UNIT II

QUANTUM MECHANICS

INTRODUCTION
 The most outstanding development in modern science is the conception of quantum
mechanics. The quantum mechanics is better than Newtonian classical mechanics in
explaining the fundamental physics. There was big development in physics between the
time of Newton and the time of quantum mechanics.
 Newton showed that the motion of planets and the free fall of an object on earth is
governed by the same law. Thus, he unified terrestrial and celestial mechanics. This was
in contrast to ancient belief that the world of the earth and heaven is governed by
different laws.
 It was earlier believed that the heat is some peculiar substance called 'caloric', which
flows from a hot object to a cold object. But latter it was proved that the heat is the
random motion or vibration of constituents of matter. Thus, thermodynamics and
mechanics were unified.
 For a long time, the phenomena of electricity, magnetism and light were treated as
independent branches and were unconnected. But in nineteenth century, Faraday and
Maxwell along with others unified these independent branches of physics. They proved
that all three phenomena are manifestations of electromagnetic field.
 The simplest example is the electric field of an electric charge that exerts a force an
another charge when it comes in the range. An electric current produces a magnetic field
that exerts a force on magnetic materials.
 Such fields can travel through space, independent of charge and magnet, in the form of
electromagnetic wave. The best example of electromagnetic wave is light. Finally,
Einstein unified space, time and gravity in his theory of relativity.
 Quantum mechanics also unified two branches of science: physics and chemistry.
 In previous developments in physics, fundamental concepts were not different from
those of everyday experience, such as particle, position, speed, mass, force, energy and
even field. These concepts are referred as 'classical'.
 The world of atoms cannot be described and understood with these concepts. For atoms
and molecules, the ideas and concepts used in dealing with objects in day to day life is
not sufficient. Thus, it needed new concepts to understand the properties of atoms.
 A group of scientists W. Heisenberg, E. Schroedinger, P.A.M. Dirac, W. Pauli, M. Born and
Neils Bohr, conceived and formulated these new ideas in the beginning of 20 th century.
This new formulation, a branch of physics, was named as quantum mechanics.
Limitations of Classical Mechanics
 The classical physics is complete and beautiful in explaining daily experiences where big
bodies are involved. But it breaks down severely at subatomic level and failed to explain
some of the phenomenon totally.
 The phenomenas which classical physics failed to explain are black body radiation,
photoelectric effect, emission of X-rays, etc.
 In classical physics, a body which is very small in comparison with other body is termed
as 'particle'. Whereas in quantum mechanics, the body which cannot be divided further
is termed as 'particle'.
 The other main difference is the quantized energy state. In classical physics, an
oscillating body can assume any possible energy. On the contrary, quantum mechanics
says that it can have only descrete non-zero energy.
Need of Quantum Mechanics
 Classical mechanics successfully explained the motions of object which are observable
directly or by instruments like microscope. But when classical mechanics is applied to the
particles of atomic levels, it fails to explain actual behaviour. Therefore, the classical
mechanics cannot be applied to atomic level, e.g. motion of an electron in an atom.
 Other phenomenas which classical mechanics failed to explain are black body radiation,
photoelectric effect, emission of X-rays, etc.
 The above problems were solved by Max Planck in 1900 by the introduction of the
formula
E = nh … (1)
where, n = 0, 1, 2, … ,
h = Planck's constant = 6.63  10–34 J/s
 This is known as 'quantum hypothesis' and marked the beginning of modern physics.
The whole microscopic world obeys the above formula.

WAVE PARTICLE DUALITY OF RADIATION AND MATTER

The wave and particle duality of radiation can be easily understood by knowing what is a
wave and what is a particle.
Wave
 A wave originates due to vibrations, and it is spread out over a large region of space. A
wave cannot be located at a particular place and mass cannot be attached to a wave.
 Actually, a wave is a spread out disturbance specified by its amplitude a, frequency ,
wavelength , phase  and intensity I.
Particle

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 A particle is located at some definite point and it has mass. It can move from place to
place. A particle gains energy when it is accelerated and it loses energy when it is slowed
down.
 A particle is characterized by mass m, velocity v, momentum p, and energy E.
 Looking at the above facts, it might appear difficult to accept wave particle duality of
radiation, i.e. radiation is a wave which is spread out over all space and that it is also a
particle which is localised at a point in space.
 But this wave particle duality of radiation has to be accepted because, sometimes
radiation has to be assigned the behaviour of a wave and at other times radiation is to
be assigned particle nature as discussed below.
 The phenomena of interference, diffraction and polarisation require the presence of two
or more waves at the same time and at the same position. It is very clear that two or
more particles cannot occupy the same position at the same time. So one has to
conclude that radiation behaves like waves.
 Spectra of black body radiation, production and scattering of X-rays, Compton effect,
photoelectric effect, etc. could not be explained on wave nature of radiation. These
phenomena established that radiant energy interacts with matter in the form of photons
or quanta. With this, Planck's quantum theory came into being to conclude that
radiation behaves like particles.
 Thus, radiation sometimes behaves as a wave and at some other times as a particle. It is
to be noted that radiation cannot simultaneously exhibit its wave and particle properties.
Now, wave-particle duality of radiation is universally accepted.

