The Sommerfeld Theory of Metals

Daniele Toffoli January 11, 2017 1 / 48

Outline

1 Ground-state properties of the electron gas

2 The Fermi-Dirac distribution

3 Thermal properties of the free electron gas

4 The Sommerfeld theory of conduction in metals

Daniele Toffoli January 11, 2017 2 / 48

 Ground-state properties of the electron gas

1 Ground-state properties of the electron gas

2 The Fermi-Dirac distribution

3 Thermal properties of the free electron gas

4 The Sommerfeld theory of conduction in metals

Daniele Toffoli January 11, 2017 3 / 48

 Ground-state properties of the electron gas

Ground-state properties of the electron gas

General remarks

Maxwell-Boltzmann velocity distribution

Drude assumed the validity of the Maxwell-Boltzmann velocity
distribution (at thermal equilibrium)
2
m 3 − mv
fB (v ) = n( ) 2 e 2kB T
2πkB T
N
R
normalized such that fB (v )dv = n, n = V
R∞ 2
check yourself ( −∞ e −αx dx = α
pπ
)
f (v )dv : number of e − with velocities in the volume element dv at v
per unit volume
Equipartition theorem follows (cv = 32 kB ; ε̄ = 23 kB T )

Daniele Toffoli January 11, 2017 4 / 48

 Ground-state properties of the electron gas

Ground-state properties of the electron gas

General remarks

Fermi-Dirac velocity distribution

Valid for Fermions, as a consequence of the Pauli exclusion principle

(m/~)3 1
f (v ) = (1
4π 3 2
2 mv −kB T0 )
e kB T
+1
R
T0 determined such that f (v )dv = n
Sommerfeld theory replaces fB (v ) of Drude’s theory with f (v )
profound consequences on ε̄ and cv

Daniele Toffoli January 11, 2017 5 / 48

 Ground-state properties of the electron gas

Ground-state properties of the electron gas

General remarks

Maxwell-Boltzmann vs Fermi-Dirac velocity distribution

Plot of Maxwell-Boltzmann and Fermi-Dirac distributions for the same n given by T = 0.01T0 .

Daniele Toffoli January 11, 2017 6 / 48

 Ground-state properties of the electron gas

Ground-state properties of the electron gas

Quantum mechanical solution

Mathematical treatment
1
The free electron gas is confined in a cube of edge L (L = V 3 )
Assume the independent electron approximation
Solve the TISE (separation of variables)

~2 2
− ∇ ψ(r ) = εψ(r )
2m
Apply Born-von Karman boundary conditions to the general solution

ψ(x, y , z + L) = ψ(x, y , z)

ψ(x, y + L, z) = ψ(x, y , z)

ψ(x + L, y , z) = ψ(x, y , z)


Fill the energy levels by using the Pauli exclusion principle

Daniele Toffoli January 11, 2017 7 / 48
 Ground-state properties of the electron gas

Ground-state properties of the electron gas

Quantum mechanical solution

Separation of variables

Ansatz ψ(r ) = X (x)Y (y )Z (z)

Upon substitution on the TISE:
 ~2 d 2
− 2m dx 2 X (x) = εx X (x)

~2 d 2
− 2m dy 2
Y (y ) = εy Y (y )
 ~2 d 2

− 2m dz 2 Z (z) = εz Z (z)

ε = εx + εy + εz

Daniele Toffoli January 11, 2017 8 / 48

 Ground-state properties of the electron gas

Ground-state properties of the electron gas

Quantum mechanical solution

Separation of variables

Ansatz ψ(r ) = X (x)Y (y )Z (z)

The boundary conditions are:

Z (z + L) = Z (z)

Y (y + L) = Y (y )

X (x + L) = X (x)


Three similar homogeneous ODEs of the second order

Daniele Toffoli January 11, 2017 9 / 48

 Ground-state properties of the electron gas

Ground-state properties of the electron gas

Quantum mechanical solution

General and particular solutions

(
d2
dx 2
+ k 2 φ(x) = 0
φ(x)
φ(x + L) = φ(x)

General solution: φ(x) = c1 e ikx + c2 e −ikx

2mε ~2 k 2
k2 = ~2 =⇒ ε = 2m
Particular (normalized) solution: φ(x) = √1 e ikx
L
2nπ
k= L , n = 0, ±1, ±2, . . .

