Intro.

to Electro-physics
Sommerfeld’s model (3rd)

Jaesang Lee
Dept. of Electrical and Computer Engineering
Seoul National University
(email: [email protected])
 Chemical potential
Fermi-Dirac statistics (1/3) : The change of free energy due to
a change of the particle number
∂U
μ≜
1 ∂N
fi = εi − μ , where μ : chemical potential
exp kBT
+1
fi

• What is it?
Increasing
Quantum statistics that Fermions must obey temperature

c.f.) Others include Maxwell-Boltzmann, Bose-Einstein statistics

Increasing
• Meaning temperature

- The probability (fi) that a single-Fermion level (εi) is occupied

εi − μ
- The mean number (n̄i = fi) of Fermions occupying the level εi

(Always n̄i ≤ 1 due to Pauli exclusion principle)

Source: Modello di Sommerfeld (Wikipedia)

 Fermi energy
Fermi-Dirac statistics (2/3) : The kinetic energy of electrons
in the highest occupied level
1 in k− space at T = 0 (K)
fi = εi − μ
exp kBT
+1
fi
- In the low temperature limit (T → 0)
1 (εi < μ) → All levels below μ are occupied.
{0
fi =
(εi > μ) → All levels above μ are NOT occupied.

- Previously in the ground state (T = 0) of the electron gas

1 (εi < εF) 2 2

{0
ℏ kF
fi = , where εF = : The Fermi energy εi − μ
(εi > εF) 2m

∴ lim μ (T) = εF
T→0

Source: Modello di Sommerfeld (Wikipedia)

Fermi-Dirac statistics (3/3)
• The Fermi energy and Fermi temperature
2 2
ℏ kF 50.1
εF ≜ = (eV) and εF ≜ kBTF
(rs /a0)
2m 2
638 (K)
6,380 (K)

- For silver, εF = 5.49 (eV) ⟶ TF = 63,800 (K)

63,800 (K)
• Temperature-dependence of Fermi-Dirac distribution
1
f= ε−μ
exp kBT
+1

- At T ≪ TF : Nearly a step function

1
‣ At ε = μ → f = regardless of T
2
- At T ≫ TF : the F-D distribution approaches the M-B distribution (HW!)
Source: Prof. Williams at Univ. of Liverpool [Thermal Physics]
 Chemical potential gdε: Number of
Chemical potential : The change of free energy due to single-electron levels
a change of the particle number in the energy range
∂U from ε to ε + dε
μ≜
• Temperature-dependence of chemical potential μ ∂N

- Derivation of μ (considering the degeneracy)

n̄i = fi ⋅ gi , where gi : # of levels with an energy εi

Let’s assume gi = g for simplicity. Then,
∞ ∞
gdε
∑ ∫0 ∫0
N= n̄i ≃ gf (ε) dε =
exp [ ]
ε−μ
i
kBT
+ 1
T = 0.3TF ≃ 19,000 (K) T = TF

( ( gkBT ) )
N
μ (T) = kBT ln exp −1

- At low temperatures (T ≪ TF) : μ (T) ≃ εF

Source: Prof. Williams at Univ. of Liverpool [Thermal Physics]

 Conversion of sum to integral:
Total energy of an electron gas (1/3) dk 8π 3
∑ ∫ Δk
= , where Δk =
k
V
• Electron gas: A collection of weakly interacting electrons that are free to move within a 1 dk
V∑ ∫ 8π 3
→ =
bounded volume V, but are unable to move beyond the boundary k

- Energy of the single electron in the gas

1
2 2 f (ε) =
ℏk exp
ε−μ
+1
ε (k) = , for whose wavevector being k kBT
2m
- Total number of electrons in the gas and Total energy of the gas

And their conversion in an integral form

N dk
f (ε (k)) ⟶ ( )
∑ ∫ 4π ( )
N=2 ≜n= f ε k Number of electrons in the gas of unit volume
k
V 3

