Quantum Mechanics THIRD EDITION EUGEN MERZBACHER University of North Carolina at Chapel Hill ® JOHN seater & SONS, INC.‘Stuart Johnson Marketing Manager Kimberly Manzi Production Editor Sandra Russell Designer ‘Madelyn Lesure Mlustration Editor Edward Starr ‘This book was set in 10/12 Times by University Graphics, Inc. and printed and bo Hamilton Printing Company. ‘The cover was printed by Hamilton Printing Company. This book is printed on acid-free paper. ©) Copyright © 1961, 1970, 1988, 1998 John Wiley & Sons, Inc. All rights reserved, No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning ‘or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, (508) 750-8400, fax (508) 750-4470, Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, (212) 850-6011, fax (212) 850.6008, E-Mail: PERMREQG@ WILEY.COM. Library of Congress Cataloging in Publication Data: Merabacher, Eugen. Quantum mechanics / Eugen Merzbacher. — 3rd ed, poem, Includes bibliographical references and index. ISBN 0-471-88702-1 (cloth : alk. paper) 1. Quantum theory. I. Title. QC174.12.M47 1998 530.12—de21 9720756 cP Printed in the United States of America 1098765432 530.12 M577 Quantum mechanics 3rd ed. Swanston LCN: 10798500 PO#: 200109006/0001 B/C: 31259006333202Dedicated to our children: Celia, Charles, Matthew, and MaryPreface The central role of quantum mechanics, as a unifying principle in contemporary physics, is reflected in the training of physicists who take a common course, whether they expect to specialize in atomic, molecular, nuclear, or particle physics, solid state physics, qudntum optics, quantum electronics, or quantum chemistry. This book was written for such a course as a comprehensive introduction to the principles of quantum mechanics and to their application in the subfields of physic The first edition of this book was published in 1961, the second in 1970. At that time there were few graduate-level texts available to choose from. Now there are many, but I was encouraged by colleagues and students to embark on a further revision of this book. While this new updated edition differs substantially from its predecessors, the underlying purpose has remained the same: To provide a carefully structured and coherent exposition of quantum mechanics; to illuminate the essential features of the theory without cutting corners, and yet without letting technical de- tails obscure the main storyline; and to exhibit wherever possible the common threads by which the theory links many different phenomena and subfields. The reader of this book is assumed to know the basic facts of atomic and sub- atomic physics and to have been exposed to elementary quantum mechanics at the undergraduate level. Knowledge of classical mechanics and some familiarity with electromagnetic theory are also presupposed. My intention was to present a self- contained narrative, limiting the selection of topics to those that could be treated equitably without relying on specialized background knowledge. The material in this book is appropriate for three semesters (or four quarters). The first 19 chapters can make up a standard two-semester (or three-quarter) course on nonrelativistic quantum mechanics. Sometimes classified as ‘* Advanced Quantum Mechanics’’ Chapters 20-24 provide the basis for an understanding of many-body theories, quantum electrodynamics, and relativistic particle theory. The pace quick- ens here, and many mathematical steps are left to the exercises. It would be pre- sumptuous to claim that every section of this book is indispensable for learning the principles and methods of quantum mechanics. Suffice it to say that there is more here than can be comfortably accommodated in most courses, and that the choice of what to omit is best left to the instructor. Although my objectives are the same now as they were in the earlier editions, Thave tried to take into account changes in physics and in the preparation of the students. Much of the first two-thirds of the book was rewritten and rearranged while I was teaching beginning graduate students and advanced undergraduates. Since most students now reach this course with considerable previous experience in quan- tum mechanics, the graduated three-stage design of the previous editions—wave mechanics, followed by spin one-half quantum mechanics, followed in turn by the full-fledged abstract vector space formulation of quantum mechanics—no longer seemed appropriate. In modifying it, I have attempted to maintain the inductive approach of the book, which builds the theory up from a small number of simple empirical facts and emphasizes explanations and physical connections over pure formalism. Some introductory material was compressed or altogether jettisoned to make room in the early chapters for material that properly belongs in the first half of this