1 Introduction

In classical physics, the laws describing the behaviour of waves and particles are fundamen-
tally dierent. Projectiles obey particle-type laws, such as Newtonian mechanics. Waves un-
dergo interference and diraction, which cannot be explained by the Newtonian mechanics
associated with particles. The energy carried by a particle is conned to a small region of
space; a wave, on the other hand, distributes its energy throughout space in its wave fronts. In
describing the behaviours of a particle we often want to specify its location, but this is not so
easy to do for a wave. How would you describe the exact location of a sound wave or a water
wave? In contrast to this clear distinction found in classical physics, quantum physics requires
that particles sometimes obey the rules established for waves, and we shall use some of the
language associated with waves to describe particles. The system of mechanics associated with
quantum systems is sometimes called wave mechanics because it deals with the wavelike
behaviours of particles.
1.1 Wave particle dualism
The concept of wave nature of matter arose from dual character of radiation which some time
behaves as a wave and at other times particle. For example, radiation is considered as a wave
in propagation experiments like interference, diraction and polarisation. These experiments
rmly establish the wave nature of radiation. On the other hand the phenomena like photo-
electric eect and Compton eect shows that radiation behaves as a particle-the photon. Thus
radiation has a dual characteristic. However, radiation does not exhibit its wave and particle
aspects simultaneously. Radiation thus behaves as a wave in transmission and as a particle
when it interacts with matter.
1.2 De Broglies Hypothesis for matter waves
The relation between the energy E of a Photon and the frequency of the associated electro-
magnetic wave is given by the Planck-Einstein equation
E = h (1.2.1)
According to the theory of relativity, the relation between the total relativistic energy E and
the relativistic momentum p of a particle of rest mass m
0
is given by
E
2
= p
2
c
2
+m
2
0
c
4
(1.2.2)
Since the photons have zero rest mass, the momentum of a photon is obtained by putting
m
0
= 0 in this equation.
Thus,
E
2
= p
2
c
2
(1.2.3)
p =
E
c
Substituting Eq(1.2.1)and c =

in Eq.(1.2.3)
p =
h

=
h

=
h
p
(1.2.4)
This equation represents the wave-particle relation for photons. In this equation is the wave-
length of the wave associated with photons of momentum p.
1
In 1924, Louis de Broglie extended the wave-particle relationship for photons to all particles in
motion(quantum particles like electrons, protons etc.)and put forth the following hypothesis:
All particles in motion have properties characteristic of waves. The wave-length and the
frequency of the wave associated with a particle in motion, are given by
=
h
p
=
h
mv
(1.2.5)
=
E
h
(1.2.6)
where, h is Plancks constant= 6.625 10
34
Js
v is particle velocity, E is the kinetic energy and m is the relativistic mass given by the relation:
m =
m
0
_
1
v
2
c
2
1.2.1 de Broglie wavelength in terms of energy and temperature:
de Broglie wavelength according to relation (1.2.5) is given by
=
h
p
=
h
mv
If E is the kinetic energy of the moving particle, then
E =
1
2
mv
2
=
1
2
m
2
v
2
m
=
p
2
2m
or p =

2mE
Hence de Broglie wavelength =
h
p
=
h

2mE
(1.2.7)
According to kinetic theory of gasses, the average kinetic energy of the material particle is
given by
E =
1
2
mv
2
=
3
2
kT
where k is the Boltzmanns constant= 1.38 10
23
JK
1
and T is the absolute temperature.
=
h

2mE
=
h

3mkT
(1.2.8)
If a charged particle carrying charge q is accelerated through a potential dierence V volts
then the kinetic energy E = qV.
=
h

2mqV
(1.2.9)
1.3 Velocity of De Broglie Wave
1.3.1 Phase velocity, v
p
For a particle of mass m moving with velocity v, the frequency of the wave associated with
the particle is related to the energy E of the particle by the equation
E = h =
h
2
2 = (1.3.1)
2
where is the angular frequency of the wave.
The momentum p of the particle is related to the de Broglie wavelength of the wave by
p =
h

