Quantum

Mechanics
Made
Simple:
Lecture
Notes

Weng
Cho
CHEW1

October
5,
2012

1The
author
is
with
U
of
Illinois,
Urbana-Champaign.
He
works
part
time
at
Hong
Kong
U
this
summer.
Contents

Preface
vii

Acknowledgements
vii

1
Introduction
1

1.1
Introduction.....................................
1

1.2
QuantumMechanicsisBizarre
..........................
2

1.3
The
Wave
Nature
of
a
Particle{Wave
Particle
Duality
.
.
.
.
.
.
.
.
.
.
.
.
.
2

2
Classical
Mechanics
7
2.1
Introduction.....................................
7

2.2
LagrangianFormulation
..............................
8

2.3
HamiltonianFormulation
.............................
10

2.4
MoreonHamiltonian................................
12

2.5
PoissonBracket...................................
12

3
Quantum
Mechanics|Some
Preliminaries
15

3.1
Introduction.....................................
15

3.2
Probabilistic
Interpretation
of
the
wavefunction
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
16

3.3
Simple
Examples
of
Time
Independent
Schrodinger
Equation
.
.
.
.
.
.
.
.
.
19

3.3.1
Particleina1DBox
............................
19

3.3.2
ParticleScatteringbyaBarrier
......................
21

3.3.3
ParticleinaPotentialWell
........................
21

3.4
TheQuantumHarmonicOscillator
........................
23

4
Time-Dependent
Schrodinger
Equation
27

4.1
Introduction.....................................
27

4.2
QuantumStatesintheTimeDomain.......................
27

4.3
CoherentState
...................................
28

4.4
Measurement
Hypothesis
and
Expectation
Value
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
29

4.4.1
Time
Evolution
of
the
Hamiltonian
Operator
.
.
.
.
.
.
.
.
.
.
.
.
.
.
31

4.4.2
UncertaintyPrinciple
...........................
32

4.4.3
ParticleCurrent
..............................
32

i
Quantum
Mechanics
Made
Simple

5
Mathematical
Preliminaries
35

5.1
AFunctionisaVector
...............................
35

5.2
Operators
......................................
38

5.2.1
MatrixRepresentationofanOperator
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
38

5.2.2
BilinearExpansionofanOperator
....................
39

5.2.3
TraceofanOperator............................
39
5.2.4
UnitaryOperators
.............................
41

5.2.5
HermitianOperators
............................
42

5.3
IdentityOperatorinaContinuumSpace
.....................
44

5.4
ChangingBetweenRepresentations
........................
47

5.4.1
TheCoordinateBasisFunction
......................
48

5.5
CommutationofOperators
............................
49

5.6
Expectation
Value
and
Eigenvalue
of
Operators
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
49

5.7
GeneralizedUncertaintyPrinciple.........................
51

5.8
Time
Evolution
of
the
Expectation
Value
of
an
Operator
.
.
.
.
.
.
.
.
.
.
.
.
53

5.9
PeriodicBoundaryCondition
...........................
54

6
Approximate
Methods
in
Quantum
Mechanics
57

6.1
Introduction.....................................
57

6.2
UseofanApproximateSubspace
.........................
57
6.3
TimeIndependentPerturbationTheory
.....................
59

6.4
TightBindingModel
................................
64

6.4.1
VariationalMethod
............................
66

6.4.2
TimeDependentPerturbationTheory
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
67

7
Quantum
Mechanics
in
Crystals
71

7.1
Introduction.....................................
71

7.2
Bloch-FloquetWaves
................................
72
7.3
Bloch-FloquetTheoremfor3D
..........................
74

7.4
E#ectiveMassSchrodingerEquation
.......................
78

7.5
DensityofStates(DOS)
..............................
79

7.6
DOSinaQuantumWell..............................
81

8
Angular
Momentum
85

8.1
Introduction.....................................
85

8.1.1
ElectronTrappedinaPillBox
......................
86

8.1.2
ElectronTrappedinaSphericalBox
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
88

8.2
MathematicsofAngularMomentum
.......................
91

8.3
L^2
Operator.....................................
92
Contents
iii

9
Spin
95

9.1
Introduction.....................................
95

9.2
SpinOperators
...................................
95

9.3
TheBlochSphere..................................
97

9.4
Spinor........................................
98

9.5
PauliEquation
...................................
99

10
Identical
Particles
101

10.1Introduction.....................................
101

10.2PauliExclusionPrinciple
.............................
102

10.3ExchangeEnergy
..................................
102

10.4
ExtensiontoMoreThanTwoParticles.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
104

10.5CountingtheNumberofBasisstates
.......................
105

10.6Examples
......................................
106

10.7ThermalDistributionFunctions..........................
107

11
Density
Matrix
111

11.1PureandMixedStates...............................
111

11.2DensityOperator
..................................
112

11.3
Time
Evolution
of
the
Matrix
Element
of
an
Operator
.
.
.
.
.
.
.
.
.
.
.
.
.
114

11.4
Interaction
of
Light
with
Two-Level
Atomic
System
.
.
.
.
.
.
.
.
.
.
.
.
.
.
115

12
Quantization
of
Classical
Fields
123

12.1Introduction.....................................
123

12.2
The
Quantum
Harmonic
Oscillator
Revisited
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
124

12.2.1
EigenfunctionbytheLadderApproach
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
126

12.3
Quantization
of
Waves
on
a
Linear
Atomic
Chain{Phonons
.
.
.
.
.
.
.
.
.
.
127

12.4
Schrodinger
Picture
versus
Heisenberg
Picture
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
132

12.5TheContinuumLimit
...............................
133

12.6
QuantizationofElectromagneticField
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
136

12.6.1
Hamiltonian.................................
137

12.6.2
FieldOperators...............................
138

12.6.3
MultimodeCaseandFockState
.....................
139

12.6.4
One-PhotonState
.............................
140

12.6.5
CoherentStateRevisited
.........................
141

13
Schrodinger
Wave
Fields
145

13.1Introduction.....................................
145

13.2FockSpaceforFermions
..............................
145

13.3FieldOperators
...................................
147
13.4SimilarityTransform
................................
149

13.5AdditiveOne-ParticleOperator
..........................
150

13.5.1
Three-ParticleCase
............................
151

13.6AdditiveTwo-ParticleOperator..........................
153

13.7MoreonFieldOperators..............................
155
Quantum
Mechanics
Made
Simple

13.8BosonWaveField
.................................
157

13.9BosonFieldOperators
...............................
158
13.10AdditiveOne-ParticleOperator
..........................
159
13.11The
Di#erence
between
Boson
Field
and
Photon
Field
.
.
.
.
.
.
.
.
.
.
.
.
.
160

14
Interaction
of
Di#erent
Particles
161

14.1Introduction.....................................
161

14.2InteractionofParticles
...............................
161
14.3Time-DependentPerturbationTheory
......................
162

14.3.1
Absorption
.................................
163

14.4SpontaneousEmission
...............................
165

14.5StimulatedEmission
................................
165

14.6Multi-photonCase
.................................
167

14.7TotalSpontaneousEmissionRate.........................
167

15
Quantum
Information
and
Quantum
Interpretation
169

15.1Introduction.....................................
169

15.2QuantumCryptography
..............................
169

15.2.1
No-cloningTheorem
............................
169

15.2.2EntangledStates
..............................
170
15.2.3
A
Simple
Quantum
Encryption
Algorithm
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
172

