APPLIED FOR CSE Stream (BPHYS102)

Module-2
Quantum Mechanics

Introduction
By the late 19th century, many physicists thought their discipline was well on the way to
explaining most natural phenomena. They could calculate the motions of material objects using
Newton’s laws of classical mechanics, and they could describe the properties of radiant energy
using mathematical relationships known as Maxwell’s equations, developed in 1873 by James
Clerk Maxwell, a Scottish physicist. The universe appeared to be a simple and orderly place,
containing matter, which consisted of particles that had mass and whose location and motion
could be accurately described, and electromagnetic radiation, which was viewed as having no
mass and whose exact position in space could not be fixed. Thus, matter and energy were
considered distinct and unrelated phenomena. Soon, however, scientists began to look more
closely at a few inconvenient phenomena that could not be explained by the theories available at
the time.Some of the experiments which cannot be explained by the Classical Physics are: Black
body Radiation, Photo Electric Effect, Compton Effect etc.
2.1 Wave Nature of Particles (Wave-particle dualism)
From the phenomenon of interference and diffraction light is considered purely as waves.
From Planck’s idea of quantizationEinstein proposed that light consists of discrete units of
energy known as photons, which was later confirmed by the photoelectric effect
experiment.Another effect that revealed the quantized nature of radiation was the elastic
scattering of light on particles, called Compton Effect or Compton Scattering. Because of such
dual nature observed of radiation and light, Louis de Broglie of France in 1924 put forward a
hypothesis that
“Nature loves symmetry, if the radiation behaves as particle under certain circumstances and as
waves under certain other circumstances, then one can evenexpect that, entities which ordinarily
behave as particles to exhibit properties attributable to only waves under appropriate
circumstances.”
De-Broglie extended the wave-particle duality of light to the material particles.
If a light wave can act as a wave and as a particle at other times, then particles such as electrons
also act as waves at times. This is known as de-Broglie hypothesis. According to de Broglie
hypothesis “Every moving particle has a wave associated with it.” The waves associated with the
particles are known as de-Broglie waves or matter waves.
2.1.1 De-Broglie wave length of matter waves:

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

As a photon travels with the velocity c, its momentum can be expressed as
𝐸 𝑕𝜈 𝑕
𝑝= = =
𝑐 𝑐 𝜆
Thus the wavelength and momentum p of a photon are related to each other through the
expression
𝑕
𝜆= − − − − − −(1)
𝑝
De-Broglie proposed that the equation (3) between the momentum and the wavelength of a
photon is a universal one and must be applicable to photons and material particles as well. The
quantities 𝜈 𝑎𝑛𝑑 𝜆 𝑎𝑟𝑒 𝑤𝑎𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑖𝑒𝑠 and the quantities E and p are particle properties. They
are tied to each other through the relations
𝑕
𝐸 = 𝑕𝜈 𝑎𝑛𝑑 𝑝 =
𝜆
which demonstrate that the wave and particle natures of a photon are related to each other. The
above equation reflect the wave-particle dualism of light.
Now let us consider a moving particle of mass “m” moving with velocity “v” carries a
momentum “p=mv” and it must be associated with a wave of wavelength
𝑕 𝑕
𝜆= =
𝑝 𝑚𝑣
The waves associated with the moving particle are called matter waves or de Broglie waves.
𝑕
The relation 𝜆 = 𝑚𝑣 is known as de-Broglie equation and the wavelength 𝜆 is called the de-
Broglie wavelength.
2.1.2 De-Broglie wavelength of accelerated electron:
If a charged particle, say an electron is accelerated by a potential difference of V volts, then its
kinetic energy is given by K.E. = eV

1
𝑒𝑉 = 𝑚𝑣 2 − − − − − − − 2
2

If p be the momentum of the electron, then,

𝑝 = 𝑚𝑣

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

Squaring both sides, we have

𝑝2 = 𝑚2 𝑣 2
From equation (2)

𝑚2 𝑣 2
𝑒𝑉 =
2𝑚
Or,
𝑝2
𝑒𝑉 =
2𝑚
𝑝 = 2𝑚𝑒𝑉
From de Broglie’s hypothesis we know that
𝑕 𝑕
𝜆= =
𝑝 2𝑚𝑒𝑉
1 𝑕
𝜆= − − − − − − − − − (3)
𝑉 2𝑚𝑒
Since h, m and e are universal physical constants. Substituting thevalue of the constants in
equation (3)

1 6.626 × 10−34
𝜆=
𝑉 2 9.11 × 10−31 1.602 × 10−19
1.226 × 10−9
𝜆=
𝑉

1.226
𝜆= 𝑛𝑚 − − − − − (4)
𝑉

2.1.3 De Broglie wavelength expressed in terms of K.E (Non-relativistic case)

If a particle has kinetic energy K.E., then K.E may be given
2 2 2
1 𝑚 𝑣 𝑝
𝑚𝑣 2 = =
2 2𝑚 2𝑚
𝑝 = 2𝑚𝐾. 𝐸

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

 𝑕 𝑕
𝜆= = − − − −(5)
𝑝 2𝑚𝐾. 𝐸

2.1.4 De-Broglie wavelength in terms of total relativistic energy:

Let E be the total relativistic energy of the particle, then

𝐸 2 = 𝑝2 𝑐 2 + 𝑚02 𝑐 4
Where m0 is the rest mass and p is the momentum of the particle.

