BNMIT, Bangalore Applied Physics (22PHY113/123) Study Material

MODULE - 1: QUANTUM MECHANICS

Introduction:
Quantum mechanics is the branch of physics which is useful in understanding the mechanics of
particles or bodies in atomic and the sub-atomic scale. Classical mechanics and quantum
mechanics have fundamentally different approaches to solve problems in mechanics. Classical
mechanics (which mainly includes Newtonian mechanics, Maxwell’s electromagnetic theory
etc.) deals the problems by deterministic approach to find solution. In contrast to classical
mechanics, quantum mechanics deals the problems by probabilistic approach to find solution.
Quantum mechanics was developed by the pioneering work of Heisenberg, Schrodinger, Dirac,
and others.

Need of Quantum Mechanics:

At the end of nineteenth century, new discoveries neither predicted nor explained by classical
mechanics began to point out inadequacy of classical mechanics. Classical mechanics failed to
explain the stability of atom, spectrum of hydrogen atom, photoelectric effect, Compton effect,
black body radiation spectrum etc.
Two laws based on classical mechanics (based on energy emitted by a black body is continuous)
namely Wein’s law and Rayleigh-Jeans law were partially successful in explaining black body
radiation spectrum. To overcome these failures/to explain these unexplained experimental
observations, scientific community though to new dimension to physics, leading to birth of new
physics / new mechanics called modern physics / quantum mechanics.
With respect to black body radiation spectrum, in 1900, Max Planck proposed a law which is based
on quantum nature of radiation called quantum theory of radiation to explain black body radiation
spectrum.

ASSUMPTIONS OF QUANTUM THEORY OF RADIATION:

The following are the assumptions of quantum theory of radiation and was proposed by Max
Planck in 1900.

1. The energy of electromagnetic radiation is discrete or quantized in small packets. This

small packet of energy is called quanta or photon. The quantized energy is given by the
following. Equation.

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E = nh; where h is Planck’s constant,  is frequency of radiation and where n =

1,2,3………. is an integer.
2. An atom or a subatomic particles may lose or gain energy by emitting or absorbing
respectively a radiation of frequency  whose value is given by  = E/h; where E is the
difference between energies of atom or a subatomic particles in the ground and excited
states.

Planck’s law of radiation:

Planck’s law of radiation is based on quantum theory of radiation It is based on the following
assumptions.
1. The walls of the black body consist of a very large number of oscillators and the energy
corresponding to each oscillator is an integral multiple of ‘h’ where h is Planck’s
constant and  is frequency of oscillation of oscillator. It means energy is discrete or
quantized.
i.e. E = nh; where n = 1,2,3……….
2. An oscillator may lose or gain energy by emitting or absorbing respectively a radiation
of frequency  whose value is given by = E/h; where E is the difference between
energies of oscillator in the ground and excited states.
According to this law, energy per unit volume of radiation E d (which is
proportional to intensity of radiation) emitted by a black body at a given temperature
‘T’ in the wavelength range ‘d’ (between  and d) is given by

8πhc 1
Eλ dλ = [ hν/kT ] dλ
λ5 e −1

In the above equation ‘c’ is velocity of light in air or vacuum and other terms have
their usual meanings as explained earlier.
Equation (3) represents the Planck’s law for energy distribution in the black body
radiation spectrum.
This law explains the entire black body radiation spectrum i.e. both shorter and longer
wavelength regions.

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de-Broglie Hypothesis:
Louis de-Broglie in 1924 proposed that just like electromagnetic radiation, matter also possesses
wave as well as particle characteristics. It means matter exhibits particle properties in certain
situations and wave properties in some other situations. The wave and particle properties are not
exhibited simultaneously.

de-Broglie hypothesis states that every moving material particle is associated with a wave and
this wave associated with moving material particle is called Matter wave or de-Broglie wave.
The wavelength () of matter wave or de-Broglie wave is given by

h h
λ= =
p mv
Where h is Planck’s constant, m is the mass of particle moving with velocity v and p=mv is the
momentum of the particle.
NOTE:
In the above equation m is the relativistic mass of the particle and is related to its rest mass m0
by the formula
m0
m=
v2
√(1 −
c2)
For velocities very small compared to velocity of light c, v2/c2 <<1. Therefore mm0.

