Unit 3: QUANTUM MECHANICS-2

Wave-function

The determination of wave-function Ψ, representing the de-broglie wave of a particle is the

principle concern of quantum mechanics. While the wave-function Ψ (r, t) is not a measurable
quantity by itself, the square of its absolute magnitude |Ψ| at any particular place and time is
proportional to the probability of finding the particle at that place and time. The magnitude of
wave-function is large in regions where the probability of finding the particle is high and vice-
versa. The linear and angular momentum, energy are other quantities that can be extracted from
the wave-function Ψ. The wave-function can be real or imaginary while its probability density
|Ψ| is always a real positive quantity.

Probability density of wave-function

The probability density of a wave-function Ψ is the product of Ψ and its complex conjugate Ψ*.
Every complex wave-function can be written in the form

Ψ = A + iB

where A and B are real functions. The complex conjugate Ψ* of Ψ is

Ψ* = A - iB

and hence,

|Ψ| = Ψ ∗ Ψ = A − i B = A + B

This proves that the probability density is always a real, positive quantity.The probability of
finding a particle between the co-ordinates x1 and x2 is equal to the integral of probability density
over that region.
,
, = |Ψ|

Probability interpretation of wave-function by Max Born

Born proposed that the square of the magnitude of the wave function |Ψ| evaluated in a particular
region represents the probability of finding the particle in that region.

Normalization
The wave-function Ψ must fulfill certain requirements. Since, |Ψ| is proportional to the
probability density P of finding the body described by Ψ, the integral of |Ψ| over all space must
be finite.

i.e.,∫ |Ψ| =∫ Ψ∗ Ψ = 1(Normalization condition)

A wave-function satisfying the above condition is said to be normalized. It is possible to normalize

any acceptable wave-function by multiplying it by an appropriate constant.

Well-behaved wave-functions

A wave-function Ψ is well-behaved (i.e., capable of yielding meaningful results) if it satisfies the

following conditions:

1. Ψ must be finite and continuous at all points in space. All its first and second-order partial
derivatives must also be finite and continuous everywhere. If Ψ is infinite, it would imply an
infinitely large probability of finding the particle in that region which would be in violation to the
uncertainty principle. Also, since Ψ is related to a physical quantity, it cannot have a discontinuity
at any point.

2. The function must be single-valued; i.e. at any point in space, the function ∫ Ψ ∗ Ψ must have
only one numerical value. This is because any physical quantity can have only one value at a point.

3. Ψ must be normalizable, i.e., Ψ must go to zero as x, y, z tends to ±∞ in order that ∫ |Ψ| =

.

4. The wave functions must be orthogonal. i.e.,∫ Ψ∗ Ψ =0 ℎ ≠ .

In thenext section, we obtain Schrödinger's equation, the fundamental equation of quantum

mechanics, analogous to the second law of motion of Newtonian mechanics. The solution of the
Schrödinger's equation should not only describe the corpuscular and wavelike behaviour of
particles like electrons and protons but must also be in complete agreement with the uncertainty
principle. Hence, the trajectory of the particle is described by the wave-function Ψ (r, t).

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

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

Ψ(x, t) = A exp (px − Et (1)

ћ

where A = amplitude of displacement of the wave

 ћ = reduced Planck constant (h/2p) = 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

p = ћk = ћ , E = ћ


Differentiating Eq. (1) once with respect to time gives,

Ψ(x, t)
= − Ψ(x, t)
ћ
or
( ,)
iћ = EΨ(x, t) (2)

Differentiating Eq. (1) twice with respect to x gives,

∂Ψ(x,t)
−iћ = pΨ(x, t) (3)
∂x

( ,)
−ћ = p Ψ(x, t) (4)

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

ћ ( ,)
− = Ψ(x, t) (5)

Now the energy E and momentum p of a free non-relativistic particle of mass m are related by the
expression

ℏ
= = (6)

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.

