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Lecturer: Dr. Zbigniew Ficek Physics Annexe(6): Rm. 436 Ph: 3365 2331 email: cek@physics.uq.edu.au

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

Contents

General Bibliography Assumed Background Introduction 5 6 9

1 Radiation (Light) is a Wave 10 1.1 Wave equation . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 1.2 Energy of the EM wave . . . . . . . . . . . . . . . . . . . . . . 12 2 Diculties of the Wave Theory 2.1 Discovery of the electron . . . 2.2 Discovery of X-rays . . . . . . 2.3 Photoelectric eect . . . . . . 2.4 Compton scattering . . . . . . 2.5 Discrete atomic spectra . . . . of Radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 17 18 20 22 23

3 Black-Body Radiation 25 3.1 Number of radiation modes . . . . . . . . . . . . . . . . . . . 25 3.2 Equipartition theorem . . . . . . . . . . . . . . . . . . . . . . 28 4 Plancks Quantum Hypothesis 4.1 Boltzmann distribution function 4.2 Plancks formula for I() . . . . 4.3 Photoelectric eect . . . . . . . 4.4 Compton scattering . . . . . . . 5 The 5.1 5.2 5.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 31 32 37 37 41 41 44 45

Bohr Model The hydrogen atom . . . . . . . . . . . . . . . . . . . . . . . . X-rays characteristic spectra . . . . . . . . . . . . . . . . . . . Diculties of the Bohr model . . . . . . . . . . . . . . . . . .

6 Duality of Light and Matter 47 6.1 Matter waves . . . . . . . . . . . . . . . . . . . . . . . . . . . 47 6.2 Matter wave interpretation of the Bohrs model . . . . . . . . 50 6.3 Wave function . . . . . . . . . . . . . . . . . . . . . . . . . . . 52 2

Physical meaning of the wave function Phase and group velocities . . . . . . . The Heisenberg uncertainty principle . The superposition principle . . . . . . Wave packets . . . . . . . . . . . . . .

. . . . .

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53 55 59 61 62 66 66 68 70 73

7 Schrdinger Equation o 7.1 Schrdinger equation of a free particle o 7.2 Operators . . . . . . . . . . . . . . . . 7.3 Schrdinger equation of a particle in an o 7.4 Equation of continuity . . . . . . . . .

. . . . . . . . . . external . . . . .

. . . . . . . . . . . . potential . . . . . .

8 Applications of the Schrdinger Equation: o tum) Wells 8.1 Innite potential quantum well . . . . . . 8.2 Finite square-well potential . . . . . . . . 8.3 Quantum tunneling . . . . . . . . . . . . .

Potential (Quan79 . . . . . . . . . . . 81 . . . . . . . . . . . 88 . . . . . . . . . . . 99

9 Multi-Dimensional Quantum Wells: Quantum Wires and Quantum Dots 104 9.1 General solution of the three-dimensional Schrdinger equation . . . . . . . . . . . . . . . . . . . . . . . 105 o 9.2 Quantum wire and quantum dot . . . . . . . . . . . . . . . . . 107 10 Linear Operators and Their Algebra 10.1 Algebra of operators . . . . . . . . . . . . . . . . . . . . . . 10.2 Hermitian operators . . . . . . . . . . . . . . . . . . . . . . 10.2.1 Properties of Hermitian operators . . . . . . . . . . . 10.2.2 Examples of Hermitian operators . . . . . . . . . . . 10.3 Scalar product and orthogonality of two eigenfunctions . . . 10.4 Expectation value of an operator . . . . . . . . . . . . . . . 10.5 The Heisenberg uncertainty principle revisited . . . . . . . . 10.6 Expansion of wave functions in the basis of orthonormal functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 110 113 113 114 117 119 124

. 127

11.2 Representations of linear operators . . . . . . . . . . . . . . . 133 12 Matrix Representation of Linear Operators 135 12.1 Matrix representation of operators . . . . . . . . . . . . . . . . 135 12.2 Matrix representation of eigenvalue equations . . . . . . . . . 137 13 First-Order Time-Independent Perturbation Theory 142

14 Quantum Harmonic Oscillator 146 14.1 Algebraic operator technique . . . . . . . . . . . . . . . . . . . 147 14.2 Special functions method . . . . . . . . . . . . . . . . . . . . . 155 15 Angular Momentum and Hydrogen Atom 160 15.1 Angular part of the wave function: Angular momentum . . . . 162 15.2 Radial part of the wave function . . . . . . . . . . . . . . . . . 168 16 Systems of Identical Particles 174 16.1 Symmetrical and antisymmetrical functions . . . . . . . . . . 175 16.2 Pauli principle . . . . . . . . . . . . . . . . . . . . . . . . . . . 179 Final Remark 181

Appendix A: Derivation of the Boltzmann distribution function Pn 183 Appendix B: Useful mathematical formulae Appendix C: Physical Constants and Conversion Factors 185 187

General Bibliography

E. Merzbacher, Quantum Mechanics, (Wiley, New York, 1998). This is an excellent book on quantum physics, and the course is aimed at this level of treatment. R.A. Serway, C.J. Moses, and C.A. Moyer, Modern Physics, (Saunders, New York, 1989). This is an excellent introductory text on quantum physics. K. Krane, Modern Physics, (Wiley, New York, 1996). A good introductory text on quantum physics. R. Eisberg and R. Resnick, Quantum Physics of Atoms. Molecules, Solids, Nuclei, and Particles, (Wiley, New York, 1985). A good introductory text on quantum physics with applications to atomic, molecular, solid state, and nuclear physics. There are many excellent books on quantum physics, a few of which are: L. Schi, Quantum Mechanics, (McGraw-Hill, New York, 1968). A. Messiah, Quantum Mechanics, (North-Holland, Amsterdam, 1962). A.S. Davydov, Quantum Mechanics, (Pergamon Press, New York, 1965). C. Cohen-Tannoudji, B. Diu, and F. Laloe, Quantum Mechanics, (Wiley, New York, 1977), Vols. I and II. J.J. Sakurai, Modern Quantum Mechanics, (Addison-Wesley, 1994).

Assumed Background

Necessary prerequisites for undertaking this course include: Any standard introductory calculus-based course covering mechanics, electromagnetism, thermal physics and optics. In particular, PHYS1002 course on special relativity and modern physics. Mathematical Level: Recommended background is MATH2000. An alternative recommended background is MATH2400. Calculus are used extensively, and students should have some familiarity with vector algebra, vector calculus, series and limits, complex numbers, partial dierentiation, multiple integrals, rst- and second-order dierential equations, Fourier series, matrix algebra, diagonalization of matrices, eigenvectors and eigenvalues, coordinate transformations, special functions (Hermite and Legendre polynomials).

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

Introduction

Quantum Physics, also known as quantum mechanics or quantum wave mechanics born in the late 1800s is a study of the submicroscopic world of atoms, the particles that compose them, and the particles that compose those particles. In 1800s 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 1800s has led to the formulation of Quantum Physics: Discovery of the electron Discovery of X-rays Photoelectric eect Observation of discrete atomic spectra The PHYS2041 lectures cover the background theory of various eects discussed from rst principles, and as clearly as possible, to introduce students to the main ideas of quantum physics and to teach the basic mathematical methods and techniques used in the elds of advanced quantum physics, atomic physics, quantum chemistry, and theoretical mathematics. Some of the key problems of quantum physics are also described, concentrating 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 useful starting point for those interested in learning more. The intention is to explore problems which have been the most inuential 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 unusual predictions of quantum physics. Moreover, this lecture notes contains numerous detailed derivations, proofs, worked examples and a wide range of exercises from simple condence-builders to fairly challenging problems, hard to nd in textbooks on quantum physics. 9

We know from classical optics that light (optical radiation) can exhibit polarization, interference and diraction 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 classical description of the radiative eld. We rst briey outline the electromagnetic 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 eld, which determines the energy of the EM wave. In particular, we will be interested in how the energy of the EM wave depends on the parameters characteristic of the wave: amplitude and frequency.

1.1

Wave equation

We start the lectures by considering the time-varying electric (E) and magnetic (B) elds that satisfy the Maxwells equations E = /0 , (1) (2) (3) (4)

B = 0 , E = B , t 1 B = 0 J + 2 E , c t

where the parameters 0 and 0 are constants that determine the property of the vacuum and are called the electric permittivity and magnetic permeability, respectively. The parameter c is equal to the speed of light in vacuum, c = 3 108 [ms1 ]. The symbol is called nabla or del. It is a vector and in the Cartesian coordinates has the form =i +j +k , x y z (5)

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 Maxwells equations are the standard scalar and vector products between two vectors. In the absence of currents and charges, J = 0, = 0, and then the above Maxwells equations describe a free EM eld, i.e. an EM eld in vacuum. We can reduce the Maxwells equations for the EM eld in vacuum into two dierential equations for E or B alone. To show this, we apply to both sides of Eq. (3), and then using Eq. (4), we nd ( Since ( and E) =

2

E) =

( t

B) =

1 2 E. c2 t2

(6)

E+

E) ,

(7)

2

1 2 E=0, c2 t2

(8)

where the operator 2 = is called Laplacian and is a scalar. Equation (8) is a very familiar dierential equation in physics, called the Helmholtz wave equation for the electric eld. It is in the standard form of a three-dimensional vector wave equation. Similarly, we can derive a wave equation for the magnetic eld as

2

1 2 B=0. c2 t2

(9)

General solution of the wave equations (8) and (9) is given in a form of plane waves U=

k

Uk ei(k tkr) ,

(10)

where U (E, B), k is the frequency of the kth wave, and Uk is the amplitude of the E or B wave propagating in the k direction. 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 nd that |k| = k /c = 2/k , where k is the wavelength of the kth wave. The solution (10) shows that the electric and magnetic elds propagate in vacuum as plane (electromagnetic) waves. Properties of these waves are determined from the Maxwells equations. The divergence Maxwells equations (1) and (2) demand that for all k: k Ek = 0 and k Bk = 0 . (11)

This means that E and B are both perpendicular to the direction of propagation k. Such a wave is called a transverse wave. The Maxwells equations (3) and (4) provide a further restriction on the elds that 1 Bk = Ek , c (12)

where = k/|k| is the unit vector in the k direction. Equation (12) shows that the electric E and magnetic B elds of an EM wave propagating in vacuum are mutually orthogonal. In summary: The electromagnetic eld propagates in vacuum in a form of electromagnetic transverse plane waves.

1.2

Consider an EM wave of the wave vector k conned in a space of volume V . We will nd 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 conned 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 eld E (z, t) = iEx (z, t) = iq (t) sin(kz) , 12 (13)

where q (t) is the amplitude of the electric eld. The energy of the EM eld is given by the Hamiltonian H= 1 2

L 0

dz 0 |E|2 +

1 |B|2 0

(14)

where 0 |E 2 |/2 is the energy density of the electric eld, and |B|2 /(20 ) is the energy density of the magnetic eld. In order to determine the energy of the EM eld, we need the magnetic eld B. Since we know the electric eld, we can nd the magnetic eld from the Maxwells 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 eld can be found from the following equation B =i 1 q (t) sin(kz) . c2 (15)

The coecients on both sides of Eq. (16) at the same unit vectors should be equal. Hence, we nd that By =0 x and By 1 = 2 q (t) sin(kz) . z c 1 q (t) cos(kz) . kc2 (17)

Thus, the energy of the EM eld, given by the Hamiltonian (14), is of the form H= Since

L 0

1 2

L 0

1 k 2 c4

0

(19)

dz sin2 (kz) =

L 0

1 dz cos2 (kz) = L , 2 13

(20)

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 (x)2 + m 2 x2 2 2 1 = p 2 + m 2 2 x2 , 2m where p = mx is the momentum of the oscillating mass m. Thus, the variables q(t) and q(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).

(22)

In summary of this lecture: We have learnt that 1. The EM eld propagates in vacuum as transverse plane waves, which can be represented by a set of harmonic oscillators. Thus, according to the Maxwells EM theory, the radiation (light) is a wave. 2. The energy (intensity) of the EM eld is proportional to the square of the amplitude of the oscillation.

14

Exercise: Show that the single mode electric eld E = E0 sin (kx x) sin (ky y) sin (kz z) sin (t + ) (23)

1 2

2 2 2 is a solution of the wave equation (8) if k = /c, where k = kx + ky + kz is the magnitude of the wave vector.

Hence, substituting Eqs. (24) and (25) into the wave equation 2 2 1 2E 2 + 2 + 2 E 2 2 =0, x2 y z c t we obtain

2 2 2 kx + k y + k z E +

(26)

2 E=0, c2

(27)

or

2 2 2 kx + k y + k z

2 E=0. c2

(28)

2 2 2 Since E = 0 and kx + ky + kz = k 2 , we nd that the lhs of Eq. (28) is equal to zero when

k2 =

2 , c2

i.e. when 15

k=

. c

(29)

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

Exercise at home: Using Eq. (12), show that Ek = c Bk , which is the same relation one could obtain from the Maxwell equation (4). (Hint: Use the vector identity A (B C) = B(A C) C(A B). )

16

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

2.1

Thomson in his famous e/m experiment, performed in 1896, found that the ratio e/m 1. Didnt depend on the cathode material. 2. Didnt depend on the residual gas in the tube. 3. Didnt depend on anything else about the experiment. This independence showed that the particles in the cathode beam are a common element of all materials. Millikan in the oil-drop experiment measured electric charge of individual oil drops. He made an important observation that every drop had a charge equal to some small integer multiple of a basic charge e (q = ne), where e = 1.602177 1019 [C]. Thus, they concluded that matter is not continuous, is composed of discrete particles (corpuscular theory of matter).

17

2.2

Discovery of X-rays

Rntgen, in 1895, was interested in the study of the passage of a cathode o 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 Youngs double slit experiment. However, any attempt to measure the wavelength using the Young doubleslit 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 n = n , from which we have sin n = n . 2d (31) (30)

For d, we have sin n 0 even for large n. Hence, in order to make sin n 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 Xrays was 0.6 nm. Typical X-ray wavelengths are in the range: 0.001 1 nm. These are very short wavelengths well outside the ultraviolet wavelengths. For a comparison, visible light wavelengths are between: 410 nm (violet) and 656 nm (red). How the radiation of such small wavelengths is generated? 18

X-rays are generated when high-speed electrons crash into the anode and rapidly deaccelerate. It is well known from the theory of classical electrodynamics that electrons when deaccelerated, they emit radiation. In other words, their kinetic energy is converted into radiation energy (braking i.e. deaccelerating radiation, often referred to by the German phrase bremsstrahlung). The total instantaneous power radiated by the deaccelerated electron is given by the Larmor formula P = 2 e2 |a|2 , 3 40 c3 (32)

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()

Figure 1: Experimentally observed spectrum of X-rays. Moreover, the minimum wavelength min was observed to depend only on the potential in the tube (min V ) and was the same for all target (anode) material. The reason was unknown! 19

2.3

Photoelectric eect

In 1887, Hertz discovered the photoelectric eect - 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 ow in response to the incident light. The following properties of the photoelectric eect were observed: 1. When a monochromatic light falls on the cathode, no electrons are emitted, regardless of the intensity of the light, unless the frequency (not the intensity) of the incident light is high enough to exceed some minimum value, called the threshold frequency. The threshold frequency depends on the material of the cathode.

I I 1 > I2 I1 I2 -V s V

Figure 2: Photoelectric eect for two dierent intensities I 1 and I2 of the incident 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 poten1 tial: eVs = 2 mv 2 ). 3. When the intensity of light is increases, while its frequency is kept the same, more electrons are emitted, but the stopping potential is the same, see Fig. 2. 20

Conclusion: Velocity of the electrons, which is proportional to the energy, is unaected by changes in the intensity of the incident light. 4. When the frequency of light is increased (2 > 1 ), the stopping potential increased (Vs2 > Vs1 ), see Fig. 3.

I

-V s 2 -V s1

Figure 3: Photoelectric eect for two dierent frequencies of the incident light,

with (2 > 1 ).

In summary: We have seen that the experiments on photoelectric eect suggest that the energy of light is not proportional to its intensity, but is rather proportional to the frequency: E or E 1 , = c . (33)

It is impossible to explain these observations by means of the wave theory 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 absorbed 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 direct conrmation that energy of light is proportional to frequency, not to the amplitude. In the Compton experiment light of a wavelength was scattered on free electrons, see Fig. 4.

E/

/ >

Ee

wavelength is scattered on free electrons and the scattered light of wavelength is detected in the 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, > . Conclusion: From the energy conservation, we have that E = E + Ee , (34)

where Ee is the energy of the scattered electrons. Since Ee > 0, then E < E, indicating that the energy of the incident light is proportional to the frequency, or equivalently, to the inverse of the wavelength E or E 22 1 . (35)

2.5

Experiments show that light emitted by a hot solid or liquid exhibits a continuous 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:

Figure 5: Discrete radiation spectrum emitted from single atoms. Each line corresponds to a dierent frequency. Dierent gases produce dierent set of lines. When we increase temperature of the gas more lines at larger frequencies are emitted. Once again, we are faced with the diculty of explaining experimental observations using the wave theory of light. Evidently, the spectra show that the energy is proportional to frequency, E , not to the amplitude of the emitted light. Moreover, this shows that the structure of atoms is not continuous. Then questions arise: What is an atom composed of? How does the discrete spectrum relate to the internal structure of the atom? These questions were left without answers at that time.

23

In summary of this lecture: We have seen that a series of experiments on 1. Properties of X-rays, 2. Properties of photoelectric eect, 3. Compton scattering, 4. Atomic spectra, suggests that energy of the radiation eld (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 eld, E .

