Unit III Quantum theory of solids

1 Basics of CFET, expressions for electrical parameters

Drude and Lorentz proposed the classical free electron theory of electrical conductivity of metals. The
model of conductivity of free electrons is based on the following assumptions:

(1) Atoms in a metal are considered to be made up of ion cores which are nuclei surrounded by inner
electrons excluding the valance electrons and the valance electrons which are free to move
anywhere inside the sample.

(2) The effect of positive ion cores on the electrons is considered to be constant and hence neglected.

(3) The electrostatic repulsion between the electrons is neglected.

(4) The electrons in the metal are considered equivalent to molecules in a gas and the gas laws are
made applicable to the electrons in a metal. Accordingly, the distribution of energy and velocity is
assumed to follow Maxwell-Boltzmann statistics.

The valence electrons in a metal are in a state of random motion in the array of ionic centers. The
average velocity of electrons in the metal is dependent on the temperature and is termed as the
3𝑘𝑇
thermal velocity of electrons 𝑣𝑡𝑕 = 𝑚
. However there is no net drift of electrons across the metal.

At 300K the thermal velocity of the electrons is ≈ 105 𝑚𝑠 −1 .

The motion of the electrons in the lattice is scattered by collisions and the mean time between
collisions is the relaxation time of the electrons in the metal. Taking the mean lattice parameter of
𝜆
10nm as the distance travelled between successive collisions 𝜆, the relaxation time 𝜏 = 𝑣𝑡𝑕
≈
10−15 𝑠.
Drift Velocity : In the presence of an Electric field E the electrons show a net drift across the metal in a
direction opposite to that of the electric field. The velocity of the electrons across the metal in the
presence is known as the drift velocity 𝑣𝑑 .
𝑑𝑣
The force equation for the electron’s motion can be described by 𝑚 𝑑𝑡 = 𝑒𝐸 − 𝒌𝑚𝑣 where the last
term accounts for the loss of energy due to the scattering which is proportional to the momentum of
the electrons and k is the coefficient of scattering loss.

In the equilibrium condition this leads to an average velocity for the electrons which is the drift
𝑒𝐸
velocity 𝑣𝑑 = 𝑘𝑚
Dimensionally k should be (T)-1.
1
The decay of the drift velocity to zero in the absence of the electric field yields that 𝒌 = where 𝜏 is
𝜏
the relaxation time – the time between successive collisions or the time for the drift velocity to fall to
1/e times its steady value in the presence of an electric field.

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Unit III Quantum theory of solids

𝑒𝜏𝐸 𝒆𝝉
The drift velocity 𝑣𝑑 = 𝑚
= 𝜇𝐸 where 𝝁 = 𝒎
is the electron mobility or the charge carrier
𝒆𝝉 𝒗𝒅
mobility. The mobility 𝝁 = 𝒎
= 𝑬
is the drift velocity per unit electric field.

The drift velocity of electrons is extremely low compared to the thermal velocity. To illustrate, the
drift velocity of electrons experiencing an electric field of 1V/m is of the order of 10-4 ms-1.

Expression for Electrical conductivity:

The current through a conductor with an electron concentration n of cross section A and length L at an
applied electric field E can be evaluated as
𝒆𝝉𝑬
𝑰 = 𝒏𝒆𝒗𝒅 𝑨 where 𝑣𝑑 is the drift velocity given by 𝒗𝒅 = 𝒎
𝒆𝝉𝑬
∴ 𝑰 = 𝒏𝒆𝑨
𝒎
𝑰 𝒏𝒆𝟐 𝝉
𝑱=
𝑨
=
𝒎
𝑬 = 𝝇 𝑬 where 𝝇 is a constant for a given metal and is the conductivity of the
𝒏𝒆𝟐 𝝉
metal 𝝇 = 𝒎 = 𝒏𝒆𝝁
𝟏 𝒎 𝟏
The resistivity of the metal is 𝝆 = = = .
𝝇 𝒏𝒆𝟐 𝝉 𝒏𝒆𝝁

The resistivity is inversely proportional to the concentration of free electrons and the relaxation time
of electrons in the metal.