Daniele Toffoli January 11, 2017 10 / 48

 Ground-state properties of the electron gas

Ground-state properties of the electron gas

Quantum mechanical solution

Eigenfunctions and eigenvalues of the problem

ψk (r ) = √1 e ik·r
V
|ψk (r )|2 dr = 1
R
normalized inside the cube:
allowed wave vectors k:
2πn
kx = 2πn y
L ; ky = L ; kz =
x 2πnz
L
nx , ny , nz = 0, ±1, ±2, . . .
~2 k 2
ε = ε(|k|) = 2m (depends only on k = |k|)

allowed wave vectors in a 2D k space

Daniele Toffoli January 11, 2017 11 / 48

 Ground-state properties of the electron gas

Ground-state properties of the electron gas

Quantum mechanical solution

Eigenfunctions and eigenvalues of the problem

ψk (r ) is eigenfunction of the momentum operator p = ~i ∇

i ∇ψk (r )
~
= pψk (r ); p = ~k
p ~k
Its velocity is v = m = m

allowed wave vectors in a 2D k space

Daniele Toffoli January 11, 2017 12 / 48

 Ground-state properties of the electron gas

Ground-state properties of the electron gas

Quantum mechanical solution

Counting the quantum mechanical solutions

8π 3
Volume per allowed wave vector in k-space: ( 2π 3
L ) = V
ΩV
For a region Ω, the number is 8π 3
2π
must be very large on the scale of L
not too irregularly shaped
V
k-space density of levels: 8π 3

allowed wave vectors in a 2D k space

Daniele Toffoli January 11, 2017 13 / 48

 Ground-state properties of the electron gas

Ground-state properties of the electron gas

Quantum mechanical solution

Occupation of the ground-state (T = 0K)

Place a maximum of two e − on each level, starting with the lowest

k = 0 =⇒ εk = 0
ψ ≡ ψkσ , σ = ± 12
εk varies with the distance squared from O
The occupied region is a sphere (Fermi sphere)
for very large N
radius kF : Fermi wave vector
volume: Ω = 4π 3
3 kF
ΩV 4πkF3 V kF3
N = 2 8π 3 = 2( 3 )( 8π 3 ) = 3π 2
V

Daniele Toffoli January 11, 2017 14 / 48

 Ground-state properties of the electron gas

Ground-state properties of the electron gas

Quantum mechanical solution

Occupation of the ground-state (T = 0K)

N
Given a density n = V, the ground-state is formed by:
occupying all levels with k < kF
all levels with k > kF are empty
1
kF = (3π 2 n) 3
Some nomenclature:
region Ω: Fermi sphere
kF : Fermi wave vector
surface of Ω: Fermi surface
pF = ~kF : Fermi momentum
vF = pmF : Fermi velocity
~2 kF2
εF = 2m : Fermi energy
εF
TF = kB : Fermi temperature
The above quantities can be estimated from n
Daniele Toffoli January 11, 2017 15 / 48
 Ground-state properties of the electron gas

Ground-state properties of the electron gas

Quantum mechanical solution

Some numbers
1
( 9π )3
kF = 4
rs = 1.92
rs = 3.63
rs Å−1
a0

rs ∼2–6 Å =⇒ kF ∼ Å−1 (λ ∼ Å)

4.20
vF = ~
m kF = rs × 108 cm/s
a0

1% of c, (classical estimate at room temperature v ∼ 107 cm/s)

~2 kF2 e 2 50.1
εF = 2m = ( 2a 0
)(kF a0 )2 = ( ars )2
eV
0
εF ∈ 1.5–15 eV
εF 58.2
TF = kB = ( ars )2
× 104 K
0
energy per electron of a classical ideal gas vanishes at T = 0K
(ε̄ = 32 kB T )