EXPRESSION FOR de-Broglie WAVELENGTH OF A FREE PARTICLE IN TERMS

KINETIC ENERGY:

For a free particle the total energy is same as its kinetic energy (because potential energy is zero)
and is given by
𝐸 = 1⁄2 𝑚𝑣 2
where m is mass and v is velocity of particle.
This equation can be rewritten as
1 2 2 1 2
𝐸= 𝑚 𝑣 = 𝑝
2𝑚 2𝑚
i.e.

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𝑝 = √2𝑚𝐸
𝒉
∴𝝀= ⇒
𝒑

h
λ=
√2mE

This is the expression for de-Broglie wavelength in terms of kinetic energy.

EXPRESSION FOR de-Broglie WAVELENGTH OF ELECTRON ACCELERATED BY

SOME POTENTIAL:
Consider an electron accelerated by a potential of ‘V’ volts.
The work done on the electron is ‘eV’, where ‘e’ is the charge of electron. This work done is
converted into kinetic energy (1/2 m2v2).

1
𝑚𝑣 2 = 𝑒𝑉
2
i.e.
1 2 2
𝑚 𝑣 = 𝑒𝑉
2𝑚
1 2
𝑝 = 𝑒𝑉
2𝑚
(because p = mv)
∴ 𝑝 = √2𝑚𝑒𝑉
According to de-Broglie hypothesis
ℎ
𝜆=
𝑝

ℎ
∴𝜆=
√2𝑚𝑒𝑉
Substituting h = 6.63x10-34Js, m = 9.1x10-31kg and e = 1.6x10-19C, we get

1 6.624 𝑋 10−34
𝜆= [ ]
√𝑉 √2 𝑋 9.1𝑋10−31 𝑋1.602𝑋10−19

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12.26 𝑜 1.226
𝜆= 𝐴= 𝑛𝑚
√𝑉 √𝑉

This is the expression for de-Broglie wavelength of electron in terms of accelerating potential V.

NOTE:

In general, the de-Broglie wavelength  of a charged particle of mass m and charge q, accelerated
by a potential of V volts is
ℎ
𝜆=
√2𝑚𝑞𝑉

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

Phase velocity is the velocity with which the plane of equal phase travels through a medium or
it the velocity with which phase of an individual component changes with time. It is given by
𝜔
𝑣𝑝 =
𝑘
Where ω is angular frequency and k is wave number.

When system of individual components superimposes one on each other, there is a formation of
resultant wave called wave group or wave packet. Group velocity is the velocity with which the
wave packet or wave group propagates. Group velocity is also the rate of change in amplitude.
Group velocity is given by
𝑑𝜔
𝑣𝑔 =
𝑑𝑘

NOTE:
1. It can be shown that group velocity is equal to particle velocity.
2. Group velocity is always less than the velocity of light ‘c’.
3. Relation between group velocity and phase velocity is given by
𝑑𝑣𝑝
𝑣𝑔 = 𝑣𝑝 − 𝜆
𝑑𝜆
4. Above relation shows that group velocity is always less than phase velocity.
5. Relation between group velocity, phase velocity and velocity of light ‘c’ is given by
𝑣𝑔 . 𝑣𝑝 = 𝑐 2

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6. Above relation shows that phase velocity is always greater than ‘c’

Matter waves (de-Broglie waves) and their characteristic properties:

Mater waves are the waves associated with a moving material particle. They are also called as
de-Broglie waves.

Characteristic properties of Matter waves:

1. The wavelength  of matter wave is given by

ℎ ℎ
𝜆= =
𝑝 𝑚𝑣
where p = mv is the momentum, m is mass and v is velocity of particle.
2. The amplitude of a matter wave in a particular region and at a particular time gives the
probability of finding the particle in the same region and at that time.
3. The wavelength associated with a moving material particle is independent of its charge.
4. The wave velocity or phase velocity of matter wave is given by Vp = c2/vg where c is
velocity of light and vg is group velocity and is same as particle velocity.
5. The wave velocity of different matter waves is not constant, but depends on mass and
particle velocity of the associated particle. Whereas wave velocity of different
electromagnetic waves is constant.

HEISENBERG UNCERTAINTY PRINCIPLE:

Statement:
In any simultaneous determination of position and momentum of a particle, the product of
corresponding uncertainties inherently present in the measurement is equal to or greater than
(h/4), where ‘h’ is Planck’s constant.

