Free Electron Theory

1 Introduction
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.

1.1 Free Electron Gas

Metals consist of positive ion cores and valence electrons moving freely in that core.The potential field of
the ion core which bound the electrons to be restricted within the metal is assumed to be constant and the
electron-electron repulsion is neglected.
The behaviour of free electron moving inside the metal is considered similar to atoms or molecules of perfect
gas. Thus free electrons are referred to as free electron gas and the theory is known as free electron gas
model.
Since these conduction electrons move in a constant electrostatic field (made by ion cores) their potential is
taken as zero. So the free(conduction) electron is free to move anywhere inside the metal of potential=0.
This is known as free electron approximation. Since the motion of the free electron is restricted to the
metal there is a potential barrier lets say V0 which prevents the electron from leaving the metal.

Free Electron inside the potential well

2 Drude’s Model
2.1 Axioms
Each of the atoms, a metal is composed of, has lost one or more of its valence electrons and so has become
a positively-charged ion. It was assumed that free electrons will obey kinetic theory of gases
• This means, electrons move freely inside the metal, except for collisions with ions
• Between elastic collisions, electrons move in a straight line with fixed velocity

• Free electrons move in random direction, and the collisions with scattering centres are instantaneous
that abruptly after the velocity of electron

1
 • The motion of these free electrons obeys classical Maxwell-Boltzmann (M-B) velocity distribution law
• Free electron approximation: neglect electrostatic interactions between electrons and ions

2.2 Electron in DC Field

A number of properties of solids, such as the electrical properties, dielectric properties, and magnetic prop-
erties, depend on the electric and magnetic fields. Therefore, it is of great interest to study, in general, the
effects of electric and magnetic fields on crystalline solids

2.2.1 Equation of Motion

We consider an electron with momentum p at time t and ask what momentum it has at t ` dt. There are 2
possibilities-
dt
1. the electron scatters to ppt ` dtq “ 0 with the probability τ
dp
2. the electron does not scatter to 0 and accelerate according to equation dt “ F and with probability
1 ´ dt
τ

Putting these 2 terms together we have

dt dt
ppt ` dtq “ p1 ´ qppptq ` F dtq ` 0
τ τ
Keeping only linear terms
dp p
“F´ (1.1)
dt τ
here the force F on electron is the Lorentz Force

F “ ´epE ` v ˆ Bq

e - Electron Charge
E - Electric Field
B - Magnetic Field= Hc

2.2.2 Electrons in Electric Field

Let us start by considering the case where electric field is non zero but the magnetic field is zero.The equation
of motion p1.1q becomes
dp p
“ eE ´
dt τ
dp
At steady state dt “ 0, so
mv “ p “ ´eτ E
We know that electrical current is also given by the equation

j “ ´nev

Substituting v “ ´ eEτ
m from the steady state equation.We obtain

e2 nτ
j “ ´nev “ E
m
We define conductivity of metal by equation j “ σ0 E.Hence we obtain the DC electrical conductivity of
metal given by
e2 nτ
σ0 “ (1.2)
m

2
So by measuring conductivity of a metal we can determine product of electron concentration and scattering
time. Resistivity of electron is given by
1 m
ρ0 “ “ 2 (1.3)
σ0 e nτ

2.2.3 Electrons in Magnetic Field

If a free electron moves in static magnetic field the equation of motion becomes
dp dv e
“m “´ vˆH
dt dt c
Considering B in only z direction B “ B ẑ.Then resolving above equation in x,y and z directions we obtain.
dvx eH
m “´ vy
dt c
dvy eH
m “´ vx
dt c
dvz
“0
dt
Velocity in z- direction is constant with time vz “ constant “ c, whereas velocity in x and y-direction can be
solved by differentiating momentum in x direction and substituting it in the y direction momentum equation.
d2 vx eH
` ωc2 vx “ 0 ωc “ (1.4)
dt2 mc

d2 vy eH
` ωc2 vy “ 0 ωc “ (1.5)
dt2 mc
Here ωc is called cyclotron frequency. Since H always acts perpendicular to velocity v, the magnetic field
does not change the energy of electron. Hence the total speed of electron is constant in magnetic
field.This gives us
vz “ constant
v02 “ vx2 ` vy2 “ constant
From above equation we see electron moves in a circular motion in x-y plane with frequency ωc perpendicular
to the magnetic field H.

