Module-2

Quantum Mechanics
Introduction:
In Classical Mechanics (or Newtonian Mechanics) the future history of the particle is
completely determined by its initial position and momentum together with the forces that act
upon it. In everyday life these measurements hold good satisfactorily. However, because of
Uncertainty principle, nature of an observable quantity is different in atomic and subatomic
world. According to this principle the initial state of a particle cannot be sufficiently accurate
and hence certainty about its future is impossible. This initiates a new approach in order to
understand and to solve problems involving atoms, molecules and matter in the solid state.
Such an approach was developed in 1925 by Schrodinger and others and it is called as
“Quantum Mechanics”. According to Paul Dirac ‘the discovery of quantum mechanics is a
total surprise which made it possible to understand a large part of Physics and the whole of
Chemistry’.
de-Broglie Hypothesis and Matter Waves:
Planck’s quantum theory and Einstein’s explanation of Photoelectric effect established the
particle nature of electromagnetic waves and Compton Effect confirmed particle nature of
PHOTON. After the success of particle nature of waves, de Brogile suggested that there must
be wave nature for a particle also. According to him when a particle of mass m is moving
with velocity v then it exhibits wave nature. The wave associated with the moving particle is
known as matter wave. Its wavelength is given by
ℎ ℎ
𝜆= =
𝑝 𝑚𝑣
The wavelength of matter wave is also given in terms of kinetic energy E, accelerating
potential V, and temperature T as follows.
ℎ ℎ ℎ
𝜆= , 𝜆= , 𝜆=
√2𝑚𝐸 √2𝑚𝑞𝑉 √3𝑚𝑘𝑇
Expression for de Broglie wavelength by analogy
The expression for the wavelength associated with a material particle can be derived on the
analogy of radiation as follows:
Considering Planck’s theory of radiation, the energy of a photon is given by
ℎ𝑐
𝐸 = ℎ𝜈 =
𝜆
Where c is the velocity of light in vacuum and 𝜆 is its wavelength.
According to Einstein’s mass energy relation
𝐸 = 𝑚𝑐 2
Comparing the above two equations we get
ℎ𝑐
𝑚𝑐 2 =
𝜆
ℎ𝑐 ℎ
or 𝜆 = 2
or 𝜆 = where mc = p (momentum associated with photon)
𝑚𝑐 𝑚𝑐
If we consider the case of a material particle of mass m and moving with a velocity v. ie
momentum mv, then the wavelength associated with this particle is given by
ℎ ℎ
𝜆= =
𝑚𝑣 𝑃

Characteristics of Matter waves:

1. Matter waves are neither mechanical waves nor non mechanical waves.
2. Unlike sound waves and light waves they do not carry energy along with them.
3. They possess two velocities namely Phase velocity (vph) and group velocity (vg).
4. Phase velocity is greater than speed of light. Hence it does not carry any physical
significance.
5. In matter waves there is a periodic variable quantity called wave function (). The
value of the wave function associated with a moving body at the particular point x in
space at the time t is related to the likelihood of finding the body there at the time.
6. The particle’s position, momentum and other parameters can be better explained by
matter waves associated with them. Hence matter waves are treated as “guiding
waves”.
Phase velocity and Group velocity:
A wave set up in a stretched string, a sound wave travelling in an isotropic medium, an
electromagnetic wave propagating in air or vacuum, they all are treated as progressive waves.
The velocity with which this wave propagates in an isotropic medium is known as phase
velocity. It is given by
𝜔
𝑣𝑝ℎ = = 𝜈𝜆
𝑘
Phase velocity represents the velocity at which phase of any one frequency component of the
wave travels.
When two or more waves of slightly different wavelength and frequency travelling in an
anisotropic medium superimpose, a group of waves is formed. This is called a wave group or
wave packet. The velocity with which wave group travels is known as group velocity (vg). It
d𝜔
is given by 𝑣𝑔 = d𝑘

Significance of the Wave group:

Wave group of matter waves represents the particle motion since its velocity is same as
velocity of the particle. It is a representative of moving particle. The particle can be located
anywhere within the group at a given time. The narrower its wave group, the more precisely
particle position can be specified. In the following figures, the position measurement is
accurate in the case of Fig.1 than in Fig.2. On the other hand, wider wave group (Fig.2) has a
clearly defined wavelength. The momentum that corresponds to this wavelength is more
accurate.

