NE 334 Week 6, October 8 and 10, 2024

Learning objectives for week 6:

• The microcanonical ensemble (N,V,E)

• Partition function for collection of N subsystems

• Concept of indistinguishability (identical particles)

• Thermodynamic properties of an ideal gas of N particles from Z

• Thermodynamic State Functions for Structureless Particles

• Nuclear and electronic states

• Thermodynamic Functions for an Atomic Gas (N particles)

4.3 The Microcanonical Ensemble

Microcanonical partition function: ⌦(E, N, V )
Concerned with an ISOLATED SYSTEM with fixed E, N, V
Limiting case of the canonical ensemble:
a degenerate canonical ensemble in which all systems have the same energy
pick out from a canonical ensemble those systems with energy Ej , and place them in thermal
isolation
canonical probability pj / e Ej /kB T for each of the ⌦(E, N, V ) systems:
X 1
pj = 1 ) pj = 8j. microcanonical probability
j
⌦

This implies that hEi = U = E ) ⌦ ⌘ ⌦(U, N, V )

Examine the expression for the entropy: use the expression given in terms of pj :
X
S(U, N, V ) = kB pj ln pj
j
X 1 ✓1◆
= kB ln
j
⌦ ⌦
✓ ◆X
1 1
= kB ln 1
⌦ ⌦ j
| {z }
⌦

or Boltzmann entropy:

S = kB ln ⌦(U, N, V ) characteristic function

This expression means that S is the characteristic function for the microcanonical ensemble
Boltzmann wrote S = kB ln W , and called W the ‘number of complexions’

54
4.4 Connection to Statistical Thermodynamics
The Boltzmann expression applies to an isolated system
If the ground state of the system is non-degenerate, then ⌦ ! 1 when T ! 0, and hence S ! 0:
cf. the third law of thermodynamics
For any isolated system, the more quantum states available to the system, the higher the entropy.
This is the origin of qualitative statements correlating entropy with ‘probability’, ‘randomness’, and
‘disorder’.
We can use the microcanonical expression for the entropy to give us an idea of the order of
magnitude of ⌦, the number of accessible states for a thermally isolated system. To do this we may
solve the entropy expression for ⌦:
Experimentally, we know that the entropy S is of order S ' N kB , so that our microcanonical
expression gives
S = kB ln ⌦ ' N kB ) ln ⌦ ' N ,
23
and hence ⌦ ' eN ⇡ e10 .
Microcanonical
From S = kB ln ⌦, we can write
1 P X µ↵
kB d ln ⌦ = dS = dU + dV dN↵ .
T T ↵
T

Greek summation index used for summation over chemical species in a mixture
This relation gives us ✓ ◆
1 @ ln ⌦
= ,
kB T @U N,V
✓ ◆
P @ ln ⌦
= ,
kB T @V U,N
✓ ◆
µi @ ln ⌦
= .
kB T @Ni U,V,N↵ 6=Ni
Objective: connect the partition functions to thermodynamic quantities. Will be useful when
we study properties of atoms, molecules, solids, electrons, etc...
Canonical
From thermodynamics we know that the Helmholtz energy is related to the internal energy U
and the entropy S by A = U T S, from which

dA = dU T dS SdT ,
The thermodynamic expression for dU is :
dU = T dS P dV + µdN thereby giving
dA = P dV SdT + µdN

Represents the adjoining of number of particles to Canonical Ensemble expressions:

If we employ these thermodynamic relations together with the relation A = kB T ln Z, we
obtain ✓ ◆ ✓ ◆
@A @ ln Z
P = = kB T ,
@V N,T @V N,T

55
 ◆ ✓ ✓ ◆
@A @ ln Z
µ= = kB T ,
@N V,T @N V,T
✓ ◆ ✓ ◆
@A @ ln Z
S= = kB ln Z + kB T .
@T N,V @T N,V

We are now thus e↵ectively treating Z ⌘ Z(N, V, T ) as a function of three variables. We shall
see later how to accomplish this.
As we already have the relation
✓ ◆
2 @ ln Z
U = kB T ,
@T N,V

and we know from thermodynamics that the enthalpy and Gibbs energy are given as
H = U + PV ,
G = H TS ,
we have essentially all of thermodynamics.

Ode to the Partition Function

There was a function, called Z or Q

We should take its log, its derivatives too
And from those we can derive
All the properties upon which we thrive

S. Crerar (excerpt from examination booklet, circa 2003)

5 Independent Subsystems
.
In all cases we shall be concerned with subsystems that are statistically independent, and in the
following, we shall ignore any interactions between these subsystems.
• distinguishable subsystems: consider two subsystems, and consider the meaning of the
above two conditions (or assumptions).
– statistical independence: subsystem a with quantum numbers i; subsystem b with quan-
tum numbers j
– weak interactions: ✏ij = ✏i + ✏j .
– canonical partition function given by
! !
X X X X X
✏ij ✏i ✏j ✏i ✏j
Z= e = e e = e e ,
ij i j i j

so canonical partition function Z for total system given by product of partition functions
for individual systems, viz,
Z = Z a Zb .