Circular motion of electron in x-y plane perpendicular to H

3
2.2.4 Electrons in Electric and Magnetic Field
Consider the Drude’s model p1.1q but with both electrical and magnetic field. The equation (1.1) becomes

dv H mv
m “ ´epE ` v ˆ q ´
dt c τ
Again taking magnetic field H in z direction we break above equation in x,y and z components
dvx e e vx
“ ´ Ex ´ vy H ´
dt m mc τ
dvy e e vy
“ ´ Ey ´ ´ vx H ´
dt m mc τ
dvz e vz
“ ´ Ez ´
dt m τ
Using J “ ´nev “ σ0 E and the equation (1.2) and (1.4), we multiply above 3 equations by neτ to obtain

dv dJ
LHS “ neτ “ ´τ
dt dt
ne2 τ eH
RHS “ ´ E´ τ nev ´ nev “ ´σ0 E ` ωc τ J ` J
m mc
dJx dJy dJz
Hence at equilibrium dt “ dt “ dt“ 0 the above 3 equations reduces to
,
Jx ` ωc τ Jy “ σ0 Ex .
´pωc τ qJx ` Jy “ σ0 Ey E “ ρJ
Jz “ σ0 Ez
-

From this we obtain a matrix relating E to J

E “ ρJ
ρ3ˆ3 is the resistivity matrix which relates current vector to electric field vector.
¨ ˛ ¨ 1 ωc τ ˛¨ ˛
Ex σ0 σ0 0 Jx
˝EY ‚ “ ˝´ ωc τ 1
0 ‚˝Jy ‚ (1)
σ0 σ0
Ez 1 Jz
0 0 σ0
looooooooooomooooooooooon
Resistivity Matrix

Substituting values of σ0 and ωc from (1.2) and (1.4) we obtain-

¨ ˛ ¨ m B
˛
ρxx ρxy ρxz ne2 τ ne 0
B m
ρ “ ρyx ρyy ρyz “ ´ ne ne2 τ
˝ ‚ ˝ 0 ‚ (1.6)
m
ρzx ρzy ρzz 0 0 ne2 τ

The diagnoal components of resistivity matrix(ρxx “ ρyy “ ρzz ) are scalar and independent of magnetic field
and called magnetoresistivity.The non diagonal element(ρxy “ ρyx ) depends on B and is called the Hall
resistivity(discussed later). In presence of both electrical and magnetic field the electron follows a helical
path.

4
 The electron follows a helical path in the direction of magnetic field(z-direction).In xy plane motion of
electron appears as a circular path as shown

2.2.5 Hall Effect

From the above discussion we obtain a very important phenonemon known as the Hall Effect. Suppose we
have magnetic field H in z- direction and current passing through a material(Jy ) in y- direction. Then from
above discussion we see that magnetic field would try to create a component of current in x direction(Jx )
which would soon be balanced by an electric field Ex (Hall Field).The experimental setup is shown below

Longitudnal Resistance = Vyy “ ρyy Iyy

Transverse(Hall) Resistance = Vxy “ ρxy Ixy

5
 1. If flow of Jy is due to electrons then top surface of material would have negative charge and bottom
surface would have positive charge hence Ex ą 0.
2. If flow of Jy is due to positive ions then top surface of material would have postive charge and bottom
surface would have negative charge hence Ex ă 0
Hence the sign of Hall Field can help us deterimine type of current flow in the material
Hall coefficient RH is defined as electric field Ex developed per unit magnetic field H,per unit current density
Jy .
Ex
RH “ (1.5)
Jy H
To calculate RH assume a general charge carrier q.The Lorentz force acting on it is given by Lorentz Force.
For magnetic field in z direction H and charge carrier moving in x direction with velocity vx , the Lorentz
force in y direction is given by ˆ ˙
1
Fx “ q Ex ` p´vy Hq
c
In equilibrium position Fy “ 0,which gives us
1
Ex “ vy H
c
We also know current density Jx is given by
Jy “ nqvy
Substituting these values in equation (1.5) we obtain

