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Module – 2: Quantum Mechanics

Syllabus (8 Hours)

de-Broglie hypothesis and Matter Waves, de Broglie wavelength and derivation of expression
by analogy, Phase Velocity and Group Velocity, Heisenberg's uncertainty principle and its
application (Non-existence of electron in the nucleus-Non Relativistic), Principle of
Complementarity, Wave Function, Time independent Schrödinger wave equation, Physical
significance and Born Interpretation, Expectation Value, Eigen functions and Eigen values,
Motion of a particle in a one dimensional potential well of infinite depth, Waveforms and
probabilities. Numerical problems.

Pre-requisites: Wave-Particle dualism

Self-learning: de Broglie Hypothesis

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DUAL NATURE OF MATTER:

Some of the properties of light (Energy) such as interference, diffraction and polarization
can be explained by using wave nature and some other properties like photoelectric effect,
Compton Effect, emission and absorption of radiations shows the particle nature (the radiation
consists of small corpuscles known as photons). Thus, it is accepted that radiation has dual
nature. Particle has mass, it occupies space, and it can move from one place to another, it gives
energy when slowed down or stopped. Thus, the particle can be specified by mass, velocity,
momentum energy and two particles cannot occupy the same space simultaneously. A wave as
it travels, spreads occupying larger region of space. A wave is specified by wavelength,
frequency, amplitude, intensity, phase and wave velocity.

De Broglie’s concept of matter waves:

It is accepted that radiation has dual nature. In 1924 Louis de Broglie put forth the
suggestion that matter, like radiation, has dual nature, i.e., matter which is made up of discrete
particles, atoms, protons, electrons etc., might exhibit wave like properties under appropriate
conditions. These waves associated with a moving material particle, are called matter waves.

Statement: “Every moving particle is associated with a set of waves known as matter waves”.

The wavelength  associated with a particle of mass ‘m’ moving with a velocity ‘v’ is
called de Broglie wavelength and is given by
ℎ ℎ
 = =
𝑚𝑣 𝑝

Where, h → Planck’s constant; p → momentum of the particle.

Expression for de Broglie wavelength in terms of energy of the particle:

Consider a particle of mass m moving with a velocity v. Let its kinetic energy be E.

E = ½ mv2

Multiplying by ‘m’ both sides,

mE = ½ m2v2

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p2
mE = (mv = p)
2

p2 = 2mE

p = √2𝑚𝐸
h
De Broglie wavelength,  =
p

ℎ
 =
√2𝑚𝐸

De Broglie wavelength associated with electrons:

Consider an electron of rest mass m and charge e, accelerated by a potential difference

of V volt from rest to a velocity v. Then work done on the electron is W = eV

This work done is converted into kinetic energy of the electron.

1
eV = mv 2 i.e., v = 2eV
2 m

h h h h
But,  = = = =
mv 2eV m 2eV 2 2meV
m
m m

h
 =
2meV

de Broglie wavelength of electrons is given by

h = 6.63  10-34 Js, m = 9.1  10-31 kg, e = 1.6  10-19 C

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6.63  10 −34 12.27

= = Å
2  9.1  10 − 31  1.6  10 −19  V V

Phase velocity (vp) and Group Velocity (vg):

The Phase velocity is defined as the velocity of the arbitrary point marked on the wave (See
Fig. 2.1).
𝜔
Mathematically, 𝑉𝑝ℎ𝑎𝑠𝑒 = 𝑉𝑝 = 𝑘 .

The Group Velocity of a Wave is defined as the Velocity at which an entire envelope of Waves
moves through a medium.
𝑑𝜔
Mathematically, 𝑉𝑔𝑟𝑜𝑢𝑝 = 𝑉𝑔 = .
𝑑𝑘

Fig. 2.1 Graphical representation of wave packet showing phase and group velocities.
The relation between phase velocity and group velocity is as follows;
𝑑𝑉𝑝
𝑉𝑔 = 𝑉𝑝 + 𝑘
𝑑𝑘

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Characteristic properties of matter waves

1. Matter waves are the waves that are associated with a moving particle. The wavelength
h h E
 and frequency  of the waves are given by  = = and  = where h – Plank’s
p mv h

constant, p and E are the momentum and energy of the particle respectively.
2. Lighter is the particle, greater is the wavelength associated with it.
3. Smaller is the velocity of the particle, greater is the wavelength associated with it.
C2
4. The wave velocity or phase velocity of the matter waves is given by VPhase =
Vgroup

Here Vgroup is same as the particle velocity, which is always lesser than the velocity of
light C. Thus velocity of matter waves is always greater than C. This indicates that
matter waves are not physical waves.
5. The velocity of matter waves depends on the velocity of material particle. i.e., it is not
a constant, while the velocity of electromagnetic wave is constant.