Substituting Eq. (2) and Eq. (5) in Eq. (6), we obtain the one-dimensional time dependent
Schrödinger equationfor a free non-relativistic particle given below

ћ
iћ = − (7)

From Eq. (2) and Eq. (3), it is evident that E and p can be represented by the following operators

E = iћ , Total-energy operator

∂
p =−iћ ∂xLinear Momentum Operator

An operator describes the operation to be carried out on the quantity following it. Thus, Eq. (7)
can also be written in the form

Ψ(x, t) = Ψ(x, t) (8)

The three-dimensional form of time dependent Schrödinger equation for a free non-relativistic
particle is obtained as follows

The initial expression for Ψ in three dimensions is given by

Ψ( , t) = A exp ( . − Et (9)
ћ

= A exp (p x + p y+p z − Et (10)

ћ

Differentiating Eq. (10) once with respect to time gives

iћ = EΨ (11)

Similarly, differentiating Eq. (10), twice with respect to the co-ordinates x, y and z of the free non-
relativistic particle yields

−ћ = p Ψ (12)

−ћ = p Ψ (13)

−ћ = p Ψ (14)

Substituting Eqns. (11-14) in the expression for energy E in three dimensions given by
 + +
= =
2 2
yields

ћ ћ
iћ = − + + = − ∇ Ψ (15)

Thus,the three-dimensional form of time dependent Schrödinger equation for a free non-relativistic
particle.

The operator representation for the components E and p in the three-dimensional case is given by

E = iћ , Total-energy operator (16)

p = −iћ∇ Linear Momentum Operator(17)

Here, ∇= + +

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

In this section, we obtain Schrödinger's equation for a particle moving in an external potential
field. Let the potential energy function V(r, t) characterize this external field. Then, according to
classical mechanics, the total energy of the particle in this external field is given by

= + ( , ) (18)

Substituting Eq. (16) and Eq. (17) in Eq. (18), we obtain

ћ
iћ = − ∇ Ψ + VΨ (19)

The above equation is the three-dimensional time dependent Schrödinger equation for particle in
a field.

Eq. (19) is usually written as

iћ = HΨ (20)
2 ћ
where = + = − ∇ +V
2

is known as the Hamiltonian operator.

The corresponding one-dimensional equation is

( ,) ћ
iћ = HΨ(x, t) = − + V(x, t) Ψ(x, t)(21)

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 Ψ and Ψ satisfy
the Schrödinger's equation then

Ψ= a Ψ + a Ψ (22)

is also a solution, where a and a are constants. Hence, the wave-functions Ψ and Ψ 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

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,

Ψ = Ψ′ (23)

where 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 = ћ
− ∇
2m
 Total Energy, E ∂Ψ
iћ
∂t
Hamiltonian H = KE (Kinetic Energy) + PE ћ
(Potential Energy) − ∇ +V
2m

Two operators and are said to commute if

Ψ= Ψ or Ψ− Ψ =0 (24)

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

, = − (25)

If two operators commute then , =0

Example:

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

Solution:

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

∴ [ , ] Ψ = iћΨ or [ , ] = iћ

Since, the operators x and pxdo not commute, they cannot be determined simultaneously

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

Ψ(x) = Ψ(x) (26)

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

andis the corresponding eigenvalue of .

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

∗( ) ( )
∫
〈 〉= ∗(
(27)
∫ ) ( )

Now, if the wave-function is normalized then ∫ Ψ∗ ( ) Ψ(x) = 1and the expectation

value is given by

〈 〉=∫ Ψ ∗ ( ) Ψ(x) (28)

Some important properties of eigenvalues and eigenfunctions.

1.If Ψ(x) is an eigenfunction of an operator with eigenvalue , then bΨ(x), where b is a constant,
is also an eigenfunction of the same operatorwith 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:

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:

, . .
(a) The probability is ∫ |Ψ| = ∫. = = 0.0251
.

(b) The expectation value is 〈 〉 = ∫ |Ψ| = ∫ =

Time Independent Schrödinger's equation

When the potential energy of a particle just depends on the position of the particle and is
independent of time, then the time dependent Schrödinger's equation given by

( ,) ћ
iћ = − + V(x) Ψ(x, t) (29)

can be simplified by removing all reference to t.This is done by using the method of separation of
variables.