Or,
𝐸 2 − 𝑚02 𝑐 4
𝑝=
𝑐
𝑕
Substituting the above value in de-Broglie equation 𝜆 = 𝑝 , we get

𝑕𝑐
𝜆= − − − − − (6)
𝐸 2 − 𝑚02 𝑐 4

2.1.5 De-Broglie wavelength in terms of relativistic kinetic energy

If K.E be the kinetic energy of the material particle,then

𝐸 = 𝑚0 𝑐 2 + 𝐾. 𝐸 − − − − − −(7)

where 𝑚0 𝑐 2 𝑖𝑠 𝑡𝑕𝑒 rest energy of the particle

As discussed above,
𝑕𝑐
𝜆=
𝐸 2 − 𝑚02 𝑐 4
Substituting the value of E from equation (7) in the equation (6)
𝑕𝑐
𝜆=
𝑚0 𝑐 2 + 𝐾. 𝐸 2 − 𝑚02 𝑐 4

𝑕𝑐
𝜆= − − − − − −(8)
𝐾. 𝐸 𝐾. 𝐸 + 2𝑚0 𝑐 2
Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60
2.1.6 De-Broglie waves are insignificant in case of macro-bodies
According to de-Broglie hypothesis a moving body is associated with matter waves and the
wavelength of the waves is given by
𝑕
𝜆=
𝑚𝑣
where v is the velocity with which the body moves. As the mass of the body increases, the
wavelength tends to be insignificant in comparison to the size of the bodies themselves even at
very low velocities. Because of the smaller magnitude of Planck’s constant h, the wavelength
𝜆 𝑤𝑖𝑙𝑙 be significant only in case of micro-particles.
For example if we consider a cricket ball of mass 500 gm flying with a velocity of 50
km/hr, its wavelength comes to

6.6 × 10−34 𝐽𝑠
𝜆= = 10−34 𝑚 = 10−24 Å
0.5 × 13.9
We can see that the wavelength is insignificant in comparison to the size of the ball.On the other
hand, if we consider the case of an electron, having energy 100 eV, the de-Broglie wavelength of
the electron is given by,

𝑕 6.62 × 10−34 𝐽. 𝑠
𝜆= = = 1.33 Å.
2𝑚𝑒𝑉 2 × 9.11 × 10−31 × 100 × 1.6 × 10−19
The size of an electron is about 10−5 Å which is far smaller than the wavelength of 1.33
Å. It means that the electron behaves more as a wave than a particle under the
circumstances.The above discussions, we may observe particle and wave nature cannot be
experienced at the same times for any entity. If particle nature has dominance, wave nature will
be insignificant and vice versa.
2.2 Matter waves and its properties:
Velocityofde Brogliewaves:
Any harmonic wave is characterized by a precise wavelength 𝜆 and constant amplitude. It is
non-localized and has no beginning and end. It means that such a wave extends over a very large
volume of space.
2.2.1 Phase Velocity:
If we consider a harmonic wave, the wave has a single wavelength and a single frequency. The
velocity of propagation of the wave is given by

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

 𝑣𝑝 = 𝜈𝜆

Using 𝜈 = 𝜔/2 𝜋 and 𝜆 = 2𝜋/𝑘 into the above equation we get

𝜔 2𝜋 𝜔
𝑣𝑝 = × =
2𝜋 𝑘 𝑘
𝑣𝑝 is called phase velocity. The velocity with which the plane of equal phase travels through a
medium is known as the phase velocity. It thus represents the velocity of propagation of the wave front.

2.2.2 Wave Packet – representsa microparticle:

We have so far assumed that a particle may be represented by a
monochromatic de Broglie wave. However, a wave spreads over a
large region of space and cannot represent a highly localized
particle. Schrödinger postulated that a wave packet rather than a
single harmonic wave represents a particle. A wave packet
consists of a group of harmonic waves. Each wave has slightly
different wavelength. The superposition of a very large number of
harmonic waves differing infinitesimally in frequency will
produce a single wave packet. The waves interfere constructively
over only a small region of space and cancel each other
everywhere except in that small region. The position of the
particle would then be approximately determined by the position
of the wave packet.
The velocity with which the wave packet propagates is called the
group velocity 𝑣𝑔 .The individual waves forming the wave packet
propagate at a velocity known as the phase velocity 𝑣𝑝 .

Group Velocity:
When a number of plane waves of slightly different wavelengths travel in the same direction,
they form wave groups or wave packets. The velocity with which the wave group advances in
the medium is known as the group velocity 𝑣𝑔 . Each component wave has its own phase
velocity,

𝑣𝑝 = 𝜈𝜆

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

The wave packet has amplitude that is large in a small region and very small outside it. The
amplitude of the wave packet varies with x and t. Such a variation of amplitude is called the
modulation of the wave. The velocity of propagation of the modulation is known as the group
velocity, υg. Here, we should note that wave packets are only theoretical artifices to aid our
visualization of various phenomena in the micro-world.
Since the velocity of matter waves must be equal to that of the particle velocity and since no
physical meaning can be associated with phase velocity, the concept of group velocity is
introduced. Group velocity is defined as:
𝑑𝜔
𝑣𝑔 =
𝑑𝑘

2.2.3 Properties of matter waves:

1. Matter waves are produced by the motion of the particles and are independent of the charge.
Therefore, they are neither electromagnetic nor acoustic waves but are new kind of waves.
2. They can travel through vacuum and do not require any material medium for their
propagation.
3. The smaller the velocity of the particle, the longer is the wavelength of the matter wave
associated with it.
4. The lighter the particle, the longer is the wavelength of the matter wave associated with it.
5. The velocity of matter waves depends on the velocity of the material particle and is not a
constant quantity.
6. The velocity of matter waves is greater than the velocity of light.
7. They exhibit diffraction phenomenon as any other waves.