U dk
ε (k) f (ε (k)) ⟶ ( )
∑ ∫ ( ) ( )
U=2 ≜u= ε k f ε k Total energy of the gas of unit volume
k
V 4π 3
 dk
Total energy of an electron gas (2/3) ∫ 4π 3 ( ( ))
n= f ε k

dk
∫ 4π ( ) ( ( ) )
• Total energy of an Fermi gas (contd.) u= ε k f ε k
3
- Expression for n and u in terms of ε (i.e., conversion of k → ε)
(The integrand depends on k only through ε (k))
∞ 2 ∞
dk 4πk dk
∫ 4π 3 ( ( ) ) ∫ ( ( ) ) ∫
n= f ε k = f ε k ⟶ g (ε) f (ε) dℰ
0 4π 3
0

2mℰ
2 2m m
k = 2 , 2kdk = 2 dℰ → kdk = 2 dℰ
ℏ ℏ ℏ
3

π 2 ( ℏ2 )
2
m 2
where g (ε) ≜ ε density of energy levels per unit volume

∞
dk
u=
∫ 4π 3
ε ( k) f ( ε (k) ) ⟶ u =
∫0
εg (ε) f (ε) dε

∞
dk
∫ 4π 3 ( ( ) ) ∫0
n= f ε k ⟶ n = g (ε) f (ε) dε
Total energy of an electron gas (3/3)
∞

∫0
•
Method of evaluating the form H (ε) f (ε) dε

- f (ϵ) di ers from its zero-temp value only in a small region about μ (Δε ≈ kBT)

- Integration of H (ε) f (ε) near (ε = μ) matters → Use Taylor’s expansion! (HW)

• Total energy of the electron gas (T ≪ TF) Ground-state energy at T = 0 (K)

12 ( TF ) ]
∞ 2

[
2
3 5π T
∫0
u= εg (ε) f (ε) dε ≃ nεF 1 + ≜ U0 + ΔU
5
Excited-state energy at T > 0 ( K)

• Speci c heat capacity at constant volume (T ≪ TF)

V ( ∂T )V ( ∂T )V ( 3 εF )
2 2
1 ∂U ∂u π T 3 π kBT
cV = = = nkB = nkB ⋅
2 TF 2
fi
ff
Specific heat capacity (1/2)
• Speci c heat capacity at constant volume (T ≪ TF)
Parameters for silver

( 3 εF )
3 π 2 kBT Mass density ρ 10,500 (kg/m3)
cV = nkB ⋅
2 Relative atomic mass A 0.108 (kg/mol)

Planck’s constant ħ 1.055 x 10-34 (J·s)

• Example: cV for Silver at T = 298 (K) Electron mass m 9.11 x 10-31 (kg)
2 2 3
ℏ kF N kF
ρNA Boltzmann’s constant kB 1.38 x 10-23 (J/K)
εF = , where n = = = Avogadro’s number NA 6.023 x 1023 (/mol)
2m V 3π 2
A
εF
εF = 5.49 (eV), TF = ≃ 63,900 (K)
kB

( 3 εF )
2
3 π kBT
∴ cV = nkB ≃ 1.74 (J/kg ⋅ K).
2

c.f.) measured cV for silver at constant pressure ≃ 235 (J/kg ⋅ K)

fi
Specific heat capacity (2/2)
• In reality
- The speci c heat = Ionic contribution + Electronic contribution
3
CV,m = γT + AT
• Associated with atomic vibrations
• Dominant at high T

• Associated with conduction electrons

• Dominant at low T
2
π T
CV,m = NAkB
2 TF

∂CV,m π 2 NAkB
⟶ γ = lim = ≃ 0.643 (mJ/mol-K ) for silver
2
T→0 ∂T 2 TF
2
- γ obtained as an intercept of the curve of CV,m /T vs. T (or T)!
fi
classic vs. quantum mechanics
• The speci c heat of the electron gas

