PHY4201

ADVANCED SOLID STATE

Free Electron Fermi Gas

Outline
• Introduction
• Energy Levels in One Dimension
• Effect of Temperature on the Fermi-Dirac Distribution
• Free Electron Gas in Three Dimensions
• Heat Capacity of the Electron Gas
• Electrical Conductivity and Ohm’s Law
• Motion in Magnetic Fields
• Thermal Conductivity of Metals
Introduction
• Many physical properties of metals can be understood in terms of the
free electron model (FEM).
• According to this model, the valence electrons of the constituent atoms
become conduction electrons and move about freely through the
volume of the metal.
• Even in metals for which the free electron model works best, the charge
distribution of the conduction electrons reflects the strong electrostatic
potential of the ion cores.
• The utility of the free electron model is greatest for properties that
depend essentially on the kinetic properties of the conduction electrons.
• FEM works so well in simple metals
• The simplest metals are the alkali metals—lithium,
sodium, potassium, cesium, and rubidium.
• In a free atom of sodium the valence electron is in a
3s state; in the metal this electron becomes a
conduction electron in the 3s conduction band.

Source: socratic.org
• A monovalent crystal which contains N atoms will have N conduction
electrons and N positive ion cores.
• The Na+ ion core contains 10 electrons that occupy the 1s, 2s, and 2p
shells of the free ion, with a spatial distribution that is essentially the
same when in the metal as in the free ion.
• The ion cores fill only about 15% of the volume of a sodium crystal, as
in Fig. 1.
• The radius of the free Na ion is 0.98 Å, whereas one-half of the
nearest-neighbor distance of the metal is 1.83 Å.
• The interpretation of metallic properties in terms of the motion of
free electrons was developed long before the invention of quantum
mechanics.
• The classical theory had several conspicuous successes, notably the
derivation of the form of Ohm’s 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.
(These are not failures of the free electron model, but failures of the
classical Maxwell distribution function.)
• There is a further difficulty with the classical model.
• From many types of experiments it is clear that a conduction electron
in a metal can move freely in a straight path over many atomic
distances, undeflected by collisions with other conduction electrons
or by collisions with the atom cores.
• In a very pure specimen at low temperatures, the mean free path may
be as long as 108 interatomic spacings (more than 1 cm).
• Why is condensed matter so transparent to conduction electrons?
• The answer to the question contains two parts:
• A conduction electron is not deflected by ion cores arranged on a periodic
lattice because matter waves can propagate freely in a periodic structure, as a
consequence of the mathematics treated in the following chapter.
• A conduction electron is scattered only infrequently by other conduction
electrons. This property is a consequence of the Pauli exclusion principle.
• By a free electron Fermi gas, we shall mean a gas of free electrons subject to the
Pauli principle.
ENERGY LEVELS IN ONE DIMENSION
• Consider a free electron gas in one dimension, taking account of
quantum theory and of the Pauli principle. An electron of mass m is
confined to a length L by infinite barriers (Fig. 2).
• The wavefunction n(x) of the electron is a solution of the Schrödinger
equation 𝝒= ; with the neglect of potential energy we have 𝝒 =
P2/2m, where p is the momentum.
• In quantum theory p may be represented by the operator -iħd/dx, so
that

where n is the energy of the electron in the orbital.

• We use the term orbital to denote a solution of the wave equation for
a system of only one electron.
• The term allows us to distinguish between an exact quantum state of
the wave equation of a system of N interacting electrons and an
approximate quantum state which we construct by assigning the N
electrons to N different orbitals, where each orbital is a solution of a
wave equation for one electron.
• The orbital model is exact only if there are no interactions between
electrons.
  2 d 2
H n     n n Orbital: solution of a 1-e Schrodinger equation
2m dx 2

For a particle in a box with infinite potential energy barriers:

Boundary conditions:  n 0   n  L   0

They are satisfied if the wavefunction is sinelike

with an integral number n of half-wavelengths between 0 and L:

(2)

n = 1,2… where A is a constant

We see that (2) is a solution of (1), because

2
 2  n 
n    (3) (energy)
2m  L 
We want to accommodate N electrons on the line.

According to the Pauli exclusion principle, no two electrons can have all their quantum
numbers identical.

That is, each orbital can be occupied by at most one electron. This
applies to electrons in atoms, molecules, or solids.

The electronic state in a 1D solid is characterized by two quantum numbers that are
n and ms, where n describes the orbital ψn(x) , and ms describes the projection of the
spin momentum on a quantization axis. Electron spin is equal to S=1/2, so that there
(2S+1)=2 possible spin states with ms = ±½. Therefore, each orbital labeled by the
quantum number n can accommodate two electrons, one with spin up and one with
spin down orientation
Quantum numbers for free electrons: (n, ms ) ms , 

Degeneracy: number of orbitals having the same

energy.
Let nF denote the topmost filled energy level, where we start filling the
levels from the bottom (n = 1) and continue filling higher levels with electrons until all
N electrons are accommodated.

