Chapter 6

Free Electron Fermi Gas

 Free electron model:
The valence electrons of the constituent atoms become conduction
electrons and move about freely through the volume of the metal.
The simplest metals are the alkali metals lithium, sodium, potassium, Na,
cesium, and rubidium.
The classical theory had several conspicuous successes, notably the
derivation of the form of Ohms law and the relation between the electrical and
thermal conductivity.
The classical theory fails to explain the heat capacity and the magnetic
susceptibility of the conduction electrons. M = B
Why the electrons in a metal can move so freely without much deflections?
(a) A conduction electron is not deflected by ion cores arranged on a periodic
lattice, because matter waves propagate freely in a periodic structure.
(b) A conduction electron is scattered only infrequently by other conduction
electrons.
Pauli exclusion principle.
Free Electron Fermi Gas: a gas of free electrons subject to the Pauli Principle
 ELECTRON GAS MODEL IN METALS
Valence electrons form the electron gas

eZa
-e(Za-Z)
-eZ

Figure 1.1 (a) Schematic picture of an isolated atom (not to scale). (b) In a
metal the nucleus and ion core retain their configuration in the free atom, but the
valence electrons leave the atom to form the electron gas.
 3.66A 0.98A

Na : simple metal
In a sea of conduction of electrons

Core ~ occupy about 15% in

total volume of crystal
 Classical Theory (Drude Model)

Drude Model, 1900AD, after Thompsons discovery of electrons in 1897

Based on the concept of kinetic theory of neutral dilute ideal gas
Apply to the dense electrons in metals by the free electron gas picture
Classical Statistical Mechanics: Boltzmann Maxwell Distribution
The number of electrons per unit volume with velocity in the range du about u
fB(u) = n (m/ 2pkBT)3/2 exp (-mu2/2kBT)
Success: Failure:

(1) The Ohms Law , (1) Heat capacity Cv~ 3/2 NKB
the electrical conductivity The observed heat capacity is only 0.01,
J = E , = n e2 / m, too small.
(2) The Weidmann Frantz Law
Ke / (e T) = L ~ a constant (2) The observed thermal power Q is also
only ~ 0.01, as Q = - Cv /3ne
for electrons,
since K = 1/3 vF2 Cv (3) Magnetic susceptibility is incorrect.
See Ashroft & Mermin, Ch. 1
(TF /T) 100 times; 0.01 times (T/TF)
 We have shown that the one-dimensional energy distribution is

but would like to have a distribution for three dimensions. A basic probability idea is
that for three independent events you take the product of the individual probabilities.
The three-dimensional probability distribution then takes the form:

It must be noted here that while this has the form of the Boltzmann distribution
for kinetic energy, it does not take into account the fact that there are more ways to
achieve a higher velocity. In making the step from this expression to the Maxwell
speed distribution, this distribution function must be multiplied by the factor 4v2 to
account for the density of velocity states available to particles.
 Maxwell Speed distribution as a sum over all directions
To put the three-dimensional energy distribution into the form of the Maxwell speed
distribution, we need to sum over all directions. One way to visualize that sum is as
the development of a spherical shell volume element in "velocity space".

The sum over the angular coordinates is just going to give the area of the sphere,
and the radial element dv gives the thickness of the spherical shell. That takes the
angular coordinates out of the distribution function and gives a one-parameter
distribution function in terms of the "radial" speed element dv.
Thermal Electrical Effect: (Seeback Effect)
As a temperature gradient is applied to a long thin bar,
it should be accompanied by an electrical field directed
opposite to the temperature gradient

E=-QT

E as the thermal electric field Q as the thermal power

Q=E/T See Ashcroft & Mermin, Ch. 1,

= - Cv / (3ne) p. 24-25

As in Drude model, Cv and Q are 100 times too small !

 Drude Model

*** Basic approximations are:

(1) Between collisions:

-- Neglect electron - ion core interaction --- Free electron approximation
-- Neglect electron - electron interaction --- Independent electron approximation

(2) During collisions:

-- Assuming electrons bouncing off the ion core
-- Assuming some form of scattering

(3) Relaxation time approximation:

-- Collision mean free time
-- Independent of electron position and velocity

(4) The collisions are assumed to maintain the thermal equilibrium

 Free Electron Gas Model (Sommerfeld) :
Quantum Statistical Mechanics:
The Pauli exclusion principle requires that the replacement of
Maxwell Boltzmann distribution with the Fermi Dirac distribution as

**Can still use the dilute, neutral gas, kinetic picture as in the classical case.

** Justifications:
One can still describe the motion of an electron classically,
If we can specify its positions and momentum as accurately as possible without
violating the Heisenberg uncertainty principle.