Classcial Quantum mechanical

4 ( πℏ )
3
1 m 1
3

( 2kBT )
Electronic m 2 mυ2
− 2k T fFD (υ) =
fMB (υ) = n e B
( )
velocity 1
mυ 2 − E0
distribution exp 2
kBT
+1

( 3 ℰF )
2
The speci c heat of 3 3 π kBT
cV = nkB cV = nkB ⋅ ~0.01 at T = 298 (K)
the electron gas 2 2

What Drude predicted What Sommerfeld revised

fi
fi
Intro. to Electro-physics
Sommerfeld’s model (4th)

Jaesang Lee
Dept. of Electrical and Computer Engineering
Seoul National University
(email: [email protected])
Velocity distribution for electrons in metals (1/2)

• Conversion of F-D dist. from ε (k) to υ

- The number of single-electron levels in a small volume element dk:

1 V
ndk = 2 × × dk = dk
(2π/L) 3 4π 3

The volume of interest

# of available k-values per unit volume

Twofold spin degeneracy

- The probability of each energy level (associated with k) is being occupied: f (ε (k))

- Total number of electrons in the volume element dk:

V
Ndk = ndk ⋅ f (ε (k)) = 3 f (ε (k)) dk
4π
Velocity distribution for electrons in metals (2/2)
• Derivation (contd.)
ℏk
- The velocity of a free electron with a wave vector k : υ =
m

- Due to 1 : 1 correspondence between k and υ, υ dυ dk

= k

# of electrons # of electrons
in a volume element dυ in a volume element dk
about υ about k

- [The number of electrons per unit volume of real space] in a velocity space element dυ:

(m/ℏ)
3

V ( 4π 3 ( ) )
Ndk 1 V dυ
f (υ) dυ = = f ε (k ) dk =

[ ]
V 4π 3
exp ( 2 mυ 2
1
− μ) /kBT + 1

(ℏ)
3
m
dk = dυ
Drude’s model vs. Sommerfeld model

Drude model Sommerfeld model

4 ( πℏ )
3
1 m 1
3

( 2kBT )
m 2 mυ2
− 2k T fFD (υ) =
Electronic fMB (υ) = n e B
( )
1
2 mυ −μ
2
velocity exp +1
distribution kBT

Maxwell-Boltzmann dist. Fermi-Dirac dist.

Free-electron approx.
Assumptions Independent approx.
Relaxation-time approx.

( 3 ℰF )
The speci c heat 3 3 π 2 kBT
cV = nkB cV = nkB ⋅
of the electron gas 2 2

m ( 3 kBT )
Mean square 3kBT 2
3kB T 2 εF
electronic velocity
2
υ = υ = ⋅
m

What Drude model derived What Sommerfeld model derived

fi
Predictions by Sommerfeld model (1/3)
• The replacement of Maxwell-Boltzmann with Fermi-Dirac distribution a ects the predictions of physical
quantities that require the electronic velocity distribution
- (1) Mean-free path, (2) Thermal conductivity (and Widemann-Franz law), (3) Thermopower

(1) Mean-free path

{τ : relaxation time (an average survival time)

υ : Average electronic speed
- The average distance an electron travels between collisions, l = υτ
−15 −14
- Estimated τ : 10 ∼ 10 (s) at T = 300 (K)
Drude model Sommerfeld model

Average 3kBT ℏkF 4.2

Electronic υ= ≃ 10 (m/s)
2−3 υ = υF = = × 106 (m/s)
speed m m rs /a0

Mean-free path l = 1 ∼ 10 (Å) l > 100 (Å)

ff
 Element 273 K 373 K
Predictions by Sommerfeld model (2/3) Li
Na
2.22
2.12
2.43

K 2.23
(2) Thermal conductivity (and Wiedemann-Franz law) Cu 2.20 2.29
Ag 2.31 2.38

- Thermal conductivity (κ) and electrical conductivity (σ) Au 2.32 2.36

Mg 2.14 2.25

1 2 ne 2τ Fe 2.61 2.88
κ = υ τcV and σ = Zn 2.28 2.30
3 m Cd 2.49
Al 2.14 2.19
- Wiedemann-Franz law In 2.58 2.60
Sn 2.48 2.54
2
κ mυ cV Pb 2.64 2.53
= = C Kaye and Laby, Table of Physical and Chemical
σT 3ne 2T Constants, Longmans Green, Longdon, 1966.

