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Module 4
Classical and Quantum Free Electron Theory of Metals

Classical Free Electron Theory

Metals are good conductors of heat and electricity. Such a high conductivity is due to
the presence of free electrons in the metals. According to the classical free electron theory a
metal can be considered to be made up of ionic cores (comprising of nucleus and inner
electrons excluding the valence electrons) and valence electrons. These ion cores are immobile
and do not take part in the conduction process. The valence electrons are considered to be free
and almost independent of the ions to which they belong. These valence electrons can move
under the influence of an applied electric field and hence contribute to the conductivity.
Assumptions of classical free electron theory:
1) A metal is imagined as the structure of 3-dimensional array of ion cores in between
which there are freely moving valence electrons confined to the body of the materials.
Such freely moving electrons cause electrical conduction under an applied field and
hence referred to as conduction electrons.
2) The free electrons are treated as equivalent to gas molecules and thus they are assumed
to obey the laws of kinetic theory of gases.
The energy associated with each electron at a temperature T is ½ mvth2=3/2kT
Where k is the Boltzmann constant and vth is the thermal velocity or rms velocity.
3) The electric potential due to the ionic cores is taken to be constant throughout the body
of the metal
4) The electrostatic repulsion between the electrons and the attractive force between the
free electrons and the ion cores are considered to be negligible.

Electrical Conductivity and Resistivity:

Consider a conductor carrying electric current  with area of cross section  perpendicular to
the current. The current density  is defined as the ratio of current  to the area of cross section
. Hence

=

It is observed that the current density is proportional to the applied electric field in a conductor.
And hence
∝
 = 
The constant of proportionality  is called Electrical Conductivity of the conductor.
Based on classical free electron theory the expression for electrical conductivity of a conductor
is
 
= 
Where  is the electrical conductivity, n is the number of free electrons per unit volume,  is
the mean collision time, m is the mass of the electron and e is the charge on the electron.

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The Electrical Resistivity  of the material is the reciprocal of the electrical Conductivity  of
the material
 
= =
 
Where R is the resistance, A is the area of cross section and l is the length of sample.
Electrical Resistivity gives the measure of opposition offered by the material during the
current flow in it.

Mobility of conduction electrons:

The mobility of the electrons is defined as the magnitude of the drift velocity acquired by
the electron in the unit field.
If E is the applied electric field in which an electron acquires a drift velocity v d, then mobility
of the electron  is given by

=


Or  = 

or = 
Mobility represents ease with which the electron could drift in the material under the influence
of an electric field.

Concept of Phonon:
A Phonon is a discrete unit or quantum of lattice vibration, the collective motion of atoms
constituting a crystal. The energies and momenta of Phonons are quantized. It is often
characterized as Heat Energy. The study of phonon is an important part of solid state physics.
The phonon plays an important role in many of the physical properties of solids such as the
thermal conductivity and the electrical conductivity. The conduction electrons in a metal
collide against lattice ions during the motion. The interaction is considered to be of type
phonon exchange. This results in non-radiative transitions.

Effect of temperature and impurity on resistivity of metals:

Resistivity of the metals is attributed to the scattering of conduction electrons. There are two
mechanisms through which scattering of conduction electron takes place, which gives rise to
two components of resistivity.

1. Resistivity ph is due to scattering of electrons by lattice vibrations (Phonons) which

increases with temperature. It is exhibited by pure specimen that is free from all defects.
Hence it is called ideal resistivity.

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 2 
Since  = 1/ and  =


 =
 
Where ph is mean collision time assuming there is no scattering by impurities.

2. Resistivity i is due to scattering of conduction electrons by the presence of impurities

and imperfections. This type is independent temperature and present even at T= 0K
i is called residual resistivity

 =
 
Where i is the mean collision time assuming that there is no scattering by lattice
vibrations.
Total resistivity  is given by Matheson’s rule. Which states that total resistivity of metal is
sum of the resistivity due to the phonon scattering and resistivity due to the scattering by
impurities.
 
