Physics

Paper No. : Solid State Physics

Module : Superconductivity I

Development Team
Prof. Vinay Gupta, Professor, Department of Physics and
Principal Investigator Astrophysics, University of Delhi.

Prof. Mahavir Singh, Professor , Department of Physics,

Paper Coordinator
Himachal Pradesh University, Shimla

Content Writer Prof. Mahavir Singh, Professor , Department of Physics,

Himachal Pradesh University, Shimla

Prof P. N. kotru, Department of Physics, University of Jammu

Content Reviewer

Solid State Physics

Physics
Superconductivity I
Description of Module
Subject Name Physics
Paper Name Solid State Physics
Module Name/Title Superconductivity I

Module Id M21

Solid State Physics

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Superconductivity I
Contents of this Unit
1. Lattice Specific Heat: An Overview
2. Dulong and Petit’s Law

3. Shortfall of Classical Theory

4. Quantization of Elastic Waves

5. Summary

The objective of the module is to understand the following

 Reviewing the concept of specific heat

 Concept of lattice specific heat in preview of lattice dynamics
 Reviewing the explanation of specific heat on the basis of classical model given by
Dulong and Petit’ law.
 Concept of quantization of elastic waves and phonons
 Understanding of the shortfall of classical theory and the need of the other.
.

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1.Lattice Specific Heat : An Overview
Since heat is not a thermodynamic quantity, however it becomes so under the constraints of constant
volume and constant pressure i.e,
dQ|p = dH
and
dQ|v = dE
where H and E are enthalpy and internal energy respectively.

The specific heat is defined as the amount of heat energy required to raise the temperature of a unit
mass of solid by one degree. Also it is the heat capacity per unit mass. Consequently

(∂H/∂T)p = Cp and (∂E/∂T)v = Cv are then the expressions for heat capacity at constant pressure and
heat capacity at constant volume respectively.

For solids and liquids, Cp ~ Cv, especially at low temperatures (~0-20K), but even at higher
temperatures (~300K), the difference is not more than 2%.

With the supply of heat energy to a solid, there is an increase in its internal energy. The increase in the
internal energy is manifested as an increase in the vibrations of the atoms about their mean positions
and also as an increase in the kinetic energies of the free electrons. The specific heat corresponding to
lattice energy is called lattice specific heat.

There are various theories of lattice specific heat. In all the theories the vibrational energy of a crystal
containing N number of atoms is considered equivalent to the energy of a 3N harmonic oscillator. The
distinction in various theories is the difference in proposed frequency spectrum of the oscillators and
the problem regarding calculations of wavelengths and frequencies of the possible modes of vibration
in the crystal remains the centric concern.

2. Dulong and Petit Law (Classical overview)

In order to understand the lattice dynamics and the phenomenon that occur when heat or thermal
energy is supplied to a solid and is consequently raised to a temperature (it occurs even at absolute
zero), it will be easier to begin with the first law of thermodynamics which states that whenever some

Solid State Physics

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amount of heat dQ is given to a system, it results in the increase in energy dE of the system plus the
amount of work done, i.e
dQ = dE+ pdV ---------------(1)

considering work done by the system is of a mechanical nature only.

Now, E is determined uniquely by the temperature and volume of the system. Hence

dE =

Equation (1) may be rewritten in the form

dQ = dT+ [ T + p] dV --------------------(2)

dQ/dT is the general expression for specific heat. Our interest remains in Specific heat at constant
volume Cv and specific heat at constant pressure Cp.

From equation (2)

Cv = = ------------------- (3)

The second law of thermodynamics is stated as relation between Cp and Cv in the form

Cp- Cv = -T --------------------(4)

Rewriting (4) in terms of the volume expansion coefficient αv and the compressibility K, defined by

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αv = (1/V) and

K = -(I/V)

Cp- Cv = αv2TV/K ---------------------(5)

Since both αv and K are positive quantities,

Cp- Cv ≥ 0

Fig (1) Temperature variation of CP and CV

As depicted from fig (1) at low temperatures their difference becomes very small
and both Cp & Cv go to zero at T = 0.
In general, the variation of Cv with time is studied. We assume that a change in volume is not much
with a small increase in temperature.