course without unduly inflating the book. I have also added several new topics and tried to refresh and improve the presentation throughout. viiviii Preface As before, the book begins with ordinary wave mechanics and wave packets moving like classical particles. The Schrédinger equation is established, the prob- ability interpretation induced, and the facility for manipulating operators acquired. ‘The principles of quantum mechanics, previously presented in Chapter 8, are now already taken up in Chapter 4, Gauge symmetry, on which much of contemporary quantum field theory rests, is introduced at this stage in its most elementary form. This is followed by practice in the use of fundamental concepts (Chapters 5, 6, and 7), including two-by-two matrices and the construction of a one-dimensional version of the scattering matrix from symmetry principles. Since the bra-ket notation is already familiar to all students, it is now used in these early chapters for matrix elements, The easy access to computing has made it possible to beef up Chapter 7 on the WKB method. In order to enable the reader to solve nontrivial problems as soon as possible, the new Chapter 8 is devoted to several important techniques that previously became available only later in the course: Variational calculations, the Rayleigh-Ritz method, and elementary time-independent perturbation theory. A section on the use of nonorthogonal basis functions has been added, and the applications to molecular and condensed-matter systems have been revised and brought together in this chapter. The general principles of quantum mechanics are now the subject of Chapters 9 and 10. Coherent and squeezed harmonic oscillator states are first encountered here in the context of the uncertainty relations. Angular momentum and the nonre- lativistic theory of spherical potentials follow in Chapters 11 and 12. Chapter 13 on scattering begins with a new introduction to the concept of cross sections, for col- liding and merging beam experiments as well as for stationary targets. Quantum dynamics, with its various ‘‘pictures’” and representations, has been expanded into Chapters 14 and 15, New features include a short account of Feynman path integration and a longer discussion of density operators, entropy and infor- mation, and their relation to notions of measurements in quantum mechanics. All of this is then illustrated in Chapter 16 by the theory of two-state systems, especially spin one-half (previously Chapters 12 and 13), From there it’s a short step to a comprehensive treatment of rotations and other discrete symmetries in Chapter 17, ending on a brief new section on non-Abelian local gauge symmetry. Bound-state and time-dependent perturbation theories in Chapters 18 and 19 have been thor- oughly revised to clarify and simplify the discussion wherever possible. The structure of the last five chapters is unchanged, except for the merger of the entire relativistic electron theory in the single Chapter 24. In Chapter 20, as a bridge from elementary quantum mechanics to general collision theory, scattering is reconsidered as a transition between free particle states. Those who do not intend to cross this bridge may omit Chapter 20. The quantum mechanics of identical par- ticles, in its ‘second quantization’” operator formulation, is a natural extension of quantum mechanics for distinguishable particles. Chapter 21 spells out the simple assumptions from which the existence of two kinds of statistics (Bose-Einstein and Fermi-Dirac) can be inferred. Since the techniques of many-body physics are now accessible in many specialized textbooks, Chapter 22, which treats some sample problems, has been trimmed to focus on a few essentials. Counter to the more usual quantization of the classical Maxwell equations, Chapter 23 starts with photons as fundamental entities that compose the electro- magnetic field with its local dynamical properties like energy and momentum. The interaction between matter and radiation fields is treated only in first approximation,Preface ix leaving all higher-order processes to more advanced textbooks on field theory. The introduction to the elements of quantum optics, including coherence, interference, and statistical properties of the field, has been expanded. As a paradigm for many other physical processes and experiments, two-slit interference is discussed repeat- edly (Chapters 1, 9, and 23) from different angles and in increasing depth. In Chapter 24, positrons and electrons are taken as the constituents of the rel- ativistic theory of leptons, and the Dirac equation is derived as the quantum field equation for chatged spin one-half fermions moving in an external classical electro- magnetic field. The one-particle Dirac theory of the electron is then obtained as an approximation to the