24

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 matter in a condensate state (solid or liquid) emits radiation with a continuous distribution of wavelengths rather than a line spectrum. Consider spectral distribution of the radiation emitted by a black body. First, we will dene what we mean by a black body. Black-body - an object which absorbs completely all radiation falling on it, independent of its frequency, wavelength and intensity. Examples: a box with perfectly reecting sides and with a small hole. The small hole can be treated as a black-body.

3.1

In 1900, Rayleigh and Jeans calculated the energy density distribution I() of the radiation emitted by the black-body box at absolute temperature T . The energy density distribution is given by I() = N E , (36)

where N is the number of modes (per unit volume and unit wavelength) inside the box 8 N= 4 , (37) and E is the average energy of each mode. Proof of Eq. (37): Number of modes inside the box Consider an EM wave conned in the volume V . We take a plane wave propagating in r direction, which in terms of x, y, z components can be written as E = E0 sin (kx x) sin (ky y) sin (kz z) sin (t + ) . 25 (38)

The wave propagating in the box interfere with waves reected 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 = n/x, ky = m/y, kz = l/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 conned 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 = 2/, we have the following the condition for a standing wave inside the box n m l 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 Vk = 3 3 = , xyz V (41)

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 N (k) = 1 4 k 3 3 , 8 Vk (42)

i.e. is equal to the volume of the octant divided by the volume occupied by a single mode. Since k = 2/c, we get N (k) = 8 3 V , 3c3 26 (43)

kz

ky

kx

Figure 6: Illustration of the positive octant of k-space. where we have increased N (k) by a factor of 2. This arises from the fact that there are two possible perpendicular polarizations for each mode. Hence, the number of modes in the unit volume and the unit of frequency is N= 8 2 1 dN (k) = 3 . V d c (44)

In terms of wavelengths , the number of modes in the unit volume and the unit of wavelength is N= which gives N= as required. 8 , 4 (46) 1 dN (k) 1 dN (k) d , = V d V d d (45)

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 associated with each degree of freedom of an atom (mode) is 1 kB T , where kB is 2 the Boltzmanns constant. The number of degrees of freedom is dened 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 2 1 2 1 2 E = mvx + mvy + mvz . 2 2 2 (47)

There are three quadratic terms in the energy, and therefore the atom has three degrees of freedom, and a thermal energy 3 kB T . 2

28

The energy of a single radiation mode is the energy of an electromagnetic wave H = 1 2 dV 0 |E|2 + 1 |B|2 0 . (48)

Because this expression contains two squared terms, Rayleigh and Jeans argued that each mode has two degrees of freedom and therefore E = kB T . Hence I() = 8 kB T . 4 (49)

The RayleighJeans 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 tends to zero, I() tends to zero. The theoretical formula goes to innity as tends to zero, leading to an absurd result that is known as the ultraviolet (uv) catastrophe. Moreover, the theoretical prediction does not even pass through a maximum.

We can summarize the presented experimental predictions as follows: Spectrum of X-rays, properties of photoelectric eect, Compton scattering, atomic spectra, and the spectrum of the black-body radiation indicate that something is seriously wrong with the wave theory of light.

Exercise: Show that the number of modes per unit wavelength and per unit length for a string of length L is given by 1 dN 2 = 2 . L d 29

Then, the number of modes per unit wavelength and per unit length is N= 1 2L 2 1 dN = 2 = 2 . L d L (52)

Exercise at home: We have shown in the lecture that the number of modes in the unit volume and the unit of frequency is N = N = 1 dN (k) 8 2 = 3 . V d c (53)

In terms of the wavelength , we have shown that the number of modes in the unit volume and the unit of wavelength is N = N = 8 . 4 (54)

Explain, why it is not possible to obtain N from N simply by using the relation = c/.

30

Shortly after the derivation of the RayleighJeans formula, Planck found a simple way to explain the experimental behavior, but in doing so he contradicted 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 could only take up energy in well dened discrete portions (small packets or quanta) each having the energy E = h = h , h= h , 2 = 2 , (55)

where the constant h is adjusted to t the experimentally observed I(). 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 denite 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 = nh. Contrast between the wave and Plancks hypothesis is that in the classical case the mode energy can lie at any position between 0 and of the energy line, whereas in the quantum case the mode energy can only take on discrete (point) values. The assumption of the discrete energy distribution required a modication of the equipartition theorem. Planck introduced discrete portions so that he might apply Boltzmanns statistical ideas to calculate the energy density distribution of the black-body radiation.

4.1

The solution to the black-body problem may be developed from a calculation of the average energy of a harmonic oscillator of frequency 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 Pn = eEn /kB T . eEn /kB T (56)

See Appendix A for the rigorous derivation of Eq. (56). For quantized energy En = n , we have h Pn = enx

n=0

(57)

enx

where x = h/kB T . Since the sum enx is a particular example of a geometric series, n=0 and | exp(nx)| < 1, the sum tends to the limit

n=0

enx =

1 . 1 ex

(58)

Hence, we can write the Boltzmann distribution function (56) in a simple form Pn = 1 ex enx . (59)

This is a very simple formula, which we will use in our calculations of the average energy E , average number of photons n , and higher statistical moments, n2 .

4.2

Assuming that n is a discrete variable, Planck showed that the average energy of the radiation mode is E =

n

E n Pn = 1 e

n=0

nenx .

(60)

32

which is called the Plancks formula, and the constant h, known as the Planck constant, adjusted such that the energy density distribution (62) agrees with the experimental results, is h = 6.626 1034 [J s] = 4.14 1015 [eV s] . (63)

Equations (49) and (62) for the radiation spectrum contrast the discrete energy distribution with the continuous. Since E = n h, we have from Eq. (61) that the average number of quanta in the radiation mode is n = e 1

h kB T

. 1

(64)

Consider the Plancks formula for two extreme values of : 1 and 1. For 1, we can expand the exponent appearing in Eq. (62) into a Taylor series and obtain ehc/kB T 1 = 1 + Then 8hc I() = 5 hc kB T

1

hc hc +... 1 . kB T kB T

(65)

8 kB T . 4

(66)

Thus, for long wavelengths ( 1) the Plancks formula agrees perfectly with the RayleighJeans formula. Outside this region, discreteness brings about Plancks quantum corrections. For 1, we can ignore 1 in the denominator of Eq. (62) as it is much smaller than the exponent. Then I() = 8hc 5 ehc/kB T 33 . (67)

When 0, ehc/kB T , and 5 0. However, ea/ function goes to innity faster than 5 goes to zero. Therefore, I() 0 as 0, which agrees perfectly with the observed energy density spectrum, see Fig. 7. In addition the Plancks formula correctly predicts the Wien displacement law max T = hc = constant , 4.9651kB (68)

where max is the value of at which I() is maximal. The factor 4.9651 is a solution of the equation 1 ex + x 1 = 0 . 5 (69)

The Wien law says that with increasing temperature of the radiating body, the maximum of the intensity shifts towards shorter wavelengths. Moreover, the Plancks formula correctly predicts the StefanBoltzmann law I= c 4

0

I()d = T 4 ,

(70)

where I is the total intensity of the emitted radiation and is a constant, called the StefanBoltzmann 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 electromagnetic theory. Proof: In the Plancks formula I() = we substitute x= hc kB T 34 (72) 8hc 5 (ehc/kB T 1) , (71)

0 0

I()d = 2hc2

hc kB T

c 4

dx

8hc

hc kB T

x5 hc 5 x e 1 kB T x2

4 0

= Since

dx

x3 kB T = 2hc2 4 x e 1 hc x3 dx 4 = , ex 1 15 kB T hc

4

dx

x3 . ex 1

(74)

(75)

4 2 5 kB = 5.67 108 15h3 c2

4 = T 4 , 15

(76)

[W/m2 K4 ] .

(77)

The constant determined from experimental results agrees perfectly with the above value derived from the Plancks formula. In order to explore the importance of the discrete distribution of the radiation energy, it is useful to compare the Plancks formula for a discrete n with that for a continuous n. Thus, assume for a moment that n is a continuous rather than a discrete variable. Then the Boltzmann distribution takes the form Pn = enx

0

(78)

dn enx 35

dn nenx dn enx = h

E = h

0 0

(1/x) h = = kB T , 1/x x

(79)

where denotes rst derivative of 1/x with respect to x. This result is the one expected from the classical equipartition theorem. Looking backwards with the knowledge of the quantum hypothesis, we see that the essence of the black-body calculation is remarkably simple and provides a dramatic illustration of the profound dierence that can arise from summing things discretely instead of continuously, i.e. making an integration.

36

4.3

Photoelectric eect

In 1905, Einstein extended Plancks hypothesis by postulating that these discrete quanta of energy h, 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 = h, and then the photoelectric eect is given by 1 2 h = W + mvmax , 2 (80)

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 T (a cuto 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 h = W . (81)

The stopping potential the potential at which the photoelectric current does drop to zero is found from 1 2 eVs = mvmax , 2 which gives Vs =

1 2 mvmax 2

(82)

h W . e

(83)

We may conclude that the Einsteins photoelectric formula (80) correctly explains the properties of the photoelectric eect discovered by Hertz.

4.4

Compton scattering

Another support of the Plancks hypothesis is Compton scattering. Assume that in the Compton scattering the incident photon has momentum p and energy E = pc. The scattered photon has momentum p and energy E = p 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 + mc2 , where m is the relativistic mass m= m0 1 (v/c)2 , (85) (84)

and v is the velocity of the scattered electron. Hence, pc p c + m0 c2 = mc2 . Taking square of both sides of Eq. (86), we obtain pc p c + m0 c2

2

(86)

(87)

2

(88)

Since the momentum of the scattered electrons is dicult to measure in experiments, we can eliminate pe using the momentum conservation law pe = p p , from which we get p2 = p2 + p 2 2pp cos , e (90) (89)

where is the angle between directions of the incident and scattered photons. Substituting Eq. (90) into Eq. (88), we get 2m0 c (p p ) = 2pp (1 cos ) , from which, we nd that pp = pp (1 cos ) . m0 c 38 (92) (91)

From the quantization of energy, we have p= and nally = h (1 cos ) . m0 c (94) E h h = = , c c (93)

This is the Compton formula. The quantity h/(m0 c) is called the Compton wavelength c = h = 2.426 1012 m0 c [m] . (95)

The quantum theory predicts correctly that the scattered light has dierent wavelength than the incident light. The classical (wave) theory predicts that = . We see from the Compton formula (94) that the transition from quantum (photon) to classical (wave) picture is to put h 0. A signicant feature of the derivation of the Compton formula is that it relied essentially on special relativity. Thus, the Compton eect not only conrms the existence of photons, it also provides a convincing proof of the validity of special relativity.

Exercise: (a) A photon collides with a stationary electron. Show that in the collision the photon cannot transfer all its energy to the electron. (b) Show that a photon cannot produce a positron-electron pair.

39

Solution: (a) Assume that the photon can transfer all its energy to the electron. Then, from the conservation of energy Ef + m0 c2 = mc2 = m 2 c4 + p 2 c2 , 0 e (96)

where Ef = h is the energy of the photon, and pe is the momentum of the electron. From the conservation of momentum, we have pf = h = pe , c (97)

which is not true, as the rhs is larger than lhs. (b) From the conservation of momentum, we have pf = m 2 c2 + p 2 + 0 e m 2 c2 + p 2 , 0 p (99)

where pp is the momentum of the positron. We see from the above equation that pf > |pe | + |pp | |pe + pp | . Hence pf > p e + p p . Exercise at home: Explain, why is it much more dicult to observe the Compton eect in the scattering of visible light than in the scattering of X-rays? (101) (100)

40

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

In 1913, the Danish scientist Niels Bohr used the Plancks 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 wavelengths 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 kinetic and potential energies of electrons are limited to only discrete particular values, as the energies of photons in a black body radiation.

5.1

In the formulation of his model, Bohr assumed that the electron in the hydrogen atom moves under the inuence of the Coulomb attraction between it and the positively charged nucleus, as assumed in classical mechanics. However, he postulated that the electron could only move in certain non-radiating orbits, which he called stationary orbits (stationary states). Next, he postulated 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 nd that the attractive Coulomb force provides the centripetal acceleration v 2 /r, such that e2 v2 =m . (102) 40 r 2 r This relation allows us to calculate kinetic energy of the electron 1 e2 K = mv 2 = , 2 80 r 41 (103)

From the kinetic energy, we can nd the velocity of the electron and its linear momentum, and the angular momentum L = mvr = me2 r . 40 (106)

In order to nd 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 Plancks formula E = h 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 2r per one turn. Since the momentum is p = mv, we obtain (mv)(2r) = nh , from which we nd that the angular momentum is quantized L = n , h n = 1, 2, 3, . . . . (108) (107)

Comparing this quantum relation for the angular momentum with Eq. (106), we can nd the radius of the orbits me2 r h2 = n2 2 , 40 4 from which we nd r = n2 42 0 h2 . me2 (110) (109)

Substituting Eq. (110) into Eq. (105), we nd the energy of the electron En = 1 me4 1 . (40 )2 2 2 n2 h (111)

From this equation, we see that the energy of the electron varies inversely as n2 . Note also that the energy is negative and becomes less negative as n increases. At n , En 0 and there is no binding energy of the electron to the nucleus. We say the atom is ionized. How the electron makes transitions between the states? Bohr introduced the hypothesis of quantum jumps, that the electron jumps from one state to another emitting or absorbing radiation of a frequency Em E n me4 = = 2 3 h 80 h or of wavelength 1 me4 = 8c2 h3 0 1 1 2 2 n m =R 1 1 2 2 n m , (113) 1 1 2 2 n m , (112)

En n

6 5 4 3

PASCHEN SERIES (INFRARED) BRACKETT SERIES

2

BALMER SERIES (VISIBLE LIGHT)

-13.6

1

LYMAN SERIES (UV)

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 E1 = me4 = 13.6 [eV] . 82 h2 0 (114)

Note that the energy levels get closer together (converge) as the n value increases. Moreover, there is an innite number of possible transitions between the energy levels. It is interesting that the transitions between the energy levels group into series.

5.2

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

e X-ray

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

44

In summary: The Plancks hypothesis of discrete energy quanta was very successful in explaining experimental results of the black-body radiation, photoelectric effect, Compton scattering, atomic spectra, and X-rays characteristic spectra.

5.3

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 stable. 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 spectral 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 dierent molecules. Experiments showed that the angular momentum cannot be n , but h rather l(l + 1) , where l = 0, 1, 2, . . . , n 1: (Zeeman eect). h

45

We see that some of these objections are really of a very fundamental nature, and much eort was expended in attempts to develop a quantum theory which would be free of these objections. As we will see later, the eort was well rewarded and led to what we now know as quantum wave mechanics. Nevertheless, the Bohr theory is still frequently employed as the rst approximation to the more accurate description of quantum eects. In addition, the Bohr theory is often helpful in visualizing processes which are dicult to visualize in terms of the rather abstract language of the quantum wave mechanics, which will be analyzed in details in next few lectures. Exercise at home: We usually visualize electrons and protons as spinning balls. Is it a true model? To answer this question, consider the following example. Suppose that the electron is represented by a spinning ball. Using the Bohrs quantization postulate, nd the linear velocity of the electrons sphere. Assume that the radius of the electron is order of the radius of a nucleus, r 1015 m (1 fm). What would you say about the validity of the spinning ball model of the electron?

Challenging problem: Collapse of the classical atom The classical atom has a stability problem. Lets 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 energy. 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 electrons 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 to be reduced to A zero? Insert appropriate numerical values for all quantities and estimate the (classical) lifetime of the hydrogen atom. 46

We have already encountered several aspects of quantum physics, but in all the discussions so far, we have always assumed that a particle is a small solid object. However, quantum physics as it developed in the three decades after Plancks 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 1. Polarization 2. Interference 3. Diraction Particle character Photoelectric eect Compton scattering Blackbody radiation

How can light be a wave and a particle at the same moment? Is a photon a particle or a wave? An obvious question arises: Is this dual character a property of light or of material particles as well? Then, one may ask: Is an electron really a particle or is it a wave? There is no answer to these questions!

6.1

Matter waves

An important step in the development of a satisfactory quantum theory occurred when Louis de Broglie postulated that: Nature is strikingly symmetrical. 47

Our universe is composed entirely of light and matter. If light has a dual wave-particle nature, perhaps matter also has this nature. The dual nature of light shows up in equations = h , p E = h . (115)

Each equation contains within its structure both a wave concept (, ), and a particle (p, E). The photon also has an energy given by the relationship from the relativity theory E = mc2 . Since E = h = hc/, we nd the wavelength = h h = , mc p (117) (116)

where p is the momentum of the photon. This does not mean that light has mass, but because mass and energy can be interconverted, it has an energy that is equivalent to some mass. De Broglie postulated that a particle can have a wave character, and predicted that the wavelength of a matter wave would also be given by the same equation that held for light, where now p would be the momentum of the particle = h h = , mv p (118)

where v is the velocity of the particle. Remember this formula! It is the fundamental matter-wave postulate and will appear very often in our journey through the developments of quantum physics.

48

If particles may behave as waves, could we ever observe the matter waves? The idea was to perform a diraction experiment with electrons. But an obvious question was: How to perform such an experiment? What wavelengths can we expect? To answer these questions, consider rst a simple example. Example: What is the de Broglie wavelength of an electron whose kinetic energy is K = 100 eV? Calculate the velocity of the electron from which we than nd the de Broglie wavelength corresponding to that velocity. The velocity of the electron of energy 100 eV is v= 2K = 5.9 103 m [km/s] .

