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pcos oi Ueg Lol'ag Richard L. Liboff INTRODUCTORY QUANTUM MECHANICS Richard L. Liboff Cornell University rn vw ADDISON: YESLEY PUBLISHING COMPANY Reading, Massachusetts: Meulo Park, California-New York Don Mills, Ontario- Wokingham, England- Amsterdam Bonn -Sydnev -Singapore- Tokyo: Madrid Bogota -Santiago-San Juan INTRONUCTORY QUANTUM MECHANICS Previously published by Holden-Day, Inc, Copyright 1980 by Addison-Wesley Publishing Company, Ie [All sights ronerved, No part of this publication may be reproduc Stored in a retticyal system, vt transmitted, in any form of by ary tneans, electronic, mechanical, photocopying, recording, or othetwisc, without the prior sritten permission of the publisher. Printed in the United Staces of Ameriea. Published simultaneously in Canada, ISBN 0-201-12221-9 ABCDEFGHIJ-HA-8987 PREFACE This work has emerged from an undergraduate course in quantum mechanics which I have taught for the past number of years. The material divides naturally inte two major components. In Part 1, Chapters 1 fo 8, fndamental concepts are developed and these are applied to problems predominantly in one dimension, In Part 11, Chapters 9 to 14, further development of the theory is pursued together with applications to problems in three dimens Part [ begins with a review of elements of classical mechanics which are important to a firm understanding of quantum mechanics. Lhe second chapter continues with a historical review of the early experiments and theoties of quan- tum mechanics. The postulates of quantum mechanics are presented in Chapter 3 together with development of mathematical notions contained in tke statements of these postulates, The time-dependent Schridinger equation emerges in this chapter. Solutions to the elementary problems of a free particle and thal of a parti in @ one-dimensional box are employed in Chupter 4 in the descriptions of Hilbert space and Hermitian operators. These abstract mathematical nouions are de- soribed in geometricul language which I have found in most instances to be easily understood by students The cornerstone of this introductory material is the superposition principle, described in Chapter 5, Tn this principle the student comes to grips with the inherent dissimilarity between classical and quantum mechatics, Commutation relations and their relation to the uncertainty principle are also described, as well ay the concept of a complete set of commuting observables, Quantuzn comer ples are presented in Chapter 6. Applications to important problems in one dimension are given in Chapters 7 and 8 Creation and annihilation operators are introduced in algebraic construction of the eigenstates of a harmonic oscillator, Transmission and reflection cocff- cients are obtained for one-dimensional barrier problems. Chapter 8 is devoted primarily to the problem of a parliele in a periodic potential. The band structure of the energy spectrum for this configuration is obtained and related to the theory of electrical conduction in solids Purt Il begins with a quantum mechanical description of angular momentum. on Fundamental commutator relations between the Cartesian components of angular momentum serve to generate cigenvalues. These commutator relations further indivate compatibility between the square of tota angular momentum and oaly one of ils Cartesian components. It is through these commutator relations that i dis tinction between spin and orbital angular momentum emerges, Properties of angu- lar momertum developed in this chapter are reemployed throughout the text In Chapter 10 the Schrédinger equation for a particle moving in three uimen- sions is unalyzed and applied to the examples of a free particle, u charged particle in 4 magnetic field, and the hydrogen atom. In Chapter 11 the theory of representations und elements of matrix mechanics are eveloped for the purpose of obtaining a more complete description, of spin angular momentum. A host of problems involving a spinning electron in a magnetic field are presented. The theory of the density matrix is developed and applied to a beam of spinning electrons: In Chapter 12 preceding formalisms are employed in conjunction with the Puuli principle, in the analysis of some basic problems in atomic and molecular physics, Also included in this chapter are brief descriptions of the quantum models for superconductivity and superfluidity Perturbation theory is developed in Chapter 13, Among the many applica- tions included is that of the problem of a patticle in a periodic potential, consid. ered previously in Chapter 8, Harmonic perturhation theory is applied in Kin- stem’s derivation of the Planck radiation formula and the theory of the laser. The text concludes with a brief chapter devoted to an elementary description of the quantum (heory of scattering, Problems abound throughout the text, and many of them include solutions Figures are also plentiful and hopefully lend to the instructional quality of the writing, A smnall introductory paragraph precedes each chapter and serves to knit the matcrial together. A fist of symbols appears before the appendixes Interspersed throughout the text, especially in the problems, one finds con cepts from other disciplines with which the student is assumed t@ have some familiarity, These include, for example: dynamics, thermodynamics, elementary relativity, and electrodynamics. This policy follows the spirit of one of my cherished late professors, Hartmut Kalman: “Physics is not a sausage that one cuts into tittle pieces.” Ltrusl that a mastery of the convepls and their applications as prevented in this work will form a solid foundation on which lo build 2 more complete study of quantum