AUTONOMOUS

1
The physical values or motion of a
macroscopic particles can be observed
directly. Classical Mechanics can be
applied to explain that motion.

But when we consider the motion of

Microscopic Particles such as
electrons, protons……etc., classical
mechanics fails to explain that motion.

Quantum Mechanics deals with motion

of microscopic particles or quantum
particles.
Classical world is Deterministic:
Knowing the position and velocity of
all objects at a particular time
Future can be predicted using known laws of force
and Newton's laws of motion.
Quantum World is Probabilistic:
Impossible to know position and velocity
with certainty at a given time.

Only probability of future state can be predicted using
known laws of force and equations of quantum mechanics.
 Waves and Particles

Wave : A wave is nothing but disturbance which

is occurred in a medium and it is specified by its
frequency, wavelength, phase, amplitude and
intensity.

Particles:
A particle or matter has mass and it is located at a
some definite point and it is specified by its mass,
velocity, momentum and energy.
 Waves and Particles : What do we mean by them?
Material Objects:
Ball, Car, person, or point like objects called particles. 
They can be located at a space point at a given time.
They can be at rest, moving or accelerating.

Falling Ball

Ground level
 Waves and Particles: What do we mean by them ?
Common types of waves: 
Ripples, surf, ocean waves, sound waves, radio waves.
Need to see crests and troughs to define them.

Waves are oscillations in space and time.

Direction of travel, velocity

Up­down
oscillations

Wavelength ,frequency, velocity  and oscillation size defines waves 
 Particles and Waves: Basic difference in behaviour

When particles collide they cannot pass through each other ! 
They can bounce or they can shatter
Before collision  After collision

Another after
collision state
shatter 
 Waves and Particles Basic difference:

Waves can pass through each other !

As they pass through each other they can enhance or cancel
each other

Later they regain their original form !
 Wavelength Frequency
Waves and Particles: 
Spread in space and time
Waves
Can be superposed – show 
interference effects

Pass through each other

Localized in space and time

Particles
Cannot pass through each other ­
they bounce or shatter.
Prince Louis-Victor
de Broglie
 Won the Nobel Prize in Physics in 1929

 Professor at the Faculty of Sciences at

Paris University

 Elected a member of the Academy of

Sciences of the French Institute in 1933

 Broglie stated that all matter has a

wave-like nature
 States that any moving particle or object
had an associated wave

 Created a new field in physics, called

wave mechanics, uniting the physics of
light and matter
de Broglie hypothesis:

In 1924 the scientist named de Broglie

introduced electromagnetic waves behaves
like particles, and the particles like electrons
behave like waves called matter waves.

He derived an expression for the wavelength

of matter waves on the analogy of radiation.
According to Planck’s radiation law
E = hϑ
c
= h ............(1)
λ
Where ‘c’ is a velocity of light and ‘λ‘is a wave length.

According to Einstein mass-energy relation

E = mc 2 ......( 2)

From 1 & 2 mc 2 = h
c
λ
h
λ=
mc
h
λ=
p

Where p is momentum of a photon.

The above relation is called de Broglile’ s matter
wave equation. This equation is applicable to all
atomic particles.

If E is kinetic energy of a particle

1 2
E= mv
2
p2
E=
2m
p = 2mE

h
λ=
Hence the de Broglie’s wave length 2mE
de Broglie wavelength associated with
electrons:
 Let us consider the case of an electron of rest mass m0 and
charge ‘ e ‘ being accelerated by a potential
1 V volts.
m0 v = eV
2

2
 If ‘v ‘ is the velocity 2eV
v=
attained by the electron m0
due to acceleration

h h m0
λ= ⇒λ =
m0 v m0 2eV
0
 The de Broglie wavelength 12.26
λ= A
V
 Characteristics of Matter waves:
Lighter the particle, greater is the wavelength
associated with it.
Lesser the velocity of the particle, longer the
wavelength associated with it.
For v = 0, λ=∞ , i.e.,wave becomes indeterminate
and if v=∞ then λ=0 This shows that matter waves
are generated by the motion of particles .These
waves are produced whether the particles are
charged particles or they are uncharged .
This fact reveals that these waves are not
electromagnetic but a new kind of waves .
The velocity of matter wave is greater than the
velocity of light
It can be proved that the matter waves E = hϑ
travel faster than light.
E = mc 2
We know that
hϑ = mc 2
mc 2
ϑ=
The wave velocity (ω) is given by h
w = ϑλ
Substituting for λ we get
mc 2
w=( )λ
As the particle velocity v cannot h
exceed velocity of light c, ω is h
λ=
greater than mv
velocity of light. mc 2 h
w=( )
h mv
c2
w=
v
 There are two experimental evidences

