QUANTUM MECHANICS

Quantum Mechanics (Wave –Mechanics)

In classical mechanics the motion of particle is usually described using the time dependent position
x(t) as the dynamical variable. For example F = ma = mẍ.

In wave mechanics the dynamical variable is a wave function.

The wave function depends on position and time and it is a complex number, i.e. ψ (r, t) Є ₡
(pronounced as ψ (psi) belongs to complex).

Quantum mechanics was developed in 1925 by Schrödinger and Heisenberg. Schrödinger method
involves partial difference equation. Heisenberg’s method employs matrices. Since former
involves the solution of wave equations, it is also called wave-mechanics; and latter, which
involves matrices, is called matrix mechanics. Though both of them are equivalent.

In this syllabus we shall mostly confine ourselves to wave-mechanics only.

The Schrödinger Equation

If a mass (particle) ‘m’ is moving along x-axis subject to a specified force F(x,t). Classical
mechanics looks to determine the position of the particle at any given time x(t). Once we know
this information v, p etc. can be determined. Relevant equation is Newton’s 2nd law of motion

F = ma
𝑑2 𝑥 ∂𝑣
or 𝑚 𝑑𝑡 2 = − ∂𝑥

Where, we have assumed i) force is not magnetic and ii) motion is not relativistic.

Quantum mechanics approaches the problem quite differently. Here we look for a wave function,
ψ (x, t), of the particle and we get it by solving the Schrödinger Equation

∂Ψ(x,t) ћ2 ∂2
iћ = [− + V(x, t)] Ψ(x, t)
∂t 2m ∂x2

The corresponding 3 dimensional equation Schrödinger Equation is

∂Ψ ћ2
iћ = [− ∇2 Ψ + VΨ]
∂t 2m

h
Here, i = √-1 and ћ = = reduced Planck’s constant ≈ 1.054 x 10-34 J-s.
2𝜋

1
Given suitable initial condition ψ (x, 0), we can determine ψ (x, t) for all future time, as in
classical mechanics Newton’s law determines x(t) for all future time.

There are several ways to develop wave equation by applying quantum concepts to various
classical equations of mechanics. One is to consider a few basic postulates, develop the wave
equation from them and rely on the accuracy of the results to serve as a justification of the
postulates.

Basic postulates

1. Each particle in a physical system is described by a wave function ψ (x, y, z, t). This
∂Ψ ∂Ψ ∂Ψ
function and its space derivative ( ∂x + + ∂z ) are continuous, finite and single
∂y
valued.
N.B.
i) ψ is related to a physical quantity, so it can’t be discontinuous at any point.
ii) If ψ is infinite it would imply infinite large probability of finding the particle ín that
region, which is in violation of uncertainty principle.
∞
iii) Single valued as the function ∫−∞ Ψ∗ Ψ 𝑑𝑥 must have oly one numerical value.
2. In dealing with classical quantities such as energy E and momentum p, we must relate these
quantities with abstract quantum mechanical operators as following

Classical variables Quantum operator

x x

f(x) f(x)
∂
p(x) - iћ
∂x

∂
E iћ
∂t

V(x) V(x)

And similarly for other directions.

3. The statistical interpretation of the wave function

By nature particle is localized, whereas the wave function is spread out in space. How can
such an object describe the state of a particle? To understand this we need to answer the
following questions. What is a wave function? What is it significance? What we can do
with it?
The answer to all of the above questions is given by Bohr’s statistical interpretation of the
wave function:

2
 |Ψ(x, t)|2 gives the probability of finding the particle at point x at time t. i.e.

|Ψ(x, t)|2 dx = probability of finding the particle between x and (x + dx) at time t.

Fig. 1. A typical wave function.

The particle would be relatively likely to be found near A, unlikely to be near B. The shaded area
represents the probability of finding the particle in the range dx.

The statistical interpretation introduces a kind of indeterminacy into quantum mechanics, i.e you
can’t predict with certainty the outcome of a simple experiment like to measure the position of a
particle. Quantum mechanics offers statistical information about possible results.

