Swami Keshvanand Institute of Technology, Management &Gramothan,

Ramnagaria, Jagatpura, Jaipur-302017, INDIA

Approved by AICTE, Ministry of HRD, Government of India
Recognized by UGC under Section 2(f) of the UGC Act, 1956
Tel. : +91-0141- 5160400Fax: +91-0141-2759555
E-mail: info@skit.ac.in Web: www.skit.ac.in

Unit- 2:Quantum Mechanics

Content:

1. Introduction of Quantum Mechanics

 Origin of Quantum Nature of Light
 de-Broglie Matter Waves
 Wave Packet
2. Wave Function and Postulates of Quantum Mechanics
 Physical Interpretation of Wave Function and its Properties
3. Schrödinger’s Equations
 Time Dependent Schrödinger’s Wave Equation
 Time Independent Schrödinger’s Wave Equation
4. Applications of Schrödinger’s Wave Equation
 Particle in One-Dimensional Potential Box
 Particle in Three-Dimensional Potential Box

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 Swami Keshvanand Institute of Technology, Management &Gramothan,
Ramnagaria, Jagatpura, Jaipur-302017, INDIA
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Recognized by UGC under Section 2(f) of the UGC Act, 1956
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1. Introduction of Quantum Mechanics:

 Quantum mechanics (QM) also known as quantum physics or quantum theory, or wave
mechanics is a fundamental theory in physics which describes the relationship between
energy and matter on an atomic and subatomic scale.
 It is a branch of physics which deals with physical phenomena at microscopic scales
(very Small size particles like electron, proton, neutron etc.)
 The motion and the behavior of the macroscopic particles with non relativistic speed (i.e.
v << c) can be completely described by the Classical mechanics or Newtonian mechanics
which is based on Newton's three laws, i.e., the law of inertia, the law of force and the
law of action and reaction. It includes the concepts of absolute mass, absolute space and
absolute time and the particle's position, mass, velocity and acceleration can be measured
accurately. But when we consider the motion of microscopic particles such as
electrons, protons etc., classical mechanics fails to explain the results accurately.
 Some failures of classical approach are given below:
(i) It could not explain the stability of atoms,
(ii) It does not hold in the region of atomic dimensions, i.e., it cannot explain the non-
relativistic motion of electrons, protons, atoms etc.
(iii) It could not explain observed spectrum of black body radiations.
(iv) It could not explain the origin of discrete spectra of atoms since according to
classical mechanics, the energy change is always continuous.
(v) It could not explain a large number of observed phenomena like Photoelectric
effect, Compton effect, Raman effect etc.
 The attempt to explain these effects led to the development of quantum mechanics or
quantum theory. The basic idea of quantum theory was introduced by Max Planck,
Einstein, and Bohr but the subsequent developments and interpretations were made by a
number of physicists including, de Broglie, Heisenberg, Schrödinger, Born and Dirac.

Origin of Quantum Nature of Light:

 We know that wave nature of light is capable of explaining many phenomena like
Interference, Diffraction, polarization etc but this wave theory is failed to explain the
observed phenomenon of photoelectric effect, Compton Effect etc. This laid the scientist
to develop a new theory to explain all these observed effects. A new theory was
developed, which becomes the origin of quantum nature of light.
 In 1900 Max Planck assumed that, light (radiation) consists of a large number of
oscillating particles (small isolated packets of energy) or quanta also called photon.
The frequency of oscillating particles is directly proportional to their energy. The

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quanta have energy E = hv, where v is the frequency of the monochromatic
radiation and h is the Planck's constant, having a value 6.63 x 10-34 J-s.
 On basis of Planck's quantum theory of light, Einstein was explained photoelectric effect.
According to Einstein, in the interaction of light with matter, the energy of light is
assumed to be in bundles (photons) of energy hv only. This is called wave-particle
duality of light. So, the quantum mechanics describes light as both a wave and a
particle, depending on the situation.
 These assumptions satisfactorily explain many experimental facts like Spectral
distribution of Black body radiation, Photoelectric effect, Compton effect, Raman effect
etc. These are the experimental evidence of quantum nature of light (radiation).
 This way the modern quantum theory was developed in the early 20th century. Quantum
physics mainly deals with waves and subatomic particles of matter therefore it is also
referred to as a quantum wave mechanics.

