UNIT 9 FREE ELECTRON THEORY OF

METALS
Structure
9.1 Introduction
Objectives
9.2 Drude - Lorentz Theory
Electrical Conductivity
Thermal Properties
9.3 Sommerfeld Model
Fermi Energy and Fermi Surface
Temperature Dependence of Electrical and Thermal Properties
9.4 Summary
9.5 Terminal Questions
9.6 Solutions and Answers

9.1 INTRODUCTION
In Blocks 1 and 2, you have learnt about crystal structure and crystal binding. These
helped you to understand the elastic properties of solids. You have studied that elastic
and to some extent, thermal properties of solids can be understood in terms of
vibrations of atoms about their respective equilibrium positions. However, many
physical properties of solids can be explained only when sub-atomic details such as
motion of electrons are taken into consideration. In this unit, you will learn one such
microscopic theory: free electron theory of metals which successfully explains some
of their electrical and therinal properties.
Metals are perhaps the most versatile materials from the point of view of utility. We
all know that due to hardness and rigidity, metals are ideal materials for making
machines, industrial equipment, household goods, automobiles, ships etc. Similarly,
iron is an essential ingredient of modem structures such as ceilings, flyovers and
pillars, because of its strength and stability. Further, metals like copper and aluminium
are used in power transmission and distribution and so on. In view of their so many
and so varied uses, it is important to understand their physical properties.
In your school physics course, you learnt that electrons are responsible for electrical
conduction in metals. This means that to understand the electrical properties, we have
to investigate the behaviour of electrons. Efforts made to this effect led to free
electron theory of metals. In (classical) free electron theory, proposed by Drude and
later developed by Lorentz, it is assumed that valence electrons in a metal are
analogous to a gas in a box. Using the method of kinetic theory of gases and Maxwell-
Boltzmann distribution law, Drude and Lorentz explained the phenomenon of
electrical conduction. You will study Drude-Lorentz theory in Sec.9.2. This theory,
however, could not satisfactorily explain experimental observations on temperature
dependence of resistivity and heat capacity. These limitations of the classical theory
were overcome to a large extent by Sommerfeld who argued that free electrons in a
metal behave as quantum mechanical particles. You will learn the details of
Sommerfeld's model and related concepts in Sec. 9.3.
Unfortunately, even Sommerfeld's model had limited success. In particular, it did not
provide a logical theoretical basis to distinguish metals from insulators and
semiconductors. To overcome this, it was proposed that free electrons in a metal are
not completely free; as such they move under the influence of a periodic potential
which arises due to ions situated at lattice points. This led to what is known as the
hand thcon qf solidc.. You will learn it in the next unit.
I Electronic Properties Objectives

I After studying this unit, you should be able to:

state basic assumptions of Drude-Lorentz theory of metals;

explain the concept of relaxation time and its role in electrical conduction;
state the limitations of Drude-Lorentz theory;
describe-Sommerfeld free electron model;
explain the concepts of Fermi level, Fermi energy and Fermi surface;
predict the nature of electrical conduction and temperature dependence of
resistivity on the basis of Sommerfeld model;
derive expressions for heat capacity and thermal conductivity of metals and
explain electronic contribution to them; and
solve numerical problems based on these concepts.

9.2 DRUDE - LORENTZ THEORY

\
We all know that metals are good conductors of electricity. When a potential
difference is applied across a metallic wire, electric current begins to flow. Since
electric current is the directed motion of electrons, it is only logical to think that
metals possesspee electrons which are responsible for electrical conduction. You
may ask: Where fromfree electrons come? Let us learn about it now.

Free Electrons in Metals

To understand the origin of free electrons in metals, let us consider the particular case
of sodium (Na) metal. In a sodium atom, 11 electrons revolve around the nucleus in
various orbits: 1 ~ ~ , 2 ~ ~ , 2This
p ~is, shown
3 ~ ~ in
. Fig.9.la. The electron in the
outermost orbit (3s) is responsible for most of the chemical properties of sodium and
0

is called the valence electron. The radius of the outermost orbit is nearly 1.9 A . The
other 10 electrons in two inner orbits are relatively tightly bound to the nucleus.

Fig.9.1: a) An isolated sodium atom; and b) sodium atoms arranged in a crystal lattice forming
sodium metal

When a large number ofNa atoms are brought closer, inter-atomic forces come into
play. As a result, Na atoms arrange themselves along a cubic lattice. Each Na atom is
located at a lattice point and is separated from its nearest neighbours by a fixed
distance (Fig.9.1b). The equilibrium separation between two neighbouring atoms in
Na metal is 3.7 A . The inter-atomic separation is less than the sum of radii of two
nearest Na atoms. This is possible only when their outermost orbits begin to overlap.
Due to this overlap, valence electron of one atom can move to the orbit of the nearby
atom and is shared by both the atoms at the same time. If this argument is extended
further, we may say that valence electrons of Na atoms belong to the entire specimen
of metallic sodium. So we may say that valence electrons constitute free electrons
 I

and they can participate in electrical conduction. These are, thef'efore, also called Free Electron Theory of
Metals
conduction electrons. The genesis
- of free electrons in monovalent sodium metal holds
true for all metals.
Drude proposed that the physical properties of metals can be understood in terms of
the free electron model. According to this model, a metal consists of positive ions and The genius of Drude lies in
valence electrons which constitute a free electron gas. The free electrons move all the fact that the numerical
values of the radii of atomic
around the volume of the metal. On the basis of this argument, Drude attempted to orbits and interatomic
explain the macroscopic properties like electrical conduction and heat capacity of separation as well as the
metals in terms of the microscopic parameters such as charge, mass, and momentum concept of overlapping orbits
of free electrons. Lorentz contributed significantly to the development of Drude's were not known to him when
he proposed the free electron
model by applying the laws of statistical mechanics (Maxwell-Boltzamann model.
distribution). Therefore, the microscopic theory developed on the basis of Drude
model is called the Drude-Lorentz theory.
For mathematical ease, following simplifying assumptions about metals are made in
Drude - Lorentz theory:
1. Valence electrons behave as free electrons and can move all around the volume of
the metal.
2. Positively charged ions located at the lattice sites offer a uniform potential and do
, not influence the motion of free electrons. That is, interaction between the
positively charged ions and free electrons can be ignored.
3. The interaction between free electrons themselves is too small and can be ignored;
therefore, the free electrons move randomely inside the metal specimen without
any change in their energy, except for the occasional collisions with the ions.
4. Free electrons behave as molecules of an ideal gas and obey kinetic theory of
gases and the Maxwell-Boltzmann (M-B) distribution law.
-

a
\ @ l a/
a
a.'
\
.,ai
-
aL a / -
/
L.
.
on

(a) ~lectron
(b) -

Fig.9.2: a) Metal specimen consisting of fixed ions (shown by bigger dots) and free electrons; and
b) metal specimen as a gas of free electrons

You may now like to know: How to visualise the physical model of metal on the basis
of Drude model? A metal specimen may be considered analogous to a three-
dimensiolial (3-D) box containing the ions fixed at the lattice sites and the gas of free
electrons. Its two-dimensional (2-D) representation is shown in Fig.9.2a. The fixed
ions do not affect the motion of free electrons (Assumption 2). Thus, for analytical
purposes, a metal specimen is equivalent to an empty box containing a gas of free
electrons (Fig.9.2b).
You will now learn how this model helped in developing an understanding of
electrical conductivity.

9.2.1 Electrical Conductivity

You know that electrical conduction is the flow of electric current in a solid specimen
when a potential difference is maintained across its two ends. The relation between
current I and potential difference V is governed by Ohm's law:

7
Electronic Properties
We can express Ohm's law in
terms of parameters
independent of physical
dimensions of the specimen by
replacing I with current
density J and potential
difference V by electric field &.
Current density is defined as
electric current flowing-
through unit cross-sectional
area, i.e., J = IlA where A is
the area of cross-section of the
specimen.
' *
I I
~.
v words, we wish to know how Drude-Lorentz theory provides physical basis of Ohm's
Fig.9.3: An electric field E
applied to a metal
specimen of length L
and cross-sectional
area A
Also, we may write the
potential difference V as
V = E L = Electric field
strength x Length of
the specimen
On substituting for l a n d Vin
the relation v = IR and
rearranging terns we obtain,
J=E(LIA)(lIR)
If we define a parameter,
called resistivity, as
p = R (AIL)
we can write
J=E/~=UE
where a (= Up) is called the
electrical conductivity.
Current density, J is defined as
J = IIA and, current is defined
as I = dqldt where dq is the
amount of charge passing
unit
area. The amount of charge
(electron) passing through the
cross-sectiona~area A in time dt
is
-nevdAdj
where, n is the number of
electrons per unit volume and
vd is the drift velocity of the
electrons. Thus
J=-.dq 1
dt A
In vector form, we can write
v=IR (9.1)
where R is electrical resistance offered by the material.
Note that Ohm's law is an empirical law; that is, it is a generalisation based on
experimental results. You may also note that Ohm's law as expressed by Eq. (9.1) is
easier to verify experimentally. For theoretical analysis however we express Ohm's
law in tem~sof current density J and electric field E (see margin remark) as
where o is electrical conductivity of the material. Electrical conductivity is one of the
important parameters that enable us to differentiate a metal from an insulator. The
value of o is very large (- I O ' ( R ~ ) - ' )for metals and very small
(- lo-'' (nm)-')for insulators.
Now, two things are desirable: a) to explain Ohm's law from atomic point of view;
and b) to obtain an expression for o on the basis of Drude-Lorentz theory. In other
law.
TO this end let us consider a metal specimen. In thermal equilibrium at temperature T,
free electrons move randomly inside the specimen (refer Fig. 9.2b) just like the
molecules of an ideal gas in a container. In the absence of an electric field, there is no
net flow of electrons along any direction due to their random motion. Thus, the
average thermal velocity along any direction in the bulk of the specimen is zero.
When an electric field (E) is applied, (randomly moving) electrons experience a net
force in the direction opposite to the electric field due to negative charge on the
electron and get accelerated. That is, electrons gain a net drift velocity (vd) due to
the presence of an electric field. You must note that drift velocity is over and above
the random thermal velocity, vtand is responsible for flow of electric current.
Under the influence of applied electric field, electron experiences acceleration and
gets drifted with velocity vd. Thus, we may write, using Newton's second law of
motion
Force e
- -&
=XT- - m
where rn is mass and e is charge of electron.
Eq. (9.3) shows that for a given electric field, the drift velocity of an electron
continuously increases with time. This inference, however, is not in agreement with
experimental observations (expressed as Ohm's law). At a given temperature,
electrical conductivity of a metal is constant. Thus, from Eq. (9.2) we may conclude
that for a given electric field, the current density should be constant suggesting that
drift velocity of the electron cannot increase infinitely (see lower margin remark) and
must obtain a steady value.
You may ask: How does Drude-Lorentz theory overcome this problem? In other
words, what makes the accelerating electron acquire a steady drift velocity? It was
suggested that accelerating electrons collide with the ions (or the impurity atoms)
within the specimen. As a result, on collision, an electron loses drift velocity
completely and it is left only with random themla1 velocity. After emerging from the
collision, an electron begins to accelerate in the electric field afresh and acquires drift
velocity. At the next collision, the drift velocity is again lost completely and this
process goes on.
 Free Electron Theory of
Now, to give you a feel for the numerical values of the drift velocity and average Metals
thermal speed of electrons, we will like you to answer an SAQ.

SAQ 1
Calculate the drift velocity of electrons in a metal wire of radius 1 0-4m carrying a
current of 2 ampere. Take the concentration of electrons in the wire to be lo2' m-3. Spend
Also calculate the value of average thermal speed of the electrons in this specimen at 5 min.
room temperature on the basis of kinetic theory of gases.
[Hint: As per the kinetic theory of gases, average kinetic energy of a gas particle at
temperature T is given-by(3/2) kBTwhere kB is the Boltzmann constant.]

While answering this SAQ, you should have obtained a value of 3.9 x 10-2 ms-' for
drift velocity and 1.16 x 10' ms-' for average thermal speed of electron. In view of
above arguments, the process of electrical conduction can be visualised as a result of
two simultaneously occurring competitive processes:
All the electronic properties of
electrons acquire a drift velocity vd due to the applied electric field, and metals are due to the motion
of the free electrons. Thus, in
accelerating electrons suffer collisions with ions (and impurities) and lose their this unit, whenever we
drift velocity and are left only with the thermal velocity, v,. mention electron, it invariably
refers to the free electron (or
We have already discussed the first process (Eq. (9.3)). To visualise the second the valance electron or the
process, we seek analogy with a mechanical system. You may recall from elementary conductlon electron).
mechanics that when a body falls through a viscous medium, its accelerated motion
becomes uniform with a constant limiting velocity. Here, an accelerating electron
suffers collisions with ions (and impurities) and attains a steady drift velocity. Thus,
the effect of collisions is analogous to a viscous (or frictional) force, F which is
proportional to mass and drift velocity of electrons:

where, 117 is the proportionality constant. 7 is known as collision time or relaxation

time for collision between electron and ions.
In fact, the nature of the
Relaxation time is assumed to be independent of energy and direction of motion of frictional processes could be
electrons. It refers to the average time interval between two successive collisions. You understood only when
may now ask: Is there some experimental evidence in favour of the existence of such a quantum nature of electron
and lattice vibrations were
viscous force in a metal? Well, so far as Drude-Lorentz theory is concerned, it was taken into consideration in
simply assumed that such a force does exist and can be represented in terms of the theory of electrical
relaxation time. They did not elaborate upon the nature of such processes. Let us see conductivity. You will study
how does this assumption influences electrical conductivity. The change in drift these processes later in this
unit when we discuss the
velocity due to collisions can be expressed, using Newton's second law of motion, as temperature dependence of
resistivity.
F vd
collision 7

he negative sign indicates that drift velocity decreases due to collisions.

Under the influence of two competing processes, a steady state is obtained and
electrons move with a constant drift velocity. That is, in the steady state, we must
have
Electronic Properties

This may be expressed as a sum of two terms:

Using Eqs. (9.3) and (9.5), we obtain

ez
Vd = -- E (9.6)
m

This expression shows that drift velocity of electrons is linearly proportional to the
electric field. To see whether or not this conclusion about vd is consistent with Ohm's
law, let us substitute J = - n e vd in Eq. (9.2);

J= -nevd=o E

0
" d =-- E (9.7)
ne

Thus, Ohm's law also predicts linear dependence of drift velocity on the applied
electric field, and is consistent with Drude-Lorentz theory. Further, on comparing
Eqs. (9.6) and (9.7), we get

2
(J=-ne z (9.8)
I72

Eq. (9.8) expresses electrical conductivity in terms of microscopic characteristics of

an electron. If the value of o given by Eq. (9.8) is in agreement with the experimental
value, we can conclude that Drude-Lorentz theory successfblly explains Ohm's law -
qualitatively as well as quantitatively. However, for calculating o , we will need a
precise value of the relaxation time z. Further, the temperature dependence of o or the
resistivity p can be understood only when we know the temperature dependence of z.
Therefore, it is desirable to learn more about .c. Before proceeding further in this
direction, it is worthwhile to solve an SAQ to have an idea as to what should be the
order of magnitude of the relaxation time.

SAQ 2
Spend The experimentally observed value of electrical conductivity of a metal is of the order
3 min.
of 10' R-'m-'. Calculate relaxation time for the electron-ion collisions. Given
e = 1.6 x 10-I9c, m = 9.1 x 1 0 - ~ ' kand
~ n = 10'~rn-~.

Having answered this SAQ, the first question that should logically come to your mind
is: What is the basis for obtaining an expression for z ? On this count, the approach
adopted by Drude was different from the one adopted by Lorentz. While Drude used
elements of kinetic theory, Lorentz used Maxwell-Boltzmann statistics. You will
study about their treatments of relaxation time now.
Relaxation Time Free Electron Th

From Eq. (9.4) you know that relaxation time is closely related to collisions between
electrons and ions in a specimen. Further, drift velocity gained by electrons is
completely lost in any such collision. In other words, due to collisions, velocity of
electrons varies between v, and vt + vd; as shown in Fig. 9.4. The time elapsed between
two consecutive minimum values of the velocity of electron is called the relaxation
time. This is shown as the time between points A and B in Fig.9.4.
1

-
. L T - 4
0
t
Fig. 9.4: Plot of velocity oElectrons vs. time showing the relaxation time

Solving SAQ 2, you know that for a typical metal, relaxation time is very small
(-10-14s). To obtain an expression for relaxation time, Drude used concepts of
elementary kinetic theory. He argued that if the average distance travelled by an
electron between two successive collisions is denoted by A, the mean free path of an
electron, the mean free time between these collisions is given by

where (lv, + v d 1) is the average speed between two successive collisions. From SAQ I
you know that vd is very small compared to vt. Therefore, for all practical purposes,
we can express above result as