 =  +  = +
   
At low temperature amplitude of oscillation is less hence scattering by phonon is negligible
ph tends to zero at very low temperature and  = i
When the temperature increases the amplitude of lattice vibration also increases and therefore
scattering of electron increases. Hence resistivity also increases.
At sufficiently high temperature scattering effect due to phonons sweeps the effect due to the
scattering by impurities. Thus at temperatures near room temperature the resistivity curve is
essentially linear.

Failures of classical free electron theory:

1. specific heat:
Molar specific heat of gas at constant volume is Cv=3/2R
According to classical free electron theory electron gas is expected to behave as
gas molecules. Therefore it must have specific heat 3/2R, which is independent of the
temperature. But experimental value of specific heat is found value is Cv= 10-4 RT. It
is very small and also proportional to the temperature T.
2. Temperature dependence of electrical conductivity:
According to the assumption of free electron theory
  
 = ℎ  where ℎ = √ or ℎ  
  

  1/vth or 

 2 
but  = and 


Therefore  ∝


According to according to free electron theory  ∝

But experimentally it is observed that for metals electrical conductivity is

inversely proportional to the temperature T i.e.  ∝


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3. Dependence of electrical conductivity on the electron concentration:

 2 
Electrical conductivity  = or   n

The theory predicts the direct dependence of electrical conductivity () on number of
free electrons per unit volume () called number density. But experimentally it is
observed that electrical conductivity of copper is more compared with the electrical
conductivity of alluminium ( >  even though the number density of copper is less
than that of alluminium ( < . Hence it fails to explain the dependence of electrical
conductivity  on the number free electrons per unit volume . The experimental
observations are as in the table below.
Metal  (Ω−1−1)  (−3)
copper 5.88 × 107 8.45 × 1028
Aluminium 3.65 × 107 18.06 × 1028

Quantum free electron theory:

Applying the quantum mechanical principles Arnold Sommerfeld succeeded in overcoming
many of the drawbacks of the classical free electron theory.
Main assumptions of quantum free electron theory are
1. The energy values of the conduction electrons are quantized. The allowed energy values
conduction electrons are discrete since their motion is confined to the boundaries of the
metal.
2. The distribution of the electron in the various allowed energy levels occurs as per Pauli’s
exclusion principle. Only a maximum of two electrons can occupy a given energy level.
This also suggests the availability of two energy states for free electrons in an energy
level corresponding to spin up and spin down states.
3. The electrons travel in a constant potential setup by the lattice ions, inside the metal but
stay confined within its boundaries.
4. The attractive force between electron and lattice and repulsive force between electrons
are neglected.

Fermi Energy:
The conduction electrons belong to the conduction band, which consists of group of
closely spaced energy levels. For example if the band is 3s band containing N atoms there will
be N allowed energy states in a band. As per the Pauli’s exclusion principle each energy level
can accommodate a maximum of two electrons, one with spin up and other with spin down.
Any system always tries to be in the state of lowest energy state. The conduction electron starts
occupying each of the allowed levels starting from the lowest one. Thus a pair of electrons one
with spin up and another with spin down occupy the lowest level. The next pair of electrons
will occupy the next higher level. And so on. The energy of the level corresponding to the
highest occupied state at absolute zero is called Fermi energy. It is denoted by EF. and the
corresponding level is Fermi level. Thus at T=0K all the energy levels lying above the Fermi
level is completely empty and those lying below the Fermi level is completely filled.

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Density of states
The number of energy levels in each band will be extremely large. The distribution of energy
levels in the band follows certain pattern and it is realized by what is called density of states.
The density of states is the number of available energy states per unit volume per unit
energy interval at a particular energy E. It is denoted by a function g(E).
The number of energy states between energies E and E+dE per unit volume is given by



 = [ ]  

3
1
8 2
=   2 Where  = [ ℎ3 ] is a constant
Plot of g(E) Vs. E is as shown in the figure.

