PHY 301

QUANTUM MECHANICS LECTURE II NOTES

by

SIFUNA, James Simiyu

Department of Natural Science

The Catholic University of Eastern Africa

THE 2024/2025 ACADEMIC YEAR

TABLE OF CONTENTS

0.1 Mathematical Axioms of Quantum Mechanics . . . . . . . . . . . . 3

0.1.1 The Basic Postulates of Quantum Mechanics . . . . . . . . . 3
0.1.2 Wave Packet . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
0.1.3 Born’s Interpretation of the Wave function . . . . . . . . . . . 4
0.1.4 Conditions of Admissibility of the Wave Function . . . . . . . 6
0.1.5 Time-Dependent Schrodinger Equation . . . . . . . . . . . . 6
0.1.6 Time- Independent Schrodinger Equation . . . . . . . . . . . 8
0.1.7 Heisenberg’s Uncertainty Principle . . . . . . . . . . . . . . . 8
0.1.8 Expectation Values . . . . . . . . . . . . . . . . . . . . . . . 8

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0.1 Mathematical Axioms of Quantum Mechanics

0.1.1 The Basic Postulates of Quantum Mechanics
Postulates are not unknown in physics. They often serve as a basis of physical theo-
ries. Though they cannot be proved, one can prove the conclusions derived on the ba-
sis of the postulates. The success or failure of the postulates depends on the strength
of the experimental results. There are different ways of stating the basic postulates of
quantum mechanics, but the following formulation seems satisfactory:-
Postulate 1: Wavefunctions
The state of a physical system is completely described by a complex mathematical
object, called the wavefunction ψ(psi, pronounced ”sigh”). At any time, the wave-
function ψ(x) is single- valued, continuous, and normalized.
The wave function ψ(x) is not ”the particle”, or ”the position of the particle”, it is a
mathematical function which carries information about the particle.
In this course, we will mostly be restricting ourselves to systems that contain a sin-
gle particle (like one electron). In such a case, the wavefunction can be written as a
function of the position coordinate⃗r of the particle, and the time: Ψ = Ψ(⃗r, t)
Often, we will simplify our lives by considering the (rather artificial) case of a parti-
cle restricted to motion in 1D, in which case we can write Ψ = Ψ(x, t). We may also
consider a particular moment in time, and focus on just Ψ(x).
In general, Ψ(x) is a complex function of x; it has a real and an imaginary parts.
Postulate 2 : Operators and Observables
To every observable physical quantity there corresponds a Hermitian operator or ma-
trix. Some of the important operators associated with observables in the co-ordinate
representation:-

Observables Classical form Operator

Co-ordinates x, y, z x, y, z
Momentum (x-component) px ∂
–ih̄ ∂x
Momentum p –ih̄∇
Energy E ∂
–ih̄ ∂t
2
h̄ ∇2
Kinetic energy T – 2m
2
h̄ ∇2 + V(x, y, z)
Hamiltonian (Total Energy) H – 2m

Postulate 3: Expectation Value

When a system is in a state described by a wave function Ψ, the expectation value of
any observable A is given by:
∗
R
⟨A⟩ = Rψ Aop ψdτ
ψ∗ ψdτ
If the wavefunction is normalized then we simply get the expectation value as
⟨A⟩ = ψ∗ Aop ψdτ
R

Postulate 4 : Eigenvalues
The possible values which a measurement of an observable, whose operator is A, can
give are the eigenvalues ai of the equation
Aψi = ai ψi
The eigenfunctions ψi form a complete set of n independent functions. The expecta-
tion value of the observable A when it is in the state ψn is given by

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⟨A⟩ = ψ∗n Aψn dτ = ψ∗n an ψn dτ = an ψ∗n ψn dτ = an

R R R

The meaning here is that when an experiment is performed to determine the value of
an observable A in a particular state, the value we expect in the measurement is its
eigenvalue. In other words, the eigenvalues of an operator are the only experimentally
measurable quantities.
Postulate 5 : Time Evolution of a Quantum System
The wavefunction of an isolated system evolves in time according to the Schrodinger
Equation:
ih̄ ∂Ψ h̄2 ∂ 2 Ψ
∂t = – 2m ∂x2 + VΨ
where V = V(x) is (classical) potential energy of the particle, which depends on the
physical system under discussion.