many-electron-positron field theory. Some important mathematical tools that were previously dispersed through the text (Fourier analysis, delta functions, and the elements of probability theory) have now been collected in the Appendix and supplemented by a section on the use of curvilinear coordinates in wave mechanics and another on units and physical con- stants. Readers of the second edition of the book should be cautioned about a few notational changes. The most trivial but also most pervasive of these is the replace- ment of the symbol y for particle mass by m, or m, when it’s specific to an electron or when confusion with the magnetic quantum number lurks. There are now almost seven hundred exercises and problems, which form an integral part of the book. The exercises supplement the text and are woven into it, filling gaps and illustrating the arguments. The problems, which appear at the end of the chapters, are more independent applications of the text and may require more work. It is assumed that students and instructors of quantum mechanics will avail themselves of the rapidly growing (but futile to catalog) arsenal of computer soft- ware for solving problems and visualizing the propositions of quantum mechanics. Computer technology (especially MathType@ and Mathematica@) was immensely helpful in preparing this new edition, The quoted references are not intended to be exhaustive, but the footnotes indicate that many sources have contributed to this book and may serve as a guide to further reading. In addition, I draw explicit atten- tion to the wealth of interesting articles on topics in quantum mechanics that have appeared every month, for as long as I can remember, in the American Journal of Physics. The list of friends, students, and colleagues who have helped me generously with suggestions in writing this new edition is long. At the top I acknowledge the major contributions of John P. Hernandez, Paul S. Hubbard, Philip A. Macklin, John D. Morgan, and especially Eric Sheldon. Five seasoned anonymous reviewers gave me valuable advice in the final stages of the project. I am grateful to Mark D. Hannam, Beth A. Kehler, Mary A. Scroggs, and Paul Sigismondi for technical as- sistance. Over the years I received support and critical comments from Carl Adler, A. Ajay, Andrew Beckwith, Greg L. Bullock, Alan J. Duncan, S. T. Epstein, Heidi Fearn, Colleen Fitzpatrick, Paul H. Frampton, John D. Garrison, Kenneth Hartt, Thomas A. Kaplan, William C. Kerr, Carl Lettenstrém, Don H. Madison, Kirk McVoy, Matthew Merzbacher, Asher Peres, Krishna Myneni, Y. S. T. Rao, Charles Rasco, G. G. Shute, John A. White, Rolf G. Winter, William K. Wootters, and Paul F. Zweifel. I thank all of them, but the remaining shortcomings are my responsibility. Most of the work on this new edition of the book was done at the University of North Carolina at Chapel Hill. Some progress was made while Iheld a U.S. Senior Scientist Humboldt Award at the University of Frankfurt, during a leave of absence at the University of Stirling in Scotland, and on shorter visits to the Institute of Theoretical Physics at Santa Barbara, the Institute for Nuclear Theory in Seattle,x Preface and TRIFORM Camphill Community in Hudson, New York. The encouragement of colleagues and friends in all of these places is gratefully acknowledged. But this ong project, often delayed by other physics activities and commitments, could never have been completed without the unfailing patient support of my wife, Ann, Eugen MerzbacherContents cuarter1 Introduction to Quantum Mechanics 1 1. Quantum Theory and the Wave Nature of Matter 1 2. The Wave Function and its Meaning 4 Problems 10 cuaprer2 Wave Packets, Free Particle Motion, and the Wave Equation 12 1, The Principle of Superposition 12 2. Wave Packets and the Uncertainty Relations 14 3. Motion of a Wave Packet 18 4, The Uncertainty Relations and the Spreading of Wave Packets 20 5. The Wave Equation for Free Particle Motion 22 Problems 24 cHAPTER3 The Schrédinger Equation, the Wave Function, and Operator Algebra 25 The Wave Equation and the Interpretation of y 25 Probabilities in Coordinate and Momentum Space 29 Operators and Expectation Values of Dynamical Variables 34 Commutators and Operator Algebra 38 Stationary States and General Solutions of the Wave Equation 41 . The Virial Theorem 47 Problems 49 avayye cHaPter4 The Principles of Wave Mechanics 51 Hermitian Operators, their Eigenfunctions and Eigenvalues 51 The Superposition and Completeness of Eigenstates 57 The Continuous Spectrum and Closure 60 A Familiar Example; The Momentum Eigenfunctions and the Free Particle 62 5. Unitary Operators. The Displacement Operator 68 6. The Charged Particle in an External Electromagnetic Field and Gauge Invariance 71 7, Galilean Transformation and Gauge Invariance 75 Problems 