Lecture Notes Prepared by Murila Musungu

INTRODUCTION TO QUANTUM
MECHANICSI
Credit Hours: 3
Pre-requisites: None
Purpose
To introduce students to principles of wave
theory and applications
Expected Learning Outcomes
By the end of the course the learner should be
able to:
i)
Describe and solve the Schrödinger
wave equations
ii) Explain the Mathematic properties
of wave functions
iii) Interpret wave function
Course Content
Schrödinger wave equation; Development of
wave equation postulates; Expectation values
and differential operation; Mathematical
properties of wave function; Eigen functions
and eigen values; Probability flux;
Interpretation of wave function; Solution to
2
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Schrödinger equation; Step potential; Barrier

potential; Tunnel effect; WKB method; Square
well; Infinite square well; Simple harmonic
oscillator and a particle in three dimension
box
Teaching / Learning Methodologies
Lectures; Tutorials; Class discussion;
Practical exercises
Course Assessment
Examination - 70%; Continuous Assessments
(Exercises and Tests) - 30%; Total - 100%
Recommended Text Books
i) GennaroAuletta, Mauro Fortunato,
Giorgio Parisi; (2009). Quantum
Mechanics.CambridgeUniversityPressISB
N: 0521869633
ii) (d. Phil.) AgarwalB.k.(2008);Quantum
Mechanics. Prentice-hall Of India Pvt
LtdISBN: 8120310071
iii) Srivastava R. K. (2007); Quantum
Mechanics. Prentice-hall Of India Pvt Ltd
ISBN: 8120332733

3
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

iv) Bass C Van (2006); Quantum Mechanics and

empiricist view; OxfordUniversity press
USA
v) LR Jauch (2004); Foundation of Quantum
Mechanics; Addison Wesley Publishing
Co. London 1968
“I think it is safe to say that no one understands
quantum mechanics.”
Physicist Richard P. Feynman

4
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

NEED FOR QUANTUM MECHANICS

Historical study leading to quantization
 Isaac Newton is the father of classical
mechanics and he considered light to be a beam
of particles (corpuscles)
 During 19th century, some experiments
concerning interference and diffraction of light
demonstrated light’s wave like natureand later
on proven to be electromagnetic (Young’s
double slit experiment).
 However the phenomenon of black body
radiation could not be explained within the
framework of electromagnetic theory.
 In 1901 Max Planck arrived at a formula
explaining blackbody radiation, and later proved
that it can be derived by assuming the
quantization of electromagnetic radiation. This
was the birth of quantum mechanics. Planck
made a brilliant suggestion that; if the vibrating
matter particles which emit radiation have
motions restricted to certain discrete energy
values or energy levels, there would be a
departure from the laws of the classical
5
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

statistical mechanics of the sort required by

experimental facts. A natural inference was then
that radiant energy is corpuscular in nature
(corpuscular - packets), Planck himself had a
strong belief in wave theory.
 In 1905, generalising Planck’s hypothesis,
Einstein proposed a return to Newton’s particle
theory of light. He claimed that a beam of light
of frequency v (wavelike nature), consists of
photons each possessing energy ℎv where
ℎ=6.62× 10 Js (Planck’s constant).Einstein showed
−34

how the introduction of the photon (packet of

light energy) could explain the unexplained
characteristics of the photoelectric effect. In
1907, Einstein showed that corpuscular concept
can solve problems involving low temperature
specific heat of solids.
 In 1913, Bohr united Rutherford nuclear
conception of atom with the energy level
hypothesis to formulate his famous theory of
structure and spectrum of hydrogen. Bohr’s
makeshift combination of classical mechanics
and quantum conditions was inadequate for the
working out an exact theory of atom structure.
6
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Moreover, periodic phenomena of molecules

and solids were practically untouched.
 Louis De Broglie and Werner Heisenberg
finally solved limitations of Bohr’s postulates.
Louis De Broglie suggested that matter may
share the dualistic characteristics of radiation by
combining the properties of waves with those of
corpuscles (duality theory of radiation).
Heisenberg described atomic dynamic systems
by means of a new kinematics based on Bohr’s
correspondence principle.
 Schrodinger modified De Broglie’s
hypothesis to a form generally accepted today
 Born and Jordan converted Heisenberg
method to a powerful matrix calculus
 Both suggestions of Born and Jordan as well
as that of Schrodinger have been fused into a
single theory which we call “Quantum
Mechanics”
 About 20 years, after Einstein discovering
photoelectric effect i.e. around 1925, the photon
was actually shown to exist as a distinct entity
(Compton Effect to be discussed soon).

7
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

BLACKBODY RADIATION
 A black body emits radiation when it is in
thermal contact with the surrounding. The
radiation contains all the wavelengths ranging
from 0 to ∞. The energy density E against
wavelength for different temperatures is shown
below.

 Kirchhoff (1859) showed that the distribution

of blackbody radiation is independent of the
nature of the blackbody and depends only on its
temperature.
 Based on pressure exerted by radiations on the
walls of the blackbody, Stefan (1879) and
Boltzmann (1884) showed that the total energy
density was proportional to 4th power of absolute
temperature of the blackbody i.e. E∝T4. Stefan’s
law of black body radiation is given by E=σT4
(Stefan – Boltzmann law). Where σ is Stefan’s
8
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

constant and σ = 5.67×10-8 W/m2K4.The law was

experimentally verified and found satisfactory.
However this law does not tell anything about
energy distribution with respect to individual
wavelengths.i.e. it can’t explain the figure above.
 Wilhelm Wien (1893) established
displacement laws which are
i). T=Constant
ii). ET-5=Constant
Where is the wavelength corresponding to the
temperature T and emissivity E of the blackbody;
combining these laws and using Maxwell
distribution, Wien obtained the following law
A − B / λT
E λ dλ= e dλ
λ5

Where A and B are constants. It was observed

that this law is valid only for short wavelength
region(High frequency region) but fails totally in
long wavelength region (Short frequency
region).
 In 1900, Rayleigh and Jeans approached the
energy distribution problem differently. They
obtained the following law
8 πkT
E λ dλ= dλ
λ4

9
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Where k is the Boltzman constant;this formula is

in agreement with the experimental results in the
long wavelength region but fails totally in short
wavelength region.
 Thus all attempts to obtain a single formula
valid over the entire range of wavelengths using
classical ideas about radiation failed miserably.
 Planck (1901) proposed a new formula for
blackbody radiation. According to him each
oscillator in the blackbody surface emits energy
not continuously but in the discrete packets of
energy
E=0 , ε , 2 ε ,3 ε , 4 ε ...

Withε =ℎv , h is called Planck’s constant having

value of 6.625×10-34 Js. This is called
quantization of energy. With this idea Planck
successfully explained the blackbody radiation.
He obtained formula for energy density as
8 πℎc 1
E λ dλ= 5 ℎc / λkT
dλ
λ (e − 1)

This is Planck’s radiation formula. This is in

agreement with the experimental results.
 It is observed that for small wavelengths
Planck’s law reduces to Wien formula and for
longer wavelengths it reduces to Rayleigh and
Jean’s formula.
10
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

PHOTOELECTRIC EFFECT EXPERIMENT

Consider the photoelectric effect experiment
shown below. This effect was discovered by
Heinrich Hertz in 1887. It was one of the processes
by which electrons can be removed from a metal
surface. A schematic diagram of the apparatus for
studying the photoelectric effect is shown below

The critical potential v is such that ev =E (The

o o max

maximum energy of the electron emitted from the

anode) is called the Stopping Potential. The
experimental results are summarised as shown
below
(a) When light shines on a metal surface, the
current flows almost instantaneously, even for a
very weak light intensity.

11
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

(b) For fixed frequency and retarding potential,

the photocurrent is directly proportional to the
light intensity.

(c) For constant frequency and light intensity, the

photocurrent decreases with the increase of the
retarding potential V, and finally reaches zero
when V = V o

(d) For any given surface, the stopping potential V o

depends on the frequency of the light but is

independent of the light intensity. For each
metal there is a threshold frequencyυ , that must 0

be exceeded for photoemission to occur; no

electrons are emitted from the metal unless υ >υ no 0

matter how great the light intensity is or for how

long the material is exposed.

12
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

The experimental correlation between the stopping

potential V and the frequency of light can be
o

represented by
e V o=ℎv −ℎ v 0

Where ℎ(Planck's constant) is the same for all

metals.

Failures of classical mechanics from the

photoelectric experiment
(a) An electron in a metal will be free to leave the
surface only after the light beam provides its
binding energy. Because of the continuous
nature of the electromagnetic radiation, we
expect the energy absorbed on the metal's
surface to be proportional to the intensity of the
light beam (energy per unit time per unit area),
the area illuminated, and the time of
illumination. A simple calculation shows that in
the case of an intensity of 10 W /m , photoemission
− 10 2

can be expected only after 100 h.

Experimentally, the delay times that were
observed for the same light intensity were not
longer than 10 s. Classical theory unable to
−9

13
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

explain the instantaneous emission of

electrons from the anode.
(b) With the increase of light energy, the energy
absorbed by the electrons in the anode increases.
Therefore, classical theory predicts that the
number of electrons emitted (and thus the
current) will increase proportionally to the
light intensity. Here classical theory is able to
account for the experimental result.
(c) This result shows that there is a distribution in
the energies of the emitted electrons. The
distribution in itself can, within the framework
of the classical theory, be attributed to the
varying degrees of binding of electrons to metal,
or to the varying amount of energy transferred
from the light beam to the electrons. But the fact
that there exists a well-defined stopping
potential independent of the intensity indicates
that the maximum energy of released electrons
does not depend on the amount of energy
reaching the surface per unit time. Classical
theory is unable to account for the existence of a
well defined stopping potential for a given
metal.
(d) According to the classical point of view,
emission of electrons from the anode depends on
the light intensity but not on its frequency. The
existence of a frequency below which no
14
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

emission occurs, however great the light

intensity, cannot be predicted within the
framework of classical theory.
In conclusion, the classical theory of
electromagnetic radiation is unable to fully explain
the photoelectric effect.

EXAMPLE
When two ultra violet beams of wavelengths
λ =280 nm and λ =490 nm fall on a lead surface they
1 2

produce photoelectrons with maximum energies

8.57eV and 6.67eV, respectively
i). Estimate the numerical value of the Planck’s
constant
ii).Calculate the work function of lead
iii). Calculate the cut off frequency of lead
SOLUTION
i) Let the kinetic energies of the beams be K and K 1 2

respectively for wavelength λ and λ . From 1 2

ℎc
photoelectric equation we will have λ =W + K and 1
1

ℎc
=W + K .We can write the kinetic energies of the
2
λ 2
ℎc ℎc
electrons as K = λ −W and K = λ −W ; the difference
1
1
2
2

between these two expressions is given by

ℎc (λ − λ ) K −K λ λ
K −K =
1 2
λ λ
2

1
hence
2
1
ℎ=
c
.
λ − λ , since
1
1 eV =1.6 × 10 J ,
2

2
1 2

1
−19

the numerical value of ℎ follows immediately

15
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

( 8.57− 6.67 ) 1.6 ×10− 19 J ( 280× 10−9 m ) ( 490 ×10 −9 m )

ℎ= .
3.0 ×108 m s− 1 490 ×10− 9 m−280 ×10 −9 m
−32
ℎ=6.62× 10 JS
ii) The work function of the data can be obtained
from either of the two data
ℎc
W= − K1
λ1
( 6.62×10 −32 js )( 3.0× 108 m s− 1)
W= −9
−8.57 ×1.6 × 10−19 J
280 ×10 m
W =−6.62 ×10− 19 J =− 4.14 eV .
iii) The cut off frequency of the metal is
W 6.62 ×10− 19 J 15
v o= = −34
=10 Hz
ℎ 6.62×10 Js

THE DUALITY OF LIGHT

 During Newton’s days he assumed light to be
made of tiny particles called corpuscles. Using
this theory he explained the experimental
phenomenon of reflection and refraction. But this
theory failed to explain the phenomenon of
interference of light.
 Huygen, Young and Fresnel proposed a wave
theory of light which was able to describe the
interference of light. This wave theory could
explain not only reflection and refraction of light
16
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

but also interference, polarization and diffraction

of light. Maxwell was able to produce light in the
laboratory and also showed that light is an
electromagnetic wave. Therefore the idea of light
being a wave was accepted worldwide.
 Hertz experiment of photoelectric effect could
not be explained based on Maxwell’s idea of
light being electromagnetic.
 Albert Einstein was able to explain the
photoelectric effect by assuming the existence of
light energy in discrete particles he called
photons.
 The double-slit experiment shows that it is not
possible to explain the experimental results if
only one of the two characteristics of light; wave
or particle; is considered. Light behaves
simultaneouslylike a wave and a flux of
particles; the wave enables us to calculate the
probability of the manifestation of a particle.
The dynamic parameters of the particles (the
energy E and the photon momentum p) are
linked to the wave parameters (the frequency v
ℎ
and the wave vector k) by the relations whereℏ= 2 π
.

MATTER WAVES
 It was discovered that an atom emits or
absorbs only light with well-determined
17
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

frequencies. This fact can be explained by

assuming that the energy of an atom can take on
only certain discrete values. The existence of
such discrete energy levels was demonstrated by
the Franck-Hertz experiment.

BOHR ATOM
 Niels Bohr interpreted Franck-Hertz
experimentin 1913 in terms of electron orbits
and proposed the following model for the
hydrogen atom.
 The electrons move in orbits restricted by the
requirement that the angular momentum be an
integral multiple ofℏ=ℎ/2 π .
 From the De Broglie’s wavelength we can find
the angular momentum as follows
ℎ ℎ
λ= =¿ P=
P λ
From the definition of angular momentum ( Ĺ), it
is the vector product of radius (ŕ ) and linear
momentum ( Ṕ). i.e. Ĺ=ŕ × Ṕ , whereas its magnitude
rℎ ℎ
will be given as L=rP= λ , (because P= λ ) but ℎ=2 πℏ,
2 πrℏ
∴ L=
λ
For n complete oscillations the distance moved is
nλ whereas this circumference is equivalent to 2 πr ,

hence nλ=2 πr
2 πrℏ nλℏ
∴ L= = =nℏ … …(i)
λ λ
This is the quantized angular momentum.
18
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

 The magnitude of angular momentum can still

be given as L=rP=m v r … …(ii)
 Equating (i) and (ii), we getm v r=nℏ … … (iii)
 The relationship between the Coulomb’s force
and the centrifugal force for a circular orbit of
radius r, and velocity v is written in the
following form:
Centrifugal force for orbiting electron
… … (iv )Coulomb’s force for an electron
2 2
v mv
F=ma=m =
r r
q1 q2
F=K 2
But K=1 , q1=q2=e
r
e2
F= … …(v)
r2

 Equating (iv) and (v) we have

m v n2 e 2
= 2 … …( vi)
r r

 Make r the subject in (iii) and replace in (vi)

n

and making velocity v , the subject we have n

nℏ
m v n r n=nℏ=¿ r n=
m vn
m v n2 e 2 e2
= 2 =¿ r n= 2
rn rn m vn

Equating the r’s we have

nℏ e2 e2 2 π e2
= ,=¿ v n = But ℏ=ℎ /2 π ∴ v n = … …(vii)
m v n m v n2 nℏ nℎ

 Make velocity vthe subject in (iii) and replace

in (vi) and making r , the subject we haven

nℏ
m v n r n=nℏ=¿ v n =
mr
2 2
m vn e e2 e
= 2 =¿ v n2= ∴ v n=
rn rn m rn √ mr n
Equating the v’s we have
e nℏ 1 nℏ 2 1 nℎ 2
=
√ mr n mr n
=¿ r n=
m e ( )
But ℏ=ℎ /2 π ∴ r n=
m 2 πe( )
… …(vii)

19
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

 The energy at quantized level n is given by

1 2 e2
En = m e v n −
2 rn
2 2
2π e 1 nℎ
But v n=
nℎ
∧r n=
m 2 πe ( )
4 π 2 e4
∧1 2 2
2 n2 ℎ 2 4 me π e
¿> v n = =
rn n2 ℎ2

2 2 2 2 4 2 4
1 2 e2 1 4 π 2 e 4 e 4 m e π e 2m e π e 4 me π e
∴ E n= m e v n − = m e 2 2 − = −
2 rn 2 n ℎ n2 ℎ2 n 2 ℎ2 n 2 ℎ2

2 me π 2 e 4 − 4 me π 2 e 4 2 me π 2 e 4
En = =−
n 2 ℎ2 n2 ℎ2

 Bohr postulated that the electrons in these

orbits do not radiate, despite their acceleration;
they are in stationary states. Electrons can make
discontinuous transitions from one allowed orbit
to another. The change in energy will appear as
radiation of frequency
E a − Eb
v ab=
ℎ
This is from the Einstein energy equation E=ℎv

2 m e π 2 e4
But En=−
n2 ℎ2

2 me π 2 e 4 2 me π 2 e 4
∴ Ea=− 2 2
∧Eb=− 2 2
na ℎ nb ℎ

2 me π 2 e4 2 me π 2 e 4 2 me π 2 e 4 1 1
Ea − E b=−
n2a ℎ2
−−
n2b ℎ2
=−
ℎ2
−
(
n 2a n2b )
20
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

E a − Eb 2 me π 2 e 4 1 1
v ab=
ℎ
=−
ℎ3
−
(
n2a n2b )
Where n and n are positive integers andn > n ; an
a b b a

indication that the transition is from an inner

orbit to the outer orbit of hydrogen atom.
 The corresponding wave number are given by
v ab Frequency
v ab=
c (Wave number=
Speed of light )
2 me π 2 e 4 1 1
v ab=−
ℎ3 c ( −
n2a n 2b )
Where
2m e π 2 e 4
=R H ( Rydberg constant )
ℎ3 c
1 1
(
v ab=− R H 2 − 2
na n b )
 The physical basis of the Bohr model
remained unclear until 1923, when Louis De
Broglie put forth a great unifying, bold
hypothesis that material particles might also
possess wave-like properties, so that, like
radiation, they would exhibit a dualistic nature.
In this way the wave-particle duality would be a
universal characteristic of nature.

