.

.
, which will become the

Canonical ensemble
The canonical partition has a fixed temperature T and number of particles N , thus the energy states fluctuate according to the Boltzmann
distribution found in the previously. For this system, the partition
func- tion Q is written as:
.
Q= .
exp

mN

.
.

0m
.

exp

0m 2

0m1

m1 m2

...

k BT
k BT
.N

0m N

...

k BT
N

.
.
= 1 + exp
..0

k BT

kBT

= qN

m=0

where we again define the single-particle partition function q.

An alternative method to derive the partition function is to extend
the microcanonical solution to the canonical solution, such that:
Q=

.
.

exp

.
= 1+
exp

(E)

k BT

0
k BT

N!

=.

..N

n=0

exp.

0
.n

n!(N
n)!

1Nn

kBT

= qN

which makes use of the binomial expansion from Module 3.

The Helmholtz free energy is found to be:
.
.
..
0
F = kBT log Q = Nk BT log q = NkB T
1+
kBT
log
exp
which is in agreement with the microcanonical approach.
Using Q as a generating function, the average energy is given by:
.
.
(E)
log
e=
= 1
log
.
0

.
=
q
Q
exp(0)
=

N
N

1+
V ,N
V ,N
exp(0)
where = 1/(kBT ).

As 0 (T ), e 0/2 (entropy-driven mix of states at large

T ).

As (T 0), e 0 (ground-state energy at zero T

). The entropy is given by:
s=
S

ef
T
B

exp(0
)

=k
0

1 + exp(0

log[1
exp( +
+ kB

)]

As 0 (T ), s kB log 2 (entropy-driven mix of states at

large T ).

Figure

1:

Thermodynamic func-

tions for the 2-state model.

The
first figure shows F /(NkBT ) (solid
curve), E/(Nk BT ) (dashed curve),
and S/(NkB ) (dashed-dotted curve)
versus kBT /0; the dashed curve
gives the asymptotic value for
entropy S kB log 2 at large T . The
figure be- low shows the energy E/
(N0 ) versus kBT /0.

As (T 0), s 0 (zero entropy at zero T ).

Ideal gas of diatomic molecules

Consider N non-interacting, diatomic molecules in a fixed volume V
and temperature T (canonical ensemble). The molecules in the gas
phase are indistinguishable, thus the partition function is given by Q
=
1 N
N !q , where q is a single-molecule partition function. In Module 1, we
analyzed the quantum mechanics of a diatomic molecule, resulting in
translational, rotational, vibrational, and electronic quantum
mechani- cal modes (Fig. 2).
Quantum mechanics predicts the energetic contributions
associated with:
h2

n +n +n

8ML2

Etrans

x
2

y
2

translational modes

z
2

k2

Erot
E

l
vib

l (l + 1)
.
1 k
j+

rotational modes

2R2
.

2
where M = m1 + m2, =

m1m2

vibrational modes
.

,=

, R is the atomic

separation,
m1 +m2

and k is the spring stiffness.

Owing to the fact that these quantum mechanical modes are
decou- pled, the single-particle partition function is separable into
quantum- mode partition functions, such that:
q = qtransqrotqvibqelec

(6)

where qtrans is the sum over translational modes, qtot is the sum over
rotational modes, etc.
We find solutions for each of these quantum-mode partition functions:

Translational partition function

The translational partition function is written as

.
exp

. .

