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The University of Queensland

Department of Physics
2004

Lecture notes of the undergraduate course


PHYS2041
QUANTUM PHYSICS

Lecturer: Dr. Zbigniew Ficek


Physics Annexe(6): Rm. 436
Ph: 3365 2331
email: ficek@physics.uq.edu.au

Contact Hours:
1. Tuesday: 11am , Rm. 7-302 (Lectures)
2. Friday: 11am , Rm. 7-302 (Tutorials)

Consultation Hours: Wednesday , 2pm − 4pm


Contents
General Bibliography 5

Assumed Background 6

Introduction 9

1 Radiation (Light) is a Wave 10


1.1 Wave equation . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.2 Energy of the EM wave . . . . . . . . . . . . . . . . . . . . . . 12

2 Difficulties of the Wave Theory of Radiation 17


2.1 Discovery of the electron . . . . . . . . . . . . . . . . . . . . . 17
2.2 Discovery of X-rays . . . . . . . . . . . . . . . . . . . . . . . . 18
2.3 Photoelectric effect . . . . . . . . . . . . . . . . . . . . . . . . 20
2.4 Compton scattering . . . . . . . . . . . . . . . . . . . . . . . . 22
2.5 Discrete atomic spectra . . . . . . . . . . . . . . . . . . . . . . 23

3 Black-Body Radiation 25
3.1 Number of radiation modes . . . . . . . . . . . . . . . . . . . 25
3.2 Equipartition theorem . . . . . . . . . . . . . . . . . . . . . . 28

4 Planck’s Quantum Hypothesis 31


4.1 Boltzmann distribution function . . . . . . . . . . . . . . . . . 31
4.2 Planck’s formula for I(λ) . . . . . . . . . . . . . . . . . . . . . 32
4.3 Photoelectric effect . . . . . . . . . . . . . . . . . . . . . . . . 37
4.4 Compton scattering . . . . . . . . . . . . . . . . . . . . . . . . 37

5 The Bohr Model 41


5.1 The hydrogen atom . . . . . . . . . . . . . . . . . . . . . . . . 41
5.2 X-rays characteristic spectra . . . . . . . . . . . . . . . . . . . 44
5.3 Difficulties of the Bohr model . . . . . . . . . . . . . . . . . . 45

6 Duality of Light and Matter 47


6.1 Matter waves . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
6.2 Matter wave interpretation of the Bohr’s model . . . . . . . . 50
6.3 Wave function . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

2
6.4 Physical meaning of the wave function . . . . . . . . . . . . . 53
6.5 Phase and group velocities . . . . . . . . . . . . . . . . . . . . 55
6.6 The Heisenberg uncertainty principle . . . . . . . . . . . . . . 59
6.7 The superposition principle . . . . . . . . . . . . . . . . . . . 61
6.8 Wave packets . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

7 Schrödinger Equation 66
7.1 Schrödinger equation of a free particle . . . . . . . . . . . . . 66
7.2 Operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
7.3 Schrödinger equation of a particle in an external potential . . 70
7.4 Equation of continuity . . . . . . . . . . . . . . . . . . . . . . 73

8 Applications of the Schrödinger Equation: Potential (Quan-


tum) Wells 79
8.1 Infinite potential quantum well . . . . . . . . . . . . . . . . . 81
8.2 Finite square-well potential . . . . . . . . . . . . . . . . . . . 88
8.3 Quantum tunneling . . . . . . . . . . . . . . . . . . . . . . . . 99

9 Multi-Dimensional Quantum Wells:


Quantum Wires and Quantum Dots 104
9.1 General solution of the three-dimensional
Schrödinger equation . . . . . . . . . . . . . . . . . . . . . . . 105
9.2 Quantum wire and quantum dot . . . . . . . . . . . . . . . . . 107

10 Linear Operators and Their Algebra 110


10.1 Algebra of operators . . . . . . . . . . . . . . . . . . . . . . . 110
10.2 Hermitian operators . . . . . . . . . . . . . . . . . . . . . . . 113
10.2.1 Properties of Hermitian operators . . . . . . . . . . . . 113
10.2.2 Examples of Hermitian operators . . . . . . . . . . . . 114
10.3 Scalar product and orthogonality of two eigenfunctions . . . . 117
10.4 Expectation value of an operator . . . . . . . . . . . . . . . . 119
10.5 The Heisenberg uncertainty principle revisited . . . . . . . . . 124
10.6 Expansion of wave functions in the basis of orthonormal func-
tions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127

11 Dirac Notation 130


11.1 Projection operator . . . . . . . . . . . . . . . . . . . . . . . . 132

3
11.2 Representations of linear operators . . . . . . . . . . . . . . . 133

12 Matrix Representation of Linear Operators 135


12.1 Matrix representation of operators . . . . . . . . . . . . . . . . 135
12.2 Matrix representation of eigenvalue equations . . . . . . . . . 137

13 First-Order Time-Independent Perturbation Theory 142

14 Quantum Harmonic Oscillator 146


14.1 Algebraic operator technique . . . . . . . . . . . . . . . . . . . 147
14.2 Special functions method . . . . . . . . . . . . . . . . . . . . . 155

15 Angular Momentum and Hydrogen Atom 160


15.1 Angular part of the wave function: Angular momentum . . . . 162
15.2 Radial part of the wave function . . . . . . . . . . . . . . . . . 168

16 Systems of Identical Particles 174


16.1 Symmetrical and antisymmetrical functions . . . . . . . . . . 175
16.2 Pauli principle . . . . . . . . . . . . . . . . . . . . . . . . . . . 179

Final Remark 181

Appendix A: Derivation of the Boltzmann distribution func-


tion Pn 183

Appendix B: Useful mathematical formulae 185

Appendix C: Physical Constants and Conversion Factors 187

4
General Bibliography

• E. Merzbacher, Quantum Mechanics, (Wiley, New York, 1998).


This is an excellent book on quantum physics, and the course is aimed
at this level of treatment.

• R.A. Serway, C.J. Moses, and C.A. Moyer, Modern Physics, (Saunders,
New York, 1989).
This is an excellent introductory text on quantum physics.

• K. Krane, Modern Physics, (Wiley, New York, 1996).


A good introductory text on quantum physics.

• R. Eisberg and R. Resnick, Quantum Physics of Atoms. Molecules,


Solids, Nuclei, and Particles, (Wiley, New York, 1985).
A good introductory text on quantum physics with applications to
atomic, molecular, solid state, and nuclear physics.

There are many excellent books on quantum physics, a few of which are:

• L. Schiff, Quantum Mechanics, (McGraw-Hill, New York, 1968).

• A. Messiah, Quantum Mechanics, (North-Holland, Amsterdam, 1962).

• A.S. Davydov, Quantum Mechanics, (Pergamon Press, New York, 1965).

• C. Cohen-Tannoudji, B. Diu, and F. Laloe, Quantum Mechanics, (Wi-


ley, New York, 1977), Vols. I and II.

• J.J. Sakurai, Modern Quantum Mechanics, (Addison-Wesley, 1994).

5
Assumed Background

Necessary prerequisites for undertaking this course include:

• Any standard introductory calculus-based course covering mechanics,


electromagnetism, thermal physics and optics. In particular, PHYS1002
course on special relativity and modern physics.

• Mathematical Level: Recommended background is MATH2000. An al-


ternative recommended background is MATH2400. Calculus are used
extensively, and students should have some familiarity with vector alge-
bra, vector calculus, series and limits, complex numbers, partial differ-
entiation, multiple integrals, first- and second-order differential equa-
tions, Fourier series, matrix algebra, diagonalization of matrices, eigen-
vectors and eigenvalues, coordinate transformations, special functions
(Hermite and Legendre polynomials).

6
”Quantum mechanics is very puzzling.
A particle can be delocalized,
it can be simultaneously in several energy states
and it can even have several different identities at once.”
S. Haroche

7
Introduction
Quantum Physics, also known as quantum mechanics or quantum wave
mechanics − born in the late 1800’s − is a study of the submicroscopic
world of atoms, the particles that compose them, and the particles that
compose those particles. In 1800’s physicists believed that radiation is a
wave phenomenon, the matter is continuous, they believed in the existence
of ether and they had no ideas of what charge was.
A series of experiments performed in late 1800’s has led to the formulation
of Quantum Physics:
• Discovery of the electron
• Discovery of X-rays
• Photoelectric effect
• Observation of discrete atomic spectra
The PHYS2041 lectures cover the background theory of various effects
discussed from first principles, and as clearly as possible, to introduce stu-
dents to the main ideas of quantum physics and to teach the basic math-
ematical methods and techniques used in the fields of advanced quantum
physics, atomic physics, quantum chemistry, and theoretical mathematics.
Some of the key problems of quantum physics are also described, concentrat-
ing on the background derivation, techniques, results and interpretations.
Due to the limited number of the contact hours, no attempt has been made
at a complete exploration of all the predictions of quantum physics, but it
is hoped that the predictions and problems explored here will provide a use-
ful starting point for those interested in learning more. The intention is to
explore problems which have been the most influential on the development
of quantum physics and formulation of what we now call modern quantum
physics. Many of the predictions of quantum physics appear to be contrary
to our intuitive perceptions, and the goal to which this lecture notes aspires is
compact logical exposition and interpretation of these fundamental and un-
usual predictions of quantum physics. Moreover, this lecture notes contains
numerous detailed derivations, proofs, worked examples and a wide range
of exercises from simple confidence-builders to fairly challenging problems,
hard to find in textbooks on quantum physics.

9
1 Radiation (Light) is a Wave
We know from classical optics that light (optical radiation) can exhibit po-
larization, interference and diffraction phenomena, which are characteristic
of waves, and some sort of wave theory is required for their explanation.
We begin our journey through quantum physics with a discussion of clas-
sical description of the radiative field. We first briefly outline the electro-
magnetic theory of radiation, and describe how the electromagnetic (EM)
radiation may be understood as a wave which can be represented by a set of
harmonic oscillators. This is followed by an description of the Hamiltonian
of the EM field, which determines the energy of the EM wave. In particu-
lar, we will be interested in how the energy of the EM wave depends on the
parameters characteristic of the wave: amplitude and frequency.

1.1 Wave equation


~ and mag-
We start the lectures by considering the time-varying electric (E)
~ fields that satisfy the Maxwell’s equations
netic (B)

~ = ρ/ε0 ,
∇·E (1)
~ = 0,
∇·B (2)
~ = −∂B
∇×E ~ , (3)
∂t
~ = µ0 J~ + 1 ∂ E
∇×B ~ , (4)
c2 ∂t
where the parameters ε0 and µ0 are constants that determine the property of
the vacuum and are called the electric permittivity and magnetic permeabil-
ity, respectively. The parameter c is equal to the speed of light in vacuum,
c = 3 × 108 [ms−1 ].
The symbol ∇ is called ”nabla” or ”del”. It is a vector and in the Carte-
sian coordinates has the form
∂ ∂ ∂
∇ = ~i + ~j + ~k , (5)
∂x ∂y ∂z

where ~i, ~j and ~k are the unit vectors in the x, y and z directions, respectively.

10
It would be more correctly to say that nabla behaves in some ways like a
vector. Nabla is incomplete as it stands, it needs something to operate on.
The result of the operation is a vector. The dot (·) and the cross (×) symbols
appearing in the Maxwell’s equations are the standard scalar and vector
products between two vectors.
In the absence of currents and charges, J~ = 0, ρ = 0, and then the above
Maxwell’s equations describe a free EM field, i.e. an EM field in vacuum.
We can reduce the Maxwell’s equations for the EM field in vacuum into
two differential equations for E~ or B~ alone. To show this, we apply ∇× to
both sides of Eq. (3), and then using Eq. (4), we find
2
∇ × (∇ × E) ~ =−1 ∂ E
~ = − ∂ (∇ × B) ~ . (6)
∂t c2 ∂t2
Since
~ = −∇2 E
∇ × (∇ × E) ~ + ∇(∇ · E)
~ , (7)
~ = 0 in the vacuum, we obtain
and ∇ · E

~− 1 ∂2 ~
∇2 E E=0, (8)
c2 ∂t2
where the operator ∇2 = ∇ · ∇ is called Laplacian and is a scalar.
Equation (8) is a very familiar differential equation in physics, called the
Helmholtz wave equation for the electric field. It is in the standard form of a
three-dimensional vector wave equation.
Similarly, we can derive a wave equation for the magnetic field as

~− 1 ∂2 ~
∇2 B B=0. (9)
c2 ∂t2
General solution of the wave equations (8) and (9) is given in a form of
plane waves

~ = ~ k e−i(ωk t−~k·~r) ,
X
U U (10)
k

where U~ ≡ (E,
~ B),
~ ωk is the frequency of the kth wave, and U
~ k is the ampli-
~ wave propagating in the ~k direction.
~ or B
tude of the E

11
The vector ~k is called the wave vector and describes the direction of
propagation of the wave with respect to an observation point ~r. From the
requirement that Eq. (10) is a solution of the wave equation (8), we find that
|~k| = ωk /c = 2π/λk , where λk is the wavelength of the kth wave.
The solution (10) shows that the electric and magnetic fields propagate
in vacuum as plane (electromagnetic) waves. Properties of these waves are
determined from the Maxwell’s equations.
The divergence Maxwell’s equations (1) and (2) demand that for all ~k:

~k · E
~k = 0 and ~k · B
~k = 0 . (11)

This means that E ~ and B~ are both perpendicular to the direction of propa-
gation ~k. Such a wave is called a transverse wave.
The Maxwell’s equations (3) and (4) provide a further restriction on the fields
that

~ k = 1 ~κ × E
B ~k , (12)
c

where ~κ = ~k/|~k| is the unit vector in the ~k direction.


Equation (12) shows that the electric E ~ and magnetic B
~ fields of an EM
wave propagating in vacuum are mutually orthogonal.

In summary: The electromagnetic field propagates in vacuum in a form


of electromagnetic transverse plane waves.

1.2 Energy of the EM wave


Consider an EM wave of the wave vector ~k confined in a space of volume V .
We will find the energy carried by the EM wave and will determine how the
energy depends on the parameters characteristic of the wave (amplitude and
frequency). For simplicity, we will limit the calculations of the energy of the
EM wave to one dimension only, i.e. we will assume that the wave is confined
in a length L and ~k · ~r = kz.
Take a plane wave propagating in the z direction and linearly polarized
in the x direction. The wave is determined by the electric field
~ (z, t) = ~iEx (z, t) = ~iq (t) sin(kz) ,
E (13)

12
where q (t) is the amplitude of the electric field.
The energy of the EM field is given by the Hamiltonian
( )
1 L
~ + 1 |B|
Z
H= dz ε0 |E| ~ 2 2
, (14)
2 0 µ0
~ 2 |/2 is the energy density of the electric field, and |B|
where ε0 |E ~ 2 /(2µ0 ) is
the energy density of the magnetic field.
In order to determine the energy of the EM field, we need the magnetic
~ Since we know the electric field, we can find the magnetic field from
field B.
the Maxwell’s equation (4). For the EM wave, the magnetic vector B ~ is
perpendicular to E ~ and oriented along the y-axis. Hence, the magnitude of
the magnetic field can be found from the following equation

~ = ~i 1 q̇ (t) sin(kz) .
∇×B (15)
c2
Since Bx = Bz = 0 and By 6= 0, and obtain
∂By ~ ∂By ~ 1
−~i +k = i 2 q̇ (t) sin(kz) . (16)
∂z ∂x c
The coefficients on both sides of Eq. (16) at the same unit vectors should be
equal. Hence, we find that
∂By ∂By 1
=0 and = − 2 q̇ (t) sin(kz) . (17)
∂x ∂z c
Then, integrating ∂By /∂z over z, we find
1 1
Z
By (z, t) = − q̇ (t) dz sin(kz) = q̇ (t) cos(kz) . (18)
c2 kc2
Thus, the energy of the EM field, given by the Hamiltonian (14), is of the
form
( )
1Z L 1
H= dz ε0 q 2 (t) sin2 (kz) + 2 4 (q̇ (t))2 cos2 (kz) . (19)
2 0 k c µ0
Since
L L 1
Z Z
2
dz sin (kz) = dz cos2 (kz) = L , (20)
0 0 2

13
and µ0 = 1/c2 ε0 , the energy H reduces to
1 1 ε0
H = ε0 Lq 2 (t) + 2
L (q̇ (t))2 . (21)
4 4ω
This is the familiar Hamiltonian of a harmonic oscillator. We know from the
classical mechanics that the energy of a harmonic oscillator is given by a sum
of the kinetic and potential energies as
1 1
Hosc = EK + Ep = m (ẋ)2 + mω 2 x2
2 2
1  2 
= p + m 2 ω 2 x2 , (22)
2m
where p = mẋ is the momentum of the oscillating mass m.

Thus, the variables q(t) and q̇(t) can be related to the position and mo-
mentum of the harmonic oscillator.

An important conclusion we can make from Eq. (21) that the energy of
the EM wave is proportional to the square of its amplitude, q (t).

In summary of this lecture: We have learnt that

1. The EM field propagates in vacuum as transverse plane waves, which


can be represented by a set of harmonic oscillators. Thus, according to
the Maxwell’s EM theory, the radiation (light) is a wave.

2. The energy (intensity) of the EM field is proportional to the square of


the amplitude of the oscillation.

14
Exercise:

Show that the single mode electric field


~ =E
E ~ 0 sin (kx x) sin (ky y) sin (kz z) sin (ωt + φ) (23)
 1
is a solution of the wave equation (8) if k = ω/c, where k = kx2 + ky2 + kz2 2

is the magnitude of the wave vector.

Solution:

Using Eq. (23), we find


~
∂2E ~ ,
= −ω 2 E (24)
∂t 2

and
~
∂2E ~
∂2E ~
∂2E
~ ,
= −kx2 E ~ ,
= −ky2 E ~ .
= −kz2 E (25)
∂x 2 ∂y 2 ∂z 2

Hence, substituting Eqs. (24) and (25) into the wave equation

∂2 ∂2 ∂2 ~ 1 ∂2E~
!
+ + E − =0, (26)
∂x2 ∂y 2 ∂z 2 c2 ∂t2
we obtain
2
~+ω E
 
− kx2 + ky2 + kz2 E ~ =0, (27)
c2
or
ω2 ~
" #
 
kx2 + ky2 + kz2 − 2 E =0. (28)
c

Since E~ 6= 0 and k 2 + k 2 + k 2 = k 2 , we find that the lhs of Eq. (28) is equal


x y z
to zero when
ω2 ω
k2 = , i.e. when k= . (29)
c2 c

15
Hence, the single mode electric field (23) is a solution of the wave equation
if k = ω/c.

Exercise at home:

Using Eq. (12), show that

~ k = −c~κ × B
E ~k ,

which is the same relation one could obtain from the Maxwell equation (4).
~ × (B
(Hint: Use the vector identity A ~ × C)
~ = B(~ A
~ · C)
~ − C(
~ A~ · B).
~ )

16
2 Difficulties of the Wave Theory of Radia-
tion
We have already learnt that light is an electromagnetic wave. The typical
signatures of the wave character of light are the polarization, interference
and diffraction phenomena. However, a series of experiments performed in
late nineteenth centenary showed that the wave model predicted from the
Maxwell’s equations is not the correct description of the properties of light. In
this lecture, we will discuss some of the experiments which provided evidence
that light, which we have treated as a wave phenomenon, has properties
that we normally associate with particles. In particular, these experiments
indicated that the energy of light is not proportional to the amplitude of the
oscillation, it is rather proportional to the frequency of the oscillation.

2.1 Discovery of the electron


Thomson in his famous e/m experiment, performed in 1896, found that the
ratio e/m

1. Didn’t depend on the cathode material.

2. Didn’t depend on the residual gas in the tube.

3. Didn’t depend on anything else about the experiment.

This independence showed that the particles in the cathode beam are a
common element of all materials.
Millikan in the oil-drop experiment measured electric charge of individual
oil drops. He made an important observation that every drop had a charge
equal to some small integer multiple of a basic charge e (q = ne), where
e = 1.602177 × 10−19 [C].
Thus, they concluded that matter is not continuous, is composed of dis-
crete particles (corpuscular theory of matter).

17
2.2 Discovery of X-rays
Röntgen, in 1895, was interested in the study of the passage of a cathode
beam through an aluminium-foil window. He noticed that a light sensitive
screen glowed brightly for no apparent reason. He called it X-rays.
In 1906, Barkla observed a partial polarization of X-rays, which indicated
that they are transverse waves.

The X-rays are invisible, and then an obvious question arises: What are
the wavelengths of X-rays?

To answer this question let us think how we could measure the wavelength
of the X-rays. One possibility, in principle at least, would be to perform
Young’s double slit experiment.
However, any attempt to measure the wavelength using the Young double-
slit experiment was unsuccessful with no interference pattern observed.
In 1912, Laue explained that no interference pattern is observed because
the wavelengths of X-rays are too small. To explore his argument, consider
the condition for observation of an interference pattern

2d sin θn = nλ , (30)

from which we have



sin θn = . (31)
2d
For λ  d, we have sin θn ≈ 0 even for large n. Hence, in order to make
sin θn ≈ 1 to see the interference fringes separated from each other, the
separation d between the slits should be very small.
Laue proposed to use a crystal for the interference experiment. In crystals
the average separation between the atoms, acting as slits, is about d ≈ 0.1
nm. From the experiment, he found that the wavelength of the measured X-
rays was λ ≈ 0.6 nm. Typical X-ray wavelengths are in the range: 0.001 − 1
nm. These are very short wavelengths well outside the ultraviolet wave-
lengths. For a comparison, visible light wavelengths are between: λ ≈ 410
nm (violet) and λ ≈ 656 nm (red).

How the radiation of such small wavelengths is generated?

18
X-rays are generated when high-speed electrons crash into the anode and
rapidly deaccelerate. It is well known from the theory of classical elec-
trodynamics that electrons when deaccelerated, they emit radiation. In
other words, their kinetic energy is converted into radiation energy (brak-
ing i.e. deaccelerating radiation, often referred to by the German phrase
bremsstrahlung). The total instantaneous power radiated by the deacceler-
ated electron is given by the Larmor formula
2 e2
P = |a|2 , (32)
3 4πε0 c3
where |a| is the magnitude of the deacceleration.
Hence, due to the continuous deacceleration of the electrons, the spectrum
of X-rays also should be continuous. However, the experimentally observed
spectrum of the X-rays was composed of two sharp lines superimposed on a
continuous background, see Fig. 1. It was observed that the position of the
two lines depends only on the material of the anode (characteristic radiation).
The origin of the two lines was unknown!

I(λ)

Figure 1: Experimentally observed spectrum of X-rays.

Moreover, the minimum wavelength λmin was observed to depend only on


the potential in the tube (λmin ∼ V ) and was the same for all target (anode)
material. The reason was unknown!

19
2.3 Photoelectric effect
In 1887, Hertz discovered the photoelectric effect - emission of electrons from
a surface (cathode) when light strikes on it. If a positive charged electrode
is placed near the photoemissive cathode to attract the photoelectrons, an
electric current can be made to flow in response to the incident light.

The following properties of the photoelectric effect were observed:

1. When a monochromatic light falls on the cathode, no electrons are


emitted, regardless of the intensity of the light, unless the frequency (not
the intensity) of the incident light is high enough to exceed some minimum
value, called the threshold frequency. The threshold frequency depends on
the material of the cathode.

I 1 > I2

I1
I2

-V s V

Figure 2: Photoelectric effect for two different intensities I 1 and I2 of the inci-
dent light.

2. Once the frequency of the incident light is greater than the threshold
value, some electrons are emitted from the cathode with a non-zero speed.
The reversed potential is required to stop the electrons (stopping poten-
tial: eVs = 21 mv 2 ).

3. When the intensity of light is increases, while its frequency is kept


the same, more electrons are emitted, but the stopping potential is the
same, see Fig. 2.

20
Conclusion: Velocity of the electrons, which is proportional to the energy,
is unaffected by changes in the intensity of the incident light.

4. When the frequency of light is increased (ν2 > ν1 ), the stopping po-
tential increased (Vs2 > Vs1 ), see Fig. 3.

-V s 2 -V s1 V

Figure 3: Photoelectric effect for two different frequencies of the incident light,
with (ν2 > ν1 ).

In summary: We have seen that the experiments on photoelectric effect


suggest that the energy of light is not proportional to its intensity, but is
rather proportional to the frequency:
1 c
 
E∼ν or E∼ , ν= . (33)
λ λ
It is impossible to explain these observations by means of the wave the-
ory of light. The wave theory of light leads one to anticipate that a long
wavelength light incident on a surface could cause enough energy to be ab-
sorbed for an electron to be released. Moreover, when electrons are emitted,
an increase in the incident light intensity should cause an emitted electron
to have more kinetic energy rather than more electrons of the same average
energy to be emitted.

21
2.4 Compton scattering
Compton scattering experiment, performed in 1924, provided additional di-
rect confirmation that energy of light is proportional to frequency, not to the
amplitude. In the Compton experiment light of a wavelength λ was scattered
on free electrons, see Fig. 4.

/
λ
E/
λ e− λ/ > λ
α
Θ
E
Ee

Figure 4: Schematic diagram of the Compton scattering. An incident light of


wavelength λ is scattered on free electrons and the scattered light of wavelength λ 0
is detected in the α direction.

It was observed that during the scattering process the intensity of the
incident light did not change, but the wavelength changed such that the
wavelength of the scattered light was larger than the incident light, λ0 > λ.

Conclusion: From the energy conservation, we have that

E = E 0 + Ee , (34)

where Ee is the energy of the scattered electrons.


Since Ee > 0, then E 0 < E, indicating that the energy of the incident light is
proportional to the frequency, or equivalently, to the inverse of the wavelength
1
E∼ν or E∼ . (35)
λ

22
2.5 Discrete atomic spectra
Experiments show that light emitted by a hot solid or liquid exhibits a con-
tinuous spectrum, i.e. light of all wavelengths is emitted. However, light
emitted by a gas shows only a few isolated sharp lines (see Fig. 5) of the
following properties:

ν
Figure 5: Discrete radiation spectrum emitted from single atoms.

• Each line corresponds to a different frequency.

• Different gases produce different set of lines.

• When we increase temperature of the gas more lines at larger frequen-


cies are emitted.

Once again, we are faced with the difficulty of explaining experimental


observations using the wave theory of light. Evidently, the spectra show that
the energy is proportional to frequency, E ∼ ν, not to the amplitude of the
emitted light. Moreover, this shows that the structure of atoms is not con-
tinuous.

Then questions arise: What is an atom composed of? How does the dis-
crete spectrum relate to the internal structure of the atom?

These questions were left without answers at that time.

23
In summary of this lecture:

We have seen that a series of experiments on

1. Properties of X-rays,

2. Properties of photoelectric effect,

3. Compton scattering,

4. Atomic spectra,

suggests that energy of the radiation field (light) is not proportional to its
amplitude, as one could expect from the wave theory of light, but rather to
the frequency of the radiation field, E ∼ ν.

24
3 Black-Body Radiation
The radiation emitted by a body as a result of its temperature is called
thermal radiation. All bodies emit and absorb such radiation. Hot gases or
individual atoms emit radiation with characteristic discrete lines. Hot mat-
ter in a condensate state (solid or liquid) emits radiation with a continuous
distribution of wavelengths rather than a line spectrum.

Consider spectral distribution of the radiation emitted by a black body. First,


we will define what we mean by a black body.

Black-body - an object which absorbs completely all radiation falling on it,


independent of its frequency, wavelength and intensity.

Examples: a box with perfectly reflecting sides and with a small hole. The
small hole can be treated as a black-body.

