Quantum Mechanics

Mechanics: the study of the behavior of physical

bodies when subjected to forces or displacements

Classical Mechanics: Quantum Mechanics:

Describing the motion Describing behavior of systems
ofmacroscopic objects. at atomic length scales and
smaller.
Macroscopic: measurable or
observable by naked eyes

Failures of Classical mechanics led to the Need of Quantum mechanics

Classical physics:
Newtonian mechanics, Maxwell electromagnetic theory and Thermodynamics guided the
growth of science and technology during the years spanning 17th to 19th centuries. These theories
explained almost all the scientific results of those times.
 The above theorems which are successful in the realm (domain) of macroscopic world are regarded
asclassical physics.
 In classical physics matter and field are treated as entirely independent entities.
 Macroscopic particles move and interact according to Newton’s laws.
Failure of classical mechanics: -
The classical theory fails to explain:
1. Black body radiation
2. Atomic spectra
3. specific heat capacity
 The behaviour of atomic particles such as electrons, protons etc., stability of atom and spectral lines
emitted by the hydrogen atom (atomic spectra).
 At the same time it also fails to explain several new discoveries during the 19 th century, such as
Black body radiation, Photoelectric effect, Compton Effect, Zeeman Effect, absorption and emission
of radiation, specific heat capacity of solids at low temperatures.
 It is therefore concluded that classical mechanics does not hold in the region of atomic dimensions.
  As physicists sought new ways to solve these puzzles, another revolutionary work took place in
physics between 1900 and 1930. A new theory is called quantum (wave) Mechanics was developed.
It is highly successful in explaining the behaviour of atoms, electrons, protons etc...
Black Body Radiation:
 A perfect black body is defined as the one which absorbs totally all the radiation of any wavelength
whichfalls on it. Such a body neither reflect nor transmit any radiation, therefore it appears black.
 The absorbing power of black body is unity.
 The radiation emitted by black body is known as black body radiation.
 When a perfectly black body is heated to suitable temperature it emits the radiation of all possible
wavelengths.
 A perfectly black body cannot be realized in practice. The most commonly used perfect black body
was designed by Ferry. It consists of a double walled metal sphere with a small hole, coated with
lamp black inside (or platinum black) nickelized outside, the interspacing between the walls being
kept evacuated toprevent loss of heat by conduction and convention as shown in Fig.

 When any radiation enters the body through tiny hole, it suffers repeated reflection from the inner
walluntil it is finally absorbed.
 Inside the sphere and directly opposite to the opening there is a projection from the wall preventing
thedirect reflection of radiation. Hence the opening behaves like a perfect absorber.
 Conversely, when the sphere is heated the radiation is emitted by the walls and the radiation coming
outof the opening will be of same nature as emitted by black bodySpectrum of Black Body:
• The experimental spectrum of black body radiation was observed by Lummer and Pringsheim in 1900.
• The thermal radiation emitted by black body is thoroughly analysed using spectrograph and bolometers.
The experimental results show that:
o The black body emits all kinds of radiations ranging from lower wavelength to higher wavelengths.
o At a given temperature, the energy is not uniformly distributed in the radiation spectrum.
 o The radiation energy density initially increases with wavelength, then peaks at a particular
wavelength λm and after that decreases finally to zero at very high wavelength.
o At a given temperature the intensity of radiation is a maximum at a particular wavelength λm.
o With increase in temperature, λm decreases
o For all wavelengths an increase in temperature causes an increase in the energy of emission.
Stefan-Boltzmann’s law:
 The area under each energy spectrum curve represents the total energy emitted at that temperature.
This area increases with increase in temperature of the body.
 According to Stefan –Boltzmann’s law the area is directly proportional to the fourth power
of thetemperature of the body.
E α T4 or E = e σ T4
• E- rate of emission of radian energy per unit area (total emissive power)
• T- absolute temperature of the body.
• E-emissivity of the surface.
• σ -Stefan-Boltzman constant = 5.6703 x10-8 W/m2 K4
Wiens Law:
In 1893 Wein derived an expression for the energy density and explained some features of energy
distributionof black body radiation (spectrum) based on thermodynamic consideration.
  Wien showed that the product of the wavelength corresponding to maximum energy λm and absolute
tempT is constant.
λmT = constant= 2.898 x10-3 m K
i.e λm α 1/T
This is called Wien’s displacement law.
 Wien also showed that maximum energy E m is proportional to the fifth power of absolute
[Link] α T5
 He derived expression for the energy emitted at given wavelength range λ and λ+dλ at given temperature

Where C1and C2 are constants.

o Wiens law holds good only in the short wavelengths (longer frequencies) but fails at longer
wavelength.
o The distribution formula also fails at high temperatures.
Rayleigh-Jeans law:-
 Rayliegh and Jeans calculated the number of standing waves in the range λ and λ+dλ and the
averageenergy of the waves from which the expression for energy density was derived.

Where k is Boltzman’s constant = 1.38x10-23J/K.

The above expression is known as Rayleigh-Jeans radiation formula.
 The Rayliegh-Jeans law holds good in the region of longer wavelength but not for shorter wavelength.
Plank’s quantum theory of black body radiation:
In order to explain black body radiations. Plank proposed some postulates. They are
a) A chamber that emits black body radiations contains a number of harmonic oscillators of molecular
dimension. The oscillators can vibrate all possible frequencies.
b) The oscillator emits the radiations and the frequency of radiation emitted is equal the frequency of vibration
of oscillator.
c) An oscillator emits discrete energy, i.e. the energy emitted by the oscillators is not continuous. If the oscillator
is oscillating with frequency 𝜈, it emits the radiation in quanta of magnitude h𝜈.
E= n hν
Where n is an integer and h is Planks constant, h=6.626 x 10 -34 Js.
 d) The emission or absorption of radiation occurs when the oscillator moves from one state to other. The amount
of energy emitted or absorbed is always an integral multiple of hν. The energy emitted by the oscillator is
0, hν, 2hν, 3hν, 4hν ........, etc.
Derivation:
Plank derived the black body radiation law on the basis of his postulates which is known as Plank’s radiation
law.
The Planks radiation law can be derived using quantum theory by considering the blackbody radiation with
large number of harmonic oscillators. If N be the total number of Plank’s oscillators and E be their total energy then

the average energy per oscillator  is given by

E
    (1)
N
Let N0, N1, N2, N3, -----------Nn------- be the number of oscillators with energy 0, ε, 2ε, 3ε, 4ε, ------------ nε
------, then the total number of oscillators N and the total energy E of the system are given by