Further, you may recall from Unit 9 of the PHE-06 course on Thermodynamics and
Statistical Mechanics that the average kinetic energy of a gas molecule at temperature
T is given by

where kg is Boltzmann constant. Since we assume that electrons in a metal behave as

an ideal gas, we can use the above expression for the average kinetic energy of an
electron in a metal at temperature T with < v >' replaced by < vt >':
Electronic Properties
attempted to resolve the
paradoxial situation with respect
to temperature variation of
resistivity arising due to
theory. He pointed out that the
flaw lied in the use of kinetic
theory of gases for obtaining
expression for average thermal
speed of electrons. Lorentz
proposed that all the electrons
do not move with constant
random thermal velocity; rather,
they obey Maxwell-Boltzmann
d~stributionlaw In view of thls,
we need to modify the
expression for the average
thermal speed of electrons. But,
even this assumption leads to
temperature dependence of
resistivity similar to the
prediction of Drude theory.
Lorentz's modification did not
bring about any qualitatrve
changein Our understanding
electrical conduct~vityof metals.
T-
Fig.9.5: Temperature variation
of resistivity for a
typical metal
On substituting for < v, > from Eq. (9.10) in Eq. (9.9), we get
Since relaxation time is of the order of 10-'~s,the mean free path of electrons in a
0
metal is about 10 A . This is of the order of the interatomic separation in a metal. It
seems, therefore, that Drude's assumption that collisions are due to electrons bumping
into larger and heavy ions is correct. However, you will learn later m this unit that this
assumption is not correct as such. Also, you will discover that quantum mechanical
treatment of electrical conductionpredicts a much larger value of the mean free path
of in a
To discover the temperature dependence of electrical conductivity, we substitute the -
value of T in Eq. (9.8) and obtain
ne2k 1
(9.12) '
"=dqJT .
Eq. (9.12) Shows that o is inversely proportional to half power of temperature. Since
1
a =-, electrical resistivity (p) varies as f i . But this prediction is at variance with
P
experimentally observed temperature variation of resistivity. In addition, Drude-
Lorentz theory was also unable to explain some other experimental observations
pertaining to electrical conduction in metals. You will learn them now.
Limitations of the Drude-Lorentz theory
Some of the experimentally observed behaviour of metals with respect to electrical
conduction which could not be explained by Drude-Lorentz theory are listed below:
1. You have seen above (Eq. 9.12) that according to Drude-Lorentz theory,
resistivity of a metal is proportional to the square root of temperature. However,
experiments show that above the Debye temperature, resistivity varies linearly
with temperature, as shown in Fig.9.5.
2. For an impure metallic specimen or a specimen with imperfections in its crystal,
the resistivity is given by the relation
P=P~+P(T)
where po, a constant, is called residual resistivity and is independent of
temperature. However, po increases with increasing impurity concentration in a
specimen. Eq. (9.13) is known as Matthiessen's rule.
3. The resistivity of some metals almost vanishes at low temperatures, i.e. they
become superconductors
Some of the unexplained features of electrical conduction were overcome by
Sommerfeld model. You will learn about it later in this unit. Now, before we proceed
to discuss the thermal properties of metals in the light of Dmde-Lorentz theory, you
should answer the following SAQ.
SAQ 3
2 mm
What is the rationale of introducing the concept of relaxation time?

9.2.2 Thermal Properties

In Unit 8, Block 2 of this course, you studied one of the thermal properties (heat
capacity) of solids. The explanation of thermal properties lies in the fact that the
thermal energy supplied to a solid is absorbed by its atoms resulting in the increase of
their internal energy. While in case of heat capacity, thermal energy increases
vibrations of atoms lions at lattice sites, in case of thermal conduction, transfer of
thermal energy across the solid specimen takes place via elastic waves. However,
these explanations are valid only for rnsulators which have no free electrons. In
metals, thermal energy can also be absorbed byfree electrons. Therefore, it is only
logical for us to expect an electronic contribution to heat capacity as well as thermal
conductivity of metals. Let us discuss these contributions.

Electronic Heat Capacity

From your elementary physics classes, you may recall that heat capacity is defined as
the amount of thermal energy absorbed by a substance to increase its temperature by
one degree. As mentioned above, in metals, the absorbed thermal energy can induce
following two processes:

increase the vibrations of lattice atoms about their respective equilibrium

positions, and
increase the kinetic energy of electrons.

In view of above, we may express the heat capacity of a metal (per mole) as a sum of
heat capacities due to lattice vibrations and due to electrons:

C = C ~ +aC e ~ (9.14)

You have already studied about CIatin Unit 8. You may recall that at a given
temperature T, it is given by

where, R (=NAkB)is universal gas constant, B is constant of proportionality, NAis the

Avogadro's number and TD is the Debye temperature.
Refer to Fig. 9.6 which depicts the temperature variation of heat capacity of a typical
solid and that of a metal (silver). You should note that in both the plots, the heat

T
(a) (b)
Fig.9.6: Heat capacity vs. temperature plot for a) a typical solid; and b) for silver
Electronic Properties
You should note that for
calculating Kc!,Eq. (9.16)
has been modified to obtain
electronic heat capacity per
unit volume. We have
rep1acedN~ by n* number
of electrons per unit
volume.
capacity saturates at 3R at high temperatures. In other words, at high temperatures,
metals obey Dulong-Petit's law like any other solid.
If electrons behave as molecules of an ideal gas obeying elementary kinetic theory,
their average energy at temperature Twill be (3 / 2) kBT. Therefore, energy of
electrons in one mole of a monovalent metal, < E > = (3 / 2)NAkBT = (3 / 2)RT.Thus,
the electronic heat capacity is given by
Combining Eqs. (9.15a) and (9.16), we find that total heat capacity of a monovalent
metal at high temperature ( T >>TD)should be
C = C,,, + C,, = 4.5 R. (9.17)
This value of heat capacity obtained on the basis of Drude-Lorentz theory is much
higher than the experimental value (Fig. 9.6b). You will naturally like to know: What
is the way out? The correct explanation was provided by Sommerfeld. Before you
learn about it in the next section, let us obtain the expression for thermal conductivity
of a metal.
Electronic Thermal Conductivity
You may recall that thermal conduction refers to the net transfer of energy from hot
end to cold end of a specimen. Thermal conductivity K is numerically equal to amount
of thermal energy crossing a unit area per unit time (Q) when unit temperature
gradient exists across a specimen:
As y6u.studied in Unit 7, the thermal energy is transported from one point to another
by lattice waves or phonons. However, in a metal free electrons can also act as carriers
of thermal energy. Thus, the thermal conductivity of metals should be expressed as
From Unit 10 of PHE-06 course you may recall that according to the kinetic theory,
thermal conductivity of an ideal gas is given by
where c, < v > and h are respectively the heat capacity per unit volume, average speed
and mean free path of gas molecules.
Thus, according to Drude-Lorentz theory, thermal conductivity of a metal due to
electron gas can be written as,
1
K,, =-c,, < vt > h
3
where eel is the electronic heat capacity per unit volume, and < v, >and h is average
thermal speed and mean free path of electrons, respectively.
 3 ,/?
If we substitute c,, = - nk,, < v, > = ---
2
( ~ ~ s . 9 . 1 6 a n d 9 . 1 0 ) a n d ~ - in
10~
Free Electron Theory of
Metals ,

-
Eq. (9.18), we find that KeI 100 ~ m -K-'' which is much higher than the
experimental value of K for a typical metal. We will discuss this discrepancy and its
resolution in the next section.
Till now, you have studied Drude-Lorentz theory in which free electrons in a metd
are treated as classical particles obeying the laws of kinetic theory. While this theory
qualitatively explained Ohm's law, it could not account for many other experimental
observations pertaining to electrical conduction; failed to explain why, like,other
solids, the heat capacity of metals saturates at 3R at high temperatures; and could not
account for the experimental values of thermal conductivity of metals. To overcome
these limitations of Drude-Lorentz theory, Sommerfeld proposed that 'electrons are
quantum particles and should be treated as such. You will now learn Sommerfeld
model.

9.3 SOMMEFWELD MODEL

The electrical conductivity and other electron related properties of metals were
investigated by Sommerfeld in the light of quantum theory and Pauli exclusion
principle. In quantum theory

the energy of electron is quantised, that is, energy values of an electron form a
discrete set, and
electrons obey Pauli exclusion principle, that is, no two electrons in a multi-
electron system can have all four quantum numbers the same.