2 Experimental temperature dependence of the resistivity

Experiments show that resistivity of metals in general vary linearly with temperature in the normal
operating temperatures. At these temperatures the resistivity results from the scattering of the electrons
moving with high velocities in random directions. This is also known as the phonon resistivity ( phonon is a
quantum particle equivalent for vibrations in materials).

However at very low temperatures the resistivity is found to saturate to a non zero finite value, which is
dependent on the impurity concentration in the metal.

Hence two independent types of resistivities determine the total resistivity of the metal. Since the
phenomena are independent of each other the net resistivity would be the sum of the two resistivity
components which is known as the Mattheissen’s rule .

𝝆 = 𝝆𝒓𝒆𝒔 + 𝝆𝒔𝒄
𝒎 𝒎 𝒎 𝟏 𝟏 𝟏
Hence = 𝒏𝒆𝟐 𝝉 + 𝒏𝒆𝟐 𝝉 . This gives us the effective relaxation time as =𝝉 +𝝉
𝒏𝒆𝟐 𝝉 𝒓𝒆𝒔 𝒔𝒄 𝝉 𝒓𝒆𝒔 𝒔𝒄

3 Draw backs of CFET and quantum corrections.

The classical free electron theory failed to correlate the experimental results of many a phenomena such
as the temperature dependence of resistivity, specific heat of electrons etc.

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𝑚
 According to the classical free electron theory the resistivity of a metal is given by 𝜌 = 𝑛𝑒 2 𝜏 . For a
given material the temperature dependence of resistivity arises from the temperature dependence of
𝜆
the relaxation time 𝜏 = 𝑣 . Since the mean free path of the electrons is assumed to be a constant,
𝑡𝑕
the temperature dependence of the thermal velocity should affect the relaxation time. For a given
3𝑘 𝐵 𝑇 1
temperature 𝑣𝑡𝑕 = and hence 𝑣𝑡𝑕 ∞ 𝑇 𝑜𝑟 𝜏 ∞ 𝑇 −2 . Since the resistivity 𝜌 ∞ 𝜏 −1 , the
𝑚

temperature dependence should be given by 𝜌 ∞ 𝑇. But the experimental observations show that
𝜌 ∞ 𝑇 and hence the classical free electron theory fails to explain the correct temperature
dependence of resistivity of metals.
𝑛𝑒2 𝜏
 The electrical conductivity of metals, given by 𝜍 = , should be dependent on the free electron
𝑚
concentration for a given temperature, assuming that the relaxation time is more or less constant.
However, it found that mono valent Copper with lesser electronic concentration has a higher
electrical conductivity as compared to trivalent Aluminum. Similarly Zinc with higher electronic
concentration has lesser conductivity than Aluminum. Experimental results show that there is no
linear dependence of the electronic concentration on the conductivity of metals.
 The contribution of electrons to the specific heat of the metal can be estimated using the principle
𝑑𝑈
that the specific heat 𝐶𝑒𝑙 = .
𝑑𝑇
3
Considering one mole of a mono valent material the energy of the electrons = 2 𝑘𝐵 𝑇. 𝑁𝑎𝑣𝑔
𝑑𝑈 3 3
Hence the specific heat of the electrons should be equal to 𝐶𝑒𝑙 = 𝑑𝑇
= 2 𝑘𝐵 . 𝑁𝑎𝑣𝑔 = 2
𝑅.
However the experimental estimation of the specific heat of electrons is only approximately 1% of
the theoretical value and is also found to be temperature dependent.
Thus the classical free electron theory fails to explain the experimental observations. It is obvious that
some of the assumptions of the CFET are over / underestimations of the physical parameters and hence
need to be corrected.

4 Quantum model of valence electrons in a metal - Fermi energy

Metals have a very high concentration of valence electrons ≅ 1028 𝑚−3 . According to the quantum
mechanical concepts valence electrons in a metal have to be in discrete energy states following Pauli’s
exclusion principle. This requires the energy states of the atomic levels to split into discrete closely spaced
energy states to accommodate all the valence electrons. At 0K such an arrangement leads to a sea of
energy levels which have a separation as small as ≅ 10−20 𝑒𝑉. The upper most occupied energy state at
0K is then termed as the Fermi energy of the metal.
The conduction electrons in a metal move in array of positive ions, colliding with the ionic centers and
other electrons resulting in the resistance of the material.
The electrostatic interactions namely, the electron – electron interaction and the electron – ion
interactions are negligible.
The electrons undergo random scattering due to the vibrating ionic centers giving rise to resistance to flow
of electrons.

