UNIT- IV

ELECTRON THEORY OF METALS

INTRODUCTION:

The electrons in the outer most orbit of the atoms which consists the solids determine its
electrical properties .The electron theory of metals aims to explain the structure and properties of solids
through their electronic structure the electron theory is applicable to the all solids both metals and non
metals .It explains the electrical thermal and magnetic properties of solids etc .The theory has been
developed in three stages.

Stage-I. THE CLASSICAL FREE ELECTRON THEORY: “Drude and Lorentz” developed this
theory in 1900. According to this theory the metals containing free electrons which move
through a constant potential and obey the laws of classical mechanics.

Stage-II. THE QUANTUM FREE ELECTRON THEORY: This Theory was developed by
“Sommerfeld” during the year 1928. According to this theory free electrons move in a
constant potential and obey quantum laws.

Stage-III. THE ZONE THEORY (OR) BAND THEORY OF SOLIDS: Bloch developed this
theory in 1928. According to this theory the free electrons move in a periodic field provided
by the lattice .This theory is also called “BAND THEORY OF SOLIDS”.

PHYSICAL PROPERTIES OF METALS

1. Metallic conductors obey ohm’s law which states that the current in the steady state is
proportional to the electric field strength.
2. Metals have high electrical and thermal conductivities.
3. At low temperatures, the resistivity is proportional to the fifth power of absolute temperature.
i.e. ρ α T5
4. The resistivity of metals at room temperatures is of the order of 10-7 ohm- meter and above
Debye’s temperatures varies linearly with temperature.
i.e . ρα T

5. For most metals, resistivity is inversely proportional to the pressure.

i.e. . ρα 1/P
6. The resistivity of an impure specimen is given by Mathiessen rule.

ρ = ρ0 + ρ(T)
Where ρ0 is a constant for impure specimen and ρ(T) is the temperature dependent resistivity of
pure specimen
 7. Near absolute zero, the resistivity of certain metals tends towards zero. i.e it exhibits the
phenomena of super conductivity.
8. The conductivity varies in the presence of magnetic field this effect is known as magneto
resistance
9. The ratio of thermal to electrical conductivity is directly proportional to absolute temperature.
This is known as Wiedemann-Franz law.

Classical free electron theory of metals:

The classical free electron theory is based on following postulates:

1) In an atom, electrons revolve around the nucleus. A metal is composed of such atoms.
2) The valence electrons of atoms are free to move about the whole volume of metals like the
molecules of perfect gas in a container. The collection of valence electrons from all the atoms
in a given piece of metal forms electron gas. It is free to move through out the volume of metals.
3) These free electrons move in random direction and collide with either positive ions fixed to the
lattice or other free electrons. All the collision are elastic. i.e. there is no loss of energy
4) The moments of free electrons obey the classical kinetic theory of gases.
5) The electron velocities in metals obey the classical Maxwell Boltzmann distributions of
velocities.
6) The free electrons move in a completely uniform potential field due to ions fixed in the lattice.
7) When an electric field is applied to the metal, the free electrons are accelerated in the direction
opposite to the direction of the applied electric field.

ELECTRICAL CONDUCTIVITY:

In metals, free electrons roam freely through the crystal lattice. In the absence of applied external field
the net current due to moment of electron is zero since they move randomly in all directions. In between
two collisions, the electrons move with uniform velocity. During every collision, both the direction and
the magnitude of velocity changes.

In 1990, Drude made electron gas model to explain the electrical conduction in metals.

Ohm’s Law governs the electrical conduction in metals at constant temperature. The current ‘I’ flowing
through a wire is directly proportional to the potential difference V applied across the wire.

i.e. V α I

I = V/ R where R is resistance of the wire.

The current is due to the motion of the conduction electrons under the influence of the electric field. The
field E exerts a force - eE on the electron. The accelerated electrons collide with the rest of the medium;
its velocity drops to zero due to such collisions. Due to the field it is again accelerated. We can consider
that there is frictional force acting on the electrons due to its collision. If v is the velocity of the electron
and τ is the time between two consecutive collisions,

The frictional force can be written as – mv / τ, where m is the effective mass of the electron.

Using Newton’s law,

m(dv/dt) = - eE – mv / τ -----------------1

Under steady state condition dv / dt = 0

Hence from eqn (1)

v = - eτE / m ------------------------------------- 2

This is the steady - state velocity of the electron.