Drude model Sommerfeld model

( 3 ℰF ) 100
The speci c heat 3 3 π 2 kBT 1
of electron gas cV = nkB cV = nkB ⋅ <
2 2

m ( 3 kBT )
Mean-square 3kB T 2
3kBT 2 ℰF
υ2 = υ = ⋅ > 100
electronic speed m

σT 2 ( e ) ( K2 ) 3 (e) ( K2 )
2 2 2
Widemann-Franz κ 3 kB −8 W⋅Ω κ π kB −8 W⋅Ω
law = = 1.11 × 10 = = 2.44 × 10
σT
fi
Predictions by Sommerfeld model (3/3) Element Q [V/K]
Na -5 x 10-6
(3) Thermopower
K -12.5 x 10-6
E = Q ∇T, where E : thermoelectric eld, Q : thermopower (V/K) Cu 1.8 x 10-6

3e dT ( 2 )
2 cV
1 d mυ 1 dℰ Be 1.5 x 10-6
Q=− =− n =−
3ne dT 3ne Al -1.8 x 10-6

Drude model Sommerfeld model

( 3 ℰF )
2
The speci c heat 3 3 π kBT
of cV = nkB cV = nkB ⋅
electron gas 2 2

kB
2e ( 3 ℰF ) ( ℰF )
Q=− = − 0.43 × 10−4 (V/K) kB π 2 kBT kBT
Thermopower 2e Q=− = − 1.42 × 10−4 (V/K)

1
∼
100
fi
fi
Common failures of both models
• Drude vs. Sommerfeld
- Commonality: Free-electron approx., Independent approx., Relaxation time approx.
- Di erence: Electronic velocity distribution (Maxwell-Boltzmann vs. Fermi-Dirac)

What aspects cannot be explainable

Hall coe cient

Magnetoresistance

pp. 58 ~ 60
Thermoelectric eld

Widemann-Franz law

Ashcroft & Mermin

DC electrical conductivity

AC electrical conductivity

Speci c heat

Nonmetallic elements
ff
fi
ffi
fi
To move further…
• 3 Key assumptions in the Drude’s model
① Free-electron approx.: No electron-ion interaction (*except collisions)
② Independent approx.: No electron-electron interaction

③ Relaxation-time approx.: τ independent of electron’s position and velocity

• Revision of ②, ③ leads to only minor improvement in predictions

• Most of the problems in Drude’s and Sommerfeld’s model stem from ①!

• The details of ① Free-electron approx.:

(i) The e ect of the ions on an electron between collisions is ignored
(ii) How the ions result in collisions is left unexplained
(iii) The contribution of the ions to physical phenomena (e.g. speci c heat, thermal conductivity) is ignored
ff
fi
To move further…
• How free-electron approx. needs to be revised: a
V x
- (i) & (ii) Electrons move in the presence of a static potential due to a
periodic array of stationary ions (“Nearly-free electron model”)
‣ Main topics: Bloch’s state and electronic band structure
- (iii) Consideration of the e ects of ionic vibrations in that array
‣ Main topic: phonon (→ temp-dependent electric conductivity, cubic
term in the speci c heat, a source of collisions, etc)

• Crystalline structure
- The ions in metals are arranged in a regular periodic array (i.e., lattice)
= A basis for the entire analytic framework of solid-state physics
- A direct characterization of the periodicity = X-ray di raction (XRD)
fi
ff
ff