15.3QuantumComputing................................
174

15.3.1
QuantumBits(Qubits)
..........................
174

15.3.2
QuantumGates...............................
175

15.3.3
QuantumComputingAlgorithms
.....................
176

15.4QuantumTeleportation
..............................
178

15.5InterpretationofQuantumMechanics
......................
180

15.6EPRParadox
....................................
181
15.7Bell'sTheorem
...................................
182

15.7.1
PredictionbyQuantumMechanics
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
183

15.7.2
PredictionbyHiddenVariableTheory
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
184

15.8AFinalWordonQuantumParallelism......................
187

A
Generators
of
Translator
and
Rotation
191

A.1
In
nitesimalTranslation
..............................
191

A.2
In
nitesimalRotation
...............................
192

A.3
DerivationofCommutationRelations
......................
193

B
Quantum
Statistical
Mechanics
195

B.1
Introduction.....................................
195

B.1.1
DistinguishableParticles..........................
195

B.1.2
IdenticalFermions
.............................
197

B.1.3
IdenticalBosons
..............................
197

B.2
MostProbableCon
guration
...........................
197

B.2.1
DistinguishableParticles..........................
198
Contents
v

B.2.2
IdenticalFermions
.............................
198

B.2.3
IdenticalBosons
..............................
199

B.3
The
Meaning
of
a
and
�
..............................
200

C
Gaussian
Wave
Packet
203

C.1
Introduction.....................................
203

C.2
DerivationfromtheWaveEquation
.......................
204

C.3
PhysicalInterpretation...............................
205

C.4
StabilityofthePlaneWaveSolution
.......................
207
Quantum
Mechanics
Made
Simple
Preface

This
set
of
supplementary
lecture
notes
is
the
outgrowth
of
a
course
I
taught,
ECE
487,
Quantum
Electronics,
at
ECE
Department,
University
of
Illinois
at
Urbana-Champaign.
It
was
intended
to
teach
quantum
mechanics
to
undergraduate
students
as
well
as
graduate
students.
The
primary
text
book
for
this
course
is
Quantum
Mechanics
for
Scientists
and
Engineers
by
D.A.B.
Miller.
I
have
learned
a
great
deal
by
poring
over
Miller's
book.
But
where
I
feel
the
book
to
be
incomplete,
I
supplement
them
with
my
lecture
notes.
I
try
to
reach
into
rst
principles
as
much
as
I
could
with
these
lecture
notes.
The
only
background
needed
for
reading
these
notes
is
a
background
in
undergraduate
wave
physics,
and
linear
algebra.

I
would
still
recommend
using
Miller's
book
as
the
primary
text
book
for
such
a
course,
and
use
these
notes
as
supplementary
to
teach
this
topic
to
undergraduates.
Weng
Cho
CHEW
October
5,
2012

Acknowledgements

I
like
to
thank
Erhan
Kudeki
who
encouraged
me
to
teach
this
course,
and
for
having
many
interesting
discussions
during
its
teaching.
I
acknowledge
interesting
discussions
with
Fuchun
ZHANG,
Guanhua
CHEN,
Jian
WANG,
and
Hong
GUO
(McGill
U)
at
Hong
Kong

U.
I
also
like
to
thank
many
of
my
students
and
researchers
who
have
helped
type
the
notes
and
proofread
them.
They
are
Phil
Atkins,
Fatih
Erden,
Tian
XIA,
Palash
Sarker,
Jun
HUANG,
Qi
DAI,
Zuhui
MA,
Yumao
WU,
Min
TANG,
Yat-Hei
LO,
Bo
ZHU,
and
Sheng
SUN.

vii
Quantum
Mechanics
Made
Simple
Chapter
1

Introduction

1.1
Introduction
Quantum
mechanics
is
an
important
intellectual
achievement
of
the
20th
century.
It
is
one
of
the
more
sophisticated
eld
in
physics
that
has
a#ected
our
understanding
of
nano-meter
length
scale
systems
important
for
chemistry,
materials,
optics,
and
electronics.
The
existence
of
orbitals
and
energy
levels
in
atoms
can
only
be
explained
by
quantum
mechanics.
Quantum
mechanics
can
explain
the
behaviors
of
insulators,
conductors,
semi-conductors,
and
giant
magneto-resistance.
It
can
explain
the
quantization
of
light
and
its
particle
nature
in
addition
to
its
wave
nature.
Quantum
mechanics
can
also
explain
the
radiation
of
hot
body,
and
its
change
of
color
with
respect
to
temperature.
It
explains
the
presence
of
holes
and
the
transport
of
holes
and
electrons
in
electronic
devices.

Quantum
mechanics
has
played
an
important
role
in
photonics,
quantum
electronics,
and
micro-electronics.
But
many
more
emerging
technologies
require
the
understanding
of
quantum
mechanics;
and
hence,
it
is
important
that
scientists
and
engineers
understand
quantum
mechanics
better.
One
area
is
nano-technologies
due
to
the
recent
advent
of
nanofabrication
techniques.
Consequently,
nano-meter
size
systems
are
more
common
place.
In
electronics,
as
transistor
devices
become
smaller,
how
the
electrons
move
through
the
device
is
quite
di#erent
from
when
the
devices
are
bigger:
nano-electronic
transport
is
quite
di#erent
from
micro-electronic
transport.

The
quantization
of
electromagnetic
eld
is
important
in
the
area
of
nano-optics
and
quantum
optics.
It
explains
how
photons
interact
with
atomic
systems
or
materials.
It
also
allows
the
use
of
electromagnetic
or
optical
eld
to
carry
quantum
information.
Moreover,
quantum
mechanics
is
also
needed
to
understand
the
interaction
of
photons
with
materials
in
solar
cells,
as
well
as
many
topics
in
material
science.

When
two
objects
are
placed
close
together,
they
experience
a
force
called
the
Casimir
force
that
can
only
be
explained
by
quantum
mechanics.
This
is
important
for
the
understanding
of
micro/nano-electromechanical
sensor
systems
(M/NEMS).
Moreover,
the
understanding
of
spins
is
important
in
spintronics,
another
emerging
technology
where
giant
magneto-resistance,
tunneling
magneto-resistance,
and
spin
transfer
torque
are
being
used.

Quantum
mechanics
is
also
giving
rise
to
the
areas
of
quantum
information,
quantum

1
2
Quantum
Mechanics
Made
Simple

communication,
quantum
cryptography,
and
quantum
computing.
It
is
seen
that
the
richness
of
quantum
physics
will
greatly
a#ect
the
future
generation
technologies
in
many
aspects.

1.2
Quantum
Mechanics
is
Bizarre
The
development
of
quantum
mechanicsis
a
great
intellectual
achievement,
but
at
the
same
time,
it
is
bizarre.
The
reason
is
that
quantum
mechanics
is
quite
di#erent
from
classical
physics.
The
development
of
quantum
mechanics
is
likened
to
watching
two
players
having
a
game
of
chess,
but
the
watchers
have
not
a
clue
as
to
what
the
rules
of
the
game
are.
By
observations,
and
conjectures,
nally
the
rules
of
the
game
are
outlined.
Often,
equations
are
conjectured
like
conjurors
pulling
tricks
out
of
a
hat
to
match
experimental
observations.
It
is
the
interpretations
of
these
equations
that
can
be
quite
bizarre.