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Unit III Quantum theory of solids

5 Fermi Dirac statistics, Fermi factor

1
All particles with spin ± 2 are classified as Fermions. Fermions follow the Fermi Dirac statistics for particles
which are indistinguishable.
1
The Fermi factor 𝐹𝑑 = 𝐸−𝐸 𝑓 gives the probability of an energy state E to be occupied at a
𝑘𝐵 𝑇
𝑒 +1

temperature T
Estimation of the Fermi factor at T=0K gives distinct results for E<Ef and E >Ef.
1
 If E<Ef then for E-Ef is negative, then the Fermi factor 𝐹𝑑 = ∆𝐸 .
−
𝑒 𝑘𝐵 𝑇 +1

1
At 0K this becomes 𝐹𝑑 = = 1. This implies that at 0K all electron states below the
𝑒 − ∞ +1
Fermi level are filled states.
 If E>Ef then for E-Ef is positive, then the
1
Fermi factor 𝐹𝑑 = ∆𝐸 .
𝑒 𝑘𝐵 𝑇 +1

1
At 0K this becomes 𝐹𝑑 = = 0.
𝑒 ∞ +1
This implies that at 0K all electron states
above the Fermi level are empty states.
 For T>0 and E=Ef the Fermi factor
1 1 1
𝐹𝑑 = 𝐸−𝐸 𝑓 = 𝑒 0 +1
= 2 = 0.5 . This
𝑘𝐵 𝑇
𝑒 +1

gives a probability of occupation of 50% for

the Fermi energy.
The Fermi energy of is weakly temperature dependent and is given by
2
𝜋 2 𝑘𝐵 𝑇
𝐸𝑓 = 𝐸𝑓0 1−
12 𝐸𝑓0
𝑘𝐵 𝑇
where Efo is the Fermi energy at zero Kelvin. At normal temperature ranges the ratio of 𝐸𝑓0
is very
low and hence can be approximated to be a constant equal to the value at zero Kelvin.

6 Fermi temperature
The arrangement of electrons in discrete energy states leads to the concept that only electrons near
the Fermi energy are excited into the conduction band and it may be really difficult to excite all the
valence electrons into the conduction band. If the temperature of the metal is T then kBT is the
thermal energy available to the electrons in the metal. The thermal energy required to excite the last
electron at the bottom of the energy band if termed as kBTf, then at temperature Tf the electron would

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Unit III Quantum theory of solids

have an energy 𝐸𝑓 = 𝑘𝐵 𝑇𝑓 . This temperature is termed as the Fermi temperature of electrons in the
metal.
Evaluating the temperature for Copper with Fermi energy as 7 eV gives the value of the Fermi
temperature as approximately 81000K. It is obvious that at such high temperatures the metal cannot
be in the solid state and hence this is only a representative temperature which highlights the point
that all valence electrons cannot be conduction electrons.

7 Fermi velocity
From the above analysis it is clear that only a small fraction of electrons close to the conduction band
can be taking part in the conduction processes. The electrons excited into the conduction band have
energies very close to the Fermi energy. These conduction electrons then possess a kinetic energy
which may be equal to the Fermi energy.
1
The kinetic energy of the electrons near the Fermi energy is 𝐸𝑓 = 2
𝑚𝑣𝑓 2 where 𝑣𝑓 the Fermi velocity
of conduction electrons is. Fermi velocity for conduction electrons in Copper gives 𝑣𝑓 =
1.06 𝑥 106 𝑚𝑠 −1 .
This velocity is greater than the thermal velocity of electrons (as per the CFET). The electrons in the
conduction band are in a state of random motion and the scattering of the electrons by the lattice is
the origin of the electrical resistance of the metal.