1
RH “ (1.6)
nqc

Taking the charge carrier as electron, The Hall coefficient in Drude Theory is given by

ρyx 1
RH “ “´ (1.7)
|B| ne

This simple relation allows us to determine two things

1. Determine density of electrons(n) from Hall effect experiment
2. If we know density of electron we can use it to determine the magnetic field.This is known as Hall
Sensor
When we calculate the value of ´ eR1H for various metals and divide it by density of atoms na tomic . This
gives us the number of free electrons per atom
1
Material ϵRH ne Valence
Li 0.8 1
Na 1.2 1
K 1.1 1
Cu 1.5 1
Be -0.2 2
Mg -0.4 2
Ca 1.5 2

We see from above Table that for many metals this Drude theory analysis seems to make sense—the “valence”
of lithium, sodium, and potassium (Li, Na, and K) are all one, which agrees roughly with the measured
number of electrons per atom. But values of Be and Mg are very wrong(infact negative), from this we
conclude that the sign of Hall coefficient for these 2 metals comes out to be incorrect. Infact the charge
carriers in Be and Mg have charge opposite to that of an electron

6
2.3 Electron in AC Field
Uptil now we have had our discussions for a free electron in static electric and magnetic field, but what
would happen if an electron is placed in alternating electric field. An alternating electric field(E) oscillating
at frequeny ω is given by
E “ E0 e´iωt (1.9)
Here we substitute above E in Lorentz Force equation. Since the field is oscillating the velocity(v) and
current density(J) would follow similar relation

v “ v0 e´iωt

J “ J0 e´iωt
where
J0 “ ´nev0
from equation (1.1) and (1.9) we get
ˆ ˙
1
m ´tω ` v0 “ ´eE0
τ
eτ
m
v0 “ ´ E0
1 ´ iωτ
Multiplying both sides by -ne we get
e2 mτ
n σ0
´nev0 “ J0 “ E0 “ E0
1 ´ iωτ 1 ´ iωτ
From above we obtain frequency dependent electrical conductivity of a metal

J0 “ σpωqE0

1
σpωq “ (1.10)
1 ´ iωτ

2.4 Thermal Transport

Besides giving equation of electron in Electric and Magnetic Field Drude also helped in calculating the
thermal conductivity(κ) of mobile electrons using Boltzman Kinetic theory.From kinetic theory of gas we
know
1
κ “ ncv xvyλ (1.6)
3

cv =Heat Capacity per paticle

xvy=Average Thermal Velocity
λ “ xvyτ =Scattering Length

For a conventional monoatomic gas

3
Cv “kB
2
and c
8kB T
xvy “
πm
Putting these values in equation 1.6 we obtain
2
4 nτ kB T
κ“
π m

7
Here the parameter τ is unknown. Same parameter occurs in electrical conductivity. So we look at the ratio
of thermal and electrical conductivity also known as Lorentz Number.
ˆ ˙2
κ 4 kB
L“ “ « 0.94 ˆ 10´8 W attOhm{K 2
Tσ π e

Hence this result proved the fact that all metals have the same value of ratio which was known for a long
time but not proved - Wiedemann–Franz law.
This was one of the big breakthroughs of the Drude Model

2.5 Successes of Drude Model

• Explained the motion of electron under the effects of electric and magnetic field

• Transport properties were predicted correctly(for example DC conductivity of a metal)

• Weidemann-Franz law was verified as the ratio of electrical conductivity to thermal conductivity( σκ )
comes out to be constant

2.6 Failures of Drude Model

• Hall coefficient frequently is measured to have the wrong sign, indicating a charge carrier with charge
opposite to that of the electron
• Experimental Metal Heat Capacity(CV ) is much smaller than the theoretical 32 kB value.This was one
of the major failures of the Drude Model which it cannot explain

• It failed to explain variation of Resistivity vs T

These drawbacks were addressed by Sommerfeld Free Electron Model which we would look over next.