Explanation:
If x is the uncertainty in the measurement of position of a particle along the x-axis, px is the
uncertainty in the measurement of momentum along the x-axis, then according to Heisenberg
Uncertainty principle
ℎ
𝛥𝑥. 𝛥𝑝𝑥 ≥
4𝜋

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The Heisenberg uncertainty principle could also be expressed in terms of uncertainties involved
in the measurement of other pair of physical variables, like angular displacement ()-angular
momentum (L), Energy (E)-time (t) as follows
ℎ
𝛥𝜃. 𝛥𝐿 ≥
4𝜋
ℎ
𝛥𝐸. 𝛥𝑡 ≥
4𝜋
Where   is the uncertainty in the measurement of angular displacement of a particle,  L is the
uncertainty in the measurement of angular momentum of a particle, E is the uncertainty in the
measurement of energy of radiation emitted by atomic system, t is the uncertainty in the
measurement of time.

APPLICATION OF HEISENBERG UNCERTAINTY PRINCIPLE:

Non- existence of electrons inside the atomic nucleus:
It is well known that electrons do not exist inside the atomic nucleus. The same can be shown
by using Heisenberg uncertainty principle as follows.
Let us assume that electrons exist inside the atomic nucleus. We know that the size of nucleus
is of the order of 10fm = 10x10-15m. For an electron to exist inside the nucleus, uncertainty in
its position x must not exceed size of the nucleus.
⟹ ∆𝑥 ≤ 10 × 10−15 𝑚
i.e. x is less than or equal to 10x10-15m.
By Heisenberg uncertainty principle we know that
ℎ
𝛥𝑥. 𝛥𝑝𝑥 ≥ ----- (1)
4𝜋

Therefore, uncertainty in the measurement of momentum of electron inside the nucleus is

ℎ
𝛥𝑝𝑥 ≥ ---- (2)
4𝜋.𝛥𝑥

Allowing maximum uncertainty for the position of electron i.e x = 10x10-15m, we get
6.63𝑥10−34
𝛥𝑝𝑥 ≥
4𝜋𝑥10𝑥10−15
i.e.
𝛥𝑝𝑥 ≥ 0.5𝑥10−20 𝑘𝑔𝑚𝑠 −1 ---- (3)

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Therefore, uncertainty in the momentum of electron is equal to or greater than

0.5𝑥10−20 𝑘𝑔𝑚𝑠 −1 .
But, the momentum of the electron 𝑝𝑥 must be at least equal to or greater than the order of
uncertainty in momentum.
i.e.
𝑝𝑥 ≥ 0.5𝑥10−20 𝑘𝑔𝑚𝑠 −1 ------- (4)

But we know that the non-relativistic expression for energy in terms of its momentum 𝑝𝑥 is

𝐸 = 𝑝𝑥2 /2𝑚 ----------(5)

where m = 9.1x10-31kg is the rest mass of electron.

By using equation (4) in equation (5), we may conclude that, if an electron exist inside the
atomic nucleus, its energy ‘E’ must be such that
𝐸 ≥ 𝑝𝑥2 /2𝑚
𝐸 ≥ (0.5𝑥10−20 )2 /(2𝑥9.1𝑥10−31 )
𝐸 ≥ 1.372𝑥10−11 𝐽
𝐸 ≥ 85𝑀𝑒𝑉
It means for an electron to exist inside the atomic nucleus its energy must be greater than or
equal to 85MeV.
But electrons emitted from nucleus in -decay experiment have energies in the range of 3 – 4
MeV. This discrepancy with respect to energy of electron indicates that electrons do not exist
inside the nucleus.

PHYSICAL SIGNIFICANCE OF HEISENBERG UNCERTAINTY PRINCIPLE:

The physical significance of Heisenberg uncertainty principle is that, one should not think of the
exact position or an accurate value for momentum of a particle. Instead, one should think of
probability of finding the particle at a certain position or the most probable value for momentum
of the particle. This principle confirms the wave nature of matter.

WAVE FUNCTION (ψ):

Wave function is the mathematical function in quantum mechanics which is determined by the
physical situation of the system and, it is the function of coordinates of a particle in space i.e x,
y, z and t. It is represented by the symbol ψ.

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Wave function ψ also contain all the possible information about the system. Hence it is also called
as state function. Such wave functions are obtained by solving Schrodinger wave equation. Once
the wave function is known for a particular system, then physical observable quantities like
energy, momentum, position etc. associated with that system can be determined.