2.3 Heisenberg’s Uncertainty Principle:

Classically the state of a particle can be defined by specifying its position and momentum at any
given time t. If a body is moving along x- direction with velocity v, its position is given by x = vt
and its momentum by p=mv. From this position may be specified as
𝑝
𝑥= 𝑡
𝑚

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

At each instant, the position and momentum can be measured to a very high accuracy. However,
when an atomic particle is conceptualized as a de Broglie wave,such a precision becomes
restricted because a wave spreads over a region of space and cannot represent a highly localized
particle. Later, Schrodinger postulated that particle may be more precisely be represented by a
wave packet than a single harmonic wave. A wave packet consists of a group of harmonic waves.
Each wave has slightly different wavelength but same amplitude. The superposition of a very
large number of harmonic waves differing infinitesimally in frequency will produce a single
wave packet. The waves interfere
constructively over only a small region
of space and cancel each other
everywhere except in that small region.
Therefore, a wave packet spreads over
a region of space. The velocity with
which the wavepacket moves is 𝑣𝑔
and this group velocity is equal to the
velocity of the particle itself inside the
wave packet, so the particle is
somewhere within the wave packet but
it is impossible to know where exactly
the particle is at a given instant.
Now the wave packet would be
wider or narrower. For wider wave packet if the linear spread of the wave packet is ∆𝑥, the
particle would be located somewhere within the region ∆𝑥. The probability of finding the particle
is maximum at the centre of the wave packet and falls off to minimum at its ends. Therefore,
there is an uncertainty ∆𝑥 in the position of the particle. If the wave packet is wide;
∆𝑥 will be large but large number of frequencies are present so wavelength will be more
precisely defined so ∆𝑝 will be small.If we consider a narrow wave packet uncertainty in
position (∆𝑥) is small; but uncertainty but wavelength is not precisely defined (less number of
waves to measure) so ∆𝑝 𝑙𝑎𝑟𝑔𝑒.

It means that the location and momentum of a micro particle cannot be simultaneously
determined with certainty. Any attempt to determine these variables will lead to uncertainties in
each of the variables.

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

In 1927 Heisenberg showed that the product of uncertainty of two canonically variables would
always be in order of Planck’s constant
Energy-position uncertainty
If ∆𝑥 be the uncertainty in the position and ∆𝑝𝑥 be the uncertainty in the momentum then
according to Heisenberg’s uncertainty principle

∆𝑥. ∆𝑝𝑥 ≈ 𝑕
or more precisely,
ℏ
∆𝑥. ∆𝑝𝑥 ≥ − − − − − −(9)
2
This is known as Heisenberg’s uncertainty principle for position and momentum, which may be
stated as follows:
“It is not possible to determine the exact position and momentum of a micro particle
simultaneously.”
The more accurately we know a particle’s position the less accurately we know its momentum
and vice-versa.

Energy –Time Uncertainty

The Heisenberg’s uncertainty principle could also be expressed in terms of the uncertainties
involved in the measurement of energy and time. The uncertainty relation for the simultaneous
measurement of energy E and time t is expressed as
ℏ
∆𝐸. ∆𝑡 ≥ − − − − − − − (10)
2

where ∆𝐸 is the uncertainty in energyand ∆𝑡 is the uncertainty in time.

Angular momentum and angular displacement uncertainty
Let ∆𝐿 be the uncertainty in angular momentum and ∆𝜃 be the uncertainty in angular
displacement, then as per Heisenberg’s uncertainty principle
ℏ
∆𝐿. ∆𝜃 ≥ − − − − − −(11)
2
2.3.1 Physical Significance of Heisenberg’s uncertainty principle:
One should not think of the exact position, or an accurate value for the momentum of a particle.
Instead, one should think of the probability of finding the particle at a certain position, or of the
probable value for the momentum of the particle.

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

2.3.2 Uncertainty Principle is not significant in case of macro-bodies:
The Heisenberg principle is of no importance for heavy bodies where the de Broglie wavelength
is negligibly small.For example, let us take the case of a cricket ball in flight. The indeterminacy
in the position of the ball is, say, 1mm. We can determine the indeterminacy of velocity of the
ball from uncertainty principle

∆𝑥. ∆𝑝 ≈ 𝑕
∆𝑥. 𝑚∆𝑣 ≈ 𝑕
𝑕 6.6 × 10−34 𝐽𝑠
∆𝑣 ≈ = ≅ 10−30 𝑚/𝑠
𝑚∆𝑥 0.5𝑘𝑔 × 10−3
The above inaccuracy is negligible and not detectable. It implies that the uncertain ty principle is
of no importance in case of macro bodies; and the position and velocity of a macro body can be
simultaneously determined with a high degree of accuracy. In contrast if we take the example of
an electron orbiting in a hydrogen atom and the accuracy in its position is
± 1A0 . The uncertainty in its speed is

