UNIT –III PRINCIPLES OF QUANTUM MECHANICS 1

UNIT-III
QUANTUM MECHANCS
Wave and particles: -
To understand the concept of dual nature one should have to know the characteristics of particles and waves.
Wave:
A wave can be simply defined as spreading out of a disturbance in a medium in all directions uniformly. It
cannot be confined to a part (or) region i.e. it is not possible to say that the wave is present here (or) there. A
wave is characterized by
• Wavelength • Frequency • Wave velocity • Amplitude • Phase • Intensity

Particle: -
. A particle has a definite mass and occupies a definite space. When a force is applied on it, it moves in the
direction of force from one point to another. A particle is characterized by
▪ Mass ▪ Velocity ▪ Momentum ▪ Energy
The particle nature of radiation can be observed in photoelectric effect and Compton effect. The wave nature
of radiation is seen in interference and diffraction experiments. Hence radiation is capable of exhibiting dual
nature. But it is not possible to exhibit both the wave nature and particle nature at the same time.
De-Broglie Hypothesis: -

In de-brogile the hypothesis material particles like electrons, protons, and neutrons can behave as wave.
According to his hypothesis, when particles are accelerated then those will be spread like a wave with a
certain wavelength.
As radiation exhibits dual nature of wave and particle; matter also must possess the same dual nature.
According to de-Brogile a moving particle, whatever its nature, has wave properties
associated with it. He proposed that the wavelength associated with any moving particle of
momentum p is given by

Such waves associated with the matter particles are called matter waves or de-Broglie waves.

Expression for de-Broglie wavelength:-

According to the Planck’s and Einstein theories the energy of a photon whose frequency  can be
expressed as E=h------ (1)
Where h is the Planck’s constant. According to Einstein’s mass energy relation

From eq (1) and (2)

Since mc= p momentum of a photon. According to de-broglie’s hypothesis, if an electron of charge ‘e’ and
mass ‘m’ is moving with a velocity ‘v’ in the presence of potential ‘V’ then the wavelength associated with that
electron can be expressed as
UNIT –III PRINCIPLES OF QUANTUM MECHANICS 2

De broglie suggested that this equation for wavelength is a perfectly general.

It can be applying for material particles as well as to photons. In case of particles
Momentum= mv
And hence the de broglie wavelength of a particle is  = h / mv ---------------(4)
2 2
In eq (4) , the expression for relativistic mass mo / (1 − (v / c ) has to be used.
If E is the kinetic energy of the material particle , then
1 1 ( mv ) 2 1 p2
E = mv 2 = = orp = 2mE
2 2 m 2 m

Hence de broglie wavelength  = h / 2mE

De Broglie wavelength associated with electrons:-

Let us consider the case of an electron of rest mass mo and charge e being accelerated by a potential V volts.
If v is the velocity attained by the electron due to acceleration then
1
mov 2 = ev or v = 2eV
2 mo

h h mo h 12.26 0
= = = = A
de Broglie wavelength mov mo 2eVmo →
2eV V
But we are taken the mass is m (m=mo) non relativistic condition
12.26
If the voltage applied to accelerate the electron V is 100 volts then  = = 1.226Ao
100

Characteristics of Matter waves:- According to de-broglie a material particle like electron (or) neutron
exhibit wave nature in their motion. These waves are called matter waves (or) de-broglie waves. Some
properties of matter waves are
1. Wave length (λ): -

The wavelength of the matter waves is . This shows that the wave length of matter wave is
inversely proportional to the momentum of the particle.
2. Group velocity :-
A wave packet comprises a group of waves, each with slightly different velocity and wavelength, with phases
and amplitudes so chosen that they interfere constructively over only a small region of space where particle
can be located ,outside of which they produce destructive interference. such wave packet moves with its own

velocity called group velocity and this group velocity of wave packet is equal to the particle velocity.
.This means material particle in motion is equivalent to group of waves or wave packet.

3. phase velocity:-
The phase velocity (or phase speed) of a wave is the rate at which the phase of the wave propagates in space.
This is the speed at which the phase of any one frequency component of the wave travels. For such a
component, any given phase of the wave (for example, the crest) will appear to travel at the phase velocity.
The phase speed is given in terms of the wavelength λ (lambda) and period T as
UNIT –III PRINCIPLES OF QUANTUM MECHANICS 3
Or, equivalently, in terms of the wave's angular frequency ω and wave number k by

4. Lighter is the particle, greater will be the wavelength associated with it.
5. Smaller is the velocity of the particle greater will be the wavelength associated with it.
6. The motion of the particles generates matter waves whether the particle is charged or uncharged.
7. Matter waves are not electromagnetic waves, usually electromagnetic radiation comes out from
moving charged particles.( Matter waves are new kind of waves and these are not em waves)
8. The wavelength of matter waves depends up on the velocity of material particles9it is not a
constant like velocity of em waves)

