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Chapter 5
The Free Electron Fermi Gas
5.1. Energy levels in one dimension
Consider a free electron gas in one dimension. An electron of mass “m” is confined to move
along the x-direction to a length “L” in a one-dimensional potential well of infinite barriers, as
shown in the figure below. It is assumed that the potential energy of the electron inside the well
is zero and infinity everywhere outside the box (well).

The observable that we are interested in the energy of the free electron, therefore, using the
quantum mechanical operator i.e., the Hamiltonian “H”.
To find the allowed energies and wave functions for the free electron, the following Eigen value
equation will be used.
𝐻ѱ𝑛 = 𝐸𝑛 ѱ𝑛
Where, 𝐸𝑛 is the energies of the electron in the orbital.
From the one dimensional time independent Schrodinger equation, we have;-
𝜕 2 ѱ 2𝑚
+ 2 (𝐸 − 𝑉)ѱ = 0 (1)
𝜕𝑥 2 ћ

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 For outside the box 0 ≥ 𝑥 ≥ 𝐿, we have 𝑉 = ∞ (i.e., for all position outside the box,
potential energies are very large in amount).
 As the electron is inside the box 0 < 𝑥 < 𝐿, therefore, we have 𝑉 = 0 (i.e., for all
position inside the box, potential energy zero).
From equation (1), we get
𝜕 2 ѱ 2𝑚
+ 2 (𝐸)ѱ = 0 (2) 𝑠𝑖𝑛𝑐𝑒, 𝑉 = 0
𝜕𝑥 2 ћ
2𝑚
Let 𝐸 = 𝑘2 (3)
ћ2

Therefore, our equation (2) become,

𝜕 2ѱ
+ 𝑘2ѱ = 0 (4)
𝜕𝑥 2
The general solution for equation (4) that gives the wave function of the free electron inside the
well is:-
ѱ = 𝐴𝑒 𝑖𝑘𝑥 + 𝐵𝑒 −𝑖𝑘𝑥
ѱ = A(cos 𝑘𝑥 + 𝑖 sin 𝑘𝑥) +B(cos 𝑘𝑥 − 𝑖 sin 𝑘𝑥)
ѱ = (𝐴 + 𝐵) cos 𝑘𝑥 + (𝑖𝐴 − 𝑖𝐵) sin 𝑘𝑥
Let 𝐴 + 𝐵 = 𝑎 sin 𝜃 𝑎𝑛𝑑 𝑖𝐴 + 𝑖𝐵 = 𝑎 𝑐𝑜𝑠𝜃
Then, we can rewrite as follows,
ѱ = (𝐴 + 𝐵) cos 𝑘𝑥 + (𝑖𝐴 − 𝑖𝐵) sin 𝑘𝑥
ѱ = 𝑎 sin 𝜃 cos 𝑘𝑥 + 𝑎 𝑐𝑜𝑠𝜃 sin 𝑘𝑥
ѱ = 𝑎(sin 𝜃 cos 𝑘𝑥 + 𝑐𝑜𝑠𝜃 sin 𝑘𝑥)
ѱ(𝑥) = 𝑎 sin(𝑘𝑥 + 𝜃) (5)
As the free electron cannot cross the infinite potential barrier at = 0, 𝑎𝑛𝑑 𝑥 = 𝐿 , therefore, we
have two boundary conditions:-
 The 1st boundary condition is ѱ(0) = 0
 The 2nd boundary condition is ѱ(𝐿) = 0
Thus, from the 1st boundary condition , i.e.,

ѱ(0) = 0

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the following equation (5) transforms as

ѱ(𝑥) = 𝑎 sin(𝑘𝑥 + 𝜃)
Become, 0 = 𝑎 sin(𝜃)
Because of 𝑥 = 0. Hence, either 𝑎 = 0 𝑜𝑟 sin 𝜃 = 0. But, 𝑎 ≠ 0 𝑡ℎ𝑒𝑛 sin 𝜃 = 0 ⇒ 𝜃 = 0
Therefore, equation (5) reduces to
ѱ(𝑥) = 𝑎 sin(𝑘𝑥) (6)
Applying the 2nd boundary condition, i.e.,

ѱ(𝐿) = 0
Then, equation (6) transforms as
ѱ(𝑥) = 𝑎 sin(𝑘𝑥)
Become,
ѱ(𝑥) = 𝑎 sin(𝑘𝐿)
0 = 𝑎 sin(𝑘𝐿)
Because of 𝑥 = 𝐿
Here, either 𝑎 = 0 𝑜𝑟 sin(𝑘𝐿) = 0
But, 𝑎 ≠ 0 𝑡ℎ𝑒𝑛 sin(𝑘𝐿) = 0
𝑛𝜋
⇒𝑘𝐿 = 𝑛𝜋 𝑜𝑟 𝑘 = . Where, 𝑛 = 0,1,2,3, , , ,,
𝐿
𝑛𝜋 2𝑚𝐸
But when, 𝑛 = 0, 𝑡ℎ𝑒𝑛 𝑘 = 0 𝑏𝑒𝑐𝑎𝑢𝑠𝑒, 𝑘 = . Then from equation (3) we have, 𝑘 2 =
𝐿 ћ2

The energy becomes 𝐸 = 0. Which is impossible!

𝑛𝜋
Therefore, the 𝑛 𝑚𝑢𝑠𝑡 𝑏𝑒 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑡 𝑓𝑟𝑜𝑚 𝑧𝑒𝑟𝑜. thus, 𝑘 = (7). Where, 𝑛 = 1,2,3, , , ,,
𝐿

Then, by substituting equation (7) into (6), we get;

𝑛𝜋
ѱ(𝑥) = 𝑎 sin( 𝑥)
𝐿
𝑛2 𝜋 2 2𝑚𝐸
Now, by squaring equation( 7), i.e., 𝑘 2 = and comparing within equation (3) i.e., 𝑘 2 =
𝐿2 ћ2
𝑛2 𝜋 2 2𝑚𝐸 𝑛2 𝜋 2 ћ2
Then, we get = . After rearranging, we obtain; 𝐸 =
𝐿2 ћ2 2𝑚𝐿2

The energies which the free electron exhibit:

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𝑛2 𝜋 2 ћ2
𝐸𝑛 =
2𝑚𝐿2
 The ‘n’ in the subscript of energy ‘E’ on the LHS appears due to the ‘n’ on the RHS.
Thus, discrete values of energy are obtained. The imposition of the boundary conditions
has restricted the energy to discrete values,
𝑛2 𝜋 2 ћ2 ћ2 𝑛𝜋
𝐸𝑛 = = 2𝑚 ( 𝐿 )2 (8)
2𝑚𝐿2
ℎ
and also by substituting ћ = 2𝜋

𝑛2 𝜋 2 ћ2 ℎ2 𝑛 2
𝐸𝑛 = = ( ) (9)
2𝑚𝐿2 8𝑚 𝐿
When we want to derive the wavelength 𝜆𝑛 corresponding to the energy 𝐸𝑛 , first we have to
know the momentum.
𝑝 = 𝑚𝑣
For ‘n’ state, 𝑝𝑛 = 𝑚𝑣𝑛 and square it.
𝑝𝑛 2 = (𝑚𝑣𝑛 )2 (*)
By dividing both side of equation (*) by 2m and taking under square root. Then, we get
𝑝𝑛 2 (𝑚𝑣𝑛 )2
=
2𝑚 2𝑚
𝑛𝑝 2 (𝑚𝑣𝑛 )2
⇒√ 2𝑚 =√ 2𝑚

𝑝𝑛 𝑚𝑣𝑛 2
⇒ =√
√2𝑚 2

⇒ 𝑝𝑛 = √2𝑚𝐸𝑛
ℎ
From de Broglie’s wavelength, we have 𝜆𝑛 = 𝑝
𝑛

Then, by substituting the value of 𝑝𝑛 , we get

ℎ
𝜆𝑛 = (10)
√2𝑚𝐸𝑛

Let us consider equation (9), and rearranging it, then we obtain

ℎ2 𝑛
i.e., 𝐸𝑛 = 8𝑚 ( 𝐿 )2
1 ℎ𝑛 ℎ𝑛
⇒𝐸𝑛 = 2𝑚 ( 2𝐿 )2 ⇒2𝑚𝐸𝑛 = ( 2𝐿 )2 then take under square root both side

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𝑛ℎ
√2𝑚𝐸𝑛 = 2𝐿
(**)

Then, by substitute equation (**) into equation (10), we get

ℎ ℎ 2𝐿
𝜆𝑛 = = =
√2𝑚𝐸𝑛 𝑛ℎ 𝑛
2𝐿
Therefore,
2𝐿
𝜆𝑛 = is the required wave-length.
𝑛

According to Pauli Exclusion Principle, no two electrons can have all their quantum numbers
identical or each orbital can be occupied by at most one electron.
In linear solid, the quantum numbers of a conduction electron orbital are
1
‘𝑛’ and ‘𝑚𝑠 ’. Where “n” is a positive integer and “𝑚𝑠 ” is ± 2 the spin orientation.