Quantum
mechanics
equations
were
postulated
to
explain
experimental
observations,
but
the
deeper
meanings
of
the
equations
often
confused
even
the
most
gifted.
Even
though
Einstein
received
the
Nobel
prize
for
his
work
on
the
photo-electric
e#ect
that
con
rmed
that
light
energy
is
quantized,
he
himself
was
not
totally
at
ease
with
the
development
of
quantum
mechanicsas
charted
by
the
younger
physicists.
He
was
never
comfortable
with
the
probabilistic
interpretation
of
quantum
mechanics
by
Born
and
the
Heisenberg
uncertainty
principle:
\God
doesn't
play
dice,�
was
his
statement
assailing
the
probabilistic
interpretation.
He
proposed
\hidden
variables�
to
explain
the
random
nature
of
many
experimental
observations.
He
was
thought
of
as
the
\old
fool�
by
the
younger
physicists
during
his
time.

Schrodinger
came
up
with
the
bizarre
\Schrodinger
cat
paradox�
that
showed
the
struggle
that
physicists
had
with
quantum
mechanics's
interpretation.
But
with
today's
understanding
of
quantum
mechanics,
the
paradox
is
a
thing
of
yesteryear.
The
latest
twist
to
the
interpretation
in
quantum
mechanics
is
the
parallel
universe
view
that
explains
the
multitude
of
outcomes
of
the
prediction
of
quantum
mechanics.
All
outcomes
are
possible,
but
with
each
outcome
occurring
in
di#erent
universes
that
exist
in
parallel
with
respect
to
each
other.

1.3
The
Wave
Nature
of
a
Particle{Wave
Particle
Duality
The
quantized
nature
of
the
energy
of
light
was
rst
proposed
by
Planck
in
1900
to
successfully
explain
the
black
body
radiation.
Einstein's
explanation
of
the
photoelectric
e#ect
further
asserts
the
quantized
nature
of
light,
or
light
as
a
photon.1
However,
it
is
well
known
that
light
is
a
wave
since
it
can
be
shown
to
interfere
as
waves
in
the
Newton
ring
experiment
as
far
back
as
1717.

The
wave
nature
of
an
electron
is
revealed
by
the
fact
that
when
electrons
pass
through
a
crystal,
they
produce
a
di#raction
pattern.
That
can
only
be
explained
by
the
wave
nature

1In
the
photoelectric
e#ect,
it
was
observed
that
electrons
can
be
knocked
off
a
piece
of
metal
only
if
the
light
exceeded
a
certain
frequency.
Above
that
frequency,
the
electron
gained
some
kinetic
energy
proportional
to
the
excess
frequency.
Einstein
then
concluded
that
a
packet
of
energy
was
associated
with
a
photon
that
is
proportional
to
its
frequency.
Introduction

of
an
electron.
This
experiment
was
done
by
Davisson
and
Germer
in
1927.
De
Broglie
hypothesized
that
the
wavelength
of
an
electron,
when
it
behaves
like
a
wave,
is

.
=
(1.3.1)

p
where
h
is
the
Planck's
constant,
p
is
the
electron
momentum,2
and
h
�
6:626
�
10..34Joule
�
second
(1.3.2)
When
an
electron
manifests
as
a
wave,
it
is
described
by
(z)
.
exp(ikz)
(1.3.3)
where
k
=2#=#.
Such
a
wave
is
a
solution
to3
@2

.
=
..k2.
(1.3.4)

@z2

A
generalization
of
this
to
three
dimensions
yields

r2 (r)=
..k2 (r)
(1.3.5)
We
can
de
ne
p
=
~k
(1.3.6)
where
.
=
h=(2#).4
Consequently,
we
arrive
at
an
equation
2

~2
p

..r2 (r)=
(r)
(1.3.7)

2m0
2m0
where

m0
�
9:11
�
10..31kg
(1.3.8)

The
expression
p2=(2m0)
is
the
kinetic
energy
of
an
electron.
Hence,
the
above
can
be
considered
an
energy
conservation
equation.
The
Schrodinger
equation
is
motivated
by
further
energy
balance
that
total
energy
is
equal
to
the
sum
of
potential
energy
and
kinetic
energy.
De
ning
the
potential
energy
to
be
V
(r),
the
energy
balance
equation
becomes

~2

r2
2m0

-
+
V
(r)
(r)=
E (r)
(1.3.9)

2Typical
electron
wavelengths
are
of
the
order
of
nanometers.
Compared
to
400
nm
of
wavelength
of
blue
light,
they
are
much
smaller.
Energetic
electrons
can
have
even
smaller
wavelengths.
Hence,
electron
waves
can
be
used
to
make
electron
microscope
whose
resolution
is
much
higher
than
optical
microscope.

3The
wavefunction
can
be
thought
of
as
a
\halo�
that
an
electron
carries
that
determine
its
underlying
physical
properties
and
how
it
interact
with
other
systems.

4This
is
also
called
Dirac
constant
sometimes.
Quantum
Mechanics
Made
Simple

where
E
is
the
total
energy
of
the
system.
The
above
is
the
time-independent
Schrodinger
equation.
The
ad
hoc
manner
at
which
the
above
equation
is
arrived
at
usually
bothers
a
beginner
in
the
eld.
However,
it
predicts
many
experimental
outcomes,
as
well
as
predicting
the
existence
of
electron
orbitals
inside
an
atom,
and
how
electron
would
interact
with
other
particles.

One
can
further
modify
the
above
equation
in
an
ad
hoc
manner
by
noticing
that
other
experimental
nding
shows
that
the
energy
of
a
photon
is
E
=
~!.
Hence,
if
we
let

i.
@t
(r,
t)
=
E (r,
t)
(1.3.10)
then
(r,
t)
=
e
..i!t (r,
t)
(1.3.11)

Then
we
arrive
at
the
time-dependent
Schrodinger
equation:

~2
.

..r2
+
V
(r)
(r;t)=
i.
 (r;t)
(1.3.12)

2m0
@t

Another
disquieting
fact
about
the
above
equation
is
that
it
is
written
in
complex
functions
and
numbers.
In
our
prior
experience
with
classical
laws,
they
can
all
be
written
in
real
functions
and
numbers.
We
will
later
learn
the
reason
for
this.

Mind
you,
in
the
above,
the
frequency
is
not
unique.
We
know
that
in
classical
physics,
the
potential
V
is
not
unique,
and
we
can
add
a
constant
to
it,
and
yet,
the
physics
of
the
problem
does
not
change.
So,
we
can
add
a
constant
to
both
sides
of
the
time-independent
Schrodinger
equation
(1.3.10),
and
yet,
the
physics
should
not
change.
Then
the
total
E
on
the
right-hand
side
would
change,
and
that
would
change
the
frequency
we
have
arrived
at
in
the
time-dependent
Schrodinger
equation.
We
will
explain
how
to
resolve
this
dilemma
later
on.
Just
like
potentials,
in
quantum
mechanics,
it
is
the
di#erence
of
frequencies
that
matters
in
the
nal
comparison
with
experiments,
not
the
absolute
frequencies.