=
h
2
.
2

= (1.3.2)
where is the propagation constant.
From these equations, we have
=
E

, and =
p

(1.3.3)
Now the phase velocity of the associated wave is given by
v
p
=

=
E

p
=
E
p
(1.3.4)
We discuss the following two cases:
(1) When the velocity v of the particle is much less than that of Light:
In this case the particle is said to be non-relativistic.
For such a particle
E =
p
2
2m
, and p = mv (1.3.5)
Therefore,
v
p
=
E
p
=
p
2
2m
.
1
p
=
p
2m
=
mv
2m
=
v
2
(1.3.6)
Thus for a non-relativistic particle, the phase velocity is half the particle velocity.
The Phase velocity has no physical meaning, and it cannot be measured.
(2) When the velocity v of the particle is comparable with that of light:
In this case the particle is said to be relativistic.
For such a particle
E = mc
2
and p = mv (1.3.7)
Therefore,
v
p
=
E
p
=
mc
2
mv
=
c
2
v
=
c
v/c
(1.3.8)
Since the term v/c in the denominator is less than unity, v
p
must be grater than c.
But a velocity larger than c cannot be measured, because according to the postulate of the theory
of relativity no signal or energy can be transmitted with a speed grater than the speed of light in free
space. Therefore, the phase velocity has no physical meaning and hence a particle in motion cannot
be represented by single wave.
1.3.2 Group Velocity v
g
De Broglie assumed that a particle in motion is represented by a group of waves i.e. a wave
packet moving with the group velocity v
g
which is given by:
v
g
=
d
dk
= lim
k0

k
(1.3.9)
Now we have
=
E

, and =
p

3
=
E

and k =
p

(1.3.10)
Substituting these values in Eq.(1.3.9), we get
v
g
= lim
p0
E

p
= lim
p0
E
p
=
dE
dp
(1.3.11)
Now we discuss the following two cases:
(1) Non-relativistic particle: For a non-relativistic particle
E = mc
2
and p = mv

E
p
=
2p
2m
=
mv
m
= v
i.e, v
g
= v (1.3.12)
(2) Relativistic particle: For a relativistic particle, we have
E
2
= p
2
c
2
+m
2
0
c
4
, and p = mv
Dierentiating the rst equation with respect to p, we get
2E
dE
dp
= 2pc
2

dE
dp
=
pc
2
E
=
(mv)c
2
mc
2
= v
i.e, v
g
= v (1.3.13)
Eqs.(1.3.12)and (1.3.13) show that the de Broglie group of waves, i.e. wave-packet associated with
a non-relativistic or relativistic particle travels with the same velocity as that of the particle.
Figure1: The wave-packet represented here by the solid curve contained in the
dashed-curve envelope, propagates with the group velocity v
g
along the x axis; the
individual waves (not drawn here), which add up to make the solid curve, move with
dierent phase velocities v
p
.
1.4 Davisson and Germer Experiment
Experimental arrangement:
Fig.2 Shows the experimental arrangement. Electrons are produced by heating a lament
(F)by a low tension battery (L.T). The electrons are then accelerated through a potential dif-
ference V in the electron gun. This electron beam falls on a large single crystal of nickel.The
electrons are scattered in all directions by the atoms in the crystal.The detector can be moved
to any angle relative to the incident beam. The energy of the electrons in the primary beam,
the angle at which they reach the target, and the position of the detector could all be varied.
4
Figure .2
Experimental procedure: The accelerating potential V is given a low value. The beam of elec-
trons falls normally on the surface of the crystal.The detector is moved to various positions and
the intensity of the diracted beam at each position is noted. The intensity of the diracted
beam is plotted against the angle between the incident beam and the beam entering the de-
tector. The method of plotting is such that the intensity at any angle is proportional to the
distance of the curve at that angle from the point of scattering. The observation are repeated
for dierent accelerating voltages and a number of curves are drawn(Figure 3) shows typical
polar graphs of electron intensity.
Figure.3
The graph remains fairly smooth, till the accelerating voltage becomes 44V when a bump
appears on the curve.
As the accelerating voltage is increased, the length of the bump increases.
The bump becomes most prominent in the curve for 54V electrons at = 50
0
.
As the accelerating voltage is further increased, the bump decreased in length and nally
disappears at 68V.
Calculation of observed wavelength
For nickel, the spacing of the atomic planes which can be measured by x-ray diraction, is
d = 0.091nm. There is an intense reection of the beam at the angle = 50
0
. The angle of
incidence relative to the family of Bragg planes shown in gure
5
Figure .4
is =
18050
2
= 65
0
. The Bragg equation for maxima in the diraction pattern in
n = 2d sin
for n = 1 the de Broglie wavelength of the diracted electrons is
= 2d sin = 0.165nm
Calculation of the expected wavelength of the electrons using de Broglies formula. The
electron kinetic energy KE is 54eV. The electron wavelength is therefore
=
h
mv
=
h