78 eee cuarteRs The Linear Harmonic Oscillator 79 1, Preliminary Remarks 79 2. Bigenvalues and Bigenfunctions 81xii Contents 3. Study of the Eigenfunctions 84 4. The Motion of Wave Packets 89 Problems 90 cHapTeR 6 Sectionally Constant Potentials in One Dimension 92 1. The Potential Step 92 2. The Rectangular Potential Barrier 97 3, Symmetries and Invariance Properties 99 4, The Square Well 103 Problems 111 cuarrer? The WKB Approximation 113 1. The Method 113 2. The Connection Formulas 116 3. Application to Bound States 121 4, Transmission Through a Barrier 125 5. Motion of a Wave Packet and Exponential Decay 131 Problems 134 cuarrers Variational Methods and Simple Perturbation Theory 138 1, The Calculus of Variations in Quantum Mechanics 135 2. The Rayleigh-Ritz Trial Function 139 3. Perturbation Theory of the Schrddinger Equation 142 4, The Rayleigh-Ritz Method with Nonorthogonal Basis Functions 146 5. The Double Oscillator 149 6. The Molecular Approximation 159 7. The Periodic Potential 165 Problems 176 cuarrero Vector Spaces in Quantum Mechanics 179 1, Probability Amplitudes and Their Composition 179 2. Vectors and Inner Products 186 3, Operators 188 4, The Vector Space of Quantum Mechanics and the Bra-Ket Notation 195 5. Change of Basis 199 6. Hilbert Space and the Coordinate Representation 202 Problems 206 CHAPTER 10 Eigenvalues and Eigenvectors of Operators, the Uncertainty Relations, and the Harmonic Oscillator 207 1. The Eigenvalue Problem for Normal Operators 207 2. The Calculation of Eigenvalues and the Construction of Eigenvectors 209Contents xiii 3. Variational Formulation of the Eigenvalue Problem for a Bounded Hermitian Operator 212 4. Commuting Observables and Simultaneous Measurements 214 5. The Heisenberg Uncertainty Relations 217 6. The Harmonic Oscillator 220 7. Coherent States and Squeezed States 225 Problems ‘231 cuater 11 Angular Momentum in Quantum Mechanics 233 1. Orbital Angular Momentum 233 2. Algebraic Approach to the Angular Momentum Eigenvalue Problem 238 3. Eigenvalue Problem for L, and L?. 242 4. Spherical Harmonics 248 5. Angular Momentum and Kinetic Energy 252 Problems 255 cuarrer 12 Spherically Symmetric Potentials 256 1, Reduction of the Central-Force Problem 256 2. The Free Particle as a Central-Force Problem 257 3. The Spherical Square Well Potential 262 4, The Radial Equation and the Boundary Conditions 263 5. The Coulomb Potential 265 6. The Bound-State Energy Eigenfunctions for the Coulomb Potential 270 Problems 275 cHarTeR 13. Scattering 278 The Cross Section 278 The Scattering of a Wave Packet 286 Green’s Functions in Scattering Theory 290 The Born Approximation 295 Partial Waves and Phase Shifts 298 Determination of the Phase Shifts and Scattering Resonances 302 Phase Shifts and Green’s Functions 308 . Scattering in a Coulomb Field 310 Problems 314 exranayne cuarrer14 The Principles of Quantum Dynamics 315 1. The Evolution of Probability Amplitudes and the Time Development Operator 315 2. The Pictures of Quantum Dynamics 319 The Quantization Postulates for a Particle 323 4, Canonical Quantization and Constants of the Motion 326iv Contents 5. Canonical Quantization in the Heisenberg Picture 331 6, The Forced Harmonic Oscillator 335 Problems 342 sHaprer 1s. The Quantum Dynamics of a Particle 344 1. The Coordinate and Momentum Representations 344 2. The Propagator in the Coordinate Representation 348 3. Feynman’s Path Integral Formulation of Quantum Dynamics 355 4. Quantum Dynamics in Direct Product Spaces and Multiparticle Systems 358 5. The Density Operator, the Density Matrix, Measurement, and Information 363 Problems 370 cuapreris The Spin 372 1, Intrinsic Angular Momentum and the Polarization of y waves 372 2. The Quantum Mechanical Description of the Spin 377 3. Spin and Rotations 381 4, The Spin Operators, Pauli Matrices, and Spin Angular Momentum 385 5. Quantum Dynamics of a Spin System 390 6. Density Matrix and Spin Polarization 392 7. Polarization and Scattering 399 8. Measurements, Probabilities, and Information 403 Problems 408 cuarter 17 Rotations and Other Symmetry Operations 410 1, The Euclidean Principle of Relativity and State Vector Transformations 410 2, The Rotation Operator, Angular Momentum, and Conservation Laws 413 3. Symmetry Groups and Group Representations 416 4. The Representations of the Rotation Group 421 5. The Addition of Angular Momenta 426 6. The Clebsch-Gordan Series 431 7. Tensor Operators and the Wigner-Eckart Theorem 432 8. Applications of the Wigner-Eckart Theorem 437 9. Reflection Symmetry, Parity, and Time Reversal 439 10. Local Gauge Symmetry 444 Problems 448 cuapter 18 Bound-State Perturbation Theory 481 1, The Perturbation Method 451 2. Inhomogeneous Linear Equations 453Contents xv 3. Solution of the Perturbation Equations 455 4, Electrostatic Polarization and the