𝑕 6.6 × 10−34 𝐽𝑠
∆𝑣 = = = 2 × 105 𝑚/𝑠
𝑚∆𝑥 9.11 × 10−31 𝑘𝑔 × 2 × 10−10 𝑚
which is of the same order as the velocity of the electron in the orbit. It means that it is not
possible to determine the velocity and the position of a microparticle at the same time.
2.3.3 Application of uncertainty principle (Non-existence of electron inside the nucleus:
Non-relativistic case):

During radioactivity, 3 kinds of rays are emitted from radioactive nuclei𝛼, 𝛽 𝑎𝑛𝑑 𝛾 𝑟𝑎𝑦𝑠. 𝛽 rays
are actually streams of electrons; the electrons which constitute 𝛽 rays are emitted with different
velocities, the corresponding kinetic energy varied from very low values to a maximum value of
about 3 to 4 MeV (maximum energy of the 𝛽- particle is about 3 to 4 MeV.)
Now the energy E of a body can be expressed as

𝑝2
𝐸= − − − − − − − (12)
2𝑚
where m is the mass of the body, and p is the momentum.
Heisenberg uncertainty principle states that
𝑕
∆𝑥∆𝑝𝑥 ≥
4𝜋
𝑕
∆𝑝𝑥 ≥ − − − − − − − −(13)
4𝜋∆𝑥
Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60
We know that the typical value of diameter of nucleus is of the order of
10−14 𝑚. We can take this value to be approximately the maximumspace of confinement.For
an electron to exist inside the nucleus; uncertainty in its position ∆𝑥 must not exceed this value.

∆𝑥 ≤ 10−14 𝑚
Using the above inequality in equation (15)

6.63 × 10−34
∆𝑝𝑥 ≥
4𝜋 × 10−14
∆𝑝𝑥 ≥ 0.5 × 10−20 𝑁𝑠
Since the momentum of the electron must at least be equal to the uncertainty in
momentum, we can state,

𝑝𝑥 ≥ 0.5 × 10−20 𝑁𝑠 − − − − − −(14)

Mass of the electron; m = 9.11 × 10−31 𝑘𝑔
By making use of the inequality (16) in equation (14), for the electron to exist within the nucleus,
its energy must be such that

0.5 × 10−20 2
𝐸≥
2 × 9.11 × 10−31
𝐸 ≥ 1.372 × 10−11 𝐽
Expressing in eV, we get

𝐸 ≥ 1.372 × 10−11 × 6.24 × 1018 𝑒𝑉

Or, 𝐸 ≥ 85 𝑀𝑒𝑉.
For an electron to exist inside the nucleus, its energy must be greater than or equal to 85 MeV.
But the experimental investigations reveal that the kinetic energy of beta particles (electrons) is
of the order of 3 to 4 MeV.Therefore,electron cannot exist inside the nucleus.
2.4 Principle of Complementarity:
Statement:
Bohr stated as “In a situation where the wave aspect of a system is revealed, its particle aspect is
concealed; and, in a situation where the particle aspect is revealed, its wave aspect is concealed.
Revealing both simultaneously is impossible; the wave and particle aspects are complementary.”

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

We know that the consequence of the uncertainty principle is both the Wave and particle nature
of the matter cannot be measured simultaneously. In other words, we cannot precisely describe
the dual nature of Light.
• If an experiment is designed to measure the particle nature of the matter,during this experiment,
errors of measurement of both position and the time coordinates must be zero and hence the
momentum, energy and the wave nature of the matter are completely unknown.
• Similarly, if an experiment is designed for measuring the wave nature of the particle, then the
errors in the measurement of the energy and the momentum will be zero, whereas the position
and the time coordinates of the matter will be completely unknown. unknown.
From the above explanation, we can conclude that, when the particle nature of the matter is
measured or displayed, the wave nature of the matter is necessarily suppressed and vice versa.

2.5 Wave function and probability interpretation

Waves represent the propagation of disturbance in a medium. We are familiar with sound
waves, light waves, and water waves. These waves are characterized by some quantity that varies
with position and time. Light waves consist of variations of electric and magnetic fields inspace,
and sound waves consist of pressure variations. Similarly, the microscopic particles (for example
electron, proton, neutron etc.) exhibit wave properties, it is assumed that aquantity ψ represents
a de-Broglie wave. This quantity is called a wave function ψ. Ψ describes the wave as a
function of position and time. However, it has no direct physical significance, as
ψ is a complex quantity.For any particle of mass “m” moving along the x-axis; at any position
and momentum time the behaviour and motion of the particle is given by the wave function
𝛹 𝑥, 𝑡 .
The wave function can be represented by

𝛹 = 𝐴𝑒 𝑖(𝑘𝑥 −𝜔𝑡 ) − − − − − − − −(15)

2.5.1 Physical Interpretation of wave function given by Max Born

The wavefunction 𝛹 𝑥, 𝑡 does not tell how much of the particle is at x at time t, but rather what
is the probability to find it at x at time t.Ψ is a complex quantity; it has no physical significance
but probability of occurrence of any particle is a real and positive quantity. To get a real and
positive value, the wave function Ψ must be multiplied by its complex conjugate Ψ ∗ .The
productΨΨ∗ is always a positive real quantity. Ψ 2 = ΨΨ∗ 𝑖𝑠 known as the probability density
i.e., the probability per unit volume that the particle is more likely to be found at the given
region. This interpretation was given by Max Born in the year 1926 called as Max Born
Interpretation.