0.1.2 Wave Packet

Matter exhibits wave-like nature under suitable conditions according to the de
Broglie’s hypothesis. When the momentum of a particle is well defined, the wave can
be of infinite extent. Therefore a free particle moving along x-axis with well defined
momentum is described by aninfinite plane wave ψ(x, t) given by:

ψ(x, t) = Ao exp[i(kx – ωt)] (1)

where the wave vector k = 2π λ and ω is the angular frequency. To describe matter
waves associated with particles in motion, we need a quantity that varies in space and
time. This variable quantity, called the wavefunction, ψ(x, t) must be large in regions
where the particles is likely to be found and small in the region where it is less likely
to be found. That is, the wavefunction of a particle in conformity with the uncertainty
principle must be localized in a small region around it. The wavefunction of the mat-
ter wave which is confined to a small region of space is termed as a wavepacket or
wavegroup.
Mathematically, a wave packet can be constructed by the superposition of an infinite
number of plane waves with slightly differing k-values as

Z ∞
ψ(x, t) = A(k)exp[ikx – iω(k)t]dk (2)
–∞

0.1.3 Born’s Interpretation of the Wave function

A particle by its nature is localized at a point, whereas the wavefunction is spread
out in space. How can such an object represent the state of a particle? The answer is
provided by the Born’s statistical interpretation of the wavefunction, which says that
in 1D case |ψ(x, t)|2 gives the probability of finding the particle at point x , at time t,
or more precisely

Z b
| ψ(x, t) |2 dx = {Probability of finding the particle between a and b, at time t}
a
(3)

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Born interpreted the product |ψ(x, t)|2 = ψ∗ (x, t)ψ(x, t) as the position probability
density.
When |ψ(x, t)|2 is integrated over the entire x dimension, one should get the total
probability which is unity. i.e.

Z ∞
|N2 | |ψ(x, t)|2 dx = 1 (4)
–∞

where N is called the normalization constant and Eq.[4] is sometimes referred to as

the normalization condition.
Example 1
Normalize the wavefunction ψ(x) = Aexp(–ax2 ) A and a are constants over the do-
main –∞ ≤ x ≤ ∞.
Solution:
Taking
R ∞ A ∗as the normalization
R∞ constant , we have
A2 –∞ ψ ψdx = A2 –∞ exp(–2ax2 )dx = 1
R∞ q
Using the standard integral –∞ exp(–2ax2 )dx = 2a π
 1
we get A = 2a π
4

and hence the  1 normalized wavefunction becomes

2a
ψ(x) = π 4 exp(–ax2 )
Example 2
Normalize the one-dimensional wavefunction given by ψ(x) = Asin( πx l ) where 0 <
x < l.
Solution:
The
R ∞ wavefunction ψ is said to be normalized if it satisfies the relation:
∗
ψ ψdx = 1
R–∞
l ∗ πx πx
0 A Rsin( l )A sin( l )dx = 1
A∗ A 0l sin2 ( πx l )dx = 1
Rl 1
|A| 0 2 [ 1 – cos( 2πx
2
l ) ] dx = 1
q
giving A = 2l and hence the normalized wavefunction is:
q
ψ(x) = 2l sin ( πx l )
Example 3
The wavefunction of a particle is given by ψ(x) = Aexp(–ax2 ), A and a are constants
over the domain –∞ ≤ x ≤ ∞. Calculate the probability of finding the particle in the
region –∞ ≤ x ≤ ∞.
Solution: 1
From example 0.1.3 the normalization constant A = ( 2a π ) 4 and hence the normalized
wavefunction1 is
ψ(x) = ( 2a π ) exp(–ax )
4 2
The Rprobability of finding the particle in the region 0 < x < ∞ is
P = 0∞ ψ∗ ψdx
1 R∞
= ( 2a
π ) 2
0 exp(–2ax )dx
2
1
q
= ( 2a 21
π ) 2 2a
π

= 12

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0.1.4 Conditions of Admissibility of the Wave Function

In this section we need to answer the question: What are the characteristics of accept-
able wavefunctions in quantum mechanics?
The admissibility conditions on the wavefunctions (well-behaved wavefunctions) are
as follows:

i. ψ(x, t) must be finite everywhere in space. This is because |ψ(x, t)|2 dx for an
infinitesimal length dx should be between 0 and 1.

ii. ψ(x, t) must be single valued everywhere. This is necessary because at any
given x, ψ(x, t) should have a unique value and then only the probability
|ψ(x, t)|2 may be uniquely defined.

iii. ψ(x, t) and its first partial derivates with respect to its variables are continous.
This implies, there must not exist any sudden change inψ(x, t) when its vari-
ables undergoes a change.

iv. ψ(x, t) must be square integrable so that the integral

R ∞ of its modulus squared is
2
finite. This is necessary as the probability P = –∞ |ψ(x, t)| = finite value or
Zero.

v. ψ(x, t) must vanish at infinity. A wavefunction is taken to represent the position

of a particle and intuitively no particle is taken to exist at infinity.

vi. ψ(x, t) is zero at any surface at which there is an infinite potential step.