DE BROGLIE'S CONCEPT OF MATTER WAVES

 Discrete particle nature of matter is very well established and now it is known that
matter is composed of atoms and that electrons, protons and neutrons are the building
blocks of all types of atoms.
 The electromagnetic wave theory explained the phenomena of interference, diffraction
and polarisation. The quantum theory provided both qualitative and quantitative
explanation of spectra of black body radiation, scattering of X-rays and Compton effect,
emission of line spectra, photoelectric effect, etc.
 These two theories coupled together established wave-particle duality of radiation. But
inspite of the success of this duality of radiation, the two fundamental postulates of
Bohr's theory of atomic structure remained unexplained for a long time.
 In the mean time Einstein's mass-energy relation, E = mc2, had been verified,
establishing that radiation and mass are mutually convertible.
 On this background, in 1924 De Broglie extended the idea of dual nature of radiation to
matter and proposed that matter possesses particle as well as wave characteristics. He

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 believed that motion of electron within an atom is guided by a peculiar kind of
waves called 'Pilot waves'.
 While adverting the concept of matter waves, De Broglie was guided by wave - particle
duality of radiation and the way in which nature manifests herself.
 De Broglie put forth following arguments:
 Nature manifests herself mainly as matter and radiation, and nature loves symmetry.
So wave particle duality of radiation points to similar duality of matter.
 The principle of least action in mechanics and the principle of least time in optics
imply similar conditions. This close analogy of these two principles from two
different branches of physics, shows the probability of the behaviour of matter as a
wave like entity under suitable circumstances. This close parallelism between
mechanics and optics also indicates similarity between matter and radiation, i.e. if
radiation has dual nature then matter must also have similar wave-particle duality.
 Bohr orbits are of definite size and are selected by quantum rules. The radii of these
quantum orbits are proportional to the square of integral numbers
 h2 0 
rn = 2 , n  and electrons stay in these orbits for a considerable time without
2
  me 
radiating energy. Thus, the stable non-radiating orbits of electrons in an atom are
governed by integer rules. Now the only phenomena involving integers in physics
are those of interference and modes of vibration of a stretched string, and both of
them imply wave motion. So there must be a latent relationship between Bohr orbits
and integers associated with them. This latent relationship can be understood by
considering the length of a Bohr orbit as consisting of integral number of
wavelengths (equal to the principal quantum number of the orbit) of the waves
associated with electrons moving in that orbit.

If the orbit length 2r is an integral number of wavelengths,

the wave will reinforce itself when it returns to the starting point A.
In the case shown, 2r = 4

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 h
 Now, the quantum condition for Bohr orbits is mvr = n . So the principal quantum
2
2mvr
number n = , and 'De Broglie wavelength' can be obtained by dividing the
h
circumference 2r of the nth permissible orbit by its principal quantum number n.
2r
So,  =
n
2r
 =
(2mvr/h)
h
 =
mv
 This expression for De Broglie wavelength, agrees with the one he postulated, namely
Planck's constant
= , on the basis of his hypothesis of matter waves.
momentum of the particle
 According to wave mechanics, electrons move around the nucleus as wave-packets
which are formed in a somewhat similar manner as standing waves are formed.
Wavelength of Matter Waves or De Broglie Wavelength
 By De Broglie's hypothesis, a moving material particle is associated with a wave whose
wavelength is called De Broglie wavelength and it is given by the ratio of Planck's
constant to the momentum of the particle.
h h
 = =
p mv
where p is the momentum of the particle, m its mass, and v the velocity.
 We can arrive at this expression for De Broglie wavelength, (1) by analogy with radiation
and (2) by relativistic considerations.
De Broglie Wavelength by Analogy with Radiation
 By Einstein's mass-energy relation, we have
E = mc2  (1)
where E is the energy equivalent of mass m, and c is the velocity of light.
 By Planck's quantum theory of radiation, the energy of a photon is given by
E = h  (2)
where h is Planck's constant and  is the frequency of oscillations.
From equations (1) and (2), we get
h = mc2
c
But  =  , (Since velocity = frequency  wavelength)
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 c
 h ·  = mc2

h h
or  = =  (3)
mc p
where p = mc is the momentum associated with the photon and  is its wavelength.
De Broglie Wavelength in terms of K.E. of the Particle
 The momentum of a particle of mass m moving with velocity v is given by p = mv; and
the De Broglie wavelength associated with the particle is given by
h h
 = =  (1)
mv p
 The K.E. of the particle is given by
1
E = mv2
2

m2 v2 p2
E = =
2m 2m

 p = 2mE  (2)

From equations (1) and (2), we have
h h
 = =  (3)
p 2mE

In equation (3), De Broglie wavelength  of a moving particle has been expressed in

terms of K.E. of the particle.