8
3 Sommerfeld Model
3.1 Background
Difference between the free electron gas and ordinary gas molecules:

1. Electrons are charged particles. So, to maintain the charge neutrality of the whole crystal, we need to
include positive ions. This is done within the jelly model: the positive charge of ions is smeared out
uniformly throughout the crystal - charge neutrality is maintained, no field on the electrons exerted
2. Free electron gas must satisfy the Pauli exclusion principle, which leads to important consequences.
So we need to include quantum phenomenon/model
This model is quite similar to Drude’s model in that it still treats the conduction electrons as if they were
the molecules of a gas that are free to move through the crystal. However, it takes quantum theory into
account and so considers the electrons to be fermions.Sommerfeld used the Fermi Dirac statistics instead
of the Maxwell Boltzman statistics to explain the behaviour of electrons in free electron gas model. In
this case the electrons are then subject to Pauli’s exclusion principle. This prevents any two electrons from
having exactly the same quantum state.... The free electron gas in this model is not confused with the free
electron gas in Drude’s model, it is known as the free electron Fermi gas, which is often called “Fermi gas”.
In this case, electrons rarely scattered by each other...and also electrons in a Fermi gas do not collide with
the +ve ions in the lattice when they are in their correct positions.

3.2 Axioms
1. The free electrons in a metal can have only discrete energy values. Thus the energies are quantized.
2. The electrons obey Pauli’s Exclusion Principle, which states that there cannot be more than two
electrons in any energy level.

3. The distribution of electrons in various energy levels obey the Fermi-Dirac quantum statistics.
4. Free electrons have the same potential energy everywhere within the metal, because the potential due
to ionic cores is uniform throughout the metal.
5. The force of attraction between electrons and lattice ions and the force of repulsion between electrons
can be neglected.
6. Electrons are treated like wave-like particles

3.3 Free Electron Gas in 1-dimensional Box

We would first consider a 1D case and then a 3D case.
Consider an electron of mass m inside a one dimensional crystal of length L. The electron is prevented from
leaving the crystal by potential barrier V0 which we take to be infinitely large.

9
 V pxq “ 0 for 0 ă x ă L

V pxq “ 8 for x ď 0 and x ě 0

The wavefunction of the electron ψn pxq is the solution of Schrodinger equation Hψn pxq “ En ψn pxq where
En represents kinetic energy of electron in nth state.Since potential=0 the Hamiltonian H only includes the
kinetic energy.
h̄2 d2
Hψn pxq “ ´ ψn pxq “ En ψn pxq
2m dx2
The general solution of the equation is of the form

ψn pxq “ Asinpkxq ` Bcospkxq (2.1)

where c
2mEn
k“
h̄2
Since ψn is a continuous function and is equal to zero beyond the length L the boundary conditions for the
wave function are ψn p0q “ ψn pLq “ 0 Using the boundary conditions and substituting them in (2.1) we get

B“0

sinpkLq “ 0
This gives us
nπ
k“
L
Solution of equation (2.1) becomes
´ nπ ¯
ψn pxq “ Asin x (2.2)
L
where A is a constant and n is an integer.Using 2 values of k obtained,we get Energy eigenvalues

h̄2 ´ nπ ¯2
En “ (2.3)
2m L
Equation (2.2) and(2.3) gives us allowed values of the wavefunctions and energy for integral value of n. This
n is called the principal quantum number.Hence the energy spectrum consists of discrete energy levels
where the spacing between the energy levels is determined by n and L.

