Sommerfeld theory of metals

• Keep most assumptions in Drude model.

• Classical mechanics → Quantum mechanics
• Electrons in metals are treated as a free electron gas
+ occasional scattering.
 Free electron gas in QM (1)
Schrödinger equation for one free electron
− 2 2  
∇ Ψ ( x ) = EΨ ( x )
2m

Solution:   2k 2
E (k ) =
2m
1 ik⋅ x
Ψ ( x) = e
V
2
Normalization ∫ Ψ ( x) dV = 1

ik y L
 2π
Periodic Boundary Condition (PBC) e ik x L
=e =e ik z L
=1 ⇒k = (nx , n y , nz )
L
 Free electron gas in QM (2)
A system of N identical free electrons
For fermions, anti-symmetric wave functions are expected
Ψ ( x1 , x2 , , xi ,  , x j ,  , x N ) = −Ψ ( x1 , x2 ,  , x j ,  , xi ,  , x N )
     
Eigenstates (without spin): e ik1 ⋅ x1
e ik 2 ⋅ x1
 e ik N ⋅ x1
     
ik1 ⋅ x2 ik 2 ⋅ x 2 ik N ⋅ x 2
e e  e
Ψ=
   
     
ik1 ⋅ x N ik 2 ⋅ x N ik N ⋅ x N
e e  e

Energy
2 2 2 2
E= (k1 + k 2 +  + k N )
2m

Occupation number representation (second quantization)

 Free electron gas in QM (3)
Ground state of N identical free electrons
Density of electrons:
4π k F3
N = 2⋅ × number of k points per unit volume in k - space
3
 2π 3
 2π  8π
3
k= (nx , n y , nz ) ⇒ 1 k - point =   =
L  L  V
4π k F3 V k F3V
⇒ N = 2⋅ × 3= 2
3 8π 3π
N k F3
⇒ n= = 2
V 3π

Fermi energy, Fermi temperature and Fermi velocity:

In typical metals E F ~ 1eV , TF ~ 10 4 K

k F−1 ~ 10 −8 cm
k F
vF = ~ 106 m / s
m
 Free electron gas in QM (4)
Ground state of N identical free electrons
Total energy:

E d 3k  2 k 2 1  2 k F5 3 N
= 2∫ = = EF
V (2π ) 3 2m 10π 2 m 5 V

E 3 3
⇒ = E F = k BTF
N 5 5

In classical mechanics

E 3
= k BT → 0 when T → 0 !
N 2

v2 2 TF
QM
= ~ 10 2 at room temperature
v2 5 T
CM
 Thermodynamics (1)
Fermi-Dirac distribution: nk = f (ε k )
1 1
f (ε ) = , β =
1 + e β (ε − µ ) k BT

Chemical potential μ is determined by electron density

d 3k
n = 2∫ n
(2π ) 3 k

At zero temperature,

1, ε < µ
f (ε ) =  ⇒ µ = EF at ground state
0, ε > µ

In general, µ ≠ EF at finite temperature.

 Thermodynamics (2)
With nk one can compute most thermodynamic quantities.

Energy (density): d 3k  2 k 2 k 2 dk  2 k 2  2k 2
U = 2∫ nk = ∫ 2 f( )
(2π ) 2m
3
π 2m 2m
= ∫ dε g (ε )ε f (ε )

Density of states: g (ε ) = ∑ δ (ε − Em )
m

k 2 dk
At 3D, = g (ε )dε
π 2

−1
k 2  dε  k2 m m 2mε
⇒ g (ε ) = 2   = 2 2 = 2 2
π  dk  π k π 2
1/ 2
3 n  ε 
=  
2 EF  EF 
 Thermodynamics (3)
Sommerfeld expansion:
ε

∫
To compute the integral I = dε H (ε ) f (ε ) , we define K (ε ) = ∫ H (ε ' )dε '
−∞

Therefore H (ε ) = dK (ε ) , and
dε
dK (ε )  df (ε ) 
I = ∫ dε f (ε ) = ∫ dε K (ε ) − ε = +∞
 + K (ε ) f (ε ) |ε = −∞
dε  dε 
∞
dn (ε − µ ) n
Using Taylor expansion about ε=μ, K (ε ) = ∑ n K (ε ) |ε = µ
n = 0 dε n!
µ
(ε − µ ) 2 n
∞
 ∂f  d 2 n −1
⇒ I = ∫ dεH (ε ) + ∑ ∫  − dε 2 n −1 H (ε ) ε = µ
−∞ n =1 (2n)!  ∂ε  dε
µ ∞
d 2 n −1
= ∫ dεH (ε ) + ∑ an (k BT ) 2n
H (ε ) ε = µ
−∞ n =1 dε 2 n −1

x 2n  d 1 
an = ∫ dx − 
(2n)!  dx 1 + e x 
 Thermodynamics (4)
Sommerfeld expansion:
µ 6
π2 7π 4  k BT 
∫ ε ε ε ∫−∞ ε ε µ µ
2 4 ( 3)
d H ( ) f ( ) = d H ( ) + ( k B T ) H ' ( ) + ( k B T ) H ( ) + O  
6 360  µ 

