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Review of Statistical Mechanics

3.1 Microcanonical, Canonical, Grand Canonical Ensembles

In statistical mechanics, we deal with a situation in which even the quantum state of the system is unknown. The expectation value of an observable must be averaged over:

O = w i i |O| i

(3.1)

i

where the states |i form an orthonormal basis of H and w i is the probability of being in state |i . The w i ’s must satisfy w i = 1. The expectation value can be written in a basis-independent form:

O = T r {ρO}

(3.2)

where ρ is the density matrix. In the above example, ρ = i w i |i i|. The condition, w i = 1, i.e. that the probabilities add to 1, is:

T r {ρ} = 1

(3.3)

We usually deal with one of three ensembles: the microcanonical emsemble, the canonical ensemble, or the grand canonical ensemble. In the microcanonical ensemble,

18

Chapter 3:

Review of Statistical Mechanics

19

we assume that our system is isolated, so the energy is fixed to be E, but all states

with energy E are taken with equal probability:

ρ = C δ(H E)

(3.4)

C is a normalization constant which is determined by (3.3). The entropy is given by,

In other words,

S

= ln C

S(E) = ln # of states with energy E

Inverse temperature, β = 1/(k B T ):

Pressure, P :

where V is the volume.

β

∂S ∂E V

P

k

B

T

∂S ∂V E

First law of thermodynamics:

dS =

∂S

E dE + V dV

∂S

dE = k B T dS P dV

Free energy:

Differential relation:

F

= E k B T S

dF = k B S dT P dV

or,

S =

1

k

B

∂F

∂T

V

(3.5)

(3.6)

(3.7)

(3.8)

(3.9)

(3.10)

(3.11)

(3.12)

(3.13)

Chapter 3:

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20

while

E

P

=

∂F ∂V T

= F + k B TS

= V

=

T F ∂T

F

∂T T

F

T 2

(3.14)

(3.15)

In the canonical ensemble, we assume that our system is in contact with a heat

reservoir so that the temperature is constant. Then,

ρ = C e βH

(3.16)

It is useful to drop the normalization constant, C, and work with an unnormalized

density matrix so that we can define the partition function:

or,

The average energy is:

Hence,

Z

= T r {ρ}

Z = e βE a

E

=

=

=

F

1

a

a

E a e βE a

Z

β ln Z

k B T 2 T ln Z

= k B T ln Z

The chemical potential, µ, is defined by

µ =

∂F

N

(3.17)

(3.18)

(3.19)

(3.20)

(3.21)

Chapter 3:

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21

where N is the particle number.

In the grand canonical ensemble, the system is in contact with a reservoir of heat

and particles. Thus, the temperature and chemical potential are held fixed and

ρ = C e β(HµN )

(3.22)

We can again work with an unnormalized density matrix and construct the grand

canonical partition function:

The average number is:

while the average energy is:

E

Z =

N,a

e β(E a µN )

N

= k B T µ ln Z

= β

ln Z + µk B T µ ln Z

(3.23)

(3.24)

(3.25)

3.2 Bose-Einstein and Planck Distributions

3.2.1 Bose-Einstein Statistics

For a system of free bosons, the partition function

Z =

E a ,N

e β(E a µN )

(3.26)

can be rewritten in terms of the single-particle eigenstates and the single-particle

energies i :

(3.27)

E a = n 0 0 + n 1 1 +

Z =

{n i }

=

i

e β ( i n i i µ i n i)

n

i

e β(n i i µn i )

Chapter 3:

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22

=

i

1

1 e β( i µ)

n i =

1

e β( i µ) 1

The chemical potential is chosen so that

The energy is given by

N = n i

E

=

i

i

1

e β( i µ) 1

= n i i

=

i

i

i

e β( i µ) 1

(3.28)

(3.29)

(3.30)

(3.31)

N is increased by increasing µ (µ 0 always). Bose-Einstein condensation occurs

when

N

> n i

i

=0

(3.32)

In such a case, n 0 must become large. This occurs when µ = 0.