EXAMPLES
1.Derive the energy of an electron in the hydrogen
atom using Bohr’s formulas
2.Derive a relation that predicts the frequencies of
the line spectra of hydrogen

21
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

3.By using the Coulombs force formula and

centrifugal force formula in an nth orbit, write
the nth velocity and nth radius of an electron in
terms of a Planck’s constant

DE BROGLIE’S HYPOTHESIS: MATTER

WAVES
 In 1924, Louis de Broglie put forward the
suggestion that matter (like radiation) also has a
dual nature, i.e. matter which is made up of
discrete particles might exhibit wavelike
properties under appropriate conditions. His
argument was: if electromagnetic radiation can
act like a wave sometimes and like a particle at
other times, then things like electrons, protons
etc, should also exhibit wave properties when
they are in motion. The waves associated with a
moving particle(s) are called matter waves.
 According to Einstein, a photon has energy
given by
E=ℎv ,Where v – Frequency of Photon; ℎ -
Planck’s constant
But ω=2 πv where ω - angular frequency
ℎω
∴ E=ℎv =
2π
∴ E=ℏω … …(1)
According to Einstein’s special theory of
relativity, only massless particles can move at
the speed of light in a vacuum, hence photons
22
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

must be massless. The energy possessed by

this massless body is given by E=mc and from 2

Einstein’s photoelectric equation E=ℎv, equating

the two equations we have
ℎv=mc 2
But momentum is defined as P=mv and a photon
travelling with velocity c will have
m c2 ℎv E
P=mc= = =
c c c
Therefore special relativity gives the relations
between the energy E and momentum P of a
massless particle.
E
P=
c
Where P – momentum and c - speed of photon
in a vacuum
∴ E=Pc … … ∗
Comparing eqn (1) and (*) we notice that
ℏω=Pc
ℏω
¿> P=
c
But wave vector k =ω / c therefore
P=ℏk … …(2)
Equations (1) and (2) are called De Broglie’s
relations or Planck-Einstein relations.

 Deriving De Broglie’s wavelength

Given the fact that a photon move at the speed
of light and from the wave equation
c
c=vλ=¿ v =
λ
From equation (1) we find
ℎc
E=ℏω=ℎv= …(∗ ∗)
λ
23
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

From equation (*) we find that

E=Pc …(∗)
Comparing equation (*) and (**) we find that
ℎc ℎ h
Pc= =¿ P= ∴ λ=
λ λ P
The de Broglie’s wavelength can thus be written as
ℎ ℎ
λ= =
P mv
It should be noted that the velocity of the de
Broglie waves (matter waves) associated with a
moving particle is not necessarily the velocity of
the particle.
Let u be the velocity of matter waves associated
with moving particle. Then,
u=vλ
ℎ ℎv m c 2 c 2
u=vλ=v = = =
mv mv mv v
c2
u=
v
Thus two different velocities are associated with a
moving particle: one refers to the mechanical
motion of the particle ( v), and the other refers to
the velocity of associated matter wave (u).

EXAMPLE 1:
Calculate the wavelength associated with a particle
of mass 2 g moving with velocity of 3.3125km/s
SOL: Here m=2 g=2×10 kg and v=3.3125 km/s=3312.5 m/s
−3

Therefore momentum p=mv=2×10 ×3.3125 −3

¿ 6625 ×10− 3 kgm/ s=6.625 kgm/s

The wavelength is
24
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

ℎ 6.625 ×10− 34 −34

λ= = =10 m
p 6.625

EXAMPLE 2:
Calculate the de Broglie wavelength of an electron
moving with speed 1/10th of the velocity of light
SOL: mass of an electron m=9.1×10 kg −31

c 1
Velocity of electron, v= 10 = 10 ×3.0 ×10 =3.0× 10 m/s8 7

Planck’s constant ℎ=6.625 ×10 js − 34

Momentum of electron
p=mv=9.1× 10−31 × 3.0 ×107=2.73× 10−23 kgm/s

The wavelength of the electron is given by

ℎ 6.625 ×10− 34 −11 − 10
λ= = =2.43× 10 m=0.234 ×10 m=0.234 Å
p 2.73 ×10 −23

EXAMPLE 3:
Obtain an expression for the de Broglie
wavelength associated with an electron accelerated
through V volts. Also find the wavelength for
100V and 54V.
Sol: The kinetic energy acquired by the electron
accelerated through V volts is
1
m v 2=eV
2

Where e is the charge on the electron and v is

the velocity of the electron.
∴ m v 2=2 eV ∧m2 v 2=2 meV
∴ p=mv=√ 2 meV

Therefore, wavelength associated with electron,

ℎ ℎ
λ= =
p √ 2 meV

25
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

We haveℎ=6.625 ×10 js , m=9.1×10 kg, and e=1.6 ×10

− 34 −31 −19
C

Using all these values we get,

12.27 × 10−10 12.27
λ= m= Å
√V √V
For V=100 Volts
12.27
λ= Å=1.227 Å
√100
For V=54 Volts
12.27
λ= Å=1.67 Å
√54
EXAMPLE 4:
Find the de Broglie wavelength of neutron whose
energy is 1eV, given the mass of a neutron being
1.676 ×10− 27 kg

SOL: Kinetic energy of neutron = 1eV =1 ×1.6 ×10 − 19

J
1
m v 2=1.6 ×10− 19 J
2
−19
2 2 ×1.6 × 10 2 ×1.6 × 10−19 8
v= = −27
=1.9093× 10
m 1.676 ×10
v=1.38 ×104 m/ s

The de Broglie wavelength is given by

ℎ ℎ 6.625 ×10− 34 − 10
λ= = = −27 4
=2.864 ×10 m=2.864 Å
p mv 1.676 ×10 × 1.38 ×10

THE COMPTON EFFECT

The Compton Effect studied by Arthur H.
Compton of United States of America, was able to
show that a photon exists as an independent entity.
In this case Compton was able to find an increase
in the photon’s wavelength as a function of the
scattering angle.
26
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Consider the figure below

By applying energy conservation principle to

the system before and after collision
ℎ v+ E =ℎ v + E … … (i)
'
0

Where E0 is the rest energy of the particle

defined as
E =m c … … (ii)
2
0 0

The magnitudes of the momentums of the

incident and scattered photons are
respectively;
λ
ℎv ℎ
P= = P =
c λ
ℎv' ℎ
c
=
λ'
… … (iii)
λ'

The scattering angle θ is the angle between the

directions of P and P . Applying the cosine law
λ λ'

of triangle in the figure below

P2=P λ2 + P λ' 2 − 2 P λ P λ' cos θ … … (iv)

From De Broglie’s wavelength we recall that

for a photon
27
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

ℎv ℎ
P= =
c λ
pc=ℎv … … (v)

Therefore multiply equation (iv) by c2 on both

sides and use idea of equation (v) to write this
equation in terms of ℎ v i.e.
P2 c 2=Pλ 2 c2 + P λ' 2 c2 −2 Pλ P λ' c 2 cos θ
P2 c 2=ℎ2 v 2 +ℎ2 v '2 −2 ℎ2 vv ' cos θ … … (vi)

By using equation (i) we notice that

ℎ v − ℎ v ' =E − E 0

… … (vii)
¿> ℎ2 v 2+ ℎ2 v ' 2 − 2ℎ 2 v v' =E2+ E02 − 2 E E 0

Relying on relativity theory we note that

E = E + P c , and if we replace this on eqn (vii) we
2 2 2 2
0

get
ℎ2 v 2 +ℎ 2 v ' 2 −2 ℎ2 v v ' =E 02+ P2 c 2+ E02 − 2 E E 0

… … (viii)
ℎ2 v 2 +ℎ 2 v ' 2 −2 ℎ2 v v ' =2 E02 −2 E E 0 + P2 c 2

Now subtracting equation (vi) from equation

(viii) we get
−2 ℎ2 v v ' (1 −cos θ)=2 E 02 −2 E E0

… … (ix)
−2 ℎ2 v v ' (1 −cos θ)=2 E 0( E0 − E)

From equation (i) E − E=ℎv ' −ℎv and putting this in

0

equation (ix) we have

−2 ℎ2 v v ' ( 1− cos θ )=2 E0 ( ℎ v ' −ℎ v )=2 E0 ℎ ( v ' −v )
−2 ℎ2 v v ' ( 1− cos θ )=− 2 E 0 ℎ ( v − v ' )

… … (x)
ℎ v v' ( 1− cos θ ) =E0 ( v − v ' )

From equation (ii) we notice that

E =m c Therefore equation (x) is written as
2
0 0

ℎ v v' ( 1− cos θ ) =m 0 c 2 ( v −v ' )

ℎ v −v '
m0 c 2
( 1 −cos θ )=
v v'
But v= cλ
28
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

c c c 1− 1
ℎ
−
λ λ'( )
λ λ' 1 1 λλ ' λλ ' λ ' − λ λ' − λ
m0 c 2
( 1 −cos θ ) =
c c
=
c 2 (
=c −
λ λ' )( )
c2
=
c ( )
λλ '
=
c
λ λ' λλ '
ℎ
( 1 −cos θ )=λ ' − λ=∆ λ
m0 c
ℎ
∆ λ=λ ' − λ= (1 − cos θ )
m0 c

This is the basic equation of the Compton Effect.

THE WAVE PACKETS AND THE WAVE
GROUP
The wave and particle of electromagnetic radiation
and matter can be united through the concept of
wave packet. A wave packet is a superposition of
waves. A wave packet can therefore be defined as
a group of waves each having slightly different
wavelength and velocity superposed on each other.
This is also called wave group. These waves
interfere constructively over a small region; and
outside the region they interfere destructively. As
time passes the wave group moves along the
direction of motion of a particle with the same
velocity as the particle. Such a wave packet is
shown in the figure below

Wave group
To understand the nature of the wave packet or
wave group and how the amplitude is modulated,
29
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

consider a wave group consisting of two waves

having slightly different wavelengths and
velocities and propagating along the positive x –
direction
Ψ 1= A sin ( ωt − kx )
Ψ 2= A sin { ( ω+dω ) t − ( k + dk ) x }
2π
Where ω=2 πv and k = λ (propagation constant) and
wave velocity or phase velocity
ω 2 πv λ
V P= = =2 πv . =vλ
k k 2π

Phase velocity is the velocity with which the wave

propagates.
According to the principle of superposition, the
resultant displacement is given by
Ψ =Ψ 1 +Ψ 2
Ψ =A [ sin ( ωt − kx ) +sin { ( ω+ dω ) t − ( k + dk ) x } ]

Ψ =2 A cos ( dω2 t − dk2 x )sin {( ω+ dω2 ) t −( k + dk2 ) x}

dωanddk are very small, therefore, above equation
can be written as
Ψ =2 A cos ( dω2 t − dk2 x )sin ( ω t −kx )
Ψ =B sin ( ω t −kx )

The above equation represents a wave travelling

ω
with wave or phase velocity V = k whose amplitude P

“B” is
B=2 A cos ( dω2 t − dk2 x)

30
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

The amplitude B itself represents another wave

travelling with velocity v called group velocity andg

it is given by
coefficient of t dω/2 dω
v g= = =
coefficient of x dk /2 dk
dω
∴ group velocity v g =
dk

For an infinitely large number of propagating

waves with slightly different wavelengths that
combine to form a group, the dependence of phase
velocity v and the group velocity v on ω, k and dω
p g

and dk is exactly the same as considered in the

above simple case of combination of only two
waves.

2π 2π
Since ω=2 πv andk = λ , we get dω=2 πdv and dk =− λ 2
dλ

dω dv
∴ vg = =− λ2
dk dλ

ω
Also note that since v = k , we can write ω=k v then
P p

dω d ( k v p ) dk d vp d vp
v g= = =v p + k =v p+ k
dk dk dk dk dk
d vp
v g=v p +k
dk

The equation above represents the relationship

between group velocity v , phase or wave velocity v
g p

and propagation constantk .

2π 2π
Since k = λ and dk =− λ dλ then 2

31
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

d vp 2π d vp 2π λ2 d v p d vp
v g=v p +k
dk ( )
=v p +
λ
( )
2π
− 2 dλ
=v p − ( )(
λ 2 πdλ ) =v p − λ
dλ
λ
d vp
v g=v p − λ
dλ

The equation above represents the relationship

between group velocity v , phase or wave velocity v
g p

and wavelength λ.

To show that the particle velocity (v) is the

same as the group velocity ( v ) g

If E and V are the total energy and potential energy

of a particle moving with velocity v, then its
kinetic energy is given by
1
m v 2=E −V
2

But the total energy

ℎ ℎ
E=ℎv= .2 πv= ω=ℏω
2π 2π

And momentum
ℎ ℎ 2π 1 2 m2 v 2 ℏ2 k 2 ℏ k2 V
p=mv= = . =ℏk ∴ m v =E −V =¿ =E −V =¿ =ℏω− V =¿ =ω −
λ 2π λ 2 2m 2m 2m ℏ
2
ℏk V
ω= +
2m ℏ

Differentiating the above with respect to k, we get

dω 2 ℏk ℏk
= =
dk 2 m m
dω
But v g=
dk and
p=ℏk=mv

dω ℏk p mv
v g= = = = =v
dk m m m
v g=v

32
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

We see that the velocity of the particle is equal to

the group velocity; hence we conclude that the
wave group propagates with the particle.

Example 1
The wavelength and frequency in a waveguide are
related by
c
λ=
√ v − v 20
2

Express the group velocity Vg in terms of c and

phase velocity V =vλ P

Solution
dω
V g=
dk

From
c
λ=
√ v − v 20
2 we v make the subject
λ ( v 2 − v 20 ) =c 2
2 c2 2
v= + v0
λ2
c2 2
v=
√ λ2
+ v0

c2 2
ω=2 πv =2 π
√ λ2
+ v0

But
2π 1 k 1 k2
k= =¿ = ∴ 2= 2
λ λ 2π λ 4π
c2 2 c2 k 2 2
ω=2 π

dω
λ2
+
√v 0 =2

2π
π
4 π2
+ v0

2 k c2
√
V g= = . 2
dk c2 k2 2 4 π
2
4 π2 √
+ v0

33
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

But
c2 2
v=
√
λ2
+ v0

2 π 2k c2 k c 2
V g= . =
2 v 4 π 2 2 πv
2π
But k=
λ
k c2 2 π c 2 c 2
V g= = =
2 πv 2 πvλ vλ

But V P =vλ

c2 c2
V g= =
vλ V P

Example 2
Find the group velocity for the following relation
v=
2 πT
√
ρλ
(water waves in shallow water; T is the
3

surface tension and ρthe density)

Solution
dω
V g=
dk
2π
But k=
λ
∧ω=2 πυ

2 πT
But υ=
√ ρ λ3
2 πT 8 π3 T k3 T
ω=2 πυ=2 π

dω 1 1
√ √
ρ λ3
3k T2
=
ρ λ3 √
=
ρ

∴ V g= = .
dk 2 3
k T ρ

3
√ ρ
4 2
k T ρ
2
3 kT
¿
√ k 3 T ρ2
¿
2 ρ
3
√
¿ VP
2
Example 3

34
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Find the group velocity for the following relation

v=
g
√
2 πλ
(water waves in deep water)
Solutions
dω 2π
V =
g
dk But k=
λ and
ω=2 πυ

g
√
Given that υ=
2 πλ
g 2 πg
ω=2 πυ=2 π
dω 1 1
√ √
2 πλ
=
λ
= √ gk

V g= = . .g
dk 2 √ gk
g2
¿
√
4 gk
g
¿
√
4k
1 gλ
¿
2 2π
1
√
¿ VP
2

HEISENBERG’S UNCERTANITY
PRINCIPLE
 In classical physics, the dynamic variables like
position, components of linear momenta etc. are
assumed to be measured with precise accuracy
at a given instant of time i.e. the basic law in
physics (such as Newton’s laws) have
deterministic Nature.
 According to Bohr and Heisenberg, the
probalistic nature is a fundamental one in
quantum physic which dominates the micro
world and deterministic nature is discarded.
35
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Careful analysis of microphysical systems

shows that there is a limit to the accuracy to
which variables like position, momentum and
angular momentum etc. are measured.
 Werner Heisenberg in 1927 proposed a very far
reaching principle called uncertainity principle.
According to this principle if we measure
accurately the position of a particle, its
momentum becomes uncertain and vice versa.
 A moving particle is considered to have wave
packet associated with it. The particle may be
anywhere in the wave packet; and if the wave
packet is small i.e. wave group is narrow, its
position can be found more accurately,
whereas the spread of wavelength, associated
with it is more. i.e. wavelength and
consequently momentum of the particle
becomes uncertain. On the other hand if the
wave packet is long the momentum of the
particle becomes more certain but the position
becomes uncertain.
 Heisenberg uncertainty principle states that it is
impossible to determine precisely and