De Broglie Matter Waves:

 According to quantum theory, light of frequency ν is composed of tiny discrete
packets or bundles of energy called “photons”, each having energy ‘hν’, momentum
and velocity ‘c’. Photons behave almost exactly like a material particle. Thus,
light has a dual nature, i.e., it posses both particle and wave properties.
 In analogy with dual character of light, Louis de Broglie in 1924 introduced the
hypothesis that all material particles in motion possess a wave character means
matter also possess dual character. Such waves associated with the material
particles are known as “matter waves” or de Broglie waves”.
 So, all fundamental material particles as electrons, protons, neutrons, atoms and
molecules etc. have waves associated with them. The wavelength of such matter
waves depends upon the momentum of the particle and it is given by

ℎ ℎ
𝜆= =
𝑚𝑣 𝑃

Where h is the Planck’s constant, m is the mass of particle moving with the
velocity v and 𝑃 = 𝑚𝑣 is the momentum of the particle.

 A material particle in motion is equivalent to a wave packet rather than a single

wave. A wave packet is a group of waves, each with slightly different frequency and
propagation constant as shown in figure.

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In quantum mechanics a particle is described by a wave packet and the square of wave amplitude
at a point is related to the probability of finding the particles at that point. So, in the region of
wave packet there is a high probability of finding the particle, the probability outside it is
negligible.

2. Wave Function and Postulates of Quantum Mechanics:

Wave Function:
 According to de Broglie's hypothesis, every moving material particle has a wave
associated with it. These waves are known as matter waves. Waves in general are
associated with quantities that vary periodically.
 In case of matter waves, the quantity that varies periodically is called wave function.
 The amplitude of matter waves is described by wave function and represented by
(r⃗, t). The wave function is not an observable quantity and has no direct physical
significance. However, the value of the wave function is related to the probability of
finding the particle at a given place at a given time. In general, wave function is a
complex quantity and it provides a complete description of the behaviour of the
particle.

Physical Interpretation of Wave Function and its Properties:

 The wave function (r⃗, t), describes the position of a particle with respect to time. It can
be considered as ‘probability amplitude since it is used to find the location of the particle.
 Max Born in 1926 proposed a meaning to the wave function . According to Max
Born  may be regarded as a measure of the probability of finding the particle at a
particular position and a particular time. Wave function itself has no physical
interpretation. However, the square of the absolute value of the wave function has a
physical interpretation.

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 The wave functions are usually complex. Therefore, the probability density for a complex
wave function  is taken as the square of the absolute magnitude of . Thus
 The probability density 𝑷(𝐫⃗, 𝐭) = |𝝍(𝐫⃗, 𝐭)|𝟐 = 𝝍 ∗ → 𝒓, 𝒕 𝝍 →
𝒓 ,𝒕
 Here 𝜓 ∗ →𝑟, 𝑡 is the complex conjugate of the wave function and for complex conjugate
‘i’ is replaced by ‘-i’.
 Then, the probability of finding the particle in the volume element dV=dxdydz
about any point → 𝒓 at time ‘t’ is given by as: 𝑷(𝐫⃗, 𝐭)dV= |𝝍(𝐫⃗, 𝐭)|𝟐 dV= 𝝍 ∗
→𝒓, 𝒕 𝝍 → 𝒓 , 𝒕 dV
 Normalization condition: If the particle is somewhere in space then the total
probability must be equal to unity for all space, i.e.
∫ 𝜓 → 𝑟 , 𝑡 𝑑𝑉 = 1
⇒ ∫ 𝜓∗ →
𝑟, 𝑡 𝜓 →
𝑟 , 𝑡 𝑑𝑉 = 1
 This is called Normalization condition. The wave function 𝝍 → 𝒓 , 𝒕 which satisfies
the above condition is said to be normalized wave function. For such normalization,
the amplitude of  is adjusted to make the integral equal to unity.

Orthogonality condition: If 𝝍i and 𝝍j are two different wave functions satisfying the
wave equation for a give system such that

𝜓 ∗ →
𝑟, 𝑡 𝜓 →
𝑟 , 𝑡 𝑑𝑉 = 𝜓 ∗ →
𝑟, 𝑡 𝜓 →
𝑟 , 𝑡 𝑑𝑉 = 0

Then this condition is known as orthogonal condition and the wave functions 𝝍i and
𝝍j are said to be mutually orthogonal.