Heisenberg’s Uncertainty Principle:

In classical mechanics, a particle occupies a definite place in space and possess a definite
momentum. By knowing the position and momentum of a particle at any given instant of time.
It is possible to evaluate its position and momentum at any later stage and the trajectory of the
particle could be continuously traced. But in quantum mechanics, since we are dealing with
atomic scale, it is not possible to determine the position and momentum of a particle
simultaneously with accuracy.

According to Heisenberg’s uncertainty principle, it is impossible to determine

simultaneously both the position and momentum of a particle with accuracy. The product of
the uncertainties in the simultaneous determination of the position and momentum of a particle

is equal to or greater than h .

4

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If p and x are the uncertainties in the momentum and position of a particle, then we
can write the mathematical form of Heisenberg’s uncertainty principle as

p.x  h
4

According to this equation, an increase in the accuracy in the measurement of position

means, a decrease in the value of x. As per the above equation, a decrement in the value of
x, must simultaneously result in the proportionate increment in the value of p, since the right
hand side of the above equation is a constant.

Heisenberg’s uncertainty principle could also be expressed in terms of the uncertainties

involved in the measurement of

a) Energy and time as E.t  h

4

b) Angular momentum (L) and angular displacement () is L.  h

4

Physical significance of Heisenberg’s uncertainty Principle:

Uncertainty principle holds good for all the objects but this principle is significant for only
microscopic particles. The energy of a photon is insufficient to make change in velocity or
momentum of bigger particles when collision occurs between them.

The uncertainty principle formally limits the precision to which two complementary
observables can be measured and establishes that observables are not independent of the

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observer. It also establishes that phenomena can take on a range of values rather than a single,
exact value.

Application of Heisenberg’s uncertainty Principle:

Non-existence of electron in the nucleus:

Consider the nuclear size is of the order of 10–14 m. If an electron is to exist inside the
nucleus then the uncertainty in its position x should not be greater than 10–14 m.

i.e., x = 10 – 14 m. ------------- (1)

Then, from HUP, the uncertainty in the momentum of electron,

ℎ
p  4𝜋.𝛥𝑥

6.626 ×10−34
p  4×3.14×10−14 = = 5.27  10−21 Ns

Then the momentum of the electron must at least be equal to the uncertainty in the
momentum i.e.,

𝑝 = 5.27  10−21 Ns ------------ (2)

We have,
𝑝2
𝐸 = 2𝑚 ----------- (3)

Where, m is the mass of the electron = 9.1x 10-31 kg; and p is the momentum of the electron.

Substituting equation (2) in (3), we get

(5.27  10−21 )2
𝐸≥ = 1.52 × 10−11 𝐽
2 × 9.1 × 10−31
1.52 × 10−11
𝐸≥ 𝑒𝑉 = 94.8 × 106 𝑒𝑉
1.6 × 10−19

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𝐸 ≥ 94.8 𝑀𝑒𝑉

This means, in order for an electron to exist inside the nucleus, its energy must be greater than
or equal to 94.8 MeV. However, the experimental results on β-decay reveals that, the kinetic
energy of electrons ejected out of nucleus is of the order of 3 to 4 MeV only. This value is
much lower than the calculated value (94.8 MeV). The electrons are pushed out of the nucleus
since the do not have sufficient energy to stay inside the nucleus. Hence, we can say that
electrons cannot exist inside the nucleus.

Principle of Complementarity.

complementarity principle, in Physics that a complete knowledge of phenomena on atomic

dimensions requires a description of both wave and particle properties. The principle was
announced in 1928 by the Danish physicist Niels Bohr.

