Chapter 3: PRINCIPLES OF QUANTUM MECHANICS

De-Broglie Hypothesis –Matter waves: An electromagnetic wave behaves like particles,

particles like electrons behave like waves called matter waves, also called de-Broglie matter
waves.

The wave length of matter waves is derived on the analogy of radiation.

Based on Planck‟s theory of radiation, the energy of a photon is given by

….. (1)

Velocity of light

Wavelength of the photon

h= Planck‟s constant

According to Einstein‟s mass energy relation

…… (2)

m= mass of the photon

Equating equations (1) and (2)

…… (3)

P = momentum of photon

de-Broglie proposed the concept of matter waves, according to which a material particle of
mass‟m‟, moving with a velocity‟s‟ should have an associated wavelength „ called de-
Broglie wavelength.

… (4) is called de-Broglie‟s wave equation.

Properties of matter waves:

1. Wavelength is associated with moving particle and independent of charge of the particle

2. Greater the mass, velocity of the particle, lesser will be the wavelength.

de-Broglie wavelength associated with an electron:

23
if a velocity „v‟ is given to an electron by accelerating it through a potential difference
„V‟,then the work done on the electron is „Ve‟,and the work done is converted into the kinetic
energy of an electron.

√ …. (5) in (4)

…… (6)
√

Ignoring relativistic corrections, m0= rest mass of electron

….. (7)
√

by substituting the values of h=6.625

m0= rest mass of electron = 9.1 and c= charge of electron=1.6 C

…… (8)
√

where V= in volt and

Experimental verification of matter waves:

G.P Thomson experiment:

1. The electrons are produced from a heated filament „F‟ and are accelerated through a
high +ve potential (25-60 KV) given to anode „A‟.
2. The electron beam passes through a fine hole in a metal block „B‟ and falls on a gold
foil „G‟ of thickness 10-8 cm.
3. The foil consists of very large number of microscopic crystals oriented at random.
The electrons after striking the gold foil diffracts according to Bragg‟s formula
2dsinθ =n .

4. The electrons passing through the foil are received on a photographic plate „P‟

24
 5. A central spot (position of undeflected electrons) surrounded by a series of concentric
diffraction rings are obtained on a photographic plate „P‟.this pattern is similar to that
of x-rays diffraction in powder method..
6. Since x-rays also produce same pattern, a magnetic test was performed: when a
magnet is brought near the beam, electrons are displaced. Since x-rays are not
deviated in the magnetic field, the pattern must be due to diffraction of electron beam
only.
7. The whole apparatus is highly evacuated, so that electrons may not lose their energy
in collisions with molecules of air.

Clearly this experiment demonstrated that the electrons behave like waves, since diffraction
can be produced only by waves. The de-Broglie equation was verified by G.P Thomson by
estimating the wavelength of the electrons with the knowledge of their velocity which
depends on accelerating voltage.

From the fig, OA is the radius of the ring.‟O‟ is the center of the ring, „Q‟is the point where
the electron strikes a particular plane on the crystal in the metallic film. „QO‟ is the distance
between the metallic film and the photographic plate.‟θ‟ is the glancing angle of electrons
with the foil.

From fig

θ (θ )

from Bragg‟s equation

2dsinθ =n .

θ …(1)
θ

From fig θ θ …(2) in (1)

the wavelength of electrons was calculated from the above expression which matched well
with the theoretical wavelength.

25
This experiment confirmed the existence of matter waves and dual nature of matter proposed
by de-Broglie.

Division and Germer’s experiment:

The first experimental evidence of the wave nature of atomic particles was proved by C.J
Division and L.H Germer in 1927.

They were studying scattering of electrons by a metal target and measuring the density of
electrons scattered in different directions.