Drift velocity and mean free path:

There are two different velocities associated with the electron. In the absence of the
field the electrons have random motion, just as gas molecules move randomly in a gas container. The
randomly moving electrons under go scattering and change the direction. This random motion
contributes zero current and the corresponding velocity is called random velocity. In the presence of a
field, in addition to random velocity, there is an additional net velocity associated with electrons called
drift velocity due to applied electric field. Due to drift velocity vd , electrons with negative charge move
opposite to the field direction. This is given by equation (2)

If n is number of conduction electrons per unit volume, then the charge per unit volume is (- ne). The
amount of charge crossing a unit area per unit time is given by current density J

J = (- ne)vd = - ne (- eτE / m ) = ne2τ E / m

Since J = σE where σ is the conductivity

σ = ne2τ / m --------------------------------------- 3

With increase of electron concentration n , the conductivity σ increases. As m increases, the motion of
electron becomes slow and hence conductivity σ decreases. τ is the mean free distance travelled by an
electron between two successive collisions in the presence of applied field is known as mean free path.

RELAXATION TIME:- The mean free life time τ is also called the relaxation time.

Let us assume that the applied field is cut off after the drift velocity of the electron has reached its steady
value.

Drift velocity after this instant is governed by

m dvd / dt = - m vd / τ
from eqn 1. , reducing E =0

or dvd / vd = - dt / τ

or vd ( t ) = vd ( 0 ) exp ( - t / τ ) ------4 where vd(0) is the steady state drift velocity .

Fig. Relaxation of electrons after electric field is cut off

To define τ, let t = τ in equation (4) then

vd ( t ) = vd ( 0 )/ e --------------------------------- 5

Hence relaxation time can be defined as the time taken for the drift velocity to decay to 1/e of its
initial value. Mobility of the electron µ is defined as steady state drift velocity < vd > Per unit electric
field.

From equation (2)

µ = < vd > / E = eτ / m ------------------------------6

Substituting this in eqn 3

σ = ne2τ / m = ne.(eτ / m)

σ= neµ --------------------------------------------7

Therefore the resistivity of the material of the conductor is given by

ρ=1/σ =1 / neµ = m / ne2τ -----------------------------------8

Equation (7) has great significance. The electrical conductivity depends as two factors, the charge
density n and their mobility µ. These two quantities depend on temperature. In metals n is constant and
µ decreases slightly with temperature and hence with increase of temperature, the conductivity
decreases. In semi conductors, the exponential increase of n with temperature is responsible for increase
of conductivity with temperature. In insulators n remains constant and above certain temperature µ
increases exponentially resulting in dielectric break down.
Success of classical free electron theory:

1) It verifies ohm’s law

2) It explains the electrical and the thermal conductivities of metals.
3) It derives Wiedemann Franz law.
4) It explains the optical properties of metals.

Draw backs of classical free electron theory:

In spite of the success seen above, classical theory has the following draw backs

 The phenomenon such as photo electric effect, Compton effect and the black body radiation
could not be explained by classical free electron theory.
 According to the classical free electron theory the values of specific heat of metals is given
by 4.5Ru where Ru is the universal gas constant where as the experimental value is nearly
equal to 3Ru . Also according to this theory, the value of electronic specific heat is equal to
(3/2)Ru while the actual value is about 0.01Ru only.
 Though K / σT is a constant (Wiedemann Franz law). According to the classical free
electron theory it is not a constant at low temperature.
 Ferromagnetism could not be explained by this theory. The theoretical value of para
magnetic susceptibility is greater than experimental value.

Quantum theory of free electrons:

Assume that the electrons move freely in a solid similar to gas molecules. They are subjected to a
constant potential V.
Assume the potential to be zero, the Schrödinger equation becomes
(- ħ2 / 2m)▼2Ψ = EΨ

Where E is total kinetic energy.

Assume a plane wave solution of the type,

Ψ = Ψ0 exp ( ik . r )----------------(1)

Where wave vector k = 2 Π / λ and r2 = x2 + y2 + z2

Hence ∂2Ψ / ∂x2 = - k2 x Ψ

∂2Ψ / ∂y2 = - k2 y Ψ

∂2Ψ / ∂z2 = - k2 z Ψ

so that ▼2 Ψ = ∂2Ψ / ∂x2 + ∂2Ψ / ∂y2 + ∂2Ψ / ∂z2

= - (kx2 + ky2 + kz2) Ψ = - k2 Ψ --------------------(2)

therefore (- ħ2 / 2m) (- k2 Ψ ) = EΨ

or E = ħ2 k2 / 2m = ( h / 2 Π )2 ( 2 Π / λ )2 . 1/ 2m

= h2 / 2 m λ2 = h2 p2 / 2 m h2 (since λ = h / p )