It is convenient to suppose that N is an even number.

The condition 2nF = N determines nF, the value of n for the uppermost filled level.

Fermi energy εF = energy of topmost filled orbital when system (of N electron) is in
ground state.

By (3) with n = nF we have in one dimension:

N
N free electrons: nF 
2
 Effect of Temperature on the
Fermi-Dirac Distribution
• The ground state is the state of the N electron system at
absolute zero.
• What happens as the temperature is increased? This is a
standard problem in elementary statistical mechanics, and the
solution is given by the Fermi-Dirac distribution function
(Appendix D and TP, Chapter 7).
• The kinetic energy of the electron gas increases as the
temperature is increased: some energy levels are occupied
which were vacant at absolute zero, and some levels are
vacant which were occupied at absolute zero (Fig. 3).
 • The Fermi-Dirac distribution gives the probability that an orbital at energy
 will be occupied in an ideal electron gas in thermal equilibrium:

1 1
Or Fermi-Dirac distribution : f    
e       1 k BT

Chemical potential μ = μ(T) is determined by N   d  g    f   g = density of states

The quantity μ is a function of the temperature; μ is to be chosen for the

particular problem in such a way that the total number of particles in the system
comes out correctly—that is, equal to N.
At absolute zero, μ = F, because in the limit T → 0 the function f() changes
discontinuously from the value 1 (filled) to the value 0 (empty) at  = F = μ.
At all temperatures f() is equal to ½ when  = μ, for then the denominator of (5) has the
value 2.
 The quantity  is the chemical potential .
At absolute zero,  (0) = F
F = Fermi energy, defined as the energy of the topmost filled orbital at absolute zero.
The high energy tail of the distribution is that part for which  -  >> kBT;
here the exponential term is dominant in the denominator of (5), so
that . This limit is called the Boltzmann or Maxwell
distribution.
Summary:
1  
At T  0: f     for
0  

1
For all f   
2
T:

For ε >> μ :

(Boltzmann/Maxwell
distribution)
FREE ELECTRON GAS IN THREE DIMENSIONS

The free-particle Schrödinger equation in three dimensions is

If the electrons are confined to a cube of edge L, the solution is the standing wave

where nx, ny, and nz are positive integers.

In many cases, it is convenient to introduce wavefunctions that satisfy periodic boundary

conditions, as we did for phonons. We now require the wavefunctions to be periodic in x,
y, z with period L. Thus

and similarly for the y and z coordinates.

Wavefunctions satisfying the free-particle Schrödinger equation and the periodicity condition
are of the form of a traveling plane wave:

We now substitute (9) in (6) we have the energy k of the orbital with wavevector k:
The linear momentum p may be represented in quantum mechanics by the operator
p = -iħ, from which after differentiating equation (9), we obtain

In the ground state of a system of N free electrons, the occupied orbitals may be
represented as points inside a sphere in k space. The energy at the surface of the
sphere is the Fermi energy; the wavevectors at the Fermi surface have a magnitude kF
such that (Fig. 4):
From (10) we see that there is one allowed wavevector—that is, one distinct triplet of
quantum numbers kx, ky, kz—for the volume element (2/L)3 of k space. Thus in the
sphere of volume 4kF3/3, the total number of orbitals is

where the factor 2 on the left comes from the two allowed values of the spin
quantum number for each allowed value of k. Then (15) gives

which depends only on the particle concentration.

(The quantity TF has nothing to do with the temperature of the electron gas!)
By using equation (14) & (16), we can obtain expression for Fermi energy:

This relates the Fermi energy to the electron concentration N/V. The electron
velocity vF at the Fermi surface is:

We now find an expression for the number of orbitals per unit energy range, D(), called the
density of states. We use (17) to obtain the total number of orbitals of energy  :

Strictly, D() is the density of

one-particle states, or density of
orbitals!
By comparing (19) and (20), then we can obtain

Within a factor of the order of unity, the number of orbitals per unit energy range at the
Fermi energy is the total number of conduction electrons divided by the Fermi energy, just
as we would expect.

The density of states normalized in such a way that the integral

gives the total number of electrons in the system. At non-zero temperature we should take
into account the Fermi distribution function so that

This expression also determines the chemical potential.!