56
 – More generally: Z = Za Zb Zc · · · .

indistinguishable subsystems:

– one set of quantum numbers

– weak interactions: e.g. ✏ij = ✏ai + ✏bj for two subsystems.

! !
X X
Z = Z a Zb ) Z = e ✏i e ✏i
= z2
i i

BUT the defining relation for Z gives

X
✏k
Z⌘ e ,
k

with values of ✏k given by the possible values of ✏ai + ✏bj ; however, as ✏ai + ✏bj = ✏aj + ✏bi , we
would count the energy twice in the product za zb , rather than only once as required by the
definition of Z for the entire system.

For N such particles, the product Z = z N overestimates the actual value that Z must have
by the number of ways of obtaining ✏ = ✏1 + ✏2 + · · · + ✏N , i.e., by N !. Hence we have

zN
ZN = .
N!

5.1 Evaluation of Z for N particles with translational motion only

For a single particle with translational motion (3–D box problem) the canonical partition
function is given by Z 1
z( , 1, V ) = ⌦(✏, 1, V )e ✏ d✏ ,
0
with ⌦ given by
✓ ◆ 32
2m 1
⌦(✏, 1, V ) = 2⇡ V ✏2 .
h2

We can therefore write z( , 1, V ) explicitly as

✓ ◆ 32 Z 1
2m 1
✏
z( , 1, V ) = 2⇡V ✏2 e d✏ .
h2 0

change variables: x2 = ✏/(kB T ) !2xdx = d✏

Z 1 Z 1 p
1
✏/(kB T ) 3
2 x2 3 ⇡
✏ e
2 d✏ = 2(kB T ) 2 xe dx = 2(kB T ) 2

0 0 4
or ✓ ◆ 32
2⇡mkB T V
z( , 1, V ) = V ⌘ ,
h2 ⇤3 (T )

57
 in which ⇤(T ), defined by
h
⇤(T ) ⌘ 1 ,
(2⇡mkB T ) 2
is known as the ‘thermal de Broglie wavelength’.
Thus, we see that the canonical partition function associated with translational motion of a
molecule can be obtained as
V
ztrans (V, T ) = 3 .
⇤ (T )

• ⇤ is used to place conditions on the required energy states of the system before it can
be described using continuum arguments, e.g., our equation for z( , 1, V ).
• The number of accessible states with energy  kB T must be very much larger than N ,
i.e.,
✓ ◆3
2⇡mkB T 2
(kB T ) ' V N
h2
or
V
N.
⇤3
⇤3 N
and ⌧1
V
Thus, we see that the canonical partition function for N particles that have only trans-
lational degrees of freedom takes the form:
z N ( , 1, V ) VN
ZN ⌘ Z( , N, V ) = = .
N! N !⇤3N
Remember that this expression for the canonical partition function only applies as it
stands to particles possessing no motions other than translational.

5.2 Thermodynamic State Functions for Structureless Particles

5.2.1 Internal Energy
We shall now apply our general formulation to the special case of structureless particles (such as
noble gases): although this will appear for now to be a rather limiting case to consider, we shall see
shortly that
the expression that we obtain will have a much larger applicability!
✓ ◆ ⇢
2 @ ln ZN 2 @ VN
U = kB T = kB T ln
@T N,V @T N !⇤3N
@
= kB T 2 {N ln V ln N ! 3N ln ⇤(T )}
@T
@
= kB T 2 3N ln ⇤(T )
@T
3 @
= N kB T 2 ln T
2 @T
or
3
Utrans = N kB T .
2

58
 3
Utrans = N kB T .
2
From our expression for Utrans , we see that the contributions to the heat capacity at constant volume
arising from translational states is given by
✓ ◆
@U 3
CV ⌘ = N kB ,
@T V,N 2

5.2.2 Pressure and Entropy

✓ ◆ ✓ ◆
@ ln ZN @ ln V N kB T
P = kB T = N kB T =
@V N,T @V N,T V
or
2
P V = N kB T = Utrans .
3
Entropy:
⇢
U VN 3
S ⌘ kB ln ZN + = kB ln + N kB
T N !⇤3N 2
3
= kB ln V N ln N ! N ln ⇤3 + N kB
2
⇢
3
= N kB ln V ln N + 1 ln ⇤3 +
2

(using Stirling’s approximation: lnN ! = N lnN N)

or ( 5 )
e2 V
Strans = N kB ln .
N ⇤3
Famous Sakur–Tetrode equation of classical thermodynamics.