8 Density of states derivation

The electrons in a metal can be approximated to the
particle in a box in three dimensions, since under normal
conditions the electrons cannot escape the boundaries of
the metal. Consider a mono valent metal in the form of a
cube of side L. Inside the metal the electrons can be
assumed to be moving in a zero potential field.
The three dimensional Schrödinger’s wave equation can be
written as three one dimensional Schrödinger’s wave
equation and their corresponding solutions analysed.
ℏ2 𝑑 2 𝜓 𝑥 .
2𝑚 𝑑𝑥 2
+ 𝐸𝜓 𝑥 = 0 which gives the Eigen energy value for the x component as

𝑕2 𝑛𝑥 2
𝐸𝑛 𝑥 =
8𝑚𝐿2
𝑕 2𝑛𝑦 2 𝑕 2𝑛𝑧 2
Similarly the energy in the other two dimensions can be evaluated as 𝐸𝑛 𝑦 = 8𝑚 𝐿2
𝑎𝑛𝑑 𝐸𝑛 𝑧 = 8𝑚 𝐿2

The total energy of the electron is given by

𝑕2 𝑕2
𝐸𝑛 = 𝑛𝑥 2 + 𝑛𝑦 2 + 𝑛 𝑧 2 = 𝑅2 --------- (1) where 𝑅 2 = 𝑛𝑥 2 + 𝑛𝑦 2 + 𝑛𝑧 2
8𝑚 𝐿2 8𝑚 𝐿2

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Unit III Quantum theory of solids

The number of states with energy E can be evaluated by studying the variation of the combinations of nx,
ny and nz. It can be deduced that every combination of nx, ny and nz result in an energy state as per
equation (1). When nx, ny and nz. are equal the energy state is unique and is non degenerate. It is also
noted that the energy states can be degenerate with degeneracy of 3 when two of the three nx, ny and nz
are equal and degeneracy of 6 when all the three are not equal. This can be evaluated analyzing the n
space formed by nx, ny and nz. It is also realized that every combination of nx, ny and nz gives additional
unit volume in n space from which we conclude that evaluating the number of states is equivalent to
evaluating the volume of the n space. It is also noticed that the degenerate energy states with the same
energy values lie on the surface of an octant of a sphere with the center at the origin. Hence it is sufficient
to find the volume of the octant of a sphere of radius R to evaluate the number of energy states up to R
i.e., the combination of nx, ny and nz.
The sensitivity of the increase in the states with increasing nx, ny and nz can be found from the change in
the volume of the octant if the radius changes from R to R+dR realizing that R >>dR.
𝜋𝑅 2 𝑑𝑅
The volume of the shell of thickness dR is then given by 2
𝐸𝑛 𝑑𝐸
𝐸𝑛 = 𝐸𝑜 𝑅 2 gives us 𝑅 2 = and 𝑑𝑅 = 1
𝐸𝑜 2 𝐸𝑛 𝐸𝑜 2

1
𝜋𝑅 2 𝑑𝑅 𝜋 𝐸𝑛 𝑑𝐸 𝜋 𝐸𝑛 2
The number of energy states between E and E+dE is given by 2
= 4 𝐸𝑜 𝐸𝑛 𝐸𝑜 1 2
= .
4 𝐸𝑜 3 2
𝑑𝐸

𝑕2
Substituting for 𝐸𝑜 = 8𝑚 𝐿2 we get the number of energy states between E and E+dE as
3
𝜋 8𝑚𝐿2 2
1
. 𝐸 2 . 𝑑𝐸
4 𝑕2
Taking into consideration the Pauli’s exclusion principle, two electrons can be accommodated in one
energy state, the number of electrons states per unit volume can be estimated and is called as the density
of states.
The density of states for electrons in a metal gives the number of electron states per unit volume with
energy E
3
𝜋 8𝑚 2 1
𝑔 𝐸 𝑑𝐸 = 2 𝑕2
𝐸2 𝑑𝐸

This shows that the distribution of electrons in energy states vary non-
linearly with increasing energy E.
The probability that an energy state is occupied is given by the fermi
factor
1
𝐹𝑑 = 𝐸−𝐸𝑓
1+𝑒 𝑘𝐵 𝑇

And hence the occupancy of the states described by N(E) is determined by the factor
𝑁 𝐸 = 𝑔 𝐸 ∗ 𝐹𝑑

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The states below Ef – kBT are completely occupied as Fd is 1. The states in the range of kBT below the Fermi
level are emptied and the probability of occupancy Fd is between 1 and 0.5. The states above Ef in a range
kBT are now occupied and the probability of occupancy lies between 0.50 and 0.00.