The
setting
during
which
Schrodinger
equation
was
postulated
was
replete
with
knowledge
of
classical
mechanics.
It
will
be
prudent
to
review
some
classical
mechanics
knowledge
next.
Introduction
Quantum
Mechanics
Made
Simple
Chapter
2

Classical
Mechanics

2.1
Introduction
Quantum
mechanics
cannot
be
derived
from
classical
mechanics,
but
classical
mechanics
can
inspire
quantum
mechanics.
Quantum
mechanics
is
richer
and
more
sophisticated
than
classical
mechanics.
Quantum
mechanics
was
developed
during
the
period
when
physicists
had
rich
knowledge
of
classical
mechanics.
In
order
to
better
understand
how
quantum
mechanics
was
developed
in
this
environment,
it
is
better
to
understand
some
fundamental
concepts
in
classical
mechanics.
Classical
mechanics
can
be
considered
as
a
special
case
of
quantum
mechanics.
We
will
review
some
classical
mechanics
concepts
here.

In
classical
mechanics,
a
particle
moving
in
the
presence
of
potential1
V
(q)
will
experience
a
force
given
by
dV
(q)

F
(q)=
-
(2.1.1)

dq

where
q
represents
the
coordinate
or
the
position
of
the
particle.
Hence,
the
particle
can
be
described
by
the
equations
of
motion

dp
dV
(q)dq

=
F
(q)=
-
,
=
p=m
(2.1.2)

dt
dq
dt

For
example,
when
a
particle
is
attached
to
a
spring
and
moves
along
a
frictionless
surface,
the
force
the
particle
experiences
is
F
(q)=
..kq
where
k
is
the
spring
constant.
Then
the
equations
of
motion
of
this
particle
are

dp
dq

=
p_=
..kq,
=
q_=
p=m
(2.1.3)

dt
dt

Given
p
and
q
at
some
initial
time
t0,
one
can
integrate
(2.1.2)
or
(2.1.3)
to
obtain
p
and
q
for
all
later
time.
A
numerical
analysist
can
think
of
that
(2.1.2)
or
(2.1.3)
can
be
solved
by
the

1The
potential
here
refers
to
potential
energy.

7
Quantum
Mechanics
Made
Simple

qV(q)
q
Figure
2.1:
The
left
side
shows
a
potential
well
in
which
a
particle
can
be
trapped.
The
right
side
shows
a
particle
attached
to
a
spring.
The
particle
is
subject
to
the
force
due
to
the
spring,
but
it
can
also
be
described
by
the
force
due
to
a
potential
well.
nite
di#erence
method,
where
time-stepping
can
be
used
to
nd
p
and
q
for
all
later
time.
For
instance,
we
can
write
the
equations
of
motion
more
compactly
as

dV

=
F(V)
(2.1.4)

dt

where
V
=[p,
q]t,
and
F
is
a
general
vector
function
of
V.
It
can
be
nonlinear
or
linear;
in
the
event
if
it
is
linear,
then
F(V)=
A
�
V.

Using
nite
di#erence
approximation,
we
can
rewrite
the
above
as

V(t
+#t)
-
V(t)=#tF(V(t)),
V(t
+#t)=#tF(V(t))
+
V(t)
(2.1.5)

The
above
can
be
used
for
time
marching
to
derive
the
future
values
of
V
from
past
values.

The
above
equations
of
motion
are
essentially
derived
using
Newton's
law.
However,
there
exist
other
methods
of
deriving
these
equations
of
motion.
Notice
that
only
two
variables
p
and
q
are
su#cient
to
describe
the
state
of
a
particle.

2.2
Lagrangian
Formulation
Another
way
to
derive
the
equations
of
motion
for
classical
mechanics
is
via
the
use
of
the
Lagrangian
and
the
principle
of
least
action.
A
Lagrangian
is
usually
de
ned
as
the
di#erence
between
the
kinetic
energy
and
the
potential
energy,
i.e.,

L(_q,
q)=
T
-
V
(2.2.1)

where
q.
is
the
velocity.
For
a
xed
t,
q
and
q.
are
independent
variables,
since
q.
cannot
be
derived
from
q
if
it
is
only
known
at
one
given
t.
The
equations
of
motion
is
derived
from
the
principle
of
least
action
which
says
that
q(t)
that
satis
es
the
equations
of
motion
between
two
times
t1
and
t2
should
minimize
the
action
integral

.
t2

S
=
L(_q(t);q(t))dt
(2.2.2)

t1
Classical
Mechanics

Assuming
that
q(t1)
and
q(t2)
are
xed,
then
the
function
q(t)
between
t1
and
t2
should
minimize
S,
the
action.
In
other
words,
a
rst
order
perturbation
in
q
from
the
optimal
answer
that
minimizes
S
should
give
rise
to
second
order
error
in
S.
Hence,
taking
the
rst
variation
of
(2.2.2),
we
have

.
.
Z##

t2
t2
t2

@L
@L

#S
=
#L(_q,
q)dt
=
#L(_q,
q)dt
=
#q_+
#q
dt
=
0
(2.2.3)

@q.
@q

t1
t1
t1

In
order
to
take
the
variation
into
the
integrand,
we
have
to
assume
that
#L(_q,
q)
is
taken
with
constant
time.
At
constant
time,
_q
and
q
are
independent
variables;
hence,
the
partial
derivatives
in
the
next
equality
above
follow.
Using
integration
by
parts
on
the
rst
term,
we
have
t2
.
t2
.
t2

@L
d
@L
@L

#S
=
#q
-
#q
dt
+
#q
dt
=
0
(2.2.4)

@q_dt
@q.
@q

t1
t1
t1

The
rst
term
vanishes
because
#q(t1)=
#q(t2)
=
0
because
q(t1)
and
q(t2)
are
xed.
Since
#q(t)
is
arbitrary
between
t1
and
t2,
we
have

d
@L
@L

-
=
0
(2.2.5)

dt
@q.
@q

The
above
is
called
the
Lagrange
equation,
from
which
the
equation
of
motion
of
a
particle
can
be
derived.
The
derivative
of
the
Lagrangian
with
respect
to
the
velocity
_q
is
the
momentum

@L

p
=
(2.2.6)

@q.
The
derivative
of
the
Lagrangian
with
respect
to
the
coordinate
q
is
the
force.
Hence

@L

F
=
(2.2.7)

@q

The
above
equation
of
motion
is
then

p_=
F
(2.2.8)

Equation
(2.2.6)
can
be
inverted
to
express
_q
as
a
function
of
p
and
q,
namely

q_=
f(p,
q)
(2.2.9)

The
above
two
equations
can
be
solved
in
tandem
to
nd
the
time
evolution
of
p
and
q.
For
example,
the
kinetic
energy
T
of
a
particle
is
given
by

T
=
mq_(2.2.10)

2
Then
from
(2.2.1),
and
the
fact
that
V
is
independent
of
_q,

@L
@T

p
===
mq.
(2.2.11)

@q.
@q.
Quantum
Mechanics
Made
Simple

or

q.
=
(2.2.12)

Also,
from
(2.2.1),
(2.2.7),
and
(2.2.8),
we
have

@V

p_=
-
(2.2.13)

@q

The
above
pair,
(2.2.12)
and
(2.2.13),
form
the
equations
of
motion
for
this
problem.