2mE
= 0.166nm
The observed wavelength agrees well with the expected wavelength. The Davission-Germer
experiment thus directly veries de Broglies hypothesis of the wave nature of moving bodies.
1.5 Bohrs Quantisation and Matter waves
In the Bohr theory of the hydrogen atom, the quantisation condition
L =
nh
2
for the angular momentum L of the electron, moving in a stationary circular orbit is only
arbitrary. On the basis of de Broglies hypothesis this condition is easily obtained. For this
purpose, the following assumptions are made:
(I) The motion of the electron in a stationary circular orbit is represented by a standing matter
wave of wavelength given by the de Broglie relation
=
h
mv
(1.5.1)
where m is the mass of the electron and v is the velocity in the orbit.
(II) The circular orbit contains an integral number of wavelengths, i.e.,
2r
n
= n (1.5.2)
where n = 1, 2, 3, .... and r
n
is the radius of the orbit.
Substituting the value of in Eq.(1.5.2)
2r
n
=
nh
mv
6
or mvr
n
=
nh
2
i.e., L =
nh
2
(1.5.3)
which is the Bohrs quantisation condition.
2 Heisenbergs Uncertainty Principle
We know that an electron in motion is associated with a wave whose wavelength is given by
the de Broglie relation, and it can be considered as a wave packet of small extension formed by
the superposition of large number of waves of wavelengths slightly dierent from the wave-
length of the associated wave. Since a wave-packet is of nite width, there will be an uncer-
tainty in specifying the position of electron. At the same time the spectral distribution of the
amplitude of a wave-packet covers a range of wavelengths. By the de Broglie relationship, this
means that the momentum of the electron will also be uncertain. Therefore, in general, it is
not possible to determine precisely and simultaneously, the position and the momentum of
the electron.
2.1 Uncertainty Principle
Statement: It is impossible to determine precisely and simultaneously the values of the both the
members of a pair of physical variables which describe the motion of an atomic system. Such pairs of
variables are called canonically conjugate variables.
Example: According to this principle, the position and momentum of a particle cannot be
determined simultaneously to any desired degree of accuracy. Taking x as the error in deter-
mining its position and p
x
the error in determining its momentum at the same instant, these
quantities are related as follows:
x.p
x

where =
h
2
= 1.054 10
34
Js.
If x is small, p
x
will be large and vice versa. It means that if one quantity is measured accu-
rately, the other quantity becomes less accurate.
In three dimensions the uncertainty relations are:
x.p
x
(2.1.1)
y.p
y
(2.1.2)
z.p
z
(2.1.3)
Uncertainty relation for energy and time:
The uncertainty relation for kinetic energy E of a particle in motion and the time t at which it
is measured is
E.t (2.1.4)
where E is the uncertainty in the energy, and t the uncertainty in the time.
NOTE:
In the uncertainty relation of x and p
x
my be dened in various ways, therefore, many ex-
pressions for the product x.p
x
are possible. If a series of measurements of x and p
x
are
taken on many identical system, and if x and p
x
are dened as the root mean square devi-
ations from their mean values, it can be shown that the minimum value of the product of the
uncertainties is given by
x.p
x
=

2
7
In solving problems in which only one set of values is involved, the minimum value of the
product should be taken as
x.p
x
=
This expression will give better estimate of one of the uncertainties, if the other is known.
2.2 Illustration: Gamma Ray Microscope
Suppose we try to measure the position and linear momentum of an electron using an imagi-
nary microscope with a very high resolving power. The electron can be observed if atleast one
photon is scattered by it into the microscope is given by the relation
x =

2sin
where x is the distance between two points which can be just resolved by microscope. This is
the range in which the electron would be visible when disturbed by the photon. Hence x is
the uncertainty involved in the position measurement of the electron.
However, the incoming photon will interact with the electron through the Compton eect.
To be able to see this electron, the scattered photon should enter the microscope within the
angle 2. The momentum imparted by the photon to the electron during the impact is of the
order of
h