Degeneracy
The number of orbitals with the same energy.
Let “𝑛𝐹 ” denote the topmost filled energy level, where the levels are filled from the bottom 𝑛 =
1 and continue until all N electrons are accommodated at higher levels. Suppose “𝑛𝐹 ” is an even
number, then
2𝑛𝐹 = 𝑁
where“𝑛𝐹 ” is the upper most filled level value “n”
Fermi energy
The energy of the topmost energy level.
Now, equation (8) may be written as for the topmost filled level as 𝑛 = 𝑛𝐹 and 𝐸𝑛 = 𝐸𝐹 for the
Fermi energy “𝐸𝐹 ”. Then, it become
ћ2 𝑛𝐹 𝜋 2
𝐸𝐹 = ( )
2𝑚 𝐿
𝑁
Since 2𝑛𝐹 = 𝑁 𝑜𝑟 𝑛𝐹 = 2 . Therefore,

ћ2 𝑁𝜋 2
𝐸𝐹 = ( )
2𝑚 2𝐿

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Quantum Energy Wave function (ѱ𝑛 )

number (n) ℎ2 𝑛 2
𝐸𝑛 = ( )
8𝑚 𝐿
3 9ℎ2
𝐸3 =
8𝑚𝐿2

2 ℎ2
𝐸2 =
2𝑚𝐿2

1 ℎ2
𝐸1 =
8𝑚𝐿2

5.2. 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. The kinetic energy of the electron gas
increases as the temperature is increased: some energy levels are occupied which were vacant at
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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 𝜖 will be occupied in an
ideal electron gas in thermal equilibrium:
1
𝑓(𝜖) = (5)
(𝜖 − 𝜇)
exp [ ⁄𝑘 𝑇] + 1
𝐵

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 = 𝜖𝐹 , because in the limit T → 0 the function 𝑓(𝜖) changes discontinuously
from the value 1 (filled) to the value 0 (empty) at 𝜖 = 𝜇 = 𝜖𝐹 . At all temperatures 𝑓(𝜖) is equal
to ½ when 𝜖 = 𝜇, for then the denominator of equation (5) has the value 2.

The quantity 𝜇 is the chemical potential, and we see that at absolute zero the chemical potential
is equal to the 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 ∈ −𝜇 ≫ 𝑘𝐵 𝑇; here the exponential
−(∈ −𝜇)
term is dominant in the denominator of (5), so that 𝑓(∈) = exp[ ⁄𝑘 𝑇]. This limit is
𝐵

called the Boltzmann or Maxwell distribution.

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In a metallic crystal, the free electrons possess different energies except the restriction put
forward by Pauli’s exclusion principle.
According to quantum theory, at absolute zero of temperature, the free electrons occupy different
energy levels continuously without any vacancy in between filled states. This can be understood
by dropping the free electrons of a metal one by one into the potential well.
o The first electron dropped would occupy the lowest available energy, 𝜀𝑜 (say), and the
next electron dropped also occupies the same energy level.
o The third electron dropped would occupy the next energy level. That is, the third electron
dropped would occupy the energy level 𝜀1 (𝜀1 > 𝜀𝑜 ) and so on because of the pauli’s
exclusion principle.
o If the metal contains N(even) number of electrons, they will be distributed in the first N/2
energy levels.
 The higher energy levels will be completely empty

What is Fermi level?

The highest filled level, which separates the filled and empty levels at 0K is known as the Fermi
level.
What is energy?
The energy corresponding to Fermi level is called Fermi energy (𝜖𝐹 ). The highest energy
possessed by an electron in the material at 0K. at 0K, the Fermi energy is represented as 𝜖𝐹𝑜 .
As the temperature of the metal is increased from 0K to TK,
 Then those electrons which are present up to a depth of 𝑘𝐵 𝑇 from Fermi energy
may take thermal energies equal to 𝑘𝐵 𝑇 and occupy higher energy level.
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 Whereas the electrons present in the lower energy levels i.e., below 𝑘𝐵 𝑇 from
Fermi energy level, will not take thermal energies because they will not find
vacant electron states.
𝑓(𝐸) is represents the probability that if a particle is dropped in an empty box
having large number of energy levels, it will occupy a particular state with energy
E electron is given by Fermi-Dirac distribution function.
1 1
𝑓(𝐸) = =
𝐸−𝜇 𝐸 − 𝐸𝐹
exp ( ) + 1 exp ( )+1
𝑘𝐵 𝑇 𝑘𝐵 𝑇
𝜇 occurs in all distributions, it has been replaced by 𝐸𝐹 , which is called the Fermi energy.
o 𝜇 is called the chemical potential, and Fermi-Dirac distribution statistics, 𝜇 = 𝐸𝐹 at 0K
absolute zero temperature.
o As the temperature increases from 0K, numerically, there is some difference between
𝜇 = 𝐸𝐹 .
o 𝜇 is a constant quantity and is always equal to Fermi energy 𝐸𝐹 at absolute
zero(designated as 𝐸𝐹𝑜 ), but 𝐸𝐹 changes with temperature. It decreases very slowly on
increasing in temperature. 𝜇 is of chemical origin or is connected with the internal energy
of the system and 𝐸𝐹 is the highest energy attained by an electron in a metal at absolute
zero temperature. Conceptually they are different, but numerically, there is insignificant
difference up to any temperature to which a metal can be heated before melting. So,
people often talk in terms of Fermi energy 𝐸𝐹 rather than the chemical potential 𝜇. Even
here, 𝐸𝐹 will be mostly used instead of 𝜇.
Analytical Treatment At T=0K;
1 1
𝑓(𝜖) = = = 1𝑓𝑜𝑟𝐸 < 𝐸𝐹 𝑎𝑛𝑑 0 𝑓𝑜𝑟 𝐸 > 𝐸𝐹
𝐸 − 𝐸𝐹 𝐸 − 𝐸𝐹
exp ( ) + 1 exp ( ) + 1
𝑘𝐵 𝑇 𝑘𝐵 (0)
The curve has step-like character with 𝑓(𝜖) = 1 for energies below 𝐸𝐹𝑜 and 𝑓(𝜖) = 0 for
energies above 𝐸𝐹𝑜 . This represents that all the energy states below 𝐸𝐹𝑜 are filled with electrons
and all those above it are empty.

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Analytical Treatment At T>0K;

1
𝑓(𝜖) =
𝐸 − 𝐸𝐹
exp ( )+1
𝑘𝐵 𝑇
1
={ 𝑖𝑓 𝐸 = 𝐸𝐹 }
2
> {0 𝑖𝑓 𝐸 > 𝐸𝐹 }
< {1 𝑖𝑓 𝐸 < 𝐸𝐹 }
As the temperature is raised from absolute zero to 𝑇1 𝐾, the distribution curve begins to depart
from step-like function and tails off smoothly to zero. Again with a further increase in
temperature to𝑇2 𝐾 and to 𝑇3 𝐾, the departure and tailing of the curves increases. This indicates
that more and more electrons may occupy higher energy states with an increase of temperature
and as a consequence the number of vacancies below the Fermi level increases in the same
proportion.

At non-zero temperatures all these curves pass through a point whose

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1
𝑓(𝐸) = 2 , at 𝐸 = 𝐸𝐹 . So 𝐸𝐹 lies half way between the filled and empty states.

5.3. Free electron gas in three dimensions

The free-particle Schrödinger equation in three dimensions is
ћ2 𝜕 2 𝜕2 𝜕2
− ( 2 + 2 + 2 ) ѱ𝑘 (𝑟) = 𝜖𝑘 ѱ𝑘 (𝑟) (6)
2𝑚 𝜕𝑥 𝜕𝑦 𝜕𝑧
If the electrons are confined to a cube of edge L, the wavefunction is the standing wave
𝜋𝑛𝑥 𝑥 𝜋𝑛𝑦 𝑦 𝜋𝑛𝑧 𝑧
ѱ𝑛 (𝑟) = A sin( )sin( )sin( ) (7)
𝐿 𝐿 𝐿
Where; 𝑛𝑥 , 𝑛𝑦 , 𝑛𝑧 are positive integers. The origin is at one corner of the cube. It is convenient
to introduce wave-functions that satisfy periodic boundary conditions. We now require the wave-
functions to be periodic in x, y, z with period L. Thus
ѱ(𝑥 + 𝐿, 𝑦, 𝑧) = ѱ(𝑥, 𝑦, 𝑧) (8)
and similarly for the y and z coordinates. Wave-functions satisfying the freeparticle Schrödinger
equation and the periodicity condition are of the form of a traveling plane wave:
ѱ𝑘 (𝒓) = exp(𝑖𝒌. 𝒓) (9)
provided that the components of the wavevector k satisfy
2𝜋 4𝜋
𝑘𝑥 = 0, ± ,± ,… (10)
𝐿 𝐿
and similarly for 𝑘𝑦 𝑎𝑛𝑑 𝑘𝑧 .
Any component of k of the form 2𝑛𝜋/𝐿 will satisfy the periodicity condition over a length L,
where; n is a positive or negative integer. The components of k are the quantum numbers of the
problem, along with the quantum number 𝑚𝑠 for the spin direction. We confirm that these values
of 𝑘𝑥 satisfy (8), for

𝑖𝑘𝑥 (𝑥 + 𝐿) 𝑖2𝜋𝑛𝑥
ѱ𝑘 (𝒓) = exp [ ] = exp [ ] exp[𝑖2𝜋𝑛]
𝐿 𝐿
𝑖2𝜋𝑛𝑥
= exp [ ]
𝐿
= exp[𝑖𝑘𝑥 𝑥] (11)
On substituting (9) in (6) we have the energy ∈𝑘 of the orbital with wavevector k:

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ћ2 2 ћ2
𝜖𝑘 = 𝑘 = (𝑘 2 + 𝑘𝑦 2 + 𝑘𝑧 2 ) (12)
2𝑚 2𝑚 𝑥
The magnitude k of the wavevector is related to the wavelength λ by 𝑘 = 2𝜋⁄𝜆. The linear
momentum p may be represented in quantum mechanics by the operator = −𝑖ћ∇ , whence for
the orbital (9)
𝒑ѱ𝑲 (𝒓) = −𝑖ћ𝛁ѱ𝑲 (𝒓) = ћ𝐤ѱ𝑲 (𝑟) (13)
so that the plane wave ѱ𝑘 is an eigenfunction of the linear momentum with the eigenvalue ћ𝒌 .
The particle velocity in the orbital k is given by 𝒗 = ћ𝒌⁄𝑚. 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):

ћ2 2
𝜖𝐹 = 𝑘 (14)
2𝑚 𝐹
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 (2𝜋⁄𝐿)3 of k space. Thus in the sphere of volume
4
𝜋𝑘𝐹 3 the total number of orbitals is
3

𝑘𝐹 3
4𝜋( 3 ) 𝑉
2. = 2 𝑘𝐹 3 = 𝑁 (15)
(2𝜋⁄𝐿)3 3𝜋

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
3𝜋 2 𝑁 1⁄
𝑘𝐹 = ( ) 3 (16)
𝑉
which depends only on the particle concentration.