Postulates of Quantum Mechanics:

 In 1926 Schrödinger, generalizing the concept of matter waves, discovered the

equation of propagation of the wave function representing a given system (particle).
The equation is known as the Schrödinger equation and it constitutes the basic
element of wave mechanics.
 Hence the mechanics related to wave function (𝐫⃗, 𝐭) is known as the wave
mechanics or quantum mechanics. In the development of quantum mechanics, there
are some basic postulates, which are called the fundamental postulates of quantum
mechanics.

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Postulate I: A physical system is completely described by a wave function(𝐫⃗, 𝐭). It

is also known as the quantum mechanical state of the system.

Properties of wave function:The acceptable wave function should have the following
properties

(i) Wave function ψ and its first derivatives , 𝑎𝑛𝑑 must be single valued,
continuous and finite everywhere.
(ii)  must obey superposition principle. If 1 &2 are two solutions of
schrödinger’sequation, then 1 + 2 is also a solution.
(iii)  must be normalized i.e., ∫|𝜓| 𝑑𝑉 = 1.

Postulate II:

 Every observable quantity can be expressed by an operator in quantum mechanics.

Any mathematical operation can be an operator like multiplication, differentiation, or
integration, which is capable of operating on a wave function and extract the value of
observable quantity. An operator is described by putting 𝐜𝐚𝐩 (∧) at any function.

If 𝑭 is an operator for an observable quantity, then

𝐹 𝜓(𝑟⃗, 𝑡) = 𝑓𝜓(𝑟⃗, 𝑡)

The value of observable quantity f is known as eigen value of the operator 𝑭 for the
wave function ψ, known as eigen function of the system.

The quantum operators for several physical quantities are shown in following table:

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Postulate III:

When a measurement of an observable quantity ‘f’ is made on a particle for which the wave
function is 𝜓(𝑟⃗, 𝑡), we get different values of f during different trials. The most probable value
of ‘f’ is given by

〈𝑓〉 = 𝜓 ∗ (𝑟⃗, 𝑡)𝐹 𝜓(𝑟⃗, 𝑡)𝑑𝑉

Where 𝐹 is the operator associated with observable quantity f and 𝜓 ∗ (𝑟⃗, 𝑡) is complex conjugate
of normalized wave function 𝜓(𝑟⃗, 𝑡). The quantity 〈𝑓〉 is called the expectation value or
average value of the observable quantity ‘f’.

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The expectation value of momentum and energy may be found by using thecorresponding
differential operator, such as:

−𝑖ℎ
< 𝑝⃗ >= 𝜓 ∗ (𝑟⃗, 𝑡) ∇ 𝜓(𝑟⃗, 𝑡)𝑑𝑉
2𝜋

And
𝑖ℎ 𝜕
< 𝐸 >= 𝜓 ∗ (𝑟⃗, 𝑡) 𝜓(𝑟⃗, 𝑡)𝑑𝑉
2𝜋 𝜕𝑡

Postulate IV:

 A particle moving in space can be represented by the following wave equation

ℎ 𝜕 𝜕 𝜕 𝑖ℎ 𝜕𝜓(𝑟⃗, 𝑡)
− + + 𝜓(𝑟⃗, 𝑡) + 𝑉(𝑟⃗)𝜓(𝑟⃗, 𝑡) =
8𝜋 𝑚 𝜕𝑥 𝜕𝑦 𝜕𝑧 2𝜋 𝜕𝑡

Or

ℏ 𝜕 𝜕 𝜕 𝜕𝜓 (𝑟⃗, 𝑡)
− + + 𝜓(𝑟⃗, 𝑡) + 𝑉 (𝑟⃗)𝜓(𝑟⃗, 𝑡) = 𝑖ℏ
2𝑚 𝜕𝑥 𝜕𝑦 𝜕𝑧 𝜕𝑡

This is called the Schrödinger’s wave equation. This equation is applicable to all cases of
particle motion and the nature of potential 𝑽(𝒓⃗) decides the solution for a particular case.

3. Schrödinger’s Equation:
 In 1926, Schrödinger proposed an equation to calculate wave function𝝍(𝒓⃗, 𝒕)
associated with a moving particle. This equation is known as the Schrödinger's
equation. The choice of the wave equation, whose solutions give the wave functions, is
governed by two main conditions:
(i) The wave equation must be linear and homogeneous so that its solution can be
superposed.
(ii) The wave equation, which has to be a differential equation, must be of the first
order with respect to time.