Schrodinger wave equation is the working equation in quantum mechanics to solve the problems
like Newton’s second law in classical mechanics. There are two types of Schrodinger wave
function namely time independent Schrodinger wave equation and time dependent Schrodinger
wave equation.

PROBABILITY DENSITY:
Probability density is defined as probability of finding the particle per unit volume at the given
point. In quantum mechanics, square of the wave function i.e |𝜓|2 at a point is nothing but
probability density.

MAX BORN INTERPRETATION OF WAVE FUNCTION:

According to Max Born interpretation, the square of absolute value of wave function i.e |𝜓|2 at a
point gives probability of finding the particle in a small volume element of volume d about that
point.
If  is the volume inside which a particle is known to be present and where exactly the particle is
situated inside  is unknown. Then, if ψ is the wave function associated with the particle, then
probability P of finding the particle in a certain volume element of volume d is given by
𝑃 = |𝜓|2 𝑑𝜏 ----- (1)
Probability P of finding the particle over the entire volume  is given by
𝜏
𝑃 = ∫0 |𝜓|2 𝑑𝜏----- (2)

If particle is not bounded in finite volume, but found somewhere in space, then Probability P of
finding the particle in space is given by
∞
𝑃 = ∫−∞|𝜓|2 𝑑𝜏------ (3)

NORMALISATION OF WAVE FUNCTION:

Normalization is the process of finding a constant present in the wave function by using the
𝜏 ∞
condition ∫0 |𝜓|2 𝑑𝜏 = 1 or ∫−∞|𝜓|2 𝑑𝜏 = 1 and substituting the constant in the wave function.

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The new wave function obtained after substituting constant is called Normalized wave function.
The normalized wave function is the working wave function and it meaningfully represents a
particular physical system.
𝜏 ∞
In normalizing a wave function, the terms ∫0 |𝜓|2 𝑑𝜏 or ∫−∞|𝜓|2 𝑑𝜏 are equated to unity, because

these two terms represent total probability in finite volume  and in space respectively and total
probability is always unity.

Example:
Let 𝜓 = 𝐴𝑥corresponds to a particle which is bounded in one dimension such that -1<x<1. Where
A is constant present in the wave function.
Then, the normalization condition is (d should be replaced by dx for one dimensional case)
1
1 1 1 𝑥3 3
∫−1|𝜓|2 𝑑𝑥 = 1 i.e ∫−1 𝐴2 𝑥 2 𝑑𝑥 = 1 i.e 𝐴2 ∫−1 𝑥 2 𝑑𝑥 = 1 𝐴2 [ ]
3 −1
=1⇒𝐴=√
2

3
Therefore, Normalized wave function is 𝜓 = √ 𝑥.
2

PROPERITIES OF WAVE FUNCTION:

When we solve Schrodinger equation for wave function, it gives several solutions for ψ. All these
solutions may not be correct wave functions. One has to choose those wave functions which
correspond meaningfully to a physical system. Such wave functions should have the following
four properties.

1. Ψ should be single valued everywhere.

If Ψ is a multi-valued function, then at a given point there are many chances of finding the
particle, which is meaningless.
Consider the function 𝑓(𝑥) which varies with position as shown
in the figure. The function 𝑓(𝑥) has three different values
𝑓1, 𝑓2, 𝑓3 at 𝑥 = 𝑃 If 𝑓(𝑥) were to be the wave function the
probability of finding the particle in all the location must be same.
But in this case 𝑓1 ≠ 𝑓2 ≠ 𝑓3 so the wave function is not
acceptable. Thus, the wave function should have a single valued
everywhere in the region of space.

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2. Ψ should be finite everywhere.

If Ψ is infinite at a given point, then at that point there is maximum probability of finding
the particle i.e one. It means certainty. This is against Heisenberg uncertainty principle.
Consider the function 𝑓(𝑥) which varies with position as
shown in the figure. The function 𝑓(𝑥) is not finite at 𝒙 = 𝑹
but 𝒇(𝒙) = ∞. Thus, it indicates large probability of finding
the particle at location, which violates uncertainty principle.
So, the wave function cannot be acceptable.

