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Table of contents :
Introductory Quantum Mechanics
HalfTitle
PrenticeHall Physics Series
TitlePage
Copyright
Preface
Contents
I Mathematical Preliminaries
1. Introduction
2. Differential Operators
3 The Operator minus dsquare over dxsquare
4 The Operator minus dsquare over dxsquare plus xsquare
5 The Operator minusi times derivative operator, x and c
6. Simultaneous Eigenfunctions
7. Degenerate Eigenvalues
8. Orthogonal Sets of Functions
II Remarks On Classical Mechanics
9. Hamiltonian Functions
10. Examples of Classical Motion
11. Distribution Functions
12. Probability Packets
III Elements Of The Schroedinger Method; One Dimension
13. Two Assumptions
14. Schroedinger Operators
15. Energy Levels of an Oscillator
16. Schroedinger Functions
17. Specification of States
18. Energy States of an Oscillator
19. Composition of States
20. Resolution of States
21. Probability Packets
22. Coherent and Incoherent Superpositions of States
23. Heisenberg Inequalities
24. The Heisenberg Principle
25. Kennard Packets
26. Summary
IV Further Problems In The Schroedinger Method
27. Linear Momentum
28. The Free Particle in One Dimension
29. OneDimensional Rectangular Potential Wells
30. The OneDimensional Box
31. Radiative Transitions
32. Properties of the OneDimensional First Schroedinger Equation
V Approximate Methods For Treating The OneDimensional Schroedinger Equation
33. Numerical Approximations
34. Expansions in Powers of h
35. A Variation Method
36. A Perturbation Method for Nondegenerate States
VI OneDimensional Probability Currents And De Broglie Waves
37. Probability Current
38. OneDimensional Potential Barriers
39. Virtual Binding
40. Waves
41. De Broglie Waves
42. A Vibrating String and a Particle in a Box
VII Constants Of Motion
43. Time Derivatives of Averages of Dynamical Variables
44. Time Derivatives of Dynamical Variables
45. Constants of Motion
46. Dirac's Expansion Theorem
47. Dynamical Variables Having no Classical Analogues
48. Constants of Motion Having no Classical Analogues
49. Potential Lattices and Energy Bands
VIII Remarks On The Momentum Method
50. The Framework of the Momentum Method
51. Energy Levels of an Oscillator
52. Concluding Remarks
IX Linear Operators And Matrices
53. Mappings of a Plane
54. Representation of Mappings by Means of Matrices
55. Different Coordinate Frames May Yield Different Representatives for a Given Operator
56. Matrices and Vectors
57. NDimensional Spaces
58. Further Remarks on Matrices
59. Function Space
60. Representation of Differential Operators by Means of Matrices
61. Concluding Remarks
X Elements Of The Heisenberg Method
62. Heisenberg Matrices
63. Heisenberg Matrices (Continued)
64. The Heisenberg Method
65. Energy Levels of an Oscillator
66. Diagonalization of Matrices
67. Approximate Diagonalization of Matrices
68. The Matrix Perturbation Method for Nondegenerate States
69. More Matrix Algebra
70. The Heisenberg Representation of States
XI Remarks On The Symbolic Method
71. Symbolic Operators and Operands
72. Energy Levels of an Oscillator
73. The Symbolic phi's
XII Problems In ThreeDimensional Motion; The Schroedinger Method
74. Mathematical Preliminaries
75. Remarks on Classical Mechanics
76. Elements of the Schroedinger Method
77. Elements of the Schroedinger Method (Continued)
78. Central Fields
79. The Free Particle; Polar Quantization
80. The Bohr Formula for the Hydrogen Atom; Fixed Nucleus
81. The Bohr Formula for the Hydrogen Atom; Free Nucleus
82. The Fine Structure of the Hydrogen Levels
83. Relativity Corrections for Hydrogen
XIII Elements Of Pauli's Theory Of Electron Spin
84. The ElectronSpin Hypothesis
85. Possible Values of Components of Angular Momenta
86. The Pauli Operators and Operands
87. The Simultaneous Eigenpsi's of Jz, Lsquare, and Jsquare
88. SpinOrbit Interaction and the Spin Correction
89. The SpinandRelativity Correction for Hydrogen
90. Space Functions and Spin Functions
XIV Elements Of Dirac's Theory Of The Electron
91. The Dirac Equation for an Electron in an Electrostatic Field
92. The Dirac gamma's
93. The Existence of a 'Spin' Angular Momentum
94. Constants of Motion for a Central Field
95. The Radial Equations
96. The Energy Levels of the Hydrogen Atom.
97. The Normal State of the Hydrogen Atom
Appendix
A few formulas involving Legendre functions and spherical harmonics
Index
Back Cover
INTRODUCTORY QUANTUM MECHANICS
PRENTICEHALL PHYSICS SERIES
INTRODUCTORY QUANTUM MECHANICS . BY
VLADIMIR ROJANSKY PROFESSOR OF PHYSICS UNION COLLEGE
ENGLEWOOD CLIFFS,
N. J.
PRENTICEHALL, INC.
Copyright, 1938, by PRENTICEHALL, INC. Englewood Cliffs, N. J. All rights reserved. No part of this book may be reproduced in any form, by mimeograph or any other means, without permission in writing from the publishers. First printing . . . October, 1938 Second printing . . . . April, 1942 Third printing. . . . . January, 1946 Fourth printing . . September, 1946 Fifth printing . . November, 1947 Sixth printing . . . . . August, 1950 Seventh printing. . . . January, 1956
PRINTED IN THE UNITED STATES OF AMERICA 50164
PREFACE This book is addressed to the reader who wishes to become familiar with some of the simpler physical ideas and mathematical methods of quantum mechanics, either because of their own intrinsic interest, or in preparation for a comprehensive and critical survey of the theory, or for a study of its applications. Although written primarily for graduate and advanced undergraduate students beginning a study of quantum mechanics, the text should also be of service to persons who are already acquainted with some of the concepts and results of the theory, and who wish to inquire into its formulation. The prerequisites are the elements of calculus and of ordinary differential equations, and a recognition of the failure of classical mechanics in the domain of atomic physics. The reader's acquaintance with partial differential equations and with matrices is assumed to be slight at best. Quantum mechanics is a large subject, and even introductory courses in it differ greatly in content and emphasis. Certain rudimentary topics, however, come up in almost every quantum mechanics course; and it is to some of these topics that this book is confined. I hope that its plan will ,be found convenient for the interpolation and addition of further material in the classroom. The discussion proceeds from the outset toward a coherent view of the main mathematical forms of the theory; but the exposition makes little pretense to rigor and often aims to make plausible rather than to prove. The arrangement of the book is essentially as follows: CHAPTERS
Mathematical topics .......................................... . I and IX ( the classical method ................... . II . I the Schroedinger (wave) method ....... . IIIVII P ro bl ems m oneVIII t" ,J the momentum met h o d ................. . . . d 1mens10na1 mo 10n I t h e H e1sen · b erg (matrix · ) met h o d ....... . x l the Dirac (symbolic) method .......... . XI Problems in threedimensional motion; the Schroedinger method. XII XIII El t . f the Pauli theory .............................. . ec ron spm \ the Dirac theory .............................. . XIV
The reader interested primarily in the Schroedinger method may take up Chapter Xli directly after Chapter VII; §§53 to 58 of Chapter IX and §69 of Chapter X will then prepare him for the two chapters on electron spin. v
vi
PREFACE
The exercises provide drill in the material already covered, tie up some of the loose ends in the discussion of the text, and clear the ground for the topics to come. Most of the exercises are short, and a good understanding of the text should enable the reader to do many of them mentally. The main results and proofs presented here are of course well known to theoretical physicists, while most of the supplementary arguments can perhaps also be found elsewhere, between the lines if not in print. The courses of Professor J. H. Van Vleck, Professor E. U. Condon, Professor P. A. M. Dirac, and Professor H. P. Robertson, various lectures by others, a few letters, and many conversations have all put their imprint on these pages. Through their reactions to different ways of presenting various topics, the persons who attended my own classes have also played a large part in shaping this book. The entire manuscript was thoroughly improved by my colleague Professor A. H. Fox, and further important refinements were made by Dr. Condon, Editor of the PrenticeHall Physics Series. In the handling of the manuscript and the preparation of the diagrams I had student asistance sponsored by the N. Y. A. To the editorial department of PrenticeHall, Inc. I am indebted for sympathetic cooperation,
V.