9 Expression for Fermi energy, average electron energy

The Fermi energy of metals can be evaluated from the fact that all available electrons occupy energy levels
below the Fermi level Ef. This means that the density of occupied states 𝑁 𝐸 = 𝑔 𝐸 ∗ 𝐹𝑑 when
evaluated for all levels from 0 to Ef, should result in the total count of electrons in the metal, ie.,
𝐸𝑓 𝐸𝑓
The total free electronic concentration 𝑛 = 0
𝑁 𝐸 𝑑𝐸 = 0
𝑔 𝐸 ∗ 𝐹𝑑 𝑑𝐸 .

We know that Fd has to be 1 for all energy levels below Ef at 0K and hence
3 3
𝐸𝑓 𝐸𝑓 𝜋 8𝑚 2 𝐸𝑓 1
𝜋 8𝑚 2 3
2
𝑛= 0
𝑁 𝐸 𝑑𝐸 = 0
𝑔 𝐸 𝑑𝐸 = 2 𝑕2 0
𝐸 𝑑𝐸 =
2
3 𝑕2
𝐸𝑓

This relation helps to relate the Fermi energy and the concentration of free electrons. Thus if the
concentration of free electrons is known, the Fermi energy of the system at 0K can be evaluated as
2
3 3 𝑕2 2
𝐸𝑓 = 𝑛 3
𝜋 8𝑚

10 Average energy of electrons in a metal at 0K

Since the distribution of electrons in the different energy states shows a non linear variation, the average
energy of the electron is not the simple average of the electron’s max and min energy. From the graph of
N(E) vs E we observe that N(E) states have energy E which implies that the total energy of all electrons in
filled states upto Ef should the summation of all N(E)*E

total energy of all electrons in different energy states

The average energy of the electron = total number of electrons
3
𝜋 8𝑚 2 𝐸𝑓 1
𝐸𝑓
𝑔 𝐸 ∗ 𝐸 ∗ 𝐹𝑑 𝑑𝐸 𝐸2 𝑑𝐸 ∗ 𝐸
0 2 𝑕2 0
𝐸𝑓 = 3
0
𝑔 𝐸 ∗ 𝐹𝑑 𝑑𝐸 𝜋 8𝑚 2 𝐸𝑓 1
𝐸2 𝑑𝐸
2 𝑕2 0

3
This on integration gives the average energy 𝐸 = 𝐸𝑓 = 0.6 ∗ 𝐸𝑓
5

11 Merits of Quantum free electron theory:

a) Heat capacity due to free electrons
The electronic specific heat (contribution to the specific heat from the conduction electrons) can be
evaluated in the light of the fact that only electrons close to the Fermi level participate in the
conduction. Hence the heat absorption happens due to that fraction of electrons. This number can

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Unit III Quantum theory of solids

be estimated as the effective number of electrons (in one mole of the metal for a mono valent metal)
𝑁𝑎
in the conduction process as 𝑛𝑒𝑓𝑓 = 𝐸𝑓
. 𝑘𝐵 𝑇.

