Quantum Physics Emergence

22/08/2016
FI 3103 Quantum Physics
Alexander A. Iskandar
Physics of Magnetism and Photonics Research Group
Institut Teknologi Bandung
General Information
 Lecture schedule
• 17 18 9136
• 51 52 9221
 Tutorial
• Teaching Assistant : Mr. Suhandoko D. Isro
• 57 58 BSC A
• During the tutorial there will be several
Quizzes and average mark of the Quizzes
will taken as one of the component of the
Final Mark
 Walk Out time : 20 minutes
 Textbook
• S. Gasiorowicz, Quantum Physics 3rd ed.,
John Wiley 2003
Alexander A. Iskandar 2
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General Information
 Evaluation :
• A Midterm Exam (week 7) and a Final Exam
 Expected Exam Answer :
• Answer should show good understanding of the physical phenomena
considered in the problem, as evident by sound arguments and clear
and correct steps in finding the solution.
• The use of correct formulas and notation (vector and scalar, integrals,
complex) and the right units.
• Final correct numerical value (if asked).
 Slide download (weekly basis):
• http://fismots.fi.itb.ac.id
Alexander A. Iskandar 3
The Emergence of Quantum Physics
Black Body Radiation

Photoelectric Effect
Compton Effect
Alexander A. Iskandar Emergence of Quantum Physics 4
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(Modern) Physics in early 20th century

 19th century physicists thought they had it all together.
 They had complete understanding of classical (Newton)
mechanics that govern particles to planetary movement.
 Newton promoted the

corpuscular (particle)
theory of light. Particles of
light travel in straight lines
or rays, which explained
sharp shadows, reflection
and refraction

 They found that it turns out electricity and magnetism are one
of the same interaction, and Maxwell realized that light is a
wave.
 
E 
0

 B  0

 B
 E  
t 
  E
  B  0 J  0 0
 t
 2 1  2  E 
   2 2     0
 v t  H 
 Further proved by interference and dif-
fraction promoted by Huygens and Fresnel.
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 They introduced the concept of thermal equilibrium,
established heat as energy, introduced the concept of internal
energy, created temperature as a measure of internal energy.
Realized limitations: some energy processes cannot take place.

 But they were surprised to find that several new experimental
results were very weird that could not be explained with
classical physics.
 Modern physics is the story of these surprises, surprises that
have changed the world beyond all recognition.
 Understanding of these surprises lead to a new physics : the
(old) quantum physics.
 The following lecture will give you a summary of these
unexplained phenomena.
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Blackbody radiation
 When matter is heated, it not only absorbs
light, but it also spontaneously emits it.
 A blackbody is a cavity with a material that
only emits thermal radiation. Incoming
radiation is absorbed in the cavity.
 Blackbodies are interesting because their

optical properties are independent of the
material and only depend on the temperature.
Blackbody radiation
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Wien’s Displacement Law

 The spectral intensity I(l, T) is the total power
radiated per unit area per unit wavelength at a
given temperature.
I
Wilhelm Wien
(Phys. 1911)
 Wien’s displacement law: The maximum of the spectrum shifts

to smaller wavelengths as the temperature is increased.
Stefan-Boltzmann Law
 The total power radiated increases
with the temperature:
I
Jozef Stefan Ludwig Boltzman

P(T )   I (l , T )dl  e T 4
0
 This is known as the Stefan-Boltzmann law, with the constant

σ experimentally measured to be 5.6705 × 10−8 W / (m2 · K4).
 The emissivity e (e = 1 for an idealized blackbody) is simply
the ratio of the emissive power of an object to that of an ideal
blackbody and is always less than 1.
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Rayleigh-Jeans Formula
 Lord Rayleigh used the classical theories
of electromagnetism and
thermodynamics to show that the
blackbody spectral distribution should be:
Lord Rayleigh James Jeans
(Phys. 1904)
I
 It approaches the data at longer
wavelengths, but it deviates badly
at short wavelengths. This
problem for small wavelengths
became known as the ultraviolet
catastrophe and was one of the
outstanding exceptions that
classical physics could not explain.
Planck’s Radiation Law

 Planck assumed that the radiation in the cavity was
emitted (and absorbed) by some sort of
“oscillators.” He used Boltzman’s statistical
methods to arrive at the following formula that fit
the blackbody radiation data.
Max Planck
(Phys. 1918)
 Planck made two modifications to the classical theory:

• The oscillators (of electromagnetic origin) can only have certain
discrete energies, En = nhn, where n is an integer, n is the frequency,
and h is called Planck’s constant:
h = 6.6261 × 10−34 J·s.
• The oscillators can absorb or emit energy in discrete multiples of the
fundamental quantum of energy given by
E  h
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Photoelectric Effects
 Hertz showed that when UV light is shone on a metal
plate in a vacuum, it emits charged particles.
 Classical predictions:
• Electric field E of light exerts H. Hertz
force F = -eE on electrons. As
intensity of light increases,
force increases, so KE of
ejected electrons should
increase.
• Electrons should be emitted
whatever the frequency n of
the light, so long as E is
sufficiently large
• For very low intensities, expect a time lag between light exposure and
emission, while electrons absorb enough energy to escape from material.
PhET:
photoelectric
Photoelectric Effects
 The actual results
• Maximum KE of ejected electrons is independent of intensity, but
linearly dependent on n
• For n < n0 (i.e. for frequencies below a cut-off frequency) no electrons
are emitted
• There is no time lag. However, rate of ejection of electrons depends
on light intensity
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Einstein’s Theory
 Einstein take Planck’s theory one step further.
 Einstein suggested that the electromagnetic radiation
field is quantized into particles called photons.
 Each photon has the energy quantum:
E  hn or, E   with  h / 2
A. Einstein
(Phys. 1905)
 An electron absorbs a single photon to leave the
material.
 Conservation of energy yields:
h  KE  f R. Millikan
where f is the work function of the metal (potential energy to

be overcome before an electron could escape).
 Verified in detail through subsequent experiments by Millikan.
Einstein’s Theory
 Electrons are bound in the target
material by electric forces,
therefore they need some
minimum energy before they will
get ejected at all (i.e., ejected with
zero kinetic energy)
 The energy of the incoming
photon goes into freeing the
electron and then whatever
energy remains goes into giving
the electron some kinetic energy
 The maximum kinetic energy can KEmax  eVstop  h  f
be measured by the stopping
potential.
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Thomson Scattering
 Thomson scattering is the elastic scattering of
electromagnetic radiation by a free charged
particle, as described by classical
electromagnetism.
 It is just the low-energy limit of Compton
scattering: the particle kinetic energy and photon
frequency are the same before and after the J.J. Thomson
scattering.
 This limit is valid as long as the photon energy is
much less than the mass energy of the particle:
hn << mc2.
Thomson Scattering
 The electric field of the incident
wave (photon) accelerates the
charged particle, causing it, in turn,
to emit radiation at the same q
frequency as the incident wave, and
thus the wave is scattered.
 In this non-relativistic case, the main
cause of the acceleration of the
particle will be due to the electric
field component of the incident
wave, and the magnetic field can be
neglected.
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Thomson Scattering
 The particle will move in the
direction of the oscillating electric
field, resulting in electromagnetic
dipole radiation. The moving q
particle radiates most strongly in a
direction perpendicular to its
motion and that radiation will be
polarized along the direction of its
motion.
 Therefore, depending on where an
observer is located, the light
scattered from a small volume
element may appear to be more
or less polarized.
Thomson Scattering
 The electric fields of the
incoming and observed beam can
be divided up into those
components lying in the plane of q
observation (formed by the
incoming and observed beams)
and those components
perpendicular to that plane.
Those components lying in the
plane are referred to as "radial"
and those perpendicular to the
plane are "tangential", since this
is how they appear to the
observer.
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Thomson Scattering
 The diagram on the right shows the
radial component of the incident
electric field causing a component
of motion of the charged particles q
at the scattering point which also
lies in the plane of observation.
 It can be seen that the amplitude of
the wave observed will be
proportional to the cosine of q, the
angle between the incident and
observed beam. Itot  1 cos 2 q
 The intensity, which is the square of the amplitude, will then
be diminished by a factor of cos2(q). It can be seen that the
tangential components (perpendicular to the plane of the
diagram) will not be affected in this way.
Compton Scattering
 Compton (1923) measured intensity of scattered X-
rays from solid target, as function of wavelength
for different angles.
A. Compton
(Phys. 1927)
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Compton Scattering
 Compton found that
the peak in scattered
radiation shifts to
longer wavelength
than source. Amount A. Compton
(Phys. 1927)
depends on q (but not
on the target
material).
Compton Scattering
 Treating the light as particle (photon) which has
momentum, Compton explains the results by assuming
“billiard ball” in-elastic collisions between particles of
light (X-ray photons) and electrons in the material.
A. Compton
(Phys. 1927)
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Compton Scattering
 The photon momentum is derived from relativistic
energy-momentum relation:
 
E  m0 c 2   pc 
2 2

1
2
A. Compton
 Using the definition of speed (Phys. 1927)
p2 dE pc 2 pc 2
E  v   c
2m dp E 
m02 c 4  p 2 c 2 1
2
 Since the speed of light is vacuum is always c, then the

momentum of a photon is given by
E h h
m0, photon  0  E  pc  p    , c  l
c c l
Compton Scattering
A. Compton
(Phys. 1927)
 Conservation of momentum
h
p i  î  p f  Pe  Pe2  pi2  p 2f  2p i  p f
li
 Conservation of energy
 
1
hi  me c 2  h f  Pe2 c 2  me2 c 4 2
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Compton Scattering
A. Compton
(Phys. 1927)
l  l f  li 
h
1 cos q 
me c
 Compton won the 1927 Nobel Prize in Physics.
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The Emergence of Quantum Physics
Wave Properties of Particle

Bohr Atom
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Wave Properties of Particle

 Louis-Victor-Pierre-Raymond, 7th duc de
Broglie (15 August 1892 – 19 March 1987) was
a French physicist who made ground breaking
contributions to quantum theory.
 In his 1924 PhD thesis (thesis advisor : Paul
Langevin), he postulated the wave nature of
electrons and suggested that all matter has de Broglie
wave properties. This concept is known as
wave-particle duality or the de Broglie
hypothesis.
h h h h de Broglie
p  
c  p mv wavelength
photon momentum
Proof of Wave Properties of Particle

Electron Diffraction
 J. J. Thomson was awarded the Physics Prize
in 1906 for showing that electrons are
particles. His son, George Paget Thomson,
received the same prize in 1937 (together
with Davisson) for showing that they also
have the properties of waves. J.J. Thomson
C.J. Davisson – L. Germer C.J. Davisson G.P. Thomson

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Bragg’s X-ray Diffraction

 Nobel Prize in Physics 1915.
 William Lawrence Bragg, was to date the
youngest Nobel Laureate (he was 25 years
old when he received the Nobel Prize). W.H. Bragg W.L. Bragg
Davisson-Germer Experiment
de Broglie relationship p  mv  2mE

 2meV
C.J. Davisson – L. Germer
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Electron Diffraction-Interference
 What happens if we send electrons
through a double slit apparatus?
• initially, the pattern looks random
• start to see interference
• characteristic interference pattern
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Louis de Broglie (15 August 1892 – 19 March 1987)

 For his wave properties of particle, de Broglie
won the Nobel Prize for Physics in 1929 for
the proposal that he put forward in 1924 and
proven by experiment in 1927.
 The wave-like behaviour of particles
discovered by de Broglie was used by Erwin
Schrödinger in his formulation of wave de Broglie
mechanics.
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Limit of Wave Properties of Particle

 Example 1.6
 At macroscopic scale, we will not be able to see the wave

nature of particles.
 A 0.1 mm diameter water droplet moving at 1 mm/s will have
a de Broglie wavelength of 10-25 m, which is tens of order of
magnitude smaller than the size of a proton.
 The smallness of Planck’s constant that makes the separation
of wave and particle properties so striking in the classical
domain.
Evolution of the Atomic Model

 Dalton atomic model (1803)
• Elements are made of extremely small
particles called atoms.
• Atoms of different elements differ in
size, mass, and other properties
• The law of multiple proportions
 Thomson atomic model (plum-
pudding model, 1904)
• The atom as being made up of negatively
charged corpuscles orbiting in a sea of
positive charge.
 Rutherford atomic model (1911)
• Atoms have their charge concentrated in
a very small nucleus, and electrons are
tiny particles orbiting the nucleus.
 Bohr atomic model (1913)
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Thomson Cathode Ray Experiment

 In 1897, Thomson showed that
cathode rays were composed of a
previously unknown negatively
charged particle, and thus is credited
with the discovery and identification
of the electron.
 J. J. Thomson was awarded the
Physics Prize in 1906 for showing that
electrons are particles.

 J. J. Thomson also performed further experiments using
magnetic field to determine the ratio of e/m.
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 Thomson’s
method of
measuring the
ratio of the
electron’s charge
to mass was to
send electrons
through a region
containing a
magnetic field
perpendicular to
an electric field.

 An electron moving through the electric
field is accelerated by a force:
Fy  ma y  eE
 Electron angle of deflection:
v y a y t eE
tan( )    t
v x v0 m v02 v0
 Then turn on the magnetic field, which deflects the electron
against the electric field force.
F  eE  ev0  B  0
 The magnetic field is then adjusted until the net force is zero.
eE
E   v0  B  v0  E / B  tan( ) 
m ( E/B)2
e E tan( )
 Charge to mass ratio : 
m B2
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Thomson’s Plum-Pudding model

 Thomson imagined the atom as being made up
of these corpuscles orbiting in a sea of positive
charge; this was his plum pudding model.
 This model was later proved incorrect when
Ernest Rutherford showed that the positive
charge is concentrated in the nucleus of the
atom. J.J. Thomson
Geiger-Marsden Experiment
 In 1909, Rutherford inspired Hans Geiger and
Ernest Marsden to perform the gold-foil
experiment.
Geiger Marsden
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Geiger-Marsden Experiment
1
N
sin 4  2
PhET:
Rutherford Scattering
Rutherford Atomic Model

 In 1911, Rutherford put forward the theory that
atoms have their charge concentrated in a very
small nucleus, and electrons are tiny particles
orbiting the nucleus.
Geiger Marsden
Rutherford model of
the atom.
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Ernst Rutherford (30 August 1871 – 19 October 1937)

 Awarded the Nobel Prize in Chemistry in 1908 for
his investigations into the disintegration of the
elements, and the chemistry of radioactive
substances, work that was done at McGill Univ.,
Canada.
 Rutherford was born in New Zealand, where he
studied at Canterbury College, University of New
Zealand.
 1895 Rutherford was awarded a scholarship to travel to England
for postgraduate study at the Cavendish Laboratory, University
of Cambridge.
 He was among the first of the 'aliens' (those without a
Cambridge degree) allowed to do research at the university,
under the inspiring leadership of J. J. Thomson.
Ernst Rutherford (30 August 1871 – 19 October 1937)

 In 1898 Thomson offered Rutherford the chance
of a post at McGill University in Montreal,
Canada.
 In 1907 he moved to Victoria University of
Manchester (today University of Manchester) in
the UK.
 He is widely credited with first "splitting the atom" in 1917 in a
nuclear reaction between nitrogen and alpha particles, in which
he also discovered (and named) the proton.
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Problem with Rutherford atomic model

 From classical EM theory, an accelerated electric charge
radiates energy (electromagnetic radiation), which means
total energy must decrease.
 And the radius r must decrease and the electron must fall to
the nucleus!
Line Spectra
 Chemical elements were observed to produce unique
wavelengths of light when burned or excited in an electrical
discharge.
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Balmer Series
 In 1885, Johann Balmer found an empirical formula
for the wavelength of the visible hydrogen line
spectra in nm:
nm (where k = 3,4,5…)
Johann Balmer
Rydberg Formula
 As more scientists discovered emission lines at
infrared and ultraviolet wavelengths, the Balmer
series equation was extended to the Rydberg
equation (1888):
J. Rydberg
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Bohr’s Postulate
 In 1913, Bohr put forward 3 postulates that govern
the atomic structure which can explained the spectral
lines and bypass the stability problem.
 These postulates are
• An atomic system can only exist in a discrete set of stationary states,
with discrete values of energy, and any change of the energy of the
system, including emission and absorption of electromagnetic
radiation must take place by a complete transition between two
stationary states.
• The radiation absorbed or emitted during a transition between two
stationary states of energies E1 and E2 (E1 > E2) is characterized by a
unique frequency given by
E1  E2

h
Bohr’s Postulate
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Bohr’s Postulate
• The stationary states corresponds to a set of allowed orbits
in the Rutherford atomic model. They are determined by the
requirement that the kinetic energy of the electron in the
orbit is related to the frequency f of the motion of the
electron in that orbit by
1
2 me v 2  12 nhf
where n = 1, 2, 3, … For circular orbits this reduces to the
statement that the angular momentum takes on integer
values in units of h/2p, so that
h v
Lcircular  me vr  n  n  f 
2p 2pr
Bohr’s Postulate
 Alternatively, for a circular orbit, we can consider that
the electron is a standing wave in an orbit around the
proton. This standing wave will have nodes and be an
integral number of wavelengths.
h
2pr  n  n
p
 Thus, the angular momentum of
the electron is
nh
L  rp   n
2p
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Quantization of Orbital Radius

 Coulomb attraction force between the nucleus and an electron
in a stationary orbit with principle quantum number n, acts as
the centripetal force to keep the electron in its circular orbit
Ze e mv 2
k 2 
rn rn
 The quantization of angular momentum L  mrn v  nh 2p gives
h
vn
2pmrn
 Substituting the velocity above yields
n2  h2 

rn   2 
2 
Z  4p mke 
 For the hydrogen atom (Z = 1),
h2
rn  n aB
2
a  = 0,529  10-10 m
4p 2 mke2
B
Quantization of Energy
 From the force equation, we can derived the kinetic energy of
an electron in a stationary orbit of principle quantum number n
1 1 Ze 2
Ek  mv 2  k
2 2 rn
 The potential energy of that electron is
Ze2
E p  k
rn
 Thus the total energy of this electron is
1 Ze2  Ze2  1 Ze2
E  Ek  E p  k    k    k
2 rn  rn  2 rn
 Substituting the expression of rn yields
Z 2 2p 2e4 mk 2
En  
n2 h2
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Hydrogen Energy Level

 For hydrogen atom with Z = 1,
1
En   E1
n2
where
2p 2e4 mk 2
E1  = 13,6 eV
h2
Hydrogen Transition Series

 From Bohr’s postulate
h  Em  En
c
 Using f  yields

1

1
Em  En 
m  n hc
 Inserting the energy level of

Hydrogen atom yields
1 E1  1 1 
  2  2
m  n hc  n m 
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Success of Bohr Atomic Model

 It explained Hydrogen’s emission and absorption spectra.
 Only works for Hydrogen-like atom, it didn’t work for other
atoms.
 With Rydberg formula given by
mcZa   1 1 
2
 Em  En  
1 1
 2 2
m  n hc 2h  n m 
 Where a is called the fine structure constant
e2
a
4p 0 c
Correspondence Principle
 The Correspondence Principle from Bohr states that the
quantum theory should merge into classical theory in the limit
which classical theory was known to apply.
 Consider the frequency of radiation emitted by an electron in
the Bohr atomic model that jumps from the orbit with
quantum number (n + 1) to n, when n is very large.
mc 2 Za   1 1 
2
c
 n 1n    2  
2 
n 1n 2h  n n  1 
mc 2 Za  n  1  n 2
2 2

n 2 n  1
2
2h
mc 2 Za 
2

hn 3
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Correspondence Principle
 Classically, an electron moving in a circular orbit at radius r
with velocity v will radiate with frequency of its motion
v 1
cl  
2p r 2p
 With velocity and radius given by
h n2  h2 
vn rn   2 
2 
2p mrn Z  4p mke 
 We obtain the classical frequency of radiation as
mc 2 Za 
2
cl 
hn 3
Genealogy
John Strutt (Rayleigh)
(Phys. 1904)
J.J. Thomson J.C. Bose