E = p2 / 2 m ---------------------------(3)

The above equation represent the energy of free particle ( ie electron ) from the fig , it is seen that
the energy is continuous. If ‘L’ is the length of the solid ,applying the boundary conditions,

K = 2 Π n / L we get

E ( n ) = ħ2 k2 / 2m = h2 n2 / 8 m L2 -------------------(4)

If ‘L’ is large, the adjacent permitted energy levels differ by about 10-19eV. Since the separation is
too small, the energy levels can be considered to form a quasi continuous band.

When an external electric field ‘E’ is applied, the force exerted on the electron is –eE. Since force
is also rate of change of momentum,

-e E = dp / dt

since momentum p = h/λ = ( h/2Π ) (2Π/λ ) = ħk

-e E = d(ħk ) / dt = ħ ( dk/dt ) -----------------(5)

or dk = - ( eE / ħ ) dt ------------------(6)

This means that origin of the k space moves through a distance dk in time dt on application of
external field. Because of collisions with imperfections, displacement of k space becomes steady ( =
Δk ) and dt is then the average collision time τ

Hence Δk = - e E τ / ħ
 Since p = m v = ħ k , incremental velocity Δv is given by

Δv = ( ħ / m ) ( eE τ / ħ )

= - eE τ / m -----------------(7)

If the number of electrons per unit volume is n, then the current density J is given by

J = n ( - e ) Δv

= n e2 E τ / m

= σ E ( Ohm’s law )

where electrical conductivity

σ = n e2 τ / m ----------------------(8)

Fermi – Dirac Distribution:

Permitted energy values for electrons in a material are represented by the energy levels in the energy
bands for that material. These energy levels are occupied by the electrons in the material in a
particular order. This is called distribution of electrons. Fermi – Dirac distribution deals with the
distribution of electrons among the permitted energy levels.

According to Fermi – Dirac distribution, the probability of electron occupying energy level E is
given by

F(E) = 1/ (1 + exp [( E – EF) / kT] ----------------(1)

Where EF is called the Fermi energy and is constant for a given system. F(E) is called Fermi function.

At T = 0K, for E < EF F(E) = 1

E < EF F(E) = 0 ------------- (2)

This means that at 0K, all quantum states with energy below EF are completely occupied and those
above EF are unoccupied. With increase of temperature, the Fermi function plot shows deviation.

At any temperature other than 0K, If E = EF

F(E) = 1 / 2 ----------------(3)

Hence, the Fermi level is that state at which the probability of electron occupation is ½ at any
temperature above 0K and also it is the level of the max. energy of the filled states at 0K. Fermi
 energy is the energy of the state at which the probability of electron occupation is ½ at any
temperature above 0K. it also the max.energy of filled states at 0K.

Electron scattering and resistance:

Sommerfeld interpreted λ and vF differently. In case of classical free electron theory, λ the mean free
path was of the same magnitude as the inter atomic distance in the metal. But sommerfeld brought forth
the wave nature of electrons and consider the movement of electrons in metals as passage of matter
waves in periodic lattice. For a perfectly periodic lattice with stationary lattice ions, the waves pass
through the arrays without being scattered at all. Their mean free path would then be infinite. But there
are always deviations from the periodicity due to defects in the lattice such as vacancies, dislocations,
presence of impurity atoms, boundaries etc. This result in scattering of waves which essentially means
the scattering of electrons and thus the lattice defects become the cause of resistivity. The mean free path
is thus decided by how the waves get scattered and not by the scattering of electrons as particles.

According to sommerfeld, only those electrons which occupy energy states near EF can participate in
conduction. Such electron possess a drift velocity which will be equal to vF the velocity possessed by
those electrons near Fermi energy.

vd= vF

But we know, τ = λ / vd

i.e. , τ = λ / vF

Temperature Dependence of Resistivity of Metals: As per sommerfeld’s treatment, the resistivity

arises because of scattering of electron waves due to the deviations from the periodicity of the lattice.
 Fig. Variation of electrical resistivity with temperature

A standstill ion in the lattice acts as a point size entity which virtually possesses zero cross-sectional
area across which the electron wave passes unaffected. As temperature increases, the ions start vibrating
with large amplitudes and affect the periodicity of the lattice more and more. Thus they offer larger
cross-sectional area and the scattering of the electron waves also increases proportionately. Increase in
scattering of electron waves gives an effect of corresponding increase in scattering of particle electrons.
The increase of scattering results in increase of resistance. This explains the temperature dependence of
resistivity of metals.

