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Department of Physics

2004

PHYS2041

QUANTUM PHYSICS

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)

Contents

General Bibliography 5

Assumed Background 6

Introduction 9

1.1 Wave equation . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

1.2 Energy of the EM wave . . . . . . . . . . . . . . . . . . . . . . 12

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

4.1 Boltzmann distribution function . . . . . . . . . . . . . . . . . 31

4.2 Planck’s formula for I(λ) . . . . . . . . . . . . . . . . . . . . . 32

4.3 Photoelectric effect . . . . . . . . . . . . . . . . . . . . . . . . 37

4.4 Compton scattering . . . . . . . . . . . . . . . . . . . . . . . . 37

5.1 The hydrogen atom . . . . . . . . . . . . . . . . . . . . . . . . 41

5.2 X-rays characteristic spectra . . . . . . . . . . . . . . . . . . . 44

5.3 Difficulties of the Bohr model . . . . . . . . . . . . . . . . . . 45

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

tum) Wells 79

8.1 Infinite potential quantum well . . . . . . . . . . . . . . . . . 81

8.2 Finite square-well potential . . . . . . . . . . . . . . . . . . . 88

8.3 Quantum tunneling . . . . . . . . . . . . . . . . . . . . . . . . 99

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

10.1 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

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

3

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

12.1 Matrix representation of operators . . . . . . . . . . . . . . . . 135

12.2 Matrix representation of eigenvalue equations . . . . . . . . . 137

14.1 Algebraic operator technique . . . . . . . . . . . . . . . . . . . 147

14.2 Special functions method . . . . . . . . . . . . . . . . . . . . . 155

15.1 Angular part of the wave function: Angular momentum . . . . 162

15.2 Radial part of the wave function . . . . . . . . . . . . . . . . . 168

16.1 Symmetrical and antisymmetrical functions . . . . . . . . . . 175

16.2 Pauli principle . . . . . . . . . . . . . . . . . . . . . . . . . . . 179

tion Pn 183

4

General Bibliography

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.

A good introductory text on quantum physics.

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:

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

5

Assumed Background

electromagnetism, thermal physics and optics. In particular, PHYS1002

course on special relativity and modern physics.

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.

~ 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

Equation (12) shows that the electric E ~ and magnetic B

~ fields of an EM

wave propagating in vacuum are mutually orthogonal.

of electromagnetic transverse plane waves.

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).

can be represented by a set of harmonic oscillators. Thus, according to

the Maxwell’s EM theory, the radiation (light) is a wave.

the amplitude of the oscillation.

14

Exercise:

~ =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

Solution:

~

∂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

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:

~ 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.

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

ratio e/m

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)

nλ

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).

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)

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.

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 ).

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 ).

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

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.

E = E 0 + Ee , (34)

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.

cies are emitted.

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?

23

In summary of this lecture:

1. Properties of X-rays,

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.

we will define what we mean by a black body.

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.

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

8π

N= 4 , (37)

λ

and hEi is the average energy of each mode.

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

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

8π

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

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

8π

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.

lows:

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:

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

8π

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)

2π

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.

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.

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

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

∞

1

e−nx =

X

. (58)

n=0 1 − e−x

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.

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

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

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

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.

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.

Stefan−Boltzmann law

c ∞

Z

I= I(λ)dλ = σT 4 , (70)

4 0

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:

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.

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

with that for a continuous n.

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

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

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)

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.

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)

m0

m= q , (85)

1 − (v/c)2

pc − p0 c + m0 c2 = mc2 . (86)

2

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

Thus

2

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

experiments, we can eliminate pe using the momentum conservation law

where α is the angle between directions of the incident and scattered photons.

Substituting Eq. (90) into Eq. (88), we get

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.

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:

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

electron.

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)

electron.

From the conservation of momentum, we have

hν

pf = = pe , (97)

c

and substituting (97) into (96), we obtain

q

2

hν + m0 c = m20 c4 + (hν)2 , (98)

q q

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

We see from the above equation that

pf > |~

pe | + |~

pp | ≥ |~

pe + p~p | . (100)

Hence

Exercise at home:

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

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.

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)

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.