36
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

simultaneously the momentum and position of

a moving particle.
 In mathematical form, the uncertainty principle
is given as: if ∆ x is the uncertain measurement of
position and ∆ p is the uncertain in the
x

measurement of momentum, then the product of

the two uncertainties is at least of the order of
Planck’s constant. It is given as
∆ x . ∆ px ≈ ℏ
1
 Precisely , ∆ x ∆ k ≥ 2 Using the De Broglie’s relation
p
p=ℏk we have k =
ℏ
p 1 ℏ
 ∆ x ∆ ℏ ≥ 2 =¿ ∆ x ∆ p ≥ 2 . This is the mathematical
x

expression for the Heisenberg uncertainty

relations in the x-component. The uncertainty
relations for the remaining components of linear
momentum are given as
ℏ
∆ y ∆ py≥
2
ℏ
∆ z ∆ pz ≥
2

NOTE:
 The wave packet is the solution to the
Schrodinger equation. The position of the wave
is given by the position of the packet.
ℏ
 Heisenberg uncertainty principle, ∆ x . ∆ p ≥ 2 , x

informs us that: the narrower the wave packet

37
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

and therefore the better defined the position of

the wave, the larger the uncertainty in the
momentum of the wave.
 Since ℏ(1.05 × 10 Js) is very small in the
−34

Heisenberg uncertainty principle; the notion of

classical physics fail. The uncertainties relation
acts to reconcile the wave-particle duality of
matter and radiation.
 The uncertainties represent the law of nature.
The uncertainties are defects in the measuring
instrument. In simple terms the principle says
that even with an ideal instrument, one cannot
get uncertainty product ∆ x . ∆ p less thanℏ /2.x

Different forms of uncertainty relations

a) Time - energy uncertainty relation:
Consider the kinetic energy of a particle
1 2 p2
E= m v =
2 2m

The uncertainty in E is ∆ E and it is given by

p
∆ E= ∆p
m

But p=mv
mv
∴ ∆ E= ∆ p=v ∆ p
m

If v is taken as the recoil velocity of the particle

due to incident light, the uncertainty in the
38
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

position is related to the uncertainty of the time

of the observation
∆x
∆ x=v ∆ t=¿ ∆ t=
v
∆x
∴ ∆ E . ∆ t=v ∆ p . =∆ p . ∆ x
v
ℏ
From the Heisenberg uncertainty relation ∆ x . ∆ p ≥ 2 x

ℏ
∴ ∆ E . ∆ t=∆ p . ∆ x ≥
2
ℏ
∴∆ E.∆t ≥
2

b) Angular momentum - angular displacement

uncertainty relation:
Consider a particle of mass m moving with
speed v as shown in the figure below:

The angular momentum at any instant is given

by
L=mvr=pr

If∆ x is the uncertainty in position along the arc

and ∆ θ is the uncertainty in the angular position,
then
∆ x=r ∆ θ

If the uncertainty in the momentum is∆ p, then

the uncertainty in the angular momentum is
∆ L=r ∆ p
39
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

∆L
∴ ∆ p=
r
∆L
¿> ∆ p ∆ x= . r ∆θ=∆ L . ∆ θ
r
¿> ∆ L ∆θ=∆ p ∆ x
ℏ
From Heisenberg uncertainty principle, ∆ x . ∆ p ≥ 2 x

ℏ
∆ L ∆ θ=∆ p ∆ x ≥
2
ℏ
∆ L∆θ≥
2

Examples
1. What is the smallest possible uncertainty in the
position of an electron moving with velocity 106
m/s?
SOLUTION
ℏ
∆ p∆ x ≥
2
ℏ ℏ ℎ
∆ x= = =
2 ∆ p 2mv 4 πmv
6.625× 10−34
∆ x=
4 π × 9.1× 10−31 × 106
∆ x=0.5793× 10−10 m=0.5793 Å

2. An electron has a speed of 6000 m/s with an

accuracy of 0.05%. Calculate the uncertainty
with which the position of the electron can be
located
SOLUTION
Mass of electron m=9.1×10 kg −31

Velocity of electron v=6000m/s

∆ p=0.05 % of p=0.05 % of mv
0.05
∆ p= ×9.1 ×10− 31 × 6000
100

40
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

∆ p=2.73× 10−30 kgm/s

ℏ
∆ p∆ x ≥
2
ℏ ℎ 6.625 ×10−34 −5
∆ x= = = =1.931×10 m
2 ∆ p 4 π ∆ p 4 π ×2.73 ×10− 30

3. Show that for a free particle the uncertainty

relation can also be written as
λ2
∆ λ ∆ x≥
4π

Where ∆ x is the uncertainty in the position and ∆ λ

is the simultaneous uncertainty in the wavelength
SOLUTION
ℏ
∆ p∆ x ≥
2

From de Broglie’s hypothesis

ℎ
p= =¿ p=ℎ λ− 1
λ
dp ℎ
=− ℎ λ−2 =− 2
dλ λ
ℎ
dp=− 2 dλ
λ

Uncertainties involve the products of only the

magnitudes
ℎ
∴ ∆ p= ∆λ
λ2

Inserting this equation in the uncertainty relation

we have
ℏ ℎ ℏ
∆ p ∆ x ≥ =¿ 2 ∆ x ∆ λ ≥
2 λ 2
ℏ λ2 λ2 ℎ λ2 λ2
∆ x ∆ λ ≥ . =ℏ = . =
2 ℎ 2 ℎ 2 π 2ℎ 4 π
2
λ
∆ x ∆ λ≥
4π
41
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

4. A typical atomic nucleus has radius 0.5×10-

14
m. Using the uncertainty principle, show that an
electron cannot exist inside the nucleus.
SOLUTION
The uncertainty in position must exceed the
diameter of the nucleus.
∆ x=d=2 r=2 ×0.5 ×10 −14 m=1× 10−14 m
ℏ
∆ p∆ x ≥
2
ℏ ℎ 6.625 ×10− 34 −21
¿> ∆ p= = = =5.272×10 kgm/ s
2 ∆ x 4 π ∆ x 4 π ×1 ×10− 14
∆ p=5.272× 10−21 kgm/s
But p ∆ p
−21 2
p 2 ( 5.272×10 )
E= = =1.527× 10−11 J =9.545 ×107 eV =95.45 MeV
2 m 2× 9.1 ×10− 31

This shows that if an electron exists in the

nucleus, its energy must be at least 95.45 MeV.
Experiments show that the electron in an atom
never has more than a very small fraction of this
energy.

WAVEFUNCTION
 In this case we are going to state the wave
function and their basic properties e.g. time
dependent Schrödinger equation and their
operators.

42
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

 In doing this consider a wave equation of a

∂2 ( 1 ∂2 (
string given by ∂ x2
A x ,t ) = . The solution for
c 2 ∂ t2
A x ,t )

this wave equation can be positive or negative.

The square of the wave function is a possible
choice for the probability (this is proportional to
the intensity for radiation).
 A propagating wave is given by
Ψ ( x , t)= A exp ( i(kx −ωt +Φ) ) or written asΨ ( x , t)= A e . The
i(kx − ωt+Φ)

wave equation describes a wave

 Propagating in the x – direction.
2π
 With wavelength λ= k
ω
 and frequency v= 2 π
This wave is interpreted as propagating beam
of particles.
NOTE: In quantum mechanics a particle is
characterised by a wave function Ψ ( r , t) which
contains information about the spatial state of the
particle at time t. Ψ ( r , t) is a complex function of
three co-ordinates x,y,z and of time t.

Interpretation of wave function equation ( Ψ ( r , t))

The probability of Ψ ( r , t) written as dρ(r , t) of the
particle being at time t in a volume element d r=dxdydz 3

located at point r is
43
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

2
dρ(r , t)=C|Ψ ( r ,t)| d 3 r … …(1)

Where C is the normalization constant. The total

probability of finding the particle anywhere in
space at time t is unity; therefore
∫ dρ(r ,t )=1 … … …(2)
According to (1) and (2)
(i). The wave function must be square
integrable i.e.
2
∫|Ψ (r , t)| d 3 r … …(3)
Is finite (has answer)
(ii). The normalization constant is given by the
relation
1 2
= |Ψ (r ,t )| d3 r … … …( 4)
C ∫

The wave function Ψ ( r , t) is normalised whenC=1.

A wave function Ψ ( r , t)must be defined and
continuous everywhere i.e.
 Ψ ( r , t) must be continuous everywhere
i.e. at each and every point in the space
 Ψ ( r , t) must be finite everywhere
 Ψ ( r , t) must be single valued
everywhere

Examples
C
(a) Normalize the wavefunction Ψ ( x )= x +a 2 2

44
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Solution
Find the square of the wave
2
|Ψ ( x)| = 2C 2 2
2

(x +a )
Compute we need to use two integrals
du 1 u du
∫ u du 1 u
= tan ( ) and ∫
( u +a ) 2 a ( u + a ) u + a
−1
= +∫ 2 2 2 2 2 2 2
+a a
2
a 2 2

Begin by using the second of these

∞ ∞ ∞ ∞
dx C2 x dx
∫ |Ψ (x )| dx=C2 ∫
−∞
2

−∞
2 2
( x 2 +a )
=
( |
2 a x + a2
2 2
−∞
+∫
−∞ x + a2
2 )
First term is evaluated at ±∞ , consider the limit
as x → ∞
x 1
lim = lim =0
x + a x →− ∞ 2 x
2 2
x→ ∞

Therefore we discard the first term all

together, and using
∫ u du = tan ( ) for the remaining part
1 u −1

+a a
2
a 2

∞ ∞ ∞
C2 dx C2 1 x
∫
−∞
|Ψ ( x |
)
2
dx= 2 ∫ 2 2
2a
= 2
−∞
tan −1
x +a 2a (a) a |−∞
2 2
C C π π C2
u→∞ 2 a
−1 −1
¿ lim 2 [ tan ( u ) − tan (− u) ]= 2 − −
2a 2 2
= 2π
2a [ ( )]
Recalling the normalization conditions
∞
2
∫ |Ψ ( x )| dx=1
−∞

C2 2 a2
2 a2
π =1=¿ C=
π √
Therefore the normalized wave function is
2 a2 1
Ψ ( x )=
√ π x 2+ a2

(b) Consider the wavefunction Ψ ( x ) =A (ax − x ) 2

for 0≤ x≤a ,
normalize the wavefunction

45
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Solution
The wave function is real. So Ψ ∗ Ψ =Ψ 2 and we
have
a a
2 2 2 2 2
∫Ψ dx=∫ A ( ax − x ) dx= A ∫ ( a2 x2 −2 a x 3+ x 4 ) dx
0 0
a
3 4 5
¿ A2 a2 [() 5
x
3
x x
−a +
2 5
5 5
]
0

a a a
¿A
2
[ − +
3 2 5 ]
Recalling the normalization conditions
∞
2
∫ |Ψ ( x )| dx=1
−∞

A2 a5 30
1=
30
=¿ A= 5
a √

THE SCHRÖDINGER EQUATION AND ITS

APPLICATION
Derivation of Schrodinger equation
Consider the classical formula for calculating total
energy given by
1
E= m v2 +V ( r , t ) … …(i)
2

Where v - is the velocity and V (r ) - is the potential

energy of a particle. Equation (i) can be written in
terms of momentum as
m2 v 2 P 2
2
P=mv =¿ m v = =
m m
2
P
E= +V ( r , t ) … …(ii)
2m

Consider the De Broglie’s relations equations

shown below
46
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

P=ℏk … …(iii)
E=ℏω … …(iv )

Replace (iii) and (iv) into (ii) we have

ℏ2 k 2
ℏω= +V ( r , t ) … …(v)
2m

Consider the wave equation Ψ =A e i (kx −ωt +Φ)

and
differentiate with respect to t, we get
∂Ψ ∂
= A e i(kx −ωt +Φ)=− iω A e i(kx −ωt +Φ)=− iωΨ
∂t ∂t
∂Ψ ∂ 1 ∂ ∂
¿>− iωΨ = =¿iω=− =¿ ω=− =i … …( vi)
∂t ∂t i ∂t ∂t

Likewise consider the same wave equation

Ψ =A e and differentiate twice with respect to x,
i (kx −ωt +Φ)

we get
∂Ψ ∂
= A e i(kx − ωt+Φ)=ik A ei (kx− ωt+ Φ) =ik Ψ
∂ x ∂x
∂2 Ψ ∂2 i(kx −ωt +Φ) ∂ i (kx −ωt +Φ) 2 2 i(kx −ωt +Φ) 2
2
= 2
Ae = ik A e =i k A e =− k Ψ
∂x ∂x ∂x
2
2 ∂Ψ 2 ∂2 2 ∂2
− k Ψ = 2 =¿− k = 2 ∴ k =− 2 … …( vii)
∂x ∂x ∂x

Replacing equation (vi) and (vii) into equation (v)

we get
ℏ2 k 2 ℏ2 2
ℏω= +V ( r , t ) =¿ ℏω= k +V ( r ,t )
2m 2m
∂ ℏ2 ∂2 ∂ ℏ2 ∂ 2
( )
ℏ i = −
∂ t 2 m ∂ x2 ( )
+V ( r , t ) =¿iℏ =−
∂t 2 m ∂ x2
+V ( r ,t ) … …( viii)

Multiply equation (viii) by Ψ ( r , t) we get

∂ ℏ 2 ∂2
iℏ Ψ (r , t)=− Ψ (x , t)+V ( r ) Ψ (r ,t )
∂t 2 m ∂ x2
2
∂ Ψ (r , t) ℏ2 ∂ Ψ (x , t)
iℏ =− +V ( r ) Ψ (r , t)… …(ix )
∂t 2m ∂ x2

Equation (xi) is called Time – dependent

Schrödinger equation.

47
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

In two dimensions the Schrödinger equation can

be written as
2 2
∂ Ψ (r , t) ℏ2 ∂ Ψ ( x ,t) ∂ Ψ ( y , t)
iℏ
∂t
=−
2m (
∂ x2
+
∂ y2 )
+V ( r ) Ψ (r , t) … …( x )

In two dimensions the Schrödinger equation can

be written as
2 2 2
∂ Ψ (r , t) ℏ2 ∂ Ψ ( x ,t) ∂ Ψ ( y , t) ∂ Ψ ( z , t)
iℏ
∂t
=−
2m (
∂ x2
+
∂ y2
+
∂ z2 )
+V ( r ) Ψ (r , t)… …(xi)

∂ Ψ (r , t) ℏ2 2
iℏ =− ∇ Ψ (r , t)+V ( r ) Ψ (r , t)… …( xii)
∂t 2m

Note:
1.When total energy is expressed in terms of
momentum, the quantity is called Hamiltonian,
2 2

thus E= 12 m v +V ( r , t ) = 2Pm +V ( r , t ) where ^H= 2Pm +V ( r ,t )

2

2.Hamiltonian is an operator that acts on the

wave function to give the energy states of a
given wave function i.e.
^ P2 Ψ ( r , t ) ℏ2 ∂2 Ψ ( r ,t )
H Ψ ( r ,t )= +V ( r ,t ) Ψ ( r , t )=− +V (r , t )Ψ (r , t)
2m 2 m ∂ x2

3.The Schrödinger equation can be expressed in

terms of the Hamiltonian operator as
^ ℏ 2 ∂2 Ψ ( r , t )
H Ψ ( r ,t )=− +V ( r , t ) Ψ ( r , t )=EΨ ( r , t )
2 m ∂ x2

The time evolution of the wave function is

governed by Schrödinger equation written in three
dimensions as
∂ Ψ (r , t) ℏ2 2
iℏ =− ∇ Ψ (r , t)+V ( r ,t ) Ψ (r , t)
∂t 2m
48
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Where a particle of mass m is subjected to a

potential V ( r ,t ) and ∇ is called the Laplacian operator
2

defined as
2 ∂2 ∂2 ∂2
∇= + +
∂ x2 ∂ y 2 ∂ z 2

Properties of Schrödinger equation

a) The Schrödinger equation is a linear and
homogeneous equation in Ψ . Consequently the
superposition principle holds; that is, if
Ψ ( r ,t ) ,Ψ ( r , t ) , … … Ψ (r , t) are solutions of the Schrödinger
1 2 n

equation then Ψ =∑ α Ψ (r ,t ) is a solution.

i=1
i j

b) The Schrödinger equation is a first order

equation with respect to time; therefore the state
at time t determines its subsequent state at all
0

times.

