Chapter 6: Basic Methods & Results

of Statistical Mechanics
Key Concepts In Statistical Mechanics
Idea: Macroscopic properties are a
thermal average of microscopic properties.
Replace the system with a set of systems
"identical" to the first and average over all of
the systems. We call the set of systems
The Statistical Ensemble.
Identical Systems means that they are all
in the same thermodynamic state.
To do any calculations we have to first
Choose an Ensemble!
The Most Common Statistical Ensembles:
1. The Micro-Canonical Ensemble:
Isolated Systems: Constant Energy E.
Nothing happens! Not I nteresting!
3
The Most Common Statistical Ensembles:
1. The Micro-Canonical Ensemble:
Isolated Systems: Constant Energy E.
Nothing happens! Not I nteresting!
2. The Canonical Ensemble:
Systems with a fixed number N of molecules
In equilibrium with a Heat Reservoir (Heat Bath).
4
The Most Common Statistical Ensembles:
1. The Micro-Canonical Ensemble:
Isolated Systems: Constant Energy E.
Nothing happens! Not I nteresting!
2. The Canonical Ensemble:
Systems with a fixed number N of molecules
In equilibrium with a Heat Reservoir (Heat Bath).
3. The Grand Canonical Ensemble:
Systems in equilibrium with a Heat Bath
which is also a Source of Molecules.
Their chemical potential is fixed.
All Thermodynamic Properties Can Be
Calculated With Any Ensemble
Choose the most convenient one for a particular problem.
For Gases: PVT properties
use
The Canonical Ensemble

For Systems which Exchange Particles:
Such as Vapor-Liquid Equilibrium
use
The Grand Canonical Ensemble
J. Willard Gibbs was the first to show that
An Ensemble Average is Equal to a
Thermodynamic Average:
That is, for a given property F,
The Thermodynamic Average
can be formally expressed as:
F
n
F
n
P
n

F
n
Value of F in state (configuration) n
P
n
Probability of the system being in state
(configuration) n.
Properties of The Canonical
& Grand Canonical Ensembles
Canonical Ensemble Probabilities
p
g e
Q
n
n
U
canon
N
n
=
|
Q
N
canon
Canonical Partition Function
g
n
Degeneracy of state n
Q g e
canon
N
n
n
U
n
=

|
Note that most texts use the notation
Z for the partition function!
Grand Canonical Ensemble Probabilities:
p
g e
Q
n
n
E
grand
n
=
|
E U N
n n n
=
Q g e
grand n
n
E
n
=

|
Q
grand
Grand Canonical Partition Function
or
Grand Partition Function
g
n
Degeneracy of state n, Chemical Potential
Note that most texts use the notation
Z
G
for the Grand Partition Function!
Partition Functions
I f the volume, V, the temperature T, & the energy
levels E
n
, of a system are known, in principle
The Partition Function Z
can be calculated.
I f the partition function Z is known, it can be used
To Calculate
All Thermodynamic Properties.
So, in this way,
Statistical Mechanics
provides a direct link between
Microscopic Quantum Mechanics &
Classical Macroscopic Thermodynamics.
Canonical Ensemble Partition Function Z
Starting from the fundamental postulate of equal
a priori probabilities, the following are obtained:
i. ALL RESULTS of Classical Thermodynamics,
plus their statistical underpinnings;
ii. A MEANS OF CALCULATI NG the
thermodynamic variables (E, H, F, G, S ) from a
single statistical parameter, the partition function Z
(or Q), which may be obtained from the energy-levels
of a quantum system.
The partition function for a quantum system in
equilibrium with a heat reservoir is defined as
W


Where
i
is the energy of the ith state.
Z
i
exp(-
i
/k
B
T)
12
Partition Function for a Quantum
System in Contact with a Heat Reservoir:
,

F

i
= Energy of the ith state.
The connection to the macroscopic entropy
function S is through the microscopic parameter
, which, as we already know, is the number of
microstates in a given macrostate.
The connection between them, as discussed in
previous chapters, is
Z
i
exp(-
i
/k
B
T)
S = k
B
ln .
Relationship of Z to Macroscopic Parameters
Summary for the Canonical
Ensemble Partition Function Z:
(Derivations are in the book!)
Internal Energy: E = - (lnZ)/
<E)
2
> = [
2
(lnZ)/
2
]
= 1/(k
B
T), k
B
= Boltzmanns constantt.
Entropy: S = k
B
+ k
B
lnZ
An important, frequently used result!
Summary for the Canonical Ensemble
Partition Function Z:
Helmholtz Free Energy
F = E TS = (k
B
T)lnZ
and
dF = S dT PdV, so
S = (F/T)
V
, P = (F/V)
T