Is this a peculiarity of the nature, a deficiency in the theory, a fault in the measurement apparatus,
or what?

If I measure the position of a particle and I find it to be at point C. Where was the particle just
before I made the measurement?

1. The realist position: It was at C. (Einstein believed this). If this is true then quantum
mechanics is an incomplete theory since the particle was at C and quantum mechanics was
unable to tell us so. (In other words, indeterminacy is not a fact of nature, but a reflection
of our ignorance).
2. The orthodox position (Copenhagen interpretation): The particle wasn’t really anywhere.
It was the act of measurement that forced the particle to take a stand.
3. The agnostic position: Refuse to answer.

In 1964 John Bell came up with an astonishing result that it makes observable difference if the
particle had a precise (though unknown) position prior to the measurement. An immediate and
repeated measurement must return the same value. It is said that the wave function collapsed upon
measurement, to a spike at the point C (say). (ψ, however, will soon spread in accordance with the
Schrödinger equation, so the second measurement must be made quickly).

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Fig. 2. Collapse of wave function immediately after the measurement found the particle at C.

Therefore, there are two distinct physical processes, (i) the ordinary one where wave function
evolves leisurely as per Schrödinger equation, and (ii) sudden and discontinuous collapse of the
eave function due to measurements.

Normalization of Wave function

The product |Ψ(x, t)|2 = Ψ ∗ Ψ, Ψ∗ being the complex conjugate of Ψ, is normalized according
to
∞ ∞
∫−∞|Ψ|2 𝑑𝑥 = ∫−∞ Ψ ∗ Ψ 𝑑𝑥 = 1

And the average or expectation value 〈𝛼〉 of any variable 𝛼 is calculated from the wave function
by using the general formula
∞
∫−∞ Ψ∗ (𝑥)𝛼 Ψ(x)𝑑𝑥
〈𝛼 〉 = ∞
∫−∞ Ψ∗ (𝑥)Ψ(x)𝑑𝑥
∞
If, however, if the wave function is normalized then ∫−∞ Ψ ∗ (𝑥) Ψ(x)𝑑𝑥 = 1 and the expectation
value is given by
∞
〈𝛼〉 = ∫−∞ Ψ ∗ (𝑥)𝛼 Ψ(x)𝑑𝑥

Once we find the wave function Ψ for particle, we can calculate its average position, energy or
momentum within the limits of uncertainty principle. So major effort in quantum mechanics is to
solve Ψ within the conditions imposed by a particular physical system.

Formulation of Schrödinger Equation

The classical equation for energy of a particle of mass m

Kinetic Energy + Potential Energy = Total Energy

4
 1
or 𝑚𝑣 2 + 𝑉 = 𝐸
2

𝑝2
or +𝑉 =𝐸 where p = mv is the momentum of the particle.
2𝑚

∂ ∂
Using quantum mechanical operators to for p (= - iћ ) and E (= iћ ) we get if we allow the
∂x ∂t
operators to operate on the wave function ψ(x,t)
ћ2 ∂2 ψ(x,t) ∂ψ(x,t)
− + V(x)ψ(x, t) = iћ (1)
2m ∂x2 ∂t

Eqn. 1 is the Schrödinger Equation for one dimensional problem. Here the operational
∂ 2 ∂2
interpretation of (∂x) is the second derivative form for , and i2 = -1.
∂x2

In three dimension the Schrödinger Equation is

ћ2 ∂Ψ
− ∇2 Ψ + VΨ = iћ (2)
2m ∂t

If we assume potential, V, is independent of time, t, then we can solve the Schrödinger Equation
by the method of separation of variables. We look for solution that are simple product

Ψ(x, t) = ψ(x)f(t) (3)

Using Eqn. 3 in Eqn. 1 we get

ћ2 ∂2 ψ(x) ∂f(t)
− 𝑓(𝑡) + V(x)ψ(x)f(t) = iћψ(x)
2m ∂x2 ∂t

Dividing both sides by ψ(x)f(t) gives

ћ2 1 d2 ψ(x) 1 df(t)
− + V(x) = iћ (4)
2m ψ(x) dx2 f(t) dt

Since left hand side is a function of ‘x’ only and right hand side is a function of ‘t’ alone, this is
true only if both sides are separately equal to a constant. Let the constant be E.