PROBABILITY DENSITY AND

PROBABILITY CURRENT (PROBABILITY
CURRENT DENSITY)

Consider a particle described by a normalized

wave functionΨ ( r , t). The probability density is
defined by
2
ρ ( r , t )=|Ψ (r , t)|

49
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

At time t the probability dP ( r , t )of finding the particle

in an infinitesimal volume d rlocated at ris equal to; 3

dP ( r , t ) =ρ ( r ,t ) d3 r

 According to Born approximation

2
ρ ( r , t ) dr=|Ψ (r , t)| d 3 r

Where |Ψ (r ,t )| =Ψ (r ,t )Ψ (r ,t ) is the
2 ∗
position
probability density
 Ψ ( r , t) satisfy normalization condition
2
∫|Ψ (r , t)| d 3 r =1
i.e. probability of finding particle somewhere
is unity within any time t.
 The normalisation condition is independent of
time i.e. probability is conserved. Which imply
that at any given time t, the particle must be
somewhere. i.e. Ψ ( r , t) is normalised
∞
2
∫ |Ψ (x , t)| d 3 r =1
−∞

At a given time, it must remain so at all times.

i.e. ❑
∂
∫ ρ ( x ,t ) dr
∂t v

 Consider the probability of finding the particle

at time t, within a finite volume v, namely
❑ ❑
2
∫ ρ ( x ,t ) dr=∫|Ψ ( x , t )| dr
v v

The rate of change of this will be given by

∂ ❑ ∂ ❑ ∂ ❑ ∗ ∂Ψ ∗ ( x , t )
❑ ❑
2 ∂Ψ ( x
∫ ρ ( x ,t ) dr= ∫ |Ψ ( x , t ) ¿| dr = ∫ Ψ ( x , t ) Ψ ( x , t ) dr =∫ Ψ ( x , t ) dr +∫ Ψ∗ ( x,t )
∂t v ∂t v ∂t v v ∂t v ∂t

Recall that Schrödinger equation and its

complex conjugate are written as
∂ Ψ (x , t) ℏ2 ∂2 Ψ ( x ,t )
iℏ =− + V (r ) Ψ ( x , t )
∂t 2 m ∂ x2

50
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

∂ Ψ∗( x , t) ℏ 2 ∂2 Ψ ∗ ( x , t )
−iℏ =− 2
+V ( r ) Ψ ∗ ( x , t )
∂t 2m ∂x
Rewriting Schrödinger equation in a form we
can replace into (1)
∂Ψ ( x , t ) ℏ ∂2 Ψ ( x , t ) i
=− − V ( r ) Ψ ( x , t ) …(2)
∂t 2 mi ∂ x 2 ℏ
∗ 2 ∗
∂Ψ ( x , t ) ℏ ∂ Ψ ( x ,t ) i
= 2
+ V ( r ) Ψ ∗ ( x , t ) …(3)
∂t 2 mi ∂x ℏ

Replacing (2) and (3) into (1) we get

❑ ❑ 2 ∗ ❑ 2
∂ ℏ ∂ Ψ ( x ,t ) i ℏ ∂ Ψ ( x ,t) i
[ ∗
] ∗
∫ ρ ( x ,t ) dr=∫ 2 mi ∂ x 2 + ℏ V ( r ) Ψ ( x , t ) Ψ ( r , t ) dr +∫ Ψ ( x , t ) − 2 mi ∂ x2 − ℏ V ( r ) Ψ
∂t v v
2 ∗
v
[
∂2 Ψ ( x ,t )
❑ ❑ ❑
∂ ℏ ∂ Ψ ( x,t ) i ∗ ℏ ❑ ∗
∫ ρ ( x ,t ) dr= ∫ Ψ ( x , t ) dr + ∫ V ( r ) Ψ ( x ,t ) Ψ ( x , t ) dr − ∫ Ψ ( x , t ) dr
∂t v 2 mi v ∂ x2 ℏ v 2 mi v ∂ x2
The 2nd and 4th parts of eqn (4) are equal in
magnitude and opposite in signs therefore they
add to zero.
∂ ❑ ℏ ❑ ∂2 Ψ ∗ ( x , t ) ℏ ❑ ∗ ∂2 Ψ ( x ,t )
∫ ρ ( x ,t ) dr= ∫ ∂ x2 Ψ ( x , t ) dr − ∫ Ψ ( x , t ) dr
∂t v 2 mi v 2 mi v ∂ x2
∂ Ψ ∗ ( x ,t )
❑ 2
∂2 Ψ ( x , t )
❑ ❑
∂
∫
∂t v
ρ ( x ,t ) dr=
ℏ
∫
2 mi v [
∂ x2
Ψ ( x , t ) dr − ∫
v
Ψ ∗
( x , t )
∂ x2
dr
]
∂2 Ψ ( x , t ) ∂2 Ψ ∗ ( x , t )
❑ ❑ ❑
∂
∫
∂t v
ρ ( x ,t ) dr=−
ℏ
2 mi [
∫ Ψ ∗ ( x ,t )
v ∂ x2
dr − ∫
v ∂ x2
Ψ ( x , t ) dr
]
∂2 Ψ ( x , t ) ∂2 Ψ ∗ ( x , t )
❑ ❑
∂ ℏ
∫
∂t v
ρ ( x ,t ) dr=− ∫
2 mi v
Ψ ∗ ( x ,t )
[ ∂ x2
−
∂ x2
Ψ ( x , t ) dr
]
∂Ψ ( x ,t ) ∂ Ψ ∗ ( x , t )
❑ ❑
∂
∫
∂t v
ρ ( x ,t ) dr=−
ℏ
∫ ∂
2 mi v ∂ x
Ψ ∗ (x , t) [ ∂x
−
∂x
Ψ ( x , t ) dr ]
By definition
∂Ψ ( x , t ) ∂Ψ ∗ ( x , t )
J́ ( x , t)=
ℏ
2mi [
∗
Ψ (x,t)
∂x
−
∂x
Ψ ( x ,t) ]
Therefore the above equation becomes
❑ ❑
∂ ∂
∫ ρ ( x ,t ) dr=−∫ J́ ( x ,t )dr
∂t v v ∂x

This implies that

∂ ρ( x , t) ∂ J́ ( x ,t )
=−
∂t ∂x

51
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

∂ ρ ( x , t ) ∂ J́ ( x , t )
+ =0
∂t ∂x
The above is the equation of continuity in one
dimension of x-axis. In three dimension it
becomes
∂ ρ( x , t)
+∇ . J́ ( x , t )=0
∂t
Whereas
ℏ
J́ (r , t)=
2 mi
[ Ψ ∗ ( r , t ) {∇ .Ψ ( r , t ) } − {∇ . Ψ ∗ ( r , t ) }Ψ ( r , t ) ]

The integral of ρ ( r , t ) over all space remains constant

at all times. Note that this does not mean that ρ ( r , t )
must be time-independent at every point r.
Nevertheless, we can express a local conservation
of probability in theform of a continuity equation,
∂ ρ(r , t )
+ ∇ . J́ ( r , t ) =0
∂t

Where J́ ( r ,t )is the probability current, defined by

ℏ
J́ ( r ,t )=
2 mi
[ Ψ ∗ ( ∇ Ψ ) −Ψ ( ∇ Ψ ∗ ) ]

1 ℏ
J́ ( r ,t )=
m [ ( )]
ℜ Ψ ∗ ∇Ψ
i

Consider two regions in a space where their

constant potentials are separated by a potential
step or barrier,

52
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

We can now define transmission and reflection

coefficients as follows;suppose that a particle (or a
stream of particles)is moving from region I
through the potential step (or barrier) to region II.
In the general case, a stationarystate describing
this situation will contain three parts.
In region I
 Incoming wave with probability current J . I

 Reflected wave of probability current J . R

In region II
 Transmitted wave of probability current J . T

The reflection coefficient is defined by

JR
R= ||JI

The transmission coefficient is defined by

JT
T=|| JI

Examples
Consider a particle described by a wave function
∂ ρ(r , t )
ρ(r, t).Calculate the time-derivative ∂t where ρ(r,
53
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

t) is the probability density and show that the

continuity equation
+ ∇ . J́ ( r , t ) =0is valid, where J(r,t ) is the probability
∂ ρ(r , t )
∂t

current

Solution
Using the Schrodinger eqn
d Ψ (r , t ) ℏ2 2 ( )
iℏ =− ∇ Ψ r , t + V (r )Ψ ( r , t )
dt 2m
¿>
d Ψ ( r ,t )
dt
=−
ℏ
2 mi
1
∇ 2 Ψ ( r , t )+ V (r )Ψ ( r , t ) … (1)
iℏ
Assume V(x) is
real, the conjugate expression (Negate any
point with complex no i) is
d Ψ ∗ (r , t ) ℏ2 2 ∗
−iℏ =− ∇ Ψ ( r , t ) +V (r )Ψ ∗ ( r , t )
dt 2m
d Ψ∗(r , t)
¿>
dt
=
ℏ 2 ∗
2 mi
1
∇ Ψ ( r , t ) − V (r)Ψ ∗ ( r , t ) … (2)
iℏ
According to the
definition of ρ(r, t),
ρ ( r , t )=Ψ ( r , t ) Ψ ( r ,t )hence,
∗

∂ ρ(r , t ) ∂ Ψ ∗( r , t )
∂t
=
∂t
Ψ ( r ,t ) +Ψ ∗ ( r , t )
∂ Ψ ( r ,t )
∂t
… … (3)
Using eqn (1) and its conjugate eqn (2) we
have
∂ ρ(r , t ) ℏ 1 ℏ 1
∂t
= ( 2 mi iℏ )
∇2 Ψ ∗ ( r ,t ) − V ( r ) Ψ ∗ ( r , t ) Ψ ( r , t )+ Ψ ∗ ( r , t ) − ( 2mi
∇2Ψ ( r , t ) + V ( r ) Ψ ( r , t )
iℏ )
ℏ 1 ℏ 1
¿ ∇ 2 Ψ ∗ ( r ,t ) Ψ ( r , t ) − V ( r ) Ψ ∗ ( r ,t ) Ψ ( r , t ) − Ψ ∗ ( r ,t ) ∇ 2 Ψ ( r , t ) + Ψ ∗ ( r ,t ) V ( r ) Ψ ( r , t )
2mi iℏ 2 mi iℏ
ℏ 1
¿ [ Ψ ( r ,t ) ∇ 2 Ψ ∗ ( r , t ) −Ψ ∗ ( r , t ) ∇ 2 Ψ ( r , t ) ] + [ Ψ ∗ ( r , t ) V ( r ) Ψ ( r , t ) −Ψ ( r , t ) V ( r ) Ψ ∗ ( r , t ) ]
2mi iℏ
∂ ρ(r , t )
∂t
=
ℏ
2 mi
[ Ψ ( r , t ) ∇2 Ψ ∗ ( r , t ) −Ψ ∗ ( r ,t ) ∇2 Ψ ( r ,t ) ] … (4)
54
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

We set
1 ℏ ℏ
J́ ( r ,t )=
m [ ( )]
ℜ Ψ ∗ ∇Ψ =
i 2 mi
[ Ψ ∗ ( r ,t ) ∇ Ψ ( r , t ) −Ψ ( r , t ) ∇ Ψ ∗ ( r ,t ) ]

Using the theorem

∇ (UA )=( ∇ U ) . A+U ( ∇ . A )we have
ℏ
∇ . J́ ( r , t ) = [ ( ∇ Ψ ∗ ) . ( ∇ Ψ ) +Ψ ∗ ( ∇ 2 Ψ ) − ( ∇ Ψ ) . ( ∇ Ψ ∗ ) − Ψ ( ∇ 2 Ψ ∗ ) ]
2 mi
∇ . J́ ( r , t ) =
ℏ
2 mi
[Ψ ∗ ∇ 2 Ψ −Ψ ∇2 Ψ ∗ ] … … (5)
Put equation (5) into equation (4); we get
∂ ρ(r , t ) ℏ
= [Ψ ∇2 Ψ ∗ −Ψ ∗ ∇ 2 Ψ ]=− ℏ [ Ψ ∗ ∇2 Ψ −Ψ ∇ 2 Ψ ∗ ] =− ∇ . J́ ( r ,t )
[ ]
∂t 2 mi 2 mi
∂ ρ(r , t )
=−∇ . J́ ( r , t )
∂t
∂ ρ ( r ,t )
¿> + ∇ . J́ ( r , t )=0
∂t

Example 2
Consider the wave function; Ψ ( r , t )= [ A e +B e ] e
2
− ipx/ ℏ ipx / ℏ −i p t /2 mℏ

Find the probability current corresponding to this

wave function

Solution
ℏ
J́ ( r ,t )= (Ψ ∗ ∇ Ψ − Ψ ∇ Ψ ∗ )
2 mi

ℏ ∂Ψ ∂Ψ ∗
J́ ( x , t )=
2mi (
Ψ∗
∂x
−Ψ
∂x )
2

Ψ ( x , t )=( A e −ipx / ℏ+ B e ipx /ℏ ) e −i p t /2 mℏ

2

Ψ ∗ ( x , t ) =( A eipx / ℏ+ B e −ipx / ℏ ) ei p t /2 mℏ

∂Ψ ip ip
( )
2

= − A e −ipx / ℏ+ B eipx / ℏ e −i p t /2 mℏ
∂x ℏ ℏ

∂Ψ ∗ ip ip
( )
2

= A eipx /ℏ − B e− ipx/ ℏ e i p t /2 mℏ
∂x ℏ ℏ
55
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

J́ ( x , t )=
ℏ
2mi {[ 2

(( A e ipx /ℏ + B e −ipx /ℏ ) e i p t / 2 mℏ ) (( −
ip
ℏ
ip
ℏ )
2

)] [ 2

A e− ipx /ℏ + B e ipx /ℏ e− i p t / 2 mℏ − ( ( A e −ipx /ℏ + B e ipx/ ℏ ) e− i p t /

J́ ( x , t )=
2mi {[
ℏ ( ipx/ ℏ ip
ℏ
ip
ℏ (
A e +B e− ipx/ ℏ ) − A e −ipx / ℏ+ B eipx / ℏ − ( A e− ipx /ℏ + B eipx / ℏ )
ip
ℏ )] ip
[
A eipx /ℏ − B e− ipx/ ℏ
ℏ ( )]}
J́ ( x , t )=
ℏ
2mi {[( −
ip 2 ip
ℏ ℏ
ip
ℏ
ip
A + AB e 2 ipx /ℏ − AB e− 2 ipx/ ℏ + B2 −
ℏ
ip 2 ip
ℏ ℏ
ip
ℏ
ip
)] [
A − AB e− 2ipx / ℏ+ AB e2 ipx /ℏ − B 2
ℏ

ℏ ip ip ip ip ip ip ip ip
J́ ( x , t )= {
2mi
− A 2+ ABe 2 ipx /ℏ − AB e −2 ipx /ℏ + B2 − A 2 + AB e− 2 ipx/ ℏ − AB e2 ipx /ℏ + B 2
ℏ ℏ ℏ ℏ ℏ ℏ ℏ ℏ }
ℏ ip ip ip ip ip ip ip ip
J́ ( x , t )=
2mi {− A − A + AB e
ℏ ℏ ℏ
2 2
− AB e
ℏ
2ipx / ℏ 2 ipx /ℏ
+
ℏ
AB e −2 ipx /ℏ − AB e −2 ipx /ℏ
ℏ
+ B+ B}
ℏ ℏ
2 2

ℏ 2 ip 2ip 2 ipℏ
J́ ( x , t )=
2mi {−
ℏ
A+
ℏ
B }= 2
2mℏi
{− A + B } 2 2 2

p
J́ ( x , t )= (|B|2 −| A|2 )
m

The term e implies that the particles are of

2
−i p t /2 mℏ

p
energy m . the amplitudes of currents are A and
B.
Example 3
Show that for a one-dimensional square -
integrable wave-packet,
∞
⟨p⟩
∫ j ( x ) dx= m
−∞

Where j ( x ), is the probability current?

Solution
∞
⟨p⟩
∫ j ( x ) dx= m
−∞

ℏ ∂Ψ ∂Ψ ∗
J́ ( x , t )=
2mi
Ψ∗(∂x
−Ψ
∂x )
56
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

∞ ∞
ℏ ∂Ψ ∂Ψ∗
∫
−∞
j ( x ) dx= ∫
2 mi − ∞
Ψ∗
∂x
−Ψ( ∂x
dx )
∞ ∞ ∞
ℏ
∫ j ( x ) dx= ∫ Ψ ∗ ∂Ψ − 2 ℏmi ∫ Ψ ∂Ψ ∗
2 mi − ∞
−∞ −∞
∞ ∞ ∞

−∞
{
∫ j ( x ) dx= 2 ℏmi ∫ Ψ ∗ ∂ Ψ − ∫ Ψ ∂ Ψ ∗
−∞ −∞
}
Integrate by parts the second part we have
∞ ∞ ∞

∫
−∞

∞
j ( x ) dx=
ℏ
2 mi {∫
−∞

∞
∗
Ψ ∂Ψ −
[∫
−∞
Ψ ∂Ψ∗
]}
∞

∫
−∞
∞
j ( x ) dx=
ℏ
2 mi {∫
−∞
∞
[
∞
∞
Ψ ∗ ∂ Ψ − Ψ Ψ ∗|− ∞ − ∫ Ψ ∗ ∂ Ψ
−∞
]}
∫
−∞
∞
j ( x ) dx=
ℏ
2 mi {∫
−∞
∞
Ψ ∂ Ψ + ∫ Ψ ∗ ∂Ψ
∗

−∞
}
∫ j ( x ) dx= 22mi
ℏ
∫ Ψ ∗ ∂Ψ
−∞ −∞
∞ ∞
⟨ p⟩
∫ j ( x ) dx= m1 ∫ Ψ ∗ ℏi ∂Ψ = m
−∞ −∞

OPERATOR
The mathematical operation like differentiation,
integration, multiplication, division, addition,
subtraction etc. can be represented by certain
symbols known as operators. An operator O^ is a
mathematical operation which may be applied to a
function f(x), which changes the function f(x) to
another function say g(x). This can be represented
as
^ f ( x )=g(x )
O

57
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

For example:
d
( 4 x2 +2 x )=8 x +2
dx
d
In operator language O^ = dx operates on the function
f ( x )=4 x + 2 x and changes the function f ( x ) to function
2

g ( x )=8 x+ 2.