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 rst tested: diraction of particles on crystals. In 1926, Davisson and Germer, and independently Thompson, performed electron scattering experiments and they found that the wavelength calculated from the diraction relation m = 2d sin m , m = 0, 1, 2, . . . (119)

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

49

Exercise at home: If, as de Broglie says, a wavelength can be associated with every moving particle, then why are we not forcibly made aware of this property in our everyday experience? In answering, calculate the de Broglie wavelength of each of the following particles: 1. A car of mass 2000 kg traveling at a speed of 120 km/h. 2. A marble of mass 10 g moving with a speed of 10 cm/s. 3. A smoke particle of diameter 105 cm (and a density of, say, 2 g/cm3 ) being jostled about by air molecules at room temperature (27o C = 300 K). Assume that the particle has the same translational kinetic energy as the thermal average of the air molecules p2 3 = kB T . 2m 2

6.2

De Broglies wave-particle theory oered another interpretation of the Bohr atom: The Bohrs condition for angular momentum of the electron in a hydrogen atom is equivalent to a standing wave condition. The quantization of angular momentum L = n means that h mvr = n h or mv = nh . 2r (120)

However, if we employ the de Broglies postulate that p = mv = then, we obtain n = 2r , n = 1, 2, 3, . . . 50 (122) h , (121)

2 r1

2 r2

n=1

n=2

Figure 10: Example of standing waves in the length of the electrons rst and

second orbit of lengths 2r1 and 2r2 , respectively.

Thus, the length of Bohrs allowed orbits (2r) exactly equals an integer multiple of the electron wavelength (n), see Fig. 10. Hence, the Bohrs quantum condition is equivalent to saying that an integer number of electron waves must t 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. Similarly, 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 matterwave postulate, whereas Bohr assumed this property. We can summarize that in quantum wave mechanics: 1. The electron motion is represented by standing waves. 2. Since only certain wavelengths can now exist, the electrons energy can take on only certain discrete values.

51

6.3

Wave function

The idea that the electrons orbits in atoms correspond to standing matter waves was taken by Schrdinger in 1926 to formulate wave mechanics. o The basic quantity in wave mechanics is the wave function (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 conned between two walls separated by a distance a. The motion of the particle along the x axis may be represented by a standing wave whose equation is (x, t) = max sin(kx) sin(t + ) , (123) where = 2 and k = 2/. The condition required for a standing wave is a=n , n = 1, 2, 3, . . . (124) 2 from which we nd that 2 n k= = , (125) a and then n (x, t) = max sin x sin(t + ) . (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 = , (127) n we can replace by h/p, and obtain h p=n . (128) 2a The momentum is related to the energy E, which gives 1 p2 h2 = n2 En . 2m 8ma2 This indicates that the energy of the particle is also quantized. Thus, the particle cannot have any energy. E= 52 (129)

6.4

We can summarize what we have already learnt, that a particle can behave like a wave, but a particle has mass and some of them have electric charge. Does this mean that the mass and charge of an electron, for example, are spread out over the extent of the wave? This would be crazy. It would mean that if we isolate just a part of the wave, we would obtain a fraction of an electron charge. How then should we interpret an electron wave? The answer is that the wave itself does not have any substance. It is a probability wave. When we talk about a particle wave, the amplitude of the wave at a particular point tells us the probability of nding 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 eld describes the distribution of the EM eld in space. From the interference and diraction theorem, we know that the intensity of the interference pattern is proportional to the square of the eld amplitude, or alternatively to the probability that the waves interfere positively or negatively at some points. In analogy to this, Born suggested that the quantity |(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 |(r)|2 dV is the probability that the particle will be found within a volume dV around the point at which |(r)|2 is evaluated. Since |(r)|2 dV is interpreted as the probability, it is normalized to one as

V

|(r)|2 dV = 1 .

(130)

Example: Consider the wave function at time t = 0 of a free particle conned between two walls, Eq. (126). In this case, the probability density of nding the particle at a point x is given by n |(x, 0)|2 = |max |2 sin2 x . (131) a 53

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

(a)

(b)

a/2

Figure 11: Probability density as a function of the position x for a free particle

conned between two walls, and (a) n = 1, (b) n = 2.

The dependence of |(x)|2 on x for two dierent values of n is shown in Fig. 11. It is seen that for n = 1 the particle is more likely to be found near the center than the ends. For n = 2 the particle is most likely to be found at x = a/4, x = 3a/4, and the probability of nding the particle at the center is zero. The strong dependence of the probability on x is in contrast 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 inexibly opposed to this interpretation which leaves so much to chance. I cannot believe that God plays dice with the cosmos Albert Einstein Remember: Wave function (r, t) of a particle is mathematical construct only. Only |(r, t)|2 has physical meaning - probability density, and |(r, t)|2 dV is the probability of nding the particle in the volume dV . 54

6.5

Is there an analogy between the matter waves and radiation? Matter waves h h = , p mv where v is the velocity of a particle of the mass m. = Particles E = mc2 = h . (133) Hence, the wave-radiation relation leads to the velocity of the matter waves h mc2 c2 = . (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 propagate at dierent velocity, called group velocity. At this velocity the energy (information) is transmitted. Usually, vg = u, but in the case of dispersion, u(), the group velocity vg < u. Thus, the matter wave should be dispersive to match the requirement of vg < u when u > c. u = = Are the matter waves dispersive? Let us answer this by rst dening the phase and group velocities. Consider two waves of slightly dierent k and , and propagating in the same direction. Let k1 = k0 + k , k2 = k0 k , 55 1 = 0 + , 2 = 0 , (135) (132)

Take a linear superposition of the two waves 1 1 (r, t) = ei(k1 r1 t) + ei(k2 r2 t) . 2 2 (136)

Then, using Eq. (135) and the Eulers formula (eix = cos x i sin x), we obtain (r, t) = 1 i[(k0 +k)r(0 +)t] 1 i[(k0 k)r(0 )t] e + e 2 2 i(k0 r0 t) = e cos (k r t) ,

(137)

where r is the distance the wave propagated, and is the unit vector in the k direction. We see from Eq. (137) that in time t the fast varying function propagates a distance r = 0 t = ut , k0 (138)

Hence, the envelope propagates at velocity vg = d/dk, which is called the group velocity. The envelope forms so called wave packets. we have already seen that the amplitude of the wave packet propagates with velocity vg . Consider energy of a particle E= 1 2 h2 2 p = k . 2m 2m (140)

from which we nd that d hk = =0. dk m Hence, if E = h then the matter waves are dispersive. Exercise 1: What is the group velocity of the wave packet of a particle moving with velocity v? Solution: From the denition of the group velocity, we have vg = d d d(h) dE = 2 = 2 = , dk dk d(hk) dp (143) (142)

where p = hk. However E 2 = m 2 c4 + p 2 c2 . 0 Thus 2EdE = 2pc2 dp . from which we nd that dE pc2 mvc2 = = =v. dp E mc2 (146) (145) (144)

Hence, vg = v, the group velocity is equal to the velocity of the particle. In other words, the velocity of the particle is equal to the group velocity of the corresponding wave packet. Exercise 2: The dispersion relation for free relativistic electron waves is k = c2 k 2 + (mc2 / )2 . h 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?

2

We see that the phase velocity u > c. From the denition of the group velocity vg = = dk 1 = dk 2 c2 k ck 1 + (mc/k )2 h 2c2 k c2 k 2 + (mc2 / )2 h = c 1 + (mc/k )2 h .

Thus, the group velocity vg < c. However, the product uvg = is constant independent of k. (b) We see from (a) that in general for dispersive waves for which u > c, the group velocity vg < c. Only when u = c, the group velocity vg = c. In the next step of our eorts to understand fundamentals of quantum physics, we will show that a localized particle is represented by a superposition 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 c 2 k k = c2 k k

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

6.6

In quantum physics, we usually work with the wave function , whose ||2 describes a probability that a given object, e.g. a particle, is moving with a velocity v0 . A non-zero probability means that we are not precisely sure that the velocity of the particle is v0 . We may say that the velocity is v0 with some error, v0 , which is called uncertainty. Consider a typical diraction experiment shown in Fig. 12.

v0

y

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

59

The position of the rst minimum in the diraction pattern is given by sin = . (147) y In order to reach the point A, the particle has to gain a velocity in the y-direction, such that vy . (148) sin = v0 Comparing Eqs. (147) and (148), we nd vy = v0 y or vy y = v0 . (149) However, from the de Broglie postulate h h = = , p mv0 and therefore py y = h ,

(150)

(151)

where py = mvy . The relation (151) is called the Heisenberg uncertainty principle and states that it is impossible to measure the momentum py and position y of a particle simultaneously with the same precision. If the particle is completely unlocalized, y , the momentum is certain, py 0. The Heisenberg uncertainty principle is not a statement about the inaccuracy of measurement instruments, nor a reection on the quality of experimental methods. It arises from the wave properties inherent in the quantum mechanical 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 question: If I do not move, does it mean that I am everywhere? How would you answer to this question? 60

6.7

(r, t) = Aei(krt) . (152)

Since, |(r, t)|2 = |A|2 = const., we see that the particle is completely unlocalized in space, that can be found anywhere in space with the same probability. However, we know that in practice particles are localized in space and their position can be given with some approximation. In other words, particles 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

h 1 (r, t) = A1 ei(p1 r/ 1 t)

(153)

h 2 (r, t) = A2 ei(p2 r/ 2 t) ,

(154)

where, |p1 p2 | 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. (r, t) = a1 (r, t) + b2 (r, t) , (155)

where a and b are complex numbers. Thus, a single wave function cannot represent a particle of a given momentum. 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(krk t)]. The sum is of course an integral (r, t) =

k

A(k)ei(krk t) d3 k ,

(156)

where d3 k is the element of volume in k-space (momentum space). In other words, the set contains an innite 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 A(k) = 2 In summary: The superposition principle is in the complete contrast with classical mechanics. 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 particle 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 superposition principle and entanglement have been exploited in recent years in three important applications. The rst 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 transmission systems. The third is proposed device called a quantum computer, where all possible calculations could be carried out simultaneously. (r, t)ei(krk t) d3 r . (157)

6.8

Wave packets

In the superposition state (156), the particle no longer has a well dened 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 (r, t) (x, t) = where k = kx . 62

A (k) ei(kxk t) dk ,

(158)

Let us suppose that A(k) has a maximum at k = k0 and rapidly goes to zero for k = k0 , and k is the region where A(k) = 0. Firstly, we will nd the shape of the wave-function at t = 0. At t = 0: (x, 0) =

A (k) eikx dk .

(159)

At x = 0, exp(ikx) = 1, indicating that all waves have the same phase. For x = 0, the waves with dierent k have dierent phases. If x is the displacement of x from x = 0, the maximal and minimal phases of the packet are 1 x k0 k 2 1 x k0 + k 2 , , minimal maximal .

Since the phases are dierent, the waves will interfere with each other. The maximum of interference appears for the dierence between the phases equal to 2. Thus, xk = 2 . (160)

Hence, the particle can be found at points for which x = 2/k, i.e. determined by the uncertainty relation. Now, we will check how the packet moves in time. In order to do it, we expand k into a Taylor series about k = k0 . Taking k = k0 + , and k0 = 0 , we get k = k0 + = 0 + d d +

k0

1 2

d2 d 2

2 + . . .

k0

(161)

If we take only rst two terms of the series and substitute to (x, t), we obtain (r, t) = ei(k0 x0 t) where vg =

d d k0

dA (k0 + ) ei(xvg t) ,

(162)

Then, for x = vg t we obtain the same packet as for t = 0, but shifted by vg t. Hence, the group velocity is the velocity of the packet moves as a whole. If we include the third term of the Taylor expansion (161), we get (r, t) = ei(k0 x0 t)

dA (k0 + ) dvg d t .

k0

exp i x vg +

(164)

plays the role of the velocity of the wave packet, The term vg + dvg d k0 which now depends on . Thus, dierent parts of the wave packet will move with dierent velocities, leading to a spreading of the wave packet. This spreading is due to dispersion, that vg depends on . We now can explain the connection between the group velocity and the phase velocity, and the role of dispersion. Phase velocity Group velocity Hence vg = d d du = (ku) = u + k . dk dk dk (165) u= , k d . dk

vg =

Thus, vg depends on k when du = 0, i.e. when the phase velocity depends dk 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 dependence of the phase velocity on k, [vg = u when du = 0]. dk

64

In summary of this lecture: We have learnt that 1. In quantum physics, localized particles are represented by a superposition of wave functions (so called wave packet) rather than a single wave function. 2. The maximum of a wave packet moves with the group velocity. 3. Since the matter waves are dispersive, a wave packet spreads out in time.

65

Schrdinger Equation o

The Schrdinger equation is the basic relationship for determining wave funco tions and energy levels of a given physical system. Consider a wave function of a particle moving along the x-axis = max ei(kxt) . (166)

We will try to nd a dierential equation representing the energy of the particle, whose the solution is the wave function (166), with the following conditions The equation must be linear. Coecients appearing in this equation should only depend on the parameters characteristic of the particle. We will limit our considerations the the non-relativistic case only.

7.1

First, we will consider the case of a free particle. In this case the energy and momentum of the particle are related by E= Since E = h and p = hk, we get = Note that: 1. Taking the rst derivative of Eq. (166) over x is equivalent to multiply (x, t) by ik. 2. Taking the rst derivative of Eq. (166) over t is equivalent to multiply (x, t) by i. 66 h 2 k . 2m (168) 1 |p|2 . 2m (167)

Thus, from Eq. (168), we can conclude that the dierential equation should be the rst order in t and the second order in x. The simplest equation of this form is (x, t) 2 (x, t) = 2 , t x2 where is a parameter, which we have to nd. Substituting Eq. (166) into (169), we nd i = 2 k 2 , and then from Eq. (168), we nd that 2 = i h . 2m (171) (170) (169)

Thus, the wave function (166) satises the following dierential equation (x, t) i 2 (x, t) h , = t 2m x2 or equivalently (x, t) h2 2 (x, t) i h =0. + t 2m x2 (173) (172)

Equation (173) is the one-dimensional Schrdinger equation for a free partio cle. It is easy to extend the equation to three dimensions i h where (r, t) = max ei(krt) . (175) (r, t) h2 + t 2m

2

(r, t) = 0 ,

(174)

67

7.2

Operators

which shows that the Schrdinger equation can be obtained from the energy o (Hamiltonian) of the free particle (E = |p|2 /2m) simply replacing E and p, respectively, by E p h i h , i t . (177)

Hence, in quantum physics the physical quantities are represented by mathematical operations, which are called operators. and /t dene operations to be carried out on the wave function . The particular operation stated in Eq. (176), /t consists of taking a partial derivative of in terms of t, and 2 consists of taking partial derivatives of in terms of Cartesian coordinates. Example: Calculate (a) Solution: (a) The partial derivative of in terms of t is = max ei(kxt) = imax ei(kxt) = i . t t (178)

t

and (b)

Thus, the operation of the operator /t on the wave function results in a constant i times the original wave function. We will see later, that such a wave function is called in quantum physics an eigenfunction of the /t operator. Solution of the part (b) is left to the students. 68

Important property of operators: In classical physics the multiplication of two quantities, say x and px , is immaterial. However, in quantum physics, where physical quantities are represented by operators, the order of multiplication is important and, for example, xpx = px x, where px = i /x. We say that the two quantities, x h and px , do not commute.1 A measure of the extent to which xpx = px x is given by the commutator bracket [, px ] = xpx pxx , x (179)

where the symbol over the functions x and px indicates that these functions are operators. Note that the coordinates of r are the same in operator and classical forms. For example, the coordinate x is simply used in operator form as x. How to calculate the commutator [, px ]? x Since operators are action operations on functions, we consider the action of this commutator on a trial function (x): [, px ] (x) = x i x h + i h (x) x x = i x h + i + i x h h = i . h x x

(180)

Hence [, px ] = i . x h (181)

It is easily to show that, in general, the components of the position and r operators satisfy the commutation relations momentum p [m , pn ] = i mn , r h

1

m, n = 1, 2, 3 ,

(182)

69

1

(183)

if if

Using the operator representation, the Schrdinger equation is often writo ten as i h

h2 where H = 2m 2

(r, t) = H(r, t) , t

(185)

7.3

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 h H= 2m

2 2

+ V (r, t) .