Ψ(x, t) = (x)T(t) (30)

Substituting Eq. (30) in Eq. (29) and dividing the entire expression by Eq. (29), we get

ћ ћ ( )
= − + V(x)(x) (31)
( ) ( )

It is observed that in the above equation, LHS is a function of time alone while RHS is a function
of space alone; hence, each side must be equal to a constant. Let that constant be E.
ћ ⁄ћ
Hence, =E ∴ T(t) = e (32)
( )

ћ ( )
and − + V(x)(x) = E
( )

ћ ( )
∴ − + V(x)(x) = E(x) (33)

Hence, on substituting Eq. (32) in Eq. (30), the solution is obtained as

Ψ(x, t) = (x)e−iEt⁄ћ (34)

Now, Eq. (33) can be written as

∴ H(x) = E(x)
ћ
where H = − + V(x) (35)

represents the Hamiltonian operator and E is the energy eigenvalue. Eq. (33) represents the time
independent Schrödinger equation. A state is called stationary if it is represented by the wave-
function given by Eq. (34). The probability density of such states are time independent and as a
result the eigenvalues of the Hamiltonian, which represent the energy levels of the system are also
time independent.

The general solution of Eq. (29) can be written in the form

Ψ(x, t) = ∑ c  (x)e−iEnt⁄ћ (36)

where (x)are the eigenfunctions of H and E are the corresponding eigenvalues while c are
constants which can be determined from the form of Ψ(x, 0).

Example: An eigenfunction of the operator d2/dx2is = e2x. Find the corresponding eigenvalue.

Solution: Let = , so,  = (e ) = 4e = 4

Comparing it with the Eq. Ψ(x) = Ψ(x) , we obtain  = 4.

Hence, the
Solutions of eigenvalue of the
Schrödinger's given operator is 4.
equation:

I. Particle in a one-dimensional infinitely deep potential well

Consider a particle of mass m in a one-dimensional infinitely deep potential well given by potential
energy function of the form
V=∞ V=∞
V(x) = 0 for 0 < x < a

= ∞ for x < 0 and x > a

Calculate the eigenfunction and the corresponding eigenvalues

of the particle. V=0

Solution:
x=0 x=a
Boundary conditions for wave-function  is

(x = 0) = (x = a) = 0 (I)

Consider the one-dimensional time-independent Schrödinger

equation for particle in a field

ћ ( )
− + V(x)(x) = E(x) (II)

For 0 < x < a, Eq. (II) becomes

 ћ d (x)
− = E(x)
2m dx
( )
or + ћ
(x) = 0

( )
or + k (x) = 0wherek = (III)
ћ

The general solution of the Eq. (III) is

(x) = A sinkx + B cos kx (IV)

Imposing the boundary condition (I) in Eq. (IV) we obtain

(x = 0) = 0 = A sin(k. 0) + B cos(k . 0) ∴ =0 (V)

and(x = a) = 0 = Asin(ka) (VI)

Hence, either A = 0 or ka = np, n = 1, 2, 3, ......

The condition A = 0 or n = 0 leads to the trivial solution of  vanishing everywhere. Hence, the
allowed energy levels are given by

p ћ
= (VII)

The spacing between the energy levels is not constant and ∝ , where n denotes the number
of state.Eq. (VII) indicates that a particle confined in a certain region can have only certain, discrete
values of energy. Thus, the energy becomes quantized due to confinement of the particle. The
energy E1is called the zero-point energy. 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.

The eigenfunctions corresponding to the above energy eigenvalues is given by

 = sin = sin 2 (VIII)

ћ

Substituting Eq. (VII) in Eq. (VIII), we obtain

 = (IX)

To find the constant A in the above equation, we normalize the wave-function in Eq. (IX)
∫  =1 (Normalization Condition)

∫  = ∫ =1

∴ ∫ 1− =1

∴ − =1

∴ = 1which gives =

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

 = where n = 1, 2, 3, ……. (X)

The wave-functions and probability densities at different energy levels for particle in a one-
dimensional infinitely deep potential well is given below.

X=a X=a

II. 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

p2 ћ2
= + + = + + 2 2
(I)

The corresponding eigenfunction in three dimensions is given by

= = sin sin sin (II)

Example: 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: Probability = ∫ . | | = ∫. = − sin
.