De Broglie Wavelength for an Electron in terms of Potential Difference

If an electron acquires velocity v on accelerating it through a potential difference of V volts,
then the work done on the electron is eV, e being charge of the electron. This work is
converted into kinetic energy of the electron,
1
i.e. E= mv2 = eV  (1)
2

If e is in coulombs, m in kg, V in volts, then velocity v will be in m/s.

h
But  =
2mE
h
From equation (1),  =  (2)
2meV
Ignoring relativistic correction, we can take m = mo
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 h
  =  (3)
2 mo eV
Now, h, mo and e are universal constants with values
h = 6.625  10–34 J - s
e = 1.6  10–19 C
mo = 9.1  10–31 kg.
Substituting these values in equation (3), we get
6.625  10–34
 = metres
2  9.1  10–31  1.6  10–19  V
12.27  10–10
= metres
V
12.27
  = Ao  (4)
V

CONCEPT OF GROUP VELOCITY AND PHASE VELOCITY

Phase Velocity
 As we know, with every material particle, a wave called De Broglie wave is associated,
which becomes important at microscopic levels.
 The speed with which a crest or trough of a wave travels, is called the 'phase velocity' of
De Broglie waves. It is also called as 'wave velocity' (u). For wave velocity, the phase
remains constant.
 For a particle of mass m, moving with a velocity v, the De Broglie wavelength  is
given by
h
 = … (1)
mv
and energy, E = h = mc2
mc2
  = … (2)
h
 The equation of motion of a plane wave of frequency  and wavelength  moving in
x direction is, y = a sin (t – kx)
where  = 2 the angular frequency … (3)
2
and k =  , the propagation constant of the wave.

 For wave velocity, the phase remains constant i.e.

t – kx = constant … (4)
dx 
 The wave velocity, u = = (by differentiating equation 4)
dt k
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 
 u = 2  =  … (5)
2
where  is the frequency of the matter waves.
Substitution of equations (1) and (2) in (5) gives
mc2 h
u = 
h mv
c2
u =
v
c2
i.e. Wave velocity, u = … (6)
v
 For any particle, as v is always less than c, the speed of light, we see that the phase
velocity u comes to be greater than c, which is an unexpected result. The difficulty raised
above can be overcome by understanding the wave group and group velocity vg.
Group Velocity
 A material particle can be represented by a wave packet or the group of waves and the
velocity of wave group is called as 'group velocity'. The individual waves travel inside
the group with their phase velocities or wave velocities.
 Wave group (wave packet) can be obtained by interference of many waves of different
frequencies and amplitudes so that resultant has a high value of amplitude near the
vicinity of the particle and gets attenuated outside this region as shown in Fig.
 We can say that the particle is somewhere in the wave packet and that wave packet
moves with velocity of the particle carrying that particle in it. It can be shown that the
group velocity vg is the same as that of the particle velocity v.

Group of waves
 Consider the superposition of two waves of equal amplitude a, different angular
frequencies 1 and 2, and propagation constants k1 and k2.
Let y1 = a sin (1t – k1x)
and y2 = a sin (2 t – k2x)
 The resultant will be
y = y1 + y2
y = a [sin (1t – k1x) + sin (2t – k2 x)]
(1 – 2) t (k1 – k2) x (1 + 2) t (k1 + k2) x
y = 2a cos  –  sin  – 
 2 2   2 2 

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 . . A+B A – B
 . sin A + sin B = 2 sin 2 cos 2 
 
(1 + 2)
The resultant wave has the angular frequency and its amplitude is
2
(1 – 2) t (k1 – k2) x
A = 2a cos  – 
 2 2 
 Thus, the amplitude of the wave group is modulated both in space and time. The
velocity with which this envelope moves is given by
1 – 2 d
vg = = … (1)
k1 – k2 dk
This is the general formula for a group velocity.
To Show that, Group Velocity vg is Equal to Particle Velocity v
Consider a particle whose kinetic energy is
1 p2
E = mv2 = … (1)
2 2m
where p = mv = momentum
We have, E = h
h
 E = H , where H = and = 2  … (2)
2
h
The De Broglie wavelength is  =
p
h h 2
 p = = 
2 
p = Hk … (3)
Using equations (2) and (3), the energy equation (1) becomes
H 2 k2
H =
2m
Hk2
 =
2m
Hkdk
which gives d =
m
d Hk
 =
dk m
Hk  d
i.e. vg =  vg = dk 
m  