3.2.2 The Planck Distribution

Suppose N is not fixed, but is arbitrary, e.g. the numbers of photons and neutrinos

are not fixed. Then there is no Lagrange multiplier µ and

n i =

1 1

e β i

Consider photons (two polarizations) in a cavity of side L with k = ¯

E

=

k = 2π

L

(m x , m y , m z )

2

m x ,m y ,m z

ω m x ,m y ,m z n m x ,m y ,m z

(3.33)

k = hck¯

and

(3.34)

(3.35)

Chapter 3:

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23

We can take the thermodynamic limit, L → ∞, and convert the sum into an

integral. Since the allowed k’s are 2π (m x , m y , m z ), the k-space volume per allowed k

L

is (2π) 3 /L 3 . Hence, we can take the infinite-volume limit by making the replacement:

Hence,

For βhck¯

and

For βhck¯

and

max 1,

max 1 ,

k

E

f( k)

=

=

1

(∆ k) 3

k

f( k) (∆ k) 3

(2π) 3 d 3

L

3

k f( k)

=

=

=

2 V

0

2 V

0

k

k

max

max

d 3 k

¯ k

(2π)

d 3 k

3

e β¯k 1

hck¯

(2π)

3

e β¯hck 1

π 2 hc) 3 T 4

B

0

V k

4

β¯hck max

x 3 dx

e x 1

E =

C V =

4

V k π 2 hc) 3 T 4

B

0

x 3 dx

e x

1

4V k

4

B

π 2 hc)

3

T 3

0

x 3 dx

e x

1

3

E = V 3π k 2

max

k B T

C

V

= V k

3 max k B

3π 2

(3.36)

(3.37)

(3.38)

(3.39)

(3.40)

(3.41)

3.3 Fermi-Dirac Distribution

For a system of free fermions, the partition function

Z =

E a ,N

e β(E a µN )

(3.42)

Chapter 3:

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24

can again be rewritten in terms of the single-particle eigenstates and the single-particle

energies i :

(3.43)

E a = n 0 0 + n 1 1 +

but now

so that

n i = 0, 1

(3.44)

Z =

{n i }


=

i

e β ( i n i i µ i n i)

1

n i =0

e β(n i i µn i )

= 1 + e β( i µ)

i

1

n i = e β( i +µ) + 1

The chemical potential is chosen so that

The energy is given by

N

E

=

i

=

i

1

e β( i +µ) +

i

1

e β( i +µ) + 1

(3.45)

(3.46)

(3.47)

(3.48)

3.4 Thermodynamics of the Free Fermion Gas

Free electron gas in a box of side L:

with

k = 2π

L

k = h¯ 2m

k

2

2

(m x , m y , m z )

(3.49)

(3.50)

Chapter 3:

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25

Then, taking into account the 2 spin states,

E

=

2

m x ,m y ,m z

m x ,m y ,m z n m x ,m y ,m z

= 2 V

0

(3.51)

k max

d 3 k

d 3 k

(2π) 3

¯h 2 k 2

2m

2m

e β h¯ 2 k 2

µ + 1

N = 2 V

0

k max

d 3 k

1

(2π) 3

e β h¯ 2 k 2

2m

µ + 1

(3.52)

At T = 0,

µ + 1 = θ µ h¯ 2 k 2

1

2m

e β h¯ 2 k 2

2m

(3.53)

All states with energies less than µ are filled; all states with higher energies are empty.

We write

(3.54)

k F = 2T =0 h¯

,

F = µ T =0

N

V

= 2

0

k

F

d 3 k

(2π)

3 =

k

3

F

3π

2

(3.55)

For k B T e F ,

N

V

m

3

2

2

1

2

=

π 2 h¯ 3

= 2 h¯ 3

m

3

2

2

1

2

π

0

0

E

V

2

=

=

2

0

1

d 3 k (2π) 3 h¯ 2 k

k

F

5

F

h¯ 2 k 2

2m

π 2

3

10m

N

=

d 3 k

5

V

F

3

2

2

1

2

(2π) 3 = m π

2 h¯ 3

1

d 2

d

1

2

1

e β( µ) + 1

µ

3

2

1

d 2 + m π 2 h¯ 3

1

2

2

0

µ

d

2

1

1

e β( µ) + 1

1 + m π 2 h¯ 3

2

2

3

2

1

µ

d

1

2

(3.56)

(3.57)

1

e β( µ) + 1

Chapter 3:

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26

(2m) 3

= 3π 2 h¯ 3

(2m) 3

=

(2m) 3

= 3π 2 h¯ 3

(2m) 3

=

2

2

3π 2 h¯ 3 µ

µ

2

2

3π 2 h¯ 3 µ

µ

3

2

3

2

2

1

2

m

π 2 h¯ 3

0

µ

d

1

2

1

3

2

2

1

2

e β( µ) + 1 + m

π 2 h¯ 3

µ

d

1

2

1

e β( µ) + 1

3

2 +

3

2

+

m

3

2

2

1

2

π 2 h¯ 3

0

(2m) 3

2

π 2 h¯ 3

n=1

k B T dx

e x + 1

(µ + k B Tx) 2 (µ k B Tx) 2 + O e βµ

Γ

1

1

1

(k B T) 2n   µ

3

2

3

2

2n

0

dx x 2n1

e x + 1

2n

(2n 1)!