ROJANSKY
CONTENTS CllAPTEB
l.
PAGE
MATHEMATICAL PRELIMINARIES. . . . . . . . . . . . . . .
1. 2. 3. 4. 5. 6. 7. 8.
II.
REMARKS ON CLASSICAL MECHANICS...........
9. 10. 11. 12.
III.
Hamiltonian functions.. . . . . . . . . . . . . . . . . . . . . Examples of classical motion. . . . . . . . . . . . . . . . . Distribution functions. . . . . . . . . . . . . . . . . . . . . . Probability packets. . . . . . . . . . . . . . . . . . . . . . . . .
ELEMENTS OF THE SCHROEDINGER METHOD; ONE DIMENSION. . . . . . . . • . . . . . . . . . . . . . . . .
13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26.
IV.
Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Differential operators. . . . . . . . . . . . . . . . . . . . . . . The operator d2/dx 2 • • • • • • • • • • • • • • • • • • • • • . • The operator d2/dx 2 + x2 • . • • • • . • • • • • • • • . • • The operators io /ox, x, and c. . . . . . . . . . . . . . Simultaneous eigenfunctions. . . . . . . . . . . . . . . . . Degenerate eigenvalues..................... Orthogonal sets of functions. . . . . . . . . . . . . . . . .
Two assumptions........................... Schroedinger operators...................... Energy levels of an oscillator. . . . . . . . . . . . . . . . Schroedinger functions..... . . . . . . . . . . . . . . . . . Specification of states. . . . . . . . . . . . . . . . . . . . . . . Energy states of an oscillator. . . . . . . . . . . . . . . . Composition of states. . . . . . . . . . . . . . . . . . . . . . . Resolution of states ......................... Probability packets. . . . . . . . . . . . . . . . . . . . . . . . . Coherent and incoherent superposition of states ................................... Heisenberg inequalities.... . . . . . . . . . . . . . . . . . . The Heisenberg principle. . . . . . . . . . . . . . . . . . . . Kennard packets ........................... Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
FURTHER PROBLEMS IN THE SCHROEDINGER METHOD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1 1 2 11 16 27 28 31 32 43 43 46 51 63
72 72 77 81 85 89
93 106 109 112 117 118 122 125 128
130 27. Linear momentum .......................... 130 28. The free particle in one dimension. . . . . . . . . . . . 144 vii
viii
CONTENTS
CHAPTER
PAGE
29. 30. 31. 32.
V.
Onedimensional rectangular potential wells.. . The onedimensional box. . . . . . . . . . . . . . . . . . . . Radiative transitions ....................... Properties of the onedimensional first Schroedinger equation.. . . . . . . . . . . . . . . . . . . . . . . . .
150 157 162 168
APPROXIMATE METHODS FOR TREATING THE 0NE
180 . 1 approx1mat10ns . . N umer1ca .................. . 180 Expansions in powers of h. . . . . . . . . . . . . . . . . . . 186 A variation method. . . . . . . . . . . . . . . . . . . . . . . . . 193 A perturbation method for nondegenerate states ................................... 198
DIMENSIONAL SCHROEDINGER EQUATION ....
33 . 34. 35. 36.
VI.
ONEDIMENSIONAL PROBABILITY CURRENTS AND
Probability current ......................... Onedimensional potential barriers........ . . . . Virtual binding. . . . . . . . . . . . . . . . . . . . . . . . . . . . Waves .................................... De Broglie waves ........................... A vibrating string and a particle in a box... . . .
207 207 211 222 230 235 239
CONST ANTS OF MOTION. . . . . . . . . . . . . . . . . . . . . . .
24 7
DE BROGLIE WAVES. . . . . . . . . . . . . . . . . . . . .
37. 38. 39. 40. 41. 42.
VII.
43. Time derivatives of averages of dynamical variables. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44. Time derivatives of dynamical variables... . . . . . 45. Constants of motion. . . . . . . . . . . . . . . . . . . . . . . . . ' s expans10n . t h eorem .................. . 46 . D irac 47. Dynamical variables having no classical analogues ................................... 48. Constants of motion having no classical analogues ................................... 49. Potential lattices and energy bands. . . . . . . . . .
VIII.
REMARKS ON THE MOMENTUM METHOD. . . . . . . .
IX.
LINEAR OPERATORS AND MATRICES. . . . . . . . . . . .
247 250 257 260 262
266 269
277 50. The framework of the momentum method.. . . . 277 51. Energy levels of an oscillator. . . . . . . . . . . . . . . . 281 52. Concluding remarks. . . . . . . . . . . . . . . . . . . . . . . . 282
285
53. Mappings of a plane. . . . . . . . . . . . . . . . . . . . . . . . 285 54. Representation of mappings by means of matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
CONTENTS
PAGE
CHAPTER
55. Different coordinate frames may yield different representatives for a given operator ......... 56. Matrices and vectors. . . . . . . . . . . . . . . . . . . . . . . 57. Ndimensional spaces. . . . . . . . . . . . . . . . . . . . . . . 58. Further remarks on matrices. . . . . . . . . . . . . . . . . 59. Function space. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60. Representation of differential operators by means of matrices. . . . . . . . . . . . . . . . . . . . . . . . 61. Concluding remarks. . . . . . . . . . . . . . . . . . . . . . . . .
x.
lX
ELEMENTS OF THE HEISENBERG METHOD. . . . . . .
62. 63. 64. 65. 66. 67. 68.