You should read Units 8 , 9 and 10 of the course on Modem Physics (PHE-11) to
appreciate these and other salient features of an electron as a quantum particle. In
order to invoke these conditions, Sommerfeld also made use of the free electron
model. He regarded metal specimen as an empty box containing free electrons. It was
also assumed that ions located at the lattice sites offer a constant potential and hence
no force acts on the free electrons in a metal. The random motion of electrons is,
however, restrained by the physical boundaries of the metal specimen represented by
the walls of the box. When we formulate this physical model of metal (electrons in an
empty box) as a quantum mechanical problem, we obtain electrons confined in a
potential box.
You should re-read Units 6
Now, you may recall from PHE- 1 1 course that the behaviour of an electron can be and PHE-ll
refresh you understanding
studied by solving the Schrodinger equation: about the wavefunction
representing a particle and
other related concepts of
--Vh2 2
y~+vv=Ey~ (9.19) quantum theory.
2m

r
whet , y~ is wavefunction describing the state of the electron, E is its energy, V is the
\potential under which electron moves, m is its mass and tz is the Planck's constant (h)
divided by 2n.
For simplicity, we first consider an electron constrained to move only along one-
dimension of the box, say, along the x-axis. If the length of the box along the x-axis is
L, we have to solve Schrodinger equation for an electron in one-dimensional (1-D)
box of length L (Fig.9.7). You may note that the potential at the boundaries (x = 0 and
x = L) of the box is infinite. It represent the fact that electron is not free to leave the
' metal specimen. Inside the box, potential is constant everywhere. The value of this
constant potential can be taken to be zero without any loss of generality.
 Electronic Properties Now, from the point of view of a metal, we are interested to know:

l'q.(9.20) is a differential equation allowed energy levels for the electron; and
whose general solution can be distribution of electrons in the allowed energy levels.
written as

where k is wave number and A' and

B' are arbitrary constants. The first
term on the right side represents a
plane wave travelling along the
positive x-direction and the second
term represents a plane wave
travelling along the negative x-
direction. Therefore, for the motion
of electron in the positive x-
direction, we can write

To see whether or not the above

solution satisfies the Schrodinger
x= 0 x=L X
-
equation, let us differentiate it twice Fig.9.7: Potential energy of an electron inside a I-D metal specimen of length L
with respect to x;
To obtain an expression for the energy of an electron in a 1-D potential box, we need
to solve the Schrodinger equation (Eq. (9.19)) in one-dimensional form. Further, we
must also invoke the condition that inside the box, potential is constant, i.e., V(x) = 0
for 0 I x I L. Thus, under these conditions, Eq. (9.1 9) reduces to:
= -kZA' e"r= -k2W(x)
(.: i x i =-I)

d Zw (I)in
Substituting this value of -
dx2
Solving this differential equation, we obtain the expression for energy of electron as
Eq. (9.20), we get
(see the margin remark for details)

and the wave function describing the position of an electron as

3 where, p = Ak is the linear

momentum of electron. Y ( ~=) Aleih + B ' ~ =- ACOS
~ ~kx+ Bsinkx

where k is wave number and p is the linear momentum of electron.

Eq. (9.21) shows that energy of a completely free electron can have all possible non-
negative values. That is, the energy spectrum of a completely free electron is
I
continuous. This conclusion is in tune with the energy of a classical particle.
However, in a metal, electrons are not completely free. It is true that, as per the
simplifying assumption, no force acts on electrons inside the metal. But, they must
reside inside the metal, that is, inside the 1-D potential box lying between x = 0 and
x = L. These restrictions on the motion of electrons are called boundary conditions and
imply that the wavefunction y (x) must be zero outside the 1-D box. Otherwise, the
probability of finding electrons outside the box will be finite. When the boundary
conditions are applied to the solution of Schrodinger equation, we obtain restrictions
on the values of k. You may now ask: What do the restrictions on the values of k
27t
signify? Since k is equal to- ,restrictions on its values imply that certain
I.
wavelengths (associated with the de Broglie wave of the electron) are not allowed. AJ
16
a result, certain values oj'energy are not permitted to the electron and the allowed Free Elcetrrrcl Theory of
Metals
energy levels, therefore, form a discrete set.
To apply the boundary
The energy of an electron in a 1-D box is given by (see margin remark) conditions

let us write the solution of the

Schrdinger equation (Eq.
(9.20)) as
where y(x)=Acoskx+Bsinkx

where, k =
i7. 2mE

Since w (x) = 0 at x = 0, the

Thus,
cosine t e n in the expression for
w (x) above must vanish, that is,
A = 0. Thus the solution reduces
to
~ ( x=)B sin kx
Further, it is also required that
And, the wavefunction associated with an electron in a box of length L is given by ~(x)=Oatx=L.
Therefore, we have
B (sin k L)= 0
Since B # 0, we have
sin k L = 0 = sin (n n);
where B is an arbitrary constant.
where n = 1, 2, 3,.. i.e. a positive
You should note that quantization of energyfollows from the boundary conditions integer.
imposed on the wavefinction. The moment we confine the electron in a limited space, Thus, k L = n n
its energy can take only discrete values given by Eq. (9.25). The allowed energy Hence, k is quantized; let us
values are determined by the values of the integer n called the principal quantum denote it by &,,;
number. The energy level with n = 1 is called ground state, energy level with n = 2 is
called$rst excited state and so on. A schematic representation of a few lower allowed
energy levels for an electron in a 1-D box is shown in Fig.9.8.
You may note that n = 0 is not
permissible because in that case,
You may now ask: How are these restrictions modified for the motion of an electron
in a 3-D box which represents an actual crystal? To find it out, Eq. (9.25) is extended
w (x) = 0 everywhere which
rules out the existence of the
to the real situation of a metal crystal which can be viewed as a cubical box of side L. electron even inside the box.
For this case, the solution of Schrodinger equation can be written as, Since k,, = -
*lt
1
--
nn which
L
\y(x,y,z)=Bsink,x sink y sink,z 2L
Y
gives k = -. If n is negative
n
integer, 1 would be negative
n,xx nyxY n,xz
= B sin- sin - s ~-
n which is not possible.
Thus, energy E (Eq.(9.21)) is
where also quantized; let us denote it
by En;

and
I Electronic Properties
I n
1-
Fig. 9.8: Five lowest allowed
energy levels for an
electron in I-D metal
specimen of length L,
where E, = -
hZ
8 r n ~ ~
(Eq.9.25)
An energy level may
corresponh to more than one
energy state. Such energy
states are called degenerate
states. Each of these energy
states have same value of
energy. However, they are
characterised by different
sets of values of the quantum
numbers.
Spend
5 min:
In order to appreciate the
difference between the energy
spectrum of a completely free
electron and an electron in a box,
let us consider the propagation of
wave on a string. A wave
propagating on an infinitely long
string can acquire all values of
wavelength (i.e. wave number)
and frequency (i.e. energy).
Similarly, a completely free
electron can have all momentum
and energy values. But, if the
two ends of the string are fixed,
standing waves of only certain
allowed wavelengths and
frequencies can be maintained.
Similarly, an electron in a box
can have only certain allowed
values of momentum and energy.
With this value of k 2, the expression for energy, Eq. (9.25), becomes
with
Here n, ,n , and n, are positive integers.
This result shows that the allowed values of energy of an electr ,n in a metal can be
obtained by assigning positive integral values to n,, ny and n Therefore,
n,, n and n, are quantum numbers. If we add the spin quar dm number m , , we have
Y
four quantum numbers specifying the allowed energy lev1 .s as well as the energy
states for an electron in a metal. Now in order to fix the: , ideas, you should answer
the following SAQ.
SAQ 4
a) The wave number of an electron can acquire .I1 possible values. What will be
the nature of its energy spectrum? What is ' .e physical significance of the
restrictions on its values?
b) Energy of the lowest allowed level for a* electron in a 1-D box is 9.2 eV. Will
the electron ever have energy equal to ' JO eV?
9.3.1 Fermi Energy and Fermi Su Lace
You have seen that Sommerfeld model pedicts a discrete energy spectrum for
electrons in a metal. Do you know wt it this discreteness of the energy spectrum
signify? To appreciate the significar ;e, we need to discuss Sommerfeld's another
modification introduced in the clas ,ical free electron theory. He suggested that free
electrons in a metal should obey Fauli exclusion principle. You may recall from
Modern Physics (PHE-11) course that according to the exclusion principle, in a
system of fermions, not more than one particle with all four same quantum
numbers can occupy the same energy state. That is, an energy state specified by a
set of values of the quantum numbers n,, n,, n, and m, can accommodate only one
electron. Further, when two possible values of m, are taken into consideration, we find
that an energy state specified by a set of values of n,, n, and n, can, at most,
accommodate two electrons -one with spin up and another with spin
down m
( s 3
= -- . It means that all the electrons in a metal cannot occupy the lowest
energy state (the ground state). In fact, most of the electrons will occupy higher
energy states.
Now, before we discuss how various energy states are filled by electrons, it is
important for you to realise the subtle difference between the terms energy level and
energy state. It readily follows (see margin remark) from Eq. (9.28) that mo,rethan Free Electron Theory bf .
Metals
one energy states can correspond to tlie same energy level, that is:
From Eq. (9.28) we note that the lowest
energy level (the ground level) is specified
some energy levels are non-degenerate and some are 3-fold degenerate; b y n , = I , n l = I andn,= I . ~ o n ' = 3 a n d t h e
a degenerate energy level will accommodate more electrons than a non-degenerate energy of this state is
energy level; and 3h2
energy of all the electrons in a degenerate energy level is the same.
El,l,,= -
8 m L'
Energy of the first exc~tedstate is given by
one of the following three combinations o f
Using Pauli's principle, let us now fill the energy states by putting (dropping) n,, n, and n,:
electrons one by one into different energy states (in the box). For simplicity, we n,= I, n, = I, n, = 2 ,
consider the filling of the energy states for an electron in 1-D box where no level n r = l , n , = 2 , n,= I;
n,= 2 , n , = l , n,= 1
is degenerate. The first electron will occupy the lowest energy state (the ground Each of these sets of values of n,, n,, and n,
state). The second electron dropped in the box can occupy the ground state only if its gives samevalue of n2, that is, 6 and the
spin is opposite to that of the first electron. The ground state is now full. So the third correspondin~nergy
electron will have to occupy the first exited state. The fourth electron can also be 3h2 =
",I' = EI.2,t = E2.1.1
accommodated in the first excited state provided its spin quantum number is different
from that of the third electron and so on. This is shown in Fig.9.9. Therefore, when energy states vecified by these three
sets of values of n,. n, and n, represent
Pauli's exclusion principle is invoked, some of the electrons will have substantial degenerate states; states having same value
energy even when the metal specimen is in the ground state, i.e., the system is alive ofenergy. Similarly you can easilyconvince
even at absolute zero of temperature. Further, if there are N electrons, they will be { e ~ ~ ~ ~ ~ ~ ~ ~
accommodated in (Nl2) energy states. Thus, lowest (NO) energy states will be full. foufi excited energy level is non-
The energy level corresponding to the ( ~ 1 2 )state
' ~ is called the Fermi level and the degenerate. The energy and various
, energy value corresponding to this level is called the Fermi energy EF. It is important ~ ~ ~ ~ ny ~