Fermi factor:
At the temperature above the absolute zero i.e. T > 0K The energy of the system of conduction
electrons is no longer the minimum. Some of the electrons, especially those electrons which
are just below the Fermi level will move up into the level above the Fermi level. The details
of which one is lifted to which level is a random statistical phenomenon.
The probability f(E) that a given energy level with energy E is occupied at steady temperature
T is given by

 = 
  
This is called Fermi factor
The Fermi factor is an expression which gives the probability of occupation of a given
energy state for a material in thermal equilibrium at any temperature.

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Let us consider the different cases of distribution as follows

1. Probability of occupation when E < EF at T=0K
when T=0K and E< EF

 = ∞ = 
 
 f(E) = 1 When E< EF
 T= 0K all the energy levels below the Fermi level are occupied.
2. Probability of occupation when E > EF at T=0K
when T=0K and E > EF

 = ∞ = 
 
 f(E) = 0 When E >EF
At T= 0 all the energy levels above Fermi level are unoccupied.
3. Probability of occupation at ordinary temperature
At ordinary temperatures though the value of the probability remains 1 for E<<E F it
starts decreasing from 1 as the value of E becomes closer to EF.
When E = EF
 
 = 0 =
  
Further for E >EF the probability value falls off to zero very rapidly.
Variation of f(E) for T > 0K is as shown in the figure.

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Superconductivity
Discovery:
Lord Kamerlingh Onnes discovered the phenomenon of superconductivity in the year 1911.
When he was studying the temperature dependence of resistance of Mercury at very low
temperature he found that resistance of Mercury decreases with the decrease in temperature
up to a particular temperature  =4.15K. Below this temperature the resistance of mercury
abruptly drops to zero. Between 4.15 and 0 Mercury offered no resistance for the flow of
electric current. This phenomenon is reversible and material becomes normal once again
when temperature was increased above 4.15K. This phenomenon is called superconductivity
and material which exhibits the property is named superconductor.
The resistance offered by certain materials to the flow of electric current abruptly drops to
zero below a threshold temperature. This phenomenon is called superconductivity. The
threshold temperature is called critical temperature.
Temperature dependence of resistance of a superconductor:
The dependence of resistance of a superconductor on temperature is as shown in the figure.

The resistance of the superconductor in the non-superconducting state decreases with decrease
in temperature as in the case of normal metal and at particular temperature Tc the resistance
abruptly drops to zero. Tc is called the critical temperature and it signifies the transition from
normal state to superconducting state. Critical temperature is different for different
superconductors. Critical temperature for mercury is 4.2 K.
Meissner effect:
If the superconductor is cooled below the critical temperature in magnetic field, the flux lines
are pushed out of the material. The expulsion of the magnetic flux from the interior of the
superconducting material when it is cooled below the critical temperature is called Meissner
effect.

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Consider a material in the normal state. When the magnetic field is applied to the material,
magnetic flux lines pass through the material. Now if the temperature is decreased below the
critical temperature, the magnetic flux lines will be expelled from inside the superconductor.
Hence we have B = 0(H+M) = 0 where M is the magnetization due to an applied magnetic
field H the magnetic susceptibility  is given by
 = M/H = -1
This indicates that material in superconductivity state is a perfect diamagnetic material. The
Meissner effect is reversible. When the temperature is raised from below Tc the flux suddenly
penetrates the material after it reaches Tc and the substance is in the normal state. It can be
showed that zero resistivity and diamagnetism of superconductors are two independent
properties.
Critical field:
A superconducting material becomes superconductor at temperature below T c. But if the
superconducting material is subjected to magnetic field, then it needs to cool the material to
still lower temperature to retain its superconducting property. Thus by the application of the
magnetic field superconductivity can be destroyed. The strength of the minimum magnetic
field required to just switch a material from superconducting state to normal state is called
critical field. The critical field Hc changes with the temperature given by the relation
2
 =  ( − )
2

Where T is the temperature of the superconducting material. Tc is the critical temperature. Ho

is the magnetic field required to destroy the superconductivity at absolute zero. The magnetic
field that destroys the superconductivity in any material need not be an externally applied field.
It may be induced magnetic field due to electric current flowing through the material. Thus it
puts the limit to the electric current that can be passed through the superconductor. Therefore
we can define critical current Ic as the current in the superconductor which just destroys the
superconductivity.