. The component of this momentum along OA is

h

sin and that along OB is

h

sin.
Hence the uncertainty in the momentum measurement in the x-direction is
p
x
=
h

sin
_
h

sin
_
=
2h

sin
x.p
x
=

2sin
.
2h

sin = h
A more sophisticated approach will show that x.p
x
. where =
h
2
It is clear that the process of measurement itself perturbs the particle whose properties are
being measured.
8
3 Schrodingers Wave Equation
3.1 Schrodingers one dimensional Time-Dependent wave equation
A plane wave moving in the positive x direction is represented in the exponential form as
= Ae
i(kxt)
(3.1.1)
where is a function of position x and time t ; = 2 ( is the frequency of the wave) and k
the propagation constant=
2

( is the wavelength of the wave )

According to de Broglie relation
p =
h

=
h
2
2

= k
where =
h
2
and k =
2

from Einstein equation

E = h =
h
2
2 =
k =
p

and =
E

(3.1.2)
substituting equation (3.1.2)in (3.1.1) we have
= Ae
i

(pxEt)
(3.1.3)
Dierentiate equation(3.1.3) partially w.r.t position x.

x
=
i

pAe
i

(xpEt)
and

2

x
2
=
p
2

2
Ae
i

(xpEt)
=
p
2

p
2
=
2

x
2
(3.1.4)
Dierentiate equation(3.1.3) partially w.r.t time t.

t
=
i

EAe
i

(xpEt)
=
i

E
E=

t
(3.1.5)
Particle subject to force: When a particle is not free but is subject to a force, its total energy is
the sum of its kinetic energy and potential energy.
For a particle of mass m. moving with a velocity v piloted by the wave function , the total
energy in a non-relativistic case is given by
E =
1
2
mv
2
+V
where
1
2
mv
2
is kinetic energy and V the potential energy of the particle-a function of both x
and t.If p is the momentum of the particle, then
p = mv and
1
2
mv
2
=
1
2m
m
2
v
2
=
p
2
2m
9
E =
p
2
2m
+V (3.1.6)
multiplying both sides by , we have
p
2
2m
+V= E
substituting the value of E from Eq.(3.1.5) and p
2
form Eq.(3.1.4) ,we have

2
2m

x
2
+V=

t
= i

2
2m

x
2
+V= i

t
(3.1.7)
This is Schrodingers one dimensional time dependent wave equation for waves associated
with a moving particle in a potential eld V.
Three dimensional wave equation: For motion of the particle in three dimensions is a func-
tion of x, y, z and t. Extending to the three dimensional case, Schrodingers time dependent
wave equation is given by

2
2m
_

x
2
+

2

y
2
+

2

z
2
_
+V= i

t
(3.1.8)
This is Schrodingers time dependent, three dimensional wave equation for waves associated
with a moving particle in a potential eld V. This equationcanbe usedonly for non-relativistic
problems.
Free particle: A particle is said to be free when no force acts on it, in such a case the po-
tential energy V of the particle is zero and the total energy E is only Kinetic Energy.
putting V = 0 in equation(3.1.7) we have

2
2m

x
2
= i

t
(3.1.9)
3.2 Schrodingers time-independent wave equation
The time dependent, one dimensional Schrodingers wave equation is

2
2m

x
2
+V= i

t
(3.2.1)
and explicitly in terms of x and t, we have

2
2m

2
(x, t)
x
2
+V(x, t) = i
(x, t)
t
When the potential V does not depend explicitly on time and is a function of x only and
the total energy E is constant, the wave function (x, t) can be written as the product of two
separate functions (x),a function only of x and f (t) a function only of t.
(x, t) = (x)f (t)
the above relation is briey written as = f

x
= f

x
and

2

x
2
= f

2

x
2
and

t
=
f
t
10
Now
= Ae
i

(pxEt)

t
=
i

EAe
i

(xpEt)
=
i

E=
i

Ef (3.2.2)
substituting in Eq.(3.2.1), we have

2
2m
f

2

x
2
+Vf = i
_
i

_
Ef (3.2.3)
Dividing both sides by f , we have

2
2m

x
2
+V = E
or

x
2
+
2m

2
(E V) = 0 (3.2.4)
Further is a function of only one variable x, we ca replace partial derivative by total deriva-
tive
d
2