BAND THEORY OF SOLIDS

Bloch Theorem: Block's theorem was formulated by the German-born US physicist Felix Bloch
(1905–83) in 1928.Accordind to this theorem, in a periodic structure, every electronic wave function can
be represented by a “Bloch function”.

A crystalline solid consists of a lattice which is composed of a large number of ionic cores at regular
intervals, and, the conduction electrons can move freely throughout the lattice.

A theorem that specifies the form of the wave functions that characterize electron energy levels in a
periodic crystal. Electrons that move in a constant potential, have wave functions that are plane waves,
having the form exp(i k · r ). Here, k is the wave vector, which can assume any value, and describes an
electron having momentum P= ħk .Electrons in a crystal experience a potential that has the periodicity
same as the crystal lattice.

Now, since the lattice is a repetitive structure of the ion arrangement in a crystal, the type of variation
of V also repeats itself. If a is the inter ionic distance, then , as we move in x-direction , the value of V
will be same at all points which are separated by a distance equal to a.

ie V(x) = V( x + a ) where, x is distance of the electron from the core.

Such a potential is said to be a periodic potential.

Bloch's theorem states that “the solution of SWequation has the form of a plane wave multiplied by
a function with the period of the Crystal lattice”,stating that the wave function ψ for an electron in
a periodic potential has the form

ψ(x) = exp(ik · x)Uk(x) in One dimensions

BLOCH FUNCTIONS

ψ(r) = exp(ik · r)U(r) in 3-dimensional motion

where k is the wave vector, r is a position vector, and U(r) is a periodic function that satisfies
U(r+a) = U(r)
for all vectors ‘a’ of the Crystal lattice of the crystal. Block's theorem is interpreted to mean that the
wave function for an electron in a periodic potential is a plane wave modulated by a periodic function.
This explains why a free-electron model has some success in describing the properties of certain metals
although it is inadequate to give a quantitative description of the properties of most metals.

In order to understand the physical properties of the system, it is required to solve the Schrödinger’s
equation. However, it is extremely difficult to solve the Schrödinger’s equation with periodic potential
described above. Hence the Kronig – Penney Model is adopted for simplification.

THE KRONIG -PENNEY MODEL:

It is assumed in quantum free electron theory of metals that the free electrons in a metal
express a constant potential and is free to move in the metal. This theory explains successfully most of
the phenomena of solids. But it could not explain why some solids are good conductors and some
other are insulators and semi conductors. It can be understood successfully using the band theory of
solids.

According to this theory, the electrons move in a periodic potential produced by the
positive ion cores. The potential of electron varies periodically with periodicity of ion core and
potential energy of the electrons is zero near nucleus of the positive ion core. It is maximum when it
is lying between the adjacent nuclei which are separated by interatomic spacing. The variation of
potential of electrons while it is moving through ion core is shown fig.

Fig. One dimensional periodic potential

V ( x ) = 0 , for the region 0 < x < a

= V0 for the region -b < x < 0 ---------------------(1)
Applying the time independent Schrödinger’s wave equation for above two regions

d2Ψ / dx2 + 2 m E Ψ / ħ2 = 0 for region-I 0 < x < a ---------------(2)

and d2Ψ / dx2 + 2 m ( E – V ) Ψ / ħ2 = 0 for region-II -b < x < a ----------------(3)

Substituting α 2 = 2 m E / ħ2 ---------------(4)

β2 = 2 m ( E – V ) / ħ2 -----------(5)

d2Ψ / dx2 + α2 Ψ = 0 for region 0 < x < a ---------------(6)

d2Ψ / dx2 + β2 Ψ = 0 for region -b < x < a --------------(7)

The solution for the eqn’s (6) and (7) can be written as

Ψ ( x ) = Uk ( x ) eikx ---------------(8)

The above solution consists of a plane wave eikx modulated by the periodic function.

Uk(x), where this Uk(x) has the periodicity same as that of the ion

i.e Uk(x) = Uk(x+a) ---------------(9)

where k is propagating constant along x-direction and is given by k = 2 Π / λ . This k is also known
asPropagation wave vector.

Differentiating equation (8) twice with respect to x, and substituting in equation (6) and (7), two
independent second order linear differential equations can be obtained for the regions-I and II.