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Using equation(14) and (16),

ћ2 3𝜋 2 𝑁 2⁄
𝜖𝐹 = ( ) 3 (17)
2𝑚 𝑉
This relates the Fermi energy to the electron concentration N/V. The electron velocity 𝑣𝐹 at the
Fermi surface is
ћ𝑘𝐹 ћ 3𝜋 2 𝑁 1⁄
𝑣𝐹 = = ( ) 3 (18)
𝑚 𝑚 𝑉
Calculated values of 𝑘𝐹 , 𝑣𝐹 , and ∈𝐹 are given in Table 1 for selected metals; also given are
∈𝐹
values of the quantity 𝑇𝐹 which is defined as ⁄𝑇 . (The quantity 𝑇𝐹 has nothing to do with
𝐵

the temperature of the electron gas!)

We now find an expression for the number of orbitals per unit energy range, D(∈), called the
density of states. Strictly, D(∈), is the density of one-particle states, or density of orbitals.
We use (17) to obtain the total number of orbitals of energy ≤∈:

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𝑉 2𝑚𝜖 3
𝑁= 2
. ( 2 ) ⁄2 (19)
3𝜋 ћ
so that the density of states (Fig. 5) is
𝑑𝑁 𝑉 2𝑚 3 1
𝐷(𝜖) = = 2 . ( 2 ) ⁄2 . 𝜖 ⁄2 (20)
𝑑𝜖 2𝜋 ћ
This result may be expressed more simply by comparing (19) and (20) to obtain at ∈
𝑑𝑁 3𝑁
𝐷(𝜖) = = (21)
𝑑𝜖 2𝜖
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.
5.4. 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
3
predicts that a free particle should have a heat capacity of 𝑘𝐵 , where 𝑘𝐵 is the Boltzmann
2

constant. If N atoms each give one valence electron to the electron gas, and the electrons are
3
freely mobile, then the electronic contribution to the heat capacity should be 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. This important discrepancy distracted the early workers, such
as Lorentz: 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 ~𝑘𝐵 T as
expected classically, but only those electrons in orbitals within an energy range 𝑘𝐵 T 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

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these lie within an energy range of the order of kBT of the top of the energy distribution. Each of
these 𝑁𝑇/𝑇𝐹 electrons has a thermal energy of the order of 𝑘𝐵 T . 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
3
following section. At room temperature 𝐶𝐶𝑙 is smaller than the classical value 2 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 𝑘𝐵 𝑇 ≪ 𝜖𝐹 . 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

Here 𝑓(𝜖) is the Fermi-Dirac function (5):

and 𝐷(𝜖)is the number of orbitals per unit energy range. We multiply the identity

by 𝜖𝐹 to obtain

We use (26) to rewrite (24) as

The first integral on the right-hand side of (27) gives the energy needed to take electrons from
𝜖𝐹 to the orbitals of energy 𝜖 > 𝜖𝐹 , and the second integral gives the energy needed to bring the

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electrons to 𝜖𝐹 from orbitals below 𝜖𝐹 . Both contributions to the energy are positive. The product
𝑓(𝜖)𝐷(𝜖)𝑑𝜖 in the first integral of (27) is the number of electrons elevated to orbitals in the
energy range 𝑑𝜖 at an energy 𝜖. The factor [ 1 − 𝑓(𝜖)] in the second integral is the probability
that an electron has been removed from an orbital 𝜖. 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(𝜖), whence we can group terms to obtain

𝜏 𝑑𝑓
At the temperatures of interest in metals, 𝜖 < 0.01, and we see from Fig. 3 that(𝜖 − 𝜖𝐹 ) 𝑑𝑇 has
𝐹

large positive peaks at energies near 𝜖𝐹 . It is a

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good approximation to evaluate the density of states D(𝜖) at 𝜖𝐹 and take it outside of the integral:

Examination of the graphs in Figs. 7 and 8 of the variation of the chemical potential 𝜇 with T
suggests that when 𝑘𝐵 𝑇 ≪ 𝜖𝐹 we ignore the temperature

dependence of the chemical potential 𝜇 in the Fermi-Dirac distribution function and replace 𝜇 by
the constant 𝜖𝐹 . We have then, with 𝜏 ≡ 𝑘𝐵 𝑇

We set

and it follows from (29) and (30) that

We may safely replace the lower limit by −∞ because the factor ex in the integrand is already
−𝜖 𝜖
negligible at 𝜒 = 𝐹⁄𝜏 if we are concerned with low temperatures such that 𝐹⁄𝜏 ~100 or
more. The integral in (32) then becomes

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whence the heat capacity of an electron gas is

From (21) we have

for a free electron gas, with 𝑘𝐵 𝑇𝐹 ≡ 𝜖𝐹 . Thus (34) becomes

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 𝜃 and the Fermi temperature TF, the
heat capacity of metals may be written as the sum of electron and phonon contributions:
𝐶 = 𝛾𝑇 + 𝐴𝑇 3 , where 𝛾 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:
𝐶⁄ = 𝛾 + 𝐴T 2 (37)
𝑇
for then the points should lie on a straight line with slope A and intercept 𝛾. Such a plot for
potassium is shown in Fig. 9. Observed values of 𝛾, called the Sommerfeld parameter, are given
in Table 2. The observed values of the coefficient 𝛾 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 (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 𝜖𝐹 is inversely proportional to the mass of the electron,
whence 𝛾 ∝ 𝑚. Values of the ratio are given in Table 2. The departure from unity involves three
separate effects:

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 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 γ. The heavy
fermion compounds include 𝑈𝐵𝑒13, 𝐶𝑒𝐴13, and𝐶𝑒𝐶𝑢2 𝑆𝑖2. It has been suggested that f electrons
in these compounds may have inertial masses as high as 1000 m, because of the weak overlap of
wavefunctions of f electrons on neighboring ions.

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Chapter 6
Dielectrics and Ferroelectrics
Introduction
Based on their electrical property materials may be classified in to two major groups:
i. Conductors: have “unlimited” supply of charges that are free to move about through the
material. They have high conductivity (𝜎 ≫ 1).
ii. Nonconductors: Non conducting materials are usually called insulators (dielectrics).
They have low conductivity (𝜎 ≪ 1). In dielectrics, all charges are attached to specific
atom or molecule loosely and move a bit within the atom or molecule.
In general, the main difference b/n a conductor and a dielectric is the number (availability) of
free electrons in the outermost shell.
6.1. Review of basic formulae
Electric field can exist in free space and material medium. There are two fundamental laws
governing electrostatic fields:
i) Coulomb’s law
The electrostatic force b/n two charges is given by
𝑞1 𝑞2
𝐹=𝑘 (6.1)
𝑟2
𝟏
Where; 𝒌 = 𝟒𝝅𝝐 is the electrostatic constant
𝟎

ii) Gauss’s law

Gauss’s law, states that the net flux through any closed surface is equal to the charge
enclosed by the surface.

⃗ . 𝑑𝐴 = 𝑞
𝜙𝐸 = ∮ 𝐷 (6.2)
Electric Field Induction (or) Flux density (or) Displacement Vector is defined as
the number of electric lines of force received by a unit area (A).
𝑞
𝐷=𝐴 (6.3)
The electric flux density⃗⃗⃗𝐷 is related to the electric field intensity (in free space) as

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⃗⃗⃗𝐷 = 𝜖0 𝐸⃗ (6.4)
𝑪
⃗⃗ is 𝟐 .
The electric flux density is also called electric displacement. The unit of 𝑫 𝒎

A dielectric material is a non-conducting substance whose bound charges are polarized under the
influence of an external electric field. In a dielectric there are no free charges present, but bound
charges, i.e. electric dipoles are present.

Figure 1: A dipole- a pair of two equal and opposite charges separated by a distance 'd’
The dipole moment of the dipole is the product of magnitude of either charges within their
separation.

𝝁 ⃗
⃗ = 𝑞𝒅 (6.5) direction: ( − → + )

A dipole placed in an electric field will experience torque and hence rotate in the field.