Now the variables can be separated and we get time dependent Schrödinger Equation
𝑑𝑓(𝑡) 𝑖𝐸
= − 𝑓(𝑡)
𝑑𝑡 ћ

𝑑𝑓(𝑡) 𝑖𝐸
Or + 𝑓(𝑡) = 0 (5)
𝑑𝑡 ћ

And the time independent Schrödinger Equation

5
 ћ2 1 d2 ψ(x)
− + V(x) = E
2m ψ(x) dx2

ћ2 d2 ψ(x)
− + V(x)ψ(x) = Eψ(x) (6)
2m dx2

Eqn. (5) and (6) are time dependent and time independent Schrödinger Equation, respectively.
Thus the separation of variables has turned a differential equation into two ordinary differential
equations.

The general solution of Eqn. (5) is C.exp(-iEt/ћ). But we may absorb the constant C into ψ, as
our quantity of interest is ψ(x)f(t). Then
−𝑖𝐸𝑡
𝑓(𝑡) = 𝑒 ћ (7)

The Eqn. (6), known as time independent Schrödinger Equation, can be solved when the potential
V is specified.

The general solution of Ψ(x, t) is

−𝑖𝐸𝑡
Ψ(x, t) = ψ(x)𝑒 ћ (8)

Properties of Schrödinger's equation

1. Linearity: The Schrödinger equation is linear in the wave-function Ψ which means that the
equation does not involve higher powers of the wave-function or its derivatives.

2. Superposition: The linearity of Schrödinger's equation implies that a linear combination of

solutions of Schrödinger's equation for any system is also a solution. Hence, if Ψ1 and Ψ2 satisfy
the Schrödinger's equation then

Ψ = a1 Ψ1 + a2 Ψ2 (9)

is also a solution, where a1 and a2 are constants. Hence, the wave-functions Ψ1 and Ψ2 obey the
superposition principle. The superposition principle is the main difference between quantum
mechanics and classical mechanics. The fact that particles can be described by waves whose
amplitudes can be added cannot be explained by classical mechanics.

Operators, Eigenfunctions, Eigenvalues, Expectation values

6
Every physical observable (quantity) in Classical Mechanics can be represented by an operator in
Quantum Mechanics which acts on the wave-function (a particular state of the particle) to produce
another wave-function. Thus,

𝑂̂Ψ = Ψ′ (10)

Where 𝑂̂ represents the operator. The following table represents the operators associated with
various observable quantities.

Observable (Quantity) Operator

Position, x x
Linear momentum, p ∂
−iћ
∂x
Potential Energy, U(x) U(x)
Kinetic Energy, KE = 2𝑚
𝑝2 ћ2 2
− ∇
2m
Total Energy, E ∂Ψ
iћ
∂t
Hamiltonian H = KE (Kinetic Energy) + PE ћ2 2
(Potential Energy) − ∇ +V
2m

̂1 and 𝑂
Two operators 𝑂 ̂2 are said to commute if

̂1 𝑂
𝑂 ̂2 Ψ = 𝑂
̂2 𝑂
̂1 Ψ or ̂ ̂2 Ψ − 𝑂
𝑂1 𝑂 ̂2 𝑂
̂1 Ψ = 0 (11)

for all Ψ. If two operators commute, they can be simultaneously determined precisely. The
̂1 and 𝑂
commutation relation for two operators 𝑂 ̂2 is given by

[𝑂̂ ̂ ̂̂ ̂̂
1 , 𝑂2 ] = 𝑂1 𝑂2 − 𝑂2 𝑂1 (12)

If two operators commute then [𝑂̂ ̂

1 , 𝑂2 ] = 0

7
Example 2

Prove that the observables position x and momentum px cannot be determined simultaneously by using the
commutation relation.