Dipole Moment 459 5. Degenerate Perturbation Theory 463 6. Applications to Atoms 467 7. The Variational Method and Perturbation Theory 473 8. The Helium Atom 476 Problems ‘ 480 CHAPTER 19 Time-Dependent Perturbation Theory 482 ‘The Equation of Motion in the Interaction Picture 482 The Perturbation Method 485 Coulomb Excitation and Sum Rules 487 The Atom in a Radiation Field 491 The Absorption Cross Section 495 The Photoelectric Effect 501 The Golden Rule for Constant Transition Rates 503 . Exponential Decay and Zeno’s Paradox 510 Problems 515 er aneene cuaPter20 The Formal Theory of Scattering 517 1. The Equations of Motion, the Transition Matrix, the S Matrix, and the Cross Section 517 2. The Integral Equations of Scattering Theory 521 3. Properties of the Scattering States 525 4. Properties of the Scattering Matrix 527 5. Rotational Invariance, Time Reversal Symmetry, and the S Matrix 530 6. The Optical Theorem 532 Problems 533 CHAPTER 21 Identical Particles 535 1, The Indistinguishability of and the State Vector Space for Identical Particles 535 2. Creation and Annihilation Operators 538 3. The Algebra of Creation and Annihilation Operators 540 4, Dynamical Variables 544 5. The Continuous One-Particle Spectrum and Quantum Field Operators 546 6. Quantum Dynamics of Identical Particles 49 Problems 552 cuarrer 22 Applications to Many-Body Systems 555 1, Angular Momentum of a System of Identical Particles 585 2. Angular Momentum and Spin One-Half Boson Operators 556xvi Contents 3. First-Order Perturbation Theory in Many-Body Systems 558 4. The Hartree-Fock Method 560 5. Quantum Statistics and Thermodynamics 564 Problems 567 CHAPTER 23 Photons and the Electromagnetic Field 569 1, Fundamental Notions 569 Energy, Momentum, and Angular Momentum of the Radiation Field 573 Interaction with Charged Particles 576 Elements of Quantum Optics 580 . Coherence, Interference, and Statistical Properties of the Field 583 Problems 591 yeey cHaPTER 24 Relativistic Electron Theory 592 The Electron-Positron Field 592 The Dirac Equation 596 Relativistic Invariance 600 Solutions of the Free Field Dirac Equation 606 Charge Conjugation, Time Reversal, and the PCT Theorem 608 The One-Particle Approximation 613 Dirac Theory in the Heisenberg picture 617 8. Dirac Theory in the Schrédinger Picture and the Nonrelativistic Limit 621 9. Central Forces and the Hydrogen Atom 623 Problems 629 Naweyne APPENDIX 630 1. Fourier Analysis and Delta Functions 630 2. Review of Probability Concepts 634 3. Curvilinear Coordinates 638 4, Units and Physical Constants 640 REFERENCES 642 INDEX 647cuarrer 1 Introduction to Quantum Mechanics Quantum mechanics is the theoretical framework within which it has been found possible to describe, correlate, and predict the behavior of a vast range of physical systems, from particles through nuclei, atoms and radiation to molecules and condensed matter. This introductory chapter sets the stage with a brief review of the historical background and a preliminary discussion of some of the essential concepts.’ 1. Quantum Theory and the Wave Nature of Matter. Matter at the atomic and nuclear or microscopic level reveals the existence of a variety of particles which are identifiable by their distinct properties, such as mass, charge, spin, and magnetic moment. All of these seem to be of a quantum nature in the sense that they take on only certain discrete values. This discreteness of physical properties persists when particles combine to form nuclei, atoms, and molecules. The notion that atoms, molecules, and nuclei possess discrete energy levels is one of the basic facts of quantum physics. The experimental evidence for this fact is overwhelming and well known. It comes most directly from observations on in- elastic collisions (Franck-Hertz experiment) and selective absorption of radiation, and somewhat indirectly from the interpretation of spectral lines. Consider an object as familiar as the hydrogen atom, which consists of a proton and an electron, bound together by forces of electrostatic attraction. The electron can be removed from the atom and identified by its charge, mass, and spin. It is equally well known that the hydrogen atom can be excited by absorbing certain discrete amounts of energy and that it can return the excitation energy by emitting light of discrete frequencies. These are empirical facts. Niels Bohr discovered that any understanding of the observed discreteness requires, above all, the introduction of Planck’s constant, h = 6.6261 x 10-** J sec = 4.136 X 107" eV sec. In the early days, this constant was often called the ‘quantum of action. By the simple relation AE = hy an it links the observed spectral frequency » to the jump AE between discrete energy levels. Divided by 27, the constant A = h/27 appears as the unit of angular mo- mentum, the