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 Interesting!

The Most Common Statistical Ensembles:

1. The Micro-Canonical Ensemble:
Isolated Systems: Constant Energy E.
Nothing happens! Not Interesting!
2. The Canonical Ensemble:
Systems with a fixed number N of molecules
In equilibrium with a Heat Reservoir (Heat Bath).

The Most Common Statistical Ensembles:

1. The Micro-Canonical Ensemble:

Isolated Systems: Constant Energy E.
Nothing happens! Not Interesting!

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

Properties of The Canonical

& Grand Canonical Ensembles
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 nFnPn

Fn Value of F in state (configuration) n

Pn Probability of the system being in state
(configuration) n.

Canonical Ensemble Probabilities

U n

g ne
pn N
Qcanon

N
Qcanon

g ne

U n

QNcanon Canonical Partition Function

gn Degeneracy of state n

Note that most texts use the notation

Z for the partition function!

Grand Canonical Ensemble Probabilities:

E n

g ne
pn
Qgrand

Qgrand g n e

E n

E n U n N n

Qgrand Grand Canonical Partition Function

or

Grand Partition Function

gn Degeneracy of state n, Chemical Potential

Note that most texts use the notation

ZG for the Grand Partition Function!

Partition Functions
If the volume, V, the temperature T, & the energy
levels En, of a system are known, in principle

The Partition Function Z

can be calculated.

If 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 CALCULATING 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

Z i exp(- i/kBT)

Where i is the energy of the ith state.

Partition Function for a Quantum

System in Contact with a Heat Reservoir:

,
Z i exp(- i/kBT)
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

S = kBln .

12

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/(kBT), kB = Boltzmanns constantt.

Entropy: S = kB + kBlnZ
An important, frequently used result!

Summary for the Canonical Ensemble

Partition Function Z:
Helmholtz Free Energy
F = E TS = (kBT)lnZ
and

dF = S dT PdV, so
S = (F/T)V, P = (F/V)T

Gibbs Free Energy

G = F + PV = PV kBT lnZ.
Enthalpy
H = E + PV = PV (lnZ)/

Canonical Ensemble:
Heat Capacity & Other Properties
Partition Function:
Z = n exp (-En), = 1/(kT)

Canonical Ensemble:
Heat Capacity & Other Properties
Partition Function:
Z = n exp (-En), = 1/(kT)
Mean Energy:
= (ln Z)/ = - (1/Z)Z/

Canonical Ensemble:
Heat Capacity & Other Properties
Partition Function:
Z = n exp (-En), = 1/(kT)
Mean Energy:
= (ln Z)/ = - (1/Z)Z/
Mean Squared Energy:
E2 = rprEr2/ rpr = (1/Z) 2Z/ 2.

Canonical Ensemble:
Heat Capacity & Other Properties

Partition Function:
Z = n exp (-En), = 1/(kT)
Mean Energy:
= (ln Z)/ = - (1/Z)Z/
Mean Squared Energy:
E2 = rprEr2/ rpr = (1/Z) 2Z/ 2.
nth Moment:
En = rprErn/ rpr = (-1)n(1/Z) nZ/ n

Canonical Ensemble:
Heat Capacity & Other Properties

Partition Function:
Z = n exp (-En), = 1/(kT)
Mean Energy:
= (ln Z)/ = - (1/Z)Z/
Mean Squared Energy:
E2 = rprEr2/ rpr = (1/Z) 2Z/ 2.
nth Moment:
En = rprErn/ rpr = (-1)n(1/Z) nZ/ n
Mean Square Deviation:
(E)2 = E2 - ()2 = 2lnZ/ 2 = - / .

Canonical Ensemble:
Constant Volume Heat Capacity

CV = /T = (/)(d/dT) = - k 2/

Canonical Ensemble:
Constant Volume Heat Capacity

CV = /T = (/)(d/dT) = - k 2/
using results for the Mean Square Deviation:
(E)2 = E2 - ()2 = 2lnZ/ 2 = - /

Canonical Ensemble:
Constant Volume Heat Capacity

CV = /T = (/)(d/dT) = - k 2/
using results for the Mean Square Deviation:
(E)2 = E2 - ()2 = 2lnZ/ 2 = - /
CV can be re-written as:

CV = k 2(E)2 = (E)2/kBT2

Canonical Ensemble:
Constant Volume Heat Capacity

CV = /T = (/)(d/dT) = - k 2/
using results for the Mean Square Deviation:
(E)2 = E2 - ()2 = 2lnZ/ 2 = - /
CV can be re-written as:

CV = k 2(E)2 = (E)2/kBT2
so that:

(E)2 = kBT2CV

Canonical Ensemble:
Constant Volume Heat Capacity

CV = /T = (/)(d/dT) = - k 2/
using results for the Mean Square Deviation:
(E)2 = E2 - ()2 = 2lnZ/ 2 = - /
CV can be re-written as:

CV = k 2(E)2 = (E)2/kBT2
so that:

(E)2 = kBT2CV
Note that, since (E)2 0
(i) CV 0 and (ii) /T 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 (qi,pi).
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 d3r1d3r2d3rN d3p1d3p2d3pN e(-E/kT)

A 6N Dimensional Integral!
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 ri & momenta pi.

E E(r1,r2,r3,rN,p1,p2,p3,pN)

CLASSICAL
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 T)]/Z

B

<A> (A)d3r1d3r2d3rN d3p1d3p2d3pNP(E)

Another 6N Dimensional Integral!