HEAT CAPACITY OF THE ELECTRON GAS
• The question that caused the greatest difficulty in the
early development of the electron theory of metals
concerns the heat capacity of the conduction electrons.
• Classical statistical mechanics predicts that a free
particle should have a heat capacity of kB, where kB is the
Boltzmann constant.
• If N atoms each give one valence electron to the electron
gas, and the electrons are freely mobile, then the
electronic contribution to the heat capacity should be
3/2NkB, just as for the atoms of a monatomic gas.
• But the observed electronic contribution at room
temperature is usually less than 0.01 of this value.
• How can the electrons participate in electrical conduction processes
as if they were mobile, while not contributing to the heat capacity?
• The question was answered only upon the discovery of the Pauli
exclusion principle and the Fermi distribution function.
• Fermi found the correct result and he wrote, “One recognizes that the
specific heat vanishes at absolute zero and that at low temperatures it
is proportional to the absolute temperature.”
• When we heat the specimen from absolute zero, not every electron
gains an energy  kBT as expected classically, but only those electrons
in orbitals within an energy range kBT of the Fermi level are excited
thermally, as in Fig. 5.
• This gives an immediate qualitative solution to the problem of the
heat capacity of the conduction electron gas.
• If N is the total number of electrons, only a fraction of the order of
T/TF can be excited thermally at temperature T, because only these lie
within an energy range of the order of kBT of the top of the energy
distribution.
• Each of these N(T/TF) electrons has a thermal energy of the order of
kBT.
• The total electronic thermal kinetic energy U is of the order of

• The electronic heat capacity is given by

• and is directly proportional to T, in agreement with the experimental

results discussed in the following section.
• At room temperature Cel is smaller than the classical value NkB by a
factor of the order of 0.01 or less, for TF  5  104 K.
• We now derive a quantitative expression for the electronic heat capacity valid at
low temperatures kBT << F.
• The increase U  U(T) -  U(0) in the total energy (Fig. 5) of a system of N
electrons when heated from 0 to T is
• The first integral on the right-hand side of (27) gives the energy
needed to take electrons from F to the orbitals of energy  > F, and
the second integral gives the energy needed to bring the electrons to
F from orbitals below F.
• Both contributions to the energy are positive.
• The product f()D()d in the first integral of (27) is the number of
electrons elevated to orbitals in the energy range d at an energy .
• The factor [1 - f()] in the second integral is the probability that an
electron has been removed from an orbital .
• The function U is plotted in Fig. 6.
• The heat capacity of the electron gas is found on differentiating
U with respect to T.
• The only temperature-dependent term in (27) is f(), whence
we can group terms to obtain

• At the temperatures of interest in metals, /F < 0.01, and we

see from Fig. 3 that ( - F) df/dT has large positive peaks at
energies near F.
• It is a good approximation to evaluate the density of states
D() at F and take it outside of the integral:
• Examination of the graphs in Figs. 7 and 8 of the variation of the
chemical potential  with T suggests that when kBT << F we ignore
the temperature dependence of the chemical potential  in the
Fermi-Dirac distribution function and replace  by the constant F.
We have then, with  = kBT,
Recall that although TF is called the Fermi temperature, it is not the electron
temperature, but only a convenient reference notation.
Experimental Heat Capacity of Metals
• At temperatures much below both the Debye temperature  and the
Fermi temperature TF, the heat capacity of metals may be written as
the sum of electron and phonon contributions: C = T + AT3, where 
and A are constants characteristic of the material.
• The electronic term is linear in T and is dominant at sufficiently low
temperatures.
• It is convenient to exhibit the experimental values of C as a plot of
C/T versus T2:

for then the points should lie on a straight line with slope A
and intercept . Such a plot for potassium is shown in Fig. 9.
• Observed values of , called the Sommerfeld parameter, are given in
Table 2.
• The observed values of the coefficient  are of the expected
magnitude, but often do not agree very closely with the value
calculated for free electrons of mass m by use of equation (17) and
(34).
• It is common practice to 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 by the
relation
• This form arises in a natural way because F is inversely proportional
to the mass of the electron, whence   m. Values of the ratio are
given in Table 2.
• The departure from unity involves three separate effects:
• The interaction of the conduction electrons with the periodic potential of the
rigid crystal lattice. The effective mass of an electron in this potential is called
the band effective mass.
• The interaction of the conduction electrons with phonons. An electron tends
to polarize or distort the lattice in its neighborhood, so that the moving
electron tries to drag nearby ions along, thereby increasing the effective mass
of the electron.
• The interaction of the conduction electrons with themselves. A moving
electron causes an inertial reaction in the surrounding electron gas, thereby
increasing the effective mass of the electron.
Heavy Fermions
• Several metallic compounds have been discovered that have
enormous values, two or three orders of magnitude higher than
usual, of the electronic heat capacity constant .
• The heavy fermion compounds include UBe13, CeAl3, and CeCu2Si2.
• It has been suggested that f electrons in these compounds may have
inertial masses as high as 1000m, because of the weak overlap of
wavefunctions of f electrons on neighboring ions (see Chapter 9,
“tight binding”).