1. Davisson and Germer ’s experiment.

2. G.P. Thomson Experiment.

 DAVISON & GERMER’S EXPERMENT:

Davison and Germer in 1927.gave the first

experimental evidence that beams of material
particle show wave like properties

They have also measured de Broglie wave lengths

of slow electrons by using diffraction methods.

Principle:
Based on the concept of wave nature of matter
fast moving electrons behave like waves.
Hence accelerated electron beam can be used for
diffraction studies in crystals.
 Experimental Arrangement

The electron gun G produces a fine beam of

electrons.

It consists of a heated filament F, which emits

electrons due to thermo ionic emission.

The accelerated electron beam of electrons

are incident on a nickel plate, called target T.
 High voltage

Nickel
Target
Anode

filament cathode G

Faraday
cylinder
S
Circular scale
c

Galvanometer

G
Working
The target crystal can be rotated about an axis
parallel to the direction of incident electron beam. A
sensitive galvanometer connected to the detector.
First of all , the accelerating potential V is given a low
value and the crystal is set at any azimuth(ө),Now
the Faraday cylinder is moved to various position on
the scale S and galvanometer current is noted for
each position.

galvanometer current is measure of intensity of

diffracted beam.

A graph is then plotted between G. current against

angle (ө)between incident beam and beam of
entering the cylinder
 Incident beam

44v
Incident beam

48v

Incident beam
50

54v

Incident beam
60v
Obseravations
With increasing potential, the bump moves
upwards
The ‘bump’ becomes most prominent in the
curve for 54volts electrons at ө=500
At higher potentials, the bumps gradually
disappear.
The bump in its most prominent state verifies
the existence of electron waves
 Result:

According to de-Broglie,the wavelength associated with

electron accelerated through a potential a V is given by
.

12 .26
λ= A0
V
According 12 .26
to experiment
λ = we have
=1.67diffracted
A0 beam at
ө=500.The 54
corresponding angle of incidence relative the
family of Bragg plane

Using the Brgg equation λ=2dsinө=2(0.91)sin65=1.65A

θ =
180 − 50
/
= 65
0
0
2
Incident electron
beam

250
650
250
650 Diffracted
beam
 This is in excellent agreement with
the experimental value.

The Davison - Germer experiment

provides a direct verification of de
Broglie hypothesis of the wave
nature of moving particle.
Drawback
The drawback of this experiment is that
whether the diffraction pattern formed is due
to electrons or electromagnetic radiation
generated by fast moving electrons is not
known
G.P THOMSON EXPERIMENT:
G.P Thomson's experiment proved that the diffraction pattern
observed due to electrons but not due to electromagnetic
radiation produced by the fast moving charged particles.

EXPERIMENTAL ARRANGEMENT:

G.P Thomson experimental arrangement consists of

(a) Filament or cathode C.
(b) Gold foil or gold plate
(c) Photographic plate (p)
(d) Anode A.

The whole apparatus is kept highly evacuated discharge tube.

 G.P THOMSON EXPERIMENT:

cathode
slit Anode Gold foil Photo
graphic
plate

Discharge tube Vacuum pump

 Working

The high energy electron beam is produced by the

cathode C.The beam is accelerated with a potential
up to 50kv.a fine pencil of accelerated beam is
obtained by allowing to it to pass through a
narrow slits.
The accelerating beam of electrons falls on a thin
film of gold. the photograph of the beam from the
from the foil is recorded on a photographic plate P
After developing the photographic plate a
symmetrical pattern consisting of concentric rings
about a central spot is obtained. As shown fig
Photographic film