306 309 320 322 327 334 340 341 341 347 353 355 360 368
Heisenberg matrices. . . . . . . . . . . . . . . . . . . . . . . . Heisenberg matrices (continued) .... .......... The Heisenberg method. . . . . . . . . . . . . . . . . . . . . Energy levels of an oscillator. . . . . . . . . . . . . . . . Diagonalization of matrices .................. Approximate diagonalization of matrices. . . . . . The matrix perturbation method for nondegenerate states. . . . . . . . . . . . . . . . . . . . . . . . . 37 4 69. :More matrix algebra ........................ 380 70. The Heisenberg representation of states ....... 386
XI.
REMARKS ON THE SYMBOLIC METHOD . . . . . . . . . .
XII.
PROBLEMS IN THREEDIMENSIONAL MOTION; THE
391 71. Symbolic operators and operands. . . . . . . . . . . . . 391 72. Energy levels of an oscillator. . . . . . . . . . . . . . . . . 393 73. The symbolic 's. . . . . . . . . . . . . . . . . . . . . . . . . . . 397
401 :Mathematical preliminaries. . . . . . . . . . . . . . . . . . 401 Remarks on classical mechanics .............. 416 Elements of the Schroedinger method. . . . . . . . . 426 Elements of the Schroedinger method (continued) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 440 Central fields. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 448 The free particle; polar quantization .......... 452 The Bohr formula for the hydrogen atom; fixednucleus ............................. 457 The Bohr formula for the hydrogen atom; free nucleus. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465 The fine structure of the hydrogen levels. . . . . . 470 Relativity corrections for hydrogen ........... 472
SCHROEDINGER NlETHOD . . . . . . . . . . . . . . . . . .
74. 75. 76. 77. 78. 79. 80. 81. 82. 83.
CONTENTS
x CHAPTER
XIII.
PAGE
ELEMENTS OF
P AULI's
THEORY OF ELECTRON
477 The electronspin hypothesis ................ 477 Possible values of components of angular momenta ................................ 479 The Patili operators and operands. . . . . . . . . . . . 482 The simultaneous eigenl/,''s of Js, L2, and J 2 ••. 490 Spinorbit interaction and the spin correction .. 496 The spinandrelativity correction for hydrogen 501 Space functions and spin functions. . . . . . . . . . . 503
SPIN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
84. 85. 86. 87. 88. 89. 90.
XIV.
ELEMENTS OF DIRAC'S THEORY OF THE ELECTRON . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
505
91. The Dirac equation for an electron in an electrostatic field. . . . . . . . . . . . . . . . . . . . . . . . . 92. The Dirac u's. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93. The existence of a 'spin' angulat momentum.. . 94. Constants of motion for a central field ........ 95. The radial equations. . . . . . . . . . . . . . . . . . . . . . . . 96. The energy levels of the hydrogen atom. . . . . . . 97. The normal state of the hydrogen atom .......
505 512 513 514 518 521 525
~PPENDIX. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
531
[NDEX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
535
NoTE: The numbering of equations, exercises, tables, and figures is lescribed on page 27 (footnote), page 29 (footnote), and page 74. Latin and Greek symbols are listed in the index, the latter in the alpha)etical order of their English names. Mathematical symbols not admitting of alphabetical listing are grouped n the index under the heading 'symbols.'
INTRODUCTORY QUANTUM MECHANICS
CHAPTER
I
MATHEMATICAL PRELIMINARIES 1. Introduction
In 1900 Max Planck introduced the idea of a quantum of action. In 1905 Albert Einstein suggested the waveparticle duality of radiation. In 1913 Niels Bohr formulated the first substantially successful theory of atomic phenomena. In 1923 Louis de Broglie injected the waveparticle duality into the theory of matter. And a quarter of a century after Planck's discovery came quantum mechanics. Quantum mechanics was invented twice: first by ·werner Heisenberg, and a few months later by Erwin Schroedinger. But Heisenberg's matrix mechanics and Schroedinger's wave mechani_cs were so different that for a time their mathematical equivalence remained unrecognized. 1 Then began the widespread and remarkably successful activity in developing the new mechanics for application to a growing range of problems in physics and chemistry. As the theory became better understood, generalized and clarifying formulations of it were put forward, notably by Paul Adrien Maurice Dirac and by Pascual Jordan. A relativistic quantum mechanics of the electron was constructed by Dirac. A mathematically rigorous formulation of the theory was given by Johann von Neumann. And, as a result of all these developments, quantum mechanics is today not only much wider in scope than it was at its inception, but also more compact, more orderly, and easier to learn. The mathematics required for the quantummechanical treatment of the motion of a particle is more elaborate than that necessary for the classical treatment of particle motion, so that a person beginning the study of the quantummechanical behavior of a particle may find his mathematical preparation quite inadequate, even though he is well versed in the corresponding classical For a vivid account of the early history of quantum mechanics see J. H. Van Vleck's reports in Jour. Optical Soc. Am. and Rev. Sci. Instr., 14, 108 (1927), and 16, 301 (1928). 1
1
2
MATHEMATICAL PRELIMINARIES
§2
problem. For this reason, whenever such background cannot be expected to have been acquired in connection with a study of classical particle motion, we shall make it a part of our aim to develop the mathematical background necessary for the work. But the purely mathematical discussion will be restricted to the necessary minimum, and will often forego mathematical rigor. In order that the reader may not be confronted concurrently with two quite distinct tasksthat of becoming acquainted with certain standard mathematical methods, and that of learning the use and the physical significance of these methods in quantum mechanicswe devote this chapter to an elementary account of the mathematical methods involved in the physical considerations of Chapter III, where quantummechanical ideas will first be introduced. 2. Differential Operators
A central part in the mathematical structure of quantum mechanics is played by operators of several types; of these we shall now consider the socalled differential operators, which are used in the theory of ordinary differential equations. Among the various mathematical operations that can be performed on a function u(x) of the variable x [such as u(x) = x3 and u(x) = sin x] are differentiation of u(x) with respect to x, multiplication of u(x) by x, and multiplication of u(x) b:Y a constant, say c. In studying the properties of these and other operations it is convenient to introduce the concepts of an operator and an operand. It is convenient, for example, to regard the expression :x u(x) as consisting of two constituents: the operator
[tx]
and the operand u(x); to regard the expression xu(x) as
consisting of the operator [x] and the operand u(x); and to regard the expression cu(x) as consisting of the operator [c] and the The operator [ d dx requirement that the relation
operand u(x).