3.1 Number of radiation modes


In 1900, Rayleigh and Jeans calculated the energy density distribution I(λ)
of the radiation emitted by the black-body box at absolute temperature T .
The energy density distribution is given by
I(λ) = N hEi , (36)
where N is the number of modes (per unit volume and unit wavelength)
inside the box

N= 4 , (37)
λ
and hEi is the average energy of each mode.

Proof of Eq. (37): Number of modes inside the box

Consider an EM wave confined in the volume V . We take a plane wave


propagating in ~r direction, which in terms of x, y, z components can be writ-
ten as
~ =E
E ~ 0 sin (kx x) sin (ky y) sin (kz z) sin (ωt + φ) . (38)

25
The wave propagating in the box interfere with waves reflected from the
walls. The interference will destroy the wave unless it forms a standing wave
inside the box. The wave forms a standing wave when the amplitude of the
wave vanishes at the walls. This happens when
sin (kx x) = 0 , sin (ky y) = 0 , sin (kz z) = 0 , (39)
i.e. when kx = nπ/x, ky = mπ/y, kz = lπ/z, where n, m, l are integer
numbers (n, m, l = 1, 2, 3, . . .).
The condition (39) are called the boundary condition, i.e. condition
imposed on the wave at the walls to form standing waves inside the box.
The standing wave condition is common to all confined waves. In vibrating
violin strings or organ pipes, for example, it also happens that only those
frequencies which satisfy the boundary condition are permitted.
Since k = 2π/λ, we have the following the condition for a standing wave
inside the box
nλ mλ lλ
x= , y= , z= , (40)
2 2 2
We see that each set of the numbers (n, m, l) corresponds to a particular
wave, which we call mode.
In the k space of the components kx , ky , kz , a single mode, say (n, m, l) =
(1, 1, 1) occupies a volume
π3 π3
Vk = = , (41)
xyz V
where V = xyz is the volume of the box.
Since kx , ky , kz are positive numbers, the modes propagate only in the
positive octant of the k-space.
The number of modes inside the octant, shown in Fig. 6, is given by
1 34 πk 3
N (k) = , (42)
8 Vk
i.e. is equal to the volume of the octant divided by the volume occupied by
a single mode.
Since k = 2πν/c, we get
8πν 3
N (k) = V , (43)
3c3

26
kz

ky

kx

Figure 6: Illustration of the positive octant of k-space.

where we have increased N (k) by a factor of 2. This arises from the fact that
there are two possible perpendicular polarizations for each mode.
Hence, the number of modes in the unit volume and the unit of fre-
quency is

1 dN (k) 8πν 2
N= = 3 . (44)
V dν c
In terms of wavelengths λ, the number of modes in the unit volume and the
unit of wavelength is

1 dN (k) 1 dN (k) dν
N= = , (45)
V dλ V dν dλ

which gives

N= , (46)
λ4
as required♦.

27
3.2 Equipartition theorem
The average energy can be found from so-called Equipartition Theorem. This
is a rigorous theorem of classical statistical mechanics which states that, in
thermodynamical equilibrium at temperature T , the average energy associ-
ated with each degree of freedom of an atom (mode) is 12 kB T , where kB is
the Boltzmann’s constant.
The number of degrees of freedom is defined to be the number of squared
terms appearing in the expression for the total energy of the atom (mode).
For example, consider an atom moving in three dimensions. The energy of
the atom is given by
1 1 1
E = mvx2 + mvy2 + mvz2 . (47)
2 2 2
There are three quadratic terms in the energy, and therefore the atom has
three degrees of freedom, and a thermal energy 23 kB T .

I
THEORY
T3
T3 > T2 > T1

T2

T1

Figure 7: Energy density distribution (energy spectrum) of the black-body radi-


ation.

28
The energy of a single radiation mode is the energy of an electromagnetic
wave
( )
1Z ~ + 1 |B|
2 ~ 2
H = dV ε0 |E| . (48)
2 V µ0

Because this expression contains two squared terms, Rayleigh and Jeans ar-
gued that each mode has two degrees of freedom and therefore hEi = kB T .
Hence

I(λ) = kB T . (49)
λ4
The Rayleigh−Jeans formula agreed quite well with the experiment in
the long wavelength region, but disagreed violently at short wavelengths, as
it is seen from Fig. 7. The experimentally observed behavior shows that for
a some reason the short wavelength modes do not contribute, i.e., they are
frozen out. As λ tends to zero, I(λ) tends to zero. The theoretical formula
goes to infinity as λ tends to zero, leading to an absurd result that is known
as the ultraviolet (uv) catastrophe. Moreover, the theoretical prediction does
not even pass through a maximum.

We can summarize the presented experimental predictions as fol-


lows:

Spectrum of X-rays, properties of photoelectric effect, Compton scattering,


atomic spectra, and the spectrum of the black-body radiation indicate that
something is seriously wrong with the wave theory of light.

Exercise:

Show that the number of modes per unit wavelength and per unit length
for a string of length L is given by

1 dN 2
= 2 .
L dλ λ

29
Solution:

Volume occupied by a single mode is


π
Vk = . (50)
L
Number of modes in the volume Vk is
k 2π L 2L
N (k) = = = . (51)
Vk λ π λ
Then, the number of modes per unit wavelength and per unit length is

1 dN 1 2L 2

N = = − 2 = 2 . (52)
L dλ
L λ λ

Exercise at home:

We have shown in the lecture that the number of modes in the unit vol-
ume and the unit of frequency is

1 dN (k) 8πν 2
N = Nν = = 3 . (53)
V dν c
In terms of the wavelength λ, we have shown that the number of modes in
the unit volume and the unit of wavelength is

N = Nλ = . (54)
λ4
Explain, why it is not possible to obtain Nλ from Nν simply by using the
relation ν = c/λ.

30
4 Planck’s Quantum Hypothesis
Shortly after the derivation of the Rayleigh−Jeans formula, Planck found a
simple way to explain the experimental behavior, but in doing so he contra-
dicted the wave theory of light, which had been so carefully developed over
the previous hundred years. Planck realized that the uv catastrophe could
be eliminated by assuming that a mode of frequency ν could only take up
energy in well defined discrete portions (small packets or quanta) each having
the energy
!
h
E = hν = h̄ω , h̄ = , ω = 2πν , (55)

where the constant h is adjusted to fit the experimentally observed I(λ).


In a paper published, Planck states: ”We consider, however − this is
the most essential point of the whole calculations − E to be composed of
a very definite number of equal parts and and use thereto the constant of
nature h”. If there are n quanta in the radiation mode, the energy of the
mode is En = nhν.
Contrast between the wave and Planck’s hypothesis is that in the classical
case the mode energy can lie at any position between 0 and ∞ of the energy
line, whereas in the quantum case the mode energy can only take on discrete
(point) values.

The assumption of the discrete energy distribution required a modification


of the equipartition theorem. Planck introduced ”discrete portions” so that
he might apply Boltzmann’s statistical ideas to calculate the energy density
distribution of the black-body radiation.

4.1 Boltzmann distribution function


The solution to the black-body problem may be developed from a calculation
of the average energy of a harmonic oscillator of frequency ν in thermal
equilibrium at temperature T .
The probability that at temperature T an arbitrary system, such as a

31
radiation mode, has an energy En is given by the Boltzmann distribution

e−En /kB T
Pn = P −En /k T . (56)
e B
n

See Appendix A for the rigorous derivation of Eq. (56).


For quantized energy En = nh̄ω, we have
e−nx
Pn = P
∞ , (57)
e−nx
n=0

where x = h̄ω/kB T .
Since the sum ∞ n=0 e
−nx
is a particular example of a geometric series,
P

and | exp(−nx)| < 1, the sum tends to the limit



1
e−nx =
X
. (58)
n=0 1 − e−x

Hence, we can write the Boltzmann distribution function (56) in a simple


form
 
Pn = 1 − e−x e−nx . (59)

This is a very simple formula, which we will use in our calculations of the
average energy hEi, average number of photons hni, and higher statistical
moments, hn2 i.

4.2 Planck’s formula for I(λ)


Assuming that n is a discrete variable, Planck showed that the average energy
of the radiation mode is
  ∞
−x
ne−nx .
X X
hEi = E n Pn = 1 − e h̄ω (60)
n n=0

Then, evaluating the sum in the above equation, he found


h̄ω
hEi = , (61)
ex−1

32
and finally
8πhc
I(λ) = , (62)
λ5 (ehc/λkB T − 1)

which is called the Planck’s formula, and the constant h, known as the
Planck constant, adjusted such that the energy density distribution (62)
agrees with the experimental results, is

h = 6.626 × 10−34 [J · s] = 4.14 × 10−15 [eV · s] . (63)

Equations (49) and (62) for the radiation spectrum contrast the discrete
energy distribution with the continuous.
Since hEi = hnih̄ω, we have from Eq. (61) that the average number of
quanta in the radiation mode is
1
hni = h̄ω . (64)
e kB T
−1
Consider the Planck’s formula for two extreme values of λ: λ  1
and λ  1.
For λ  1, we can expand the exponent appearing in Eq. (62) into a
Taylor series and obtain
  hc hc
ehc/λkB T − 1 = 1 + +...− 1 ≈ . (65)
λkB T λkB T
Then
!−1
8πhc hc 8π
I(λ) = 5 = kB T . (66)
λ λkB T λ4

Thus, for long wavelengths (λ  1) the Planck’s formula agrees perfectly


with the Rayleigh−Jean’s formula.
Outside this region, discreteness brings about Planck’s quantum correc-
tions. For λ  1, we can ignore 1 in the denominator of Eq. (62) as it is
much smaller than the exponent. Then
8πhc
I(λ) = . (67)
λ5 ehc/λkB T

33
When λ → 0, ehc/λkB T → ∞, and λ5 → 0. However, ea/λ function goes to
infinity faster than λ5 goes to zero. Therefore, I(λ) → 0 as λ → 0, which
agrees perfectly with the observed energy density spectrum, see Fig. 7.

In addition the Planck’s formula correctly predicts the


Wien displacement law
hc
λmax T = = constant , (68)
4.9651kB
where λmax is the value of λ at which I(λ) is maximal. The factor 4.9651 is
a solution of the equation
1
e−x + x − 1 = 0 . (69)
5
The Wien law says that with increasing temperature of the radiating body,
the maximum of the intensity shifts towards shorter wavelengths.

Moreover, the Planck’s formula correctly predicts the


Stefan−Boltzmann law
c ∞
Z
I= I(λ)dλ = σT 4 , (70)
4 0

where I is the total intensity of the emitted radiation and σ is a constant,


called the Stefan−Boltzmann constant. The factor c/4, where c is the speed
of light, arises from the relation between the intensity spectrum (radiance)
and the energy density distribution. The relation follows from classical elec-
tromagnetic theory.

Proof:

In the Planck’s formula


8πhc
I(λ) = , (71)
λ5 (ehc/λkB T − 1)
we substitute
hc
x= (72)
λkB T

34
and change the variable from λ to x:
hc 1 hc 1
λ= so that dλ = − dx . (73)
kB T x k B T x2
Hence, substituting for I(λ) and dλ in Eq. (70), we obtain

c ∞ c ∞ 8πhc x5 hc
Z Z
I = I(λ)dλ = dx  5
4 0 4 0 hc e x − 1 k B T x2
kB T
!4 Z
∞ 2πhc2 x3 kB T ∞ x3
Z
= dx  4 x = 2πhc2 dx . (74)
0 hc e −1 hc 0 ex − 1
kB T

Since
∞ x3 dx π4
Z
= , (75)
0 ex − 1 15
we obtain
!4
2 kB T π4
E = 2πhc = σT 4 , (76)
hc 15
where
2π 5 kB
4
σ= = 5.67 × 10−8 [W/m2 · K4 ] . (77)
15h3 c2
The constant σ determined from experimental results agrees perfectly with
the above value derived from the Planck’s formula.

In order to explore the importance of the discrete distribution of the ra-


diation energy, it is useful to compare the Planck’s formula for a discrete n
with that for a continuous n.

Thus, assume for a moment that n is a continuous rather than a discrete


variable. Then the Boltzmann distribution takes the form
e−nx
Pn = R∞ , (78)
dn e−nx
0

35
and hence the average energy is given by

dn ne−nx
R
(1/x)0 h̄ω
hEi = h̄ω 0∞ = −h̄ω = = kB T , (79)
R
dn e−nx 1/x x
0

where 0 denotes first derivative of 1/x with respect to x.


This result is the one expected from the classical equipartition theorem.

Looking backwards with the knowledge of the quantum hypothesis, we


see that the essence of the black-body calculation is remarkably simple and
provides a dramatic illustration of the profound difference that can arise from
summing things discretely instead of continuously, i.e. making an integration.

36
4.3 Photoelectric effect
In 1905, Einstein extended Planck’s hypothesis by postulating that these
discrete quanta of energy h̄ω, that can be absorbed by a mode, can be con-
sidered like particles of electromagnetic radiation (particles of light) which
he termed photons.
The energy of a single photon is E = h̄ω, and then the photoelectric effect
is given by
1 2
h̄ω = W + mvmax , (80)
2
where W is the work function required to remove an electron from the plate,
and vmax is the maximal velocity of the removed electrons.
Photons with frequencies less than a threshold frequency νT (a cutoff
frequency) do not have enough energy to remove an electron from a particular
plate. The minimum energy required to remove an electron from the plate is

h̄ω = W . (81)

The stopping potential − the potential at which the photoelectric current


does drop to zero − is found from
1 2
eVs = mvmax , (82)
2
which gives
1 2
2
mvmax hν − W
Vs = = . (83)
e e
We may conclude that the Einstein’s photoelectric formula (80) correctly
explains the properties of the photoelectric effect discovered by Hertz.

4.4 Compton scattering


Another support of the Planck’s hypothesis is Compton scattering.
Assume that in the Compton scattering the incident photon has momen-
tum p and energy E = pc. The scattered photon has momentum p0 and
energy E 0 = p0 c. The electron is initially at rest, so its energy is Ee = m0 c2 ,
and the initial momentum is zero.

37
From the energy conservation, we have

E + Ee = E 0 + mc2 , (84)

where m is the relativistic mass


m0
m= q , (85)
1 − (v/c)2

and v is the velocity of the scattered electron. Hence,


 
pc − p0 c + m0 c2 = mc2 . (86)

Taking square of both sides of Eq. (86), we obtain


 2
pc − p0 c + m0 c2 = (mc2 )2 = (m0 c2 )2 + (pe c)2 , (87)

where pe is the momentum of the scattered electron.


Thus
2
(p − p0 ) + 2m0 c (p − p0 ) = p2e . (88)

Since the momentum of the scattered electrons is difficult to measure in


experiments, we can eliminate pe using the momentum conservation law

p~e = p~ − p~0 , (89)

from which we get

p2e = p2 + p02 − 2pp0 cos α , (90)

where α is the angle between directions of the incident and scattered photons.
Substituting Eq. (90) into Eq. (88), we get

2m0 c (p − p0 ) = 2pp0 (1 − cos α) , (91)

from which, we find that

pp0
p − p0 = (1 − cos α) . (92)
m0 c

38
From the quantization of energy, we have
E hν h
p= = = , (93)
c c λ
and finally
h
λ0 − λ = (1 − cos α) . (94)
m0 c
This is the Compton formula.
The quantity h/(m0 c) is called the Compton wavelength

h
λc = = 2.426 × 10−12 [m] . (95)
m0 c
The quantum theory predicts correctly that the scattered light has different
wavelength than the incident light. The classical (wave) theory predicts that
λ0 = λ.

We see from the Compton formula (94) that the transition from quantum
(photon) to classical (wave) picture is to put h → 0.

A significant feature of the derivation of the Compton formula is that it


relied essentially on special relativity. Thus, the Compton effect not only
confirms the existence of photons, it also provides a convincing proof of the
validity of special relativity.

Exercise:

(a) A photon collides with a stationary electron.


Show that in the collision the photon cannot transfer all its energy to the
electron.

(b) Show that a photon cannot produce a positron-electron pair.

39
Solution:

(a) Assume that the photon can transfer all its energy to the electron. Then,
from the conservation of energy
q
Ef + m0 c2 = mc2 = m20 c4 + p2e c2 , (96)

where Ef = hν is the energy of the photon, and pe is the momentum of the


electron.
From the conservation of momentum, we have

pf = = pe , (97)
c
and substituting (97) into (96), we obtain
q
2
hν + m0 c = m20 c4 + (hν)2 , (98)

which is not true, as the rhs is larger than lhs.

(b) From the conservation of momentum, we have


q q
pf = m20 c2 + p2e + m20 c2 + p2p , (99)

where pp is the momentum of the positron.


We see from the above equation that

pf > |~
pe | + |~
pp | ≥ |~
pe + p~p | . (100)

Hence

p~f > p~e + p~p . (101)

Exercise at home:

Explain, why is it much more difficult to observe the Compton effect in


the scattering of visible light than in the scattering of X-rays?

40
”Anyone who is not shocked
by quantum theory has not
understood it”
Niels Bohr

5 The Bohr Model


In 1913, the Danish scientist Niels Bohr used the Planck’s concept to propose
a model of the hydrogen atom that had a spectacular success in explanation
of the discrete atomic spectra. The model also correctly predicted the wave-
lengths of the spectral lines. We have seen that the atomic spectra exhibit
discrete lines unique to each atom. From this observation, Bohr concluded
that atomic electrons can have only certain discrete energies. That is, the ki-
netic and potential energies of electrons are limited to only discrete particular
values, as the energies of photons in a black body radiation.

5.1 The hydrogen atom


In the formulation of his model, Bohr assumed that the electron in the hy-
drogen atom moves under the influence of the Coulomb attraction between it
and the positively charged nucleus, as assumed in classical mechanics. How-
ever, he postulated that the electron could only move in certain non-radiating
orbits, which he called stationary orbits (stationary states). Next, he pos-
tulated that the atom radiates only when the electron makes a transition
between states.
Let us illustrate the Bohr model in some details. We start from the
classical equation of motion for the electron in a circular orbit, and find that
the attractive Coulomb force provides the centripetal acceleration v 2 /r, such
that
e2 v2
= m . (102)
4πε0 r 2 r
This relation allows us to calculate kinetic energy of the electron
1 e2
K = mv 2 = , (103)
2 8πε0 r

41
which together with the potential energy

e2
U =− (104)
4πε0 r
gives the total energy of the electron as

e2
E =K +U =− . (105)
8πε0 r
From the kinetic energy, we can find the velocity of the electron and its linear
momentum, and the angular momentum
s
me2 r
L = mvr = . (106)
4πε0
In order to find the radius of the orbit, Bohr further postulated that the
angular momentum is quantized. This idea came from the following
observation:
It is seen from the Planck’s formula E = hν that h has the units of
energy multiplied by time (J.s), or equivalently of momentum multiplied by
distance. The electron in the atom travels a distance 2πr per one turn. Since
the momentum is p = mv, we obtain

(mv)(2πr) = nh , (107)

from which we find that the angular momentum is quantized

L = nh̄ , n = 1, 2, 3, . . . . (108)

Comparing this quantum relation for the angular momentum with Eq. (106),
we can find the radius of the orbits
me2 r h2
= n2 2 , (109)
4πε0 4π
from which we find
ε 0 h2
r = n2 . (110)
πme2

42
Substituting Eq. (110) into Eq. (105), we find the energy of the electron

1 me4 1
En = − . (111)
(4πε0 )2 2h̄2 n2

From this equation, we see that the energy of the electron varies inversely
as n2 . Note also that the energy is negative and becomes less negative as n
increases. At n → ∞, En → 0 and there is no binding energy of the electron
to the nucleus. We say the atom is ionized.

How the electron makes transitions between the states?

Bohr introduced the hypothesis of quantum jumps, that the electron jumps
from one state to another emitting or absorbing radiation of a frequency

Em − E n me4 1 1
 
ν= = 2 3 2
− 2 , (112)
h 8ε0 h n m
or of wavelength

1 me4 1 1 1 1
   
= − 2 =R 2− 2 , (113)
λ 8cε20 h3 n 2 m n m
where R is the Rydberg constant.

En n

6
-0.54 5
-0.85 4
BRACKETT
SERIES
-1.51 3
PASCHEN SERIES
(INFRARED)
-3.4 2
BALMER SERIES
(VISIBLE LIGHT)

-13.6 1
LYMAN SERIES (UV)

Figure 8: Energy-level diagram with possible electron transitions.

43
It is convenient to represent the energies in an energy-level diagram,
shown in Fig. 8. The lowest level is called the ground state, and in the
hydrogen atom has the energy
me4
E1 = − = −13.6 [eV] . (114)
8ε20 h2
Note that the energy levels get closer together (converge) as the n value in-
creases. Moreover, there is an infinite number of possible transitions between
the energy levels. It is interesting that the transitions between the energy
levels group into series.

5.2 X-rays characteristic spectra


In 1913, Moseley studied X-rays characteristic spectra in detail, and he
showed how the characteristic X-ray spectra can be understood on the basis
of the energy levels of atoms in the anode material. His analysis was based
on the Bohr model.

e
X-ray

Figure 9: X-ray emission from a multi-electron atom.

In a multi-electron atom, the fast electrons from the cathode knock elec-
trons out of the inner orbits of the anode atoms, see Fig. 9. The outer elec-
trons jump to these empty places emitting X-ray (short-wavelength) photons.

44
In summary:

The Planck’s hypothesis of discrete energy quanta was very successful in


explaining experimental results of the black-body radiation, photoelectric ef-
fect, Compton scattering, atomic spectra, and X-rays characteristic spectra.

5.3 Difficulties of the Bohr model


The Bohr model was very successful in explaining the discrete atomic spectra
of one-electron atoms.
However, there were many objections to the Bohr theory, and to complete
our discussion of this theory, we indicate some of its undesirable aspects:

• The model contains both the classical (orbital) and quantum (jumps)
concepts of motion.

• The model was applied with a mixed success to the structure of atoms
more complex than hydrogen.

• Classical physics does not predicts the circular Bohr orbits to be sta-
ble. An electron in a circular orbit is accelerating towards the center
and according to classical electrodynamic theory should gradually lose
energy by radiation and spiral into the nucleus.

• The model does not tell us how to calculate the intensities of the spec-
tral lines.

• If the electron can have only particular energies, what happens to the
energy when the electron jumps from one orbit to another.

• How the electron knows that can jump only if the energy supplied is
equal to Em − En .

• The model does not explain how atoms can form different molecules.

• Experiments
q showed that the angular momentum cannot be nh̄, but
rather l(l + 1)h̄, where l = 0, 1, 2, . . . , n − 1: (Zeeman effect).

45
We see that some of these objections are really of a very fundamental na-
ture, and much effort was expended in attempts to develop a quantum theory
which would be free of these objections. As we will see later, the effort was
well rewarded and led to what we now know as quantum wave mechanics.
Nevertheless, the Bohr theory is still frequently employed as the first approxi-
mation to the more accurate description of quantum effects. In addition, the
Bohr theory is often helpful in visualizing processes which are difficult to
visualize in terms of the rather abstract language of the quantum wave me-
chanics, which will be analyzed in details in next few lectures.

Exercise at home:

We usually visualize electrons and protons as spinning balls. Is it a true


model? To answer this question, consider the following example.
Suppose that the electron is represented by a spinning ball. Using the Bohr’s
quantization postulate, find the linear velocity of the electron’s sphere. As-
sume that the radius of the electron is order of the radius of a nucleus,
r ≈ 10−15 m (1 fm). What would you say about the validity of the spinning
ball model of the electron?

Challenging problem: Collapse of the classical atom

The classical atom has a stability problem. Let’s model the hydrogen atom as
a non-relativistic electron in a classical circular orbit about a proton. From
the electromagnetic theory we know that a deaccelerating charge radiates en-
ergy. The power radiated during the deacceleration is given by the Larmor
formula (32).

(a) Show that the energy lost per cycle is small compared to the electron’s
kinetic energy. Hence, it is an excellent approximation to regard the orbit as
circular at any instant, even though the electron eventually spirals into the
proton.

(a) How long does it take for the initial radius of r0 = 1 Å to be reduced to
zero? Insert appropriate numerical values for all quantities and estimate the
(classical) lifetime of the hydrogen atom.

46
6 Duality of Light and Matter

We have already encountered several aspects of quantum physics, but in all


the discussions so far, we have always assumed that a particle is a small solid
object. However, quantum physics as it developed in the three decades after
Planck’s discovery, found a need for an uncomfortable fusion of the discrete
and the continuous. This applies not only to light but also to particles.
Arguments about particles or waves gave way to a recognized need for both
particles and waves in the description of radiation. Thus, we will see that
our modern view of the nature of radiation and matter is that they have a
dual character, behaving like a wave under some circumstances and like a
particle under other.
In last few lectures, we discussed the wave and particle properties of light,
and with our current knowledge of the radiation theory, we can recognize the
following wave and particle aspects of radiation:
Wave character Particle character
1. Polarization Photoelectric effect
2. Interference Compton scattering
3. Diffraction Blackbody radiation
How can light be a wave and a particle at the same moment?
Is a photon a particle or a wave?

An obvious question arises: Is this dual character a property of light or


of material particles as well?
Then, one may ask: Is an electron really a particle or is it a wave?

There is no answer to these questions!

6.1 Matter waves

An important step in the development of a satisfactory quantum theory


occurred when Louis de Broglie postulated that:
• Nature is strikingly symmetrical.

47
• Our universe is composed entirely of light and matter.

• If light has a dual wave-particle nature, perhaps matter also has this
nature.

The dual nature of light shows up in equations


h
λ= , E = hν . (115)
p
Each equation contains within its structure both a wave concept (λ, ν), and
a particle (p, E).
The photon also has an energy given by the relationship from the rela-
tivity theory

E = mc2 . (116)

Since E = hν = hc/λ, we find the wavelength


h h
λ= = , (117)
mc p
where p is the momentum of the photon.
This does not mean that light has mass, but because mass and energy
can be interconverted, it has an energy that is equivalent to some mass.

De Broglie postulated that a particle can have a wave character, and


predicted that the wavelength of a matter wave would also be given by the
same equation that held for light, where now p would be the momentum of
the particle
h h
λ= = , (118)
mv p
where v is the velocity of the particle.

Remember this formula! It is the fundamental matter-wave postulate


and will appear very often in our journey through the developments of quan-
tum physics.

48
If particles may behave as waves, could we ever observe the matter waves?

The idea was to perform a diffraction experiment with electrons. But an


obvious question was: How to perform such an experiment? What wave-
lengths can we expect? To answer these questions, consider first a simple
example.

Example: What is the de Broglie wavelength of an electron whose kinetic


energy is K = 100 eV?

Calculate the velocity of the electron from which we than find the de Broglie
wavelength corresponding to that velocity.
The velocity of the electron of energy 100 eV is
s
2K
v= = 5.9 × 103 [km/s] .
m
Hence, the de Broglie wavelength corresponding to this velocity is
h h
λ= = = 1.2 [Å] .
p mv
The wavelength is very small, it is about the size of a typical atom. Such
small wavelengths can be tested in the same way that the wave nature of
X-rays was first tested: diffraction of particles on crystals.
In 1926, Davisson and Germer, and independently Thompson, performed
electron scattering experiments and they found that the wavelength calcu-
lated from the diffraction relation

mλ = 2d sin θm , m = 0, 1, 2, . . . (119)

is in excellent agreement with the wavelength calculated from the de Broglie


relation λ = h/p.
They repeated the experiment not only with electrons, but also with many
other particles, charged or uncharged, which also showed wave-like character.
Thus, for matter as well as for light, we must face up to the existence of a
dual character: Matter behaves is some circumstances like a particle and in
others like a wave.