Daniele Toffoli January 11, 2017 16 / 48

 Ground-state properties of the electron gas

Ground-state properties of the electron gas

Quantum mechanical solution

Some numbers

Daniele Toffoli January 11, 2017 17 / 48

 Ground-state properties of the electron gas

Ground-state properties of the electron gas

Quantum mechanical solution

Total energy of the ground-state (T = 0K)

P P ~2 k 2
E =2× k<kF εk = k<kF 2× 2m
Standard way of treating summations:
X V X
F (k) = F (k)∆k
8π 3
k k
Z
1 X F (k)
lim F (k) = dk
V →∞ V 8π 3
k

Therefore:
dk ~2 k 2 1 ~2 kF5
Z
E
=2 =
V k<kF 8π 3 2m π 2 10m

Daniele Toffoli January 11, 2017 18 / 48

 Ground-state properties of the electron gas

Ground-state properties of the electron gas

Quantum mechanical solution

Total energy of the ground-state (T = 0K)

2 5
E 1 ~ kF
V = 2
π 10m
energy density of the electron gas
E
N = 53 kB TF
E
for a classical particle N = 32 kB T =⇒ T = 25 TF ∼ 104 K

Daniele Toffoli January 11, 2017 19 / 48

 Ground-state properties of the electron gas

Ground-state properties of the electron gas

Quantum mechanical solution

Bulk properties of the ground-state

2E
Electronic pressure: P = 3V
exerted by the electron gas
Compressibility: K = − V1 ( ∂V
∂P )
1 5 10 E 2
Bulk modulus: B = K = 3 P = 9 V = 3 nεF
Numerically: B = ( r6.13
s /a0
)5 × 1010 dynes/cm2

Daniele Toffoli January 11, 2017 20 / 48

 The Fermi-Dirac distribution

1 Ground-state properties of the electron gas

2 The Fermi-Dirac distribution

3 Thermal properties of the free electron gas

4 The Sommerfeld theory of conduction in metals

Daniele Toffoli January 11, 2017 21 / 48

 The Fermi-Dirac distribution

Thermal properties of the free-electron gas

The Fermi-Dirac distribution

The partition function

If T6= 0, N-electron excited states become populated
thermal equilibrium is assumed
Boltzmann distribution law
− k ET
e B
PN (E ) = N
Eα
P −k
αe
BT

PN (E ): probability of finding the system in the state of energy E

P − EαN
Z = α e kB T is the partition function

Daniele Toffoli January 11, 2017 22 / 48

 The Fermi-Dirac distribution

Thermal properties of the free-electron gas

The Fermi-Dirac distribution

The partition function

FN
−k
FN = U − TS = −kB T ln(Z ) =⇒ Z = e BT

Helmholtz free energy

E −FN
−
PN (E ) = e kB T

Daniele Toffoli January 11, 2017 23 / 48

 The Fermi-Dirac distribution

Thermal properties of the free-electron gas

The Fermi-Dirac distribution

Derivation
The N-electron state is specified by a list of the one-electron levels
occupied
states ψkσ (r )
Define fi N = PN (EαN )
P

probability that the one-electron level i is occupied in the N-electron

state
Pauli exclusion principle requires 0 ≤ fi N ≤ 1
mean occupation of the level i
We will find an explicit expression for fi N

Daniele Toffoli January 11, 2017 24 / 48

 The Fermi-Dirac distribution

Thermal properties of the free-electron gas

The Fermi-Dirac distribution

Derivation

fi N = 1 − PN (EγN )
P

γ labels N-electron states where i is not occupied

fi N PN (EαN+1 − εi )
P
=1−
EγN= EαN+1 − εi
N + 1-electron states obtained from γ’s by placing an electron in level i
εi −µ
Defining µ = FN+1 − FN =⇒ fi N = 1 − e PN+1 (EαN+1 )
kB T
P
εi −µ
fi N = 1 − e kB T
fi N+1