Applying the boundary conditions to the solution of above equations, for linear equations in terms
of A,B,C and D it can be obtained (where A,B,C,D are constants ) the solution for these equations
can be determined only if the determinant of the coefficients of A , B , C , and D vanishes, on
solving the determinant.

(β2 - α2 / 2 α β)sin hβb sin αa + cos hβb cos αa = cos k ( a + b ) ---------- ---- (10)

The above equation is complicated and Kronig and Penney could conclude with the equation. Hence
they tried to modify this equation as follows

Let Vo is tending to infinite and b is approaching to zero. Such that Vob remains finite. Therefore
sin hβb → βb and cos hβb→1

β2 - α2 = ( 2 m / ħ2 ) (Vo – E ) – ( 2 m E / ħ2 )
 = ( 2 m / ħ2 ) (Vo – E - E ) = ( 2 m / ħ2 ) (Vo – 2 E )

= 2 m Vo / ħ2 ( since Vo >> E )

Substituting all these values in equation (10) it verities as

( 2 m Vo / 2 ħ2 α β ) β b . sin α a + cos α a == cos k a

( m Vo b a / ħ2 ) ( sin α a / α a ) + cos α a == cos k a

( P / α a ) sin α a + cos α a == cos k a -------------------(11)

Where P = [ m Vo b a / ħ2 ] ------------------(12)

and is a measure of potential barrier strength.

The left hand side of the equation (11) is plotted as a function of α for the value of P = 3 Π / 2 which
is shown in fig, the right hand side one takes values between -1 to +1 as indicated by the horizontal
lines in fig. Therefore the equation (11) is satisfied only for those values of ka for which left hand
side between ± 1.

From fig , the following conclusions are drawn.

The energy spectrum of the electron consists of a number of allowed and forbidden energy bands.
The width of the allowed energy band increases with increase of energy values ie increasing the
values of αa. This is because the first term of equation(11) decreases with increase of αa.

( P / α a ) sin α a + cos α a == 3 Π / 2
 Fig. a) P=6pi b) p--> infinity c) p--> 0

With increasing P, ie with increasing potential barrier, the width of an allowed band decreases. As
P→∞, the allowed energy becomes infinitely narrow and the energy spectrum is a line spectrum
as shown in fig.

If P→∞, then the equation (11) has solution ie

Sin αa = 0

αa = ± n Π

α=±nΠ/a
 α2 = n2 Π2 / a2

But α2 = 2 m E / ħ2

Therefore 2 m E / ħ2 = n2 Π2 / a2

E = [ ħ2 Π2 / 2 m a2] n2

E = n h2 / 8 m a2 ( since ħ = h / 2 Π )

This expression shows that the energy spectrum of the electron contains discrete energy levels separated
by forbidden regions.

4) When P→0 then

Cos αa = cos ka

α=k, α 2 = k2

but α2 = 2 m E / ħ2

therefore k2 = (h2 / 2 m ) ( 1 / λ2 ) = (h2 / 2 m ) (P2 / h2 )

E = P2 / 2 m

E =1/2mv2 ----------------(14)

The equation (11) shows all the electrons are completely free to move in the crystal without any
constraints. Hence , no energy level exists ie all the energies are allowed to the electrons and shown in
fig(5). This case supports the classical free electrons theory.

[ ( P / α a ) sin α a + cos α a ] , P → 0

Velocity of the electron in periodic potential.:

According to quantum theory, an electron moving with a velocity can be treated as a wave packet
moving with the group velocity vg
 v = vg = dω / dk -----------------(1)

where ω is the angular frequency of deBroglie wave and k = 2 Π / λ is the wave vector.

The energy of an electron can be expressed as

E = ħ ω ---------------------(2)

Differentiating the equation (2) with respect to k

dE / dk = ħ dω / dk -------------(3)

from (1) & (3)

vg = 1 / ħ (dE / dk ) -----------------(4)

According to band theory of solids, the variations of E with k as shown in fig(1). Using this graph and
equation (4), the velocity of electron can be calculated. The variation of velocity with k is shown in
fig(2). From this fig, it is clear that the velocity of electron is zero at the bottom of the energy band. As
the value of k increases, the velocity of electron increases and reaches to maximum at K=k.Further ,the
increases of k, the velocity of electron decreases and reaches to zero at K= Π / a at the top of energy
band.

Origin Of Energy Bands In Solids:

Solids are usually moderately strong, slightly elastic structures. The individual atoms are held
together in solids by interatomic forces or bonds. In addition to these attractive forces, repulsive forces
also act and hence solids are not easily compressed.