One is able to specify the position of an electron on a scale small compared

with a distance over which the field or temperature varies.
 Free Electron Gas Model (Sommerfeld) :

Success:
Resolve the heat capacity anomaly
Give correct CV , thermal power, consistent with the experiments for
simple metals
Good at low T, room T, but not at medium T for noble metals?
transition metals?

Approximations:
Neglect the effect of ions between collisions.
The role of ions as a source of collision is unspecified.
The contribution of ions to the physical phenomenon is not included.

Ashroft & Mermin: Chapter 2

 Fermi Dirac Distribution
(a) fMB fFD fFD = [exp(x) + 1] -1

X
(b)

X = mu2/2KBT

Maxwell Botzmann distributuion

fMB v2 exp(-mv2/2KBT)

X
 Ground State : at absolute zero temperature, how about for T > 0 ?

Chemical Potential u is a function of T, and u is such that D(e)f(e) de = N

u = at T 0 For < m , f() = 1; for > m , f() = 0
1.

2.

3.

4.
 Fermi Dirac Distribution Function (5)

0.5

for = u
T=0

T>0
 Free Electron Gas in One Dimension
Quantum Theory and Pauli Principle
Electron of mass M, in a 1-D line of length L confined to an infinite barrier

Fixed boundary conditions Standing wave solution

N (n/2) = L K = np / L
 nF = N/2

Fermi wavevector kF
Fermi Temperature TF
or N (n/2) = L
K

So n = 2 L/N
n=3

n=2

n =1

p2
 FREE ELECTRON GAS IN THREE DIMENSIONS

(1) For electrons confined to a cubic of edge L standing wave k=np/L

(2) Periodic boundary conditions

Wave functions satisfying the free particle Schrdinger equation and the
periodicity condition are of the form of a traveling plane wave:

Exp (ikL) = 1
k = n 2p / L
Fermi Sphere
At the surface f , Kf
Fermi Surface

Linear momentum operator

at the Fermi surface F, kf

F , VF , kF , TF See Table 1
 From eq. 17

ln N = In + constant ; =
At T = 0, D( ) ~ 1/2 in 3-D

f(,T) D()
Heat Capacity of the Electron Gas
Classical theory, Cv = 3/2 NKB for electrons

T=0

T>0

N ~ N (T/TF) , U ~ N (T/TF) KBT

X2

T/TF ~ 0.01
 The equipartition theorem
The name "equipartition" means "equal division,"
The original concept of equipartition was that the total kinetic energy of a system
is shared equally among all of its independent parts, on the average, once the
system has reached thermal equilibrium. Equipartition also makes quantitative
predictions for these energies.
For example, it predicts that every atom of a noble gas, in thermal equilibrium at
temperature T, has an average translational kinetic energy of (3/2)kBT, where kB
is the Boltzmann constant. As a consequence, since kinetic energy is equal to
1/2(mass)(velocity)2, the heavier atoms of xenon have a lower average speed
than do the lighter atoms of helium at the same temperature.
In this example, the key point is that the kinetic energy is quadratic in the velocity.
The equipartition theorem shows that in thermal equilibrium, any degree of
freedom (such as a component of the position or velocity of a particle), which
appears only quadratically in the energy, has an average energy of 12 kBT and
therefore contributes 12 kB to the system's heat capacity.
It follows that the heat capacity of the gas is (3/2)NkB and hence, in particular,
the heat capacity of a mole of such gas particles is (3/2)NAkB.
If the electrons obeyed classical Maxwell-Boltzmann statistics,

so that for all electrons, then the equipartition theorem would give

E = 3/2 N KBT

Cv = 3/2 N KB
 The total energy increase for heating to T from T = 0

Since at T = 0, f() =1
for < F

From (26) to (27),

see derivation
next page

< F

Since only f() is temperature dependent

 Eq.(24)

Eq. (24)