The
above
can
be
generalized
to
multidimensional
problems.
For
example,
for
a
one
particle
system
in
three
dimensions,
qi
has
three
degrees
of
freedom,
and
i
=1,
2,
3.
(The
qi
can
represent
x,
y,
z
in
Cartesian
coordinates,
but
r,
#,
f
in
spherical
coordinates.)
But
for
N
particles
in
three
dimensions,
there
are
3N
degrees
of
freedom,
and
i
=1;:::,
3N.
The
formulation
can
also
be
applied
to
particles
constraint
in
motion.
For
instance,
for
N
particles
in
three
dimensions,
qi
may
run
from
i
=1;:::,
3N
-
k,
representing
k
constraints
on
the
motion
of
the
particles.
This
can
happen,
for
example,
if
the
particles
are
constraint
to
move
in
a
manifold
(surface),
or
a
line
(ring)
embedded
in
a
three
dimensional
space.

Going
through
similar
derivation,
we
arrive
at
the
equation
of
motion

d
@L
@L

-
=
0
(2.2.14)

dt
@q_i
@qi

In
general,
qi
may
not
have
a
dimension
of
length,
and
it
is
called
the
generalized
coordinate
(also
called
conjugate
coordinate).
Also,
q_i
may
not
have
a
dimension
of
velocity,
and
it
is
called
the
generalized
velocity.

The
derivative
of
the
Lagrangian
with
respect
to
the
generalized
velocity
is
the
generalized
momentum
(also
called
conjugate
momentum),
namely,

@L

pi
=
(2.2.15)

@q_i

The
generalized
momentum
may
not
have
a
dimension
of
momentum.
Hence,
the
equation
of
motion
(2.2.14)
can
be
written
as

@L

p_i
=
(2.2.16)

@qi

Equation
(2.2.15)
can
be
inverted
to
yield
an
equation
for
q_i
as
a
function
of
the
other
variables.
This
equation
can
be
used
in
tandem
(2.2.16)
as
time-marching
equations
of
motion.

2.3
Hamiltonian
Formulation
For
a
multi-dimensional
system,
or
a
many
particle
system
in
multi-dimensions,
the
total
time
derivative
of
L
is

dL
@L
@L

=
q_i
+
qi
(2.3.1)

dt
@qi
@q_i

i
Classical
Mechanics

Since
@L=@qi
=
d
dt
(@L=@q_i)
from
the
Lagrange
equation,
we
have
dL
.
.
d
.
@L
.
@L
.
d
.
.
@L
.
dt
=
i
dt
@q_i
q_i
+
@q_i
qi
=
dt
i
@q_i
q_i
(2.3.2)
or
.
.

d
@L

q_i
-
L
=
0
(2.3.3)

dt
@q_i

The
quantity

@L

H
=
q_i
-
L
(2.3.4)

@q_i

is
known
as
the
Hamiltonian
of
the
system,
and
is
a
constant
of
motion,
namely,
dH=dt
=
0.
As
shall
be
shown,
the
Hamiltonian
represents
the
total
energy
of
a
system.
It
is
a
constant
of
motion
because
of
the
conservation
of
energy.

The
Hamiltonian
of
the
system,
(2.3.4),
can
also
be
written,
after
using
(2.2.15),
as

H
=
q_ipi
-
L
(2.3.5)
i

where
pi
=
@L=@q_i
is
the
generalized
momentum.
The
rst
term
has
a
dimension
of
energy,
and
in
Cartesian
coordinates,
for
a
simple
particle
motion,
it
is
easily
seen
that
it
is
twice
the
kinetic
energy.
Hence,
the
above
indicates
that
the
Hamiltonian

H
=
T
+
V
(2.3.6)

The
total
variation
of
the
Hamiltonian
is

#H
=
#piq_i
-
#L
i
@L
@L

=
(_qi#pi
+
pi#q_i)
-
#qi
+
#q_i
(2.3.7)

@qi
@q_i

ii

Using
(2.2.15)
and
(2.2.16),
we
have

#H
=
(_qi#pi
+
pi#q_i)
-
(_pi#qi
+
pi#q_i)
ii

=
(_qi#pi
-
p_i#qi)
(2.3.8)
i

From
the
above,
we
gather
that
the
Hamiltonian
is
a
function
of
pi
and
qi.
Taking
the
rst
variation
of
the
Hamiltonian
with
respect
to
these
variables,
we
have

@H
@H

#H
=
#pi
+
#qi
(2.3.9)

@pi
@qi

i
12
Quantum
Mechanics
Made
Simple

Comparing
the
above
with
(2.3.8),
we
gather
that

@H

q_i
=
(2.3.10)

@pi
@H

p_i
=
-
(2.3.11)

@qi

These
are
the
equations
of
motion
known
as
the
Hamiltonian
equations.

The
(2.3.4)
is
also
known
as
the
Legendre
transformation.
The
original
function
L
is
a
function
of
_qi,
qi.
Hence,
#L
depends
on
both
#q_i
and
#qi.
After
the
Legendre
transformation,
#H
depends
on
the
di#erential
#pi
and
#qi
as
indicated
by
(2.3.8).
This
implies
that
H
is
a
function
of
pi
and
qi.
The
equations
of
motion
then
can
be
written
as
in
(2.3.10)
and
(2.3.11).
2.4
More
on
Hamiltonian
The
Hamiltonian
of
a
particle
in
classical
mechanics
is
given
by
(2.3.6),
and
it
is
a
function
of
pi
and
qi.
For
a
non-relativistic
particle
in
three
dimensions,
the
kinetic
energy

p
�
p

T
=
(2.4.1)

2m
and
the
potential
energy
V
is
a
function
of
q.
Hence,
the
Hamiltonian
can
be
expressed
as
p
�
p

H
=+
V
(q)
(2.4.2)

2m
in
three
dimensions.
When
an
electromagnetic
eld
is
present,
the
Hamiltonian
for
an
electron
can
be
derived
by
letting
the
generalized
momentum

pi
=
mq_i
+
eAi
(2.4.3)

where
e
is
the
electron
charge
and
Ai
is
component
of
the
vector
potential
A.
Consequently,
the
Hamiltonian
of
an
electron
in
the
presence
of
an
electromagnetic
eld
is

(p
-
eA)
�
(p
-
eA)

H
=+
e#(q)
(2.4.4)

2m
The
equation
of
motion
of
an
electron
in
an
electromagnetic
eld
is
governed
by
the
Lorentz
force
law,
which
can
be
derived
from
the
above
Hamiltonian
using
the
equations
of
motion
provided
by
(2.3.10)
and
(2.3.11).