(186)

The wave function of the particle moving in the external potential can be dierent from that of the free particle. The wave function is found solving the Schrdinger equation the with following conditions o 1. The wave function must be determined and continuous in any point of the space (r, t). 2. The wave function vanishes at . 70

We will try to solve the Schrdinger equation assuming that the Hamilo does not explicitly depend on time, i.e. V (r, t) = V (r). In this tonian H case, the Schrdinger equation (SE) contains two terms: one dependent on o time t, and the other dependent on r, i.e. i h H =0 , t (187)

where H depends solely on r. Since the time and r dependent parts are separated, the solution of the SE will be in the form of a product of two functions (r) and f (t): (r, t) = (r)f (t) . Substituting this equation into the SE, we get i (r) h df (t) = f (t)H(r) dt 1 df 1 i h = H , f dt (188)

(189)

where f f (t), and (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: i h 1 df = E, f dt 1 H = E . (190) (191)

We can easily solve Eq. (190), and the solution can be written directly as

f (t) = Ce h Et , i

(192)

which is called the stationary (time-independent) Schrdinger equation, or o the eigenvalue equation for the Hamiltonian H. Hence, the solution of the SE is of the form

(r, t) = C(r)e h Et , i

(194)

where (r) satises the eigenvalue equation (193). Note, that the probability density |(r, t)|2 = |C(r)|2 , (195)

is independent of time. Thus, when the Hamiltonian of a particle is independent of time, the probability of nding 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 consequences. Physically, such states have a permanence in time, which allows their long time experimental investigations. Mathematically, they reduce the Schrdinger equation to the eigenvalue equation for the Hamiltonian. o Thus, in order to obtain specic values of energy and corresponding wave functions, we operate on the wave function with the Hamiltonian and solve the resulting dierential equation. However, not all mathematically possible solutions are accepted. Physics imposes some limits on the solutions of the Schrdinger equation. o The solution of the Schrdinger equation should satisfy the following cono ditions: 1. The wave function must be nite in all points of the space. 2. The wave function must be continuous, and should have continuous rst derivatives. 3. The wave function must be a single-value function at any point r. 4. The wave function must be normalized. 72

When an operation on a wave function gives a constant times the original wave function, that constant is called an eigenvalue and the wave function is called an eigenfunction or eigenstate. Thus, the wave function which satises the stationary Schrdinger equation is the eigenfunction of the o Hamiltonian H, and E is the eigenvalue of the Hamiltonian in the state . The complete set of eigenvalues of the Hamiltonian H is termed energy spectrum. The energy spectrum can be nondegenerated (dierent eigenfunctions have dierent eigenvalues), or degenerated (all or few eigenfunctions have the same eigenvalues), but it is not allowed that one eigenfunction could have few dierent eigenvalues. In summary of the lecture on the Schrdinger equation: o We have learnt that 1. In quantum physics, physical quantities are represented by operators. 2. The operator representing the energy of a system is the Hamiltonian H. 3. The eigenvalues of H are energies E. 4. If the potential V is independent of time, then separation of variables is possible, and we can write the wave function as (r, t) = (r)f (t). 5. The wave function (r) is the eigenfunction of the time-independent Hamiltonian H and can be found by solving the stationary Schrdinger o equation H(r) = E(r).

7.4

Equation of continuity

V

|(r)|2 dV = 1 .

(196)

The normalization must be valid for any wave function evaluated at any point r and at any time t. We will show that the Schrdinger equation o 73

guarantees the conservation of normalization of the wave function. In other words, if was normalized at t = 0, it will remain normalized at all times. In addition, there is a ow of the probability density or particle current density associated with a moving particle. Therefore, we will also dene what the particle probability current density is in terms of the particle wave function. Suppose we have a particle described by a wave function in a volume V enclosed by a surface S. Consider the time evolution of the particle wave function, that is given by the time-dependent Schrdinger equation o h2 2 = +V . t 2m Take complex conjugate of the above equation i h i h (197)

h2 2 = +V . (198) t 2m Multiplying Eq. (197) by and Eq. (198) by , and subtracting the resulting equations, we get i h However and using the relation uA = we nd that ( ) =

2

+ t t

h2 2m

(199)

+ = ||2 , t t t uA+u A ,

(200)

(201)

+

2

( )

( ) (202)

. 74

Thus ||2 + t Introducing a notation h ( ) = J , 2im we get the continuity equation + t J =0 . (205) ||2 = , h ( ) = 0 . 2im (203)

(204)

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 , and J is the probability current density.

^ dS = n dS

dS

Figure 13: Probability current density J crossing a surface S, with n the unit

vector normal to the surface.

To interpret the continuity equation, it is convenient to integrate Eq. (205) over the volume V closed by a surface S, see Fig. 13: t

V

||2 dV = 75

JdV .

(206)

V

JdV =

J dS ,

(207)

we get t

V

||2 dV =

J dS .

(208)

The lhs of this equation is the time rate of increase of probability of nding 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 times, i.e. does not cross the surface S, then J dS = 0, and we get that t

V

||2 dV = 0 ,

(209)

which shows that the Schrdinger equation guarantees the conservation of o normalization of the wave function. In other words, if was normalized at t = 0, it will remain normalized at all times. Suppose that particles inside the surface are represented by plane waves in (r) = Aeik1 r + Beik1 r , and outside the surface out (r) = Ceik2 r , (211) (210)

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 densities inside and outside the surface, and nd Jin = and Jout = h h k2 2 ( |C| . out out out out ) = 2im m 76 (213) h hk1 ( in in ) = |A|2 |B|2 in in 2im m , (212)

Inside the surface, the current density can be written as Jin = Ji + Jr where Ji = hk1 2 |A| m (215) (214)

is interpreted as the reected particle current. The current density outside the surface Jt = hk2 2 |C| m (217)

is interpreted as the transmitted particle current. We can dene the reection coecient of the surface R= | Jr | | Ji | , (218)

which is given by the probability current density reected from the surface divided by the probability current density incident on the surface. We can also dene the transmission coecient of the surface T = | Jt | | Ji | , (219)

which is given by the probability current density transmitted through the surface divided by the probability current density incident on the surface.

77

Using Eqs. (215)(217), we can write the reection and transmission coecients as R= |B|2 , |A|2 T = k2 |C|2 , k1 |A|2 (220)

where k1 = |k1 | and k2 = |k2 |. Thus, if |B|2 = |A|2 then R = 1, i.e. all the particles that are incident on the surface are reected.

Exercise at home: It is easy to show from the denition of the probability current density, Eq. (204), that in general when the wave function of a particle in a given region is real, the current density J = 0 in this region. How would you interpret this result?

78

We have seen that the wave nature of particles plays an important role in their physical properties that, for example, particles conned into a small bounded area can have only particular discrete energies. However, the question we are most interested in is: can we create an articial 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 eects when are located in such structures, we will solve the time-independent Schrdinger o equation H(r) = E(r) , (221)

to nd the eigenvalues E and the eigenfunctions (r) of a particle of a mass m moving in a potential V (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 h2 d2 H= + V (x) . 2m dx2 (222)

With this Hamiltonian we get, from the SE, a second-order dierential equation for the wave function of the particle d2 (x) 2m = 2 (E V (x)) (x) , dx2 h which can be written as d2 (x) = k 2 (x)(x) , dx2 where k (x) =

2

(223)

(224)

2m E V (x) h2 79

(225)

When V (x) is independent of x, i.e. the particle is moving along the x axis under the inuence 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 (x) = k 2 (x) . (226) dx2 This is a linear dierential equation with a constant coecient. 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 (x) = Aeikx + Beikx , (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 (x) = Cekx + Dekx , (E < V ) , (228) that the exponents are real and no longer represent an oscillating wave function. They represent a wave function with damped amplitudes. Important note: The general solution (227) with both constants A and B dierent from zero is physically acceptable. However, the general solution (228) with both constants C and D dierent 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 = 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 = 0 will satisfy the condition of (x) 0 as x . Another important observation: The solutions (227) and (228) are single value solutions for the wave function (x). Thus, for the particle moving in an unbounded area where the potential V is constant, there are no restrictions 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 dierent. 80

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

8.1

Let us consider one dimensional structures, quantum wells. As the rst example, consider an innite 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

Figure 14: An innite potential well. For the innite potential well V (x) = 0 V (x) = for for a a x , 2 2 a a x< and x > . 2 2

(229)

According to classical physics, the particle trapped between the walls will bounce back and forth indenitely, its energy will be constant E = mv 2 /2. 81

Moreover, the probability of nding 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 function (x), which satises the Schrdinger equation and some boundary cono ditions. One of the boundary conditions says that the wave function (x) must be nite everywhere. Thus, in the regions x < a/2 and x > a/2, the wave function (x) must be zero to satisfy this condition that V (x)(x) must be nite everywhere. In the region a x a , the potential V (x) = 0, and then the 2 2 Schrdinger equation for the wave function is o d2 (x) = k 2 (x) , 2 dx (230)

where now k 2 = 2mE/ 2 . h Since k 2 is positive, the Schrdinger equation (230) has a simple solution o a a (x) = Aeikx + Beikx , 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 nd the constant B in terms of A, and then we nd the remaining constant A from the normalization condition that the wave function is normalized to one, i.e.

dx |(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 (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 (x) = 0 when Ae

ika 2

+ Be

ika 2

=0.

(233)

82

ika 2

+ Be

ika 2

=0.

(234)

From Eq. (233), we nd that B = Aeika , whereas from Eq. (234), we nd that B = Aeika . (236) (235)

We have obtained two dierent solutions for the coecient B. Accepting these two dierent solutions, we would accept two dierent 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 nd 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 eika = eika , which will be satised when e2ika = cos(2ka) + i sin(2ka) = 1 , or when cos(2ka) = 1 , i.e. when k=n , a with n = 0, 1, 2, . . . . (240) (239) (238) (237)

Thus, for a particle conned in the innite well there is a restriction for k, that k can only take discrete values. Since k 2 = 2mE/ 2 , we see that the energy of the particle cannot be h arbitrary, it can only takes on certain discrete values! En = 2 h2 h2 2 k = n2 . 2m 2ma2 83 (241)

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 articial structures of desired quantum properties, which could be observed if the dimensions of the structures are very small.

E4

n=4

E3 E2 E1

Figure 15: Energy-level spectrum of a particle inside the innite 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 nd the wave function of the particle inside the well n (x) = Ae

ika 2

sin

a n x a 2

n = 1, 2, 3, . . . .

(242)

The solution for n = 0 is not included as in this case the wave function (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 = 2 h2 /2ma2 . Since E1 > 0, the particle can never have zero energy. 84

The coecient A appearing in Eq. (242) is found from the normalization condition

+

|n (x)|2 dx = 1 ,

(243)

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

(x )

(x )

(x )

a/2

a/2

x

n=1

n=2

n=3

Figure 16: Plot of the wave function of the particle for the rst three energy

levels.

Figure 16 shows the wave functions of the particle for the rst three values 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 ns 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 located anywhere between the walls. Moreover, the lowest energy (n = 1) is non-zero, which indicates that the particle can have non-zero energy even if the potential energy is zero.

In summary of this lecture: We have learnt that 1. The energy of a particle in a quantum well can only take on certain discrete values. All other values of the energy are forbidden. We say that the energy of the particle is quantized. 85

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

Exercise: An electron is conned in an innite potential well of width a = 0.1 nm (approximate size of an atom). (a) What is its lowest energy? (b) What is the equivalent temperature? Solution: (a) The lowest energy of the electron corresponds to n = 1. Using Eq. (241), we nd E1 = (1)2 2 h2 h2 (6.626 1034 )2 = = 2ma2 8ma2 8 9.109 1031 (1010 )2 = 6.025 1018 [J] = 37.6 [eV] .

(b) Since n = 1, we nd from the formula (64) that e kB T = 2 , from which, we get E1 1, kB T i.e. T E1 /kB = 6.025 1018 / 1.381 1013 = 43.6 [K] . 86

E1

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 nding the particle at the center of the well is also zero. Then, a question arises: how does the particle move from one side of the well to the other if the probability of being at the center is zero? (2) Solve the Schrdinger equation with appropriate boundary conditions o for an innite square well with with a centered at a/2 V (x) = 0 V (x) = for for 0xa, x < 0 and x > a .

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

87

8.2

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

(244)

V0

II V=0

III

V0

a/2

a/2

Figure 17: Finite square-well potential. In classical physics a particle is trapped in the well if the energy E of the particle is less than V0 . In this case, the probability of nding the particle outside the well is zero. When the energy E is larger than V0 , the particle can freely move in all three regions. Lets 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 nite 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 Schrdinger equation reduces to o d2 2 (x) 2 = k2 2 (x) , dx2 (245)

2 where k2 = 2mE/ 2 , and 2 (x) is the wave function of the particle in the h region II. 2 Since k2 is positive, the solution of Eq. (245) is of the form

(246)

that is the same as for the particle in the potential well. Thus, we expect that similar to the case of the innite potential barrier, the energy of the particle will be quantized in the region II. In the regions I and III, the potential is dierent from zero V (x) = V0 , and then

2 k1 =

(247)

Solution of the above equation depends on the relation between V0 and E. 2 For E > V0 the parameter k1 is positive, and then the solution of Eq. (248) is of the form 1 (x) = Ceik1 x + Deik1 x , (249)

indicating that the probability of nding the particle in the regions I and III is similar to that in the region II. It is not dicult 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 . However, we may obtain nonzero reection coecient at the boundaries, which 89

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

2 More interesting is the case of E < V0 . For E < V0 the parameter k1 is a negative real number, and then the solution of Eq.(248) is in the form of exponential functions

a x< 2 a x> . 2

(250)

In order to get 1 (x) nite for each |x| > a/2, in particular at x , we have to choose D = F = 0. Otherwise, the wave function would be innite at x = . Hence, the solution (250) reduces to I. III. 1 (x) = CekI x , 1 (x) = GekI x , for for a x< 2 a x> . 2

(251)

Assume for a moment that C, G = 0, then the probability |(x)|2 has interesting properties, shown in Fig. 18. The most striking features of the wave

V0

V0

-a/2

a/2

Figure 18: Probability function of the particle inside the potential well.

I leave it as an exercise for students to show that the reection coecient is nonzero at the boundaries.

2

90

function (x) are the tails that extend outside the well. The non-zero values of (x) outside the well means that there is a non-zero probability for ndings the particle in the regions I and III. The regions I and III are forbidden by classical physics because the particle would have to have negative kinetic energy. Since the total energy of the particle E < V0 and E = Ek + V0 , we have that Ek + V 0 < V 0 in the regions I and III . (252)

Therefore, the penetration of the barrier is a quantum eect that has no classical analog. Quantum mechanical penetration of the barrier has come to be regarded as a paradoxical, controversial, non-intuitive aspect of quantum physics. How far the particle can penetrate the barrier? This depends on V0 . To show this, consider the wave function in the region III. In this case 1 (x) = Gek1 x , with k1 = 1 2m (V0 E) . h (254) x> a , 2 (253)

Since the parameter k1 is a positive real number, it plays a role of the damping coecient 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 eect really exist, we have to demonstrate that the constants C and G are really non-zero. To show this, we will turn to the details, and carry out the complete solution for the wave function of the particle.

91

k I(1) >> k I kI kI

(1) (2) (1)

(2) (2)

V 0 >> V 0

a/2

Figure 19: The dependence of exp(k1 x) on x for two dierent values of k1 . We start from the general solution of the Schrdinger equation for the wave o function of the particle inside the square-well potential, which is of the form: I. 1 (x) = Cek1 x , x< a 2

a a x 2 2 (255)

In order to nd the constants A, B, C, and G, we use the property of the wave function, that (x) and the rst-order derivative d(x)/dx must be nite and continuous everywhere, in particular, at the boundaries x = a/2 and x = a/2. Hence, at x = a/2 : Ce 2 ak1 = Aei 2 ak2 + Bei 2 ak2 . At x = a/2 : Ge 2 ak1 = Aei 2 ak2 + Bei 2 ak2 .

1 1 1 1 1 1

(256)

(257)

We remember, that also d/dx must be continuous across the same boundaries. 92

Since I. II. III. d1 = Ck1 ek1 x , dx d2 = iAk2 eik2 x iBk2 eik2 x , dx d1 = Gk1 ek1 x , dx

(258)

we nd that at x = a/2: Ck1 e 2 ak1 = ik2 Ae 2 iak2 Be 2 iak2 and at x = a/2: Gk1 e 2 ak1 = ik2 Ae 2 iak2 Be 2 iak2 Dividing both sides of Eq. (259) by k1 , we obtain Ce 2 ak1 = i Ae 2 iak2 Be 2 iak2 where = k2 /k1 . Comparing Eqs. (256) and (261), we get Aei 2 ak2 + Bei 2 ak2 = i Ae 2 iak2 Be 2 iak2 from which we nd that A= (i + 1) iak2 . Be (i 1) (263)

1 1 1 1 1 1 1 1 1 1 1 1 1

(259)

(260)

(261)

(262)

1 2i Be 2 ak1 (i+1) . (i 1)

(264)

Since B = 0, as the particle exists inside the well, we have that C = 0 indicating that there is a non-zero probability of nding the particle in the region I. The probability is given by |1 (x)|2 , that is |1 (x)|2 = |C|2 e2k1 |x| , 93 (265)

a 4 2 e2k1 (|x| 2 ) . 2 + 1) (

(266)

The probability is dierent from zero and decreases exponentially with the rate 2k1 . The constant |B| is found from the normalization of (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 reection, the particle coming towards the barrier will eventually be found moving back. Eventually, because the reversal of direction is not sudden. Quantum barriers are spongy in the sense the quantum particle may penetrate them in a way that classical particles may not. Consider now the continuity conditions at x = a/2. From the symmetry of the system, we expect that the constant G, similar to C, will be dierent 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 nd two solutions for the constant G in terms of B: Ge 2 ak1 = B ue 2 iak2 + e 2 iak2 Ge where u= (i + 1) . (i 1) (269)

1 ak1 2

1 3 1

, ,

(267) (268)

= iB ue

3 iak2 2

1 iak2 2

Here, we have two solutions for G. However, we cannot accept both of the solutions as it would mean that there are two dierent probabilities of nding the particle at a point x inside the region III. Therefore, we have to nd under which circumstances these two solutions are equal. Dividing Eq. (268) by (267), we obtain i ue2iak2 1 (ue2iak2 + 1) 94 = 1 , (270)

from which we nd that the solutions (267) and (268) are equal when tan(ak2 ) = 2k1 k2 . 2 2 k2 k 1 (271)

2 2

2mE h2

(272) (273)

2 where

1 2mV0 a = 2 h

(274)

1 We see from the relation = 2 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 , and nd

tan =

(275)

This is a transcendental equation which, can be solved graphically as follows. Introducing the notation p( ) = q( ) = tan , 2

2

(276)

we nd 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 gure that the equation p( ) = q( ) is satised only for discrete (nite) values of . Since the energy E is proportional to , see Eq. (272), we nd 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 , but always is nite. We see from Fig. 20 that there we have one solution two solutions three solutions 95 for for for <, < 2 , < 3 ,

p( )

p( ) q( )

p( )

.