26
1. From fig, the electron beam from electron gun which consists of a tungsten filament
„F‟ heated by a low tension battery „B1‟ are accelerated to a desired velocity by
applying suitable potential from a high tension battery „B2‟.
2. The accelerated electrons are collimated into a fine beam by allowing them to pass
thorough a system of pinholes in the cylinder „C‟.
3. The fast moving electron beam is made to strike the target (nickel crystal) capable of
rotating about an axis perpendicular to the plane of diagram.
4. The electrons are scattered in all directions by atomic planes of a crystal and intensity
of scattered electron beam in all directions can be measured by the electron collector
and can be rotated about the same axis as the target.
5. The collector is connected to a sensitive galvanometer whose deflection is
proportional to the intensity of electron beam entering the collector.
6. When electron beam accelerated by 54 V was directed to strike the given nickel
crystal, a sharp max in the electron diffraction occurred at an angle of 500 with the
incident beam.
7. The incident beam and the diffracted beam make an angle of 650 with the family of
Bragg‟s planes.
8. The whole instrument is kept in an evacuated chamber.
9. The spacing of planes in Nickel crystal as determined by x-ray diffraction is 0.091nm

From Bragg‟s law

2dsinθ = n .

=0.615nm

Therefore for a 54 V electron beam, the de-Broglie wavelength associated with the
electron is given by

27
 =0.166nm
√

This wavelength agrees well with the experimental value.

Thus division experiment provides a direct verification of de-Broglie hypothesis of
wave nature of moving particles.

Schrodinger time independent wave equation:

According to de-Broglie ,a particle of mass „m‟ moving with a velocity‟v‟ is always

associated with a wave whose wavelength is given by

Schrodinger describes the wave nature of a particle in mathematical form and is known as
Schrodinger‟s wave equation.

Consider a plane wave moving along +ve x- direction with velocity „v‟. The equation of the
wave is written in the from

( )…(1)

Where

a= amplitude of wave

y=displacement of wave in y- direction

x= displacement along x- axis at any instant of time „t‟.

taking first order derivative w.r.to „x‟ on both sides of eqn(1)

( )

( ) ( )( )….(2)

Substitute (1) in (2)

( ) …(3)

This is known as differential plane wave equation.

In complex wave ,the displacement „y‟ is replaced by „ψ‟ and wavelength‟ ‟ is replaced by
de-Broglie‟s wavelength ‟ in eqn(3)

ψ
( ) ψ

28
 ψ
ψ ….(4)

For a moving particle, the\ total energy is ….(5)

Where E= total energy

V= potential energy

U= kinetic energy =

….(6),substitute (5) in (6)

( ) ….(7) substitute (7) in(4)

ψ ( )
ψ

ψ ( )
ψ ….(8)

This equation is known as Schrodinger‟s time independent wave equation in one dimension.

In three dimensions, it can be written as

( )
ψ ψ …(9)

( )
ψ ψ

For a free particle, the P.E is equal to zero i.e V=0 in equation (9)

Therefore the Schrodinger‟s time independent wave equation for a free particle is

ψ ψ

Physical significance of ( )

1. The wave function enables all possible information about the particle.
2. is a complex quantity and has no direct physical meaning.
3. It is only a mathematical tool in order to represent the variable physical quantities in
quantum mechanics.
4. Born suggested that, the value of wave function associated with a moving particle at
the position co-ord(x,y,z) in space, and at the time instant „t‟ is related in finding the
particle at certain location and certain period of time „t‟.
5. If represents the probability of finding the particle, then it can have two cases.
Case 1: certainty of its Presence: +ve probability
Case 2: certainty of absence :- ve probability, but –ve probability is meaningless,
hence the wave function is complex number and is of the form a+ib

29
 6. Even though has no physical meaning, the square of its obsolete magnitude | |
gives a definite meaning and is obtained by multiplying the complex number with its
complex conjugate
7. Then | | represents the probability density „p‟ of locating the particle at a place at a
given instant of time. And has real and positive solutions.
( )

( )
| |
Where „P‟ is called the probability density of the wave function.

8. If the particle is moving in a volume „V‟,then the probability of finding the particle in
a volume element dv, surrounding the point x,y,z and at instant „t‟ is Pdv

∫| |

. = 0 if particle does not exist

This is called normalization condition.