5.2.3 Gibbs Energy and Chemical Potential

We have seen earlier that the canonical partition function for N structureless particles in the gas
phase is given by
✓ ◆N
VN eV
ZN = ' .
N !⇤3N N ⇤3
Gibbs energy: We shall continue to work within the ideal gas law, so that the Gibbs energy G is
given by

G = A + PV = kB T ln ZN + N kB T
eV
= N kB T ln N ⇤3
+ N kB T ln e

59
or ✓ ◆
V
G= N kB T ln
N ⇤3
Chemical Potential
As V = N kB T /P (ideal gas law again), we can also write
✓ ◆
kB T
G = N kB T ln ,
P ⇤3
and from the connection that we have seen between the Gibbs energy and the chemical potential
for a pure substance, we obtain for µ the expression
✓ ◆
G kB T
µ= = kB T ln .
N P ⇤3

Thermodynamics: µ(T, P ) = µ0(T ) + kBT ln P

Let us rearrange this expression for the chemical potential into the form with which we are
familiar from chemical thermodynamics, namely,
✓ 3 ◆
⇤
µ = kB T ln + kB T ln P ,
kB T
from which we may deduce that µ0 (T ) is given by
✓ ◆
⇤3
µ0 (T ) = kB T ln .
kB T
We have obtained a chemical potential expression consistant with thermodynamics and can also
calculate µ0 (T ).

5.3 The Role of Nuclear States

The canonical partition function for nuclear energy states has the same structure as that already
discussed for electronic energy states, i.e., the nuclear partition function can be expressed in the
form
n ⇥ ✏n
⇤
znuc (T ) = e ✏0 !0n + !1n e 1 + ··· .
The lowest excited nuclear energy state is typically several MeV above the ground nuclear state,
and consequently we really need to take into account only the ground nuclear (spin) state:
✏n
znuc (T ) = !0n e 0 .
Often, the electronic and nuclear states are considered together to give
n e ⇥ ✏e1 ✏e2
⇤
zel (T )znuc (T ) = !0n e (✏0 +✏0 ) !0e + !1e e + !2e e + ··· .
Note, however, that ✏ei ⌘ ✏ei ✏0 , with ✏0 ⌘ ✏n0 + ✏e0 , rather than simply ✏eo . If ✏n0 + ✏e0 is now chosen
as the zero of energy, then zel (T )znuc becomes
⇥ ✏e1 ✏e2
⇤
zel (T )znuc = !0n !0e + !1e e + !2e e + ··· ,
so that zatom (T, V ) is given by
V
zatom (T, V ) = !0n zel (T ) .
⇤3 (T )

60
5.4 Thermodynamic Functions for an Atomic Gas (N particles)
If we write the canonical partition function for an individual atom as zatom (T, V ) = znuc zel (T )ztrans (T, V ),
then the canonical partition function for a macroscopic gas sample containing N such atoms will
be
z N (T, V ) N N
ZN (T, V ) = trans znuc zel (T ) .
N!
The Helmholtz energy A will then be obtained as

A(T, V, N ) = Atrans (T, V, N ) + Anuc + Ael (T )

⇢
eV
= N kB T ln N kB T ln znuc N kB T ln zel (T ) ,
N ⇤3 (T )
or ⇢
eV !0n zel (T )
A(T, V, N ) = N kB T ln .
N ⇤3 (T )
If there are no thermally–accessible electronic states for temperature T , then zel (T ) reduces
simple to !0e , and A becomes
⇢
eV !0n !0e
A(T, V, N ) = N kB T ln .
N ⇤3 (T )

If there are no thermally–accessible electronic states for temperature T ...

The internal energy U , the heat capacity CV , and the pressure P are unchanged from their
expressions for translational motion, and the entropy S becomes

S(T, V, N ) = Strans (T, V, N ) + N kB ln(!0n !0e ) .

Similarly, the chemical potential µ(T, V, N ) is obtained as

µ(T, V, N ) = µtrans (T, V, N ) kB T ln(!0n !0e )

⇢
V !0n !0e
= kB T ln .
N ⇤3 (T )

If there is one or more thermally–accessible electronic states for temperature T , then we write
the electronic partition function as
1
X
✏ei
zel (T ) = !ie e ,
i=0

with ✏ei ⌘ ✏ei ✏0 .

The internal energy U (T, N ) (ideal gas) will be given by

U (T, N ) = Utrans (T, N ) + Uel (T, N ) ,

61
with Uel (T, N ) given by

d ln zel (T )
Uel (T, N ) = N kB T 2
dT !
X1
2 d ✏ei
= N kB T ln !ie e
dT i=0
1
!
1 d X
✏ei
= N kB T 2 !ie e ,
zel (T ) dT i=0

or
1
X ✏ie
e
Uel (T, N ) = N !ie ✏ei
i=1
zel (T )
1
X
=N pi ✏ei .
i=1

The expression for the pressure P is una↵ected because zel does not depend upon the volume
V.
The electronic contribution to the Helmholtz energy A becomes
1
!
X
e ✏ei
Ael (T, N ) = N kB T ln !i e ,
i=0

and the electronic contribution to the entropy S can then be obtained from

Uel (T, N ) Ael (T, N )

Sel (T, N ) = .
T
Because the internal energy now has a temperature dependent contribution from the excited
electronic states, we will also have a corresponding electronic contribution to the heat capacity,
namely, 2
1 ✓ e ◆2 1
!2 3
dUel (T, N ) X ✏i X e
✏i
CV,el (T, N ) = = N kB 4 pi pi 5 ,
dT i=1
k B T i=1
k B T

associated with the excited electronic states of the atom.

62