Solution:

∂Ψ ∂ ∂Ψ ∂Ψ ∂x
[𝑥, 𝑝𝑥 ] Ψ = (x𝑝𝑥 − 𝑝𝑥 x) Ψ = −iћ (x − (xΨ)) = −iћ (x − (x + Ψ ))
∂x ∂x ∂x ∂x ∂x

∴ [𝑥, 𝑝𝑥 ] Ψ = iћΨ or [𝑥, 𝑝𝑥 ] = iћ

Since, the operators x and px do not commute, they cannot be determined simultaneously with 100%
accuracies.

Given an operator 𝑂̂, it is possible to find a wave-function Ψ(x) such that

𝑂̂ Ψ(x) = Ψ(x) (13)

Where  is a constant independent of x. The function Ψ(x)is called an eigenfunction of 𝑂̂ and  is

the corresponding eigenvalue of 𝑂̂.

N.B.

Eigenvalues
The eigenvalues are related to observed values in experimental measurements in the following
manner. The observed value obtained from a single measurement is an eigenvalue.
Expectation values
In a large number of measurements (or measurement over a prolonged period of time), the
measured value is an average value or expectation value. The expectation value of any observable
quantity  is given by
∞
∫−∞ Ψ∗ (𝑥)𝛼 Ψ(x)𝑑𝑥
〈𝛼 〉 = ∞ (14)
∫−∞ Ψ∗ (𝑥)Ψ(x)𝑑𝑥
∞
Now, if the wave-function is normalized then ∫−∞ Ψ ∗ (𝑥) Ψ(x)𝑑𝑥 = 1 and the expectation
value is given by
∞
〈𝛼 〉 = ∫−∞ Ψ ∗ (𝑥 )𝛼 Ψ(x)𝑑𝑥 (15)

8
Some important properties of eigenvalues and eigenfunctions

1. If Ψ(x) is an eigenfunction of an operator 𝑂̂ with eigenvalue , then bΨ(x), where b is a

constant, is also an eigenfunction of the same operator with the same eigenvalue . Hence,
multiplying an eigenfunction with a constant does not change the eigenvalue.

2. If there are two eigenfunctions having the same eigenvalue, then the eigenfunctions are said to
be degenerate eigenfunctions.

3. An operator is termed as a Hermitian operator if all its eigenvalues are real and the
eigenfunctions corresponding to different eigenvalues are orthogonal.

Example 3

A particle limited to the x axis has wave-function Ψ = ax between x = 0 and x = 1; while Ψ = 0

elsewhere, (a) Find the probability that the particle can be found between x = 0.45 and x = 0.55, (b)
Find the expectation value of the particle's position.

Solution:
0.55
,𝑥 0.55 𝑥3
(a) The probability is ∫𝑥 2|Ψ|2 𝑑𝑥 = 𝑎2 ∫0.45 𝑥 2 𝑑𝑥 = 𝑎2 [ ] = 0.0251𝑎2
1 3 0.45

1 1 𝑎2
(b) The expectation value is 〈𝑥〉 = ∫0 𝑥|Ψ|2 𝑑𝑥 = 𝑎2 ∫0 𝑥 3 𝑑𝑥 = 4

Example 4

An eigenfunction of the operator d2/dx2 is  = e2x. Find the corresponding eigenvalue.

Solution:
Solutions of Schrödinger's equation:
𝑑2 𝑑2
Let 𝑂̂ = 𝑑𝑥 2, so, 𝑂̂ = 𝑑𝑥 2 (e2x ) = 4e2x = 4
I. Particle in a one-dimensional infinitely deep potential well
Comparing it with the Eq. 𝑂̂ Ψ(x) = Ψ(x) , we obtain  = 4.

Hence, the eigenvalue of the given operator is 4.

