Unit 3 - Quantum mechanics – II

Quantum mechanics

Introduction Discovery of microscopic particles of atomic dimensions of the order

of 10-10 m and their experimental observations could not be explained by Newtonian
mechanics (classical mechanics). The attempts made to explain the experimental
results like black body radiation spectrum, specific heat of solids at low
temperatures, photoelectric effect, Compton effect, atomic spectra etc…. led to the
development of quantum mechanics.

In 1924 de Broglie extended wave particle duality to micro particles, which says that
particles in motion possess wave nature along with particle nature. In 1926 Erwin
Schrodinger developed an equation for the waves associated with these elementary
particles which would describe the behaviour of particles. The Schrodinger equation
plays the same role in quantum mechanics as that played by Newton’s laws and
conservation laws in classical mechanics.

Wave function: Every microscopic particle or system particles are associated with
a quantity called wave function whose variation makes up the de Broglie waves or
matter waves. It describes the quantum state of the particle.

The wave function 𝜓(𝑟, 𝑡) determines the entire space – time behaviour of a system.
The value of wave function associated with a moving particle at a particular point x,
y, z in space at the time ‘t’ is related to the probability of finding the particle there at
that time.

Properties of wavefunction
1. The wave function contains all measurable information about the particle.
2. The wave function 𝜓 must be single valued everywhere in space. It should be
unique and should not possess more than one value at the same location.
3. 𝜓 must be finite everywhere in space. ie. The wave function cannot be infinite
at a point as it signifies a large probability of finding the particle. This violates
the uncertainty principle and the wave function is unacceptable.
4. 𝜓 and its first derivatives with respect to its variables must be continuous
everywhere.
5. For bound states, 𝜓 must vanish at infinity. If 𝜓 is a complex function then
𝜓 ∗ 𝜓 must vanish at infinity.
6. 𝜓 must be normaizable. This means 𝜓 must go to zero as 𝑥 → ± ∞, 𝑦 → ± ∞
and 𝑧 → ± ∞ in order that ∫|𝜓|2 𝑑𝑉 over all space be a finite quantity.
7. The wave function allows energy calculations by using Schrodinger’s
equation.

V Semester B.Sc., Physics Dr. K S Suresh Page 1

Unit 3 - Quantum mechanics – II

8. The wave function allows the calculation of effective average value of a

variable (Expectation value).
9. The wave function for a free particle is a sine function, implying precisely
determined momentum and highly uncertain position of a particle
(Heisenberg Uncertainty principle).

Physical significance of wave function

1. The wave function signifies the probability of finding the particle at the point
(x, y, z) and at time t.
2. The wave function can interfere with itself. (Electron diffraction)
3. The wave function 𝜓 is a complex quantity and has no direct physical
significance by itself. The product 𝜓𝜓 ∗ is a real quantity where 𝜓 ∗ is the
complex conjugate of 𝜓.
4. Probability density - It is the probability of finding the particle per unit
volume. It is given by 𝜓𝜓 ∗ or |𝜓|2 . Thus the term |𝜓(𝑟, 𝑡)|2 =
𝜓 ∗ (𝑟, 𝑡) 𝜓(𝑟, 𝑡)𝑑𝑉 is proportional to the probability of finding the particle in
the interval V and V + dV at the time t. The total probability of finding the
+∞
particle anywhere in space is 𝑃 = ∫−∞ |𝜓(𝑟, 𝑡)|2 𝑑𝑉.

Max Born’s interpretation of wave function

The space time behaviour of an atomic system is determined by the laws of
probability. The intensity of light at different points in interference or diffraction
experiments is determined by square of the amplitude of electric vector of light wave
(𝐸 2 ) . Similarly in case of an atomic system like electron, the probability of finding
the electron at a point in space is determined by the square of amplitude of wave
function.

Max Born also proposed four conditions on the wave function which are used in
finding many solutions of the Schrödinger equation.

Max Born’s conditions to be imposed on the wave function are

1. The wave function must be single valued. This means that for any given
values of and , 𝜓(𝑥, 𝑡) must have a unique value. This is a way of
guaranteeing that there is only a single value for the probability of the system
being in a given state.
2. The wave function must be square-integrable. In other words, the integral of
|𝜓|2 over all space must be finite. This is another way of saying that it must
be possible to use |𝜓|2 as a probability density, since any probability density
must integrate over all space to give a value of 1, which is clearly not possible

V Semester B.Sc., Physics Dr. K S Suresh Page 2

Unit 3 - Quantum mechanics – II

if the integral of |𝜓|2 is infinite. One consequence of this proposal is

that 𝜓 must tend to 0 for infinite distances.
3. The wave function must be continuous everywhere. That is, there are no
sudden jumps in the probability density when moving through space.
4. All first-order derivatives of the wave function must be continuous.
Following the same reasoning as in condition 3, a discontinuous first
derivative would imply an infinite second derivative, and since the energy of
the system is found using the second derivative, a discontinuous first
derivative would imply an infinite energy, which again is not physically
realistic.

Normalization of wave function : As 𝜓 itself is complex quantity and has no

physical significance but 𝜓2 has the significance. The integral of 𝜓2 taken over all
+∞
space must be equal to one. ie. ∫−∞ |𝜓(𝑟, 𝑡)|2 𝑑𝑉 = 1 such a wave function is called
normalized wave function.

The process of integration over all space to give unity is called normalization.

If 𝜓(𝑟, 𝑡) is multiplied by a constant C such that 𝜓𝑁 (𝑟, 𝑡) = 𝐶𝜓(𝑟, 𝑡) where 𝜓𝑁 (𝑟, 𝑡)

+∞ +∞
satisfies the relation ∫−∞ |𝜓𝑁 (𝑟, 𝑡)|2 𝑑𝑉 = |𝐶|2 ∫−∞ |𝜓(𝑟, 𝑡)|2 𝑑𝑉 = 1 then 𝜓𝑁 (𝑟, 𝑡) is
1
said to be normalized wave function. The term |𝐶|2 is given by |𝐶|2 = +∞
∫−∞ |𝜓(𝑟,𝑡)|2 𝑑𝑉
where C is called the normalization constant. Thus a wave function is normalizable
+∞
if ∫−∞ |𝜓(𝑟, 𝑡)|2 𝑑𝑉 remains finite over all space.

Time dependent Schrodinger’s equation (Free particle)

Consider a plane wave travelling in the X – direction with a frequency ν, wavelength
2𝜋
λ and velocity 𝜐 so that 𝜔 = 2𝜋𝜈 and 𝑘 = where 𝜔 is the angular frequency and
𝜆
k is the propagation constant of the wave. The equation of a wave can be represented
by 𝜓 = 𝐴 𝑒 −𝑖(𝜔𝑡−𝑘𝑥) ……….(1)
𝐸
According to quantum theory, the energy of the wave is 𝐸 = ℎ𝜈 and hence 𝜈 = .
ℎ

2𝜋𝐸 𝐸 ℎ
As 𝜔 = 2𝜋𝜈 = = where ℏ = .
ℎ ℏ 2𝜋

Momentum 𝑝𝑥 of the wave along the positive x-direction is given by

ℎ 1 𝑝𝑥
𝑝𝑥 = 𝑜𝑟 = .
𝜆 𝜆 ℎ

2𝜋 2𝜋𝑝𝑥 𝑝𝑥
The propagation constant is given by 𝑘 = = or 𝑘 =
𝜆 ℎ ℏ

V Semester B.Sc., Physics Dr. K S Suresh Page 3

Unit 3 - Quantum mechanics – II

𝐸 𝑝
𝐸 𝑝𝑥 −𝑖( 𝑡− 𝑥 𝑥)
Substituting for 𝜔 = and 𝑘 = in equation (1) we get 𝜓 = 𝐴 𝑒 ℏ ℏ
ℏ ℏ

𝒊
( 𝒑 𝒙−𝑬𝒕)
or 𝝍 = 𝑨 𝒆ℏ 𝒙 ………(2) where 𝜓 is the one dimensional wave function of
a unrestricted particle (free particle) which is a function of 𝑥 and t.

Differentiating equation (2) with respect to time 𝑡

𝑖 𝑖
𝜕𝜓 ( 𝑝𝑥 𝑥−𝐸𝑡) 𝑖𝐸 𝜕𝜓 𝑖𝐸 ( 𝑝𝑥 𝑥−𝐸𝑡)
= 𝐴 𝑒ℏ (− ) or = (− ) 𝜓 ….(3) where 𝜓 = 𝐴 𝑒ℏ
𝜕𝑡 ℏ 𝜕𝑡 ℏ

ℏ 𝜕𝜓 𝜕𝜓
Rearranging equation (3), 𝐸 𝜓 = − or 𝐸 𝜓 = 𝑖ℏ 𝜕𝑡 ……….(4)
𝑖 𝜕𝑡

Differentiating equation (2) with respect to 𝑥, we get

𝑖
𝜕𝜓 ( 𝑝𝑥 𝑥−𝐸𝑡) 𝑖 𝑝𝑥 𝑖𝑝𝑥
= 𝐴 𝑒ℏ ( ) = ( ) 𝜓 ….(5)
𝜕𝑥 ℏ ℏ

𝜕2𝜓 𝑖
( 𝑝𝑥 𝑥−𝐸𝑡) 𝑖 𝑝𝑥 2
Differentiating equation (5) again, we get = 𝐴 𝑒ℏ ( )
𝜕𝑥 2 ℏ

𝜕2𝜓 𝑖 𝑝𝑥 2 𝜕2𝜓
or =( ) 𝜓 , rearranging this equation, we get 𝑝𝑥2 𝜓 = − ℏ2 …..(6)
𝜕𝑥 2 ℏ 𝜕𝑥 2

For a particle of mass 𝑚 moving with a velocity 𝜐, the total energy of the particle is
given by 𝐸 = 𝐸𝐾 + 𝐸𝑃 where 𝐸𝐾 is the kinetic energy and 𝐸𝑃 is the potential
energy represented by V.
1
𝐸𝐾 is given by 𝐸𝐾 = 𝑚𝑣 2 . Multiplying and dividing this equation by 𝑚
2

𝑚2 𝑣 2 𝑝𝑥2
we get 𝐸𝐾 = . As 𝑝𝑥 = 𝑚𝑣, we get 𝐸𝐾 = .
2𝑚 2𝑚

𝑝𝑥2 𝑝𝑥2
Thus the total energy is 𝐸 = + 𝑉 or 𝐸𝜓= 𝜓 + 𝑉 𝜓 ……….(7)
2𝑚 2𝑚

Substituting for 𝐸 and 𝑝𝑥 from (4) and (6) in (7) we get,

𝝏𝝍 ℏ𝟐 𝝏𝟐 𝝍
𝒊ℏ =− + 𝑽𝝍 ………..(6) This is the schrodinger’s time dependent
𝝏𝒕 𝟐𝒎 𝝏𝒙𝟐
equation in one dimension for a free particle.