Torque felt

⃗ =𝝁
𝝉 ⃗
⃗ 𝒙𝑬 (6.6)

Potential energy

⃗ . ⃗𝑬
𝑈 = −𝝁 (6.7)

Figure 2: A dipole in a uniform electric field ⃗𝑬

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Polarization: The process of producing electric dipoles out of neutral atoms or molecules is
known as polarization. The total dipole moment per unit volume is also defined as the dielectric
⃗⃗ ).
polarization (𝑷

⃗𝑷
⃗ = 𝑁𝝁
⃗ (6.8)

This is nothing but induced charge per unit area. Hence polarization is also defined as induced
surface charge per unit area.
𝑞
𝑃 = 𝑖𝑛𝑑 (6.9)
𝐴
𝐶
The dipole moment density has unit 𝑚2 .
Relation among E, D & P: Figure below shows a parallel plate capacitor with a dielectric, ‘𝑞’ is
charge on each plate and ‘𝑞1 = 𝑞𝑖𝑛𝑑 ’ is the induced charge on the surface of the dielctric.The net
charge enclosed in the gaussian surface is (𝑞 − 𝑞𝑖𝑛𝑑 )

Figure 3: A parallel plate capacitor filled with a dielectric

From Gauss’ law,

𝑞𝑒𝑛𝑐 𝑞 − 𝑞𝑖𝑛𝑑
⃗⃗ . 𝑑𝑨
∮𝑬 ⃗⃗ = =( )
𝝐𝟎 𝝐𝟎
𝑞 𝑞𝑖𝑛𝑑
𝐸𝐴 = 𝝐 − (5.10)
𝟎 𝝐𝟎

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Using, eqn. (5.3) and (5.9) in eqn. (5.10), we obtain 𝜖0 𝐸 = 𝐷 − 𝑃 ; Hence

𝐷 = 𝜖0 𝐸 + 𝑃 (6.11)

Again the electric displacement in a material can be related to the electric field strength
𝐷 = 𝜖0 𝐸 + 𝑃 = 𝜖𝐸 = 𝜖0 𝜖𝑟 𝐸
𝜖
where 𝜖𝑟 = 𝜖 is relative permittivity/ dielectric constant. Permittivity is a quantity that
0

describes the effect of a material on an electric field: the higher the permittivity, the more the
material tends to reduce any field set up in it/permittivity expresses the ability of a material to
polarise in response to an applied field. (Dielectric constant can vary significantly with
frequency).
Polarizability: The strength of the induced dipole moment is directly proportional to the strength
of the external applied field, i.e. μ ∝ E.
𝜇 = 𝛼𝐸 (6.12)
Where; 𝛼 is known as dielectric polarizability
Succeptibility(𝝌-'chi'): It is defined as polarization per unit electric field. The electric
susceptibility of the material is more or less a measure of how susceptible (or sensitive) a given
dielectric is to electric fields.
𝑃
𝜒𝑒 = 𝜖 (6.13)
0𝐸
𝑁𝛼
𝐷 = 𝜖0 𝐸 + 𝑁𝛼𝐸 = 𝜖0 (1 + )𝐸 (6.14)
𝜖0
Since; 𝐷 = 𝜖0 𝜖𝑟 𝐸, it follows that
𝑁𝛼
𝜖𝑟 = (1 + ) (6.15)
𝜖0
Define electrical susceptibility 𝜒such that 𝑃 = 𝜖0 𝜒𝐸 = 𝑁𝛼𝐸 which gives
𝑁𝛼
𝜒= (6.16)
𝜖0
Finally from eqn. (5.15) and (5.16), we can infer that
𝜖𝑟 = (1 + 𝜒) (6.17)
6.2. The microscopic concept of polarization
The Electric field which appears in the Maxwell’s equation is macroscopic electric field 𝐸⃗ . The
value of the field that acts at the site of the atom in the crystal, called local (internal) field, is
significantly different from that of the macroscopic field.

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The total field acting at the atom site or dipole in a system is due to external sources and other
dipoles present in the specimen. The local field determines the dipole moment of the atom.
Consider a spherical cavity of radius ′r′ within a dielectric, which is placed between the two
charged parallel plates. The total field experienced by it is

Figure 4: The internal electric field on an atom in a crystal is the sum of the external applied
field ⃗⃗⃗⃗
𝐸0 and of the field due to the other atoms in the crystal.
𝐸⃗𝑙𝑜𝑐𝑎𝑙 = 𝐸⃗0 + 𝐸⃗1 + 𝐸⃗2 + 𝐸⃗3 (6.18)
Here
𝐸⃗0 = field produced by fixed charges external to the body
𝐸⃗1 =depolarization field, from a surface charge density 𝒏.
̂𝑷 ⃗⃗ on the outer surface of the specimen

𝐸⃗2 =Lorentz cavity field: field from polarization charges on inside of a spherical cavity cut out of
the specimen with the reference atom as center, as in Fig.4
𝐸⃗3 =field of atoms inside cavity
−𝑷 ⃗⃗
Depolarization field, ⃗𝑬𝟏 =3𝜖
0

⃗⃗
⃗ 𝟐= 𝑷
Lorentz Field,𝑬 3𝜖 0

The field ⃗𝑬
⃗ 𝟐 , due to the polarization charges on the surface of the fictitious cavity is the negative
of the depolarization field ⃗𝑬𝟏 in a polarized sphere, so that ⃗𝑬𝟏 + ⃗𝑬𝟐 = 𝟎 for a sphere.

⃗𝟑
Field of Dipoles inside Cavity, 𝑬

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The field ⃗𝑬
⃗ 𝟑 , due to the dipoles within the spherical cavity is the only term that depends on the
crystal structure. But, for a reference site with cubic surroundings in a sphere 𝐸⃗3 = 0. The total
local field at a cubic site is then,
⃗⃗
𝑬 ⃗⃗ + 𝑷
⃗ 𝑙𝑜𝑐𝑎𝑙 = 𝑬 (6.19)
3𝜖 0

This is the Lorentz relation: the field acting at an atom in a cubic site is the macroscopic field 𝑬
⃗𝑷
⃗
plus 3𝜖 , from the polarization of the other atoms in the specimen.
0

Where 𝐸⃗𝑀𝑎𝑥𝑤𝑒𝑙𝑙 = ⃗𝑬
⃗ = 𝐸⃗0 + 𝐸⃗1

⃗𝑬
⃗ 𝑙𝑜𝑐𝑎𝑙 = microscopic field which fluctuates within the medium

6.3. Langevins theory of polarization in polar dielectrics

Polar molecules in liquids or gases such as 𝐻2 𝑂𝑜𝑟 𝑁𝐻3 , have a permanent dipole moment which
can be partially aligned with an applied field. The alignment of polar molecules in an electric
field is upset by random thermal motion, so that Maxwell-Boltzmann statistics can be used to
find the average polarization. The expression for the polarization can be obtained from
Langevin-Debye theory as
𝜇 𝑬 2
< 𝑃⃗ >= 3𝑘𝑇 (6.20)

This is the average moment per molecule in the direction of the applied field. The magnitude of
the mean orientationalpolarizabilityis
𝑃 𝜇2
𝛼𝑜 = 𝐸 = 3𝑘𝑇 (6.21)

6.4. Clausius-Mosotti relation

Clausius-Mosotti equation gives the relation between the macroscopic quantity (dielectric
constant of an insulator) and the microscopic quantity (polarizability of atoms or molecules) of
an insulator. We know that, from Eqn. (6.11) 𝐷 = 𝜖0 𝐸 + 𝑃. But, again 𝐷 = 𝜖𝐸 .
Therefore, 𝜖𝐸 = 𝜖0 𝐸 + 𝑃 → solving for 𝐸 yields
𝑃
𝐸 = 𝜖−𝜖 (6.22)
𝑜

Substituting Eqn. (6.22) in (6.19) we obtain,

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𝑃 𝑃
𝐸𝑙𝑜𝑐𝑎𝑙 = +
𝜖 − 𝜖𝑜 3𝜖0
𝑃 𝜖+2𝜖
𝐸𝐿 = 3𝜖 ( 𝜖−𝜖 0 ) (6.23)
0 𝑜

If 𝑁is the number of molecules per unit volume, 𝛼 the molecular polarizability then
𝑃
𝑃 = 𝑁𝛼𝐸𝐿 → 𝐸𝐿 = 𝑁𝛼 (6.24)

From equations, (6.23) and (6.24)

𝑃 𝑃 𝜖 + 2𝜖0
= ( )
𝑁𝛼 3𝜖0 𝜖 − 𝜖𝑜
Which upon rearrangement gives;-
𝑁𝛼 𝜖 − 𝜖𝑜
=( )
3𝜖0 𝜖 + 2𝜖0
𝜖
Using the relation 𝜖𝑟 = 𝜖 the above equation can be simplified to give
0

𝑁𝛼 𝜖 −1
= (𝜖𝑟 +2) (6.25)
3𝜖0 𝑟

Equation (6.25) is known as Clausius-Mosotti relation, which relates the macroscopic dielectric
constant (𝜖𝑟 ) with the microscopic polarizability (𝛼).
6.5. The static dielectric constant of solids and liquids (Elemental dielectrics, Polarization
of ionic crystals)
The static dielectric constant1 is simply the dielectric constant related to the material behavior
in low frequency or constant electric fields. The value of the static dielectric constant of any
material is always greater than one, its value for a vacuum. Polarizability is a consequence of the
fact that the molecules, which are the building blocks of all substances, are composed of both
positive charges (nuclei) and negative charges (electrons).When a field acts on a molecule, the
positive charges are displaced along the field, while the negative charges are displaced in a
direction opposite to that of the field. The effect is therefore to pull the opposite charges apart,
i.e., to polarize the molecule. There are three different types of polarization processes, depending
on the structure of the molecules which constitute the solid:
6.5.1. Dipolar (Orientational) Polarizability

1
The static dielectric constant is the dielectric constant under direct current
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Orientation polarization is due to the alignment of dipoles of polar molecules in the presence of
applied electric field. This type of polarization occurs in polar substances (dielectrics). Polar
substances show random distribution of their dipoles in space in the absence of electric field.
This leads to the zero net dipole moment of the substance. When dielectric is kept under an
electric field, the field produces a torque in individual dipoles and dipoles align with the field. If
the field is so strong enough, the dipoles may completely be aligned along the field direction.
𝜇2
With increasing temperature, orientational polarizability, decreases (𝛼𝑑 = 3𝑘 𝑇).
𝐵