Now suppose that an experiment is constructed in such a way that it is designed to measure the
particle nature of the matter. This implies that, during this experiment, errors of measurement
of both position and the time coordinates must be zero or absent, this in turns explains that 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.

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.
The inability to observe the wave nature and the particle nature of the matter simultaneously is
known as the complementarity principle. It was first explained by Niels Bohr in the year 1928
and hence it is familiarly known as the Bohr’s Complementarity principle.

What Bohr explained or Bohr exact words were “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

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is revealed, its wave aspect is concealed. Revealing both simultaneously is impossible; the
wave and particle aspects are complementary.”

Wave function

The quantity that characterizes the de Broglie waves is called the wave function. It is usually

represented by (x, y, z t) or ( r , t). It is a function of space variable and time.

Physical interpretation of the wave function:


d

Fig. 2.2 Presence of electron in a certain region

In classical mechanics, the square of a wave amplitude associated with electromagnetic

radiation is interpreted as a measure of radiation intensity. This suggests that we should make
a similar interpretation for De Broglie waves associated with electron or any particle. Hence if
we consider a system of electrons and if  is the wave function associated with the system,
then |2| may be regarded as a measure of density of electrons. Also, if  is a volume inside
which an electron is known to be present (Fig. 2.2), but where exactly the electron is situated
inside  is not known, and if  is the wave function associated with the electron, then the
probability of finding the electron in a certain element of volume d of  is equal to ||2 d. For
this reason ||2 is called the probability function. Since the electron must be somewhere inside

 ||
2
the volume , the integration of ||2 over the entire volume  must be unity i.e., d = 1.

This condition is known as normalization condition.

EIGEN FUNCTIONS & EIGEN VALUES

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In order to find , the Schrodinger’s equation has to be solved. But since, it is a second
order differential equation, there are several solutions. But all of them may not be the correct
wave functions which we are searching for. We have to select only those functions which would
correspond meaningfully to a physical system. Such wave functions are said to be acceptable
wave functions and it has to satisfy the following conditions

1.  must be single valued and finite everywhere

2.  must be continuous and should have a continuous first derivative everywhere

 ||
2
3. The wave function must be normalized i.e., it has to satisfy the conditions d = 1

Such acceptable wave functions are called Eigen functions

Once the Eigen functions are known, they could be used in Schrodinger’s equation to evaluate
energy values. These values are called Eigen values.

SCHRODINGER’S WAVE EQUATION

Schrodinger equation is the fundamental equation of Quantum mechanics. It is the wave

equation in the variable .Sound waves and waves in strings are described by the equations of
Newtonian mechanics. Light waves are described by Maxwell’s equations. Matter waves are
described Schrodinger’s equation. In 1925, Schrodinger used de Broglie’s ideas to set up a
mathematical theory to describe the dual nature of matter.

Time independent Schrodinger’s wave equation:

According to De Broglie’s theory, a moving particle of mass ‘m’ is always associated

h h
with a wave whose wavelength is given by a  = = . If the particle has wave like
mv p

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properties, then there must be some sort of wave equation which describe the behavior of the
particle.

Let x, y, z be the coordinates of the particle and , the wave displacement for the de Broglie
waves at any time t.

The classical differential equation for a wave motion is given by

 2  = v2    +   +   
2 2 2
 ------------- (*) → for three dimensions
t 2
 x 2 y 2 z 2 
 

Let us restrict our study to only one dimensional case such that  is a function of ‘x’ only.

2 2
 Equation (*) becomes d 2 = v2 d 2
----------- (1)
dt dx

The solution of equation (1) is given by

 = Ae - it --------------------------------------- (2)

where A is the amplitude and  is the angular frequency of the wave. Differentiating equation
(2) w.r.t ‘t’ twice

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d
= - i Ae - it
dt

d2  = - i (- i) Ae - it
2
dt

= i22 (Using equation (2)) [ i2 = -1]

= - 2 ----------------------------- (3)

2 2
2d 
Substituting the value of d 2
in equation (1), we get - 2
 = v 2
dt dx

2 2
- 2  = d 2
v dx

2
or d  + 2  = 0 -------------------- (4)
2 2
dx v

But  = 2 Also v =  (using v = f)

Substituting for  & v in equation (4) d2  + 42  2  = 0

dx2  2 2

d2  + 42  = 0
dx2 2

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h
Using de Broglie wavelength equation  =
mv

2
 d  + 4 2 m2v2 = 0 ------------- (5)
2 2
dx h

Consider a particle moving in an electric field. Then, it will have a potential energy (V) also,
in addition to kinetic energy.

