CH6 Free Electron Fermi Gas

Very large mean

free path (> 1cm)
 Free Electron Model
A free electron model is the simplest way to represent the electronic structure of metals. Although
the free electron model is a great oversimplification of the reality, surprisingly in many cases it
works pretty well, so that it is able to describe many important properties of metals.
• Treat conduction electrons as free particles.
 Continuum states – density of states
 Fermi statistics – occupancy of states
 Thermal properties – heat capacity, heat conductivity,….
 Electrical and thermal transports – scatterings of conduction electron, frequently
happened due to the Pauli exclusion principle.
 Magnetic field effect
 Energy Levels in One Direction
• Consider a free electron gas in one direction, taking account of quantum theory and of the
Pauli principle. An electron of mass (m) is confined to a length (L) by infinite barrier.

kinetic energy (K) + potential energy (U) = Total Energy (E)

From the Schrödinger equation, the solution is

neglect because the electron is free

Two boundary condition:

0 L x
• n: the quantum number, referring to the electron orbital.

The Schrödinger equation:

The solution form:

• 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.
• nF is the value of n for the uppermost filled level.
𝟐 𝟐 𝟐 𝟐
𝑭
(2nF = N) 𝑭
• Similar to the periodic chain described in Ch5:

Density of states: (one state every k-interval)

(spin degeneracy)
ℏ
𝜖 = 𝑘
2𝑚
 Free Electron Gas in Three Dimensions
• The free-particle Schrödinger equation in 3D is:

• If the electrons are confined to a cube of edge L, the solution is:

• To make it satisfy periodic boundary conditions,

𝒙 𝒚 𝒛

𝟐 𝟐 𝟐
𝟐 𝟐 𝟐 𝟐
𝒌 𝒙 𝒚 𝒛

• The linear momentum p may be represented in quantum mechanics by the operator p

the particle velocity

 Density of states:

𝒙 𝒚 𝒛

Density of conduction electrons: n=N/V

Difference between electrons and phonons

Electrons Phonons

Number N=nV (fixed) N varies with T (Max.: 𝑫 𝑩 )

• two per orbital state (↑↓) • n per mode excited

Degeneracy • Fermi-Dirac statistics • Planck distribution
• Fermions • Bosons
Dispersion
Density of states
• In the ground state of a system of N electrons, the occupied orbitals may be represented as
points inside a sphere in k space,
𝟐 • Fermi sphere–volume in k-space
𝟐
𝑭 𝑭
occupied by electrons in the ground
states.
• The energy at the surface of the
sphere is the Fermi energy ( 𝑭 ).

The total no. of orbitals for allowed spins (N) is:

𝟑
𝟐 𝟏⁄𝟑 𝟑 𝟑
𝑭 𝟐 𝑭
𝑭

𝟐⁄𝟑
𝟐 𝟐 (spin degeneracy) ( )
𝑭

𝟐 𝟏⁄𝟑 (volume of
𝑭 Fermi sphere)
𝑭
n ~ 1022 – 1023 cm-3 ~ 108 cm-1 ~ 1-10 eV
At T=0, the total number of orbital energy

𝝐𝑭 ⁄

𝟎 𝟎

⁄
⁄

Within a factor of the order of unity, the number of

orbitals per unit energy range at Fermi energy is the
total number of conduction electrons divided by Fermi
energy, just as we would expect.
 Effect of Temperature on The Fermi-Dirac Distribution
• The ground state is the state of N electron system at absolute zero.
• The kinetic energy of the electron gas increases as the temperature is increased: some energy
levels are occupied which were vacant at absolute zero.