3. Ψ and its first derivatives with its variables (x, y, z and t) should be continuous everywhere.
Ψ and its first derivatives with its variables should be continuous, because then only second
2
order derivative of Ψ with respect to its variables (∂ ψ⁄∂x 2 ) exist. This is very much
required as the Schrodinger wave equation has this term.
From figure, the wave function f(x) is discontinues at x =
Q,, f(x) is truncated at A and restarts at B, between A and B
the state of the system is not defined. Hence the wave
function is not acceptable.

4. For bound states ψ2 which represents probability should vanish at potential boundary and
outside. If ψ is a complex function, then “ψ*ψ” must vanish at infinity. Here ψ* is the
conjugate of ψ.

The Schrodinger Wave Equation:

Schrodinger equation gives us a detailed account of the form of the wave functions or probability
waves that control the motion of some smaller particles. The equation also describes how these
waves are influenced by external factors.

The Schrodinger equation has two forms, one in which time explicitly appears, and so describes
how the wave function of a particle will evolve in time. The other is the equation in which the
time dependence has been removed and hence is known as the time independent Schrodinger
equation.

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ONE-DIMENSIONAL TIME INDEPENDENT SCHRODINGER WAVE EQUATION

(Derivation):

Schrodinger developed a mathematical theory based on de-Broglie hypothesis of matter waves.

According to this hypothesis a material particle is associated with a wave whose wavelength  is
given by
ℎ ℎ
𝜆= = − − − −(1)
𝑝 𝑚𝑣
Where h is Planck’s constant and p = mv is the momentum of particle, m is mass and v is velocity
of the particle.
Since particle has wave properties, there should be some sort of wave equation which describes
the behavior of the particle. Consider a system of stationary waves associated with a particle. Let
x, y, z be the coordinates of a particle and ψ be wave displacement for the de-Broglie wave at any
time t.
We know that classical one-dimensional differential equation for a wave motion is given by
∂2 ψ ∂2 ψ
= v2 ----- (2)
∂t2 ∂x2
This equation is similar to
𝜕2𝑦 2
𝜕2𝑦
= 𝑣 ;
𝜕𝑡 2 𝜕𝑥 2
Where y replaces ψ & v is the wave velocity.
The solution for equation (2) is
𝜓(𝑥, 𝑡) = 𝐴𝑒 −𝑖(𝜔𝑡−𝑘𝑥) ------ (3)

Where A is constant,
 is angular frequency and
k is wave number for the wave.

In order to get time independent equation, we must eliminate time dependent term in
equation (2).
𝜕2𝜓
In order to achieve this, differentiate equation (3) with respect to time t twice to get ;
𝜕𝑡 2

By differentiating equation (3) once with respect to time t, we get

𝜕𝜓
= 𝐴𝑒 −𝑖(𝜔𝑡−𝑘𝑥) (−𝑖𝜔)
𝜕𝑡
Differentiating the above equation one more time with respect to time t, we get

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𝜕2𝜓
= 𝐴𝑒 −𝑖(𝜔𝑡−𝑘𝑥) (−𝑖𝜔)(−𝑖𝜔)
𝜕𝑡 2
𝜕2𝜓
⟹ = −𝜔2 𝐴𝑒 −𝑖(𝜔𝑡−𝑘𝑥)
𝜕𝑡 2
𝜕2 𝜓
∴ = −𝜔2 𝜓 ----- (4)
𝜕𝑡 2

(∵ 𝜓(𝑥, 𝑡) = 𝐴𝑒 −𝑖(𝜔𝑡−𝑘𝑥) )
Substituting equation (4) in equation (2) we get

𝜕2𝜓
−𝜔2 𝜓 = 𝑣 2
𝜕𝑥 2
or
𝜕2𝜓 𝜔2
+ 𝜓 = 0 ---- (5)
𝜕𝑥 2 𝑣2

But we know that

 = 2 = 2(v/); ( ∵ 𝜈 = 𝑣/𝜆 )

i.e.
𝜔 2𝜋 2𝜋 2𝜋𝑝 2𝜋𝑚𝑣
= = = =
𝑣 𝜆 ℎ ℎ ℎ
( )
𝑝
𝜔2 4𝜋2 𝑚2 𝑣 2
⇒ = -- (6)
𝑣2 ℎ2
ℎ
(∵ 𝜆 = 𝑎𝑛𝑑 𝑝 = 𝑚𝑣)
𝑝