Classification of superconductors:
Superconductors are classified as Type I and Type II superconductors based on their magnetic
behaviour.

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Type I superconductors (soft): Type I super conductors exhibit complete Meissner effect
below critical field Hc. When the magnetic field H < Hc the material is in the superconducting
state and it is a perfect diamagnetic

As soon as the applied field H exceeds Hc, material looses superconductivity abruptly and
again magnetic field penetrates fully. Resistance value increases from zero to some finite value
and the material becomes normal.
The dependence of the magnetization on the applied magnetic field H is as shown in the figure.
The critical field value for type I superconductors is found to be very low. Hence, they are
called as soft superconductors.
Example: Lead, mercury etc.

Type II superconductors (Hard):

The type II superconductors are characterized by two critical fields, Hc1 known as lower critical
field and Hc2 known as upper critical field. If the value of field is below H c1 the material is
perfect diamagnetic and hence the magnetic flux is completely pushed out of the material.
Within this region perfect Meissner effect occurs. At Hc1 field starts to penetrate the specimen
and penetration of the field continues till Hc2 is reached. At Hc2 diamagnetism vanishes
completely and specimen becomes normal conducting material. The region between the H c1
and Hc2 is the mixed state known as vertex state. Dependence of the magnetization on the
external magnetic field is as shown in the figure.

In vertex state though there is flux penetration the material retains zero resistance property.
Hence it is still superconductor in that region. In the vertex region, flux penetration occurs
through small canalized parts of the body called filaments. These filaments increase in number

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with increase in H till H = Hc2, when they spread into the entire body and the material becomes
a normal conductor as a whole.
It is noted that in the case of type I Superconductor there is an abrupt fall of magnetism at the
critical field, whereas in the type II it is gradual. The value of critical magnetic field H c2 for
type II is about 100 times more than Hc for Type I. Therefore Type II is more useful.
Examples: Most of inhomogeneous Nb-Zn, Nb-Ti alloys etc.

Comparison of the characteristics of typeI and type II superconductors

Type I Type II
1). These are usually elements in their pure 1). These are impure elements, alloys or
form compounds
2). The transition to normal state occurs 2). The transition to the normal state starts at
abruptly at a critical magnetic field, Hc. Hc1 and is complete only at Hc2.
3). The value of the critical field Hc is 3). Though the value Hc1 is small Hc2 is large.
usually very small. 4). Meissner effect is complete up to Hc1. At
4). They exhibit complete Meissner effect Hc1 flux penetration starts and flux
up to Hc. penetration completes at Hc2. At Hc2 the
5). The superconductivity is observed up material becomes normal.
to critical magnetic field Hc 5). Zero resistivity continues till field reaches
6). Applications are limited. Hc2.
6 ). It has got wide applications.

BCS Theory:
In 1957 Bardeen, Cooper and Schrieffer gave a theory to explain the phenomenon of
superconductivity which is known as BCS theory of superconductivity. The BCS theory is
based upon the formation of the cooper pair which is purely quantum mechanical
phenomenon.
In an ordinary metal the electrical resistance is the result of collision of the conduction
electrons with the vibrating ions in the crystal lattice. In superconductors electrons pair up with
one another due to special type of attractive interaction. When an electron approaches a
positive ion core, it suffers attractive coulomb interaction. The ion core will be displaced from
its position due to this interaction. This is called lattice distortion. Now second electron which
comes near that place will also interact with the distorted lattice, which tends to reduce the
energy of the electron. Thus second electron interacts attractively with the first electron
through the lattice distortion. Since lattice distortion is quantized in terms of phonons, the
above interaction can be interpreted as electron-electron interaction through phonons as the
mediator. The attractive force established between the two electrons will be maximum if the
two electrons have equal and opposite spin and opposite momentum. This attractive force
exceeds the coulomb repulsive force between the two electrons at temperature below the
critical temperature leading to formation of cooper pairs.
Cooper pairs are the bound pair of electrons formed by the interaction between the
electrons with opposite spin and momenta in the phonon field.
The attraction between electrons in cooper pair is very weak and the pair can be
separated by a small increase in temperature which causes thermal vibrations.
At very low temperature density of cooper pair is very large. The dense cloud of cooper
pairs forms a collective state and the motion of all the cooper pairs is correlated. Since the

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density of the cooper pair is very high even a small velocity produces large current. The small
velocity of the cooper pairs minimizes the collision process and leads to zero resistivity.