to mention that this description is valid only for specimen at T = 0. summarised in the following table.
Energy Ener- Various Degen
levels gy combi- eracy
The distribution of fermions among energy levels as per Pauli exclusion principle nations
leads to Fermi-Dirac (F-D) distribution. You have learnt about it in Unit 15 of 01 n,, n,
and n,
PHE-06 course. You may recall that for F-D distribution, the Fermi function f (E) giving
gives the probabiliry that an electron will occupy an energy level with energy E at same n
(Energy
temperature T. The Fermi function is expressed mathematically as states)
Ground jhl (1 11) Non-
-
8mC
degenerate
=
1
f (9.30) First (21 1). Three fold
(E-E,) excited 6hI (121). degenerate
e ~ B T+ I state 8niL1 (1 12)
Second gh2 ( 1 22), Tllreeiold
where EF is the Fermi energy, E is the energy of the level whose occupancy is being
considered.
z$Td (2 12),
(121)
degenerate

Third 1]h2 (1 13), Three fold

excited 8,C (131). degenerate
The energy variation of the Fermi function at absolute zero is depicted in Fig.9.10. slate (311)
Note that f (E) = 1 for E < EF. It means that Fermi energy is the energy of highest Fourth (222) Non-
filled state. And its value is a few eV. This is a direct consequence of application of excited IZh' degenerate
- State 8mL2
the principles of quantum mechanics to free electrons in a metal. You should note that
according to quantum theory, even at absolute zero of temperature, some of the
electrons have significant value of energy (the Fermi energy). Compare it with the
conclusions of classical mechanics. According to classical mechanics, all motion
ceases to exist at T = 0 K; electrons have no energy. This brings out the significance
of the discreteness of the energy spectrum for electrons in a metal.
E,
An important concept related to Fermi energy is Fermi surface. To understand this, let
us recall (Eq. 9.28) that energy of an allowed level is a function of n only. However, Eledmn
we note from Eq. (9.29) that the value of n depends on the values of nx,nyand n,.
Now, let us draw a radius vector n in a coordinate system with axes nx,nyand n, as
shown in Fig.9.1 la. For integral values of n,, n, and n, each point in this space
represents an energy state. since the value of eiergy is determined by n, asphere of Fig.9-9: Filling of energy states of a
radius n in this &ace represents the locus ofpoints having same energy. Further, if I-D metal crystal by
electrons according to the
we draw a sphere of radius n~(corresponding to Fermi energy EF)we find that all . PauIi exclusion principle
points inside the sphere are filled and those outside it will be empty (Fig.9.l lb). It is
 Electronic Properties because the outer points represent energy states with energy greater than EF. This-
sphere is known as the Fermi sphere and its surface is called the Fermi surface. E

These concepts are very useful in understanding the phenomena of electrical and
thermal conduction.

surface

01
E--,
I
EF
-
Figi9.10: Plot of Fermi
function vs.
energy at absolute
zero temperature.

Fig.9.11: a) Sphere of constant energy in n-space; and b) Fermi sphere in n-space

SAQ 5
Spend Explain the concept of Fermi surface in k-space and velocity-space.
3 min.
nn
[Hint: Use relations k = -and p = hk]
L

011 thebasis of above discussion, you must have realised that there can be more than
two electrons with same energy. Thus, the question is: How are the electrons in a
metal distributed among the allowed energy levels? You will learn it now.

Distribution of free electrons among energy levels

Let us restate the problem: A metal specimen has a large number of free electrons.
Their energy spectrum is discrete and an allowed energy state can accommodate only
two electrons with different quantum numbers. Under these conditions, we wish to
know how these electrons are distributed among the allowed energy levels. In other
words, we wish to obtain an expression for the number of electrons in different energy
levels. This expression is of great help in calculating physically important parameters
of metals such as Fermi energy and average kinetic energy of electrons.
To find the number of electrons in a metal with energy E, we need to know the

a) total number of energy states corresponding to any particular energy E per unit
energy interval, that is, the density of states at E, and
b) Fermi functionf (E), i.e., probability that an electron will occupy the level with
energy E.

If we denote the number of electrons per unit energy range about energy E by N (E)
and the number of energy states per unit energy range about E by Z (E), we may
express the number of electrons in the energy interval E and E + dE as
 Free Electron Theory of
Metab
You have already learnt in Unit 15 of PHE-06 course how to derive an expression for
the number of momentum states for a fermion in the momentum rangep a n d p + dp.
Similarly it is easy to show that the number of energy states for electrons in the energy
range E and E + dE is (see Terminal Question 1)

Note that factor of 2 arises because any given energy state can accommodate two
electrons with opposite spins.
Thus, the density of energy states in the energy intehal dE per unit volume is

You may note that all parameters in RHS of Eq. (9.33), except energy, are constant.
The variation of the density of states with energy is shown in Fig.9.12.
Substituting Eqs. (9.30) and (9.32) in Eq.(9.3 I), we get the number of electrons in the
t
$
energy interval E and E + dE as

;
-
N(E)dE =- [8;~)"'(E)l12dE -
1
E-EF (9.34)
E dE
e k ~ T+ I *
Fig.9.12: Density of states
What does Eq. (9.34) signify physically? For a given metal, the number of electrons in vs. energy plot
for a free electron
a given energy level is a function of energy E of the level under consideration, the
gas
Fermi energy EFand absolute temperature T. Before we use this relation to derive an
expression for the Fermi energy of a metal, how about solving an SAQ?

SAQ 6 Spend
3 min.
For electrons in a metallic specimen, calculate the density of energy states below 2eV.

To obtain an expression for Fermi energy, let us consider the simpler case
corresponding to T = 0 K. As mentioned earlier, at T = 0 K, all the energy levels
below EFare completely filled and all those above EF are empty. Thus, we are
concerned only with the distribution of electrons among the energy levels between the
ground level and the Fermi level. For these energy levels, f (E) = land Eq. (9.34)
reduces to