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)

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.

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

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:

explaining experimental results of the black-body radiation, photoelectric ef-

fect, Compton scattering, atomic spectra, and X-rays characteristic spectra.

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:

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?

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

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?

of material particles as well?

Then, one may ask: Is an electron really a particle or is it a wave?

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.

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)

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.

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.

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?

obvious question was: How to perform such an experiment? What wave-

lengths can we expect? To answer these questions, consider first a simple

example.

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)

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:

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

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.

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

nπ

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.

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:

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.

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”.

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.

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

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 .

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:

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

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:

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:

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.

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

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.

A

v0 θ

∆y

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.

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

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:

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.

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)

−∞

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.

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)

−∞

dω

where vg = dβ k0

is the group velocity of the packet.

63

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

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

dω

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

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

function.

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

particle, whose the solution is the wave function (166), with the following

conditions

• The equation must be linear.

rameters characteristic of the particle.

We will limit our considerations the the non-relativistic case only.

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.

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

ih̄

Γ2 = . (171)

2m

Thus, the wave function (166) satisfies the following differential equation

= , (172)

∂t 2m ∂x2

or equivalently

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

! !

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

h̄

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:

∂ ∂

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:

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

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.

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

It is easily to show that, in general, the components of the position ~ˆr and

momentum pˆ~ operators satisfy the commutation relations

1

Commutation consists in reversing the order of two quantities in an algebraic

operation.

69

where

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

1 if m=n

δmn = (184)

0 if m 6= n .

ten as

∂Ψ(~r, t)

ih̄ = ĤΨ(~r, t) , (185)

∂t

2

h̄

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

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

the space (~r, t).

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

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):

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)

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:

first derivatives.

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.

We have learnt that

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

Hamiltonian Ĥ and can be found by solving the stationary Schrödinger

equation Ĥφ(~r) = Eφ(~r).

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.

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.

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∗ ∇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 ,

h̄

(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.

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

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

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.

|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.

|J~t |

T = , (219)

|J~i |

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

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:

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

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.

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

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)

B = −Ae−ika , (235)

B = −Aeika . (236)

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

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.

−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.

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:

(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] .

E1

e kB T = 2 ,

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?

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

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

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

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

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

classical analog. Quantum mechanical penetration of the barrier has come

to be regarded as a paradoxical, controversial, non-intuitive aspect of quan-

tum physics.

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)

h̄

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

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)

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)

(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

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.

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

97

Exercise at home:

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

(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

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

iη

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.

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

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

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.

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

separable into three independent functions Ψx , Ψy , and Ψz . In this case, we

can find the solution of the Schrödinger equation in product form

Substituting this into the Schrödinger equation and dividing both sides by

Ψx Ψy Ψz , we obtain

− − − =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

− =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

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:

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 Â is linear if for arbitrary functions fi and gi , and arbitrary

complex numbers ci , such that

The sum of two operators Â and B̂ and their product are defined as

Â + B̂ f = Âf + B̂f , (319)

ÂB̂ f = Â B̂f . (320)

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)

2

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

commutative.

110

We can define a commutator:

h i

Â, B̂ = ÂB̂ − B̂ Â , (323)

h i

Â, B̂ = 0 . (324)

n o h i

Â, B̂ ≡ Â, B̂ = ÂB̂ + B̂ Â , (325)

+

h i

Â, B̂ =0. (326)

+

Inverse operator:

1̂f = f . (328)

functions f and g that vanish at infinity

Z Z ∗

∗

f ÂgdV = Â† f gdV . (329)

†

1. Â† = Â . (330)

111

Proof:

Z Z ∗ Z ∗ Z ∗

∗ † † ∗ †

f ÂgdV = Â f gdV = g Â f dV = g Â f dV

Z † ∗ ∗ Z †

= Â† g f dV = Â† g f ∗ dV

Z †

= f∗ Â† g dV , (331)

as required♦.