6.5.2. Electronic Polarizability

Electronic polarization is due to the displacement of charge centers of electron cloud (negative
charge center) and nucleus (positive charge center) of an atom in the presence of an applied
electric field. It’s is given by 𝛼𝑒 = 4𝜋𝜖𝑜 𝑅 3, where R is atomic radius.
Electronic polarizability arises from displacement of electron clouds relative to nucleus in an
atom in the presence of external electric field 𝐸⃗ . It depends on frequency of 𝐸⃗ .
5.5.3. Ionic polarizability
It is rises from change in the distance between the ions on application of electric field. It’s given
by
𝑒2 1 1
𝛼𝑖 = 2 ( + )
𝜔0 𝑚1 𝑚2
𝜔0 = natural frequency
𝑚1 &𝑚2 = masses of ions/atoms, 𝛼𝑖 depends on frequency of applied field, but not temperature
In general, therefore, the total polarizability is given by
𝛼 = 𝛼𝑒 + 𝛼𝑖 + 𝛼𝑑 , (6.26)
That is the sum of the electronic, ionic, and dipolar polarizabilities, respectively.
The electronic contribution is present in any type of substance, but the presence of the other two
terms depends on the material under consideration. The relative magnitudes of the various
contributions in (6.26) are such that in nondipolar, ionic substances the electronic part is often of
the same order as the ionic. In dipolar substances, however, the greatest contribution comes from
the dipolar part.
6.6. Ferroelectricity
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The creation of large induced dipole moment even ina weak electric field, and the existence of it
even when the field is removed is called Ferroelectricity. Materials exhibiting this property are
ferroelectric materials. A tiny region of ferroelectric in which all the electric dipoles align in the
same direction is known as electric domain.
Important characteristics of ferroelectrics
 Ferroelectrics exhibit spontaneous polarization.
 The spontaneous polarization becomes zero at transition temperature (or) Curie
temperature.
 Ferroelectrics possess very high dielectric constant values.
 Ferroelectric exhibits reverse polarization.
 Below transition temperature they give hysteresis loop.
 Above transition temperature hysteresis loop disappears and the Ferroelectric behaves
like an ordinary dielectric
 All Ferroelectrics are pyroelectrics and piezoelectrics, but reverse may not be true.
 The property by which electric polarization is induced by the thermal energy is known as
pyroelectricity.
 Tourmaline crystal is a pyroelectric and not Ferroelectric.
 Quartz is a piezoelectric but not ferroelectric.
 Ferroelectric crystals exhibit double refraction
Dielectric Hysteresis
 When an electric field is applied to a specimen of a ferroelectric crystal, the polarization
first rises rapidly with the applied field to a value, above which the dependence is linear,
as shown in the figure below.
 Linear extrapolation to zero fields gives 𝑃𝑠 , the saturation polarization.
 On subsequently reducing the field to zero, the polarization 𝑃𝑟 remains and is known as
remanent or residual or spontaneous polarization.
 The negative field to reduce the polarization to zero is called coercive field and is
represented by ±𝐸𝐶 .

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 The existence of dielectric hysteresis loop in dielectric material implies that the substance
possesses spontaneous polarization.

Figure 5: Dielectric hysteresis

The height and width of the hysteresis loop decreases with increase of temperature below the
transition temperature. At transition temperature (or) Curie temperature, the loop merges into a
straight line and ferroelectric behavior of the material disappears.
Applications of Ferroelectrics:-
 Due to their high dielectric constant values, they are used for manufacturing of
small size capacitors with high capacitance.
 The property of hysteresis used as memory for electronic computers
6.7. Piezoelectricity
The term piezoelectricity refers to the fact that, when a crystal is strained, an electric field is
produced within the substance. As a result of this field, a potential difference develops across the
sample, and by measuring this potential one may determine the field. The inverse effect - that an
applied field produces strain - has also been observed. The piezoelectric effect is very small.
A field of 103 V/cm in quartz (SiO2) produces a strain of only10−7. That is, a rod 1 cm long
changes its length by 10Å. Conversely, even small strains can produce enormous electric fields.

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The piezoelectric effect is often used to convert electrical energy into mechanical energy, and
vice versa; i.e., the substance is used as a transducer. For instance, an electric signal applied to
the end of a quartz rod generates a mechanical strain, which consequently leads to the
propagation of a mechanical wave - a sound wave - down the rod. Quartz is the most familiar
piezoelectric substance, and the one most frequently used in transducers.
The microscopic origin of piezoelectricity lies in the displacement of ionic charges within the
crystal. In the absence of strain, the distribution of the charges at their lattice sites is symmetric,
so the internal electric field is zero. But when the crystal is strained, the charges are displaced. If
the charge distribution is no longer symmetric, then a net polarization, and a concomitant electric
field, develops. It is this field which operates in the piezoelectric effect.

Figure 6: Crystal with center of inversion exhibits no piezoelectric effect, (b) Origin of
piezoelectric effect in quartz: crystal lacks a center of inversion.
It follows that a substance can be piezoelectric only if the unit cell lacks a center of inversion.
Figure 6 (a) shows this, and demonstrates that if a center of inversion is present, it persists even
after distortion, and consequently the polarization remains zero. However, when there is no
center of inversion, as in Fig. 6 (b), distortion produces a polarization. We see, therefore, that no
regular cubic lattice can exhibit piezoelectricity.
The lack of inversion center, however, is not sufficient to guarantee piezoelectricity, and only
relatively few substances, exhibit this phenomenon.
Terminal Questions and Problems
1. Distinguish between polar and nonpolar dielectrics.
2. Identify the different types of polarizabilities (electronic, ionic, etc…)
3. What ate the merits of using a dielectric in a capacitor?
4. Can 𝜖𝑟 attain a value less than 1?

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5. What is the value of deviation of electric susceptibility from unity?

6. A slab of dielectric material has a 𝜖𝑟 = 3.8 and contains a uniform electric flux density
𝑛𝐶
of 8 𝑚2 . If the material is lossless; find

a) 𝐸 b) 𝑃
7. Show that the potential energy of a dipole 𝝁in an electric field 𝑬 may be written as −𝝁 ⃗⃗
⃗ .𝑬
. Also show that if𝛼is the polarizability of an atom, the energy of the atom in an electric
field 𝐸 is given by −(𝛼/2)𝐸 2 .
8. Distinguish between Ferroelectricity and piezoelectricity.
9. What is the physical origin of piezoelectricity?

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Chapter 7
Magnetism
7.1. Magnetic permeability (𝝁)
𝜇: − Is the characteristic property of a medium.It indicates the ease with which the material
allows the magnetic lines of force to pass through it. OR It is the measure of the ability of a
material to support the formation of a magnetic field within itself. OR, In other words, it is the
degree of magnetization that a material obtains in response to an applied magnetic field.
SI-UNITS: Henry per meter (H/m) or Newton per Ampere square (𝑁. 𝐴−2 )
The Magnetic induction 𝐵 is proportional to theapplied Magnetic field intensity, H → 𝐵 ∝ 𝐻 ⇒
𝐵
𝐵 = 𝜇𝐻, Hence, 𝜇 = 𝐻

7.2. Magnetization
It is a measure of how the material responds when magnetic field is applied to it. A magnetic
⃗⃗ or the magnetic field
field can be described by either of two vectors: The magnetic induction𝑩
⃗⃗⃗ , which are related in vacuum by
intensity𝑯
⃗𝑩
⃗ = 𝜇𝑜 ⃗𝑯
⃗⃗ (7.1)
Where 𝜇𝑜 = 4𝜋𝑥10−7 𝐻/𝑚 is the permeability of free space. The magnetic flux density B has a
unit of Wb/m2 or Tesla(T).
When a material medium is placed in a magnetic field, the medium is magnetized. This
magnetization is described by the magnetization vector ⃗𝑴
⃗⃗ , the dipole moment per unit volume.
The magnetic induction inside the medium is then given by the relation
⃗𝑩
⃗ = 𝜇𝑜 ⃗𝑯
⃗⃗ + 𝜇𝑜 ⃗𝑴
⃗⃗ (7.2)
⃗⃗⃗ is generated by the external sources, and
The induction is composed of two parts: the part 𝜇𝑜 𝑯
the part 𝜇𝑜 ⃗𝑴
⃗⃗ , due to the magnetization of the medium.

Since the magnetization is induced by the field, we may assume that ⃗𝑴

⃗⃗ is proportional to ⃗𝑯
⃗⃗ , the
external field:
⃗𝑴
⃗⃗ = χ𝑯
⃗⃗⃗ (7.3)

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Where the proportionality constant χ is the magnetic susceptibility of the medium2.Its value may
be zero, positive or negative.
Subbing Eqn. (7.3) in (7.2),
⃗⃗ = 𝜇𝑜 (1 + χ)𝑯
𝑩 ⃗⃗⃗ (7.4)
⃗⃗ and 𝑯
Thus the vectors 𝑩 ⃗⃗⃗ are proportional to each other,
⃗𝑩
⃗ = 𝜇𝑯
⃗⃗⃗ (7.5)
And the proportionality constant
𝜇 = 𝜇𝑜 (1 + χ) (7.6)
Is known as the permeability of the medium. Define the relative permeability as 𝜇𝑟 = 𝜇/𝜇𝑜 .
Therefore,
𝜇𝑟 = 1 + 𝜒 (7.7)
A relation connecting the permeability and susceptibility of the medium.
Materials may be grouped into three magnetic classes, depending on the sign and magnitude of
⃗⃗ is parallel to 𝑯
the susceptibility. Those materials for which 𝜒 is positive (i.e., for which 𝑀 ⃗⃗⃗ ) are
⃗⃗ is opposite to
known as paramagnetic, whereas those for which 𝜒 is negative (i.e., for which 𝑀
⃗𝑯
⃗⃗ ) are diamagnetic.
The Origin of Permanent Magnetic Dipoles
All known magnetic properties of matter are attributable to the rotation of electric charges.
Accordingly, atomic magnetic dipoles originate from:
i) The orbital motion of the electrons
ii) The electron spin
iii) The nuclear spin
 Nuclear magnetic moments are smaller than those associated with the 𝑒 − by a
factor of ~103 .
 They are the result of the nuclear angular momentum(nuclear spin)
An electric current loop acts like a magnetic dipole of moment

2
Magnetic susceptibility 𝜒 bears no physical relationship to the electric susceptibility, although the same
symbol is used for both.