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 p
vg = (from equation (3)
m
mv
vg = =v
m
 vg = v  (4)
Thus, group velocity vg is equal to particle velocity v.
Hence the packet can guide the motion of the particle. A wave group or wave packet is
associated with a moving body and that the phase velocity (or wave velocity u) has no
physical significance.
Thus, De Broglie wave associated with a moving body is a wave group which travels with the
same speed as that of the body.

Phase Velocity in Terms of Wavelength

Consider a particle of mass m and velocity v which is accelerated through a p.d. of V volts.
Then
1
E = mv2 = eV … (1)
2
Also, we have, E = h
E
  = … (2)
h
From equations (1) and (2), we get
E 1/2 mv2 eV
 = = =
h h h
h
Multiplying and dividing by ,
2m
h eV 2m h 1
 = · = … (3)
2m h h 2m 2
 h h 
as  = = 
 2 mE 2 meV
Using u = 
h h
= ·=
2m2 2m
h
 The phase velocity, u =
2m
Hence, the wave velocity of matter wave depends inversely on the wavelength . This is the
basic difference between matter waves and light waves.
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PROPERTIES OF MATTER WAVES
Matter waves are generated by a moving matter particle. If a particle of mass m moves with
velocity v, then the wavelength of matter waves associated with it is given by
h c2
= and these waves travel with velocity u = .
mv v
From this, properties of matter waves can be stated as:
 Lighter the particle, greater would be the wavelength of the matter waves associated
 1 
with it.   ‚ for v constant.
 m 
 Smaller the velocity of the particle, greater would be the wavelength of the matter
 1 
waves.   ‚ for m constant.
 v 
 For v = ,  becomes zero and for v = 0,  becomes infinity i.e. the wave becomes
indeterminate when v = 0. This simply means that matter waves are produced by
particles moving with finite velocities.
 Matter waves are different from electromagnetic waves, because matter waves can
be produced by a moving particle which may be charged or uncharged, whereas
electromagnetic waves are produced only by a moving charged particle. As the
h
De Broglie wavelength  = is independent of charge, it is evident that matter
mv
waves are not electromagnetic waves.
 The velocity of matter waves depends on the velocity of the particle generating them
 c2
u = v  and it is not constant.
 
 Matter waves travel faster than light, because the particle velocity v cannot exceed
c2
the velocity of light c. So the velocity of matter waves u = is greater than c.
v
 A wave is spread out in space and it cannot be localised at any point. So the wave
nature of matter introduces a certain uncertainty in the position of the particle.

CONCEPT OF WAVE FUNCTION  AND PROBABILITY

INTERPRETATION OF ||2 

 A wave motion appears in almost all branches of physics. A wave motion is defined as a
periodic disturbance travelling with finite velocity through a medium or space.
 The simplest form of vibration is simple harmonic motion (S.H.M.) and a particle
executing S.H.M. acts as a source which radiates waves.
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 The wave motion provides a way for energy and momentum to move from one place to
another without material particles making that journey.
 The waves can be classified according to their broad physical properties into mainly
three categories:
 Electromagnetic waves which need not require any medium to propagate.
 Matter waves which give the probability amplitude of finding a particle at a given
position and time.
 Mechanical Waves: The mechanical waves are simplest one to understand because
they are produced by some sort of mechanical vibrations which we can see.
 When a mechanical wave passes through a medium, the medium particles perform an
S.H.M. given by equation
y = A cos t … (1)
where A is the amplitude of the oscillation and  = 2, where  is the frequency.
 This equation is applicable to all individual particles affected by the wave. Suppose the
wave is progressing forward with velocity v. If P is the origin of the wave, then a particle
at Q at a distance x from P will receive the wave x/v sec later than P did.