N  N 0  N1  N 2  N 3         N n       N n    (2)
n 1


E  0 N 0  N1  2N 2  3N 3       nN n       nN n    (3)
n 1

According to Maxwell- Boltzmann statistics the number of oscillators with the energy nε is given by
  nε 
N n  N 0exp      (4)
 K BT 
Where KB is Boltzmann constant, substituting the values of N1, N2, N3, ----------- from Eq(4) in Eq(2) and Eq(3) we
get.
The total number of oscillators is
 ε    2ε    3ε    nε 
N  N 0  N 0 exp    N 0 exp    N 0 exp           N 0 exp       
 K BT   K BT   K BT   K BT 
 ε    2ε    3ε    nε 
N  N 0 {1  exp    exp    exp           exp      }
 B 
K T  B 
K T  B 
K T  B 
K T

N0 1
N    (5) (since 1  x  x 2  x 3        )
 ε  1 x
1  exp  
 K BT 
The total energy E is given by
 ε    2ε    3ε    nε 
E  0N 0  N 0 exp    2N 0 exp    3N 0 exp        nN 0 exp      
 K BT   K BT   K BT   K BT 
  ε   ε    2ε    3ε    (n - 1)ε  
E   N 0 exp   1  2 exp    3 exp    4 exp         n exp       
 
 K BT    K BT   K BT   K BT   K BT  

 ε  1
E   N 0 exp   2
   (6)
 B 
K T   ε 
1  exp  
  K B T 

1
(since 1  2 x  3x 2  4 x 3        )
1 - x 2
Therefore, the average energy of oscillator is given by
 ε   ε 
 N 0exp  
1  exp  
E  K BT   K BT 
  2

N    ε  N0
1  exp  
  K B T 
 ε 
 exp  
 K BT   hν
       (7)
   ε    ε     hν  
1  exp   exp    1 exp    1
  K B T    K BT     K BT  
The number of oscillators per unit volume in frequency range ν and ν +dν is given by
8π 2
N dν    (8)
c3
Therefore, the total energy per unit volume in the frequency range ν and ν +dν is

8π 2 hν
E ν dν  dν
c   hν  
3

exp    1
  K BT  
8h 3 1
E ν dν  dν    (9)
c 3
  hν  
exp    1
  K BT  
This relation is known as Plank’s radiation law. It can be written in terms of wavelength λ as
8hc 1
E  d  d    (10)
 5
  hc  
exp    1
   K B T  

 hc 
The plank’s formula reduces to Wien’s formula for small wavelengths. When λ s small then exp    1
 K B T 
 8hc   hc 
 E  d  exp  d
  K B T 
5

Which is Wien’s law with C1 = 8hπc and C2=hc/KB

The plank’s formula also reduces to Rayleigh –Jean’s law for longer wavelength. When λ s larger then

  hc  hc
exp    1  (neglecting higher powers)
 K B T  K B T
8K B T
 E  d  d
4
This represents Rayleigh – Jean’s formula. Thus Plank’s formula agrees with experimental results throughout
the whole range of wavelengths.

Photoelectric Effect:
The emission of electrons from a metal surface when illuminated by light or any other radiation
suitable frequency (or wavelength) is called photoelectric effect. The emitted electrons are called
photoelectrons and the current constituted by these electrons is known as photo current.
• This phenomenon was first observed by Heinrich Hertz in 1887, when ultra violet light falls on zinc
plateand it was studied in detail by Philip Lenard, a student of Hertz. Lenard received Nobel prize
in Physics in 1905 for his work on cathode rays.
• The phenomenon was experimentally verified by Hallwachs, Lenard, [Link], R.A. Millikan
and others.
• After wards it was discovered that alkali metal like sodium, lithium, potassium, rubidium and cesium
ejected electrons when visible light falls o them.
• Millikan, investigated the effect with number of alkali metal over a wide range of light frequencies
andwas given Noble prize 1923
Experimental Study of photoelectric effect:
 • A simple experimental study of photo electric effect is shown in above fig.
• The apparatus consists of two photosensitive surfaces A and B enclosed in an evacuated quartz bulb.
• The plate A is connected to the negative terminal of a potential divider while the plate B is connected to
the positive terminal through an Ammeter A.
• In the absence of any light, there is no flow of current and hence the Ammeter reading is zero.
• But when monochromatic light is allowed to fall on plate A, a current start flowing in the circuit which is
indicated by Ammeter at non-zero.
• The current is known as photo current. This shows that when light falls on the metallic surface, electrons
are ejected.
• The number of electrons emitted and their kinetic energy depend up on the following factors:
• The potential difference between the two electrodes i.e. between plate A and B
• The intensity of incident radiation.
• The frequency of incident radiation.
• The photo metal used.
Characteristics of photo electrons:

1. The effect of potential difference:

• For a given photo metallic surface A, keeping the intensity and frequency of the incident radiation
fixed, let us consider the effect of potential difference as shown in fig.
• When the positive potential of the plate B is increased, phototelectric current is also increased.
• However, if the positive potential is further increased such that it is large enough to collect all the
photo electrons emitted from plate A, photo electric current reaches a certain maximum value,
knownas saturation current.
• If the potential difference is kept zero, it is observed that photo electric current still flows in same
direction. This shows that the incident radiation not only eject the photo electrons but also gives
theman electromagnetic fore.
 • If the potential of the plate B is made negative i.e. the retarding potential is increased, the photo current
decreased and finally becomes zero at a particular value.
• The negative potential of the plate B at which the photo electric current become zero is called as
cutoffpotential or stopping potential.
2. Effect of intensity of incident radiation

• Let us observe the effect of intensity of incident radiation, of course of the same frequency.
• Above figure shows the variation of photo current as a function of potential difference between the
plates for different intensities of incident radiation.
• If the intensity of incident radiation is increased from I to 2I and the experiment is repeated, then the
photo electric current increases in the same ratio for all positive values of V.
• As V is made negative, the photoelectric current decreases sharply and reaches to zero at the same
value of the V0.
Conclusion:
• The Stopping potential is independent of intensity of incident radiation.
• The saturation current is proportional to the intensity of incident radiation.
3. The effect of frequency of incident radiation.