[tx]
u(x)
J is, in fact, defined by the
=
u'(x)
(1)
3
MATHEMATICAL PRELIMINARIES
§2
hold for an arbitrary differentiable function u(x), u'(x) being the first derivative of u(x) obtained by the rules of differential calculus; the operator [x] is defined by the requirement that
[x]u(x) = xu(x)
(2)
for an arbitrary u(x), the right side of (2) being the algebraic product of x and u(x); and the operator [c] is defined by the requirement that [c]u(x)
= cu(x)
(3)
for an arbitrary u(x), the right side of (3) being the algebraic product of u(x) and the constant c. We shall usually denote the operators
[:x], [x],
and [c] by
:x (or d/dx), x, and c, respectively; brackets were used above in order that Equations (1) to (3) might not appear trivial. The operator symbols d/dx, x, and c must not be confused with symbols representing ordinary functions and numbers. This is perhaps clear at once in the case of. the operator d/ dx; that this is also so in the case of the operators x and c will become clear later. The reader should acquire the habit of inquiring whether a mathematical expression that he encounters in a quantummechanical calculation has to do with operators, or with ordinary functions and numbers, or with operators and ordinary functions and numbers. The processes of operating with the operators d/dx, x, and c, are called, respectively, differentiation with respect to x, multiplication by x, and multiplication by the constant c. Among the operators of type c are the operator 1 (the unit ·operator~ idemfactor, or simply unity), which leaves every operand unaltered, and the operator O (the zero operator or simply zero), which annihilates every operand. Operators of type c are often called constants. When discussing operators in general, we usually denote them by Greek letters. If the respective results of operating on the operand u with the operators a and {3 are added together, then the final result
au+ {3u
(4)
is usually denoted by
(a
+ {3)u,
(5)
4
MATHEMATICAL PRELIMINARIES
§2
this convention being suggested by the notation of algebra; thus the expression (d/dx)u(x) + xu(x), that is, the sum of the respective results of operating on u(x) with d/dx and with x, is written as (d/dx + x)u(x). This notation is readily extended to sums of the respective results of operating on the same operand with more than two operators. Another convention concerns consecutive operations. If we first operate on u with the operator a, getting the result au, and next operate on this result with the operator {1, then the final result
{3(au)
(6)
of the two successive operations is usually denoted by
{3au,
(7)
it being understood that to evaluate an expression of type (7) we must first operate on u with a, and next operate on the result so obtained with {3. For example, if we first operate on u(x) with the operator x, getting xu(x), and next operate on this result with d/dx, then the final result d/dx[xu(x)] must be written in the conventional notation as (d/dx)xu(x); on the other hand, if we first operate on u(x) with d/dx, getting (d/dx)u(x), and next operate on this result with x, then the final result x[(d/dx)u(x)] must be written as x(d/dx)u(x). Incidentally, by the rule for differentiating a product, (d/dx)[xu(x)] == x(d/dx)u(x) + u(x), that is, d d dx xu(x) == x dx u(x)
+ u(x),
(8)
so that d d dx xu(x) ~ x dx u(x)
(9)
unless u(x) = 0. The inequality (9) illustrates the importance of remembering the order in which the individual operations must be carried out when the conventional notation is used for successive operations. Extending this notation to cases involving more than two consecutive operations, we write ')'{3au for 'Y[f3( au)], {3a7u for {3[a(yu)], oy{3au for o{'Y[{3(au)]}, and so forth; if a certain operation is repeated without the intervention of other opera
5
MA THEMATIC AL PRELIMINARIES
§2
tions, we use the exponent notation and write, for example, 3 a{ia {3au for a{3{3aaa{3au. Operator algebra. In investigating the properties of a given class of operators, we may proceed along two lines. One is to consider the results of operating with the operators on various operands, and to obtain the desired information through a study of the relations among the results of the operations. The other is to introduce the concept of certain relations among the operators themselves, to define (using operands) the criteria for the existence of such relations, to establish (using operands) the existence of certain fundamental relations among some of the operators of the class, and then, by deducing additional relations among the operators from the fundamental ones, to continue the study without further reference to operands. The latter method, that of operator algebra, rests on the following definitions of equality, sum, and product of operators. If the operators a and {3 are of such a nature that au= {3u
(10)
for every operand u on which both can operate, then a and {3 are defined to b2 equal to each other, and we write a= {3,
(11)
adopting the notation of ordinary algebra. We need not consider here the possibility of existence of operands on which one of the operators can operate and the other cannot. Relations of type (11) between operators are called operator equations, and in stating such symbolic equations in words we use the language of ordinary algebra. Two operators, a and {3, are said to be unequal if there exists an operand u on which both can operate and for which (10) does not hold. If the operators a, {3, and 1' are of such a nature that ')'U
=au+ {3u
(12)
for every operand u for which the operations involved in (12) can be carried out, then 'Y is defined to be the sum of a and {3, and we write 'Y
=
a
+ {1.
(13)
6
MATHEMATICAL PRELIMINARIES
§2
In particular, we may regard the symbol a + {3 in (a + {3)u as a distinct operator, the sum of 'a and {3. For example, d/dx + x in (d/dx + x)u(x) may be regarded as a distinct operator, defined as the sum of d/dx and x, and having properties of its own. If the operators a, {3, and 'Y are of such a nature that 'YU
= a({3u)
(14)
for every operand u for which the operations in (14) can be carried out, then 'Y is defined to be the product a{3 of a and (3, and we write 'Y
=
a.{3.
(15)
In particular, we may regard a{3 in a{3u as a distinct operator, the product a{3 of a and {3. For example, (d/dx)x in (d/dx)xu(x) may be regarded as a distinct operator. Incidentally, the operator (d/dx)x may serve to illustrate the importance of not confusing the operator x with the ordinary function x: the operator symbol (d/dx)x must be understood to symbolize the double operation of first multiplying an operand by x and then differentiating the result so obtained with respect to x; no numerical value must be ascribed to this symbol, even though the symbol, when no operand is written after it, may be mistaken for the derivative of the function x with respect to x. Note that 'Y 'in (14) was defined as the product a{3 of a and (3, rather than simply the product of a and {3. The reason for this is that the product {3a may be different from the product a{3; for example, it follows from (9) that
d
d
dx x ~ x dx.