The total energy of particle, E = kinetic energy + Potential energy

1 1
i.e., E = mv2 + V or mv2 = E – V
2 2

Multiplying by m on both sides,

1 2 2
m v = m (E – V) or m2v2 = 2m (E – V) ----------- (6)
2

Substituting equation (6) in equation (5)

d2  2
+ 42 2m (E – V) = 0
dx2 h

2 2
or d 2 + 8 2m (E – V)  = 0
dx h

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This is the time independent Schrodinger wave equation in one dimension

d2  𝑑2𝜓 𝑑2𝜓 2
In three dimension + + + 8 2m (E – V)  = 0
dx2 𝑑𝑦 2 𝑑𝑧 2 h

2
𝛁 𝟐  + 8 2m (E – V)  = 0
h

Application of Schrodinger Wave Equation

I. Particle in one dimensional potential well of infinite height (or particle in a box)

Consider a free particle of mass ‘m’ confined to a box of width ‘L’ with infinitely high
walls (Fig. 2.3). The condition for particle motion is  

1. The particle moves along x – axis between x = 0 and x = L V=0 V=

2. The particle is a free particle i.e., not subjected to any x=0 x=L

external force.
Fig. 2.3 Potential well
Therefore, the potential energy (V) is zero inside the box.

i.e. V = 0 for 0 < x < L. The potential outside the box is infinite.

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3. The value of the wave function  outside the box is zero. i.e.,  = 0

which means that the particle cannot be found outside the box

The Schrodinger equation for a particle in one dimension is

d2  2
+ 8 2m (E – V) = 0
dx2 h

Outside the box, the equation becomes

d2  2
+ 8 2m (E – )  = 0 (Since V = , outside)
2
dx h

Inside the box the equation becomes

d2  2
+ 8 2m E = 0 (Since V = 0) ---------- (1)
2
dx h

2
Let 8 2mE = k2 ---------------------- (2)
h

2
 Equation (1) becomes, d 2 + k2 = 0 ------------- (3)
dx

The solution of Equation (3) is given by

 = A cos kx + B sin kx ------------- (4)

where A and B are the constants depending on the boundary condition

Applying the boundary conditions

1. At x = 0,  = 0 cos 0 = 1 sin 0 = 0

Hence equation (4) becomes 0 = A cos 0 + B sin 0

 A = 0 ------------ (5)

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2. At x = L,  = 0

 Equation (4) becomes, 0 = A cos kL + B sin kL

But A = 0 from equation (5)

 0 = B sin kL

B need not be equal to zero

 sin kL = 0 ------------ (6)

We have

Sin 0 = 0, Sin  = 0, Sin 2 = 0, Sin 3 = 0…

Sin n = 0 ------------- (7), n = 0, 1, 2, 3…

Comparing equation (6) and (7)

n
n = kL or k= ----------- (8)
L

Substituting the value of A and k in equation (4)

n
 = B sin x -------------- (9)
L

To evaluate B in equation (9) we have to perform the normalization of the wave function. Since
the particle is inside the box, the probability of finding the particle is 1. Hence
L
0 2 dx = 1

L n 1
0 B2 sin2
L
x dx = 1 But sin2  =
2
(1 – cos 2)

L 1  2n 
0 B2 1 − cos
2 
x  dx = 1
L 

B2  L  2n  
2 
 
0
1 − c os
 L
x  dx = 1
 

B2  L L 2n 
2 

 0
dx −  0
cos
L
xdx  = 1


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 L  L 2n  
L
B2
 x0 −  sin x  =1 
sin n
L  0 
Using cos n d =
2  2n n

B2  L 2nL 
2 L − 0 − 2n sin L − 0 = 1
 

B2  L 
2 L − 2n sin 2n = 1 (sin 2n = 0)
 

B 2L 2 2
 = 1  B2 = or B = ----------- (10)
2 L L

2 n
 Equation (9) becomes,  = sin x ---------- (11)
L L

2 n
From equation (2) 8 2mE = k2 Now k =
h L

82mE = n2 2 , 2 2
E = n h 2 --------------- (12)
h2 L2 8mL

This equation gives the allowed values of energy for different value of n.