Γ 5

2

3

2

1 +

3

k B T

µ

2

2 I 1 + O T 4  

(3.58)

with

We will only need

I k =

0

dx

k

x + 1

e

x

2

I 1 = π 12

(3.59)

(3.60)

Hence,

( F ) 2 3 = µ

3

2

  1 +

3

k B T

µ

2

2 I 1 + O T 4  

To lowest order in T , this gives:

µ

=

=

F

1 k B T 2 I 1 + O(T 4 ) F

F   1 π

12

k B T

2

F

2 + O(T 4 )

(3.61)

(3.62)

E

V

m

3

2

2

1

2

3

2

1

=

π 2 h¯ 3

= π 2 h¯ 3

=

d

d

m

3

2

2

1

2

(2m) 3

2

0

0

µ

5π 2 h¯ 3

(2m)

(2m) 3

2

e β( µ) + 1

3

2

3

2

1

+ m π 2 h¯ 3

2

2

3

2

2

1

2

0

µ

d

0

n=1

0

µ

3

2

1

1

e β( µ) + 1

3

2

1 + m π 2 h¯ 3

2

2

2

1

2

µ

d

3

2

3

2

1

µ

d

3

2

1

e β( µ) + 1

d

3

2

µ 2 m

5

π 2 h¯ 3

2 + m π 2 h¯ 3

3

2

2

1

2

5

5

2

+ (2m) 3 π 2 h¯ 3

2

3

2

e β( µ) + 1 + m

(µ + k B Tx) 3

2

5

2 2n

1

e β( µ) + 1

π 2 h¯ 3

k B T dx e x + 1

1

(µ k B Tx) 3 + O e βµ

2

Γ

5

2

2n

0

dx x 2n1

e x + 1

=

5π 2 h¯ 3 µ

= 5π 2 h¯ 3 µ

(k B T) 2n   µ

(2n 1)!

Γ

7

2

Chapter 3:

Review of Statistical Mechanics

27

=

=

(2m)

5π 2 h¯ 3 µ

3

3

2


5

2

15

2

k B T

µ

k B T

2 I 1 + O(T 4 )

2 + O(T 4 )

N

5

V

1 +

F

1 + 5π 2

12

F

(3.63)

Hence, the specific heat of a gas of free fermions is:

2

C V = π 2 Nk B

k B T F

(3.64)

Note that this can be written in the more general form:

C V

= (const.) · k B

· g ( F ) k B T

(3.65)

The number of electrons which are thermally excited above the ground state is

g ( F ) k B T ; each such electron contributes energy k B T and, hence, gives a specific

heat contribution of k B . Electrons give such a contribution to the specific heat of a

metal.

3.5 Ising Model, Mean Field Theory, Phases

Consider a model of spins on a lattice in a magnetic field:

H = B B S

z

i

i

2h S

z

i

i

with S

z = ±1/2. The partition function for such a system is:

i

Z

= 2 cosh

T N

h

k

B

The average magnetization is:

z

i

S

=

1

2

h

tanh k B T

The susceptibility, χ, is defined by

χ =

∂h

i

z

i

S

h=0

(3.66)

(3.67)

(3.68)

(3.69)

Chapter 3:

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28

For free spins on a lattice,

(3.70)

2 N

A susceptibility which is inversely proportional to temperature is called a Curie suc-

septibility. In problem set 3, you will show that the susceptibility is much smaller for

a system of electrons.

Now consider a model of spins on a lattice such that each spin interacts with its

neighbors according to:

(3.71)

1

1

k B T

χ =

= 1

2

H

i,j

JS z S z

i

j

This Hamiltonian has a symmetry

z

i

S

z

i

→ −S

(3.72)

For k B T J, the interaction between the spins will not be important and the

susceptibility will be of the Curie form. For k B T < J, however, the behavior will be

much different. We can understand this qualitatively using mean field theory.

Let us approximate the interaction of each spin with its neighbors by an interaction

with a mean-field, h:

with h given by

H = hS

z

i

i

h = J S

z

i

i

= Jz S

z

i

 

(3.73)

(3.74)

where z is the coordination number.

2 cosh

h

T and

k

B

In this field, the partition function is just

S z = tanh

h

k B T

(3.75)

Using the self-consistency condition, this is:

S z = tanh Jz k B S T z

(3.76)

Chapter 3:

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29

= 0 which break the symmetry

> Jz,

there is only the solution S z = 0. In this phase the symmetry is unbroken and the

is no spontaneous magnetization. At k B T = Jz, there is a critical point at which a

phase transition occurs.

For k B T < Jz, this has non-zero solutions, S z

→ −S

z

i

.

S

z

i

In this phase, there is a spontaneous magnetization.

For k B T