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Schrödinger's equation : Time-Dependent Form for a free particle

The one-dimensional time dependent Schrödinger equation for a free non-relativistic particle (V =
0) is given below
ћ2 ∂2 ψ(x,t) ∂ψ(x,t)
− 2m = iћ (1)
∂x2 ∂t

A free particle of total energy E and momentum p moving in the +x direction can be described by
the wave-function Ψ of a place monochromatic wave. The expression for Ψ is given by
i
Ψ(x, t) = A exp ( (px − Et)) (2)
ћ

where A = amplitude of displacement of the wave

ћ = reduced Planck constant (h/2) = 1.05457 x 10-34 J.s

The energy E and momentum p of the particle are related to its wave-vector k and frequency  by
the relations
2𝜋
p = ћk = ћ , E = ћ


Differentiating Eq. (2) once with respect to time gives,

𝜕Ψ(x, t) 𝐸
= −𝑖 Ψ(x, t)
𝜕𝑡 ћ
or
∂Ψ(x,t)
iћ = EΨ(x, t) (3)
∂t

Differentiating Eq. (2) twice with respect to x gives,

∂Ψ(x,t)
−iћ = pΨ(x, t)
∂x

∂2 Ψ(x,t)
−ћ2 = p2 Ψ(x, t) (4)
∂x2

Dividing both sides of Eq. (4) by (1/2m), we obtain,

ћ2 ∂2 Ψ(x,t) p2
− = Ψ(x, t) (5)
2m ∂x2 2m

Comparing equations (1), (3) and (5), the energy E and momentum p of a free non-relativistic
particle of mass m are related by the expression
𝑝2 ℏ2 𝑘 2
𝐸= = (6)
2𝑚 2𝑚

10
As the particle is free, there are no boundary conditions to be applied to the particle motion and
hence there are no restrictions on wave-vector k. As a result, the particle can possess any value of
energy or the energy is not quantized. Thus, a freely moving particle possesses a continuous energy

spectrum as given in the adjoining figure.

Some applications of Schrödinger's equation

Infinite Square-well Potential
V=∞ V=∞
Let us solve the problem of infinite potential well.

Let us assume that a particle of mass m trapped in a

one-dimensional infinitely deep potential well with

V=0
V(x) = 0 except at boundaries x=0 and x=L, where

it is infinitely large as shown in the figure. x=0 x=L

Therefore,

V(x) = 0 for 0 < x < L

= ∞ for x ≤ 0 and x ≥ L (1)

We have to find out the eigenfunction and the corresponding eigenvalues for this problem.

Inside the well V(x) = 0. Therefore, the time independent Schrödinger equation can be written as

d2 (x) 2mE
+ (x) = 0 0<x<L (2)
dx2 ћ2
d (x)
2
+ k 2 (x) = 0 (3)
dx2

2mE
Where k 2 =
ћ2

11
This is simple harmonic oscillator equation. The general solution is

(x) = A sinkx + B cos kx (4)

Where A and B are the arbitrary constants that can be found from boundary conditions.

Continuity of ψ(x) requires

ψ(0) = ψ(L) = 0 (5) ∴

(0) = A sin(k. 0) + B cos(k . 0) = 0

Therefore, 𝐵=0
and (x) = A sin(kx) (6)

Now (L) = Asin(kL) = 0

Since A cannot be zero as it will give trivial, non normalizable solution ψ(x) = 0, we have

sin (kL) = 0 or kL = 0, ±, ±2, ±3, ….

Again k=0 is not acceptable as it will imply ψ(x) = 0 and the ‘-’ve sign can be absorbed into
A. Therefore we have
𝑛𝜋
𝑘𝑛 = n = 1, 2, 3, ...... (7)
𝐿

From Eqn. (3) and (7), we solve for the total energy En for each value of the integer n

√(2𝑚𝐸𝑛 ) 𝑛
=
ћ 𝐿

2 𝑛2 ћ2
𝐸𝑛 = (8)
2𝑚𝐿2

In contrast to the classical case, a quantum particle in the infinite square well can have only certain,
discrete values of energy depending on the value of n. Thus, the energy becomes quantized due to
confinement of the particle. Hence, a particle in an infinite potential well can have only bound
states.

The energy E1 is called the zero-point energy. Obviously, the energy is not zero in this case. The
zero-point energy is the consequence of the uncertainty principle. If the energy of the particle is
zero, its momentum is also zero. Then according to uncertainty principle, the position of the
particle would become infinite and the particle cannot be confined to the box. Therefore, the
particle cannot have zero energy.