. n2 + n2 + n2.

h2

nx =1 ny =1 nz

8k B TML 2

(7)

z
2

=1

trans =8k hML 2 ,

B

Define the translational temperature

translational partition function:
.
..
trans
. .
3

2
exp
n
qtrans =
T

resulting the

n=1

The translational temperature is generally very small. For example,

O2 in a box with L = 1cm results in trans = 1.5 1015K. This

Figure 2: Three quantum mechanical modes that are relevant to the

thermodynamic
behavior
of
a
diatomic
molecule.
Quantum
mechanics associ- ated with electronic
states are not de- picted.

temperature represents the temperature where the translational

modes become excited.
For any appreciable temperature (T
the summation by an integral:
.

trans

qtrans

dne

..3
=

where we have used V = L3, and

trans) we can approximate

ax2

2Mk BT 3/2

.
=

4trans

.3/2

dx =

h2

1,

We can define the de Broglie wavelength =2Mk h

the final result qtrans =

to arrive at

Rotational partition function

For each l-index value, there are (2l + 1) m-index values (degeneracy).
Therefore, the rotational partition function is:
qrot =

.
(2l + 1)

2k T
1)

exp

k2
R2

l=0

We define the rotational temperature rot =

qrot=
.
.
.
l=0(2l

(8)

l(l +

2k

, resulting in

BR

ro

+ 1) exp
t T l(l + 1) . The rotational temperature

is
generally small (though larger than trans), e.g. the rotational temperature for O2 is rot = 2.08K.
For any appreciable temperature (T rot), the rotational partition
function is approximated by the integral:
.
.

T
l(l
+
1)
qrot
(9)
dl(2l + 1)
rot
rot
=
exp

0
T
We must correct for rotational symmetries in the molecule, such that
qrot = rot . The symmetry factor accounts for the number of equivaT
lent orientations ( = 1 for heteronuclear diatomic molecules and =
2 for homonuclear diatomic molecules).

Vibrational partition function

The vibrational partition function is written as:
qvib =

exp

k
kBT

.
j+

..
(10)

j=0
k

We define the vibrational temperature vib = , which dictates

kB
when vibrational modes become excited. This temperature
is usually
T
large; for example, the vibrational temperature for O2 is qvib =

2274K.

Using the property

j=

qvib = e

vib /(2T )

exp

, we have:
.
vib

1z

evib /(2T )

= 1 evib /

(11)

(T )

j=0

This exact result for qvib is valid over the entire temperature range,
which is necessary since vib tends to be very large. In comparison,
the approximate solutions for qtrans and qrot are valid at temperatures
T
trans, rot (note, trans, rot are very small).

Electronic partition function

Thermal excitation of the electronic states in a molecule leads to the
electronic partition function:
qelec = g0 + g1e1 /kBT + g2e2 /kBT ...

(12)

where gi is the electronic degeneracy of the ith state, and i are the
electronic excitation energy of the ith state relative to the ground state.
We define the electronic temperature elec = 1/kB , which is typically extremely large (elec 104 105K).
For most applications with T elec, the electronic partition function is written as qelec g0. The ground-state electronic degeneracy g0
must be found for the molecule (or atom) of interest. Typically, these
are tabulated for many simple molecules (for example, see page 207 of
Dill and Bromberg1). For O2, the ground-state degeneracy is g0 = 3
(see page 158 of Hill2).

Statistical thermodynamics of O2
The partition function for O2 is given by:

Q=

qN

=
N!

..

. . /(2T . .
T
e vib
N
rot )
g0

. .

V
N!

(13)

1 evib /
(T )

.
where =

h2
2Mk B
gT0 = 3

10

1/2

, rot = 2.08K, = 2, vib =

= 4.410T 1/2
2274K, and
(valid for trans, rot
T
elec).
The Helmholtz free energy is found using F = kBT log Q to be:
F=
kBT

.
N
log

.
V + N log (qrotqvibqelec) logN !
.

3
=
k B TN

.
.
.
.
+
log
(q
q
q
)
+
lo
rot
vib
elec
V
N
1
g
3

(14)

Ken A. Dill and Sarina Bromberg.