 Schrödinger's equation is a fundamental equation of quantum mechanics in the

same sense as the newton's second law of motion in classical mechanics.

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Time Dependent Schrödinger’s Equation:

 Let us consider a particle is moving in the +x direction. According to de Broglie, a wave

is associated with this particle. Let us consider the wave function of this wave is:
( )
𝜓 (𝑥, 𝑡) = 𝐴𝑒 .…(1)

This is a plane wave equation.

Here, the wave vector k is defined as; 𝑘 = =ℏ .…(2) [where, 𝜆 = and ℏ = ]

or 𝑝 = ℏ𝑘

and Angular frequency  is defined as; 𝜔 = 2𝜋𝜈 = = …. (3) [where, 𝐸 = ℎ𝜈 ]

ℏ

or 𝐸 = ℏ𝜔

Now put equation (2) & (3) in equation (1), then

𝒊
𝝍 (𝒙, 𝒕) = 𝑨𝒆ℏ(𝒑𝒙 𝑬𝒕)
.…(4)

where E is the total energy of the particle and p is its momentum.

Differentiating equation (4) with respect to ‘x’

𝜕𝜓 (𝑥, 𝑡) 𝑖
= 𝑝𝐴𝑒 ℏ( )
𝜕𝑥 ℏ
( , )
𝑜𝑟, = ℏ
𝑝 𝜓 (𝑥, 𝑡) ….(5)

ℏ 𝜕𝜓 (𝑥, 𝑡) 𝜕𝜓 (𝑥, 𝑡)
⇒ 𝑝 𝜓 (𝑥, 𝑡) = = −𝑖ℏ … . (6)
𝑖 𝜕𝑥 𝜕𝑥
From equation (6) we get momentum operator in x-direction, i.e.

𝑝̂ x= −𝑖ℏ ….(7)

Now again differentiating equation (5) with respect to ‘x’

𝜕 𝜓(𝑥, 𝑡) 𝑖
= 𝑝 𝜓 (𝑥, 𝑡)
𝜕𝑥 ℏ

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𝜕 𝜓(𝑥, 𝑡) 𝑝
⇒ = − 𝜓 (𝑥, 𝑡)
𝜕𝑥 ℏ
( , )
Or, 𝑝 𝜓 (𝑥, 𝑡) = −ℏ ….(8)

Now differentiating equation (4) with respect to ‘t’

𝜕𝜓 (𝑥, 𝑡) 𝑖
= − 𝐸𝐴𝑒 ℏ( )
𝜕𝑡 ℏ
( , )
𝑜𝑟, = − 𝐸 𝜓 (𝑥, 𝑡)
ℏ

ℏ 𝜕𝜓 (𝑥, 𝑡) 𝜕𝜓 (𝑥, 𝑡)
⇒ 𝐸 𝜓 (𝑥, 𝑡) = − = 𝑖ℏ … . (9)
𝑖 𝜕𝑡 𝜕𝑡
From equation (9) we get Energy operator, i.e.

𝐸 = 𝑖ℏ ….(10)

For non-relativistic case where v << c, the total energy of the particle E is sum of kinetic energy
and potential energy, i.e.

𝐸= +𝑉 .…(11)

here, potential energy ‘V’ is the function of x and t, i.e. V(x,t).

By acting this energy operator on wave function ψ (𝑥, 𝑡) or multiplying equation (11) by 𝜓(𝑥 , 𝑡)
on both sides, then we obtain

𝐸𝜓(𝑥, 𝑡) = 𝜓(𝑥, 𝑡) + 𝑉𝜓(𝑥, 𝑡) .…(12)

Substituting equations (8) and (9) in equation (12) we get,

𝝏𝝍(𝒙,𝒕) ℏ𝟐 𝝏𝟐 𝝍(𝒙,𝒕)
𝒊ℏ =− + 𝑽𝝍(𝒙, 𝒕) .…(13)
𝝏𝒕 𝟐𝒎 𝝏𝒙𝟐

Equation (13) is known as one–dimension time dependent Schrödinger’s equation.