𝜕𝜓 ℏ2 𝜕2𝜓 𝜕2𝜓 𝜕2𝜓

Extending it to three dimensions, we have 𝑖ℏ 𝜕𝑡 = − ( 𝜕𝑥 2 + + )+ 𝑉𝜓
2𝑚 𝜕𝑦 2 𝜕𝑧 2

𝜕2 𝜕2 𝜕2
As ∇2 = + +
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2

𝝏𝝍 ℏ𝟐
The above equation can be written as 𝒊ℏ =− 𝛁𝟐𝝍 + 𝑽 𝝍
𝝏𝒕 𝟐𝒎

V Semester B.Sc., Physics Dr. K S Suresh Page 4

Unit 3 - Quantum mechanics – II

Time independent schrodinger’s equation : (Steady state equation)

𝜕𝜓 ℏ2 𝜕2𝜓
The Schrodinger time dependent equation is given by 𝑖ℏ 𝜕𝑡 = − + 𝑉 𝜓 …(1)
2𝑚 𝜕𝑥 2

In the above equation, potential energy depends both on position and time. The
Schrodinger equation in which potential energy of the system is independent of time
and varies only with the position is called the steady state equation or time
independent Schrodinger equation. This equation can be arrived at using separation
of variables as given below. The one dimensional wave function of an unrestricted
particle can be written in the form
𝑖 𝑖 𝑖
( 𝐸𝑡− 𝑝𝑥 𝑥) − ( 𝐸)𝑡 ( 𝑝𝑥 )𝑥
𝜓 = 𝐴 𝑒− ℏ or 𝜓=𝐴𝑒 ℏ 𝑒 ℏ

𝑖 𝑖
− ( 𝐸)𝑡
or 𝜓 = 𝜓0 𝑒 ℏ …..(2) where, we assume 𝜓0 = 𝐴 𝑒 (ℏ 𝑝𝑥 )𝑥

Equation (2) shows that 𝜓 is the product of position dependent function 𝜓0 and a
𝑖
time dependent function 𝑒 − (ℏ 𝐸)𝑡 .

Differentiating equation (2) with respect to time t, we get

𝑖
𝜕𝜓 𝑖𝐸
= (− ) 𝜓0 𝑒 − (ℏ𝐸)𝑡 ….(3)
𝜕𝑡 ℏ

𝑖
𝜕𝜓 𝜕𝜓0
Differentiation equation (2) with respect to 𝑥, = 𝑒 − (ℏ𝐸)𝑡
𝜕𝑥 𝜕𝑥

𝑖
𝜕2𝜓 𝜕2 𝜓0
Differentiating the above equation again, = 𝑒 − (ℏ𝐸)𝑡 ….. (4)
𝜕𝑥 2 𝜕𝑥 2

By substituting equations (3) and (4) in (1), we get, we get

𝑖 𝑖 𝑖
𝑖𝐸 ℏ2 𝜕2 𝜓0
𝑖ℏ (− ) 𝜓0 𝑒 − (ℏ𝐸)𝑡 = − 𝑒 − (ℏ𝐸)𝑡 + 𝑉 𝜓0 𝑒 − (ℏ 𝐸)𝑡
ℏ 2𝑚 𝜕𝑥 2

Cancelling the exponential terms on either side of the above equation, we get

ℏ2 𝜕2 𝜓0 𝜕2 𝜓0 2𝑚
𝐸 𝜓0 = − + 𝑉 𝜓0 Rearranging + (𝐸 − 𝑉) 𝜓0 = 0 .
2𝑚 𝜕𝑥 2 𝜕𝑥 2 ℏ2

𝒅𝟐 𝝍 𝟐𝒎
The above equation in general can be written as + (𝑬 − 𝑽) 𝝍 = 𝟎
𝒅𝒙𝟐 ℏ𝟐

This is the steady state form of Schrodinger’s equation or the time independent
Schrodinger’s equation. In three dimensions, the above equation is written as

𝟐𝒎 𝟖 𝝅𝟐 𝒎
𝛁𝟐𝝍 + (𝑬 − 𝑽) 𝝍 = 𝟎 or 𝛁 𝟐 𝝍 + (𝑬 − 𝑽) 𝝍 = 𝟎
ℏ𝟐 𝒉𝟐

V Semester B.Sc., Physics Dr. K S Suresh Page 5

Unit 3 - Quantum mechanics – II

ℎ
Where ℏ is expressed as ℏ = .
2𝜋

Operators in quantum mechanics

An operator is a mathematical rule (or procedure) operating on one function
transforms it into another function. For example an operator like differential d/dx
operated on a function x3 results in another function 3x2.

In quantum mechanics each dynamic variable is represented by an operator. An

operator (α) is said to be an linear operator if 𝛼(𝜓1 + 𝜓2 ) = 𝛼 𝜓1 + 𝛼 𝜓2 and
𝛼(𝑎𝜓) = 𝑎𝛼𝜓 . An operator α acting on any two wave functions 𝜓1 𝑎𝑛𝑑 𝜓2 is said
to be Hermitian, if ∫ 𝜓1∗ (𝛼𝜓2 ) 𝑑𝜏 = ∫ 𝜓2 (𝛼𝜓1 )∗ 𝑑𝜏 .

An operator when applied to a wave function gives the corresponding observable

quantity of the system multiplied by the wave function.
𝑖
( 𝑝𝑥 𝑥−𝐸𝑡)
1. The wave function is 𝜓 = 𝐴 𝑒ℏ . Differentiating this equation with
𝑖
𝜕𝜓 ( 𝑝𝑥 𝑥−𝐸𝑡) 𝑖 𝑝𝑥 𝑖𝑝𝑥
respect to x, we get = 𝐴𝑒 ℏ ( ) = ( ) 𝜓 . simplifying, we get
𝜕𝑥 ℏ ℏ
ℏ 𝜕𝜓 𝜕𝜓
𝑝𝑥 𝜓 = ( 𝑖 ) 𝜕𝑥 or 𝑝𝑥 𝜓 = −𝑖ℏ 𝜕𝑥 . This equation shows that 𝑝𝑥 is the
𝝏
momentum operator given by 𝒑𝒙 = −𝒊ℏ 𝝏𝒙 and when operated on 𝜓 gives
𝜕
𝑝𝑥 (𝜓) = −𝑖ℏ 𝜕𝑥 (𝜓). The observable quantity here is the linear momentum 𝑝𝑥
multiplied by the wave function 𝜓.
𝑖
( 𝑝𝑥 𝑥−𝐸𝑡)
2. The wave function is 𝜓 = 𝐴 𝑒ℏ . Differentiating with respect to time
𝜕𝜓 𝑖𝐸 𝜕𝜓 𝜕
= (− )𝜓 or 𝐸 𝜓 = 𝑖ℏ 𝜕𝑡 . Here the operator is 𝐸 = 𝑖ℏ 𝜕𝑡 . The
𝜕𝑡 ℏ
observable quantity is the total energy E multiplied by the wave function 𝜓.

The table below gives list of operators used in quantum mechanics

Operator (quantity) Classical Quantum operator

definition
Position R r
Linear momentum P −𝑖ℏ 𝜕𝑥 or
𝜕
−𝑖ℏ∇
Angular momentum r ×p −𝑖ℏ(𝑟 × ∇)
Kinetic energy 𝑝2 ℏ2
− 2𝑚 ∇2
2𝑚
Potential energy V V
Total energy (time E 𝜕
𝑖ℏ 𝜕𝑡
dependent)
Hamiltonian (time 𝐻 = 𝑝2
+𝑉
ℏ2
− 2𝑚 ∇2 + V
independent) 2𝑚

V Semester B.Sc., Physics Dr. K S Suresh Page 6

Unit 3 - Quantum mechanics – II

Eigenvalues and Eigenfunctions

If an operator 𝐴̃ operating on a function 𝜓(𝑥) multiplies the latter by a constant ,

then 𝜓(𝑥) is called the eigen function of 𝐴̃ belonging to the eigen value .

A set of eigen values 𝜆𝑛 and a set of eigen functions 𝜓𝑛 (𝑥) belong to an operator 𝐴̃ ,
then 𝐴̃ 𝜓𝑛 (𝑥) = 𝜆𝑛 𝜓𝑛 (𝑥) . This equation is referred to as an eigen value equation.

Hence eigen functions 𝜓𝑛 (𝑥) are a set of functions which when operated by an
operator 𝐴̃ remains unchanged and are multiplied by the corresponding eigen values
𝜆𝑛 . (eigen means proper or characteristic)

𝑑2 𝑑2
Example : If 𝐴̃ = and 𝜓(𝑥) = 𝛼 𝑒 −2𝑥 , then 𝐴̃ 𝜓(𝑥) = (𝛼 𝑒 −2𝑥 ) = 4𝛼 𝑒 −2𝑥 or
𝑑𝑥 2 𝑑𝑥 2
𝐴̃ 𝜓(𝑥) = 4𝜓(𝑥) where 4 is the eigen value and 𝜓(𝑥) is the eigen function.

The wave function for a given physical system contains the measurable information
about the system. To obtain specific values for physical parameters, for example
energy, you operate on the wave function with the quantum mechanical operator
associated with that parameter. The operator associated with energy is the
Hamiltonian, and the operation on the wave function is the Schrodinger equation.
Solutions exist for the time independent Schrodinger equation only for certain values
of energy, and these values are called "eigenvalues" of energy.
Corresponding to each eigenvalue is an "eigen function". The solution to the
Schrodinger equation for a given energy Ei involves also finding the specific
function 𝜓𝑖 which describes that energy state.
𝜕𝜓 ℏ2 𝜕2𝜓
The Schrodinger’s wave equation is 𝑖ℏ 𝜕𝑡 = − + 𝑉𝜓
2𝑚 𝜕𝑥 2

ℏ2 𝜕2 𝜕
where − + 𝑉 = 𝐻𝑜𝑝 is the Hamiltonian which is the operator and 𝑖ℏ 𝜕𝑡 = 𝐸
2𝑚 𝜕𝑥 2
is the energy eigen value. Thus the above equation can be written as 𝐻𝑜𝑝 𝜓𝑖 = 𝐸𝑖 𝜓𝑖
which is the solution of the time independent Schrodinger equation.

The eigenvalue concept is not limited to energy. When applied to a general operator
Q, it can take the form

If the function 𝜓𝑖 is an eigen function for that operator, the eigenvalues qi may be
discrete, and in such cases we can say that the physical variable is "quantized" and
that the index i plays the role of a "quantum number" which characterizes that state.