10
 En vs n
The solution of (2.2) corresponds to standing waves with different number of nodes within the potential
well as shown below

3.4 Free Electron Gas in 3-dimensional box

Considering now behaviour of free electron gas in 3-dimensional metallic crystal. The 3 dimensional model
may be regarded as cubic box with length of the edge L.The Schrodinger equation in 3 dimensions take the
from
h̄2 2 h̄2
ˆ 2
B2 B2
˙
B
Hψprq “ ´ ∇ ψprq “ ´ ` ` ψprq “ Eψprq (2.4)
2m 2m Bx2 By 2 Bz 2
If the electrons are confined to cube of length L the solution is a standing wave as previously discussed
c
8 ´ n πx ¯
x
´ n πy ¯
y
´ n πz ¯
z
ψk prq “ sin sin sin
L3 L L L
where nx ,ny and nz are positive integers.
The probability of finding a free electron at any point in space is same so it is more convenient to work with
plane travelling wave solution.
ψk prq “ Aeik.r “ Aeipkx x`ky y`kz zq (2.5)
where
2m
k2 “ Ek
h̄2
In many cases, however, it convenient to introduce periodic boundary conditions, as we did for lattice
vibrations. The advantage of this description is that we assume that our crystal is infinite and disregard the
influence of the outer boundaries of the crystal on the solution. We require then that our wavefunction is
periodic in x, y, and z directions with period L, so that
ψpx ` L, y, zq “ ψpx, y, zq
ψpx, y ` L, zq “ ψpx, y, zq
ψpx, y, z ` Lq “ ψpx, y, zq
Substiuting the above boundary conditions in equation (2.5)
eikx L “ 1
2πnx 2πny 2πny
kx “ ; ky “ ; kz “ (2.6)
L L L
where nx ,ny and nz are positive or negative integers The allowed energy eigenvalues for wavevector k is
obtained as
h̄2 k 2 h̄2 2
Ek “ “ pk ` ky2 ` kz2 q (2.7)
2m 2m x
We can see from above equation that energy spectrum consist of discrete energy levels very closely placed
to each other

11
 Ek as a function of —k— for 3 dimensional electron gas

The eigenvalue of momentum ish̄k. The velocity of electron is defined by

p h̄k
v“ “
m m

3.5 Fermi Energy

A Fermi System is concept in quantum mechanics where a system containing charged particles don’t interact
(collide). At absolute zero temperature, two electrons with opposite spins will occupy the lowest available
energy level. The next two electrons with opposite spins will occupy the next energy level and so on. Thus,
the top most energy level occupied by electrons at absolute zero temperature is called Fermi-energy level.
This concept comes from Fermi-Dirac statistics. The energy corresponding to that energy level is called
Fermi-energy. The energy of the highest occupied level at zero degree absolute is called Fermi energy, and
the energy level is referred to as the Fermi level. The Fermi energy/level is denoted as Ef . All energy
levels below Fermi level are completely filled and above which all energy levels are completely empty. At
temperatures above absolute zero, the electrons get thermally excited and move up to higher energy levels.
As a result there will be many vacant energy levels below as well as above Fermi energy level.
In a ground state system of N electrons occupy state with lowest possible energies.Therefore all the occupied
states lie inside a sphere of radius kF . The energy at the surface of this sphere is Fermi Energy.
The magnitude of wavefactor kF and Fermi Energy are related by the following equation.

h̄2 2
EF “ k (2.8)
2m F

12
 Fermi Sphere in 3 dimensional free electron gas
The Fermi Energy(EF ) and Fermi wavevector(kF ) are determined by number of valence electrons in the
system. In order to find relationship between N and EF we first need to study Fermi Dirac Statistics(Fermi
Distribution) as well as the density of states.

3.6 Fermi Distribution Function

Under thermal equilibrium, the distribution of electrons among various energy levels is given by statistical
function f pEq. The function f pEq is called Fermi-factor and this gives the probability of occupation of a
given energy level under thermal equilibrium.

1
f pEq “ E´Ef (2.9)
e kT `1
Where f pEq is called Fermi-Dirac distribution function or Fermi factor, EF is the Fermi energy, k is the
Boltzmann constant and T is the temperature of metal under thermal equilibrium.
1. The Fermi-Dirac distribution function f pEq is used to calculate the probability of an electron occupying
a certain energy level.
2. The distribution of electrons among the different energy levels as a function of temperature is known
as Fermi-Dirac distribution function.
For temperature greater than 0K, the Fermi level may not be the topmost filled level since some of the
electrons may be excited to a higher state.
The distribution function f pEq for electrons at T =0K takes the form
f pEq “ 1 for E ď EF
f pEq “ 0 for E ě EF
That is all levels below EF are completely filled and all levels above EF are completely empty.