High temperature superconductors.

The conventional superconductors attain that state at a very low temperature close to the
absolute zero, as they have very low transition or critical temperature. Their application
becomes limited, as they have to use expensive liquid helium to reach their superconducting
state.
High temperature superconductors are one which is having high critical temperature (Tc
around 100K value. Liquid nitrogen can be used to attain those temperatures. The high
temperature superconductors of recent times are not metals and inter-metallic compounds, but
are different types of oxides of copper in combination with other elements. The modern high
temperature superconductors have a complex unit cell structure with oxygen, called the
Perovskite structure. Such cells are made up of one atom of rare earth metal, two barium atoms,
three copper atoms and seven oxygen atoms. Such compounds are popularly referred to as 1-
2-3 superconductors. Scientists have developed many such 1-2-3 superconductor, one of them
is comprising Yttrium, barium, copper and oxygen,(YBa2Cu3O7) having a critical temperature
of Tc=90K. It is interesting to note that the critical temperature is higher for those which have
more number of copper-oxygen layers in the structure unit. The formation of superconductors
in high Tc superconductors is direction dependent. The super currents are strong in the copper
oxygen planes, and weak in the direction perpendicular to the planes.

Quantum Tunnelling:
Tunnelling is a quantum mechanical phenomenon when a particle is able to penetrate through
a potential energy barrier that is higher in energy than the particle’s kinetic energy. In classical
mechanics, when a particle has insufficient energy, it would not be able to overcome a potential
barrier. In the quantum world the particles can often behave like waves. On encountering
barrier, a quantum wave will not end abruptly. Rather its amplitude decreases exponentially.
This drop in amplitude correspond to a drop in the probability of finding the particle further
into the barrier. If the barrier is thin enough then the amplitude may be non zero on the other
side. This would imply that there is finite probability that some of the particle will tunnel
through the barrier.

Josephson Junctions:
A Josephson junction is simply an arrangement of two superconductors separated by a thin
insulating barrier. When the barrier is thin enough cooper pairs from one superconductor can
tunnel through the barrier and reach the other super conductor. Based on his theory Josephson
proposed that this kind of tunnelling leads to dc and ac Josephson effect.

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DC Josephson Effects:
Consider a Josephson junction consisting of two superconducting metal films separated by a
thin oxide barrier of 10 to 20 Å thick. The cooper pairs in a superconductor can be represented
by a wave function which is the same for all pairs. The cooper pair tunnel from one side of the
junction to the other side easily. The effect of insulating layer is that it introduces the phase
difference between the wave functions of the cooper pairs on one side of the insulating layer
and wave function of the cooper pairs on the other side. because of this phase difference, super
current appears across the junction even though the applied voltage is zero. This is known as
the dc Josephson effect. Josephson showed that the super current through the junction is given
by IS=IC sin o
Where o is the phase difference between the wavefunctions describing the cooper pairs on
both sides of the barrier. Ic is the critical current at zero voltage condition. Ic depends on the
thickness width of the insulating layer and temperature.

AC Josephson Effects:
If we apply a dc voltage across the Josephson junction, it introduces an additional phase on
cooper pairs during tunnelling. As a result new phenomenon will be observed. The dc voltage
generates an alternating current I given by
I =IC sin(o+)
Because of dc voltage V applied across the barrier, energies of cooper pairs on both sides of
barrier differ in energy 2eV. Using quantum mechanical calculations, it can be shown that

 = ( )
ℎ
Alternating current has the frequency 2eV/h.