OPERATOR IN QUANTUM MECHANICS

The wave function for a one dimensional motion
of a free particle along x – axis is given as
i
( px − Et )
Ψ ( x , t )= A e ℏ

Differentiating Ψ ( x , t ) with respect to x we get

i
∂Ψ ( x , t ) ip ℏ
( px − Et ) ip
= Ae = Ψ ( x ,t )
∂x ℏ ℏ
ℏ ∂ ∂
¿> p Ψ = =−iℏ
i ∂x ∂x
∂
p Ψ =− iℏ … …(∗)
∂x

Differentiating Ψ ( x , t ) with respect to t we get

i
∂Ψ ( x , t ) iE ( px− Et ) iE
=− A e ℏ =− Ψ ( x , t )
∂t ℏ ℏ
∂
E Ψ =iℏ Ψ … …(∗ ∗)
∂t

Equation (*) and (**) are operators associated for

momentum and energy respectively.
There are two sets of important operators
(a) The spatial operatorsX, Y,and Z are
defined by
XΨ ( x , y , z , t )=x Ψ ( x , y , z , t )
YΨ ( x , y , z , t ) = y Ψ ( x , y , z , t )
ZΨ ( x , y , z ,t )=z Ψ ( x , y , z ,t )

58
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

(b) The momentum operators P , x Py , and P are

z

defined by
∂
P x Ψ ( x , y , z , t ) =−iℏ Ψ ( x , y , z ,t )
∂x
∂
P y Ψ ( x , y , z ,t )=− iℏ Ψ ( x , y , z ,t )
∂x
∂
P z Ψ ( x , y , z , t )=−iℏ Ψ ( x, y , z,t )
∂x
In three dimensions, the momentum operator is
^p=− iℏ∇

Other operators include Energy operator

∂
E Ψ =iℏ Ψ
∂t
We have Schrödinger time independent equation
given as
dΨ ℏ2 2
iℏ =− ∇ Ψ +V Ψ
dt 2m
ℏ2 2
E Ψ =− ∇ Ψ +V Ψ
2m
ℏ2 2
E Ψ= −(2m
∇ +V Ψ )
E Ψ =H Ψ
H Ψ =E Ψ
ℏ2 2
Where H=−
2m
∇ +V is called the Hamiltonian
operator, since H=k . e+ p . e=T +V is the Hamiltonian of

the system

EIGENFUNCTIONS AND EIGENVALUES

When an operator A acts on some vector/function
|Ψ ⟩ and suppose the result is the same vector or a

result proportional to the initial vector, then we say

A|Ψ ⟩ =a|Ψ ⟩

59
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

– Eigen-vector / Eigen-function for operator A

|Ψ ⟩
a – Corresponding Eigen-values e.g. the time

independent stationary solution equation is an

Eigen-function – Eigen-value equation.
The Hamiltonian operator H acts on an Eigen –
functionΨ , the result is an Eigen – value E,
accompanied by the Eigen – functionΨ .
H Ψ =E Ψ

EXPECTATION VALUES
The mean value also called expected value or
expectation of an operator Ain the state Ψ ( r )is
defined by
Ψ ∗ ( r ) A Ψ ( r ) d3 r
⟨ A ⟩=
∫
∫ Ψ ∗ (r )Ψ (r ) d3 r
If the wave function is normalised then
∫ Ψ ∗ ( r ) Ψ ( r ) d 3 r=1
Thus
∗
⟨ A ⟩=∫ Ψ (r ) A Ψ (r ) d3 r

The expectation value for position, momentum and

energy for a normalised wave function will be
∞

⟨ −∞
∞
∗
x ⟩= ∫ Ψ x Ψ dx
∞ ∞

⟨ −∞
∞
∗
p x ⟩ = ∫ Ψ p x Ψ dx = ∫ Ψ −iℏ
−∞
∞
∗
( ∂
∂x )
Ψ dx=−iℏ ∫ Ψ
∞
−∞
∗ ∂Ψ
∂x
dx

⟨ −∞
∞
∗
E ⟩ =∫ Ψ E Ψ dx =∫ Ψ iℏ
−∞
∗
( )
∞
∂
∂t
Ψ dx=iℏ ∫ Ψ
−∞
∗ ∂Ψ
∂t
dx
∞
ℏ2 2
⟨ ∗ 3
H ⟩= ∫ Ψ ( r ) H Ψ ( r ) d r =∫ Ψ ( r ) −
−∞ −∞ 2m
∗ 3
( −∞
∗
) 3
∇ Ψ ( r ) d r + ∫ Ψ ( r )( V ) Ψ ( r ) d r

60
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

∞ ∞
ℏ2
⟨ H ⟩=− ∫ Ψ ∗ ( r ) ∇2 Ψ ( r ) d 3 r +∫ Ψ ∗ ( r ) V Ψ ( r ) d 3 r
2m −∞ −∞

EHRENFEST’S THEOREM
Ehrenfest theorem states that the average motion
of wave packet agrees with the motion of the
corresponding classical motion of particles. The
classical relations between the variables associated
with the moving particles hold provided the
physical quantities are replaced by their respective
expectation values.
According to Heisenberg’s uncertainty
principle, x and p cannot be determined x

simultaneously with arbitrary accuracy. From the

dx p dr p
relation p=mv we find that p =m dt therefore dxdt = m or dt = m .
x
x

The question that arises is: what is the relation

p dr p
corresponding to dxdt = m or =
dt m in quantum x

mechanics? The answer lies with the Ehrenfest

theorem. There are two Ehrenfest theorems
i). Ehrenfest’s first theorem:
d ⟨ x ⟩ ⟨ px ⟩
=
dt m
In any direction it can be written as
d ⟨r ⟩ ⟨ p ⟩
=
dt m

ii). Ehrenfest’s second theorem:

d ⟨ px ⟩ dV
dt ⟨ ⟩
= −
dx

In general it can be written as

61
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

d ⟨ p⟩
=⟨− ∇ V ⟩
dt

Example (Ehrenfest’s theorem)

Consider a particle of mass m confined in a finite
one-dimensional potential well V (x )as shown in the
figure below

Prove that
d ⟨x⟩ ⟨ p⟩
(a) dt = m
d ⟨ P⟩ dV
(b) dt
= −⟨dx ⟩
Where ⟨ x ⟩and ⟨ p ⟩are the mean values of the
coordinate and momentum of the particle,
dV
respectively, and ⟨ − dx ⟩is the mean value of the
force actingon the particle.

Solution
(a) The Schrödinger equation is written as
∂ Ψ ( x ,t ) ℏ2 ∂ 2 (
iℏ =− Ψ x ,t ) +V ( x , t ) Ψ ( x ,t ) … …(i)
∂t 2 m ∂ x2

And its conjugate is

62
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

∂ Ψ ∗ (x ,t) ℏ2 ∂ 2 ∗
−iℏ =− 2
Ψ ( x , t )+V ( x ,t ) Ψ ∗ ( x , t ) … …(ii)
∂t 2m ∂x

Rewriting equation (i) and (ii) we have

∂Ψ ( x , t) iℏ ∂2 i
= 2
Ψ ( x , t ) − V ( x , t ) Ψ ( x , t ) … …(iii)
∂t 2m ∂ x ℏ

∂Ψ ∗( x , t) iℏ ∂ 2 ∗ i
=− 2
Ψ ( x ,t ) + V ( x , t ) Ψ ∗ ( x , t ) … …(iv)
∂t 2m ∂ x ℏ

Therefore by definition of expectation of x

written as ⟨ x ⟩ and performing first derivative
with respect to time we get
∞
d ⟨x⟩ d
= ∫ Ψ ∗ ( x , t ) x Ψ ( x , t ) dx … …(v)
dt dt −∞

Perform partial derivative on (v) we get

∞ ∞ ∞
d ⟨x⟩ d Ψ ∗ ( x ,t ) dx d Ψ (x , t)
=∫
dt − ∞ (
dt )
x Ψ ( x ,t ) dx+ ∫ Ψ ∗ ( x , t )
−∞
( )
dt −∞
(
Ψ ( x , t ) dx + ∫ Ψ ∗ ( x , t ) x
dt ) dx … …( vi)

xis not a function of time in eqn (vi) therefore,

the differentiation with respect to time in the
middle part becomes zero. Therefore we will
have
∞ ∞
d ⟨x⟩ d Ψ ∗ ( x ,t ) d Ψ ( x ,t )
=∫
dt − ∞ (
dt )
x Ψ ( x ,t ) dx+ ∫ Ψ ∗ ( x , t ) x
−∞
( dt )dx … …(vii)

Substituting the Schrödinger equation (iii) and

its conjugate (iv) into (vii) gives
∞ ∞
d ⟨x⟩ iℏ ∂2 ∗ i iℏ ∂2 i
=∫ − (
dt − ∞ 2m ∂ x 2
ℏ
∗
) −∞
∗
Ψ ( x , t )+ V ( x , t ) Ψ ( x ,t ) x Ψ ( x , t ) dx + ∫ Ψ ( x ,t ) x (
2m ∂x 2
Ψ ( x , t )− V ( x , t
ℏ

∞ ∞ ∞
d ⟨x⟩ iℏ ∂2 Ψ ∗ ( x ,t ) i ∗ iℏ ∗ ∂2 Ψ ( x , t )
dt
=− ∫ ∂ x 2 x Ψ ( x , t ) dx + ℏ ∫ V ( x , t ) Ψ ( x ,t ) x Ψ ( x , t ) dx+ 2 m ∫ Ψ ( x , t ) x ∂ x 2 dx
2 m −∞ −∞ −∞

63
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

The second and the fourth parts of equation

(viii) are equal and opposite to each other
hence results to zero, hence equation (viii) will
be written as
∞ ∞
d ⟨x⟩ iℏ ∂2 Ψ ∗ ( x ,t ) iℏ ∗ ∂2 Ψ ( x , t )
=− ∫ 2
x Ψ ( x , t ) dx + ∫ Ψ ( x , t ) x 2
dx … …(ix )
dt 2 m −∞ ∂x 2m −∞ ∂x

Consider the integration by parts equation

below
b b
b
∫ U d V =UV |a −∫ V d U
a a

Integration by parts eqn (xi); Consider first

∗

part of eqn (xi) whereby U =x Ψ ( x , t )and d V =∂ ( ∂Ψ∂ xx , t ),

( )

therefore
∞ ∞ ∞ ∞
∂2 Ψ ∗ ( x , t ) ∂Ψ ∗ ( x , t ) ∂ Ψ∗( x , t) ∂Ψ ∗ ( x , t )
∫
−∞ ∂ x2
x Ψ ( x , t ) dx= ∫
−∞
(∂
∂x
x)Ψ ( x , t ) =
∂x
x Ψ ( x , |
t ) − ∫
−∞ − ∞ ∂x
∂[ xΨ ( x,t

Likewise consider the second part of eqn (xi)

∂Ψ ( x ,t )
whereby U =Ψ ( x ,t ) x and d V =∂ ( ∂ x ), therefore
∗

∞ ∞ ∞ ∞
∂2 Ψ ( x ,t ) ∂Ψ ( x , t ) ∂ Ψ ( x ,t ) ∂ Ψ (x , t
∫
−∞
Ψ ( ∗
x ,t ) x
∂x 2
dx= ∫ Ψ ∗ ( x , t ) x ∂
−∞
(
∂x )
=Ψ ∗ ( x , t ) x
∂x |
−∞
− ∫ ∂ [Ψ∗( x , t) x ]
−∞ ∂x

Putting equations (x) and (xi) into eqn (ix) we

get
∗ ∞ ∞ ∞ ∞
∂ Ψ ∗ ( x ,t ) ∂
d ⟨x⟩
dt
=−
2m ∂x [
iℏ ∂Ψ ( x , t )
xΨ (x,t ) −∫
−∞ − ∞ ∂x| ∂x
[ x Ψ ( x , t ) ] dx +
iℏ
2m ] [
Ψ ∗ ( x ,t ) x
∂Ψ ( x ,t )
∂x | −∞
−∫
−∞

∗ ∞ ∞ ∞ ∞
∂ Ψ ∗ ( x ,t ) ∂
d ⟨x⟩
dt
=−
2m ∂x [
iℏ ∂Ψ ( x , t )
xΨ (x,t ) −∫
−∞ − ∞ ∂x| ∂x
[ x Ψ ( x , t ) ] dx − Ψ ∗ ( x ,t ) x
∂Ψ ( x ,t )
∂x |−∞
+∫
−∞
∂
∂x
[Ψ

We need to note that in this calculation we

were dealing with a real V(x), therefore
64
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

∫ |Ψ ( x , t )| dxmust be finite, therefore

2

−∞

2 2
lim |Ψ ( x ,t )| = lim |Ψ ( x ,t )| =0
x→ ∞ x →− ∞
∂ Ψ (x , t ) ∂Ψ ( x ,t )
lim = lim =0 … …( xiii )
x→ ∞ ∂x x→ − ∞ ∂x

By putting condition in eqn (xiii) into eqn (xi),

it first and third term becomes zero, hence eqn
(xii) becomes
∞ ∞
∂ Ψ ∗ ( x ,t ) ∂
d ⟨x⟩
dt
=−
iℏ
−∫
2m −∞ ∂x [ ∂x
[ x Ψ ( x , t ) ] dx + ∫
∂
−∞ ∂ x
[ ∗
Ψ (x , t) x ]
∂Ψ (x,t )
∂x
dx
]
… … … .(xiv)
Solving equation (xiv) further it reduces as
shown below
∞ ∞ ∞ ∞
∂ Ψ ∗ ( x ,t ) ∂ x ∂ Ψ ∗ ( x , t ) ∂Ψ ( x ,t ) ∂Ψ ∗ ( x , t ) ∂ Ψ ( x , t )
d ⟨x⟩
dt
=−
iℏ
−∫
2m −∞ ∂x [ ∂x
Ψ ( x , t ) dx − ∫
−∞ ∂x
x
∂x
dx + ∫
−∞ ∂x
x
∂x
dx+ ∫
−

∞ ∞ ∞ ∞
∂ Ψ ∗ ( x ,t ) ∂ Ψ∗( x, t ) ∂ Ψ ( x, t ) ∂ Ψ ∗ ( x , t ) ∂ Ψ ( x ,t )
d ⟨x⟩
dt
=−
iℏ
−∫
2m −∞ ∂x [ ∞
Ψ ( x , t ) dx − ∫
−∞ ∂x
∞
x
∂x
dx+ ∫
−∞ ∂x
x
∂x
dx + ∫ Ψ
−∞

∂ Ψ ∗ ( x ,t )
d ⟨x⟩
dt
=−
iℏ
−
2m −∞ ∂x [∫ ∗
Ψ ( x , t ) dx+ ∫ Ψ ( x , t )
−∞
∂Ψ ( x ,t )
∂x
dx …( xv)
]
Integrating the first part of eqn (xv) by parts,
where U =Ψ ( x , t ) and d V =∂ Ψ ( x , t ) ∗

∞ ∞ ∞
∂Ψ ∗ ( x , t ) ∞
∫ Ψ ( x , t ) dx= ∫ ∂ [ Ψ ∗ ( x , t ) ] Ψ ( x , t )=Ψ ∗ ( x ,t ) Ψ ( x , t )|− ∞ − ∫ Ψ ∗ ( x ,t ) ∂ [Ψ ( x ,t ) ]
−∞ ∂x −∞ −∞
∞ ∞
∂Ψ ∗ ( x , t ) ∞ ∂Ψ ( x , t )
∫ Ψ ( x , t ) dx=Ψ ∗ ( x , t ) Ψ ( x , t )|−∞ − ∫ Ψ ∗ ( x , t ) dx
−∞ ∂x −∞ ∂x

The first part of this integration based on

equation (xiii) is equal to zero hence
∞ ∞
∂Ψ ∗ ( x , t ) ∂Ψ (x,t )
∫ Ψ ( x , t ) dx=− ∫ Ψ ∗ ( x , t ) dx … …( xvi)
−∞ ∂x −∞ ∂x