Davisson and Germer experiment

The first practical evidence for the matter waves was given by C.J.Davisson and L.H.Germer in 1927. This
was the first experimental support for De-Broglie’s hypothesis

Experimental arrangement: -

The experimental arrangement is shown in fig. it consists of three parts; they are electron gun, target set up and
circular scale arrangement. The whole experiment is kept in vacuum.
The electron gun produces a fine beam of electrons of a required velocity. It consists of filament (F), low
tension battery (LTB), high tension battery (HTB) and pin holes provided in the cylinder (C).
When tungsten filament ‘F’ is heated by low tension batteries (LTB) then electrons are produced. These
electrons are accelerated to a required velocity by applying sufficient potential through the high tension battery
(HTB), across the cylinder ‘C’.
The accelerated electrons are collimated into a fine beam of pencil by passing them through a system of pin
holes provided in the cylinder ‘C’. The target set up help to get diffraction pattern.
The target is typically nickel crystal. The fast moving beam of electrons from electron gun is made to incident
on the nickel target, which can be rotated about an axis perpendicular to the plane of the diagram.
UNIT –III PRINCIPLES OF QUANTUM MECHANICS 4
The electrons are reflected in all possible directions by rows of a atoms in the surface planes, which acts as a
diffraction grating. In the circular scale arrangement, an electron collector is fixed to a circular scale which can
collect the electrons and can move along the circular scale.
The electron collector is connected to a sensitive galvanometer to measure the intensity of electron beam
entering the collector.
Calculation of the wavelength associated with electrons:-

When a potential of 54v is applied the first order diffraction maximum is observed at angle of 500 between
incident and reflected rays.
It can be observed in the plot of variation of number of scattering electrons with the angle of diffraction as 650.
The inter planar spacing (d) of nickel crystal is 0.091nm, which is measured by the x-ray diffraction method.

Applying Bragg’s law

We know that

Now from the Bragg’s law equation

The de-Brogile wavelength associated with the electron, when a potential difference of 54v is applied.
According to de-brogile wave length

The wavelength of the electron beam calculated from Bragg’s law and de-Brogile’s equation are in good
agreement. Hence the wave nature of the particle is proved experimentally. The drawback of this experiment is
that whether the diffraction pattern formed is due to electrons (or) electromagnetic radiation generated by fast
moving electrons are not

Heisenberg’s uncertainty principle

“It is impossible to know the exact position and exact momentum of an object at the same time”.
UNIT –III PRINCIPLES OF QUANTUM MECHANICS 5
• According to “uncertainty principle” if we obtained a perfect knowledge of the position of an
electron we have no way of knowing its momentum, and the reverse.
• If particle is moving based on classical mechanics, at any instant we can find its position and
momentum.
• In wave mechanics, we regard a moving particle as a wave group. The particle that corresponds to this
wave group may be located anywhere within the group at any given time.
• In the middle of the group, the probability of finding the particle is more but the probability of finding
the particle at any other point inside the wave group is not zero.
• Narrow the wave group higher will be the accuracy of locating the particle. At the same time, one cannot
define the define the wavelength.

If ∆xand ∆p are the uncertain in the position and momentum measurements then, according to uncertainty
principle.
h
x.p 
4
According to classical theory, it is possible for a particle to occupy a fixed position and have a
definite momentum and it is possible to predict neatly its position and momentum.
But according to uncertainty principle it is not possible to determine accurately the simultaneous
Values of position and momentum of a particle at any time.
The same relation holds for the energy and time if ∆E is the error in measuring energy and ∆t is the error
in measuring time then
h
E.t 
4
Thus the uncertainty principle is a direct consequence of the wave nature of particle.
Another form of the uncertainty concerns energy and time. If the energy is emitted in the form of
electromagnetic waves, we cannot measure the frequency v of the waves accurately in the limited time available.

The probability that a particle will be found at a given place in space at a given instant of time is characterized
by the function  . x y z t It is called the wave function. This function can be either real or complex.
A satisfactory interpretation of the wave function  associated with a moving particle was given by Born in
1926. He postulated that the square of the magnitude of the wave function

evaluated at a particular point at any instant represents the probability of

finding the particle at that point.

is called the ‘probability density’ and  is the ‘probability amplitude’. According to this interpretation,
the probability of finding the particle within an element of volume.

, since the particle is certainly somewhere in space. So the integral of

2
over all space must be unity, that is   d = 1
UNIT –III PRINCIPLES OF QUANTUM MECHANICS 6
The wave function that obeys this equation is said to be ‘normalised’.
There are certain limitations to take as a solution for the Schrödinger wave equation, they are
(1) must be finite every where: – if for instance  is infinite for a particular point, the same would be true for
the wave function  .* It would mean an infinitely large probability of finding the particle at that point. This
would violate the uncertainty principle. There fore  must have a finite or zero value at any point.
(2)  must be single-valued : - if  has more than one value at any point, it would mean more than one
value of probability of finding the particle at that point which is obviously ridiculous.
(3)  must be continuous and have a continuous first derivative every where

d 2
It necessary for the Schrödinger equation is that must be finite every where. This can be so only if
dx 2

d  d 
has no discontinuity at any boundary. So is a continuous function then  is also continuous
dx dx

across the boundary.