(Phys. 1906)
E. Rutherford W. H. Bragg C.G. Barkla N. Bohr F.W. Aston C.T.R. Wilson P. Langevin O.W. Richardson
(Chem. 1908) (Phys. 1915) (Phys. 1917) (Phys. 1922) (Chem. 1922) (Phys. 1927) (Phys. 1928)
W. L. Bragg
(Phys. 1915) L. de Broglie C.J. Davisson G.P. Thomson
(Phys. 1929) (Phys. 1937) (Phys. 1937)
C.F. Powell E.T.S. Walton

(Phys. 1950) (Phys. 1951)
L. Germer
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Basic Concepts in Quantum Physics
Wave Particle Duality

Wave Packet
Alexander A. Iskandar Basic Concepts in Quantum Physics 2
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Wave Interference-Diffraction
 From Fundamental Physics course, we learn
that a double slits interference pattern seen
on a screen can be obtained as a linear
superposition of the waves that is
transmitted from each of the slits
       
E1 r , t   E0 ei ( k r t ) , E2 r , t   E0 ei ( k r t  )
 To yield
     
ER r , t   E1 r , t   E2 r , t 
 Thus the observed interference intensity at
the screen is calculated as
 
  2  
ER2  E1  E2  E12  E22  2 E1  E2
 E02  E02  2 E0  E0 cos   
PhET:
Wave Interference
2
25/09/2014
 Shooting single photon (particle of light) at a time, also
resulted in the same intensity pattern.
 That is to say that, if the Probability of finding a photon on the
screen with

• slit 2 closed is P1 r , t  and

• slit 1 closed is P2 r , t 
 Then the probability of finding a photon on the screen as the
two slits are open is not
  
PR r , t   P1 r , t   P2 r , t 
 To reconcile with the results of the experiment,   we have to
associate to the photons an electric field e r , t  , which will
interfere with itself, so that with the presence of a two slits,
the photon electric field
     
eR r , t   e1 r , t   e2 r , t 
Electron Interference-Diffraction
3
25/09/2014
Wave Representation of a Particle

 From the similarity of the Electron Interference-Diffraction
pattern with wave interference-diffraction pattern, we
conclude that we need to represent the electron (particle)

with a wave function  r , t  that satisfy a linear equation
such that linear superposition of its solutions that yield the
interference pattern still holds .
Interlude: Plane Wave

 Plane wave: travelling wave (with planar wave front)
 k ( x, t )  Aei ( kx t )  Be i ( kx t )
 Satisfying the linear wave equation
 2 k 1  2 k
 0
x 2 v 2 t 2
with the relations
2 
k   
   k  v   
2 v T
  2  
T 
 These harmonic wave solutions (of different frequency) are
orthogonal waves, hence can be used as basis to build more
complicated wave (recall Fourier series!)

 ( x, t )   ( x  L, t )   ak k ( x, t )
k 0
4
25/09/2014
Interlude: Wave Packet

 An a-periodic wave or a wave packet can also be written as a
linear combination of harmonic waves

 A(k )e
i ( kx t )
 ( x, t )  dk

A(k) is called the spectral distribution.
 ( k  k 0 ) 2
 An example is the Gaussian wave packet, i.e. A(k )  e
k0

 At t = 0, we have
 
 A(k )e dk   e 0 e dk
 ( k  k ) ikx
 ( x,0) 
2
ikx
 
Writing k′ = k – k0, yields
2
 x2   ix 
ik 0 x    k  
2 
e e
 ( k  ) 2  ik x
 ( x,0)  e ik 0 x
dk   e 4 
dk 
 
ix
 With q  k   , we found that initially
2 (x,0)
the wave packet has a Gaussian shape.
x2 
ik 0 x 
e
q 2
 ( x,0)  e 4
dq

 ik x  4x
2

0
e

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25/09/2014

 Define a measure for the wave packet as the half width of the
absolute squared shape when the amplitude is e-½ = 0.6 of its
maximum
  D2x
2
 ( Dx,0)  e  Dx  
2

1
A(k  Dk ) 2  e  2 ( k0  Dk )  k0 
2
 Dk 
2 
1 1
 Note that DkDx   DkDx  |(x,0)|2
2 2
2Dx
A(k)2
k0
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25/09/2014
Travelling Wave Packet

Probability and Born Interpretation
Schrödinger Equation
1
25/09/2014

 An a-periodic wave or a wave packet can also be written as a
linear combination of harmonic waves

 A(k )e
i ( kx t )
 ( x, t )  dk

A(k) is called the spectral distribution.
 ( k  k 0 ) 2
 An example is the Gaussian wave packet, i.e. A(k )  e
k0

 At t = 0, we have
 
 A(k )e dk   e 0 e dk
 ( k  k ) ikx
 ( x,0) 
2
ikx
 
Writing k′ = k – k0, yields
2
 x2   ix 
ik 0 x    k  
2 
e e
 ( k  ) 2  ik x
 ( x,0)  e ik 0 x
dk   e 4 
dk 
 
ix
 With q  k   , we found that initially
2 (x,0)
the wave packet has a Gaussian shape.
x2 
ik 0 x 
e
q 2
 ( x,0)  e 4
dq

 ik x  4x
2

0
e

2
25/09/2014

 Define a measure for the wave packet as the half width of the
absolute squared shape when the amplitude is e-½ = 0.6 of its
maximum
  D2x
2
 ( Dx,0)  e  Dx  
2

1
A(k  Dk ) 2  e  2 ( k0  Dk )  k0 
2
 Dk 
2 
1 1
 Note that DkDx   DkDx  |(x,0)|2
2 2
2Dx
A(k)2
k0
Interlude: Traveling Wave Packet

 How does the wave packet moves?
 Needs a relation between k and (k).
 Suppose A(k) is peaked at k = k0, and
make an approximation on (k) as
follows
k0
   1   2 
 (k )   (k0 )  (k  k0 )   (k  k0 ) 2  2 
 k  k  k0 2  k  k  k0
 Thus, the phase of the wave packet takes the form
     1 2   
2
(kx   t )  k0 x  0t   (k  k0 )  x    t   (k  k0 )  2  t
  k  k0  2  k  k0
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25/09/2014

 Inserting
     1 2   
2
(kx   t )  k0 x  0t   (k  k0 )  x    t   (k  k0 )  2  t
  k  k0  2  k  k0
into the wave packet representation

 A(k )e
i ( kx t )
 ( x, t )  dk


 i

i ( k  k0 ) x v g t  ( k  k0 ) 2  t
 A(k )e
i ( k 0 x 0t )
e 2
dk

where we have introduce

     2 
vg    : group velocity ,    2 
 k  k0  k  k0

 Take a Gaussian amplitude,

 i

i ( k  k0 ) x v g t  ( k  k0 ) 2  t
 ( x, t )  ei ( k x  t )  A(k )e
0 0 2
dk


 i

i ( k  k0 ) x v g t  ( k  k0 ) 2  t
e
i ( k 0 x 0t )  ( k  k 0 ) 2
e e 2
dk

 Writing k′ = k – k0 and completing the square, we have

 i

ik  x  v g t  ( k  ) 2  t
 ( x, t )  ei ( k x  t )  e  ( k ) e dk 
2
0 0 2

2
 x vg t 

1

x vg t 2  
1
2  it  k i 
2  it 
 e i ( k0 x 0t ) e e dk 
4  i 2 t 2 

4
25/09/2014

x  vg t
 Introducing , q  k   i , we have
2  i t

1
x vg t 2 

1
2  it q 2
e
i ( k 0 x 0t )
 ( x, t )  e e 4  i 2 t 2
dq

2  x v g t  1 2
 ei ( k0 x 0t ) e 4 i 2 t
2  it
 Taking the modulus square, Travelling Gaussian shape
}
2
2  x v g t 2
 ( x, t )  4 2   2t 2
2
e
}
4 2   2t 2
}
Width increasing
Amplitude shorten

 Non-dispersive case   kc
 Dispersive case    (k )
5
25/09/2014
Born Interpretation
 Recall that we need  to represent an electron (particle) with a
wave function  r , t  that satisfy a linear equation, such that
linear superposition of its solutions holds
        
 R r , t    1 r , t   2 r , t   ER r , t   E1 r , t   E2 r , t 
 It is tempting to represent a particle with a wave packet since
a wave packet has a definite dimension as a particle.
 However, representing a particle with a wave packet does not
seems to be correct, since as the wave packet travels, it
becomes broader.
 Thus, the wave function does not represent a particle, but
instead it is used to represent the probability of finding the
particle.
Born Interpretation
 In order to explain the electron interference-diffraction
pattern, Born suggested that the modulus square of this wave
function should be interpreted as the probability density of
finding the electron
 2   2
 R r , t    1 r , t   2 r , t 
 2  2 
 
  1 r , t    2 r , t   2 Re  1 r , t  2* r , t  
similar to
 
  2  
ER2  E1  E2  E12  E22  2 E1  E2
 The probability of finding an electron, describe by the wave
function   x, t  , in the region lying between x and x+ dx is
given by
P( x, t )dx    x, t  dx
2
6
25/09/2014
Born Interpretation
 However note that
• The wave function is in general a complex function
• The wave function must satisfies some linear equation
• As a wave packet spread out when travelling, the probability density of
finding a particle also spread (position of the particle becomes less
certain)
Newtonian deterministic trajectory Quantum theory in-deterministic

‘trajectory’
Wave Particle Duality
7
25/09/2014
 To find the necessary equation to be satisfied by the wave
function, we start from the wave packet representation
 i
1 ( px  Et )
 ( x, t )  
2  
 ( p )e  dp
where we have use

• de Broglie relation : k  p 
• Planck relation :   E 
 Use the above wave function to represent the probability of a
free particle whose energy is
p2
E
2m
 Differentiate the wave packet with respect to time t yields
 

i i
1 ( px  Et ) 1 p 2  ( px  Et )
2   2  
i   ( p) Ee 
dp   ( p) e dp
t 2m
 On the other hand,

 
i
1 ( px  Et )
i x
 
2  
 ( p) pe  dp
and

         
2 i
1 ( px  Et )
   
i x  i x   i x  
2  
 ( p) p 2e  dp
 Thus, combining the two relations, we have, for a free particle,

 2 2
i  ( x, t )    ( x, t )
t 2m x 2
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25/09/2014
 2 2
 ( x, t )  
i  ( x, t )
t 2m x 2
 This Schrodinger equation for a free particle can also be viewed
from the classical energy relation by the identification of
 
p2  E  i t
E  
2m 
 p  i
 x
 What about particle moving in a potential V ?
 From classical mechanics, we know
p2
V E
2m
 Assume that the potential is just a function of position, V(x),
then we can generalize the previous Schrodinger equation for
free particle into
 2 2
i  ( x, t )    ( x, t )  V ( x) ( x, t )
t 2m x 2
or,
  2 2 
i  ( x, t )     V ( x) ( x, t )
t  2m x
2

 This is known as the Time dependent Schrödinger equation.
9
25/09/2014
What is  (p) ?
 i
1 ( px Et )
 ( x, t )  
2  
 ( p )e  dp
 The spectral amplitude (p) of the wave packet in the solution

of the Schrodinger equation is none other than the Fourier
Inverse Transform of the wave packet at t = 0
 i
1 px
2  
 ( x,0)   ( p ) e 
dp
 i
1  px
2  
 ( p)   ( x ,0) e 
dx
10
25/09/2014
Probability and Expectation Value

Heisenberg Uncertainty Principle
Wave Function in Momentum Space
1
25/09/2014
Review on Probability
 Recall the concept of probability density function.
 Consider the following example
• A manufacturer of insulation randomly selects 20 winter days and
records the daily high temperature
24, 35, 17, 21, 24, 37, 26, 46, 58, 30,
32, 13, 12, 38, 41, 43, 44, 27, 53, 27
• Put in a class table
Probability Density Function
Class Ti Freq. Rel. Freq. (fi)
10
10 < T 20 15 3 0.15 Histogram: Highest
Temperature
Frequency
20 < T 30 25 6 0.30
30 < T 40 35 5 0.25 5
40 < T 50 45 4 0.20

50 < T 60 55 2 0.10 0
N = 20 1.00 5 15 25 35 45 55 More
 Consider the following example
• A manufacturer of insulation randomly selects 20 winter days and
records the daily high temperature
24, 35, 17, 21, 24, 37, 26, 46, 58, 30,
32, 13, 12, 38, 41, 43, 44, 27, 53, 27
• The average temperature can be calculated using the probability
density function as
average 
 (mid .value)( frequency)
number of data
  (mid .value)( prob. dist. funct.)
thus,
T 
T f  T P
i i
 Pi 
fi
i i
N N
2
25/09/2014
• One other important statistical quantity is the standard deviation,
   T  T 
2
  T  T
2 2 i fi
N

  Ti 2  T
2
 2Ti T Pi 
  Ti 2 Pi  2 T T P  P
2
i i T i
 T2 2 T T  T
2
or,
2  T2  T
2
Probability Interpretation of Wave Funct.

 As stated by Born, the modulus of the wave function  ( x, t )
of a particle is interpreted as the probability density function
associated with the particle
P( x, t )dx    x, t  dx
2
 Then the wave function  ( x, t ) has to satisfy the following

 
 P( x, t )dx    x, t  dx  1
2
 
 However, one can always normalize the wave function by
multiplying it with a constant, N ( x, t ) .
 Hence the condition needed to be satisfied by the wave
function is that the initial state of the wave function must be a
square integrable function

   x ,0  dx  
2

3
25/09/2014
Probability Interpretation of Wave Funct.

 Example : Normalize the wave function
 x( L  x) 0  x  L
 ( x, t )  
 0 elsewhere
 To normalize the wave function, we
multiply it with a number N, and impose
the normalization condition
 
1  N  x, t  dx  N 2    x, t  dx
2 2
 
 1 2 1 L 2

L 5
 N 2  x 4  2 Lx 3  L2 x 2 dx  N 2 L5      N
0  5 4 3  30
 Thus, the normalized wave function is
30
~ ( x, t )  N ( x, t )  x( L  x) , 0  x  L
L5
Expectation Value from Probability

 In analogy with probability concept, the expectation value of
the particle’s position is
  
x   xP( x, t )dx   x x, t  dx   x, t  x x, t  dx
2 *
  
 Or in general expectation value of any function f(x) should be
calculated as

f ( x)   *  x, t  f ( x)  x, t  dx

 And uncertainty of the particle’s position measurement is
x 2  x 2  x
2
2

 * 
  ( x, t ) x  ( x, t ) dx    ( x, t ) x ( x, t ) dx 
* 2
  
4
25/09/2014

 Example : For the normalize the wave
function
 30 x( L  x) 0  x  L
 ( x, t )   L5
 0 elsewhere
Calculate x , x 2 and hence x.
 L
x    x, t  x  x, t  dx  
30 3
*
5
x ( L  x) 2 dx
 0
L
  1 2 1 L
L
30
5 
 L2 x 3  2 Lx 4  x 5 dx  30 L    
L 0 4 5 6 2

function
 30 x( L  x) 0  x  L
 ( x, t )   L5
 0 elsewhere
Calculate x , x 2 and hence x.
 L
   x, t  x   x, t  dx  
30 4
x 2 * 2
5
x ( L  x) 2 dx
 0
L
  2 1 2 1  2 L2
L
30
L5 0
 L2 4
x  2 Lx 5
 x 6
dx  30 L    
5 6 7 7
2 1 L
x  x2  x L  
2
7 4 2 7
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25/09/2014
Conservation of Probability
 If we normalize the wave function at one time, will it stay
normalized? I.e. does

   x, t  dx  1
2

hold for all time? In short, is probability conserved?
 Take a time derivative of the probability density function
P( x, t )   ( x, t )
2
  ( x, t )  ( x, t )
   ( x, t )    ( x, t )
t t t t
 Use the Schrodinger equation to replace the time derivative
and assume that the potential function V(x) is real.
 Recall the complex conjugate of the Schrodinger equation
  ( x, t )  2  2  ( x, t )
 i   V ( x)  ( x, t )
t 2m x 2
 Then
P( x, t )   ( x, t )  ( x, t )
  ( x, t )    ( x, t )
t t t
1     
2 2 
 
2
   2    2 
i  2m  x x 
        
     
x  2im  x x 
 Define the probability flux or probability current as
      
j ( x, t )    
2im  x x 
 Hence, we get
P( x, t ) j ( x, t )
 0
t x
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25/09/2014
 If we integrate over all space, we get
 
 
  ( x, t ) dx   P( x, t ) dx
2
t  t 

P( x, t )
 

t
dx

j ( x, t )
 dx  0

 x
 The last step follows from the fact that for square integrable
function j(x,t) vanishes at .
Probability Current
P( x, t ) j ( x, t )
 0
t x
 The last relation is similar to the continuity equation found in
classical mechanics or electromagnetism, which states that
probability is conserved not only globally but also locally.
 It means that if the probability of finding particle at a certain
point decreases, this probability does not only turns up at
another point, but instead it flows to this other region.
 Hence the name probability current for
      
j ( x, t )    
2im  x x 
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25/09/2014
Expectation Value of Momentum

 How do we calculate the expectation value of the momentum
of the particle p associated with the wave function (x,t)?
 Recall the classical expression for momentum
dx
p  mv  m
dt
 Take the expectation value of this expression, yields

d d
p m x  m   ( x, t ) x ( x, t ) dx
dt dt 

   ( x, t )  ( x, t ) 
 m x ( x, t )   ( x, t ) x  dx
 
t t 
 Note that, the position x does not have a time dependence.
 The time dependence of x comes from the time
dependence of (x,t).

 Use the Schrodinger equation, to obtain

   ( x, t )  ( x, t ) 
p  m x ( x, t )   ( x, t ) x  dx
 
t t 

   2  ( x, t )  2 ( x, t ) 
2i  x 2
  x ( x, t )  ( x, t ) x

 dx
x 2 
 Note that
 2           
x   x    x
x 2 x  x  x x x
      
 
x  x

x       
 x x
         
2
  x    x 2
x  x  x x
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25/09/2014

 Thus,
 
           
p   
2i  x  x
x   x
x
   


dx  
2i 
2
x
dx
         

 x   x         dx
2i  x x    i x 
 Since the wave function is square integrable function, it
means that it vanishes at , hence the first term does not
contribute to the evaluation.
 Thus, we have

  
p      dx
  i x 
which suggest to associate the momentum to the operator
 
p
i x

function
 30 x( L  x) 0  x  L
 ( x, t )   L5
 0 elsewhere
Calculate p , p 2 and hence p.

  
p    ( x, t )  ( x, t ) dx
  i x 
L
30
iL5 0
 x( L  x)( L  2 x) dx
 
L
30
 5  2 x 3  3Lx 2  L2 x dx  0
iL 0
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25/09/2014

function
 30 x( L  x) 0  x  L
 ( x, t )   L5
 0 elsewhere

 2 
p 2    ( x, t )   2 2  ( x, t ) dx
  x 
L
30 2
  5  x( L  x)(2) dx
L 0
 2 x 
L
30 2 10 2
 2
 2 Lx dx 
L5 0
L2

function
 30 x( L  x) 0  x  L
 ( x, t )   L5
 0 elsewhere

p  p2  p  10
2
L
L
 Recall the previous results of x  , then
2 7
   L 
px   10    0.6
 L  2 7 
 Which is consistent with px   2 .
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25/09/2014

 The expectation value of position x is a real value, as can be
easily seen from the definition,
 
x   xP( x, t )dx   x x, t 
2
dx
 
 However, because of the form of momentum operator that

involves the imaginary number as well as a differentiation,

  
p    ( x, t )  ( x, t ) dx
  i x 
will the expectation value of the momentum be a real value?
 In fact, it can be proved that the momentum expectation
value is always a real number.