65
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Replacing equation (xvi) into equation (xv) we

have
∞ ∞
d ⟨x⟩
dt
=−
iℏ
2m [ −∞
∞
∗ ∂Ψ (x,t )
−∞
∞
∂Ψ (x,t )
∫ Ψ ( x ,t ) ∂ x dx + ∫ Ψ ∗ ( x ,t ) ∂ x dx ]
d ⟨x⟩ 2 iℏ ∂Ψ ( x , t ) ℏ ∂ Ψ ( x ,t )
=− ∫ Ψ∗ (x,t ) dx= ∫ Ψ ∗ ( x ,t ) dx
dt 2 m −∞ ∂x mi − ∞ ∂x
∞
d ⟨x⟩ 1 ℏ ∂
= ∫ Ψ∗( x, t ) Ψ ( x , t ) dx …( xvii)
dt m −∞ i ∂x

By definition
∞
ℏ ∂
⟨ P ⟩= ∫ Ψ ∗ ( x , t ) Ψ ( x , t ) dx
−∞ i ∂x
∞
d ⟨ x⟩ 1 ℏ ∂ ⟨P⟩
∴ = ∫ Ψ∗ (x , t) Ψ ( x , t ) dx=
dt m −∞ i ∂x m
d ⟨ x ⟩ ⟨ P⟩
∴ =
dt m

(b) Consider the time derivative of ⟨ P ⟩

∞ ∞
d ⟨ P⟩ d ℏ ∂ ℏ d ∂ Ψ (x , t)
= ∫ Ψ ∗ ( x ,t ) Ψ ( x ,t ) dx= ∫ Ψ ∗( x, t ) dx
dt dt − ∞ i ∂x i dt −∞ ∂x
∞ ∞
d ⟨ P ⟩ ℏ d Ψ ∗ ( x ,t ) ∂Ψ ( x , t ) ℏ d ∂Ψ ( x , t )
dt
= ∫
i −∞ dt ∂x
dx+ ∫ Ψ ∗ ( x , t )
i −∞ dt ∂x [ dx ]
d ∂Ψ ( x ,t ) ∂ d Ψ ( x ,t )
But dt [
∂x
=
∂x ] [ dt ], therefore
∞ ∞
d ⟨ P⟩ ℏ d Ψ ∗ ( x , t ) ∂ Ψ ( x ,t ) ∂ d Ψ ( x ,t)
dt
=
i {∫
−∞ dt ∂x −∞
[
dx + ∫ Ψ ∗ ( x ,t )
∂x dt ]} dx …(1)

Consider Schrödinger equation and its

conjugate as shown in equation (iii) and (iv)
above we have them as
∂Ψ ( x , t) iℏ ∂2 i
= 2
Ψ ( x , t ) − V ( x , t ) Ψ ( x , t ) … …(2)
∂t 2m ∂ x ℏ

∂Ψ ∗( x , t) iℏ ∂ 2 ∗ i
=− Ψ ( x ,t ) + V ( x , t ) Ψ ∗ ( x , t ) … …(3)
∂t 2 m ∂ x2 ℏ

66
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Replace (2) and (3) into (1) we have

∞ ∞
d ⟨ P⟩ ℏ iℏ ∂2 ∗ ∂Ψ (x,t ) ∂ iℏ ∂2
dt
=
i {∫ [
−∞
−
2 m ∂ x2
∞
Ψ ( x , t ) +
i
ℏ
V ( x ,t ) Ψ ∗
( x , t )
∂x
∞
dx
]+ ∫
−∞
Ψ ∗
( x ,t )
∂ x 2 m ∂x 2
i
Ψ (x , t) − V
ℏ [
∞
2
d ⟨ P⟩ ℏ ∂2 ∗ ∂ Ψ ( x ,t ) ∂Ψ ( x ,t ) ∂ ∂Ψ
dt
= −
i
iℏ
{∫
2 m −∞ ∂ x 2
Ψ
∞
( x ,t )
∂x
dx +
i
∫
ℏ −∞
V ( x , t
∞
) Ψ ∗
( x , t )
∂x
dx +
iℏ
∫
2 m −∞
Ψ ∗
( x , t )
∂x
∞
[
∂2 Ψ ∗ ( x , t ) ∂ Ψ ( x , t ) 2
d ⟨ P⟩ ℏ2 ∂Ψ (x,t) ℏ2 ∂ ∂ Ψ (x,t )
dt
=− ∫ ∂ x2
2m −∞ ∂x −∞
∗
dx + ∫ V ( x , t ) Ψ ( x ,t )
∂x
dx +
2m − ∞
∗
∫ Ψ ( x , t ) ∂ x ∂ x2 [
Integrate the first term by parts whereby
∗
∂ Ψ ( x ,t ) ∂Ψ ( x , t )
U=
∂x and d V =∂ (
∂x ) we have
∞ ∞ ∞ ∞
∂2 Ψ ∗ ( x , t ) ∂ Ψ ( x , t ) ∂ Ψ ∗ ( x , t ) ∂ Ψ ( x , t ) ∂Ψ ∗ ( x , t ) ∂Ψ ( x ,t ) ∂ Ψ ∗ ( x ,t ) ∂ Ψ ( x ,
∫
−∞ ∂ x2 ∂x
dx= ∫
−∞
∂
∂x ( ∂x ) =
∂x ∂x |
−∞
−∫
−∞ ∂x
∂ (∂x

Based on the fact that

2 2
lim |Ψ ( x ,t )| = lim |Ψ ( x ,t )| =0
x→ ∞ x →− ∞
∂ Ψ (x , t) ∂Ψ ( x ,t )
lim = lim =0 … …(6)
x→ ∞ ∂x x→ − ∞ ∂x

Equation (5) becomes

∞ ∞
∂2 Ψ ∗ ( x , t ) ∂ Ψ ( x , t ) ∂ Ψ∗( x , t) ∂ ∂ Ψ ( x, t )
∫
−∞ ∂x
2
∂x
dx=− ∫ ∂ x ∂ x ∂ x dx …(7)
−∞
( )
Integrate the right hand side of eqn (7) by
∂Ψ ( x ,t )
parts, whereby U = ∂∂x ( ∂ x ) and d V =∂ (Ψ ( x , t ) ) we ∗

have
∞ ∞ ∞
∂Ψ ∗ ( x , t ) ∂ ∂Ψ ( x ,t ) ∂ ∂Ψ ( x ,t ) ∂2 ∂ Ψ ( x , t )
∫
−∞
∂x ∂x ∂x ( )
dx=Ψ ∗ ( x ,t )
∂x ∂x ( )|
−∞
− ∫ Ψ ∗ ( x ,t )
−∞ ∂ x2 ∂x( dx …(8) )
Based on conditions in eqn (6) eqn (8)
becomes
∞ ∞
∂Ψ ∗ ( x , t ) ∂ ∂Ψ ( x ,t ) ∂2 ∂Ψ ( x , t )
∫
−∞ ∂x ∂x ∂x ( −∞
)∗
dx=− ∫ Ψ ( x , t ) 2
∂x ∂x
dx …(9) ( )
Putting eqn (9) into eqn (7) we have
∞ ∞ ∞
∂2 Ψ ∗ ( x , t ) ∂ Ψ ( x , t ) ∂2 ∂ Ψ ( x , t ) ∂2 ∂ Ψ ( x , t )
∫
−∞ ∂x
2
∂x
dx=− − ∫
−∞
Ψ ∗
( x ,t )
∂x
2
∂x (
dx= ∫
−∞
Ψ ∗
( x ,t )
∂x)2
∂x
dx …(10) ( )
Putting eqn (10) back to eqn (4) we have
67
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

∞ ∞ ∞
∂2 Ψ ∗ ( x , t ) ∂ Ψ ( x , t ) 2
d ⟨ P⟩ ℏ2 ∂Ψ (x,t) ℏ2 ∂ ∂ Ψ (x,t )
dt
=− ∫
2m −∞
∞
∂ x2 ∂x
dx + ∫
−∞
V
∞
( x , t ) Ψ ∗
( x ,t )
∂x
dx + ∫
2m − ∞
Ψ
∞
∗
( x , t )
∂x ∂ x2
2
[
d ⟨ P⟩ ℏ2 ∂2 ∂ Ψ ( x , t ) ∂ Ψ (x , t) ℏ2 ∂ ∂ Ψ (x
dt
=− ∗
( ) ∗
∫ Ψ ( x ,t ) ∂ x 2 ∂ x dx+ ∫ V ( x , t ) Ψ ( x , t ) ∂ x dx+ 2 m ∫ Ψ ( x , t ) ∂ x ∂ x 2
2 m −∞ −∞ −∞
∗
[
Simplify the above equation we get
∞ ∞ ∞ ∞
d ⟨ P⟩ ℏ2 ∂3 Ψ ( x , t ) ∂Ψ (x,t ) ℏ2 ∂3 Ψ ( x ,t )
Ψ ∗ ( x ,t ) ∗ ∗
=− ∫ 3
dx + ∫ V ( x , t ) Ψ ( x ,t ) dx + ∫ Ψ ( x , t ) 3
dx − ∫
dt 2m −∞ ∂x −∞ ∂x 2m − ∞ ∂x −∞

The first and the third term in eqn (11) are

equal in magnitude and opposite to each other
therefore they reduce to zero reducing the
equation to the below equation
∞ ∞
d ⟨ P⟩ ∂Ψ ( x , t ) ∂
=∫ V ( x , t )Ψ ∗ ( x , t ) dx − ∫ Ψ ∗ ( x , t ) [ V ( x ,t ) Ψ ( x ,t ) ] dx … (12)
dt −∞ ∂x −∞ ∂x

Differentiating the second part of eqn (12) we

have
∞ ∞ ∞
d ⟨ P⟩ ∂Ψ ( x , t ) ∂ ∂ Ψ ( x ,t )
=∫ V ( x , t )Ψ ∗ ( x , t ) dx − ∫ Ψ ∗ ( x , t ) [ V ( x ,t ) Ψ ( x ,t ) ] dx= ∫ V ( x , t ) Ψ ∗ ( x ,t )
dt −∞ ∂x −∞ ∂x −∞ ∂x

But Ψ ( x , t ) V ( x , t ) =V ( x , t ) Ψ
∗ ∗
( x ,t ) therefore eqn (13)
becomes
∞
d ⟨ P⟩ ∂ V (x , t)
=− ∫ Ψ ∗ ( x , t ) Ψ ( x , t ) dx …(14)
dt −∞ ∂x

By definition
∞
∂V ∂V (x,t )
⟨ ⟩ = ∫ Ψ ∗ ( x ,t )
∂ x −∞ ∂x
Ψ ( x , t ) dx

Therefore
∞
d ⟨ P⟩ ∂ V (x , t) ∂V
dt
=− ∫ Ψ ∗ ( x , t )
−∞ ∂x
Ψ ( x , t ) dx= −
∂x ⟨ ⟩
d ⟨ P⟩ ∂V
dt ⟨
= −
∂x ⟩
HERMITIAN OPERATOR
If ^A is an operator corresponding to certain
observable quantity and Ψ is the wave function of
68
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

the system, then the expectation value for a

normalised system is given by
❑
⟨ A ⟩ =∫ Ψ ∗ ^A Ψ dτ
τ

is a real number. Consequently,

⟨ A⟩ ^
A must satisfy
the condition
❑ ❑
∗ ∗
∫ Ψ ( ^A Ψ ) dτ=∫ ( ^A Ψ ) Ψ dτ
τ τ

for every state Ψ of the system. The operator which

obeys the above condition is called Hermitian
operator. It will be shown that Hermitian operators
are real.

EXAMPLE 1:
Prove that eigenvalue of the Hermitian operator is
real
SOLUTION:
Eigenvalue equation of any operator ^A has the
following form
^
AΨ=λΨ

Where λ is the eigenvalue of operator ^

A

corresponding to the functionΨ . Then

∫ Ψ ∗ ^A Ψ dτ=∫ Ψ ∗ ( λΨ ) dτ=λ ∫ Ψ ∗ Ψ dτ
If the eigenfunction is normalised∫ Ψ ∗
Ψ dτ=1 , then
∫ Ψ ∗ ^A Ψ dτ=λ … … (i)
Also
∗
∫ ( ^A Ψ ) Ψ dτ=∫ ( λ∗ Ψ ∗ ) Ψ dτ=λ ∗∫ Ψ ∗ Ψ dτ= λ∗

69
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

∗
∫ ( ^A Ψ ) Ψ dτ=λ ∗ … …(ii)

Where λ is the complex conjugate of λ

∗

For Hermitian operator we have

∗
∫ Ψ ∗ ^A Ψ dτ=∫ ( ^A Ψ ) Ψ dτ

Using (i) and (ii) we find that

∴ λ= λ∗

This is possible only when λ is real. This is true for

all eigenvalues of the operator ^A . Thus eigenvalues
for Hermitian operators are real.

EXAMPLE 2:
∂
Show that the momentum operator−iℏ ∂ x is
Hermitian operator. Obtain eigenfunction of
momentum operator
SOLUTION:
For Hermitian operator we have
∗
∫ Ψ ∗ ^A Ψ dτ=∫ ( ^A Ψ ) Ψ dτ

If momentum operator is Hermitian, it should

satisfy the following condition
∞ ∞ ∗
∂Ψ ∂Ψ
∫ Ψ ∗ −iℏ
−∞
( ∂x )
dx= ∫ −iℏ
−∞
(
∂x ) Ψ dx
Or
∞ ∞
∂Ψ ∗ ∂Ψ ∗
−iℏ ∫ Ψ dx=iℏ ∫ Ψ dx … …( i)
−∞ ∂x −∞ ∂ x

Consider the LHS of equation (i) integral

∞
∂Ψ
−iℏ ∫ Ψ ∗ dx … …(ii)
−∞ ∂x

70
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Integrating by parts equation (ii) of the following

integral is
b b
∂V (x) b ∂U ( x)
∫ U ( x) ∂x
dx=[ U ( x )V ( x) ] a −∫ V ( x)
∂x
dx
a a

Thus
∞ ∞
∂Ψ ∗ ∗ ∞ ∂Ψ∗
∫ Ψ ∂ x dx= [Ψ Ψ ]− ∞ − ∫ Ψ ∂ x dx
−∞ −∞

BothΨ andΨ tend to zero at infinity.∴ ( Ψ

∗ ∗
Ψ )→0 . Hence
∞ ∗ ∞

∫ Ψ ∂∂Ψx dx=− ∫ Ψ ∂∂Ψx dx

∗

−∞ −∞

Putting this back in equation (ii) we have

∞ ∞ ∗
∂Ψ ∂Ψ
−iℏ
( ∫ Ψ∗
−∞
∂x ) (
dx =− iℏ − ∫ Ψ
−∞
∂x
dx
)
∞ ∞
∂Ψ ∗ ∂Ψ ∗
−iℏ ∫ Ψ dx=iℏ ∫ Ψ dx … … …( iii)
−∞ ∂x −∞ ∂x

Equation (iii) is similar to equation (i) an

indication that the LHS of equation (i) is equal to
the RHS of the same equation (i). Now operating
on equation (iii) we have
∞ ∞
∂Ψ ∗ ∂Ψ ∗
−iℏ ∫ Ψ dx=iℏ ∫ Ψ dx
−∞ ∂x −∞ ∂x
∞
∂Ψ∗
¿ ∫ Ψ iℏ
−∞
( ∂x
dx )
∞ ∗
∂Ψ
−∞
( ) dx
¿ ∫ Ψ − iℏ
∂x
∞ ∞ ∗
∫ Ψ (−iℏ ∂∂Ψx ) dx= ∫ Ψ ( −iℏ ∂∂Ψx ) dx
∗

−∞ −∞
∞ ∞

∫ Ψ ∗ ^p x Ψ dx= ∫ Ψ ( ^p x Ψ ) ∗ dx
−∞ −∞
∞ ∞

∫ Ψ ∗ ^p x Ψ dx= ∫ ( ^p x Ψ )∗ Ψ dx
−∞ −∞

From the definition of Hermitian we find the

momentum operator is Hermitian.
71
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Let λ be the eigenvalue of the momentum operator ^p x

. Then
^p x Ψ =λ Ψ
∂Ψ
∴ −iℏ =λ Ψ
∂x
dΨ
−iℏ =λ Ψ
dx
dΨ λ
=i dx
Ψ ℏ

If we integrate this equation, we get

Ψ =C e (iλ /ℏ ) x

Where C is a constant
The above equation gives eigenfunction of ^p . x

COMMUTATORS
If ^A and ^B are two operators satisfying the
following equations
^A Ψ =a Ψ
^BΨ =b Ψ

Ψis the simultaneous eigenfunction of operators ^

A

and ^B belonging to the eigenvalues a and b

respectively.
The above equations imply that
^B ^
A Ψ = ^B ( a Ψ )=a B
^ Ψ =ab Ψ
^
A ^B Ψ = ^
A ( b Ψ )=b ^
A Ψ =ba Ψ

Because a and b are scalars then ab=ba implying that

^B ^
AΨ − ^
AB^ Ψ =( B
^^A− ^
AB^ ) Ψ =0 … … ∗

This equation shows that Ψ is also an eigen

function of the operator ^B ^A − ^A B^ belonging to the
72
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

eigen value zero. Thus the condition * is necessary

that Ψ be a simultaneous Eigen function of A and
B. For simplicity it is denoted by [ ^B , ^A ]
∴[B
^,^ ^^
A ]= B A −^
A ^B
[ ^B , ^A ]is called COMMUTATOR BRACKET
If[ ^B , ^A ]=0, then the two operators ^A and ^B are said to
COMMUTE.
NOTE:
In QM 2, you will discuss more on the
commutation relationship