†

2. ÂB̂ = B̂ † Â† . (332)

Proof:

Z † Z ∗ Z h i∗

f ∗ ÂB̂ gdV = ÂB̂f gdV = Â B̂f gdV . (333)

Z ∗ Z Z ∗

∗ †

Âu gdV = u Â gdV = B̂f Â† gdV

Z

= f ∗ B̂ † Â† gdV . (334)

†

Thus, ÂB̂ = B̂ † Â† ,

as required♦.

112

10.2 Hermitian operators

Â† = Â , (335)

i.e. when

Z Z ∗

∗

f ÂgdV = Âf gdV . (336)

1. Â + B̂ is Hermitian,

Z Z ∗ Z ∗

∗ ∗

f cÂ gdV = cÂf gdV = c Âf gdV , (337)

as required♦.

Proof:

†

ÂB̂ = B̂ † Â† = B̂ Â . (338)

†

Hence, ÂB̂ 6= ÂB̂ unless Â 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 Â and B̂ are Hermitian.

Proof:

h i† † † †

Â, B̂ = ÂB̂ − B̂ Â = ÂB̂ − B̂ Â

h i

= B̂ † Â† − Â† B̂ † = B̂ Â − ÂB̂ = − Â, B̂ , (339)

as required♦.

h i

6. However, i Â, B̂ is Hermitian.

Proof:

† †

ÂÂ† = Â† Â† = ÂÂ† , (340)

as required♦.

8. If Â is non-Hermitian, Â + Â† and i Â − Â† are Hermitian. Hence,

Â can be written as a linear combination of two Hermitian operators

1 1

Â = Â + Â† + i Â − Â† . (341)

2 2i

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).

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

h̄

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

as required♦.

nian of a particle, see Section 7.3. The idea of eigenvalues and eigenfunctions

can be extended to arbitrary operators. Thus, we can state:

115

Example:

Â = 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 Â = d/dx with an eigenvalue α = 2.

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

represent physical quantities. This importance arises from the fact that

eigenvalues of an Hermitian operator are real.

Proof:

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

Z +∞

Ψ∗1 (~r)Ψ2 (~r)dV = 0 . (348)

−∞

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)

The complex functions Ψi form a complex linear vector space. The infinite-

dimensional vector space of orthonormal functions is called Hilbert space.

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.

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.

an important property of eigenfunctions of a linear Hermitian operator.

ferent eigenvalues are orthogonal.

Proof:

Â 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)

Z

(f, g) = f ∗ gdV = 0 , (357)

as required♦.

118

10.4 Expectation value of an operator

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

then the scalar product

Z

Ψi , ÂΨi = Ψ∗i ÂΨi dV (359)

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.

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

* +

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.

are real. In term of the scalar product this is characterized by

∗

Ψi , ÂΨi = Ψi , ÂΨi . (363)

∗

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:

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 Â and B̂ Hermitian?

Solution:

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)

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)

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

two Hermitian operators that do not commute. In other words, if Â 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:

holds

hÂÂ† 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)

Hence, from Eq. (378), we find

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

Hence

1

hÂ2 ihB̂ 2 i ≥ − h[Â, B̂]i2 , (384)

4

as required.

Finally, since

where ∆Û = Û − hÛ i, (Û = Â, B̂), and replacing in Eq. (384), Â → ∆Â 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.

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.

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

tion of the orthonormal vectors ~en .

of orthonormal wave functions Ψn as

X

Ψ= cn Ψ n , (399)

n

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)

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 .

Z

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

V

128

Proof:

Z Z

Ψ∗ (~r)Ψ(~r)dV = |Ψ(~r)|2 dV

VZ Z Z V

V Vn Vm

Z Z Z

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

V Vn V

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:

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

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|Â† |ii , (407)

or

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 Â associates with every ket |ii another ket |ji:

such that

and

Âλ|ai = λ Â|ai , (413)

where λ is a number.

states as

X

|ai = cn |ni . (414)

n

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

131

The product ket-bra (|nihn|) is called a projection operator, and the rela-

tion (418) is called the completeness relation.

|cn |2 = 1 .

X

(419)

n

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.

mitian.

Proof:

Since

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

∗

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 Â 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 Â on both sides by unity in the form

X

1= |mihm| , (426)

m

and obtain

! !