(16)
The definitions of equality, sum, and product of operators given above enable us to construct any number of distinct operators from our three fundamental operators d/dx, x, and c, such as d/dx + x, d/dx + x + 3, x2, 3d/dx, d/dx, (d/dx)2, (d/dx)2 + x2, (d/dx + x)2, and so forth; for lack of a more descriptive short term, we shall call these operators differen#al operators. The operatoralgebraic rules for handling differential operators are quite similar to those of ordinary algebra, the conspicuous exception being, however, that the order of the factors in a product is, in general, important. An algebra in which the order of the '.actors may affect the significance of a product is said to be
7
MATHEMATICAL PRELIMINARIES
§2
noncommutative. The algebra of the differential operators is noncommutative, as illustrated by (16). If the products a{3 and {3a of two operators a and (3 are equal, we say that a and (3 commute; otherwise we say that they do not commute. We may add equal operators to both sides of an operator equation without destroying the equality; but if the algebra is noncommutative we must be careful in multiplying an equation through by 1 an operator; for example, if a = (3, then ')la = 'Yf3, and a')' = f3'Y, but a')I does not necessarily equal 'Yf3, nor does ')la necessarily equal {h. The process of getting ')la = 'Yf3 from a = (3 is called multiplication by 'Y from the left; that of getting a')' = f3'Y from a = (3 is called multiplication by 'Y from the right. Commutators. The operator a(3  {3a is called the commutator of the operators a and (3. The commutator of two operators may sometimes be identified with an operator having a simpler form than the defining expression a{3 (3a. For example, the commutator d d xx(17) dx dx of the operators d/dx and x can be put into a simpler form as follows: we write (8) as
:xxu(x) =
(x :x + 1)u(x);
(18)
smce (18) holds for an arbitrary differentiable operand u(x), we have d d (19) x=x+1 dx dx ' that is,
d
d
xx=1. dx dx
(20)
The commutator of d/dx and x is thus the unit operator. Similarly, the commutator of x and d/dx is 1. The commutator of d/dx and x 2 can be simplified in appearance as follows: By the rules of the calculus,
x ( !!:._ dx
2

x 2 !!:._) u(x)
dx
= 2xu(x)
= !!:._ x2 u(x)  x2 !!:._ u(x) dx
+x
2
dx
2
:x u(x)  x :x u(x) = 2xu(x);
(21)
8
MATHEMATICAL PRELIMINARIES
§2
hence the equation
(:x x2  :x) u(x) 2xu(x) x
2
=
(22)
holds for an arbitrary differentiable u(x), and we have d 2 2 d  x  x  = 2x. dx dx
(23)
The commutators of pairs of more complicated operators can often be simplified in appearance in a similar manner. The commutator of two commuting operators is, of course, the operator zero. Let us now illustrate the symbolic methods of operator algebra by deriving (23) from· (20) without further reJerence to operands. Multiplication of (20) by x from the left yields d 2 d x dx x  x dx = x,
(24)
while multiplication of (20) by x from the right gives
d
d
2
dx x  x dx x = x;
(25)
adding (24) and (25), we now get d 2 2 d xx=2x dx dx '
(26)
in agreement with (23). Linear operators. An operator a 1s said to be linear if for arbitrary operands u and v a(u
+ v)
=
au
+ av,
(27)
and for an arbitrary constant c ac
= ca.
•
(28)
The simple differential operators discussed above are examples of linear operators. In quantum mechanics we are concerned almost exclusively with linear operators, and throughout our work the term operator will be used to mean linear operator, unless the contrary is explicitly stated.
§2
MATHEMATICAL PRELIMINARIES
9 Exercises
1. Verify that the result of operating on the operand sin x with the operator [ (d/ dx)x] 2 is sin x 3x cos x  x 2 sin x, and that the result of operating on the same operand with the operator [x(d/dx)] 2 is x cos x  x 2 sin x. 2. Verify that (d/dx 1) 2 = (d/dx) 2 2d/dx 1, and that (d/dx x) 2 = 2 2 (d/dx) + (d/dx)x x(d/dx) x • Note that (d/dx + x) 2 is not equal 2 2 to (d/dx) 2(d/dx)x x • 3. In ordinary algebra we have: {a /3) (a  /3) = a 2  fJ 2 • Under what condition can this formula be used when a and /3 are operators? What formula should be used instead when this condition is not fulfilled? 4. Consider the products a/31', a,,{3, /31'a, f3a'Y, 'Ya/3, and 'Y/3a of operators a, /3, and 'Y. How many of these products are different operators if no two of the three operators a, {3, and 'Y commute? If a and /3 commute with each other, but neither a nor /3 commutes with 'Y? If a commutes with {3 and with 1', but /3 and 1' do not commute? If every two of the three operators commute? Illustrate each of these possibilities, using operators of the types discussed in the text. 6. Show that the commutator of the operator x and the operator (cos 2 a)x(d/dx) (sin 2 a)(d/dx)x, where a is a constant, is independent of a. Show that the commutator of d/dx and (cos 2 a)x(d/dx) (sin 2 a)(d/dx)x is also independent of a. 6. Show, using calculus, that for all positive integral values of n we have: (d/dx)xn  xn(d/dx) = nxn 1 • 7. Show by operator algebra that, if a/3  {3a = 1, then a/3 2  {3 2a = 2/3, 3 a/3  {3 3 a = 3/3 2, and, in general, a/3n  {3na = n13n 1 • 8. Derive the result of Exercise 6, taking for granted (20) and the result of Exercise 7. 9. Reduce the commutator of (d/dx)n and x to a form not involving the operator x. 10. Verify the following identities, in which the Greek letters denote arbitrary linear operators, c denotes a constant, and {a, /3} denotes
+
+
+
+
+
+
+
+
+
+
+
+
afJ  {3a:
{t, 17}
= {'7,
{t, c}
= 0
{ ~l
+
{t, f/1
+ {t2 , '7} = {~, 11d + {~, 112} {t1, 11}t2 + h{t2, 71} {t, 11d112 + 11dt, 112}
~2 , '7} = { tI , '7}
+
f/2}
{~1~2, 17} =
{t, '71'72} It, {11,
tl
=
r} J + h, {r,
~J}
(29 ag)
+ {r, {~, 11l J = o.
11. Show that the operator a/ax, which stands for partial differentiation of any operand (now explicitly allowed to be a function of several variables) with respect to x, satisfies the equation
a
a
ax
ax
xx
=
1.
(30)
10
§2
MATHEMATICAL PRELIMINARIES
12. By a generalization of the arguments given below, prove the following theorem for the case when the operand u can be expanded into a power series in the variable x: if the operator a commutes with x and with o /ox, that is, if axxa=O (31) and
a
a ox
a
(32)
a=O ox '
then, for an arbitrary u,
(33)
au = cu,
where c is independent of x and o /ox, so that, insofar as dependence on x and o /ox is concerned, a is a constant. 2 [Let u = u1 = 1; then, in view of (32), (o/ox)au1 = a(o/ox)u1 = 0, and
a
(34)
ax (au1) = 0, so that au1
c, where c is independent of x, or
(35) Next let u = u 2 = x, so that au2 = ax, or au2 = axu 1 , axu 1 being the result of operating with a on the product of the variable x and the number 1. Now, we may regard x in axu 1 as being the operator x instead of the variable x, and write axu1 = (ax)u1 without affecting the result; but, in view of (31), (ax)u1 = xau1, so that, because of (35), we haYe au2 = xc, and hence
(36) Thus (33) follows from (31) and (32) in the two special cases u = l and u = x.] 13. Show that, if a satisfies the two operator equations xa  ax= 0,
o ax
a ax
 a  a= 2x,
(37)
then the operator (a  x2 ) commutes with x and with a/ox; then, using the result of Exercise 12, show that the general solution of Equations (37) is a= x 2
+
c,
(38)
where c is a constant insofar as dependence on x and a/ox is concerned. Show in a similar way that the general solution of the simultaneous operator equations xa  ax = O and (a /fJx)a  a(o /ox) = Axn, where A is a constant, is a = A (n + 1)1 xn+i c.