BASIC COMMUTATORS IN QUANTUM

MECHANICS
Basic operators in quantum mechanics are
position, momentum, Hamiltonian, angular
momentum operators. For simplicity we are going
to avoid using (❑^ ) symbol for operators.
Let us consider the action commutator [ x , p ] on the x

arbitrary wave function Ψ ( x , y , z )

∂ ∂
[ x , px ] Ψ = [ x ,− iℏ
∂x ]
Ψ =−iℏ x , [
∂x
Ψ ]
∂ ∂ ∂Ψ ∂
(
¿ −iℏ x −
∂x ∂x ) (
x Ψ =− iℏ x −
∂x ∂x
(x Ψ ) )
∂Ψ ∂Ψ ∂x
¿ −iℏ ( x
∂x)
−x −Ψ
∂x ∂x
∂x
¿ −iℏ ( −Ψ
∂x)
=−iℏ ( −Ψ ) =iℏΨ

[ x , p x ] Ψ =iℏ Ψ

73
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

∴ [ x , p x ] =iℏ

NOTE
You should be able to show that
i). [ x , p ]=[ y , p ]=[ z , p ]=iℏ
x y z

ii). [ p , x ]=[ p , y ]=[ p , z ]=−iℏ

x y z

iii). [ x , p ] =[ x , p ]=[ y , p ]=[ y , p ]= [ z , p ]=[ z , p ]=0

y z x z x y

iv). [ p , x ] =[ p , x ]=[ p , y ]=[ p , y ]= [ p , z ]=[ p , z ]=0

y z x z x y

PARTICLE IN A TIME – INDEPENDENT

POTENTIAL (TIME – INDEPENDENT
SCHRÖDINGER EQUATION)
Wave function in a time – independent potential
V ( r ) satisfies the Schrödinger equation
∂ Ψ (r , t) ℏ2 2
iℏ =− ∇ Ψ (r , t)+V ( r ) Ψ (r , t)
∂t 2m

Performing separation of variables Ψ ( r , t )=ϕ ( r ) χ (t) we

notice that the Schrödinger equation become
χ ( t )=A e (A and ω are constants) whereas ϕ ( r ) satisfies
−iωt

the equation
ℏ2 2 ( )
− ∇ ϕ r +V ( r ) ϕ ( r )=ℏωϕ ( r )
2m

Note: E=ℏω is the energy of state whent=0 , therefore

the above equation can be written as
ℏ2 2 ( )
− ∇ ϕ r +V ( r ) ϕ ( r )=Eϕ ( r ) … …(∗)
2m

74
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Equation (∗) is called stationary Schrödinger

equation and is used in calculating stationary
states.
∴ Ψ ( r , t )=ϕ ( r ) χ ( t ) =ϕ ( r ) e− iωt
E
But E=ℏω=¿ ω=
ℏ
E Et
−i t −i
−iωt ℏ ℏ
∴ Ψ ( r , t )=ϕ ( r ) e =ϕ ( r ) e =ϕ ( r ) e … … (∗∗)

Equation (∗ ∗) is the stationary solution of

Schrödinger equation, since the probability density
does not depend on time.
n
Ψ n (r , 0)=∑ ϕn ( r )
i =1

Where ϕ ( r ) are the spatial parts of the stationary

n

stateΨ (r , t)=ϕ ( r ) e . In this case according to the

n n
− i ωnt

superposition principle, the time evolution of Ψ ( r , 0 )

is described by
n
Ψ ( r , t )=∑ ϕn ( r ) e− i ω t n

i=1

This is due to the superposition of waves.

For a free particle (V ( r ,t )=0)

The Schrödinger is satisfied by the solution of the
form
Ψ ( r , t )=ϕ ( r ) χ (t)

Where χ (t )= A e whereas because V ( r ,t )=0 it implies

−i ( k . r −ωt )

that ϕ ( r ) is a constant, let it be B. Therefore the

above solution to the Schrödinger equation
becomes
75
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Ψ ( r , t )= AB e −i (k . r −ωt )=C e− i( k .r − ωt ) … …(∗ ∗∗)

This is because Ψ depends only on time and not

positionϕ ( r ). It should be noted that k and ω satisfy
2

the relationω= ℏ2mk , whereas C= AB is a common

constant for the whole process. Solution of the
form (∗ ∗∗) is called plane waves. Since Ψ ( r , t ) are not
square integrable, they cannot represent a particle.
On the other hand a superposition of plane waves
can yield an expression that is square integrable
and can therefore describe the dynamic of particle,
1
Ψ ( r , t )= 3/ 2 ∫
g (k ) e− i (k .r −ω (k )t) d 3 k … …(∗ ∗∗∗)
(2 π )

A wave function of the form (∗ ∗∗∗) is called a wave

– packet. We often study the case of one
dimensional wave packet
∞
1
Ψ ( x , t )= ∫ g( k )e −i ( k . x− ω(k)t ) dk
2 π −∞

Examples 1
Consider a particle subjected to a time –
independent potential V(r).
a)Assume that a state of the particle is described
by a wave function of the form Ψ ( r , t )=ϕ ( r ) χ (t)show
that χ ( t )=A e (A is a constant) and that ϕ ( r )must
−iωt

satisfy the equation

ℏ2 2 ( )
− ∇ ϕ r +V ( r ) ϕ ( r )=ℏωϕ ( r )
2m

Where mis the mass of the particle

76
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

b) Prove that the solution of the Schrödinger

equation of part (a) leads to a time –
independent probability density.

Solution
a)The Schrodinger equation is written as
d ( ) ℏ2 2 ( )
iℏ Ψ r ,t =− ∇ Ψ r , t +V (r)Ψ ( r , t )
dt 2m

Substitute Ψ ( r , t )=Φ ( r ) χ (t) into the Schrodinger

equation
d ℏ2 2 ( )
iℏ Φ ( r ) χ (t)=− χ (t ) ∇ Φ r + χ (t )V ( r) Φ ( r )
dt 2m

Divide bothsides of the Equationby Φ ( r ) χ (t)

1 ℏ2 2 ( )
iℏ
1 dχ (t)
χ (t) dt
=− Equation above is a
Φ (r ) 2 m
∇ Φ r +V (r )

function of time ton the LHS and depends on

r on the RHS
Consider the LHS
1 dχ (t) d [ ln χ (t) ]
iℏ =iℏ =ℏω
χ (t) dt dt

Therefore
ln χ ( t)=∫ −iωdt =−iωt + c
χ ( t )=A e −iωt

Likewise the RHS is also equal be ℏω

1 ℏ2 2 ( )
− ∇ Φ r +V ( r )=ℏω
Φ (r ) 2 m
Multiply bothsides by Φ ( r )
ℏ2 2 ( )
− ∇ Φ r +V ( r ) Φ ( r )=ℏω Φ ( r )
2m

77
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

b) For a function of the form Ψ ( r , t )=ϕ ( r ) e − iωt

, the
probability density is by definition
2
ρ ( r , t )=|Ψ ( r ,t )|
∗
ρ ( r , t )= [ ϕ ( r ) e− iωt ][ ϕ ( r ) e −iωt ]
ρ ( r , t )= [ ϕ ( r ) e− iωt ][ ϕ ∗ ( r ) eiωt ]
2
ρ ( r , t )=ϕ ( r ) ϕ∗ ( r )=|ϕ ( r )|

Note:Probability density does not depend on

time. This is why this type of solution is
called stationary.

Example 2
Consider the Hamiltonian for a one dimensional
system of two particles of masses m and m 1 2

subjected to a potential that depends only on the

distances between the particles
x=x 1 − x2

P21 P22
H= + +V ( x 1 − x 2)
m1 m2

a)Write the Schrödinger equation using the new

variable x and X where x=x − x (relative distance) 1 2

m1 x1 +m 2 x2
X= (centre of mass)
m1 +m 2

b) Use a separation of variable to find the

equations governing the evolution of the centre
of mass and the relative distance of the particle.
Interpret your results.
78
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

SOLUTIONS
a)Wavefunction of the two particles is governed
by Schrodinger eqn in terms of x1 and x2.
d Ψ (x 1 , x 2 , t)
iℏ =H Ψ ( x 1 , x 2 ,t)
dt
2 2
ℏ2 d Ψ ( x 1 , x 2 , t) ℏ2 d Ψ (x 1 , x 2 , t)
¿−
2 m1 d x1
2
−
2 m2 d x2
2
+V (x 1 − x 2)Ψ (x 1 , x 2 ,t) …
(i)
In order to transform to variables x and X, we
2 2
∂ ∂
have to express the differentiations ∂ x and ∂ x 1
2
2
2

in terms of the new variables

m1

x=x 1 − x2 =¿
∂ x 1∧∂ x
= =−1 X =
m1 x 1+ m2 x2
=¿
∂ X m1 +m 2
=
∧∂ X
=
m2 ...
∂ x1 ∂ x2 m 1+ m2 ∂ x1 ∂ x2 m1 +m2

(ii)
For an arbitrary function f (x , x ) we obtain 1 2

∂ f ( x1 , x2 ) ∂ f ( x , X ) ∂ x ∂ f ( x , X ) ∂ X
= +
∂ x1 ∂x ∂ x1 ∂ X ∂ x1

∂ f (x , X ) m1 ∂ f (x , X )
¿ + … …(iii )
∂x m1 +m2 ∂ X

Similarly;
∂ f ( x1 , x2 ) ∂ f ( x , X ) ∂ x ∂ f ( x , X ) ∂ X
= +
∂ x2 ∂x ∂ x2 ∂ X ∂ x2

∂f (x, X) m2 ∂ f ( x , X )
¿ ( −1 ) +
∂x m1 +m 2 ∂ X

∂f ( x, X) m 2 ∂ f (x , X )
¿− + … … (iv)
∂x m 1+ m 2 ∂ X

79
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Or
∂ ∂ m1 ∂

∂
∂ x2
= +
∂ x 1 ∂ x m1 +m2 ∂ X

=−
∂
+
m2 ∂
∂ x m1+ m2 ∂ X
… … …. (v )
}
For the 2nd derivative in x1 and x2 we have
∂2 ∂ m1 ∂ ∂ m1 ∂
∂ x1 2
=
(∂ x
+
m 1 + m2 ∂ X )( +
∂ x m1 +m2 ∂ X )
2
∂2 m1 ∂2 2 m1 ∂ ∂
¿
∂x 2
+(m1+ m2 ) 2
+
∂ X m1+ m2 ∂ x ∂ X
......( vi)

∂2 ∂ m2 ∂ ∂ m2 ∂
∂ x2 2 (
=− +
∂ x m1 +m 2 ∂ X
− +
)(
∂ x m 1+ m 2 ∂ X )
2
∂2 m2 ∂2 2 m2 ∂ ∂
¿
∂x
2
+(m 1+ m2 ) 2
−
∂ X m 1+ m2 ∂ x ∂ X
......( vii)

Substitute (vi) and (vii) into (i) we get

d Ψ ( x 1 , x2 , t ) ℏ2 ∂2 m 1 2 ∂2 2 m1 ∂ ∂ ℏ 2 ∂2 m 2 2 ∂2
iℏ
dt
=−
( (+ + )
2 m1 ∂ x 2 m1 +m2 ∂ X 2 m1 +m2 ∂ x ∂ X )
Ψ ( x , X , t )− +
( (
2 m2 ∂ x 2 m1 +m2 ∂ X 2 )
d Ψ ( x 1 , x2 , t ) 2
ℏ2 1 1 ∂ Ψ ( x , X , t ) ℏ2 1 ∂2Ψ ( x , X , t )
iℏ
dt
=−
( +
2 m1 m2 ∂ x2 ) +V ( x ) Ψ ( x , X , t ) −
(
2 m1 +m2 ) ∂X2
...(viii)

b) Since the Hamiltonian is time independent

Ψ ( x , X , t )=Φ ( x , X ) χ (t) [we separate the time and the

spatial variables]
Where Φ ( x , X ) is the stationary part i.e. t = 0. The
equation governing the stationary part is given
by
HΦ ( x , X ) ≅ Etotal Φ ( x , X ) where E is the total energy.
total

Substituting in the (viii) above we get

80
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

2
ℏ2 m1 +m 2 ∂ Φ ( x , X ) ℏ2 1 ∂2 Φ ( x , X )
− (
2 m 1 m2 )
∂ x2
+V ( x ) Φ ( x , X ) −
(
2 m 1 +m 2 )
∂ X2
=E total Φ ( x , X ) ..(ix)

Performing the separation of variables on

Φ ( x , X ,t ) we get Φ ( x , X )=ξ ( x ) η( X) and eqn (ix) becomes

2 2
ℏ2 1 m1 +m 2 ∂ ξ ( x ) ℏ2
− (
2 ξ ( x ) m 1 m2 ∂ x2) +V ( x ) =
1
(1 ∂ η( X )
2 m1+ m2 η( X ) ∂ X 2 )
+ E total ...( x ) LHS of
eqn (x) depends on x while the RHS is a
function of X, and thus equal to a constant Ecm.
2
ℏ2 1 1 ∂ η (X )
−
( )
2 m1 +m 2 η( X ) ∂ X 2
=Ecm

ℏ2 ∂2 η( X )
−
( 1
)
2 m1 +m 2 ∂ X 2
=E cm η(X ) ......(xi ) Equation for the relative
position of the two particles is given by
2
ℏ2 m1 +m 2 ∂ ξ ( x )
− (
2 m 1 m2 )
∂ x2
+V ( x ) ξ ( x )=E total − Ecm

STATIONARY STATES
The time dependendent Schrodinger equation is
written as
d Ψ (r , t ) ℏ2 2 ( )
iℏ =− ∇ Ψ r , t + V (r )Ψ ( r , t )
dt 2m

In one dimension state i.e. x-direction we have

dΨ ( x ,t) ℏ2 d2Ψ ( x , t )
iℏ =− +V (x )Ψ ( x ,t )
dt 2m dx 2

It should be remembered that time – independent

Schrodinger equation gives a solution called
STATIONARY STATE.

Remember that
81
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Ψ ( r , t )=ϕ ( r ) χ (t)

Therefore the schrodinger equation in one

dimension can be written as
2
dϕ ( x ) χ ( t ) ℏ2 d ϕ ( x ) χ (t)
iℏ =− +V (r ) ϕ ( x ) χ (t )
dt 2m dx 2

ℏ2 d 2 ϕ ( x )
¿>−
2 m dx 2
+ V ( r ) ϕ ( x )=Eϕ ( x ) ... ... *
The eqn * is called time independent Schrodinger
equation and its solution are set of stationary states
ϕ ( x ).

Note that V(x) is of paramount importance in

quantum mechanics.

From equation * we will study three complete

analytical solutions. In the discussion we will limit
ourselves to one dimension of space.
(i).The infinite square well
(ii). The finite potential barrier
(iii). The harmonic oscillator

THE INFINITE SQUARE WELL POTENTIAL

(PARTICLE IN A BOX)
We consider a particle in box bound by the
following conditions
V ( x )=¿

The drawing of the same will give us

82
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

A consistent way of interpreting this is to say that

there is zero probability of the particle to escape
from the interior region of the well into the shaded
region. The particle is just confined into the four
corners of the box. This is ensured if the boundary
conditions are:
ϕ(x )|x=± a=0

i.e. ϕ ( x )=0 at –a and at +a but continuous at all other

points.

The Schrödinger equation will now be written as

2
+V ( x ) ϕ ( x )=Eϕ ( x ) ... ... (1)
2
ℏ d ϕ(x)
− 2
2 m dx

Inside the box V ( x )=0=¿V ( x ) ϕ ( x ) =0

Therefore equation 1 becomes
2
=Eϕ ( x ) ... ...(2)Equation (2) can further be written
2
ℏ d ϕ(x)
− 2
2 m dx

as
d 2 ϕ ( x ) 2 mE
− = 2 ϕ(x)
dx 2 ℏ

This can further be written as

d 2 ϕ ( x ) 2 mE
+ 2 ϕ ( x )=0 … … (3)
dx 2 ℏ

83
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

1
2 mE
Given that ( )
k=
ℏ2
2
then equation (3) can be written
as
d2ϕ ( x ) 2
+ k ϕ ( x ) =0 … …(4)
dx 2

The linearly independent solutions to equation (4)

are
ϕ ( x )= A sin( kx) … …(5)
ϕ ( x )= A' cos( kx)… …( 6)

Applying boundary conditions to equation (5) we

have
ϕ(x )| =0 onϕ ( x )= A sin( kx) gives
x=± a

sin(± ka)=0

It should be noted that sine of an angle is zero if

the angle is a multiple of pie. Hence
ka=nπ where n=1 ,2 , 3 , … ,n Trivial solutions

n=−1 , −2 ,− 3 , … Are non linearly

independent

From equation (3) and (4)

1
2 m En
k n a=( ℏ2 ) 2
a=nπ

2 m E n 12
¿> nπ= (
ℏ2
a )
2 2 2m En 2
n π= 2 a
ℏ

Making E the subject we get n

n 2 π 2 ℏ2 1 πℏn 2
En = =
2 m a2 2 m a
… … …(7) ( )

84
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

The n notation means the nth odd energy level.