*

       
p  p   * ( x, t )  ( x, t )dx    * ( x, t )  ( x, t )dx 
*
  i x     i x  

   ( x, t )   * ( x, t ) 
  * ( x , t )
i x
  ( x , t )
i x 
 dx

  ( x, t )   ( x, t ) 
 i
 
 * ( x , t )
x
  ( x , t )
x 
 dx
 
 
i  x
 

   * ( x, t ) ( x, t ) dx   * ( x, t ) ( x, t )  0
i 
 In the last step, the square integrability property of the wave

function, (x,t), has been used, where it states the the wave
function is a localized function so that (x,t)  0 as x  .
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25/09/2014

 The result of the last example on product of the expectation
values of x and px, it was found that

p x x 
2
 This relation is called the Heisenberg Uncertainty principle.
 It states one of the fundamental concept of quantum world,
that is measurement of position and linear momentun cannot
be done simultaneously with the highest accuracy.
 If measurement of position is done very accurately, x = 0,
then the value of the linear momentum is not known, since
according to Heisenberg uncertainty principle yields px  ,
and vice versa.
 Position and momentum are said to complementary variables.

 One observation can be used to
see this principle.
p x 2
 From wave optics, the spread of  2
the diffraction pattern as
  2

a p x 2
 Considering the light as photons,
at the slit, the position of the
photon is within the measurement’s uncertainty of x  a, but
the momentum’s uncertainty has spread.
 Thus
p 
 x  p x a  p x  p x x  h
px a
2
where p x  k   .

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25/09/2014

 Note that the Heisenberg uncertainty principle between the
position and momentum holds for all direction (x, y and z).
 One other Heisenberg uncertainty relation is the uncertainty
between energy and time

Et 
2
excited
excited
state
E  E  state
1 2E
   ground
ground t  state
state
 

 Recall that the spectral distribution function of the wave
packet is none other than the Inverse Fourier transform of the
wave function at t = 0,
 i
1  px
2  
 ( p)   ( x,0)e dx

 Calculate the following

   i
1  px
  ( p) ( p) dp   ( p) 2   ( x)e dx dp
  

  i
1  px
  ( x ) 

( p )e 
dp dx
 2  

  ( x)  ( x) dx  1

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25/09/2014

 
  ( p) ( p) dp   ( x) ( x) dx  1
 
 
 Fourier transform of a normalized wave function is normalized.
 Next, consider the following

  
p    ( x)  ( x) dx
  i x 
 
 d  1
i
px
   ( x)    ( p)e  dp dx
  i dx  2  
  i 
1 px
   ( p) p  
( x ) e 
dx dp     ( p) p ( p) dp
 2   
 Which is a statement that the momentum expectation value can
also be calculated from (p) using the momentum operator p
itself.


p     ( p ) p ( p ) dp

 This last statement is similar to


x   *  x, t  x  x, t  dx

 Thus if (x,t) is the wave function in spatial domain, (p) should

be interpreted as the wave function in momentum space, with
the probability density function of finding a particle with
momentum p is given by |(p)|2.

 In this momentum space, the position operator is given by i
p
 Hence, the expectation value of position is

  
x     ( p ) i  ( p ) dp
  p 
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25/09/2014

 Example 2.4
Consider a particle whose normalized wave function is
2  xe  x 0 xL
 ( x, t )  
 0 elsewhere
a. For what value of x does P(x)
(x)
= |(x)|2 peak?
2
b. Calculate x and x .
c. What is the probability that
the particle is found between
x = 0 and x = 1/?
d. Calculate (p) and use this to
calculate p and p 2 .
1/ x
Summary
 Physical quantity (an observable) is represented by an
operator.
 Measurement of observable is evaluated as calculating
expectation value

ˆ
phys. quantity    ( x, t ) O  ( x, t ) dx

 There are two ways to calculate the expectation value, in

spatial space or in momentum space.
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25/09/2014
Summary
Momentum
Spatial space
space
Wave function  ( x, t )  ( p)

Position x i
p
 
Momentum p
i x
 i
1 ( px Et )
 ( x, t )  
2  
 ( p )e  dp
 i
1  px
 ( p)  
2  
 ( x,0)e  dx
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11/09/2015
Time Independent Schrödinger

Equation
Time Independent Schrödinger Equation
Eigenvalue Equation
Particle in a box
Alexander A. Iskandar Time Independent Schrodinger Equation 2
1
11/09/2015
Time Independent Schrödinger Eq.

 From the last lecture, we have “derived” the time-dependent
Schrödinger equation
 ( x, t )  2  2 ( x, t )
i   V ( x) ( x, t )  Hˆ ( x, t )
t 2m x 2
 The symbol Hˆ stands for Hamiltonian operator.
 Because the potential V(x) does not depend on time, we can
reduce the partial differential equation above into two
ordinary differential equations, by separation of variables
 ( x, t )  T (t )u( x)
 Substitution yields
1 dT (t ) 1   2 d 2u ( x) 
i   2
 V ( x)u ( x)
T (t ) dt u ( x)  2m dx 
Time Independent Schrödinger Eq.

 In the last equality, the left hand-side is only a function of
time and the right hand-side is a function of space.
 Since this equality has to be satisfied for all values of x and t,
then we can say that each side is equal to a constant E, hence
for the left hand-side we have
dT (t )
 ET (t )  T (t )  Ce iEt 
i
dt
 And, the right hand-side becomes
 2 d 2u ( x )
  V ( x)u ( x)  Eu ( x)
2m dx 2
 This last equation is known as Time-Independent Schrödinger
equation.
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11/09/2015
Eigenvalue Equation
 An equation like Time-Independent Schrödinger equation
above is classified as an Eigenvalue equation.
 Recall that the LHS of this equation can be written as the
Hamiltonian operator Hˆ acting on the wave function u(x)
 2 d 2  ˆ
 2
 V ( x ) u ( x)  Hu ( x)  Eu ( x)
 2m dx 
ˆ
 The operation of an arbitrary operator O to a function f(x) is
determined by a specific rule that we have to perform on f(x)
ˆ
O f ( x)  f ( x)  x
2 ˆ

O f ( x)  d f ( x) dx
2

2 3
O f ( x)   f ( x)
ˆ ˆ
O f ( x)  df ( x) dx  2 f ( x)
2
Linear Operator
 There is a special kind of operator called the Linear operator
that has the following properties
L  f1 ( x)  f 2 ( x)  Lf1 ( x)  Lf 2 ( x)
ˆ ˆ ˆ
L cf ( x)  cLf ( x),

ˆ ˆ
c is a constant
 This linear operator can be thought as a mapping process
from f(x) to its map.
 A special case is when the mapping is unto the function itself
up to a constant multiplication
ˆ
Lf ( x)  lf ( x), l is a constant
ˆ
 Equation of this kind is called an eigenvalue equation, with L
is the eigen operator, f(x) is called the eigenfunction (eigen
vector) and l is known as the eigenvalue
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11/09/2015
Spectrum of Eigenvalue Equation

 Example 3.1
 From the above example we see that there maybe an infinite

number of eigenvalues ln and for each eigenvalue, it is
associated an eigenfunction un(x).
 Then a general solution of the eigenvalue problem can be
written as a linear combination of all these eigenfunctions.
 In particular, if un(x) is the solution of the time-independent
Schrödinger equation with eigenvalue En
ˆ
Hu n ( x )  E n u n ( x )
then a general solution of the Schrödinger equation can be
written as
 ( x, t )   Cnun ( x)e iEnt    C ( E )u E e iEnt  dE
n
Particle in a Box
 Consider a particle in an infinite potential well defined as
V
 x0

V ( x)   0 0  x  a
 ax
 x
0 a
 Since at x < 0 and x > a, the potential is infinite, then the only
possible solution on this region is
u( x)  0 x  0 and x  a
 To find the solution inside the box, we need to solve
2 d 2 d2 2mE
 u ( x)  Eu ( x) or u ( x)   2 u ( x)
2m dx 2 dx 2

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11/09/2015
Eigen Solution of Particle in a Box

 We see that if E < 0, then the solution of the above eigen
problem is a hyperbolic sine or cosine function.
 But since both functions can not satisfies the boundary
condition at u(x = 0) = 0 and u(x = a) = 0, we conclude that
this particle in a box problem will never have a solution with
negative E.
 With E > 0, we have solutions of the form
2mE
u ( x)  A sin(kx)  B cos(kx), k 2 
2
 The boundary condition at x = 0 tells us that B = 0, and the
boundary condition at x = a yields
ka  n , n  1, 2, 3, 

 Thus, we have the eigen solution for the particle in a box
problem as follows
 nx  n 2 2
un  A sin , En  , n  1, 2, 3, 
 a  2ma2
 The constant A is chosen in such a way that the eigenfunction
un(x) is normalized. Recall the orthogonality relation of the
harmonic functions

 sinkxcosnx dx  0


 k  n 
 k  n
 sin kx sin nx dx    cos kx cos nx dx  
 0 k  n  0 k  n
5
11/09/2015

 Recall the orthogonality relation of the harmonic functions
 k   n 
L
 sin
L
L
x  cos
  L
x dx  0

0 kn
 k   n  
L
 sin L x  sin L x dx  L k  n  0

L 0 k  n  0

0 kn
 k   n  
L
Lcos L x  cos
  L
x dx   L k  n  0
 2 L k  n  0


 Thus, we have
2  nx  n 2 2 2
un  sin , En  , n  1, 2, 3, 
a  a  2ma2
V  2 2
E4  16
2ma 2
 2 2
E3  9
2ma 2
 2 2
E2  4
2ma 2

2 2
E1 
0 x a 2ma 2
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11/09/2015

 The orthonormality condition of the eigenfunctions is
a
 dx u ( x)u ( x)   nm
*
n m
0
 Remarks:
• Recall that classically, for • From the results above,
particle in a potential well of quantum mechanically, the
V(x) = 0, the lowest energy lowest energy is
would be E = 0.  2 2
E1 
2ma 2
• Classically, the energy of the • From the results above,
particle in the box could have quantum mechanically, the
any value (continuous). particle can only have discrete
energy values (quantized).
n 2  2 2
En  , n  1, 2, 3, 
2ma 2

 Remarks:
• Further, note that as the well becomes bigger, a bigger, the lowest
energy state, the cut-off, shifted to lower values.
 2 2
E1 
2ma 2
• And the energy difference between two consecutive energy states
becomes smaller
  2ma  2 2
2 2
E  En 1  En  (n  1) 2  n 2 2
 2n
2ma 2
7
11/09/2015

 Remarks:
• Since the eigenfunctions are real, then the expectation value of
momentum is
 du ( x)  d un ( x)
a a 2
p   dx un ( x)  i n   i  dx
0  dx  0
dx 2
i
 
  un (a) 2  un (0) 2  0
2
• With a similar method, we obtain the expectation value of momentum
squared as
 2 2 n 2
p 2  2mEn 
a2

 Wave functions (eigen functions) E4
of the particle in a box have
symmetry that can be make
clear by shifting the potential
well as follows: E3
a
x  x
2
E2
 As it is readily seen that the odd
states are symmetric to the E1
–1.5 –1 –0.5
vertical axis mirror inversion,
while the even states are
antisymmetric to mirror
inversion.
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11/09/2015

 Note, that with the given shift, E4
the sine function becomes
 n  a 
sin   x  
 a  2 
 nx   n  E3
 sin   cos 
 a   2 
 nx   n  E2
 cos  sin  
 a   2 
E1
 Hence the wave function is –1.5 –1 –0.5
separated into
2  nx  2  nx 
un  cos , n  1, 3,  and un  sin  , n  2, 4, 
a  a  a  a 

 Example 3.2
 Example 3.3
9
26/09/2014

Equation
Expansion Postulate and Its Interpretation
Momentum Eigenfunction
1
26/09/2014

 The eigen solution of the particle in a box problem is
2  nx  n 2 2 2
un  sin , En  , n  1, 2, 3, 
a  a  2ma2
V  2 2
V E4  16
2ma 2
 2 2
0 a x E3  9
2ma 2
a
 2 2
 dx un ( x)um ( x)   nm
*
E2  4
2ma 2
0

2 2
E1 
0 x a 2ma 2
Expansion Postulate
 Recall from Fourier theory, that an arbitrary function y(x) that
satisfies the boundary conditions y(0) = 0 and y(a) = 0 can
be written (expanded) as a linear combination of the basis
function sin nx a  :

 nx 
y ( x)   Cn sin 
n 1  a 
ˆ
 Since the eigenfunctions of H in the infinite potential well
are also proportional to sin nx a , then an arbitrary function
y(x) can also be expanded in terms of the eigenfunctions
un(x)

y ( x)   Anun ( x)
n 1
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26/09/2014
Expansion Postulate
 With the orthonormality relation of the eigenfunctions, we
can calculate the combination coefficients An as follows
a a 
 dx um ( x)y ( x)   dx um  Anun ( x)
* *
0 0 n 1
 a
  An  dx um* ( x)un ( x)
n 1 0

  An nm  Am
n 1
 Then time evolution of the wave function can be written as


y ( x, t )   Anun ( x)e iE t  n
n 1
ˆ
where, Hun ( x)  Enun ( x).
Expansion Postulate and Eigenval. Spectr.

 From the example of particle in a box, we see that there
maybe an infinite number of eigenvalues En and for each
eigenvalue, it is associated an eigenfunction un(x).
 Then a general solution of the eigenvalue problem can be
written as a linear combination of all these eigenfunctions.
 It could also possible that a system does not only have
discrete eigenvalue spectrum, but also a continuous
eigenvalues.
 Hence, the complete expansion of an arbitrary state is
y ( x, t )   Cnun ( x)e iE t    C ( E )u E e iE t  dE
n n
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26/09/2014
Interpretation of the Expansion Coeff.


y ( x, t )   Anun ( x)e iE t  n
n 1
 What is the physical meaning of the expansion coefficient An?

 Consider the example of particle in a box again, and calculate
the expectation value of energy of an arbitrary state y(x,t),
ˆ
i.e. the expectation value of the Hamiltonian, H .
a a 
ˆ

ˆ
H  y ( x, t )Hy ( x, t ) dx  y ( x, t )H


 ˆ
 A u ( x )e
n 1
n n
iE n t 
dx
0 0
a  
   Am um ( x)e iEmt   An Enun ( x)e iEnt  dx
0 m 1 n 1
  a 
  En A An e  i ( Em  En ) t 
 um ( x)un ( x)dx   En An
 2
m
n 1 m 1 0 n 1

 Further, note that we can normalize the wave function y(x,t)
as

y ( x, t )y ( x, t ) dx  1


 Thus,

  * iE m t   

iE n t  
1 
m 1
A u
m m ( x ) e   Anun ( x)e
  n 1
 dx

  a
   Am An ei ( Em  En )t   um* ( x)un ( x) dx
m 1 n 1 0

  An
2
n 1
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26/09/2014

 In other words, |An|2 is interpreted as the probability density
of our measurement yields the energy En.
 
Eaverage  Hˆ   En Pn   En An
2
n 1 n 1
with,
a
An   dx un* ( x)y ( x)
0
 So, we interpret that the arbitrary state

y ( x, t )   Anun ( x)e iE t 
n
n 1
consist of linear combination of all possible energy eigen-

functions and each energy state’s contribution is determined
by the expansion coefficient, An, i.e. with probability |An|2.
Repeated Measurements
 Consider an arbitrary state represented as

y ( x, t )   Anun ( x)e iE t 
n
n 1
 A measurement taken on this arbitrary state will yield a

specific energy, for example Em.
 And, any subsequent measurement on this state will always
yield the same energy, i.e. Em.
 This means that with a measurement, we projected the
arbitrary state to a specific eigenfunction (eigenstate).
 And once we have projected into a specific state, the arbitrary
state will take this specific state for all subsequent time, which
will always give the same energy for all subsequence
measurements.
5
26/09/2014

 Example 3.4
 Example 3.5
Momentum Eigenfunctions
 Another example of eigenvalue equation is the eigenvalue
equation of the linear momentum operator
 
pˆ   pû p ( x)  pu p ( x)
i x
 With solution
u p ( x)  Ce ipx 
where C is a constant to be determined by normalization and
the eigenvalue p is real (so that the eigenfunction does not
blow up at ).
 Thus, the range of the eigenvalue p is a continuum, hence we
say that the operator p̂ has a continuous spectrum.
 These eigenfunctions are also orthogonal to each other.
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26/09/2014
 Orthogonality of the eigenfunction can be shown as follows,
 
u e
i ( p  p ) x 

( x)u p ( x)dx  C dx  2 C  ( p  p)
2 2
p
 
recalling the definition of the Dirac Delta function

1
 ( p  p)  
2 
e i ( p  p) x dx
 Thus, the orthonormalized momentum eigenfunction is

1
u p ( x)  eipx 
2
 Note that the range of the eigenvalue p of the momentum
operator p̂ is a continuum, and the orthonormality
condition is defined with a Dirac Delta function instead of a
Kronecker Delta.
 An arbitrary wave function can also be written as linear
combination of these momentum eigenfunction as follows,

e ipx 
y ( x)   f ( p) dp
 2  
 With expansion coefficient f(p) given by
 ipx 
e
f ( p)   y ( x) dx
  2
 And its absolute-squared value |f(p)|2 is interpreted as the

probability of a measurement of the momentum for an
arbitrary packet y(x) yields an eigenvalue p.
 This is the same as the conclusion that f(p) is the wave
function in momentum space (see Lecture03a).
 Example 3.6.
7
26/09/2014

Equation
Degeneracy
Parity
1
26/09/2014
Degeneracy
 It may happens that more than one independent
eigenfunctions corresponds to the same eigenvalue.
 This is called degeneracy, and the state corresponding to that
particular eigenvalue is called degenerate.
 Example of degenerate eigenvalue (matrix eigen value

problem).
 The corresponding eigenfunctions of this degenerate state can

be orthonormalized (using the Gramm-Schmidt method).
Parity
 As can be seen from previous example of particle in a box, if
the position of the box is between –a/2 to a/2, the eigenfunc-
tions are either an odd function (sine) of an even function
(cosine).
V
 x  a 2

V ( x)   0  a 2  x  a 2
 a 2 x
 x
-a/2 0 a/2
 This property of the solution is called a parity.

 Further, as time evolve the parity of the solution is not change
2  nx  2  nx  iEnt 
 ( x)   An cos    ( x, t )   An cos e
n a  a  n a  a 
2
26/09/2014
Parity
 Thus, a parity is a constant of motion, and it is therefore we
ˆ
can assigned an operator P this parity observable,
ˆ
P  ( x)   ( x)
 For an even function   (x) , we have
ˆ 
P  ( x)   ( x)

and for an odd function  (x)


ˆ
P  ( x)   ( x)
 
in other words, the eigenvalues of the parity operator is ±1.