X X X

Â = |mihm| Â |nihn| = |mihm|Â|nihn|

m n m,n

X X

= hm|Â|ni|mihn| = Amn P̂mn , (427)

m,n m,n

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

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 Â 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 Â 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:

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

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

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

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

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

Â as

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

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 :

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 Â in the orthonormal basis |ni.

Example:

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

Â = . (443)

n 0

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

Denote

Since

Â|1i = n|2i ,

Â|2i = −n|1i , (445)

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

Hence

h1|Â|1i = 0 , h2|Â|2i = 0 ,

h1|Â|2i = −n , h2|Â|1i = n . (447)

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

The ket vector |ai is an eigenvector of a linear operator Â if the ket vector

Â|ai is a constant α times |ai, i.e.

137

The complex constant α is called the eigenvalue and |ai is the eigenvector

corresponding to the eigenvalue α.

Eigenvectors of an operator Â 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

XX X

cn |mihm|Â|ni = α cm |mi , (451)

n m m

!

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

A21 A22 . . . A2n

c2

c2

. . .

= α . (455)

.

.

.

. . .

An1 An2 . . . Ann cn cn

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 Â with eigenvalues

αn = Ann .

2. If the matrix Āmn is not diagonal, then we can find the eigenvalues

and eigenvectors of Â 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

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 Â = 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

−nc2 = inc1

or

c1 = ic2 . (460)

! !

ic2 i

Ψ α1 = = c2 . (461)

c2 1

!

2 i

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

1

given by

!

1 i

Ψ α1 =√ , (463)

2 1

or

1

Ψα1 = √ [i sin(nx) + cos(nx)] . (464)

2π

ing to the eigenvalue α2 is of the form

1

Ψα2 = √ [−i sin(nx) + cos(nx)] . (465)

2π

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

Â is in the state |1i or in the state |2i.

by a normalized column vector of expansion coefficients in the basis of

orthonormal states.

by a matrix, whose the elements Amn are given by scalar products

(Ψm , ÂΨn ).

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)

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

cmn |φ(0)

X X

n i = m ihφm |φn i = m i , (477)

m m

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

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

from Eq. (481).

Example:

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

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

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

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)

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.

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 :

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, â† satisfy

the commutation relation

h i

â, â† = 1̂ . (494)

1 1

Ĥ = h̄ω â† â + ââ† = h̄ω â† â + . (495)

2 2

Hence, the eigenvalue equation

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† â|φi + =E . (498)

2

Since

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 â† :

1

h̄ω â† â† â + â† |φi = Eâ† |φi . (501)

2

Using the commutation relation (494), we can write Eq. (501) as

1 †

h̄ω â† â − â |φi = Eâ† |φi . (502)

2

Adding to both sides h̄ωâ† |φi, we obtain

1 †

†

h̄ω â â + â |φi = (E + h̄ω) â† |φi . (503)

2

Introducing a notation |Ψi = â† |φi, we see that |Ψi is an eigenfunction of Ĥ

with eigenvalue E + h̄ω.

Thus, the operator â† acting on the state |φi of energy E transforms this

state to the state |Ψi of energy E + h̄ω. Therefore, the operator â† is called

the raising operator or creation operator.

148

Now, multiplying Eq. (503) from the left by â† , we obtain

1

h̄ω â â â + â† |Ψi = (E + h̄ω) â† |Ψi .

† †

(504)

2

Proceeding similar as above, we get

1 †

h̄ω â† â + â |Ψi = (E + 2h̄ω) â† |Ψi . (505)

2

Thus, the state â† |Ψi = â† â† |φi is an eigenfunction of Ĥ with an eigenvalue

E + 2h̄ω.