• Let us observe the effect of varying frequency of the incident radiation while keeping the
 sameemitting surface and same intensity of the incident radiation.
• The above figure shows the variation of stopping potential with frequency of incident radiation.
• The graph shows that at frequency , the stopping potential is zero.
• The frequency is called threshold frequency and the corresponding wavelength as threshold
wavelength.
Threshold frequency:
The minimum frequency of incident radiation which can cause photoelectric emission i.e. this
frequencyis just able to liberate electron without additional energy.
4. Effect of photometal used

• The above figure shows a graph between stopping potential V0 and frequency for a number of
photometals.
• From the graph it is clear that all the lines have the same slope but their interactions with with the
frequency axis are different.
• Thus we conclude that the threshold frequency is a function of photometal used.
Fundamental laws of photoelectric effect:
• Electrons are emitted from photosensitive surfaces. Each material has a definite minimum
frequencyνo below which the photoelectric emission does not occur. This minimum frequency is
called threshold frequency
• For 𝜈 > νo, photocurrent is proportional to the intensity of incident radiation.
• For 𝜈 > νo, The KE of photoelectrons increase with increase in frequency of incident light.
• For a given metal, stopping potential V0 is directly proportional to frequency but is independent
of the intensity of incident radiation.
• Emission of photo electrons is instantaneous (less than 10-8s) no matter how feeble the
incident light may be.
• The rate at which electrons are emitted from a photocathode is independent of its temperature,
 whichshows that photoelectric effect is different from thermoionic emission.
Einstein theory of photo electric effect:
• According to Einstein’s explanation, in photo electric effect one photon is completely absorbed by one
electron, which there by gains the quantum of energy and may be emitted from the metal.
• A part of its energy is used to free the electron from the atom and away from the metal surface. This
energy is known as “Photoelectric work function” for the metal and denoted by Wo.
According to law of conservation of energy:

Energy of photon = Energy needed to liberate the electron + Maximum KE of liberated electron.

Equations (1) and (2) are known as Einstein photoelectric equations. Equation (2) is also written as

Where Vs is stopping potential (since )

When the photon energy is just sufficient to emit the electron from metal, then KE of electron is zero
Equation (3) becomes

Where νo is called threshold frequency. Threshold frequency may be defined as the minimum frequency
which can cause the photo emission.

Where Wo is expressed in Joules. If Wo is expressed in eV then

 Wave and particle duality of radiation
To understand the wave and particle duality, it is necessary to know what is particle and what a wave is.
A wave is specified by its: Frequency ‘f’, Wavelength ‘λ’ , phase or wave velocity, Amplitude and Intensity.
Moreover, a wave spreads out and occupies a relatively large region in space.
A particle is specified by its: Mass ‘m’, Velocity ‘v’, Momentum ‘p’ and Energy ‘E’. Moreover, a particle occupies
definite positions in space and hence is very small.
In view of the above, it is difficult to accept the conflicting ideas that radiation has dual nature i.e. radiation
is a wave which spreads out over a space and also particle which is localized at a point in space. However, this
acceptance is essential because radiation sometimes behaves as a wave and at other times as a particle as explained
below.
1) Radiation including visible light, Infrared, Ultraviolet and X rays etc. behave as waves in experiment based on
interference, diffractions etc. This is due to the fact that these phenomena require the presence of two waves at
the same position at the same time. Obviously it is impossible for the two particles to occupy the same position
at the same time.
2) However, the radiation behaves as a particle in interaction experiments which include black-body radiation,
photo electric effect and Compton effect. Here, radiation interacts with matter in the form of photons or quanta.
Thus the radiation sometimes behaves as a particle and at some other times behaves as a wave. But the
radiation cannot exhibit its particle and wave properties simultaneously

de Broglies concept of matter waves (de Broglies hypothesis):

In 1924 the French physicist Louis de Broglie, put forward the bold suggestions that matter, like radiations
has dual nature. i.e. matter which is ordinarily considered as made up discrete particles, molecules atoms, protons,
electrons possess wave like properties under appropriate conditions. de Broglie’s hypothesis was based on the
following facts.
1) Nature loves symmetry: According to this principle the two fundamental forms, matter and radiations available
in nature must possess mutually symmetrical properties. Since radiation has been shown to possess dual nature
wave and particle, matter also must possess the same dual nature.
2) The close parallelism between mechanics and optics:The principle of least action in mechanics stating that a
moving particle chooses always that path for which the action is minimum. According to the fermat’s principle
of least time in optics, a light ray chooses always that path for which the time of transit is minimum. This close
analogy of the two principles belong to two different branches of physics shows that matter behaves like a
wave under suitable circumstances.
3) Bohr’s theory of atomic structure: According to Bohr’s theory, the stable states of electrons in the atom were
governed by integer rules. Since the only phenomena involving integers in physics were those of interference
 and modes of vibration of stretched string both of which imply the wave motion. Hence the electron in the stable
orbits must also be supplemented with wave aspect.
With these considerations de Broglie proposed that matter also behaves like a wave under appropriate conditions.
Expression for de- Broglie wave length:
The dual nature of light possessing both wave and particle properties is clearly illustrated by combing plank’s
relation for energy of a photon E=hυ with Einstein mass energy relation E=mc 2,
Considering the photon to be a particle of mass ‘m’ moving with velocity ‘c’ the energy associated with it is given
by Einstein’s mass energy relation as
E=mc2 − −→ (1)
According to plank’s hypothesis, energy of photon of frequency ‘υ’ is given by
hc
E = hν = − −→ (2)
𝜆
Where h is plank’s constant, from (1) and (2) we have
mc2 = hν
hν h
mc = = − −→ (3)
c 𝜆
Where ‘λ’ wavelength of light. The momentum of photon is given by
𝑝 = 𝑚𝑐 − −→ (4)
From (3) and (4)
h
p=
𝜆
h
𝜆= − −→ (5)
p
The relation (5) was generalized by de Broglie, for any particle of mass ‘m’ and moving with velocity ‘v’. The
momentum of the particle is p=mv
h
𝜆= − −→ (6)
mv
eq (6) gives de Broglies wave length for any particle of mass ‘m’ moving with velocity ‘v’ . Hence de Broglie
wavelength depends upon mass of the particle and its velocity.
For larger values of ‘v’, ‘m’ depends on velocity. According to theory of relatively
m0
m
v2
1
c2
where m0 is the rest mass of the particle.
These waves are not electromagnetic waves but are a new kind of waves. They are pilot waves in the sense that
their function is to pilot or guide the matter particles.
 Case 1. Wavelength of a particle moving with velocity ‘v’:
If ‘m’ is the mass and ‘v’ is the velocity of the material particle then
p = mv
h
𝜆=
mv
Case 2 wavelength of charged particle:
If the charged particle carrying charge ‘q’ is accelerated by a potential difference of ‘v’ volts. Then
KE=qV
1 2
mv  qV
2
mv2  2qV

mv  2mqV
h

2mqV
If the charged particle is electron, then
h

2meV
For an electron e = 1.602×10-19 C , mass m = 9.1 X 10-31 kg

6.626×10−34
∴ 𝜆 = +
√2×9.1×10−31×1.602×10−19 × 𝑉

150 12.26
λ= √ = A0
𝑉 √𝑉

1.226
 nm
V
Case 3. de Broglie wavelength in terms of Kinetic energy:
If ‘m’ is mass and Ek is KE of the material particle then
1
KE  mv2  Ek
2