3
Hence if the average thermal energy of the electrons is taken to be 2 𝑘𝐵 𝑇 then the total energy of
3 3 𝑁𝑎 3 𝑁𝑎
electrons in one mole of the material 𝑈 = 𝑛𝑒𝑓𝑓 . 𝑘 𝑇
2 𝐵
= 2 𝑘𝐵 𝑇 𝐸𝑓
. 𝑘𝐵 𝑇 = .
2 𝐸𝑓
. 𝑘𝐵 2 𝑇 2

𝑑𝑈 𝑁 𝑘𝑇
Hence the specific heat 𝐶𝑒𝑙 = 𝑑𝑇
= 3. 𝐸𝑎 . 𝑘𝐵 2 𝑇 = 3𝑅. 𝐸 .
𝑓 𝑓

Thus the electronic specific heat is temperature nx, ny and nz dependent and is a fraction of the value
predicted by the CFET. This analysis gives the correct correlation with the experimental results.
A more accurate evaluation of the electronic specific heat of mono valent metals results in the relation
𝝅𝟐 𝑘 𝟐𝑻
𝑪𝒆𝒍 = 𝑵∗ 𝐵
𝟐 𝑬𝒇

b) Temperature dependence of the resistivity

According to the classical free electron theory resistivity of the electrons originates from the scattering
mechanism in which the ionic centers are stationary.
The quantum free electron theory takes into account the thermal vibrations of the ionic array which
accounts for the scattering of electrons. The amplitude of the random vibrations of the lattice ions
increase with increasing temperature and hence increase the probability of electron scattering. This
reduces the mean free path of the electrons.

When the ions vibrate the lattice presents an effective cross sectional area for scattering of 𝒓𝟐 where
r is the amplitude of vibration. The electron mean free path λ is inversely proportional to the
scattering cross section and hence 𝜆 ∞ 1/𝑇
𝒏𝒆𝟐 𝝉 𝒏𝒆𝟐 𝝀
The expression for conductivity 𝝇 = = shows that the conductivity is proportional to the
𝒎 𝒎𝒗𝒇
mean free path. Hence the conductivity will be inversely proportional to temperature or resistivity
𝜌 ∞ 𝑇 as is found experimentally.
c) Relation between electrical conductivity and thermal conductivity (Wiedemann-Franz law
and Lorenz number)
From the discussions of the electronic arrangement it is obvious that the electrons close to the Fermi
energy are responsible for the electrical or thermal conduction and hence it should be possible to find
a relation between the two.
𝟏 𝑪
It is known that the thermal conductivity of the metal 𝑲 = . . 𝒗. 𝑳
𝟑 𝑽

𝝅𝟐 𝒌𝑩 𝟐 𝑻
Where C is the electronic specific heat given by 𝑪𝒆𝒍 = 𝟐
𝑵. 𝑬𝒇
,

V the volume, v is the velocity of electrons and L the mean free path. The mean free path of electrons
is given by 𝐿 = 𝑣. 𝜏. Taking velocity to be the Fermi velocity 𝑣𝐹 (since most of the conduction

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Unit III Quantum theory of solids

electrons are located about the Fermi energy) the expression for the thermal conductivity can be
written as
𝟏 𝟏 𝝅𝟐 𝒌𝑩 𝟐 𝑻 𝝅𝟐 𝒌𝑩 𝟐 𝑻
𝑲= . .
𝟑 𝑽 𝟐
𝑵. 𝑬𝒇
. 𝒗𝑭 . 𝒗𝑭 𝝉 = 𝟔
. 𝒏. 𝑬𝒇
. 𝒗𝟐𝑭 . 𝝉.

𝑵
where 𝒏 = 𝑽
is the concentration of free electrons.

𝝅𝟐 𝒌𝑩 𝟐 𝑻 𝒎𝒗𝟐𝑭 𝝅𝟐 𝒌𝑩 𝟐 𝑻
𝑲= . 𝒏. . .𝝉 = . 𝒏. .𝝉
𝟑 𝑬𝒇 𝟐𝒎 𝟑 𝑬𝒇
𝒏𝒆𝟐 𝝉
The electrical conductivity of the metal is then given by 𝝇 = 𝒎

The ratio of the thermal conductivity to electrical conductivity can be calculated as

𝑲 𝝅𝟐
= 𝟐 𝒌𝑩 𝟐 𝑻.
𝝇 𝟑𝒆
𝑲 𝝅𝟐
This is the Wiedemann-Franz law. It was noticed by Lorenz that the ratio 𝝇𝑻 = 𝟑𝒆𝟐 𝒌𝑩 𝟐 is a constant
irrespective of the metal and is called the Lorenz number.
The Lorenz number has a value = 2.4 x10-8 WΩK-2.
12 Demerits of quantum free electron theory
The quantum free electron theory though successful in giving correct dependencies of some of the
electrical parameters and the specific heat of electrons, was not able to explain
 Differences in conduction in metal, semiconductor and insulator. The origin of the band gap in
semiconductors and insulators are not explained.
 Experimentally observed positive Hall co-efficient observed in some metals like Zinc.
These demerits could be reflective of the real potentials of the ionic centers in the metal which was
ignored in the development of the model. The presence of the potentials can significantly affect the wave
function of the electrons.