x
Heisenberg’s Uncertainty Principle:
From the Significance of wave group one thing is clear. From a given wave group which is a
representative of moving particle one cannot know both the exact position and exact
momentum of the particle at the same time. If importance is given to the precise measurement
of position of the particle then there will be error in its momentum and vice versa. Thus we
have an uncertainty in the measurements. The uncertainty principle states that
In the simultaneous measurements of both position and momentum of a particle, there is
always some error. The product of error in the position and momentum is greater than or
equal to (h/4).
If x is the error in position and p is that in momentum then
ℎ
Δ𝑥Δ𝑝 ≥
4𝜋

Uncertainty principle is also expressed in terms of energy (E) and time interval (t) as
ℎ
Δ𝐸Δ𝑡 ≥
4𝜋
If the width of the wave group (x) is small then position measurement is accurate but not the
momentum. If we reduce p somehow, a broader wave group is inevitable and hence x is
large. These uncertainties are not due to inadequate apparatus but to the imprecise character
in nature of the quantities involved.
Significance of the Uncertainty principle:
According to this principle, particle’s position or momentum or energy or time interval spent
in the excited states cannot be measured accurately. All these measurements are just
probabilistic. This suggests that in quantum world of particles, no measurement is accurate;
there exists always some uncertainty. Therefore we should rely only on probabilistic values.
This is the significance of uncertainty principle.

To show that electrons cannot exist inside the nucleus: (Using Uncertainty principle)
According to Einstein’s special theory of relativity, the energy E of a particle is given by
𝐸 2 = 𝑝2 𝑐 2 + 𝑚02 𝑐 4 = 𝑐 2 (𝑝2 + 𝑚02 𝑐 2 ) − − − − − − − (1)
Where m0 is rest mass of the particle, c is speed of light and P is momentum
According to Heisenberg’s uncertainty principle
ℎ
Δ𝑥Δ𝑝 ≥
4𝜋
ℎ
Δ𝑝 ≥ ---------------------(2)
4𝜋Δ𝑥
We know that the typical value of radius of the nucleus is of the order of 5× 10−15 m. If an
electron is to exist inside the nucleus, then the uncertainty in its position Δ𝑥 must not exceed
this value.
Therefore Δ𝑥 ≤ 5× 10−15 m
ℎ 6.63×10−34
Δ𝑝 ≥ = = 1.1 × 10−20 Ns
4𝜋∆𝑥 4𝜋×5×10−15
Since the momentum of the electron must at least be equal to R
uncertainty in the momentum, we can write
𝑝 ≥ 1.1 × 10−20 Ns ----------------(3)
From equation (3), it is clear that for the electron to exist within the nucleus, its energy E
must be such that
𝐸 2 ≥ 𝑐 2 (𝑝2 + 𝑚02 𝑐 2)
𝐸 2 ≥ (3 × 108 )2 [(1.1 × 10−20 )2 + (9.11 × 10−31 )2 (3 × 108 )2 ]
𝐸 2 ≥ (3 × 108 )2 [1.21 × 10−40 + 7.469 × 10−44 ]
Since the second term in the bracket is less than the first term, it can be neglected. Therefore,
𝐸 ≥ 3.3 × 10−12J
𝐸 ≥ 20 𝑀𝑒𝑉
This means, in order that the electron may exist inside the nucleus, its energy must be greater
than or equal to 20 MeV. But, experiments have revealed that kinetic energy of beta particles
which come from inside the nucleus during the decay is of the order of 3 to 4 MeV. This
clearly indicates that, emitted electrons cannot exist within the nucleus.