49
Exercise at home:

If, as de Broglie says, a wavelength can be associated with every moving


particle, then why are we not forcibly made aware of this property in our
everyday experience? In answering, calculate the de Broglie wavelength of
each of the following ”particles”:
1. A car of mass 2000 kg traveling at a speed of 120 km/h.
2. A marble of mass 10 g moving with a speed of 10 cm/s.
3. A smoke particle of diameter 10−5 cm (and a density of, say, 2 g/cm3 )
being jostled about by air molecules at room temperature (27o C = 300
K). Assume that the particle has the same translational kinetic energy
as the thermal average of the air molecules
p2 3
= kB T .
2m 2

6.2 Matter wave interpretation of the Bohr’s model

De Broglie’s wave-particle theory offered another interpretation of the


Bohr atom: The Bohr’s condition for angular momentum of the electron in a
hydrogen atom is equivalent to a standing wave condition. The quantization
of angular momentum L = nh̄ means that
mvr = nh̄
or
nh
mv = . (120)
2πr
However, if we employ the de Broglie’s postulate that
h
p = mv = , (121)
λ
then, we obtain
nλ = 2πr , n = 1, 2, 3, . . . (122)

50
2π r1 2π r2

n=1 n=2

Figure 10: Example of standing waves in the length of the electrons’ first and
second orbit of lengths 2πr1 and 2πr2 , respectively.

Thus, the length of Bohr’s allowed orbits (2πr) exactly equals an integer
multiple of the electron wavelength (nλ), see Fig. 10. Hence, the Bohr’s
quantum condition is equivalent to saying that an integer number of electron
waves must fit into the circumference of a circular orbit.
The de Broglie wavelength of an electron in the smallest orbit turns out
to be exactly equal to the circumference of the orbit predicted by Bohr. Sim-
ilarly, the second and third orbits are found to contain two and three de
Broglie wavelengths, respectively. From this picture, it now becomes clear
why only certain orbits are allowed.

Note that de Broglie arrived to this conclusion from the fundamental matter-
wave postulate, whereas Bohr assumed this property.

We can summarize that in quantum wave mechanics:

1. The electron motion is represented by standing waves.

2. Since only certain wavelengths can now exist, the electron’s energy can
take on only certain discrete values.

51
6.3 Wave function
The idea that the electron’s orbits in atoms correspond to standing matter
waves was taken by Schrödinger in 1926 to formulate wave mechanics.
The basic quantity in wave mechanics is the wave function Ψ(~r, t), which
measures the wave disturbance of matter waves at time t and at a point (~r, t).
Before we explain the physical meaning of the wave function, consider an
example in which we will describe the wave function in terms of a standing
wave.
Consider a free particle of mass m confined between two walls separated
by a distance a. The motion of the particle along the x axis may be repre-
sented by a standing wave whose equation is
Ψ(x, t) = Ψmax sin(kx) sin(ωt + φ) , (123)
where ω = 2πν and k = 2π/λ.
The condition required for a standing wave is
λ
a=n , n = 1, 2, 3, . . . (124)
2
from which we find that
2π nπ
k= = , (125)
λ a
and then

 
Ψ(x, t) = Ψmax sin x sin(ωt + φ) . (126)
a
The wave equation carries the information that the amplitude of the motion
of the particle is quantized. Also, the linear momentum is quantized. Since
2a
λ= , (127)
n
we can replace λ by h/p, and obtain
h
p=n . (128)
2a
The momentum is related to the energy E, which gives
1 p2 h2
E= = n2 ≡ En . (129)
2m 8ma2
This indicates that the energy of the particle is also quantized.
Thus, the particle cannot have any energy.

52
6.4 Physical meaning of the wave function
We can summarize what we have already learnt, that a particle can behave
like a wave, but a particle has mass and some of them have electric charge.
Does this mean that the mass and charge of an electron, for example, are
spread out over the extent of the wave? This would be crazy. It would mean
that if we isolate just a part of the wave, we would obtain a fraction of an
electron charge.

How then should we interpret an electron wave?

The answer is that the wave itself does not have any substance. It is a
probability wave. When we talk about a particle wave, the amplitude of
the wave at a particular point tells us the probability of finding the particle
at that point.
The wave function of a particle describes the probability distribution of
a particle in space, just as the wave function of an electromagnetic field
describes the distribution of the EM field in space.
From the interference and diffraction theorem, we know that the intensity
of the interference pattern is proportional to the square of the field ampli-
tude, or alternatively to the probability that the waves interfere positively
or negatively at some points.
In analogy to this, Born suggested that the quantity |Ψ(~r)|2 at any point ~r
is a measure of the probability density that the particle will be found near
that point. More precisely, the quantity |Ψ(~r)|2 dV is the probability that
the particle will be found within a volume dV around the point at which
|Ψ(~r)|2 is evaluated.
Since |Ψ(~r)|2 dV is interpreted as the probability, it is normalized to one as
Z
|Ψ(~r)|2 dV = 1 . (130)
V

Example:

Consider the wave function at time t = 0 of a free particle confined be-


tween two walls, Eq. (126). In this case, the probability density of finding
the particle at a point x is given by
2 nπ
 
2 2
|Ψ(x, 0)| = |Ψmax | sin x . (131)
a

53
This formula shows that the probability depends on the position x and the
distance between the walls.

P (a)
P (b)

0 a x 0 a/2 a x

Figure 11: Probability density as a function of the position x for a free particle
confined between two walls, and (a) n = 1, (b) n = 2.

The dependence of |Ψ(x)|2 on x for two different values of n is shown


in Fig. 11. It is seen that for n = 1 the particle is more likely to be found
near the center than the ends. For n = 2 the particle is most likely to be
found at x = a/4, x = 3a/4, and the probability of finding the particle at
the center is zero. The strong dependence of the probability on x is in con-
trast to the predictions of classical physics, where the particle has the same
probability of being anywhere between the walls.

These ideas are not easy to grasp as they seem to contradict our intuitive
understanding of the physical world. It often leads people to question the
physical models developed in physics. The probabilistic nature of quantum
physics is in itself a psychological barrier for many people. Even Einstein was
inflexibly opposed to this interpretation which ”leaves so much to chance”.

”I cannot believe that God plays


dice with the cosmos”
Albert Einstein

Remember:
Wave function Ψ(~r, t) of a particle is mathematical construct only.
Only |Ψ(~r, t)|2 has physical meaning - probability density, and |Ψ(~r, t)|2 dV
is the probability of finding the particle in the volume dV .

54
6.5 Phase and group velocities
Is there an analogy between the matter waves and radiation?

Matter waves
h h
λ= = , (132)
p mv
where v is the velocity of a particle of the mass m.

Particles
E = mc2 = hν . (133)
Hence, the wave-radiation relation leads to the velocity of the matter waves
h mc2 c2
u = λν = = . (134)
mv h v
The velocity u is called a phase velocity of the matter waves. Thus, the
velocity of the matter waves is larger than speed of light in vacuum, u > c,
unless v > c.
This result seems disturbing because it appears that the matter waves
would propagate faster than the speed of light and would not be able to keep
up with particles whose motion they govern.
However, the phase velocity of a wave is the velocity of the wave front,
not its amplitude. The maximum of the amplitude of a given wave can prop-
agate at different velocity, called group velocity. At this velocity the energy
(information) is transmitted. Usually, vg = u, but in the case of dispersion,
u(ν), the group velocity vg < u. Thus, the matter wave should be dispersive
to match the requirement of vg < u when u > c.

Are the matter waves dispersive?

Let us answer this by first defining the phase and group velocities.

Consider two waves of slightly different k and ω, and propagating in the


same direction. Let
k1 = k0 + ∆k , ω1 = ω0 + ∆ω ,
k2 = k0 − ∆k , ω2 = ω0 − ∆ω , (135)

55
Take a linear superposition of the two waves
1 ~ 1 ~
Ψ(~r, t) = ei(k1 ·~r−ω1 t) + ei(k2 ·~r−ω2 t) . (136)
2 2
Then, using Eq. (135) and the Euler’s formula (e±ix = cos x ± i sin x), we
obtain
1 i[(k0 +∆k)~κ·~r−(ω0 +∆ω)t] 1 i[(k0 −∆k)~κ·~r−(ω0 −∆ω)t]
Ψ(~r, t) = e + e
2 2
i(k0 ~κ·~r−ω0 t)
= e cos (∆k~κ · ~r − ∆ωt) , (137)

where ~κ · ~r is the distance the wave propagated, and ~κ is the unit vector in
the ~k direction.

We see from Eq. (137) that in time t the fast varying function propagates a
distance
ω0
~κ · ~r = t = ut , (138)
k0
whereas the envelope propagates a distance
∆ω dω
~κ · ~r = t= t = vg t . (139)
∆k dk
Hence, the envelope propagates at velocity vg = dω/dk, which is called the
group velocity.

The envelope forms so called wave packets. we have already seen that
the amplitude of the wave packet propagates with velocity vg .

Consider energy of a particle

1 2 h̄2 2
E= p = k . (140)
2m 2m
If the energy of the particle is quantized, E = h̄ω, and then

h̄2
h̄dω = 2kdk , (141)
2m

56
from which we find that
dω h̄k
= 6= 0 . (142)
dk m
Hence, if E = h̄ω then the matter waves are dispersive.

Exercise 1:

What is the group velocity of the wave packet of a particle moving with
velocity v?

Solution:

From the definition of the group velocity, we have


dω dν d(hν) dE
vg = = 2π = 2π = , (143)
dk dk d(hk) dp
where p = h̄k. However

E 2 = m20 c4 + p2 c2 . (144)

Thus

2EdE = 2pc2 dp . (145)

from which we find that


dE pc2 mvc2
= = =v. (146)
dp E mc2
Hence, vg = v, the group velocity is equal to the velocity of the particle. In
other words, the velocity of the particle is equal to the group velocity of the
corresponding wave packet.

Exercise 2:

The dispersion relation for free relativistic electron waves is


q
ωk = c2 k 2 + (mc2 /h̄)2 .

57
(a) Calculate expressions for the phase velocity u and group velocity vg
of these waves and show that their product is constant, independent of k.

(b) From the result (a), what can you conclude about vg if u > c?

Solution:

(a) From the definition of the phase velocity


v
!2
mc2
u
ωk u
u= = t
c2 + .
k kh̄
We see that the phase velocity u > c.
From the definition of the group velocity
dωk 1 2c2 k
vg = = q
dk 2 c2 k 2 + (mc2 /h̄)2
c2 k c
= q =q .
ck 1 + (mc/kh̄)2 1 + (mc/kh̄)2
Thus, the group velocity vg < c.
However, the product
c 2 k ωk
uvg = = c2
ωk k
is constant independent of k.

(b) We see from (a) that in general for dispersive waves for which u > c, the
group velocity vg < c. Only when u = c, the group velocity vg = c.

In the next step of our efforts to understand fundamentals of quantum


physics, we will show that a localized particle is represented by a super-
position of wave functions (so called wave packet) rather than a single wave
function. Important steps on the way to understand the concept of wave
packets are the uncertainty principle between the position and momentum
of the particle, and the superposition principle.

58
”What the electron is doing during its journey in the interferometer?
During this time the electron is a great smoky dragon,
which is only sharp at its tail (at the source) and at its mouth,
where it bites the detector”
J.A. Wheeler

6.6 The Heisenberg uncertainty principle

In quantum physics, we usually work with the wave function Ψ, whose |Ψ|2
describes a probability that a given object, e.g. a particle, is moving with a
velocity v0 . A non-zero probability means that we are not precisely sure that
the velocity of the particle is v0 . We may say that the velocity is v0 with
some error, ∆v0 , which is called uncertainty.

Consider a typical diffraction experiment shown in Fig. 12.

A
v0 θ
∆y

Figure 12: Schematic diagram of a diffraction experiment. A beam of particles


emerging from the slit of width ∆y interfere to form on the observing screen an
interference pattern.

59
The position of the first minimum in the diffraction pattern is given by
λ
sin θ = . (147)
∆y
In order to reach the point A, the particle has to gain a velocity in the
y-direction, such that
∆vy
sin θ = . (148)
v0
Comparing Eqs. (147) and (148), we find
∆vy λ
=
v0 ∆y
or
∆vy ∆y = v0 λ . (149)
However, from the de Broglie postulate
h h
λ= = , (150)
p mv0
and therefore
∆py ∆y = h , (151)
where ∆py = m∆vy .
The relation (151) is called the Heisenberg uncertainty principle and
states that it is impossible to measure the momentum py and position y of a
particle simultaneously with the same precision. If the particle is completely
unlocalized, ∆y → ∞, the momentum is certain, ∆py → 0.

The Heisenberg uncertainty principle is not a statement about the inaccuracy


of measurement instruments, nor a reflection on the quality of experimental
methods. It arises from the wave properties inherent in the quantum mechan-
ical description of nature. Even with perfect instruments and techniques, the
uncertainty is inherent in the nature of things.

Exercise:

Last year after the lecture on uncertainty principle, a student asked a ques-
tion: ”If I do not move, does it mean that I am everywhere”?
How would you answer to this question?

60
6.7 The superposition principle
In quantum physics, a particle is represented by a wave function
~
Ψ(~r, t) = Aei(k·~r−ωt) . (152)
Since, |Ψ(~r, t)|2 = |A|2 = const., we see that the particle is completely unlo-
calized in space, that can be found anywhere in space with the same proba-
bility. However, we know that in practice particles are localized in space and
their position can be given with some approximation. In other words, par-
ticles are partly localized. Therefore, a wave function such as (152) cannot
represent a real physical system.
According to the uncertainty principle, a particle partly localized (∆~r)
has an uncertainty in the momentum (∆~ p). Hence, if
Ψ1 (~r, t) = A1 ei(~p1 ·~r/h̄−ω1 t) (153)
is a wave function of the particle located at ~r, then
Ψ2 (~r, t) = A2 ei(~p2 ·~r/h̄−ω2 t) , (154)
where, |~
p1 − p~2 | ≤ ∆~
p, is also a wave function of the particle.
Moreover, any linear combination of the two wave-functions is also a
wave-function of the particle, i.e.
Ψ(~r, t) = aΨ1 (~r, t) + bΨ2 (~r, t) , (155)
where a and b are complex numbers.
Thus, a single wave function cannot represent a particle of a given mo-
mentum.
Equation (155) is an example of the superposition principle which, in
general, holds for an arbitrary number of the wave functions.
It follows from the superposition principle that the wave function of a
particle is represented by the sum of a set of sinusoidal waves exp[i(~k·~r−ωk t)].
The sum is of course an integral
Z
~
Ψ(~r, t) = A(~k)ei(k·~r−ωk t) d3 k , (156)
k

where d3 k is the element of volume in ~k-space (momentum space). In other


words, the set contains an infinite number of waves with continuously varying
wave-number k.

61
One can see from Eq. (156) that the mathematics used in carrying out
the procedure of obtaining a superposition wave function involves the Fourier
transformation (Fourier integral). If the superposition function is known, the
amplitude A(~k) can be found employing the inverse Fourier transformation
1 Z ~
A(~k) = √ Ψ(~r, t)e−i(k·~r−ωk t) d3~r . (157)
2π V

In summary:

The superposition principle is in the complete contrast with classical me-


chanics. In classical mechanics a superposition of two states would be a
complete nonsense as it would imply that a particle could simultaneously
occupy two or more points in space. According to quantum physics, a par-
ticle can exist in two or more states at the same time. If more particles are
involved, a superposition of these particles is called entanglement. The su-
perposition principle and entanglement have been exploited in recent years
in three important applications. The first is quantum cryptography, where
a communication signal between two people can be made completely secure
from eavesdroppers. The second is quantum communication, where capacities
of transmission lines can be increased in compare with that of classical trans-
mission systems. The third is proposed device called a quantum computer,
where all possible calculations could be carried out simultaneously.

6.8 Wave packets


In the superposition state (156), the particle no longer has a well defined
momentum. Such a superposition is named a free particle wave packet.
The relation (156) also shows that the momentum and then also the position
distribution are roughly pictured by the behavior of |A(~k)|2 .
We now consider the motion of a free particle wave packet. For simplicity,
we consider the motion in one-dimension (1D). In this case
Z ∞
Ψ(~r, t) → Ψ(x, t) = A (k) ei(kx−ωk t) dk , (158)
−∞

where k = kx .

62
Let us suppose that A(k) has a maximum at k = k0 and rapidly goes to
zero for k 6= k0 , and ∆k is the region where A(k) 6= 0.
Firstly, we will find the shape of the wave-function at t = 0.
At t = 0:
Z ∞
Ψ(x, 0) = A (k) eikx dk . (159)
−∞

At x = 0, exp(ikx) = 1, indicating that all waves have the same phase.


For x 6= 0, the waves with different k have different phases. If ∆x is the
displacement of x from x = 0, the maximal and minimal phases of the packet
are
1
 
∆x k0 − ∆k , minimal
2
1
 
∆x k0 + ∆k , maximal .
2
Since the phases are different, the waves will interfere with each other. The
maximum of interference appears for the difference between the phases equal
to 2π. Thus,

∆x∆k = 2π . (160)

Hence, the particle can be found at points for which ∆x = 2π/∆k, i.e. de-
termined by the uncertainty relation.

Now, we will check how the packet moves in time.


In order to do it, we expand ωk into a Taylor series about k = k0 . Taking
k = k0 + β, and ωk0 = ω0 , we get

d2 ω
! !
dω 1
ωk = ωk0 +β = ω0 + β+ β2 + . . . (161)
dβ k0
2 dβ 2 k0

If we take only first two terms of the series and substitute to Ψ(x, t), we
obtain
Z ∞
i(k0 x−ω0 t)
Ψ(~r, t) = e dβA (k0 + β) eiβ(x−vg t) , (162)
−∞
 

where vg = dβ k0
is the group velocity of the packet.

63
If we increase x by ∆x, i.e. x → x + ∆x, then

eiβ(x−vg t) = eiβx eiβ(∆x−vg t) . (163)

Then, for ∆x = vg t we obtain the same packet as for t = 0, but shifted by


vg t. Hence, the group velocity is the velocity of the packet moves as a whole.
If we include the third term of the Taylor expansion (161), we get
Z ∞
i(k0 x−ω0 t)
Ψ(~r, t) = e dβA (k0 + β)
−∞
" ! ! #
dvg
× exp iβ x − vg + β t . (164)
dβ k0
 
The term vg + dv g
dβ k0
β plays the role of the velocity of the wave packet,
which now depends on β. Thus, different parts of the wave packet will move
with different velocities, leading to a spreading of the wave packet. This
spreading is due to dispersion, that vg depends on β.
We now can explain the connection between the group velocity and the
phase velocity, and the role of dispersion.
ω
Phase velocity u= ,
k

Group velocity vg = .
dk
Hence
dω d du
vg = = (ku) = u + k . (165)
dk dk dk
Thus, vg depends on k when du dk
6= 0, i.e. when the phase velocity depends
on k. The dependence of u on k is called dispersion.
Thus, we can say that the spread of the wave packet is due to the depen-
dence of the phase velocity on k, [vg 6= u when du
dk
6= 0].

64
In summary of this lecture: We have learnt that

1. In quantum physics, localized particles are represented by a superposi-


tion of wave functions (so called wave packet) rather than a single wave
function.

2. The maximum of a wave packet moves with the group velocity.

3. Since the matter waves are dispersive, a wave packet spreads out in
time.

65
7 Schrödinger Equation

The Schrödinger equation is the basic relationship for determining wave func-
tions and energy levels of a given physical system.
Consider a wave function of a particle moving along the x-axis

Ψ = Ψmax ei(kx−ωt) . (166)

We will try to find a differential equation representing the energy of the


particle, whose the solution is the wave function (166), with the following
conditions
• The equation must be linear.

• Coefficients appearing in this equation should only depend on the pa-


rameters characteristic of the particle.
We will limit our considerations the the non-relativistic case only.

7.1 Schrödinger equation of a free particle


First, we will consider the case of a free particle. In this case the energy and
momentum of the particle are related by
1
E= p|2 .
|~ (167)
2m
Since E = h̄ω and p~ = h̄~k, we get
h̄ 2
ω= k . (168)
2m
Note that:
1. Taking the first derivative of Eq. (166) over x is equivalent to multiply
Ψ(x, t) by ik.

2. Taking the first derivative of Eq. (166) over t is equivalent to multiply


Ψ(x, t) by −iω.

66
Thus, from Eq. (168), we can conclude that the differential equation
should be the first order in t and the second order in x. The simplest equation
of this form is
∂Ψ(x, t) ∂ 2 Ψ(x, t)
= Γ2 , (169)
∂t ∂x2
where Γ is a parameter, which we have to find.
Substituting Eq. (166) into (169), we find

−iω = −Γ2 k 2 , (170)

and then from Eq. (168), we find that

ih̄
Γ2 = . (171)
2m
Thus, the wave function (166) satisfies the following differential equation

∂Ψ(x, t) ih̄ ∂ 2 Ψ(x, t)


= , (172)
∂t 2m ∂x2
or equivalently

∂Ψ(x, t) h̄2 ∂ 2 Ψ(x, t)


ih̄ + =0. (173)
∂t 2m ∂x2
Equation (173) is the one-dimensional Schrödinger equation for a free parti-
cle.
It is easy to extend the equation to three dimensions

∂Ψ(~r, t) h̄2 2
ih̄ + ∇ Ψ(~r, t) = 0 , (174)
∂t 2m
where
~
Ψ(~r, t) = Ψmax ei(k·~r−ωt) . (175)

67
7.2 Operators

We can write the Schrödinger equation as


! !
h̄ ∂ 1 h̄ h̄
− Ψ(~r, t) = ∇ ∇ Ψ(~r, t) , (176)
i ∂t 2m i i
which shows that the Schrödinger equation can be obtained from the energy
p|2 /2m) simply replacing E and p~,
(Hamiltonian) of the free particle (E = |~
respectively, by
h̄ ∂
E → − ,
i ∂t

p~ → ∇. (177)
i
Hence, in quantum physics the physical quantities are represented by math-
ematical operations, which are called operators.
∇ and ∂/∂t define operations to be carried out on the wave function Ψ.
The particular operation stated in Eq. (176), ∂Ψ/∂t consists of taking a
partial derivative of Ψ in terms of t, and ∇2 Ψ consists of taking partial
derivatives of Ψ in terms of Cartesian coordinates.

Example:

∂Ψ
Calculate (a) ∂t
and (b) ∇2 Ψ, where Ψ = Ψmax ei(kx−ωt) .

Solution:

(a) The partial derivative of Ψ in terms of t is


∂ ∂
Ψ = Ψmax ei(kx−ωt) = −iωΨmax ei(kx−ωt) = −iωΨ . (178)
∂t ∂t
Thus, the operation of the operator ∂/∂t on the wave function Ψ results in a
constant −iω times the original wave function. We will see later, that such
a wave function is called in quantum physics an eigenfunction of the ∂/∂t
operator.
Solution of the part (b) is left to the students.

68
Important property of operators:

In classical physics the multiplication of two quantities, say x and px , is


immaterial. However, in quantum physics, where physical quantities are
represented by operators, the order of multiplication is important and, for
example, xpx 6= px x, where px = −ih̄∂/∂x. We say that the two quantities, x
and px , do not commute.1
A measure of the extent to which xpx 6= px x is given by the commutator
bracket

[x̂, p̂x ] = x̂p̂x − p̂xx̂ , (179)

where the symbol ”ˆ” over the functions x and px indicates that these func-
tions are operators.

Note that the coordinates of ~r are the same in operator and classical forms.
For example, the coordinate x is simply used in operator form as x.

How to calculate the commutator [x̂, p̂x ]?

Since operators are ”action” operations on functions, we consider the action


of this commutator on a trial function Ψ(x):
!
∂Ψ ∂
[x̂, p̂x ] Ψ(x) = x −ih̄ + ih̄ (xΨ)
∂x ∂x
∂Ψ ∂Ψ
= −ih̄x + ih̄Ψ + ih̄x = ih̄Ψ . (180)
∂x ∂x
Hence

[x̂, p̂x ] = ih̄ . (181)

It is easily to show that, in general, the components of the position ~ˆr and
momentum pˆ~ operators satisfy the commutation relations

[r̂m , p̂n ] = ih̄δmn , m, n = 1, 2, 3 , (182)


1
Commutation consists in reversing the order of two quantities in an algebraic
operation.

69
where

r̂1 = x̂ , r̂2 = ŷ , r̂3 = ẑ ,


p̂1 = p̂x , p̂2 = p̂y , p̂3 = p̂z , (183)

and δmn is called Kronecker δ function, defined as




 1 if m=n
δmn = (184)
0 if m 6= n .

Using the operator representation, the Schrödinger equation is often writ-


ten as
∂Ψ(~r, t)
ih̄ = ĤΨ(~r, t) , (185)
∂t
2

where Ĥ = − 2m ∇2 is the Hamiltonian (energy operator) of the free particle.

7.3 Schrödinger equation of a particle in an external


potential
In physics, we often deal with problems in which particles are free within
some kind of boundary, but have boundary conditions set by some external
potentials. The particle in a box problem, discussed before, is the simplest
example.
In the presence of an external potential V (~r, t), the Hamiltonian of the
particle takes the form

h̄2 2
Ĥ = − ∇ + V̂ (~r, t) . (186)
2m
The wave function of the particle moving in the external potential can be
different from that of the free particle. The wave function is found solving
the Schrödinger equation the with following conditions

1. The wave function must be determined and continuous in any point of


the space (~r, t).

2. The wave function vanishes at ±∞.

70
We will try to solve the Schrödinger equation assuming that the Hamil-
tonian Ĥ does not explicitly depend on time, i.e. V̂ (~r, t) = V̂ (~r). In this
case, the Schrödinger equation (SE) contains two terms: one dependent on
time t, and the other dependent on ~r, i.e.
!

ih̄ − Ĥ Ψ = 0 , (187)
∂t

where Ĥ depends solely on ~r.


Since the time and ~r dependent parts are separated, the solution of the
SE will be in the form of a product of two functions φ(~r) and f (t):

Ψ(~r, t) = φ(~r)f (t) . (188)

Substituting this equation into the SE, we get


df (t)
ih̄φ(~r) = f (t)Ĥφ(~r)
dt
1 df 1
ih̄ = Ĥφ , (189)
f dt φ
where f ≡ f (t), and φ ≡ φ(~r).
The left-hand side of Eq. (189) is a function of only one variable t, whereas
the right-hand side is a function of only the position ~r, i.e. each side is
independent of any changes in the other. Thus, both sides must be equal to
a constant, say E:
1 df
ih̄ = E, (190)
f dt
1
Ĥφ = E . (191)
φ
We can easily solve Eq. (190), and the solution can be written directly as
i
f (t) = Ce− h̄ Et , (192)

where C is a constant.
Equation (191) can be written as

Ĥφ = Eφ , (193)

71
which is called the stationary (time-independent) Schrödinger equation, or
the eigenvalue equation for the Hamiltonian Ĥ.
Hence, the solution of the SE is of the form
i
Ψ(~r, t) = Cφ(~r)e− h̄ Et , (194)

where φ(~r) satisfies the eigenvalue equation (193).

Note, that the probability density

|Ψ(~r, t)|2 = |Cφ(~r)|2 , (195)

is independent of time.
Thus, when the Hamiltonian of a particle is independent of time, the
probability of finding the particle in an arbitrary point ~r is independent
of time. Such a state (wave function) is called a stationary state of the
particle.
The existence of stationary states has two very useful practical conse-
quences. Physically, such states have a permanence in time, which allows
their long time experimental investigations. Mathematically, they reduce
the Schrödinger equation to the eigenvalue equation for the Hamiltonian.
Thus, in order to obtain specific values of energy and corresponding wave
functions, we operate on the wave function with the Hamiltonian and solve
the resulting differential equation. However, not all mathematically possible
solutions are accepted. Physics imposes some limits on the solutions of the
Schrödinger equation.