Similarly, we can show that the state |φn i = (â† )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† â + |φn i = (E + nh̄ω) |φn i = En |φn i . (506)

2

Multiplying Eq. (506) from the left by â, we get

1

h̄ω ââ† â + â |φn i = (E + nh̄ω) â|φn i , (507)

2

and using the commutation relation (494), we obtain

3

h̄ω â† 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 >

in Fig. 28, forms a ladder of equally spaced levels separated by h̄ω, which

one ascends by the action of â† 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 + 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)

1 1

Ĥ|φ0 i = h̄ω â† 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 = â† |φ0 i , |φ2 i = â† |φ0 i , . . . , |φn i = â† |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 â† 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 â† |φ0 i

= |cn |2 hφ0 |ân â†n |φ0 i

= |cn |2 hφ0 |ân−1 ââ†n |φ0 i . (515)

h n i n−1

â, â† = n â† , (516)

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)

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

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) = â† φ0 (x) . (526)

Using the definition of â† (Eq. (493)), we can find φn (x) in terms of the

position x:

"r !#

mω 1 d

= x − i√ −ih̄ φ0 (x) . (527)

2h̄ 2mh̄ω dx

dφ0 mω

=− xφ0 . (528)

dx h̄

Hence

√ r

mω

φ1 (x) = 2 x φ0 (x) . (529)

h̄

Similarly, we can find that

1 mω 2

φ2 (x) = √ 2 x − 1 φ0 (x) . (530)

2 h̄

We can introduce a new parameter

mω

r

α= x, (531)

h̄

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

− 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.

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

h̄

|x| ≤ . (537)

mω

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.

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

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).

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

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.

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:

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

2β

158

Substituting

y 2 = 2βx2 ,

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

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

h̄

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)

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

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

!

∂ ∂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

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

mentum

In fact, Eq. (561) is the eigenvalue equation for the square of the angular

momentum operator

L (562)

1 ∂2Y

( ! )

2 2 1 ∂ ∂Y

L̂ = −h̄ sin θ + . (563)

sin θ ∂θ ∂θ sin2 θ ∂φ2

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

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

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

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(i2πm) = 1 . (573)

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)

2π

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

Introducing

l = j0 + |m| , (582)

α = −l(l + 1) , l = 0, 1, 2, . . . (583)

Hence, we see that the eigenvalues of the angular momentum are quantized

q

L̂ λ = h̄ l(l + 1) . (584)

Since l ≥ |m|, the number m is limited to absolute values not larger than l.

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)

2π

Consider the z-component, L̂z , of the angular momentum.

We will try to find the eigenvalues and eigenfunctions of L̂z :

L̂z Φ = µΦ . (586)

∂

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)

h̄

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

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:

√

~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.

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

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).

1

Y00 (θ, φ) = √ ,

4π

s

3

Y10 (θ, φ) = cos θ ,

4π

s

3

Y11 (θ, φ) = − sin θeiφ ,

8π

s

3

Y1−1 (θ, φ) = sin θe−iφ . (593)

8π

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

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

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)

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).

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 ,

is the distance between the electron and the nucleus. Show the following:

171

(a) The expectation value of r is 23 ao .

Solution:

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 .

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.

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

identical and independent particles, whose the Hamiltonian is given by

N

X

Ĥ = Ĥi , (610)

i=1

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

Proof:

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

N

X N

X

ĤΨ(r) = Ĥi Ψ(r) = Ĥi φ1 (r2 )φ2 (r1 ) . . . φN (rN ) .

i=1 i

174

Since

PN

we get that ĤΨ(r) = i=1 Ei Ψ(r).

Even if

we get that

N

X

ĤΨ(r) = Ei Ψ(r) , (613)

i=1

as required♦.

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.

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

(|1i ↔ |2i), then we obtain

1 h i

Ψ0 (r) = √ eiφ Ψ(r12 ) + Ψ(r21 ) . (617)

2

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:

has the same symmetry as Ψ(r).

Proof:

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:

∂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

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:

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:

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.

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

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

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:

understands quantum mechanics.”

it means you do not know anything.”

181

Appendix A

Derivation of the Boltzmann distribution function Pn

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)!

is the energy of each particle.

... .. . . .. ...

Figure 34: Example of possible distributions of three particles between two

states.

ln n! = n ln n − n , (625)

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

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

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 .

(

0 if x 6= 0

Z ∞

δ(x) = such that f (x)δ(x)dx = f (0) ,

∞ if x = 0 , −∞

186

Appendix C: Physical Constants and

Conversion Factors

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 J = 6.241 × 1018 [eV] ; π = 3.142 ; e = 2.718 .

187

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