dx
2
.
We can therefore, write equation (3.2.4) as
d
2

dx
2
+
2m

2
(E V) = 0 (3.2.5)
This is one dimensional, time independent Schrodingers equation.
Three dimensional time independent equation: For motion of the particle in three dimen-
sional is a function of x, y and z. In such a case the time independent or stationary state form
of Schrodingers wave equation is given by
_

x
2
+

2

y
2
+

2

z
2
_
+
2m

2
(E V) = 0 (3.2.6)
3.3 Physical Interpretation of the Wave function .
We have assumed that the wave associated with a particle in motion is represented by a com-
plex variable quantity (x, y, z, t) called the wave function. Therefore, it cannot have a direct
physical meaning. Since it is a complex quantity, it may be expressed in the form
(x, y, z, t) = a +ib (3.3.1)
where a and b are real function of the variables (x, y, z, t) and i =

1.
The complex conjugate of which is denoted by

is obtained by changing i to i.Therefore,

we have

(x, y, z, t) = a ib (3.3.2)
Multiplying Eq.(3.3.1)by Eq.(3.3.2)
(x, y, z, t)

(x, y, z, t) = a
2
+b
2
(3.3.3)
On the left-hand side of this equation the product is denoted by
|(x, y, z, t)|
2
|(x, y, z, t)|
2
= a
2
+b
2
(3.3.4)
11
Thus the product of and

is real and positive if 0. Its positive square root is denoted

by |(x, y, z, t)| and it is called the modulus of . The fact expressed by Eq.(3.3.4) has been
used by Max Born to give interpretation of which is as follows:
for the motion of a particle in three dimensions the product
(x, y, z, t)

(x, y, z, t) = |(x, y, z, t)|

2
(3.3.5)
is the probability density P(x, y, z, )( probability per unit volume) for the particle at position
(x,y,z) at time t. Hence the product of the probability density and the volume element
d = dxdydz
P(x, y, z)d = (x, y, z, t)

(x, y, z, t)d = |(x, y, z, t)|

2
d (3.3.6)
is the probability that the particle will be found in a volume element d = dxdydz surround-
ing the point at position(x,y,z)at time t.
Dimensions in 3D is [L]

3
2
.
3.4 Normalization of Wave function
Even before we consider the actual calculation of , we can establish certain requirements it
must always fulll. For one thing, since ||
2
is proportional to the probability density P of
nding the body described by , the integral ||
2
over all space must be nite-the body is
somewhere, after all. If
_

||
2
d = 0 (3.4.1)
the particle does not exist, and the integral obviously cannot be and still mean anything.
Furthermore, ||
2
cannot be negative or complex because of the way it is dened.The only
possibility left is that the integral be a nite quantity if is to describe properly a real body.
It is usually convenient to have ||
2
be equal to the probability density P of nding the particle
described by , rather than merely be proportional to P. If ||
2
is to equal P, then it must be
true that
_

||
2
d = 1 (3.4.2)
Awave function that obeys Eq.(3.4.2) is said to be normalized. Every acceptable wave function
can be normalized by multiplying it by an appropriate constant.
3.5 Limitations on
Because of above interpretation of ||
2
as a probability density, the solution that can be allowed
for from the Schrodinger equation are subjected to certain limitations. The most important
limitations are:
must be nite for all values of x,y,z.
must be single valued, ie. for each set of values of x,y,z, must have one value only.
must be continuous in all regions expect in those regions where the potential energy V =
.
The partial derivatives

x

z
must be continuous everywhere. A wave function which
satises these conditions is called a well behaved function.
12
3.6 Operators, Eigen functions, Eigen value and Eigen Value Equation
An operator is a rule which a changes a function into another function. For example, the
operator
d
dx
represents dierentiation with respect to x. When it operates on a function ,e.g
f (x) = x
n
then
df
dx
= nx
n1
if a function f (x) is such that an operator A which operates on f (x) gives
Af (x) = af (x) (3.6.1)
where a is a constant, then
f (x) is called eigen-function of the operator.
the constant a is called the eigen value of the operator belonging to the eigen function f (x)
and
the equation Eq.(3.6.1) is called the eigen value equation.
Thus an eigen value equation states that an operator, acting on a function,
reproduced the same function multiplied by a constant factor.
3.6.1 Operator for Momentum
The eigen value equation for x component of the momentum is give by

x
= p
x
(3.6.2)
The equation shows that

x
is the operator for momentum in x direction.
is the eigen function of the operator.
Similarly for y and z components of the momentum, the operators are
p
y
=

i

y
p
z
=

i

z
(3.6.3)
The momentum operator is dened as the operator which, operating on the wave function,
reproduces the wave function multiplied by the momentum.
3.6.2 Operator for Kinetic Energy
eigen value equation for kinetic energy is given by

