Chapter Six

Free Electron Fermi Gas

• Energy levels in one dimension
• Free electron gas in three dimensions
• Effect of temperature on the Fermi-Dirac
distribution
• Heat capacity of the electron gas
• Electron conductivity and Ohm’s law
• Motion in magnetic field
• Thermal conductivity of metal
 In a theory which has given
results like these, there must
certainly be a great deal of true.

Hendrik A. Lorentz
---H. A. Lorentz
The Nobel Prize in Physics 1902
1853-1928
 Basic idea : pushing atoms together to form a crystal

discrete energy levels splitting of levels band of states

Atom = Ion + Valence electrons

Ion = Nucleus + Core electrons

 Free electron model
–treat conduction electrons as free particles

• Continuum states–density of states�

• Fermi statistics–occupancy of states
• Thermal properties–Thermal energy, heat capacity, …
• Electrical and thermal transports–scatterings of
conduction electron�
• Magnetic field effect

The models of Drude and Sommerfeld: free electron gas

Free conduction electrons in the box

Not interacting electrons

(except w/. walls of the box)

p 2 ( k ) 2 3
  K .E .    k BT
2m 2m 2
In reality, interactions of electrons :
Ions – steady Coulomb interaction (electron binding)
But
• Screening by core electrons weakens the attraction at
large distance
• Pauli exclusion principle requires that conduction
electrons stay away from core electrons localized at the
atoms.
Electrons – strong Coulomb repulsion
But
• Coulomb repulsion
• Pauli exclusion principle
Electrons tend to stay apart
In one dimension (1D chain)
U(x)= 0 0 ≤x ≤L
Schrödinger equation ∞ elsewhere
2 d 2
 2
  U ( x )   
2m dx U-> ∞
m
Boundary condition

 n ( 0)   n ( L )  0

 n  A sin( k n x) n ( k n ) 2  2 ( n ) 2
W\. kn  and   
L 2m 2mL2
 How to accommodate N electrons on the line ?
Pauli exclusion principle
+ spin degeneracy
(two spins ↑↓ per level)

Start to fill the levels from

the bottom (n=1) and continue
to fill higher levels with
electrons until all N electrons
are accommodated.

1,…, nF, where nF is the value of n for the uppermost filled level.
In general cases, such as periodic chain
n 2
Boundary condition:  n ( x)   n ( x  L) kn  
L
One state every k-interval: Δk = 2π/L
1 1 L
Density of states: D (k )   
k n ( 2 / L) 2
2 D(k )dk  D ( )d
2 D(k )dk 2( L / 2 )
D( )  
d d / dk
and  = ħ2k2/2m
2( L / 2 ) mL 2m
D( )  
 2k / m 2 (k )
2

mL 1

2 

singly spin density of states in

one dimension
In three dimensions
Schrödinger equation

2  2 2 2 
  2  2  2   U ( x, y, z )  
2m  x y z 

Boundary condition : Ψ is periodic in x, y, and z with period L

One state every k-volume interval: ΔkxΔkyΔkz = (2π/L)3

3
1 1  L  V
D(k )     
k x k y k z (2 / L)  2  2 3
3

2 V 1
D    d   D  k  4 k dk
2
 3
4 k d
 2  d  / dk

2 2
2
4k V m V 2m   3
k
 3
d  2 d 
2   k
2
4  3
2m
 V  2m 
3/ 2 singly spin density of states in
D   2  2   three dimensions
4   
x 2 for spin degeneracy

Conduction electrons: free to move through the crystal

Density of conduction electrons: n = N/V
typically n ~ 1022 ~ 1023 cm-3
mostly “s” orbital electrons but also “p” and “d” electrons
Difference between electrons and phonons (3D)

Electrons Phonons
Number N = nV fixed N ~ kBT varies w/. T

Degeneracy Fermions Bosons

(Fermi-Dirac statistics) (Bose-Einstein statistics)
two per orbital state ↑↓ n per mode excited
Dispersion ε∝k2  ∝k

Density of D(ε) ∝ ε1/2 D()∝ω2

states
up to D Debye
How do we determine ground states ?
Ground states T = 0, fill energy level from bottom:
2 per level ↑↓
n

F
highest level occupied w/. F
4
3
2 Fermi energy
1

Energy Maximum energy : F = ħ2kF2/2m

 kz
States w/. k ≤ kF are occupied.

Fermi sphere – volume in k-space occupied

kF
by electrons in the ground states

ky
Fermi surface – kF states w/.  = F
kx 44 V
N  2 kkF3F3 3
# of electrons
33 2 

spin volume of D(k)

Fermi sphere
2 1/ 3 2/3
2 2
 3 N 
k F      3 N 
and F   
 V  2m  V 
typically, ~ 108 cm-1 ~ 1 –10 eV
 TF
n F
Fermi-Dirac distribution

N   D( ) f ( )d
0
F
  D( )d
0

f() is the probability that a

state of energy  is occupied.

1,    F
f    
 0,   

Fermi energy is important because electronic

properties are dominated by states near F only.
 Finite temperatures

What is the probability of occupancy of

an electron state?