Progressive wave moving with velocity v

 Hence, its displacement at time t and distance x from the origin will be
 x
y = A cos  t –  … (2)
 v
The wave equation of such a wave is
d2 y d2 y
= v2 … (3)
dt2 dx2
The solution of equation (3) is given by
y = Ae–i (t – x/v) … (4)
 In a string we can represent the wave disturbance by the transverse displacement of y.
Similarly, for light waves the field vectors E and B vary in space and time, for sound
waves, pressure P varies in space and time. In the same way, for matter waves, the wave
function  varies in space and time.
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 So  in wave mechanics is analogous to electric field E in electromagnetic waves or to
pressure P in the sound waves. However,  itself unlike E and P has no direct physical
significance, but gives a measure of the probability of finding a particle at a particular
position. Hence, it is called probability amplitude.
 However, a probability is always real and positive, whereas  can be positive or negative.
Therefore,  2 is taken which is always positive. In general,  is complex, therefore, one
takes ||2 instead of  2, where ||2 =  * ,  * denoting the complex conjugate of . In
any case,  *  is always real and positive.
 If dv is a volume element located at a point, then the probability of finding the particle
in the volume element at time t is proportional to *dv. By analogy with ordinary mass
density, the square of the wave function  * is called the probability density i.e.
probability per unit volume.
Physical Significance of the Wave Function 
 Schroedinger interpreted  in terms of charge density. If A is the amplitude of an
electromagnetic wave, then the energy per unit volume, i.e. energy density is equal to
A2. Also, the photon energy h is constant. So the number of photons per unit volume,
A2
i.e. the photon density is equal to , and it is proportional to the amplitude square.
h
 Similarly, if  is the amplitude of matter waves at any point in space, the particle density
at that point may be taken as proportional to 2. So 2 is a measure of particle density
and on multiplying this by the charge of the particle, we shall get the charge density.
Thus, 2 is a measure of 'charge density'.
 According to Max Born, the value of  2 at a point at a given time is related to the
probability of finding the body described by its wave function  at that point at that
instant. A large value of 2 means a strong possibility of the presence of the body,
while a small value of 2 means a slight possibility of its presence. As long as 2 is not
actually zero somewhere, there is a definite chance, however small, of detecting the
body there.
 Although the wave function  of a particle is spread out in space, this does not mean
that the particle itself is also thus spread out. When an experiment is performed to
detect a particle, an electron for instance, a whole electron is either found at a certain
place and time, or it is not. There is nothing like 20 % of an electron. However, it is
certainly possible that there is 20 % chance that the electron be found at that place and
time, and it's likelihood that is specified by 2 or *, * being the complex conjugate
of .
 2 or * is taken as the probability density, i.e. the probability of finding the particle
in unit volume. So the probability of the particle being present in a volume element

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 dx·dy·dz is 2 dx dy dz. Then, the wave function  is called the 'probability density
amplitude'.
 Since the particle is certainly to be found somewhere in space, we must have,

2 dx dy dz = 1  (1)

the triple integral extending over all possible values of x, y, z.
 A function  satisfying this relation is called a 'normalised wave function' and
equation (1) is known as the 'normalisation condition'. Thus,  has to be a
normalisable function.
Besides being normalisable,  must also satisfy the following conditions:
  must be a single valued function, because  is related to the probability of
finding the particle at a given place and time, and the probability can have only one
value at a given point and time.
  must be finite, because the particle exists somewhere in space, and so integral
over all space must be finite.
  
  and its derivatives , , must be continuous everywhere in the region
x y z
where  is defined.

SCHROEDINGER'S WAVE EQUATION

 Schroedinger started with De Broglie's idea of matter waves and developed it into a
mathematical theory known as 'wave mechanics'. Schroedinger's wave equation is the
mathematical representation of matter waves associated with a moving particle. There
are two types of Schroedinger's wave equations:
 Schroedinger's time independent wave equation
 Schroedinger's time dependent wave equation.
Schroedinger's Time Independent Wave Equation
 According to De Broglie's theory, a particle of mass m moving with a velocity v has a
h
wave system of some kind associated with it, and its wavelength is given by  = . The
mv
waves are produced only when something oscillates. Though we do not know the
quantity that vibrates to produce the matter waves, but we can indicate that quantity
by .
 The periodic changes in  produce the wave system associated with the particle, just as
the periodic changes in the displacement y of a string produce a wave system along the
string.
 In quantum mechanics,  corresponds to the displacement y of wave motion in a string.
However, , unlike y, is not itself a measurable quantity and it may be complex.
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 Consider a system of stationary waves associated with a particle. Let (x, y, z) be the
coordinates of the particle and let  denote the wave displacement of matter waves at
time t.
 By analogy with the wave equation
d2 y d2 y
= v2 of a two-dimensional wave (in xy plane), the
dt2 dx2
wave equation for a three-dimensional wave with wave velocity u can be written as
2  2 
2  2  2  
= u  + + 
t2  x2 y2 z2 
2 
= u2 2   (1)
t2
2 2 2
where 2 = 2 + 2 + is the 'Laplacian operator'.
x y z2
The solution of equation (1) is
 (x, y, z, t) =  0 (x, y, z) e–i  t  (2)
where  0 (x, y, z) represents the amplitude of the wave at the point considered.
 The position vector of a point whose Cartesian coordinates are (x, y, z) is given by
 ^ ^ ^
r = x i + y j + zk
^ ^ ^
i , j , k being unit vectors along the axes. So equation (2) can be written as
 