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

"The square of the magnitude of the given wavefunction gives the probability
of finding the particle in that particular region. "
This may be understood as
If Ψ = 𝐴 + 𝑖𝐵 and its conjugate counterpart as Ψ∗ = 𝐴 − 𝑖𝐵, the productΨΨ ∗ = Ψ 2
= 𝐴2 +
𝐵 2 is always a real number

Let V be a volume inside which particle is knownto be present but

where exactly the particle is situated inside V is not known then the
probability of finding the particle in infinitesimal volume dV is
given by
2
P=Ψ dV .

2.5.2 Normalization condition

If at all the particle exists, it must be found somewhere within the wave packet. If
Ψ be the wave function associated with a particle, then Ψ 2 dV is represented as thep
robability of finding the particle in the volumedV as discussed above.
If the particle is definitely present in a particular region of space of volume 𝑉, then, as per the
statistical rule,
𝑉
P= 0
𝛹 2 𝑑V=1 − − − − − − − (16)
Probability = 1 means, it is clearly a certainty. If we are not at all certain about locating the
particle in a finite volume anywhere in wave packet, then “it does not exist within the
wavepacket”.

Limit in equation (16) extend from −∞ 𝑡𝑜 + ∞, and the probability becomes

+∞
P= −∞
𝛹 2 𝑑V=1; particle exist somewhere within the wave packet.

This process is called as normalization.

2.5.3 Properties of the wave function:
The Born Interpretation of a wave function has placed 4 restrictions on an acceptable wave
function. An acceptable wave function must be normalized and fulfill the following
requirements.

Property 1: Wave function is single valued everywhere.

Property 2: Wave function is finite everywhere.

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

Property 3: Wave function and its first derivative with respect to its variableare continuous
everywhere.

2.5.4 Expectation Value:

In quantum mechanics the expectation value is the probabilistic expected value of the result
(measurement) of an experiment. It can be thought of as an average of all the possible outcomes
of a measurement as weighted by their likelihood. Expectation value as such it is not the most
probable value of a measurement. In the real sense the expectation value may have zero
probability of occurring.
Let us consider a particle moving along the x axis. The result of a measurement of the position x
is a continuous random variable. Consider a wave function 𝜓(𝑥, 𝑡). 𝜓(𝑥, 𝑡) 2 value is a
probability density for the position observable and 𝜓(𝑥, 𝑡) 2 𝑑𝑥 is the probability of finding the
particle between 𝑥 and 𝑥 + 𝑑𝑥 at time t. Thus, if a measurement of position is repeated many
times in an identical way on an identical particle in identical circumstances, many possible
outcomes are possible and the expectation value of these outcomes is, according to the following
equation
+∞
𝒙 = 𝒙 𝜓(𝑥, 𝑡) 2 𝑑𝑥
−∞

2.6 Schrodinger equation:

As per de-Broglie hypothesis every moving particle has a wave associated with it, which is also
known as matter wave. Further, Erwin Schrödinger in continuation to de-Broglie’s hypothesis
introduced a differential wave equation of second order to explain the wave nature of matter and
particle associated to wave. Schrodinger equation plays the same role in Q.M as Newton’s laws
in classical mechanics. To solve the Schrodinger equation one require the knowledge of
(i) Potential energy of the particle
(ii) Initial conditions, and

(iii) Boundary conditions

The Schrodinger equation can be set up in two contexts
 Time Dependent Schrodinger equation in which position and timevariation of the wave
function. It involves the imaginary quantity“i”.
 Time Independent Schrodinger equation in which the wave function can have variation only
with position but not with time. It doesnot involve “i”.
2.6.1 Time Independent Schrodinger equation

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

Consider a particle is moving along x-axis and exhibiting the simple harmonic wave pattern
represented by
𝑑 2𝑦 1 𝑑 2𝑦
= − − − − −(17)
𝑑𝑥 2 𝑣2 𝑑 𝑡 2

The solution of equation (17) is

𝑦 = 𝐴𝑒 −𝑖 𝑘𝑥 −𝜔𝑡
− − − − − − − − − − − (18)
where y is the displacement, ω is the angular frequency, A is the amplitude and
v is the velocity of the wave.
The matter waves associated with the matter behaves same as mentioned in the equation (17),
then equation (17) can be written as

𝑑2 𝜓 1 𝑑2 𝜓
= − − − − − − − − − − − − − 19
𝑑𝑥 2 𝑢2 𝑑𝑡 2
where u is the velocity of the matter waves and 𝜓 is the wave function.
The solution for the equation (19) can be written as

𝜓 = 𝜓0 𝑒 −𝑖(𝑘𝑥 −𝜔𝑡 ) − − − − − − − − − −(20)

Where 𝜓0 is the amplitude of the matter wave.
Differentiating equation (20) with respect to “t”
𝑑𝜓
= 𝑖𝜔𝜓0 𝑒 −𝑖(𝑘𝑥 −𝜔𝑡 )
𝑑𝑡
Again differentiating the above equation

𝑑2 𝜓
= 𝑖 2 𝜔2 𝜓0 𝑒 −𝑖 𝑘𝑥 −𝜔𝑡
= −𝜔2 𝜓0 𝑒 −𝑖 𝑘𝑥 −𝜔𝑡
𝑑𝑡 2
𝑑2 𝜓
2
= −𝜔2 𝜓 − − − − − − − 21
𝑑𝑡
Substituting equation (23) to equation (21), we get