V Semester B.Sc., Physics Dr. K S Suresh Page 7

Unit 3 - Quantum mechanics – II

Degeneracy : In quantum mechanics, an energy level is said to be degenerate if it

corresponds to two or more different measurable states of a quantum system.
Conversely, two or more different states of a quantum mechanical system are said to
be degenerate if they give the same value of energy upon measurement. The number
of different states corresponding to a particular energy level is known as the degree
of degeneracy of the level. It is represented mathematically by the Hamiltonian for
the system having more than one linearly independent eigenstate with the same
eigenvalue

Expectation values of dynamical variables

To relate a quantum mechanical calculation to an observation made in the
laboratory, the "expectation value" of the measurable parameter is calculated. For the
position x, the expectation value is defined as

This integral can be interpreted as the average value of x that we would expect to
obtain from a large number of measurements. Alternatively it could be viewed as the
average value of position for a large number of particles which are described by the
same wave function. For example, the expectation value of the radius of the electron
in the ground state of the hydrogen atom is the average value you expect to obtain
from making the measurement for a large number of hydrogen atoms.
While the expectation value of a function of position has the appearance of an
average of the function, the expectation value of momentum involves the
representation of momentum as a quantum mechanical operator.
+∞
The expectation value of momentum is given by 〈𝑝〉 = ∫−∞ 𝜓 ∗ (−𝑖ℏ∇)𝜓 𝑑𝑉

+∞ 𝜕
The expectation value of energy is given by 〈𝐸〉 = ∫−∞ 𝜓 ∗ (𝑖ℏ ) 𝜓 𝑑𝑉
𝜕𝑡

+∞
The expectation value of position variable is 〈𝑥〉 = ∫−∞ 𝜓 ∗ 𝑥 𝜓 𝑑𝑉 .

The Postulates of Quantum Mechanics

1. Associated with any particle moving in a conservative field of force is a wave
function which determines everything that can be known about the system.
2. With every physical observable q there is associated an operator Q, which
when operating upon the wave function associated with a definite value of
that observable will yield that value times the wave function.
3. Any operator Q associated with a physically measurable property q will be
Hermitian.

V Semester B.Sc., Physics Dr. K S Suresh Page 8

Unit 3 - Quantum mechanics – II

4. The set of eigen functions of operator Q will form a complete set of linearly
independent functions.
5. For a system described by a given wave function, the expectation value of any
property q can be found by performing the expectation value integral with
respect to that wave function.
6. The time evolution of the wave function is given by the time dependent
Schrodinger equation.

Applications of Schrodinger’s wave equation

1. Free particle
A free particle is one which is subject to no forces of any kind. Thus it moves in a
region of constant potential. The particle motion is confined to x – direction only. Let
the potential be considered as zero i.e. V = 0.

𝑑2 𝜓 2𝑚
The time independent Schrodinger’s equation is + (𝐸 − 𝑉)𝜓 = 0
𝑑𝑥 2 ℏ2

𝑑2 𝜓 2𝑚 𝑑2 𝜓
As V = 0, thus + ( ℏ2 𝐸) 𝜓 = 0 ....(1) or + 𝑘2 𝜓 = 0 ……….(2)
𝑑𝑥 2 𝑑𝑥 2
2𝑚 √2𝑚𝐸
where 𝑘 2 = 𝐸 or 𝑘 =
ℏ2 ℏ

The solution of the equation (2) is 𝜓 = 𝐴𝑒 𝑖𝑘𝑥 + 𝐵𝑒 −𝑖𝑘𝑥 .......(3)

Let B = 0, then the above equation becomes 𝜓 = 𝐴𝑒 𝑖𝑘𝑥 .....(4)

Equation (4) describes a particle moving in the positive x – direction.

A free particle in an ideal condition has infinite length. There are no boundaries.
+∞
To normalize the wave function, consider the equation ∫−∞ 𝜓 ∗ 𝜓 𝑑𝑥 = 1.
+∞
Substituting for the wave function ∫−∞ 𝐴𝑒 −𝑖𝑘𝑥 𝐴𝑒 𝑖𝑘𝑥 𝑑𝑥 = 1.
+∞ +∞
This equation becomes ∫−∞ 𝐴2 𝑑𝑥 = 1 or 𝐴2 ∫−∞ 𝑑𝑥 = 1
+∞
∫−∞ 𝑑𝑥 is infinite. Thus A must be zero. This difficulty arises since we are
considering an ideal case of infinite length. But in practice, the particle is confined to
a finite length so that normalization is possible. For a free particle, there is no
restriction on the energy. Generally, for bound systems like electron trapped in an
atom, the energies are discrete. But the unbound systems like free particle will give
continuum energy.

The probability density for the particle is 𝜓 ∗ 𝜓 = 𝐴2 , a constant independent of x.

Consequently the particle is equally likely to be found any where. So we have an
V Semester B.Sc., Physics Dr. K S Suresh Page 9
Unit 3 - Quantum mechanics – II

infinite amount of uncertainty in its position i.e. ∆𝑥 = ∞. According to the

ℏ
uncertainty expression ∆𝑥 ∆𝑝𝑥 ≥ , ∆𝑝 must be zero.
2

+∞ 𝜕 +∞
Let us prove this, 〈𝑝〉 = ∫−∞ 𝜓 ∗ (−𝑖ℏ 𝜕𝑥) 𝜓 𝑑𝑥 = ℏ𝑘 ∫−∞ 𝜓 ∗ 𝜓 𝑑𝑥 = ℏ𝑘 .

From the above relation it is clear that 〈𝑝〉 is positive, ie the particle has momentum
exactly ℏ𝑘 and is moving towards right.

+∞ 𝜕2 +∞
〈𝑝2 〉 = ∫−∞ 𝜓 ∗ (−ℏ2 ) 2 𝜓 𝑑𝑥 = −ℏ2 (−𝑘 2 ) ∫−∞ 𝜓 ∗ 𝜓 𝑑𝑥 = ℏ2 𝑘 2
𝜕𝑥

∴ (∆𝑝)2 = 〈𝑝2 〉 − 〈𝑝〉2 = 0. Thus the momentum of the particle is precisely defined.

2. Particle in a one dimensional box (particle in a infinite potential

well)
Consider a particle of mass m trapped in a one
dimensional box of length L. The walls are of V=0
infinite potential energy. The particle is restricted to V=∞ V=∞
𝜓≠0
move inside the box between x = 0 and x = L.
𝜓=0 𝜓=0
The particle does not lose energy when it collides
with the walls of the box, so that its total energy
X=0 x=L
remains constant.

The potential energy V of the particle is 𝑉 = 0 𝑓𝑜𝑟 0 <𝑥 <𝐿.

The wave function 𝜓 is 𝜓 ≠ 0 𝑓𝑜𝑟 0 <𝑥 <𝐿

𝜓=0 𝑓𝑜𝑟 𝑥 ≤ 0 𝑎𝑛𝑑 𝑥 ≥ 𝐿.

These are the boundary conditions. The particle cannot exist outside the box as it
cannot have infinite amount of energy.

From the steady state Schrodinger wave equation in one dimension (time
independent wave equation), we have

𝑑2 𝜓 2𝑚
+ (𝐸 − 𝑉)𝜓 = 0 …………(1)
𝑑𝑥 2 ℏ2

𝑑2 𝜓 2𝑚
As V = 0 inside the box, we have + ( ℏ2 𝐸) 𝜓 = 0
𝑑𝑥 2

𝑑2 𝜓 2𝑚 √2𝑚𝐸
or + 𝑘2 𝜓 = 0 ……….(2) where 𝑘 2 = 𝐸 or 𝑘 =
𝑑𝑥 2 ℏ2 ℏ

The general solution of equation (2) is of the form

V Semester B.Sc., Physics Dr. K S Suresh Page 10
Unit 3 - Quantum mechanics – II

√2𝑚𝐸 √2𝑚𝐸
𝜓 = 𝐴 𝑠𝑖𝑛𝑘𝑥 + 𝐵 𝑐𝑜𝑠𝑘𝑥 or 𝜓 = 𝐴 𝑠𝑖𝑛 ( )𝑥 + 𝐵 𝑐𝑜𝑠 ( )𝑥 …..(3)
ℏ ℏ

where A and B are the constants to be evaluated using boundary conditions.

Expression for Energy eigen value

Applying the first boundary condition 𝜓 = 0 𝑎𝑡 𝑥 = 0 to equation (3)

√2𝑚𝐸 √2𝑚𝐸
0 = 𝐴 𝑠𝑖𝑛 ( ) × 0 + 𝐵 𝑐𝑜𝑠 ( ) × 0 or 𝐵=0.
ℏ ℏ

√2𝑚𝐸
Now the equation (3) can be written as 𝜓 = 𝐴 𝑠𝑖𝑛 ( )𝑥 ……(4)
ℏ

Applying the second boundary condition 𝜓 = 0 𝑎𝑡 𝑥 = 𝐿 and 𝐵 = 0,

√2𝑚𝐸
Now the equation (3) becomes 0 = 𝐴 𝑠𝑖𝑛 ( )𝐿
ℏ

√2𝑚𝐸
As 𝐴 ≠ 0 , thus 𝑠𝑖𝑛 ( )𝐿 =0.
ℏ

√2𝑚𝐸𝑛 √2𝑚𝐸𝑛 𝑛𝜋
This implies 𝐿 = 𝑛 𝜋 …..(5) or =
ℏ ℏ 𝐿

2𝑚𝐸𝑛 𝑛2 𝜋 2 𝑛 2 𝜋 2 ℏ2 𝑛2 ℎ 2 ℎ
Squaring the above equation = or 𝐸𝑛 = = where ℏ =
ℏ2 𝐿2 2𝑚𝐿2 8𝑚𝐿2 2𝜋

𝒏𝟐 𝒉 𝟐
The energy of the particle in a one dimensional box is 𝑬𝒏 = .
𝟖𝒎𝑳𝟐

The above equation indicates that the energy of the particle can have only certain
values which are called eigen values. These eigen values constitute the energy levels
of the system. For different levels the eigen values are

ℎ2 4 ℎ2 9ℎ2
𝑓𝑜𝑟 𝑛 = 1 𝐸1 = , 𝑓𝑜𝑟 𝑛 = 2 𝐸2 = , 𝑓𝑜𝑟 𝑛 = 3 𝐸3 = etc….
8𝑚𝐿2 8𝑚𝐿2 8𝑚𝐿2

The energy corresponding to n = 1 is called the ground state energy. The other
energies are called the excited state energies.

Expression for Eigen function

The wave function for particle in a box is given by substituting B = 0 in equation (3)
√2𝑚𝐸𝑛
𝜓𝑛 = 𝐴 𝑠𝑖𝑛 ( )𝑥 ………(6)
ℏ

√2𝑚𝐸𝑛 √2𝑚𝐸𝑛 𝑛𝜋
Also from equation (5) 𝐿= 𝑛𝜋 or = …….(7)
ℏ ℏ 𝐿

𝒏𝝅
Thus from (6) and (7) , we get 𝝍𝒏 = 𝑨 𝒔𝒊𝒏 ( 𝑳 ) 𝒙 ……….(8)

Equation (7) gives the Eigen function corresponding to energy eigen value En.
V Semester B.Sc., Physics Dr. K S Suresh Page 11
Unit 3 - Quantum mechanics – II

Normalization of wave function – To find constant A

+∞
From the normalization condition ∫−∞ |𝜓|2 𝑑𝑥 = 1 ……(9)

As the particle is confined to a one dimensional box, the limits are x = 0 to x = L .