Molecular Driving Forces: Statistical
Thermodynamics in Chemistry and
Bi- ology. Garland Science, 2003. ISBN
0815320515
2
Terrell L. Hill. An Introduction to
Statistical Thermodynamics. Courier
Dover Publications, 1960.
ISBN
0486652424
1

which exhibits the necessary property that F (T , V , N ) is a

homogeneous first-order function of V and N , which only occurs when
1

the indistin- guishability factor of

is included in Q.
N
!
From thermodynamics, we write the equation of state:
.

F
V

Nk B T
pV = Nk B T
V

= p =

T,
N

(15)

which is the ideal gas equation of state.

The heat capacity is found to be:

CV = T

=
S
. V ,N T
T

2F
. V ,N
evib /T
T 2
2
vib

NkB + NkB + NkB

T2

. evib /T .2

(16)

1
which is valid for trans, rot
T
elec.
The first contribution of 3NkB /2 is associated with the 3N translational degrees of freedom (kB /2 from each direction), and the second
term of NkB is associated with the 2N rotational angles and (contributing kB /2 each). As T passes through vib, the heat capacity goes
from 5NkB /2 to 7NkB /2, thus a single vibrational mode contributes
kBT to the heat capacity. As the temperature is raised, the individual degrees of freedom get turned on in order to further maximize the
entropy, since more active degrees of freedom (non-zero probability)
con- tribute to the entropy (Fig. 3).

Equipartition theorem
For T
trans, rot , the heat capacity receives kB /2 for each
of freedom, thus the average energy per particle to be:
() = (trans)(rot) =
3

kB T

k BT
+

degree

(17)

2
2
which suggests that the average energy of a thermally active degree of
freedom contributes kBT /2 to the energy.
Consider a microscopic energy function that is quadratic, such that
(x) = cx2, where x is a generalized degree of freedom:
Translational
modes
both fit in this category,
2 and rotational modes
k2
since: Etrans = h n2 and Erot =
l(l + 1).
n

8mL2

2R2

The average energy is:

.
.
.
(x)

kBT
x (x) exp
() =

.
x

exp

(x)

BT

.
.
2
ex kcx
BT
cx p
.
.
.
kcxT2
x
B
exp
2

(18)

Figure 3: The heat capacity of a gas of

diatomic molecules versus temperature.

At large T , the sums can be approximated by the integrals:

.

dxcx2 exp cx
.
()
2

.
exp
k

(19)

kB
.
cx 2T
BT

Noting the mathematical properties:

1/2
dxeax 2 =

a1/2

dC0
1/2
2
=
=
2
ax

C1 =
dxx e
da

C0 =

(20)

2a3/2
and setting a = c/(kBT ), we have:
() = c

1/2
2 [c/(kBT
)]

[c/(kBT
)]

3/2

=
kB T

1/2

1/2

(21)
2

The equipartition theorem states that the total energy will partition the amount kBT /2 into each thermally active degree of
freedom, provided the microscopic energies obey quadratic energy
functions.
Consider a microscopic energy function that is linear, such that (x)
=
cx, where x is a generalized degree of freedom:
.
(vib)
1.
Vibrational modes fit in this category, since E
= j+
k.
j

The average energy for this function gives:

0

dxcx exp

() =

exp

k cxT
B
cx .

.
= kB T

(22)

BT

The equipartition theorem predicts that the average energy per particle for temperatures vib T elec is given by:
() = 3 kBT
2
2

kBT
+

+ k BT

(23)

where 3 translational modes contribute kBT /2 each, 2 rotational

modes contribute kBT /2 each, and 1 vibrational mode contributes
k BT
This picture is only valid at temperatures where the modes are
active. For example for T vib, the discrete vibrational quantum modes

are frozen down to the ground state energy level vib = k/2
(independent of temperature).

References
Ken A. Dill and Sarina Bromberg. Molecular Driving Forces:
Statistical Thermodynamics in Chemistry and Biology. Garland
Science, 2003. ISBN 0815320515.
Terrell L. Hill. An Introduction to Statistical Thermodynamics. Courier
Dover Publications, 1960. ISBN 0486652424.