 An arbitrary solution  (x) can always be written as a sum of
an even and an odd function
 ( x)  12  ( x)  ( x)  12  ( x)  ( x)
  e ( x)  o ( x)
Parity
 Will the parity of the solution changes as it evolves?
 Note, that we can write the odd and even wave function as
 
 e ( x, t )  12 1  Pˆ  ( x, t )
 o ( x, t )  12 1  Pˆ  ( x, t )
 Recall that the solution (x,t) satisfies the Schrodinger
equation
 ( x, t )
 Hˆ ( x, t )
i
t
 Apply the parity operator on the above, we have
i
 ˆ
t
  
ˆ ˆ
P ( x, t )  P H ( x, t ) 
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26/09/2014
Parity
ˆ ˆ ˆ ˆ
 Provided PH  HP , then


i Pˆ ( x, t )  Hˆ Pˆ ( x, t )
t
  
ˆ
 
i.e. P ( x, t ) satisfy the same Schrodinger equation.
 Thus, combining with
 
 e ( x, t )  12 1  Pˆ  ( x, t )
 o ( x, t )  12 1  Pˆ  ( x, t )
one can conclude that the even and odd wave function
evolves into even and odd wave function respectively.
 And since an arbitrary wave function can always be
decompose of even and odd function, then the parity of this
wave function is conserved.
Parity
 Since the parity of an arbitrary wave function does not change
as it evolves, it is a constant of motion or a conserved
quantity.
 Note that for the above to be correct, we must have Parity
operator and Hamiltonian operator commutes with each
other,
ˆ ˆ
PH  HP
ˆ ˆ

ˆ ˆ ˆ ˆ
HP  PH  H , P  0  ˆ ˆ
 In fact this is a general statement, i.e. operator of a constant
of motion always commutes with Hamiltonian.
4
26/09/2014
1D Potentials
Step Potential
Potential Well
Alexander A. Iskandar 1D Potentials 2
1
26/09/2014
Step Potential
 Consider a step potential V
E
V0
0 x0
V ( x)  
V0 x0
x
0
 Inserting the value of the potential into the Time-Independent

Schrodinger equation
2 d 2
 u ( x)  V ( x)u ( x)  Eu ( x)
2m dx 2
 For the region x < 0 we have
d2 2mE
2
u ( x)  k 2u ( x), for x  0 with k 2 
dx 2
Step Potential
 The most general solution given by
u( x)  eikx  R eikx , for x  0
where eikx can be viewed as an incoming wave and because of
the presence of the potential, part of this wave is reflected,
Re–ikx.
 Further, we can calculate the probability flux in the positive x-
direction as follows
j
  * du du *  k
u  u 
2im  dx dx  m
1 R
2
 
k 2
 We see that the probability flux of the reflected wave is R
m
2
26/09/2014
Step Potential
 For region x > 0, we have V
E
d 2
2m( E  V0 ) V0
2
u ( x)  q 2u ( x), with q 2 
dx 2
x
 With a general solution 0
u ( x)  T eiqx , for x  0
we did not add the term e–iqx because this term describe a
wave incoming from the right.
 The corresponding probability flux in the positive x-direction
is as follow
  * du du *  q 2
j u  u  T
2im  dx dx  m
Step Potential
 The probability flux on the left of the jump must be equal to
the probability flux on the right, thus
k
m

1 R 
2 q 2
m
T 
 Further, the solution for x < 0 and x > 0 has to be continuous
and smooth (the same first derivative) at the boundary x = 0,
thus we have
1 R  T
ik (1  R)  iqT
 From the last two equations, we can find R and T in terms of k
and q
k q 2k
R , T
k q k q
3
26/09/2014
Step Potential
 Remarks
• When E > V0, in contrast with classical mechanics, the step potential
resulted in reflection whose probability is not zero.
• For E >> V0 (or q  k), the ratio of the reflected flux to the incident
flux approaches zero, |R|2  0
• For E < V0, q becomes imaginary, hence the solution in the region x >
0 becomes
qx
u ( x)  T e , for x  0
• If we calculate the reflected flux, we get
*
 k i q  k  i q 
R     1
2
 k  i q 
 k i q  
thus the particle is reflected.
Step Potential
 Remarks
• But, we note that
2k
T
k iq
is not zero, thus the wave penetrate the classically forbidden region.
• However, the probability flux for x > 0 is zero.
  * du du *  q 2
j u  u  T 0
2im  dx dx  m
4
26/09/2014
Potential Well
 Consider a finite potential well
–a a
 0 x  a x

V ( x)   V0 x a
 0 xa –V0

with
2mE 2mE  V0 
k2 
2
and q 2 
 2
we can write the wave function solution as
u ( x)  eikx  Re ikx x  a
iqx
u ( x)  Ae iqx
 Be x a
u ( x)  Te ikx
xa
Potential Well
 The previous solution corresponds to an incoming flux
2
from the left, a reflected flux k R m and a transmitted flux
2
k T m to the right.
 Inside the well, there are waves going in both direction
because of reflection at the discontinuities ±a.
 The flux conservation yields
k
m
1 R 
2
q 2
m

A B 
2 k 2
m
T  
 Continuity condition of the wave function at ±a can
combined into the requirement that the following ratio be
continues
1 du ( x)
u ( x) dx
5
26/09/2014
Potential Well
 Continuity at x = –a yield
iqAe iqa  iqBe iqa ikeika  ikReika
 ika
Ae iqa  Be iqa e  Re ika
and at x = a
iqAe iqa  iqBe iqa ikTeika
  ik
Ae iqa  Be iqa Teika
 After a little algebra, we can eliminate A and B to yield
R  ie  2ika
q  k 2 sin 2qa
2


2kq cos 2qa  i q 2  k 2 sin 2qa
2kq
T  e  2ika
 
2kq cos 2qa  i q 2  k 2 sin 2qa
Potential Well
R  ie  2ika
q 
 k 2 sin 2qa
2
 
2kq
T  e  2ika
 
 Remarks
• If E >> V0, (q2 – k2) << 2kq, then R  0, no reflection
• If E  0, k  0 hence T  0, no transmission
• For positive energy, if sin 2qa = 0, then there will be no reflection and
n 2 2 2
E  V0  n  1,2,3
8ma2
This a peculiarity since the positive energy E is discrete.
In wave language, there is destructive interference of the wave
reflected at x = –a and the multiple reflection wave at x = a.
4a
2qa  n   , n  1,2,3
n
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26/09/2014
Potential Well
 Bound state of the finite potential well problem occur when
–V0 < E < 0.
–a a
x
E
–V0
 The solutions outside the well should be bounded at infinity,
thus for the region x < –a we have
2mE 2m E
u( x)  C1ex 2   2  2
 
and for the region x > a we have
u( x)  C2e x
 While inside the well we write
2mV0  E 
u( x)  A cos(qx)  B sin(qx) q2 
2
Potential Well
 Since the potential (and hence, the Hamiltonian) is symmetric
under reflection on the origin (x  – x), we may classify the
solutions by their parity (odd and even).
 Clearly, for even solution C1 = C2 and B = 0, while for odd
solution, C1 = –C2 and A = 0.
7
26/09/2014
Potential Well
1 du ( x)
 Continuity condition at x = a, for even solutions
yield u ( x) dx
  q tan qa
and for odd solutions
  q cot qa
 Consider the even solutions,
a
 tan qa
qa
introduce y = qa, and recall
2mE 2m E 2mV0  E a 2 2mV0 a 2
2    (qa ) 2    (a ) 2
2 2 2  2
Potential Well
2mV0  E a 2
2mV0 a 2
(qa)  2
2
 2
 (a) 2
 
 Then for the even solution, we have
a   y2 2mV0 a 2
 tan qa   tan y,   , y  qa
qa y 2
 And for odd solutions
  y2
  q cot qa    cot y
y
8
26/09/2014
Potential Well
 The eigenvalue (dispersion) relation above for even solutions
are graphed below.
a   y2 2mV0 a 2
 tan qa   tan y,   , y  qa
qa y 2
Larger 
 Note that the deeper the
potential (larger ), there are
more solutions. And no matter
how deep the potential, there is
always a solution.
 2 3 4
Potential Well
 The eigenvalue (dispersion) relation above for odd solutions
are graphed below.
  y2
  q cot qa    cot y
y
 Note that the deeper the
potential (larger ), there are
more solutions.
 However, a solution can only be
found if
2mV0 a 2  2
  2 4  0  
2 4
 2 3 4
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26/09/2014
Potential Well
 The discrete eigenvalues comes about because of the
requirement that the wave function vanishes at infinity.
 x
 The decay rate of this vanishing wave function, e , is
proportional to , with   2mEB  where EB is the binding
2 2
energy of the particle.

 Large binding energy means a rapidly falling exponential.
 The even solution (cos qa) with q  2mV0    , must tie-on
2 2 2
continuously with the exponential decay solutions. Thus, larger

binding energy (larger ) yields a flatter cosine function, hence
it is difficult for it to match continuously with the exponential
decay solution.
 However, when we reduce the binding energy, matching
becomes possible, and we get a discrete solutions.
Potential Well
Flat cosine
because of Fat cosine
large binding Matching because of
energy not possible small binding Matching
Fast decay energy possible
because of Slow decay
large binding because of
energy small binding
energy
–a a
x x
–a a
EB EB
–V0 –V0
10
26/09/2014
Potential Well
 The first excited state, with an odd parity (sin qa), vanishes at
the origin.
 Thus for sine function to tie onto the exponential decay tail of
the wave function, it must have a change to turn over inside
the well. The minimum condition is that it turn over just
enough to tie-in with a straight line  = 0), that is sin qa = 1,
or qa = /2.
 This is the same as what have been found
2mV0 a 2  2
  4  0 
2

2 4
q 2  2mV0  2   2
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10/10/2014
1D Potentials
Double Potential Well

Potential Barrier
1
10/10/2014
Double Well Potential

 Consider a system of two identical well separated by a
distance that is larger than the width of the wells.
 Recall that in the single well case of the lowest energy
solution (even parity), the cosine wave function must match
the falling exponential decay, thus the cosine function
determines the rate of the falling exponentials, which in turn
determines the binding energy.
 In the double well case, the exponential decay can fall of more
rapidly and still match with the fairly flat wave function in the
region between the wells.
Fast decay
because of large
binding energy
Fast decay
because of large
binding energy
 Thus, because of the fast exponential decay of the tails, the

double well potential can bind particle more strongly than the
single well potential.
 This is not because that the double well is somewhat stronger
than the single well, but because we can maintain an almost
constant wave function between the wells. And this means
that the bound particle has a high probability of being
anywhere between the potentials.
2
10/10/2014

 When the wells are far apart, then a particle that is bound in,
say, the right well does not know that there is a well on the
left, and vice versa.
 If the wave function for this right-bounded particle is uR(x),
and uL(x) for the left-bounded particle, then a symmetric and
antisymmetric wave functions can be formed as follows
ueven ( x) 
1
u R ( x)  uL ( x)
Ne
1
uR ( x)  u L ( x)
uodd ( x) 
No
with some normalization constants.

 Because there is a small overlap of the wave functions uR(x),
and uL(x), the eigenvalues of these wave functions are not
exactly the same. Thus, uR(x), and uL(x) do not represent
stationary states.
 For example, the wave function of particle that is localized on
the right will be approximately given by
u( x)  Cueven ( x)  uodd ( x)
 If this is the wave function of the system at t = 0, then at later
time the wave function will be

u ( x, t )  C ueven ( x)e iEet   uodd ( x)e iEot  

 Ce iEet  ueven ( x)  uodd ( x)e iEt  
with E  Eo  Ee
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10/10/2014

 After a time t such that eiEt   1 , i.e.

t
E
the wave function becomes one that is approximately
localized on the left side.
 Thus the particle oscillates between the two wells with
angular frequency
E Eo  Ee
 
 
 This phenomena is observed in the
ammonia molecule (NH3), where the
three H nuclei forms a triangular base of
a pyramid and the N nucleus oscillates
between the two apexes of the pyramid.
Potential Barrier
 Consider the potential barrier given by
V0
0 x  a

V ( x)  V0 x a E
0 xa
 x
–a a
 We consider only the case E < V0, then inside the barrier the
Schrodinger equation gives
d2
u ( x)  2 E  V0 u ( x)  0
2m
2
dx 
 Whose solution is given as
2m( E  V0 )
u ( x)  Aex  B e x , for x  a 2  
2
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10/10/2014
Potential Barrier
 And the solution at the outside regions are
u( x)  eikx  R eikx , for x  a
u( x)  T eikx ,
for x  a
2 mE
with k 2  2

 These solutions are similar to the potential well case, with the
replacement of q  i, thus we can read off the transmission
coefficient as
2k
T  e 2ika

2k cosh 2a  i k 2   2 sinh 2a 
Potential Barrier
2k
T  e 2ika

2k cosh 2a  i k 2   2 sinh 2a 
 Which implies that the probability flux is proportional to
T 
2 2k 2

2k 2  k 2   2 sinh 2 2a 
 When a >> 1, sinh 2a  ½e2a, and
 4k  4a
2
T  2
2
2 
e
 k  
i.e. there is transmission even though the energy lies below
the top barrier, this tunneling is a quantum mechanical
phenomena.
 Note that the wave function does not vanish inside the
barrier, hence there is some probability of finding the particle
with negative kinetic energy. How is this possible ?
5
10/10/2014
Potential Barrier
 To overcome this paradox, we look at the uncertainty
principle.
 An experiment to study the particle inside the potential
barrier must be able to localized with accuracy x  2a .
 This measurement will transfer to the particle momentum,
with an uncertainty p   2a which correspond to a
transfer of energy
E   2 8ma2
 In order to observe the negative kinetic energy, this
uncertainty must be much less than |E – V0|, thus
 2 2 2
 E 
2m 8ma2
 Which implies 2a >> 1, under this circumstances, the
quantity to be measured |T|2 is vanishingly small.
Potential Barrier
 The approximate ratio of transmitted probability flux with
respect to the incident probability is extremely sensitive to
the width of the barrier (2a) and to the amount by which the
barrier exceed the incident energy, since
12
 2ma 2 (V0  E ) 
a   
 2 
6
10/10/2014
Irregular Potential Barrier

 In general, the potential barrier is not square.
 The proper way to study an irregular shape barrier is with
Wentzel-Kramers-Brillouin (WKB) approximation.
 However, we wanted to know the transmission probability
coefficient |T|2 through this irregular shape barrier.
 Observe, that the approximate expression
 4k  4a
2
T  2
2
2 
e
 k  
consist of a product of a pre-factor and a rapidly decaying
exponential. We can isolate this rapid variation by writing
ln T  const  2 2a 
2
i.e. the energy dependent factor 2 multiplies the width 2a.

 A smooth curved barrier, can be considered as a juxtaposition
of the square potential barriers.
 The total transmission probability is a product of all

transmission probabilities of each square potentials. Thus, the
overall transmission coefficient is a product of the
transmission coefficient of a single barrier,
ln T   ln T  2 xn 
2 2
slice n
slices n
xn is the slice width and  is the average value of  for
that barrier.
7
10/10/2014

 For a continuous summation, the above becomes
ln T  2  dx 2mV ( x)  E   2
2
barrier
 And hence,
 
T  C exp  2  dx 2mV ( x)  E   2 
2
 barrier 
8
05/10/2015
1D Potentials
Harmonic Oscillator
1
05/10/2015
Equilibrium Potential
U(r)
rmin
A system in equilibrium
r
will be at the minimum of
the potential
Around an equilibrium
point, potential is
approximately quadratic
Diatomic molecular potential
Equilibrium Potential
2
05/10/2015
Hamiltonian of Harmonic Oscillator

 The classical Hamiltonian is
p2 1 2
H
 kx
2m 2
 Thus, the time-independent Schrödinger equation of a
Harmonic Oscillator is
2 d 2 1
 2
u ( x)  kx 2u ( x)  Eu ( x)
2m dx 2
k
 Introducing the frequency of the oscillator as   , and
m
2E m
writing   and change the variable into y  x , we
have  
d 2u
dy 2
 
   y 2 u( y)  0
Asymptotic Behaviour
d 2u
dy 2
 
   y 2 u( y)  0
 For any eigenvalue , as y2  , the term involving  is

negligible, thus we require that y(y) asymptotically satisfy
d2
y 0 ( y)  y 2y 0 ( y)  0
dy 2
 Multiply with 2dy 0 dy, we can rewrite the above as
2
d  dy 0 

dy  dy 
  y 2
d
dy
 
y 02  0
or
d  dy 0  
2

dy  dy 
   2 yy
  y 2 y 02 2
0
 
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05/10/2015
 Assume that the term 2 yy 02 is negligible compared to
dy
  
d 2 2
y y0
 Then, integrating and assuming that the solution of y0(y) and its
derivative dy 0 dy vanishes at ±, we find the solution to be
d  dy 0  
2
   y 2 y 02   2 yy 02 dy 0

 C  y 2y 02
12

dy  dy   dy

 With the above asymptotic behavior, we must have C = 0,
hence
dy 0
  yy 0
dy
 Whose solution acceptable at ± is
y 0 ( y)  e  y
2
2
y 0 ( y)  e  y
2
2
 Assume that the term 2 yy 02 is negligible compared to

d 2 2
dy
y y0   
 Now, we can check if our assumption that
2 yy 02  2 ye  y
2
is small compared to
d 2 2
dy
y y0   
for large y is indeed satisfied
dy
  
d 2 2
y y0 
dy

d 2  y2
ye 
 2 y 3e  y
2
4
05/10/2015
The full solution

 Knowing the asymptotic behaviour, we write that the full
wavefunction as
u ( y )  h( y )y ( y )  h( y )e  y
2
2
 Inserting to the equation for u(x) we obtain,

d 2u
dy 2
   y 2
u( y ) 

d 2h
dy 2
 2y
dh
dy
 (   1)h( y )  0
 This differential equation for h(y) can be solved by series

method,

h( y )   an y n  s
n 0
 By substitution we will get: s = 0, and a recursion relation:
2n    1
an  2  an
n  1n  2
The full solution

2n    1
an  2  a
n  1n  2 n
 Starting from a0, we will get all even term of an : a0 , a2 , a4 , a6 , 
 Starting from a1, we will get all even term of an : a1 , a3 , a5 , a7 , 
 We should have 2 constants: a0 and a1
 This series is not convergent, hence the series must be truncated
to make it convergent. Making the series a polynomial.
2n    1
 Make a condition where the factor n  1n  2 has a value of
zero.
 It is achieved when   2n  1
 Combine with   2 E with those above condition we will get:

 2n  1; n  0,1,2, 

1
E
2
5
05/10/2015
Hermite Polynomials
Orthogonality of Hermite Polynomials

d 2H dH
2
 2y  2nH ( y )  0
dy dy
 Integrating factor
 p ( y) 
h( y )  exp   1  
dy   exp  (2 y )dy  e  y
2
 p0 ( y ) 
 Self-adjoint form
d 2H 2 dH
e y  2 ye  y  2ne  y H ( y )
2 2
2
dy dy
d   y 2 dH n 
  2ne  y H n ( y )
2

dy 
e
dy 
6
05/10/2015
Orthogonality of Hermite Polynomials

 Orthogonality can be found as follows

 d   y 2 dH n  d   y 2 dH m  
 
 
H m ( y )
dy 
e
dy 
 H n ( y )
dy 
e dy
dy  

 2n  m  e  y H n ( y ) H m ( y )dy
2

 Thus,

 e H n ( y) H m ( y)dy  N n nm
y2

Hermite Polynomials
7
05/10/2015
Wavefunct. and Probability Distribution

 Constant energy gap of the
energy eigen values.
 Lowest allowed energy is
not zero.
 As in finite potential well,
wave function penetrate
into non-classical region.
 Probability density is not
constant, and higher
probability near the well
walls.
Quantum vs Classical Harmonic Osc.