Principle of Complementarity:
The inability to observe the wave and particle aspects of matter at the same time is known as
Principle of Complementarity. This principle was stated by N. Bohr in 1928.
Statement: “In a situation where the wave aspect of a system is revealed, the particle aspect
is concealed; and in a situation where the particle aspect is revealed, its wave aspect is
concealed. Revealing both particle and wave nature simultaneously is impossible. The wave
and particle aspects are complementary”
Explanation: We know that the consequence of the uncertainty principle is both wave and
particle nature of 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 a particle, during this
experiment, errors in measurement of both position and time coordinates must be zero and
hence the momentum, energy and wave nature of matter are completely unknown.
Similarly, if an experiment is designed to measure the wave nature of a particle, then the
errors in the measurement of energy and momentum will be zero, whereas the position and
time coordinates of matter are completely unknown.
Thus, if particle nature of matter is revealed, wave nature is suppressed and vice-versa.
 Like Newton’s second law of motion is fundamental equation of Newtonian
mechanics, Schrodinger’s equation is for quantum mechanics and it contains a variable .
Schrodinger 1-D time independent wave equation:
A progressive wave propagating along x-axis can be represented in the form of 2nd order
differential equation as follows.
𝑑2𝑦 1 𝑑2 𝑦
=
𝑑𝑥 2 𝑣 2 𝑑𝑡 2
Where y is f(x,t).
Similarly a wave equation for a matter wave can be represented as
𝑑2𝜓 1 𝑑2 𝜓
= − − − − − (1)
𝑑𝑥 2 𝑣 2 𝑑𝑡 2
The solution for this equation is
𝜓 = 𝐴𝑒 𝑖(𝑘𝑥−𝜔𝑡) where the symbols have their usual meanings.
𝑑𝜓
= 𝐴𝑒 𝑖(𝑘𝑥−𝜔𝑡) (−𝑖𝜔)
𝑑𝑡
𝑑2𝜓
= 𝐴𝑒 𝑖(𝑘𝑥−𝜔𝑡) (−𝑖𝜔)2 = −𝜔2 𝜓
𝑑𝑡 2
Hence equation (1) becomes
𝑑2𝜓 1
= (−𝜔2 𝜓)
𝑑𝑥 2 𝜔 2
( )
𝑘
𝑑2𝜓 2
−4𝜋 2
= (−𝑘 𝜓) = 𝜓
𝑑𝑥 2 𝜆2
𝑑2𝜓 2
1
= (−4𝜋 𝜓) −−−−− (2)
𝑑𝑥 2 𝜆2
The total energy of a particle is
E = KE + PE  KE = E – PE
If P is the momentum of the particle and V is its PE then
KE =p2/2m and
𝑃2
=𝐸−𝑉
2𝑚
2
ℎ2
𝑃 = 2𝑚(𝐸 − 𝑉) ⟹ 2 = 2𝑚(𝐸 − 𝑉)
𝜆
1 2𝑚
2
= 2 (𝐸 − 𝑉) −−−−−− (3)
𝜆 ℎ
Substitute (3) in (2)
𝑑2𝜓 2
2𝑚
= (−4𝜋 𝜓) (𝐸 − 𝑉)
𝑑𝑥 2 ℎ2
𝒅𝟐 𝝍 𝟖𝝅𝟐 𝒎
+ (𝑬 − 𝑽)𝝍 = 𝟎
𝒅𝒙𝟐 𝒉𝟐
This is 1-D time independent Schrodinger wave equation.
In 3-D
𝑑 2 𝜓 𝑑 2 𝜓 𝑑2 𝜓 8𝜋 2 𝑚
+ + + (𝐸 − 𝑉)𝜓 = 0
𝑑𝑥 2 𝑑𝑦 2 𝑑𝑧 2 ℎ2

2
8𝜋 2 𝑚
∇ 𝜓+ (𝐸 − 𝑉)𝜓 = 0
ℎ2
Physical significance of wave function:
Waves are normally associated with some periodically variable quantities. For ex, in sound
waves pressure and volume vary with respect to (x,t). In Electromagnetic waves both electric
field and magnetic field vary mutually perpendicular to each other. Similarly there is a
quantity called wave function () which varies in matter waves. The wave function itself
does not have direct physical meaning. It only represents the probability of finding a body (or
particle) at a given place and at a given time. It must lie between 0 and 1 and the maximum
probability is analogous to amplitude of an ordinary wave. Amplitude of a wave can be
positive as well as negative but negative probability is meaningless. In order to overcome this
problem Max Born gave an approximation (called Born’s approximation) as follows.
The probability of finding a particle described by the wave function  at a point x and at time
t is proportional to probability density |𝜓2 | at (x,t).
Probability density is equivalent to radiation density or intensity (I=A2). Even though  can
be imaginary, positive or negative |𝜓2 | is always positive. Hence the probability density is
more significant than probability alone. It is obtained by multiplying the wave function by its
complex conjugate.
∴ |𝜓2 | = 𝜓 ∗ 𝜓

Normalization:
Consider a particle enclosed in 3-dimenstional contour of volume V. Its probability density
(probability of finding the particle) over a small volume dV is |𝜓2 |𝑑𝑉. If make several
attempts to find the particle over the entire volume, then obviously integral (or total) cannot
be ZERO or INFINTY. The only possibility is, it is equal to ONE.
 𝑉
∫ |𝜓2 |𝑑𝑉 = 1
0