 ( r , t) =  0 ( r ) e–i  t  (3)
Differentiating equation (3) twice with respect to time t, we get

= – i   o (r) e–i  t
t
2  
and = (– i)2  0 ( r ) e–i  t = – 2   (4)
t2
From equations (1) and (4), we get
u2 2  = – 2 
2
 2  +  = 0  (5)
u2
But  = 2  , and u =  
 Equation (5) becomes
4 2
2  +  = 0  (6)
2
 The De Broglie wavelength of the waves associated with the particle is given by
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 h h
 = =  (7)
mv p
Substituting equation (7) in (6), we get
4 2 p2
2  +  = 0  (8)
h2
1
 The total energy E of the particle is the sum of it's K.E. = mv2 and potential energy V.
2
1
 E = mv2 + V
2
p2
E = + V
2m
This gives p2 = 2 m (E – V)  (9)
Substituting equation (9) in (8), we get
8 2 m (E – V)
2  +  = 0  (10)
h2
 Equation (10) is called 'Schroedinger's time independent wave equation'.
h
Taking H = , equation (10) becomes
2
2 m (E – V)
2  +  = 0  (11)
H2
Schroedinger's Time Dependent Wave Equation
 Schroedinger's time independent wave equation is
8 2 m
2  + (E – V)  = 0  (1)
h2
 The time dependent wave equation is obtained by eliminating E from the time
independent equation.
Consider a system of stationary waves associated with a particle. Let (x, y, z) be the
coordinates of the particle and let  denote the wave displacement of the matter waves at
time t. If u be the wave velocity, then the equation for a three-dimensional wave motion can
be written as,
2  2 
2  2  2  
 t2
= u  + +  = u2 2   (2)
 x2 y2 z2 
2 2 2
where 2 = + + is the 'Laplacian operator'
x2 y2 z2
The solution of equation (2) is

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 
 (x, y, z, t) =  0 (x, y, z) e– i  t =  0 ( r ) e– i  t  (3)
where  0 (x, y, z) is the amplitude of the wave at the point considered.
 Differentiating equation (3) with respect to time t, we get
 
= (– i )  0 ( r ) e–i  t = – i    (4)
t
E
Now,  = 2 and E = h or  =
h
2E
  =
h
Putting this value of  in equation (4), we get
 2E
= –i   (5)
t h
Multiplying both sides of equation (5) by i,
 2
i = i2 E
t h
h  
 E = i = iH  (6)
2 t t
From equations (1) and (6), we get
8 2 m i h  
2 + 2 t – V   = 0
h2  
– h2
Multiplying both sides of this equation by , we get
82 m
h2 i h 
– 2  – +V = 0
8 m
2 2 t
 h2  i h 
– 82 m 2 + V  = 2 t  (7)
 
– h2 2  
or  2m  + V  = i H t  (8)
 
Equation (8) is called 'Schroedinger's time dependent wave equation'.
 h2  – H2 2 
Taking H = –  + V = 
2  + V as 'Hamiltonian operator'
 8 2 m   2m 
ih  
and E = = i H as 'Eigen operator',
2 t t
equation (8) becomes
H  = E   (9)

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APPLICATIONS OF SCHROEDINGER'S TIME INDEPENDENT WAVE
EQUATION
 In quantum mechanics, the wave function of a system gives the description of that
system. We apply Schroedinger's wave equation to a system, and then solve it to find
the wave function of the system. We shall study how Schroedinger's time independent
wave equation can be applied to a system and then solved to find the energy and wave
function of the system under given conditions.
 We also aim at learning characteristic properties of solutions of this equation and
comparing the predictions of quantum mechanics with those of Newtonian mechanics.
 As simple applications of Schroedinger's time independent wave equation, here we shall
discuss the problems of:
 Particle in a rigid box
 Particle in a non-rigid box
 Tunneling effect.