discrete numbers nf (n = 0, 1/2, 1, 3/2, 2,...) being the only values which a component of the angular momentum of a system can assume. All of this is true for systems that are composed of several particles, as well as for the particles themselves, most of which are no more ‘‘elementary’’ than atoms and nuclei. The composite structure of most particles has been unraveled by quantum theoretic "Many references to the literature on quantum mechanics are found in the footnotes, and the bibliographic information is listed after the Appendix. It is essential to have at hand a current summary of the relevant empirical knowledge about systems to Which quantum mechanics applies. Among many ‘good choices, we mention Haken and Welf (1993), Christman (1988), Krane (1987), and Perkins (1982). 12 Chapter 1 Introduction to Quantum Mechanics analysis of “‘spectroscopic’” information accumulated in high-energy physics experiments. Bohr was able to calculate discrete energy levels of an atom by formulating a set of quantum conditions to which the canonical variables g, and p; of classical mechanics were to be subjected. For our purposes, it is sufficient to remember that in this ‘‘old quamtum theory"” the classical phase (or action) integrals for a condi- tionally periodic motion were required to be quantized according to $ pidg; = mh (2) where the quantum numbers n, are integers, and each contour integral is taken over the full period of the generalized coordinate q,. The quantum conditions (1.2) gave good results in calculating the energy levels of simple systems but failed when applied to such systems as the helium atom. Exercise 1.1. Calculate the quantized energy levels of a linear harmonic os- cillator of angular frequency w in the old quantum theory. Exercise 1.2, Assuming that the electron moves in a circular orbit in a Cou- lomb field, derive the Balmer formula for the spectrum of hydrogenic atoms from the quantum condition (1.2) and the Bohr formula (1.1). It is well known that (1.1) played an important role even in the earliest forms of quantum theory. Einstein used it to explain the photoelectric effect by inferring that light, which through the nineteenth century had been so firmly established as a wave phenomenon, can exhibit a particle-like nature and is emitted or absorbed only in quanta of energy. Thus, the concept of the photon as a particle with energy E = hv emerged. The constant h connects the wave (v) and particle (E) aspects of light. Louis de Broglie proposed that the wave-particle duality is not a monopoly of light but is a universal characteristic of nature which becomes evident when the magnitude of h cannot be neglected. He thus brought out a second fundamental fact, usually referred to as the wave nature of matter. This means that in certain experi- ments beams of particles with mass give rise to interference and diffraction phe- nomena and exhibit a behavior very similar to that of light. Although such effects were first produced with electron beams, they are now commonly observed with slow neutrons from a reactor. When incident on a crystal, these behave very much like X rays. Heavier objects, such as entire atoms and molecules, have also been shown to exhibit wave properties. Although one sometimes speaks of matter waves, this term is not intended to convey the impression that the particles themselves are oscillating in space. From experiments on the interference and diffraction of particles, we infer the very simple law that the infinite harmonic plane waves associated with the motion of a free particle of momentum p propagate in the direction of motion and that their (de Broglie) wavelength is given by ast (13) B This relation establishes contact between the wave and the particle pictures. The finiteness of Planck's constant is the basic point here. For if h were zero, then no1 Quantum Theory and the Wave Nature of Matter 3 matter what momentum a particle had, the associated wave would always correspond to A = 0 and would follow the laws of classical mechanics, which can be regarded as the short wavelength limit of wave mechanics in the same way as geometrical optics is the short wavelength limit of wave optics. A free particle would then not be diffracted but would go on a straight rectilinear path, just as we expect classically. Let us formulate this a bit more precisely. If x is a characteristic length involved in describing the motion of a body of momentum p, such as the linear dimension of an obstacle in it path, the wave aspect of matter will be hidden from our sight, if aah aay x ice., if the quantum of action h is negligible compared with xp. Macroscopic bodies, to which classical mechanics is applicable, satisfy the condition xp >> h extremely well. To give a numerical example, we note that even as light a body as an atom moving