0.1.5 Time-Dependent Schrodinger Equation

We derive below the one-dimensional time dependent Schrodinger equation for a free
particle. The wave function of a localized free particle is given by Eq.[4] as
Z ∞
ψ(x, t) = A(k)exp[ikx – iω(k)t]dk (5)
–∞
For a free particle, the classical expression for energy is

p2x
E= (6)
2m
Replacing px by kh̄ and E by h̄ω, we get

h̄k2
ω= (7)
2m
Substituting this value of ω in Eq.[5] gives
Z ∞
h̄k2
ψ(x, t) = A(k)exp[ i( kx – t) ] dk (8)
–∞ 2m
Differentiating ψ(x, t) with respect to t , we get
Z ∞
∂ψ ih̄ h̄k2
=– k2 A(k)exp[i(kx – t)]dk (9)
∂t 2m –∞ 2m

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Differentiating ψ(x, t) twice with respect to x , we get

Z ∞
∂ 2ψ 2
2 A(k)exp[i(kx – h̄k t)]dk
= – k (10)
∂t2 –∞ 2m
Comparing Eqs.[9] and Eqs.[10] we have
h̄2 ∂ 2 ψ ∂ψ
– = ih̄ (11)
2m ∂x2 ∂t
which is the one-dimensional Schrodinger equation for a free particle.
Modification of the free particle equation to a system moving in a one-dimensional
potential V(x) can easily be done. The classical energy expression for such a system
is given by
p2
E= + V(x, t) (12)
2m
Now we can simply substitute E and p by heir respective operators:
∂
E −→ ih̄ and (13)
∂t
∂
p −→ ih̄ (14)
∂x
So we have
∂ ∂ 1
ih̄ = ( –ih̄ ) 2 + V(x, t) (15)
∂t ∂x 2m
and by letting each operator term act on ψ(x, t) we get the time-dependent
Schrodinger equation for a particle of mass m moving in a potential V(x,t) as
h̄2 ∂ 2 ∂ψ(x, t)
[– + V(x, t)]ψ(x, t) = ih̄ (16)
2m ∂x2 ∂t
The quantity in the bracket of Eq.[16] is the Hamiltonian Operator of the system.
Extension to Three Dimensions
The one-dimensional treatment given above can easily be extended to three dimen-
sions. The three dimensional wave packet can be written as
Z ∞
ψ(r, t) = A(k)exp[i((k · r) – ωt)]dkx dky dkz (17)
–∞
Proceeding on similar lines as in the one-dimensional case we get the three dimen-
sional Schrodinger equation for a free particles as
–h̄2 2 ∂ψ(r, t)
– ∇ ψ(r, t) = ih̄ (18)
2m ∂t
giving the energy and momentum operators as
∂
E −→ ih̄ and (19)
∂t

p −→ –ih̄∇ (20)
Similarly in three dimensions Eq.[16] , when involving a three dimensional potential
V(r,t) is simply re-written as
h̄2 2 ∂ψ(r, t)
[– ∇ + V(r, t)]ψ(r, t) = ih̄ (21)
2m ∂t

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0.1.6 Time- Independent Schrodinger Equation

The time –dependent Schrodinger equation, Eq. [16] describes the evolution of quan-
tum systems using time-dependent wavefunction ψ(r, t). It completely neglects the
time dependence of the operators. If the Hamiltonian operator does not depend on
time, the variables r and t of the wavefunction ψ(r, t) can be separated into two func-
tions φ(r) and Φ(t) as
ψ(r, t) = φ(r)Φ(t) (22)
Substituting this value in Eq.[21] and dividing throughout by φ(r)Φ(t) we get

1 dΦ(t) 1 h̄2
ih̄ = (– ∇2 + V(r))φ(r) (23)
Φ(t) dt φ(r) 2m
The left hand-side of Eq.[23] is a function of time and the right hand side a function
of space co-ordinates . Since t and r are independent variables, each side must be
equal to a constant, say E (the total energy which is conserved). This gives rise to the
equations
1 dΦ(t) iE
=– (24)
Φ(t) dt h̄

h̄2 2
[–∇ + V(r)]ψ(r) = Eψ(r) (25)
2m
Eq.[25] is the time-independent Schrodinger equation.