mv  2mEk
h

2mEk
Properties of matter waves
1) Lighter the particle, greater is the wavelength associated with it
2) Lesser the velocity of the particle, longer the wavelength associated with it.
3) When v=0 then    i.e. wave behaves indeterminate and of v   then   0 . This shows that matter
waves are generated by motion of the particles.
4) These waves are produced whether the particles are charged or uncharged. This fact reveals that these waves
are not electromagnetic waves but they are new kind of waves (EM waves are produced only by the motion
of charged particles)
5) The velocity of matter waves depends on the velocity of material particle i.e. it is not constant while the
velocity of EM wave is constant.
6) The velocity of matter wave is greater than the velocity of light.
7) Wave and particle aspects of moving bodies can never appear together in the same experiment.
8) The wave nature of matter introduces an uncertainty in the location of the position of the particle. Because a
wave cannot be said exactly at this point or at that point. However, when the wave is large (strong) there is a
good chance of finding the particle, while, where the wave is small(Weak) there is very small chance of
finding the particle.
Experimental verification of matter waves:
According to de Broglies hypothesis, a beam of material particles must possess were like characteristics. This
conclusion was experimentally proved by C.J Davisson and [Link] in 1927 with low velocity electrons. Later
in 1928 [Link] using high velocity electron.
Davisson and Germer electron diffraction experiment:
The first experimental support for the concept of matter waves i.e. wave nature of atomic particles come from
experiments done by Davisson and Germer. They succeeded in measuring the de Broglie wavelength associated with
slow electrons.
Davisson and Germer were studying the reflection of electrons from nickel target. Accidentally the nickel target
was subjected to such a heat treatment that the reflection became anomalous. Now the reflected intensity showed
striking maxima and minima. Thus they suspected that electrons are diffracted like x-rays i.e. they behave like waves
under certain conditions.
 The experimental arrangement is shown in fig.1. The electron beam is produced from electron gun. The electron
gun consists of a tungsten filament (F) coated with barium oxide, when heated to dull red (by a low tension battery)
the electrons are emitted due to thermo ionic emission. These electrons can be accelerated to desired velocity by an
electric field of known potential difference which can be varied from 40 to 70 Volts. The electrons are collimated
by a suitable slit to obtain a fine beam. The beam of electrons is directed to fall on a large single crystal of nickel.
The target can be rotated about an axis parallel to the axis of incident beam, the electrons are reflected from the
nickel crystal in different directions. The angular distribution is measured using a electron detector (Faraday
cylinder) which is connected to a galvanometer. The faraday cylinder can be moved along a graduate circular scale
between 200 to 900 to receive the reflected electrons. The faraday cylinder consists of two walls insulated from each
other. A retarded potential is applied between them so that only fast moving electrons produced by the collision with
atoms from nickel target are reflected by the faraday cylinder.
The faraday cylinder was moved on a circular scale and for a given accelerating voltage ‘V’, the scattering curve
showed a peak in a particular direction ‘ф’. When the electron beam incident perpendicular to the crystal surface,
the pronounced scattering direction was found to be 500 for the electron accelerated to 54Volts.
Under these conditions, the surface rows of atoms acts like the ruling of diffraction grating, producing the first
order spectrum of 54V, electron at ф = 500 as shown in fig (2).
From x-ray diffraction technique, the inter planer spacing (d) is measured as
d = 0.91 x 10-10 m
The Bragg angle θ = 90 – 25 = 650
From the Bragg formula
2d Sinθ = nλ
1 x λ = 2 x 0.91 x 10-10 Sin 650
λ = 1.65 x 10-10m =1.65 A0
The theoretical value of de Broglie electron wave is given by
12.26 12.26
   1.66 A0
V 54
The close agreement between the two values confirms de Broglie hypothesis of matter waves.
Wave packet:
According to Schrodinger postulate material particle is equivalent to a wave packet. Which consists of a
group of waves with slightly different velocities and wavelengths. The phases and amplitudes are such that there is
a constructive interference over a small region of space where the particle can be located and there is destructive
interference outside of this region where the amplitude is zero. The envelope of the packet has finite special extent
and the sum of amplitude of all the plane wave component is zero except the place where particle is localized.
 dω
The velocity with which the wave packet moves is called the group velocity v𝑔 =
dk
ω
The average velocities of individual waves are called phase velocities. v𝑝 =
k

The velocity of material particle v is same as group velocity of wave packet. v = v𝑔

The wave packet geometrically represents an object with wave and particle properties. It has wave properties
since it is constructed from waves and it has wave like form. It also behaves like a particle because it is localized.
Heisenberg’s Uncertainty Principle:
In 1927, Heisenberg proposed an interesting principle, which is a direct consequence of the dual nature of
matter, known as uncertainty principle. According to this principle ‘It is not possible to measure both position and
momentum of particle at the same time exactly or it is impossible to measure both the position and momentum of
the particle simultaneously to any desired degree of accuracy.
Qualitatively this principle states that there is always some uncertainly (Δx) in the specification of positions
and some uncertainty (ΔP) in specifications of momentum. The product of uncertainty Δx and ΔP is related as
x.P  
h
where  
2
From the above relation it is clear that if x  0 then P   , so that the product may be non zero.
Similarly ΔP  0 then x   . Thus both Δx and ΔP are non zero, so that their product is the order of  .
Also if an electron has definite momentum then from de Broglie relation it will have definite wavelength. So
the wave will expand all over the space and uncertainty in positions infinite, which is consistent with uncertainty
principle.
In classical mechanics, moving particle at any instant has a fixed position in space and a definite momentum
which can be determined if the initial values are known.
However in wave mechanics the particle is described in terms of wave packet. According to Born’s,
probability interpretation. The particle may be found anywhere within the wave packet. In that case Δx is not infinite
but has some finite value depending as extension of the wave packet. When wave packet is small, the positions of
the particle may be fixed but the particle will spread rapidly and hence velocity becomes indeterminate. On the other
hand when the wave packet is large the velocity (momentum) can be fixed but there is large uncertainty in position.