No Quantum Classical
1. Energy is discrete Energy continue
2. The minimum value of energy: 1
2  The minimum value
of energy: 0
3. Energy gap or spatial is always the
same, E  
4. There is a uncertainty to find the
electron outside the OH well.
5. For higher energy levels, the highest
probability to find the electron is near
to the OH well.
8
10/10/2016
General Structure of
Wave Mechanics and Operator Methods
Eigenfunction Vector Space
Hilbert Space
Hermitian Operator
Alexander A. Iskandar Wave Mechanics and Operator Methods 2
1
10/10/2016
Eigenfunctions and Eigenvalues

 The state of a physical system is described by a wave functions
which should contains all information about the system.
 Time dependence of the wave function is given by
 ( x, t )
i  Hˆ ( x, t )
t
ˆ
 The operator H is the Hamiltonian that governs the time
evolution of the system.
ˆ pˆ 2 
H   V (xˆ ), pˆ  i
2m x
 If the potential V (xˆ ) does not has an explicit time
dependence, then
ˆ
 ( x, t )  uE ( x)eiEt  Hu E ( x)  Eu E ( x)

 Eigenfunctions that correspond to different eigenvalues are
orthogonal (for E1  E2)

 dx u

E1 ( x)u E2 ( x)  0
 The eigenfunction forms a complete set, i.e. for any arbitrary

square integrable function

 dx  (x) 
2

then,  (x) can be expanded in terms of the eigenfunctions of

ˆ
. , for example if the spectrum of Hˆ involve discrete as
H
well as continuous energy, then
 ( x)   Cnun ( x)   dE C ( E )uE ( x)
n
2
10/10/2016

 The eigenfunctions can be normalized

 dx u ( x)un ( x)   mn
*
m

 If initially the wave function at t = 0 is (x,0) = (x) , then at
later time the time dependence is simply
 ( x, t )   CE uE ( x)e iEt 
E
Observables
 The energy is an example of an observable, other examples
are position, linear momentum as well as angular momentum.
 For example, the eigenfunction of momentum operator is
u ( x) 1
pû p ( x)  i p  pu p ( x)  u p ( x)  e ipx 
x 2
that is normalized with orthonormality condition given as

 dx u ( x)u p2 ( x)   ( p1  p2 )
*
p1

 And the expansion theorem now reads

 ( x)   dp f ( p)u p ( x)

 Where f(p) is also called the wave function in momentum

space.
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10/10/2016
Observables
 Like the energy operator (the Hamiltonian Hˆ ), momentum
operator p̂ has real eigenvalues since they represent physical
quantities.
 Operators that have real eigenvalues are called Hermitian
operators.
 In other words, all physical observables must be represented
by a Hermitian operators. For example an arbitrary observable
a, we have
ˆ
Au a ( x)  au a ( x)

 dx u ( x)ua2 ( x)   a1a2
*
a1


 ( x )   Ca u a ( x ) Ca   dx ua* ( x) ( x)
a 
Interpretation of Expansion Coefficients

 Suppose a collection of systems, each represented by the
wave function (x) that is a normalized wave function

 dx ( x) ( x)  1
*

 The result of any given measurement can only be one of the
eigenvalues a.
 The probability that an eigenvalue a will be found, or the
fraction of the system in the collection that have the
eigenvalue a, is |Ca|2.
 If, after a measurement on a particular member of the
collection yields an eigenvalue a1, then that particular system
must be projected by the measurement to the state ua1 ( x) .
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10/10/2016
Interpretation of Expansion Coefficients

 Since the probability of the eigenvalue a is |Ca|2, then
 
 
1   dx * ( x) ( x)   dx   Ca*ua* ( x)  ( x)   Ca*Ca   Ca
2
   a  a a
 On the other hand, this formula implies

   
a CaCa  a   dx ua ( x) ( x)   dy ua ( y) * ( y) 
*
 *
    
 
   dxdy
*
( y ) ( x) ua ( y )ua* ( x)  1
   a
or
 u ( y)u ( x)   ( x  y)
a
a
*
a
 This property describe the completeness relation of the wave

functions that is equivalent to the expansion theorem.
Vector Space
 The expansion theorem states that any state of a system can
be regarded as a linear combination of the eigenfunctions of
the problem, just like any arbitrary vector can be expanded as
a linear combination of the unit vectors.
 Eigenfunctions are unit vectors in some abstract linear vector
space, i.e. it is labeled by a continuous variable, in most cases
the position variable x.
 The vector space is generally complex and continuously
infinite-dimensional.
 A wave function (x) is a realization of a state of a physical
system and it is represented by a vector in this vector space.
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Vector Space – Hilbert Space

 This vector space obey the usual rules of a vector space, i.e.
the sum of two vector is again a vector in the vector space
and in particular the scalar product (the analogy of a dot
product) is realized as the following integral

 dx f ( x) ( x)
*

 The convergence of this integral is guaranteed by the choice

that the vector space has to be a Hilbert space.
 An operator transform a vector into another vector, and we
are only interested in a linear operators
A 1 1 ( x)   2 2 ( x)  1A 1 ( x)   2A 2 ( x)
ˆ ˆ ˆ
Hermitian Conjugate
 In the Hilbert Space, a Hermitian conjugate of an operator Oˆ ,
denoted by Oˆ , is defined as
 
 
ˆ ˆ *
 dx  ( x)O  ( x)   dx O  ( x)  ( x)
*
 
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Hermitian Conjugate
 
 
ˆ ˆ *
 dx  ( x)O  ( x)   dx O ( x)  ( x)
*
 
 Example: find the Hermitian Conjugate of operator Oˆ  d .
Assume: operator Oˆ  d works on (x)
dx
dx
  
 d  d 
  dx 

dx    ( x )   dx  ( x)

dx
 
d
  dx
d 
dx
 
    dx  
dx
 

d
   
   dx  

dx

 0   dx  
d
 x 

dx
Hermitian Conjugate
 
 
ˆ ˆ *
  O    O   ( x)
*
dx ( x ) ( x ) dx ( x )
 
 Example: find the Hermitian Conjugate of operator Oˆ  d .
Assume: operator Oˆ  d works on (x)
dx
dx
 
ˆ 
 ˆ ˆ
 dx O     dx O   dx  O 

 
 Hence
ˆ
O  Oˆ
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Hermitian Conjugate
 A Hermitian conjugate of an operator Oˆ , denoted by Oˆ , is
defined as
 
 
ˆ ˆ *
 dx  ( x)O  ( x)   dx O ( x)  ( x)
*
 
 From the condition that a Hermitian operators have real
eigenvalues, i.e. its expectation value is real, we have
*
ˆ ˆ
A  A
*

ˆ * ˆ

  A    dx  ( x) A ( x)
*
dx ( x ) ( x )
 
 
 
  dx A ( x)  ( x)   dx ( x)* Aˆ  ( x)
ˆ *
 
Hermitian Operators
 Comparing the last result, we see that a Hermitian operator
satisfy
ˆ ˆ
A A
and
 
 
ˆ ˆ *
 dx f ( x)A ( x)   dx Af ( x)  ( x)
*
 
 Thus, the previous example of operator Oˆ  d is not
Hermitian, since dx
 dxO     dx
ˆ 

 Oˆ   Oˆ   Oˆ
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Hermitian Operators
 Example: Momentum Linear operator is a Hermitian operator
u ( x) 1
pû p ( x)  i p  pu p ( x)  u p ( x)  eipx 
x 2
Using the definition of Hermitian Conjugation
 
 
ˆ ˆ *
  O    O   ( x)
*
dx ( x ) ( x ) dx ( x )
 
we can show
  
  pû x  u x dx    i x u x  u x dx

   
p p p p
   
 
 1 ip ipx  
    i e  u p  x dx
  2  
 
 pu x u x dx   u x  pû x dx

 
 p p p p
 
Hermitian Operators
 A Hermitian operator satisfy
ˆ ˆ
A A
 We can further show that eigenfunctions of a Hermitian
operator corresponding to different eigenvalues are orthogonal
ˆ
u2* ( x)Aû1 ( x)  a1u2* ( x)u1 ( x)
Au1 ( x)  a1u1 ( x)
ˆ

Au 2 ( x)  a2u 2 ( x) u1* ( x)Aû2 ( x)  a2u1* ( x)u2 ( x)
 Take a complex conjugation of the first equation and recalling
ˆ ˆ
that A  A and the eigenvalues are real, and then subtract.
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Hermitian Operators
 The Hermitian conjugate of a combination of any two
operators is obtain as follows
   
 
ˆ ˆ ˆ
 ( x), Bˆf ( x)   ( x)
* *


dx AB f ( x )  ( x )   dx A ( x )


  dx  * ( x)Aˆ  ( x)

 

  dx Bˆf ( x) Aˆ  ( x)
*

 
 

  dx f * ( x)Bˆ Aˆ  ( x)   dx f * ( x) AˆBˆ  ( x)
 
 Thus AˆBˆ    Bˆ Aˆ.


 
Hermitian Operators
 For any operator Oˆ , the combinations Oˆ  Oˆ  , i Oˆ  Oˆ  , OÔˆ   
are Hermitian.
 The product of two Hermitian operators, is not necessary
Hermitian.
AˆBˆ   Bˆ Aˆ

 
 
 BÂˆ  AˆBˆ  AˆBˆ  BÂˆ  AˆBˆ  Aˆ, Bˆ  
 Thus, the product of two Hermitian operators is also Hermitian
 
if the quantity Aˆ, Bˆ , called the commutator of operators A
ˆ
ˆ
and B , vanishes.
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Commutation Relation
 A commutation relation is anti-symmetric, i.e.
Aˆ, Bˆ  Bˆ, Aˆ
 When calculating a commutation relation, we have to
remember that the operators have to act on a wave function
in order that its action make sense.
 So for example the commutation of the linear momentum
operator and the position operator is evaluated as follows.
xˆ , pˆ  ( x)  xˆpˆ  pˆxˆ  ( x)  x   i x     i x x  ( x)

     

  xi  ( x)  i  x ( x)  i ( x)
x x

 Thus, xˆ , pˆ  i. 
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Simultaneous Eigenvector and Degeneracy
Time Dependence of Expectation Value
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Simultaneous Observables
 Suppose u(x) is an eigenfunction of operator Aˆ with an
eigenvalue a and it is also simultaneously an eigenfunction of
ˆ
operator B with an eigenvalue b
ˆ
A u ( x)  au ( x)
ˆ
B u ( x)  bu ( x)
 Then,
ˆ ˆ ˆ
BA u ( x)  aB u ( x)  abu ( x)
ˆ ˆ ˆ
AB u ( x)  bA u ( x)  abu ( x)
 If this relation holds for all eigenfunctions, then for all square
integrable wave function  ( x)   Caua ( x) , we have
AˆBˆ  BÂˆ ( x)  AˆBˆ  BÂˆ C u ( x)   C AˆBˆ  BÂˆu ( x)  0

a
a a a a
a a
 Thus, the condition that two operators have simultaneous
eigenfunctions is that their commutator vanishes
 From the above,

Aˆ, Bˆ  0
ˆ ˆ ˆ ˆ ˆ
AB u a ( x)  BA u a ( x)  aB u a ( x)
ˆ
we see that B ua ( x) must be proportional to ua (x)
ˆ
B u a ( x)  bu a ( x)
 This means that ua (x) is a simultaneous eigen vector of the
operator Aˆ and Bˆ and denote it as uab (x)
ˆ
A u ab ( x)  au ab ( x)
ˆ
B u ab ( x)  bu ab ( x)
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 A set of operators which are commute to each others are
called as CCS (Complete Commuting Set), and observables
that are represented by this CCS are the most complete
identification of the system.
Example:
For an electron (without spin) in an atom, the CCS is:
Hˆ , Lˆ , Lˆ 
2
z
For an electron (with spin) in an atom, the CCS is:
Hˆ , Lˆ , Lˆ , Sˆ , Sˆ 
2
z
2
z
Degeneracy
 Suppose the operator Aˆ with eigenvalue a is degenerate, i.e.
A u a  x   au a  x 
ˆ 1 1
A ua
ˆ 2 
x   aua2  x 
ˆ ˆ
 If B and A commute, then
B u a  x   b11u a  x   b12u a x 
ˆ 1 1 2 
B u a  x   b21u a  x   b22u a  x 
ˆ 2  1 2 
 Ideally, we would like to have

B uab  x   b1uab  x 
ˆ 1 1
B uab  x   b2uab  x 
ˆ 2  2 
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Degeneracy
 To remove that mixture one can make a linear combination
between ua1  x  and ua2   x  in such a way that:
B vab  x   b1vab  x 
ˆ 1 1
B vab  x   b2 vab  x 
ˆ 2  2 
and
A vab  x   avab  x 
ˆ 1 1
A vab  x   avab  x 
ˆ 2  2 
 In other words, vab x  and vab2  x  are simultaneous eigen-

1
functions of the operators Aˆ and Bˆ which are commute to

each other.

ˆ
 The expectation value of A :

 dx x, t A x, t 

ˆ  ˆ
A 

 Calculate the time derivative

    ˆ   dAˆ 
A   x, t    dx  x, t    x, t 
d ˆ
A   dx

dt  t   dt 
   

  
  dx Aˆ 
  t 
 Remember the Schrodinger equation:

  1 ˆ     
i  Hˆ   H and  
t t i t  t 
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 Then,
dAˆ
  
1 ˆ  ˆ  ˆ 1 ˆ 
A   dx H  A  x, t    dx A  H  
d ˆ
dt   i    i  dt
  dAˆ

1 ˆ  ˆ
H A  x, t  
1  ˆ ˆ
   dx
i 
dx A H  
i dt
dAˆ

1  ˆ ˆ
  1  ˆ ˆ
i  i 
 dx H A x , t  dx A H  
dt
dAˆ

   dx HA  x, t    dx A H 
1  ˆ ˆ 1  ˆ ˆ
i i   dt
ˆ
 Recall that H  Hˆ

 Then we obtain,
d ˆ
dt i
 ˆ ˆ ˆ ˆ

A    dx HA  AH   x, t  
1 dAˆ
dt

or,
d ˆ
dt
A 
dAˆ
dt
i

  dx  ( x) Hˆ , Aˆ  ( x)


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ˆ
 For example, A is not an explicit function of t, then
d ˆ
dt
i

 ˆ ˆ

A   dx ( x) H , A  ( x) 
 If Hˆ , Aˆ 0 then
d ˆ
dt
A  0 , which means
ˆ
A : conserved
 Any operator Aˆ that is commute with Hˆ will have physical
quantity which is conserved.
 Remember that the conservation laws are very important in
physics, such as momentum conservation law and energy
conservation law .
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Time Dependence of Operator
Dirac’s Notation
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Time Dependence of Operators

 The equation that describes the evolution of a system is the
time-dependent Schrodinger equation
d
 (t )  Hˆ  (t )
i
dt
 This is an operator equation in an abstract space, with  (t )
is a vector in that space and it points is a direction that
depends on time.
 This equation describes how a wave function  (t ) evolve
with time as the operators themselves are fixed in time.
 This formalism is called the Schrodinger picture.
 The solution of the above equation is
ˆ
 (t )  e iHt   (0)
Alexander A. Iskandar Dirac Notation 3

 The exponential function of the Hamiltonian operator above is
defined as
n
1  iHˆ t 

e    
iHˆ t 


n 0 n!   
 The evolution of the expectation of an operator B̂ that does
not have an explicit time dependence can be calculated as
Bˆ   (t ) Bˆ  (t )   (0) eiHt  Bˆ e iHt   (0)
ˆ ˆ
  (0) Bˆ (t )  (0)
 Thus, the expectation value of a time-independent operator B̂
in a state that varies with time  (t ) can be written as the ex-
pectation value of a time-dependent operator Bˆ (t )  eiHt  Bˆ e iHt 
ˆ ˆ
in a time-independent state  (0) .
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 The last formalism of quantum mechanics is very useful, since
it is convenient to set up a basis of orthonormal eigenvectors
in an abstract space once and for all and not worry how the
basis vector changes with time. This formalism is called the
Heisenberg picture.
 Where as keeping the operator time-independent means that
we are working in Schrodinger picture.
 The result is the same, whatever picture we use.
 In Heisenberg picture the state vectors are fixed, we need not
refer to them. How an observable varies with time is given as
d ˆ i i ˆ
B(t )  Hˆ eiHt  Bˆ e iHt   eiHt  Bˆ e iHt  Hˆ
ˆ ˆ ˆ
dt  
i

   i

 Hˆ Bˆ (t )  Bˆ (t ) Hˆ  Hˆ , Bˆ (t )

Vector Space
 A state of a system is describe by a (complex) wave function  (x)
that is a vector in a vector space. It usually composed as linear
combination of its eigenfunctions:
  x    cn u n  x 
 The eigenfunction un x  can be made orthonormal by definition:


 dxu x u x   

n m nm

 These eigenfunctions define a vector space with infinite in

dimensionality and its basis are un x  .
 In other words, any wave function  (x) can be seen as a vector in
that vector space.
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Dirac Notations
 We introduce Dirac notation of that vector as:
 : Ket vector
 In analogy with (x) and  (x) we introduce the bra vector as
pair of its ket vector:

: Bra vector
 The inner product of any arbitrary function:

 dx x  x 


is represented by a “bracket”:

  dx  x   x    



Dirac Notations
 and applies linearity properties of the inner product
operation:
 1 1   2 2  1   1   2   2
 In that vector space, an operator transform a certain vector to
be another vector:
Oˆ   Oˆ 
 and that’s why we can write:

 Oˆ    Oˆ 

  dx   x Oˆ   x 

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Dirac Notations
 The Hermitian Conjugate operation of an operator based on
definition:
 
 
 dx Oˆ  x   x    dx x Oˆ  x 
 * 
 
 In the Dirac notation it becomes:

Oˆ     Oˆ  
 So, a Hermitian operator in the Dirac notation can be written

as
 Oˆ     Oˆ 
Dirac Notations
 An arbitrary vector that can be written a linear combination of
basis vectors, where these basis vectors are eigen vectors
from an eigen equation:
Oˆ un  x   anun  x 
Oˆ n  n n
 so that,
  x    cn n
 Where

cn   dxun  x   x   n

 These basis are orthonormal to each others:

n m   nm
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Dirac Notations
 And they are formed a complete set (completeness):
  x    cn n
  n n
 The completeness is expressed by
n n 1
Operations with Dirac Notations

 Prove that a Hermitian operator Ô have real eigen values
and eigen vectors with different eigen values are orthogonal
to each other.
Oˆ un  x   anun  x 
 
 dxu x Oˆ u x    dxu x Oˆ u x 

  
m n m n
 
 

  dx Oˆ um  x  un  x 


 
an  dxum  x un  x   am  dxum  x un  x 
 

a n  am   dxu x u x   0

m n


Take: um x   un x  , then  dxun x un x   0

It means: an  an  an : real

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 We have just get that for a Hermitian operator its eigen value
is real, then

an  am   dxum x un x   0

If an  am , then

 dxu x u x   0 : orthogonal

m n


 Do it again that above exercise using Dirac notation.
Oˆ n  n n
 Calculate: m Oˆ n  n m n
 Also n Oˆ m  m n m
n Oˆ m  m n m
 Take the complex conjugate of the last equation:

n Oˆ m  Oˆ m n m n m  n m n

 m Oˆ  n m m n  n m n
 m Oˆ n
m 

n m n 0
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 In particular,
n 

n n n 0
0
 It means, n  n : real
 We can get also,
m  n  m n  0  m n   mn
Interpretation of Combination Coeff.