Daniele Toffoli January 11, 2017 25 / 48

 The Fermi-Dirac distribution

Thermal properties of the free-electron gas

The Fermi-Dirac distribution

Derivation

Assuming that fi N = fi N+1 for N ∼ 1022

1
fi N = (εi −µ)
e kB T
+1
P N
P 1
N= i fi = i (εi −µ)
e kB T +1
N (or n = VN ) as a function of T and µ
We can express µ as a function of n and T

Daniele Toffoli January 11, 2017 26 / 48

 Thermal properties of the free electron gas

1 Ground-state properties of the electron gas

2 The Fermi-Dirac distribution

3 Thermal properties of the free electron gas

4 The Sommerfeld theory of conduction in metals

Daniele Toffoli January 11, 2017 27 / 48

 Thermal properties of the free electron gas

Thermal properties of the free-electron gas

Applications of the Fermi-Dirac distribution

Limiting form of fi N

In the ground-state:
(
fkσ = 1 ε(k) < εF
fkσ = 0 ε(k) > εF

For the fi N distribution we have

(
fkσ = 1 ε(k) < µ
fkσ = 0 ε(k) > µ

Therefore limT →0 µ = εF
µ ∼ εF also at room temperature

Daniele Toffoli January 11, 2017 28 / 48

 Thermal properties of the free electron gas

Thermal properties of the free-electron gas

Applications of the Fermi-Dirac distribution

Total energy of the electron gas

P
At any T, U = 2 k ε(k)f (ε(k)):

1
f (ε(k)) = (ε−µ)
e kB T
+1
U
Defining u = V Z
dk
u= ε(k)f (ε(k))
4π 3
P
From N = 2 k f (ε(k)):
Z
dk
n= f (ε(k))
4π 3

Daniele Toffoli January 11, 2017 29 / 48

 Thermal properties of the free electron gas

Thermal properties of the free-electron gas

Applications of the Fermi-Dirac distribution

Density of levels
Working in spherical coordinates:
Z Z ∞ 2 Z ∞
dk k dk
F (ε(k)) = F (ε(k)) = dεg (ε)F (ε)
4π 3 0 π2 −∞

g (): density of levels (per unit volume)

( q
m 2mε
~2 π 2 ~2
ε>0
g (ε) =
0 ε<0

mkF
At the Fermi level: g (εF ) = ~2 π 2

Daniele Toffoli January 11, 2017 30 / 48

 Thermal properties of the free electron gas

Thermal properties of the free-electron gas

Applications of the Fermi-Dirac distribution

Density of levels
Alternatively: (
3 n ε 1/2
2 εF ( εF ) ε>0
g (ε) =
0 ε<0
3 n
At the Fermi level: g (εF ) = 2 εF

Daniele Toffoli January 11, 2017 31 / 48

 Thermal properties of the free electron gas

Thermal properties of the free-electron gas

Applications of the Fermi-Dirac distribution

Total energy and density of the electron gas

R∞
u = −∞ dεg (ε)εf (ε)
R∞
n = −∞ dεg (ε)f (ε)
valid for any non-interacting electron systems

Daniele Toffoli January 11, 2017 32 / 48

 Thermal properties of the free electron gas

Thermal properties of the free-electron gas

Applications of the Fermi-Dirac distribution

The Sommerfeld expansion

For metals, T << TF even at room temperature
For T 6= 0 f (ε) differs little from its T=0 form
region ∆ε ∼ kB T around µ

Fermi function f for given µ at T = 0K (top) and room temperature (bottom)

Daniele Toffoli January 11, 2017 33 / 48
 Thermal properties of the free electron gas