+
2
. an examp1e o f a const an t.m d"1sgmse. . The operator d x  x d 1s
dx
dx
MATHEMATICAL PRELIMINARIES
11
§3
d2 3. The Operator  dx 2 We shall be concerned for the present with real and complex functions u(x) of the real variable x, and shall usually write 2 u, u', u", and so forth, for u(x), du(x)/dx, d u(x)/dx2, and so forth. The moduli (or absolute values, see §8) of x and u(x) will be denoted, respectively, by I x I and I u I; since our x is real, Ix I equals x when xis positive, and x when xis negative. The statement that a function of x remains finite when x ~ oo will mean that when x increases without limit this function does not tend to oo (as does, say, ex) or to  oo (as•does, say, e2), and does not oscillate with amplitude approaching oo (as do, say, x sin x and x cos 2 x); the meaning of the statement that a function of x remains finite when x ~  oo is similar. The words "when I x I ~ oo " will mean "when x ~ oo and also when X ~ 
00 ."
If u(x) and du(x)/dx are both continuous for all real values of x, we say that u(x) satisfies our standard continuity conditions. If u(x) [or I u I, if u is complex or pure imaginary] remains finite when I x I ~ oo, we say that u(x) satisfies our standard boundary conditions. 3 If u(x) (a), satisfies our standard continuity conditions, (b), satisfies our standard boundary conditions, and (c), is not identically zero, we call u(x) a wellbehaved function. For example, the four functions shown in the top row of Fig. 1 are wellbehaved, while the
x
U=X
1/ x
x
Fig. 1. Top row: examples of wellbehaved functions; bottom row: examples of illbehaved functions. 3
It should perhaps be emphasized that to satisfy our boundary condi
tions a function must remain finite when x
~ oo
and also when x+  oo.
12
MATHEMATICAL PRELIMINARIES
§3
four functions in the bottom row are illbehaved, that is, not wellbehaved. The problem of immediate interest to us is to consider the conditions under which certain secondorder differential equations possess wellbehaved solutions. Some differential equations have a wellbehaved general solution; for example, the general solution of (1) u" = u IS
u
= A sin x
+ B cos x,
(2)
and satisfies our standard boundary and eontinuity conditions for any choice of the arbitrary constants 4 A and B, so that (2) is well behaved for any choice of A and B except A = B = 0. Some differential equations do not have any wellbehaved solutions at all; for example, the general solution of u"
=u
(3)
x + B e;
(4)
IS
u= A ex
the first term in (4) increases without limit when x ~ oo, and the second does so when x ~  oo ; hence no adjustment of A and B (except A = B = 0) yields a solution satisfying our boundary conditions. Finally, a differential equation may not possess wellbehaved solutions in general, but does possess them if a numerical constant appearing in the equation is suitably chosen. This case will be of special interest to us, and we shall illustrate it by several examples, the first of which will be to determine the values of the numerical constant X for which the equation d2
 2 u
dx
=
(5)
Xu '
In anticipation of working with several independent variables, note that the statement that a quantity involved in a mathematical expression is a constant means only that this quantity does not depend on the independent variable or variables explicitly appearing in the expression; for example, the statement that A in (2) is a constant means that A does not depend on x, but does not exclude the possibility that A depends on independent variables other than x. 4
13
MATHEMATICAL PRELIMINARIES
§3
of which (1) and (3) are special cases, possesses wellbehaved solutions, and to find these solutions. Now, if X ~ 0, the general solution of (5) is u = A1 cos X' x
+ A2 sin X1 x,
(6)
where the A's are arbitrary constants, and where X1 denotes +0. The solution (6) satisfies the continuity conditions regardless of the values of the A's, and it remains to be seen if the boundary conditions are also fulfilled; in doing this we shall consider several cases separately. First, let (7) X > 0, so that X' is a nonvanishing positive number; (6) then remains finite everywhere, and hence the boundary conditions are satisfied. Next, let (8) X < 0, so that X1 is a nonvanishing pure imaginary number, say ia, where a is positive. It is convenient in this case to write the general solution of (5) as (9) u = B 1eax + Bax 2e rather than as (6), and it is seen thnt if X < 0, then neither the general solution of (5) nor any of its particular solutions are well behaved. We shall leave it to the reader to show that if X is a complex or a pure imaginary number, then (5) does not possess any wellbehaved solutions, and we shall proceed to the remaining case, X = 0.
(10)
The general solution of (5) is now u =Bx+ C,
(11)
where B and C are arbitrary constants. The term Bx does not satisfy our boundary conditions, while the term C does; hence the special solution
u=C
'
(12)
obtained by setting B  0 in (11), satisfies all our conditions, and consequently (5) does possess wellbehaved solutions when X = 0. Note that the results in the two cases X > 0 and X = 0
14
MATHEMATICAL PRELIMINARIES
§3
differ in an important respect. In the case A > 0 the general solution itself is wellbehaved; while in the case A = 0 the general solution is not, but the particular solution (12), containing a single arbitrary constant, is. Note also that, although (6) is not the general solution of (5) wh.en A = 0, the substitution A = 0 into (6) yields, nevertheless, the solution (12), that is, the solution satisfying the boundary conditions when X = 0. To summarize: Equation (5) possesses wellbehaved solutions· if, and only if, A> O· (13) 
'
and the wellbehaved 8olutions have the form (6), or the equivalent form (14.) u = A eiA1x + B eiX1x, which for most of our purposes is more convenient than (6); it is to be understood that the trivial case A == B == 0 in (14) is to be excluded. Eigenvalues and eigenfunctions. To simplify further discussion, we introduce the following terminology. If, for the specific value Ai of the numerical constant A, a wellbehaved operand ui satisfies the equation au = Xu,
(15)
where a is a given operator (that is, if (16)
and Ui is well behaved), we say that the number Ai is an eigenvalue5 of the operator a, that the operand ui is an eigenfunction6 of a, and that the eigenvalue Ai and the eigenfunction Ui of the operator a belong to each other. For example, since the operand sin 3x is wellbehaved, and since d2 . .   2 sm 3x = 9 sm 3x, dx
(17)
we say that the number 9 is an eigenvalue of the operator d 2 /dx 2 , that the operand sin 3x is an eigenfunction of the operator d 2 /dx 2 , and that This term is halftranslated (to use Professor Kemble's expression) from the German Eigenwert; alternative terms are proper value (or number) and characteristic value (or number). 6 Alternative terms are proper function and characteristic function. 6
15
MATHEMATICAL PRELIMINARIES
§3
the eigenvalue 9 and the eigenfunction sin 3x of the operator d 2 /dx 2 belong to each other.