Fermi-Dirac function,
𝑭
𝑩

• is the chemical potential to conserve

when T < 0.1 electron number. ( 𝑭 at absolute
TF, 𝑭
zero).
• At finite T, when , .
• When 𝑩 ,

Boltzmann distribution
 Heat Capacity of the Electron Gas
Total thermal energy and heat capacity of electrons at T:
𝟑
• Classical statistical mechanics predicts that a free particle should have a heat capacity of 𝑩.
𝟐

• In reality, the observed electronic contribution at room temperature is usually less than 0.01
of this value.
𝟑
• Not every electrons gains energy 𝑩 , but only those electrons
𝟐

in orbitals within an energy range 𝑩 of the Fermi level are

excited thermally.
• The total electronic thermal kinetic energy U is of the order of:

𝒆𝒍 𝑩
𝑭

𝒆𝒍 𝑩
𝑭
• Derive a quantitative expression for the electronic heat capacity valid at low temperatures

𝑩 𝑭. The increase in the total energy ( ) of a system of N electrons when heated from
0 to T is:

𝝐𝑭

𝟎 𝟎
𝑩

𝝐 𝝐𝑭
𝝐𝑭
𝑭 𝑭
𝟎
𝟎 𝟎 𝟎 𝝐𝑭

𝝐𝑭
𝑭 𝑭
𝝐𝑭 𝟎

𝒆𝒍 𝑭 𝑭
𝟎 𝟎

(when 𝒌𝑩 𝑻 ≪ 𝝐𝑭 , 𝝁 = 𝝐𝑭 )
• Define 𝑩 and 𝑭

𝑭 𝑭
𝟐 𝟐
𝑭

𝒙 𝟐
𝒆𝒙 𝝅𝟐
𝒅𝒙 𝒙 =
𝟐 𝟐 𝒆𝒙 + 𝟏 𝟐 𝟑
𝒆𝒍 𝑩 𝑭 𝒙 𝟐
𝝐𝑭 ⁄ 𝝉
(We may safely replace the lower limit
𝒙 by −∞ because the factor 𝒆𝒙 in the
𝟐 𝟐 integrand is already negligible at 𝒙 ≡
𝑩 𝑭 𝒙 𝟐
−𝝐𝑭 ⁄𝝉 if we are concerned with low
temperatures such that −𝝐𝑭 ⁄𝝉 ~ 100 or
more.)
𝟐 𝟐
𝑩 𝑭

𝟐 𝒆𝒍 𝒆𝒍
𝑩
𝟑𝑵 𝑭
𝑫 𝝐𝑭 =
𝟐𝝐𝑭
𝟑𝑵
=
𝟐𝒌𝑩 𝑻𝑭
 Experimental Heat Capacity of Metals
• When 𝑫 and 𝑭 𝑭 𝑩, the heat capacity of metals may be written as the sum
of electron and phonon contributions:
𝟑
𝒕𝒐𝒕𝒂𝒍 𝒆𝒍 𝒑𝒉

𝟐
𝑩 𝟏
𝑭
𝑭

• 𝒕𝒉 (thermal effective mass) can be obtained from measurement of 𝒐𝒃 , but often do not
agree well with the value of free electrons.

𝒕𝒉 𝒐𝒃
• Interaction between conduction electrons with
periodic potential of the crystal lattice
𝒆 𝒇𝒓𝒆𝒆
 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.
Heavy Fermions

• Several metallic compounds have been discovered that have enormous values, 2 or 3 orders of
magnitude higher than usual, of the electronic heat capacity constant . ( 𝒕𝒉 𝒆, i.e.
CeAl3, CeCu2Si2, … and other exotic superconductors.)
 Electrical Conductivity and Ohm’s Law
• The momentum of a free electron is related to the wavevector by

In an electric field E and magnetic field B, the force F on an electron of charge – e is

(CGS) Newton’s second law

• In the absence of collisions, the Fermi sphere moves in k space at a uniform rate by a constant
applied E.

𝜹𝒌
• What limes ?
→ impurities, lattice imperfections, and phonons.
→ Collision time
→ The incremental velocity is

Current density ( )
𝟐
Ohm’s law

𝟐
electrical conductivity of free electron model

𝟐 electrical resistivity
 Approaches to a “steady state” value
non-equilibrium

ime

• In classical picture, all electrons carry charge – e at a constant drift velocity 𝒅.

𝟐
𝒅

• Only electrons near the Fermi surface contribute to current.