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As the temperature increases from absolute zero, there is a rapid increase in specific heat and it finally
levels off at a nearly constant value (6 cal/mole) at high temperature. This is the classical approach put
forward as in Dulong Petit’s Law.

The physical properties of the solids is roughly assumed to be

 due to the contributions resulting from the atomic vibrations (as in crystals)
 due to additional contribution to specific heat from electronic system (as in metals and
semiconductors). Although this contribution is relatively small to that of lattice vibrations.

3. Shortfall of Classical Theory

In comparison to the translational motion of the ideal gas molecules, the constituent atoms in a crystal ,
have almost fixed positions which vibrate about their mean positions executing simple harmonic
motion. The total energy of the oscillator at an instant is a composition of its instantaneous potential
energy and kinetic energy.
Classically a harmonic oscillator vibrating with its natural frequency ω has energy expression as

Є = P2/2m +mω2q2/2

where p is the momentum in kinetic energy term and q is the displacement from equilibrium position
in potential energy term .
The average energy of the harmonic oscillator is given as

= dЄ -------------------- (6)

= kT

This implies that the total vibrational energy of a crystal having N(Avogadro no.) atoms is

E = 3NkT --------------------- (7)

Eq (7) is a frequency independent expression.

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The specific heat at constant volume as obtained for a solid containing N number of atoms is given as

Cv = 3Nk = 3R = 5.96 cal/ mole.

This is the level off value of the experimental results at high temperature.
This does not explain the decrease of specific heat at low temperatures as observed for all solids.

The discrepancy to a certain extent is removed by using quantum theory but before that it is important
to understand the concept of quantization of elastic waves and the concept of phonons.

4. Quantization of Elastic Waves:

As is a well understood concept that the atoms in solids vibrate about their equilibrium positions and
these lattice vibrations can be expressed in the form of waves, like repetitive and systematic sequence
of atomic displacements that can be longitudinal or transverse or even a combination of both.
The energy of a lattice vibration is quantized and the quantum of energy is called ‘Phonon’, analogous
to quanta of electromagnetic energy – photon.
We have assumed vibrations of a linear lattice connected through springs and their particle motion can
be quantized in a similar way as that for a harmonic oscillator or a combination of coupled harmonic
oscillators. The Hamiltonian for a harmonic oscillator is

H = (1/2M) p2 + ½ Cx2

With energy eigen values for n = 1, 2 , 3 ,….

Hence average thermal energy of the oscillator is

Єn= (n + ½)ħω

Where ω is the angular frequency.

The term ½ ħω is called zero point energy of the mode.

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 Fig (2) Descrete energy levels of harmonic oscillator

Thus thermal lattice vibrations are thermally excited phonons. Thermal conduction in non metallic
crystals is a consequence of annihilation or creation of a phonon. The energy of phonons is ~0.1 ev.

We know that if the particles have zero spin then these follow Bose – Einstein statistics and the
probability of such particles having energy E is given as

fBE =

if the particles are not constant with time then α = 0

fBE =

The following observations confirm the experimental evidence for the quantization of lattice
vibrational energy:
 at absolute zero the lattice contribution of heat energy always approaches zero
 the neutrons and X rays are scattered inelastically by crystals and the changes in energy and
momentum correspond to creation or absorption of phonons.
(Which is discussed in detail in the later section of the modules.)

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 5. Summary:

After the completion of this module we are able to understand and correlate the following

 Heat capacity, a thermodynamic concept as a function of temperature.

 Classical theory of specific heat capacity and discrepancy with the experimental results
obtained at lower temperatures.

 Shortfall of the Dulong Petit’s classical theory and need of new (quantum) approach.

 Quantization of elastic waves, its physical significance and mathematical treatment.

 Introduction of concept of phonons and its relevance in lattice dynamics.

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