Our definitions can be restated as follows: an eigenfunction of the operator a is a wellbehaved operand such that operating on it with a is equivalent to multiplying it by a numerical constant, this constant then being the corresponding eigenvalue of a. If (18)
a=
Equation (15) goes over into (5), and consequeudy the problem concerning (5) treated above (our first example of the eigenvalue problem) can be stated as follows: to find the eigenvalues and the 2 eigenfunctions of the operator  d2/ dx • And our conclusions can be stated thus: any positive number, zero included, is an eigenvalue of the operator  d2/ dx2, and the eigenfunction of  d2/ dx 2 belonging to the eigenvalue X is (14). We call the totality of the eigenvalues of an operator its eigenvalue spectrum, or simply its spectrum; thus we say that the 2 spectrum of the operator d2 / dx consists of all positive numbers, zero included. The eigenvalue problem, which plays a fundamental part in the quantum mechanics of particle motion, arises also quite frequently in classical theoretical physics, particularly in the theory of continuous media; but the definition of good behavior of a function is then usually somewhat different from that adopted above, and the problem usually goes over into what is called the SturmLiouville problem.
Exercises 1. Show that the function cos 4x is an eigenfunction of the operator 2 d 2/ dx 2 belonging to the eigenvalue 16. Show that the function xelx is an eigenfunction of the operator d 2 /dx 2 x~ belonging to the eigenvalue 3. Show that the function sinh 2x is not an eigenfunction of the operator d2 /dx2 in spite of the equation (d 2 /dx 2 ) sinh 2x = 4 sinh 2x. 2. Show that the operator d 2 /dx 2 has no complex or pure imaginary eigenvalues. 3. Show that, if Ui is an eigenfunction of a linear operator a belonging to the eigenvalue Ai , then Cui , where C is an arbitrary nonvanishing constant, is also an eigenfunction of a belonging to the e~genvalue Ai . 4. The operator 8 2 /ax 2 is of interest when the operands are explicitly permitted to be functions not only of x but also of other independent variables. Show that, if the operands are required to be well behaved so far as their dependence on xis concerned, then the spectrum of fJ 2 /8x 2
+
16
MATHEMATICAL PRELIMINARIES
§4
is the same as that of d 2 /dx 2 found in the text, and that the eigenfunctions of a 2 /ax 2 have the form (14) and can depend on independent variables other than x only through the coefficients A and B.
d2
4. The Operator   2 dx
+x
2
Our next problem is to determine the eigenvalues and the eigenfunctions of the operator
d2
dx2
+
2
(1)
x,
that is, to find the values of the numerical constant X for which the equation au = Xu possesses wellbehaved solutions when a is the operator (1), and to find these solutions. The operator (I) will come into play in connection with the first dynamical system that we shall study from the quantummechanical standpoint, namely, the linear harmonic oscillator. Remarks on curvature. If a curve u = u(x) is concave downward wherever it lies above the xaxis, and concave upward wherever it lies below the xaxis, we say that it is concave toward the xaxis in the region in question; for example, the function sin x is concave toward the xaxis throughout the infinite region. Now, according to a theorem in elementary calculus, u is concave downward if u" is negative, and concave upward if u" is positive. Hence u is concave toward the xaxis if u and u" have opposite algebraic signs; in other words, u is concave toward the xaxis if u" /u
0.
(2b)
The results (2a) and (2b) will find immediate application in our study of the operator ( 1).
When a is the particular operator (I), the eigenvalue equation au = Xu becomes the differential equation 2
d (  dx 2
+ x2\} u
= Xu.
(3)
The general solution of (3) cannot be expressed in any simple way in terms of the elementary functions; consequently, we shall have
MATHEMATICAL PRELIMINARIES
17
§4
to proceed in a manner less direct than that of §3, and a few preliminary remarks are perbaps in order. Since, as the reader will verify,
+ ( _ .!!::_ dx 2
x 2) et:2
=
1 · elz 2 ,
(4)
and the function elz2 (Fig. 3) is wellbehaved, the operator (1) has the eigenvalue 1. Similarly, since
(  :: + x2) xelz'
(5)
= 3xelz',
and the function xetz 2 (Fig. 4) is wellbehaved,7 the operator (1) has also the eigenvalue 3. The question may now be asked: Does the operator (1) have the eigenvalue 2? To answer it we must find whether the equation 2
d2 (  dx
+x
2)
(6)
u = 2u
has wellbehaved solutions. To get an idea of the behavior of the solutions of (6), we calculate by numerical integration8 two particular solutions U o and U 1 of (6) satisfying the following conditions at x = 0: Uo(O) = 1
U~(O) = 0
U1(0) = O
u;(o)
=
1.
(7)
Graphs of U o and U 1 are shown in the lower part of Fig. 2; in the upper part are plotted the parabola x 2 and the constant X = 2. The graphs (In this footnote, as well as in some other places, we write exp s fore•.) When x ~ ± oo the first factor of x exp ( !x 2) approaches ± oo w~ile the second approaches zero, so that the product, as it stands, becomes indeterminate. To resolve the indeterminacy, we rewrite x exp (!x 2 ) as x/exp (!x 2 ) and recall (see indeterminate forms in a calculus text) that, if the ratio of two functions of x becomes indeterminate for some value of x, then it can be replaced at this value of x by the ratio of the derivatives of the numerator and the denominator; thus, the limit of x/exp (!x 2) when x ~ oo or x ~  oo may be replaced by the corresponding limit of [dx/dx]/[d exp (!x 2 )/dx], that is, of 1/x exp (!x 2 ), and we conclude that x exp (lx 2)+ 0 when l x I ~ oo. Similar arguments show that the product of exp ( !x 2 ) and of any polynomial in x (that is, any terminating power series in x) approaches zero when I x I ~ oo. 8 Even when the general solution of an ordinary differential equation cannot be obtained analytically, particular solutions satisfying prescribed numerical initial conditions can usually be evaluated by numerical methods; for references, see §33. 7
18
MATHEMATICAL PRELIMINARIES
§4
suggest that U o is even 9 in x, while U 1 is odd in x; that this is indeed so will be shown rigorously later. Also, we observe that in the region I x I < V2 (where the parabola in the upper part of Fig. 2 lies below the line >. = 2) both U's are concave toward the xaxis, while in the regions I x I > V2 (where the parabola lies above the line >. = 2) both U's are convex toward the xaxis. That the curvature of any solution of (6) has these properties can be shown, without reference to graphs, as follows: For u ~ 0, Equation (6) can be ·written as u" ju = x 2  2, and therefore
u" I u
}..l, then this solution is illbehaved. Show further that (39) has n nodes in the region V2n + 1 < x < V2n + 1, one node at x =  oo, and another at x = oo, that is, n + 2 nodes in all. 5. Show that the functions (39) satisfy the identities XUn
=
nAn A Un1 n1
An
+ 2 A Un+l ,
(51)
An A 2 11+1
(52)
n+l
and
d dx 
Un =
nAn A
Un1 
nI
Un+l •
Then deduce directly from (51) and (52) that x 2 Un
d2
_

dx2u n 
n(n  l)An An2 n(n  l)An A n2
Un2
+
Un2 
1 2(2n
)
~
+ 1 Un + 4A n+2 Un+2 '
!(2n
+
l)un
An
+ 4A n+2
Un+2'
(53) (54)
Rolle's theorem states that, if u(x) satisfies our standard continuity conditions and vanishes at x = a and at x = b, then there is at least one point within the interval a < x < b at which u'(x) = 0. 16
27
§4
MATHEMATICAL PRELIMINARIES
and d ( dx
+x
)k Un=
2kn!An (n  k)! Ank
for k
Unk,
~
n.