Now let us assume that the total number of free electrons in the cubical box is N. At
T = 0 K, these N electrons are accommodated in the energy states having energies in
the range 0 to EF. This condition is expressed as
 Electronic Properties
Table 9.1: Fermi energies and
Fermi temperatures
of a few metals
You have seen that in
Sommerfeld model,
electrons in a metal are
treated as a quantum
mechanical system.
However, the analysis of
electrical conduction based
on this model is semi-
classical in nature because
the results of kinetic theory
are used.
Integrating both side of Eq.(9.35) and substituting Eq. (9.36) in it, we get
If n denotes the number density of thefree electrons, we can write this equation as
312
( E ~3 1)2 ; since L~ = V(Volume)
By inverting this result, we obtain expression for Fermi energy:
Let us pause for a moment and consider what have we achieved so far. We have
obtained expression for Fermi energy which depends on the number density of the
free electrons in a metal. This is physically understandable because larger the number
of free electrons in a metal, more energy levels will be occupied leading to higher
Fermi energy. Fermi energies of a few typical metals are given in Table 9.1.
Note that Fermi energy for metals is of the order of several electron volts. As per
classical theory, an electron has energy of the order of kBTat temperature T. The value
of kBTat room temperature is 0.025 eV which is much less than EF, Fermi energy of
electrons at T = 0 K. You may like to know: At what temperature classical electrons
in a metal will acquire energy equal to Fermi energy? We know from kinetic theory
that the energy of a particle at temperature T is equal to kB T. Thus, we can write for
the temperature corresponding to Fermi energy, called Fermi temperature:
Classical electrons must be heated to this temperature to acquire energy equal to EF.
The numerical values of TFfor a few metals are also given in Table 9.1. You may
realise how high the Fermi temperature is if you note that most metals would melt
much below their Fermi temperatures!
You are now familiar with the basic features of Sommerfeld model and its
consequences as far as the kinematics of electrons in a metal is concerned. Now, you
will learn how this model helps us in understanding the experimental results
pertaining to electrical conduction and thermal properties of metals.
9.3.2 Temperature Dependence of Electrical and Thermal Properties
Electrical Conduction
Sommerfeld, like Drude and Lorentz, assumed that a steady state motion of electrons
is obtained as a result of two competing processes: acceleration of electrons due to
applied electric field and deceleration due to collisions between electrons and lattice
ions. However, Sommerfeldproposed that relaxation time should be a function of the
energy of electrons -electrons in the vicinity of the Fermi level because it is mainly
these electrons which participate in the conduction process. In view of this Free Electron Theory of
Metals
assun~ption,t is replaced by TF in Eq. (9.8):

where, tFis relaxation time for electrons at the Fermi level. Eq. (9.41) shows that, on
the one hand, o depends on the number of electrons per unit volume and on the other You must realize that energy
hand, it also depends on the relaxation time of only those electrons which are at the dependence of relaxation
Fermi level! To resolve this seemingly paradoxial situation, refer to Fig.9.13. The time is a unique feature of
Sornmerfeld theory. In
circle drawn in solid lines (Fig.9.13a) represents the Fermi surface of a 2-D metal Drude-Eorentz theory,
specimen in the velocity-space in the absence of an electric field. In this relaxation time is considered
independent of energy.

Fig.9.13: Fermi surface of a 2-D metal crystal when a) no electric field is applied; and b) an electric
field E is applied along the negativex-direction

representation, VF denotes the speed of electrons at the Fermi level. You should note
that Fermi surface is symmetrical and represents an electron moving with a particular
speed. The symmetry of Fermi surface implies that for each point within the circle
representing the velocity of an electron in one direction, there is a corresponding point
representing the velocity of another electron in the opposite direction. For example,
for an electron represented by v, in the first quadrant, there is another electron
represented by -vl in the third quadrant. This is consistent with the observation that
in the absence of an applied electric field, electrons have no net velocity along any
preferred direction and there is no electrical conduction.
When an electric field is applied, say, along the negative x-direction (Fig.9.13b),
electrons acquire a drift velocity vd along the positive x-direction. This results in a
shift of the Fermi surface as a whole by an amount v d along the x-axis. As a result, the
Fermi surface shifts in the velocity space along positive x-direction. The shift is
shown by the shaded portion in Fig.9.13b. You must note that even in this situation,
velocities of electrons in the hnshaded region cancel each other in pairs. However,
velocity of electrons in the shaded region and near the Fermi surface towards the
positive x-direction remains uncompensated. As a result, there is a flow of electric
current in the metal specimen. We find that when an electric field is applied, all free
electrons are accelerated (the Fermi surface shifts as a whole). But, a net velocity (the
Electronic Properties therefore, justified to assume that only those electronsparticipate in electrical
conduction which are in the vicinity of Fermi level.
You may like to know: What are the consequences of the above assumption? As you
know, energy (and hence velocity) of electrons at Fermi level is very high.
Therefore, the mean free path of electrons will be high because it can be
approximated as h = z F v FTaking
. TF - -
10- l 4 s, and V F 10 ms-', we get
0
)
1 = (10-l4s)x (1o6 ms-I = 10' A . This value for the mean free path is in agreement
with the value obtained from experimental results. Also, recall from sub-section 9.2.1
(see page no. 12) that the value is much higher than the value predicted by Drude-
Lorentz theory. Such a high value of mean free path seems unrealistic in view of the
fact that the density of electrons is very high and also that the ions are densely packed
in a metal. Sommerfeld model, however, does provide an explanation. According to
deBroglie, electrons, like light, exhibit wave-particle duality depending on its energy.
That is, electron is a matter-wave. When such a wave propagates through a crystal, its
energy is absorbed by the lattice atoms and subsequently reradiated. As a result, it
continues its journey without any change in direction and intensity. If a metal crystal
were truly periodic, electrons would move through it uninterrupted. That is,for a pure
crystal, electrical conductivity is in$nite! Thus, quantum nature of electron leads us to
another extreme conclusion not supported experimentally. In fact, as you will study
later in this unit, even in a pure crystal, conduction electrons must face resistance to
their uninterrupted motion resulting in finite conductivity. Nevertheless, the quantum
theory does provide us a basis to explain the large value of mean free path for
electrons in a metal.
You will now agree that the basic difference between Drude-Lorentz theory and
Sommerfeld theory of electrical conduction is that whereas in the former, all electrons
moving with average velocity are assumed to participate in the electrical conduction
and according to the latter, only those close to Fermi energy take part in it. Let us
now learn how Sommerfeld model account for the temperature dependence of
resistivity of metals.

Temperature dependence of resistivity

To understand the nature of relationship between a (or p) and T, we need to obtain an
expression for T F . In view of the fact that an electron moves uninterrupted in a
perfectly periodic crystal, any resistance to its motion will be caused by deviations in
the periodicity. What are the causes of this deviation? These can broadly be classified
into two categories:

thermal vibrations of ions at lattice sites; and

impurity atoms and lattice defects such as vacancies and dislocations which
disturb the periodicity of crystal lattice.

To understand the temperature dependence of p, we only need to investigate the effect

of thermal vibrations on the mean free path. The second cause listed above is
independent of temperature.
The ions at lattice sites vibrate due to their thermal energy and produce elastic waves
which scatter electrons. The question is: How does this scattering influence the mean
free path of electrons? The kinetic theory suggests that mean free path of an electron
for electron-lattice scattering depends on the number of ions per unit volume and the
scattering cross-section of thermal vibrations, i.e,

(9.42)
NS
where N is the number of atoms per unit volume and S is the scattering cross-section Free Electron Theory ef
Metals
for electron-lattice scattering. The scattering cross-section is proportional to the square
To obtain an expression for the amplitude
of the amplitude of vibration, that is, of vibration of a lattice ion, let us write
its equation of motion. Let M be the
mass, y be the displacement and (-k y) be
the restoring force. Then the equation of
motion of the atomic oscillator is
where B is constant of proportionality and y is the amplitude of vibration of the lattice
atoms. Using Eqs. (9.42) and (9.43), we get

k
where o2= -.
1 M
where B I =- . By solving the equation of motion of an atomic oscillator, you can Since the lattice atom vibrates as an
B harmonic oscillator, its potential energy
can be written as
readily show (see margin remark) that

where M is mass of the atom and TD is Debye temperature. Substituting Eq. (9.45) in
Eq. (9.44), we get

According to kinetic theory, the energy

associated with each degree of freedom
of an atomic oscillator at temperature T is
ksT. Since the energy of an oscillator is
half kinetic and half potential, we can
Thus, relaxation time for the electrons at Fermi level is given by write
1
P.E. = -k,T
2
Comparing above two expressions for the
potential energy of the oscillator, we get
1
2 ~ ~ ~ v 2~ ~ ~ (i)
= - k , T
Substituting Eq. (9.47) in Eq. (9.41), and in view of the fact that for monovalent metal Further, we assume that the angular
the number of atoms per unit volume is equal to the number of free electrons per unit frequency of vibration of the lattice atom,
volume, we get the required expression for electrical conductivity: w is such that
o = oE = OD
That is, we are considering high
temperature regions ( P > T D )where
Einstein and Debye frequencies
( o, and oDrespectively) are
essentially the same. Thus, we may write
1
Note that cr is inversely proportional to temperature. And since the resistivity, p = -
0
we have, from Eq. (9.48)

Thus, replacing v by rn and substituting

This result shows that by incorporating the effect of collision between electrons and this expression for % in (i), we get
vibrations of ions at lattice sites, Sommerfeld predicted linear dependence of
resistivity on temperature. Note that this prediction is valid for temperatures above the
Debye temperature, TD.This is in conformity with the experimental curve shown in
Fig.9.5.
Electronic Properties Matthiessan rule

You may now ask: Why does p versus T plot (Fig. 9.5) attains saturation to a value po
as T approaches absolute zero? To address this question, we need to consider
scattering of electrons by the impurities present in a crystal. We can qualitatively
describe this scattering similar to scattering of electrons by lattice vibrations as
discussed above and write the mean free path of electrons for electron-impurity
scattering as

where N, is the number of impurity atoms per unit volume and Si is the scattering
cross-section for electron-impurity scattering. Since both N, and Si are independent of
temperature, we expect that the mean free path and the corresponding relaxation time
for electron-impurity scattering will be independent of temperature. Therefore, the
resistivity due to the scattering of electrons by impurities will be independent of
temperature:

pi = constant = po .