𝐿 𝑛𝜋 2
Thus substituting for 𝜓 from (8) in (9), we get ∫0 |𝐴 𝑠𝑖𝑛 ( 𝐿 ) 𝑥| 𝑑𝑥 = 1

𝐿 𝑛𝜋 𝐴2 𝐿 𝑛𝜋
or ∫0 𝐴2 𝑠𝑖𝑛2 ( 𝐿 ) 𝑥𝑑𝑥 = 1. This equation can be written as ∫0 2 𝑠𝑖𝑛2 ( 𝐿 ) 𝑥𝑑𝑥 = 1
2

𝐴2 𝐿 2𝑛𝜋
or ∫0 [1 − 𝑐𝑜𝑠 ( ) 𝑥] 𝑑𝑥 = 1 ( ∵ 2𝑠𝑖𝑛2 𝜃 = 1 − 𝑐𝑜𝑠2𝜃 )
2 𝐿

2𝜋𝑛 𝐿
𝐴2 sin( )𝑥
Integrating the above equation, [𝑥 − 𝐿
2𝜋𝑛 ] =1
2 ( )
𝐿 0

𝐴2 𝐴2 𝐿 2
[(𝐿 − 0) − 0] = 1 or =1 or 𝐴 = √𝐿
2 2

Thus the normalizes wavefunction of a particle in a one dimensional box is given by

𝟐 𝒏𝝅
𝝍𝒏 = √ 𝒔𝒊𝒏 ( ) 𝒙
𝑳 𝑳

The Eigen functions corresponding to the states n = 1, 2, 3, ….. are

2 𝜋 2 2𝜋 2 3𝜋
𝜓1 = √𝐿 𝑠𝑖𝑛 ( 𝐿 ) 𝑥 , 𝜓2 = √𝐿 𝑠𝑖𝑛 ( 𝐿 ) 𝑥 , 𝜓3 = √𝐿 𝑠𝑖𝑛 ( 𝐿 ) 𝑥 etc……..

These functions are

identical with the 𝜓3 𝜓32
allowed amplitude
E3 E3
functions for the
stationary waves in a 𝜓2 𝜓22
vibrating string fixed
E2 E2
at both the ends.
𝜓1 𝜓12
The energy levels,
corresponding wave E1 E1
X=0 x=L X=0 x=L
functions and the
probability densities for the first three states are as shown in the graph.

Schrodinger’s equation for a particle in a three dimensional box

Consider a particle of mass m which is restricted to move in a box with sides a, b and
c. The potential function V(x,y,z) is equal to zero inside the box.

V Semester B.Sc., Physics Dr. K S Suresh Page 12

Unit 3 - Quantum mechanics – II

i.e. 𝑉 = 0 𝑓𝑜𝑟 0 < 𝑥 < 𝑎 and 𝑉 = 0 𝑓𝑜𝑟 0 < 𝑥 < 𝑏 and 𝑉 = 0 𝑓𝑜𝑟 0 < 𝑥 < 𝑐

The potential outside the box is infinite. The Schrodinger’s time independent wave
equation for particle inside the box is

𝜕2𝜓 𝜕2𝜓 𝜕2𝜓 2𝑚

+ + 𝜕𝑧 2 + 𝐸 𝜓 = 0 .....(1)
𝜕𝑥 2 𝜕𝑦 2 ℏ2

This equation can be solved by the method of separation of variables. Assuming that
function 𝜓 can be written as product of three functions X, Y and Z,

𝜓(𝑥, 𝑦, 𝑧) = 𝑋(𝑥) 𝑌(𝑦) 𝑍(𝑧) ......(2)

Each function depends on only one of the co-ordinates

𝜕2𝜓 𝜕2𝜓 𝜕2𝜓

= 𝑋 ′′ 𝑌 𝑍 , = 𝑋 𝑌 ′′ 𝑍 and = 𝑋 𝑌 𝑍 ′′
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2

Substituting the above in equation (1) and dividing by XYZ , we get

𝑋 ′′ 𝑌 ′′ 𝑍 ′′ 2𝑚𝐸
+ + + =0 .....(3)
𝑋 𝑌 𝑍 ℏ2

Each variable is independent. For this equation to be valid, each term in equation (3)
must be equal to a constant. Thus

𝑋 ′′ 𝑌 ′′ 𝑍 ′′
= − 𝛼2 , = −𝛽 2 and = − 𝛾2 .....(3a)
𝑋 𝑌 𝑍

2𝑚𝐸
Now equation (3) becomes 𝛼 2 + 𝛽 2 + 𝛾 2 = ℏ2

𝑑2 𝜓 𝑑2 𝜓
The equations (3a) can be written as + 𝛼2 𝑋 = 0 , .....(4) + 𝛽 2 𝑌 = 0 ....(5)
𝑑𝑥 2 𝑑𝑦 2
𝑑2 𝜓 Y
and + 𝛾 2 𝑍 = 0 .....(6) c
𝑑𝑧 2

The general solutions of equations (4), (5) and (6) are

b
𝑋 = 𝐴1 𝑠𝑖𝑛𝛼𝑥 + 𝐵1 𝑐𝑜𝑠𝛼𝑥
X
𝑌 = 𝐴2 𝑠𝑖𝑛𝛽𝑦 + 𝐵2 𝑐𝑜𝑠𝛽𝑦 ......(7a)
a
𝑍 = 𝐴3 𝑠𝑖𝑛𝛾𝑧 + 𝐵3 𝑐𝑜𝑠𝛾𝑧 Z

Applying the boundary conditions, i.e. 𝜓 = 0 at the boundary walls at which V = ∞

𝜓(0, 𝑦, 𝑧) = 𝜓 (𝑥, 0, 𝑧) = 𝜓 (𝑥, 𝑦, 0) = 0 ....(7b)

and 𝜓(𝑎, 𝑦, 𝑧) = 𝜓 (𝑥, 𝑏, 𝑧) = 𝜓 (𝑥, 𝑦, 𝑐) = 0 .....(7c)

Applying the boundary condition (7b) to (7a) we get 𝐵1 = 𝐵2 = 𝐵3 = 0

V Semester B.Sc., Physics Dr. K S Suresh Page 13

Unit 3 - Quantum mechanics – II

𝑛𝑥 𝜋
Applying condition (7c) in (7a) we get 𝑠𝑖𝑛𝛼𝑎 = 0 𝑜𝑟 𝛼𝑎 = 𝑛𝑥 𝜋 𝑜𝑟 𝛼 = 𝑎

𝑛𝑦 𝜋 𝑛𝑧 𝜋
Similarly 𝛽 = and 𝛾= where 𝑛𝑥 , 𝑛𝑦 and 𝑛𝑧 are the integers.
𝑏 𝑐

𝑛𝑥 𝜋𝑥 𝑛𝑦 𝜋𝑦 𝑛𝑧 𝜋𝑧
Equations (7a) becomes 𝑋 = 𝐴1 𝑠𝑖𝑛 , 𝑌 = 𝐴2 𝑠𝑖𝑛 and 𝑍 = 𝐴3 𝑠𝑖𝑛
𝑎 𝑏 𝑐

Substituting these values in equation (2) we get

𝑛𝑥 𝜋𝑥 𝑛𝑦 𝜋𝑦 𝑛𝑧 𝜋𝑧 𝑛𝑥 𝜋𝑥 𝑛𝑦 𝜋𝑦 𝑛𝑧 𝜋𝑧
𝜓(𝑥, 𝑦, 𝑧) = 𝐴1 𝐴2 𝐴3 𝑠𝑖𝑛 𝑠𝑖𝑛 𝑠𝑖𝑛 = 𝐴 𝑠𝑖𝑛 𝑠𝑖𝑛 𝑠𝑖𝑛
𝑎 𝑏 𝑐 𝑎 𝑏 𝑐

where a is the normalization constant. A can be found using normalization condition

𝑎 𝑏 𝑐
∫0 ∫0 ∫0 𝜓 𝜓 ∗ 𝑑𝑥 𝑑𝑦 𝑑𝑧 = 1

𝑎 𝑏 𝑐 𝑛𝑥 𝜋𝑥 𝑛𝑦 𝜋𝑦 𝑛𝑧 𝜋𝑧
or ∫0 ∫0 ∫0 𝑠𝑖𝑛2 ( ) 𝑠𝑖𝑛2 ( ) 𝑠𝑖𝑛2 ( ) 𝑑𝑥 𝑑𝑦 𝑑𝑧 = 1
𝑎 𝑏 𝑐

𝑎𝑏𝑐 2√2
This results in 𝐴2 2 2 2 = 1 or 𝐴=
√𝑎𝑏𝑐

8 𝑛𝑥 𝜋𝑥 𝑛𝑦 𝜋𝑦 𝑛𝑧 𝜋𝑧
The normalizes wave function is 𝜓(𝑥, 𝑦, 𝑧) = √𝑎𝑏𝑐 𝑠𝑖𝑛 𝑠𝑖𝑛 𝑠𝑖𝑛 ....(8)
𝑎 𝑏 𝑐

2𝑚𝐸
As 𝛼 2 + 𝛽 2 + 𝛾 2 = ℏ2

2 𝜋2 2 𝜋2
𝑛𝑥 𝑛𝑦 𝑛𝑧2 𝜋 2 2𝑚𝐸
Substituting for 𝛼, 𝛽 𝑎𝑛𝑑 𝛾 in the above equation, we get + + =
𝑎2 𝑏2 𝑐2 ℏ2

2
ℏ2 𝜋 2 𝑛2 𝑛𝑦 𝑛𝑧2
Simplifying, 𝐸𝑛𝑥 𝑛𝑦 𝑛𝑧 = [𝑎𝑥2 + 𝑏2 + ] ……….(8)
2𝑚 𝑐2

ℏ2 𝜋 2
For a cubical system = 𝑏 = 𝑐 , thus 𝐸𝑐𝑢𝑏𝑒 = [𝑛𝑥2 + 𝑛𝑦2 + 𝑛𝑧2 ]
2𝑚𝑎2

For the ground state, energy values are found by putting 𝑛𝑥 = 𝑛𝑦 = 𝑛𝑧 = 1 .

3ℏ2 𝜋 2
Thus 𝐸111 = . There is only one set of quantum numbers that gives this energy
2𝑚𝑎2
state and this level is said to be non-degenerate.

For the first excited state, there are three possibilities 𝑛𝑥 = 2, 𝑛𝑦 = 𝑛𝑧 = 1 and

𝑛𝑦 = 2, 𝑛𝑥 = 𝑛𝑧 = 1 and 𝑛𝑧 = 2, 𝑛𝑥 = 𝑛𝑦 = 1

3ℏ2 𝜋 2
This results in the equation 𝐸211 = 𝐸121 = 𝐸112 = .
𝑚𝑎2

In this case there are three sets (211), (121) and (112) of the quantum numbers nx, ny
and nz that will give the same energy level. i.e. several distinct quantum states

V Semester B.Sc., Physics Dr. K S Suresh Page 14

Unit 3 - Quantum mechanics – II

possess the same energy level. This property is called degeneracy. In this case the
level is triply degenerate.