2.5
Poisson
Bracket
Yet
another
way
of
expressing
equations
of
motion
in
classical
mechanics
is
via
the
use
of
Poisson
bracket.
This
is
interesting
because
Poisson
bracket
has
a
close
quantum
mechanics
analogue.
A
Poisson
bracket
of
two
scalar
variables
u
and
v
that
are
functions
of
q
and
p
is
de
ned
as

@u
@v
@v
@u

fu,
v}
=
-
(2.5.1)

@q
@p
@q
@p
Classical
Mechanics

In
this
notation,
using
(2.3.10)
and
(2.3.11),

du
@u
dq
@u
dp
@u
@H
@u
@H

=+=
-

dt
@q
dt
@p
dt
@q
@p
@p
@q

=
fu,
H}
(2.5.2)

which
is
valid
for
any
variable
u
that
is
a
function
of
p
and
q.
Hence,
we
have
the
equations
of
motion
as

q_=
fq,
Hg;p_=
fp,
H}
(2.5.3)

in
the
Poisson
bracket
notation.
As
we
shall
see
later,
similar
equations
will
appear
in
quantum
mechanics.
The
algebraic
properties
of
Poisson
bracket
are

fu,
v}
=
..fv,
u}
(2.5.4)

fu
+
v,
w}
=
fu,
w}
+
fv,
w}
(2.5.5)
fuv,
w}
=
fu,
wgv
+
ufv,
w}
(2.5.6)
fu,
vw}
=
fu,
vgw
+
vfu,
w}
(2.5.7)

ffu,
vg;w}
+
ffv,
wg;u}
+
ffw,
ug;v}
=
0
(2.5.8)

These
properties
are
antisymmetry,
distributivity,
associativity
and
Jacobi's
identity.
If
we
de
ne
a
commutator
operation
between
two
noncommuting
operator
^u
and
^v
as

[^u,
^u^v^(2.5.9)

v]=
^v
-
^u,

it
can
be
shown
that
the
above
commutator
have
the
same
algebraic
properties
as
the
Poisson
bracket.
An
operator
in
quantum
mechanics
can
be
a
matrix
operator
or
a
di#erential
operator.
In
general,
operators
do
not
commute
unless
under
very
special
circumstances.
Quantum
Mechanics
Made
Simple
Chapter
3

Quantum
Mechanics|Some
Preliminaries

3.1
Introduction
With
some
background
in
classical
mechanics,
we
may
motivate
the
Schrodinger
equation
in
a
more
sanguine
fashion.
Experimental
evidence
indicated
that
small
particles
such
as
electrons
behave
quite
strangely
and
cannot
be
described
by
classical
mechanics
alone.
In
classical
mechanics,
once
we
know
p
and
q
and
their
time
derivatives
(or
_p,
q_)
of
a
particle
at
time
t0,
one
can
integrate
the
equations
of
motion

p_=
F,
q_=
p=m
(3.1.1)

or
use
the
nite
di#erence
method
to
nd
p
and
q
at
t0
+#t,
and
at
all
subsequent
times.

In
quantum
mechanics,
the
use
of
two
variables
p
and
q
and
their
derivatives
is
insu#cient
to
describe
the
state
of
a
particle
and
derive
its
future
states.
The
state
of
a
particle
has
to
be
more
richly
endowed
and
described
by
a
wavefunction
or
state
function
(q,
t).
The
state
function
(also
known
as
a
state
vector)
is
a
vector
in
the
in
nite
dimensional
space.

At
this
juncture,
the
state
function
or
vector
is
analogous
to
when
we
study
the
control
theory
of
a
highly
complex
system.
In
the
state
variable
approach,
the
state
of
a
control
system
is
described
by
the
state
vector,
whose
elements
are
variables
that
we
think
are
important
to
capture
the
state
of
the
system.
For
example,
the
state
vector
V,
describing
the
state
of
the
factory,
can
contain
variables
that
represent
the
number
of
people
in
a
factory,
the
number
of
machines,
the
temperature
of
the
rooms,
the
inventory
in
each
room,
etc.
The
state
equation
of
this
factory
can
then
be
written
as

V(t)=
A
�
V(t)
(3.1.2)

dt

It
describes
the
time
evolution
of
the
factory.
The
matrix
A
causes
the
coupling
between
state
variables
as
they
evolve.
It
bears
strong
similarity
to
the
time-dependent
Schrodinger

15
Quantum
Mechanics
Made
Simple

Figure
3.1:
The
state
of
a
particle
in
quantum
mechanics
is
described
by
a
state
function,
which
has
in
nitely
many
degrees
of
freedom.

equation,
which
is
used
to
describe
the
time-evolution
of
the
state
function
or
the
wavefunction
of
an
electron.
In
the
wavefunction,
a
complex
number
is
assigned
to
each
location
in
space.

In
the
Schrodinger
equation,
the
wavefunction
(q,
t)
is
a
continuous
function
of
of
the
position
variable
q
at
any
time
instant
t;
hence,
it
is
described
by
in
nitely
many
numbers,
and
has
in
nite
degrees
of
freedom.
The
time
evolution
of
the
wavefunction
(q,
t)
is
governed
by
the
Schrodinger
equation.
It
was
motivated
by
experimental
evidence
and
the
works
of
many
others
such
as
Planck,
Einstein,
and
de
Broglie,
who
were
aware
of
the
wave
nature
of
a
particle
and
the
dual
wave-particle
nature
of
light.

3.2
Probabilistic
Interpretation
of
the
wavefunction
The
wavefunction
of
the
Schrodinger
equation
has
de
ed
an
acceptable
interpretation
for
many
years
even
though
the
Schrodinger
equation
was
known
to
predict
experimental
outcomes.
Some
thought
that
it
represented
an
electron
cloud,
and
that
perhaps,
an
electron,
at
the
atomistic
level,
behaved
like
a
charge
cloud,
and
hence
not
a
particle.
The
nal,
most
accepted
interpretation
of
this
wavefunction
(one
that
also
agrees
with
experiments)
is
that
its
magnitude
squared
corresponds
to
the
probabilistic
density
function.
In
other
words,
the
probability
of
nding
an
electron
in
an
interval
[x,
x
+#x]
is
equal
to

j (x,
t)j2#x
(3.2.1)

For
the
3D
case,
the
probability
of
nding
an
electron
in
a
small
volume
#V
in
the
vicinity
of
the
point
r
is
given
by

j (r;t)j2#V
(3.2.2)

Since
the
magnitude
squared
of
the
wavefunction
represents
a
probability
density
function,
it
must
satisfy
the
normalization
condition
of
a
probability
density
function,
viz.,

dV
j (r;t)j2
=
1
(3.2.3)
Quantum
Mechanics|Some
Preliminaries

with
its
counterparts
in
1D
and
2D.
The
magnitude
squared
of
this
wavefunction
is
like
some
kind
of
\energy�
that
cannot
be
destroyed.
Electrons
cannot
be
destroyed
and
hence,
charge
conservation
is
upheld
by
the
Schrodinger
equation.

Motivated
by
the
conservation
of
the
\energy�
of
the
wavefunction,
we
shall
consider
an
\energy�
conserving
system
where
the
classical
Hamiltonian
will
be
a
constant
of
motion.
In
this
case,
there
is
no
\energy�
loss
from
the
system.
The
Schrodinger
equation
that
governs
the
time
evolution
of
the
wavefunction
.
is

H.
=
i~(3.2.4)

dt

where
H^
is
the
Hamiltonian
operator.1
One
can
solve
(3.2.4)
formally
to
obtain

..i

(t)=
e
.
^t (t
=
0)
(3.2.5)

Since
the
above
is
a
function
of
an
operator,
it
has
meaning
only
if
this
function
acts
on
the
^

eigenvectors
of
the
operator
H.
It
can
be
shown
easily
that
if
A
�
Vi
=
#iVi,
exp(A)
�
Vi
=
exp(#i)Vi
(3.2.6)

If
H
is
a
Hermitian
operator,
then
there
exists
eigenfunctions,
or
special
wavefunctions,
n,
such
that
^

H n
=
En n
(3.2.7)

where
En
is
purely
real.
In
this
case,
the
time
evolution
of
n
from
(3.2.5)
is

..i
En
..i!nt n

n(t)=
e
.
t n(t
=
0)
=
e
(t
=
0)
(3.2.8)

In
the
above,
En
=
~!n,
or
the
energy
En
is
related
to
frequency
!n
via
the
reduced
Planck
constant
~.
The
reduced
Planck
constant
is
related
to
the
Planck
constant
by
.
=
h=(2#)
and
h
=6:626068
�
10..34
J
s.