The particle has discrete energy levels.

2 2 
For n = 1 E1 = h 2 and wave function 1 = sin x
8mL L L

2 2 2
For n = 2 E2 = 4h 2 and wave function 2 = sin x
8mL L L

2 2 3
For n = 3 E3 = 9h 2 and wave function 3 = sin x
8mL L L

These values of energy are called Eigen values of energy. The energy corresponding to n = 1
is called the ground state energy (or zero point energy). The other energies are called excited
states

Case (i): When n = 1 (ground state) (Fig. 2.4)

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2 
1 = sin x
L L
1 |1|2

1 = 0 when x = 0 and x = L
x=0 L/2 x=L x=0 L/2 x=L
L
1 is maximum at x =
2 Fig. 2.4 Plots of wave function and probability, n=1
( sin 90 = 1)  the particle is not found near the walls and the probability of finding the
2
particle is maximum at the central region and energy in the ground state is E1 = h 2
8mL

Case (ii): n = 2 (1st excited state, Fig. 2.5) |2|2

2 2 2
2 = sin x
L L
x=0 L 0 L/4 L/2 3L/4 L
L
2 = 0, when x = 0, , L
2

L 3L
2 is max for x = and  In the 1st excited state the particle cannot be observed
4 4
L
either at the walls or at the center. The particle is most likely to be found at x = and
4
3L
and energy in the 1st excited state is 4 times the zero-point energy
4
2
i.e., E2 = 4h 2
8mL

Case (iii): n = 3 (2nd excited state)

3 |3|2
(Fig. 2.6

3 0 L/3 2L/3 L L
2 0
3 = sin x
L L

L 2L
3 = 0 for x = 0, , and L
3 3

L L 5L
3 is max for x = , ,
6 2 6

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L L 5L
 The particle is most likely to be present at x = , and
6 2 6

9ℎ2
Energy in the 2nd excited state is 9 times the zero-point energy i.e. 𝐸 = 8𝑚𝐿2

II. Case of a free particle:

Schrodinger’s wave equation for a particle of mass m, total energy E and potential energy
V is written as

d2  2
+ 8 2m (E – V)  = 0
dx2 h

Free particle means, it is not under the influence of any kind of field or force. Thus it
has zero potential energy i.e., V = 0. Hence Schrodinger’s becomes

 d2  + 82m E =0  d2  + k2 = 0
2 2 2
dx h dx

The solution of this equation is given by

(x) = A cos (kx) + B sin (kx)

Since the particle is free, the constants A, B and K can take any value. That is energy of a free
ℎ2 𝑘 2
particle is not quantized and it is given by 𝐸 = 8𝜋2 𝑚

Graphical representation of 𝐸𝑛 , ψ𝑛 (𝑥) and P𝑛 (𝑥) for n = 1, 2 & 3 quantum states

Eigen values Eigen functions Probability densities

𝑛2 ℎ 2 𝑛𝜋𝑥 2 𝑛𝜋𝑥
𝐸𝑛 = ψ𝑛 (𝑥) = √2⁄𝐿 𝑠𝑖𝑛 ( 𝐿 ) P𝑛 (𝑥) = (𝐿) 𝑠𝑖𝑛2 ( ) 𝑑𝑥
8𝑚𝐿2 𝐿

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Fig. 2.7 Graphical representation of energy, wavefunction and probability

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QUESTION BANK

1. Explain De-Broglie’s hypothesis.

2. What are matter waves? Mention their characteristic properties.
3. Define phase velocity & group velocity.
4. State & explain Heisenberg’s uncertainty principle. Give its physical significance.
5. Show that electrons cannot exist in the nucleus of an atom based on Heisenberg’s
uncertainty principle.
6. What is a wave function? Explain the properties of wave function.
7. Write the physical significance of wave function.
8. Set up time independent one-dimensional Schrödinger’s wave equation.
9. Write down the condition for a normalized wave function.
10. What are Eigen values & Eigen functions?
11. Find the Eigen functions & Eigen values for a particle in one dimensional potential
well of infinite height & discuss the solutions.

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