In this way uncertainty of momentum involves uncertainly in positions and certainty in positions involves uncertainty
in momentum.
Other forms of uncertainty principle
In more general form uncertainly principle state that “It is impossible to specify precisely and simultaneously
the value of both members of particular pairs of physical variables that describe the behavior of an atomic system”
The pairs other than positions and momentum are energy and time, angular momentum and angle. Thus
according to uncertainty principle
∆E ∆t≈ 
and ∆J ∆θ≈ 
where ΔE and Δt are uncertainties in determining energy and time, while ΔJ and Δθ are uncertainties in
determining angular momentum and angle.
The exact statement of uncertainty principle is “The product of uncertainties in determining positions and

momentum of a particle can never be smaller than the order of ”.
2

So we have
 h
∆x ∆P ≥ =
2 4𝜋


Similarly ∆E ∆t≥
2


∆J ∆θ ≥
2
Consequences of uncertainty principle:
1) Explains the absence of electron in the nucleus
2) Proof for existences of protons and neutrons inside the nucleus
3) Energy of electron in atom
Schrodinger time dependent wave equation
In order to explain the de Broglie wave associated with a material particle, Schrodinger developed a wave
equation. This is the basic equation for quantum mechanics. In quantum mechanics, without giving a specific value
for a physical quantity, the probability of possessing that particular value is discussed. The function which expresses
the probability of finding a particle at a position is called wave function ψ.
Let us consider a free particle of mass m moving with velocity v, the total energy of the particle (electron)
is the sum of its KE and PE.
Total energy = KE + PE
1 2
E mv  V ( x, t )
2
1 m2v 2
  V ( x, t )
2 m
p2
E  V ( x, t )
2m
V can be a function of both position ‘x’ and time ‘t’
p2
E    V ( x, t ) - - - - - - - - - (1)
2m
The wave function 𝜓 for a particle moving freely in the positive x-direction has the same form as the solution
for un-damped, harmonic waves in the positive x-direction.
𝜓(𝑥, 𝑡) = 𝐴 exp(−𝑖 (𝜔t − kx)) − −→ (2)
ℎ
Where wave function 𝜓 is a function of ‘x’ and ‘t’. From de Broglie’s relation 𝜆 = 𝑝

h 2𝜋
p= × = k
2𝜋 𝜆
p
⇒ k=

From Planks relation
hω
E=hν= = ω
2𝜋
E
⇒ ω=

Substituting the values of k and ω in equation (2)
E p
𝜓(𝑥, 𝑡) = 𝐴 exp (−𝑖 ( t - 𝑥))
 

𝑖
𝜓(𝑥, 𝑡) = 𝐴 exp (− (Et − px)) − − − − − − (3)

The equation (3) is correct only for freely moving particle. Hence a fundamental differential equation is required for
ψ which may be then solved in the specific situation.
Differentiation equation (3) with respect to time‘t’ once

  i  iE 
 A exp  Et  px  
t     
iE


 
E   - - - - - - - (4)
i t
Differentiating the equation (3) with respect to ‘x’ twice
  i  ip 
 A exp  Et  px 
x     
 2
2
 i  ip 
 A exp 
   Et  px   
x 2
 p2
 2 

 2
p   
2 2
- - - - - (5)
x 2
Substituting the values of E and p  from equation (4) and (5) in equation (1) we get
2

   2  2
   V
i t 2m x 2
  2  2
i   V
t 2m x 2
   2  2
  V - - - - - - - (6)
i t 2m x 2
This equation (6) is known as one dimensional Schrodinger’s time dependent wave equation. This equation is a
complex equation because of the presence of factors i. This means that ψ is a complex function, but of real variables
x and t. ψ cannot, therefore, be observed like displacement of a string.
In three dimensions the time dependent Schrodinger 's wave equation is
2
𝜕𝜓 − 𝜕2 𝜓 𝜕2 𝜓 𝜕2 𝜓
𝑖 = ( + + ) + V 𝜓 − − − − (5)
𝜕𝑡 2𝑚 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2
2
𝜕𝜓 − 𝜕2 𝜕2 𝜕2
𝑖 = ( + + )𝜓 + V 𝜓
𝜕𝑡 2𝑚 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2
 Here 𝜓 is a function of x, y, z & t
2
𝜕𝜓 −
𝑖 = ∇2𝜓 + V 𝜓 − − − (6)
𝜕𝑡 2𝑚
𝜕2 𝜕2 𝜕2
Where ∇2 = 2
+ 2
+ Laplacian operator
𝜕𝑥 𝜕𝑦 𝜕𝑧 2

We can write the above eq (6) as

𝐸𝜓 = 𝐻𝜓
2
−
Here H=( ∇2 + V) is called the Hamiltonian operator
2𝑚
𝜕
𝐸 = 𝑖 is Energy operator
𝜕𝑡
Schrodinger time independent wave equation
Consider a situation in which the potential energy of the particle does not depend explicitly on time and the
forces that act upon it. Hence ‘V’ the potential energy varies only with the position of the particle.
In this case the Schrödinger time dependent equation
   2  2
  V    (1)
i t 2m x 2
reduces to the time independent form. It is always possible to find the solutions of Equation (1) so that the wave
function ψ is independent of time. If a particle can be described by such a wave function, it is considered to be in
stationary state.

The wave associated with a moving particle can be described as

 i
 x, t   A exp  Et  px 
  

 iEt   ipx 
 A exp   exp 
     
 iEt   ipx 
Let  t   exp   and   x   exp 
     
Then  x, t  =  x  𝜙(𝑡)
 iEt 
 x, t   A x  exp       (2)
  
  iE   iEt 
 A   x exp         (3)
t     
   iEt    x 
 A exp  
x    x
 2  iEt    x 
2
 A exp         (4)
x 2    x
2

Substituting in equation (1)

   iAE ( x)    iEt  
2
  iEt    ( x)
2
  iEt 
  exp   A exp    V ( x) A exp  
i     2m    x   
2


 2  2 ( x)
 E ( x)   V ( x)
2m x 2
 2 2m
 E  V   0      (6)
x 2  2
Here ψ is a function of position ‘x’ only and it is independent of time ‘t’. Equation (6) is one dimensional time
independent Schrodinger equation. In three dimensions equation can be written as
 2  2  2 2m
   E  V   0
x 2 y 2 z 2  2

 2 
2m
E  V   0      (7)
2

8 2 m
 2  E  V   0      (8)
h2

Physical significance and Born’s interpretation of wave function ψ:

The quantum mechanics deals with wave function ψ of a body. The wave function by its self has no physical
significance as it is not an observable quantity. We cannot give a physical interpretation of the wave function.
2
However ψ i.e. square of its absolute magnitude at a particular position and at a particular time indicates the

probability of finding the particle there at that time. Knowledge of ψ enables us to establish the linear momentum,
2
energy and other parameters. ψ is called probability density.

Since the wave function ψ is a complex quantity it may be

ψx, y, z, t   a  ib - - - -  (1)

Where ‘a’ and ‘b’ are real functions of variable x,y,z and t and i   1 . The complex conjugate of ψ which is
denoted by ψ* is obtained by changing i to –i
ψ* x, y, z, t   a  ib - - - -  (2)
multiplying above two equation
ψψ*  (a  ib)(a  ib)  a 2  b 2 - - - -  (3)
The product on the left side of this equation denoted by P
P  ψx, y, z, t   ψψ *  a 2  b 2 - - - -  (4)
2
Thus

Thus the product ψ and ψ* is real and +ve if ψ ≠ 0.  x, y, z, t  is called probability density. The fact
2

expressed in equation (4) has been used by Max Born (1882 -1970) a German physicist to give the interpretation of
2 2
ψ. According to Born’s interpretation ψψ * or ψ is probability density. ψ dv gives the probability of finding

a particle in the region of ‘dv’.