0

3

2

=

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 ma2 V0 1 2 2 . 2 = a2 k1 + k 2 = 4 2 2 h Thus, is determined by the dimensions of the well. (277)

96

Example: Consider a potential well with = 4. Since < 2, 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 nd the allowed values of the energy E. Since 1 = ak2 , 2 and k1 = we get 2 from which we nd

2 2

1 = ak1 , 2

(278)

2m (V0 E) , h2

k2 =

2m E, h2

(279)

k1 = k2

V0 E , E

(280)

2

V0 .

(281)

E2

V0

E1

97

Exercise at home: A rectangular potential well is bounded by a wall of innite high on one side and a wall of high V0 on the other, as shown in Fig. 22. The well has a width a and a particle located inside the well has energy E < V0 . (a) Find the wave function of the particle inside the well.

V0

0 region I

region II

(b) Show that the energy of the particle is quantized. (c) Discuss the dependence of the number of energy levels inside the well on V0 .

98

8.3

Quantum tunneling

When the potential barrier has a nite width, the tunneling eect 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 eect depends on the relation between V0 and E and also on the thickness of the barrier (see Fig. 23).

II V0

III

x

Figure 23: Tunneling eect through a potential barrier of a thickness a. How can we understand this process of a particle tunneling through a seemingly impenetrable barrier? How large is the probability that the particle passes through the barrier? To answer these questions, we can use a wave picture of the particle. We have already learnt that the particle wave function does not terminate abruptly at the edge of the barrier, but actually leaks out the barrier. Let us perform the detailed calculations of the tunneling probability. Rigorous calculations: Consider a particle moving from the left and acting on the rectangular potential barrier, Fig. 23. Assume that E < V0 . The solution of the Schrdinger o equation for the three regions is I. 1 (x) = Aeik1 x + Beik1 x , II. 2 (x) = Cek2 x + Dek2 x , III. 1 (x) = F eik1 x + Geik1 x , 99 a x< 2 a a x 2 2 a x> 2

(282)

where k1 = 2mE/ and k2 = 2m(V0 E)/ . h h The continuity conditions for the wave function and the rst-order derivative at x = a/2 are Aeik1 2 + Beik1 2 = Cek2 2 + Dek2 2 , a a a a ik2 Aeik1 2 Beik1 2 = Cek2 2 Dek2 2 k1

a a a a a a a a

(283)

The continuity conditions at x = a/2 are Cek2 2 + Dek2 2 = F eik1 2 + Geik1 2 , a a a a ik1 Cek2 2 + Dek2 2 = F eik1 2 Geik1 2 k2 1+ 1 = 2 1 = 1 2 1+

ik2 k1 ik2 k1

(284)

The continuity conditions (283) and (284) can be written in matrix forms as A B and C D ek2 2 +ik1 2 e

a a

k2 a ik1 a 2 2

1+

ik2 k1 ik2 k1

ek2 2 +ik1 2 e

k2 a ik1 a 2 2

C D

, (285)

ik1 k2 ik1 k2

ek2 2 +ik1 2 e

1+ 1

k2 a +ik1 a 2 2

ik1 k2 ik1 k2

ek2 2 ik1 2 e

k2 a ik1 a 2 2

F G

. (286)

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

i 2

F G (287)

k1 with = k2 k1 and = k2 + k2 . The solution with G = 0 is of particular k1 k2 k1 interest as it represents the situation where no particles are incident on the barrier from the right. In this case

(288)

Hence, the transmission coecient of the particle current is |F |2 T = = cosh2 (k2 a) + 2 |A| 2

2 2

sinh (k2 a)

1

= =

1+

+ 1 sinh (k2 a)

1

(289)

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

1

(290)

First, note that if there is no barrier, V0 = 0, and then there is 100% transmission. Thus, there is nothing particularly remarkable about the solution when V0 = 0. Its physical interest lies in what happens when V0 = 0. For V0 = 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 reection). Thus, tunneling eect for E < V0 and partial reection at the barrier for E > V0 are quantum phenomena. In the classical limit of h 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 coecient (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 k2 a = n, n = 1, 2, 3, . . ., there is 100% transmission from region I to III. This phenomenon is analogous to the behavior of coated lenses in optics. Otherwise, quantum eect (partial reection) appears.

101

Quantum tunneling is important in the understanding of number of physical phenomena such as thermonuclear reactions and conduction in metals and semiconductors. In 1928, Gamov, Condon and Gurney used quantum tunneling to explain the -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 voltage V with respect to the probe needle. However, for electrons to pass from the needle to the object, they have to overcome the work function of the needle material. This creates a potential barrier through which electrons can tunnel. As they tunnel through the potential barrier they generate a current whose the variation tells us about the distance between the needle and the object.

Challenging problem: Quantum tunneling from and into a semi-nite well In the problem discussed in lecture, we have shown there are no restrictions on the energy of a particle to tunnel through the barrier. The explanation of this eect 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 innite high on one side and a barrier of high V0 and innite 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

E

0 region I

a region II 2a

region III

and width a.

(a) Now imagine what happens if the thickness of the barrier (region II) is nite 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 coecient 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

We have seen that in the one-dimensional case, particles conned 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 eects, 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.

a a

x L

well V = 0. The potential is innite at the xy walls and can be set zero at the z walls (quantum wire), or innite (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 tunnel. 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 oor. This is precisely how the particles appear to behave in a quantum wire.

9.1

Let us nd the wave function of a particle located inside the well and its energies. The wave function and the energies are found from the threedimensional Schrdinger equation o h2 2m

2

+V=E .

(291)

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 . x y z

(292)

Since x, y, z are independent (separable) variables, the wave function is also separable into three independent functions x , y , and z . In this case, we can nd the solution of the Schrdinger equation in product form o (x, y, z) = x (x)y (y)z (z) . (293)

Substituting this into the Schrdinger equation and dividing both sides by o x y z , we obtain h2 d2 x h2 d2 y h2 d2 z =E , 2mx dx2 2my dy 2 2mz dz 2 (294)

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 h2 d2 x h2 d2 y h2 d2 z =E+ + . 2 2 2mx dx 2my dy 2mz dz 2 (295)

The lhs involves all of the x dependence. If we change x any way we want, the rhs is not aected. Thus, it must be that both sides are equal to a constant, say Ex : h2 d2 x = Ex , 2mx dx2 h2 d2 z h2 d2 y 2 2my dy 2mz dz 2 = E Ex . (296) (297)

Equation (297), that depends only on y and z variables can be written as h2 d2 z h2 d2 y = E Ex + . 2 2my dy 2mz dz 2 (298)

Again, both sides depend on dierent variables, the lhs depends only on y and the rhs depends only on z, thus both sides are equal to a constant, say Ey : h2 d2 y 2my dy 2 h2 d2 z 2mz dz 2 = Ey , = E E x Ey . (299) (300)

Hence, after the separation of the variables, one dierential equation in three variables has turned into three independent equations of one variable each h2 d2 x = Ex , 2mx dx2 h2 d2 y = Ey , 2my dy 2 h 2 d2 z = Ez , 2mz dz 2 106 (301) (302) (303)

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 innite square well in one dimension, and are given by x = A sin y with energies Ex = n 2 1 2 h2 2ma2 and E y = n2 2 2 h2 . 2ma2 (307) n1 x a n2 = B sin y a , , n1 = 1, 2, 3, . . . , n2 = 1, 2, 3, . . . , (305) (306)

9.2

The solution for the z component of the motion, Eq. (303), depends on whether the z sides of the well have zero or innite potential. For zero potential, the z direction is free for the motion of the particle (quantum wire), and is given by the wave function z = Ceikz z , (308)

2 where kz = 2mEz / 2 , and Ez can have arbitrary values. h If the potential at the z sides is innite, 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

z = C sin

3

n3 z L

n3 = 1, 2, 3, . . . ,

(309)

It would be more correct to call the quantum dot a quantum box, but in many calculations, quantum dots that have spherical symmetries are approximated by rectangular boxes.

107

Thus, we can summarize that for a quantum wire, the wave functions of the particle are of the form n1 ,n2 = D sin n1 n2 x sin y eikz z , a a (311)

where D = ABC is a constant which is found from the normalization condition of the wave function. It is easy to show that D= 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 oor of the wire. Because the motion of the particle is restricted (quantized) in two dimensions, a quantum wire is sometimes 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 n1 ,n2 ,n3 2 = a

3 2

2 a

2 . L

(313)

sin

n1 n2 n3 x sin y sin z a a a

(314)

and the corresponding energies are given by E= 2 h2 n2 + n 2 + n 2 2 3 2ma2 1 , with 108 n1 , n2 , n3 = 1, 2, 3, . . . . (315)

Thus, energy of the particle in a quantum dot is quantized in all three directions. Because the motion of the particle is now restricted in all three dimensions (quantum connement), a quantum dot is sometimes referred to as a zero-dimensional system. Quantum dots are also regarded as articial 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 signicant dierence 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 3 2h2 , (316) 2ma2 and there is only one wave function (singlet) corresponding to this energy. However, there are three wave functions corresponding to energy E= 6 2h2 , (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 2,1,1 , 1,2,1 , and 1,1,2 . 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. E=

Exercise at home: Find the number of wave functions (energy states) of a particle in a quantum well of the sides of equal lengths corresponding to energy 9 2h2 , 2ma2 i.e. for the combination of n1 , n2 and n3 whose squares sum to 9. E= 109

10

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 specied by a linear operator. An operator A is linear if for arbitrary functions fi and gi , and arbitrary complex numbers ci , such that Af1 = g1 the linear superposition is A (c1 f1 + c2 f2 ) = c1 Af1 + c2 Af2 = c1 g1 + c2 g2 . (318) and Af2 = g2 ,

10.1

Algebra of operators

A + B f = Af + Bf , AB f = A Bf .

The sum of two operators A and B and their product are dened as (319) (320)

The power of an operator and the sum of two operators is dened as 1. A2 = AA , A3 = AAA , etc. 2 2. A + B = A + B A + B = A2 + B 2 + AB + B A . (322) In general, AB = B A. Thus, multiplication of operators is not necessarily commutative. 110

We can dene a commutator: A, B = AB B A , and say, that two operators commute if A, B = 0 . We can also dene anticommutator as A, B A, B

+

(323)

(324)

= AB + B A ,

(325)

+

=0.

(326)

Inverse operator: The inverse of an operator A, if it exists, is dened by 1 AA1 = A1 A = , where is the unit operator dened by 1 =f . 1f Hermitian adjoint: (Hermitian conjugate) Operator A is the Hermitian adjoint of an operator A if for two functions f and g that vanish at innity f AgdV = Properties of Hermitian conjugate: 1. A

(327)

(328)

A f

gdV .

(329)

=A.

(330)

111

Proof: f AgdV = = = f A A

A f g

gdV =

g A f A

dV =

g A f dV

f dV

g f dV (331)

g dV ,

as required. 2. Proof: f AB

AB

= B A .

(332)

gdV =

ABf

gdV =

A Bf

gdV .

(333)

gdV =

u A gdV =

Bf

A gdV (334)

f B A gdV .

= B A ,

as required.

112

10.2

Hermitian operators

(335)

gdV .

(336)

10.2.1

If A and B are Hermitian then: 1. A + B is Hermitian, 2. A2 , A3 , etc. are Hermitian, 3. cA is Hermitian if c is a real number. Proof of the property 3: f cA gdV = as required. 4. AB is Hermitian only if A and B commute. Proof: AB

cAf

gdV = c

Af

gdV ,

(337)

= B A = B A .

(338)

5. From the property 4, we have that the commutator A, B is not Hermi tian, even if A and B are Hermitian. Proof: A, B

= B A A B = B A AB = A, B , as required. 6. However, i A, B is Hermitian. Proof is left for the students. 7. For an arbitrary operatorA, the product AA is Hermitian. Proof: AA as required.

= AB B A

= AB

BA

(339)

= A

A = AA ,

(340)

8. If A is non-Hermitian, A + A and i A A are Hermitian. Hence, A can be written as a linear combination of two Hermitian operators 1 A + A + 1 i A A A= 2 2i 10.2.2 Examples of Hermitian operators . (341)

1. Position operator is Hermitian. r Since |r| is a real number and is just a multiplication of the function rg g by r, we have f rgdV = gdV = rf 114 rf

gdV .

(342)

gdV =

h i h = i =

h f i V h (f g) dV + i (f g) dV +

V

gdV =

h i

( f ) gdV

f ( g) dV h g dV . i (343)

Using the Gausss divergence theorem, we get that Eq. (343) can be written as = h i

S

f gdS +

f pg dV .

(344)

First integral in Eq. (344) vanishes as f and g vanish at innity, and therefore we get

V

pf

gdV =

f pg dV ,

(345)

which means that p is Hermitian, as required. We have dened before the eigenvalues and eigenfunctions of the Hamiltonian of a particle, see Section 7.3. The idea of eigenvalues and eigenfunctions can be extended to arbitrary operators. Thus, we can state: If A = , then is an eigenfunction of A with eigenvalue .

115

Example: Determine if the function = e2x is an eigenfunction of the operators (a) A = d/dx, (b) B = ()2 , and (c) C = dx. (a) Operating on the wave function with the operator A, we obtain d 2x A = e = 2e2x = 2 , dx (346)

which is a constant times the original function. Therefore, = e2x is an eigenfunction of the operator A = d/dx with an eigenvalue = 2. I leave the solution of the parts (b) and (c) to the students. Hermitian operators play the important role in quantum mechanics as they represent physical quantities. This importance arises from the fact that eigenvalues of an Hermitian operator are real. Proof: Assume that is an eigenvalue of an Hermitian operator A corresponding to the eigenfunction f (that vanishes at innity). Then =

V V

|f |2 dV = f dV =

V

f f dV =

f Af dV

V

Af

f f dV =

|f |2 dV = ,

(347)

as required.

116

10.3

+

(r)2 (r)dV = 0 . 1

(348)

The orthogonality of two functions is related to the orthogonality of two vectors. The vectors are orthogonal when the scalar product of the vectors is zero. In analogy, we can write a scalar product of two functions as (i , j ) = (r)j (r)dV = aj ij , i (349)

where aj is a positive constant and ij is the Kronecker delta function. When aj = 1, we say that the functions are orthonormal. The complex functions i form a complex linear vector space. The innitedimensional vector space of orthonormal functions is called Hilbert space. The scalar product (i , i ) = ||i || = |i |2 dV , (350)

where i is a square integrable function, is called the norm of the state (vector) . For a state function that represents physical quantity the norm is nite. If the functions are orthonormal, the norm ||i || = 1. Example of orthogonal functions: Examples of orthogonal functions are sines and cosines functions. Their product with any other function of the same class gives zero when integrated over all ranges of variable, unless the two multiplied functions are identical.

2 0

0 for m = n for m = n

(351)

2 0 2 0

cos(m) cos(n) d =

0 for m = n for m = n

(352) (353)

From the orthogonality of the sines functions, we see that the eigenfunctions of a particle in an innite square well potential, Eq. (242), corresponding to dierent energies (n = m) are orthogonal. Having available the denition of orthogonal functions, we can formulate an important property of eigenfunctions of a linear Hermitian operator. Eigenfunctions of a linear Hermitian operator belonging to different eigenvalues are orthogonal. Proof: Consider a Hermitian operator A. Let f and g are two eigenfunctions of A corresponding to two dierent eigenvalues f and g , respectively, Af = f f , Ag = g g , where f , g are real numbers. Since Af = f f , we can write Af However Af

(354)

gdV

f Ag dV = (f g ) gdV = f Ag dV ,

f gdV .

(355)

(356)

and therefore the lhs of Eq. (355) vanishes. Since, f = g , we have (f, g) = as required. 118 f gdV = 0 , (357)

10.4

In classical physics, an expectation or average or mean value of an arbitrary quantity A is obtained by weighting each measured value Ai by the associated probability Pi and summing over all the measurements N . Thus, A =

i

Pi A i

i = 1, 2, . . . , N ,

(358)

where Pi is a probability of measuring the value Ai . How do we calculate expectation values in quantum physics? Consider an operator A acting on a function i . Suppose that Ai exists, then the scalar product i , Ai = Ai dV i (359)

is called the expectation or average or mean value of the operator A in the state i . Similarly as in classical physics, the expectation value can be calculated from the probability density as A = A(r)dV = A |i |2 dV = Ai dV , i (360)

where the order of the factors under the integral is not important. Properties of the expectation value 1. Expectation value of a Hermitian operator is real. Proof: A = = as required. Ai dV = i i Ai

Ai

i dV

dV =

Ai dV i

= A

(361)

119

2. Expectation value of an arbitrary operator B satises the following equation of motion d B = dt Proof: Since B we have d B = dt BdV + t B dV + t B dV . t = Bi dV , i B t + i h H, B . (362)

From the Schrdinger equation o i h and its complex conjugate i h we obtain d B = dt B t + i h i H BdV h B HdV . = H , t = H , t

120

Thus, expectation value of the operator B can depend on time even if the operator does not depend explicitly on time ( B/t = 0). B] = 0, we have that d B /dt = 0, and then the expectation value When [H, is constant in time. In analogy to classical physics, we call B a constant of motion. We have already shown that expectation values of Hermitian operators are real. In term of the scalar product this is characterized by i , Ai = i , Ai

(363)

From this property, we have in general, that for Hermitian operators i , Aj = j , Ai Proof: i , Aj = = as required. The properties (363) and (364) is very often used to check whether operators are Hermitian. Example: Consider two operators A = d/dx and B = d2 /dx2 acting on two orthonormal wave functions 1 = a sin(nx) and 2 = a cos(nx), where n is a real number, a = 1/ and x , . Are the operators A and B Hermitian? Solution: First, consider the operator A = d/dx. Since d A1 = a sin(nx) = an cos(nx) = an2 , dx 121 (365) Aj dV = i Ai dV j

(364)

Ai

j dV =

j Ai

dV

= j , Ai

and d A2 = a cos(nx) = an sin(nx) = an1 , dx we nd the following values of the scalar products 1 , A1 = an (1 , 2 ) = 0 , (366)

1 , A2 = an (1 , 1 ) = an , 2 , A2 = an (2 , 1 ) = 0 , 2 , A1 = an (2 , 2 ) = an . (367)

Hence 1 , A1 = 2 , A2 but 1 , A2 = an = 2 , A1 Thus, the operator A = d/dx is not Hermitian. Consider now the operator B = d2 /dx2 . Since d2 B1 = a 2 sin(nx) = an2 sin(nx) = an2 1 , dx and

2 2 = a d cos(nx) = an2 cos(nx) = an2 2 , B dx2

(368)

= an .