Diffraction pattern.
Observations
This pattern is similar as produced by X-ray
diffraction powder method .
To be sure that this pattern is due to the
electrons or due to X-rays generated by the
electrons in their passage through the foil, the
cathode rays in the discharge tube are deflected
by magnetic field
The observed rings can only be interpreted by
considering that the diffraction pattern of
incoming beam is due to the diffractions of
electrons by the foil.
As the diffraction pattern can only be produced
by waves and not by the particles
conclusions
Thomson experiment clearly demonstrated
the existence of matter waves because the
diffraction can be produced by the waves

Thomson calculated the wavelength

associated with the electrons with help of
diffraction rings
 E

R
Incident Gold foil
electron radius
beam θ
B θ c
A o
θ L
Brage plane

Tan 2θ = R / L
If θ is very small 2θ = R / L
2θ = R / L ………. (1)
2d sin θ = nλ
if , θ ..is..very.small
2d (θ ) = nλ
for., n = 1
λ
d= .......(2)
2θ
frm,.eq n .....(1)
L
d = λ..............(3)
r
According to de Broglie’ s wave equation

h
λ= ( for., electron)
2m0 eV
where., m0 ..is..a., relatavestic..mass
n
from., eq (3)
L h
d= ( )
r 2m0 eV
d = 4.08 A0
The value of ‘d’ so obtained agreed well with
the values using X-ray techniques.

In the case of gold foil the values of “d”

obtained by the x-ray diffraction method is
4.060A.
Werner Heisenberg
Won Nobel Prize in 1932 in Physics "for the creation of quantum
mechanics, the application of which has, inter alia, led to the
discovery of the allotropic forms of hydrogen".
Heisenberg pointed out that it is impossible to know both the exact
position and the exact momentum of an object at the same time. 
Applying this concept to the electron we realize that in order to get
a fix on an electron's position at any time, we would alter its
momentum.  Any attempt to study the velocity of an electron will
alter its position.  This concept, called the Heisenberg Uncertainty
principle, effectively destroys the idea of electrons traveling around
in neat orbits.  Any electron that is subjected to photons will have
its momentum and position affected.
Determinism of Classical
Mechanics
Suppose the positions and speeds of all
particles in
the universe are measured to sufficient
accuracy at
a particular instant in time

It is possible to predict the motions of every

particle
at any time in the future (or in the past for that
matter)
Heisenberg realised
that ...
In the world of very small particles, one
cannot measure any property of a particle
without interacting with it in some way

This introduces an unavoidable uncertainty

into the result

One can never measure all the

properties exactly

Werner Heisenberg (1901-1976)

Heisenberg’s Uncertainty
Principle

The more accurately you know the position (i.e.,

the smaller ∆ x is) , the less accurately you know
the momentum (i.e., the larger ∆ p is); and vice
versa applet
Implications
It is impossible to know both the position and
momentum exactly, i.e., ∆ x=0 and ∆ p=0

These uncertainties are inherent in the

physical world and have nothing to do with
the skill of the observer

Because h is so small, these uncertainties are

not observable in normal everyday situations
Summary: Lessons from
Heisenberg

The idea of a perfectly predictable universe

cannot be true

There is no such thing as an ideal, objective

observer
Consequences of uncertainty principle:

Explanation for absence of electrons in the

nucleus.

Existence of protons and neutrons inside

nucleus.

Uncertainty in the frequency of light emitted by

an atom.

Energy of an electron in an atom.

Schrödinger Wave
Mechanics
In 1926 Schrödinger described the amplitude
of the matter waves by a complex quantity
Ψ(x,y,z,t) known as Wave function or the state
of the system .

It describes the particular dynamical system

under observation.

The wave function ,in general, is

complex,finite ,single valued and continuous.
Schrödinger time independent wave
equation:

Schrödinger wave equation is a basic principle of a

fundamental Quantum mechanics.