PARTICLE IN A RIGID BOX

 Consider a particle confined to a rigid box and restricted to travelling along x-axis
between x = 0 and x = L (See Fig. 7.7). Such a box has infinitely hard walls, and a
particle does not lose energy when it collides with such walls. So the total energy E of
the particle remains constant. The case under discussion is also called 'infinite potential
well'.
 As shown in Fig., the potential energy V of the particle is infinite on both sides of
the box, while V is constant (say V = 0 for convenience) inside the box. This means that
V (x) = 0 in the region 0 < x < L; and V (x) =  for x ≤ 0 and x ≥ L.
 The particle cannot have an infinite amount of energy. So it cannot exist outside the box
and hence particle wave function  is zero for x ≤ 0 and x ≥ L. We now find the wave
function  of the particle within the box, i.e. in the region 0 < x < L. We use
Schroedinger's time independent wave equation and solve it for this purpose.

Infinite potential well

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 Schroedinger's time independent wave equation is
8 2 m
2  + (E – V)  = 0  (1)
h2
 Now, the motion of the particle is along x-axis. So 2 can be replaced by the total
d2 
derivative . Also V (x) = 0 inside the box. So for this problem, Schroedinger's
dx2
equation (1) becomes
d2  82 m E
+  = 0
dx 2 h2
d2 
i.e. + k2  = 0  (2)
dx2
82 m E
where k2 =  (3)
h2
 Equation (2) is a total differential equation of second order with imaginary roots, and its
general solution will involve two arbitrary constants. So the solution of equation (2) can
be taken as
 (x) = A ei k x + B e– i k x  (4)
 We now apply boundary conditions, namely (0) = 0 and (L) = 0. So from equation (4),
we get
From first boundary condition, (0) = 0.
(0) = A + B = 0 i.e. B = – A
and from second boundary condition, (L) = 0.
(L) = A ei k L + B e– i k L = 0
Taking B = – A, we get
A ei k L – A e– i k L = 0
Multiplying and dividing by 2i.
(ei k L – e– i k L)
 2i·A = 0
2i
or 2 i A sin k L = 0  (5)
As A ≠ 0, we infer from equation (5) that
sin k L = 0
i.e. k L = n , where n = 1, 2, 3, ........
n
 k =  (6)
L
From equations (3) and (6), we have
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 82 m E n2 2
k2 = =
h2 L2
n2 · h2
or En =  (7)
8 mL2
 Equation (7) gives the energy values of the particle and it is evident that the energy of
the particle can have only certain specific values as specified by equation (7). These
energy values are called 'Eigen values'.
 Thus, the energy of a particle confined to a rigid box is quantized. It cannot have an
arbitrary energy; the fact of its confinement leads to restrictions on its wave function that
permit it to have only those energies as specified by equation (7).
 The integer n corresponding to the energy level En is called its 'quantum number'.
n = 0 is not possible because the particle cannot have zero energy; and if it did, the
particle wave function  would have to be zero everywhere in the box, and this means
that the particle cannot be present there.
 The exclusion of E = 0 as a possible value for the energy of a trapped particle, like the
limitation of E to a discrete set of definite values, is a quantum mechanical result.
Classically, all energies, including zero, are presumed possible.
Putting m = 9.1  10–31 kg, h = 6.63  10–34 J-s and L = 10–10 m in equation (7), we get
En = 6  10–18 n2 joules
6  10–18
= n2 eV
1.6  10–19
 38 n2 eV
 The energy levels of such electron trapped in a potential well of width 1 A is shown in
Fig. 7.8.

Energy levels of electron in a rigid box of width 1 A

Wave Function of a Particle in a Rigid Box

 The wave function  (x) of a particle inside a rigid box of width L is given by
 (x) = 2 i A sin k x  (1)

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 8 2m E n 
where k = =  (2)
h2 L
From equations (1) and (2),
n
(x) = 2 i A sin x  (3)
L
Equation (3) gives Eigen functions corresponding to energy Eigen values
n2 h2
En =  (4)
8 m L2
The complex conjugate of (x) is
n
(x) = –2 i A sin x
L
To evaluate the constant A, we use the normalization condition.
L
i.e. 
 * dx = 1
0

L
n

 4 A2 sin2 L x dx = 1
0

1
This gives 2 A2 L = 1 or A =
2L
 Putting this value of A in equation (3), we get the normalized wave function of the
particle as
2i n 2 n
n = sin x = i · sin · x  (5)
2L L L L

 The normalized wave functions  1,  2 and  3 together with the corresponding

probability densities  2,  22 and  32 are shown in Fig. 7.9 (a) and (b) respectively.