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Similarly, in three dimensions wave function 𝝍(𝒙, 𝒚, 𝒛, 𝒕) = 𝝍(𝒓⃗, 𝒕) it shall be

( ⃗, ) ℏ
𝑖ℏ =− + + 𝜓(𝑟⃗, 𝑡) + 𝑉𝜓(𝑟⃗, 𝑡) ….(14)

( ⃗, ) ℏ
𝑜𝑟, 𝑖ℏ =− 𝛻 𝜓(𝑟⃗, 𝑡) + 𝑉𝜓(𝑟⃗, 𝑡) .…(15)

here, + + = ∇ ….(16) ; known as Laplacian operator.

Equation (15) is known as three- dimensional time dependent Schrödinger’s equation.

Equation (15) can also be written as

ℏ
− 𝛻 + 𝑉 𝜓(𝑟⃗, 𝑡) = 𝐸𝜓(𝑟⃗, 𝑡)

or 𝑯𝝍 = 𝑬𝝍 ….(17)

Equation (17) is known as Hamiltonian form of Schrödinger’s equation, where

ℏ
𝐻= − 𝛻 +𝑉 = Hamiltonian operator ….(18)

and 𝐸 = 𝑖ℏ = Energy operator

𝐻 and 𝐸 are both total energy operator but 𝐻 depends on space and time coordinate and 𝐸
depends on time derivative.

For a free particle where V = 0, the time dependent Schrödinger’s equation in 3-D case is:

( ⃗, ) ℏ
𝑖ℏ =− 𝛻 𝜓(𝑟⃗, 𝑡) ….(19)

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Time Independent Schrödinger’s Equation:

 The wave function can be separated into time independent and time dependent part
as:
∵ 𝜓 (𝑥, 𝑡) = 𝐴𝑒 ℏ( )
….(1)

∴ 𝜓(𝑥 , 𝑡) = 𝐴𝑒 ℏ 𝑒 ℏ = 𝜓(𝑥 )𝑒 ℏ ….(2)

Differentiating equation (2) with respect to ‘x’ twice, then

( , ) ( )
= 𝑒 ℏ ….(3)
and differentiating equation (2)with respect to ‘t’
( , )
= − 𝐸 𝜓(𝑥) 𝑒 ℏ ….(4)
ℏ
Now put equations (3) & (4) in time dependent Schrödinger’s equation. As time dependent
Schrödinger’s equation in 1-D case is
ℏ 𝜕 𝜓(𝑥, 𝑡) 𝜕𝜓(𝑥, 𝑡)
− + 𝑉𝜓(𝑥, 𝑡) = 𝑖ℏ
2𝑚 𝜕𝑥 𝜕𝑡
ℏ ( )
So, − 𝑒 ℏ + 𝑉𝜓(𝑥)𝑒 ℏ = 𝑖ℏ( ) 𝜓(𝑥)𝑒 ℏ
ℏ

𝒅𝟐 𝝍(𝒙) 𝟐𝒎
Or, + (𝑬 − 𝑽)𝝍(𝒙) = 𝟎 ….(5)
𝒅𝒙𝟐 ℏ𝟐

Equation (5) is known as time independent Schrödinger’s equation in one–dimension.

For 3-D time independent Schrödinger’s equation, let us consider 𝜓 →

𝑟 = 𝜓(𝑥, 𝑦, 𝑧), then

𝜕 𝜓 →𝑟 𝜕 𝜓 →𝑟 𝜕 𝜓 →𝑟 2𝑚
+ + + [𝐸 − 𝑉 ]𝜓 →
𝑟 =0
𝜕𝑥 𝜕𝑦 𝜕𝑧 ℏ

𝜵𝟐 𝝍 →
𝒓 + 𝟐 [𝑬 − 𝑽]𝝍 →
𝟐𝒎
Or, 𝒓 =𝟎 ….(6)
ℏ

The above equation (6) is called time independent Schrödinger equation in 3-D.

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For a free particle, the potential energy V →

𝒓 = 0, so the time independent Schrödinger
equation becomes

𝛻 𝜓 →
𝑟 + 𝐸𝜓 →
𝑟 =0 ….(7)
ℏ

Equation (7) is time independent Schrödinger equation for a free particle in 3-D.