Thus, the total resistivity of a metal can be expressed as a combination of two

components po and p(T) , i.e.,

This relation is known as Matthiessan rule.

At low temperature (T << TD),amplitude of lattice vibrations is very small. The
electron-lattice scattering cross-section would be small leading to a small value of
p (0.It means that electron-impurity scattering dominates over electron-lattice
scattering at low temperatures. As the temperature increases (T >> TD),scattering of
electrons by lattice vibrations overtakes the impurity scattering.
So far, we have confined our discussion to theoretical explanation of various
experimental results pertaining to electrical conduction. You have seen that the semi-
classical analysis of the phenomenon qualitatively explains most of the experimental
observations. The basic process involved in electrical conduction is transfer of energy
from one end of a metal specimen to another under the influence of an electric field.
You may, therefore, ask: Will energy also be transferred by electrons in a metal if
electric field is replaced by thermal gradient? Or, does internal energy of a metal
increase due to-absorption of thermal energy by electrons? These are the questions we
will address now in the light of Sommerfeld model. However, before you proceed
further, you should solve the following SAQ.

SAQ 7
Spend
2 min. Is it correct to say that for a perfectly pure metal specimen, the resistivity is infinite as
T -P 0 K? If not, what is the correct statement to make.

,
Thermal
. Properties
YOU have seen that Drude-Lorentz theory is unable to predict experimentally observed
values of heat capacity and thermal conductivity of metals. According to Sommerfeld,
the genesis of these descripencies lies in the nature of the Fermi function for T z 0 K.
Let US rewrite the expression for Fermi function,
 1
f (El = ,-$
-
e k ~ T+1

For T # 0 K, the exponent vanishes at E = EF SO that the exponential term equals unity
and the Fermi function equals one-half. It means that at finite temperatures, the Fermi
energy in a metal is the energy of that state whose occupation probability is 50
percent. The energy variation off (E) is depicted in Fig.9.14.
Note that as temperature rises from absolute zero, the Fermi function develops a tail.
It implies that as temperature rises, electrons below Fermi level jump to energy states
above Fermi level. At any given temperature T, width of this region is of the order of
kg T. It means that energy of electrons confined to kB T around E = EFcan change as
temperature is raised. In other words, only those electrons participate in thermal
processes whose energies lie within kg T around E = EF.
For electrons much below the Fermi level, empty levels are not available to which
they can be excited. However, electrons near the Fermi level may get excited to empty
energy levels above the Fermi level. It is important to note that at room temperature
kgT is approximately 0.025 eV whereas, the Fermi energy of a typical metal is 5 to
9 eV. It means that the number of electrons which might absorb thermal energy is Fig-9-14:Variation ofthe
very small. Moreover, only this fraction of electrons would contribute to the heat Fermi function,
/ ( E ) with the
capacity of metals. energy for finite
temperatures
To obtain an expression for the electronic heat capacity, we must know the average (T,>T,>T,>O K )
energy of the electrons near the Fermi level. Here again, instead of presenting its
detailed quantum mechanical derivation, it suffices to say that at temperature T, the
thermal energy that an electron can absorb is kBT.Thus, for one mole of a monovalent
k ~ .Tin
metal, the fraction of electrons contributing to electronic heat capacity is N A -
EF
view of this, the average energy of electrons contributing to heat capacity per mole of
the metal can be written as

The electronic heat capacity is therefore given by

It shows that electronic heat capacity varies linearly with temperature. This is in
conformity with experimental results (Fig.9.15). Further, at room temperature,
R
kBT= 0.025 eV and the Fermi energy of a typical metal, EF= 5 eV, so that, C = -.
- 100
On comparing Eqs. (9.16) and (9.50), we find that
 Flg.9.15: Lattice and electronic heat capacities vs. temperature plot for a typical metal

Let us now re-examine the phenomenon of thermal conduction in the light of

Sommerfeld model. As in electrical conduction, only those electrons participate in
thermal conduction which are in the vicinity of the Fermi level. Therefore, in the
expression for electronic thermal conductivity (Eq. 9.18) we must replace <v,> and h
by V F and h ~respectively.
, Thus, Eq. (9.18) takes the form

1
K ~ =I TC" VFI F-

Substituting for eel= 2n [-

!:) (by modiiying 4.9.50 to get electronic heat capacity
per unit volume), we get

1
Using h F = v , ~ ,and - mv: = E , ,we get
2

4n k: T T~
Kel = (9.5 1)
3m

Eq. (9.5 1) gives electronic thermal conductivity.

At room temperature ( T = 300 K ) and for TF = 10 -14s, Eq. (9.5 1) gives
KeI= 50.3 ~ m - K-'.
' This value is very close to the experimentally observed value of
K (= Kel+ Kl,J at room temperature. It suggests that at room temperature most of the
thermal energy is transported by electrons.
Thus, we find that Sommerfeld model provides a satisfactory understanding of
electrical and thermal conduction in metals. It also provides microscopic explanation
of Weidemann-Franz Law. You may recall that, according to this law, the ratio of
thermal conductivity and electrical conductivity is a constant at a given temperature,
1.e.
-
 -K
=L
aT

where L is called the Lorenz number. The experimentally obtained values of Lorenz
number for some metals at room temperature are given in Table 9.2. You will note
Table 9.1:
that L is a constant independent of the material. obtained Lorenz
numbers for a
To obtain an expression for L in terms of microscopic parameters, let us write the ratio few metals
of K and a using Eqs. (9.41) and (9.5 I):

Sodium (Na) 2 . 1 7 lo-'

~

On comparing Eqs. (9.52) and (9.53) we get

Silver (Ag) 2.34~10~'

- ' e = 1.6 x 1 0 - l ~in ~Eq. (9.54), we obtain

By substituting kB= 1.38 x I O - ~ ~ J Kand For 1 mole of substance, the
L E Ix w S Z K - ~This
. value is very close to the experimental values (Table 9.2). number density of electrons
n can be replaced by NA.
It shows that the semi-classical analysis of the phenomena of thermal and electrical A,,,, at roomte,perature,
conduction on the basis of Sommerfeld model is quite satisfactory. It also highlights K. K ~ , ,
the fact that thermal and electrical conductions in metals are intimately related: in
both the processes, energy is essentially transported by electrons; the contribution of
lattice wave is very small.
In this unit, you have studied the basics of the free electron theory of metals and learnt
the microscopic explanations of the phenomena of electrical conduction, heat capacity
and thermal conduction. You may now like to ask: Does free electron theory provide
qualitative as well as quantitative explanation of all the physical properties of metals?
No; it fails to answer questions like: Why some solids are metals and others
insulators? Why some metals have positive Hall coefficient (meaning thereby that the
electric charge carriers in such metals are positively charged)? The shortcomings of
free electron theories arise because of the over-simplified assumption that the ions in a
metal crystal do not affect the motion of electrons. The fact of the matter is otherwise.
The motion of electrons is influenced by the periodic potential field of the ions. When
the effect of this field is taken into consideration, the energy spectrum of electrons is
changed completely; instead of isolated energy levels, we obtain bands of allowed and
forbidden energy levels. This leads us to what is known as the band theory of solids.
The band nature of the energy spectrum has far reaching consequences for the
physical properties of solids. You will learn about it in the next unit.
Let us now summarise what you have learnt in this unit.

9.4 SUMMARY

In Drude's model, free electrons in a metal are considered to behave like an ideal
gas.

According to Drude-Lorentz theory,electrical conduction in metals is

characterised by simultaneously occurring two competitive processes, namely,
a) electrons acquire a drift velocity due to applied electric field and b) electrons ,

suffer coIlisions with ions and impurities. Effect of collisions is represented by a

constant called relaxation time or collision time.
Electronic Properties a Relaxation time is the average time between two successive collisions between
electrons and ions.
a According to Drude-Lorentz theory, the electrical conductivity of a metal is
given by

a Drude-Lorentz theory explains Ohm's law qualitatively, but it fails to explain the
temperature dependence of resistivity, Mathiessen rule and occurrence of
superconductivity.
a The electronic contribution to heat capacity of metals leads to a very high
value of total heat capacity which does not agree with experimental observations.
Similarly, Drude-Lorentz theory could not account for the experimentally
observed values of thermal conductivity of metals.