The distribution function f pEq at T “ 0K and T ě OK

For temperature greater than 0K but less than melting point of metal kB T ! Ef ,the distribution function
loses it step character. The probability of occupation f pEq decreases gradually from 1 to 0 near EF .This
indicates that some of the states below EF are empty and some of the states above EF are filled(as seen in
figure).
Thus for temperatures T 0, the Fermi level may be defined as level where probability of occupation is 12
1
f pEF q “
2

13
3.7 Density of States
From the previous section we know the Fermi Function f pEq which tells us the probability of a electron
being at Energy level E, now to find the distribution of electron across the energy E we also have to know
the density of electronic states available to electrons or D(E).
D(E) is the total number of electronic states per unit energy available at energy E.
Now we want to find the relation between Fermi energy and Fermi wavevector and the total number of valence
electrons in the system.In a system of N free electrons. The occupied space/orbitals may be represented
by points inside a sphere in k-space.The energy corresponding to surface of sphere is then known as Fermi
Energy. We have seen this before when we were explaining the concept of Fermi Energy. There are 2 available
spin states for a given set of kx , ky and kz . From equation (2.6) the volume of k-space that is occupied the
3
one state is 2π 4π 3
L . Thus in the Fermi sphere of volume 3 kF , the total number of states are-
4π 3
k V
2 3 F
2π 3
“ k3
3π 2 F
“ N = Number of States
p q
L

Factor of 2 comes because of spin degeneracy,

The bigger dots represent filled electronic states inside Fermi sphere.The smaller dots represent empty
electronic states outside the sphere

From the above relation we obtain

˙ 31
3π 2 N
ˆ
kF “ (2.10)
V

This gives us the relation between kF and npN {V q

Similarly we obtain relation between EF and npN {V q by using (2.8) in (2.10)

˙2{3
h̄2 3π 2 N
ˆ
EF “ (2.11)
2m V

and the Fermi velocity

˙1{3
3π 2 N
ˆ
h̄
vF “ (2.12)
m V

14
The density of states is obtained by using the fact that in ground state all the energy states below the level
EF is occupied and we get
ż EF
DpEqdE “ N
0
Substituting value of N from equation (2.11) we obtain
ż EF ˆ ˙3{2
V 2mEF
DpEqdE “
0 3π 2 h̄2
Removing the limits and differentiating on both sides we get

V 2m 3{2 1{2
DpEqdE “ E dE
2π 2 h̄2
ˆ ˙3{2
V 2m
DpEq “ E 1{2 (2.13)
2π 2 h̄2
Hence the variation of D(E) with E is parabolic as shown in the figure. The density of filled electronic
states N(E) at any temperature T is obtained by multiplying density state D(E) at 0 K by
probability occupation f pEq at the given temperature T.

N pEq “ DpEqf pEq

The number of filled electronic states between energy E and E+dE is

N pEqdE “ DpEqf pEqdE

The total number of electrons can be obtained by integrating above equation.

ż8
N“ DpEqf pEqdE (2.14)
0

Density of single-particle states as a function of energy, for a free electron gas in three dimensions

Similar analysis can be done for density of state of 2D and 1D free electron gas

15
4 Heat Capacity
We now turn to examine heat capacity of the metal.It was observed that the heat capacity value predicted
by the classical model was in order of 100 times more than the experimental value. It was assumed that in
classical model all N conduction(free) electrons contribute to specific heat. We now know this assumption
is wrong thanks to Sommerfeld Model
Heat Capacity(CV )is define as change in internal energy U of solid with temperature T at constant volume
V ˆ ˙
BU
CV “ (2.15)
BT

4.1 Classical Heat Capacity

The average kinetic energy of free electron given by classical statistics mechanics is
3
E“ kB T
2
If metal contains N free electron total kinetic energy becomes
3
U “ NE “ N kB T
2
Hence the Classical Electronic Heat Capacity comes out to be

3
CV “ N kB (2.16)
2

4.2 Quantum Gas Heat Capacity

We observe that at room temperature the observed value of CV is not more than 0.01 times the predicted
value in (2.16). This discrepancy was resolved only upon the discovery of the Pauli exclusion principle and
the Fermi distribution function. When we heat the specimen from absolute zero not every electron gains an
energy kB T as classically expected, but only those electron which have an energy within the energy range
kB T of Fermi level can be thermally excited.These electrons gain energy which itself isof the order of kB T .