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𝜇𝑚 = 𝐼𝐴 (7.8)
Where; 𝐼 is the current and 𝐴 is the area of the loop.
The direction of 𝝁
⃗ 𝑚 ,which is a vector, is normal to the plane of the loop, and such that the
current flows counterclockwise relative to an observer standing along 𝝁
⃗ 𝑚.

⃗ 𝒎 associated with a current loop.Vector ⃗𝑳 is angular

Figure 7: Magnetic dipole moment 𝝁
momentum of electron producing the current.
The current loops in an atom are composed of rotating electrons. Let’s establish a simple relation
⃗ 𝒎 and ⃗𝑳of the electrons.
b/n 𝝁
𝑞 𝜔
𝐼= ⃗ = 𝑚𝑟 2 𝜔
= 𝑒 (2𝜋),𝐴 = 𝜋𝑟 2 &𝑳
𝑡

𝜔 ⃗𝑳
⇒ 𝜇𝑚 = 𝐼𝐴 = −𝑒 ( )𝜋( )
2𝜋 𝑚𝜔
𝑒
⃗ 𝑚 = (− 2𝑚) ⃗𝑳
𝝁 (7.9)
𝑒
The(– )indicates that𝝁 ⃗ . The coefficient− relating 𝝁
⃗ 𝑚 is parallel to 𝑳 ⃗ 𝑚 to⃗⃗⃗𝑳is calledthe
2𝑚

gyromagnetic ratio.
In addition to its orbital rotation, the electron also rotates about its own axis, a motion referred to
as spin. Thus there is a magnetic moment associated with the spin, and this moment may be
related to the spin angular momentum 𝑆.The relation is
𝑒
⃗ 𝑚 = (− 𝑚) ⃗𝑺
𝝁 (7.10)

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𝑒
which shows that the spin gyromagnetic ratio (− 𝑚) is twice the value obtained for the orbital

motion in (7.9).
Let us now think about the dynamics of a classical dipole in a magnetic field. The equation of
motion is
⃗
𝑑𝐿
=𝜏 (7.11)
𝑑𝑡

Where 𝝉
⃗ =𝝁 ⃗⃗ is the torque. Substitution for 𝝉
⃗ 𝑚 𝑥𝑩 ⃗ and⃗⃗⃗𝑳gives
𝑑𝝁
⃗ 𝑒
= (− 2𝑚) 𝝁 ⃗⃗
⃗ 𝒙𝑩 (7.12)
𝑑𝑡

This relation represents a precessional motion (see Fig.2), of frequency

𝑒𝐵
𝜔𝐿 = 2𝑚 (7.13)

known as the Larmor frequency.The dipole simply precesses around the direction
of the field, always maintaining the same angle. For an electron at B =0.1 Wb/m2
𝜔𝐿 ≅l0GHz.

⃗ in a magnetic induction ⃗𝑩
Figure 8: Precession of a dipole moment𝝁 ⃗.
⃗⃗ it
When a magnetic dipole moment is placed in a magnetic field whose induction is 𝑩
experiences a couple whose torque is

⃗ =𝝁
𝝉 ⃗⃗
⃗ 𝑚 𝑥𝑩 (7.14)
The effect of this torque is to turn the dipole and align it with the field. Because of the torque, the
dipole has an orientation potential energy given by
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⃗ 𝑚 . ⃗𝑩
𝑉 = −𝝁 ⃗ = −𝜇𝑚 𝐵 cos 𝜃 (7.15)
Where; 𝜃 is the angle between the field and the dipole directions.
The minimum energy, −𝜇𝐵, occurs at 𝜃 = 0, where the dipole lies along the field. The maximum
energy is achieved at 𝜃 = 𝜋, where the dipole is oriented opposite to the field.
⃗⃗ without ever
Activity1: According to Larmor precession, the dipole merely rotates around 𝑩
getting closer to the direction of the field. If so, how does the dipole tend to align itself with the
field?
Using Eq. (7.9) the potential energy of the dipole (7.15)𝐸 = −𝜇𝐵 cos 𝜃 can also be written as
𝑒
𝐸 = + 2𝑚 𝐿𝑧 𝐵 (7.16)

⃗⃗ is taken to be in the Z-direction, and 𝐿𝑧 is the Z-component of the angular momentum.

Here 𝑩
 𝐿𝑧 = 𝑚𝑙 ℏ, whaere 𝑚𝑙 = −𝑙 𝑡𝑜 𝑙
Thus, Eq. (6.16) may also be written as
𝑒ℏ
𝐸 = (2𝑚) 𝐵𝑚𝑙 (7.17)
𝑒ℏ
The ratio 𝜇𝐵 = 2𝑚is called the Bohr Magneton, and has the numerical value 𝜇𝐵 =

9.3𝑥10−24 𝐽𝑚2 /𝑊𝑏.

We may hence write Eq. (7.17) as
𝐸 = 𝜇𝐵 𝐵𝑚𝑙 (7.18)
As 𝑚𝑙 takes its various allowed values, the energy also takes its appropriate values in the
presence of the magnetic field. For 𝑙 = 1, 𝑚𝑙 takes the values − 1, 0, and 1 and the corresponding
three energy levels are illustrated in Fig. 3.

Figure 9: Splitting of an atomic level by a magnetic field (Zeeman Effect) for 𝑙 = 1

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The splitting of an atomic level by the magnetic field in the manner just described is known as
Zeeman splitting. The interval between any two adjacent levels is the same, and is given by
∆𝐸 = 𝜇𝐵 𝐵 (7.19)
⃗ is opposite to 𝑩
N.B.: 1. The lowest level, 𝑚𝑙 = −1, corresponds to the orientation in which 𝑳 ⃗⃗ ,
⃗⃗ , in agreement with the classical picture.
⃗ ∥ 𝑩
and hence𝝁
⃗ is opposite to ⃗𝑩
2. The highest level 𝑚𝑙 = 1, corresponds to the orientation in which 𝝁 ⃗.
In the case of the spin, the Zeeman energy (7.18) is given by
𝐸 = 2𝜇𝐵 𝐵𝑚𝑠 (7.20)
where the factor 2 arises from the fact that the spin gyromagnetic ratio is twice the classical
1 1 1
value.Since the spin quantum number 𝑠 = 2, the allowed values are𝑚𝑠 = − 2 𝑎𝑛𝑑 + 2.The

corresponding Zeeman splitting, composed of only two lines, is shown in Fig. 4.The difference
in energy between the two levels is
∆𝐸 = 2𝜇𝐵 𝐵 (7.21)
which is double the orbital separation.

Figure 10: Zeeman Effect for the spin case.

It is useful to establish a correspondence between the classical and quantum descriptions of the
dipole motion in a magnetic field. Note that for the orbital case, the energy splitting ∆𝐸 = 𝜇𝐵 𝐵 is
also equal to ℏ𝜔𝐿 ,where 𝜔𝐿 is the Larmor frequency given by (7.13).Thus the quantum
frequency for the transition between the Zeeman levels is equal to the classical Larmor
frequency. The same correspondence applies to spin, where both the Larmor frequency and the
Zeeman spacing are twice as large.

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In this section the orbital and spin angular momenta have been treated separately, but when an
electron has both types of momenta, as frequently happens, there is an interaction between them,
and the two should be treated simultaneously.
The Use of Quantum Numbers
A few remarks may be made here to refresh the reader’s memory on the use of QNs in the theory
of atoms.
1. The Principal Quantum Number (𝑛)
 Determines the energy of the orbit
 Takes only integer values 𝑛 = 1,2,3, ….
 The corresponding electronic shells are called the K,L,M,…shells
2. The angular momentum of the orbit is determined by the quantum number 𝑙, which is
restricted to the set of values 𝑙 = 0,1,2,3, … , (𝑛 − 1).
 The total angular momentum associated with a given value of 𝑙 is quantized and

given by 𝐿 = ℏ√𝑙(𝑙 + 1)
 𝑙 = 0 → 𝑠, 𝑙 = 1 → 𝑝, 𝑙 = 2 → 𝑑, 𝑙 = 3 → 𝑓 orbitals
N.B. Electrons in an s-state always have zero angular momentum and thus a vanishing magnetic
moment.
3. Magnetic Quantum Number (𝑚𝑙 )
 Specifies the direction of possible components of the angular momentum
 𝑚𝑙 is restricted to the set of values: 𝑚𝑙 = −𝑙 𝑡𝑜 𝑙
4. Spin Quantum Number (𝑠)
 The electron (𝑒 − ) itself has an angular momentum known as spin.
1
 𝑚𝑠 = ± 2

5. The orbital angular momentum and spin may be combined vectorially to give the total
angular momentum (𝑗).
1 1
Thus, for an 𝑒 − with a certain 𝑙 and a spin of2 , 𝑗 can accept the value 𝑙 ± 2. In atoms containing

a number of electrons, the 𝑙 vectors may be combined to form a resultant 𝐿, and the 𝑠 vectors
combine to yield a resultant 𝑆. This type of coupling is called Russell-Saunders coupling.