The wave function that obeys this equation is said to be normalized and the whole process is
known as Normalization.
𝑥
Normalization in 1-dimension is ∫0 |𝜓2 |𝑑𝑥 = 1
And normalization for a particle in space is
∞
∫ |𝜓2 |𝑑𝑥 = 1
−∞

Expectation value:
Consider a particle confined to a one-dimensional infinite potential well of length L and
described by the wave function 𝛙(x,t). Due to its wave nature, the particle occupies different
positions at different times. The expectation value of the position (given by the symbol <x>)
of the particle can be determined by a simple weighted average of the product of the
probability of finding the particle at a certain position and the position. ie
𝐿
〈𝑥〉 = ∫ 𝑥𝑃𝑟𝑜𝑏(𝑥)𝑑𝑥
0

or
𝐿
〈𝑥〉 = ∫ 𝑥|𝜓|2 𝑑𝑥
0

Properties of wave function:

There can be many solutions to the Schrodinger wave equation but only wave functions with
following properties must be considered as “well behaved” or “proper” wave functions. Only
they can give physically meaningful results when used in calculations. The properties are
i.  must be continuous and single valued everywhere.
𝜕𝜓 𝜕𝜓
ii. and must be continuous and single valued everywhere.
𝜕𝑥 𝜕𝑡

iii.  must be normalizable and it should not be .

Wave function possessing all these properties is known as eigen function and the energy
value obtained by solving Schrodinger wave equation using eigen function is known as eigen
value.
Application of Schrodinger wave equation:
Motion of a particle in 1-D potential well (Infinite depth):
This is the simplest quantum mechanical problem taken to explain the application of
Schrodinger wave equation. In this model a quantum particle (say electron) is assumed to be
trapped in a 1- dimensional potential well of infinite height and width of a. its walls are
extremely hard so that the collision between wall and particle is perfectly elastic. The
potential energy of the particle is zero inside and infinity outside the well. Particle is
restricted to move only along x-axis (i,e from x = 0 to x = a). The boundary conditions are as
follows.
i. 𝜓 = 0 and 𝑉 = ∞ outside the well.
ii. 𝜓 ≠ 0 and 𝑉 = 0 for 0 < 𝑥 < 𝑎 (inside the well).
iii. 𝜓 = 0 for 𝑥 ≤ 0 and 𝑥 ≥ 𝑎.
Case-1:
Outside the well, V = . Hence Schrodinger wave equation
𝑑 2 𝜓 8𝜋 2 𝑚
+ (𝐸 − 𝑉)𝜓 = 0 −−− (1)
𝑑𝑥 2 ℎ2
becomes
𝑑 2 𝜓 8𝜋 2 𝑚
+ (𝐸 − ∞)𝜓 = 0
𝑑𝑥 2 ℎ2
The possible solution for this equation is  = 0. This means that the probability of finding the
particle and hence probability density outside the well is ZERO.
Case-2:
Inside the well, V = 0 and hence equation (1) becomes
𝑑 2 𝜓 8𝜋 2 𝑚
+ (𝐸 − 0)𝜓 = 0
𝑑𝑥 2 ℎ2
Even though  = 0 is a possible solution it cannot be considered for obvious reason.
8𝜋2 𝑚𝐸
Put 𝑘2 = −−−−− (2)
ℎ2
𝑑2𝜓
+ 𝑘2𝜓 = 0
𝑑𝑥 2
This is a second order differential equation and its solution is
𝜓 = 𝐶 cos 𝑘𝑥 + 𝐷 sin 𝑘𝑥 −−−− (3)
Put x = 0 and  = 0, we get
C = 0.
Again, put x = a and  = 0, we get
0 = 0 cos 𝑘𝑎 + 𝐷 sin 𝑘𝑎
𝐷 sin 𝑘𝑎 = 0 ⟹ 𝐷 ≠ 0 and sin 𝑘𝑎 = 0
∴ 𝑘𝑎 = 𝑠𝑖𝑛−1 (0) ⟹ 𝑘𝑎 = 𝑛𝜋
𝑛𝜋
∴𝑘= −−−−− (4)
𝑎
Here n = 1,2,3,4…
From equation (2) and (3) we get
8𝜋 2 𝑚𝐸 𝑛𝜋 2
= ( )
ℎ2 𝑎
𝑛2 ℎ2
𝐸=
8𝑚𝑎2
Or,
𝒏𝟐 𝒉𝟐
𝑬𝒏 =
𝟖𝒎𝒂𝟐
If n =1, then we get ground state energy of the particle. It is also called as ZERO POINT
energy.
𝒉𝟐
𝑬𝒁𝑬𝑹𝑶 =
𝟖𝒎𝒂𝟐
Substitute C and k in equation (3) we get
𝑛𝜋
𝜓𝑛 = 𝐷 sin 𝑥 −−−− (5)
𝑎
Normalization (To find D):
Consider
𝑎
∫ |𝜓2 𝑛 |𝑑𝑥 = 1
0
𝑎
𝑛𝜋 2
∫ (𝐷 sin 𝑥) 𝑑𝑥 = 1
0 𝑎
𝑎
𝑛𝜋𝑥
∫ 𝐷2 𝑠𝑖𝑛2 𝑑𝑥 = 1
0 𝑎
𝐷2 𝑎 2𝑛𝜋𝑥
∫ (1 − 𝑐𝑜𝑠 ) 𝑑𝑥 = 1 because 𝑠𝑖𝑛2 𝜃 = (1 − 𝑐𝑜𝑠2𝜃)/2
2 0 𝑎
𝐷2 𝑎 𝑎
2𝑛𝜋𝑥
[∫ 𝑑𝑥 − ∫ 𝑐𝑜𝑠 𝑑𝑥] = 1
2 0 0 𝑎
𝐷2 𝑎 2𝑛𝜋𝑎
[(𝑎 − 0) − (𝑠𝑖𝑛 − sin 0)] = 1
2 2𝑛𝜋 𝑎
𝐷2 𝑎
[𝑎 − (sin 2𝑛𝜋 − sin 0] = 1
2 2𝑛𝜋
𝐷2 𝑎
[𝑎 − (0 − 0)] = 1
2 2𝑛𝜋
𝐷2
𝑎=1
2