The solution of the Schrödinger equation should satisfy the following con-
ditions:

1. The wave function φ must be finite in all points of the space.

2. The wave function φ must be continuous, and should have continuous


first derivatives.

3. The wave function φ must be a single-value function at any point ~r.

4. The wave function must be normalized.

72
When an operation on a wave function gives a constant times the original
wave function, that constant is called an eigenvalue and the wave func-
tion is called an eigenfunction or eigenstate. Thus, the wave function
which satisfies the stationary Schrödinger equation is the eigenfunction of the
Hamiltonian Ĥ, and E is the eigenvalue of the Hamiltonian in the state φ.
The complete set of eigenvalues of the Hamiltonian Ĥ is termed energy
spectrum. The energy spectrum can be nondegenerated (different eigen-
functions have different eigenvalues), or degenerated (all or few eigenfunc-
tions have the same eigenvalues), but it is not allowed that one eigenfunction
could have few different eigenvalues.

In summary of the lecture on the Schrödinger equation:


We have learnt that

1. In quantum physics, physical quantities are represented by operators.

2. The operator representing the energy of a system is the Hamiltonian Ĥ.

3. The eigenvalues of Ĥ are energies E.

4. If the potential V̂ is independent of time, then separation of variables


is possible, and we can write the wave function as Ψ(~r, t) = φ(~r)f (t).

5. The wave function φ(~r) is the eigenfunction of the time-independent


Hamiltonian Ĥ and can be found by solving the stationary Schrödinger
equation Ĥφ(~r) = Eφ(~r).

7.4 Equation of continuity

We know that the probability is normalized to one, i.e.


Z
|Ψ(~r)|2 dV = 1 . (196)
V

The normalization must be valid for any wave function evaluated at any
point ~r and at any time t. We will show that the Schrödinger equation

73
guarantees the conservation of normalization of the wave function. In other
words, if Ψ was normalized at t = 0, it will remain normalized at all times.

In addition, there is a flow of the probability density or particle current


density associated with a moving particle. Therefore, we will also define
what the particle probability current density is in terms of the particle wave
function.

Suppose we have a particle described by a wave function Ψ in a volume V


enclosed by a surface S.
Consider the time evolution of the particle wave function, that is given
by the time-dependent Schrödinger equation
∂Ψ h̄2 2
ih̄
=− ∇ Ψ + V̂ Ψ . (197)
∂t 2m
Take complex conjugate of the above equation
∂Ψ∗ h̄2 2 ∗
−ih̄=− ∇ Ψ + V̂ Ψ∗ . (198)
∂t 2m
Multiplying Eq. (197) by Ψ∗ and Eq. (198) by Ψ, and subtracting the result-
ing equations, we get
∂Ψ∗ h̄2  ∗ 2
!
∗ ∂Ψ

ih̄ Ψ +Ψ =− Ψ ∇ Ψ − Ψ∇2 Ψ∗ . (199)
∂t ∂t 2m
However
∂Ψ ∂Ψ∗ ∂
Ψ∗ +Ψ = |Ψ|2 , (200)
∂t ∂t ∂t
and using the relation
 
~ = ∇u · A
∇ · uA ~ + u∇ · A
~, (201)
we find that
∇ · (Ψ∗ ∇Ψ − Ψ∇Ψ∗ )

= ∇Ψ∗ · ∇Ψ + Ψ∗ ∇ · (∇Ψ) − ∇Ψ · ∇Ψ∗ − Ψ∇ · (∇Ψ∗ )

= Ψ∗ ∇2 Ψ − Ψ∇2 Ψ∗ . (202)

74
Thus
!
∂ h̄
|Ψ|2 + ∇ · (Ψ∗ ∇Ψ − Ψ∇Ψ∗ ) = 0 . (203)
∂t 2im
Introducing a notation
|Ψ|2 = ρ ,

(Ψ∗ ∇Ψ − Ψ∇Ψ∗ ) = J~ , (204)
2im
we get the continuity equation
∂ρ
+ ∇ · J~ = 0 . (205)
∂t
This equation is well known from hydrodynamics and electrodynamics and
shows the conservation of matter or the conservation of charge. In our case,
the continuity equation shows the conservation of the probability density ρ,
and J~ is the probability current density.

J ^
dS = n dS

dS

Figure 13: Probability current density J~ crossing a surface S, with n̂ − the unit
vector normal to the surface.

To interpret the continuity equation, it is convenient to integrate Eq. (205)


over the volume V closed by a surface S, see Fig. 13:

Z Z
2
|Ψ| dV = − ~
∇ · JdV . (206)
∂t V V

75
From the Gauss’s divergence theorem
Z I
~
∇ · JdV = J~ · dS
~ , (207)
V S

we get

Z I
2
|Ψ| dV = − J~ · dS
~ . (208)
∂t V S

The lhs of this equation is the time rate of increase of probability of finding
the particle inside the volume V . The integral on the rhs is the probability
per unit time of the particle leaving the volume V through the surface S.
The scalar product J~ · dS~ is the probability that the particle will cross an
~
area dS on the surface. When the particle remains inside the volume for all
~ then J~ · dS
times, i.e. does not cross the surface S, ~ = 0, and we get that

Z
|Ψ|2 dV = 0 , (209)
∂t V

which shows that the Schrödinger equation guarantees the conservation of


normalization of the wave function. In other words, if Ψ was normalized at
t = 0, it will remain normalized at all times.

Suppose that particles inside the surface are represented by plane waves
~ ~
Ψin (~r) = Aeik1 ·~r + Be−ik1 ·~r , (210)
and outside the surface
~
Ψout (~r) = Ceik2 ·~r , (211)

where ~k1 and ~k2 are the wave vectors of the particle inside and outside the
surface, respectively.
To interpret the wave functions, we calculate the probability current den-
sities inside and outside the surface, and find
h̄ h̄~k1  2 
J~in = (Ψ∗in ∇Ψin − Ψin ∇Ψ∗in ) = |A| − |B|2 , (212)
2im m
and
h̄ h̄~k2 2
J~out = (Ψ∗out ∇Ψout − Ψout ∇Ψ∗out ) = |C| . (213)
2im m

76
Inside the surface, the current density can be written as

J~in = J~i + J~r (214)

where

h̄~k1 2
J~i = |A| (215)
m
is interpreted as the incident particle current, and

h̄~k1 2
J~r = |B| (216)
m
is interpreted as the reflected particle current. The current density out-
side the surface

h̄~k2 2
J~t = |C| (217)
m
is interpreted as the transmitted particle current.

We can define the reflection coefficient of the surface

|J~r |
R= , (218)
|J~i |

which is given by the probability current density reflected from the surface
divided by the probability current density incident on the surface.

We can also define the transmission coefficient of the surface

|J~t |
T = , (219)
|J~i |

which is given by the probability current density transmitted through the


surface divided by the probability current density incident on the surface.

77
Using Eqs. (215)−(217), we can write the reflection and transmission co-
efficients as
|B|2 k2 |C|2
R= , T = , (220)
|A|2 k1 |A|2

where k1 = |~k1 | and k2 = |~k2 |.

Thus, if |B|2 = |A|2 then R = 1, i.e. all the particles that are incident
on the surface are reflected.

Exercise at home:

It is easy to show from the definition of the probability current density,


Eq. (204), that in general when the wave function Ψ of a particle in a given
region is real, the current density J~ = 0 in this region.
How would you interpret this result?

78
8 Applications of the Schrödinger Equation:
Potential (Quantum) Wells
We have seen that the wave nature of particles plays an important role in their
physical properties that, for example, particles confined into a small bounded
area can have only particular discrete energies. However, the question we
are most interested in is: can we create an artificial structure which exploits
discrete energy levels? We can produce such structures, they involve potential
barriers. One dimensional structures such constructed are called quantum
wells, two dimensional are called quantum wires, and three dimensional
are called quantum dots.
To illustrate that particles really exhibit unusual quantum effects when
are located in such structures, we will solve the time-independent Schrödinger
equation

Ĥφ(~r) = Eφ(~r) , (221)

to find the eigenvalues E and the eigenfunctions φ(~r) of a particle of a mass m


moving in a potential V̂ (~r) that varies with the position ~r.
In this and the following lecture, we will limit our calculations to the
one-dimensional case, in which the Hamiltonian of the particle is given by

h̄2 d2
Ĥ = − + V̂ (x) . (222)
2m dx2
With this Hamiltonian we get, from the SE, a second-order differential equa-
tion for the wave function of the particle
d2 φ(x) 2m
= − (E − V (x)) φ(x) , (223)
dx2 h̄2
which can be written as
d2 φ(x)
= −k 2 (x)φ(x) , (224)
dx2
where
 
2m E − V̂ (x)
k 2 (x) = . (225)
h̄2

79
When V̂ (x) is independent of x, i.e. the particle is moving along the x
axis under the influence of no force because the potential is constant, the
parameter k 2 (x) = k 2 , and then Eq. (224) reduces to a simple harmonic
oscillator equation
d2 φ(x)
= −k 2 φ(x) . (226)
dx2
This is a linear differential equation with a constant coefficient. The solution
of Eq. (226) depends on whether k 2 > 0 or k 2 < 0. For k 2 > 0, the general
solution of Eq. (226) is in the form of an oscillating wave
φ(x) = Aeikx + Be−ikx , (E > V ) . (227)
where A and B are amplitudes of the particle wave moving to the right and
to the left, respectively.
For k 2 < 0, the general solution of Eq. (226) is in the form
φ(x) = Ce−kx + Dekx , (E < V ) , (228)
that the exponents are real and no longer represent an oscillating wave func-
tion. They represent a wave function with damped amplitudes.

Important note: The general solution (227) with both constants A and
B different from zero is physically acceptable. However, the general solution
(228) with both constants C and D different from zero cannot be accepted.
We have learnt that the wave function must vanish for x → ±∞. Thus, if
the particle moves in the direction of positive x, then only the wave function
with C 6= 0 and D = 0 will satisfy this condition, and vice versa, if the
particle moves in the direction of negative x, only the wave function with
C = 0 and D 6= 0 will satisfy the condition of φ(x) → 0 as x → −∞.

Another important observation: The solutions (227) and (228) are single
value solutions for the wave function φ(x). Thus, for the particle moving in
an unbounded area where the potential V̂ is constant, there are no restric-
tions on k which, according to Eq. (225), means that there are no restrictions
on the energy E of the particle. Hence, the energy E of the particle can have
any value ranging from zero to +∞ (continuous spectrum). It is also valid
for x-dependent potentials, where V (x) slowly changes with x.
For potentials rapidly changing with x the particle can be trapped in
potential holes, and then E can be different.

80
Consider three examples of particles moving in potentials rapidly changing
with x:
1. Infinite potential quantum well.
2. Square-well potential.
3. Tunneling through a potential barrier.

8.1 Infinite potential quantum well


Let us consider one dimensional structures, quantum wells. As the first
example, consider an infinite potential well, shown in Fig. 14. The term
”well” is a bit misleading since the particle is actually only trapped in one
direction. It is still free to move in other two directions.

V(x)

−a/2 a/2 x

Figure 14: An infinite potential well.

For the infinite potential well


a a
V (x) = 0 for − ≤x≤ ,
2 2
a a
V (x) = ∞ for x<− and x > . (229)
2 2
According to classical physics, the particle trapped between the walls will
bounce back and forth indefinitely, its energy will be constant E = mv 2 /2.

81
Moreover, the probability of finding the particle at any point between the
walls is constant, and anywhere outside the walls is zero. In fact, if we know
the initial momentum and position of the particle, we can specify the location
of the particle at any time in the future. The classical case seems trivial. But,
what quantum physics tells us about the behave of the particle?
According to quantum physics, the particle is described by a wave func-
tion φ(x), which satisfies the Schrödinger equation and some boundary con-
ditions. One of the boundary conditions says that the wave function φ(x)
must be finite everywhere. Thus, in the regions x < −a/2 and x > a/2,
the wave function φ(x) must be zero to satisfy this condition that V (x)φ(x)
must be finite everywhere.
In the region − a2 ≤ x ≤ a2 , the potential V (x) = 0, and then the
Schrödinger equation for the wave function is
d2 φ(x)
2
= −k 2 φ(x) , (230)
dx
where now k 2 = 2mE/h̄2 .
Since k 2 is positive, the Schrödinger equation (230) has a simple solution
a a
φ(x) = Aeikx + Be−ikx , − ≤x≤ , (231)
2 2
where A and B are constants, that in general are complex numbers.
In order to determine the unknown constants A and B, we will use the
boundary condition that the wave function must be continuous at x = −a/2
and x = a/2.
Usually, we find the constant B in terms of A, and then we find the re-
maining constant A from the normalization condition that the wave function
is normalized to one, i.e.
Z ∞
dx |φ(x)|2 = 1 . (232)
−∞

Since in the regions x < −a/2 and x > a/2, the wave function is equal to
zero, and the wave function must be continuous at x = −a/2 and x = a/2,
we have that φ(x) = 0 at these points. In other words, the wave functions
must join smoothly at these points.
Thus, at x = −a/2, the wave function φ(x) = 0 when
ika ika
Ae− 2 + Be 2 =0. (233)

82
At x = a/2, the wave function φ(x) = 0 when
ika ika
Ae 2 + Be− 2 =0. (234)

From Eq. (233), we find that

B = −Ae−ika , (235)

whereas from Eq. (234), we find that

B = −Aeika . (236)

We have obtained two different solutions for the coefficient B. Accepting


these two different solutions, we would accept two different solutions for
the wave function. However, we cannot accept it, as one of the conditions
imposed on the wave function says that the wave function must be a single
value function. Therefore, we have to find a condition under which the two
solutions (235) and (236) are equal. It is easily to see from Eqs. (235) and
(236) that the two solutions for B will be equal if

e−ika = eika , (237)

which will be satisfied when

e2ika = cos(2ka) + i sin(2ka) = 1 , (238)

or when

cos(2ka) = 1 , (239)

i.e. when
π
k=n , with n = 0, 1, 2, . . . . (240)
a
Thus, for a particle confined in the infinite well there is a restriction for k,
that k can only take discrete values.
Since k 2 = 2mE/h̄2 , we see that the energy of the particle cannot be
arbitrary, it can only takes on certain discrete values!

h̄2 2 π 2h̄2
En = k = n2 . (241)
2m 2ma2

83
Thus, the energy of the particle is quantized, that the energy of the particle
can have only discrete values (discrete spectrum), that depend on the integer
variable n. We indicate this by writing a subscript n on E. The integer
number n is called the quantum number. The energy-level spectrum is
shown in Fig. 15. Note from Eq. (241) that the energy levels in a quantum
well depend on the dimensions of the well and the mass of the particle. This
means that we can build artificial structures of desired quantum properties,
which could be observed if the dimensions of the structures are very small.

n=4
E4

n=3
E3

n=2
E2
n=1
E1

Figure 15: Energy-level spectrum of a particle inside the infinite potential well.
Note that the separation between the energy levels increases in increasing n.

Finally, substituting one of the solutions for B, Eq. (235) or (236), into
the general solution (236), we find the wave function of the particle inside
the well
nπ a
  
ika
φn (x) = Ae 2 sin x− , n = 1, 2, 3, . . . . (242)
a 2
The solution for n = 0 is not included as in this case the wave function
φ(x) = 0 for all x inside the well. This would mean that the particle is not
in the box. Thus, the minimum energy state in which the particle can be
inside the well is that with the energy E1 = π 2 h̄2 /2ma2 . Since E1 > 0, the
particle can never have zero energy.

84
The coefficient A appearing in Eq. (242) is found from the normalization
condition
Z +∞
|φn (x)|2 dx = 1 , (243)
−∞

from which
q by performing the integral with φn (x) given by Eq. (242), we find
|A| = 2/a. Details of the integration are left to the students.

φ(x ) φ(x ) φ(x )

−a/2 −a/2 a/2


−a/2 a/2 x a/2 x x

n=1 n=2
n=3

Figure 16: Plot of the wave function of the particle for the first three energy
levels.

Figure 16 shows the wave functions of the particle for the first three val-
ues of n. It is seen that for n = 1 the particle is more likely to be found near
the center than the ends. For all n’s the probability is not constant and for
n > 1 has zeros for some values of x. This is in contrast to the predictions
of classical physics, where the particle has the same probability of being lo-
cated anywhere between the walls. Moreover, the lowest energy (n = 1) is
non-zero, which indicates that the particle can have non-zero energy even if
the potential energy is zero.

In summary of this lecture: We have learnt that

1. The energy of a particle in a quantum well can only take on certain


discrete values. All other values of the energy are forbidden. We say
that the energy of the particle is quantized.

85
2. The quantization of the energy arises from the condition of the continu-
ity of the particle wave function at the boundaries between two regions
of different potential.
3. The lowest energy the particle can have inside the well is not zero.
4. The probability of finding the particle at an arbitrary position x is not
constant, it even has zeros.

Exercise:

An electron is confined in an infinite potential well of width a = 0.1 nm


(approximate size of an atom).
(a) What is its lowest energy?
(b) What is the equivalent temperature?

Solution:

(a) The lowest energy of the electron corresponds to n = 1. Using Eq. (241),
we find
π 2h̄2 h2 (6.626 × 10−34 )2
E1 = (1)2 = =
2ma2 8ma2 8 × 9.109 × 10−31 × (10−10 )2
= 6.025 × 10−18 [J] = 37.6 [eV] .

(b) Since n = 1, we find from the formula (64) that


E1
e kB T = 2 ,

from which, we get


E1
≈1,
kB T
i.e.
 
T ≈ E1 /kB = 6.025 × 10−18 / 1.381 × 10−13 = 43.6 [µK] .

86
Exercises at home:

(1) One may notice from Fig. 16 that the wave function for n = 2 is zero
at x = 0, i.e. at the center of the well. This means that the probability of
finding the particle at the center of the well is also zero. Then, a question
arises: how does the particle move from one side of the well to the other if
the probability of being at the center is zero?

(2) Solve the Schrödinger equation with appropriate boundary conditions


for an infinite square well with with a centered at a/2

V (x) = 0 for 0≤x≤a,


V (x) = ∞ for x < 0 and x > a .

Check the the allowed energies are consistent with those derived in lecture
for an infinite well of width a centered at the origin. Confirm that the wave
function φn (x) can be obtained from those found in lecture if one uses the
substitution x → x + a/2.

87
8.2 Finite square-well potential
The infinite potential well is an idealized example. More realistic problems
in physics have finite energy barriers. In such systems, one of the most
interesting differences between classical and quantum descriptions of behavior
of particles concerns the phenomenon of barrier penetration.
Consider a particle moving in a finite square-well potential as shown
in Fig. 17:
a
I. V (x) = V0 , x<−
2
a a
II. V (x) = 0 , − ≤x≤
2 2
a
III. V (x) = V0 , x> . (244)
2

I II III
V0 V0
V=0

−a/2 a/2 x

Figure 17: Finite square-well potential.

In classical physics a particle is trapped in the well if the energy E of the


particle is less than V0 . In this case, the probability of finding the particle
outside the well is zero. When the energy E is larger than V0 , the particle
can freely move in all three regions. Let’s look at these situations from the
point of view of quantum physics.
Before going into the detailed calculations of the particle wave function,
we should point out that in behavior of the particle in a finite square-well

88
potential, it must be recognized that the wave function of the particle can
exist in all space, that all regions in space are accessible for the particle even
if the energy E is less than V0 .
In the region II, −a/2 ≤ x ≤ a/2, the potential V (x) = 0, and then the
Schrödinger equation reduces to
d2 φ2 (x)
= −k22 φ2 (x) , (245)
dx2
where k22 = 2mE/h̄2 , and φ2 (x) is the wave function of the particle in the
region II.
Since k22 is positive, the solution of Eq. (245) is of the form

φ2 (x) = Aeik2 x + Be−ik2 x , (246)

that is the same as for the particle in the potential well. Thus, we expect
that similar to the case of the infinite potential barrier, the energy of the
particle will be quantized in the region II.
In the regions I and III, the potential is different from zero V (x) = V0 ,
and then
2m 2m
k12 = − 2 (V0 − E) = (E − V0 ) . (247)
h̄ h̄2
In this case, the the Schrödinger equation is given by
d2 φ1 (x)
= −k12 φ1 (x) . (248)
dx2
Solution of the above equation depends on the relation between V0 and E.
For E > V0 the parameter k12 is positive, and then the solution of Eq. (248)
is of the form

φ1 (x) = Ceik1 x + De−ik1 x , (249)

indicating that the probability of finding the particle in the regions I and III
is similar to that in the region II. It is not difficult to show, (the details of the
calculations are left to the students), that in this case the energy spectrum of
the particle is continuous in all regions. Thus, one could conclude that there
is nothing particularly interesting about the solution when E > V0 . How-
ever, we may obtain nonzero reflection coefficient at the boundaries, which

89
is a quantum effect. Classically, one would expect that the particle of energy
E > V0 should travel from region I to region III without any reflection at the
boundaries.2

More interesting is the case of E < V0 . For E < V0 the parameter k12 is
a negative real number, and then the solution of Eq.(248) is in the form of
exponential functions
a
φ1 (x) = Cek1 x + De−k1 x , x<−
2
a
φ1 (x) = F ek1 x + Ge−k1 x , x> . (250)
2
In order to get φ1 (x) finite for each |x| > a/2, in particular at x → ±∞, we
have to choose D = F = 0. Otherwise, the wave function would be infinite
at x = ±∞. Hence, the solution (250) reduces to
a
I. φ1 (x) = CekI x , for x<−
2
a
III. φ1 (x) = Ge−kI x , for x> . (251)
2
Assume for a moment that C, G 6= 0, then the probability |φ(x)|2 has inter-
esting properties, shown in Fig. 18. The most striking features of the wave

V0 V0

-a/2 a/2 x

Figure 18: Probability function of the particle inside the potential well.
2
I leave it as an exercise for students to show that the reflection coefficient is nonzero
at the boundaries.

90
function φ(x) are the ”tails” that extend outside the well. The non-zero val-
ues of φ(x) outside the well means that there is a non-zero probability for
findings the particle in the regions I and III.
The regions I and III are forbidden by classical physics because the par-
ticle would have to have negative kinetic energy. Since the total energy of
the particle E < V0 and E = Ek + V0 , we have that

Ek + V 0 < V 0 in the regions I and III . (252)

Therefore, the penetration of the barrier is a quantum effect that has no


classical analog. Quantum mechanical penetration of the barrier has come
to be regarded as a paradoxical, controversial, non-intuitive aspect of quan-
tum physics.

How far the particle can penetrate the barrier?

This depends on V0 . To show this, consider the wave function in the re-
gion III. In this case
a
φ1 (x) = Ge−k1 x , x> , (253)
2
with
1q
k1 = 2m (V0 − E) . (254)

Since the parameter k1 is a positive real number, it plays a role of the damping
coefficient of the exponential function. For V0  E, the parameter k1  0,
and then the penetration is very small (vanishes for V0 → ∞). For V0 ≈ E,
the parameter k1 ≈ 0, and then the penetration is very large. These two
situations are shown in Fig. 19.

In order to prove that the penetration effect really exist, we have to demon-
strate that the constants C and G are really non-zero.

To show this, we will turn to the details, and carry out the complete so-
lution for the wave function of the particle.

91
(2)
k I(1) >> k I
(2) (1) (2)
kI V 0 >> V 0
(1)
kI

a/2 x

Figure 19: The dependence of exp(−k1 x) on x for two different values of k1 .

We start from the general solution of the Schrödinger equation for the wave
function of the particle inside the square-well potential, which is of the form:
a
I. φ1 (x) = Cek1 x , x<−
2
a a
II. φ2 (x) = Aeik2 x + Be−ik2 x , − ≤x≤
2 2
a
III. φ1 (x) = Ge−k1 x , x> . (255)
2
In order to find the constants A, B, C, and G, we use the property of the
wave function, that φ(x) and the first-order derivative dφ(x)/dx must be fi-
nite and continuous everywhere, in particular, at the boundaries x = −a/2
and x = a/2.

Hence, at x = −a/2 :
1 1 1
Ce− 2 ak1 = Ae−i 2 ak2 + Bei 2 ak2 . (256)

At x = a/2 :
1 1 1
Ge− 2 ak1 = Aei 2 ak2 + Be−i 2 ak2 . (257)

We remember, that also dφ/dx must be continuous across the same bound-
aries.

92
Since
dφ1
I. = Ck1 ek1 x ,
dx
dφ2
II. = iAk2 eik2 x − iBk2 e−ik2 x ,
dx
dφ1
III. = −Gk1 e−k1 x , (258)
dx
we find that at x = −a/2:
1 1 1
 
Ck1 e− 2 ak1 = ik2 Ae− 2 iak2 − Be 2 iak2 , (259)

and at x = a/2:
1 1 1
 
−Gk1 e− 2 ak1 = ik2 Ae 2 iak2 − Be− 2 iak2 . (260)

Dividing both sides of Eq. (259) by k1 , we obtain


1 1 1
 
Ce− 2 ak1 = iβ Ae− 2 iak2 − Be 2 iak2 , (261)

where β = k2 /k1 .
Comparing Eqs. (256) and (261), we get
1 1 1 1
 
Ae−i 2 ak2 + Bei 2 ak2 = iβ Ae− 2 iak2 − Be 2 iak2 , (262)

from which we find that


(iβ + 1) iak2
A= Be . (263)
(iβ − 1)
Hence, substituting Eq. (263) into Eq. (256), we find that
2iβ 1
C= Be 2 ak1 (iβ+1) . (264)
(iβ − 1)
Since B 6= 0, as the particle exists inside the well, we have that C 6= 0
indicating that there is a non-zero probability of finding the particle in the
region I. The probability is given by |φ1 (x)|2 , that is

|φ1 (x)|2 = |C|2 e−2k1 |x| , (265)

93
where |x| = −x for x < 0. Thus,
4β 2
e−2k1 (|x|− 2 ) .
a
|φ1 (x)|2 = |B|2 2
(266)
(β + 1)
The probability is different from zero and decreases exponentially with the
rate 2k1 . The constant |B| is found from the normalization of φ(x).

Exercise:

Show that the particle probability current density J~ is zero in region I, and
deduce that R = 1, T = 0. This is the case of total reflection, the particle
coming towards the barrier will eventually be found moving back. ”Eventu-
ally”, because the reversal of direction is not sudden. Quantum barriers are
”spongy” in the sense the quantum particle may penetrate them in a way
that classical particles may not.

Consider now the continuity conditions at x = a/2. From the symmetry


of the system, we expect that the constant G, similar to C, will be differ-
ent from zero, and may be found in a similar way as we have found the
constant C.
From Eqs. (257) and (260), and using Eq. (263), we find two solutions for
the constant G in terms of B:
1 3 1
 
Ge− 2 ak1 = B ue 2 iak2 + e− 2 iak2 , (267)
− 12 ak1 3
− 21 iak2
 
iak2
Ge = −iβB ue 2 −e , (268)
where
(iβ + 1)
u= . (269)
(iβ − 1)
Here, we have two solutions for G. However, we cannot accept both of the
solutions as it would mean that there are two different probabilities of finding
the particle at a point x inside the region III. Therefore, we have to find under
which circumstances these two solutions are equal.
Dividing Eq. (268) by (267), we obtain
 
iβ ue2iak2 − 1
= −1 , (270)
(ue2iak2 + 1)

94
from which we find that the solutions (267) and (268) are equal when
2k1 k2
tan(ak2 ) = . (271)
k22 − k12
To proceed further, we introduce dimensionless parameters
s
2
1 1 2mE

 = ak2 = a , (272)
2 2 h̄2
q 1
ξ 2 − 2 = ak1 , (273)
2
where
2
1 2mV0

2
ξ = a . (274)
2 h̄
We see from the relation  = 12 ak2 that determining  we can get the
energy E of the particle inside the well. In order to show this, we rewrite
Eq. (271) in terms of  and ξ, and find
q
 tan  = ξ 2 − 2 . (275)
This is a transcendental equation which, can be solved graphically as follows.
Introducing the notation
p() =  tan  ,
q
q() = ξ 2 − 2 , (276)
we find solutions of the equation p() = q() by plotting separately p() and
q(). The functions p() and q() are shown in Fig. 20. The intersection
points of the two curves gives the solutions of the equation p() = q(). We
see from the figure that the equation p() = q() is satisfied only for discrete
(finite) values of . Since the energy E is proportional to , see Eq. (272),
we find that the energy of the particle is quantized in the region II, i.e. the
energy spectrum is discrete.
The number of solutions, which will give us the number of energy levels,
depends on ξ, but always is finite. We see from Fig. 20 that there we have
one solution for ξ<π,
two solutions for ξ < 2π ,
three solutions for ξ < 3π ,

95
p( ε ) p( ε ) p( ε )

. q( ε )

0 π π 3π 2π ε
2 2
ε=ξ
Figure 20: p() and q() as a function of .

and so on. The number of solutions determines the number of energy levels
inside the well.
We remember that
1   ma2 V0
ξ 2 = a2 k12 + k22 = . (277)
4 2h̄2
Thus, ξ is determined by the dimensions of the well.