Substituting equation (6) in equation (4) we get

𝜕2 𝜓 4𝜋2
+ 𝑚2 𝑣 2 𝜓 = 0 ----- (7)
𝜕𝑥 2 ℎ2
If E and V are the total energy and potential energies of particle respectively,
Then kinetic energy ½ mv2 is given by
1
𝑚𝑣 2 = 𝐸 − 𝑉,  
2
(∵ Total energy E = ½ mv2+V)
∴ 𝑚2 𝑣 2 = 2𝑚(𝐸 − 𝑉) -----(8)

Substituting equation (8) in equation (7) we get

𝜕 2 𝜓 4𝜋 2
+ 2  2𝑚(𝐸 − 𝑉)𝜓 = 0
𝜕𝑥 2 ℎ

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𝜕2 𝜓 8𝜋2 𝑚
+ (𝐸 − 𝑉)𝜓 = 0 -- -- (9)
𝜕𝑥 2 ℎ2

Equation (9) is called time independent one-dimensional Schrodinger wave equation.

For a free particle potential energy V=0.
𝜕2 𝜓 8𝜋2 𝑚
+ 𝐸𝜓 = 0 ----- (10)
𝜕𝑥 2 ℎ2

Equation (10) is called time independent one-dimensional Schrodinger wave equation for a free
particle.

The Time dependent Schrodinger wave equation is given by

ħ2 𝜕 2 𝜓 ∂ψ
2
+ 𝑉(𝑥)𝜓 = −𝑖ħ
2𝑚 𝜕𝑥 ∂t
Where ψ is now the wave function of a particle moving in the presence of a potential V(x).

The solutions to the time dependent Schrodinger equation will describe the dynamical behavior of the
particle. By solving Schrodinger’s equation, we get wave function ψ(x, t) which tells us (after we square
the wave function) how the probability of finding the particle in some region in space varies as a function
of time.
EIGEN FUNCTIONS AND EIGEN VALUES:

Eigen functions:
Eigen functions are those wave functions in quantum mechanics which possess properties that
they are single valued and finite everywhere, and also their first order derivatives with respect to
their variables are continuous everywhere.

Eigen values:
^
Eigen values are the physical observables which are obtained by satisfying the condition𝐴𝜓 =
^
𝑎𝜓. Where 𝐴 is called quantum mechanical operator corresponding to a physical observable, ψ
is the wave function of a physical system and “a” is called eigen value corresponding to a physical
observable.

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^
If 𝐴 is energy operator, then the physical observable quantity we get is energy and is called
^
energy eigen value. If 𝐴is momentum operator, then the physical observable quantity we get is
momentum and is called momentum eigen value.
Examples for quantum mechanical operators:
^ ℎ2 𝜕2
Energy operator: 𝐸 = −
8𝜋2 𝑚 𝜕𝑥 2
^ 𝑖ℎ 𝜕
Momentum operator: 𝑃 = −
2𝜋 𝜕𝑥
^ 𝑑
Example: If ψ = eax, 𝐴 =
𝑑𝑥
^ 𝑑
Consider 𝐴𝜓 = (𝑒 𝑎𝑥) = 𝑎𝑒 𝑎𝑥 = 𝑎𝜓
𝑑𝑥
^
Therefore “a” is called Eigen value corresponding to operator 𝐴.

APPLICATIONS OF SCHRODINGER WAVE EQUATION:

1) To find Eigen Functions and Energy Eigen values for a particle in a one-dimensional
potential well of finite width and infinite height (Infinite potential well)
Consider a particle of mass ‘m’ moving along the x-axis between two rigid walls A and B at x = 0
and x = a as shown in figure. The particle is free to move between the walls.

The potential energy V of the particle between the two walls is constant, as there is no force acting
on it and is taken to be zero for mathematical simplicity. When the particle strikes any one of the
walls, it is bounced back immediately as the walls are perfectly rigid. Therefore, potential energy
of the particle becomes infinite at the walls. Thus, potential energy function is defined as flows;

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𝑉 (𝑥) = ∞ 𝑓𝑜𝑟 0 ≥ 𝑥 ≥ 𝑎
𝑉(𝑥) = 0 𝑓𝑜𝑟 0<𝑥<𝑎 ------ (1)
The Schrodinger wave equation for a particle of energy E and potential energy V is
𝜕 2 𝜓 8𝜋 2 𝑚
+ (𝐸 − 𝑉)𝜓 = 0 − − − (2)
𝜕𝑥 2 ℎ2
But, for the region where particle is present (0<x<a) V = 0. Therefore equation(2) becomes
𝜕 2 𝜓 8𝜋 2 𝑚
+ 𝐸𝜓 = 0 − − − (3)
𝜕𝑥 2 ℎ2
Let,
8𝜋 2 𝑚
𝐸 = 𝑘 2 − − − (4)
ℎ2
Equation (3) becomes
𝜕2𝜓
+ 𝑘 2 𝜓 = 0 − − − (5)
𝜕𝑥 2
The general solution of the equation (5) is given by