mechanics Many individuats have been helpful in the prepuration of this text. I remain indebted to these kind, patient, and well-informed collegues: D. Heffernan, M Guillen, E, Dorchak, D. Faulconer, G. Lasher, I. Nebenzahl, M. Nelkin, F, Fine. R. McFarlane, C. Tang, K. Gottfried, and G, Severe. Sincere gratitude is exe tended to my publisher, Frederick H. Murphy, for his undaunted patience and. confidence in this work, During visits at the Université Libre de Bruneltes and later at dhe Université de Paris XI-Centre d’Orsay, [was able to work on material retated to this text. 1 am extremely grateful to Professor 1. Prigogine and Professor I. L. Deleroix for the intellectual freedom accorded me during these occasions RT, TAROFF Preface pare Chapter 1 Chapter 2 Chapter 3 CONTENTS ELEMENTARY PRINCIPLES AND APPLICATIONS TO PROBLEMS IN ONE DIMENSION Review of Concepts of Classical Mechat L1 Generalized or Good" Coordinates 12 Energy, the Hamiltonian, and Angular Momentum 1.3. The State of a System 1.4 Properties of the Ong-Dimensional Potential Function Historical Review: Experiments and Theories 21 Dates 2.2, ‘The Work of Planck. Blackbody Radiation 2.3 The Work of Einstein. The Photoelectric Effect 2.4. The Work of Bohr. A Quantum Theory of Atomic States 28 Waves versus Particles 2.6 The de Broglie Hypothesis and the Davisson-Germer Experiment The Work of Heisenberg. Uncertainty as a Cornerstone of Natural Law 2.8 The Work of Born, Probability Waves 2.4 Semiphilosophical Epilogue to Chapter 2 The Postulates of Quantum Mechanies. Operators, Figenfunctions, and Eigenvalues 3.1 Observables and Operators 3.2, Measurement in Quantum Mechanics 2.3 The State Function and Expectation Values 3.4 Time Development of the State Function 3.5 Solution lo the Initial Value Problem in Quantum Mechanics all covrenty Chapter 4 Chapter § Chapter 6 Chapter 7 Prepuratory Concepts. Function Spaces and Hermitian Operators 4.1 Particle ina Box and Further Remarks on Normalization 4.2, The Bohr Correspondence Principle 4.3 Direc Notation 4.4 Hilbert Space 4.8 Hermitian Operators 4.6 Properties of Hermitian Operators Superposition and Compatible Observables 5.1. The Superposition Principle 5.2. Commutator Relations in Quantum Mechanics 5.2. More on the Commutator Theorem 5.4 Commutator Relations and the Uncertainty Principle 5.5 ~Comptete’’ Sets of Commuting Observables ‘Time Deselopmeat, Conservation Theorems, and Parity 6.1. Time Development of State Functions. 6.2. Time Development of Expectation Values 6.2 Conservation of Energy, Linear and Angular Momentum 6.4 Conservation of Parity Additional One-Dimensional Problems. Bound und Unbound States 7.1. General Properties of the One-Dimensional Schrodinger Equation 7.2. The Harmonie Oscillator 7.3 Figenfunctions of the Harmonic Oscillator Hamiltonian 4 The Harmonic Oscillator in Momentum Space 5 Unbound States 6 One-Dimensional Barrier Problems 7 The Rectangular Barrier, Tunneling R The Ramsauer Effect 7.9 Kinetic Properties of a Wave Packet Scattered from a Potential Barrier 7.10 The WKB Approximation 36 86 a 8 94 ree 104 109 109 124 mai 1B4 nt M43 143 159 163 167 76 Chapter § Finite Potential Well, Periodic Lattice, and Some Simple Eroblems with Two Degrees of Freedom 256 8.1 The Finite Potential Well 2 8.2 Periodic Lattice. Energy Gaps 267 8.3. Standing Waves at (he Band Edges 28a 8.4 Brief Qualitative Description of the Theory of, Conduction in Solids 291 8.5 Two Beads ona Wire and a Particle in a Two-Dimensional Box 294 8.6 Two-Dimensional Harmonic Oscillator 300 vakr Il FURTHER DEVELOPMENT OF THE THEORY AND APPLICATIONS TO PROBLEMS IN THREE, DIMENSIONS 307 Chapter 9 Angular Momentum 309 9.4 Basic Properties 310 9.2 walues of the Angular Munsentum Operators 318 9.3. Eigenfunctions of the Orbital Angular Momentum Operators £¢ and f., 326 9.4 Addition of Angulat Momentum 345 9.5 Total Angular Momentum for Two or More Flectrons 353 Chapter 10 Problems in Three Dimensions 359 10.1. The Free Particle in Cartesian Coordinates 359 10.2 The Free Particle in Spherical Coordinates 365 10.3 The Free-Particle Radial Wavefunction 37 10.4 A Charged Particle in a Magnetic Field 380 10.5. The Two-Perticle Problem 383 1.6 The Hydrogen Atom 394 10,7 Elementary Theory of Rediation 4a) Chapter 11 Elements of Matrix Mechanics. Spin Wavefunctions 418 11.1. Basis and Representations ag 11.2 Elementary Matrix Properties 426 11.3. Unitary and Similarity Transformations in Quantum Mechanics 430 114 The Energy Representation 36 1.5. Angular Momentum Matrices a My CONTENTS Chapter 12 Chapter 13 Chapter 14 List of Symbols 11.6 The Pauli Spin Matrices 117 Free-Particle Wavefunetions, Including Spin 11.8 The Magnetic Moment of an Electron 11.9 Precession of an Electron in a Magnetic Field 11.10 The Addition of Two Spins 11.11 The Density Matrix Application to Atomic and Molecular Physics. Elements of Quantum Statistics 12.1. The Total Angular Momentum, J 12.2. One-Electron Atoms 12,3 The Pauli Principle 12.4 The Periadie Table 12.5 The Slater Determinant 12.6 Application of Symmetrization Rules to the Helium Alom 12.7 The Hydrogen and Deuterium Molecule 12.8 Brief Description of Quantum Models for Superconductivity and Superfiuidity Perturbation Theory 13.1 ‘Time-Independent, Nondegenerate Perturbation Theory 13.2. Time-Independent, Degenerate Perturbation Theory 13.3 The Stark Effect 13.4. The Nearly Free Electron Model 13.5. Time-Dependent Perturbation Theory (3.6 Harmonic Perturbation 13.7 Application of Harmonic Perturbation Theory 12.8. Selective Perturbations in Time Scattering in Three Dimensions 14.1 Partial Waves 14.2, 5-Wave Scattering 14.3 Center-of-Mass Frame 14.4 The Born Approximation 627

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