Quantum Mechanics

WAVES
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.
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, protonsetc.,
classical mechanics fails to explain that motion.

Quantum mechanics deals with motion of
microscopic particles or quantum particles.
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 Plancks
radiation law


Where c is a velocity of
light and is a wave length.


According to Einstein
mass-energy relation
From 1 & 2


Where p is momentum of a photon


.
) 1 ..( ..........

0
c
h
h E
=
=
p
h
mc
h
c
h mc
=
=
=

2
) 2 ......(
2
mc E =
The above relation is called de Broglie s matter wave
equation. This equation is applicable to all atomic
particles.

If E is kinetic energy of a particle







Hence the de Broglies wave length
mE
h
2
=
mE p
m
p
E
mv E
2
2
2
1
2
2
=
=
=
de Broglie wavelength associated with
electrons:
Let us consider the case of an electron of rest mass m
0
and
charge e being accelerated by a potential V volts.
If v is the velocity attained by the electron due to
acceleration


The de Broglie
wavelength
0
2
0
2
2
1
m
eV
v
eV v m
=
=
A
V
m
eV
m
h
v m
h
0
0
0
0
26 . 12
2
=
= =

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, = . This means that only with moving
particle matter wave is associated.

Whether the particle is charged or not, matter wave is
associated with it. This reveals that these waves are not
electromagnetic but a new kind of waves .
It can be proved that the matter waves travel faster than
light. We know that



The wave velocity () is given by



As the particle velocity v cannot
exceed velocity of light c,
is greater than velocity of light.
h
mc
mc h
mc E
h E
2
2
2
= =
=
=
0 0
0
v
c
w
mv
h
h
mc
where
mv
h
h
mc
w
w
2
2
2
&
) )( (
=
= =
=
=
0
0
Experimental evidence for matter waves

1. Davisson and Germer s Experiment.

2. G.P. Thomson Experiment.
DAVISON & GERMERS EXPERMENT

Davison and Germer first detected electron waves in 1927.

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. The target crystal can be rotated about an axis
perpendicular to the direction of incident electron beam.

The distribution of electrons is measured by using a detector called
faraday cylinder c and which is moving along a graduated
circular scale S.

A sensitive galvanometer connected to the detector.
High voltage
Faraday
cylinder
Galvanometer
Nickel
Target
Circular scale
cathode
Anode
filament
G
S
c
G
Results
When an electron beam accelerated by 54 volts was
directed to strike the nickel crystal, a sharp maximum in
the electron distribution occurred at scattered angle of
50
0
with the incident beam.

For that scattered beam of electrons the diffracted angle
becomes 65
0 .

For a nickel crystal the inter planer separation is
d = 0.091nm.
I

0
V = 54v
50
0

C
U
R
R
E
N
T
25
0

25
0

65
0

Incident electron beam
Diffracte
d beam
65
0

nm
nm
n d
165 . 0
1 65 sin 091 . 0 2
sin 2
0
=
=
=

u
nm
A
A
V
166 . 0
54
26 . 12
26 . 12
0
0
=
=
=

According to Braggs law

For a 54 volts , the de Broglie wave
length associated with the electron is
given by

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.
G.P THOMSONS EXPERIMENT

G.P Thomson's experiment proved that the diffraction pattern
observed was 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
(d) Anode A.

The whole apparatus is kept highly evacuated discharge tube.
When we apply potential to cathode, the electrons are
emitted and those are further accelerated by anode.

When these electrons incident on a gold foil, those are
diffracted, and resulting diffraction pattern getting on
photographic film.

After developing the photographic plate a symmetrical
pattern consisting of concentric rings about a central spot
is obtained.
G.P THOMSON EXPERIMENT
Discharge tube
cathode
Anode Gold foil
Vacuum pump
slit
Photo
graphic
plate
Photographic film
Diffraction pattern.
If is very small 2 = r / L
Tan 2 = r / L
2 = r / L . (1)
E
Incident
electron
beam
radius
Gold foil
L
o
r


A
B
c

Brage plane
According to Braggs law
2
2
0
0
1
2
) (
2
) ( 2
) 1 , ( sin 2
c
v
m
m
eV m
h
r
L
d
L
r
d d
n d
n and n d

=
=
= = =
=
= << =

u
u u
According to de Broglie s wave
equation
Where m
0
is a relativistic mass of an electron
A d
eV m
h
r
L
d
r
L
d
eq from
n
0
0
08 . 4
)
2
(
) 3 ( .,
=
= =
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 4.06
0
A.
Heisenberg uncertainty principle

This principle states that the product of uncertainties in
determining the both position and momentum of
particle is approximately equal to h / 4.