96
Example:

Consider a potential well with ξ = 4. Since ξ < 2π, we see from Fig. 20
that in this case there are two solutions for : 1 = 1.25 and 2 = 3.60.
Once we have the allowed values of , we can find the allowed values of
the energy E. Since
1 q 1
 = ak2 , ξ 2 − 2 = ak1 , (278)
2 2
and
s s
2m 2m
k1 = (V0 − E) , k2 = E, (279)
h̄2 h̄2
we get
√ 2 s
ξ − 2 k1 V0 − E
= = , (280)
 k2 E
from which we find
2
E= V0 . (281)
ξ2
Hence, for 1 = 1.25 and 2 = 3.60, we get E1 = 0.098V0 and E2 = 0.81V0 ,
respectively.

E2 V0

E1

Figure 21: Energy levels inside the well with ξ = 4.

97
Exercise at home:

A rectangular potential well is bounded by a wall of infinite high on one


side and a wall of high V0 on the other, as shown in Fig. 22. The well has a
width a and a particle located inside the well has energy E < V0 .

(a) Find the wave function of the particle inside the well.

V0

0 region I a region II x

Figure 22: Potential well of semi-infinite depth.

(b) Show that the energy of the particle is quantized.

(c) Discuss the dependence of the number of energy levels inside the well
on V0 .

98
8.3 Quantum tunneling
When the potential barrier has a finite width, the tunneling effect can appear,
that the particle with energy E < V0 can not only penetrate the barrier, it can
even pass through the barrier and appear on the other side. This phenomenon
is known as quantum tunneling. This effect depends on the relation between
V0 and E and also on the thickness of the barrier (see Fig. 23).

I II III
V0

Figure 23: Tunneling effect through a potential barrier of a thickness a.

How can we understand this process of a particle tunneling through a


seemingly impenetrable barrier? How large is the probability that the particle
passes through the barrier? To answer these questions, we can use a wave
picture of the particle. We have already learnt that the particle wave function
does not terminate abruptly at the edge of the barrier, but actually leaks out
the barrier.
Let us perform the detailed calculations of the tunneling probability.

Rigorous calculations:

Consider a particle moving from the left and acting on the rectangular po-
tential barrier, Fig. 23. Assume that E < V0 . The solution of the Schrödinger
equation for the three regions is
a
I. φ1 (x) = Aeik1 x + Be−ik1 x , x<−
2
a a
II. φ2 (x) = Ce−k2 x + Dek2 x , − ≤x≤
2 2
a
III. φ1 (x) = F eik1 x + Ge−ik1 x , x> (282)
2

99
√ q
where k1 = 2mE/h̄ and k2 = 2m(V0 − E)/h̄.
The continuity conditions for the wave function and the first-order deriva-
tive at x = −a/2 are
a a a a
Ae−ik1 2 + Beik1 2 = Cek2 2 + De−k2 2 ,
a a ik2  k2 a a

Ae−ik1 2 − Beik1 2 = Ce 2 − De−k2 2 . (283)
k1
The continuity conditions at x = a/2 are
a a a a
Ce−k2 2 + Dek2 2 = F eik1 2 + Ge−ik1 2 ,
a a ik1  ik1 a a

−Ce−k2 2 + Dek2 2 = F e 2 − Ge−ik1 2 . (284)
k2
The continuity conditions (283) and (284) can be written in matrix forms as
   a a
  a a

ik2 ik2
ek2 2 +ik1 2 e−k2 2 +ik1 2
! !
A 1 1+ k1 
1− k1  C
=   a a
 a a
 , (285)
B 2 1− ik2
ek2 2 −ik1 2 1+ ik2
e−k2 2 −ik1 2 D
k1 k1

and
   a a
  a a

ik1 ik1
ek2 2 +ik1 2 ek2 2 −ik1 2
! !
C 1 1− k2
1+ k2 F
=   a a
 a a
 . (286)
D 2 1+ ik1
e−k2 2 +ik1 2 1− ik1
e−k2 2 −ik1 2 G
k2 k2

The relationship between the solution on the left of the barrier and the
solution on the right can now be obtained by substituting the matrix equation
(286) into the right hand side of the matrix equation (285), and then we
obtain
!
A
=
B
   

cosh k2 a + i2 sinh k2 a eik1 a
!
2
sinh k2 a F
   
iη G
− 2 sinh k2 a cosh k2 a − i2 sinh k2 a e−ik1 a
(287)
with  = kk12 − kk12 and η = kk21 + kk12 . The solution with G = 0 is of particular
interest as it represents the situation where no particles are incident on the
barrier from the right. In this case
F e−ik1 a
= . (288)
A cosh(k2 a) + 12 i sinh(k2 a)

100
Hence, the transmission coefficient of the particle current is
#−1
|F |2
"  2

T = 2
= cosh2 (k2 a) + 2
sinh (k2 a)
|A| 2
"  2 ! #−1
 2
= 1+ + 1 sinh (k2 a)
2
#−1
V02 sinh2 (k2 a)
"
= 1+ . (289)
4E(V0 − E)

When E > V0 , the solution changes only in the region II, and the new
0
solution
q can be obtained from the old solution by replacing k2 by ik2 , where
k20 = 2m(E − V0 )/h̄. So that the expression for T changes to
#−1
V02 sin2 (k20 a)
"
T = 1+ . (290)
4E(E − V0 )

First, note that if there is no barrier, V0 = 0, and then there is 100% trans-
mission. Thus, there is nothing particularly remarkable about the solution
when V0 = 0. Its physical interest lies in what happens when V0 6= 0.
For V0 6= 0, one could expect from the classical mechanics that T = 0 for
E < V0 , and T = 1 for E > V0 . However, Eq. (289) shows that T is not
zero for E < V0 (non-zero transmission), and Eq. (290) shows that T < 1 for
E > V0 (non-zero reflection).
Thus, tunneling effect for E < V0 and partial reflection at the barrier
for E > V0 are quantum phenomena. In the classical limit of h̄ → 0, the
parameter k2 → ∞, and then T → 0. Hence, in the classical limit, there is no
possibility of the particle of an energy E < V0 to pass the barrier. Moreover,
since that k2 is proportional to mass of the particle, the transmission coeffi-
cient (289) is large for light particles and decreases with the increasing m.

There is the further interesting phenomenon for the case of E > V0 . One
can see from Eq. (290) that if k20 a = nπ, n = 1, 2, 3, . . ., there is 100% trans-
mission from region I to III. This phenomenon is analogous to the behavior
of coated lenses in optics. Otherwise, quantum effect (partial reflection) ap-
pears.

101
Quantum tunneling is important in the understanding of number of phys-
ical phenomena such as thermonuclear reactions and conduction in metals
and semiconductors. In 1928, Gamov, Condon and Gurney used quantum
tunneling to explain the α-decay of unstable nuclei, in which an alpha particle
(a helium nucleus) is emitted from a radioactive nucleus. The alpha particle
has energy which is less than the high of the potential barrier keeping the
particle inside the nucleus. Nevertheless, alpha particles tunnel through the
barrier and are detected outside the nucleus.
Tunneling has also been used in a number of electronic devices. One is a
tunnel diode in which the current of electrons is controlled by adjusting the
energy E of the electrons. This changes the value of k2 and thus the rate the
electrons tunnel through the device.
The most advanced application of quantum tunneling is the scanning
tunneling microscope. A probe needle is held very close (< 1 nm) above a
conducting object and scanned across it. The object is at a positive volt-
age V with respect to the probe needle. However, for electrons to pass from
the needle to the object, they have to overcome the work function of the
needle material. This creates a potential barrier through which electrons can
tunnel. As they tunnel through the potential barrier they generate a current
whose the variation tells us about the distance between the needle and the
object.

Challenging problem: Quantum tunneling from and into a semi-finite well

In the problem discussed in lecture, we have shown there are no restrictions


on the energy of a particle to tunnel through the barrier. The explanation of
this effect is simple: The particle of an arbitrary energy can tunnel through
the barrier because there are no restrictions on energies which the particle
can have in the region III. Lets us consider the exercise from page 98, a
rectangular potential well of width a bounded by a wall of infinite high on
one side and a barrier of high V0 and infinite thickness on the other. We
have learnt that inside the well, region I, a particle can have only a limited
number of discrete energies.

102
V0

0 region I a region II 2a region III x

Figure 24: Potential well of semi-infinite depth limited by a barrier of high V 0


and width a.

(a) Now imagine what happens if the thickness of the barrier (region II)
is finite and the particle of energy E < V0 is inside the potential well. Do
you expect the energy levels of the particle in region I are still discrete?

(b) Suppose that the particle of energy E < V0 is in the region III on
the right of the barrier and moves towards the barrier, as shown in Fig. 24.
Find the tunneling coefficient and determine whether for each E, in the range
0 < E < V0 , the particle can tunnel to the region I, i.e. determine whether
the energy spectrum in the region I is discrete or continuous. Would you
expect this result without the detailed calculations?

103
9 Multi-Dimensional Quantum Wells:
Quantum Wires and Quantum Dots
We have seen that in the one-dimensional case, particles confined into a
small region can have quantized energies, can be be found in ”classically
forbidden” region and even can tunnel through this region. Although the
one-dimensional case is very useful in the illustration and understanding of
the quantum effects, we need a full three-dimensional treatment if we want
to illustrate applications of quantum mechanics to atoms, solid state, and
nuclear physics. The application to atoms will be discussed in a separate
lecture on Angular Momentum and Hydrogen Atom, Chapter 15. In this
lecture, we extend the concept of quantum wells from one to three dimensions.

                x
                
                



                      L



                     



 
 
 
 
 
 
 







  
    


   


   


 

        

         

Figure 25: A three dimensional well of sides x = a, y = a, and z = L. Inside the


well V = 0. The potential is infinite at the xy walls and can be set zero at the z
walls (quantum wire), or infinite (quantum dot).

We can picture a quantum wire as a pipe, shown in Fig. 25, and particles
moving freely along this pipe, just like cars driving through a mountain tun-
nel. However, we must be careful when using analogies to describe quantum

104
phenomena. We expect the cars to drive along the bottom of the tunnel, but
we would be surprised to see the cars driving through mid-air a few meters
above the tunnel floor. This is precisely how the particles appear to behave
in a quantum wire.

9.1 General solution of the three-dimensional


Schrödinger equation
Let us find the wave function of a particle located inside the well and its
energies. The wave function and the energies are found from the three-
dimensional Schrödinger equation

h̄2 2
− ∇ Ψ+VΨ=E . (291)
2m
We see that in cartesian coordinates ∂ 2 /∂x2 in the one-dimensional case is
replaced in three dimensions by the Laplacian

2 ∂2 ∂2 ∂2
∇ = 2+ 2+ 2 . (292)
∂x ∂y ∂z

Since x, y, z are independent (separable) variables, the wave function is also


separable into three independent functions Ψx , Ψy , and Ψz . In this case, we
can find the solution of the Schrödinger equation in product form

Ψ(x, y, z) = Ψx (x)Ψy (y)Ψz (z) . (293)

Substituting this into the Schrödinger equation and dividing both sides by
Ψx Ψy Ψz , we obtain

h̄2 d2 Ψx h̄2 d2 Ψy h̄2 d2 Ψz


− − − =E , (294)
2mΨx dx2 2mΨy dy 2 2mΨz dz 2

where, as before, we have put V = 0 inside the well, but outside the well we
will set V = ∞.
Since each term on the left-hand side of Eq. (294) is a function of only one
variable, each will be independent of any change in the other two variables.

105
Thus, Eq. (294) can be separated into three independent equations. To
illustrate this, we write this equation as

h̄2 d2 Ψx h̄2 d2 Ψy h̄2 d2 Ψz


− =E+ + . (295)
2mΨx dx2 2mΨy dy 2 2mΨz dz 2
The lhs involves all of the x dependence. If we change x any way we want, the
rhs is not affected. Thus, it must be that both sides are equal to a constant,
say Ex :

h̄2 d2 Ψx
− = Ex , (296)
2mΨx dx2
h̄2 d2 Ψy h̄2 d2 Ψz
− − = E − Ex . (297)
2mΨy dy 2 2mΨz dz 2
Equation (297), that depends only on y and z variables can be written as

h̄2 d2 Ψy h̄2 d2 Ψz
− = E − E x + . (298)
2mΨy dy 2 2mΨz dz 2
Again, both sides depend on different variables, the lhs depends only on y
and the rhs depends only on z, thus both sides are equal to a constant,
say Ey :

h̄2 d2 Ψy
− = Ey , (299)
2mΨy dy 2
h̄2 d2 Ψz
− = E − E x − Ey . (300)
2mΨz dz 2
Hence, after the separation of the variables, one differential equation in three
variables has turned into three independent equations of one variable each

h̄2 d2 Ψx
− = Ex , (301)
2mΨx dx2
h̄2 d2 Ψy
− = Ey , (302)
2mΨy dy 2
h̄2 d2 Ψz
− = Ez , (303)
2mΨz dz 2

106
where Ez = E − Ex − Ey .
The wave function of the particle inside the well and its energies are
found from these three independent equations. The parameters Ex , Ey and
Ez are separation constants, and represent energies of motion along the three
Cartesian axis x, y and z. It is easily to see that these three constants satisfy
the equation
Ex + E y + E z = E . (304)
The solutions of the equations (301) and (302) are the same as that for
the infinite square well in one dimension, and are given by
n1 π
 
Ψx = A sin x , n1 = 1, 2, 3, . . . , (305)
a
n2 π
 
Ψy = B sin y , n2 = 1, 2, 3, . . . , (306)
a
with energies
π 2 h̄2 π 2h̄2
Ex = n21 and Ey = n22 . (307)
2ma2 2ma2

9.2 Quantum wire and quantum dot


The solution for the z component of the motion, Eq. (303), depends on
whether the z sides of the well have zero or infinite potential. For zero
potential, the z direction is free for the motion of the particle (quantum
wire), and is given by the wave function
Ψz = Ceikz z , (308)
where kz2 = 2mEz /h̄2 , and Ez can have arbitrary values.
If the potential at the z sides is infinite, we have an example of quantum
3
dot . In this case, the solution of Eq. (303) is the same as for the x and y
components
n3 π
 
Ψz = C sin z , n3 = 1, 2, 3, . . . , (309)
L
3
It would be more correct to call the quantum dot a quantum box, but in many cal-
culations, quantum dots that have spherical symmetries are approximated by rectangular
boxes.

107
with the Ez energy taking only discrete values

π 2h̄2
Ez = n23 . (310)
2mL2
Thus, we can summarize that for a quantum wire, the wave functions of
the particle are of the form
n1 π n2 π
   
Ψn1 ,n2 = D sin x sin y eikz z , (311)
a a
and the corresponding energies are given by

π 2h̄2  2 2

E= n + n 2 + Ez , with n1 , n2 = 1, 2, 3, . . . , (312)
2ma2 1
where D = ABC is a constant which is found from the normalization condi-
tion of the wave function. It is easy to show that
s
2 2
D= . (313)
a L
The proof is left to the students.

Interesting observation:
Since the energy of the particle in the y direction can never be zero, the
particle will never move at the floor of the wire. Because the motion of the
particle is restricted (quantized) in two dimensions, a quantum wire is some-
times referred to as a one-dimensional system.

For a quantum dot with L = a, the wave functions of the particle inside
the well are of the form
 3
2 n1 π n2 π n3 π
     
2
Ψn1 ,n2 ,n3 = sin x sin y sin z , (314)
a a a a
and the corresponding energies are given by

π 2 h̄2  2 2 2

E= n + n + n , with n1 , n2 , n3 = 1, 2, 3, . . . . (315)
2ma2 1 2 3

108
Thus, energy of the particle in a quantum dot is quantized in all three di-
rections. Because the motion of the particle is now restricted in all three
dimensions (quantum confinement), a quantum dot is sometimes referred to
as a zero-dimensional system. Quantum dots are also regarded as artificial
atoms.
One can notice that the results obtained for the three-dimensional case
are similar to that obtained for the one-dimensional case. However, there is
a significant difference between these two cases. For the three-dimensional
case there might be few wave functions corresponding to the same energy.
We can illustrate this on a simple example of energies and the corresponding
wave functions of a quantum dot:
The lowest energy state (the ground state), for which n1 = n2 = n3 = 1, has
energy
3π 2h̄2
E= , (316)
2ma2
and there is only one wave function (singlet) corresponding to this energy.
However, there are three wave functions corresponding to energy
6π 2h̄2
E= , (317)
2ma2
as there are three combinations of n1 , n2 and n3 whose squares sum to 6.
These combinations are n1 = 2, n2 = 1, n3 = 1, or n1 = 1, n2 = 2, n3 = 1, or
n1 = 1, n2 = 1, n3 = 2. The three wave functions corresponding to this energy
are Ψ2,1,1 , Ψ1,2,1 , and Ψ1,1,2 . We say that the energy level is degenerate.
It is easy to see from Eq. (315) that the degeneracy of the energy levels
is characteristic of quantum wells whose the sides are of equal lengths. The
degeneracy can be lifted, if the sides of the well were of unequal lengths.

Exercise at home:

Find the number of wave functions (energy states) of a particle in a quantum


well of the sides of equal lengths corresponding to energy
9π 2h̄2
E= ,
2ma2
i.e. for the combination of n1 , n2 and n3 whose squares sum to 9.

109
10 Linear Operators and Their Algebra
We have seen that in quantum physics energy and momentum appear as
mathematical operations, which we call operators. We now extend the idea
of operators into arbitrary quantities, and postulate that any quantity in
quantum physics is specified by a linear operator.
An operator  is linear if for arbitrary functions fi and gi , and arbitrary
complex numbers ci , such that

Âf1 = g1 and Âf2 = g2 ,

the linear superposition is

 (c1 f1 + c2 f2 ) = c1 Âf1 + c2 Âf2 = c1 g1 + c2 g2 . (318)

10.1 Algebra of operators


The sum of two operators  and B̂ and their product are defined as
 
 + B̂ f = Âf + B̂f , (319)
   
ÂB̂ f = Â B̂f . (320)

The operators obey the following algebraic rules:

1. Â + B̂ = B̂ + Â ,   
2. Â + B̂ + Ĉ = Â + B̂ + Ĉ = Â + B̂ + Ĉ ,
   
3. ÂB̂ Ĉ = Â B̂ Ĉ = ÂB̂ Ĉ ,
 
4. Â + B̂ Ĉ = ÂĈ + B̂ Ĉ . (321)

The power of an operator and the sum of two operators is defined as

1. Â2 = ÂÂ , Â3 = ÂÂÂ , etc.


 2   
2. Â + B̂ = Â + B̂ Â + B̂ = Â2 + B̂ 2 + ÂB̂ + B̂ Â . (322)

In general, ÂB̂ 6= B̂ Â. Thus, multiplication of operators is not necessarily


commutative.

110
We can define a commutator:
h i
Â, B̂ = ÂB̂ − B̂ Â , (323)

and say, that two operators commute if


h i
Â, B̂ = 0 . (324)

We can also define anticommutator as


n o h i
Â, B̂ ≡ Â, B̂ = ÂB̂ + B̂ Â , (325)
+

and we say that two operators anticommute if


h i
Â, B̂ =0. (326)
+

Inverse operator:

The inverse of an operator Â, if it exists, is defined by

ÂÂ−1 = Â−1 Â = 1̂ , (327)

where 1̂ is the unit operator defined by

1̂f = f . (328)

Hermitian adjoint: (Hermitian conjugate)

Operator † is the Hermitian adjoint of an operator  if for two


functions f and g that vanish at infinity
Z Z  ∗

f ÂgdV = † f gdV . (329)

Properties of Hermitian conjugate:


 †
1. † =  . (330)

111
Proof:
Z Z  ∗ Z  ∗ Z ∗
∗ † † ∗ †
f ÂgdV =  f gdV = g  f dV = g  f dV
Z  † ∗ ∗ Z  † 
= † g f dV = † g f ∗ dV
Z  † 
= f∗ † g dV , (331)

as required♦.

 †
2. ÂB̂ = B̂ † † . (332)

Proof:
Z  † Z  ∗ Z h  i∗
f ∗ ÂB̂ gdV = ÂB̂f gdV = Â B̂f gdV . (333)

Introducing the notation B̂f = u, we get


Z  ∗ Z Z  ∗
∗ †
Âu gdV = u  gdV = B̂f † gdV
Z
= f ∗ B̂ † † gdV . (334)
 †
Thus, ÂB̂ = B̂ † † ,

as required♦.

112
10.2 Hermitian operators

Operator  is called Hermitian if

† =  , (335)

i.e. when
Z Z  ∗

f ÂgdV = Âf gdV . (336)

10.2.1 Properties of Hermitian operators

If  and B̂ are Hermitian then:

1. Â + B̂ is Hermitian,

2. Â2 , Â3 , etc. are Hermitian,

3. c is Hermitian if c is a real number.

Proof of the property 3:


Z   Z  ∗ Z  ∗
∗ ∗
f c gdV = cÂf gdV = c Âf gdV , (337)

as required♦.

4. ÂB̂ is Hermitian only if  and B̂ commute.

Proof:
 †
ÂB̂ = B̂ † † = B̂  . (338)
 †
Hence, ÂB̂ 6= ÂB̂ unless  and B̂ commute,
as required♦.

113
h i
5. From the property 4, we have that the commutator Â, B̂ is not Hermi-
tian, even if  and B̂ are Hermitian.

Proof:
h i†  †  †  †
Â, B̂ = ÂB̂ − B̂ Â = ÂB̂ − B̂ Â
h i
= B̂ † † − † B̂ † = B̂  − ÂB̂ = − Â, B̂ , (339)

as required♦.
h i
6. However, i Â, B̂ is Hermitian.

Proof is left for the students.

7. For an arbitrary operatorÂ, the product † is Hermitian.

Proof:
 †  †
† = † † = † , (340)

as required♦.
 
8. If  is non-Hermitian,  + † and i  − † are Hermitian. Hence,
 can be written as a linear combination of two Hermitian operators
1  1   
 =  + † + i  − † . (341)
2 2i

10.2.2 Examples of Hermitian operators

1. Position operator ~ˆr is Hermitian.

Since |~r| is a real number and ~ˆr g is just a multiplication of the function
g by ~r, we have
Z Z Z  ∗
∗ˆ
f ~rgdV = ~ˆrf ∗ gdV = ~ˆrf gdV . (342)

114
2. Potential V̂ (~r).

Since ~ˆr is Hermitian, an arbitrary function of ~r is also Hermitian.

3. Momentum operator is Hermitian.

Proof:
!∗
∗ h̄ h̄
Z  Z Z
pˆ~f gdV = ∇f gdV = − (∇f ∗ ) gdV
V V i i V
h̄ h̄
Z Z
=− ∇ (f ∗ g) dV + f ∗ (∇g) dV
i V i V !
h̄ Z ∗
Z
∗ h̄
=− ∇ (f g) dV + f ∇g dV . (343)
i V V i

Using the Gauss’s divergence theorem, we get that Eq. (343) can be written
as

I Z
f ∗ pˆ~g dV .
 
=− f ∗ gdS + (344)
i S V

First integral in Eq. (344) vanishes as f and g vanish at infinity, and therefore
we get
Z  ∗ Z
pˆ~f f ∗ pˆ~g dV ,
 
gdV = (345)
V V

which means that pˆ~ is Hermitian,

as required♦.

We have defined before the eigenvalues and eigenfunctions of the Hamilto-


nian of a particle, see Section 7.3. The idea of eigenvalues and eigenfunctions
can be extended to arbitrary operators. Thus, we can state:

If ÂΨ = αΨ, then Ψ is an eigenfunction of  with eigenvalue α.

115
Example:

Determine if the function Ψ = e2x isR an eigenfunction of the operators (a)


 = d/dx, (b) B̂ = ()2 , and (c) Ĉ = dx.

(a) Operating on the wave function Ψ with the operator Â, we obtain

d 2x
ÂΨ = e = 2e2x = 2Ψ , (346)
dx
which is a constant times the original function. Therefore, Ψ = e2x is an
eigenfunction of the operator  = d/dx with an eigenvalue α = 2.

I leave the solution of the parts (b) and (c) to the students.

Hermitian operators play the important role in quantum mechanics as they


represent physical quantities. This importance arises from the fact that
eigenvalues of an Hermitian operator are real.

Proof:

Assume that α is an eigenvalue of an Hermitian operator  corresponding


to the eigenfunction f (that vanishes at infinity). Then
Z Z Z
2 ∗
α=α |f | dV = f αf dV = f ∗ Âf dV
V V VZ
Z  ∗ Z
∗ ∗ ∗
Âf f dV = α f f dV = α |f |2 dV = α∗ , (347)
V V V

as required♦.

116
10.3 Scalar product and orthogonality of two eigen-
functions

Two functions Ψ1 (~r) and Ψ2 (~r) are orthogonal if


Z +∞
Ψ∗1 (~r)Ψ2 (~r)dV = 0 . (348)
−∞

The orthogonality of two functions is related to the orthogonality of two


vectors. The vectors are orthogonal when the scalar product of the vectors
is zero. In analogy, we can write a scalar product of two functions as
Z
(Ψi , Ψj ) = Ψ∗i (~r)Ψj (~r)dV = aj δij , (349)

where aj is a positive constant and δij is the Kronecker delta function.

When aj = 1, we say that the functions are orthonormal.

The complex functions Ψi form a complex linear vector space. The infinite-
dimensional vector space of orthonormal functions is called Hilbert space.

The scalar product


Z
(Ψi , Ψi ) = ||Ψi || = |Ψi |2 dV , (350)

where Ψi is a square integrable function, is called the norm of the state (vec-
tor) Ψ. For a state function that represents physical quantity the norm is
finite. If the functions are orthonormal, the norm ||Ψi || = 1.

Example of orthogonal functions:

Examples of orthogonal functions are sines and cosines functions. Their


product with any other function of the same class gives zero when integrated
over all ranges of variable, unless the two multiplied functions are identical.
(
Z 2π 0 for m 6= n
sin(mφ) sin(nφ) dφ = (351)
0 π for m = n

117
(
Z 2π 0 for m 6= n
cos(mφ) cos(nφ) dφ = (352)
0 π for m = n
Z 2π
sin(mφ) cos(nφ) dφ = 0 for all m and n . (353)
0

From the orthogonality of the sines functions, we see that the eigenfunc-
tions of a particle in an infinite square well potential, Eq. (242), corresponding
to different energies (n 6= m) are orthogonal.