For the motion of the particle the quantity
P dv  ψx, y, z, t ψ * x, y, z, t dv

 ψx, y, z, t  dv
2

Is the probability that the particle will be found in a volume element dv. Surrounding the point at position (x,y,z) at
the instant ‘t’.

ψx, y, z, t  Represent probability per unit volume.

2

For the motion of the particle in one dimension.

Pdx  ψx, t ψ * x, t dx  ψx, t  dx

2

Is the probability that the particle will be found over a small distance dx at a position ‘x’ at the instant‘t’. ψx, t 
2

is the probability per unit length.

If the particle (electron) must exist somewhere in a volume V, it is mathematically stated as

ψ dv 1
2

If the particle exist somewhere in the universe



ψ dv  1
2



This condition is known as normalized condition. A wave function that satisfies the above condition is said to be
normalized
If the particle does not exist


ψ dv  0
2



The probability value lies between 0 and 1. If it has a value of 0.2 or 0.6 it means that there is a 20% or 60%
chance of locating the particle within the selected volume.
Limitations
1) Ψ must be finite for all values of x,y,z
2) Ψ must be single valued i.e. for each set of values of x,y,z . Ψ must have only one value.
 3) Ψ must be continuous in all regions except those where the potential energy V(x,y,z) = ∞
4) The first derivative of Ψ must be continuous

Particle in a box
When the motion of a particle is confined to a limited region such that the particle moves back and forth in
the region, then the particle is said to be in a bound state. If one dimensional motion of a particle is assumed to be
takes place with zero potential energy over a fixed distance and if the potential is assumed to became infinite at the
extremities of the distance, then it is described as a particle in one dimensional box.
Let us consider a particle of mass ‘m’ bouncing back and forth between the walls of one dimensional box.
Suppose that the particle moves only along x axis and confined between x=0 and x=a, the particle does not loose any
energy due to the collision with the walls.

The potential function is defined in the following way

V(x)=∞ for x≤0 and x≥0

V(x)=0 for 0<x< a

-----------(1)
The wave function ψ n of the particle (e-) occupying nth state is determined from the Schrodinger wave equation.

 2 ψ n 2m
 2 E n  V ψ n  0
x 2 
As V=0

 2 ψ n 2m
 2 En ψn  0
x 2 
 2mE n 2mE n
Let k2  ⇒ k
2 
 2ψn
 k 2 ψ n  0      (3)
x 2

The solution of equation (3) is of the form of sin kx or cos kx. The general solution is given by
ψ n x   ASinkx  BCoskx - - - - - -  (4)
where A and B are constants. The values of these constants can be obtained by applying the boundary conditions
of the problem.
a) At x=0; ψ n x   0
0=Asin k(0) + Bcos k (0)
⇒ B=0
∴ ψ n x   ASinkx - - - -  (5)
b) At x=a ; ψ n x   0
ψ n a   ASinka  0

Here either A = 0 or Sinka =0, but A ≠0 because if A =0 the entire function will be zero
∴ Sin ka = 0
⇒ ka = nπ where n= 1,2,3,……..

     6
nπ
k
a
Now the wave function becomes

ψ n x   ASin
nπ
x - - - -  (7)
a
From equation (6)
2
 nπ 
k2   
 a 
2
2mE n  nπ 
 
2  a 

n 2h 2
En       (8)
8ma 2
i) The lowest energy of the particle is obtained by taking n=1
h2
E1 
8ma 2
 4h 2
E2   4 E1
8ma 2
 E n  n 2 E1
E1 is the zero point energy of the system.
ii) The possible values of energy of the particle in a potential box are discrete corresponding to n =
1,2,3……i.e energy is quantized.

The spacing between nth energy level and next higher level increases as n  1 E1  n 2 E1  (2n  1)E 1
2
iii)
The values of En for which steady state equation of Schrodinger can be solved is called eigen value. The wave
function ψn corresponding to En is called Eigen function of the particle. The integer ‘n’ corresponding to the energy
En is called quantum number of the energy level E n.

The constant ‘A’ in equation (7) can be determined by using the condition that the probability of finding the
particle somewhere on the line is unity i.e.
a a

 ψ x .ψ x dx   ψ x  dx  1
* 2
n n n
0 0

 nπ 
a

 A Sin  x dx  1
2 2

0  a 

A2   2nπ  
a

0 2 1  Cos a x  dx  1

 a
A2  a 2nπ 
2 x  2nπ Sin a x   1
0

A2
 a 1
2
2
A      (9)
a
Substituting equation (9) in equation (7), we get normalized wave function as

ψ n x  
2 nπ
Sin x - - - -  (10)
a a

Probability of the location of the particle:

The probability of finding a particle over a small distance dx at a x is given by
2  nπ 
p(x)dx  Sin 2  x dx - --  (11)
a  a 
The probability density for the one dimensional motion is
2  nπ 
p(x)  Sin 2  x     (12)
a  a 
It is maximum when
nπ π 3π 5π
x  , , ........
a 2 2 2
a 3a 5a
x , , ......
2n 2n 2n
Thus for the state n=1 the most possible position for the particle is at x=a/2
For n=2, the most possible position are at x=a/4, 3a/4,
KHIT, Guntur Applied Physics Study Material Free Electron Theory & Band Theory

UNIT III – FREE ELECTRON THEORY & BAND THEORY OF SOLIDS

FREE ELECTRON THEORY

Introduction:
In solids, electrons in outer most orbits of atoms determine its electrical properties.
Electron theory is applicable to all solids, both metals and non metals. In addition, it
explains the electrical, thermal and magnetic properties of solids. The structure and
properties of solids are explained employing their electronic structure by the electron
theory of solids. It has been developed in three main stages.
1. Classical free electron theory
2. Quantum Free Electron Theory.
3. Zone Theory.

1. Classical free electron theory: The first theory was developed by Drude and Lorentz
in 1900. According to this theory, metal contains free electrons which are responsible for
the electrical conductivity and electrons obey the laws of classical mechanics.

2. Quantum Free Electron Theory: In 1928 Sommerfeld developed the quantum free
electron theory. According to Sommerfeld, the free electrons move with a constant
potential. This theory obeys quantum laws.

3. Zone Theory: Bloch introduced the band theory in 1928. According to this theory,
free electrons move in a periodic potential provided by the lattice. This theory is also
called “Band Theory of Solids”. It gives complete informational study of electrons.

1) What are the assumptions of classical free electron theory?