with a kinetic energy corresponding to a temperature of T = 10~* K still has a wavelength no greater than about a micron or 10~° m! We thus expect that classical mechanics is contained in quantum mechanics as a limiting form (h—>0). Indeed, the gradual transition that we can make conceptually as well as prac- tically from the atomic level with its quantum Iaws to the macroscopic level at which the classical laws of physics are valid suggests that quantum mechanics must not only be consistent with classical physics but should also be capable of yielding the classical laws in a suitable approximation. This requirement, which serves as a guide in discovering the correct quantum laws, is called the correspondence principle. Later we will see that the limiting process which establishes the connection between quantum and classical mechanics can be exploited to give a useful approximation for quantum mechanical problems (see WKB approximation, Chapter 7). ‘We may read (1.3) the other way around and infer that, generally, a wave that propagates in an infinite medium has associated with it a particle, or quantum, of momentum p = h/. If a macroscopic wave is to carry an appreciable amount of momentum, as a classical electromagnetic or an elastic wave may, there must be associated with the wave an enormous number of quanta, each contributing a very small amount of momentum. For example, the waves of the electromagnetic field are associated with quanta (photons) for which the Bohr-Einstein relation E = hv holds. Since photons have no mass, their energy and momentum are according to relativistic mechanics related by E = cp, in agreement with the connection between energy (density) and momentum (density) in Maxwell’s theory of the electromag- netic field. Reversing the argument that led to de Broglie’s proposal, we conclude that (1.3) is valid for photons as well as for material particles. At macroscopic wavelengths, corresponding to microwave or radio frequency, a very large number of photons is required to build up a field of macroscopically discernible intensity. Such a field can be described in classical terms only if the photons can act coher- ently. As will be discussed in detail in Chapter 23, this requirement leads to the peculiar conclusion that a state of exactly n photons cannot represent a classical field, even if n is arbitrarily large. Evidently, statistical distributions of variable numbers of photons must play a fundamental role in the theory. The massless quanta corresponding to elastic (e.g., sound) waves are called phonons and behave similarly to photons, except that c is now the speed of sound, and the waves can be longitudinal as well as transverse. It is important to remember that such waves are generated in an elastic medium, and not in free space.4 Chapter 1 Introduction to Quantum Mechanics 2. The Wave Function and Its Meaning. As we have seen, facing us at the outset is the fact that matter, say an electron, exhibits both particle and wave aspects.” This duality was described in deliberately vague language by saying that the de Broglie relation “‘associates”” a wavelength with a particle momentum. The vagueness re- flects the fact that particle and wave aspects, when they show up in the same thing such as the electron, are incompatible with each other unless traditional concepts of classical physics are modified to a certain extent. Particle traditionally means an object with a definite position in space. Wave means a pattern spread out in space and time, and it is characteristic of a wave that it does not define a location or position sharply. Historically, the need for a reconciliation of the two seemingly contradictory concepts of wave and particle was stressed above all by Bohr, whose tireless efforts at interpreting the propositions of quantum mechanics culminated in the formulation of a doctrine of complementarity. According to this body of thought, a full descrip- tion and understanding of natural processes, not only in the realm of atoms but at all levels of human experience, cannot be attained without analyzing the comple- mentary aspects of the phenomena and of the means by which the phenomena are observed. Although this epistemological view of the relationship between classical and quantal physics is no longer central to the interpretation of quantum mechanics, an appreciation of Bohr’s program is important because, through stimulation and provocation, it has greatly influenced our attitude toward the entire subject.