4. Applications of Schrödinger’s Equation:

(i) Particle in a rigid One-Dimensional Potential Box (Infinite square well
potential):

Particle confined in an infinite square well potential

 Let us consider the particle of mass ‘m’ restricted to move along x-axis in one
dimensional potential box which has perfectly rigid walls of infinite potentials at x
=0 and x = a. Suppose the potential energy ‘V’of the particle is zero inside the box,
i.e. the particle is free to move between the walls. So, mathematically the potential
energy of this particle can be written as

V(x) = 0 ; for 0<x<a

V(x) = ∞; for x  0 and x  a ….(1)

Because the particle cannot have an infinite amount of energy it cannot exist outside the box, so
its wave function ‘ψ’ is zero for x  0 and x  a. Now our aim is to find out the wave function
within the box between x=0 and x = a. Using time independent Schrödinger’s equation in 1-D
case, i.e.

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( )
+ ℏ
(𝐸 − 𝑉)𝜓(𝑥) = 0 ….(2)

From equation (1) inside the box, i.e. 0<x<a, the potential energy V=0. So, equation (2) reduces
to
( )
+ ℏ
𝐸𝜓(𝑥 ) = 0

( )
Or, + 𝑘 𝜓(𝑥) = 0 ….(3)

where, = 𝑘 ….(4)
ℏ

Equation (3) is a second order differential equation and the general solution of this equation is

(x) = A sin kx + B cos kx .…(5)

Where, A and B are constants which can be determined by applying boundary conditions.

Since the particle cannot penetrate the hard walls and cannot exist outside the box, the
wavefunction ψ will be zero outside the box and at the wall of the box, i.e. x = 0 and x = a. So,
the boundary conditions for the wavefunction can be written as:

(x) = 0 at x = 0

& (x) = 0 at x = a ….(6)

Using first boundary condition i.e. (x) = 0 at x = 0 in equation (5)

𝐴𝑠𝑖𝑛(𝑘0) + 𝐵𝑐𝑜𝑠(𝑘0) = 0

 B=0 ….(7)

Put equation (7) in equation (5), then the wave function reduces to

(x) = A sin kx .…(8)

Now, using second boundary condition i.e. (x) = 0 at x = a in equation (8), then

𝐴𝑠𝑖𝑛(𝑘0) = 0

⇒ ka = sin-1(0) = nπ

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⇒ k= ….(9)

So the wave function of a particle in 1-D box is

𝜓 (𝑥) = 𝐴 𝑠𝑖𝑛 ….(10)

where, n = 1, 2, 3 ...; here 𝒏 ≠ 𝟎

[If n=0 it means that (x) =0, i.e., probability of finding the particle inside the box is zero,
whereas the particle is in the box. Hence n cannot be zero.]

For normalization wave function, ∫ 𝜓 ∗ (𝑥 ) 𝜓 (𝑥)𝑑𝑥 = 1

𝑛𝜋
⇒ 𝐴 𝑠𝑖𝑛 𝑥𝑑𝑥 = 1
𝑎

a
⇒ A2 1
2

⇒ 𝐴= .…(11)

So, from equation (10) the normalized wave function of a particle moving in one
dimensional box is

𝟐 𝒏𝝅𝒙
𝝍𝒏 (𝒙) = 𝐬𝐢𝐧 .…(12)
𝒂 𝒂

This is also called eigen function (Solution of Schrödinger’s equation).

Now, for energy eigen value, from equations (4) & (9)

𝟐𝒎𝑬 𝒏𝝅
𝒌= =
ℏ𝟐 𝒂

𝒏𝟐 𝝅𝟐 ℏ𝟐 𝒏𝟐 𝒉𝟐
⇒𝑬= = .…(13)
𝟐𝒎𝒂𝟐 𝟖𝒎𝒂𝟐

where, n = 1, 2, 3 ...

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So, the energy eigen value of a particle corresponding to the quantum number ‘n’ in one
dimensional box is given by

𝒏𝟐 𝝅𝟐 ℏ𝟐 𝒏𝟐 𝒉𝟐
𝑬𝒏 = 𝟐𝒎𝒂𝟐
= 𝟖𝒎𝒂𝟐
.…(14)

From equations (14) and (12),

ℏ
𝐸 = = and 𝜓 (𝑥) = sin ; for n=1

ℏ
𝐸 = = and 𝜓 (𝑥) = sin ; for n=2 .…(15)

ℏ
𝐸 = = and 𝜓 (𝑥) = sin ; for n=3

& so on…

Thus, from equation (15), it can be concluded that in an infinite potential well the particle
cannot have an arbitrary energy, but can take only certain discrete energy values
corresponding to quantum number n = 1, 2, 3 ...these are called eigen values of the particle
in the well and constitutes the energy level of the system. Hence particle energies in infinite
potential well are E1:E2: E3..=1:4:9…That means the energy of the particle is quantized
(shown in figure given below).