Equation (8) indicates that the energy value of a particle in a box (infinitely deep
potential well) are not continuous but discrete. The particle has different bound
states inside the potential well.

3. One dimensional linear harmonic oscillator (LHO)

If a system vibrates about an equilibrium position such that (a) the magnitude of the
force acting on it is directly proportional to displacement from the equilibrium
position and (b) the direction of the force is opposite to that of displacement, then it
is called linear harmonic oscillator.

Let x be the displacement of a particle of mass m, at any instant of time t, during its
vibration, then the restoring force is directly proportional to the displacement.

i.e. 𝐹 ∝ 𝑥 or 𝐹 = −𝑘𝑥 .....(1) where k is a constant. From Newton’s second

𝑑2 𝑥 𝑑2 𝑥
law, = 𝑚𝑎 = 𝑚 𝑑𝑡 2 . Thus 𝑚 𝑑𝑡 2 = −𝑘𝑥

𝑑2 𝑥 𝑘 𝑑2 𝑥 𝑘
or + 𝑥= 0 or + 𝜔2 𝑥 = 0 .....(2) where 𝜔2 = , 𝜔 is called
𝑑𝑡 2 𝑚 𝑑𝑡 2 𝑚
the angular frequency given by 𝜔 = 2𝜋𝜈 .
𝑑𝑉(𝑥)
The restoring force is given by 𝐹 = − where 𝑉(𝑥) is the potential energy of
𝑑𝑥
𝑑𝑉(𝑥)
the particle. Substituting for F in equation (1), we get − = −𝑘𝑥 ....(3)
𝑑𝑥

𝑥 𝑑𝑉(𝑥) 𝑥 1
Integration equation (3) ∫0 − = − ∫0 −𝑘𝑥 𝑑𝑥 Thus 𝑉(𝑥) = 𝑘𝑥 2 ....(4)
𝑑𝑥 2

1
As 𝑘 = 𝑚𝜔2, equation (4) can be written as 𝑉(𝑥) = 𝑚𝜔2 𝑥 2 ....(5)
2

From the Schrodinger time independent equation, we have

ℏ2 𝑑 2 𝜓 𝑑2 𝜓 2𝑚
− + 𝑉(𝑥) = 𝐸 𝜓 or + (𝐸 − 𝑉(𝑥)) 𝜓 = 0 ........(6)
2𝑚 𝑑𝑥 2 𝑑𝑥 2 ℏ2

𝑑2 𝜓 2𝑚 1
Substituting for 𝑉(𝑥) from (5) in (6), we get + (𝐸 − 2 𝑚𝜔2 𝑥 2 ) 𝜓 = 0
𝑑𝑥 2 ℏ2

𝑑2 𝜓 2𝑚𝐸 𝑚2 𝜔 2
Simplifying the above equation, + 𝜓− ( ) 𝑥 2 𝜓 = 0 ....(7)
𝑑𝑥 2 ℏ2 ℏ2

2𝑚𝐸 𝑚2 𝜔 2 𝑚𝜔
Let = 𝛼 and = 𝛽2 or =𝛽
ℏ2 ℏ2 ℏ

𝑑2 𝜓
Thus the Schrodinger’s equation is + (𝛼 − 𝛽 2 𝑥 2 ) 𝜓 = 0 ….(8)
𝑑𝑥 2

V Semester B.Sc., Physics Dr. K S Suresh Page 15

Unit 3 - Quantum mechanics – II

𝑦2
Let an independent variable be introduced as y given by 𝑦 = √𝛽 𝑥 or 𝑥 2 = 𝛽

𝑑𝜓 𝑑𝜓 𝑑𝑦 𝑑𝜓 𝑑𝑦
Also = × = × √𝛽 . (since 𝑦 = √𝛽 𝑥 𝑎𝑛𝑑 = √𝛽 )
𝑑𝑥 𝑑𝑦 𝑑𝑥 𝑑𝑦 𝑑𝑥

𝑑2 𝜓 𝑑 𝑑𝜓 𝑑 𝑑𝜓 𝑑𝑦 𝑑 𝑑𝜓 𝑑𝑦 𝑑 𝑑𝜓 𝑑𝑦 𝑑2 𝜓 𝑑𝑞
= ( ) = 𝑑𝑥 ( 𝑑𝑦 )= ( ) = 𝑑𝑦 ( 𝑑𝑦 √𝛽) 𝑑𝑥 = 𝛽 . (since 𝑑𝑥 = √𝛽 )
𝑑𝑥 2 𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑦 𝑑𝑥 𝑑𝑥 𝑑𝑦 2

𝑑2 𝜓 𝑑2 𝜓
The above equation is = 𝛽
𝑑𝑥 2 𝑑𝑦 2

Substituting the above term in equation (8), we get

𝑑2 𝜓 𝑦2 𝑑2 𝜓
𝛽 𝑑𝑦 2 + (𝛼 − 𝛽 2 ) 𝜓 = 0 or 𝛽 𝑑𝑦 2 + (𝛼 − 𝛽𝑦 2 )𝜓 = 0
𝛽

𝑑2 𝜓 𝛼
or + (𝛽 − 𝑦 2 ) 𝜓 = 0
𝑑𝑦 2

𝑑2 𝜓 𝛼 2𝐸
or + (𝜆 − 𝑦 2 ) 𝜓 = 0 ....(9) where 𝜆 = 𝛽 = ℏ𝜔 .
𝑑𝑦 2

Eigen value of LHO

2𝐸𝑛
For the acceptable solution of the above equation, 𝜆 = (2𝑛 + 1) where 𝜆 =
ℏ𝜔

2𝐸𝑛
Thus from the above equations 2𝑛 + 1 = ℏ𝜔

ℏ𝜔 𝟏
or 𝐸𝑛 = (2𝑛 + 1) or 𝑬𝒏 = (𝒏 + 𝟐) ℏ𝝎 where n = 0, 1, 2, 3, ......
2

𝟏 ℎ
or 𝑬𝒏 = (𝒏 + 𝟐) 𝒉𝝂 where ℏ𝜔 = × 2𝜋𝜈 = ℎ𝜈
2𝜋

The above equation indicates that energy eigen values are discrete that are equally
1 3 5
spaced. For n = 0, 𝐸0 = ℎ𝜈 for n = 1 𝐸1 = ℎ𝜈 for n = 2 𝐸2 = ℎ𝜈 .....
2 2 2

1
For n =0, 𝐸0 = ℎ𝜈 Here 𝐸0 is called zero point energy of the oscillator.
2

Significance of the zero point energy

According to old quantum theory, the energy of the oscillator is given by 𝐸𝑛 = 𝑛ℎ𝜈 .
For n = 0, the value of E is zero, i.e., the ground state energy of the oscillator is zero.
But from the new quantum mechanical theory of the oscillator the ground state
1
energy is not zero but is given by 𝐸0 = ℎ𝜈 . Thus a clear contradiction between the
2
two theories exist.

V Semester B.Sc., Physics Dr. K S Suresh Page 16

Unit 3 - Quantum mechanics – II

The existence of the zero point energy is consistent with the Heisenberg uncertainty
principle. The old quantum theory is not consistent with the uncertainty principle as
explained below.

If both the kinetic and the potential energy of the oscillator are zero, then the ground
state total energy of the oscillator is zero. As x = 0, ∆𝑥 = 0. Also as kinetic energy is
zero, the momentum is also zero i.e. ∆𝑝𝑥 = 0. Therefore, ∆𝑥 ∆𝑝𝑥 = 0 which is a
contradiction to uncertainty relation ∆𝑥 ∆𝑝𝑥 ≥ ℏ .

But the zero point energy of LHO according to the new quantum theory is consistent
with the uncertainty principle.

Wave functions for LHO

2 /2
The possible solution of equation (9) is 𝜓(𝑦) = 𝑒 −𝑦 𝑓(𝑦) .....(10)

Differentiating equation (10) and putting in (9), we get

𝑑2 𝑓 𝑑𝑓
− 2𝑦 𝑑𝑦 + (𝜆 − 1) 𝑓 = 0 ....(11)
𝑑𝑦 2

𝑑2 𝑓 𝑑𝑓
Writing 𝜆 − 1 = 2𝑛 above equation becomes − 2𝑦 + 2𝑛 𝑓 = 0 ….(12)
𝑑𝑦 2 𝑑𝑦

The above equation is called Hermite’s equation. The solutions of equation (12) are
𝑑𝑛
called Hermite polynomials, given by 𝐻𝑛 (𝑦) = 𝑓(𝑦) = (−1)𝑛 exp 𝑦 2 𝑑𝑦 𝑛 (𝑒𝑥𝑝(−𝑦 2 ))

Therefore the eigen function of harmonic oscillator is 𝜓𝑛 (𝑦) = 𝑁𝐻𝑛 (𝑦)𝑒𝑥𝑝(−𝑦 2 /2)

where N is the normalization constant.

The normalized general formula for the nth wave function is

2𝑚𝜈 1/4 2 /2
𝜓𝑛 = ( ) (2𝑛 𝑛!)−1/2 𝐻𝑛 (𝑦)𝑒 −𝑦
ℏ

The energy level diagram and the corresponding wave functions are plotted as
shown.

E
𝜓𝑛 𝜓𝑛2 ⬚

𝐸4
𝐸3
𝐸2
𝐸1
𝐸0 x x x

V Semester B.Sc., Physics Dr. K S Suresh Page 17

Unit 3 - Quantum mechanics – II

Characteristics of LHO
1. The energies are quantized.
2. The possibility of finding the particle outside the allowed classical range is
not zero. (Continuous curve in the above graph is the classical range)
3. For all odd states, the probability of finding the particle at the centre is zero.
4. Foa a large n, the classical and quantum position distributions are almost
same.
5. The least energy of the classical oscillator is zero but the quantum oscillator
1
has a zero point energy 𝐸0 = ℎ𝜈 according to uncertainty principle.
2

4. Hydrogen atom
A hydrogen atom has a single electron moving around a nucleus having a proton
under the action of a central force arising out of the Coulombian electrostatic
attractive force.

1 𝑍𝑒 2
The potential energy of such a system is 𝑉(𝑟) = − 4𝜋𝜀0 𝑟

The Schrodinger’s time independent equation of the this system is

8𝜋 2 𝑚
∇2 𝜓 + (𝐸 − 𝑉(𝑟))𝜓 = 0
ℎ2

In spherical polar co-ordinates, the position of the electron is given by co-ordinates r

(radius vector), 𝜃 (the polar angle) and 𝜙 (the azimuth angle) as shown.

The rectangular co-ordinates are

related to polar co-ordinates as
𝑧
𝑟 = √𝑥 2 + 𝑦 2 + 𝑧 2 , 𝜃 = cos−1 (𝑟)

𝑦
and 𝜙 = tan−1 (𝑥 ).