Where x is the uncertainty in determine the position
and p is the uncertainty in determining momentum.

This relation shows that it is impossible to determine
simultaneously both the position and momentum of the
particle accurately.

t 4
h
p x > A A
This relation is universal and holds for all canonically conjugate
physical quantities like
1. Angular momentum & angle
2. Time & Energy
t
t
u
4
4
h
E t
h
j
> A A
> A A
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.
Physical significance of the wave function

The wave function has no direct physical meaning.
It is a complex quantity representing the variation of a
Matter wave.

The wave function ( 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.

*
or
2
is the

probability density function.

*
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.





The above relation shows thats a normalization
condition of particle.
1
1
2
-
-
*
=
=
}
}
+

dxdydz
dxdydz

Schrdinger wave Equation

Schrdinger wave equation is a basic principle of a
fundamental Quantum mechanics.
Consider an electron of mass m and moving with a
velocity v .
We know that electrons exhibit wave nature and for such an
undamped, harmonic electron wave equation, the general
solution is given by
)} ( exp{
v
x
t i A y = e
Where y represents the displacement at time t
at a position x ,
w is the angular frequency and v is the velocity.
Quantum mechanically we represent the wave associated
with a moving particle by a wave function .
u
tu e

u t
e
=
=
=
=
v
where
x
t i t r
v
x
t i A t r
2
.,
) 1 .( )}........ ( 2 exp{ ) , (
)} ( exp{ ) , (
Now we are going to derive an expression for energy of
electron.
total energy of the electron is the sum of its K.E. and P.E.
) 2 ...( )......... (
2
) (
2
) (
2
1
. .
.,
2
2
2
x V
m
p
E
x V
m
p
E
x V mv E
E P E K E
energy total
+ =
+ =
+ =
+ =

t

t
u

u t
2
.,
) 3 ( )}..., ( exp{ ) , (
)} (
2
exp{ ) , (
)} ( 2 exp{ ) , (
) 2 ( ...... ., .,
.,
) 2 .( )}........ ( 2 exp{ ) , (
h
where
px Et
i
A t x
px Et
h
i
A t x
p
h
x
t
h
E
i A t x
eq values these ng substituti
p
h
h E
x
t i t r
n
=
=
=
=
= =
=

Now we have to get expressions for E and

p
2
from equation 3.

Differentiating the equation (3) with respect to t .,
) 4 .........( ..........
)} ( exp{ ) (
)}] ( exp{ [
t i
E
E
t i
E
i
t
px Et
i
A E
i
t
px Et
i
A
t t
c
c
=
=
c
c
=
c
c
=
c
c

c
c
=
c
c

Differentiating the equation (3) with respect to time x

) 5 ( ..........
)} ( exp{ ) (
)} ( exp{ ) (
)}] ( exp{ [
2
2
2 2
2
2
2
2
2
2
2
x
p
p
x
px Et
i
p
i
x
px Et
i
A p
i
x
px Et
i
A
x x
c
c
=
=
c
c
=
c
c
=
c
c

c
c
=
c
c

Substituting the values of E and p

2
from 4 and 5 in
equation 2 we get
) 6 .......( } {
2
., .
} {
2
2
2 2
2
2 2
t i
V
x m
e i
V
x m t i
c
c
=
c
c
+
c
c
=
c
c

This is known as on e dimensional Schrdinger's time dependent wave
equation. Extending this to three dimensional problem.
t i
V
z y x m c
c
=
c
c
+
c
c
+
c
c

} {
2
2
2
2
2
2
2 2
For our purpose, it is sufficient to consider situations in
which the potential energy of the particle doesnt depend
explicitly on time. The forces that act on it, and hence V, then
vary only with the position of the particle.
In this case equation 6 reduces to the time independent form.
) exp( ) (
) exp( ) (
.,
) 7 )........( ( ) ( ) , (
) exp( ) exp( ) , (
)} ( exp{ ) , (
Et
i
t
ipx
x
where
t x A t x
ipx
Et
i
A t x
px Et
i
A t x