Gibbs Free Energy
G = F + PV = PV k
B
T lnZ.
Enthalpy
H = E + PV = PV (lnZ)/
Canonical Ensemble:
Heat Capacity & Other Properties
Partition Function:
Z = E
n
exp (-|E
n
), | = 1/(kT)
Canonical Ensemble:
Heat Capacity & Other Properties
Partition Function:
Z = E
n
exp (-|E
n
), | = 1/(kT)
Mean Energy:
= c(ln Z)/c| = - (1/Z)cZ/c|
Canonical Ensemble:
Heat Capacity & Other Properties
Partition Function:
Z = E
n
exp (-|E
n
), | = 1/(kT)
Mean Energy:
= c(ln Z)/c| = - (1/Z)cZ/c|
Mean Squared Energy:
<E
2
> = E
r
p
r
E
r
2
/E
r
p
r
= (1/Z)c
2
Z/c|
2
.
Canonical Ensemble:
Heat Capacity & Other Properties
Partition Function:
Z = E
n
exp (-|E
n
), | = 1/(kT)
Mean Energy:
= c(ln Z)/c| = - (1/Z)cZ/c|
Mean Squared Energy:
<E
2
> = E
r
p
r
E
r
2
/E
r
p
r
= (1/Z)c
2
Z/c|
2
.
n
th
Moment:
<E
n
> = E
r
p
r
E
r
n
/E
r
p
r
= (-1)
n
(1/Z) c
n
Z/c|
n

Canonical Ensemble:
Heat Capacity & Other Properties
Partition Function:
Z = E
n
exp (-|E
n
), | = 1/(kT)
Mean Energy:
= c(ln Z)/c| = - (1/Z)cZ/c|
Mean Squared Energy:
<E
2
> = E
r
p
r
E
r
2
/E
r
p
r
= (1/Z)c
2
Z/c|
2
.
n
th
Moment:
<E
n
> = E
r
p
r
E
r
n
/E
r
p
r
= (-1)
n
(1/Z) c
n
Z/c|
n

Mean Square Deviation:
<(E)
2
> = <E
2
> - ()
2
= c
2
lnZ/c|
2
= - c/c| .
Canonical Ensemble:
Constant Volume Heat Capacity
C
V
= c/cT = (c/c|)(d|/dT) = - k|
2
c/c|
Canonical Ensemble:
Constant Volume Heat Capacity
C
V
= c/cT = (c/c|)(d|/dT) = - k|
2
c/c|
using results for the Mean Square Deviation:
<(E)
2
> = <E
2
> - ()
2
= c
2
lnZ/c|
2
= - c/c|
Canonical Ensemble:
Constant Volume Heat Capacity
C
V
= c/cT = (c/c|)(d|/dT) = - k|
2
c/c|
using results for the Mean Square Deviation:
<(E)
2
> = <E
2
> - ()
2
= c
2
lnZ/c|
2
= - c/c|
C
V
can be re-written as:
C
V
= k|
2
<(E)
2
> = <(E)
2
>/k
B
T
2


Canonical Ensemble:
Constant Volume Heat Capacity
C
V
= c/cT = (c/c|)(d|/dT) = - k|
2
c/c|
using results for the Mean Square Deviation:
<(E)
2
> = <E
2
> - ()
2
= c
2
lnZ/c|
2
= - c/c|
C
V
can be re-written as:
C
V
= k|
2
<(E)
2
> = <(E)
2
>/k
B
T
2

so that:
<(E)
2
> = k
B
T
2
C
V
Canonical Ensemble:
Constant Volume Heat Capacity
C
V
= c/cT = (c/c|)(d|/dT) = - k|
2
c/c|
using results for the Mean Square Deviation:
<(E)
2
> = <E
2
> - ()
2
= c
2
lnZ/c|
2
= - c/c|
C
V
can be re-written as:
C
V
= k|
2
<(E)
2
> = <(E)
2
>/k
B
T
2

so that:
<(E)
2
> = k
B
T
2
C
V
Note that, since <(E)
2
> 0
(i) C
V
0 and (ii) c/cT 0.
Ensembles in Classical
Statistical Mechanics
As weve seen, classical phase space for a
system with f degrees of freedom is f
generalized coordinates & f generalized
momenta (q
i
,p
i
).
The classical mechanics problem is done in
the Hamiltonian formulation with a
Hamiltonian energy function H(q,p).
There may also be a few constants of
motion such as
energy, number of particles, volume, ...
The Canonical Distribution in
Classical Statistical Mechanics
The Partition Function
has the form:
Z d
3
r
1
d
3
r
2
d
3
r
N
d
3
p
1
d
3
p
2
d
3
p
N
e
(-E/kT)
A 6N Dimensional I ntegral!
This assumes that we have already solved the
classical mechanics problem for each particle in the
system so that we know the total energy E for the N
particles as a function of all positions r
i
& momenta p
i
.
E E(r
1
,r
2
,r
3
,r
N
,p
1
,p
2
,p
3
,p
N
)
CLASSI CAL
Statistical Mechanics:
Let A any measurable, macroscopic
quantity. The thermodynamic average of
A <A>. This is what is measured. Use
probability theory to calculate <A> :
P(E) e
[-E/(k
B
T)]
/Z
<A> (A)d
3
r
1
d
3
r
2
d
3
r
N
d
3
p
1
d
3
p
2
d
3
p
N
P(E)
Another 6N Dimensional I ntegral!