(369)

(370)

(371)

we nd the following values of scalar products 1 , B1 = an2 (1 , 1 ) = an2 , 2 , B2 = an2 (2 , 2 ) = an2 , (372)

1 , B2 = an2 (1 , 2 ) = 0 ,

2 , B1 = an2 (2 , 1 ) = 0 . 122

(373)

(374)

Exercise at home: Prove, using the condition (364) and the wave functions 1 and 2 of the above example, that the momentum operator px = i /x is Hermitian. h

123

10.5

In Section 6.6, we have shown that the uncertainties in the position and momentum of a particle satisfy the relation ypy = h . (375)

This relation says the position and momentum of a particle cannot be measured simultaneously with the same precision. This is known as the Heisenberg 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 [, py ] = i . y h (376)

In fact, the Heisenberg uncertainty relation can be formulated for arbitrary two Hermitian operators that do not commute. In other words, if A and B 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 (A)2 = A2 A 2 and (B)2 = A2 A Hermitian operators satisfy the inequality (A)2 (B)2 1 [A, B] 4

2 2

of two

(377)

which is called the Heisenberg inequality. Proof: First, we prove that for an arbitrary operator A the following inequality holds AA 0 . 124 (378)

It is easy to prove the above inequality using the denition of the expectation value AA = AA dV = A

A dV =

2 A dV 0 . (379)

Now, we prove that for two Hermitian operators the following inequality is satised 1 A2 B 2 [A, B] 4 To prove it, we introduce an operator D = A + iz B , where z is an arbitrary real number. Hence, from Eq. (378), we nd DD = = (A + iz B)(A iz B) A2 iz( AB B A ) + z 2 B 2 0 . (381)

2

(380)

(382)

This inequality is satised when AB B A 2 4 A2 B 2 0 . Hence 1 A2 B 2 [A, B] 4 as required. Finally, since [A, B] = [A, B] , (385)

2

(383)

(384)

where U = U U , (U = A, B), and replacing in Eq. (384), A A and B, we obtain the required Heisenberg uncertainty relation (377), B as required.

125

Example 1. The Heisenberg uncertainty relation for the position and momentum operators. Since [, px ] = i , x h we obtain by substituting into Eq. (377), A = x and B = px 1 ()2 (x )2 h2 , x p 4 or in terms of the standard deviations (uctuations) 1 xpx h , 2 (387) (386)

(388)

x p where x = ()2 and px = (x )2 . Similarly, we can show that for the y and z components of the position and momentum 1 1 ypy h and zpz h . (389) 2 2 Note that the relation (375) satises the Heisenberg inequality as h > h/2.

Example 2. The Heisenberg uncertainty relation for the components of the electron spin. Since [x , y ] = 2iz , (390)

(For a poof, see Tutorial Set 8), where x , y , z are the operators corre sponding to the three components of the electron spin, we obtain (x )2 (y )2 z or x y | z | . (392)

2

(391)

The uncertainty relation (392) shows that the components of the electron spin cannot be measured simultaneously with the same precision. 126

10.6

We now consider the most important property of orthonormal functions, which similar to the orthogonality, arises from the properties of vectors. To illustrate this connection, consider a simple example: In the Cartesian coordinates an arbitrary vector A can be written as a linear combination of the orthonormal unit vectors A = (i A)i + (j A)j + (k 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 arbitrary vector A may be presented in terms of components Ax , Ay , Az , and three unit vectors oriented in the directions of the coordinate axis A = Ax i + Ay j + Az k . (394)

Since the components are the projections of the vector A on the coordinate axis Ax = i A , Ay = j A , Az = k A , (395)

we nd that the vector (394) can be written in the form A = (i A)i + (j A)j + (k A)k , as required. We can extend this property to n dimensional space and state that an arbitrary vector A can be written as a linear combination of the coordinate (basis) unit vectors e as

m

(396)

A = e1 A e1 + e2 A e2 + . . . + en A en = 127

n=1

en A en , (397)

where en A is the scalar product of en and A, (nth component of A), and ei ej = ij . The norm (magnitude) of the vector A is ||A||2 = |A| =

n

en A

(398)

Thus, we see that an arbitrary vector can be expressed as a linear combination of the orthonormal vectors en . In analogy, an arbitrary wave function can be expanded in terms of orthonormal wave functions n as =

n

cn n ,

(399)

(discrete spectrum of n ), or in the case of a continuous spectrum of n (r) = cn (r)n (r)dVn , (400)

where cn are arbitrary (unknown) expansion coecients, and dVn is the volume element of the space the orthonormal functions n (r) are spanned. We can nd the coecients cn (r) by multiplying Eq. (400) by (r) and m integrating over all space as follows (r)(r)dV = m cn (r) (r)n (r)dV dVn = cm (r) , m (401)

where we have used the orthonormality property of the n functions (r)n (r)dVn = nm . m (402)

In general, the coecients cm (r) are complex numbers and are called the components of the function in the basis of the orthonormal functions m . The components determine the function completely, and very often the coecients cm (r) are called a representation of the wave function in the basis m . The coecients cm (r) satisfy the following relation

V

(403)

V

(r)(r)dV =

V V Vn Vn Vm

|(r)|2 dV

= =

V

V

|cm (r)|2 dV .

(404)

|cm (r)|2 dV = 1,

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 (r), is in the state described by the wave function m (r). Example: Let A is an operator and (r) is an unknown wave function that is not an eigenfunction of A. Suppose, that we cannot nd the explicit form of (r) because we cannot solve the Schrdinger equation for (r). However, o we can nd a form of the wave function in the basis of the eigenfunctions of A. If m (r) is an eigenfunction of A, then (r) = cm (r)m (r)dVm . (405)

129

11

Dirac Notation

Dirac introduced a very useful (compact) notation of state vectors (wave functions) i in terms of bra i| and ket |i vectors. For example, a wave function i can be expressed by a ket vector |i , and by a bra vector i |. This notation can be further simplied to |i i and i|, respectively. Let us illustrate what kind of simplications we will get using the Dirac notation. In the Dirac notation, a scalar product is written as (i , j ) = i |j = i|j , (406)

which is called a bracket. For orthonormal vectors we have used the notation (i , j ) = ij , which in the Dirac notation takes the form i|j = ij . Since (i , j ) = (j , i ) , we have in the Dirac notation i|j = j|i . In the bra-ket notation, the denition of the Hermitian adjoint becomes i|A|j = or j|A |i = i|A|j Thus, for a Hermitian operator i|A|j = j|A|i

j|A |i

(407)

(408)

(409)

Expectation value of an operator A in a state |i is given by i|A|i . We write a linear superposition of ket states as |a = or |a = (x)|x dx . continuous states 130 (411)

n

n |n ,

discrete states

(410)

The bra-ket notation also extends to action of operators on state vectors. A linear operator A associates with every ket |i another ket |j : A|i = |j , such that A (|a + |b ) = A|a + A|b , A|a = A|a where is a number. Hermitian conjugate of A|i is i|A . An arbitrary ket state |a can be expanded in terms of orthonormal ket states as |a =

n

(412)

and

(413)

cn |n .

(414)

n

cn m|n =

n

cn nm = cm .

(415)

n n

(416)

|n n|a .

(417)

|n n| = , 1

(418)

131

The product ket-bra (|n n|) is called a projection operator, and the relation (418) is called the completeness relation. From Eq. (414) and a|a = 1, we have

n

|cn |2 = 1 .

(419)

11.1

Projection operator

Pmn = |m n| . Pmn |a = |m n|a . 2 Pnn = Pnn , (420)

This operator projects an arbitrary state vector |a onto the ket state |m : (421) When m = n and n|n = 1, the projection operator Pnn satises the relation (422)

which is easy to prove 2 Pnn = |n n|n n| = Pnn . Thus, the square of Pnn equals itself. Note that Pnn is a Hermitian operator, but Pmn , (m = n) is not Hermitian. Proof: Since i|Pmn |j = i|m n|j = im nj , we have that, m|Pmn |n = 1, but n|Pmn |m = 0, and then m|Pmn |n = as required. 132 n|Pmn |m

(423)

(424)

(425)

11.2

Consider an arbitrary operator A. We can represent the operator A in terms of projection operators of the orthonormal states |m . To show this, we use the completeness relation for the states |m and multiply the operator A on both sides by unity in the form 1=

m

|m m| ,

(426)

and obtain A =

m

|m m| A

|n n| =

m,n

m,n

|m m|A|n n| (427)

=

m,n

m|A|n |m n| =

Amn Pmn ,

where Amn = m|A|n . Thus, an arbitrary operator can be written (represented) as a linear com bination of projection operators Pmn . Since an arbitrary state |a can be expanded in terms of orthonormal states |m , i.e. |a =

n

cn |n ,

(428)

we can obtain the following expression for the expectation value A in the state |a as A = a|A|a = n|A|m c cm . n (429)

m,n

m,n n

An |cn |2 .

(430)

Thus, the modulus square of the expansion coecients is the probability that the quantity described by the operator A is in the state |n . is a weighted sum of the eigenvalues, this suggests that the eigenAs A values represent the possible results of measurement, while |cn |2 is the probability 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 measurement of a physical quantity at any time always leads to a denite 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 eigenvalues of Hermitian operators are real, we postulate that every physical quantity that is measurable is specied in quantum physics by a linear Hermitian op erator A that is also called an observable. In quantum physics the set of possible measured values for a physical quantity is the set of eigenvalues of a linear Hermitian operator specifying the physical quantity. Example: Consider a particle specied by a wave function a , or in the Dirac no tation, by |a . Let H is the Hamiltonian (energy) of the particles and |n are known eigenfunctions of H. If |a is an eigenfunction of H, then H|a = Ea |a , (431) where Ea is the eigenvalue (energy) of the particle. Thus, Ea = a|H|a . then we can expand |a in terms of If |a is not an eigenfunction of H, the eigenfunctions |n as |a = and nd that a|H|a =

n n

cn |n ,

(432)

En |cn |2 .

(433)

Hence, the measurement of energy of the particle in the state |a leads to a range of possible results, each occurring with probability |cn |2 . Thus, |cn |2 is the probability that the measurement of H will give the value En . Since, |a = cn |n , we say that the state of the particle is a superposi tion of the eigenfunctions of H. 134

12

Using an orthonormal basis, we can represent an arbitrary state |a as a linear superposition of the basis states |a =

n

cn |n ,

(434)

where, in general, the coecients cn are complex numbers, and n |cn |2 = 1. The set of the expansion coecients c1 , c2 , . . . denes the state |a and is called the representation of |a in the basis of the orthonormal states |n . We can write the set of the coecients cn as a column (ket) vector

|a =

c1 c2 . . . cn

(435)

12.1

Using the representation (436), we will try to write in a matrix form the relationship between two ket states |a and |b related through a linear operator A as |b = A|a . Let |a |b =

n

(437)

cn |n , bm |m . (438)

=

m

135

n

cn m|A|n =

n

Amn cn ,

(439)

where Amn = m|A|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 :

b1 b2 . . . bn

c1 c2 . . . cn

(440)

Thus, the scalar product (m , An ), or m|A|n represents a matrix element in the orthonormal basis |n . of the operator A Example: Find the matrix representation of the operator A = d/dx in the basis of two orthonormal states 1 = a sin(nx) and 2 = a cos(nx), where a = 1/ and x , . Since A1 = A2 we nd 1 , A1 = n (1 , 2 ) = 0 , 2 , A2 = n (2 , 1 ) = 0 , 2 , A1 = n (2 , 2 ) = n . 136 d sin(nx) = n2 , dx d = cos(nx) = n1 , dx

(441)

1 , A2 = n (1 , 1 ) = n , (442)

Hence A= 0 n n 0 . (443)

The solution of this problem is more simple if we use the Dirac notation. Denote |1 = a sin(nx) , Since A|1 A|2 = n|2 , = n|1 , |2 = a cos(nx) . (444)

(445)

the operator A written in the basis |1 , |2 , has the form A = n (|2 1| |1 2|) . Hence 1|A|1 = 0 , 1|A|2 = n , 2|A|2 = 0 , 2|A|1 = n . (446)

(447)

Note that the operator A is not Hermitian A = n (|1 2| |2 1|) = A , and therefore the states |1 , |2 are not the eigenfunctions of A. (448)

12.2

The ket vector |a is an eigenvector of a linear operator A if the ket vector is a constant times |a , i.e. A|a A|a = |a . 137 (449)

The complex constant is called the eigenvalue and |a is the eigenvector corresponding to the eigenvalue . Eigenvectors of an operator A can be found in terms of a linear superposition of orthonormal vectors |n . Since |a = cn |n , we have A|a =

n

cn A|n =

m

cm |m .

(450)

n m

cn |m m|A|n =

cm |m ,

(451)

m n

|m =

(cm )|m .

m

(452)

Hence cn m|A|n = cm ,

n

(453)

or cn Amn = cm .

n

(454)

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

c1 c2 . . . cn

c1 c2 . . . cn

(455)

138

The following conclusions arise from the matrix eigenvalue equation: 1. When the matrix Amn is diagonal, i.e. Amn = 0 for m = n, the or thonormal states |n are the eigenstates of the operator A with eigenvalues n = Ann . 2. If the matrix Amn is not diagonal, then we can nd the eigenvalues and eigenvectors of A diagonalizing the matrix Amn . The eigenvalues are obtained from the characteristic equation A11 A12 . . . A1n A21 A22 . . . A2n . =0. . . An1 An2 . . . Ann

(456)

This is of the form of a polynomial equation of degree n, and shows that n eigenvalues can be found from the roots of the polynomial. For each eigenvalue i found by solving the characteristic equation, the corresponding eigenvector is found by substituting i into the matrix equation. Example: Consider the example from Section. 12.1. In the matrix representation, the operator A = d/dx has the form given in Eq. (443). Since the matrix is not diagonal, the states 1 and 2 are not eigenstates of the operator A. We in terms of linear superpositions of the states can nd the eigenstates of A, 1 and 2 , simply by the diagonalization of the matrix (443). We start from the eigenvalue equation, which is of the form 0 n n 0 c1 c2 = c1 c2 . (457)

from which we nd two eigenvalues 1 = +in and 2 = in. For 1 = in the eigenvalue equation takes the form 0 n n 0 from which, we nd that nc2 = inc1 c1 = ic2 . (460) c1 c2 = in c1 c2 , (459)

or

Hence, the eigenfunction corresponding to the eigenvalue 1 is of the form 1 = ic2 c2 = c2 i 1 . (461)

Thus, the normalized eigenfunction corresponding to the eigenvalue 1 is given by 1 1 = 2 or 1 1 = [i sin(nx) + cos(nx)] . 2 (464) i 1 , (463)

Similarly, we can easily show that the normalized eigenfunction corresponding to the eigenvalue 2 is of the form 1 2 = [i sin(nx) + cos(nx)] . 2 140 (465)

In the Dirac notation, the normalized eigenvectors can be written in a compact form as |1 |2 1 = (i|1 + |2 ) , 2 1 = (i|1 + |2 ) . 2

(466)

The physical interpretation of the superposition states (466) is as follows: The eigenfunctions |1 and |2 in the form of the linear superpositions tell us that e.g. with the probability 1/2 the system described by the operator A is in the state |1 or in the state |2 .

1. In quantum physics, an arbitrary wave function may be represented by a normalized column vector of expansion coecients in the basis of orthonormal states. 2. In an orthonormal basis, an arbitrary operator A may be represented by a matrix, whose the elements Amn are given by scalar products (m , An ). 3. Using an orthonormal basis, an eigenvalue equation of an arbitrary operator may be written in a matrix form. In this case, the problem of nding eigenvalues and eigenvectors of the operator reduces to a simple problem of diagonalization of the matrix.