2
𝐷=√
𝑎

Hence equation (5) becomes

𝒏𝝅
𝝍𝒏 = √𝟐/𝒂 𝐬𝐢𝐧( )𝒙
𝒂
This is the eigen function.

Eigen functions, energy eigen values and probability densities for a particle in a box
(Waveforms and Probabilities):
Consider a particle present in 1-dimentional potential well of infinite height and finite width
a. its eigen function and eigen value, in general, are given by
𝑛𝜋
𝜓𝑛 = √2/𝑎 sin( )𝑥
𝑎
and
𝑛2 ℎ2
𝐸𝑛 =
8𝑚𝑎2
Case-1:
Put n =1, then we get ground state energy as
ℎ2
𝐸0 =
8𝑚𝑎2
The eigen function becomes
𝜋
𝜓1 = √2/𝑎 sin(𝑎 )𝑥

(i) Put x =0, 𝜓1 = 0 and 12

1
|𝜓12 | = 0
𝜋
2 ( )𝑎 2
𝑎
(ii) Put x =a/2, 𝜓1 = √ sin =√ and
𝑎 2 𝑎

|𝜓12 | = 2/𝑎
(iii)Put x =a, 𝜓1 = 0 and
|𝜓12 | = 0
Case-2:
Put n =2, we get 𝐸1 = 4𝐸0
The eigen function becomes
2𝜋
𝜓2 = √2/𝑎 sin( 𝑎 )𝑥

2 22
(i) Put x=0, 𝜓2 = 0 |𝜓22 | = 0

2𝜋
2 ( )𝑎 2
𝑎
(ii) Put x=a/4, 𝜓2 = √ sin =√ |𝜓22 | = 2/𝑎
𝑎 4 𝑎

(iii)Put x=a/2, 𝜓2 = 0 |𝜓22 | = 0

2𝜋
2 ( )3𝑎 2
𝑎
(iv) Put x=3a/4, 𝜓2 = √ sin =−√ |𝜓22 | = 2/𝑎
𝑎 4 𝑎

(v) Put x=a, 𝜓2 = 0 |𝜓22 | = 0

Case-3: Similarly if n =3, 𝐸2 = 9𝐸0 and
3𝜋
𝜓3 = √2/𝑎 sin( )𝑥
𝑎
The graphical representation of 3 and 32 is as follows.

a/2

a/6 5a/6
3 32
The eigen functions and probability densities are presented in the above diagrams for
different quantum numbers. An interesting observation made from these diagrams is as
follows.
At a particular place in the box the probability density differs for different quantum numbers
(n). For ex, at a/2, the particle has highest probability density in its least energy state (n=1)
where as in its first excited state the particle can never be seen at all. Moreover, the diagrams
resemble the stationary waves set up in stretched string. This shows that the same wave
equation can be used to explain the waves in a stretched string as well as waves associated
with moving particle.