The Fermi-Dirac Statistics

The thermodynamic probablity Wk of macrostate k is the

number of microstates that correspond to macrostate k:
g j!
Wk  
j N j ! g j  N j !

The Fermi-Dirac distribution is

gj
Nj  
   j 
e 1
 If the gas molecules have integral angular momentum 24
gj gj F
Nj  
  j  1   j kT 
e e F kT
e 1 kT
The Fermi Function

N  d   f  g  d 

f     / kT
1
e F
1
At absolute zero
temperature (T=0)
f  
1
F (0), 
1
e 1
f   
1
F (0), 0
e 1
1. The Fermi-Dirac Gas

 N j   N  d   N
j 0
 F 0  
N   N  d    f g d    f g d 
0 0 F 0 

F 0 
N  g d 
0

The states to occupy a volume d of phase space will be:

d
g2 3
h
For 3He gas that is free from the external force field, the number of
available energy states in the energy range  to +d is given by:
 32
 2m 
g d  V .4  2  1 2 d 
h 
p2
where:  and V   dxdydz
2m
V

F 0  32
 2m 

the total number of
N V . 4  2  1 2 d 
particles
0 h 

23
Fermi energy h  3N 2

at absolute zero F 0   

temperature
2m  8V 
Fermi temperature (TF) is defined as:

k TF  F 0

Gas F(0) (eV) TF (K)

3He 0,94 x 10-3 10
Electron gas in lithium 4,7 54.000
Electron gas in potassium 2,1 24.000

The effect of Pauli exclusion principle on the energy distribution for

molecular gas will be small at room temperature.

A Maxwell-Boltzmann gas.
2. The electron gas

The free electrons in a metallic conductor (the outer valence

electrons) can move freely troughout the metal as an electron gas.
At room temperature T so that kT << F

 F kT  f  

1
 0,73
e 1  1

f  
1
 F  0,5
e 1
0

 F  kT  f  
1
 0,27
e 1
N  d   f  g  d 
32
 2m 
g   V .4  2  1 2
h 

The mean energy of electrons at T = 0 is

 F 0  F 0 
  N  d    g  d    d
32

0  F 0
3
0

 0
F 0 
 0
F 0 

5
 N  d   g  d    d
12

0 0 0
The total energy U of the electrons at T = 0 is

3
U (T  0)  N F (0)
5

Silver is monovalent, we assume one free electron per atom.

The density of silver is 10.5 x 103 kg m-3 and its atomic weight is 107.
The mass of an electron is 9.11x10-31 kg and h = 6.63x10-34 J s.
Calculate:
a. its fermi energy at T = 0. (F = 9.1x10-19 J = 5.6 eV)
b. the mean (kinetic) energy per electron at T = 0.  (0)  3.4 eV

The mean energy of a gas molecule at room temperature is about

0.03 eV.
Thus, the mean kinetic energy of the electrons in a metal (even at T=0)
is much greater than that of anordinary gas.
How to find the effect on the distribution due to raising the
temperature above the absolute zero (T << TF)?
Obtain the value for the Fermi energy as a function of T

  2  T 2 
F F 01    
 12 TF  
2
 T 
2
for TF  30 x10 K
3 5
At room temperature    8 x10
12  TF 
1  1 
The mean energy of electrons at T is     N d    f g d 
N 0 N 0
3  T 2  2 
  F 0    
 5  TF  4 
 
The constant volume specific heat per mole electron gas is

cV 
 

 N A  2 R T  2  k T 
   R
T 2 TF 2  F (0) 
cv is zero at T = 0 and increases linearly with the temperature T.
For silver at T= 300 K, cv = 2.25x10-2 R.
The molal specific heat capacity of a monatomic ideal gas is
cv =(3/2) R.
The molal specific heat capacity of metallic conductors or
nonconductors (dulong Petit) is 3R.

If the electrons behaved like the molecules of an ideal gas, they

should make an addition contribution of 3R/2 to the specific heat
capacity, resulting a much larger value that it observed.
The fact only electrons having energy near the fermi level can
increase their energies as temperature T is increased.
Electrons make only a negligible contribution to the heat capacity