𝒚 𝑭

𝒌 𝒌 𝒇 𝒇 𝒆 𝒇
newly filled 𝒇
𝒌
𝒇 𝒆 𝒇
𝒙
newly participating states
emptied 𝒆
 Experimental Electrical Resistivity of Metals
Electron scattering processes

• Conductivity σ is limited by , l
• For a perfect crystal, no scattering

☼ Regime I:
Large angle e-ph scatterings,

☼ Regime II:
Small angle e-ph scatterings, 𝟓 I
II
☼ Regime III: IV III
𝟐
e-e scatterings,

☼ Regime IV:
𝟎
impurity scatterings,
𝟎
Umklapp Scattering

• When the Fermi surface does not intersect the

zone boundary, there is some minimum phonon
wavevector 𝟎 for umklapp scattering. umklapp process
• At intermediate T, the number of phonons
available for umklapp scattering falls as
, where is a characteristic
temperature calculable from the geometry of
the Fermi surface inside the Brillouin zone. normal process

(regime I close to the regime II, umklapp

scattering)
• At very low T, the number of umklapp
processes is negligible (regime II and below,
the normal scattering)
 Multiple scattering mechanisms  Residual resistance ratio (RRR)

Matthiessen’s rule

𝑳 𝒊 𝒆 𝒑𝒉 𝒆 𝒆 𝒆 𝒊𝒎𝒑𝒖𝒓𝒊𝒕𝒚
, perfect crystal
𝟐 𝟒
𝒆 𝒑𝒉 𝒆 𝒆 𝒆 𝒊𝒎𝒑𝒖𝒓𝒊𝒕𝒚 In general, for
pure metals
𝒆 𝒑𝒉 𝒆 𝒆 𝒆 𝒊𝒎𝒑𝒖𝒓𝒊𝒕𝒚

K
The different intercepts at
0K are attributed to different
concentrations of impurities
and static imperfections in
the two specimens.
 Motion in Magnetic Fields

In an Electric field:

In an magnetic field: (Lorentz force ⊥motion direction)

If , then the equation of motion is 𝒅 𝟏 𝑩

𝒎 + 𝝊𝒙 = −𝒆 𝑬𝒙 + 𝝊𝒚
𝒅𝒕 𝝉 𝒄
𝒅 𝟏 𝑩
𝒎 + 𝝊𝒚 = −𝒆 𝑬𝒚 − 𝝊𝒙
𝒅𝒕 𝝉 𝒄
𝒅 𝟏
𝒎 + 𝝊 = −𝒆𝑬𝒛
𝒛 𝒅𝒕 𝝉 𝒛

B 𝒙 𝒙 𝒄 𝒚

𝒚 cyclotron frequency
𝒚 𝒚 𝒄 𝒙
Circular motion in both 𝒄
real and k-spaces in free 𝒛 𝒛
𝒙 electron model
Hall Effect
• Consider a rod-shaped specimen in a longitudinal electric field Ex and a transverse magnetic
field B
• The current cannot flow out of the rod, → 𝒚
Define Hall coefficient
𝒚
𝒚 𝒄 𝒙 𝒙 𝑯
𝒙

𝟐
𝒙
𝒙 𝒙

𝒙
𝑯 𝟐
(CGS)
𝒙

(SI)

Hall effect relates to density and sign of

charge carriers
 Alkali metals : excellent
agreement

− Higher-valent metals: right

− values but wrong sign
 Thermal Conductivity of Metals

phonon electron

hot cold

• In CH5, we have known the expression for thermal conductivity is

For free electrons

𝟐 𝟐
𝑩

 In pure metal, the electronic contribution is dominate at all T.

 In impure metals or disordered materials, τ is reduced by
collisions with impurities, and the phonon contribution may
be comparable with the electronic contribution.
Ratio of Thermal to Electrical Conductivity

Wiedemann-Franz law: ratio of thermal to electrical conductivity

At not too low temperature:

𝟐 𝟐 𝟐 𝟐
𝑩 𝑩
𝟐

𝟐 𝟐
𝑩
Lorenz number L:
• A temperature-independent Lorenz number depends on the relaxation processes for electrical
and thermal conductivity being the same –which is not true at all temperatures
 Homework

Problem # 1, 5, 6