Likewise for the even solutions consider equation
(6), and by considering the boundary conditions
we will have
cos (± ka)=0 … … …( 8)

This implies that

ka= n −( 12 ) π
1
2 mE
Given that ( ) , the energies of even space wave
k=
ℏ2
2

function cos (kx ) is thus

2 mE 12 1
( ) ( )
ℏ 2
a=ka= n− π
2
1

( 2ℏmE ) a=( n− 12 ) π
2
2

2m En 1 2 2
ℏ2 ( ) 2
a = n−
2
π
2 2
1 1
E=
( n− ) π ℏ
2
=
1
ℏπ ( n − )
2 2
2
( ) … … …( 9)
n
2 m a2 2m a

Qualitative plots of lowest few odd and even wave

functions are given below

Odd solutions

85
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

Even solutions

Example1
A particle of mass mis trapped in a one
dimensional box with a potential described by
V ( x )= {∞0 0≤x ≤a
Otherwise

Solve the Schrödinger equation for this potential

Solution
Inside the boxV ( x )=0, therefore Schrödinger equation
takes the form
dΨ ( x ,t) ℏ2 d2Ψ ( x )
iℏ =−
dt 2 m dx 2

TakingΨ ( x , t )=Ψ ( x ) e , the time independent potential

−iEt / ℏ

with zero potential is

ℏ2 d 2 Ψ ( x )
E Ψ ( x )=−
2 m dx 2

86
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

ℏ2
Dividing through by 2m and moving all terms to
one side, we have
d 2 Ψ ( x ) 2 mE
+ 2 Ψ ( x ) =0
dx 2 ℏ
2 mE
If we set k 2= 2
ℏ , we obtain:
2
d Ψ (x) 2
+ k Ψ ( x )=0
dx 2

The solution of this equation is:

Ψ ( x )= A sin(kx)+ B cos( kx)OrΨ ( x )= A e i(kx −ωt )

Example 2
Consider a particle of mass m held in a one-
dimensional potentialV (x ). Suppose that in some
region V (x )is constantV (x )=V . For this region, find the
stationary states of the particle when (a) E>V ,(b) E<V ,
and (c) E=V , where E is the energy of the particle.
Solution
(a) The stationary states are the solutions of
2
+V ( x ) ϕ ( x )=Eϕ ( x ) For E>V , we introduce the
2
ℏ d ϕ(x)
− 2
2 m dx
ℏ2 k 2
positive constant k defined by 2m
=E −V , so that
d2ϕ ( x ) 2
+ k ϕ ( x ) =0
dx 2

The solution of this equation can be written in

the form
ϕ ( x )= A e ikx + A ' e− ikx

Where A and A' are arbitrary constants.

87
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

(b) We introduce the positive constant ρ

2 2

defined by ℏ2 mρ =V − E , hence the schrodinger

equation can be written as
d2ϕ ( x )
2
− ρ2 ϕ ( x )=0
dx

The general solution of

ϕ ( x )=B e ρx + B ' e − ρx

Where В and B' are arbitrary complex

constants
(c) When E=V we have
d2ϕ ( x )
=0
dx 2

So ϕ ( x ) is a linear function of x, ϕ ( x )=Cx+ C ' where C

and C ' are complex constants.

THE FINITE POTENTIAL BARRIER

The following can be concluded based on the

figure above
oe - Represents a wave with momentum P =ℏk
−i (kx− ωt)
x

travelling in the +x direction.

88
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

o Suppose a wave is travelling from left to right of

the figure above i.e. from region I to region III
through region II, then
 A – Represents amplitude of incidence
plane wave from left to right in region I
 B – Represents amplitude of a reflected
plane wave after hitting the barrier at x=± a in
region I.
 C – Represents amplitude of incidence
plane wave from left to right in region II
 D – Represents amplitude of a reflected
plane wave after hitting the barrier at x=+ a in
region II.
 E – Represents amplitude of transmitted
plane wave from left to right in region III.
o F – Represents amplitude of a reflected plane
wave in region III. But because the wave in
region III is not reflected because there is no
barrier that reflect the incident wave in this
region III, then F=0.
We will separately solve the Schrödinger equation
for each of the three sections (regions).

Regions I and III

89
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

The general Schrödinger equation for the regions I

and III is given as
ℏ 2 d2 ϕ ( x )
− =Eϕ ( x )
2 m dx 2

This is because in these two regionsV =0.

Its solutions can be written as
ϕ I ( x ) =A ei k x + B e −i k x ... ...(i) ϕ III ( x )=E e i k x + F e −i k x ... ...(ii)
I I I I

But F=0 thereforeϕ ( x ) becomes III

ϕ ( x )=E e ... ...(iii)Where

i kI x
III

2 mE
k I=
√ ℏ2

Region II
In region II the Schrödinger equation is of the
form
ℏ 2 d2 ϕ ( x )
− =( E −V o ) ϕ ( x )
2 m dx 2

Where its solution depends on whether E>V o or E<V .

o

When E>V which imply E>0 we have

o

ϕ II ( x )=C e i k x + D e− i k x … … …(iv)
2 2

Where
2 m( E −V 0 )
Our solutions are equations (i), (iii), and
k 2=
√ ℏ
2

(iv). We need to find the 5 coefficients i.e. A, B,

C, D and E.

Conditions satisfied by the coefficients

 They obey the normalization condition i.e.
∫|ϕ x|2 dx=1

90
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

 The continuinity of wave function at all

positions. This imply the wave function and
their first derivatives must be continuous in the
neighbourhood of joining positions of regions
I, II and III. This will give us four conditions
on our coefficients which is enough to
determine the four unknown ratios;
D
∧E
B C A
i. e . , , .
A A A

At x=− a we find that

ϕ I ( −a )=ϕ II ( −a )
A e −i k a +B ei k a=C e− i k a + D e i k
I I 2 2 a

From continuinity of ϕ (x) the first derivative

becomes
ϕ ' I ( − a )=ϕ' II ( − a )
i k I A e −i k a − ik I B e i k a=i k 2 C e− i k a − ik 2 D ei k
I I 2 2 a

k I A e− i k a − k I B ei k a=k 2 C e− i k a − k 2 D e i k
I I 2 2 a

At x=a, we get the equations

ϕ II ( x )=ϕ III ( x )
C e i k a + D e− i k a=E e i k a
2 2 I

From continuinity of ϕ (x) the first derivative

becomes
ϕ ' II ( x ) =ϕ' III ( x )
i k 2 C ei k a −i k 2 D e −i k a=i k 1 E ei k a
2 2 I

k 2 C e i k a − k 2 D e− i k a =k 1 E ei k
2 2 I a

91
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

From the definition of transmission and reflection

coefficients
2 2
E B
T=|| ||
A
R=
A

Note:T + R=1
i k 2 k 1 −2 i k a
B
=
( −
2 k 1 k2
e ) sin ( 2 k 2 a )
1

A i k 2 k1
cos ( 2 k 2 a ) −
(+
2 k 1 k2
sin ( 2 k 2 a )
)
1 k
C
=
2 ( )
1+ 1 e− i k a e −i k a
k2
1 2

A i k 2 k1
cos ( 2 k 2 a − ) ( ) +
2 k 1 k2
sin ( 2 k 2 a )

1 k
D
=
2 ( )
1 − 1 e −i k a e− i k a
k2
1 2

A i k2 k 1
) (
cos ( 2 k 2 a −
) +
2 k1 k 2
sin ( 2 k 2 a )

E e− 2i k a 1

=
A i k 2 k1
cos ( 2 k 2 a ) − (
2 k 1 k2
+ sin ( 2 k 2 a ))
The coefficients T and R are thus
1
T= 2
1 k 2 k1
cos2 ( 2 k 2 a ) + ( +
4 k1 k2 )
sin 2 ( 2k 2 a )

2
1 k 2 k1

R=
( −
4 k 1 k2
2
)
sin ( 2 k 2 a )
2
1 k2 k1
cos 2 ( 2k 2 a )+
(
+
4 k1 k2 )
sin 2 ( 2 k 2 a )

92
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

In this case, the wave function in regions I and III

are as shown above.

Consider region II, substitute k →+ik everywhere in 2

the above equation (iv),

ϕ ( x )=C e + D e
II To get
i k2 x − i k2 x

ϕ II ( x )=C e − kx+ D e kx

Where
2 m(E −V 0 ) 2 m(V 0 − E) 2 m(V 0 − E)
k 2=
√ ℏ 2
√
= (−1)
ℏ 2
=i
√ ℏ2
=ik

2 m(V 0 − E)
k=
√ ℏ2

We find that when E<V , then 0

1
T= 2
1 k k1
2
cosh ( 2 ka ) + (
−
4 k1 k )
sinh2 ( 2 ka )

2
1 k k1

R=
+(
4 k1 k )
2
sinh ( 2 ka )
2
1 k k1
2
cosh ( 2 ka ) +
(
−
4 k1 k )
sinh 2 ( 2 ka )

Putting the above equations together and plotting a

graph of T ( E) we have

93
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

At E<V , 0 T ( E)≠ 0 this cannot be explained classically.

THE HARMONIC OSCILLATOR

A simple harmonic oscillator equation of motion is
described by

m ẍ + kx=0 … …(1)

If we integrate equation (1) with respect to t, we

get an equation for energy of the system

1 1
E=∫ ( m ẍ +kx ) dt= m ẋ 2 + k x2
2 2
1 1
E= m ẋ 2+ k x 2 … …(2)
2 2

Putting k =m ω into equation (2) we have

2

1 1
E= m ẋ 2+ mω 2 x 2 … … (3)
2 2

The equation of motion (1) for harmonic oscillator

will thus be written as

m ẍ +m ω2 x=0
m ẍ =−m ω2 x

94
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

d2 x 2
m 2
=− m ω x
dt
2
d x ω2 2
2
=− x =−ω x
dt m

d2 x 2
2
+ ω x=0 … …( 4)
dt

The solution for equation (4) will be

x ( t )= A cos ( ωt )+ B sin ( ωt ) … …(5)

Equation (4) and (5) shows a harmonic oscillator

behaving classically. Quantum mechanically we
will consider equation (3) and see if we will be
able to solve it.

1 1
E= m ẋ 2+ mω 2 x 2
2 2
2
p 1 2 2
E= + m ω x … …( 6)
2m 2

The quantum Hamiltonian operator is thus going

to be

1 2 1 2 2 ℏ2 d 2 1 2 2
H= p + mω x =− 2
+ mω x … … … (7)
2m 2 2 m dx 2

And thus we have to solve the Schrödinger

equation

ℏ 2 d2 ϕ ( x ) 1
− + m ω2 x2 ϕ ( x )=Eϕ ( x ) … …(8)
2 m dx 2 2
95
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

In order to treat this equation (8) in a better way,

we remove the physical constants and go over
dimensionless coordinates

mω
y=
√ ℏ
x
2 E … …(9)
ξ=
ℏω
ϕ ( x )=U ( y)

When we substitute equation (9) into (8), by first

of all applying chain rule unto the differentiation
we have
df ( y ) dy df ( y ) mω dy df ( y ) mω df ( y )
dx
= .
dx dy √
=¿ y=
ℏ
x will give .
dx dy
=
√ ℏ dy

d 2 f ( y ) mω d 2 f ( y ) ℏ ℏ 2 ξℏω
dx 2
=
ℏ dy 2
√
; x= y
mω
=¿ x 2=
mω
y ; E=
2

Hence equation (8) becomes

2
ℏ 2 mω d U ( y ) 1 ℏ 2 1
− 2
+ m ω2 y U ( y )= ξℏωU ( y) … …(10)
2m ℏ dy 2 mω 2

Cancelling the common factor ℏω we find

2
ℏω d U ( y ) 1 1
− 2
+ ℏω y 2 U ( y )= ξℏωU ( y)
2 dy 2 2
2
d U ( y)
2
+ ξU ( y ) − y 2 U ( y )=0
dy

96
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

d2 2
2
U ( y)+ ( ξ − y ) U ( y )=0 … … (11)
dy

Behaviour of large |y|

A keen look at how |y| behave is similar to how|x|
behaves. This is because y is proportional to x.
For very large|y|, whatever the value ofξ ; ξ ≪< y and 2

thus equation (11) becomes

d2U 2
2
− y U =0
dy

d2U 2
= y U … … …(12)
d y2

Equation (12) has two types of solutions i.e.

i. One proportional to e
2
y /2

ii. Another solution proportional toe

2
− y /2

We reject the case (i) because it is not

normalisable.
SubstituteU ( y )=H ( y )e and noting that
2
− y /2

d e − y /2 2

=− y e − y /2
dy
2 … … … … …(13)
d 2 e − y /2 2 2

2
=( − y )( − y ) e − y /2= y 2 e − y /2
dy

We find that
2

dU ( y ) d e − y /2 − y /2 dH ( y ) 2 2 2

=H ( y ) +e =− yH ( y ) e − y /2 + H ' ( y ) e− y / 2
dy dy dy
d2U ( y ) d d 2 2

2
= ( − yH ( y ) e − y /2 ) + ( H ' ( y ) e − y /2 )
dy dy dy
2 2

d2U ( y ) '
− y / 2 dy
2
− y /2 dH ( y )
2
d e− y / 2 − y /2 d H ( y )
2
' d e − y /2
=− H ( y ) e − y e − yH ( y ) +e + H ( y )
d y2 dy dy dy dy dy

97
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

d2U ( y ) 2 2 2 2 2

2
=− H ( y ) e− y / 2 − yH ' ( y ) e− y / 2+ y 2 H ( y ) e− y / 2+ H ' ' ( y ) e − y /2 − y H ' ( y ) e− y / 2
dy

d2U ( y ) 2 2 2

2
=H ' ' ( y ) e− y / 2 − 2 yH ' ( y ) e − y /2 +( y 2 − 1) H ( y ) e − y /2 … …(14)
dy

Based on equation (11), equation (14) can be

expressed in terms of H ( y ) as
d2 2
2
U ( y)+ ( ξ − y ) U ( y )=0
dy
2 2 2 2

H ' ' ( y ) e− y / 2 − 2 yH ' ( y ) e− y / 2+ ( y 2 −1 ) H ( y ) e− y /2 + ( ξ − y 2 ) H ( y ) e − y /2 =0

H ' ' ( y ) − 2 yH ' ( y ) + ( y 2 −1 ) H ( y ) + ( ξ − y 2 ) H ( y )=0
H ' ' ( y ) − 2 yH ' ( y ) + ( ξ − y 2 + y 2 − 1 ) H ( y )=0

H ' ' ( y ) − 2 yH ' ( y ) + ( ξ − 1 ) H ( y )=0 … … …(15)

Equation (15) will be solved by substitution and

infinite series (Taylor series) and showing that it
will have to terminate somewhere i.e. H ( y ) is a
polynomial.

Taylor series solution

Let us substitute a Taylor series for H ( y )
∞
H ( y )=∑ a p y p … …(16)
p=0

This leads to
∞ ∞
H ' ( y ) =∑ p a p y p −1 ; if q=p − 1; H ' ( y )=∑ ( q +1 ) aq+1 y q … …(17)
p=0 q=0

98
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

∞ ∞
'' p −2
; if r= p −2 ; H ( y )=∑ ( r +1 )( r +2 ) ar +2 y r … …(18)
''
H ( y )= ∑ p ( p −1 ) a p y
p=0 r=0

Let’s collect terms of the same order of y

y 0 :2 a2+ ( ξ −1 ) a 0=0
y 1 : 6 a3 − 2 a2 + ( ξ − 1 ) a 1=0

.......................................................
.......................................................
y n : ( n+1 ) ( n+2 ) as +2 − ( 2n+1 − ξ ) an =0 … … …(19)

Therefore all the coefficients of this series must

vanish:
( n+1 ) ( n+2 ) an +2+ ( ξ −2 n −1 ) a n=0

2n+1 − ξ
a n+2= a … …(20)
( n+1 ) ( n+2 ) n

We set a ≠ 0 and a =0 to obtain the values ofa , a ,a ,… … a

0 1 2 4 6 2m

(m=¿ positive integer), and similarly a =0 and a ≠ 0 to 0 1

obtain the values of a , a , a , … … a (m = positive

3 5 7 2 m −1

integer). Thea ora values are computed using a

0 1

normalization condition for the wave function.

In order to find the energy associated with the

harmonic oscillator, set the values of coefficient
H ( y )=0 for some value s. In this case we obtain

2 n+1 −ξ=0

Making ξ the subject we find

99
BPY 4103 –QUANTUM MECHANICS 1
 Lecture Notes Prepared by Murila Musungu

ξ=2 n+1 … …(21)

Considering the value of ξ from equation (9) we

find that
2E
ξ= =2 n+1
ℏω
2 E=ℏω ( 2n+1 )
1
( )
En =ℏω n+ … … …(22)
2

Hence, we obtain the quantization condition for

the energy Eigenvalues.
Without an energy source, the system reaches its
minimal energy eigenvalue at T=0, given by
1
E0 = ℏω
2

This value is imposed by the uncertainty relation

∆ x ∆ p= and is the minimal energy eigenvalue the
ℏ
2

system can have.

100
BPY 4103 –QUANTUM MECHANICS 1