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The resultant 𝐿 and 𝑆 then combine to form the total angular momentum 𝐽 of the whole
electronic system of the atom ⇒ 𝐽 = 𝐿 + 𝑆.
The magnetic dipole moment associated with the electronic system of a given atom can be
predicted using Pauli principle and Hund’s rules:
1. Pauli principle- only one 𝑒 − can occupy a state defined by the set of quantum numbers
𝑛, 𝑙, 𝑚𝑙 & 𝑠.
 This leads to the conclusion that filled 𝑒 − shells do not contribute to the magnetic
moment of an atom.
 Thus the magnetic moment in atoms must result from incompletely filled shells!!
With regard to the latter, Hund’s rule state that for the ground state of such atoms:
1. The e− spins add to give the maximum possible 𝑆 consistent with the Pauli principle
2. The orbital momenta combine to give the max. value for 𝐿 that’s consistent with (i)
3. For an incompletely filled shell, we’ve:
𝐽 = 𝐿 − 𝑆 , for a shell less than half filled
𝐽 = 𝐿 + 𝑆 , for a shell more than half occupied
Example: Consider the 𝐶𝑟 2+ ion with e− configuration: 1s22s2 2p63s2 3p6 3d4
All shells are filled except the 3d shell w/c contains 4e− 𝑠. For a d-shell, 𝑙 = 2 ⇒ 𝑚𝑙 has 2𝑙 +
1
1 = 5 possible values. Each of this can accommodate 2e− 𝑠(𝑠 = ± 2), so that the max. number of

e− 𝑠 in the 3d level is 10.

In the 𝐶𝑟 2+ ion, the 3d shell is less than half filled. According to Hund’s rule (i), we’ve S=2. The
1
possible 𝑚𝑙 values are +2, +1,0, −1, −2. If we place the 4e− 𝑠 all with a spin of + 2 in the first

four of these, one obtains 𝐿 = 2, w/c is the max. value consistent with the spin distribution.
Hence, according to (iii), we’ve in this case 𝐽 = 0.Other atoms/ions may be treated similarly and
from the 𝑆, 𝐿 𝑎𝑛𝑑 𝐽 values, the magnetic moment may be calculated.
7.3. Diamagnetism
Diamagnetism is a quantum mechanical effect found in all materials. The origin of diamagnetism
is the induced dipole moment due to change in the orbital motion of electrons in atoms by the
applied field.

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What causes diamagnetism?

When an external magnetic field is applied to a molecule/atom having paired electrons in
orbitals, the e− orbital motion (velocity) is altered, w/c contributes to the magnetic flux being
altered. Such molecule/atom is called diamagnetic.
 A diamagnetic s/b is one whose atoms have no permanent magnetic dipole moment
 Diamagnetic substances are weakly repelled by a magnetic field
 When an external magnetic field is applied to a diamagnetic substance a weak magnetic
dipole moment is induced in the direction opposite the field.
 Diamagnetic susceptibility is:
 Negative , typically −10−6 𝑡𝑜 − 10−5
 Independent of temperature
 Always present, even when there is no permanent dipole moment on the atom
 Some diamagnetic elements are:
 Bi, Hg, Ag, C, Pb, Cu,Zn,…
Activity2:What causes diamagnetic susceptibility negative?
7.4. Paramagnetism
Paramagnetism refers to the magnetic state of an atom with one or more unpaired 𝑒 − 𝑠. The
unpaired 𝑒 − 𝑠 are attracted by a magnetic field due to the electron’s magnetic dipole moment.
 Hund’s rule states that 𝑒 − 𝑠 must occupy every orbital singly before any orbital is doubly
occupied. This may leave the atom with many unpaired 𝑒 − 𝑠. Because unpaired 𝑒 − 𝑠 can
spin in either dxn, they display magnetic moment in any dxn. This capability allows
paramagnetic atoms to be attracted to magnetic fields.
An atom whose shells are not completely filled has a permanent magnetic moment,
which arises from the combination of the orbital and spin motions of its electrons.
 Some paramagnetic elements :
 Al, O, Na, U, Pt,…etc
What is the effect of a magnetic field on the permanent magnetic moment?
Classical Theory of Paramagnetism
The potential energy of a magnetic dipole in a magnetic field is given by

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⃗ . ⃗𝑩
𝑉=𝝁 ⃗ (7.15)
The energy is least when the moment is parallel to the field, and thus the moment tends to line up
with the field. The effect of temperature is to randomize the direction of the dipole. The result of
these two competing processes is that some magnetization is produced. Solving the problem
analytically (similar to the problem of dipolar electrical polarization) we’ve
𝜇𝑧 = 𝜇𝐿(𝑣) (7.22)
where 𝜇𝑧 , is the average of 𝜇𝑧 , the component of the moment along the direction of
the field (taken in the z-direction) and 𝐿(𝑣) is the Langevin function3,
1 𝜇𝐵
𝐿(𝑣) = coth 𝑣 − 𝑣 and 𝑣= (7.23)
𝑘𝑇
𝜇𝐵
Figure 5 shows a plot of 𝜇𝑧 , versus . We see that, at low field,𝜇𝑧 , is proportional to the
𝑘𝑇

⃗ increases in value, 𝜇 , begins to saturate, eventually reaching the

magnetizing field B, but as , 𝐵 𝑧

maximum value 𝜇. It achieves this maximum value when the dipole lies exactly parallel to the
field.

𝜇𝐵
Figure 11: Average dipole moment component 𝜇𝑧 , versus𝑣 = 𝑘𝑇 . Dashed line representslow-fieldapproximation.

𝜇𝐵
In most practical situations, the ratio 𝑘𝑇 is very small compared to unity.

Thus for 𝜇 = 𝜇𝐵 ,𝐵 = 0.1𝑊𝑏/𝑚2 , and 𝑇 = 100𝐾, this ratio is about 0.001.Therefore

1
we may approximate the function 𝐿(𝑣) ≅ 3 𝑣, which leads to

3Langevinderived the formula (7.22) for dipolar magnetization before its electricalanalog. His treatment
was adapted to the electrical case by Debye.
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𝜇2 𝐵
𝜇𝑧 = (7.24)
3𝑘𝑇

The magnetizarion is given by

𝑁𝜇 2 𝐵
𝑀 = 𝑁𝜇𝑧 = (7.25)
3𝑘𝑇

where𝑁 is the atomic concentration, and the susceptibility is given by

𝑁𝜇𝑜 𝜇 2
𝜒= (7.26)
3𝑘𝑇

Equation (7.26) is referred to as the Curie law. The susceptibility given by Eq. (7.26)is also
referred to as the Langevin paramagnetic susceptibility.
1
 Note in particular that 𝜒 ∝ 𝑇. This is in marked contrast to the diamagnetic susceptibility,

which isessentially temperature independent.

Activity3: How do you tell whether a substance is paramagnetic or diamagnetic?
Activity4: Is 35
17𝐶𝑙 paramagnetic or diamagnetic?

7.5.Ferromagnetism
 Both dia- and para- magnetic materials are considered as non-magnetic because they
exhibit magnetization only in presence of an external field.
 Certain materials possess permanent magnetic moments even in the absence of an
external field.
 This is result of permanent unpaired dipoles formed from unfilled energy levels.
 These dipoles can easily line-up with the imposed magnetic field due to the exchange
interaction or mutual reinforcement of the dipoles. These are chrematistics of
ferromagnetism.
 Materials with ferromagnetism (Examples: Fe, Co, Ni, Gd) possess magnetic
susceptibilities approaching106 .
 Above the Curie temperature, ferromagnetic materials behave as para-magnetic materials
and their susceptibility is given by the Curie-Weiss law, defined as

𝑪
𝝌𝒎 = (7.27)
𝑻−𝑻𝒄

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 Bule Hora University, Dep’t of Physics

Where; C – material constant, T – temperature, Tc– Curie temperature.

• Ferromagnets are very strong; dipoles line-up permanently upon application ofexternal field.

Ferromagnetism has two sub-classes:-

i) Antiferromagnetism
ii) Ferrimagnetism
i) Antiferromagnetism
o Dipoles line-up, but in opposite directions, resulting in zero
Figure 12:Magnetic ordering
magnetization. Eg: Mn, Cr, MnO, NiO, CoO, MnCl2 of Ferromagnetic Materials

o Exchange interaction which is responsible for parallel

alignment of spins is extremely sensitive to inter-atomic spacing and to the atomic positions.
This sensitivity causes anti-parallel alignment of spins.
o When the strength of anti-parallel spin magnetic moments is equal, no net spin moment
exists, and resulting susceptibilities are quite small.
o One noticeable characteristic of antiferromagnets is they attain maximum susceptibility at a
critical temperature called Neel temperature. At temperatures above this, antiferromagnets
become para-magnetic.

Figure 13: Magnetic Ordering of Antiferromagnetic Materials

ii) Ferri-magnetism
 Some ceramic materials exhibit net magnetization.
Eg: Fe3O4, NiFe2O4
• In a magnetic field, the dipoles of a cation may line up with the field, while dipoles of other
cation may not. These ceramics are called ferrites, and the effect is known as ferrimagnetism.

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 Bule Hora University, Dep’t of Physics

• Ferri-magnetism is similar to anti-ferro-magnetism in that the spins of different atoms

or ions line up anti-parallel. However, the spins do not cancel each other out, and anet spin
moment exists.
• Below the Neel temperature, therefore, ferromagnetic materials behave very much like
ferromagnetic materials and are paramagnetic above the Neel temperature.
• These materials exhibit a large but field dependent magnetic susceptibility similar to ferro
magnets.
• They also show Curie-Weiss behavior. As these ceramics are good
insulators, electrical losses are minimal, and hence ferrites have lot of
applications in devices such as high frequency transformers.