2
2m

x
2
= K (3.6.4)

2
2m

2
x
2
is the operator for kinetic energy for a particle moving in x direction.
in Three dimensions the operator for K is

K =

2
2m

2
(3.6.5)
3.6.3 Operator for total Energy
The eigen value equation for total energy E of the particle moving in the x-direction.
_

2
2m

2
x
+V
_
= E (3.6.6)
13

2
2m

2
x
+V is the operator for total energy for the motion of the particle along the x direction.
This operator is denoted by H and is called the Hamiltonian operator.

H
x
=

2
2m

2
x
+V (3.6.7)
in three dimensions

H =

2
2m

2
+V (3.6.8)
where
2
=

2
x
2
+

2
y
2
+

2
z
2
The Hamiltonian operator operating on the wave function reproduces the same function mul-
tiplied by the total energy E.
3.6.4 Operators for Angular Momentum
In classical mechanics the angular momentum

L of a particle is dened by

L =r p (3.6.9)
where r is the position vector of the particle relative to some arbitrary origin and p is its linear
momentum. From Eq.(3.6.9) the components L
x
, L
y
and L
z
of

L, along x, y and z axes, are
respectively given by
L
x
= yp
z
zp
y
L
y
= zp
x
xp
z
L
z
= xp
y
yp
x
Now using the expression for linear momentum operators, the operators for L
x
, L
y
and L
z
are
given by

L
x
= i
_
y

z
z

y
_

L
y
= i
_
z

x
x

z
_

L
z
= i
_
x

y
y

x
_
These operators can be transformed into spherical polar coordinates(r, , ), which is given by

L
x
= i
_
sin

cot cos

L
y
= i
_
cos

cot sin

L
z
= i

14
3.7 Expectation values
The expression for the wave function , which we get as a solution of a Schrodingers wave
equation for a particle under given condition contains all the information about the variables
of the particle subject to the uncertainty principle. Expect for those variables for which the
solution gives quantized values, the information is in the form of probabilities and not denite
values. The interpretation of

dx as the probability that the particle will be found over

small distance dx at position x, at time t makes it possible to nd the average or the expecta-
tion value < x > of the position of the particle along the x axis. First we dene the expectation
value of a dynamical quantity.
The expectation value of a dynamical quantity is the mathematical expectation for the re-
sult of a single measurement. Or it is dened as the average of the results of large number
of measurements on independent identical systems,i.e, the system represented by identical
wave function
When a given system is in a state which need not be an eigen function of the operator

A, the
average of large number of independent measurements of an observable corresponding to the
operator

A is given by
< A >=
_

Ad
_

(3.7.1)
< A > is called the Expectation value of the observable.
For a normalized function;
_

= 1
< A >=
_

Ad (3.7.2)
3.7.1 Expectation value of position x
In one dimensional case the expectation value of position co-ordinate x is given by
< x >=
_

xdx =
_

x||
2
dx (3.7.3)
3.7.2 Expectation value for the momentum
vector p is given by
< p >=
_

d (3.7.4)
In one dimensional case
< p
x
>=
_

i

x
dx (3.7.5)
3.8 Postulates of Quantum Mechanics
We have seen that in Schrodingers formulation of quantum mechanics, a complex variable
quantity , called the wave function, is introduced to represent the wave associated with a
particle in motion. Based on our discussion in the earlier sections, now we give ve postulates
which are sucient to describe a single-particle system.
1. For a system consisting of particle moving in conservative force, there is an associated
complex wave function (x, y, z, t), where x,y,z are the space coordinates and t is the time. This
function enables us to obtain a description of the behaviour of the system, consistent with the
principle of uncertainty.
15
2. With every observable dynamical quantity there is an operator.
3. The wave function and its partial derivatives

x
,

y
,

z
must be nite, continuous and
single valued for all values of x, y, z and t.
4. The product of