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Discrete energy levels in infinite square well potential

 It is also observed from equation (15), the particle cannot have zero energy inside the
𝒉𝟐
potential box. The minimum energy of the particle is 𝑬𝟏 = . It is called zero-
𝟖𝒎𝒂𝟐
point energy of the particle and the corresponding state of this energy is called
ground state.
 From equation (15) It is also observed that for each energy eigen value there is just one
eigen wave function. So, such energy levels are called non-degenerate energy levels.

The wavelengths associated with the matter wave of the particle inside one-dimensional box are
given by

2𝜋 2𝜋𝑎
𝜆= =
𝑘 𝑛𝜋

𝜆= .…(16)

the size of the box

𝑎 = , 𝜆, …. .…(17)

The Eigen functions 1, 2, and 3 and probability densities|𝜓 | , |𝜓 | and |𝜓 | for n = 1, 2, 3,
are shown in fig as a function of x.

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Wave functions 𝝍𝒏 (𝒙) and probability density |𝝍𝒏 (𝒙)|𝟐 of a particle inside an infinite square well potential

From this figure it is found the probability of finding a particle inside the box is different
at different points and there are points (called nodes) where the particle is never found. Further,
at a particular point, the probability of finding the particle different for different energy states.
For example, for a particle in the lowest energy state (n = 1), the probability is maximum at the
mid of the box, whereas for n=2, the probability at the mid of the box is zero. But according to
classical mechanics the probability of finding a particle is constant everywhere inside a box.

(ii) Particle in Three-Dimensional Rigid Potential Box: Consider a three-dimensional

rectangular potential box of sides a, b and c which are parallel to axis x, y and z,
respectively. The box confined a particle of mass ’m’. The particle can freely move
within the region 0<x<a, 0<y<b and 0<z<c, i.e. inside the box potential energy
V(x,y,z)=0 and outside the box it is infinite.

Particle in a three-dimensional potential box

The Schrödinger time independent equation for the motion of a particle inside a box is

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+ + + ℏ
𝜓=0 .…(1)

For solving the equation (1) the wave function  can be represented as the product of three
independent functions of x, y and z. let the solution of equation (1) is:

𝜓(𝑥, 𝑦, 𝑧) = 𝑋(𝑥)𝑌(𝑦)𝑍(𝑧) .…(2)

Taking partial derivative of equation (2), we get

( )
= 𝑌(𝑦)𝑍(𝑧) [Since Y(y) and Z(z) are not function of x]

( )
= 𝑍(𝑧)𝑋(𝑥) ….(3) [Since X(x) and Z(z) are not function of y]

( )
= 𝑋(𝑥)𝑌(𝑦) [Since X(x) and Y(y) are not function of z]

Substituting equation (3) in equation (1) and then dividing by𝑋(𝑥 )𝑌(𝑦)𝑍(𝑧), we get

+ + =− ℏ
.…(4)

All the three terms on the L.H.S. are independent to each other, so that each term can be put
equal to some constant.

= −𝑘 or +𝑘 𝑋 =0 ….(5)

= −𝑘 or +𝑘 𝑌 =0 ….(6)

= −𝑘 or +𝑘 𝑍 =0 ….(7)

So, the equation (4) can be written as:

𝑘 +𝑘 +𝑘 = ….(8)
ℏ

The solution of equation (5) is given by

𝑋(𝑥) = 𝐴 𝑠𝑖𝑛 𝑘 𝑥 + 𝐵 𝑐𝑜𝑠 𝑘 𝑥 .…(9)

Where, A and B are the constants and can be determined by the boundary conditions, i.e. at x = 0
and x = a, the wave function X(x) = 0. So, using these boundary conditions, we get

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X(x) = 0 at x = 0  𝐴 𝑠𝑖𝑛 𝑘 0 + 𝐵 𝑐𝑜𝑠 𝑘 0 = 0