0.1.7 Heisenberg’s Uncertainty Principle

Heisenberg’s Uncertainty Principle should more appropriately be called Heisenberg’s
Indeterminacy Principle since we can measure either x or px with very low ‘uncer-
tainty’ but we cannot measure both. If one is certain, the other is indeterminate!
Heisenberg’s Uncertainty Principle is stated as
h
ΔxΔpx ≥ (26)
4π
where Δx is the uncertainty in the position, ΔPx is the uncertainty in the component
of the momentum in the x direction and h is Planck’s constant.
(The symbol ≥ means greater than or equal to.)
Quantum mechanics can show that there are other pairs of quantities that have this
indeterminacy, for example energy and time
h
ΔEΔt ≥ (27)
4π
where ΔE is the uncertainty in energy and Δt is the uncertainty in time.

0.1.8 Expectation Values

For a particle in state ψ(x, t) the expectation or mean or average value of x is
Z ∞
⟨x⟩ = ψ∗ (x, t)xψ(x, t)dx (28)
–∞

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if ψ(x, t) is normalized.
In general, the expectation value of any dynamical variable A whose operator is Aop
is expressed as R ∗
ψ Aop ψdτ
⟨A⟩ = R ∗ (29)
ψ ψdτ
However, it is important to note that if ψ is normalized already then the denominator
in Eq.[29] will be equal to 1 ( by normalization condition) and therefore the expecta-
tion value is simply evaluated as
Z
⟨A⟩ = ψ∗ Aop ψdτ (30)

The expectation value is the average of repeated measurements on an ensemble of

identically prepared systems and not the average of repeated measurements on one
and the same system.
Closely related to the expectation values are the standard deviations associated with
a measurement of a dynamical variable A and this is written as
q
ΔA = ⟨A2 ⟩ – ⟨A⟩2 (31)

Note that Eq.[30] would be important in evaluating quantities such as Δx, Δpx e.t.c.
Example 1
Show that the expectation value of Hamiltonian operator H is the total energy of the
system.
Solution:
We haveR the expectation value of H as
⟨H⟩ = ψ ∗ Hψdτ
= Rψ∗ Eψdτ
R

= E ψ∗ ψdτ
= E, the total energy of the system.
Example 2
1 e– ar where a is a
q
Calculate the value of ⟨r⟩ related to the wavefunction ψ(r) =
πa3
constant.
Solution:
SinceRthis is a radial wavefunction it is better to work in spherical co-ordinates.
⟨r⟩ = ψ∗ rψdτ
= 0∞ r2 dr 0π sin θdθ 02π dΦ(ψ∗ rψ) [Remember dτ = r2 sin θdrdθdΦ]
R R R
2r
= 13 4π 0∞ r3 e– a dr [Use standard integral 0∞ xn e–ax dx = n+1n!
R R
πa a
= 13 4π × 83 a4
πa
= 32 a
Example 3 q
Calculate ⟨p⟩, ⟨p2 ⟩ and Δp for the normalized wavefunction ψ(x) = 2 sin πx
L L for
0 < |x| < L
Solution:
R∞ ∗
⟨p⟩ = –∞ ψ pψdx
L
= 21 –L ( L2 ) sin πx d
R πx
L (–ih̄ dx ) sin L dx

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RL 2
= 12 –L ( L ) sin πx π πx
L (–ih̄) L cos L dx
R L
= πh̄2 –L 2 sin πx πx
L cos L dx
2iL R
L
= πh̄2 –L sin 2πx
L dx
2iL
=0
R∞ ∗
⟨p2 ⟩ = –∞ ψ pψdx
RL ∗ 2
= –L ψ ( –h̄2 d 2 ) ψdx
dx
h̄2 2 π 2RL
= 2 L ( L ) –L sin πx πx
L sin L dx
2 2 L
= π h̄3 –L 2 sin2 πx
R
2L L dx
= π2 h̄2
L2
p
Δp = ⟨p2 ⟩ – ⟨p⟩2 = πh̄
L

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