13 Motion of electron in periodic potential (one

dimensional treatment)
The free electrons in a metal are not free from electrostatic
potentials and move in a periodic potential due to the
regular arrangement of the ionic centers.
The potential is lower close to the positive ions in the lattice
(and in some cases basis) positions. The electrons
experience a potential with the same periodicity as the
lattice. The columbic potential in the real crystal can be
approximated by rectangular potentials.
If V(x) is the potential at x then, it can be seen from the

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Unit III Quantum theory of solids

figure that
V(x + a) = V(x) which means that the potential is periodic and invariant under the translation through
the lattice parameter.
However the wave function of the electrons
𝝍 𝒙 = 𝒆𝒊𝒌𝒙 is affected by the periodic potential and can be written as
𝝍 𝒙 = 𝒆𝒊𝒌𝒙 . 𝑽𝒌 (𝒙) where k is the wave number of the electron waves. This is known as the Bloch
function.

14 Kronig Penny model, allowed energy zones/energy bands

In the Kronig-Penney model the periodic potential is
approximated as a long chain of coupled finite square wells,
of barrier height V0, with a period ‘a’, and barrier thickness
c.

The wave function of the electron is a modulated wave of

the form 𝝍 𝒙 = 𝒆𝒊𝒌𝒙 . 𝑽𝒌 (𝒙) .

A solution to the Schrödinger’s equation exists if the

dispersive wave number of the electron k is related to the
energy through the equation
𝒎𝒂 𝑺𝒊𝒏(𝑲𝒂)
𝑪𝒐𝒔 𝒌𝒂 = 𝑽 . 𝒄. 𝑲𝒂 +
ℏ𝟐 𝒐
𝐜𝐨𝐬(𝑲𝒂)

𝟐𝒎(𝑽𝒐 −𝑬) 𝟐𝒎𝑽𝒐 )

where 𝑲 = ℏ𝟐
= 𝝁𝟐 − 𝒌𝟐 𝑤𝑕𝑒𝑟𝑒 𝜇 = ℏ𝟐
.
We notice that the above is a transcendental equation and
has approximate solutions.

The left hand side of the equation is bound with upper and
lower limits of +1 to -1. The right side of the equation has
oscillations of decreasing amplitude with increasing 𝜶𝒂.
However, the solutions exist only for those allowed range
𝝅
of 𝒌 = 𝒏 𝒂. Thus there exists a range of allowed energy
states and forbidden energy states.
The E(k) –k diagram for the system show discontinuity in the
𝝅
energy at the zone boundary of 𝒌 = ±𝒏 𝒂. (The parabolic
variation of E for the free electrons is shown for
comparison).
Since the functions are symmetric (and periodic with period
𝝅
of 𝟐 ), it is possible to represent the energy band diagram
𝒂
𝛑 𝛑
in a single zone of + 𝐚 𝐭𝐨 − 𝐚 . The lowest band (shaded) is
the completely filled inner band followed by a band of
forbidden energy states. The next band of allowed states
represents the valence band. The conduction band is above

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Unit III Quantum theory of solids

energy band gap.

Materials are then classified as metals, semiconductors or insulators on the basis of the Fermi energy of
the material.
In the case of conductors the Fermi level is in the uppermost band the conduction band. All states below
the Fermi level are filled and all levels above the Fermi energy are empty. Thus metal are characterized by
a partially filled conduction band.
In the case of materials with a completely filled valence band and completely empty conduction band, the
Fermi energy is theoretically the midpoint of the energy band gaps. Materials with energy gap of 3-5 eV
are classified as semiconductors. Materials with energy band gap greater than 5eV At normal
temperatures it is possible for the electrons in the valence band to move into the conduction in the case
of metals and semiconductors.