𝑑2 𝜓 1 2
= − 𝜔 𝜓
𝑑𝑥 2 𝑢2
𝑑2 𝜓 1 2
+ 𝜔 𝜓 = 0 − − − − − − − − − (22)
𝑑𝑥 2 𝑢2

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

If 𝜆 𝑎𝑛𝑑 𝜈 are the wavelength and frequency of the wave, then

𝜔 = 2𝜋𝜈and𝑢 = 𝜈𝜆
Substituting 𝜔 𝑎𝑛𝑑 𝑢, equation (22) becomes
𝑑 2𝜓 4𝜋 2
2
+ 𝜓=0
𝑑𝑥 𝜆2

Substituting 𝜆 = 𝑕/𝑝 in the above equation, we get

𝑑 2 𝜓 4𝜋 2 𝑝2
+ 𝜓 = 0 − − − − − − − − − (23)
𝑑𝑥 2 𝑕2
The total energy of the particle in the non-relativistic case is given by
E = Kinetic Energy +Potential Energy
1
𝐸 = 𝑚𝑣 2 + 𝑉
2
If p is the momentum of the particle along X-direction then p=mv, the above
equation may be written as

𝑝2
𝐸= +𝑉
2𝑚
𝑝2 = 2𝑚 𝐸 − 𝑉
Substituting the value of 𝑝2 𝑖𝑛 the equation (23), we get

𝑑 2 𝜓 8𝜋 2 𝑚
+ 𝐸 − 𝑉 𝜓 = 0 − − − − − − 24
𝑑𝑥 2 𝑕2
Equation (24) is called as Time Independent Schrodinger equation in one-dimension.
2.6.2 Eigen functions and Eigenvalues:
By solving the Schrodinger wave equation to a particular system we get many expressions for
wave function (𝜓). However, all wave functions are not acceptable. Only those wave functions
which satisfy certain conditions are acceptable. Such wave functions are called Eigen functions
for the system. The energy values corresponding to the Eigen functions are called Eigen values.
“Eigen functions are those wave functions of quantum mechanics which possess the properties
that they are single valued and finite everywhere, and also their first derivatives with respect to
theirvariables are continuous everywhere.
2.6.3 Operator Mechanism in Quantum Mechanics:

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

Related to each type of measurement there is one kind of operator, to obtain energy values there
is energy operator; to obtain momentum value there is momentum operator. All eigen functions
when operated by the operators may not give proper value or result for that physical observable.
It is also postulated in quantum mechanics that only possible values can be observed on a
physical quantity like energy, angular momentum etc. of a system

𝐴𝜓 = 𝜆𝜓 … … … … … 25
In equation (25) 𝐴 is the operator for the physical quantity, 𝜓 should be such that the operator
operating on it produces back the wave function multiplied by a constant (in equation (25))it is 𝜆.
Such values obtained for a physical observable are called as eigen values.
2.7 Applications of Schrödinger wave equation:
2.7.1 Particle in one-dimensional infinitely deep potential well:
The particle in a box model (also known as the infinite potential well) describes a particle free to
move in a small space surrounded by impenetrable barriers. In classical systems, for example, a
particle trapped inside a large box can move at any speed within the box and it is no more likely
to be found at one position than another. However, when the well becomes very narrow (on the
scale of a few nanometers), quantum effects become important. The particle may only occupy
certain positive energy levels. Likewise, it can never have zero energy, meaning that the particle
can never "sit still". Additionally, it is more likely to be found at certain positions than at others,
depending on its energy level. The simplest form of the particle in a box model considers a one-
dimensional system.
Let us consider a particle of mass “m” confined to a one-dimensional rigid box of width
“a”. It can move freely within the region 0 < 𝑥 < 𝑎 but subject to strong forces at x = 0 and x =
a. Therefore, it can never cross to the right of the region 𝑥 > 𝑎 or to the left of 0. It means that
V(x) = 0 in the region 0 < 𝑥 < 𝑎 𝑎𝑛𝑑 𝑟𝑖𝑠𝑒𝑠 𝑡𝑜 infinity (𝑉 𝑥 = ∞) at x=0 and x=a. This
situation is called a one-dimensional potential box.

In terms of boundary conditions imposed by the problem, the potential function is given as
V(x) =0; for 0< x< a

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

V(x) = ∞ 𝑓𝑜𝑟 𝑥 ≥ 𝑎 𝑎𝑛𝑑 𝑥 ≤ 0
Inside the well, the Schrodinger equation is given by
𝑑 2𝜓 8𝜋 2 𝑚
+ E𝜓 = 0, (V=0) − − − − − − (26)
𝑑𝑥 2 𝑕2
8𝜋 2 𝑚
Let E = 𝐾 2 − − − − − − − (27)
𝑕2

Substituting equation (27) in equation (26)

𝑑2 𝜓
2
+ 𝐾 2 𝜓 = 0 − − − − − (28)
𝑑𝑥
The solution of the equation (30) is given by

𝜓 = 𝐴𝑒 𝑖𝐾𝑥 + 𝐵𝑒 −𝑖𝐾𝑥 − − − − − (29)

Boundary value

𝜓 = 0 𝑎𝑡 𝑥 = 0 ………….. Condition I

𝜓=0 𝑥=𝑎 ………….. Condition II

Substituting Condition I in equation (29)

𝐴𝑒 0 + 𝐵𝑒 0 =0
or, A=-B − − − − − − − (30)
Substituting Condition II in equation (29)