Only those electrons in energy range ∆kB T are thermally excited

This happens because when electron gas is heated upto temperature T they acquire energy of order of kB T
and jump to energy states. Deep lying electrons cannot do so because unfilled energy states are not available
to these electrons.Hence these electrons do not participate in specific heat.
The number of electrons that contribute to specific heat is

n “ DpEF q∆E “ DpEF qkB T

16
Total change in energy as each electron acquires energy kB T

∆U “ npkB T q “ DpEF qpkB T q2

3N
Proof DpEF q “ 2E F
From equation (2.11) ˜ ¸
V 2m 3{2 3{2
N“ EF
3π 2 h̄2
which can be written as ˜ ¸
3N V 2m 3{2 1{2
“ 2 EF (1)
EF π h̄2
From equation (2.13) ˜ ˜ ¸ ¸
V 2m 3{2 1{2
DpEF q “ 1{2 EF (2)
π2 h̄2
From (1) and (2) we can see that
3N
DpEF q “ (2.17)
2EF
Substituting (2.17) in ∆U equation we obtain

3N
“ pkB T q2
2EF
So we obtain equation for quantum specific heat
ˆ ˙
δU 3N
CV “ “ kB p2kB T q (2.18)
δT 2EF

One of the most important observation we see is that quantum specific heat is directly proportional
to temperature while classical specific is independent of temperature.
Equation (2.18) can also be written as ˆ ˙
3 T
CV “ N kB
2 TF
where TF is ther Fermi Temperature defined by the expression

EF “ kB TF

The specific heat calculated above agrees with the experimental calculations.
From experimental observations we know that

CV “ Celectronic ` Clattice “ γT ` AT 3 (2.19)

So we just calculated the theoretical value of electronic heat capacity(Celectronic ), which agrees with the
experimental value above
3N
CV “ Celectronic “ kB p2kB T q “ γ0 T
2EF
where
γ Ñ Experimental Gamma

γ0 Ñ Theoretical Gamma

We observe that both theoretical and experimental values are quite close to each other as shown

17
 Element γ p10´5 Jmol´1 K ´2 q γ0 p10´5 Jmol´1 K ´2 q
Cu 2.9 3.8
Au 3.6 3.8
Ag 3.6 3.8
Na 6.2 8.3
K 9.6 11.2
Rb 10.0 13.9
Cs 12.7 18.4
Zn 4.3 3.3
Fe 3.6 28.7
Al 5.3 7.2

This match only hold for low value of temperatures where Celectronic dominates ,at higher temperature T 3
from Clattice would start dominating.

5 Successes of Free Electron Theory

• It found the DC electrical conductivity of a metal and verified the Ohm’s law
• It explained the thermal and electrical properties of metal and also derived the Widemann-Franz
law.
• Lorentz Number or the Widemann-Franz ratio comes out right for most values.
κ
L“
σT

• Sommerfeld model gave the concept of Fermi surface and concept of k-states
• It explained temperature dependence of specific heat and conductivity of metals.

6 Failures of Free Electron Theory

• It failed to explain metallic properties exhibited by only certain crystals
• The theory fails to distinguish between a metal , semiconductor and an insulator

• Free Electron Theory predicts Hall coefficient has a constant value(RH “ ´ nec1
), which is independent
of temperature or magnetic field, however observed Hall coefficients value depend on both temperature
and magnetic field,
• Why some metals(like Fe) are magnetic even in absence of a magnetic field
• Sometimes Hall coefficient comes out with a negative sign which could not be explained(Like electrons
behave as positive charge)

18