Also 𝑥 = 𝑟 𝑠𝑖𝑛𝜃 𝑐𝑜𝑠𝜙, 𝑦 = 𝑟 𝑠𝑖𝑛𝜃 𝑠𝑖𝑛𝜙 and 𝑧 = 𝑟 𝑐𝑜𝑠𝜃

Schrodinger’s equation in polar co-ordinates is

1 𝜕 𝜕𝜓 1 𝜕 𝜕𝜓 1 𝜕2 𝜓 8𝜋 2 𝑚
(𝑟 2 𝜕𝑟 ) + (𝑠𝑖𝑛𝜃 𝜕𝜃 ) + 𝑟 2 𝑠𝑖𝑛2 𝜃 𝜕𝜙2 + (𝐸 − 𝑉(𝑟))𝜓 = 0 ……(1)
𝑟 2 𝜕𝑟 𝑟 2 𝑠𝑖𝑛𝜃 𝜕𝜃 ℎ2

This equation can be separated by variables 𝑟 , 𝜃 and 𝜙 by substituting

𝜓(𝑟, 𝜃, 𝜙) = 𝑅(𝑟) 𝑌(𝜃, 𝜙) where R is the radial function and Y is the angular
function. Thus equation (1) can be written as

V Semester B.Sc., Physics Dr. K S Suresh Page 18

Unit 3 - Quantum mechanics – II

1 𝑑 2 𝑑𝑅 1 𝜕 𝜕𝑌 1 𝜕 2𝑌 8𝜋 2 𝑚
(𝑟 )𝑌 + 2 (𝑠𝑖𝑛𝜃 ) 𝑅 + 2 2 𝑅+ (𝐸 − 𝑉(𝑟))𝑅𝑌 = 0
𝑟 2 𝑑𝑟 𝑑𝑟 𝑟 𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑟 𝑠𝑖𝑛 𝜃 𝜕𝜙 2 ℎ2

Multiplying entire equation by 𝑟 2 /𝑅𝑌 and rearranging, we get

1 𝑑 2 𝑑𝑅 8𝜋 2 𝑚𝑟 2 1 1 𝜕 𝜕𝑌 1 𝜕 2𝑌
(𝑟 )+ (𝐸 − 𝑉(𝑟)) = − [ (𝑠𝑖𝑛𝜃 ) + ]
𝑅 𝑑𝑟 𝑑𝑟 ℎ2 𝑌 𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑠𝑖𝑛2 𝜃 𝜕𝜙 2

The LHS of the above equation depends on R and RHS depends on 𝜃 𝑎𝑛𝑑 𝜙.

For the above equation to be correct, both sides of the equation should be equal to a
constant, say 𝑙(𝑙 + 1). Thus the above equation can written as

1 𝑑 𝑑𝑅 8𝜋 2 𝑚𝑟 2
(𝑟 2 𝑑𝑟 ) + (𝐸 − 𝑉(𝑟)) = 𝑙(𝑙 + 1) …..(2)
𝑅 𝑑𝑟 ℎ2

1 1 𝜕 𝜕𝑌 1 𝜕2𝑌
− 𝑌 [𝑠𝑖𝑛𝜃 𝜕𝜃 (𝑠𝑖𝑛𝜃 𝜕𝜃) + 𝑠𝑖𝑛2 𝜃 𝜕𝜙2] = 𝑙(𝑙 + 1) …..(3)

Equation (3) can be further separated by substituting Y(𝜃, 𝜙) = (𝜃) 𝚽(𝜙). This gives

1 1 𝜕 𝜕 1 𝜕2 𝚽
−  𝚽 [𝑠𝑖𝑛𝜃 𝜕𝜃 (𝑠𝑖𝑛𝜃 𝜕𝜃 ) 𝚽 + 𝑠𝑖𝑛2 𝜃 𝜕𝜙2 ] = 𝑙(𝑙 + 1) . Multiplying this equation by𝑠𝑖𝑛2 𝜃
1 𝜕 𝜕 2 1 𝜕2𝚽
and rearranging we get 𝑠𝑖𝑛𝜃 (𝑠𝑖𝑛𝜃 ) + 𝑙(𝑙 + 1)𝑠𝑖𝑛 𝜃 = −
 𝜕𝜃 𝜕𝜃 𝚽 𝜕𝜙2

Again for this equation to be correct, both sides of the above equation should be
equal to a constant say, 𝑚𝑙2 . Thus the above equation can be written as

1 𝑑 𝑑 1 𝑑2 𝚽
𝑠𝑖𝑛𝜃 (𝑠𝑖𝑛𝜃 𝑑𝜃 ) + 𝑙(𝑙 + 1)𝑠𝑖𝑛2 𝜃 = 𝑚𝑙2 ……..(4) and − 𝚽 𝑑𝜙2 = 𝑚𝑙2 …..(5)
 𝑑𝜃

𝑑2 𝚽
Equation (5) can be written as 𝑑𝜙2 + 𝑚𝑙2 𝚽 = 0 ………(6)

The solution of equation (6) is 𝚽𝑚𝑙 (𝜙) = 𝐴𝑒 𝑖𝑚𝑙 𝜙 where 𝑚𝑙 = 0, ±1, ±2, … … and 𝑚𝑙
is called magnetic quantum number.
1
The azimuth wave function is 𝚽(𝜙) = 𝑒 𝑖𝑚𝑙 𝜙 …….(7)
√2𝜋

𝑑 𝑚𝑙2
]  = 0 ….(8)
1 𝑑
Equation (4) can be written as 𝑠𝑖𝑛𝜃 𝑑𝜃 (𝑠𝑖𝑛𝜃 𝑑𝜃 ) + [𝑙(𝑙 + 1) − 𝑠𝑖𝑛2 𝜃

The solution equation (8) is

|𝑚|
𝑙𝑚𝑙 (𝜃) = |𝑚|
𝑁𝑙𝑚𝑙 𝑃𝑙 (𝑐𝑜𝑠𝜃) where 𝑃𝑙 (𝑐𝑜𝑠𝜃) is the
associated Legendre polynomial where 𝑙 = |𝑚𝑙 |, |𝑚𝑙 + 1|, |𝑚𝑙 + 2| … … ..

or 𝑚𝑙 = 0, ±1, ±2, … … … ± 𝑙 . 𝑙 is called the orbital quantum number.

2𝑍𝑒 2 2𝑍𝑒
The solution of equation (2) is 𝑅𝑛𝑙 (𝑟) = 𝑁𝑛𝑙 𝑒 −𝑍𝑒/𝑛𝑎0 (𝑛𝑎 ) 𝐿2𝑙+1
𝑛+1 (𝑛𝑎 )
0 0

V Semester B.Sc., Physics Dr. K S Suresh Page 19

Unit 3 - Quantum mechanics – II

2𝑍𝑒
Here 𝐿2𝑙+1
𝑛+1 (𝑛𝑎 ) is the associated Laguerre polynomial.
0

ℎ 2 𝜀0
In the above equation 𝑎0 is the first Bohr radius given by 𝑎0 = and the
𝜋𝑚𝑒 2
𝑚𝑒 4
corresponding energy of the nth state is 𝐸𝑛 = − where n is called the
8𝜀02 𝑛2 ℎ2
principal quantum number given by 𝑛 = 𝑙 + 1, 𝑙 + 2, … … 𝑜𝑟 𝑙 = 0, 1, 2, 3, … (𝑛 − 1).

The total eigen function of the hydrogen atom is

𝜓𝑛𝑙𝑚𝑙 (𝑟, 𝜃, 𝜙) = 𝑅𝑛𝑙 (𝑟) 𝛉𝑙𝑚𝑙 (𝜃) 𝚽𝑚𝑙 (𝜙) . The ground state eigen function is

1 𝑍 3/2
𝜓100 = ( ) 𝑒 −𝑍𝑒/𝑎0 where Z = 1 with n = 1 and the ground state energy is 𝐸1 =
√ 𝜋 𝑎
0
𝑚𝑒 4
− . The value of E1= - 13.6 eV and for n = 2, E2 = - 3.4 eV…… The degeneracy
8𝜀02 ℎ2
of the nth state is 𝑁(𝑛) = ∑𝑛−1 2
𝑙=0 (2𝑙 + 1) = 𝑛 , where degeneracy is the number of
eigen states for a given eigen value.

5. Rigid rotator
A rigid rotator is a system of two spherical masses m1 and
m2 situated at fixed distance r1 and r2 from the centre of
mass of the system. It is capable of rotating about an axis
passing through the centre of mass and normal to the
plane containing the two particles.

If the particles can rotate in a plane then the axis of rotation is fixed and it is called
rigid rotator with fixed axis. If the axis is free to take any orientation in space, then it
is called rigid rotator with free axis.

According to classical theory, the kinetic energy of the rigid rotator is

1
𝐸= 𝐼𝜔2 … (1) where 𝐼 is the moment of inertia of the system and 𝜔 is the
2
angular frequency of rotation.

If L is the angular momentum of the system, then 𝐿 = 𝐼𝜔. Putting this in (1) we get

𝐿2
𝐸= . The moment of ineria is = 𝑚1 𝑟12 + 𝑚2 𝑟22 . Putting the definition of centre of
2𝐼
𝑚1 𝑚2
mass 𝑚1 𝑟1 = 𝑚1 𝑟1 and 𝑅 = 𝑟1 + 𝑟2 in the above equation, we get 𝐼 = 𝑚 𝑅2
1 + 𝑚2

Or 𝐼 = 𝜇 𝑅 2 where 𝜇 is the reduced mass of the system.

Wave function for the rigid rotator

The time independent Schrodinger equation is given by

V Semester B.Sc., Physics Dr. K S Suresh Page 20

Unit 3 - Quantum mechanics – II

2𝑚
∇2 𝜓 + (𝐸 − 𝑉)𝜓 = 0 . In polar co-ordinates, the equation can be written as
ℏ2

1 𝜕 𝜕𝜓 1 𝜕 𝜕𝜓 1 𝜕2 𝜓 2𝑚
(𝑟 2 𝜕𝑟 ) + (𝑠𝑖𝑛𝜃 𝜕𝜃 ) + 𝑟 2 𝑠𝑖𝑛2 𝜃 𝜕𝜙2 + (𝐸 − 𝑉)𝜓 = 0
𝑟 2 𝜕𝑟 𝑟 2 𝑠𝑖𝑛𝜃 𝜕𝜃 ℏ2

The wave function 𝜓(𝑟, 𝜃, 𝜙) is a function of , 𝜃 𝑎𝑛𝑑 𝜙 . For a rigid rotator there is no
potential energy (V = 0). Thus 𝜓 is independent of r . The above equation becomes

1 𝜕 𝜕𝜓 1 𝜕2𝜓 2𝑚
(𝑠𝑖𝑛𝜃 𝜕𝜃 ) + 𝑟 2𝑠𝑖𝑛2 𝜃 𝜕𝜙2 + 𝐸𝜓=0
𝑟 2 𝑠𝑖𝑛𝜃 𝜕𝜃 ℏ2

Rigid rotator can be visualised as equivalent to a system of one particle of mass I

situated at a distance r = 1 from the origin. In other words, rigid rotator is just like a
single particle of mass I moving on the surface of a sphere of radius unity.