Wave function Probability densities

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 While  n may be negative as well as positive,   n2 is always positive. It is seen from
Fig. that
 In every case  n2 = 0 at x = 0 and x = L, the boundaries of the box.
 The probability of the particle being present at a particular point in the box may be
different for different quantum numbers. e.g. For n = 1, the probability is maximum
L L
at x = . For n = 2 there is zero probability of the particle being present at x =
2 2
L 3L
and there are two maxima at x = and x = . Classical physics predicts the same
4 4
probability for the particle to be present anywhere in the box.
 The wave function shown in Fig. resembles the possible vibrations of a string fixed at
both ends. This is so because the waves in a stretched string and the waves representing
a particle obey wave equation of the same form, and when similar restrictions are placed
upon each kind of wave, the solutions are identical.
Comparison of Quantum Mechanical and Classical Mechanical
Predictions
Quantum Mechanical Classical Mechanical
1. The energy of the particle confined is 1. The energy of the particle has
quantized i.e. can have only discrete continuous values i.e. can have all
energy levels. possible values from 0 to .
2. Energy E = 0 is not possible as the 2. Can have energy E = 0.
result of Heisenberg's uncertainty
principle.
3. Probability of finding the particle is 3. Probability of finding the particle is
different at different position. same energy where.
4. Probability of finding the particle 4. Probability of finding the particle is
depends on the principle number and independent of energy level.
hence on energy state.
5. Probability is zero at the walls of the 5. Probability is maximum at the walls of
potential well. the potential well i.e. at the boundaries.

POTENTIAL BARRIER AND TUNNELING EFFECT

 The phenomenon of the particles penetrating the potential barrier is called the 'tunnel
effect' or 'tunneling'. The examples of tunneling are tunnel diode, alfa decay, tunneling
microscope, etc. The kinetic energy of -particle is only few MeV but still it can escape
from a nucleus whose potential wall is 25 MeV due to tunneling.
 Consider a particle approaching the potential barrier from the left i.e. from Ist region. If
the particle has energy less than height of potential barrier Vo i.e. E < Vo, classically, the
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 particle will be always reflected back and hence will not penetrate the barrier. However,
by quantum mechanics, there is some probability of penetrating to region III. The
probability of penetration increases if (Vo – E) and L i.e. height and width of potential
barrier are smaller.
 On the other hand, if E > Vo classical mechanics predicts that the particle will always be
transmitted. But quantum mechanics says that there is a finite probability of
transmission and hence it is not certain that the particle will penetrate the barrier.
 Let us consider the one-dimensional potential barrier, where the height of the barrier is
Vo and width is L. The potential function is defined as V(x) = 0 for x ≤ 0 and x ≥ L and
V(x) = Vo for 0 < x < L as shown in Fig.

 The Schroedinger's time independent equation is

82m
2 + (E – V)  = 0 … (1)
h2
d2 
 As the motion of the particle is in x-direction, so 2 can be replaced by . For
dx2
regions I and III, V(x) = 0, therefore equation (1) becomes
d2  82m
+ E = 0
dx2 h2
82m
Let k2 = E … (2)
h2
d2 
 + k2  = 0 … (3)
dx2
 The equation (3) is a total differential equation of second order with imaginary roots and
its general solution will involve two arbitrary constants. So the solution can be written as,
For region I, i.e. x ≤ 0,
 I (x) = A eikx + B e–ikx … (4)
For region III, i.e. x ≥ L
 III (x) = C eikx + D e–ikx … (5)
 In equation (5), the first term represents the wave travelling along positive X-axis in
region III i.e. the wave transmitted at x = L. The second term represents the wave
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 travelling along negative X-axis in region III, but no wave travels back from infinity in
region III. Therefore, taking D = 0 in equation (5),
 III (x) = C eikx … (6)
For region II i.e. 0 < x < L the V(x) = Vo, so the equation (1) becomes
d2  82m
+ (E – Vo)  = 0
dx2 h2
82m
Let (E – Vo) = k'2 … (7)
h2
d2 
 + k' 2  = 0 … (8)
dx2
The solution of above differential equation is given by

 II (x) = P eik'x + Q e–ik'x … (9)

 The first term of the solution represents the wave travelling along positive X-axis in
region II i.e. the wave transmitted at x = 0 and second term represents the wave
travelling along negative X-axis in region II i.e. the wave reflected at x = L.
 For determining the constants A, B, C, P and Q, the boundary conditions are applied at
x = 0 and x = L.
i.e.  I =  II
 I  II
= at x = 0
x x
and  II =  III
 II  III
= at x = L
x x
 The property of the barrier penetration is due to the wave nature of matter and is similar
to the total internal reflection of light. If two glass plates are placed close to each other
with a thin layer of air trapped between them, then the light coming from one plate will
be transmitted by the second plate even if the angle is greater than the critical angle. But
the intensity of the transmitted light will decrease exponentially with the thickness of the
barrier.
 If a particle incidenting on the potential barrier with energy less than the height of the
potential barrier, there is always some probability of transmission through the barrier.
This phenomenon of crossing the barrier is called the 'tunneling effect'.

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