SQUID:
A superconducting quantum interference device (SQUID) is a device used to measure
extremely weak magnetic flux. It is basically a sensitive magnetometer. The heart of the
SQUID is a superconducting ring, which contains one or more Josephson junction. There are
two main types of SQUID DC SQUID and RF(or AC) Squid.

DC SQUID:
Direct current SQUID consists of two Josephson Junctions connected in parallel in a
superconducting loop. The superconducting loop encloses the flux ϕ to be detected. The dc
supercurrent known as bias current is applied to the SQUID. The current I that enters will be
divided into two components I1 and I2 which will pass through the two junctions and recombine
to produce output current. If an external magnetic field is applied, it modifies the phase of the
two currents through two junctions, which in turn modifies the output current. The output

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current varies periodically with the applied magnetic flux. Thus if a magnetic field is applied
to SQUID its output current changes. In practice, instead of the current, voltage across the
SQUID is measured, which also oscillates with the changing magnetic field.

RF Squids:
The RF SQUID consists of a single Josephson junction incorporated into the superconducting
loop and circuit operates with RF bias. The SQUID is coupled to the inductance of an LC
circuit driven by RF current source. Here the current induced in the inductor depends on the
magnetic field enclosed by the superconducting loop. Thus by measuring RF current or RF
voltage across the circuit one can find the applied magnetic field. Although it is less sensitive
than the DC SQUID, it is cheaper and easier to manufacture.

Applications in Quantum Computing:

Superconductive technology is one of the most promising approaches to quantum computing
because it offers devices with little dissipation. The most important element of any quantum
computing architecture is qubit, a two level quantum system that serves as memory register
for the computer. The three primary superconducting qubit archetypes are the charge, flux and
phase qubit.

Charge qubit:
In quantum computing, a charge qubit is also known as Cooper-pair box. It is a qubit whose
basis states are charge states. The states represent the presence or absence of excess Cooper
pairs in the island(dotted region in the figure). In superconducting quantum computing, a
charge qubit is formed by a tiny superconducting island coupled by a Josephson junction to a
superconducting reservoir. The state of the qubit is determined by the number of Cooper pairs
that have tunnelled across the junction.

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Flux qubit:
Flux qubits (also known as persistent current qubits) are micrometer sized loops of
superconducting metal that is interrupted by a number of Josephson junctions. These devices
function as quantum bits. During fabrication, the Josephson junction parameters are
engineered so that a persistent current will flow continuously when an external magnetic flux
is applied. Only an integer number of flux quanta are allowed to penetrate the superconducting
ring, resulting in clockwise or counter-clockwise supercurrents.

Phase qubit:
The phase qubit is a current-biased Josephson junction, operating in a zero-voltage state with
a non-zero current bias. The phase qubit is a superconducting device based on
the superconductor–insulator–superconductor (SIS) Josephson junction, this employs a single
Josephson junction and the two levels are defined by quantum oscillations of the phase
difference between the electrodes of the junction. Dc SQUID is a type of Phase qubit.

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Module 4
Question Bank
1. Define Phonon. Describe Matthiessen’s rule.
2. Explain the failure of Classical free electron theory of metals.
3. Mention the assumptions of classical free electron theory of metals.
4. Mention the assumptions of quantum free electron theory.
5. Explain the concept of Fermi level, Fermi energy, density of states.
6. Define Fermi factor. Discuss the variation of Fermi factor with energy and temperature
and represent graphically
7. Discuss the discovery of superconductivity and hence discuss the variation of
resistivity with temperature in superconductor with critical temperature as reference.
8. State and explain Meissner’s effect.
9. Define critical field and hence explain its variation with temperature below critical
temperature.
10.Explain Type-I and Type-II superconductors.
11.Explain high Temperature superconductivity.
12.Explain the BCS theory of superconductivity.
13.Explain the phenomenon of quantum tunnelling.
14.Define Josephson’s junction and hence explain the AC and DC Josephson effect.
15.Define Squid and describe Dc and RF SQUIDS.
16.Brief the application of superconductivity in quantum computing.

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