, where

is the complex conjugate of , is always a real quantity. The

product is called the probability density and

d is interpreted as the probability that the

particle will be found in the volume element d at x, y, z and t. Since the total probability that
the particle will be somewhere in space must be equal to 1, we have
_

= 1
This integral is taken over all space.
5. The average or expectation value of an observable quantity A with which an operator

A is
associated is dened by:
< A >=
_

Ad
where is normalized, the integral begin taken over all space.
4 Applications of Schrodingers wave equation
4.1 The Particle in a Box: Innite Square Well Potential
Consider a particle of mass m moving inside a box along x-direction. The particle is bouncing
back and forth between the walls of the box. The box has insurmountable potential barriers at
x = 0 and x = L i.e, the box is supposed to have walls of innite height at x = 0 and x = L. The
particle has a mass m and its position x at any instant is given by 0 < x < L.
Figure.5 Innite square well potential energy. For 0 < x < L, the potential energy V(x) is zero.
Outside this region, V(x) is innite. The particle is conned to the region in the well 0 < x < L.
The potential energy V of the particle is nite 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
V(x) =
_

_
0 for 0 < x < L,
for x 0
for x L.
The particle cannot exist outside the box and so its wave function is 0 for x 0 and x L.
Our task is to nd what is within the box.viz, between x = 0 and x = L.
With in the box, the Schrodingers equation becomes
d
2

dx
2
+
2m

2
E= 0 (4.1.1)
16
Putting
2mE

2
= k
2
,in the eq.(4.1.1)becomes
d
2

dx
2
+k
2
= 0 (4.1.2)
The general solution of this equation is
= A sinkx +B coskx (4.1.3)
The boundary condition can be used to evaluate the constants A and B in equation(4.1.3)
= 0 at x = 0 and hence B = 0
= 0 at x = L, hence 0 = A sinkL
Since A 0, kL = n where n is an integer or k =
n
L
Thus

n
(x) = Asin
nx
L
k
2
=
n
2

2
L
2

2mE

2
=
n
2

2
L
2
The energy of the particle
E
n
=
n
2

2
2mL
2
; n = 1, 2, 3....
Wave function:
It is certain that the particle is somewhere inside the box. Hence for a normalised wave func-
tion
_
L
0

dx = 1 ; A
2
_
L
0
sin
2
_
nx
L
_
dx = 1
i.e.,
A
2
_
L
0
_

_
1 cos
2nx
L
2
_

_
dx = 1 or A
2
L
2
= 1
or A =
_
2
L
The normalised wave function of the particle is given by

n
=
_
2
L
sin
nx
L
; n = 1, 2, 3, 4...... (4.1.4)
The normalised wave function
1
,
2
and
3
are plotted in Figure.
Figure.6 shows the 1. wave function 2.Probability density 3.corresponding energy
17
Particle in 3D box:
For particle in 3D box Schrodingers equation is given by
_

x
2
+

2

y
2
+

2

z
2
_
+
2mE

= 0 (4.1.5)
and the energy of the particle is given by
E(n
x
, n
y
, n
z
) =

2

2
2m
_

_
n
2
x
L
2
x
+
n
2
y
L
2
y
+
n
2
z
L
2
z
_

_
(4.1.6)
wave function is given by
(n
x
, n
y
, n
z
) =
_
8
L
x
L
y
L
z
sin
n
x

L
x
sin
n
y

L
y
sin
n
z

L
z
(4.1.7)
4.2 Potential Step and Potential barrier
4.2.1 Potential step:
A potential step corresponding to the force eld acting on a particle being zero every where
except in a limited region. A single Step potential is shown in Figure.7(a) and is represented
by
V(x) =
_

_
0 for x<0,
V
0
for x0.
The height of the potential step is said to be V
0
.
Figure 7: (a)Potential Step (b)Potential barrier
4.2.2 Potential barrier:
A potential barrier has a double step, rst from V(x) = 0 to V(x) = V
0
and the second from
V(x) = V
0
to V(x) = 0, as show in Figure.7(b).
The distance between the two steps is known as the width of the barrier. A potential barrier is
therefore, represented as
V(x) =
_

_
0 for x<0,
V
0
for 0 x L
0 for x>L
18