Figure 14: Magnetic Ordering in ferrimagnetic Materials

7.6. Quantum Theory of Paramagnetismand Ferromagnetism
The magnetic moment 𝝁
⃗ of the atom interms of the total angular momentum𝑱 is
𝑒
⃗ = 𝑔 (− 2𝑚) 𝑱
𝝁 (6.28)

where𝑔 is a constant known as the Land𝑒̀ factor. Its value depends on the relative orientations of
the orbital and spin angular momenta.

Figure 15: Quantum description of paramagnetic susceptibility. Arrows under 𝝁

⃗ indicate the
orientation of the moment for the various levels.

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When a magnetic field is applied to the atom, a Zeeman splitting results whose Zeeman energy is
given by

⃗ . ⃗𝑩
𝐸=𝝁 ⃗ = 𝑔𝜇𝐵 𝐵𝑚𝑗 (7.29)
1
If the angular momentum quantum number 𝑗is 2, the component 𝑚𝑗 can take the values 𝑚𝑗 =
1 1
− 2 𝑜𝑟 + 2, resulting in a double splitting, as shown in Fig. 9. The difference in energy between

the levels is
∆𝐸 = 𝑔𝜇𝐵 𝐵 (7.30)
1
N.B.: The lower level,𝑚𝑗 = − 2 , corresponds to the momentparallel to the field, while the upper

level corresponds to the moment opposite to the field.

The magnetization 𝑀 is given by
𝑀 = 𝑔𝜇𝐵 (𝑁1 − 𝑁2 ) (7.31)
Where 𝑔𝜇𝐵 is the z-component of the moment when it is fully aligned with the field, and 𝑁1 , 𝑁2
are the concentrations of atoms in the lower and upper levels, respectively.These two
concentrations are related by
𝑁2
= 𝑒 −∆𝐸⁄𝑘𝑇 (6.32)
𝑁1

Where; the term in the exponent on the right is the familiar Boltzmann factor. Since these
concentrations also satisfy the relation 𝑁1 + 𝑁2 = 𝑁, where 𝑁 is thetotal concentration, we may
use these two equations to solve for 𝑁1 &𝑁2 N.When we do this, and substitute the results into
(6.31), we obtain
𝑒 𝑥 −𝑒 −𝑥
𝑀 = 𝑁𝑔𝜇𝐵 (𝑒 𝑥 +𝑒 −𝑥 ) = 𝑁𝑔𝜇𝐵 tanh 𝑥 (7.33)

Where 𝑥 = 𝑔𝜇𝐵 𝐵⁄𝑘𝑇.

46 | P a g e Handout on introduction to condensed matter of

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Tadese D.
 Bule Hora University, Dep’t of Physics

1
Figure 16: Magnetization 𝑀 versus 𝑥 = 𝑔𝜇𝐵 𝐵⁄𝑘𝑇for a system with 𝑗 = 2.

The magnetization is plotted versus the field in Fig. 10. At low field, 𝑀 is proportional to 𝐵, but
at higher fields 𝑀 begins to saturate, eventually reaching the maximum value 𝑁𝑔𝜇𝐵 when all the
dipoles are in exact alignment with the field. Qualitatively, this is the same conclusion reached
earlier on the basis of the classical treatment.
Let us take a closer look at the physical process of magnetization in the quantum treatment. For
1
𝑗 = 2, the dipole can take only two orientations, one parallel to

the field, corresponding to the lower level of Fig. 9, and the other opposite to
the field, corresponding to the upper level. As the magnetic field is raised, the
spacing between the levels increases and the dipoles drop from the higher to the
lower level, leading to magnetization
For a weak field, the ratio 𝑥 ≪ 1 and tanh 𝑥 ≅ 𝑥,which, when substituted in to
(7.33), leads to the susceptibility
𝜇𝑜 𝑁(𝑔𝜇𝐵 )2
𝜒= (7.34)
𝑘𝑇

This is the same as the classical result, provided we assume that the effective
moment of the atom is given by 𝜇𝑒𝑓𝑓 = √3 𝑔𝜇𝐵 .
Our quantum derivation was based on the simplest type of Zeeman splitting, i.e., one involving
1
only two levels. If 𝑗 were larger than 2, then, in general, the number of levels would be (2𝑗 +

𝑙), which leads to the susceptibility

47 | P a g e Handout on introduction to condensed matter of

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 Bule Hora University, Dep’t of Physics

𝜇𝑜 𝑁𝜇𝑒𝑓𝑓 2
𝜒= (7.35)
3𝑘𝑇

Where
𝜇𝑒𝑓𝑓 = 𝑝𝜇𝐵 and 𝑝 = 𝑔[𝑗(𝑗 + 1)]1⁄2 (7.36)
The number 𝑝 is called the effective number of Bohr magnetons for the atom.We can see,
therefore, that quantum-mechanical treatment leads to the same conclusions as classical
treatment.
7.7. The Domain Model
A magnetic domain is a region within a magnetic material in which the magnetization is in a uniform
direction. This means that the individual magnetic moments of the atoms are aligned with one another and
they point in the same direction. When cooled below a temperature called the Curie temperature, the
magnetization of a piece of ferromagnetic material spontaneously divides into many small regions called
magnetic domains. The magnetization within each domain points in a uniform direction, but the
magnetization of different domains may point in different directions. Magnetic domain structure is
responsible for the magnetic behavior of ferromagnetic materials like iron, nickel, cobalt and their alloys,
and ferrimagnetic materials like ferrite. This includes the formation of permanent magnets and the
attraction of ferromagnetic materials to a magnetic field. The regions separating magnetic domains are
called domain walls, where the magnetization rotates coherently from the direction in one domain to that
in the next domain. The study of magnetic domains is called micromagnetics. Magnetic domains form in
materials which have magnetic ordering; that is, their dipoles spontaneously align due to the exchange
interaction.
These are the ferromagnetic, ferrimagnetic and antiferromagnetic materials.
Paramagnetic and diamagnetic materials, in which the dipoles align in response to an external field but do
not spontaneously align, do not have magnetic domains.
DOMAIN THEORY
This theory was proposed by Weiss 1907. It explains the hysteresis and the properties of
ferromagnetic materials.
Magnetic Domains
A ferromagnetic material is divided into a large number of
small regions called domains.
Each domain is spontaneously magnetized.
48 | P a g e Handout on introduction to condensed matter of
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 Bule Hora University, Dep’t of Physics

The direction of magnetization various from domain to domain and the net magnetization is
zero, in the absence external mag. field.
The two domain separates by domain wall or Block wall.
When the magnetic field is applied to Ferromagnetic material, the
magnetizations are produced by two ways:
1. By the motion of Domain walls
The weak magnetic field is applied, the domains having dipoles parallel to theapplied
magnetic field increases in area by the motion of domain walls.
2. By the rotation of Domains
If strong magnetic field is applied, the domains are rotated parallel to the field direction

Energies involved in the domain growth

The total internal energy of the domain structure in a ferromagnetic material is
made up from the following contributions:
1. Exchange energy
2. Crystalline energy
3. Domain wall energy
4. Magnetostriction energy
1. Exchange energy is defined as, “ The interaction
energy whichmakes the adjacent dipoles align
themselves”

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 Bule Hora University, Dep’t of Physics

2. Anisotropy energy : In ferromagnetic materials there are two types of

directions of Magnetization namely,
a. Easy direction b. Hard direction
In easy direction of magnetization, weak field can be applied and in hard direction of
magnetization, strong field should be applied.
For example, in BCC iron the easy direction is [100], the medium direction is [110], and the hard
direction [111].The energy difference between hard and easy direction to magnetize the material
is about. This energy is very important in determining the characteristic domain boundaries.
3. Domain wall energy or Bloch wall energy
Based on the spin alignments, two types of Bloch walls may arise, namely
a. Thick wall :
When the spins at the boundary are misaligned
and if the direction of the spin changes gradually
as shown figure,

b. Thin wall: When the spins at the boundaries changes abruptly, as shown in fig. below

4. Magnetostriction energy
When a material is magnetized, it is found that it suffer a change in dimensions. This
phenomenon is known as Magnetostriction. The work done by the magnetic field against these
elastic restoring forces is called magnetoelastic energy or Magnetosrictive energy.

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The magnetization process and Hysteresis loop

A magnetic hysteresis, otherwise known as a hysteresis loop, is a representation of the
magnetizing force (H) versus the magnetic flux density (B) of a ferromagnetic material. A
Ferromagnetic sample is usually in the demagnetized state. In order to magnetize it, one applies
an external field. Figure below illustrates the progress of the magnetization process as the
external field increases. Starting at the origin, the magnetization M increases slowly at first, but
more rapidly as the field is increased, and eventually M saturates at the point, A.

Figure 17: Hysteresis loop in a ferromagnet

If the field is now reduced, the new curve does not retrace the original curve OA;
rather it follows the line, AD shown in the figure. Even when the field is reduced
to zero, some magnetization 𝑀𝑟 , known as remanent magnetization, still survives.
To destroy the magnetization completely, a negative field - −ℋ𝐶 is required,
which is called the coercive force. The sample clearly exhibits hysteresis, and if the

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field ℋ alternates periodically, the magnetization traces the solid curve in Fig.11,
which is the hysteresis loop.
Hysteresis implies the existence of energy losses in the system. These losses are
proportional to the area of the loop.

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