4
Chemical potential: µ
π2 k T 
n = ∫ dε g (ε ) f (ε ) = ∫ dε g (ε ) + (k BT ) 2 g ' ( µ ) + O B 
0
6  µ 
EF µ
π2 π2
n = ∫ dε g (ε ) ⇒ ∫ dε g (ε ) + ( k BT ) g ' ( µ ) = 0 ⇒ ( µ − E F ) g ( E F ) +
2
( k BT ) 2 g ' ( E F ) = 0
0 EF
6 6

(π k BT ) 2 g ' ( EF )
µ = EF −
6 g ( EF )

1/ 2
3 n  ε   1  π k T 2 
g (ε ) =   ⇒ µ = EF 1 −  B  
2 E F  EF   3  2 EF  
 Thermodynamics (5)
Sommerfeld expansion:
µ 6
π2 7π 4  k BT 
∫ ε ε ε ∫−∞ ε ε µ µ
2 4 ( 3)
d H ( ) f ( ) = d H ( ) + ( k B T ) H ' ( ) + ( k B T ) H ( ) + O  
6 360  µ 

Energy density:
µ 4
π2 k T 
u = ∫ dε g (ε )ε f (ε ) = ∫ dε g (ε )ε + (k BT ) [µg ' ( µ ) + g ( µ )] + O B 
2

−∞
6  µ 
Specific heat:
∂u ∂µ π 2 2 π2 ∂µ
CV = = g (µ )µ + k BT [µg ' ( µ ) + g ( µ )] + (k BT ) 2 [µg ' ' ( µ ) + µg ' ( µ ) + g ' ( µ )]
∂T ∂T 3 6 ∂T
3
∂µ π 2 2 k T 
= g ( EF ) EF + k BT [EF g ' ( E F ) + g ( EF )] + O B 
∂T 3  EF 
3
(π k BT ) 2 g ' ( EF ) π 2 k B2 k T 
µ = EF − ⇒ CV = Tg ( EF ) + O B 
6 g ( EF ) 3  EF 
 Conduction in metals (1)
Reexamine the Drude model:
 Maxwell-Boltzmann distribution should be replaced by Fermi-Dirac
distribution.
 Can one describe the motion of an electron classically? Namely, can we
specify its position and momentum as accurately as necessary without
violating Heisenberg’s uncertainty principle?
 Quantized energy levels, e.g., Landau levels in a magnetic field
 The condition ΔE >> kBT is required.

Where we assume a knowledge of the position of an electron:

 Spatially varying EM fields are applied
 Temperature gradient are applied
 Typical size of electron localization (~a) << mean free path (l~100Å)
 Conduction in metals (2)
Electric conductivity:

ne 2τ σ0
σ0 = , σ (ω ) =
m 1 − iωτ
Mean free path:

Using Fermi velocity as a measure of the typical electron speed

l = v Fτ

Mean free path typically can reach 100 Å at room temperature

 Conduction in metals (3)
Thermal conductivity:
1
κ = v 2τ CV
3
vF2 EF 2 TF π 2 k B2 π 2 k B23 n π 2kB n T
= = CVQM
= Tg ( E F ) = T× =
v2 3 3 T 3 3 2 EF 2 TF
CM k BT
2
3k B n
C VCM =
2
C VQM π2 T
=
C VCM 3 TF

vF2 C VQM π2
2 2π 2
= × = Drude model is qualitative correct.
v2 C VCM 3 3 9
CM
 Conduction in metals (4)
Thermopower:
CV
Q=−
3ne

QM
Q QM C V π2 T −2
CM
= CM
= ~ 10 at room temperature
Q CV 3 TF
Discussions on free electron model
• The role of ion: the source of collision?
– Classical mechanics vs. Quantum mechanics
• Free electron approximation
– Crystal lattice may change the typical velocity, say, Fermi velocity
– Density of states
– Lattice contribution to specific heat and thermoconductivity
• Independent electron approximation
– Fermi-liquid theory
– Another source of collision
– Compressibility
• Relaxation time approximation
– The outcome of collision is assumed not to depend on the incoming states
– Relaxation time may depend on energy or energy exchange, thereby,
become temperature dependent
• Deviation of Wiedemann-Franz law
– When strong electron interaction is involved
– In some extreme case, the material can even become electrical insulating
but thermal conducting !
 Summary
• Quantum mechanics will bring huge difference on thermodynamics
as well as transport.
• Scales in metals
EF ~ 1eV , TF ~ 10 4 K
k F−1 ~ 10 −8 cm
k F
vF = ~ 106 m / s
m

• Mean free path l = v Fτ

• Specific heat
π 2 k B2
CV = Tg ( EF )
3