Scalar
variables
that
are
measurable
in
classical
mechanics,
such
as
p
and
q,
are
known
as
observables
in
quantum
mechanics.
They
are
elevated
from
scalar
variables
to
operators
in
quantum
mechanics,
denoted
by
a
\^�
symbol
here.
In
classical
mechanics,
for
a
one
particle
system,
the
Hamiltonian
is
given
by

H
=
T
+
V
=+
V
(3.2.9)

2m

The
Hamiltonian
contains
the
information
from
which
the
equations
of
motion
for
the
particle
can
be
derived.
But
in
quantum
mechanics,
this
is
not
su#cient,
and
H
becomes
an
operator

p^

^+^

H
=
V
(3.2.10)

2m

1Rightfully,
one
should
use
the
bra
and
ket
notation
to
write
this
equation
as
H^
j .
=
i.
j i.
In
the
less

dt

rigorous
notation
in
(3.2.4),
we
will
assume
that
H
is
in
the
representation
in
which
the
state
vector
.
is
in.

That
is
if
.
is
in
coordinate
space
representation,
H
is
also
in
coordinates
space
representation.
Quantum
Mechanics
Made
Simple

This
operator
works
in
tandem
with
a
wavefunction
.
to
describe
the
state
of
the
particle.
The
operator
acts
on
a
wavefunction
(t),
where
in
the
coordinate
q
representation,
is
(q,
t).
When
(q,
t)
is
an
eigenfunction
with
energy
En,
it
can
be
expressed
as

..i!nt

n(q,
t)=
 n(q)e
(3.2.11)

where
En
=
~!n.
The
Schrodinger
equation
for
n(q)
then
becomes2

p^

H n(q)=
+
V^ n(q)=
En n(q)
(3.2.12)

2m

For
simplicity,
we
consider
an
electron
moving
in
free
space
where
it
has
only
a
constant
kinetic
energy
but
not
inuenced
by
any
potential
energy.
In
other
words,
there
is
no
force
acting
on
the
electron.
In
this
case,
V^=
0,
and
this
equation
becomes

p^

n(q)=
En n(q)
(3.2.13)

2m

It
has
been
observed
by
de
Broglie
that
the
momentum
of
a
particle,
such
as
an
electron
which
behaves
like
a
wave,
has
a
momentum

p
=
~k
(3.2.14)

where
k
=2#=.
is
the
wavenumber
of
the
wavefunction.
This
motivates
that
the
operator
^p
can
be
expressed
by

p^=
..i.
(3.2.15)

dq

in
the
coordinate
space
representation.
This
is
chosen
so
that
if
an
electron
is
described
by
a
state
function
(q)=
c1eikq,
then
^p (q)=
~k (q).
The
above
motivation
for
the
form
of
the
operator
^p
is
highly
heuristic.
We
will
see
other
reasons
for
the
form
of
^p
when
we
study
the
correspondence
principle
and
the
Heisenberg
picture.

Equation
(3.2.13)
for
a
free
particle
is
then

~2
d2
-
n(q)=
En n(q)
(3.2.16)

2m
dq2

Since
this
is
a
constant
coe#cient
ordinary
di#erential
equation,
the
solution
is
of
the
form

n(q)
=
e
#ikq
(3.2.17)
which
when
used
in
(3.2.16),
yields
~2k2
2m
=
En
(3.2.18)
Namely,
the
kinetic
energy
T
of
the
particle
is
given
by
~2k2
T
=
2m
(3.2.19)
2Forn
the
Schrodinger
equation
in
coordinate
space,
^V
turns
out
to
be
a
scalar
operator.
Quantum
Mechanics|Some
Preliminaries

where
p
=
~k
is
in
agreement
with
de
Broglie's
nding.

In
many
problems,
the
operator
V^is
a
scalar
operator
in
coordinate
space
representation
which
is
a
scalar
function
of
position
V
(q).
This
potential
traps
the
particle
within
it
acting
as
a
potential
well.
In
general,
the
Schrodinger
equation
for
a
particle
becomes

~2
@2
.
-
+
V
(q)
(q,
t)=
i.
(q,
t)
(3.2.20)

2m
@q2
@t

For
a
particular
eigenstate
with
energy
En
as
indicated
by
(3.2.11),
it
becomes

~2
d2
-
+
V
(q)
n(q)=
En n(q)
(3.2.21)

2m
dq2

The
above
is
an
eigenvalue
problem
with
eigenvalue
En
and
eigenfunction
n(q).
These
eigenstates
are
also
known
as
stationary
states,
because
they
have
a
time
dependence
indicated
by
(3.2.11).
Hence,
their
probability
density
functions
j n(q,
t)j2
are
time
independent.

These
eigenfunctions
correspond
to
trapped
modes
in
the
potential
well
de
ned
by
V
(q)
very
much
like
trapped
guided
modes
in
a
dielectric
waveguide.
These
modes
are
usually
countable
and
they
can
be
indexed
by
the
index
n.

In
the
special
case
of
a
particle
in
free
space,
or
the
absence
of
the
potential
well,
the
particle
or
electron
is
not
trapped
and
it
is
free
to
assume
any
energy
or
momentum
indexed
by
the
continuous
variable
k.
In
(3.2.18),
the
index
for
the
energy
should
rightfully
be
k
and
the
eigenfunctions
are
uncountably
in
nite.
Moreover,
the
above
can
be
generalized
to
two
and
three
dimensional
cases.

3.3
Simple
Examples
of
Time
Independent
Schrodinger
Equation
At
this
juncture,
we
have
enough
knowledge
to
study
some
simple
solutions
of
time-independent
Schrodinger
equation
such
as
a
particle
in
a
box,
a
particle
impinging
on
a
potential
barrier,
and
a
particle
in
a
nite
potential
well.

3.3.1
Particle
in
a
1D
Box
Consider
the
Schrodinger
equation
for
the
1D
case
where
the
potential
V
(x)
is
de
ned
to
be
a
function
with
zero
value
for
0
<x<a
(inside
the
box)
and
in
nite
value
outside
this
range.
The
Schrodinger
equation
is
given
by

~2
d2
-
+
V
(x)
(x)=
E (x)
(3.3.1)

2m
dx2

where
we
have
replaced
q
with
x.
Since
V
(x)
is
in
nite
outside
the
box,
(x)
has
to
be
zero.
Inside
the
well,
V
(x)
=
0
and
the
above
equation
has
a
general
solution
of
the
form

(x)=
A
sin(kx)+
B
cos(kx)
(3.3.2)
Quantum
Mechanics
Made
Simple

The
boundary
conditions
are
that
(x
=0)=0
and
(x
=
a)
=
0.
For
this
reason,
a
viable
solution
for
(x)
is

(x)=
A
sin(kx)
(3.3.3)

where
k
=
n#=a,
n
=1;:::,
1.
There
are
in
nitely
many
eigensolutions
for
this
problem.
For
each
chosen
n,
the
corresponding
energy
of
the
solution
is

(~n#=a)2

En
=
(3.3.4)