Sommerfeld suggested that the shortcomings of Drude-Lorentz theory are due to

the fact that it treats electrons as classical particles. He argued that free electrons
in a metal constitute a quantum rather than a classical system. The energy of
electrons is quantized and they obey Pauli exclusion principle.
a As per Sommerfeld model, energy of an electron in a 1-D metal specimen of
length L is given by

and for a cubical metallic specimen of side L, energy of an electron is given by

where n 2 = n 2, + n 2Y + n 2, ; n, =1,2 ,...; n =1,2 ,... ; n =1,2 ,....

Y

a Fermi energy is the energy of the highest filled state in a metal specimen at
absolute zero. All the energy states within the Fermi sphere are filled and all the
states outside it are empty. The surface of this sphere is called Fermi surface. At
temperature other than zero, Fermi energy represents the energy level whose
occupation probability is half.

The relation between number density of electrons (n) and the Fermi energy of
metal at T = 0 K is given by

By arguing that only those electrons participate in electrical conduction which are
in the vicinity of Fermi level, Sommerfeld obtained an expression for resistivity
which predicted its linear dependence on temperature:
 Sommerfeld also explained experimental results on heat capacity and thermal
conductivity on the basis of the assumption that only those electrons contribute to
these parameters of metals which are close to the Fermi level.

The expression for electronic heat capacity is

The expression for electronic thermal conductivity is

Sommerfeld theory also gives a microscopic expression for the Lorenz number:

which is very close to experimentally observed values.

9.5 TERMINAL QUESTIONS Spend 45 min.

1. For a cubical metal specimen of side L, show that the number of energy states in
the energy range E and E + dE is given by

2. a) If the interatomic separation in a solid is increased manifold, how will its

mean free path be affected?

b) Suppose that a metal specimen is equivalent to a classical free electron gas in

an otherwise empty box and the random velocity of electrons is due to their
thermal motion. What will be the temperature dependence of resistivity of the
specimen?

3. Fermi energy of silver is 5.5 eV. Assuming that Fermi energy is independent of
temperature, calculate the electronic heat capacity and electronic thermal
conductivity at room temperature. Take relaxation time at Fermi level, TF r 10-I4s.
4. Fermi energy of gold is 5.5 1 eV. Calculate the fraction of electrons excited a b w e
the Fermi level at room temperature.
Electronic Properties

9.6 SOLUTIONS AND ANSWERS

Self-Assessment Questions (SAQs)
1. Current density is given by

where I is current in the wire, A is its area of cross-section and n is the

concentration of electrons. Putting the values of I,A, n and e, we get

2 ampere
vd = =3.9~ ms-'.
n ( 1 0 - ~ m )~~ ( 1 m-')x
0 ~ ~( 1 . 6 ~10-19C)

For calculating the average thermal speed, we use the expression for average
kinetic energy of a particle obtained on the basis of kinetic theory of gases:

Thus, the value of random thermal speed is very high compared to the drift
velocity.

2. From Eq.(9.8),

where o is electrical conductivity and t is relaxation time. Putting the values of cr,
e, m and n, we get

3. Relaxation time represents the effect of collisions between electrons and ions or
impurities on electrical conduction in a metal. In the absence of such collisions,
the drift velocity acquired by electrons due to applied electric field will go on
 increasing. This will lead to infinite conductivity of metals; a conclusion which is Free Electron T W y of
Metals
not consistent with experimental observations.
4. a) According to quantum theory, energy of a free electron (Eq. 9.2 1) is given
h2k2
asE=- . Thus, if the wave number k can acquire all possible values, the
2m
energy spectrum of electron will be continuous similar to that of a classical
particle. Restrictions on the values of k signify that certain energy values are
not permitted to electrons in a metal because the wave number
k = - 271: , and energy, E = hv = -.hc
3L 3L

h2 2 n = l , 2 , 3 ,....
b) From Eq. (9.25) we recall that En = -n ,
8rnL2

For ground state, n = 1. Thus, the ground state energy

Energy of nth excited state can be expressed in terms of the ground state
energy as

E n = E l .n 2 .

As per the problem, we have El = 9.2 eV and En = 500 eV. Therefore,

I

n 2 =A=--
500eV -54.35
El 9.leV
so that

n = 7.4.

Since only the integral values of n are permissible, electron cannot acquire
500 eV energy.

5. We know that energy of electron in a cubical box of side L is given by

(Eq. (9.28))

---(n: h2 +n:
n n z gm L2

kL kL
Substituting n, = An
, = 2- ~ z ,Lwe get
and n, = -
n y X X

E =-k2
tt ; k2=kx2+kZ+ki.
" 2rn

If we draw a vector k in k-space with coordinates k,, ky and k, as shown in

Fig.9.16a7all points specified by allowed values of k,k, and k, (corresponding to
integral values of n,, ny and n,) represent allowed energy states.
 Thus, a sphere of radius kF in this space is the Fermi sphere enclosing

all allowed energy states. Similarly, Ferrni sphere in the velocity space can be
drawn using the relation, E F = -1 rn vF
2 . In the velocity space, Fermi surface is the
2
surface of the sphere of radius v~(Fig.9.16b) enclosing all allowed values of
velocity for electrons.
f"

Flg.9.16: Ferml surfaces in a) k-space; ana ti) velocity-space

6. Density of states for electron in the energy range E and E + dE is given by

Eq. (9.33) as

Thus, the density of states in the energy range from zero upto certain energy E
can be written as

Thus, density of states below 2 eV

7. No; the correct statement is: For a perfectly pure metal specimen at T = 0 K,
resistivity is zero, that is, conductivity is infinite.

Terminal Questions (TQs)

1. For a cubical metal specimen of side L, energy of an electron is given by
(Eq. 9.28)
 Free Electron Theory of
2
with, n = n,
2
+ ny2 + n,;2 n =1,2,..; ny =1,2,...; and n, =1,2,... Metals

This shows that the number of energy states corresponding to a particular value of
energy (i.e. for constant n) depends on the number ofaossible combinations of
integer values of n,, n, and n,, all giving the same value 6'f.q.Thus, to obtain the
total number of such states, we draw a radius vector n in n-spke with coordinates
n,, n, and n, as shown in Fig.9.17.
R

h
J
\-

Fig.9.17: Energy states in n-space

A spherical surface in the n-space centred at the origin is a surface of constant n

and hence of constant energy. Further, since every integer value of n,, n, and n,
specifies an allowed state, a unit cube (n, = 1, n, = 1, n, = 1) will contain one
state. Hence, number of state in a given volume in this space is equal to the
numerical value of the volume. In view of this, total number of states upto n
4
corresponding to energy E is-x n 3 . Since only positive values of n,, n, and n, are
3
allowed, the total number of allowed states upto energy E is

Similarly, total number of allowed states upto energy E + dE is

Thus, number of allowed states in the energy range E and E + dE is

Now, from Eq. (9.28), we have

Eleowa;lrt;e Properties Substituting for n2 and dn in the expression for Z(E) dE we get

1
2. a) Fmm Eq. (9.40), we note that the mean free path is given by h = -,where N
NS
is the number of atoms per unit volume and S is the scattering cross-section
for electron-lattice scattering. As the interatomic separation is increased, the
number of atoms per unit volume will decrease. Therefore, in the light of
above expression, mean free path of the solid will increase.

b) From Eq. (9.12), we note that electrical conductivity is given by

1
Since resistivity, p = -, we can write
o

Since the metal specimen has been considered equivalent to a classical

electron gas in an empty box, we must know the effect of temperature on the
mean free path of the particles in such a gas. To that end, kinetic theory
suggests that mean free path is a hnction of density of ions N, in the metal
1
and scattering cross-section S between electron and lattice, i.e., h = -.
NS
Further, from Eq. (9.43), we have S = B y2.For a classical electron gas, the
amplitude ( y) of vibration of lattice atoms is given as (see margin remarks on
Page 25)

Thus,

S=AT

BkB = constant. So that the mean free path 1 = -1

where A =
4n2M v2 NAT '

Therefore, we have

This will be the temperature dependence of resistivity.

3. From Eq. (9.50), we have electronic heat capacity

We have,

EF = 5.5 eV = 5.5 x 10-19J; T = 300 K

Further, from Eq. (9.5 l), we have electronic thermal conductivity

4. According to the kinetic theory, at temperature T, the thermal energy gaiaed by an

electron is kBT.In a monovalent metal like gold, the total number of free electrons
per mole is NA,the Avogadro's number. However, not each of these electrons
gains an energy equal to kBT.Only those electrons which are in the range of kBT
of the Fermi energy can be excited thermally. Therefore, fraction of electrons
which might absorb energy kBTattemperature Tand get excited above the Fermi
level is