According to de Broglie, a particle of mass m is always

h
λ=
associated with a wave whose wavelength is given by
p
h
λ= .......... .(1)
mv
If the particle is wave proprieties ,it is expected that
there should be some sort of wave equation which
describe the behavior of the particle.
Consider a system of stationary waves associated with
a particle
Let x,y,z be the coordinates of the particle and Ψ the
wave displacement for the de-Broglie at any time t.Ψ is
the called as wave function ..
The classical differential equation of a wave motion is
given by
∂ψ 2 ∂ ψ ∂ψ ∂ψ 
2 2 2 2

=υ  2 + 2 + 2 
∂t 2
 ∂x ∂y ∂z 
∂ 2ψ
= υ ∇ψ
2 2
(2)
∂t 2
The solution of eq.(2)is given by
Ψ=Ψ0 sinωt
Ψ= Ψ0 sin2πvt (3)

where v is the frequency of the stationary wave associated

with the particle .
Differentiating eq.(3) twice weget ∂ψ
= ψ 0 (2π )νcos2π tν
∂t
∂ 2ψ
= −ψ 0 ( 2π )
ν
2
sin 2π vt
∂t 2
∂ 2ψ
= − 4π 2 v 2ψ
∂t 2

∂ 2ψ 4π 2υ 2
(4)
=− 2 ψ
∂t 2 λ

 υ
 ν = 
 λ 
Substituting the value of
∂ 2ψ  from eq .(3)in eq.
 2 
(2).weget  ∂t 


4π υ
2 2
υ ∇ψ =− 2 ψ
2 2

λ
4π 2
∇ 2ψ + 2 ψ = 0 (5)
λ

h
λ=
p
 Now de Broglie relation h
λ= .......... .(1)
mv
 4π 2 2 2
∇ ψ + 2 mυ ψ =0
2 (6)

h
If E and V the total and potential energies of the particle respectively,
Then its Kinetic energy is given by

1
mυ 2 + V = E
2
1
mυ 2 = E − V
2
m 2υ 2 = 2m( E − V ) (7)
From eqs(6)&(7) we have

4 π 2
∇ 2ψ + 2 × 2m( E − V )ψ = 0
h
8π 2
m
∇ ψ + 2 ( E − V )ψ = 0
2

h (8)
 Eq (8) is known as Schrödinger time independent wave
equation
h
=
2π
Substituting in eq (8) the Schrödinger wave equation
can be written as
2m
∇ ψ + 2 ( E − V )ψ = 0
2
(9)

Eq (9) can also be expressed in the following way:

 2  2
 ∇ ψ + ( E − V )ψ = 0
 2m 
2 2
∇ ψ − Vψ = − Eψ
2m
 2 2 
 − ∇ + V ψ = Eψ
 2m 

H ψ = Eψ
 Physical significance of the wave
function:

The wave function ‘Ψ’ has no direct physical

meaning. It is a complex quantity representing the
variation of a Matter wave.

The wave function Ψ( r, t ) describes the position

of a particle with respect to time.

It can be considered as ‘probability amplitude’

since it is used to find the location of the particle.
ΨΨ* or ‫׀‬Ψ2‫ ׀‬is the probability density function.
ΨΨ* dx dy dz gives the probability of finding the
electron in the region of space between x and x + dx,
y and y + dy, z and z + dz.
+∞

∫ dxdydz = 1
ψ ψ*

-∞
+∞ 2

∫ψ
-∞
dxdydz = 1

The above relation shows that ‘normalization

condition’ of particle.
 Besides being normalizable the wave function Ψ must fulfil the
following requirements.
 ** It must be finite everywhere: If Ψ is infinite at a particular
point, then it would mean an infinitely large probability of
finding the particle at that point .this is not possible. Hence ,Ψ
must have a finite or zero value at any point .

 ** It must be single valued: Let us consider that Ψ has more

than one value at any point .It means that there is more than
one value of probability finding the particle at that point. This is
obviously ridiculous.

d 2ψ
 ** It must be continuous : For Schrödinger equation
d x2 must
be finite everywhere .This is possible
dψonly when has
discontinuity at any boundary wheredxpotential changes .This
implies Ψ must be continuous across the a boundary
 ∞ ∞

m
V V

A B

X=0 X=a
Let us consider the case of a particle of mass m
moving along x-axis between the two rigid walls A
and B at x=0 and x=a

The particle is free to move between the walls. the

potential energy of the particle between the two
walls is constant because no force is acting on the
particle .