=
=
=
=
=
|

0 ) (
2
2
) exp( ) exp( ) exp(
2
)......... 6 ( ., .. .,
) exp(
) exp(
) exp(
) exp( ) , (
2 2
2
2
2 2
2
2 2
2
2
2
2
= +
c
c
=
c
c

=
c
c

c
c
=
c
c
c
c
=
c
c

=
c
c
=

V E
m
x
E V
x m
iEt AEi
i
iEt
VA
x
iEt
A
m
eq in ng substituti
x
iEt
A
x
x
iEt
A
x
iEt AEi
t
iEt
A t x
n

This equation is referred to as time-independent

Schrdinger equation in one dimension.
In three dimensions time independent Schrdinger
equation can be written as
0 ) (
2
., .
0 ) (
2
) (
2
2
2 2
2
2
2
2
2
= + V
= +
c
c
+
c
c
+
c
c

V E
m
e i
V E
m
z y x

Particle in a one dimensional potential box

Consider an electron of mass m in an infinitely deep
one-dimensional potential box with a width of a L units
in which potential is constant and zero.
L x x x v
L x x v
> s =
( ( =
& 0 , ) (
0 , 0 ) (
X=0
X=L
V=0
The motion of the electron in one dimensional box can
be described by
the Schrdinger's equation.
0 ] [
2
2 2
2
= +

V E
m
dx
d

Inside the box the potential V =0

E
m
k where k
dx
d
E
m
dx
d
2
2 2
2
2
2 2
2
2
, , 0
0 ] [
2

= = +
= +

( ) sin cos ..........(1) x A kx B kx = +

The solution to above equation can be written as
Where A,B and K are unknown constants and to
calculate them, it is necessary to apply boundary
conditions.
When X = 0 then = 0 i.e. ||
2
= 0 . a
X = L = 0 i.e. ||
2
= 0 b

Applying boundary condition ( a ) to equation ( 1 )
A Sin K(0) + B Cos K(0) = 0
B = 0
Substitute B value equation (1)
(x) = A Sin Kx


Applying second boundary condition for equation (1)






Substitute B & K value in equation (1)

To calculate unknown constant A, consider normalization
condition.


L
n
k
n kL
kL
kL A
kL kL A
t
t
=
=
=
=
+ =
0 sin
0 sin
cos ) 0 ( sin 0
L
x n
A x
) (
sin ) (
t
=
L A
L
A
L
nx
n
L
x
A
dx
L
x n
A
dx
L
x n
A
dx x
L
L
o
L
o
L
/ 2
1
2
1 ]
2
sin
2
[
2
1 ]
2
cos[ 1 [
2
1
1 ] [ sin
1 ) (
2
0
2
2
2 2
0
2
=
=
=
=
=
=
}
}
}
t
t
t
t
Normalization
condition
2
2 2
2 2
2 2
2
2
8
2
& ,.
2
2
2
2
sin / 2
mL
h n
E
h
L
n
k where
m
h
L
n
E
m
k
E
mE
k
x
L
n
L
n
=
= =
|
.
|

\
|
|
.
|

\
|
=
= =
=
t
t
t
t
t

The wave functions n and the corresponding energies E

n

which are called Eigen functions and Eigen values, of the
quantum particle.
The normalized wave function is
The particle Wave functions & their energy Eigen values
in a one dimensional square well potential are shown in
figure.

L
z n
L
y n
L
x n
L
n
t t t

3 2 1
3
sin sin sin ) / 2 ( =
Normalized Wave function in
three dimensions is given by
X=0 X=L
E
2
=4h
2
/8mL
2
E
1
=h
2
/ 8mL
2
E
3
=9h
2
/ 8mL
2
n = 1
n = 2
n = 3
L / 2
L / 2
L / 3 2L / 3
(2 / L)
2
2 2
8mL
h n
E
n
=
L
x n
L
n
t
sin / 2 =
Conclusions
1.The three integers n
1
,n
2
and n
3
called Quantum numbers
are required to specify completely each energy state.

2.The energy E depends on the sum of the squares of the
quantum numbers n
1
,n
2
and n
3
but not on their individual
values.

3.Several combinations of the three quantum numbers may
give different wave functions, but not of the same energy
value. Such states and energy levels are said to be
degenerate.
THE END