𝜓 = 𝐴 𝑆𝑖𝑛 𝑘 𝑥 + 𝐵 𝐶𝑜𝑠 𝑘 𝑥 − − − (6)

Where A and B are constants. The values of A and B can be obtained by applying boundary

conditions.

The first boundary condition is on the wall A i.e at x = 0, ψ = 0 (ψ = 0 means particle is not existing

on the wall A)

Equation (6) gives

0 = A Sin (k.0) + B Cos (k.0)  0 = A Sin0 + B Cos 0

i.e 0 = 0 + B  B = 0

The second boundary condition is on the wall B i.e at x = a, ψ = 0 (ψ = 0 means particle is not
existing on the wall B)
Equation (6) gives
0 = A Sin (k.a) + B Cos (k.a); But B = 0

0 = A sinka  ka = n where n = 0, 1, 2…….

i.e k = n/a ---- (7)

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Equation (6) become

𝑛𝜋
𝜓 = 𝐴 𝑠𝑖𝑛 𝑘 𝑥 = 𝐴 𝑠𝑖𝑛 ( 𝑥) − − − (8)
𝑎
The value of A can be determined by using the normalization condition
𝑎 𝒂 𝒏𝝅
∫0 |𝜓|2 𝑑𝑥 = 1 𝑖. 𝑒 ∫𝟎 𝑨𝟐 𝒔𝒊𝒏𝟐 ( 𝒂 𝒙) 𝒅𝒙 = 𝟏
𝒂
𝟏 𝟐𝒏𝝅 𝟏
𝑨𝟐 ∫ (𝟏 − 𝒄𝒐𝒔 𝒙) 𝒅𝒙 = 𝟏| ∵ 𝒔𝒊𝒏𝟐 𝜽 = (𝟏 − 𝒄𝒐𝒔 𝟐 𝜽)
𝟎 𝟐 𝒂 𝟐
𝑨𝟐 𝒂 𝒂 𝟐𝒏𝝅 𝑨𝟐 𝒂 𝟐𝒏𝝅 𝒂
[∫𝟎 𝒅𝒙 − ∫𝟎 𝒄𝒐𝒔 𝒅𝒙] = 𝟏𝒊. 𝒆 [𝒙|𝒂𝟎 − 𝒔𝒊𝒏 𝒙| ] = 𝟏
𝟐 𝒂 𝟐 𝟐𝒏𝝅 𝒂 𝟎

𝑨𝟐 𝒂 𝟐
[(𝒂 − 𝟎) − (𝟎 − 𝟎)] = 𝟏 ⇒ 𝑨 = √
𝟐 𝟐𝒏𝝅 𝒂

 Equation (8) becomes

2  n 
= sin  x  − − − (9) where n = 1, 2, 3, …………..
a  a 
Equation (9) is called the Eigen function for a particle in an one
dimensional potential well of finite width and infinite height.
From Equations (4) and (7) we get

8𝜋 2 𝑚 𝑛2 𝜋 2
𝐸= 2
ℎ2 𝑎

𝑛2 ℎ 2
∴ 𝐸= ----- (10) where n = 1, 2, 3, ………….
8𝑚𝑎2

Equation (10) is called the Energy Eigen value for a particle in an one dimensional potential well
of finite width ‘a’ and infinite height. From equation (10), it is clear that energy eigen values are
discrete or quantized.

Discussion on Eigen functions and Energy Eigen values:

Eigen functions:

2 𝑛𝜋
From Equation (9) we have the Eigen function as 𝜓 = √ 𝑠𝑖𝑛 ( 𝑥)
𝑎 𝑎

2 𝜋
For n = 1 (Ground state), 𝜓1 = √ 𝑠𝑖𝑛 ( 𝑥)
𝑎 𝑎

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2 2𝜋
For n = 2 (First excited state), 𝜓2 = √ 𝑠𝑖𝑛 ( 𝑥)
𝑎 𝑎

2 3𝜋
For n = 3 (Second excited state), 𝜓3 = √ 𝑠𝑖𝑛 ( 𝑥) etc.
𝑎 𝑎

The Eigen functions ψ’s together with probability densities ψ2’s for first three states (n=1, 2, 3)
are plotted in figure below.