𝐴𝑒 𝑖𝐾𝑎 +𝐵𝑒 −𝑖𝐾𝑎 = 0

A(cosKa+isinKa)+B(cosKa-isinKa)=0
Using equation (30)
A(cosKa+isinKa)-A(cosKa-isinKa)=0
2iAsinKa = 0

Since 2i𝐴 ≠ 0, 𝑠𝑖𝑛𝐾𝑎 = 0

Or, Ka = n𝜋
𝑛𝜋
K= − − − − − − − (31)
𝑎

where n = 0,1,2,3, ……..

n is called quantum number which is either zero or a positive integer
Substituting equation (31) and equation (30) in equation (29)

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

 𝑛𝜋
𝜓𝑛 = 2𝑖𝐴𝑠𝑖𝑛 𝑥
𝑎
𝑛𝜋
𝜓𝑛 = 𝐶𝑠𝑖𝑛 𝑥 − − − − − − (32); where 2iA = C
𝑎

Now from the equation (27)

𝐾 2 𝑕2
𝐸= 2
8𝜋 𝑚
Using equation (31), the above equation becomes
𝑛2𝑕2
𝐸𝑛 = − − − − − − − − (33)
8𝑚 𝑎 2

As already mentioned, n can have only integer values 0,1,2,3,…….. The corresponding values
that E takes are the energy eigen values.In equation (33), the value zero for n is not acceptable
because whenn=0, 𝜓𝑛 = 0which means that the electron is not present inside the box which is
not true.Hence the lowest acceptable value for n is 1. Hence the lowest allowed energy
corresponds to n = 1 which is called zero-point energy.
The zero-point energy of an electron in an infinite potential well is given by

𝑕2
𝐸𝑧𝑒𝑟𝑜 = 𝐸0 =
8𝑚𝑎2

From equation (33), we can write

𝐸𝑛 = 𝑛2 𝐸0
The lowest permitted state of energy is referred to as the ground state energy. Thus zero point
energy is taken as the ground state energy. The energy state corresponding to n>1 are called
excited states.
Visualization of quantum energy
The energy eigen value for the nth state

𝑛2 𝑕2
𝐸𝑛 = − − − − − − − (34)
8𝑚𝑎2
For (n+1)th state

(𝑛 + 1)2 𝑕2
𝐸𝑛+1 = − − − − − − − −(35)
8𝑚𝑎2
Subtracting (35)-(34),

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

 𝑕2 2 2
𝑕2
∆𝐸 = (𝑛 + 1) − 𝑛 = (2𝑛 − 1)
8𝑚𝑎2 8𝑚𝑎2
From above equation as 𝑎 → ∞, ∆𝐸 → 𝑜
Therefore, if the width of the box is not in microscale, the difference of energy
spectrum becomes continuous and it takes classical values
Normalization
The normalization condition is given as
+∞
−∞
𝜓 2 d𝑉 = 1
Since it is one-dimensional potential well, we write d𝑉 as dx.
Since the well extends over a width from x=0 to x=a.
Normalization condition can be written as
𝑎
𝜓 2 𝑑𝑥 = 1
0

Substituting for ψn from equation 32 , we have,

𝑎 𝑛𝜋
0
𝐶 2 𝑠𝑖𝑛2 xdx = 1
𝐿
𝑎 𝑎
2
1 1 2𝑛𝜋
𝐶 𝑑𝑥 − 𝑐𝑜𝑠 𝑥𝑑𝑥 = 1
2 0 2 𝑜 𝑎
𝐶2 𝑎
𝑎− sin⁡
(2𝑛𝜋) = 1
2 2𝑛𝜋

𝐶2𝑎
= 1 (sin 2𝑛𝜋 = 0)
2

Thus the normalized wave function of a particle in an one-dimensional potential

well is given by
2 𝑛𝜋
𝜓𝑛 = 𝑠𝑖𝑛 𝑥−−−−−−− (36)
𝑎 𝑎

2.7.2 Eigen functions, Probability densities and Energy Eigenvalues for particle in an
Infinite Potential Well
Since the particle in an infinite potential well is a problem under quantum mechanical
conditions, the prime questions to be considered are the most probable location of the particle in
the well and its energies, both to be evaluated for the different permitted states.

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

Eigen function for particle in infinite potential well

2 𝑛𝜋
𝜓𝑛 = 𝑠𝑖𝑛 x
𝑎 𝑎

From equation (36) we can write the eigenfunctions 𝜓1 , 𝜓2 , 𝜓3 , … ….

for particle in the well by putting n =1, 2, 3,………. respectively in the equation
Let us consider the first 3 cases
Case (i), n = 1:
This is the ground state and the particle is found in this state.
For n =1, the eigen function is

2 𝜋
𝜓1 = 𝑠𝑖𝑛 𝑥 − − − −(36)
𝑎 𝑎
𝜋
From equation (36) 𝜓1 = 0 when 𝑠𝑖𝑛 𝑥=0
𝑎

𝜋
𝑠𝑖𝑛 𝑥 = sin𝑚𝜋; m = 0, 1, 2, 3, …….
𝑎

For m = 0; x=0 and m =1; x = a

So 𝜓1 = 0 for both x = 0 and x = a
𝜋
From equation (36),𝜓1 has maximum value when 𝑠𝑖𝑛 𝑥 has maximum value
𝑎

𝜋 𝑘𝜋
𝑠𝑖𝑛 𝑥 = 𝑠𝑖𝑛 ; k =1,3,5,7,……..
𝑎 2

𝜋 𝜋 𝑎
For k = 1; 𝑠𝑖𝑛 𝑥 = 𝑠𝑖𝑛 𝑥 = 2 ; 𝜓1 has maximum value
𝑎 2

Regarding the energy of the particle, using equation (34), the energy in the ground state by
putting n = 1.
𝑕2
𝐸1 = = E0 ………………. (38)
8𝑚 𝑎 2

This is the energy eigen value for the ground state.