By putting r = 1 and m = I, in the above equation,

1 𝜕 𝜕𝜓 1 𝜕2𝜓 2𝐼
(𝑠𝑖𝑛𝜃 )+ = − 𝐸𝜓=0 …..(1)
𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑠𝑖𝑛2 𝜃 𝜕𝜙2 ℏ2

Putting 𝜓 = 𝑌(𝜃, 𝜙) and rearranging, we get

1 𝜕 𝜕 1 𝜕2
− ℏ2 [𝑠𝑖𝑛𝜃 𝜕𝜃 (𝑠𝑖𝑛𝜃 𝜕𝜃) + 𝑠𝑖𝑛2 𝜃 𝜕𝜙2 ] 𝑌(𝜃, 𝜙) = 2𝐼𝐸 𝑌(𝜃, 𝜙)

or 𝐿2 𝑌(𝜃, 𝜙) = 2𝐼𝐸 𝑌(𝜃, 𝜙) …..(2) where 𝐿2 is the angular momentum operator.

The eigen function 𝑌𝑙𝑚 (𝜃, 𝜙) for the rigid rotator are the solutions of the equation (1)
2𝑙+1 (𝑙−𝑚)! 1/2
and are given by 𝑌𝑙𝑚 (𝜃, 𝜙) = [ ] (−1)𝑚 𝑒 𝑖𝑚𝜙 𝑃𝑙𝑚 (𝑐𝑜𝑠𝜃) with 0 ≤ 𝑚 ≤ 𝑙 .
4𝜋 (𝑙+𝑚)!

Also 𝐿2 𝑌(𝜃, 𝜙) = 𝑙(𝑙 + 1)ℏ2 𝑌(𝜃, 𝜙) ….(3)

𝑙(𝑙+1)ℏ2
Comparing (2) and (3) , 2𝐼𝐸 = 𝑙(𝑙 + 1)ℏ2 or 𝐸𝑙 = where 𝑙 = 0,1,2,3 ….
2𝐼

Thus the energy eigen values of the rigid rotator depends on l alone. For each l (l >
0), there are 2l + 1 values of m, i.e. 𝑚 = 0, ±1, ±2, … . ±𝑙. The above equation
represents the allowed energy values of the rigid rotator with free axis.

Rigid rotator with fixed axis - When the rotator is confined to rotate in the x-y plane
only, the polar angle 𝜃 = 𝜋/2 and 𝜓 does not depend on r. Now the Schrodinger’s
equation can be written as

𝑑2 𝚽 2𝐼 1 𝑑2 𝚽 2𝐼 1 𝑑2 𝚽 2𝐼
+ 𝐸𝚽=0 or =− 𝐸 or =− 𝐸 = −𝑚2 (a constant)
𝑑𝜙2 ℏ2 𝚽 𝑑𝜙2 ℏ2 𝚽 𝑑𝜙2 ℏ2

𝑑2 𝚽 2𝐼
The above equation can be written as + 𝑚2 𝚽 = 0 ….(4) where 𝑚2 = ℏ2 𝐸
𝑑𝜙2

The possible solution of equation (4) is 𝚽𝑚 = 𝐴 𝑒 𝑖𝑚𝜙 where A is a constant.

V Semester B.Sc., Physics Dr. K S Suresh Page 21

Unit 3 - Quantum mechanics – II

A can be found by normalizing the wavefunction as follows.

2𝜋 ∗ 2𝜋 2𝜋
∫0 𝚽𝑚 𝚽𝑚 𝑑𝚽 = 1 or 𝐴2 ∫0 𝑒 −𝑖𝑚𝜙 𝑒 𝑖𝑚𝜙 𝑑𝚽 = 1 or 𝐴2 ∫0 𝑑𝚽 = 1

1
Simplifying 𝐴2 2𝜋 = 1 Thus 𝐴 = . The normalized wavefunction is given by
√2𝜋
1
𝚽𝑚 = 𝑒 𝑖𝑚𝜙 .
√2𝜋

𝑚 2 ℏ2
The energy eigen value of the rigid rotator with a fixed axis is given by 𝐸𝑚 = .
2𝐼

Descriptive questions, numerical problems and conceptual

questions
PART-A
1. a) What is wave function? What are the basic properties of wave function?
b) Outline Max Born’s interpretation of wave function.
2. Arrive at Schrodinger’s time independent equation for free particle in one
dimension. Write the equation for three diemnsions.
3. (a) Explain the terms eigen value, eigen function and degeneracy.
(b) What are expectation values? Explain. Explain the concept of normalization.
4. Arrive at Schrodinger’s time dependent equation for a free particle in one
dimension and write the equation for three diemnsions.
5. Obtain the Schrodinger’s equation for a particle in a one dimensional box and
solve it to obtain the energy eigen values and eigen functions. Also represent the
first three energy eigen functions in a graph.
6. a) Derive an expression for energy eigen values of a particle trapped in one-
dimensional box of infinite depth.
b) Derive an expression for normalised wave function.
7. (a) Define expectation value of an observable in quantum mechanics. What are the
expectation values of position and momentum of a particle for a wave function?
(b) What is probability density? Give Born interpretation of wave function and
explain normalization.
8. (a) What are operators? Give two examples.
(b) Develop the Schrodinger’s equation for a free particle. Mention the eigen value
and eigen function of the free particle.
9. (a) Develop the Schrodinger’s equation for a one dimensional linear harmonic
oscillator. Mention the eigen value and eigen function of the oscillator.
10. Show that the energy of a harmonic oscillator is quantised in steps of h. Explain
the existence of zero point energy.

V Semester B.Sc., Physics Dr. K S Suresh Page 22

Unit 3 - Quantum mechanics – II

11. Develop the Schrodinger’s equation for a rigid rotator. Mention the energy eigen
values of the rotator and draw the energy level diagram.
12. Develop the Schrodinger’s equation for a hydrogen atom. Mention the energy
eigen value and eigen function for the ground state.

PART B
ℎ
ℎ = 6.625 × 10−34 𝐽𝑠, ℏ =
,
2𝜋
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 𝑚 = 9.1 × 10−31 𝑘𝑔, 1𝑒𝑉 = 1.6 × 10−19 𝐽
1. An electron is constrained in a one dimensional box of side 1 nm. Obtain the first
three eigen values in eV.
𝑛 2 ℎ2 𝑛 2 ℎ2 1
[𝐻𝑖𝑛𝑡 ∶ 𝐺𝑖𝑣𝑒𝑛: 𝐿 = 1 × 10−9 𝑚, 𝐸𝑛 = 𝐽, = × 𝑒𝑉. 𝐹𝑜𝑟 𝑛 = 1, 2, 3 𝐹𝑖𝑛𝑑 𝐸1 , 𝐸2 , 𝐸3 ]
8𝑚𝐿2 8𝑚𝐿2 1.6 ×10−19

2. An electron is confined in a one dimensional box of side 2A 0. How much energy

is required to excite the electron from the ground state to the third excited state?
[𝐻𝑖𝑛𝑡 ∶ 𝐺𝑖𝑣𝑒𝑛 𝐿 = 2 × 10−10 𝑚, 𝑛 = 1 𝑓𝑜𝑟 𝑔𝑟𝑜𝑢𝑛𝑑 𝑠𝑡𝑎𝑡𝑒, 𝑛 = 4 𝑓𝑜𝑟 𝑡ℎ𝑖𝑟𝑑 𝑒𝑥𝑐𝑖𝑡𝑒𝑑 𝑠𝑡𝑎𝑡𝑒, 𝐸𝑛 =
𝑛 2 ℎ2
, 𝐹𝑖𝑛𝑑 𝐸1 𝑓𝑜𝑟 𝑛 = 1, 𝐸4 𝑓𝑜𝑟 𝑛 = 4 𝑎𝑛𝑑 𝑐𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒 𝐸4 − 𝐸1 ]
8𝑚𝐿2

4. The eigen value of an electron confined to a one dimensional box of side 0.2 nm is
84.78 eV. What is the order of the state?
𝑛 2 ℎ2
[𝐻𝑖𝑛𝑡 ∶ 𝐺𝑖𝑣𝑒𝑛: 𝐿 = 0.2 × 10−9 𝑚, 𝐸𝑛 = 84.78 𝑒𝑉 = 84.78 × 1.6 × 10−19 𝐽, 𝐴𝑠 𝐸𝑛 = 𝐽, 𝑛 =
8𝑚𝐿2

8𝑚𝐿2 𝐸𝑛 𝐿
√ = √8𝑚𝐸𝑛 . 𝐹𝑖𝑛𝑑 𝑛 ]
ℎ2 ℎ

5. Find the momentum and energy values for an electron in a box of length 1 A 0 for
ℎ 𝑛𝜋 𝑛ℎ 𝑛 2 ℎ2
n = 2 and n = 3. [𝐻𝑖𝑛𝑡: 𝐺𝑖𝑣𝑒𝑛 𝐿 = 1 × 10−10 𝑚, 𝑝 = ℏ𝑘 =
2𝜋
×
𝐿
=
2𝐿
𝑎𝑛𝑑 𝐸𝑛 =
8𝑚𝐿2
𝐽]
6. An electron is confined to move between two rigid walls separated by 10 A0. Find
the de Broglie wavelength representing the first three allowed energy states of
the electron and the corresponding energies. [𝐻𝑖𝑛𝑡: 𝐺𝑖𝑣𝑒𝑛 𝐿 = 10 × 10−10 𝑚,
𝜆
𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑡ℎ𝑒 𝑟𝑖𝑔𝑖𝑑 𝑤𝑎𝑙𝑙𝑠 𝑚𝑢𝑠𝑡 𝑏𝑒 𝑒𝑞𝑢𝑎𝑙 𝑡𝑜 𝑖𝑛𝑡𝑒𝑔𝑟𝑎𝑙 𝑚𝑢𝑙𝑡𝑖𝑝𝑙𝑒𝑠 𝑜𝑓 ]
2
𝑛𝜆 2𝐿
[𝑇ℎ𝑢𝑠 𝐿 = 𝑜𝑟 𝜆 = . 𝐶𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒 𝜆 𝑓𝑜𝑟 𝑛 = 1, 2, 3. ]
2 𝑛
7. The third eigen value of an electron confined to a one dimensional box is 77.4 eV.
Find the size of the box.
𝑛 2 ℎ2 𝑛ℎ
[𝐻𝑖𝑛𝑡 ∶ 𝐺𝑖𝑣𝑒𝑛: 𝐸 = 77.4 𝑒𝑉 = 77.4 × 1.6 × 10−19 𝐽, 𝑛 = 3, 𝐸𝑛 = 𝑜𝑟 𝐿 = ]
8𝑚𝐿2 √8𝑚𝐸𝑛

8. The frequency of a linear harmonic oscillator is 6 × 1012 Hz. Find the energy of the
oscillator in the fourth excited state.
1
𝐻𝑖𝑛𝑡: 𝐺𝑖𝑣𝑒𝑛 𝜈 = 6 × 1012 𝐻𝑧, 𝐹𝑜𝑟 𝑓𝑜𝑢𝑟𝑡ℎ 𝑒𝑥𝑐𝑖𝑡𝑒𝑑 𝑠𝑡𝑎𝑡𝑒, 𝑛 = 4, 𝑎𝑛𝑑 𝐸𝑛 = (𝑛 + ) ℎ𝜈 𝑖𝑛 𝑗𝑜𝑢𝑙𝑒
[ 2 ]
𝐶𝑜𝑛𝑣𝑒𝑟𝑡 𝑡𝑜 𝑒𝑉
9 A particle in a 1 dimensional deep potential well of width L has a function 𝜓 =
𝑛𝜋
𝐴 𝑠𝑖𝑛 ( 𝐿 ) 𝑥 where A is a constant. Normalize the wave function and find the

V Semester B.Sc., Physics Dr. K S Suresh Page 23

Unit 3 - Quantum mechanics – II

value of A. What is the normalized wave function?