Schrödinger wave equation:- (time independent wave equation)

In 1926 Schrödinger presented his famous wave equation as a development of de Broglie ideas of the wave
properties of matter.
The Schrödinger‘s equation is the fundamental equation of quantum mechanics in the same sense as the Newton’s
second law of motion of classical mechanics. It is the differential equation for the de-broglie waves associated
with particles and describes the motion of the particles.
Schrödinger introduced a mathematical function  which is the variable quantity associated with the moving
particle, and is a complex function of the space co-ordinates of the particle and the time.  is called “wave
function” as is characterizes the waves associated with the particle. If a particle of mass ‘m’ moving with a velocity
‘v’ is associated with group of waves. Let us consider a simple form progressing wave traveling in positive x-
direction as time t is
 =  O Sin(t − Kx ) Where  =  (x,t) and  o is the
amplitude.

Differentiating  partially with respect to x twice,

 2
= k 2 Sin(t − Kx ) = k2 
x 2

 2  2 4 2
 + k  = 0 or
2
+  = 0 ----------------(3) where k=2  / 
x 2
x 2
 2
Equation (2) is the differential form of the classical wave equation. Now we incorporate de Broglie wavelength
expression  = h/mv into equation (3). Thus we obtain
 2 4  2 2 2
+ m v  = 0 -----------------(4)
2 2
x h
The total energy E of the particle is sum of its kinetic energy K and potential energy V,
i.e. E= K+ V------------------------------------ (5)
1
and K .E = mv 2 ------------------------------- (6)
2
m2v2=2m(E-V)----------------------------------(7)
Substituting equation (7) in equation (4)
UNIT –III PRINCIPLES OF QUANTUM MECHANICS 7
2
 2
8  m( E − V )
+  =0
x 2
2
h
In quantum mechanics, the value h/2 occurs most frequently. Hence we denote  = Using this notation, we
2
have
 2 2 m ( E −V )
+  = 0 --------------------(8)
x 2 2
 2  2  2 2 m ( E −V )
Where (x,t)s + + +  = 0 ----------------(9)
x 2
y 2
z 2 2

Using Laplacian operator,

2 2 2
2 = + + ----------------(10)
x 2 y 2 z 2

The equation (10) can be written as

2 m ( E −V )
2 + 2
 =0

This Schrödinger time independent wave equation.

Particle in one dimensional potential box

Consider a particle moving inside a box along the X-direction. The particle is bouncing back and forth between
the walls of the box. The box has potential barriers at X=0 and X=L i.e. the box is supposed to have walls of
infinite height at X = 0 and X = L. the particle has mass m and its position x at any instant is given by 0 < X< L.
The potential energy V of the particle is infinite on both sides of the box. The potential energy V of the particle
can be assumed to be zero between X = 0 and X = L.

In terms of the boundary conditions imposed by the problem, the potential function is

The particle cannot exist outside the box and so its wave function  is 0 for X  0 and X  .L Our task is to
find what  is within the box i.e. in between x = 0 and x = L. Within the box, the Schrödinger’s equation
becomes
 2 8 2 m
+ E = C ---------------(1)
x 2 h2
2  2
putting 8 m E = k 2 ------(a) the equation becomes + k 2 = C -----------------(2)
h 2 x 2
The general solution of equation (2) is  ( x) = ASinkx + BCoskx -------------(3)
UNIT –III PRINCIPLES OF QUANTUM MECHANICS 8
The boundary conditions can be used to evaluate the constants A and B in equation (3)

 = 0 at x=L and hence 0 = ASinkL

n
 n ( x) = ASin --------------------(4)
L

En = n 2h 2 n
The energy of the particle (By substituting k =value in the equation (a) )
8mL2 L
For each value of n, there is an energy level and the corresponding wave function is given by Equation (4). Each
value of En is called an eigen – value and corresponding  n is called wave function. Thus inside the box the
particle can only have discrete energy values specified by equation (6). Note that particle cannot have zero
energy.
The value of ‘A’ in equation (4) can be obtained by applying normalization condition. Since the particle is
inside the box of length L, the probability that the particle is found inside the box is unity.
2 L
L 2 2 nx
0  x dx = 1   A Sin L dx = 1
0

 
L
A  1 − Cos 2nx dx = 1
2 1
(as cos 2 = 1 − 2 Sin 2 )
2 L
0
 A2   
L
 x −
L
Sin 2 n x =1
 2   2n L  0

A2 L 2
i.e =1 i.e A =
2 L
2 nx
The normalized wave function is  n = Sin
L L
UNIT –III PRINCIPLES OF QUANTUM MECHANICS 9