 B=0

 𝑋(𝑥) = 𝐴 𝑠𝑖𝑛 𝑘 𝑥 ….(10)

Now, using X (x) = 0 at x = a in equation (10)

𝐴 𝑠𝑖𝑛 𝑘 𝑎 = 0 ⇒ sin kxa = 0

or, kxa = nx ⇒ 𝑘 = 𝑥 .…(11)

Where nx is a positive integer 1, 2, 3…

So, 𝑋(𝑥) = 𝐴 𝑠𝑖𝑛 𝑥 .…(12)

Now applying the normalization condition in equation (12) between x = 0 and x = a, we have

∫ 𝑋 ∗ (𝑥) 𝑋(𝑥)𝑑𝑥 = 1

or 𝐴 ∫ 𝑠𝑖𝑛 𝑥𝑑𝑥 = 1

 𝐴=

And 𝑋(𝑥) = 𝑠𝑖𝑛 𝑥 .…(13)

Similarly, we can solve equations (6) & (7) and obtain

𝑌(𝑦) = 𝑠𝑖𝑛 𝑦 ….(14)

𝑍(𝑧) = 𝑠𝑖𝑛 𝑧 ….(15)

Here nx, ny, & nz are positive integers 1, 2, 3… and

𝑘 = 𝑦 & 𝑘 = 𝑧 ….(16)

Thus, from equation (2), the total wave function of a free particle in a three-dimensional
potential box is

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𝜓(𝑥, 𝑦, 𝑧) = 𝑠𝑖𝑛 𝑥 𝑠𝑖𝑛 𝑦 𝑠𝑖𝑛 𝑧 .…(17)

This is also called Eigen wave function for a particle in 3-D potential box dependent on nx,
ny, & nz integer quantum number. So, the eigen wave function can be written as:

𝜓 , , (𝑥, 𝑦, 𝑧) = 𝑠𝑖𝑛 𝑥 𝑠𝑖𝑛 𝑦 𝑠𝑖𝑛 𝑧 .…(18)

And for the energy eigen value, substituting the values of kx, ky and kz in equation (8), we get

𝑛 𝜋 𝑛 𝜋 𝑛 𝜋 2𝑚𝐸
+ + =
𝑎 𝑏 𝑐 ℏ
Hence the energy eigen values for a particle in 3-D potential box is

ℏ
𝐸 , , = + + = + + ….(19)

For a cubical potential box i.e. a = b = c, the normalized wave function of the particle is

𝜓 , , (𝑥, 𝑦, 𝑧) = 𝑠𝑖𝑛 𝑥 𝑠𝑖𝑛 𝑦 𝑠𝑖𝑛 𝑧 ….(20)

and allowed values of total energy is

ℏ
𝐸 , , = 𝑛 +𝑛 +𝑛

or, 𝐸 , , = 𝑛 +𝑛 +𝑛 ….(21)

Degeneracy of energy levels:

 A situation when different sets of quantum numbers (𝑛 , 𝑛 , 𝑛 ) have exactly the same
energy is known as degeneracy and energy levels are said to be degenerate.
 When there is only one wave function corresponding to a particular energy eigen value,
the energy level is known as non-degenerate but when there are a number of wave
functions corresponding to a single energy eigen value, the energy level is known as
degenerate.
 In the lowest quantum state (1, 1, 1) in which nx = ny = nz = 1, there is an energy level
E1,1,1= , corresponding to a single wave function ψ1,1,1. Hence this energy level is
non-degenerate. Similarly, we can see that energy levels E2,2,2 (i.e. nx = ny = nz = 2), E3,3,3

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(i.e. nx = ny = nz = 3), E4,4,4 (i.e. nx = ny = nz = 4) and so on, will also be "non-
degenerate".
 In case of energy , there are three sets (1, 1, 2), (1, 2, 1) and (2, 1, 1) of the quantum
number which will give the same energy corresponding to three different wave function
ψ1,1,2 , ψ1,2,1 , ψ2,1,1. Hence this energy level is a degenerate level with degree of
degeneracy 3, known as three fold degenerate energy level. Similarly, we can consider
the degeneracy of other levels. The possible number of sets of integers nx, ny, nz or the
number of different wave functions associated with the particle of given energy is called
degree of degeneracy (p).

Energy of the different energy levels, degree of degeneracy and quantum numbers for a cubical potential box

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