2
[𝐻𝑖𝑛𝑡: 𝑆𝑒𝑒 𝑡ℎ𝑒 𝑛𝑜𝑟𝑚𝑎𝑙𝑖𝑧𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑤𝑎𝑣𝑒 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛 𝑖𝑛 𝑐𝑎𝑠𝑒 𝑜𝑓 1 𝑑𝑖𝑚𝑒𝑛𝑠𝑖𝑜𝑛𝑎𝑙 𝑏𝑜𝑥, 𝐴 = √ 𝑎𝑛𝑑 𝜓 =
𝐿

2 𝑛𝜋
√ 𝑠𝑖𝑛 ( ) 𝑥]
𝐿 𝐿

2 𝑛𝜋
10 The wave function of a particle confined to a box of length L is 𝜓 = √𝐿 𝑠𝑖𝑛 ( 𝐿 ) 𝑥
in the region 0 < 𝑥 < 𝐿. Calculate the probability of finding the particle in the
region 0 < 𝑥 < 𝐿/2.[𝐻𝑖𝑛𝑡: 𝑃𝑟𝑜𝑏𝑎𝑏𝑖𝑙𝑖𝑡𝑦 𝑃 = ∫0𝐿/2 𝜓 ∗ 𝜓 𝑑𝑥 = 2 𝐿/2 𝜋𝑥 1
∫0 𝑠𝑖𝑛2 𝐼𝑛𝑡𝑒𝑔𝑟𝑎𝑡𝑖𝑛𝑔, 𝑃 = .]
𝐿 𝐿 2

11. The period of linear harmonic oscillator is 1 millisecond. Find its zero point
1 1
energy. [𝐻𝑖𝑛𝑡: 𝐺𝑖𝑣𝑒𝑛 𝑇 = 1 × 10−3 𝑠, 𝐹𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦 𝜈 =
𝑇
𝑎𝑛𝑑 𝐸0 =
2
ℎ𝜈 ]
12. The energy of a linear harmonic oscillator is 0.2 eV in the third excited state.
Calculate its frequency of oscillation.
1
[𝐻𝑖𝑛𝑡: 𝐺𝑖𝑣𝑒𝑛 𝐸3 = 0.2 𝑒𝑉 (𝑐𝑜𝑛𝑣𝑒𝑟𝑡 𝑡𝑜 𝑒𝑉) 𝑛 = 3 𝑈𝑠𝑒 𝐸𝑛 = (𝑛 + ) ℎ𝜈 ]
2

13. An eigen value of an electron confined to a one dimensional box of length 0.2 nm
is 151 eV. What is the order of excited state?
𝑛 2 ℎ2
[𝐻𝑖𝑛𝑡 ∶ 𝐺𝑖𝑣𝑒𝑛: 𝐿 = 0.2 × 10−9 𝑚, 𝐸𝑛 = 151 𝑒𝑉 = 151 × 1.6 × 10−19 𝐽, 𝐴𝑠 𝐸𝑛 = 𝐽, 𝑛 =
8𝑚𝐿2

8𝑚𝐿2 𝐸𝑛 𝐿
√ = √8𝑚𝐸𝑛 . 𝐹𝑖𝑛𝑑 𝑛 ]
ℎ2 ℎ

14 A proton is confined to a nucleus of radius 𝑟 = 10−14 𝑚. Calculate the lowest and

the next two energy eigen values of proton, given mass of the proton 𝑚𝑝 =
𝑛 2 ℎ2 𝑛 2 ℎ2 1
1.67 × 10−27 𝑘𝑔. [𝐻𝑖𝑛𝑡 ∶ 𝐺𝑖𝑣𝑒𝑛: 𝑟 = 𝐿 = 10−14 𝑚, 𝐸𝑛 = 8𝑚𝑝 𝐿2
𝐽, =
8𝑚𝑝 𝐿2
×
1.6 ×10−19
𝑒𝑉. 𝐹𝑜𝑟 𝑛 =

1, 2, 3 𝐹𝑖𝑛𝑑 𝐸1 , 𝐸2 , 𝐸3 ]

15 Calculate the zero point energy in eV and the spacing of energy levels in eV in a
one dimensional oscillator of frequency 2.5 kHz.
1
[𝐻𝑖𝑛𝑡: 𝐺𝑖𝑣𝑒𝑛, 𝐹𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦 𝜈 = 2.5 × 103 𝐻𝑧 𝑎𝑛𝑑 𝐸0 = ℎ𝜈, 𝐶𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒 𝐸1 𝑏𝑦 𝑝𝑢𝑡𝑡𝑖𝑛𝑔 𝑛 = 1 𝑖𝑛 𝐸𝑛 =
2
1
(𝑛 + ) ℎ𝜈. 𝐹𝑖𝑛𝑑 𝐸1 − 𝐸0 ]
2

16 A particle of mass 1 mg is attached to a spring of spring constant 10−3 𝑁𝑚−1.

Calculate its zero point energy and classical value of amplitude of zero point

vibration. [𝐻𝑖𝑛𝑡: 𝑚 = 1 × 10−6 𝑘𝑔, 𝑠𝑝𝑟𝑖𝑛𝑔 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑘 = 10−3 𝑁𝑚−1 , 𝐹𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦 𝜈 =

1 𝑘 1 1 𝑘
√ 𝑎𝑛𝑑 𝐸0 = 2 ℎ𝜈. 𝐶𝑙𝑠𝑠𝑖𝑐𝑎𝑙 𝑡𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝐸 = 2 𝑚𝑎2 𝜔2 𝑤ℎ𝑒𝑟𝑒 𝜔2 = . 𝑇ℎ𝑢𝑠 𝐸 =
2𝜋 𝑚 𝑚

1 2𝐸0
𝑘𝑎2 . 𝐴𝑠 𝐸 = 𝐸0 , 𝑎𝑚𝑝𝑙𝑖𝑡𝑢𝑑𝑒 𝑎 = √ ]
2 𝑘

PART C
1. What is the difference between a free particle and a particle in a box?
[Ans: A free particle moves in space without any restriction in zero potential having continuous energy.

V Semester B.Sc., Physics Dr. K S Suresh Page 24

Unit 3 - Quantum mechanics – II

A particle in a box has a boundary with in a potential well with either finite or zero potential having discrete
energies.]
2. A bound particle has quantised energy values whereas it is not so for a free
particle. Explain.
[Ans: A bound particle has a boundary with boundary conditions in a potential well with either finite or
zero potential. It takes quantized energies. Thus it has discrete energies A free particle moves in space
without any restriction in zero potential. Thus has continuous energy..]
3. Give the physical significance of zero point energy.
[Ans: According to old quantum theory, the energy of the oscillator is given by 𝐸𝑛 = 𝑛ℎ𝜈 . For n = 0, the
value of E is zero, i.e., the ground state energy of the oscillator is zero. But according to new quantum
1
mechanical theory of the oscillator 𝐸𝑛 = (𝑛 + ) ℎ𝜈 . Thus the ground state energy is not zero but is given
2
1
by 𝐸0 = ℎ𝜈 ].
2

4. Explain the Bohr’s stationary orbits on the basis of quantum mechanical model.
[Ans: From quantum mechanics the allowed wave functions have discrete energies. The probability density
and the corresponding energies are time indeoendent and hence non radiating.]
5. What is the significance of probability density?
[Ans : The wave function 𝜓 is a complex quantity and has no direct physical significance by itself. The
product 𝜓𝜓 ∗ is a real quantity where 𝜓 ∗ is the complex conjugate of 𝜓. The probability density
+∞
∫−∞ 𝜓𝜓 ∗ 𝑑𝑉 is the probability of find the particle at a position in a given time.]
6. Is zero point energy of a harmonic oscillator zero? Explain.
1
[Ans: According to quantum mechanical theory of the oscillator 𝐸𝑛 = (𝑛 + ) ℎ𝜈 . Thus the ground state
2
1
energy is not zero but is given by 𝐸0 = ℎ𝜈 𝑎𝑠 𝑛 = 0].
2

7. Why should the wave function representing a moving particle be complex?

[Ans: The probability density or the probability of finding a particle at a point in space at a given time is
+∞
found by ∫−∞ 𝜓𝜓 ∗ 𝑑𝑉 which is real. This is possible if the wave function is complex.]
8. Why do we normalize a wave function?
+∞
[Ans: ∫−∞ 𝜓𝜓 ∗ 𝑑𝑉 is the probability density for finding the particle at point x, at time t. It follows that the
+∞
integral of ∫−∞ 𝜓𝜓 ∗ 𝑑𝑉 = 1 (the particle's got to be somewhere. The time-dependent Schrödinger equation
which is a linear and homogeneous, reveals that if Ψ(x,t) is a solution, so too is AΨ(x,t), where A is any
(complex) constant. What we must do, then, is pick this undetermined multiplicative factor A so as to ensure
+∞
∫−∞ |𝜓 2 |𝑑𝑉 = 1 is satisfied. This process is called normalizing the wave function].

9. The concept of trajectory has no significance in quantum mechanics. Explain.

[Ans: The Heisenberg’s uncertainty principle says it is not possible to measure position and momentum of a
particle simultaneously. Also quantum mechanics deals with probabilities and not certainty of a particle.
Thus trajectories has no significance in quantum mechanics].
10. Can one eigen value have many eigen functions? If so, what are they called?
[Ans: : Yes. In quantum mechanics, an energy eigen value can have two or more eigen states. It is referred
to as degeneracy. Conversely, two or more different states of a quantum mechanical system are said to be
degenerate if they give the same value of energy upon measurement].

V Semester B.Sc., Physics Dr. K S Suresh Page 25