Having available the definition of orthogonal functions, we can formulate


an important property of eigenfunctions of a linear Hermitian operator.

Eigenfunctions of a linear Hermitian operator belonging to dif-


ferent eigenvalues are orthogonal.

Proof:

Consider a Hermitian operator Â. Let f and g are two eigenfunctions of


 corresponding to two different eigenvalues αf and αg , respectively,

Âf = αf f ,
Âg = αg g , (354)
where αf ,αg are
∗
real numbers.
Since Âf = αf f ∗ , we can write
Z  ∗ Z   Z
Âf gdV − f ∗ Âg dV = (αf − αg ) f ∗ gdV . (355)

However
Z  ∗ Z  
Âf gdV = f ∗ Âg dV , (356)

and therefore the lhs of Eq. (355) vanishes. Since, αf 6= αg , we have


Z
(f, g) = f ∗ gdV = 0 , (357)

as required♦.

118
10.4 Expectation value of an operator

In classical physics, an expectation or average or mean value of an arbitrary


quantity A is obtained by weighting each measured value Ai by the associated
probability Pi and summing over all the measurements N . Thus,
X
hAi = Pi A i i = 1, 2, . . . , N , (358)
i

where Pi is a probability of measuring the value Ai .

How do we calculate expectation values in quantum physics?

Consider an operator  acting on a function Ψi . Suppose that ÂΨi exists,


then the scalar product
  Z
Ψi , ÂΨi = Ψ∗i ÂΨi dV (359)

is called the expectation or average or mean value of the operator  in the


state Ψi .
Similarly as in classical physics, the expectation value can be calculated
from the probability density as
Z Z Z
2
hÂi = Âρ(~r)dV = Â |Ψi | dV = Ψ∗i ÂΨi dV , (360)

where the order of the factors under the integral is not important.

Properties of the expectation value

1. Expectation value of a Hermitian operator is real.

Proof:
Z Z  ∗
hÂi = Ψ∗i ÂΨi dV = ÂΨi Ψi dV
Z  ∗ Z ∗
= Ψi ÂΨi dV = Ψ∗i ÂΨi dV = hÂi∗ , (361)

as required♦.

119
2. Expectation value of an arbitrary operator B̂ satisfies the following equa-
tion of motion
* +
d ∂ B̂ i Dh iE
hB̂i = + Ĥ, B̂ . (362)
dt ∂t h̄

Proof:

Since
Z
hB̂i = Ψ∗i B̂Ψi dV ,

we have
∂Ψ∗
! ! !
d ∂ B̂ ∂Ψ
Z Z Z
hB̂i = B̂ΨdV + Ψ∗ ΨdV + Ψ∗ B̂ dV .
dt ∂t ∂t ∂t
From the Schrödinger equation
∂Ψ
ih̄ = ĤΨ ,
∂t
and its complex conjugate
∂Ψ∗
−ih̄ = ĤΨ∗ ,
∂t
we obtain
* +
d ∂ B̂ i i
Z Z

hB̂i = + ĤΨ B̂ΨdV − Ψ∗ B̂ ĤΨdV .
dt ∂t h̄ h̄

Since Ĥ is Hermitian, we finally get


* +
d ∂ B̂ i Z ∗ 
hB̂i = + Ψ Ĥ B̂ − B̂ Ĥ ΨdV
dt ∂t h̄
* +
∂ B̂ i Dh iE
= + Ĥ, B̂ ,
∂t h̄
as required♦.

120
Thus, expectation value of the operator B̂ can depend on time even if the
operator does not depend explicitly on time (∂ B̂/∂t = 0).
When [Ĥ, B̂] = 0, we have that dhB̂i/dt = 0, and then the expectation value
is constant in time. In analogy to classical physics, we call B̂ a constant of
motion.

We have already shown that expectation values of Hermitian operators


are real. In term of the scalar product this is characterized by
   ∗
Ψi , ÂΨi = Ψi , ÂΨi . (363)

From this property, we have in general, that for Hermitian operators


   ∗
Ψi , ÂΨj = Ψj , ÂΨi . (364)

Proof:
  Z Z  ∗ Z  ∗
Ψi , ÂΨj = Ψ∗i ÂΨj dV = ÂΨi Ψj dV = Ψj ÂΨi dV
Z ∗  ∗
= Ψ∗j ÂΨi dV = Ψj , ÂΨi ,

as required♦.

The properties (363) and (364) is very often used to check whether oper-
ators are Hermitian.

Example:

Consider two operators  = d/dx and B̂ = d2 /dx2 acting on two orthonor-


mal wave functions
√ Ψ1 = a sin(nx) and Ψ2 = a cos(nx), where n is a real
number, a = 1/ π and x ∈ h−π, πi.
Are the operators  and B̂ Hermitian?

Solution:

First, consider the operator  = d/dx. Since


d
ÂΨ1 = a sin(nx) = an cos(nx) = anΨ2 , (365)
dx

121
and
d
ÂΨ2 = a cos(nx) = −an sin(nx) = −anΨ1 , (366)
dx
we find the following values of the scalar products
 
Ψ1 , ÂΨ1 = −an (Ψ1 , Ψ2 ) = 0 ,
 
Ψ1 , ÂΨ2 = −an (Ψ1 , Ψ1 ) = −an ,
 
Ψ2 , ÂΨ2 = −an (Ψ2 , Ψ1 ) = 0 ,
 
Ψ2 , ÂΨ1 = an (Ψ2 , Ψ2 ) = an . (367)

Hence
   ∗
Ψ1 , ÂΨ1 = Ψ2 , ÂΨ2 , (368)

but
   ∗
Ψ1 , ÂΨ2 = −an 6= Ψ2 , ÂΨ1 = an . (369)

Thus, the operator  = d/dx is not Hermitian.

Consider now the operator B̂ = d2 /dx2 . Since

d2
B̂Ψ1 = a sin(nx) = −an2 sin(nx) = −an2 Ψ1 , (370)
dx2
and
d2
B̂Ψ2 = a 2 cos(nx) = −an2 cos(nx) = −an2 Ψ2 , (371)
dx
we find the following values of scalar products
 
Ψ1 , B̂Ψ1 = −an2 (Ψ1 , Ψ1 ) = −an2 ,
 
Ψ1 , B̂Ψ2 = −an2 (Ψ1 , Ψ2 ) = 0 ,
 
Ψ2 , B̂Ψ2 = −an2 (Ψ2 , Ψ2 ) = −an2 ,
 
Ψ2 , B̂Ψ1 = −an2 (Ψ2 , Ψ1 ) = 0 . (372)

122
Hence
   ∗
Ψ1 , B̂Ψ1 = −an2 = Ψ2 , B̂Ψ2 , (373)

and
   ∗
Ψ1 , B̂Ψ2 = 0 = Ψ2 , B̂Ψ1 . (374)

Thus, the operator B̂ = d2 /dx2 is Hermitian.

Exercise at home:

Prove, using the condition (364) and the wave functions Ψ1 and Ψ2 of the
above example, that the momentum operator p̂x = −ih̄∂/∂x is Hermitian.

123
10.5 The Heisenberg uncertainty principle revisited

In Section 6.6, we have shown that the uncertainties in the position and
momentum of a particle satisfy the relation

∆y∆py = h . (375)

This relation says the position and momentum of a particle cannot be mea-
sured simultaneously with the same precision. This is known as the Heisen-
berg uncertainty relation, or the Heisenberg uncertainty principle, and
we will show that the relation is a direct consequence of the noncommutivity
of the position and momentum operators

[ŷ, p̂y ] = ih̄ . (376)

In fact, the Heisenberg uncertainty relation can be formulated for arbitrary


two Hermitian operators that do not commute. In other words, if  and B̂
are two Hermitian operators that do not commute, the physical quantities
represented by the operators cannot be measured simultaneously with the
same precision.

Theorem:

The variances h(∆Â)2 i = hÂ2 i − hÂi2 and h(∆B̂)2 i = hÂ2 i − hÂi2 of two
Hermitian operators satisfy the inequality
1
h(∆Â)2 ih(∆B̂)2 i ≥ − h[Â, B̂]i2 , (377)
4
which is called the Heisenberg inequality.

Proof:

First, we prove that for an arbitrary operator  the following inequality


holds

h† i ≥ 0 . (378)

124
It is easy to prove the above inequality using the definition of the expectation
value
∗
† 2
Z Z  Z
† ∗ † † †
hÂÂ i = Ψ ÂÂ ΨdV = Â Ψ Â ΨdV = Â Ψ dV ≥ 0 . (379)

Now, we prove that for two Hermitian operators the following inequality
is satisfied
1
hÂ2 ihB̂ 2 i ≥ − h[Â, B̂]i2 . (380)
4
To prove it, we introduce an operator

D̂ = Â + iz B̂ , (381)

where z is an arbitrary real number.


Hence, from Eq. (378), we find

hD̂ D̂ † i = h(Â + iz B̂)(Â − iz B̂)i


= hÂ2 i − iz(hÂB̂ − B̂ Âi) + z 2 hB̂ 2 i ≥ 0 . (382)

This inequality is satisfied when

−hÂB̂ − B̂ Âi2 − 4hÂ2 ihB̂ 2 i ≤ 0 . (383)

Hence
1
hÂ2 ihB̂ 2 i ≥ − h[Â, B̂]i2 , (384)
4
as required.

Finally, since

[∆Â, ∆B̂] = [Â, B̂] , (385)

where ∆Û = Û − hÛ i, (Û = Â, B̂), and replacing in Eq. (384),  → ∆ and
B̂ → ∆B̂, we obtain the required Heisenberg uncertainty relation (377),
as required♦.

125
Example 1. The Heisenberg uncertainty relation for the position and mo-
mentum operators.

Since
[x̂, p̂x ] = ih̄ , (386)
we obtain by substituting into Eq. (377), Â = x̂ and B̂ = p̂x
1
h(∆x̂)2 ih(∆p̂x )2 i ≥ h̄2 , (387)
4
or in terms of the standard deviations (fluctuations)
1
δxδpx ≥ h̄ , (388)
2
q q
where δx = h(∆x̂)2 i and δpx = h(∆p̂x )2 i.
Similarly, we can show that for the y and z components of the position
and momentum
1 1
δyδpy ≥ h̄ and δzδpz ≥ h̄ . (389)
2 2
Note that the relation (375) satisfies the Heisenberg inequality as h > h̄/2.

Example 2. The Heisenberg uncertainty relation for the components of


the electron spin.

Since
[σ̂x , σ̂y ] = 2iσ̂z , (390)
(For a poof, see Tutorial Set 8), where σ̂x , σ̂y , σ̂z are the operators corre-
sponding to the three components of the electron spin, we obtain
h(∆σ̂x )2 ih(∆σ̂y )2 i ≥ hσ̂z i2 , (391)
or
δσx δσy ≥ |hσ̂z i| . (392)
The uncertainty relation (392) shows that the components of the electron
spin cannot be measured simultaneously with the same precision.

126
10.6 Expansion of wave functions in the basis of or-
thonormal functions
We now consider the most important property of orthonormal functions,
which similar to the orthogonality, arises from the properties of vectors.

To illustrate this connection, consider a simple example:

~ can be written as a linear


In the Cartesian coordinates an arbitrary vector A
combination of the orthonormal unit vectors
~ = (~i · A)
A ~ ~j + (~k · A)
~ ~i + (~j · A) ~ ~k , (393)

where ~i, ~j and ~k are unit vectors in the directions x, y and z, respectively.

Proof:

We know from the vector analysis that in the Cartesian coordinates an ar-
~ may be presented in terms of components Ax , Ay , Az , and
bitrary vector A
three unit vectors oriented in the directions of the coordinate axis
~ = Ax~i + Ay~j + Az~k .
A (394)
~ on the coordinate
Since the components are the projections of the vector A
axis
~,
Ax = ~i · A ~,
Ay = ~j · A Az = ~k · A
~, (395)
we find that the vector (394) can be written in the form
~ = (~i · A)
A ~ ~j + (~k · A)
~ ~i + (~j · A) ~ ~k , (396)
as required♦.

We can extend this property to n dimensional space and state that an ar-
bitrary vector A~ can be written as a linear combination of the
coordinate (basis) unit vectors ~e as
      m  
~ ~e1 + ~e2 · A
~ = ~e1 · A ~ ~e2 + . . . + ~en · A
~ ~en = ~ ~en , (397)
X
A ~en · A
n=1

127
 
where ~en · A ~ is the scalar product of ~en and A,
~ (nth component of A),
~
and ~ei · ~ej = δij .
The norm (magnitude) of the vector A ~ is
X 2
~ 2 = |A|
||A|| ~ = ~
~en · A . (398)
n

Thus, we see that an arbitrary vector can be expressed as a linear combina-


tion of the orthonormal vectors ~en .

In analogy, an arbitrary wave function Ψ can be expanded in terms


of orthonormal wave functions Ψn as
X
Ψ= cn Ψ n , (399)
n

(discrete spectrum of Ψn ), or in the case of a continuous spectrum of Ψn


Z
Ψ(~r) = cn (~r)Ψn (~r)dVn , (400)

where cn are arbitrary (unknown) expansion coefficients, and dVn is the vol-
ume element of the space the orthonormal functions Ψn (~r) are spanned.
We can find the coefficients cn (~r) by multiplying Eq. (400) by Ψ∗m (~r) and
integrating over all space as follows
Z Z Z
Ψ∗m (~r)Ψ(~r)dV = cn (~r) Ψ∗m (~r)Ψn (~r)dV dVn = cm (~r) , (401)

where we have used the orthonormality property of the Ψn functions


Z
Ψ∗m (~r)Ψn (~r)dVn = δnm . (402)

In general, the coefficients cm (~r) are complex numbers and are called the
components of the function Ψ in the basis of the orthonormal functions Ψm .
The components determine the function completely, and very often the co-
efficients cm (~r) are called a representation of the wave function Ψ in the
basis Ψm .

The coefficients cm (~r) satisfy the following relation


Z
|cm (~r)|2 dV = 1 . (403)
V

128
Proof:

Multiplying Eq. (400) by Ψ∗ (~r) and integrating over V , we obtain


Z Z
Ψ∗ (~r)Ψ(~r)dV = |Ψ(~r)|2 dV
VZ Z Z V

= c∗m (~r)cn (~r)Ψn Ψm dVn dVm dV


V Vn Vm
Z Z Z
= c∗m (~r)cn (~r)δmn dVn dV = |cm (~r)|2 dV . (404)
V Vn V

Since, V |Ψ|2 dV = 1, we get |cm (~r)|2 dV = 1,


R R
V
as required♦.

From Eqs. (400) and (403), we see that |cm (~r)|2 can be interpreted as
the probability that a system, described by the wave function Ψ(~r), is in the
state described by the wave function Ψm (~r).

Example:

Let  is an operator and Ψ(~r) is an unknown wave function that is not


an eigenfunction of Â. Suppose, that we cannot find the explicit form of
Ψ(~r) because we cannot solve the Schrödinger equation for Ψ(~r). However,
we can find a form of the wave function in the basis of the eigenfunctions of
Â. If Ψm (~r) is an eigenfunction of Â, then
Z
Ψ(~r) = cm (~r)Ψm (~r)dVm . (405)

129
11 Dirac Notation
Dirac introduced a very useful (compact) notation of state vectors (wave
functions) Ψi in terms of ”bra” hi| and ”ket” |ii vectors.
For example, a wave function Ψi can be expressed by a ket vector |Ψi i,
and Ψ∗i by a bra vector hΨi |. This notation can be further simplified to |ii
and hi|, respectively.
Let us illustrate what kind of simplifications we will get using the Dirac
notation.
In the Dirac notation, a scalar product is written as

(Ψi , Ψj ) = hΨi |Ψj i = hi|ji , (406)

which is called a bracket.


For orthonormal vectors we have used the notation (Ψi , Ψj ) = δij , which
in the Dirac notation takes the form hi|ji = δij .
Since (Ψi , Ψj ) = (Ψj , Ψi )∗ , we have in the Dirac notation hi|ji = hj|ii∗ .
In the bra-ket notation, the definition of the Hermitian adjoint becomes
 ∗
hi|Â|ji = hj|† |ii , (407)

or

hj|† |ii = hi|Â|ji∗ . (408)

Thus, for a Hermitian operator

hi|Â|ji = hj|Â|ii∗ . (409)

Expectation value of an operator  in a state |ii is given by hi|Â|ii.

We write a linear superposition of ket states as


X
|ai = λn |ni , discrete states (410)
n

or
Z
|ai = λ(x)|xidx . continuous states (411)

130
The bra-ket notation also extends to action of operators on state vectors.
A linear operator  associates with every ket |ii another ket |ji:

Â|ii = |ji , (412)

such that

 (|ai + |bi) = Â|ai + Â|bi ,


and  
Âλ|ai = λ Â|ai , (413)

where λ is a number.

Hermitian conjugate of Â|ii is hi|† .

An arbitrary ket state |ai can be expanded in terms of orthonormal ket


states as
X
|ai = cn |ni . (414)
n

Since |ni are orthonormal (hm|ni = δij ), we get for cn :


X X
hm|ai = cn hm|ni = cn δnm = cm . (415)
n n

Thus

cn = hn|ai , (416)

and then
X
|ai = |nihn|ai . (417)
n

Hence
X
|nihn| = 1̂ , (418)
n

where 1̂ is the unit operator.

131
The product ket-bra (|nihn|) is called a projection operator, and the rela-
tion (418) is called the completeness relation.

From Eq. (414) and ha|ai = 1, we have


|cn |2 = 1 .
X
(419)
n

11.1 Projection operator


In general, we can define projection operator of two different bra-ket states as
P̂mn = |mihn| . (420)
This operator projects an arbitrary state vector |ai onto the ket state |mi:
P̂mn |ai = |mihn|ai . (421)
When m = n and hn|ni = 1, the projection operator P̂nn satisfies the relation
2
P̂nn = P̂nn , (422)
which is easy to prove
2
P̂nn = |nihn|nihn| = P̂nn . (423)
Thus, the square of P̂nn equals itself.

Note that P̂nn is a Hermitian operator, but P̂mn , (m 6= n) is not Her-


mitian.

Proof:

Since
hi|P̂mn |ji = hi|mihn|ji = δim δnj , (424)

we have that, hm|P̂mn |ni = 1, but hn|P̂mn |mi = 0, and then


 ∗
hm|P̂mn |ni 6= hn|P̂mn |mi , (425)
as required♦.

132
11.2 Representations of linear operators
Consider an arbitrary operator Â. We can represent the operator  in terms
of projection operators of the orthonormal states |mi.
To show this, we use the completeness relation for the states |mi and
multiply the operator  on both sides by unity in the form
X
1= |mihm| , (426)
m

and obtain
! !
X X X
 = |mihm|  |nihn| = |mihm|Â|nihn|
m n m,n
X X
= hm|Â|ni|mihn| = Amn P̂mn , (427)
m,n m,n

where Amn = hm|Â|ni.


Thus, an arbitrary operator can be written (represented) as a linear com-
bination of projection operators P̂mn .
Since an arbitrary state |ai can be expanded in terms of orthonormal
states |mi, i.e.
X
|ai = cn |ni , (428)
n

we can obtain the following expression for the expectation value hÂi in the
state |ai as
hn|Â|mic∗n cm .
X
hÂi = ha|Â|ai = (429)
m,n

If |mi is an eigenfunction of Â, i.e. Â|mi = Am |mi, then


c∗n cm Am δmn = An |cn |2 .
X X
hÂi = (430)
m,n n

Thus, the modulus square of the expansion coefficients is the probability that
the quantity described by the operator  is in the state |ni.
As hÂi is a weighted sum of the eigenvalues, this suggests that the eigen-
values represent the possible results of measurement, while |cn |2 is the prob-
ability that the eigenvalue An will be obtained as the result of any individual
measurement.

133
This is in contrast to classical physics. In classical physics the measure-
ment of a physical quantity at any time always leads to a definite result. In
quantum physics the measurement of the physical quantity at any time leads
to a range of possible results, each occurring with a certain probability. In
this sense quantum physics is probabilistic.
Results of any measurement in physics are real numbers. Since eigenval-
ues of Hermitian operators are real, we postulate that every physical quantity
that is measurable is specified in quantum physics by a linear Hermitian op-
erator  that is also called an observable.

In quantum physics the set of possible measured values for a physical quan-
tity is the set of eigenvalues of a linear Hermitian operator specifying the
physical quantity.

Example:

Consider a particle specified by a wave function Ψa , or in the Dirac no-


tation, by |ai. Let Ĥ is the Hamiltonian (energy) of the particles and |ni are
known eigenfunctions of Ĥ.
If |ai is an eigenfunction of Ĥ, then
Ĥ|ai = Ea |ai , (431)
where Ea is the eigenvalue (energy) of the particle. Thus, Ea = ha|Ĥ|ai.
If |ai is not an eigenfunction of Ĥ, then we can expand |ai in terms of
the eigenfunctions |ni as
X
|ai = cn |ni , (432)
n

and find that


En |cn |2 .
X
ha|Ĥ|ai = (433)
n

Hence, the measurement of energy of the particle in the state |ai leads to a
range of possible results, each occurring with probability |cn |2 . Thus, |cn |2 is
the probability that the measurement of Ĥ will give the value En .
Since, |ai = cn |ni, we say that the state of the particle is a superposi-
P

tion of the eigenfunctions of Ĥ.

134
12 Matrix Representation of Linear Opera-
tors
Using an orthonormal basis, we can represent an arbitrary state |ai as a
linear superposition of the basis states
X
|ai = cn |ni , (434)
n

where, in general, the coefficients cn are complex numbers, and n |cn |2 = 1.


P

The set of the expansion coefficients c1 , c2 , . . . defines the state |ai and is
called the representation of |ai in the basis of the orthonormal states |ni.
We can write the set of the coefficients cn as a column (ket) vector

c1
 

 c2 

.
 
 
|ai =   . (435)

 . 

.
 
 
cn

Then, the bra state ha| can be written as

ha| = (c∗1 , c∗2 , . . . , c∗n ) . (436)

12.1 Matrix representation of operators


Using the representation (436), we will try to write in a matrix form the rela-
tionship between two ket states |ai and |bi related through a linear operator
 as

|bi = Â|ai . (437)

Let
X
|ai = cn |ni ,
n
X
|bi = bm |mi . (438)
m

135
Then
X X
bm = hm|bi = hm|Â|ai = cn hm|Â|ni = Amn cn , (439)
n n

where Amn = hm|Â|ni.


The right-hand side of Eq. (439) is the result of multiplication of a matrix
composed of the elements Amn and the column vector cn :

b1 A11 A12 . . . A1n c1


    

 b2 


 A21 A22 . . . A2n 
 c2 

. . .
    
    
  =    . (440)

 . 


 . 
 . 

. . .
    
    
bn An1 An2 . . . Ann cn

Thus, the scalar product (Ψm , ÂΨn ), or hm|Â|ni represents a matrix element
of the operator  in the orthonormal basis |ni.

Example:

Find the matrix representation of the operator  = d/dx in the basis√of


two orthonormal states Ψ1 = a sin(nx) and Ψ2 = a cos(nx), where a = 1/ π
and x ∈ h−π, πi.
Since
d
ÂΨ1 = sin(nx) = nΨ2 ,
dx
d
ÂΨ2 = cos(nx) = −nΨ1 , (441)
dx
we find
 
Ψ1 , ÂΨ1 = −n (Ψ1 , Ψ2 ) = 0 ,
 
Ψ1 , ÂΨ2 = −n (Ψ1 , Ψ1 ) = −n ,
 
Ψ2 , ÂΨ2 = −n (Ψ2 , Ψ1 ) = 0 ,
 
Ψ2 , ÂΨ1 = n (Ψ2 , Ψ2 ) = n . (442)

136
Hence
!
0 −n
 = . (443)
n 0

The solution of this problem is more simple if we use the Dirac notation.

Denote

|1i = a sin(nx) , |2i = a cos(nx) . (444)

Since

Â|1i = n|2i ,
Â|2i = −n|1i , (445)

the operator  written in the basis |1i, |2i, has the form

 = n (|2ih1| − |1ih2|) . (446)

Hence

h1|Â|1i = 0 , h2|Â|2i = 0 ,
h1|Â|2i = −n , h2|Â|1i = n . (447)

Note that the operator  is not Hermitian

† = n (|1ih2| − |2ih1|) = − , (448)

and therefore the states |1i, |2i are not the eigenfunctions of Â.

12.2 Matrix representation of eigenvalue equations


The ket vector |ai is an eigenvector of a linear operator  if the ket vector
Â|ai is a constant α times |ai, i.e.

Â|ai = α|ai . (449)

137
The complex constant α is called the eigenvalue and |ai is the eigenvector
corresponding to the eigenvalue α.
Eigenvectors of an operator  can be found in terms of a linear superpo-
sition of orthonormal vectors |ni.
Since |ai = cn |ni, we have
P

X X
Â|ai = cn Â|ni = α cm |mi . (450)
n m

Using the completeness relation to the lhs of Eq. (450), we get


XX X
cn |mihm|Â|ni = α cm |mi , (451)
n m m

which can be written as


!
X X X
cn hm|Â|ni |mi = (αcm )|mi . (452)
m n m

Hence
X
cn hm|Â|ni = αcm , (453)
n

or
X
cn Amn = αcm . (454)
n

The lhs of Eq. (454) is the product of a column vector composed of the
elements cn and a matrix composed of the elements Amn . Thus, we can write
Eq. (454) in the matrix form as

A11 A12 . . . A1n c1 c1


    

 A21 A22 . . . A2n 
 c2 


 c2 

. . .
    
    
   = α  . (455)

 . 
 . 


 . 

. . .
    
    
An1 An2 . . . Ann cn cn

This is a matrix eigenvalue equation.

138
The following conclusions arise from the matrix eigenvalue equa-
tion:

1. When the matrix Āmn is diagonal, i.e. Amn = 0 for m 6= n, the or-
thonormal states |ni are the eigenstates of the operator  with eigenvalues
αn = Ann .

2. If the matrix Āmn is not diagonal, then we can find the eigenvalues
and eigenvectors of  diagonalizing the matrix Āmn . The eigenvalues are
obtained from the characteristic equation


A11 − α A12 . . . A1n


A21 A22 − α . . . A2n

.


=0. (456)

.

.



An1 An2 . . . Ann − α

This is of the form of a polynomial equation of degree n, and shows that


n eigenvalues can be found from the roots of the polynomial. For each
eigenvalue αi found by solving the characteristic equation, the corresponding
eigenvector is found by substituting αi into the matrix equation.

Example:

Consider the example from Section. 12.1. In the matrix representation, the
operator  = d/dx has the form given in Eq. (443). Since the matrix is not
diagonal, the states Ψ1 and Ψ2 are not eigenstates of the operator Â. We
can find the eigenstates of Â, in terms of linear superpositions of the states
Ψ1 and Ψ2 , simply by the diagonalization of the matrix (443).
We start from the eigenvalue equation, which is of the form
! ! !
0 −n c1 c1
=α . (457)
n 0 c2 c2
First, we solve the characteristic equation

−α −n
=0, (458)

n −α

139
from which we find two eigenvalues α1 = +in and α2 = −in.
For α1 = in the eigenvalue equation takes the form
! ! !
0 −n c1 c1
= in , (459)
n 0 c2 c2

from which, we find that

−nc2 = inc1
or
c1 = ic2 . (460)

Hence, the eigenfunction corresponding to the eigenvalue α1 is of the form


! !
ic2 i
Ψ α1 = = c2 . (461)
c2 1

From the normalization of Ψα1 , we get


!
2 i
1 = (Ψα1 , Ψα1 ) = |c2 | (−i, 1) = 2 |c2 |2 . (462)
1

Thus, the normalized eigenfunction corresponding to the eigenvalue α1 is


given by
!
1 i
Ψ α1 =√ , (463)
2 1
or
1
Ψα1 = √ [i sin(nx) + cos(nx)] . (464)

Similarly, we can easily show that the normalized eigenfunction correspond-


ing to the eigenvalue α2 is of the form
1
Ψα2 = √ [−i sin(nx) + cos(nx)] . (465)

140
In the Dirac notation, the normalized eigenvectors can be written in a com-
pact form as
1
|α1 i = √ (i|1i + |2i) ,
2
1
|α2 i = √ (−i|1i + |2i) . (466)
2
The physical interpretation of the superposition states (466) is as follows:
The eigenfunctions |α1 i and |α2 i in the form of the linear superpositions tell
us that e.g. with the probability 1/2 the system described by the operator
 is in the state |1i or in the state |2i.