141

13

In many situations in physics, the Hamiltonian H of a given system is so complicated that the solution of the stationary Schrdinger equation is praco tically impossible or very dicult. In some situations, however, the Hamiltonian can be split into two parts H = H0 + V , (467)

such that we can solve the eigenvalue equation for H0 , i.e. we can nd (0) eigenvalues En and eigenvectors (0) of the Hamiltonian H0 , and we can n treat the part V as a small perturber to H0 . Thus, the problem of solving the eigenvalue equation H = H0 + V = E (468)

(0) reduces to nd E and when we know the eigenvalues En and the eigen vectors (0) of H0 . n Since V appears as a small perturber to H0 , we will try to nd E and in the form of a series

(469)

where (1) is the rst order correction to the unperturbed eigenstate (0) , n n (1) (0) and En is the rst order correction to the unperturbed eigenvalue En . The subscript n indicates that the Hamiltonian H0 can have more than one eigenvalue and eigenvector. Substituting the series expansion (469) into the eigenvalue equation (468), we get H0 + V

(0) (1) (0) + (1) = En + En n n

(0) + (1) n n

(470)

Expanding both sides of Eq. (470) and equating terms of the same order in V , we obtain

(0) H0 (0) = En (0) zeroth order in V , n n (0) (1) n n H0 (1) + V (0) = En (1) + En (0) rst order in V . n n

(471) (472)

142

We know the solution of Eq. (471). In order to solve Eq. (472), we write this equation in the form

(0) (1) n H0 En (1) = En (0) V (0) . n n

(473)

(0) (0) Assume that the eigenvalues En are non-degenerated, i.e. for a given En there is only one eigenfunction (0) . n Multiplying Eq. (473) from the left by (0) , and integrating over dV , we n obtain (0) (1) (0) , H0 (1) (0) , En (1) = En (0) , (0) (0) , V (0) n n n n n n n n

. (474)

Since

(0) (0) , H0 (1) = H0 (0) , (1) = En (0) , (1) n n n n n n

(475)

(1) En = (0) , V (0) = (0) |V |(0) = n|V |n . n n n n

(476)

(0) Thus, the rst order correction to the eigenvalue En is equal to the expec tation value of V in the state (0) . n In order to nd the rst-order correction to the eigenstate |(0) , we exn pand |(1) state in terms of |(0) , using the completeness relation, as n n

|(1) = n

cmn |(0) , m

(477)

where cmn = (0) |(1) . m n We nd the coecients cmn from Eq. (473) by multiplying this equation from the left by (0) | (m = n), and nd m

(0) (1) (0) |H0 |(1) En (0) |(1) = En (0) |(0) (0) |V |(0) . m n m n m n m n

(478)

(0) n (0) |H0 |(1) = Em (0) |(1) , m m n

and

(479)

143

(0) (0)

En E m

(0) |V |(0) m n

(0)

(0)

(480)

m=n

En E m

|(0) . m

(481)

(0) (1) Since we know En and |(0) , we can nd En from Eq. (476) and |(1) n n from Eq. (481).

Example: Consider a particle in an innite one-dimensional potential well, as shown in Fig. 26.

V1 a/2 0 d a/2 x

Figure 26: Innite potential well with a small potential (perturber) barrier V 1 . Assume that inside the innite well there is a small potential barrier of high V1 and thickness d. Treating the barrier V1 as a small perturber, nd the eigenvalues and eigenstates of the particle valid to the rst order in V1 .

144

Solution: We know from Section 8.1 that the eigenstates of the particle in the innite well, without V1 , are (0) = n 2 x sin n a a , (482)

(0) En = n 2

2 h2 , 2mp a2

(483)

where mp is the mass of the particle. (0) Thus, the rst order correction to the eigenvalue En is 2V1 (1) En = (0) , V1 (0) = n n a

d 0

dx sin2

nx a

(484)

In order to nd the rst order correction to the eigenstate (0) , we have to n calculate the matrix element (scalar product) 2V1 Vmn = (0) , V1 (0) = m n a

d 0

dx sin

nx mx sin a a

(485)

(1) En =

(486) , (487)

Vmn =

where = n/a and = m/a. Hence, the rst order correction to the eigenstate (0) is n (1) = n 2mp a2 2 h2 Vmn (0) . 2 m2 m m=n n 145 (488)

14

We have illustrated in Section 8.2 the solution of the stationary Schrdinger o 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 Schrdinger equation for a similar o problem, but with V (x) strongly dependent on x, Fig. 27, such that 1 V (x) = m 2 x2 . 2 This is the well known potential of a harmonic oscillator. (489)

V(x)

Figure 27: Potential of a harmonic oscillator. In one dimension, the Hamiltonian of an oscillating mass m is given by 1 2 1 H= p + m 2 x2 , (490) 2m 2 where p2 /2m is the kinetic energy and m 2 x2 /2 is the potential energy of the mass. We will nd energies (eigenvalues) and eigenfunctions of the harmonic oscillator by solving the stationary Schrdinger equation (eigenvalue equation) o for the harmonic oscillator using two dierent approaches. 146

In the rst, we will solve the equation using algebraic operator technique which is based on the Dirac notation. This approach has several denite advantages and exploits the commutation relations among the operators involved and their properties. In the second approach, we will transform the stationary Schrdinger o equation into a second-order dierential equation, and will nd the solution of the equation in terms of special functions.

14.1

The algebraic operator technique is based on the commutation relation of two Hermitian operators involved in the evolution of the harmonic oscillator: position x and momentum p = px : [, p] = i . x h We will introduce a non-Hermitian operator dened as a= 1 m x + i p, 2 h 2m h (492) (491)

Using the commutation relation (491), we nd that the operators a, a satisfy the commutation relation 1 a, a = . This allows us to write the Hamiltonian H in a compact form 1 1 H = h a a + aa = h a a + 2 2 Hence, the eigenvalue equation H| = E| , 147 (496) . (495) (494)

Multiplying Eq. (497) from the left by |, and using the normalization | = 1, we get h Since | a| = (| , a| ) 0 , a a we have that 1 E h . 2 (500) (499) | a| + a 1 =E . 2 (498)

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 a : 1 a h a a a + a | = E | . 2 Using the commutation relation (494), we can write Eq. (501) as h a a 1 a | = E | . a 2 (502) (501)

Introducing a notation | = a | , we see that | is an eigenfunction of H with eigenvalue E + h. Thus, the operator a acting on the state | of energy E transforms this state to the state | of energy E + h. Therefore, the operator a is called the raising operator or creation operator. 148

Now, multiplying Eq. (503) from the left by a , we obtain 1 h a a a + a | = (E + h) a | . 2 Proceeding similar as above, we get h a a + 1 a | = (E + 2 ) a | . h 2 (505) (504)

Thus, the state a | = a a | is an eigenfunction of H with an eigenvalue E + 2 . h Similarly, we can show that the state |n = ( )n | is an eigenfunction a of H with an eigenvalue E + n . h Now, consider the action of the operator a on the eigenfunctions and eigen values. Consider the eigenvalue equation for |n : h a a + 1 |n = (E + n ) |n = En |n . h 2 (506)

Multiplying Eq. (506) from the left by a, we get 1 h aa a + a |n = (E + n ) a|n , h 2 and using the commutation relation (494), we obtain 3 h a aa + a |n = (E + n ) a|n . h 2 Hence h a a + 1 a|n = [E + (n 1) h] a|n . 2 (509) (508) (507)

Thus, the state |n1 = a|n is an eigenfunction of H with an eigenvalue En h. Therefore, the operator a is called the lowering operator or anni hilation operator. Suppose that the state |0 of energy E is the lowest (ground) state of the harmonic oscillator. Thus, the energy spectrum (eigenvalues), shown 149

^+ a ^ a

Figure 28: Energy spectrum of the harmonic oscillator. in Fig. 28, forms a ladder of equally spaced levels separated by h, which one ascends by the action of a and descends by the action of a. The quantum harmonic oscillator therefore has a discrete energy spectrum. Consider the action of a on the ground state h a a + 1 a|0 = (E h) a|0 . 2 (510)

This equation cannot be satised. Otherwise there would exist another eigenvalue E h lower than E. Thus, a|0 must be identically zero: a|0 0 . Hence, the eigenvalue equation for the ground state is 1 1 H|0 = h a a + |0 = h|0 . 2 2 Thus, the energy (eigenvalue) of the ground state is E = h/2. We can summarize our ndings, that the energy eigenvalues of the harmonic oscillator are discrete En = n + 1 h , 2 150 n = 0, 1, 2, . . . (513) (512) (511)

2

|0 , . . . , |n = a

|0 . (514)

From the above equation, it follows that starting with |0 , we may obtain the complete set of eigenvectors of the harmonic oscillator by repeatedly applying the operator a on the eigenstate |0 . However, the eigenstates found in this way are not normalized. The n normalization of n (x) = cn a 0 (x) gives 1 = n |n = |cn |2 0 | an

n n1

|0 (515)

(Proof: by induction, leave for the students as a tutorial problem), we can continue Eq. (515) as a = |cn |2 0 |n1 nn1 + an a |0 a a = |cn |2 n 0 |n2 (n 1)n2 + an1 a |0 a = |cn |2 n(n 1) 0 |n2 an2 |0 . a 1 = |cn |2 n! . Thus, the normalized eigenfunctions of the harmonic oscillator are 1 |n = a n!

n

(517)

|0 .

(519)

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 |0 . Thus, it is enough to know the ground state eigenfunction to nd all the eigenfunctions of the harmonic oscillator. This is the complete solution to the problem. It is remarkable that the commutation relation (494) was all what we needed to deal with the harmonic oscillator completely. In a very eective way, we extracted the essential structure of the problem and have founded the eigenvalues and eigenvectors of the harmonic oscillator. Using the denition of the ground state (511), we may nd the explicit form of the ground state eigenfunction. Substituting for a from Eq. (492) and using the explicit form of p = i d/dx, we get h m 1 d0 x0 + i i h 2 h dx 2 m h that simplies to d0 m + x0 = 0 , dx h where 0 |0 . Hence d0 m xdx . = 0 h Integrating Eq. (522), we obtain ln from which we nd 0 (x) = 0 (0) exp m 2 x 2 h . (524) m 2 0 (x) = x , 0 (0) 2 h (523) (522) (521) =0, (520)

1 4

exp 152

m 2 x 2 h

(525)

Thus, the wave function of the ground state is a Gaussian. The wave functions n (x) of the other states can be found from the relation n (x) = a

n

0 (x) .

(526)

Using the denition of a (Eq. (493)), we can nd n (x) in terms of the position x: 1 (x) = a 0 (x) m 1 d = x i i h 2 h dx 2m h From Eq. (521), we have that m d0 = x0 . dx h Hence 1 (x) = Similarly, we can nd that 1 m 2 2 (x) = 2 x 1 0 (x) . h 2 We can introduce a new parameter = and write the wave functions as 1 1 () = H1 ()0 () , 2 1 2 () = H2 ()0 () , 2 2 where Hn () are Hermite polynomials of degree n. 153 m x, h (531) (530) 2 m x 0 (x) . h (529) (528)

0 (x) .

(527)

(532)

E h

| 1| 2

| 0 |

E=3/2

2

E=1/2

x0

Figure 29: First two energy eigenvalues and eigenfunctions of the harmonic oscillator.

Consider the harmonic oscillator in the ground state. Using the classical representation of energy, we have 1 p2 1 h = + m 2 x2 . 2 2m 2 154 (535)

Since, p2 0, the particle must be restricted to positions x, such that 1 1 m 2 x2 h , 2 2 i.e. |x| h . m (537) (536)

The maximum of |x| x0 = h/m is called the classical turning point. Since the wave function 0 (x) is not restricted to x x0 , see Fig. 29, quantum mechanics predicts that the harmonic oscillator can be in the classically forbidden region.

14.2

We will carry out the solution of the eigenvalue equation of the harmonic oscillator again, this time using the stationary Schrdinger equation in a form o of a second-order dierential equation. The starting point is the stationary Schrdinger equation for the harmonic o oscillator whose the Hamiltonian is of the form 1 2 1 H= p + m 2 x2 . 2m 2 (538)

Since in one dimension, p = i d/dx, the Schrdinger (eigenvalue) equation h o takes the form 1 h2 d2 + m 2 x2 = E , 2m dx2 2 (539)

or multiplying by 2m and dividing by h2 , we obtain a second-order dier ential equation d2 2m m 2 2 + 2 E x =0. dx2 2 h 155 (540)

This is not a linear dierential equation, and it is not easy to obtain a solution. We can proceed in the following way. Introducing new variables 2m m2 2 E, 2 = , h2 h2 we can write Eq. (540) in a simpler form = (541)

d2 + 2 x2 = 0 . (542) dx2 Despite of the diculty, we will try to solve the dierential equation (542). First, we will nd the solution of Eq. (542) in the asymptotic limit of large x (x 1). In this limit, we can ignore the term as being small compared 2 2 to x , and obtain d2 2 x2 = 0 . 2 dx Solution of Eq. (543) is of the form 1 (x) = C exp x2 2 where C is a constant. (543)

(544)

Hence, we will try to nd the solution of Eq. (542) in the form 1 (x) = f (x) exp x2 , 2 i.e. in the form satisfying the asymptotic solution (544). Substituting Eq. (545) into Eq. (542), we get

(545)

d2 f df 2x + ( )f = 0 . (546) dx2 dx Introducing a new variable = x, and a new function f (x) H(), for which df dH d dH = = , dx d dx d d2 f = dx2 d2 H d d2 H = 2 , d2 dx d 156 (547)

This equation is identical to the dierential equation for Hermite polynomials, with 1 = 2n , where n is integer. Thus, the wave functions of the harmonic oscillator are of the form 1 n (x) = NHn () exp 2 2 , (550) (549)

where N is a normalization constant. Since n is integer, we nd from Eqs. (549) and (541) that the energy eigenvalue E is E = n+ 1 h . 2 (551)

In summary, the solution of the Schrdinger equation given in the difo ferential form agrees perfectly with the results obtained by the algebraic operator technique.

157

2. The energy levels are equally spaced. This is an important point to remember. The dierence in energy between adjacent energy levels is equal to the energy of a single photon, h. 3. The lowest energy the oscillator can have is E0 = 1 h, which is non 2 zero. Thus, the oscillator can never be made stationary. 4. The oscillator can be found in the classically forbidden region. This is an another example of penetration of a potential barrier or quantum tunneling.

Exercise: Assume that the Harmonic oscillator is in the ground state n = 0. Calculate the probability that the oscillator will be found in the classically forbidden region, where the kinetic energy is negative. Solution: We have shown in lecture that the wave function of the ground state is 0 (x) = Aex , where m A= h

1 4 2

and

m . 2 h

Classically forbidden regions are x x0 and x x0 , where x0 = h/m is the classical turning point, see Fig. 29. Probability of nding the Harmonic Oscillator in the classically forbidden region is P =

x0 2

|0 (x)|2 dx +

x0

x0

|0 (x)|2 dx

2 1

= 2A

2x2

dx = 2A

e2x dx .

158

1

and

1 dx = dy . 2

2 2 ey dy =

ey dy = 1 Erf(1) = 0.16 ,

x 0

ey dy .

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 harmonic oscillator energy eigenfunction obeys the following uncertainty relation xp = h (2n + 1) , 2

2

159

15

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 = n , h n = 1, 2, 3, . . . . (552)

However, a careful analysis of the observed spectra showed that the angular momentum cannot be n , but rather l(l + 1), where l = 0, 1, 2, . . . , n 1. h It follows from the Bohr postulate that energy and also electrons 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 (r), which satises the stationary Schrdinger equation o H(r) = E(r) , where the Hamiltonian is 2 =h H 2m with e2 1 V (r) = . 40 r (555)

2

(553)

+ V (r) ,

(554)

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

1 r2 r 2 r r

1 2 . r 2 sin2 2

(556)

Z X

Figure 30: Spherical coordinates representation of the position vector r. In the spherical coordinates the Schrdinger equation can be written as o 2m r2 + 2 r 2 (E V (r)) r r h 1 1 2 + sin + =0. sin sin2 2

r Y

(557)

Equation (557) has two separate parts: the rst part depends only on the distance r, whereas the second part depends only on the polar angle and the azimuthal angle . Thus, the wave function is of the separable form (r) = R(r)Y (, ) . Hence, we can write Eq. (557) as 1 d dR 2mr 2 r2 + (E V (r)) R dr dr h2 1 1 Y 1 2Y = sin + Y sin sin2 2 (558)

(559)

Both sides of Eq. (559) depend on dierent variables, thus must be equal to 161

the same constant, say : 1 d dR 2m r2 + 2 (E V (r)) R + 2 R = 0 , 2 dr r dr r h 1 Y 1 2Y sin + Y = 0 . sin sin2 2 First, we consider Eq. (561) that depends on , . (560) (561)

15.1

In fact, Eq. (561) is the eigenvalue equation for the square of the angular momentum operator L = p = i r hr , (562)

that in the spherical coordinates L2 is of the form L2 = 2 h Y 1 sin sin + 1 2Y sin2 2 . (563)

Since the eigenvalue equation for L2 can be written as L2 Y (, ) = Y (, ) , we have that = / 2 , where is the eigenvalue of L2 . h Thus, we can write the eigenvalue equation for L2 as sin Y sin sin2 Y + 2Y =0. 2 (565) (564)

This equation contains two separate parts, one dependent only on and the other dependent only on . Therefore, the solution of Eq. (565) will be of the form Y (, ) = X()() . (566)

162

Hence, substituting Eq. (566) into (565), and dividing both sides by X()(), we obtain 1 d dX sin sin X d d sin2 = 1 d2 , d2 (567)

where X X() and (). As before, both sides must be equal to a constant, say m2 . Thus d dX 1 sin sin X d d 2 1d = m2 . d2 sin2 = m2 , (568) (569)

First, we will solve Eq. (569) for the azimuthal part of the wave function, which we can write as d2 = m2 , d2 and the solution of Eq. (570) is () = A exp(im) , (571) (570)

where A is a constant. Since in rotation, and + 2 correspond to the same position in space: () = ( + 2), which is satised when exp(im) = exp[im( + 2)] . From this we nd that exp(i2m) = 1 . (573) (572)

However, this is satised only when m is an integer, m = 0, 1, 2, . . .. Hence, the constant m2 is not an arbitrary number, is an integer. Normalization of () gives 1=

2 0

(574)

The next step in the solution is to nd X(), the polar component of the wave function. From Eq. (568), if we multiply both sides of the equation by X and divide by sin2 , and rearrange, we obtain 1 d dX sin sin d d + m2 X=0. sin2 (576)

(577)

(578)

Equation (578) is known in mathematics as the generalized Legendre dierential equation, and its solutions are the associated Legendre polynomials. For m = 0, the equation is called the ordinary Legendre dierential equation whose solution is given by the Legendre polynomials. Solution of Eq. (578), that is regular at z = 1, is assumed to be represented by a power series of the form X(z) = (1 z)

1 |m| 2

j=0

aj z j .