Classical free electron theory of metals (Drude – Lorentz theory of metals):

Drude and Lorentz proposed this theory in 1900. According to this theory, the metals
containing the free electrons obey the laws of classical mechanics.

Assumptions (or) Salient features in classical free electron theory

1. In metals there are a large number of free electrons moving freely in all possible
directions.
2. These free electrons behave like gas molecules in a container obeying the laws of
kinetic theory of gases.
3. In the absence of field the energy associated with each electron at a temperature T is
given by kT. It is related to kinetic energy as kT= mvth2. Where vth is the thermal
velocity and k is Boltzmann constant.
4. In metals, the positive ion cores are at fixed positions and the free electrons move
randomly and collide either with positive ion cores or with other free electrons or with
boundaries. Hence these collisions are elastic. Therefore the electric conduction is due
to free electrons only.
5. Electron velocities in a metal obey Maxwell-Boltzmann distribution of velocities.
6. The free electrons move in a constant potential field. Hence the potential energy of the

Dr. G. Sreenivasulu, Assoc. Professor 1

KHIT, Guntur Applied Physics Study Material Free Electron Theory & Band Theory
electrons is constant.
7. When an electric field is applied to a metal, free electrons are accelerated in the
direction opposite to the direction of applied electric field with a velocity called drift
velocity represented as vd.

2. What are the merits and demerits of classical free electron theory?
Success or Advantages or Merits classical free electron theory
1) It verifies ohm’s law.
2) It explains electrical and thermal conductivities of metals.
3) It derives Widemann-Franz law.
4) It explains optical properties of metals.
Limitations or drawbacks or Demerits classical free electron theory
1) It fails to explain the electrical conductivity of semiconductors and insulators.
2) It fails to explain the temperature variation of electrical conductivity at low
temperature.
3) It fails to explain the concept of specific heat of metals.
4) It fails to explain the mean free path of the electrons.
5) The phenomenon like photo electric effect, Compton effect and black body radiation
could not be explained by classical free electron theory.
6) It fails to explain temperature dependence of paramagnetic susceptibility and
ferromagnetism.

3) What are the assumptions of quantum free electron theory?

Quantum Free Electron Theory:
Quantum free electron theory was proposed by Sommerfeld in 1928. It overcomes many
of the drawbacks of classical theory. Sommerfeld explained them by choosing Fermi-
Dirac statistics instead of Maxwell-Boltzmann statistics. He developed this theory by
applying the principles of quantum mechanics.
Assumptions of Quantum Free Electron Theory
1) Valence electrons move freely in a constant potential within the boundaries of metal
and is prevented from escaping the metal at the boundaries (high potential). Hence the
electron is trapped in a potential well.
2) The distribution of electrons in various allowed energy levels occurs as per Pauli
Exclusion Principle.
3) The attraction between the free electrons and lattice ions and the repulsion between
electrons themselves are ignored.
4) The distribution of energy among the free electrons is according to Fermi-Dirac
statistics.
5) The energy values of free electrons are quantized.
6) To find the possible energy values of electron Schrodinger time independent wave
equation is applied. The problem is similar to that of particle present in a potential box.

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KHIT, Guntur Applied Physics Study Material Free Electron Theory & Band Theory

Energy of electron is = , Where n=1, 2, 3,…

4. What are the merits and demerits of quantum free electron theory?
Merits of quantum free electron theory
1. It successfully explains the electrical and thermal conductivity of metals.
2. It can explain the Thermionic phenomenon.
3. It explains temperature dependence of conductivity of metals.
4. It can explain the specific heat of metals.
5. It explains magnetic susceptibility of metals.
6. It can explain photo electric effect, Compton Effect and block body radiation etc.
7. It gives the correct mathematical expression for the thermal conductivity of metals.

Demerits of quantum free electron theory

1. It is unable to explain the metallic properties exhibited by only certain crystals.
2. It is unable to explain why the atomic arrays in metallic crystals should prefer certain
structures only.
3. This theory fails to distinguish between metal, semiconductor and Insulator.
4. It also fails to explain the positive value of Hall Co-efficient.
5. According to this theory, only two electrons are present in the Fermi level and they
are responsible for conduction which is not true.

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KHIT, Guntur Applied Physics Study Material Free Electron Theory & Band Theory
9. Explain Bloch theorem or electrons in a periodic potential.
Electrons in a periodic potential - Bloch theorem:

A crystalline solid consists of a lattice, which is composed of a large number of ion

cores at regular intervals, and the conduction electrons that can move freely throughout
the lattice. The conduction electrons move inside periodic positive ion cores. Hence
instead of considering uniform constant potential as we have done in the electron
theory, we have to consider the variation of potential inside the metallic crystal with the
periodicity of the lattice as shown fig.

The potential is minimum at the positive ion sites and maximum between the two ions.
The one-dimensional Schrödinger equation corresponding to this can be written as

²
+ ( − #)ψ=0 where ђ = h / 2 Π
² ħ
² $
+ ( − #(&))ψ=0 −−−−−(1)
² %
The periodic potential V(x) may be defined by means of the lattice constant ‘a’ as

#(&) = #(& + () --------- (2)

Bloch has shown that the one-dimensional solution of the Schrödinger equation is of the
form.

ψ(x)= e ikx .Uk (&) -----------(3)

In the above equation Uk(&) is called “modulating function”. Because free electron wave is
modulated by Uk(&) is periodic with the periodicity at the crystal lattice. Let us now
consider a linear chain of atoms of length L in one-dimensional case with „N‟ number of
atoms in the chain. Then
Uk(&)= Uk(&+Na) ------------------ (4)
Where ‘a’ is lattice distance.
ik(x+Na)
From equation (3) and (4), we have ψ(x+Na)= e .Uk (& + )()
ikNa ikx
=e .Uk (&) e
ψ(x+Na) = ψ(x). e ikNa ------------------ (5)
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KHIT, Guntur Applied Physics Study Material Free Electron Theory & Band Theory
This is referred to as Bloch condition. Similarly, the complex conjugate of eq.(5) can be
written as
ψ∗(x+Na) = ψ∗(x). e –ikNa --------------(6)
From eq(5) and eq(6)
ψ(x+Na) . ψ∗(x+Na) = ψ(x). ψ∗(x)

|ψ(x+Na)|2 = |ψ(x)|2 --------(7)

This means that the electron is not localized around ones particular atom and the
probability of finding the electron is same throughout the crystal.

ikNa
Hence in eq(5), e =1

kNa=2Πn , where n is an integer

k=(2Πn)/Na

k=(2Πn)/L

Where L is the length of the chain of atoms and n= ±1, ±2, ±3, ±4, ………
When n=N/2, we have k=Π/a. This is the edge of first Brillouin zone.