Thermal properties of the free-electron gas

Applications of the Fermi-Dirac distribution

The Sommerfeld expansion

R∞
Applied to integrals of the type −∞ H(ε)f (ε)dε.
If H(ε) does not vary much for ∆ε ∼ kB T around µ
Taylor expansion of H(ε) around µ
assumed to converge rapidly for well-behaved H(ε)
Z ∞ Z µ
H(ε)f (ε)dε = H(ε)dε
−∞ −∞
π2 7π 4 kB T 6
+ (kB T )2 H 0 (µ) + (kB T )4 H 000 (µ) + O( )
6 360 µ

Daniele Toffoli January 11, 2017 34 / 48

 Thermal properties of the free electron gas

Thermal properties of the free-electron gas

Applications of the Fermi-Dirac distribution

Specific heat of the electron gas

Apply the Sommerfeld expansion to both u and n:
Z µ
π2
u = εg (ε)dε + (kB T )2 [µg 0 (µ) + g (µ)] + O(T 4 )
0 6
Z µ 2
π
n = g (ε)dε + (kB T )2 g 0 (µ) + O(T 4 )
0 6

Also, to order T 2 :
Z µ Z εF
H(ε)dε = H(ε)dε + (µ − εF )H(εF )
0 0

Daniele Toffoli January 11, 2017 35 / 48

 Thermal properties of the free electron gas

Thermal properties of the free-electron gas

Applications of the Fermi-Dirac distribution

Specific heat of the electron gas

Therefore:
εF
π2
Z  
2 0
u = εg (ε)dε + εF (µ − εF )g (εF ) + (kB T ) g (εF )
0 6
π2
+ (kB T )2 g (εF )
6
Z εF
π2
 
2 0
n = g (ε)dε + (µ − εF )g (εF ) + (kB T ) g (εF )
0 6

Note:
Rε
n = 0 F g (ε)dε
Rε
u0 = 0 F εg (ε)dε

Daniele Toffoli January 11, 2017 36 / 48

 Thermal properties of the free electron gas

Thermal properties of the free-electron gas

Applications of the Fermi-Dirac distribution

Deviation of µ from εF
From:
π2
0 = (µ − εF )g (εF ) + (kB T )2 g 0 (εF )
6
We get:

π2 g 0 (εF )
µ = εF − (kB T )2
6 g (εF )
 
1 πkB T 2
= εF 1 − ( )
3 2εF

The difference is ∼ 0.01% even at room T

Daniele Toffoli January 11, 2017 37 / 48

 Thermal properties of the free electron gas

Thermal properties of the free-electron gas

Applications of the Fermi-Dirac distribution

Specific heat capacity, cv

From:
π2
u = u0 + (kB T )2 g (εF )
6
We get:

π2 2
 
∂u
cv = = k Tg (εF )
∂T v 3 B
2
 
π kB T
= nkB
2 εF

varies linearly with T

compare with the classical result cv = 32 nkB ( kεBFT ∼ 10−2 )
electronic contribution is negligible even at room T

Daniele Toffoli January 11, 2017 38 / 48

 Thermal properties of the free electron gas

Thermal properties of the free-electron gas

Applications of the Fermi-Dirac distribution

Specific heat capacity, cv : qualitative considerations

From the T-dependence of the Fermi function f (ε):

nr. of electrons excited (per unit volume): ∼ g (εF ) × kB T
excitation energy: ∼ kB T
energy density: ∼ (kB T )2 g (εF ) → cv ∼ kB2 Tg (εF )

Fermi function at T 6= 0

Daniele Toffoli January 11, 2017 39 / 48

 Thermal properties of the free electron gas

Thermal properties of the free-electron gas

Applications of the Fermi-Dirac distribution

π2
 
kB T
Experimental verification of cv = 2 εF
nkB

At room T cv is determined by the ionic contribution (∝ T 3 for

T → 0)
cv = γT + AT 3
cv
Experimental data (of cp ) are fitted to the equation: T = γ + AT 2
electronic contribution is comparable to the ionic at T of few K
extrapolate at T → 0
ZNA
Experimentally [C ] = [ Kcal
mol ]. Multiply by n :