 We note that physical observation must be related with
Hermitian operator, because eigen values of Hermitian
operators are real, and eigenfunctions with different eigen
values are orthogonal to each other.
 How about continuous spectrum of eigenvalues?
For example: position or linear momenta.
 An arbitrary function or vector can be written as linear
combination of eigen function (continuum case):
   dxcx  x
 Where basis vectors x are orthogonal:
x x    x  x 
 The linear combination c(x) can be calculated as:
c  x   x 
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 Remember that c x  is probability to find the particles at a
2
location of x until (x+dx).

 According to Born interpretation, this probability is given by
 x 
2
 So that we can write:

 x   x 
 This is wave function   x  that is represented by vector  .

 Similarly for linear momentum:   p   p 
 These continuum bases are complete with completeness is
given by:  dx x x  1
 dp p p  1
 So that  x   x    dp x p p
  dp x p   p 
 Remember that wave function for a free particle with

momenta p:  x   1 dp  p eipx 
2 
1
 Compared with x p  eipx 
2
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Harmonic Oscillator
Raising and Lowering Operator
Matrix Representation
Alexander A. Iskandar Quantum Harmonic Oscillator 2
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Harmonic Oscillator
 The classical Hamiltonian for the harmonic oscillator has the
form
p2 1
H  m 2 x 2
2m 2
 Note that this classical Hamiltonian can be rewritten as
 m p  m p 
H    x i 
 2 x  i 2m


 2 2m  
 The quantum mechanical Hamiltonian can be obtained by
substituting the linear momentum and position variables
above with their corresponding operators, i.e.
pˆ 2 1 
Hˆ   m 2 xˆ 2 , pˆ  i , xˆ, pˆ   i
2m 2 x
Quantum Harmonic Oscillator

 Introduce the following raising and lowering operators
m pˆ
Aˆ   xˆ  i
2 2m
 The commutation of these operators can be easily calculated
with the help of the commutation relation of the linear
momentum and position operators
Aˆ , Aˆ  1
 
 Thus, the Harmonic Oscillator Hamiltonian can be rewritten as

 1
Hˆ    Aˆ  Aˆ   
 2
 And further, we can also calculate

Hˆ , Aˆ   Aˆ  
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Eigenstate of Harmonic Oscillator

 Assume that E is an eigenvector of the Hamiltonian, i.e.
Hˆ E  E E
 Then we can show the following
 
Hˆ Aˆ  E  Aˆ  Hˆ  Aˆ  E  E   Aˆ  E
i.e. Aˆ  E is also an eigenstate of the Hamiltonian with
energy raised (lowered) by  , hence the name “raising” and
“lowering” operator or “ladder” operator.
 The lowering cannot go on forever, because the expectation
value of Ĥ in any state is positive. Recall that
 pˆ 2   pˆ  pˆ   0
and similarly for the operator x̂ 2 since both are hermitian.

 This means that there is a state with the lowest energy. The
ground state, 0 , that must satisfy
Aˆ  0  0
 And it follows that the ground state energy is
 
Hˆ 0   Aˆ  Aˆ   1 0  1  0
2 2
i.e. there is a non vanishing zero-point energy just as we have

seen in the Schrodinger equation treatment of the Harmonic
Oscillator problem.
 Consider the state Aˆ  0 , its energy is
 
Hˆ Aˆ  0  Aˆ  Hˆ  Aˆ  0    12  1Aˆ  0
i.e. the energy is raised by one unit of  .
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 Thus repeated application of raising operators will increase the
energy by a multiple of  unit. After n applications, Aˆ  0
n
 
the energy of this state is
 
Hˆ Aˆ 
n
0   n  12  Aˆ  n
0

 Repeated application of raising operators on the ground state
 
Aˆ  0 yield a state with energy En
n
n
 
Hˆ Aˆ  0   n  1  Aˆ  0
n
2
 
 This means that the state Aˆ   0 is proportional to n
 n
Aˆ  0  C n
 n
n
 The constant of proportionality is obtained by considering the

product
 
Aˆ  Aˆ  0  Aˆ  Aˆ  Aˆ  Aˆ   Aˆ  0
n

and moving the Â operator to the right until finally it
annihilate 0 .
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 
Aˆ  Aˆ   n
   0
0  Aˆ  Aˆ   Aˆ  , Aˆ  Aˆ 
n 1
 Aˆ  0  Aˆ Aˆ Aˆ  0
 n 1    n 1
 Aˆ  0  Aˆ Aˆ Aˆ  Aˆ , Aˆ Aˆ  0

 n 1       n2
 2Aˆ  0  Aˆ  Aˆ Aˆ  0

 n 1  2   n2
 2Aˆ  0  Aˆ  Aˆ Aˆ  Aˆ , Aˆ Aˆ  0

 n 1  2      n 3
   nAˆ  0  Aˆ  Aˆ 0  nAˆ  0

 n 1  n   n 1
Thus, the application of Â on Aˆ  0 is like differentiating  n




with respect to Â , i.e.
d
dAˆ 

 In particular, 0 Aˆ
 m ˆ n
  
A 0 , if m > n, then the n Â
differentiate all the factors on the right and we end up with
0 Aˆ 
mn
0 0  
If m < n, we end up with
0 0  
0 Aˆ 
nm
since we can consider the operator Aˆ    nm

acts on 0 .
 Finally, if m = n, we end up with
 
n
 d 
0    Aˆ  0  n(n  1)(n  2)  0 0  n!
n
 dAˆ 
 Thus, we found that the constant of proportionality is
n 
1 ˆ n
Cn
A 0 
1 ˆ n
n!
A 0    
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 We also found from the above the orthogonality of the
eigenstates
  
m n  0 Aˆ  Aˆ  0  
m n
mn
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Angular Momentum
Angular Momentum Operator and its Commutation Relations

Raising and Lowering Operator
Alexander A. Iskandar Angular Momentum 2
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Labelling a physical system

▪ As we have learned from previous lecture, that the complete
identification of a physical system can be constructed using
quantum numbers of a Complete Commuting Set (CCS).
▪ For an atomic system, the Hamiltonian is given by the
following
 pˆ 2
ˆ 
H ( r , t )  
 V (r ) (r , t )  E (r , t )
 2m 
▪ Where the interaction potential between the electron and the
nucleus is Coulomb interaction
Ze 2
V (r )  
4 0 r
which is a central potential.
Labelling a physical system

▪ Recall that in a central potential problem, angular momentum
is conserved, i.e.
dL dLˆ
0  0
dt dt
▪ Thus, according to Heisenberg picture (Heisenberg equation
of motion), we have
Hˆ , Lˆ  0
i.e. the Hamiltonian and the angular momentum operators
commute, they form part of a CCS.
▪ And hence, their eigenvalues can be used to label the physical
system.
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Angular Momentum Operator

▪ In quantum mechanics we get linear Hermitian angular
momentum operators from the classical expressions using the
postulates
r  rˆ  r, p  pˆ  i 
L  r p  L ˆ  i r  
Lx  ypz  zp y Lˆx  ypˆ z  zpˆ y

Ly  zpx  xpz Lˆ y  zpˆ x  xpˆ z
Lz  xp y  ypx Lˆz  xpˆ y  ypˆ x
Commutation Relations
▪ The components of Angular Momentum operators do not
commute with each other
   
Lˆ x , Lˆ y  yˆ pˆ z  zˆpˆ y , zˆpˆ x  xˆpˆ z   yˆ pˆ x  xˆpˆ y   iLˆ z

i
▪ And the other commutation relations can also be calculated
to yield
  
Lˆ y , Lˆ z  iLˆ x and Lˆ z , Lˆ x  iLˆ y 
▪ Or, with short-hand notation using the Levi-Civita totally anti-
symmetric tensor,

Lˆ j , Lˆk  i jkl Lˆl 
▪ We can also show that each components of the angular
momentum commutes with L̂2
Lˆ , Lˆ   Lˆ , Lˆ  Lˆ
j
2
j
2
x
2
y 
 Lˆ2z  0
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Commutation Relations
▪ Thus, we can form a CCS consisting of the Hamiltonian, a
component of the angular momentum and the length of the
angular momentum, i.e.
H ,L 
ˆ ˆ2
, L̂ z 
▪ Define the simultaneous eigenvalue problem for the z-
component of the angular momentum and the length of the
angular momentum as
Lˆ 2 , m   2   1 , m
Lˆ z , m  m , m
▪ The simultaneous eigenvector , m is assumed to be
orthonormal, i.e.
, m , m    mm
Raising and Lowering Operators

▪ As we have learned from the Quantum Harmonic Oscillator
example, the representation content of the eigenvector can
be obtained by applying a raising and lowering operator on a
state.
▪ Define the raising and lowering operators to be
Lˆ  Lˆ  iLˆ
 x y
▪ Whose commutation relations are

Lˆ , Lˆ   2Lˆ
  z
Lˆ , Lˆ   Lˆ
z  
Lˆ , Lˆ   0
2

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Raising and Lowering Operators

▪ Further, we also have
  
Lˆ Lˆ  Lˆ x  iLˆ y Lˆ x  iLˆ y  Lˆ 2  Lˆ2z  Lˆ z
▪ And similarly,
  
Lˆ Lˆ  Lˆ x  iLˆ y Lˆ x  iLˆ y  Lˆ 2  Lˆ2z  Lˆ z
▪ Thus,
Lˆ 2  Lˆ Lˆ  Lˆ2z  Lˆ z  Lˆ Lˆ  Lˆ2z  Lˆ z
Representation Content
▪ Consider the vector Lˆ , m , let us check if this vector is an
2
eigenvector of the operators L̂ and L̂z ,
Lˆ 2 Lˆ , m   2 (  1) Lˆ , m
 
Lˆ z Lˆ , m   (m  1) Lˆ , m
▪ Thus, it is found that Lˆ , m is an eigenvector of L̂2 with the
same eigenvalue, while the eigenvalue of L̂z is raised or
lowered by one unit of  .
Lˆ , m  C (, m) , m  1
 
Lˆ , m  C (, m) , m  1
▪ The normalization can be calculated to yield
C   (  m)(  m  1)
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▪ Or
Lˆ , m   (  m)(  m  1) , m  1
Lˆ , m   (  m)(  m  1) , m  1
▪ From the above, it is readily seen that when m  
Lˆ , m     (  )(    1) ,   1  0

Lˆ , m     (  )(    1) ,  1  0

▪ Recall that norm of a vector has to be positive, hence
(  m)(  m  1)  0
(  m)(  m  1)  0
whose solutions are
   m  (  1)
 (  1)  m  
▪ Thus, the possible value of m are
m  ,  1,  2, ,   1, 
▪ Hence, for each  there are (2  1) state.
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Angular Momentum
Matrix Representation of Angular Momentum

Angular Momentum Operator in Spherical Coordinate
Spherical Harmonics Function
Zeeman Effect
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Matrix Repr. of Angular Momenta

▪ Remember: simultaneous eigen vector of the L̂2 and L̂z
operators is , m
Lˆ2 , m   2   1 , m
Lˆ z , m  m , m

and Lˆ2 , Lˆ z  0 
▪ Note that
 
, m Lˆ2 , Lˆ z , m  0
, m Lˆ Lˆ  Lˆ Lˆ , m

2
z z
2
0
, m Lˆ2 Lˆ z , m  , m Lˆ z Lˆ2 , m  0

 2   1    1 , m Lˆ z , m  0
Matrix representation of L̂z


▪ So, the matrix representation for L̂z is defined for a certain
value of   
▪ Then
, m Lˆ z , m  m , m , m  m m ,m   m  
▪ Matrix representation for L̂z depend on the chosen value of 
 1 0 0 
 
  1  m  1,0,1 Lˆ z   0 0 0 
 0 0 1
 
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▪ And another example is   2  m  2,1,0,1,2
 2 0 0 0 0 
 
 0 1 0 0 0 
Lz    0
ˆ 0 0 0 0 
 
 0 0 0 1 0 
 0 
 0 0 0 2 

▪ Remember that:
Lˆ , m     1  mm  1 , m  1
with    
, m Lˆ , m     1  mm  1 , m , m  1
 m,m 1
▪ For example, if we choose   1
0 2 0   0 0 0
   
Lˆ   0 0 2 Lˆ   2 0 0
   0
0   2 0 
0 0
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▪ We can show that
 0 2 0  0 0 0
 
 

Lˆ , Lˆ    0 0
2
2  2 0 0

 0 0 
0  0 2 0 

 0 0 0  0 2 0 
  
 2 0 0  0 0 2 
 0  
 2 0  0 0 0 

 2 0 0   2 0 0  1 0 0 
     
   0 2 0   0 0 2 0   2  0 0 0   2Lˆ z
2 2
 0 0 0   0 0 2   0 0  1
 
 
and Lˆ , Lˆ  2Lˆ z
Angular Momentum in spherical coord.

▪ Spherical polar coordinates are the x  r sin q cos f
natural coordinate system in which to z y  r sin q sin f
describe angular momentum: θ z  r cos q
r y
x, y, z  r ,q ,f
φ
▪ The angular momentum operators only
depend on the angles q and f and not x
on the radial coordinate r.
     cos f  
Lˆx  i  y  z  Lˆx  i  sin f  
 z y   q tan q f 
     sin f  
Lˆ y  i  z  x  Lˆ y  i   cos f  
 x z   q tan q f 
   
Lˆz  i  x  y  Lˆz  i
 y x  f
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Angular Momentum in spherical coord.

▪ And,
 1     1 2 
Lˆ2  Lˆ2x  Lˆ2y  Lˆ2z   2
 sin q q  q  
q  sin 2 q f 2 
sin
 
▪ Note: The angular momentum operators commute with any
operator which only depends on r. The operator L̂2 is closely
related to the angular part of the Laplacian
1   2   Lˆ2
2 
r 
r 2 r  r   2 r 2
▪ Further, the raising and lowering operators are given as
   
Lˆ  e if    i cot q 
 q f 
Spherical harmonics
2
▪ The simultaneous eigenfunctions of L̂ and L̂z are usually
written in terms of the spherical harmonics
Ylm (q , f )  q , f l , m  N lm Pl m (cos q ) exp(imf )
▪ Proportionality constant Nlm is chosen to ensure normalization.
▪ So that
LˆzYlm q , f   m Ylm q , f 
Lˆ2Ylm q , f   l  l  1 2Ylm q , f 
▪ And this yields

2l  1 (l  m)!
N lm  (1) m
4 (l  m)!
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Spherical harmonics
▪ A few examples of the Spherical Harmonics functions
1
Y00 (q , f ) 
4
3 3 ( x  iy )
Y11 (q , f )   sin q exp(if )  
8 8 r
3 3 z
Y10 (q , f )  cos q 
4 4 r
3 3 ( x  iy )
Y11 (q , f )  sin q exp(if ) 
8 8 r
Y20 q , f  
5
16
 3cos 2 q  1
Shapes of the spherical harmonics
Y00 Y11 Y10

z
y
Re[Y11 ] l  1, m  0
x
l  0, m  0
3
1 Y10  cos q
Y00  4
4
l  1, m  1 Imaginary
3
Y11   sin q exp(if )
8
Real
To read plots: distance from origin corresponds to magnitude
(modulus) of plotted quantity; colour corresponds to phase (argument).
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Shapes of the spherical harmonics

Y22 Y21 Y20
z
y
x Re[Y22 ] Re[Y21 ]
l  2, m  0
5
Y20  (3cos 2 q  1)
16
l  2, m  2 l  2, m  1 Imaginary
15 15
Y22  sin 2 q exp(2if ) Y21   sin q cos q exp(if )
32 8
Real
To read plots: distance from origin corresponds to magnitude (modulus)
of plotted quantity; colour corresponds to phase (argument).
Orthonormality of spherical harmonics

▪ The spherical harmonics are eigenfunctions of Hermitian
operators. Solutions for different eigenvalues are therefore
automatically orthogonal when integrated over all angles (i.e.
over the surface of the unit sphere). They are also normalized
so they are orthonormal.
▪ Integration is over the solid angle d   sin q dq df which
comes from
d 3r  r 2 drd 
 r 2 dr sin q dq df
2 
 df  dq sin q Y (q  f )Yl ' m ' (q  f )  1 if l  l ' and m  m '

*
lm
0 0
 0 otherwise
 d Y (q  f )Yl ' m ' (q  f )   ll '  mm '

*
lm
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Completeness of spherical harmonics

▪ The spherical harmonics are a complete, orthonormal set for
functions of two angles. Any function of the two angles q and
f can be written as a linear superposition of the spherical
harmonics.
 l
f q , f     almYlm (q  f ) l  m  l
l  0 m  l
▪ Using orthonormality we can show that the expansion

coefficients are``1`
alm   d  Ylm* (q  f ) f (q  f )
2 
  df  dq sin q Y (q  f ) f (q  f )
*
lm
0 0
Magnetic Dip. in External Magnetic Field

▪ Consider a (physical) dipole, i.e. there is a finite distance of
separation between the positive and negative charges.
▪ When placed in a region of constant electric field, the total
force on the dipole is zero.
x +q  
F  qE

E d z
 
F  qE
–q
▪ However, the electric field produces a torque on the dipole.

          
        
  r  F  r  F  d 2  qE   d 2   qE
   
 qd  E  p  E
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▪ Consider a dipole initially perpendicular to the field (position
a). The field tends to pull it into alignment (position b). To
push it to position c, we have to do a work:
x
a
c b
 q
E z
q q q
    
W    dq    p  E dq   pE  sin q dq    pE cos q   p  E
  
2 2 2
▪ The work that we do to oppose the force of the electric field is

(by definition) the potential energy
 
U  pE

 
m  Ia
a F  IwB
I
F  IwB
▪ The torque on the loop in an uniform magnetic field is

  
  F sin q xˆ  I wB sin q xˆ  m  B
▪ Note the similarity with torque on an electric dipole
  
  p E
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▪ The force on the magnetic dipole when placed in an external
magnetic field can be calculated in terms of dipole moment
and magnetic field.
▪ As the force is given in terms of a grad, we can further define
the work associated with this turning force (torque), i.e. its
potential energy,
  
F  U  U  m  B
 
(the electric dipole potential energy : U   p  E ).
▪ Magnetic dipoles thus tend to align in magnetic fields in the
same way that electric dipoles align in electric fields.
Atoms in magnetic fields

▪ Classical theory: Interaction of
μ
orbiting electron with magnetic field.
▪ Orbiting electron behaves like a r
current loop:
v
ev
(- sign because charge  e)
Loop current=
2 r
Magnetic moment   current  area
 ev  e L
  r   me vr    B
2
=
 2 r  2me
e
where  B  (the Bohr magneton).
2me
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Atoms in magnetic fields

▪ In a magnetic field B, classical interaction energy is:
H  μ.B
▪ Recalling that the magnetic moment is
Lˆ
μˆ    B

▪ Thus, orbiting electron behaves like a current loop:

Hˆ  μˆ  B  B Lˆ  B

Atomic en. levels splitting (Zeeman eff.)