(579)

Substituting Eq. (579) into Eq. (578), we obtain the recursion relation for the coecients aj : aj+2 = (j + |m|)(j + |m| + 1) + aj . (j + 1)(j + 2) 164 (580)

Since aj+2 > aj , the series diverges (logarithmically) for z = 1. Therefore, in order to get the wave function nite everywhere in the space, we have to terminate the series at some j = j0 . In other words, we assume that aj0 +1 = aj0 +2 = . . . = 0. The series terminating at j = j0 indicates that (j0 + |m|)(j0 + |m| + 1) + = 0 . Introducing l = j0 + |m| , we see that l |m|, and = l(l + 1) , L2 L l = 0, 1, 2, . . . (583) Hence, we see that the eigenvalues of the angular momentum are quantized = h2 l(l + 1) , = h l(l + 1) . (584) (582) (581)

The integer number l is called the angular momentum quantum number. Since l |m|, the number m is limited to absolute values not larger than l. Physical interpretation of the quantum number m We have already shown that the azimuthal part of the wave function is given by 1 () = exp(im) , 2 m = 0, 1, 2, . . . , l . (585)

Consider the z-component, Lz , of the angular momentum. We will try to nd the eigenvalues and eigenfunctions of Lz : Lz = . In the spherical coordinates , Lz = i h 165 (587) (586)

and then we get from Eq. (586) a simple dierential equation i h whose solution is () = A exp i h , (589) = , (588)

where A is a constant. Using the same argument as before, that in rotation, and + 2 correspond to the same position in space, we nd that = m , h m = 0, 1, 2, . . . (590)

Thus, the azimuthal part of the wave function is the wave function of the zcomponent of the angular momentum, and the number m is the z-component angular momentum quantum number. Example: Consider angular momentum with l = 1. In this case, the eigenvalue of L is 2 , and Lz can have three values + , 0, . Thus, the orientation h h h of L along the z-axis is quantized. The vector L processes around z axis, sweeping out cones of revolution around that axis. This is shown in Fig. 31. The quantization of the orientation of L along its z-axis is called space quantization. Now we return to the analysis of the properties of the polar component X(z) of the wave function. After the termination of the series, we get the solution for the wave function X(z) in terms of the associated Legendre polynomials Xlm (z) = (1 z)

1 |m| 2

l|m|

aj z j .

j=0

(591)

166

Lz

m=+1

m=0

Ly

m=-1

Lx

Figure 31: Angular momentum quantization for l = 1. The rst few associated Legendre polynomials are X00 (z) = a0 , X10 (z) = a1 z , X11 (z) = a0 1 z 2 ,

(592)

where the coecients a0 , a1 , . . . are found from the normalization of the wave functions Xlm (z). The rst few angular function Y (, ) = X()() are: 1 , Y00 (, ) = 4 3 Y10 (, ) = cos , 4 3 Y11 (, ) = sin ei , 8 Y11 (, ) = 167 3 sin ei . 8 (593)

15.2

In the nal step of the solution of the Schrdinger equation, we consider the o remaining the radial part R of the wave function, Eq.(560). We can simplify Eq. (560) introducing new variables 2 = 2mE , h2 = me2 , 40h2 = 2r , (594)

and substituting the explicit form for V (r) (Eq. (555)), and = l(l + 1). After this simplication, the dierential equation (560) takes the form 1 d dR 1 l(l + 1) R=0. 2 + 2 d d 4 2 We will try to nd the solution of Eq. (595) in the form R() = e 2 l

j

1

(595)

bj j .

(596)

As before, the series diverges and therefore we must terminate the series at some j = j0 such that j0 = l 1. Denoting j0 + l + 1 = n, we have = n, and n = 1, 2, 3, . . .. Moreover, we see that n > l. We call n- the principal quantum number. We have found (= n), so that we have , and from that, we nd energy E= We can introduce a constant ao = called the Bohr radius, and then E= 1 e2 . 40 2ao n2 (599) 40h2 , me2 (598) 1 me4 1 . (40 )2 2 2 n2 h (597)

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 = 2r, and = 1/(ao n), the radial part of the wave function can be written as Rnl (r) = er (2r)l Ll (r) , n where

nl1

(600)

Ll (r) = n

j=0

bj (2r)j

(601)

are the associated Laquerre polynomials of order (n l 1). The coecients bj are found from the normalization of the radial function

0

(602)

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 nlm (r, , ) = Rnl (r)Ylm (, ) . (603)

In summary of this lecture: The eigenvalues of the energy of the electron in the hydrogen atom are quantized En = 1 e2 , 40 2ao n2 (604)

and the corresponding eigenfunctions are nlm (r, , ) = Rnl (r)Ylm (, ) , where the discrete (quantum) numbers are n = 1, 2, 3, . . . , , l = 0, 1, 2, . . . , n 1 , m = 0, 1, 2, . . . , l . 169 (605)

(606)

Few normalized eigenfunctions of the electron 100 = 200 = 210 = 1 a3 o 1 er/ao , 1 r er/(2ao ) , 2ao (607)

Note that eigenfunctions with l = 0 have spherical symmetry, i.e. are independent of and . The absolute square of the wave function |nlm (r, , )|2 is the probability density of nding the electron at the point r(r, , ), and Pnlm = |nlm (r, , )|2 dV = 4r 2 |nlm (r, , )|2 drdd (608)

is the probability of nding the electron in a small volume dV = drdd around the point r.

P 100

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, diers from the expectation (average) distance r , given by r = rnlm dV . nlm 170 (609)

Examples of the probability function Pnlm are shown in Figs. 32 and 33.

P 200

3+ 5

r/ao

Figure 33: Probability function of the electron in the state (nlm) = (200). Interesting properties of the probability function Pnlm : 1. For n = 1, the probability has one maximum at r = ao . 2. For (n = 2, l = 0, m = 0), the probability shows two maxima located at r = 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 (r) = Aer/ao , where A = 1/a3 is a constant, ao = 4oh2 /me2 is the Bohr radius, and r o is the distance between the electron and the nucleus. Show the following:

171

Solution: (a) From the denition of expectation value, we nd r = (r) r (r) dV = 4A2

0

r 3 e2r dr ,

where = 1/ao , and we have transformed the integral over dV into spherical coordinates with dV = 4r 2 dr. Performing the integration, we obtain r = 4A2 6 24 A2 3 1 3 = = 3 a4 = ao . o (2)4 16 4 2 ao 2

Thus, the average distance of the electron from the nucleus in the state is 3/2 of the Bohr radius. (b) The most probable value of r is that where the probability of nding the electron is maximal. Thus, we rst calculate the probability of nding the electron at a point r: P (r) = 4r 2 | (r) |2 = 4r 2 A2 e2r = Maximum of P (r) is where dP (r)/dr = 0. Hence dP (r) 8r 2 8r = 3 e2r 3 e2r . dr ao ao Thus dP (r) =0 dr from which, we nd r= when r = 1 , 4r 2 2r e . a3 o

1 = ao . 172

Note that this result agrees with the prediction of the Bohr model, that the radius of the n = 1 orbit is equal to ao . In summary of the solution: The expectation and most probable values of r are not the same. This is because the probability curve P100 (r) is not symmetric 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 r exceeding ao for this probability distribution.

Challenging problem: Eigenfunctions of the angular momentum The eigenfunctions of the angular momentum L of the electron in a Hydrogen atom for l = 1 are Y10 (, ) = 3 cos , 4 Y11 (, ) = 3 sin ei . 8

(a) Show that the eigenfunctions are also eigenfunctions of the Lz component of the angular momentum. (b) Show that the eigenfunctions are not eigenfunctions of the Lx component of the angular momentum. (c) Find the matrix representation of Lx in the basis of the eigenfunctions of L. (d) Find the eigenvalues and eigenfunctions of Lx in the basis of the eigen functions of L.

173

16

Consider a system composed of N parts (subsystems), e.g. a system of N identical and independent particles, whose the Hamiltonian is given by H= and the wave function is (r) = 1 (r1 )2 (r2 ) . . . N (rN ) , (611)

N i=1

Hi ,

(610)

where i (ri ) is the wave function of the ith particle located at the point rj , or equivalently we can say that i (rj ) is the wave function of the jth particle being in the ith state. However, the wave function (r) is not the only eigenfunction of the system. For example, a wave function (r) = 1 (r2 )2 (r1 ) . . . N (rN ) , is also an eigenfunction of the system with the same eigenvalue. Proof: Consider the eigenvalue equation with the eigenfunction (611): H(r) = =

i N i=1 N

(612)

N

Ei (r) .

i=1

Consider now the eigenvalue equation with the eigenfunction (612) H(r) =

N i=1

Hi (r) =

N i

174

N i=1

H(r) = as required.

Ei (r) ,

i=1

(613)

In fact there are a total N ! permutations of i (rj ) which are eigenfunctions of the system. Moreover, an arbitrary linear combination of the wave functions i (rj ) is also an eigenfunction of the system. We will illustrate this for N = 2.

16.1

1 |a|2 + |b|2

Consider an arbitrary linear combination of two wave functions (r) = [a(r12 ) + b(r21 )] , (614)

where (r12 = 1 (r1 )2 (r2 ) and (r21 = 1 (r2 )2 (r1 ). Then H(r) = H1 + H2 (r) 1 = [a (E1 + E2 ) (r12 ) + b (E1 + E2 ) (r21 )] |a|2 + |b|2 = (E1 + E2 ) (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 |1 , and the particle 2 is in a state |2 . 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 dierent. However, for two identical particles, the probabilities should be the same as we cannot distinguish between two identical particles. Thus, for two identical particles |a| = |b|. Hence, the parameters a and b can only dier by a phase factor: b = a exp(i), where is a real number: 1 (r) = (r12 ) + ei (r21 ) . 2

(616)

If we exchange the positions of the particles (r1 r2 ) or energy states (|1 |2 ), then we obtain 1 (r) = ei (r12 ) + (r21 ) . 2 (617)

Thus, the exchange of r1 r2 or |1 |2 is equivalent to multiplying (r) by ei and taking e2i = 1. Hence ei = 1 , (618)

and therefore the wave functions of identical particles are either symmetrical or antisymmetrical 1 s (r) = [(r12 ) + (r21 )] , 2 1 a (r) = [(r12 ) (r21 )] . 2 Note that s (r12 ) = s (r21 ) , a (r12 ) = a (r21 ) . 176

(619)

(620)

Properties of symmetrical and antisymmetrical functions: 1. If H = H12 = H21 , i.e. the Hamiltonian is symmetrical, then H(r) has the same symmetry as (r). Proof: Take (r) = s (r). Denote f12 = H12 s (r12 ), then f21 = H21 s (r21 ) = H12 s (r12 ) = f12 . Take now (r) = a (r). Then f21 = H21 a (r21 ) = H12 (s (r12 )) = f12 , as required. 2. Symmetry of the wave function does not change in time, i.e. wave function initially symmetrical (antisymmetrical) remains symmetrical (antisymmetrical) for all times. Proof: Consider an evolution of a wave function (t) in a time dt: (t + dt) = (t) + dt . t

Thus, symmetry of the wave function depends on the symmetry of /t. From the time-dependent Schrdinger equation o i h = H , t

we see that /t has the same symmetry as H. From the property 1, we has the same symmetry as . Therefore, (t + dt) has the know that H same symmetry as (t), as required.

177

Dierence between symmetric and antisymmetric functions Antisymmetric function can be written in a form of a determinant, called the Slater determinant: 1 (r1 ) 1 (r2 ) . . . 1 (rN ) 2 (r1 ) 2 (r2 ) . . . 2 (rN ) 1 . a (r) = . N! . N (r1 ) N (r2 ) . . . N (rN )

(621)

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 a (r) = 0. Thus, two particles determined by the antisymmetric function cannot be at the same point. Similarly, if two particles are in the same state, 1 (r1 ) = 1 (r2 ), and again two columns are equal giving a (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 antisymmetric functions called fermions, and those determined by symmetrical functions called bosons. Examples: Fermions: electrons, protons, neutrons. Bosons: photons, mesons, 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 energy level. How many electrons does it take to ll an energy level? The answer to this question is given by the Pauli principle. Pauli principle: No two electrons can have the same quantum numbers (n, l, m, s) in a multi-electron atom. It is also known as the exclusion principle, for the simple reason that if an electron has the quantum numbers (nlms) than at least one of the quantum numbers of any further electrons must be dierent. In an atom, for a given n, there are 2(2l + 1) degenerate states corresponding 1 to l = 0, 1, 2, . . ., m = l, . . . , l, and s = 2 , + 1 . Thus, for a given n the 2 total number of electrons in the energy state n is

l=m

2(2l + 1) = 2n2 .

l=m

(622)

Following the Pauli principle, we can nd numbers of electrons in the energy states 1s , 2 2s , 2 2p , 6 3s , 2 3p , 6 4s , 2 3d , 10 4p , 6 5s , 2 4d , 10 5p 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 dierent ground state congurations for dierent 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 congurations will have similar chemical properties. Examples: The Alkali metals: Lithium (1s)2 2s, Sodium (1s)2 (2s)2 (2p)6 3s, and Potassium (1s)2 (2s)2 (2p)6 (3s)2 (3p)6 4s. This is the explanation from quantum physics of the periodic structure of the elements.

180

Final Remark

It is appropriate to close our lectures on quantum physics by emphasizing the importance of quantum phenomena in the development of new areas in science and technology. The predictions of quantum physics have turned research and technology into new directions and have led to numerous technological 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 technology 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 understanding, and continues to excite our imagination. Feynman in his lectures on quantum physics referred in the following way to our understanding of quantum physics:

In summary of the subject, I think I can safely say: If you think you now know quantum physics, it means you do not know anything.

181

Appendix A

Derivation of the Boltzmann distribution function Pn Assume that we have n identical particles (e.g. photons), each of energy E, which can occupy g identical states. The number of possible distributions of n particles between g states is given by t= (n + g 1)! . n!(g 1)! (623)

For example: n = 3, g = 2 gives t = 4, see Fig. 34. We will nd maximum of t with the condition that nE =const., where E is the energy of each particle.

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

Figure 34: Example of possible distributions of three particles between two states. Taking ln of both sides of Eq. (623), we get ln t = ln(n + g 1)! ln n! ln(g 1)! . Using the Sterlings formula ln n! = n ln n n , and assuming that g 1, i.e. g 1 g, we obtain ln t = g ln n+g n+g + n ln . g n 183 (626) (625) (624)

We nd maximum of ln t using the method of Lagrange undetermined multipliers. In this method, we construct a function where is called a Lagrange undetermined multiplier, and nd the extremum K =0. (628) n Thus, we get n ln + E = 0 , (629) n+g from which, we nd g n = E . (630) e 1 This is the Bose-Einstein distribution function. Since n is dimensionless, should be inverse of energy. We choose = 1/(kB T ), where kB T is the energy of free, non-interacting particles. When g/n 1, we can approximate Eq. (630) by n = ge

k ET

B

K = ln t nE ,

(627)

(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 dierent 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 Pn = ae

k ET

B

,

n

n

k ET B

k ET

B

k ET B

Useful properties of trigonometrical functions: sin( ) = sin cos sin cos cos( ) = cos cos sin sin 1 sin2 = (1 cos 2) 2 1 cos2 = (1 + cos 2) 2

0 2 0 2 0 2 0

sin3 d =

0

4 x3 dx = ex 1 15 ex dx =

2 2

xex dx = 0

2

x2 ex dx = 185

1 2

r n er dr =

n! , n+1

from which, we nd

0 0

er dr =

1 , 2 , 3

rer dr =

1 , 2 6 4

r 2 er dr =

r 3 er dr =

Taylor series k = k0 + = 0 + ex = 1 x +

2

d d

3

+

k0

1 2

d2 d 2

2 + . . .

k0

x3 3! x2 cos x = 1 2! sin x = x

Kronecker function mn = 1 0 if m = n if m = n .

f (x)(x)dx = f (0) ,

Bohr magneton mB = 9.724 1024 [J/T] Bohr radius ao = 5.292 1011 [m] Boltzmann constant kB = 1.381 1023 [J/K] charge of an electron e = 1.602 1019 [C] permeability of vacuum 0 = 4 107 [H/m] permittivity of vacuum 0 = 8.854 1012 [F/m] Planck constant h = 6.626 1034 [J.s] = 4.14 1015 [eV.s] (Planck constant)/2 h = 1.055 1034 [J.s] = 6.582 1016 [eV.s] rest mass of electron me = 9.110 1031 [kg] rest mass of proton mp = 1.673 1027 [kg] Rydberg constant R = 1.097 107 [m1 ] speed of light in vacuum c = 2.9979 108 [m/s] Stefan Boltzmann constant = 5.670 108 [W/m2 K4 ]

1 = 1010 [m] ; 1 fm = 1015 [m] ; 1 eV = 1.602 1019 [J] A 1 J = 6.241 1018 [eV] ; = 3.142 ; e = 2.718 .

187

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