In summary of this lecture: We have learnt that

1. In quantum physics, an arbitrary wave function may be represented


by a normalized column vector of expansion coefficients in the basis of
orthonormal states.

2. In an orthonormal basis, an arbitrary operator  may be represented


by a matrix, whose the elements Amn are given by scalar products
(Ψm , ÂΨn ).

3. Using an orthonormal basis, an eigenvalue equation of an arbitrary


operator may be written in a matrix form. In this case, the problem of
finding eigenvalues and eigenvectors of the operator reduces to a simple
problem of diagonalization of the matrix.

141
13 First-Order Time-Independent Perturba-
tion Theory
In many situations in physics, the Hamiltonian Ĥ of a given system is so
complicated that the solution of the stationary Schrödinger equation is prac-
tically impossible or very difficult.
In some situations, however, the Hamiltonian can be split into two parts
Ĥ = Ĥ0 + V̂ , (467)
such that we can solve the eigenvalue equation for Ĥ0 , i.e. we can find
eigenvalues En(0) and eigenvectors φ(0)
n of the Hamiltonian Ĥ0 , and we can
treat the part V̂ as a small perturber to Ĥ0 .
Thus, the problem of solving the eigenvalue equation
 
Ĥφ = Ĥ0 + V̂ φ = Eφ (468)

reduces to find E and φ when we know the eigenvalues En(0) and the eigen-
vectors φ(0)
n of Ĥ0 .
Since V̂ appears as a small perturber to Ĥ0 , we will try to find E and φ
in the form of a series
φ = φ(0) (1)
n + φn + . . . ,
E = En(0) + En(1) + . . . , (469)
where φ(1)
n is the first order correction to the unperturbed eigenstate φn ,
(0)
(1) (0)
and En is the first order correction to the unperturbed eigenvalue En .
The subscript n indicates that the Hamiltonian Ĥ0 can have more than one
eigenvalue and eigenvector.
Substituting the series expansion (469) into the eigenvalue equation (468),
we get
     
Ĥ0 + V̂ φ(0) (1)
n + φn = En(0) + En(1) φ(0) (1)
n + φn . (470)

Expanding both sides of Eq. (470) and equating terms of the same order
in V̂ , we obtain
Ĥ0 φ(0)
n = En(0) φ(0)
n zeroth order in V̂ , (471)
Ĥ0 φn + V̂ φn = En φn + En(1) φ(0)
(1) (0) (0) (1)
n first order in V̂ . (472)

142
We know the solution of Eq. (471). In order to solve Eq. (472), we write this
equation in the form
 
Ĥ0 − En(0) φ(1)
n = En(1) φ(0) (0)
n − V̂ φn . (473)

Assume that the eigenvalues En(0) are non-degenerated, i.e. for a given En(0)
there is only one eigenfunction φ(0)
n .
Multiplying Eq. (473) from the left by φ(0)∗
n , and integrating over dV , we
obtain
       
φ(0) (1)
n , Ĥ0 φn − φ(0) (0) (1)
n , E n φn = En(1) φ(0) (0)
n , φn − φ(0) (0)
n , V̂ φn . (474)

Since
     
φ(0) (1)
n , Ĥ0 φn = Ĥ0 φ(0) (1)
n , φn = En(0) φ(0) (1)
n , φn , (475)

the lhs of Eq. (474) vanishes, giving


 
En(1) = φ(0) (0)
n , V̂ φn = hφ(0) (0)
n |V̂ |φn i = hn|V̂ |ni . (476)

Thus, the first order correction to the eigenvalue En(0) is equal to the expec-
tation value of V̂ in the state φ(0)
n .
In order to find the first-order correction to the eigenstate |φ(0)n i, we ex-
pand |φ(1)
n i state in terms of |φ (0)
n i, using the completeness relation, as

|φ(1) |φ(0) (0) (1)


cmn |φ(0)
X X
n i = m ihφm |φn i = m i , (477)
m m

where cmn = hφ(0) (1)


m |φn i.
We find the coefficients cmn from Eq. (473) by multiplying this equation
from the left by hφ(0)
m | (m 6= n), and find

hφ(0) (1) (0) (0) (1) (1) (0) (0) (0) (0)
m |Ĥ0 |φn i − En hφm |φn i = En hφm |φn i − hφm |V̂ |φn i . (478)

Since

hφ(0) (0)
m |φn i = 0
and
hφ(0) (1) (0) (0) (1)
m |Ĥ0 |φn i = Em hφm |φn i , (479)

143
we get

hφ(0) (0)
m |V̂ |φn i
cmn = hφ(0) (1)
m |φn i = (0) (0)
. (480)
En − E m
Hence

hφ(0) (0)
m |V̂ |φn i
|φ(1) |φ(0)
X
n i = (0) (0) m i . (481)
m6=n En − E m

Since we know En(0) and |φ(0) (1) (1)


n i, we can find En from Eq. (476) and |φn i
from Eq. (481).

Example:

Consider a particle in an infinite one-dimensional potential well, as shown


in Fig. 26.

V1

−a/2 0 d a/2 x

Figure 26: Infinite potential well with a small potential (perturber) barrier V 1 .

Assume that inside the infinite well there is a small potential barrier of
high V1 and thickness d. Treating the barrier V1 as a small perturber, find
the eigenvalues and eigenstates of the particle valid to the first order in V1 .

144
Solution:

We know from Section 8.1 that the eigenstates of the particle in the infi-
nite well, without V1 , are
s
2 πx
 
φ(0)
n = sin n , (482)
a a
and the corresponding eigenvalues

π 2 h̄2
En(0) = n2 , (483)
2mp a2

where mp is the mass of the particle.


Thus, the first order correction to the eigenvalue En(0) is
2V1 d nπx
  Z  
En(1) = φ(0) (0)
n , V̂1 φn = dx sin 2
. (484)
a 0 a
In order to find the first order correction to the eigenstate φ(0)
n , we have to
calculate the matrix element (scalar product)
2V1 d mπx nπx
  Z    
Vmn = φ(0) (0)
m , V̂1 φn = dx sin sin , (485)
a 0 a a
where m 6= n.
Performing the integrations in Eqs. (484) and (485), we get
V1 1
 
En(1) = d− sin (2dα) , (486)
a 2a
( )
V1 1 1
Vmn = sin [(α − β) d] − sin [(α + β) d] , (487)
a α−β α+β

where α = nπ/a and β = mπ/a.


Hence, the first order correction to the eigenstate φ(0)
n is

2mp a2 X Vmn
φ(1)
n = φ(0) . (488)
π h̄ m6=n n − m m
2 2 2 2

145
14 Quantum Harmonic Oscillator

We have illustrated in Section 8.2 the solution of the stationary Schrödinger


equation for a particle in a square-well potential, where V (x) had a special
simple structure (step function).
Now, we will show a solution of the Schrödinger equation for a similar
problem, but with V (x) strongly dependent on x, Fig. 27, such that
1
V̂ (x) = mω 2 x̂2 . (489)
2
This is the well known potential of a harmonic oscillator.

V(x)

Figure 27: Potential of a harmonic oscillator.

In one dimension, the Hamiltonian of an oscillating mass m is given by


1 2 1
Ĥ = p̂ + mω 2 x̂2 , (490)
2m 2
where p̂2 /2m is the kinetic energy and mω 2 x̂2 /2 is the potential energy of
the mass.
We will find energies (eigenvalues) and eigenfunctions of the harmonic os-
cillator by solving the stationary Schrödinger equation (eigenvalue equation)
for the harmonic oscillator using two different approaches.

146
In the first, we will solve the equation using algebraic operator technique
which is based on the Dirac notation. This approach has several definite
advantages and exploits the commutation relations among the operators in-
volved and their properties.
In the second approach, we will transform the stationary Schrödinger
equation into a second-order differential equation, and will find the solution
of the equation in terms of special functions.

14.1 Algebraic operator technique


The algebraic operator technique is based on the commutation relation of
two Hermitian operators involved in the evolution of the harmonic oscillator:
position x̂ and momentum p̂ = p̂x :

[x̂, p̂] = ih̄ . (491)

We will introduce a non-Hermitian operator defined as


mω 1
r
â = x̂ + i √ p̂ , (492)
2h̄ 2mh̄ω
and the adjoint of this operator
mω 1
r

â = x̂ − i √ p̂ . (493)
2h̄ 2mh̄ω

Using the commutation relation (491), we find that the operators â, ↠satisfy
the commutation relation
h i
â, ↠= 1̂ . (494)

This allows us to write the Hamiltonian Ĥ in a compact form


1  1
  
Ĥ = h̄ω ↠â + â↠= h̄ω ↠â + . (495)
2 2
Hence, the eigenvalue equation

Ĥ|φi = E|φi , (496)

147
can be written as
1
 

h̄ω â â + |φi = E|φi . (497)
2
Multiplying Eq. (497) from the left by hφ|, and using the normalization
hφ|φi = 1, we get
1
 
h̄ω hφ|↠â|φi + =E . (498)
2
Since

hφ|↠â|φi = (â|φi, â|φi) ≥ 0 , (499)

we have that
1
E ≥ h̄ω . (500)
2
Thus, the energy of the quantum harmonic oscillator can never be zero.

From Eq. (497), we can generate a new eigenvalue equation multiplying this
equation from the left by ↠:
1
 
h̄ω ↠↠â + ↠|φi = E↠|φi . (501)
2
Using the commutation relation (494), we can write Eq. (501) as
1 †
 
h̄ω ↠â − â |φi = E↠|φi . (502)
2
Adding to both sides h̄ω↠|φi, we obtain
1 †
 

h̄ω â â + â |φi = (E + h̄ω) ↠|φi . (503)
2
Introducing a notation |Ψi = ↠|φi, we see that |Ψi is an eigenfunction of Ĥ
with eigenvalue E + h̄ω.
Thus, the operator ↠acting on the state |φi of energy E transforms this
state to the state |Ψi of energy E + h̄ω. Therefore, the operator ↠is called
the raising operator or creation operator.

148
Now, multiplying Eq. (503) from the left by ↠, we obtain
1
 
h̄ω â â â + ↠|Ψi = (E + h̄ω) ↠|Ψi .
† †
(504)
2
Proceeding similar as above, we get
1 †
 
h̄ω ↠â + â |Ψi = (E + 2h̄ω) ↠|Ψi . (505)
2
Thus, the state ↠|Ψi = ↠↠|φi is an eigenfunction of Ĥ with an eigenvalue
E + 2h̄ω.
Similarly, we can show that the state |φn i = (↠)n |φi is an eigenfunction
of Ĥ with an eigenvalue E + nh̄ω.

Now, consider the action of the operator â on the eigenfunctions and eigen-
values.
Consider the eigenvalue equation for |φn i:
1
 
h̄ω ↠â + |φn i = (E + nh̄ω) |φn i = En |φn i . (506)
2
Multiplying Eq. (506) from the left by â, we get
1
 
h̄ω â↠â + â |φn i = (E + nh̄ω) â|φn i , (507)
2
and using the commutation relation (494), we obtain
3
 
h̄ω ↠ââ + â |φn i = (E + nh̄ω) â|φn i . (508)
2
Hence
1
 

h̄ω â â + â|φn i = [E + (n − 1) h̄ω] â|φn i . (509)
2
Thus, the state |φn−1 i = â|φn i is an eigenfunction of Ĥ with an eigenvalue
En − h̄ω. Therefore, the operator â is called the lowering operator or anni-
hilation operator.
Suppose that the state |φ0 i of energy E is the lowest (ground) state of
the harmonic oscillator. Thus, the energy spectrum (eigenvalues), shown

149
E+3hω | φ3 >
a+
^
E+2hω | φ2 >
^
a
E+hω | φ 1>

E | φ0 >

Figure 28: Energy spectrum of the harmonic oscillator.

in Fig. 28, forms a ladder of equally spaced levels separated by h̄ω, which
one ascends by the action of ↠and descends by the action of â. The quantum
harmonic oscillator therefore has a discrete energy spectrum.
Consider the action of â on the ground state
1
 
h̄ω ↠â + â|φ0 i = (E − h̄ω) â|φ0 i . (510)
2
This equation cannot be satisfied. Otherwise there would exist another eigen-
value E − h̄ω lower than E. Thus, â|φ0 i must be identically zero:

â|φ0 i ≡ 0 . (511)

Hence, the eigenvalue equation for the ground state is


1 1
 
Ĥ|φ0 i = h̄ω ↠â + |φ0 i = h̄ω|φ0 i . (512)
2 2
Thus, the energy (eigenvalue) of the ground state is E = h̄ω/2.

We can summarize our findings, that the energy eigenvalues of the harmonic
oscillator are discrete
1
 
En = n + h̄ω , n = 0, 1, 2, . . . (513)
2

150
with corresponding eigenfunctions
 2  n
|φ0 i , |φ1 i = ↠|φ0 i , |φ2 i = ↠|φ0 i , . . . , |φn i = ↠|φ0 i . (514)

From the above equation, it follows that starting with |φ0 i, we may obtain
the complete set of eigenvectors of the harmonic oscillator by repeatedly
applying the operator ↠on the eigenstate |φ0 i.
However, the eigenstates found
n in this way are not normalized. The

normalization of φn (x) = cn â φ0 (x) gives
 †  n
1 = hφn |φn i = |cn |2 hφ0 | â†n ↠|φ0 i
= |cn |2 hφ0 |ân â†n |φ0 i
= |cn |2 hφ0 |ân−1 ââ†n |φ0 i . (515)

Using the commutation relation


h  n i  n−1
â, ↠= n ↠, (516)

(Proof: by induction, leave for the students as a tutorial problem),


we can continue Eq. (515) as
 
= |cn |2 hφ0 |ân−1 nâ†n−1 + â†n â |φ0 i
= |cn |2 nhφ0 |ân−1 â†n−1 |φ0 i
 
= |cn |2 nhφ0 |ân−2 (n − 1)â†n−2 + â†n−1 â |φ0 i
= |cn |2 n(n − 1)hφ0 |ân−2 â†n−2 |φ0 i . (517)

Proceeding further, we find that Eq. (515) reduces to

1 = |cn |2 n! . (518)

Thus, the normalized eigenfunctions of the harmonic oscillator are


1  † n
|φn i = √ â |φ0 i . (519)
n!
Equation (519) shows that an nth eigenfunction can be generated from the
ground state eigenfunction by the n-times repeated action of the creation

151
operator on |φ0 i. Thus, it is enough to know the ground state eigenfunction
to find all the eigenfunctions of the harmonic oscillator.

This is the complete solution to the problem. It is remarkable that the com-
mutation relation (494) was all what we needed to deal with the harmonic
oscillator completely. In a very effective way, we extracted the essential struc-
ture of the problem and have founded the eigenvalues and eigenvectors of the
harmonic oscillator.

Using the definition of the ground state (511), we may find the explicit form
of the ground state eigenfunction. Substituting for â from Eq. (492) and
using the explicit form of p̂ = −ih̄d/dx, we get
!
mω 1 dφ0
r
xφ0 + i √ −ih̄ =0, (520)
2h̄ 2h̄mω dx

that simplifies to
dφ0 mω
+ xφ0 = 0 , (521)
dx h̄
where φ0 ≡ |φ0 i.
Hence
dφ0 mω
=− xdx . (522)
φ0 h̄
Integrating Eq. (522), we obtain

φ0 (x) mω 2
ln =− x , (523)
φ0 (0) 2h̄
from which we find
mω 2
 
φ0 (x) = φ0 (0) exp − x . (524)
2h̄
We find φ0 (0) from the normalization, which finally gives
1
mω mω 2
  
4
φ0 (x) = exp − x . (525)
πh̄ 2h̄

152
Thus, the wave function of the ground state is a Gaussian.
The wave functions φn (x) of the other states can be found from the rela-
tion
 n
φn (x) = ↠φ0 (x) . (526)

Using the definition of ↠(Eq. (493)), we can find φn (x) in terms of the
position x:

φ1 (x) = ↠φ0 (x)


"r !#
mω 1 d
= x − i√ −ih̄ φ0 (x) . (527)
2h̄ 2mh̄ω dx

From Eq. (521), we have that

dφ0 mω
=− xφ0 . (528)
dx h̄
Hence
√ r


φ1 (x) = 2 x φ0 (x) . (529)

Similarly, we can find that
1 mω 2
   
φ2 (x) = √ 2 x − 1 φ0 (x) . (530)
2 h̄
We can introduce a new parameter

r
α= x, (531)

and write the wave functions as
1
φ1 (α) = √ H1 (α)φ0 (α) ,
2
1
φ2 (α) = √ H2 (α)φ0 (α) , (532)
2 2
where Hn (α) are Hermite polynomials of degree n.

153
First few Hermite polynomials

H0 (α) = 1 , H1 (α) = 2α , H2 (α) = 4α2 − 2 , . . . (533)

Hermite polynomials satisfy the differential equation

d2 Hn (α) dHn (α)


− 2α + 2nHn (α) = 0 . (534)
dα2 dα

E
V hω
| φ 1|
2

E=3/2
|φ 0 |
2

E=1/2

x0 x

Figure 29: First two energy eigenvalues and eigenfunctions of the harmonic oscil-
lator.

Consider the harmonic oscillator in the ground state.


Using the classical representation of energy, we have

1 p2 1
h̄ω = + mω 2 x2 . (535)
2 2m 2

154
Since, p2 ≥ 0, the particle must be restricted to positions x, such that
1 1
mω 2 x2 ≤ h̄ω , (536)
2 2
i.e.
s

|x| ≤ . (537)

q
The maximum of |x| ≡ x0 = h̄/mω is called the classical turning point.
Since the wave function ψ0 (x) is not restricted to x ≤ x0 , see Fig. 29,
quantum mechanics predicts that the harmonic oscillator can be in the clas-
sically forbidden region.

14.2 Special functions method

We will carry out the solution of the eigenvalue equation of the harmonic
oscillator again, this time using the stationary Schrödinger equation in a form
of a second-order differential equation.
The starting point is the stationary Schrödinger equation for the harmonic
oscillator whose the Hamiltonian is of the form
1 2 1
Ĥ = p̂ + mω 2 x̂2 . (538)
2m 2
Since in one dimension, p̂ = −ih̄d/dx, the Schrödinger (eigenvalue) equation
takes the form
h̄2 d2
!
1
− + mω 2 x2 φ = Eφ , (539)
2m dx2 2

or multiplying by −2m and dividing by h̄2 , we obtain a second-order differ-


ential equation

d2 φ 2m mω 2 2
!
+ E − x φ=0. (540)
dx2 h̄2 2

155
This is not a linear differential equation, and it is not easy to obtain a solu-
tion.
We can proceed in the following way. Introducing new variables
2m 2 m2 ω 2
λ= E , β = , (541)
h̄2 h̄2
we can write Eq. (540) in a simpler form
d2 φ  2 2

+ λ − β x φ=0. (542)
dx2
Despite of the difficulty, we will try to solve the differential equation (542).
First, we will find the solution of Eq. (542) in the asymptotic limit of large
x (x  1). In this limit, we can ignore the λ term as being small compared
to β 2 x2 , and obtain
d2 φ
2
− β 2 x2 φ = 0 . (543)
dx
Solution of Eq. (543) is of the form
1
 
φ(x) = C exp − βx2 , (544)
2
where C is a constant.

Hence, we will try to find the solution of Eq. (542) in the form
1 2
 
φ(x) = f (x) exp − βx , (545)
2
i.e. in the form satisfying the asymptotic solution (544).

Substituting Eq. (545) into Eq. (542), we get


d2 f df
− 2βx + (λ − β)f = 0 . (546)
dx2 dx

Introducing a new variable α = βx, and a new function f (x) → H(α), for
which
df dH dα q dH
= = β ,
dx dα dx dα
d2 f q d2 H dα d2 H
= β = β , (547)
dx2 dα2 dx dα2

156
the differential equation (546) transforms to

d2 H
!
dH λ
− 2α + −1 H =0 . (548)
dα2 dα β

This equation is identical to the differential equation for Hermite polynomi-


als, with
λ
− 1 = 2n , (549)
β
where n is integer.

Thus, the wave functions of the harmonic oscillator are of the form
1
 
φn (x) = N Hn (α) exp − α2 , (550)
2
where N is a normalization constant.
Since n is integer, we find from Eqs. (549) and (541) that the energy
eigenvalue E is
1
 
E = n+ h̄ω . (551)
2
In summary, the solution of the Schrödinger equation given in the dif-
ferential form agrees perfectly with the results obtained by the algebraic
operator technique.

In summary of this lecture: We have learnt that

1. The energy of a harmonic oscillator is quantized, with the sequence of


values
1
 
En = n + h̄ω , n = 0, 1, 2, . . .
2

157
2. The energy levels are equally spaced. This is an important point to
remember. The difference in energy between adjacent energy levels is
equal to the energy of a single photon, h̄ω.
3. The lowest energy the oscillator can have is E0 = 12 h̄ω, which is non-
zero. Thus, the oscillator can never be made stationary.
4. The oscillator can be found in the classically forbidden region. This is
an another example of penetration of a potential barrier or quantum
tunneling.

Exercise:

Assume that the Harmonic oscillator is in the ground state n = 0. Calculate


the probability that the oscillator will be found in the classically forbidden
region, where the kinetic energy is negative.

Solution:

We have shown in lecture that the wave function of the ground state is
2
φ0 (x) = Ae−βx ,
where
1
mω mω

4
A= and β= .
πh̄ 2h̄
q
Classically forbidden regions are x ≤ −x0 and x ≥ x0 , where x0 = h̄/mω
is the classical turning point, see Fig. 29.
Probability of finding the Harmonic Oscillator in the classically forbidden
region is
Z −x0 Z ∞
P = |φ0 (x)|2 dx + |φ0 (x)|2 dx
−∞ x0
Z ∞ Z∞
2 −2βx2 2 2
= 2A e dx = 2A e−2βx dx .
x0
√1

158
Substituting

y 2 = 2βx2 ,

we change the variable


1 1
x= √ y and dx = √ dy .
2β 2β
Hence
2A2 ∞ 2 ∞
Z Z
−y 2 2
P = √ e dy = √ e−y dy = 1 − Erf(1) = 0.16 ,
2β 1 π 1

where Erf(x) is the error function, defined as


2 x
Z
2
Erf(x) = √ e−y dy .
π 0

Thus, there is about a 16% chance that the oscillator will be found in the
classically forbidden region.

Exercise at home:

Use the operator approach developed in lecture to prove that the nth har-
monic oscillator energy eigenfunction obeys the following uncertainty relation

δxδp = (2n + 1) ,
2
q q
where δx = hx̂2 i − hx̂i2 and δpx = hp̂2x i − hp̂x i2 are fluctuations of the
position and momentum operators, respectively.

159
15 Angular Momentum and Hydrogen Atom
In order to explain the observed discrete atomic spectra, Bohr postulated
that angular momentum of the electron in a hydrogen atom is quantized, i.e.

L = nh̄ , n = 1, 2, 3, . . . . (552)

However, a careful analysis of the observed


q spectra showed that the angular
momentum cannot be nh̄, but rather l(l + 1), where l = 0, 1, 2, . . . , n − 1.
It follows from the Bohr postulate that energy and also electron’s orbits
are quantized, that the electron can be only at some particular distances
from the nucleus. A question arrises, where really is the electron when it
makes a transition from one orbit to another?
Here, we will give the answer to this question analyzing the motion of
the electron in the hydrogen atom from the point of view of quantum wave
mechanics. In this approach, rather than worrying about the position and
motion of the electron, we will classify the electron in terms of the amount of
energy that the electron has. In this description, the electron is represented
by a wave function Ψ(~r), which satisfies the stationary Schrödinger equation

ĤΨ(~r) = EΨ(~r) , (553)

where the Hamiltonian is


h̄2 2
Ĥ = − ∇ + V̂ (r) , (554)
2m
with
e2 1
V̂ (r) = − . (555)
4πε0 r
Thus, the potential depends only on the distance r of the moving electron
from the nucleus (central force).
Since the potential V (r) has a spherical symmetry, we will work in the
spherical coordinates, shown in Fig. 30, in which

∂2
! !
2 1 ∂ ∂ 1 ∂ ∂ 1
∇ = 2 r2 + 2 sin θ + . (556)
r ∂r ∂r r sin θ ∂θ ∂θ r 2 sin2 θ ∂φ2

160
Z

θ
r

φ Y

Figure 30: Spherical coordinates representation of the position vector ~r.

In the spherical coordinates the Schrödinger equation can be written as


!
∂ ∂Ψ 2m
r2 + 2 r 2 (E − V (r)) Ψ
∂r ∂r h̄
1 ∂2Ψ
!
1 ∂ ∂Ψ
+ sin θ + =0. (557)
sin θ ∂θ ∂θ sin2 θ ∂φ2

Equation (557) has two separate parts: the first part depends only on the
distance r, whereas the second part depends only on the polar angle θ and
the azimuthal angle φ. Thus, the wave function is of the separable form

Ψ(~r) = R(r)Y (θ, φ) . (558)

Hence, we can write Eq. (557) as

2mr 2
" ! #
1 d dR
r2 + (E − V (r))
R dr dr h̄2
1 ∂2Y
" ! #
1 1 ∂ ∂Y
=− sin θ + . (559)
Y sin θ ∂θ ∂θ sin2 θ ∂φ2

Both sides of Eq. (559) depend on different variables, thus must be equal to

161
the same constant, say −α:
!
1 d dR 2m α
2
r2 + 2 (E − V (r)) R + 2 R = 0 , (560)
r dr dr h̄ r
1 ∂2Y
!
1 ∂ ∂Y
sin θ + − αY = 0 . (561)
sin θ ∂θ ∂θ sin2 θ ∂φ2

First, we consider Eq. (561) that depends on θ, φ.

15.1 Angular part of the wave function: Angular mo-


mentum
In fact, Eq. (561) is the eigenvalue equation for the square of the angular
momentum operator

~ˆ = ~ˆr × pˆ~ = −ih̄~ˆr × ∇ ,


L (562)

that in the spherical coordinates L̂2 is of the form

1 ∂2Y
( ! )
2 2 1 ∂ ∂Y
L̂ = −h̄ sin θ + . (563)
sin θ ∂θ ∂θ sin2 θ ∂φ2

Since the eigenvalue equation for L̂2 can be written as

L̂2 Y (θ, φ) = λY (θ, φ) , (564)

we have that α = −λ/h̄2 , where λ is the eigenvalue of L̂2 .


Thus, we can write the eigenvalue equation for L̂2 as

∂2Y
!
∂ ∂Y
sin θ sin θ − α sin2 θY + =0. (565)
∂θ ∂θ ∂φ2

This equation contains two separate parts, one dependent only on θ and the
other dependent only on φ. Therefore, the solution of Eq. (565) will be of
the form

Y (θ, φ) = X(θ)Φ(φ) . (566)

162
Hence, substituting Eq. (566) into (565), and dividing both sides by X(θ)Φ(φ),
we obtain
1 d2 Φ
!
1 d dX
sin θ sin θ − α sin2 θ = − , (567)
X dθ dθ Φ dφ2

where X ≡ X(θ) and Φ ≡ Φ(φ).