▪ Let B-field in the z direction, the total Hamiltonian for the atom is
 B
Hˆ  Hˆ 0  B z Lˆz
▪ The energy eigenfunctions of the original atom are

eigenfunctions of so they are also eigenfunctions of the new
Hamiltonian
(Hence the name “magnetic
E  E0  mB Bz l  m  l quantum number” for m.)
m = +1
m=0
B = 0: (2l+1) degenerate m = -1
states with m = -l,…+l
B ≠ 0: (2l+1) states with distinct energies
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Atomic en. levels splitting (Zeeman eff.)
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Schrodinger Equation in 3D
The Central Potential

Hydrogenic Atom
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Schrödinger equation in 3D
▪ For a 3D problem, we extend the representation of the wave
function and potential function of the 1D case into 3D as
  x     r     x, y , z 
V  x   V  r   V  x, y , z 
▪ And the 3D linear momentum operator becomes
px2 p2 px2  p y2  pz2
 
2m 2m 2m
2
 2 2 2
 2 2 2 
    2
   
2m x 2 2m 2m  x 2 y 2 z 2 
▪ So that the Time-independent Schrödinger equation in 3D is
given as
2
  2  r   V  r   r   E  r  Ĥ  r   r   E  r 
2m
Alexander A. Iskandar Schrodinger Equation in 3D 3
Schrödinger equation in 3D
▪ Interpretation of wavefunction:
 (r, t )
2 probability density at r
(probability per unit volume)
probability of finding particle in

d 3r  (r, t )
2
a volume element centred on r
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Hamiltonian for a hydrogenic atom

▪ H-atom is our first example of the 3D Schrödinger equation.
▪ In a hydrogenic atom or ion with nuclear charge +Ze there is
the Coulomb attraction between electron and nucleus. This
has spherical symmetry – potential only depends on r. This is
known as a CENTRAL POTENTIAL.
-e
Ze 2
r V (r )  
4 0 r
+Ze
▪ The Hamiltonian operator is
2
Ze2
Hˆ   2 
2me 4 0 r
Hamiltonian for a hydrogenic atom

▪ The natural coordinate system is spherical polars. In this case
the Laplacian operator becomes
1     Lˆ2
2  2  r 2   2 2
r r  r   r
▪ Then the Hamiltonian becomes
2
Ze2 2
 2  Lˆ2 Ze2
Hˆ  r    2    r   
2me 4 0 r 2me r 2 r  r  2me r 2 4 0 r
▪ And TISE for H-like atom is
Ĥ  r   r   E  r 
or (m = me from now on)
2
  2  (r)  Lˆ2 (r) Ze2
 r    (r)  E (r)
2mr 2 r  r  2mr 2 4 0 r
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The angular wavefunction

▪ In the spherical coordinate system, this suggests we look for
separated solutions of the form
 (r)   (r   )  R(r )Ylm (   )
▪ The angular part are the eigenfunctions of the total angular
momentum operator L̂2. These are the spherical harmonics,
so we already know the corresponding eigenvalues and
eigenfunctions
Lˆ Y  ,    m Y  ,  
z lm lm
Lˆ2Ylm  ,    l  l  1 2Ylm  ,  
l = orbital quantum number.
m = magnetic quantum number (2l + 1 possible values).
▪ Note: this argument works for any spherically-symmetric
potential V(r), not just the Coulomb potential.
The radial equation

▪ Substitute separated solution into the time-independent
Schrödinger equation
 (r , ,  )  R(r )Ylm ( ,  )
  2   Lˆ2
2
Ze2
  r     (r)  E (r)
2mr 2 r  r  2mr 2 4 0 r
▪ Using separation of variables method, we obtain the equation
for the radial part as
2
d  2 dR  l (l  1) 2
Ze2
 r  R R  ER
2mr dr  dr 
2
2mr 2 4 0 r
or,
 d 2 2 d 2m  Ze 2  2l (l  1) 
 2   
2 
E    R(r )  0
 dr r dr   4 0 r 2 mr 2

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The radial equation

▪ Introduce the parameter
8m E
r
r
2
▪ The above equation could be recast as
 d2 2 d l (l  1)   1 
 2      R( r )  0
 dr r dr r2  r 4 
where,
Ze 2 m

4 0  2 E
▪ The solution of the above equation is obtained like previous
example, i.e. by first finding the asymptotic behaviour (large r
as well as small r).
The radial equation

 d2 2 d l (l  1)   1 
 2      R( r )  0
 dr r dr r2  r 4 
▪ The behavior of R(r) if r >> :

d 2 R r  1
 Rr   0 R r   e  r 2
or e  r 2
dr 2 4
▪ Thus, we write the solution for R(r) as
R  r   e  r 2 G r 
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The radial equation

 d2 2 d l (l  1)   1 
 2      R( r )  0
 dr r dr r2  r 4 
▪ With Rr   e  r 2Gr , yields the equation for G(r) as
d 2G r   2  dG r     1   1
 1     G r   0
dr 2  r  dr  r r 2 
▪ The behavior as r << is governed by the equation

d 2G r  2 dG r    1
  G r   0
dr 2
r dr r2
▪ With solutions
G r   r  or r   1
The radial equation

d 2G r   2  dG r     1   1
 1     G r   0
dr 2  r  dr  r r 2 
▪ Thus the general solution for G(r) is written as
G r   r  H r 
▪ Substituting, yields the governing equation for H(r) as

d 2 H r   2  2  dH r      1
   1  H r   0
dr 2  r  dr r
▪ Whose solution can be obtained as a series solution.
▪ Further, to have a convergent solution,  (= nr + l + 1) has to
be an integer, and the solution is known as the Laugerre
polynomials.
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The radial solution

▪ R(r) depends on n and l but not on m
R ( r )  G ( r )e  r 2
Rl ( r )  H ( r ) r l e  r 2
Rnl ( r )  L(n2ll11) ( r ) r l e  r 2
▪ The associated Laugerre polynomials
The radial solution

▪ Rnl(r) depends on n and l but not on m
3/ 2
Z
R10 (r )  2   exp( Zr / a0 )
 a0 
3/ 2
1  Z   Zr    Zr 
R21 (r )      exp  
3  2a0   
a0  2a0 
3/ 2
 Z   Zr    Zr 
R20 (r )  2   1   exp  
 2a0   2 a0   2a0 
3/ 2 2
4  Z   Zr    Zr 
R32 (r )      exp  
27 10  3a0   a0   3a0 
3/ 2
4 2 Z   Zr  Zr    Zr 
R31 (r )    1    exp  
9  3a0   6 a0  0 
a  3a0 
3/ 2
 Z   2Zr 2Z 2 r 2    Zr 
R30 (r )  2   1   2 
exp  
 3a0   3a0 27a0   3a0 
▪ For atomic units set a0 = 1
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Hydrogenic Solution
▪ The wave function solution is obtained as
 (r , ,  )  Rnl (r )Ylm ( ,  )
with,
Rnl ( r )  L(n2ll11) ( r ) r l e  r 2
▪ And the energy associated with this wave function is

Ze 2 m 1 ( Z ) 2
  E   (mc 2 )
4 0  2 E 2 2
where,
e2 1
 
4 0 c 137
is called the fine structure constant.
Energy Spectrum and Degeneracy

▪ Recall that we found for a Hydrogenic atom, the energy is
given by
2 mc ( Z )
1 2 2
En  
n2
where we introduced the principle quantum number n as
n  nr  l  1
with
l  0, 1, 2,  
  n  nr  l  1  1, 2, 
nr  k  0, 1, 
▪ Thus, the ground state, n = 1 has only one possibility
nr  0  l
▪ While, the first excited state, n = 2 has two possibilities
nr  0, l  1 and nr  1, l  0
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n=3
n=2
n=2
n=1
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Spin
Spin Operator
Spin ½ Eigenstate Representation
Alexander A. Iskandar Spin 2
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Evidence for the need of new quant. #

▪ Recall the Zeeman Effect on a orbiting electron
m
Hˆ  μˆ  B  B Lˆ  B

mBB
m BB

▪ Instead of the following Hydrogen spectrum
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▪ It was observed a Fine Structure in the Hydrogen spectrum

▪ For some other elements, it was found that there is an even
number of splitting (anomalous Zeeman Effect)
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Stern – Gerlach Experiment

▪ The prediction, already made by the ‘old’ quantum theory
that developed out of Bohr’s work, was that the spatial
components of angular momentum could only take discrete
values, so that the direction of angular momentum vector was
restricted to only number of limited possibilities.
▪ This could be tested by making use of the fact that orbiting
electron will give rise to a magnetic moment proportional to
the orbital angular momentum of the electron.
▪ So, by measuring the magnetic moment of an atom, it should
be possible to determine whether or not space quantization
existed.

▪ The expectation based
on classical physics is
that due to random
thermal effects in the
oven, the magnetic
dipole moment vectors
of the atoms will be
randomly oriented in
space, so there should be
a continuous spread in
the direction of the magnetic moments of the silver atoms as
they emerge from the oven, ranging from −|μ| to |μ|. A line
should then appear on the observation screen along the z
direction.
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▪ To explain the result of Stern-Gerlach experiment (1922, Nobel

prize in Physics 1943), Pauli (1924, Nobel in Physics 1945) , Uhlenbeck and
Goudsmit (1925) and to introduce a new physical quantity
called the spin.
▪ Spin is an intrinsic (angular momentum) properties of a
particle (an electron or atoms) that does not have a classical
analogue.
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Spin Operator
▪ Introduce the spin operator (in analogy with the angular
momentum operator) as
Sˆ , Sˆ   iSˆ
x y z cyclic
▪ With eigen-equation
Sˆ 2 s, ms   2 s ( s  1) s, ms
Sˆ z s, ms  ms s, ms with ms   s, , s
▪ From which to obtain the two-splitting, we have to choose s =

½.
▪ Further, as was done for the angular momentum operator, we
define the raising and lowering operator for the spin as
Sˆ  Sˆ  iSˆ  x y
▪ From the eigen-equation, we can find the matrix
representation of the spin operator
S  s, m Sˆ s, m  m  
z s z s s ms , ms
1 2 0   1 0  
        z
 0  1 2  2  0  1 2
▪ And from
S   s, ms Sˆ s, ms   s ( s  1)  ms (ms  1) ms ,ms 1
the matrix representation of the raising and lowering
operators are obtained as
0 1 0 0
S     and S    
 0 0   1 0 
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▪ From the raising and lowering operators, we can find the
matrix representation of the other spin operators
 0 1   0  i 
Sx     x and S y    y
2  1 0  2 2  i 0  2
▪ The matrices x, y and z are called the Pauli matrices that
satisfy the following commutation and anti-commutation
relation
 x 
,  y  2i z and cyclic permutation
 x ,  y    x y   y x  0 and also  y ,  z   0   x ,  z 
▪ Further, these Pauli matrices have the following property
1 0
 x2   y2   z2   
0 1
Representation of Spin ½ Eigenstate

▪ Using the matrix representation of the spin operators, we can
find the representation of its eigen-state.
▪ For spin ½ state, the eigen-state of Sz will be represented as a
two-component column vector called spinor.
 u    1 0  u   u 
S z          
 v  2  0  1 v  2 v
▪ Which gives
1 0
     and     
0 1
corresponding to spinor of spin up ms   12   and spin down
ms   12   respectively.
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Representation of Spin ½ Eigenstate

▪ Any arbitrary spinor can be expanded in terms of this
complete set of eigen-spinor
a  1 0
a      a     a     a     a   
a   0 1
▪ For a normalized spinor state, the following condition of the
expansion coefficients has to be satisfied
a  a  1
2 2
▪ And from the expansion postulate, the probability of the Sz

measurement on the state a yielding the eigen-spinor +
(spin up) is a  and the probability of finding it in the eigen-
2
spinor - (spin down) is a  .

2
A complete set of quantum numbers

▪ Hence the full wavefunction of an electron in the H atom is
 nlmsm (r)  Rnl (r )Ylm (q , ) s ,m

s s
▪ Where the eigenspinnor is given as

1  0
1/ 2,1/ 2    , 1/ 2,1/ 2   
0 1
▪ Note that the spin functions  do not depend on the electron
spatial coordinates r, q, j ; they represent a purely internal
degree of freedom.
▪ The complete set of quantum numbers is:
n,l,m,s,ms with s = ½ and ms = +/- ½.
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More on Matrix Representation

▪ It is not necessary to have a diagonal matrix representation of Sx.
▪ Consider the eigensystem of the following operator (the
parameter l is given to make the equation more flexibility)
S x cos   S y sin   uv    l  uv 

  2  
or,
 0 cos   i sin   u   0 e  i  u  u 
     i    l  
 cos   i sin  0  v   e 0  v  v
▪ Yielding,
e  i v  l u
e i u  l v
▪ Hence,
uv(1  l2 )  0  l  1

▪ Hence, for l = 1, then e  i v  u and, the eigenvector is
1 1
 i 
2  e 
▪ Since we can multiply a state vector by an arbitrary constant
phase, then we can write the above eigenvector as
1  e  i 2 
u   
2  ei 2 
▪ And for l = –1, the eigenvector has to be orthogonal to the
previous eigenvector, then we have
1  e  i 2 
u   
2   ei 2 
▪ Example : find the matrix representation of Sz using this
eigenvectors.
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▪ Example 1
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Spin
Intrinsic Magnetic Moment in External Magnetic Field

Addition of Angular Momentum
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Recall : Atoms in magnetic fields

▪ Classical theory: Interaction of
μ
orbiting electron with magnetic field.
▪ Orbiting electron behaves like a r
current loop:
 ev v
Loop current 
2r
Magnetic moment    current  area
 ev
  r 2
2 r
e L Lˆ
  me v r    B  μˆ    B
2me  
e
B  : Bohr magnetron
2me
Intrinsic Magnetic Moment of Spin ½

▪ Taking the analogy from angular momentum, we can define
the magnetic moment of spin ½ as
e ˆ eg ˆ
μˆ   L  μˆ S   S
2me 2me
where g = gyromagnetic ratio with a magnitude of
g = 2 (Dirac’s relativistic theory)
= 2.00231930437 (Quantum Electrodynamics)

▪ Placing this electron in an external magnetic field B  B zˆ, as
in the classical electromagnetic case, the system has an
additional energy in the form of potential energy as

U  μˆ S  B
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The complete Hamiltonian

▪ The complete Hamiltonian of H atom in magnetic field, with
spin included:
 ˆ  gSˆ )
Hˆ  Hˆ 0  B B  (L
g  2 (Dirac's relativistic theory)

g  2.00231930437 (Quantum Electrodynamics)
with g = gyromagnetic ratio
Evolution of spin state

▪ If we want to know how is the time evolution of the spin
vector, then we solve the time dependent Schrodinger
equation.

i  Hˆ 
t
where the Hamiltonian consisted of
Hˆ  Hˆ  Hˆ 0 1
2

Hˆ 0    2  V r 
2
eg ˆ
Hˆ 1  μˆ S  B   BS z
2me
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▪ If we want to know how is the time evolution of the spin
vector, then we solve the time dependent Schrodinger
equation, and focusing our attention to Ĥ1 :

i  Hˆ 1
t
 eg  1 0 
i  B 
t 4me  0  1
▪ Assume that the solution of the above has the form as
     i t
 t   e it    e          
  

▪ This substitution will give
   eg    
     B 
    4me     
▪ We will have 2 eigen values: o, with
eg
o  B
4me
▪ Assume that at t = 0 we have
a
 0     a   b 
b
▪ Then for any arbitrary time we get
 t   ae i t    bei t  
o o
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Precession of Spin
▪ Suppose at t = 0, the spin
a
 0     a   b 
b
is an eigenstate of Sx with eigen value  2
  0 1  a    a 
     
2  1 0  b  2  b 
hence,
a 1 1
 0      
b 2 1
▪ Thus, at later times,
1  e  i 0 t 
 t   ae  i o t
   be i o t
   
2  ei0t 
Precession of Spin
▪ Furthermore, we can calculate the expectation value of the
spin components
 i 0 t  0 1  1  e  i 0 t  
Sx 
 1 i 0 t
e e    
 i t   cos(20t )
e 0  2
2 2  1 0  2  
 0  i  1  e  i 0 t  
Sy  e 
 1 i 0 t
e i0t     i t   sin(20t )
 
2 2 i 0  2  e 0  2
 1 0  1  e  i 0 t 
Sz  e 
 1 i 0 t

e i0t    i t   0
 
2 2  0  1 2  e 0 
▪ Thus, the spin precesses about the direction of the external
magnetic field with frequency
eg eB
2o  B  gC  C  : cyclotron freq.
2me 2me
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Precession of Spin
▪ In general, when the spin makes an angle q with respect to
the direction of the magnetic field, then we have a precession
as depicted in the animation below

▪ In classical mechanics, angular momenta add vectorially.
  
L moon  sun  L moon earth  L earth  sun
▪ Thus, this addition carry over in quantum world?
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▪ Suppose two electron systems, each of them have spin value
ħ/2 and spin operators: Ŝ1 and Ŝ 2
▪ Each of spin operators follow the commutation relations:
Sˆ1j 
, Sˆ1k  i jkl Sˆ1l , Sˆ 2j 
, Sˆ2 k  i jkl Sˆ2l , and Sˆ , Sˆ   0
1 2
▪ Eigen vectors of Ŝ jz are:  j  and  j  , with j = 1 and 2.