The attractive forces between the atoms are basically electrostatic in origin. The bonding is
strongly dependent on the electronic structure of the atoms. The attraction between the atoms brings
them closer until the individual electron clouds begin to overlap. A strong repulsive force arises to
comply with Pauli’s exclusion principle. When the attractive force and the repulsive force between any
two atoms occupy a stable position with a minimum potential energy. The spacing between the atoms
under this condition is called equilibrium spacing.

In an isolated atom, the electrons are tightly bound and have discrete, sharp energy levels. When
two identical atoms are brought closer , the outermost orbits of these atoms overlap and interact. When
the wave functions of the electrons on different atoms begin to overlap considerably, the energy levels
corresponding to those wave functions split. if more atoms are brought together more levels are formed
and for a solid of N atoms, each of the energy levels of an atom splits into N levels of energy. The levels
are so close together that they form an almost continuous band. The width of this band depends on the
degree of overlap of electrons of adjacent atoms and is largest for the outermost atomic electrons. In a
solid many atoms are brought together so that the split energy levels form a set of bands of very closely
spaced levels with forbidden energy gaps between them.
Classification Of Materials:

The electrons first occupy the lower energy bands and are of no importance in determining many
of the electrical properties of solids. Instead, the electrons in the higher energy bands of solids are
important in determining many of the physical properties of solids. Hence the two allowed energy bands
called valence and conduction bands are required. The gap between these two allowed bands is called
forbidden energy gap or band gap since electrons can’t have any energy values in the forbidden energy
gap. The valence band is occupied by valence electrons since they are responsible for electrical, thermal
and optical properties of solids. above the valence band we have the conduction band which is vacant at
0K. According to the gap between the bands and band occupation by electrons, all solids can be
classified broadly into two groups.

In the first group of solids called metals there is a partially filled band immediately above the
uppermost filled band .this is possible when the valence band is partially filled or a completely filled
valence band overlaps with the partially filled conduction band.

In the second group of solids , there is a gap called band gap between the completely filled
valence band and completely empty conduction band. Depending on the magnitude of the gap we can
classify insulators and semiconductors.

Insulators have relatively wide forbidden band gaps. For typical insulators the band
gap Eg > 3 eV. On the other hand , semiconductors have relatively narrow forbidden bands. For typical
semiconductors Eg ≤ 1 eV.

Effective mass of the electron: When an electron in a period potential is accelerated by an electric field
(or) magnetic field, then the mass of the electron is called effective mass ( m*).

Let an electron of charge ‘e’ and mass ‘m’ moving inside a crystal lattice of electric field E.
Acceleration a = eE / m is not a constant in the periodic lattice of the crystal. It can be considered that
its variation is caused by the variation of electron’s mass when it moves in the crystal lattice.

Therefore Acceleration a = eE / m*

Electrical force on the electron F = m* a --------------(1)

Considering the free electron as a wave packet , the group velocity vg corresponding to the particle’s
velocity can be written as

vg = dw / dk = 2 Π dv/ dk = (2 Π / h ) dE / dk ------------------(2)

where the energy E = h υ and ħ = h / 2 Π.

Acceleration a = d vg / dt = ( 1 / ħ ) d2E / dk dt = ( 1 / ħ ) ( d2E / dk2 ) dk / dt

Since ħk=p and dp / dt = F,

dk / dt = F / ħ

Therefore a = ( 1 / ħ2 ) ( d2E / dk2 ) F

Or F = ( ħ2 / ( d2E / dk2 ) ) a -----------------------(3)

Comparing eqns . (1) and (3) we get

m*= ħ2 / ( d2E / dk2 ) ---------------(4)

This eqn indicates that the effective mass is determined by d2E / dk2 .

Questions:

1. Explain classical free- electron theory of metals.

2. Define electrical resistance
3. Give the basic assumptions of the classical free electron theory.
4. Explain the following: Drift velocity, mobility, relaxation time and mean free
path.
5. Based on free electron theory derive an expression for electrical conductivity of
metals.
6. Explain the failures of classical free theory.
7. Explain the salient features of quantum free electron theory.
8. Explain the Fermi- Dirac distribution for free electrons in a metal. Discuss its
variation with temperature.
9. Explain the following i) Effective mass, ii) Bloch theorem.
10. Discuss the band theory of solids based on Kronig –Penney model. Explain the
important features of this model.
11. Explain the origin of energy bands in solids.
12. Distinguish between metals, semiconductors and insulators.