What is free electrons contribution to

heat capacity?

CV  T3 or Constant
Finite temperatures

Kinetic energy of electron increases due to the

increase of thermal energy

occupy higher energy levels

What is the probability of occupancy of an

electron state w/. energy ε at T ?

Boltzmann factor exp(-/kBT)? For phonons (Bosons)

Electrons are Fermions
------ quantum effects such as Pauli exclusion principle
 亥姆霍兹自由能
Standard problem in statistics Helmhotlz free energy
F = U − TS
Fermi-Dirac distribution

1
f ( ) 
exp    / k BT   1
where  is the chemical potential to
conserve electron number.

• At T = 0 K  = F, when  =  = F, f() changes discontinuously

• At finite T, when  = , f() = 1/2
• When ( -) >> kBT, f() Boltzmann distribution
 1
f ( ) 
(1) 0 ≤ f(,T) ≤1 exp    / k BT   1

when T< 0.1TF,  ≈ F, and f(,T) = 1/2 when  = EF

when  < , f(,T) > 1/2

when  > , f(,T) < 1/2 27

 (2) Electrons excited from below F to above F as T is increased.

 ~ kBT

Spread energy region increases with increasing temperature.

 (3)  = (T) decreases as T increased

why ?
What does determine ? Total number of electrons is conserved

N   dD ( ) f ( , T )

V 2m 3  1
N   d
0 0
4 2
3 exp     / k BT   1

  2  k T 2 
 T    F 1   B  
 12   F  
 

Homework: Calculate the (T) when temperature is finite.

29
 (4) Useful expression for D()

3
dnstate V 2m
D( )   2 3
 c 
d 2 

N   d D   f   T=0
0
F
2c 3
  d c   F
0
3

3N 3N  3N
where c  , D   and D F  
2  3
F 2  F3 2 F
Total thermal energy and heat capacity of electrons at T

Classical point of view, U = Ne(3kBT/2) and CV = Ne(3kB/2)

In reality, much smaller at room T

Not every electrons gains energy
3kBT/2
 
U   dD  f  , T 
0

At ground state, T = 0 K
F
3N 3N 2 5
U   d   F
3 5
0 2  F3 2 F

3N
 F
5

Average energy of each electron <> = 0.6F

At finite temperature (T ≠ 0 ), electrons are excited to
higher energy states and U(T) increases.

The filled orbital at finite

temperature
• Fermi-Dirac distribution function is a symmetric function;
at finite temperatures, the same number of levels below
EF is emptied and same number of levels above EF are
filled by electrons. 1
f ( ) 
exp    / k BT   1
n(E,T)
D(E)

T=0

T>0

E
EF
Qualitative arguments n(E,T)
D(E)

When we heat the T=0

specimen from absolute
zero not every electron T>0

gains an energy ~kBT as

expected classically. E
EF
energy range kBT of the Fermi level

number of electrons excited NkBT/EF

thermal energy of each electron 3/2kBT
total electronic thermal kinetic energy U~3/2 (NkBT/EF)kBT
electronic heat capacity Cel = dU/dT~3NkB(kBT/EF)
 Total energy

U T    dD  f  , T   U 0 K   U T 
0

 F
U T    dD   f  , T    dD  
0 0

 F
U   d    F D  f     d  F   D 1  f  
F 0

The first integral gives energy The secend integral gives

needed to take electrons from energy needed to bring
F to the orbitals of energy  electrons to F from the orbitals
> F. of below F.
 Heat Capicity
 F
U   d    F D  f     d  F   D 1  f  
F 0

f  , T 

dU
Ce   d    F D  
dT 0 T

In general, T/TF < 0.01, df/dT has non-zero value within couples of kBT
D() is about D(F) in the energy regime F±kBT

f  , T 

Ce  D  F  d    F 
0
T
 
f  , T 
Ce  D F  d    F 
0
T

Ignore the variation of the chemical potential with temperature


ex
Ce  D F k B2T  dx x 2

 F / k B T e x
1 
2

Lower T


ex
Ce  D F k B2T  dxx 2
 e x
1 
2
 2  2 3N
Ce  D F k B2T  k B2T 
2 ex 2
3 3 2k BTF  dxx 
1 T  e x
1 
2
3
  2 Nk B T
2 TF

Free electrons contribution to heat capacity

In general, when T << D and T << TF = F/kB
C = T + AT3 sum of electron and phonon contributions

In experiment C/T=  + AT2

Sommerfeld parameter
 2/3
  3 2 N 
2
 2 Nk B F   
 ∝ TF-1 ∝ m (mass of electron) 2m  V 
2 TF

mth  (observed )
Thermal effective mass 
m  ( free)
mth, obtained from measured  observed, is different from me.
 Three separate effect

• Interaction between conduction electrons with periodic potential of

the crystal lattice.
------Band effective mass
• Interaction between conduction electrons with phonons.
moving electrons drag nearby ions along
• Interaction between conduction electrons with themselves.
A moving electron causes an inertial reaction in the
surrounding electron gas.

For some materials, mth can be 1000me. Heavy Fermions

such as CeAl3, CeCu2Si2, … and other exotic
superconductors.