* How a synthesis of the wave and particle concepts might be achieved can, for a start, perhaps be understood if we recall that the quantum theory must give an account of the discreteness of certain physical properties, e.g., energy levels in an atom or a nucleus. Yet discreteness did not first enter physics with the Bohr atom. In classical macroscopic physics discrete, ‘‘quantized,’” physical quantities appear naturally as the frequencies of vibrating bodies of finite extension, such as strings, membranes, or air columns, We speak typically of the (natural) modes of such sys- tems. These phenomena have found their simple explanation in terms of interference between incident and reflected waves. Mathematically, the discrete behavior is en- forced by boundary conditions: the fixed ends of the string, the clamping of the membrane rim, the size and shape of the enclosure that confines the air column. Similarly, it is tempting to see in the discrete properties of atoms the manifestations of bounded wave motion and to connect the discrete energy levels with standing waves. In such a picture, the bounded wave must somehow be related to the con- finement of the particle to its ‘torbit,’” but it is obvious that the concept of an orbit as a trajectory covered with definite speed cannot be maintained. A wave is generally described by its velocity of propagation, wavelength, and amplitude. (There is also the phase constant of a wave, but, as we shall see later, for one particle this is undetermined.) Since in a standing wave it is the wavelength (or frequency) that assumes discrete values, it is evident that if our analogy is mean- ingful at all, there must be a correspondence between the energy of an atom and the 71 will be convenient to use the generic term electron frequently when we wish to place equal emphasis on the particle and wave aspects of a constituent of matter. The electron has been chosen only for definiteness of expression (and historical reasons). Quantum mechanics applies equally to protons, neutrons, mesons, quarks, and so on. *For a compilation of original articles on the foundations of quantum mechanics and an extensive bibliography, see Wheeler and Zurek (1985). Also see the resource letters in the American Journal of Physics: DeWitt and Graham (1971), and L. B. Ballentine (1987).2. The Wave Function and Its Meaning 5 wavelength of the wave associated with the particle motion. For a free particle, one that is not bound in an atom, the de Broglie formula (1.3) has already given us a relationship connecting wavelength with energy (or momentum). The connection between wavelength and the mechanical quantities, momentum or energy, is likely to be much more complicated for an electron bound to a nucleus as in the hydrogen atom, or for a particle moving in any kind of a potential. Erwin Schrisdinger dis- covered the wave equation that enables us to evaluate the “proper frequencies”” or eigenfrequencie’ of general quantum mechanical systems. The amplitudes or wave fields, which, with their space’ and time derivatives, appear in the Schrédinger equation, may or may not have directional (i.e., polariza- tion) properties. We will see in Chapter 16 that the spin of the particles corresponds to the polarization of the waves. However, for many purposes the dynamical effects of the spin are negligible in first approximation, especially if the particles move with nonrelativistic velocities and are not exposed to magnetic fields. We will neglect the spin for the time being, much as in a simple theory of wave optical phenomena, where we are concerned with interference and diffraction or with the geometrical optics limit, the transverse nature of light can often be neglected. Hence, we attempt to build up quantum mechanics with mass (different from zero) first by use of scalar waves. For particles with zero spin, for example, pions and K mesons, this gives an appropriate description. For particles with nonzero spin, such as electrons, quarks, nucleons, or muons, suitable corrections must be made later. We will also see that the spin has profound influence on the behavior of systems comprised of several, or many, identical particles. Mathematically, the scalar waves are represented by a function Y(x, y, z 1), which in colorless terminology is called the wave function, Upon its introduction we immediately ask such questions as these: Is ya measurable quantity, and what precisely does it describe? In particular, what feature of the particle aspect of the particle is related to the wave function? We cannot expect entirely satisfactory answers to these questions before we have become familiar with the properties of these waves and with the way in which ‘is used in calculations, but the questions can be placed in sharper focus by reex- amining the de Broglie relation (1.3) between wavelength, or the wave number k 2m/n, and particle momentum: 2a h Dosa ne ie as) Suppose that a beam of particles having momentum p in the x direction is viewed from a frame of reference that moves uniformly with velocity v, along the x axis For nonrelativistic velocities of the particles and for u