U -

+
 3-D

U / NF

kBT/ F
3-D
 m is determined by satisfying
1-D D() f() d = N
At very low T, lim m = F
For the 3-D case, see Ashcroft
& Mermin, P. 45-47
m = F [ 1-1/3 (p kBT/ 2 F)2]
For the 2-D case, see Kittel
problem 6.3
3-D

kT /F
From Fig. 3,

Judging from Figs. 7 and 8, the variation of m with T, at very low T, lim m = F

F / >> 1
 Compare with CV = 2NkBT/TF
where F = kBTF

K metal

= NkBT/TF Since F TF 1/m m (See Eq. 17)

At low T, the electronic term dominates

Express the ratio of the observed to the free electron values of the electronic
heat capacity as a ratio of a thermal effective mass mth to the electron mass m,
where mth is defined

See Table 2

The departure from unity involves three separate effects:

A: The interaction of the conduction electrons with the periodic potential of the
rigid crystal lattice band effective mass.
B: The interaction of the conduction electrons with phonons.
C: The interaction of the conduction electrons with themselves.

(tight binding model)

 ELECTRICAL CONDUCTIVITY AND OHMS LAW
In an electrical field E , magnetic field B, the force F on an electron ,
the Newton second law of motion becomes q = -e

First considering B = 0, in zero magnetic field

If the field is applied at time t then at a later time t the sphere will be displaced
to a new center at
 The displacement of Fermi sphere
At the ground state under force F


q = -e

Conductivity Ohms Law

Resistivity See Table 3

Lattice phonons To a good approximation the
rates are often independent.
Imperfections
And can be summed together

Since r ~ 1/

Matthiessens Rule.
 ri (0)

rL (T)

Resistivity Ratio = r (300K)/ ri(0)

 Potassium metal

At T >
r T
Different ri (0) , but the same rL

Nph T r T
Umklapp Scattering
Umklapp scattering of electrons by phonons (Chapter 5) accounts for most of
the electrical resistivity of metals at low temperatures. These are electron-
phonon scattering processes in which a reciprocal lattice vector G is involved,
the normal electron-phonon collision k = k + q. Normal process
This scattering is an umklapp process, k = k + q + G Umklapp process
qo: the minimum phonon wavevector for Umklapp process
At low enough temperatures the number of phonons available for umklapp
scattering falls as exp ( U /T),
where qo, u are related to the geometry of
the Fermi surface

Bloch obtained an analytic result for the dominating normal scattering, with
/ at very low temperatures. Blochs T5 Law
 The temperature dependence of resistivity:
The electrical resistivity of most materials changes with temperature.
If the temperature T does not vary too much, a linear approximation is typically used:

Metals
In general, electrical resistivity of metals increases with temperature. Electronphonon
interactions can play a key role. At high temperatures, the resistance of a metal increases
linearly with temperature. As the temperature of a metal is reduced, the temperature
dependence of resistivity follows a power law function of temperature.
Mathematically the temperature dependence of the resistivity of a metal is given by the
BlochGrneisen formula:

A is a constant that depends on the velocity of electrons at the Fermi surface, the Debye
radius and the number density of electrons in the metal. R is the Debye temperature as
obtained from resistivity measurements and matches very closely with the values of Debye
temperature obtained from specific heat measurements.
n is an integer that depends upon the nature of interaction.
1. n=5 implies that the resistance is due to scattering of electrons by phonons,
(simple metals).
2. n=3 implies that the resistance is due to s-d electron scattering, (as is the case for
transition metals).
3. n=2 implies that the resistance is due to electronelectron interaction.
 MOTION IN MAGNETIC FIELDS
The free particle acceleration term is (/) k and the effect of collisions
(the friction) is represented by k/ , where is the collision time.
The equation of motion is

B is along the z axis

 Hall Effect
The Hall field is the electric field developed across two faces of a conductor,
in the direction of j x B.
If current cannot flow out of the rod in the y direction we must have Vy = 0
and Vy = 0, transverse electric field (53)
BZ

Ey jx, Ex

Hall resistance

assume all relaxation for both thermal

and electrical conduction are equal.

= BRH = Ey / jx (55a)
When the transverse field Ey
(Hall field) balances the Lorentz force
neEy = - ejxB/c

RH = Ey/jx B
= -1/nec
 See RH listed in Table 4

by the energy band theory.

Al, In are in disagreements with the prediction,

with 1 positive hole, not 3 negative electrons
 Thermal conductivity of Metals
From eq. (36) for CV in K, and F = 1/2 mvF2
CV = 1/2p2NkBT/TF

See Table 5 for L

It does not involve ,

if the relaxation times are identical for electrical and thermal processes.
Home work, Chapter 6
No.1
No.3
No.6