When the particle strikes any one of the walls ,it is

reflected back immediately as the walls are perfectly
rigid .Now the force acting on the particle abruptly
changes from zero to a finite value F within a
distance of zero at the wall .
 ∂V
We know thatF = ∂x we should have Δv ∞ as Δx 0∂∂Vx
such that has finite value F.So the potential energy of
the particle becomes infinite at the walls.
The potential function is definited in the following way :

V(x)=∞ for x<0 and x>a

(1)
And V(x)=0 for 0<x<a

The Schrödinger Wave equation for the particle is given by

d 2ψ 8π 2 m
2
+ ( E − V )ψ = 0
(2) dx h
As V=0 between the walls ,hence the equation has the
following form
d 2ψ 8π 2 m (3)
+ 2 Eψ = 0
dx 2 h

8π 2 m
E = k 2 4
h2
Let
then eq(3) takes the the form
d 2ψ 5
2
+ k 2
ψ =0
dx

The general soln of eq(5) is

ψ ( x) = A sin kx + B cos kx 6
Where A and B are two constants
The values of these constants can be obtained by
applying the boundary condition of the problem
 Ψ2represents the probability of finding the particle
at any instant. The particle cannot penetrate the
walls.hence Ψ=0 at x=0 and Ψ=0 at x=a. These are
the boundary condition .Apply boundary condition
we have

0=A sin0+B cos0,i.e B=0

7
Ψ(x)=A sin kx
Again 0 =A sin ka
 sin ka=0 0r ka=nπ or k=nπ/a 8

Now the wave function becomes Ψ(x)=Asin nπx/a

9
From eq (8) k2=n2π2/a2

From Eq(4)

8π 2 m n 2π 2 Using Enfor E,in general

2
En =
h a2
n2h2 2 π 
2 2
En = 2
=n 2
.......... ...( 10 )
8ma 2ma
It is clear from expression (10) that inside an infinitely
deep potential well the particle can have discrete set of
values of energy, the energy of the particle is
quantized .
But According to Classical Mechanics ,the particle may
take any continuous range of values between zero and
infinity.

The constant of eq (9) can be obtained by applying this

2
normalization condition ∫ψ( x)
a
dx =1
0

nπx
a

∫ A sin dx =1
2 2

a
 nπx
a
A2 ∫ sin 2 dx = 1
0
a
2 nπ x 
a
1
A ∫ 1 − cos
2
 dx = 1
o 
2 a 
a
A 2
 a 2nπx 
x −
 2πn Sin =1
a 
0
2
A2 a 2 2
= 1orA = orA =
2

2 a a
2 nπ x
ψ ( x) = sin ..............(11)
a a
Eq (11)gives the wave function of the particle enclosed in
infinitely deep potentialwell.
The normalized wave functions Ψ1,Ψ2,and Ψ3 together with
the probability
ψ 1 , ψ densities
2 2
and ψ
2
2 3 areplotted

Ψ(x)
For n = 1: |Ψ(x)|²

x
 For n = 2:

Ψ(x) |Ψ(x)|²

x
 ψ n = 2 / a sin
nπx n2h2
a En =
8ma 2

E3=9h2 / 8ma2
n =3

E2=4h2/8ma2
n=2

√ (2 / a)
E1=h2 / 8ma2
n=1
X=0 a/2 X=a
According to classical mechanics the probability distribution
is constant .Ψn2=0at x=0 and x=a. At particular point , the
probability of the particle being present is different for
different quantum numbers .
ψ1
2

Eg has it maximum value of a/2in the middle.

Thus ,a particle in the lowest energy level of n=1 is most

likely to be in the middle while a particle in the next higher
state of n=2 never there .
Conclusions;
1.The three integers n1,n2 and n3 called quantum
numbers are required to specify completely each
energy state. since for a particle inside the box, ‘
Ψ ’ cannot be zero, no quantum number can be
zero.

2.The energy ‘ E ’ depends on the sum of the

squares of the quantum numbers n1,n2 and n3 and
no on their individual values.

3.Several combinations of the three quantum

numbers may give different wave functions, but of
the same energy value. such states and energy
levels are said to be degenerate.
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