12
The eigenfunctions corresponding to the above energy eigenvalues is given by

2𝑚𝐸𝑛
𝑛 = 𝐴 sin 𝑘𝑥 = 𝐴 sin √ 2 𝑥 (9)
ћ

The constant A can be found from the normalization condition,

𝐿 2 𝐿 𝑛𝜋𝑥 𝐿
∫0 |𝑛 | 𝑑𝑥 = 𝐴2 ∫0 𝑠𝑖𝑛2 ( 𝐿
) 𝑑𝑥 = 𝐴2 2 = 1

2
Or 𝐴 = √𝐿 (10)

Hence, the normalized wave-functions for a particle in a one-dimensional infinitely deep potential
well is given by

2 𝑛𝜋𝑥
𝑛 (𝑥) = √𝐿 𝑠𝑖𝑛 𝐿
where n = 1, 2, 3, ……. (11)

First three wave functions are shown above.

Particle trapped in a three-dimensional box

For particle trapped in a three-dimensional square box of length a, the energy eigenvalues are given
by

13
 2 ћ2
𝐸 = 𝐸𝑥 + 𝐸𝑦 + 𝐸𝑧 = (𝑛𝑥2 + 𝑛𝑦2 + 𝑛𝑧2 ) 2𝑚𝑎2 (I)

The corresponding eigenfunction in three dimensions is given by

3
2 𝑛𝑥 𝜋𝑥 𝑛𝑦 𝜋𝑦 𝑛𝑧 𝜋𝑧
𝜓 = 𝜓𝑥 𝜓𝑦 𝜓𝑧 = (√𝑎) sin sin sin (II)
𝑎 𝑎 𝑎

Example 5

Find the probability that a particle trapped in a box L wide can be found between 0.45L and
0.55L for the ground and first excited states.

Solution:

0.55𝐿 2 0.55𝐿 𝑛𝜋𝑥 𝑥 1 2𝑛𝜋𝑥 0.55 𝐿

Probability = ∫0.45𝐿 |𝜓𝑛 |2 𝑑𝑥 = ∫ 𝑠𝑖𝑛2 𝑑𝑥 = [𝐿 − 2𝑛𝜋 sin ]
𝐿 0.45𝐿 𝐿 𝐿 0.45 𝐿

For the ground state, i.e., n = 1, Probability = 0.198 = 19.8%

For the first excited state, i.e., n = 2, Probability = 0.0065 = 0.65%

Example 6

Find the expectation value for the position <x> and momentum <p> of a particle trapped in a
box of width L.

Solution:
𝐿
∞ 2 𝐿 𝑛𝜋𝑥 2 𝑥2 𝑥 sin(2𝑛𝜋𝑥⁄𝐿 ) cos (2𝑛𝜋𝑥⁄𝐿 )
〈𝑥〉 = ∫−∞ 𝑥|𝜓|2 𝑑𝑥 = ∫0 𝑥𝑠𝑖𝑛2 𝑑𝑥 = 𝐿 [ 4 − − ]
𝐿 𝐿 (4𝑛𝜋⁄𝐿 ) 8(𝑛𝜋⁄𝐿 )2 0

Putting sin 𝑛𝜋 = 0, cos 2𝑛𝜋 = 1 𝑎𝑛𝑑 𝑐𝑜𝑠0 = 1, we obtain

2 𝐿2 𝐿
〈𝑥〉 = ( )=
𝐿 4 2

2 𝑛𝜋𝑥 𝑑𝜓 2 𝑛𝜋 𝑛𝜋𝑥
𝜓 ∗ = 𝜓 = √𝐿 𝑠𝑖𝑛 ; = √𝐿 cos
𝐿 𝑑𝑥 𝐿 𝐿

∞ ∞ 𝐿
∗
𝑑 2 𝑛𝜋 ∗
𝑛𝜋𝑥 𝑛𝜋𝑥
〈𝑝〉 = ∫ 𝜓 𝑝̂ 𝜓 𝑑𝑥 = ∫ 𝜓 (−𝑖ℏ ) 𝜓 𝑑𝑥 = −𝑖ℏ ∫ 𝑠𝑖𝑛 cos 𝑑𝑥
𝑑𝑥 𝐿 𝐿 𝐿 𝐿
−∞ −∞ 0

1
Now, ∫ sin 𝑎𝑥 cos 𝑎𝑥 𝑑𝑥 = 𝑠𝑖𝑛2 𝑎𝑥
2𝑎

𝑛𝜋 14
Substituting a = , we get 〈𝑝〉 = 0
𝐿
Particle trapped in a finite potential well or a square potential well with finite barriers

Consider a particle of mass m and energy E in a finite potential well with finite barriers.