▪ It means
Sˆ 2    2 s ( s  1)    2 1  1  1  3 
2
j j j 2 2 j 4 j

Sˆ jz  j   ms  j     j 
2
Sˆ j   j    ( s  ms )( s  ms  1)  j    j 
Sˆ j   j    ( s  ms )( s  ms  1)  j   0

▪ We introduce the total spin operator as
Sˆ  Sˆ  Sˆ 1 2
▪ We check its commutation relation:
Sˆ , Sˆ   Sˆ  Sˆ , Sˆ  Sˆ 
x y 1x 2x 1y 2y
 Sˆ , Sˆ  Sˆ , Sˆ  Sˆ

1x 1y 2x 1y 1x 
, Sˆ2 y  Sˆ2 x , Sˆ2 y 
 i Sˆ  Sˆ   iSˆ
1z 2z z
▪ The total spin operator still satisfy the standard commutation

relation for angular momentum.
▪ In other words, that definition for total spin operator is a right
definition.
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▪ Because the total spin operator is the sum of each spin
operator, then it representation consist of all combination of
each spinor:
1 , 1  and  2 ,  2 
▪ Thus, the possible combinations are
1  2 ; 1  2 ; 1  2 ; 1  2
Combination of states
▪ We have to prove that the above vector combinations are
eigen vector of the total spin operator:
 
Sˆ z 1  2  Sˆ1z  Sˆ2 z 1  2
  
 Sˆ1z 1  2  1 Sˆ2 z  2 
  2 1  2  1  2  2 
 1  2
  
Sˆ z 1  2  Sˆ1z 1  2  1 Sˆ2 z  2 
  2 1  2  1  2  2 
 0  Sˆ  
z 1 2
Sˆ z 1  2  1  2
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Addition of Spin
▪ There are two families for the addition of the spins:
• addition of spin resulting in singlet state:
S = 0  mS = 0
• Addition of spin resulting in triplet states:
S = 1  mS = -1, 0, 1
where,
Sˆ 2  tot   2 S S  1 tot
Sˆ   m 
z tot S tot
▪ It is clear that the eigen vectors 1  2 and 1  2  belong to

the triplet families.
▪ Then, we have to decide among 1  2 and 1  2 , which
of them is belong also to the triplet families.
Addition of Spin

Sˆ 1  2  Sˆ1  Sˆ2 1  2 
 
 Sˆ1 1  2  1 Sˆ2  2  
 1  2  1  2 
 1  2  1  2 
21  2  1  2 

2
Write
 
1
1  2  1  2 
2
Calculate:

Sˆ    Sˆ1  Sˆ2   
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Addition of Spin
▪ Define
 
1
1  2  1  2 
2
then
Sˆ    0
Sˆ    0
Sˆ    0
Addition of Spin
▪ Family of eigen vectors from the total spin operator:
 
1 2 , 1  2  1  2 , 1  2 
1
  1  2   1  2  
2
1
2
Calculate the eigen value of Ŝ 2

Sˆ 2  Sˆ  Sˆ
 
 Sˆ 1  Sˆ 2  Sˆ 1  Sˆ 2 
 Sˆ 2  Sˆ 2  2Sˆ  Sˆ
1 2 1 2
Look at
Sˆ 1 Sˆ 2  Sˆ1x Sˆ2 x  Sˆ1 y Sˆ2 y  Sˆ1z Sˆ2 z
Remember that Sˆ j   Sˆ jx  iSˆ jy with j = 1, 2
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Addition of Spin
▪ We have
     
Sˆ1 Sˆ2  Sˆ1 Sˆ2  Sˆ1x  iSˆ1 y Sˆ2 x  iSˆ2 y  Sˆ1x  iSˆ1 y Sˆ2 x  iSˆ2 y  
 2 Sˆ1x Sˆ2 x  2 Sˆ1 y Sˆ2 y
Now we can write
Sˆ 2  Sˆ 12  Sˆ 22  2Sˆ1z Sˆ2 z  Sˆ1 Sˆ2  Sˆ1 Sˆ2
Now do it on the 1
2
1  2  1  2  state
Addition of Spin
 
 Sˆ12 1  2  Sˆ12 1  2

  


 1 Sˆ22  2  1 Sˆ22  2    

 
Sˆ 2 12 1  2  1  2   12  2 Sˆ1z 1 Sˆ2 z  2  2 Sˆ1z 1 Sˆ2 z  2     

 ˆ ˆ ˆ  ˆ
 S1 1 S 2  2  S1 1 S 2  2     

 1 1 2 2 
 Sˆ  Sˆ   Sˆ  Sˆ 
1 1 2 2     

 1
2
 2  34  34  12  11  2   34  34  12  11  2 
0
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Addition of Spin
▪ Please do it also for
Sˆ 2    ...
1 2
Sˆ 2 1
2
1  2  1  2   ...  
Answer : 2 2
Sˆ 2 1  2  ...
Summary: eigen vectors for a system of combination of 2 spins

consist of 2 families with definition:  S ,mS
Sˆ 2  S ,mS   2 S S  1 S ,mS
Sˆ z  S ,mS  mS  S ,mS
with S = 0 or 1 and
mS   S ,..., S
12
22/11/2017
Realistic Atom
Addition of Orbital and Spin Angular Momentum

Spin-Orbit Coupling
Realistic Atom 2
1
22/11/2017
Addition of Spin ½ and Orbital Ang. Mom.

▪ The eigen value equation for orbital and spin angular
momentum:
Lˆ2Y   2   1Y
 ,m  ,m
Lˆ zY ,m  mY ,m
Sˆ 2     2 34  
Sˆ   m 
z  s 
▪ The orbital and spin angular momentum operators are

independent set of operators, they are part of the CCS, hence
Lˆ , Sˆ   0
Realistic Atom 3

▪ Define, the total angular momentum operator as
Jˆ  Lˆ  Sˆ
▪ It can be easily prove that the above definition of total
angular momentum still satisfy the standard commutation
relation of angular momentum.
▪ How to find the eigenvector of this total angular momentum
operator?
▪ Make an ansatz for the eigenvector as follows
 j ,m   Y ,m    Y ,m 1  
1
2
▪ We can readily show that this is an eigenvector of Ĵ z with

eigenvalue m  12 
Jˆ  1   m   1
1
z j ,m  2 2 j ,m  2
Realistic Atom 4
2
22/11/2017

▪ What is the length of this eigenvector?
Jˆ 2 j ,m  1  ?
2
▪ Recall that
Jˆ 2  Lˆ2  Sˆ 2  2 Lˆ  Sˆ
 Lˆ2  Sˆ 2  2 Lˆ z Sˆ z  Lˆ Sˆ  Lˆ Sˆ
And
LˆY ,m     m   m  1Y,m1

LˆY ,m     m   m  1Y,m1
Sˆ    0 Sˆ     
Sˆ      Sˆ   0
 
Realistic Atom 5

▪ Thus, applying
 
Jˆ 2 j ,m  1  Lˆ2  Sˆ 2  2 Lˆ z Sˆ z  Lˆ Sˆ  Lˆ Sˆ  j ,m  1
2 2
    1Y ,m    34 Y ,m    mY ,m  

2
  m   m  1Y,m1  

  2   1Y ,m 1    34 Y ,m 1  
 2m  1 12 Y ,m 1      m   m  1Y ,m   
▪ But, on the other hand, we want

Jˆ 2 1   j ( j  1)
2
j ,m  2 j , m  12
  2 j ( j  1)Y ,m    Y ,m 1   
Realistic Atom 6
3
22/11/2017

▪ Comparing, we obtain
j ( j  1)Y ,m    Y ,m 1   
 
  (  1)  34  m   (  m)(  m  1) Y ,m  
 
  (  m)(  m  1)   (  1)  34  m  1 Y ,m 1  
or,
j  j  1     1  34  m     m   m  1
j  j  1     m   m  1     1  34  m  1
Realistic Atom 7

▪ The above two equations can be combined to yield
  m   m  1
  j  j  1    1  34  m  j  j  1    1  34  m  1
▪ This equation has two solutions

   1
j  j  1    1  34  
 
▪ Which yield two possibilities for the value of j :
  1
j   12
  2
Realistic Atom 8
4
22/11/2017

▪ And after a lengthy algebra, we can also find the Clebsch-
Gordon coefficient  and  in the eigenvector
 j ,m  1  Y ,m    Y ,m 1  
2
▪ For j    1
2
  m 1 m
 
2  1 2  1
▪ For j    12
m   m 1
  
2  1 2  1
Realistic Atom 9

▪ Thus, the eigenvector of the total angular momentum
operator can be written compactly as
j , m j   , m; 12   , m  1; 12
with
  1
j   12  j  mj  j
  2
Realistic Atom 10
5
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Recall : Hydrogenic Solution

▪ The wave function solution is obtained as
 (r , ,  )  Rnl (r )Ylm ( ,  )
with,
Rnl (  )  L(n2ll11) (  )  l e   2
▪ And the energy associated with this wave function is

Ze 2 m 1 ( Z ) 2
n  E   (mc 2 )
4 0  2 E 2 n2
where,
e2 1
 
4 0 c 137
is called the fine structure constant.
Realistic Atom 11
Recall : En. Spectrum and Degeneracy

▪ Recall that we found for a Hydrogenic atom, the energy is
given by
2 mc ( Z )
1 2 2
En  
n2
where we introduced the principle quantum number n as
n  nr  l  1
with
l  0, 1, 2,  
  n  nr  l  1  1, 2, 
nr  0, 1,  
▪ Thus, the ground state, n = 1 has only one possibility
nr  0  l
▪ While, the first excited state, n = 2 has two possibilities
nr  0, l  1 and nr  1, l  0
Realistic Atom 12
6
22/11/2017
Recall : Spectrum of Hydrogen
Realistic Atom 13
Spin-Orbit Coupling
▪ The electron “sees” the proton revolves around it, hence the
proton creates magnetic field that is experienced by the
electron
   
vE v  rÊ
B 2  2
c c
▪ This magnetic field interacts with the intrinsic magnetic
moment of the electron
eg ˆ
μˆ S   S
2me
i.e.

 μˆ S  B  Sˆ  Lˆ
Realistic Atom 14
7
22/11/2017
Spin-Orbit Coupling
▪ Recall, from the definition of total angular momentum,
ˆ  Sˆ
Jˆ  L
we have
Jˆ  Jˆ  Jˆ 2  Lˆ2  Sˆ 2  2Sˆ  Lˆ
or
Sˆ  Lˆ  1
2
Jˆ 2
 Lˆ2  Sˆ 2 
▪ Thus, using this relation in the Spin-Orbit Coupling
Hamiltonian, we can apply it to the eigenstate of the total
angular momentum,
  12
j , m j   , m; 12   , m  1; 12 j 1  j  mj  j
  2
Realistic Atom 15
Spin-Orbit Coupling
▪ Applying Sˆ  Lˆ  1
2
Jˆ 2

 Lˆ2  Sˆ 2 on the   2 , m  2 we obtain
1 1
Sˆ  Lˆ   12 , m  12  1
2
Jˆ 2

 Lˆ2  Sˆ 2   12 , m  12
 12  2  j ( j  1)  (  1)  12 ( 12  1)   12 , m  12
 12  2 (  12 )(  12 )  (  1)  34    12 , m  12
  12  2 (  1)   12 , m  12
and, on   12 , m  12 yields
Sˆ  Lˆ   12 , m  12  1
2
Jˆ 2

 Lˆ2  Sˆ 2   12 , m  12
 12  2 (  12 )(  32 )  (  1)  34    12 , m  12
 12  2    12 , m  12
Realistic Atom 16
8
22/11/2017
Spectrum of Hydrogen
Realistic Atom 17
Spin-Orbit Coupling
Realistic Atom 18
9
22/11/2017
Realistic Atom
Anomalous Zeeman Effect
Realistic Atom 2
1
22/11/2017

▪ For some elements, it was found that in an external magnetic
field there are even number of spectral lines splitting
Total Angular Momentum in External B

▪ Interaction between external magnetic field and electrons in
the atom can be expressed by the following Hamiltonian:
Hˆ 1  μˆ tot  B
where
 e ˆ   eg ˆ 
μˆ tot    L     S 
 2me   2me 

2me

e ˆ
L  2Sˆ  g=2
▪ For B  Bzˆ , we have

Hˆ 1  
eB ˆ
2me

Lz  2 Sˆ z 

eB ˆ
2me

J z  Sˆ z 
Realistic Atom 4
2
22/11/2017
Realistic Atom 5

▪ Note that the eigenvalue of Jz, Lz and Sz are all conserved
quantities.
Realistic Atom 6
3
22/11/2017

▪ Since Ŝ and L̂ precess along Ĵ , and that they have a fixed
length, then to calculate the z-projection of the spin we
observe that
 
Sˆ  Jˆ
Sˆ  Jˆ 2
Jˆ
 
Sˆ  Jˆ
Sˆ  Jˆ 2
Jˆ
Realistic Atom 7

▪ Note that
Jˆ  Lˆ  Sˆ Lˆ  Jˆ  Sˆ
 
Lˆ 2  Jˆ  Sˆ  Jˆ  Sˆ 
 Jˆ 2  Sˆ 2  2Sˆ  Jˆ
▪ Then
1

Sˆ  Jˆ  Jˆ 2  Sˆ 2  Lˆ 2
2

▪ So that
 
Sˆ  Jˆ
Sˆ  Jˆ 2  Jˆ

Jˆ 2  Sˆ 2  Lˆ2 
Jˆ 2Jˆ 2
▪ Hence,
j  j  1  34    1
Sˆ z  Jˆ z
2 j  j  1
Realistic Atom 8
4
22/11/2017

▪ In the external magnetic field, the energy correction term
yields
 j ,m 1/ 2 Hˆ 1  j ,m 1/ 2 
eB
2me
 
 j ,m 1/ 2 Lˆ z  2Sˆ z  j ,m 1/ 2

eB
2me
 
 j ,m 1/ 2 Jˆ z  Sˆ z  j ,m 1/ 2
eB
  l ,m 1/ 2 Jˆ z  l ,m 1/ 2
2me
eB
  j ,m 1/ 2 Sˆ z  j ,m 1/ 2
2me
eB eB
 mj   j ,m 1/ 2 Sˆ z  j ,m 1/ 2
2me 2me
Realistic Atom 9

▪ Recall, that the expectation value of the z-projection of the
spin can be calculated as
j  j  1  34    1
Sˆ z  Jˆ z
2 j  j  1
▪ Thus, the complete energy correction term:
e 2 B  j  j  1  34    1
EB  Hˆ 1  m j 1  
2me  2 j  j  1 
with  j  m j  j and
l  1
j   12
l  2
Realistic Atom 10
5
22/11/2017

▪ For j    12
e 2 B  1 
EB  m j 1 
2me  2  1
and for j    12
e 2 B  1 
EB  m j 1 
2me  2  1
Realistic Atom 11

 1  j    12  3
2
Realistic Atom 12
6
22/11/2017

▪ Example of the Sodium Doublet
Realistic Atom 13

▪ Example of the Sodium Doublet
Realistic Atom 14
7
22/11/2017
Time Independent Perturbation Theory
Non-degenerate Case
1
22/11/2017
Un-perturbed System
▪ Consider, an un-perturbed quantum system given by the
following eigenvalue problem
Hˆ   E ( 0 ) 
0 n n n
▪ Where, the energy eigenstate are non-degenerate

orthonormal set of eigenvectors, i.e.
 n  m   nm
Time Independent Perturbation Theory 3
Perturbed Hamiltonian System

▪ Consider a time-independent small perturbation to the
original Hamiltonian, i.e.
Hˆ  Hˆ 0  lHˆ 1
where, l is a small perturbation parameter.
▪ We assume that this complete Hamiltonian has the following
eigenvalue problem
 
Hˆ  n  Hˆ 0  lHˆ 1  n  En  n
▪ Since, l is a small parameter, we will expand the eigen-
solution as a power series of this small parameter.
2
22/11/2017
Perturbed Eigenstates
▪ Let us write the eigenvector of the total Hamiltonian Ĥ as
 
 n  N (l )  n   Cnk (l )  k 
 k n 
▪ We require that as l  0,  n   n , then
N (l  0)  1
Cnk (l  0)  0
▪ More generally, we have
Cnk (l )  lCnk(1)  l2Cnk( 2 )  
En  En( 0 )  lEn(1)  l2 En( 2 )  
▪ We use these in the total Hamiltonian eigenvalue problem
and solve for each order of the perturbing parameter l.
Perturbed Eigenstates
▪ Hence, the total Hamiltonian eigenvalue problem yields
Hˆ 0  
 lHˆ 1   n  l  Cnk(1)  k  l2  Cnk( 2 )  k  

 k n k n 
 
 
 En( 0 )  lEn(1)  lEn( 2 )     n  l  Cnk(1)  k  l2  Cnk( 2 )  k  
 k n k n 
▪ Note, that the normalization factor N (l ) does not appear in
the above, because it will be determined later.
▪ The above equation is solved order-by-order of the small
parameter l.
3
22/11/2017
The First Order Correction

▪ Taking the first order terms with respect to l from both sides
we have
Hˆ  C (1)   Hˆ   E ( 0 )  C (1)   E (1) 
0 nk k 1 n n nk k n n
k n k n
▪ Recall that Hˆ 0  n  En( 0 )  n , then

En(1)  n  Hˆ 1  n   Ek( 0 )  En( 0 ) Cnk(1)  k 
k n
▪ Take a scalar product with  n , yields

En(1)   n Hˆ 1  n
i.e. the first order correction is none-other than the
expectation value of the perturbing Hamiltonian.
The First Order Correction

▪ Taking a scalar product with  m , yields
 m Hˆ 1  n  Em( 0)  En( 0)  Cnm
(1)
0
or,
 m Hˆ 1  n
(1)
Cnm 
En( 0 )  Em( 0 )
▪ Thus, the eigenstate solution up to the first order is given by
 Hˆ 
 n   n  l  (k0) 1 ( 0n)  k
k  n En  Ek
with energy
En  En( 0 )  l  n Hˆ 1  n
4
22/11/2017
Example
▪ Consider the following total Hamiltonian
1  l 0 0 
 
Ĥ   0 1  l 1  2l 
 0 1  2l 1  l 

with l is a small perturbation coefficient.
▪ Find the corrections for energy and eigenstate for the first
order of l.

Quantum Physics Emergence

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Quantum Physics Emergence

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22/08/2016

FI 3103 Quantum Physics

The Emergence of Quantum Physics

Black Body Radiation

Alexander A. Iskandar Emergence of Quantum Physics 4

(Modern) Physics in early 20th century

 Newton promoted the

(Modern) Physics in early 20th century

(Modern) Physics in early 20th century

Alexander A. Iskandar Emergence of Quantum Physics 7

(Modern) Physics in early 20th century

Alexander A. Iskandar Emergence of Quantum Physics 8

 Blackbodies are interesting because their

Alexander A. Iskandar Emergence of Quantum Physics 10

Wien’s Displacement Law

 Wien’s displacement law: The maximum of the spectrum shifts

Jozef Stefan Ludwig Boltzman

 This is known as the Stefan-Boltzmann law, with the constant

Planck’s Radiation Law

 Planck made two modifications to the classical theory:

Alexander A. Iskandar Emergence of Quantum Physics 16

where f is the work function of the metal (potential energy to

Alexander A. Iskandar Emergence of Quantum Physics 18

Alexander A. Iskandar Emergence of Quantum Physics 19

Alexander A. Iskandar Emergence of Quantum Physics 20

Alexander A. Iskandar Emergence of Quantum Physics 21

Alexander A. Iskandar Emergence of Quantum Physics 22

Alexander A. Iskandar Emergence of Quantum Physics 24

Alexander A. Iskandar Emergence of Quantum Physics 25

Alexander A. Iskandar Emergence of Quantum Physics 26

 Since the speed of light is vacuum is always c, then the

Alexander A. Iskandar Emergence of Quantum Physics 27

hi  me c 2  h f  Pe2 c 2  me2 c 4 2

Alexander A. Iskandar Emergence of Quantum Physics 28

 Compton won the 1927 Nobel Prize in Physics.

Alexander A. Iskandar Emergence of Quantum Physics 29

FI 3103 Quantum Physics

The Emergence of Quantum Physics

Wave Properties of Particle

Alexander A. Iskandar Emergence of Quantum Physics 2

Wave Properties of Particle

Proof of Wave Properties of Particle

C.J. Davisson – L. Germer C.J. Davisson G.P. Thomson

Bragg’s X-ray Diffraction

Alexander A. Iskandar Emergence of Quantum Physics 5

de Broglie relationship p  mv  2mE

C.J. Davisson – L. Germer

Alexander A. Iskandar Emergence of Quantum Physics 6

Alexander A. Iskandar Emergence of Quantum Physics 7

Alexander A. Iskandar Emergence of Quantum Physics 8

Alexander A. Iskandar Emergence of Quantum Physics 9

Louis de Broglie (15 August 1892 – 19 March 1987)

Alexander A. Iskandar Emergence of Quantum Physics 10

Limit of Wave Properties of Particle

 At macroscopic scale, we will not be able to see the wave

Alexander A. Iskandar Emergence of Quantum Physics 11

Evolution of the Atomic Model

Alexander A. Iskandar Emergence of Quantum Physics 12

Thomson Cathode Ray Experiment

Alexander A. Iskandar Emergence of Quantum Physics 13

Thomson Cathode Ray Experiment

Alexander A. Iskandar Emergence of Quantum Physics 14

Thomson Cathode Ray Experiment