Canonical Ensemble

p(E)

p(E) eE/kT

NOT!

p({p, q}) eH({p,q})/kT

8.044 L13B1

ADVANTAGES OF CANONICAL OVER MICROCANONICAL ENSEMBLE

1) ONE INTEGRATES OVER ALL PHASE SPACE

MICROCANONICAL

CANONICAL

SURFACE OF
CONSTANT E

8.044 L13B2

2) SEPARATION

let H = Ha + Hb ,

then eH/kT = eHa/kT eHb/kT

p({p, q}) = p({p, q}a) p({p, q}b) (a & b are SI)

Z = Za Zb F = Fa + Fb S = Sa + Sb etc.

8.044 L13B3

 For N similar, non-interacting systems

Z = (Z1)N ,

F = N F1 ,

S = N S1

For N indistinguishable particles

(Z1)N
Z=
,
N!

correct Boltzmann counting

8.044 L13B4

Example Non-interacting classical monatomic gas

N
N

N
N
pi p i
H =
=
Hi
i=1 2m
i=1

H1(p
p, p
r) =

(Z1)N
Z=
N!

px2 + py2 + pz2

2m
2
2
(p2
x +py +pz )/2mkT

p1(p,
p p
r) = e

/(Z1h3)

2 + p2 >= 3mkT

Gaussian px < p p >=< p2

+
p
x
y
z

< H1 >= 3/2 kT

8.044 L13B5

Z1 =

2
2
(p2
x +py +pz )/2mkT

dpxdpy dpz dxdydz

h3

= (2mkT )3/2LxLy Lz /h3 = V

2mkT 3/2
V
=
2
h
(T )3

Where (T ) (or (T ) ) h/ 2mkT , the thermal

de Broglie wavelength.

1 V
Z(T, V, N ) =
N ! (T )3

8.044 L13B6

F = kT ln Z

kT

ln N + N + N

ln

V
(T )3

V
kT N ln
kT N

3
N (T )
'

'V

T 3/2

"

8.044 L13B7

F
1 {}
N kT
P =
= (1)(kT N )
=
V T,N
{} V
V

F
3 1 {}

S =
= kN ln{} kT N
+ kN
T V,N
2 {} T

V
= kN ln
+ (5/2)N k

3
N (T )

E = F + T S = (3/2) N kT
8.044 L13B8

Find the adiabatic path, S = 0.

V
V
is constant 3/2 is constant
S = 0

3
N (T )
T

3/2

V
T

=
V0
T0

8.044 L13B9

Example Classical Harmonic Oscillator

1
p2
H1(p, x) =
+ Kx2
2m
2
1
p2
p(p, x) =
exp[
]

2mkT
2mkT
x2

exp[
]
2(kT /K)
2(kT /K)
1

2 m
Z1 =
kT
h K

8.044 L13B10

Now assume there are N similar stationary oscilla

tors so that we can extract thermodynamic infor
mation.
Z = Z1N

2 m
F = kT ln Z = kT N ln
kT

h K

F
1 {}

S =
= kN ln{} + kT N
T N
{} T

2 m
= kN ln
kT + N k
h K

This shows that an adiabatic path for a collection

of classical harmonic oscillators is one of constant
temperature.

8.044 L13B11

E = F + T S = N kT

This shows that the heat capacity is a constant

C = N k independent of temperature. This would
be true even if the oscillators had a variety of dif
ferent frequencies.

8.044 L13B12

Canonical Ensemble

CLASSICAL

p({p, q}) =

Z=

eH({p,q})/kT /Zh

eH/kT

{dp, dq}/h

QUANTUM

p( state) = eEstate/kT /Z

eEstate/kT

Z=
states

where depends on the dimensionality of the phase

space.

8.044 L13B13

EXAMPLE 2 LEVEL SYSTEM: STATES OF AN IMPURITY IN A SOLID

E=0

E=

EXCITED

GROUND
STATE

g-FOLD

DEGENERACY

LOCATION

ENERGY LEVELS

INTERNAL

PHYSICAL DIFFERENCE

8.044 L13B1

STATES:

|0 >/ , \|1 >, |g >

E=0

E=E

eEstate/kT = 1 e0 + g eE/kT = 1 + geE/kT

Z1 =
states

p(state) = eEstate/kT /Z1

1
=
1 + ge
E/kT

for |0 >

eE/kT

=
1 + geE/kT

for |i > i = 1, g

8.044 L13B15

1+ g

p(E= )

1+ g

p(state = i = 0)

/ k

8.044 L13B1

Heat Capacity of a Two Level System

1.60

1.40

g=1

1.20

g=2
g=3

C/Nk

1.00

g=4
g=5

0.80

0.60

0.40

0.20

0.00
0.0

0.3

0.5

0.8

1.0

1.3

1.5

1.8

2.0

2.3

2.5

2.8

kT/

8.044 L13B17

Assume
N impurities (N 1)

E = E0(V /V0)
V0

Z = Z1N

F (T, V, N ) = kT ln Z = N kT ln Z1

F
S=
=
T V

E )eE/kT
g(
2

kT

N k ln Z1 + N kT

E/kT
1 + ge

8.044 L13B18

E/kT
E
e
S = N k ln(1 + geE/kT ) + gN k
kT 1 + geE/kT

g E eE/kT

U = F + TS = N
= N E p(E = E)
E/kT
1 + ge
F
F
E
P =
=
V T,N
E T V T
E

= N kT

g
) eE/kT
( kT

1 + geE/kT

E
U

=
V
V
8.044 L13B19

ALTERNATIVE WAY OF FINDING U

Usually (but not always) U =< H > .

If so, U =

But Z = c

H({p, q}) p({p, q}) {dp, dq}

eH({p,q}) {dp, dq}

1/kT

8.044 L13B20

Z
=c

N,V

H({p, q})eH({p,q}) {dp, dq}

1
Z

=
Z
N,V

eH({p,q})

H({p, q})

' '
eH({p ,q })

"

{dp', dq '}

p({p,q})

{dp, dq}

1
Z

=U
Z
N,V

8.044 L13B21

Example Monatomic Gas

1 N 2mkT 3N/2
3N/2

Z=
V
=

N!
h2

U =

1
3N/2

3N 1
3
3N/2

= N kT
2
2

8.044 L13B22

Example 2 Level System

Z =

1 + geE

U = 1 + geE

N 1

N 1 + geE

EgeE

gN E eE/kT
=
1 + geE/kT

8.044 L13B23

MIT OpenCourseWare
http://ocw.mit.edu

8.044 Statistical Physics I

Spring 2013

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