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

( ⁄ ) ( ⁄ )
Solution: 〈 〉 = ∫ | | = ∫ = − ( ⁄ )
− ( ⁄ )

Substituting sin = 0, cos 2 =1 0 = 1, we obtain

2
〈 〉= =
4 2

∗
= = ; = cos

∗ ∗
2
〈 〉= ̂ = −ℏ = −ℏ cos

Now, ∫ sin cos =

Substituting a = , we get 〈 〉 = 0
 I. 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 given
by potential energy function of the form

≤ 0
V(x) = 0 0< <
≥

The energy E of the particle is less than the height of

the potential barrier U. According to classical mechanics,

when the particle strikes the sides of the barrier, it bounces back without entering regions I and
III. In quantum mechanics also, the particle bounces back and forth but now there is a finite
probability of the particle penetrating into regions I and III even though its energy E < U.

The Schrödinger’s equation in region I and III is

+ ( − ) =0 (I)
ℏ

or
<0
− =0 (II)
>
( )
where = ℏ

The solution to Eq. (II) is given by

= + (III)

= + (IV)

In region I, as → −∞, → ∞. Hence, the coefficient D in Eq. (III) must be equal to 0, so

that is finite in region I.

Similarly, in region III, as as → ∞, → ∞. Hence, the coefficient F in Eq. (IV) must be equal
to 0, so that is finite in region III.

This leads to
 = (V)

= (VI)

The wave-functions given by Eq. (V) and Eq. (VI) decrease exponentially inside the barriers at the
sides of the well.

The Schrödinger’s equation in region II is given by

+ ℏ
=0 (VII)

Its solution is given by

√ √
= sin + cos (VIII)
ℏ ℏ

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. This is known as tunnel effect.

The approximate transmission probability T for a particle having energy E to pass through the
barrier of height U is given by

( )
where = ℏ

and L denotes the width of the barrier. The above equation shows that the probability of particle
penetration through a potential barrier depends on the height U and width L of the barrier. The
probability decreases rapidly with increasing barrier width L.

Quantum Harmonic Oscillator

Harmonic motion occurs when a system of some kind vibrates about an equilibrium configuration
such as simple pendulum, block on a spring, electromagnetic waves, vibrating molecules etc. The
condition of harmonic motion is the presence of a restoring force which returns the system to its
equilibrium configuration when it is disturbed. The harmonic oscillator is a fundamental problem
of classical mechanics as well as quantum mechanics. Classical mechanics can be effectively
employed to study macroscopic oscillations where the de Broglie wavelength of the particle is
much less than the amplitude of oscillation. On the other hand, if the de Broglie wavelength of the
particle is comparable to the amplitude of oscillation such as vibrations of molecules, then the
motion of the particle can be described by quantum mechanics.
The Schrödinger’s equation for a harmonic oscillator having potential = is given by

+ − =0 (1)
ℏ

where E is the energy of the particle and k is the force constant which is related to the frequency
of oscillation and mass m of the particle by the relation

= (2)

Eq. (1) can be simplified by introducing the dimensionless quantities

/
= ℏ
√ and = (3)

The purpose of introducing these quantities in Eq. (1) is to change the units in x and E to
dimensionless units.

Schrödinger’s equation in terms of y and is given by

+ ( − ) =0 (4)

The acceptable solutions to this equation are limited by the condition that →0 → ∞. This
condition is fulfilled when

= 2n + 1, where n = 0, 1, 2, 3, ….. (5)

Substituting the value of from Eq. (3) in Eq. (5), the energy levels of a harmonic oscillator with
frequency of oscillation is given by

= + ℎ , n = 0, 1, 2, 3, …. (6)

It is observed that the energy of a harmonic oscillator is

quantized and the energy levels are all equally spaced.

The energy corresponding to the ground state i.e, n = 0 is

1
= ℎ
2
The lowest value of energy of a harmonic oscillator is called

zero-point energy because a harmonic oscillator in equilibrium

with its surroundings will approach this value and not E = 0 as

temperature approaches 0K.