Heisenberg’s uncertainty principle:

1. According to Classical mechanics, a moving particle at any instant has fixed

position in space and definite momentum which can be determined simultaneously
with any desired accuracy. This assumption is true for objects of appreciable size,
but fails in particles of atomic dimensions.
2. Since a moving atomic particle has to be regarded as a de-Broglie wave group,
there is a limit to measure particle properties.
3. According to Born probability interpretation, the particle may be found anywhere
within the wave group moving with group velocity.
4. If the group is considered to be narrow, it is easier to locate its position, but the
uncertainty in calculating its velocity and momentum increases.
5. If the group is wide, its momentum is estimated easily, but there is great
uncertainty about the exact location of the particle.

Heisenberg a German scientist in 1927, gave uncertainty principle which states that

“The determination of exact position and momentum of a moving particle

simultaneously is impossible’’.

In general, if △x represents the error in measurement of position of particle along x-

axis, and △p represents error in measurement of momentum, then

30
 △ △
Or limitation to find the position and momentum of a particle is
(△ ) (△ )
π
i.e Heisenberg uncertainty principle states that both the position and momentum
cannot be measured simultaneously with perfect accuracy.

Particle in 1-Dimensional potential box:

1. The wave nature of a moving particle leads to some remarkable consequences

when the particle is restricted to a certain region of space instead of being able to
move freely.i.e when a particle bounces back and forth between the walls of a
box.
2. If one –dim motion of a particle is assumed to take place with zero potential
energy over a fixed distance, and if the potential energy is assumed to become
infinite at the extremities of the distance, it is described as a particle in a 1-D box,
and this is the simplest example of all motions in a bound state.
3. The Schrodinger wave equation will be applied to study the motion of a particle in
1-D box to show how quantum numbers, discrete values of energy and zero point
energy arises.
4. From a wave point of view, a particle trapped in a box is like a standing wave in a
string stretched between the box‟s wall.
5. Consider a particle of mass „m‟moving freely along x- axis and is confined
between x=0 and x= a by infinitely two hard walls, so that the particle has no
chance of penetrating them and bouncing back and forth between the walls of a 1-
D box.
6. If the particle does not lose energy when it collides with such walls, then the total
energy remains constant.
31
7. This box can be represented by a potential well of width „a‟ ,where V is uniform
inside the box throughout the length „a‟ i.e V= 0 inside the box or convenience
and with potential walls of infinite height at x=0 and x=a, so that the PE „V‟ of a
particle is infinitely high V=∞ on both sides of the box.
8. The boundary condition are

( ) ( ) ….(1)
( ) ( ) …(2)

Where ( ) is the probability of finding the particle.

The Schrodinger wave equation for the particel in the potential well can be written as

ψ
ψ …(3)

In the simplest form eqn (3) can be written as

ψ
ψ ….(4)

Where k= propagation constant and is given by √ ….(5)

The general solution of equation (4) is

ψ( ) … (6)

where A and B are arbitrary constants, and the value of these constant can be
obtained by applying the boundary conditions.
Substitute eqn(1) in (6)
( ) ( )

Implies B=0 in eqn(6)

ψ( ) …(7)

Substituting eqn(2) in (7)

32
 ( )

But „A‟ 0 as already B=0 & if A= 0,there is no solution at all.

Therefore sinka=0( if sinθ=0,then general solution is θ=nП)

Ka=nП

…….(8)

Where n= 1,2,3,4,…and n≠0,because if n=0,k=0,E=0 everywhere inside the box and

the moving particle cannot have zero energy.

From (8) ( )

From (5)

= the discrete energy level…(9)

The lowest energy of a particle is given by putting n=1 in the eqn (9)

=lowest energy, minimum energy, ground state energy or zero point energy of the
system.

The wave functions ψ corresponding to are called Eigen functions of the particle,.the
integer‟n‟ corresponding to the energy is called the quantum number of the energy level
.

Substituting (8) in (7)

… ..(10)

Normalization of wave function:

33
The wavefunctions for the motion of the particel are

According to normalization condition, the total probability that the particle is somewhere in
the box must be unity.

∫ ∫ | | dx=1

From eqn(10)

∫ [ ]

( ) [ ]

The second term of the integrand expression becomes zero at both the limits.

The normalized wave function is √

34