π2 kB Tg (εF )
C = ZR
3 n
1 2 Z rs
=⇒ γ = π R = 0.169Z ( )2 × 10−4 cal mol−1 K −2
2 TF a0

Daniele Toffoli January 11, 2017 40 / 48

 Thermal properties of the free electron gas

Thermal properties of the free-electron gas

Applications of the Fermi-Dirac distribution

π2
 
kB T
Experimental verification of cv = 2 εF
nkB

Daniele Toffoli January 11, 2017 41 / 48

 The Sommerfeld theory of conduction in metals

1 Ground-state properties of the electron gas

2 The Fermi-Dirac distribution

3 Thermal properties of the free electron gas

4 The Sommerfeld theory of conduction in metals

Daniele Toffoli January 11, 2017 42 / 48

 The Sommerfeld theory of conduction in metals

Sommerfeld theory of conduction in metals

Fermi-Dirac velocity distribution

Velocity distribution for electrons in a metal

Consider an element of volume dk around k
V V
number of one-electron levels: 2 × ( (2π) 3 ) = (4π 3 ) dk

probability of occupation: f (ε(k))

V
total number of electrons: f (ε(k)) (4π 3 ) dk

with velocity v = ~k
m → dk = ( m 3
~ ) dv
therefore the number of electrons with velocity ∈ (v , v + dv ) is:

( m~ )3 1
f (v )dv = 1/2mv 2 −µ
dv
4π 3
e kB T
+1

probability density (per unit volume)

Daniele Toffoli January 11, 2017 43 / 48

 The Sommerfeld theory of conduction in metals

Sommerfeld theory of conduction in metals

Validity of the classical description

∆x∆p ∼ ~
Sommerfeld used the Fermi-Dirac velocity distribution in an otherwise
classical theory
Classical description of electron dynamics is valid if:
r and p can be specified as accurately as necessary
without violating the uncertainty principle (∆x∆p ∼ ~)
The classical description is valid if:
∆p << ~kF ∼ p
∆x ∼ ∆p
~
>> k1F ∼ rs ∼ 2–6Å

Daniele Toffoli January 11, 2017 44 / 48

 The Sommerfeld theory of conduction in metals

Sommerfeld theory of conduction in metals

Validity of the classical description

∆x∆p ∼ ~
Electronic position must be specified in some instances:
for applied electromagnetic fields (∆x << λ)
for applied T gradients
Conclusions of the models were valid if E or T vary negligibly in the
scale of ∆x
valid for UV-vis radiation, not X-rays (QM must be used)
usually valid for normal ∇T ’s
We assumed ∆x << l, the mean free path
l ∼ 100Å at room T

Daniele Toffoli January 11, 2017 45 / 48

 The Sommerfeld theory of conduction in metals

Sommerfeld theory of conduction in metals

Improvements over Drude’s theory

The use of Fermi-Dirac velocity distribution

Affected properties:
mean free path
thermal conductivity
thermopower
Properties not affected:
magnetoresistance
Hall coefficient
DC and AC conductivities

Daniele Toffoli January 11, 2017 46 / 48

 The Sommerfeld theory of conduction in metals

Sommerfeld theory of conduction in metals

Improvements over Drude’s theory

Mean free path

(rs /a0 )2
From l = vF τ → l = ρµ × 92 Å
l ∼ 100 Å are possible at room T

Thermal conductivity

From κ = 31 v 2 τ cv

κ π 2 kB 2
= ( ) = 2.44 × 10−8 watt · ohm/K 2
σT 3 e

excellent agreement with exp.

Daniele Toffoli January 11, 2017 47 / 48

 The Sommerfeld theory of conduction in metals

Sommerfeld theory of conduction in metals

Improvements over Drude’s theory

Thermopower
With Sommerfeld estimate of the specific heat:

π 2 kB kB T kB T
Q=− ( ) = −1.42( ) × 10−4 volt/K
6 e εF εF

smaller by O( kεBFT ) ∼ 0.01 at room T

Daniele Toffoli January 11, 2017 48 / 48