The general formula for the nth normalized wave function of a harmonic oscillator in terms of the
Hermite polynomial ( )is given by
⁄
(2 ⁄ ⁄
= ℏ
!) ( ) (7)

The lowest-order Hermite polynomials are given below:

( ) = 1; ( )=2 ; ( )=4 − 2; ( )=8 − 12

Example: Find the expectation value <x> for the first two states of harmonic oscillator.
⁄ ⁄ ⁄
⁄ ⁄
Given: = ℏ
= ℏ
(2 ) = ℏ

Solution: 〈 〉 = ∫ | |

We will initially begin with y and then replace it by x.

n = 0; ∫ | | = ∫ =0

n = 1; ∫ | | = ∫ =0

<x> = 0

Hydrogen Atom

The constituents of a hydrogen atom are a proton and an electron. For the sake of simplicity, it is
assumed that the proton is stationary and the electron is revolving around it.

The Schrödinger’s equation for the electron in three dimensions i.e., hydrogen atom is

+ + + ( − ) =0 (1)
ℏ

Here, U represents the electric potential energy between the proton and electron separated by a
distance r and is given by

= − (2)
Substituting Eq. (2) in Eq. (1), we get

+ + + ℏ
+ =0 (3)

It is difficult to solve Eq.(3) in Cartesian co-ordinates. However, if the Cartesian co-ordinates (x,
y, z) are transformed to spherical polar co-ordinates (r, θ, ), then Eq. (3) can be easily solved.
Here, r is the length of the radius

vector from the origin O to the point P.

θ represents the angle between the radius vector and

+z axis. It is termed as the zenith angle.

represents the angle between the projection of the radius

vector in the xy plane and +x axis. It is termed as the

azimuthal angle.

The Cartesian co-ordinates are related to spherical co-ordinates by the following relations.

= + +

= sin cos

= sin sin

= cos

The Schrödinger’s equation in spherical polar co-ordinates is given by

+ sin + + ℏ
+ =0 (4)

The above equation can be separated easily into three independent equations, each involving only
one variable. After carrying out appropriate substitutions and separating the variables, the
following three total differential equations are obtained

Azimuthal wave equation

+ Φ=0 (5)

Polar wave equation

 sin + ( + 1) − Θ=0 (6)

Radial wave equation

( )
+ + − =0 (7)
ℏ

The solution of the azimuthal wave equation (5) is given by

Φ( ) = (8)

The condition that the wave function Φ must have a single value at a given point in space. Now,
( )
since and + 2π represent a single point in space =

This is possible only if is 0 or a positive or negative integer.

i.e., = 0, ±1, ±2, ±3, ……….

The constant is known as the magnetic quantum number.

The polar wave equation (6) has a complex solution in terms of associated Legendre functions
provided that the constant in Eq. (6) is an integer equal to or greater than the absolute value of the
magnetic quantum number i.e., | |. This implies

= 0, ±1, ±2, ±3, ………., ± .

The constant is termed as the orbital quantum number.

The radial wave equation (7) has a complex solution in terms of associated Laguerre polynomials
under the following conditions.

(i) The energy E in eq. (7) have one of the negative values En(signifying that the electron is
bound to the atom) given by
= − = = 1, 2, 3, …. (9)
ℏ
(ii) The constant n in Eq. (9), known as the principal quantum number must be equal to or
greater than + 1.This condition means that
= 0, 1, 2, 3, … … . . , ( − 1)

Hence, the three quantum numbers needed to describe the three-dimensional motion of the electron
in the hydrogen atom are , and and they must satisfy the following conditions.

(a) Principal quantum number, ≥ 1; = 1, 2, 3, ….

(b) Orbital quantum number, ≤ ( − 1); = 0, 1, 2, 3, … … … … … , ( − 1)
(c) Magnetic quantum number, | | ≤ ; = 0, ±1, ±2, ±3, ………., ±
The wave function for the ground state of hydrogen atom is

⁄
= ⁄ (10)
√

where is the radius of the innermost orbit of the hydrogen atom also termed as first Bohr radius.

The probability P(r)dr of finding an electron at any radial distance within a spherically symmetric
shell of thickness and volume 4 is given by

( ) = | | 4

The probability of finding the electron in the ground state of the hydrogen atom is given by

∗
1 ⁄
( ) = | | 4 = 4 = 4

The total probability of finding the electron at all points of distance r from the nucleus of the
hydrogen atom indicates that the probability is greatest for r = .