As before, both sides must be equal to a constant, say m2 . Thus
!
1 d dX
sin θ sin θ − α sin2 θ = m2 , (568)
X dθ dθ
2
1dΦ
= −m2 . (569)
Φ dφ2

First, we will solve Eq. (569) for the azimuthal part of the wave function,
which we can write as
d2 Φ
= −m2 Φ , (570)
dφ2

and the solution of Eq. (570) is

Φ(φ) = A exp(imφ) , (571)

where A is a constant.
Since in rotation, φ and φ + 2π correspond to the same position in space:
Φ(φ) = Φ(φ + 2π), which is satisfied when

exp(imφ) = exp[im(φ + 2π)] . (572)

From this we find that

exp(i2πm) = 1 . (573)

However, this is satisfied only when m is an integer, m = 0, ±1, ±2, . . ..


Hence, the constant m2 is not an arbitrary number, is an integer.
Normalization of Φ(φ) gives
Z 2π
1= |Φ(φ)|2 dφ = 2π|A|2 , (574)
0

163
which leads to the final form of Φ(φ) as
1
Φ(φ) = √ exp(imφ) . (575)

The next step in the solution is to find X(θ), the polar component of the
wave function.

From Eq. (568), if we multiply both sides of the equation by X and divide
by sin2 θ, and rearrange, we obtain
m2
! !
1 d dX
sin θ − α+ X=0. (576)
sin θ dθ dθ sin2 θ
Introducing a new variable z = cos θ, and noting that
d √ d
= − 1 − z2 , (577)
dθ dz
we find
 d2 X 2
!
 dX m
1 − z2 − 2z − α+ X=0,
dz 2 dz 1 − z2
or
m2
" # !
d  2 dX

1−z − α+ X=0. (578)
dz dz 1 − z2
Equation (578) is known in mathematics as the generalized Legendre differ-
ential equation, and its solutions are the associated Legendre polynomials.
For m = 0, the equation is called the ordinary Legendre differential equation
whose solution is given by the Legendre polynomials.
Solution of Eq. (578), that is regular at z = 1, is assumed to be repre-
sented by a power series of the form
1

|m|
aj z j .
X
X(z) = (1 − z) 2 (579)
j=0

Substituting Eq. (579) into Eq. (578), we obtain the recursion relation for
the coefficients aj :
(j + |m|)(j + |m| + 1) + α
aj+2 = aj . (580)
(j + 1)(j + 2)

164
Since aj+2 > aj , the series diverges (logarithmically) for z = ±1. Therefore,
in order to get the wave function finite everywhere in the space, we have
to terminate the series at some j = j0 . In other words, we assume that
aj0 +1 = aj0 +2 = . . . = 0.
The series terminating at j = j0 indicates that

(j0 + |m|)(j0 + |m| + 1) + α = 0 . (581)

Introducing

l = j0 + |m| , (582)

we see that l ≥ |m|, and

α = −l(l + 1) , l = 0, 1, 2, . . . (583)

Hence, we see that the eigenvalues of the angular momentum are quantized

L̂2 λ = h̄2 l(l + 1) ,


q
L̂ λ = h̄ l(l + 1) . (584)

The integer number l is called the angular momentum quantum number.


Since l ≥ |m|, the number m is limited to absolute values not larger than l.

Physical interpretation of the quantum number m

We have already shown that the azimuthal part of the wave function is given
by
1
Φ(φ) = √ exp(imφ) , m = 0, ±1, ±2, . . . , ±l . (585)

Consider the z-component, L̂z , of the angular momentum.
We will try to find the eigenvalues and eigenfunctions of L̂z :

L̂z Φ = µΦ . (586)

In the spherical coordinates



L̂z = −ih̄ , (587)
∂φ

165
and then we get from Eq. (586) a simple differential equation

∂Φ
−ih̄ = µΦ , (588)
∂φ
whose solution is
i
 
Φ(φ) = A exp µφ , (589)

where A is a constant.
Using the same argument as before, that in rotation, φ and φ + 2π corre-
spond to the same position in space, we find that

µ = mh̄ , m = 0, ±1, ±2, . . . (590)

Thus, the azimuthal part of the wave function is the wave function of the z-
component of the angular momentum, and the number m is the z-component
angular momentum quantum number.

Example:

Consider angular momentum with l = 1. In this case, the eigenvalue of



~ˆ is 2h̄, and L̂z can have three values +h̄, 0, −h̄. Thus, the orientation
L
of L~ˆ along the z-axis is quantized. The vector L ~ˆ processes around z axis,
sweeping out cones of revolution around that axis. This is shown in Fig. 31.
The quantization of the orientation of L̂ along its z-axis is called space quan-
tization.

Now we return to the analysis of the properties of the polar component


X(z) of the wave function.

After the termination of the series, we get the solution for the wave function
X(z) in terms of the associated Legendre polynomials
l−|m|
1
|m|
aj z j .
X
Xlm (z) = (1 − z) 2 (591)
j=0

166
Lz

m=+1

m=0
Ly

m=-1
Lx

Figure 31: Angular momentum quantization for l = 1.

The first few associated Legendre polynomials are


X00 (z) = a0 ,
X10 (z) = a1 z ,

X11 (z) = a0 1 − z 2 , (592)
where the coefficients a0 , a1 , . . . are found from the normalization of the wave
functions Xlm (z).

The first few angular function Y (θ, φ) = X(θ)Φ(φ) are:


1
Y00 (θ, φ) = √ ,

s
3
Y10 (θ, φ) = cos θ ,

s
3
Y11 (θ, φ) = − sin θeiφ ,

s
3
Y1−1 (θ, φ) = sin θe−iφ . (593)

167
15.2 Radial part of the wave function
In the final step of the solution of the Schrödinger equation, we consider the
remaining the radial part R of the wave function, Eq.(560).
We can simplify Eq. (560) introducing new variables

2mE me2
β2 = − , λ= , ρ = 2βr , (594)
h̄2 4πε0h̄2 β
and substituting the explicit form for V (r) (Eq. (555)), and α = −l(l + 1).
After this simplification, the differential equation (560) takes the form
! " #
1 d dR λ 1 l(l + 1)
2
ρ2 + − − R=0. (595)
ρ dρ dρ ρ 4 ρ2

We will try to find the solution of Eq. (595) in the form


1
R(ρ) = e− 2 ρ ρl bj ρ j .
X
(596)
j

As before, the series diverges and therefore we must terminate the series at
some j = j0 such that j0 = λ − l − 1.
Denoting j0 + l + 1 = n, we have λ = n, and n = 1, 2, 3, . . .. Moreover,
we see that n > l. We call n- the principal quantum number.
We have found λ (= n), so that we have β, and from that, we find energy

1 me4 1
E=− . (597)
(4πε0 )2 2h̄2 n2
We can introduce a constant
4πε0h̄2
ao = , (598)
me2
called the Bohr radius, and then

1 e2
E=− . (599)
4πε0 2ao n2
Thus, the energy of the electron in the hydrogen atom is quantized. Note
that Eq. (599) agrees perfectly with the prediction of the Bohr theory of the

168
hydrogen atom (see Eq.(111)).

Since ρ = 2βr, and β = 1/(ao n), the radial part of the wave function can
be written as
Rnl (r) = e−βr (2βr)l Lln (r) , (600)
where
n−l−1
Lln (r) = bj (2βr)j
X
(601)
j=0

are the associated Laquerre polynomials of order (n − l − 1).


The coefficients bj are found from the normalization of the radial function
Z ∞
drr 2 |Rnl (r)|2 = 1 . (602)
0

Once the radial part of the wave function is known, the solution for the
problem of the hydrogen atom is completed by writing down the normalized
wave function of the electron
Ψnlm (r, θ, φ) = Rnl (r)Ylm (θ, φ) . (603)

In summary of this lecture:

The eigenvalues of the energy of the electron in the hydrogen atom are quan-
tized
1 e2
En = − , (604)
4πε0 2ao n2
and the corresponding eigenfunctions are
Ψnlm (r, θ, φ) = Rnl (r)Ylm (θ, φ) , (605)
where the discrete (quantum) numbers are
n = 1, 2, 3, . . . , ∞ ,
l = 0, 1, 2, . . . , n − 1 ,
m = 0, ±1, ±2, . . . , ±l . (606)

169
Few normalized eigenfunctions of the electron
1
Ψ100 = q e−r/ao ,
πa3o
1 r
 
Ψ200 = q 1− e−r/(2ao ) ,
8πa3o 2ao
1 r −r/(2ao )
Ψ210 = q e cos θ . (607)
32πa3o ao
Note that eigenfunctions with l = 0 have spherical symmetry, i.e. are inde-
pendent of θ and φ.
The absolute square of the wave function |Ψnlm (r, θ, φ)|2 is the probability
density of finding the electron at the point ~r(r, θ, φ), and
Pnlm = |Ψnlm (r, θ, φ)|2 dV = 4πr 2 |Ψnlm (r, θ, φ)|2 drdθdφ (608)
is the probability of finding the electron in a small volume dV = drdθdφ
around the point ~r.

P100

1 2 r/a o

Figure 32: Probability function of the electron in the state (nlm) = (100).

The maximum value of Pnlm , which is the most probable distance of the
electron from the nucleus, differs from the expectation (average) distance hri,
given by
Z
hri = Ψ∗nlm rΨnlm dV . (609)

170
Examples of the probability function Pnlm are shown in Figs. 32 and 33.

P200

3+ 5 r/ao

Figure 33: Probability function of the electron in the state (nlm) = (200).

Interesting properties of the probability function Pnlm :

1. For n = 1, the probability has one maximum at r = ao .

2. For (n = 2, l = 0, m = 0), the probability shows two maxima located


at r 6= n2 ao .

3. Only for states such that n = l+1, the probability shows one maximum
located at r = n2 ao .

Exercise:

The normalized wave function for the ground state of a hydrogen atom has
the form

Ψ (r) = Ae−r/ao ,

where A = 1/πa3o is a constant, ao = 4πεoh̄2 /me2 is the Bohr radius, and r


is the distance between the electron and the nucleus. Show the following:

171
(a) The expectation value of r is 23 ao .

(b) The most probable value of r is r = ao .

Solution:

(a) From the definition of expectation value, we find


Z Z ∞
∗ 2
hri = Ψ (r) rΨ (r) dV = 4πA r 3 e−2βr dr ,
0

where β = 1/ao , and we have transformed the integral over dV into spherical
coordinates with dV = 4πr 2 dr.
Performing the integration, we obtain
6 24 πA2 3 1 4 3
hri = 4πA2 = = π a = ao .
(2β)4 16 β 4 2 πa3o o 2
Thus, the average distance of the electron from the nucleus in the state Ψ
is 3/2 of the Bohr radius.

(b) The most probable value of r is that where the probability of finding
the electron is maximal.
Thus, we first calculate the probability of finding the electron at a point r:
4r 2 −2βr
P (r) = 4πr 2 |Ψ (r) |2 = 4πr 2 A2 e−2βr = e .
a3o
Maximum of P (r) is where dP (r)/dr = 0. Hence
dP (r) 8r 8βr 2
= 3 e−2βr − 3 e−2βr .
dr ao ao
Thus
dP (r)
=0 when βr = 1 ,
dr
from which, we find
1
r= = ao .
β

172
Note that this result agrees with the prediction of the Bohr model, that the
radius of the n = 1 orbit is equal to ao .

In summary of the solution: The expectation and most probable values of r


are not the same. This is because the probability curve P100 (r) is not sym-
metric about the maximum at ao , see Fig. 32. Thus, values of r greater
than ao are weighted more heavily in the equation for the expectation value
than values smaller than ao . This results in the expectation value hri exceed-
ing ao for this probability distribution.

Challenging problem: Eigenfunctions of the angular momentum

The eigenfunctions of the angular momentum L̂ of the electron in a Hy-


drogen atom for l = 1 are
s s
3 3
Y10 (θ, φ) = cos θ , Y1±1 (θ, φ) = ∓ sin θe±iφ .
4π 8π

(a) Show that the eigenfunctions are also eigenfunctions of the L̂z component
of the angular momentum.

(b) Show that the eigenfunctions are not eigenfunctions of the L̂x component
of the angular momentum.

(c) Find the matrix representation of L̂x in the basis of the eigenfunctions
of L̂.

(d) Find the eigenvalues and eigenfunctions of L̂x in the basis of the eigen-
functions of L̂.

173
16 Systems of Identical Particles

Consider a system composed of N parts (subsystems), e.g. a system of N


identical and independent particles, whose the Hamiltonian is given by
N
X
Ĥ = Ĥi , (610)
i=1

and the wave function is

Ψ(r) = φ1 (r1 )φ2 (r2 ) . . . φN (rN ) , (611)

where φi (ri ) is the wave function of the ith particle located at the point rj ,
or equivalently we can say that φi (rj ) is the wave function of the jth particle
being in the ith state.

However, the wave function Ψ(r) is not the only eigenfunction of the
system. For example, a wave function

Ψ(r) = φ1 (r2 )φ2 (r1 ) . . . φN (rN ) , (612)

is also an eigenfunction of the system with the same eigenvalue.

Proof:

Consider the eigenvalue equation with the eigenfunction (611):


N
X
ĤΨ(r) = Ĥi Ψ(r)
i=1
XN N
X
= Ĥi φ1 (r1 )φ2 (r2 ) . . . φN (rN ) = Ei Ψ(r) .
i i=1

Consider now the eigenvalue equation with the eigenfunction (612)


N
X N
X
ĤΨ(r) = Ĥi Ψ(r) = Ĥi φ1 (r2 )φ2 (r1 ) . . . φN (rN ) .
i=1 i

174
Since

Ĥ1 φ1 (r2 ) = E1 φ1 (r2 ) , and Ĥ2 φ2 (r1 ) = E2 φ2 (r1 ) ,


PN
we get that ĤΨ(r) = i=1 Ei Ψ(r).
Even if

Ĥ1 φ1 (r2 ) = E2 φ1 (r2 ) , and Ĥ2 φ2 (r1 ) = E1 φ2 (r1 ) ,

we get that
N
X
ĤΨ(r) = Ei Ψ(r) , (613)
i=1

as required♦.

In fact there are a total N ! permutations of φi (rj ) which are eigenfunctions


of the system.
Moreover, an arbitrary linear combination of the wave functions φi (rj ) is
also an eigenfunction of the system.
We will illustrate this for N = 2.

16.1 Symmetrical and antisymmetrical functions


Consider an arbitrary linear combination of two wave functions
1
Ψ(r) = q [aΨ(r12 ) + bΨ(r21 )] , (614)
|a|2 + |b|2

where Ψ(r12 = φ1 (r1 )φ2 (r2 ) and Ψ(r21 = φ1 (r2 )φ2 (r1 ).
Then
 
ĤΨ(r) = Ĥ1 + Ĥ2 Ψ(r)
1
=q [a (E1 + E2 ) Ψ(r12 ) + b (E1 + E2 ) Ψ(r21 )]
|a|2 + |b|2
= (E1 + E2 ) Ψ(r) . (615)

We know that in the linear combination |a|2 /(|a|2 + |b|2 ) is the probability
that the particle ”1” is at the position r1 and the particle ”2” is at r2 .

175
Equivalently, for r1 = r2 , we can say that this is the probability that the
particle ”1” is in a state |1i, and the particle ”2” is in a state |2i.
Similarly, |b|2 /(|a|2 + |b|2 ) is the probability that the particle ”1” is at the
position r2 , and the particle ”2” is at r1 .
Note, that in general, the probabilities are different. However, for two
identical particles, the probabilities should be the same as we cannot distin-
guish between two identical particles.
Thus, for two identical particles |a| = |b|. Hence, the parameters a and b
can only differ by a phase factor: b = a exp(iφ), where φ is a real number:

1 h i
Ψ(r) = √ Ψ(r12 ) + eiφ Ψ(r21 ) . (616)
2

If we exchange the positions of the particles (r1 ↔ r2 ) or energy states


(|1i ↔ |2i), then we obtain

1 h i
Ψ0 (r) = √ eiφ Ψ(r12 ) + Ψ(r21 ) . (617)
2

Thus, the exchange of r1 ↔ r2 or |1i ↔ |2i is equivalent to multiplying Ψ(r)


by eiφ and taking e2iφ = 1. Hence

eiφ = ±1 , (618)

and therefore the wave functions of identical particles are either symmetrical
or antisymmetrical
1
Ψs (r) = √ [Ψ(r12 ) + Ψ(r21 )] ,
2
1
Ψa (r) = √ [Ψ(r12 ) − Ψ(r21 )] . (619)
2
Note that

Ψs (r12 ) = Ψs (r21 ) ,
Ψa (r12 ) = −Ψa (r21 ) . (620)

176
Properties of symmetrical and antisymmetrical functions:

1. If Ĥ = Ĥ12 = Ĥ21 , i.e. the Hamiltonian is symmetrical, then ĤΨ(r)


has the same symmetry as Ψ(r).

Proof:

Take Ψ(r) = Ψs (r). Denote f12 = Ĥ12 Ψs (r12 ), then

f21 = Ĥ21 Ψs (r21 ) = Ĥ12 Ψs (r12 ) = f12 .

Take now Ψ(r) = Ψa (r). Then

f21 = Ĥ21 Ψa (r21 ) = Ĥ12 (−Ψs (r12 )) = −f12 ,

as required♦.

2. Symmetry of the wave function does not change in time, i.e. wave function
initially symmetrical (antisymmetrical) remains symmetrical (antisymmetri-
cal) for all times.

Proof:

Consider an evolution of a wave function Ψ(t) in a time dt:

∂Ψ
Ψ(t + dt) = Ψ(t) + dt .
∂t
Thus, symmetry of the wave function depends on the symmetry of ∂Ψ/∂t.
From the time-dependent Schrödinger equation
∂Ψ
ih̄ = ĤΨ ,
∂t

we see that ∂Ψ/∂t has the same symmetry as ĤΨ. From the property 1, we
know that ĤΨ has the same symmetry as Ψ. Therefore, Ψ(t + dt) has the
same symmetry as Ψ(t),
as required♦.

177
Difference between symmetric and antisymmetric functions

Antisymmetric function can be written in a form of a determinant, called


the Slater determinant:

φ1 (r1 ) φ1 (r2 ) . . . φ1 (rN )




φ2 (r1 ) φ2 (r2 ) . . . φ2 (rN )




1 .

Ψa (r) = √

, (621)
N!

.

.



φN (r1 ) φN (r2 ) . . . φN (rN )


where 1/ N ! is the normalization constant.
If two particles are at the same point, r1 = r2 , and then two columns
of the determinant (621) are equal, giving Ψa (r) = 0. Thus, two particles
determined by the antisymmetric function cannot be at the same point. Sim-
ilarly, if two particles are in the same state, φ1 (r1 ) = φ1 (r2 ), and again two
columns are equal giving Ψa (r) = 0.
Symmetrical function cannot be written in a form of a determinant. Thus,
particles which are determined by symmetrical functions can be in the same
point or in the same state.
Hence, particles can be divided into two types: those determined by anti-
symmetric functions – called fermions, and those determined by symmetrical
functions – called bosons.

Examples:

Fermions: electrons, protons, neutrons.


Bosons: photons, π mesons, α particles.

From experiments, we know that fermions have half integer spins, whereas
bosons have integer spins.
Since, an arbitrary number of bosons can be in the same state, they
can be condensated to a single state. We call this process Bose-Einstein
condensation.

178
16.2 Pauli principle

In atoms, a limited number of electrons (fermions) can occupy the same en-
ergy level. How many electrons does it take to fill an energy level? The
answer to this question is given by the Pauli principle.

Pauli principle:

No two electrons can have the same quantum numbers (n, l, m, s) in


a multi-electron atom.

It is also known as the exclusion principle, for the simple reason that if an
electron has the quantum numbers (nlms) than at least one of the quantum
numbers of any further electrons must be different.

In an atom, for a given n, there are 2(2l + 1) degenerate states corresponding


to l = 0, 1, 2, . . ., m = −l, . . . , l, and s = − 21 , + 21 . Thus, for a given n the
total number of electrons in the energy state Φn is
l=m
2(2l + 1) = 2n2 .
X
(622)
l=−m

Following the Pauli principle, we can find numbers of electrons in the


energy states
1s , 2s , 2p , 3s , 3p , 4s , 3d , 4p , 5s , 4d , 5p
2 2 6 2 6 2 10 6 2 10 6
The Pauli principle prevents the energy states being occupied by an arbitrary
number of electrons. The state 1s can be occupied by two electrons. Hence,
as more electrons are added, the energy of the atom grows along with its
size. Thus, the Pauli principle prevents all atoms having the same size and
the same energy. This is the quantum physics explanation of atomic sizes
and energies.
Since the number of electrons on given energy levels is limited, we get
different ground state configurations for different atoms. The ground state
of a many electron atom is that in which the electrons occupy the lowest
energy levels that they can occupy.

179
If the number of electrons for a given nl is 2(2l + 1), we say that there is
a closed shell. Examples: Helium, Beryllium, Neon.
Since the chemical properties of atoms depend on the number of electrons
outside the closed shells, the atoms with similar outer configurations will have
similar chemical properties. Examples: The Alkali metals: Lithium (1s)2 2s,
Sodium (1s)2 (2s)2 (2p)6 3s, and Potassium (1s)2 (2s)2 (2p)6 (3s)2 (3p)6 4s.
This is the explanation from quantum physics of the periodic structure of
the elements.

180
Final Remark

It is appropriate to close our lectures on quantum physics by emphasizing


the importance of quantum phenomena in the development of new areas in
science and technology. The predictions of quantum physics have turned
research and technology into new directions and have led to numerous tech-
nological innovations and the development of a new technology on the scale
of single atoms and electrons, called quantum technology or nanotechnology.
The ability to manufacture and control of the dimensions of tiny structures,
such as quantum dots, allows us to engineer the unique properties of these
structures and predict new devices such as quantum computers. The technol-
ogy for creating a quantum computer is still in its infancy, but is developing
very rapidly with little sign of the progress slowing.
We have seen in our journey through the backgrounds of quantum physics
that despite its long history, quantum physics still challenges our understand-
ing, and continues to excite our imagination. Feynman in his lectures on
quantum physics referred in the following way to our understanding of quan-
tum physics:

”I think I can safely say that nobody


understands quantum mechanics.”

In summary of the subject, I think I can safely say:

”If you think you now know quantum physics,


it means you do not know anything.”

Continue study of Quantum Physics with PHYS3040.

181
Appendix A
Derivation of the Boltzmann distribution function Pn

Assume that we have n identical particles (e.g. photons), each of energy


E, which can occupy g identical states. The number of possible distributions
of n particles between g states is given by

(n + g − 1)!
t= . (623)
n!(g − 1)!

For example: n = 3, g = 2 gives t = 4, see Fig. 34.

We will find maximum of t with the condition that nE =const., where E


is the energy of each particle.

... .. . . .. ...
Figure 34: Example of possible distributions of three particles between two
states.

Taking ln of both sides of Eq. (623), we get

ln t = ln(n + g − 1)! − ln n! − ln(g − 1)! . (624)

Using the Sterling’s formula

ln n! = n ln n − n , (625)

and assuming that g  1, i.e. g − 1 ≈ g, we obtain


n+g n+g
ln t = g ln + n ln . (626)
g n

183
We find maximum of ln t using the method of Lagrange undetermined multi-
pliers. In this method, we construct a function
K = ln t − λnE , (627)
where λ is called a Lagrange undetermined multiplier, and find the extremum
∂K
=0. (628)
∂n
Thus, we get
n
ln + λE = 0 , (629)
n+g
from which, we find
g
n = λE . (630)
e −1
This is the Bose-Einstein distribution function. Since n is dimensionless, λ
should be inverse of energy. We choose λ = 1/(kB T ), where kB T is the
energy of free, non-interacting particles.
When g/n  1, we can approximate Eq. (630) by
− k ET
n = ge B , (631)
which is known in statistical physics as the Boltzmann distribution. This
gives the number of particles n of energy E.
If there are particles, among N particles, which can have different energies
Ei , then
ni g − E
= e kB T (632)
N N
is the probability that ni particles of the total N particles have energy Ei .
Thus, we can write
− k ET
Pn = ae B , (633)
where a is a constant.
Since the probability is normalized to one ( n Pn = 1), we finally get
P

− k ET
e B
Pn = P − k ET
. (634)
n e B

− k ET
The sum e is called the partition function.
P
B
n

184
Appendix B: Useful mathematical formulae

Useful properties of trigonometrical functions:

sin(α ± β) = sin α cos β ± sin β cos α


cos(α ± β) = cos α cos β ∓ sin α sin β
1
sin2 α = (1 − cos 2α)
2
1
cos2 α = (1 + cos 2α)
2
Z π 4
sin3 θ dθ =
0 3
(
Z 2π 0 for m 6= n
sin(mφ) sin(nφ) dφ =
0 π for m = n
(
Z 2π 0 for m 6= n
cos(mφ) cos(nφ) dφ =
0 π for m = n
Z 2π
sin(mφ) cos(nφ) dφ = 0 for all m and n
0

Useful integral expressions

Z ∞ x3 π4
dx =
0 ex − 1 15
∞ π
Z r
−αx2
e dx =
−∞ α
Z ∞ 2
xe−αx dx = 0
−∞

∞ 1 π
Z r
2 −αx2
x e dx =
−∞ 2α α

185
∞ n!
Z
r n e−αr dr = ,
0 αn+1
from which, we find
∞ 1 ∞ 1
Z Z
−αr
e dr = , re−αr dr = ,
0 α 0 α2
∞ 2 ∞ 6
Z Z
r 2 e−αr dr = , r 3 e−αr dr =
0 α3 0 α4

Taylor series

d2 ω
! !
dω 1
ωk = ωk0 +β = ω0 + β+ β2 + . . .
dβ k0
2 dβ 2 k0
2 3
x x
e±x = 1 ± x + ± +...
2! 3!
x3 x5 x7
sin x = x − + − +...
3! 5! 7!
x2 x4 x6
cos x = 1 − + − +...
2! 4! 6!

Kronecker δ function
(
1 if m = n
δmn =
0 if m 6= n .

The Dirac delta function


(
0 if x 6= 0
Z ∞
δ(x) = such that f (x)δ(x)dx = f (0) ,
∞ if x = 0 , −∞

for any function f (x).

186
Appendix C: Physical Constants and
Conversion Factors

Bohr magneton mB = 9.724 × 10−24 [J/T]


Bohr radius ao = 5.292 × 10−11 [m]
Boltzmann constant kB = 1.381 × 10−23 [J/K]
charge of an electron e = −1.602 × 10−19 [C]
permeability of vacuum µ0 = 4π × 10−7 [H/m]
permittivity of vacuum ε0 = 8.854 × 10−12 [F/m]
Planck constant h = 6.626 × 10−34 [J.s] = 4.14 × 10−15 [eV.s]
(Planck constant)/2π h̄ = 1.055 × 10−34 [J.s] = 6.582 × 10−16 [eV.s]
rest mass of electron me = 9.110 × 10−31 [kg]
rest mass of proton mp = 1.673 × 10−27 [kg]
Rydberg constant R = 1.097 × 107 [m−1 ]
speed of light in vacuum c = 2.9979 × 108 [m/s]
Stefan − Boltzmann constant σ = 5.670 × 10−8 [W/m2 · K4 ]

1 Å = 10−10 [m] ; 1 fm = 10−15 [m] ; 1 eV = 1.602 × 10−19 [J]


1 J = 6.241 × 1018 [eV] ; π = 3.142 ; e = 2.718 .

187