Energy Eigen values:

𝑛2 ℎ2
From Equation (10) we have the Energy Eigen value as 𝐸 =
8𝑚𝑎2

ℎ2
For n = 1 (Ground state energy or zero point energy), 𝐸1 =
8𝑚𝑎2

4ℎ2
For n = 2 (First excited state energy), 𝐸2 = = 4𝐸1
8𝑚𝑎2

9ℎ2
For n = 3 (Second excited state energy), 𝐸3 = = 9𝐸1 etc.
8𝑚𝑎2

From above equations it is clear that E1:E2:E3:……..=1:4:9:…….. It means that energy levels are
not equally spaced as shown in below figure.

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2) Finite potential well

The finite potential well (also known as finite square well) is an extension of the infinite potential
well, in which a particle is confined to a ‘box’, but one which has finite potential walls. Unlike the
infinite potential well, there is a probability associated with the particle being found outside the
box, ie., there is a non-zero probability of the particle being outside the box even when the energy
of the particle is less than the potential energy barrier of the walls.
The finite height barrier is described by the following potential energy function:
𝑉(𝑥) = 𝑉0 , 𝑤ℎ𝑒𝑛 𝑥 < 0
𝑉(𝑥) = 0, 𝑤ℎ𝑒𝑛 0 ≤ 𝑥 ≤ 𝐿
𝑉(𝑥) = 𝑉0 , 𝑤ℎ𝑒𝑛 𝑥 > 𝐿

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In case of finite potential well, the wavefunction inside the potential well will have the same form
as that for the infinite square well, but without the boundary condition necessitating it to become
zero at the boundaries of the well.
The equations for the region I and III will take the form as
𝜕 2 𝜓 8𝜋 2 𝑚
+ (𝐸 − 𝑉0 ) 𝜓 = 0
𝜕𝑥 2 ℎ2

For the given energy E, the tern (E – V0) will always be negative as long as E < V0. This implies
that the RHS of the above equation will be non-zero and positive, which in turn implies that
the wavefunction will be a combination of exponential functions. Thus, the wavefunction will
become,

It can be noticed that inside the well, the wavefunction is the same as that for the infinite square
well. Outside the well, i.e., in the boundaries, it behaves exponentially.

I. Wave function and Probability function when particle is in its ground state:

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Finite Potential Well Infinite Potential Well

II. Wave function and Probability function when particle is in its first excited state:
Finite Potential Well Infinite Potential Well

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Quantum Tunneling:
Quantum tunneling is a phenomenon where a wavefunction can propagate through a potential
barrier or a particle can penetrate a potential energy barrier with a height greater than the total
energy of the particles. Tunneling is a quantum mechanical effect. A Tunneling current occurs
when electrons move through a barrier that they classically should not be able to move through.
Quantum mechanics tells us that electrons have both wave and particle like properties and
tunneling is an effect of the wavelike nature.

Consider a particle with energy E in the inner region of a one-dimensional potential well V(x). In
classical mechanics, if E < V (the maximum height of the potential barrier), the particle remains
in the well forever; if E > V , the particle escapes. In quantum mechanics, the situation is not so
simple. The particle can escape even if its energy E is below the height of the barrier V, although
the probability of escape is small unless E is close to V. In that case, the particle may tunnel through
the potential barrier and emerge with the same energy E.

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For a quantum particle to tunnel through the barrier, the following three conditions must be met.

1. The height of the potential barrier must be finite and the thickness of the barrier must be
thin
2. The potential energy of the barrier exceeds the kinetic energy of the particle.
3. The particle must have the wave properties because the wave function is able to penetrate
through the barrier. This suggests that the tunnelling, can only be apply to microscopic
objects such as electrons, protons and so and does not apply to macroscopic objects.
If these conditions are met, there would be a probability of finding the particle on the other side of
the barrier.

Applications:

• Nuclear fusion

• Radioactive decay

• Quantum conductivity

• Scanning tunnelling microscope

• Tunnel diode

• Tunnel field-effect transistors

• Quantum biology
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