The finite potential well is an extension of the infinite potential well. The main difference
between these two systems is that now the particle has a non-zero probability of finding itself
outside the well, although its kinetic energy is less than that required, according to classical
mechanics, for scaling the potential. This type of problem is more realistic, but more difficult
to solve due to the yielding of transcendental equations. The particle is again confined to a box,
but one which has finite, not infinite, potential walls.

V (x)
The Finite Potential Well

V0

III I II
Here,
x
-L/2 0 L/2

Let E be the energy of the particle incident on this potential well of height Vo.

When the energy of the particle is less than that of the potential, i.e., when E < V0, it gives rise to
a bound state. The energy spectrum of the bound states is discrete, unlike free particles, which
have a continuous spectrum.

On the other hand, when the energy of the particle is greater than that of the potential, i.e., when
E > V0, it gives rise to an unbound state. The unbound states have a continuous energy spectrum.

Consider that the total energy E of the particle in region I is less than V0 i.e., E < V0. According to
classical mechanics, when the particle strikes the sides of the barrier, it bounces back without
entering regions II and III. This are the classically forbidden region since the particle would reflect
off from the potential wall completely. The same system in quantum mechanics gives a non-zero
probability that the particle will be transmitted into the regions II and III. This is a wave
phenomenon, but in quantum mechanics particles exhibit wave-like properties.

The phenomenon of barrier penetration by a particle is termed as quantum tunnelling. Hence,

quantum particles can be found in regions where a classical particle could never go, since, it would
have negative kinetic energy. But in quantum theory, too, the eigenvalues of kinetic energy cannot
be negative. How, then, can a quantum particle “tunnel”?

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The apparent paradox is resolved by noting that the wave-function of a tunnelling particle only
partly overlaps the forbidden region. There is no wave function that represents a particle restricted
to a region where its potential energy is larger than its total energy.

The wavefunction of the tunneling particle decreases exponentially in the barrier. The approximate
transmission probability or tunneling probability T for a particle having energy E to pass through
the barrier of height 𝑉0 is given by

𝑇 = 𝑒 −2𝛼𝐿

√2𝑚(𝑉0 −𝐸)
where 𝛼 = ℏ

The tunneling probability is strongly dependent on the width of the barrier, the mass of the particle,
and the quantity V-E. For instance, the ratio of tunneling probability for protons to electrons is
around a factor of 10^-91. So electrons are much more likely(!) than protons at the same energy to
tunnel through the same barrier. Similarly, if the walls of the potential well of finite height are
infinitely thick, then the particle is forever trapped inside the potential well if its energy is less than
the height of the barrier. However, if the barrier has finite width, then the particle with energy less
than the height of the barrier can pass through it and emerge from the other side.

A measure of the depth of tunnelling is determined by the penetration depth (). It is related to 
by the relation  = 1/ . At the distance equal to the penetration depth, the wave-function is reduced
by a factor of 1/e.

The energy of the particle in a finite potential well is

ℏ 2 𝑘𝑛
2 𝑛
𝐸= where 𝑘𝑛 =
2𝑚 𝐿

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

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Comparison between infinite and finite potential well

1. The wave-function 𝜓(𝑥) is confined to the infinite well while 𝜓(𝑥) spreads out beyond
the finite well.
2. The energy levels in a finite potential well are lower than the infinite well as the wave-
function spreads out (by penetrating the classically forbidden region) which reduces its
kinetic energy.
3. There are no unbound states in an infinite potential well while there are unbound states in
a finite potential well when E > V0.

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