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KHIT, Guntur Applied Physics Study Material Free Electron Theory & Band Theory
10. Explain Kronig-Penny model

Kronig – Penny Model:

Kronig – Penny Model proposed a simpler potential in the form of an array of square
wells as shown in the fig.

Schrodinger equation for one dimensional periodic potential field denoted by V(x) can be
written as

² $
+ ( − #(&))ψ=0 −−−−−(1)
² %
According to Bloch theorem the solutions of this equation have the form

ψ(x)= e ikx .Uk (&) -----------(2)

Where Uk (&) is periodic with the periodicity of the lattice. That is,

Uk (& + () = Uk (&)

As Vo increases the width of the barrier ω decreases so that the product Voω remains
constant. It turns out that solutions are possible only for energies given by the relation

. /01∝3
cos -( = + cos ∝ ( -------------(3)
∝3

4$ 3 $
Where P = Voω and ∝= √28
P is called scattering power of the barrier and Voω is called barrier strength.

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

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KHIT, Guntur Applied Physics Study Material Free Electron Theory & Band Theory
1) The energy spectrum of the electron consists of a number of allowed and forbidden
energy bands.
2) As ‘∝a’ increases the width of the allowed energy band increases and the width of
forbidden band decreases.
3) With increasing potential barrier P, the width of an allowed band decreases.
4) As P→∞, the allowed energy becomes infinitely narrow and the energy spectrum is a
line spectrum as shown in fig.
5) When P→0 then all the electrons are completely free to move in the crystal without
any constraints. Hence, no energy level exists that is all the energies are allowed to the
electrons as shown in fig. This case supports the classical free electrons theory.

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KHIT, Guntur Applied Physics Study Material Free Electron Theory & Band Theory
11. Explain Brillouin zones with the help of E-K diagram.
Brillouin Zones (E-K curve):
. /01∝3
Using the equation cos -( = + cos ∝ (
∝3
it is possible to plot a curve showing the energy E as a function of K as shown in fig.

$
From fig. it is clear that energy of electron is continuously increasing from K=0 to . The
3
$
left hand side of above equation becomes +1 or -1 for values of K=± 3
and hence
$
discontinuity appears in E-K graph, at K=± 3 . From fig it is seen that energy spectrum
of electron consists of allowed regions and forbidden regions. The allowed region extends
$ $
from - to + . This is known as first Brillouin Zone. After a discontinuity in energy
3 3
$ $ $ $
called forbidden gap another allowed region extends from - to - and to . This is
3 3 3 3
known as second Brillouin Zone. Similarly other higher order Brillouin zones can be
defined.

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KHIT, Guntur Applied Physics Study Material Free Electron Theory & Band Theory
12. Explain the origin of energy bands in crystalline
rystalline solids.
Origin of Energy Bands in Solids:
An isolated atom possesses discrete energies of different electrons. Suppose two isolated
atoms are brought to very close proximity, then the electrons in the orbits of two atoms
interact with each other.
her. So, that in the combined system, the energies of electrons will
not be in the same level but changes and the energies will be slightly lower and larger
than the original value. So, at the place of each energy level, a closely spaced two energy
levels exists. If ‘N’’ number of atoms are brought together to form a solid and if these
atoms’ electrons interact and give ‘N’‘ ’ number of closely spaced energy levels in the place
of discrete energy levels, it is known as bands of allowed energies.

The width of energy band depends on the degree of over lapping of electrons of adjacent
atoms and is largest for outermost electrons. The band corresponding to outer most
orbits is called conduction band and next inner band is called valence band. The gap
between these two allowed bands is called forbidden energy gap or band gap Eg.

13. On the basis of band theory how the crystalline solids are classified into
metals, semiconductors and Insulators.
Insulators

Classification of crystalline solids:

Based on the width of forbidden band, solids are classified into insulators,
Semiconductors and conductors.

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KHIT, Guntur Applied Physics Study Material Free Electron Theory & Band Theory
Conductors: The valence band and conduction bands are overlapped with each other
and the energy gap Eg is zero. At room temperatures, free electrons already exist in huge
number at conduction band. Hence these solids are good electrical conductors as well as
good thermal conductors. The electrical resistivity increases at high temperature by
collisions among the free electrons.
Ex: Al, Cu, Ag, Au etc.,

Semiconductors: The valence band and conduction bands are separated with a small
energy band gap Eg ≈ 1 eV. At low temperatures (0 K), free electrons are not available in
conduction band. Hence they behave like insulators at low temperatures. The electrical
conductivity increases at high temperatures by the transition of free electrons from
valence band to conduction band. Thus these solids behave like electrical conductors at
high temperatures.
Ex: Silicon Eg = 1.1 ev, Germanium Eg = 0.7ev

Insulators: The valance band and conduction bands are separated by a very large
energy gap Eg ≥ 3 eV. At room temperatures conduction band is empty and valance band
is full of electrons. Hence they these solids are electrical insulators. Even at high
temperatures valence electrons are unable to jump in to conduction band.
Ex: Glass, Mica, Ebonite, Rubber etc.,

14. Explain the effective mass of electron and concept of hole.

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

:; :( $=) := 2Π :( =) :@
vg = = = 2Π =( ) = ---------(2)
:< :< :< h :< ħ :<

where, the energy E = hυ and ħ =

2Π

1D 2
:Vg :( ) 1 D : @ :< : @ :<
Acceleration a = = ħ D-
= ħ [Link] = ( )( ) = ( )( )
:B :B ħ :<.:< :B ħ :< :B
:. :< F
Since ħk = p and = F, =
:B :B ħ

: @
∴a= ( )F
ħ2 :<
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KHIT, Guntur Applied Physics Study Material Free Electron Theory & Band Theory
ħ
F=[ G H
]a ------------(3)
( )
GI

Comparing equations (1) and (3) we get

ħ
m*=[ G H
]---------------(4)
( )
GI

: @
This equation indicates that the effective mass is determined by .
:<

a. Variation of E with K: Variation of E with

K corresponds to first Brillouin Zone. Using
this type of variation velocity can be
calculated.

b. Variation of V with K: For K=0 velocity is

zero and as k value increases V also increases
reaching its maximum value at Ko known as
point of inflexion. Beyond Ko velocity
decreases and reaches to 0 at K=π/a.

c. Variation of m* with K: Near K=0, m*=m.

As K value increases m* also increases
reaching its maximum value at Ko. Above Ko ,
m* is negative and decreases as K tends to
π/a. Beyond Ko velocity decreases and hence
retarding force acts on electron and it
behaves as positively charged particle referred
to as hole.

d. Variation of fk : Degree of freedom of an

electron is defined as fk=m/m*. fk is measure
of the extent to which the electron is free in a
state K. If m* is large fk is small, particle
behaves as heavy particle. If fk=1, electron
behaves as free electron.

Dr. G. Sreenivasulu, Assoc. Professor 16