Case (ii), n = 2
This is the first excited state i.e., the next immediate higher state permitted for the particle after
the ground state.

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

From equation (38) the eigenfunction for this state is,

2 2𝜋
𝜓2 = 𝑠𝑖𝑛 𝑥
𝑎 𝑎
2𝜋
Now 𝜓2 = 0 when 𝑠𝑖𝑛 𝑥=0
𝑎

2𝜋
𝑠𝑖𝑛 𝑥 = sin 𝑚𝜋; 𝑚 = 0,1,2,3,..
𝑎

For m=0, x =0; m=1, x=a/2 and m=2, x=a

𝜓2 = 0 at x = 0, a/2 and a
2𝜋
𝜓2 𝑖𝑠 𝑚𝑎𝑥𝑖𝑚𝑢𝑚 when 𝑠𝑖𝑛 𝑥 is maximum
𝑎

2𝜋
𝑠𝑖𝑛 𝑥 = sin k𝜋/2; 𝑘 =1,3,5,..
𝑎

For k=1, x =a/4 and k=3, x=3a/4

𝜓2 is maximum at x = a/4, 3a/4.
Further from equation (36), for the first excited states; n=2
𝑕2
𝐸2 = 4 represents the energy eigen value for the 2nd excited state
8𝑚 𝑎 2

𝐸2 = 4𝐸0
Thus the energy in the first excited state is 4 times the zero point energy.
Case (iii), n = 3:
This is the second excited state.
Following the same analysis as carried out earlier,

2 3𝜋
Eigen function𝜓3 = 𝑠𝑖𝑛 𝑥
𝑎 𝑎

3𝜋
Now 𝜓3 = 0 when 𝑠𝑖𝑛 𝑥=0
𝑎

3𝜋
𝑠𝑖𝑛 𝑥 = sin 𝑚𝜋; 𝑚 = 0,1,2,3,..
𝑎

For m=0, x =0; m=1, x=a/3, m=2, x=2a/3 and m =3, x = a

𝜓3 = 0 at x = 0, a/3, 2a/3 and a
3𝜋
𝜓3 𝑖𝑠 𝑚𝑎𝑥𝑖𝑚𝑢𝑚 when 𝑠𝑖𝑛 𝑥 is maximum
𝑎

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

 3𝜋
𝑠𝑖𝑛 𝑥 = sin k𝜋/2; 𝑘 =1,3,5,..
𝑎

For k=1, x =a/6; k=3, x=a/2, k=5, x=5a/6

𝜓3 is maximum at x = a/6, a/2 and 5a/6
3𝜋
𝜓3 𝑖𝑠 𝑚𝑎𝑥𝑖𝑚𝑢𝑚 when 𝑠𝑖𝑛 𝑥 is maximum
𝑎

3𝜋
𝑠𝑖𝑛 𝑥 = sin k𝜋/2; 𝑘 =1,3,5,..
𝑎

For k=1, x =a/6; k=3, x=a/2, k=5, x=5a/6

𝜓3 is maximum at x = a/6, a/2 and 5a/6.
Using equation (36), the energy in this state is given by,
𝑕2
𝐸3 = 9 represents the energy eigen value for the 2nd excited state
8𝑚 𝑎 2

𝐸3 = 9𝐸0
The wave functions and the probability densities for the first three values of “n” areshown below.
𝑎
It can be seen that in the figure that 𝜓1 is 0 both at x = 0 and x = “a” and maximum at x =2 . It
means that in the ground state the particle cannot be found at all the walls of the well and the
probability of finding the particle is maximum at the central region. For the first excited state the
particle cannot be observed either at the walls, or at the center. The wavefunction ψ2 is 0
𝑎
𝑎𝑡 𝑥 = 0, 2 𝑎𝑛𝑑 𝑎. In the second excited state 𝑎𝑡 x=a/6, a/2 and 5a/6 the particle is most likely
to be found and at x=0,a/3,2a/3 the probability of finding the particle is zero.

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

 Model Questions
1. State and Explain de Broglie hypothesis.
2. What are matter waves and mention the properties.
3. Define Phase velocity and Group velocity.
4. State and Explain Heisenberg’s uncertainty principle. Mention its physical significance.
5. Explain why electron cannot exist inside the nucleus?
6. State and Explain the Principle of Complementarity.
7. Define wave function? Mention its basic properties.
8. Derive Time independent Schrodinger wave equation for a particle moving in three
dimension.
9. Discuss the physical interpretation of wave function?
10. Elucidate expectation value.
11. Describe Eigen functions and Eigen values.
12. Discuss the motion of a particle in one dimensional potential well of infinite height.
13. Discuss the energies of a free particle using time independent Schrodinger equation.

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60

Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60
Dr. Nityanand Choudhary, Professor, JSSATE, Bangalore-60