Concept of Effective mass

The moment of the electrons in the crystal is governed by the energy equation
ℏ𝟐 𝒌𝟐
𝑬= which shows that the energy is nonlinearly dependent on the
𝟐𝒎
propagation constant k.
Differentiating the expression twice with respect to k
𝒅𝟐 𝑬 ℏ𝟐
=
𝒅𝒌𝟐 𝒎∗
−𝟏
𝟏 𝒅𝟐 𝑬
it is observed that 𝒎∗ = 𝟐 𝟐 is not a constant and depends on the non
ℏ 𝒅𝒌
linearity of E. This means that the charge carriers have an effective mass which
𝒅𝟐 𝑬
depends on the curvature of E-k. Higher curvature ( larger 𝟐 ) means smaller
𝒅𝒌
effective mass and smaller curvature results in higher effective mass.
It can be seen that the slope of the E-K curve is minimum at the band edges and
hence the effective mass of the charge carriers are highest at the band edges.
Since curvature of the E-k is positive in the conduction band the effective mass is
+ve and the curvature in the valence band is negative indicating a negative mass. However, this can be
construed to be the motion of a charge carrier with a charge of the opposite type as that of electrons. This
leads to the concept of hole conduction in the valence band. The effective mass of can be higher or lower
than the rest mass of the electrons and depends on the position of the electron in the particular band.

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Unit III Quantum theory of solids

Problem set

1. A certain conductor has a free electron concentration of 5.9 x 10 28 m-3. What current density in the
conductor will correspond to a drift velocity of 1/1.6 mm s-1? Calculate the mobility of charge
carriers given conductivity as 6.22x107 (Ωm)-1. (Ans :
2. Calculate the free electron concentration, mobility and drift velocity of electrons in an Al wire of
diameter 0.5mm, length 5m, resistance of 60 milli ohms that carries a current of 15A . Al has 3 free
electrons At wt of Al=26.98 and density 2.7 x 103 kg m-3.
3. Find the relaxation time and mobility of conduction electrons in a metal having 6.5 x 1028 electrons
m-3 if the resistivity of the metal is 1.43x 10-8 ohm m
4. There are 1020 electrons per m-3 in a material having a resistivity of 0.1 ohm -m. Find the charge
mobility and the electric field needed to produce a drift velocity of 1ms-1.
5. A copper wire of radius 1mm and length 10 meter carries a direct current of 5 ampere. Calculate the
drift velocity of electrons in copper if n = 5 × 1028/m3.
6. Silver has a density of 10.5 x 103 Kgm-3 and atomic weight of 107.9. If conductivity of silver at 27o C is
6.8 x 107 (ohm-m)-1, find the mean free path of electrons as per the classical free electron theory.
7. Calculate the relaxation time of conduction electrons in a metal of resistivity of 1.55 x 10-8 Ω – m and
an electronic concentration of 6 x 1028 per m3.
8. Show that the probability of occupancy of an energy level ΔE above the Fermi level is the same as
that of the probability of non-occupancy of an energy level ΔE below the Fermi level.
9. Estimate the probability of occupancy of an energy level 0.1 eV above the Fermi level for Copper
with Ef= 7.0eV for i) 100K ii) 300K iii) 1000K
10. Find the temperatures at which the occupancy of an energy state 0.3 eV above the Fermi level has
an occupancy probability of i) 0.01 and ii) 0.05
11. Calculate the Fermi energy of electrons in a mono valent metal with atomic weight 132.9 x 10-3 kg /
mol and density of 1.9 x 103 kg/m3 at 0K.
12. Estimate the energy for which the probability of occupation at 300K is 0.1 for copper with Fermi
energy of 7.0eV. Comment on the probability of this level to be 0.5.
13. The Fermi temperature of two metals A and B are in the ratio 1.103. If the electron concentration of
metal A is 5.86x1028 m-3, find the Fermi velocity of electrons in metal B. (Ans: 1.325 x 106 ms-1.)

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