2m

These
energy
values
are
the
eigenvalues
of
the
problem,
with
the
corresponding
eigenfunctions
given
by
(3.3.3)
with
the
appropriate
k.
It
is
seen
that
the
more
energetic
the
electron
is
(high
En
values),
the
larger
the
number
of
oscillations
the
wavefunction
has
inside
the
box.
The
solutions
that
are
highly
oscillatory
have
higher
k
values,
and
hence,
higher
momentum
or
higher
kinetic
energy.
The
solutions
which
are
even
about
the
center
of
the
box
are
said
to
have
even
parity,
while
those
that
are
odd
have
odd
parity.
One
other
thing
to
be
noted
is
that
the
magnitude
squared
of
the
wavefunction
above
represents
the
probability
density
function.
Hence,
it
has
to
be
normalized.
The
normalized
version
of
the
wavefunction
is

(x)=
2=a
sin(n#x=a)
(3.3.5)

Moreover,
these
eigenfunctions
are
orthonormal
to
each
other,
viz.,

a
dx.
*
(x) m(x)=
#nm
(3.3.6)
n

The
orthogonality
is
the
generalization
of
the
fact
that
for
a
Hermitian
matrix
system,
where

the
eigenvectors
are
given
by
H
�
Vi
=
#iVi
(3.3.7)
then
it
can
be
proven
easily
that
V�
j
�
Vi
=
Cj
#ij
(3.3.8)
Moreover,
the
eigenvalues
are
real.

Figure
3.2:
The
wavefunctions
of
an
electron
trapped
in
a
1D
box
(from
DAB
Miller).
Quantum
Mechanics|Some
Preliminaries

3.3.2
Particle
Scattering
by
a
Barrier
In
the
previous
example,
it
is
manifestly
an
eigenvalue
problem
since
the
solution
can
be
found
only
at
discrete
values
of
En.
The
electron
is
trapped
inside
the
box.
However,
in
an
open
region
problem
where
the
electron
is
free
to
roam,
the
energy
of
the
electron
E
can
be
arbitrary.
We
can
assume
that
the
potential
pro
le
is
such
that
V
(x)=0
for
x<
0
while
V
(x)=
V0
for
x>
0.
The
energy
of
the
electron
is
such
that
0
<E<V0.
On
the
left
side,
we
assume
an
electron
coming
in
from
..8
with
the
wavefunction
described
by
A
exp(ik1x).
When
this
wavefunction
hits
the
potential
barrier,
a
reected
wave
will
be
present,
and
the
general
solution
on
the
left
side
of
the
barrier
is
given
by

ik1x
..ik1x

1(x)=
A1e
+
B1e
(3.3.9)

where
(~k1)2=(2m)=
E
is
the
kinetic
energy
of
the
incident
electron.
On
the
right
side,
however,
the
Schrodinger
equation
to
be
satis
ed
is

~2
d2

2(x)=(E
-
V0) 2(x)
(3.3.10)

2m
dx2

The
solution
of
the
transmitted
wave
on
the
right
is
2(x)=
A2e
ik2x
(3.3.11)

where

k2
=2m(E
-
V0)=.
(3.3.12)

Given
the
known
incident
wave
amplitude
A1,
we
can
match
the
boundary
conditions
at
x
=0
to
nd
the
reected
wave
amplitude
B1
and
the
transmitted
wave
amplitude
A2.
By
eyeballing
the
Schrodinger
equation
(3.3.1),
we
can
arrive
at
the
requisite
boundary
conditions
are
that
.
and
@ =@x
are
continuous
at
x
=
0.

Since
E<V0,
k2
is
pure
imaginary,
and
the
wave
is
evanescent
and
decays
when
x
!1.
This
e#ect
is
known
as
tunneling.
The
electron
as
a
nonzero
probability
of
being
found
inside
the
barrier,
albeit
with
decreasing
probability
into
the
barrier.
The
larger
V0
is
compared
to
E,
the
more
rapidly
decaying
is
the
wavefunction
into
the
barrier.

However,
if
the
electron
is
energetic
enough
so
that
E>V0,
k2
becomes
real,
and
then
the
wavefunction
is
no
more
evanescent.
It
penetrates
into
the
barrier;
it
can
be
found
even
a
long
way
from
the
boundary.

It
is
to
be
noted
that
the
wavefunction
in
this
case
cannot
be
normalized
as
the
above
represents
a
ctitious
situation
of
an
electron
roaming
over
in
nite
space.
The
above
example
illustrates
the
wave
physics
at
the
barrier.

3.3.3
Particle
in
a
Potential
Well
If
the
potential
pro
le
is
such
that

V
(x)=

.
>.
>.

V1
if
x<
..a=2,
region
1

V2
=0
if
jx|
<
a=2,
region
2
(3.3.13)
V3
if
x
>
a=2,
region
3
Quantum
Mechanics
Made
Simple

Figure
3.3:
Scattering
of
the
electron
wavefunction
by
a
1D
barrier
(from
DAB
Miller).

then
there
can
be
trapped
modes
(or
states)
inside
the
well
represented
by
standing
waves,
whereas
outside
the
well,
the
waves
are
evanescent
for
eigenmodes
for
which
E<V1
and
E<V3.

The
wavefunction
for
jx|
<
a=2
can
be
expressed
as

2(x)=
A2
sin(k2x)+
B2
cos(k2x)
(3.3.14)

where
k2
=2mE=~.
In
region
1
to
the
left,
the
wavefunction
is

1(x)=
A1e
#1x
(3.3.15)

where
#1
=2m(V1
-
E)=~.
The
wave
has
to
decay
in
the
left
direction.
Similar,
in
region
3
to
the
right,
the
wavefunction
is

3(x)=
B3e
..#3x
(3.3.16)

where
#3
=2m(V3
-
E)=~.
It
has
to
decay
in
the
right
direction.
Four
boundary
conditions
can
be
imposed
at
x
=
#a=2
to
eliminate
the
four
unknowns
A1,
A2,
B2,
and
B3.
However,
non-trivial
eigensolutions
can
only
exist
at
selected
values
of
E
which
are
the
eigenvalues
of
the
Schrodinger
equation.
The
eigenequation
from
which
the
eigenvalues
can
be
derived
is
a
transcendental
equation.

To
illustrate
this
point,
we
impose
that
.
is
continuous
at
x
=
#a=2
to
arrive
at
the
following
two
equations:

..#1a=2

A1e
=
..A2
sin(k2a=2)
+
B2
cos(k2a=2)
(3.3.17)

..#3a=2

A3e
=
A2
sin(k2a=2)
+
B2
cos(k2a=2)
(3.3.18)

We
further
impose
that
@ =@x
is
continuous
at
x
=
#a
to
arrive
at
the
following
two
equations:

..#1a=2

#1A1e
=
k2A2
cos(k2a=2)
+
k2B2
sin(k2a=2)
(3.3.19)

..#3a=2

..#3A3e
=
k2A2
cos(k2a=2)
-
k2B2
sin(k2a=2)
(3.3.20)
Quantum
Mechanics|Some
Preliminaries
23

The
above
four
equations
form
a
matrix
equation

M
�
V
=
0
(3.3.21)

where
V
=[A1;A2;B2;B3]t,
and
the
elements
of
M,
which
depend
on
E,
can
be
gleaned
off
the
above
equations.
Non-trivial
solutions
exists
for
V
only
if