2.

Elements of Ensemble Theory

1. Phase Space of a Classical System

2. Liouvilles Theorem & Its Consequences
3. The Microcanonical Ensemble
4. Examples
5. Quantum States & the Phase Space

At equilibrium:
Each macrostate represents a huge number of microstates.

Observed values ~ time averaged over microstates.

Ensemble theory:
Ensemble average = Time average

2.1.

Phase Space of a Classical System

Hamiltonian formulism of mechanics:

Each dynamical state of a system of N particles is specified by 3N
position coordinates { qi }, and 3N momentum coordinates { pi },
i.e., by a point { qi , pi } in the 6N D phase space of the system.
Time evolution of the system is described by a path in phase space satisfying

qi

H
pi

p i

H
qi

For a conservative system, its phase space

trajectory is restricted to the hypersurface
For a system in thermal equilibrium with a
heat reservoir, its phase space trajectory is
restricted to the hypershell

i 1, 2,,3N

H qi , pi E
H qi , pi E E , E E

Ensemble of a system:
Set of identical copies of a system that includes every distinct state that satisfies
the given boundary conditions and gives rise to the given macrostate.

In the thermodynamical limit ( N, V , N / V = finite ) ,

the phase points of the ensemble form a continuum.
The ensemble average of a dynamical function f is given by

3N

q d 3 N p f q, p q, p, t

3N

q d

An ensemble is stationary if

3N

= density function

p q, p , t

0
t

f is t indep.

Ensemble of a system in equilibrium must be stationary.

2.2.

Liouvilles Theorem & Its Consequences

d qi , pi , t

H H

qi
p i

dt
t

q
i
i
i
i
i
i
i
i

, H
dt
t

f H f H
f
,
H

pi qi
i qi pi

where the Poisson bracket is defined as :

# of phase points are conserved

Liouvilles theorem

d
0
dt

The current density of phase points is a 6N-D vector

j v

v qi , p i

j v

v qi , p i

qi p i

p i

i
pi
pi
i qi
i qi
where

qi p i
i q p
i
i

qi p i
i q p , H
i
i

H
H

q
i
i
i
i i

Hence, the Liouville eq. is just the equation of continuity of the phase points :

j 0
dt
t

0
For a system in equilibrium
t

H H

0
qi pi pi qi

, H
i

 H H

, H
0

q
i
i
i
i
i

Solution 1:

q, p

const
0

q, p

otherwise

region of acceptible microstates in phase space.

Principle of equal a priori probability :

Solution 2:

d 3 N q d 3 N p f q, p

q, p H q, p

, H
i

Chap 3:

d
dH

H H H H

0
qi pi pi qi

kT

q, p exp

Canonical
ensemble

Microcanonical
ensemble

2.3.
const
q, p
0

The Microcanonical Ensemble

1. Hypersurface

q, p
otherwise

H q, p E
1
H q, p E
2

2. Hypershell

f ensemble average of f
= time average of f

for systems in eqm.

= time average of f

2 av are indep

= long time average of f over 1 ensemble member

= f measured
Let 0 fundamental volume of one microstate.

S k ln k ln

Then

2.4.

Examples

d 3 N q d 3 N q, p d 3 N q d 3 N p

Microcanonical

Classical ideal gas:

3N

q V N

3N

3N

pr2

2m
2
r 1

Surface area of an n-D sphere (App.C) is

R 2mE

d 3N

d 3N p

3N

2 mE

d 3N y

r 1

2 n /2
Sn R
R n 1
n / 2

1
1

R 2m E 2m E
2
2

2 3 N /2
3 N 1 /2
p
2
mE

3N / 2

yr2

2m

2m
3 N /2

N 2 mE
V
3N / 2

3 N /2

2 mE
V N
3N / 2

Sec 1.4 :

3N V

2 E h3

3 N /2

2 mE
3N / 2 !

Volume of state per degree of freedom = h

h3N

Single Free Particle Confined to V

1 P

1 p

P2
E
2m
p2

2m

1
1 4 3
3
3
d
q
d
p

V
P
3
3

P
h
h
3
d 1
dp

1
2
V
4

p
p g p p
3
h

1 E

V 4
3/2
2
mE

h3 3

d 1
2 V
3 2m 3/2 1/2 a
d
h

Simple Harmonic Oscillator

p2 1 2
H
kq
2m 2

q A cos t

k
m

p m A sin t
E

q2
p2

1
A2 m A 2

1 E
1

1
m 2 A2
2

q2
p2

1
2
2E / m
2mE

2E
m 2

2mE

Ellipse

d 1

n n
2

2.5.

Quantum States & the Phase Space

Phase space volume of 1 quantum state may

be estimated from the uncertainty principle:

Among the first to suggest 0

h DoF are Tetrode, Sackur, & Bose.

h
p
c

Bose (black-body radiation) :

q p

for photons

2
4

d q d p V 4

h V c 3
c c
3

4 2
Cf. Rayleighs number of modes V

3
c

0 h 3

Caution: Above formulae consider only a single polarization component.