(55)
6. By a kfold application of (53), the function x 2kun can be expressed as x 2k Un = · · ·
+
Cn4 Un4
+
Cn2 Un2
+
Cn Un
+
Cn+2 U n+2
+
Cn+4 Un+4
+ ••· . (56)
Show, without evaluating the e's, but by comparing the structures of (53) and (54), that d'l.k
(l)k dx2k
Un
= ··· +
Cn4 Un4 
Cn2Un2
+ Cn Un 
Cn+2Un+2
+ Cn+4 Unt4

(57)
where the e's are, respectively, the same as those in (56). 7. Show that, if the operands are required to be wellbehaved so far as their dependence on xis concerned, then the spectrum of a 2 /ax 2 + x2 is the same as that of d 2 /dx 2 + x 2 found in the text, and that the eigenfunctions of a 2 /ax 2 + x 2 have the form (39) and can depend on independent variables other than x only through the coefficient An .
5. The Operators  i !_, x, and c
ax
An operator of fundamental imp9rtance m quantum mechanics is
.a
'l,
ax'
(1)
where i 2 = 1. In the case of this operator, the eigenvalue equation 153 (see footnote 17 ), that is,
au= AU,
(2)
In cross references, we specify the section number by a superscript (a notation patterned after that of E. U. Condon and G. H. Shortley). For example, the symbol 15 3 denotes Equation (15) of §3; similarly, 'Exercise 744 ' denotes Exercise 7 of §44. Section numbers are printed at the right of page headings, so that the number in the upper right of a reference symbol is the number in the upper right of a page. Note that the section number heading a page on which one section ends and another begins usually refers to the former section. References to the Appendix carry the superscript A. The figures and the tables are numbered consecutively throughout the book; but to help in locating them we sometimes append the section number as a superscript. For example, the superscript in 'Fig. 22 16' means that Fig. 22 appears in §15. · 11
28
MATHEMATICAL PRELIMINARIES
§5
IS
.a ax
 i  u = Xu
'
(3)
and its general solution is
u = A eiXx,
(4)
where A is independent of x, but is otherwise arbitrary. This solution is wellbehaved if X is any real number (positive, negative, or zero), but is illbehaved if X is a nonvanishing complex or a pure imaginary number. The spectrum of ia/ax thus consists of all real numbers, and the eigenfunctions of i·a;ax belonging to the eigenvalue X are (4). This spectrum is quite 2 different from the continuous spectrum of  a2 / ax because it contains all real numbers. To determine the eigenvalues and eigenfunctions of an operator of type c, we set a = c in (2), and obtain cu= Xu.
(5)
In view of the definition of the operator c, this equation is satisfied if, and only if, X = c, when the trivial case u = 0 is excluded. The operator c thus has only one eigenvalue, the number c. When X = c, any uin particular, any wellbehaved usatisfies (5), so that any wellbehaved function is an eigenfunction of the operator c. To find the eigenvalues and eigenfunctions of the operator x, we set a = x in (2) and consider the equation xu
= Xu.
(6)
Since u is not permitted to be identically zero, and since x is a variable, while X is a constant, we conclude that u must vanish for all values of x except the value x = X, for which it must not vanish. A function of this kind will be discussed at the end of §12, where, with the help of a nonrigorous argument, we shall conclude that every real number (positive, negative, or zero), and no other number, is an eigenvalue of the operator x. The operators x and ia/ax thus have spectra of the same type. 6. Simultaneous Eigenfunctions The wellbehaved function (1)
§6
MATHEMATICAL PRELIMINARIES
29
ia/ax
is an eigenfunction of the operator eigenvalue 3 of ia/ax, since
. a e3ix
i 
ax
=
belonging to the
3e3ix ·
(2)
'
the function (1) is also an eigenfunction of the operator (belonging to the eigenvalue 9 of  a2/ax2 ), since
a2/ax 2
2
a e3ix = 9e3ix . 2
(3)
ax
An operand that is an eigenfunction of two or more operators is said to be a simultaneous eigenfunction of these operators; for exam,ple, (1) was shown above to be a simultaneous eigenfunction 2 of ia/ax and a2/ax • An eigenfunction u of an operator a belonging to the eigenvalue X of a is simultaneously an eigenfunction of the operator a 2 belonging to the eigenvalue '1'. 2 of cl; indeed, if au
= Xu,
(4)
2
then a u  a(au)  aXu = Xau = '1'. 2u, that is, 2
2
au= '1'. u.
(5)
We can thus conclude, for example, that, since a2/ax2 = (ia/ax)2, an eigenfunction of ia/ax belonging to the eigenvalue '1'. of ia/ax is simultaneously an eigenfunction of a2/ax2 belonging to the eigenvalue '1'.2 of a2/ax2 ; Equations (2) and (3) illustrate this result for the case of the function (1). The converse of this theorem is in general not true: an eigenfunction of a 2 need not be simultaneously an eigenfunction of a. To illustrate: the general eigenfunction of the operator a2/ax2 belonging to the eigenvalue '1'., that is, 18
u = A eiX!x
+ Be
iX!x
,
(6)
is, in ge~eral, not an eigenfunction of the operator 
. a u = ·d(A eiX!x  B eiXlx)
1, 
ax
18
I\
'
ia / ax,
since (7)
The marginal number at the left of an equation is its old number, or the number of an equation which, for one reason or another, might advantageously be recalled.
30
MATHEMATICAL PRELIMINARIES
§6
so that
.a
i 
ax
u
~
constant X u,
(8)
unless A, B, or )\ is zero. Certain pairs of operators (for example, the operators ia/ax 2 and a2 /ax + x2 ) do not have any eigenfunctions in common. If an operand u is a simultaneous eigenfunction of two operators a and ~' so that {3u
au= Xu,
=
µu,
(9)
where X and µ are numerical constants, then u is also an eigenfunction of the operator a.{3  {3a, and belongs to the eigenvalue O of a.{3  {1a. Indeed, in view of (9), aµu
=
µau = µXu,
(10)
Bau= {1Xu
=
X{3u
= Xµu,
(11)
a{3u
=
and so that
(a{1  {3a)u = 0;
(12)
Equation (12) can be written as (a.{3  {3a)u  0 · u,
(13)
and the theorem is proved. Exercises 1. Show that an eigenfunction of ia /ax belonging to the eigenvalue X of ia /ox is an eigenfunction of ia 3 /ax 3 belongin~ to the eigenvalue X3 of ia 3 /ox 3 • 2. Show that, if u is an eigenfunction of a belonging to the eigenvalue A, then u is also an eigenfunction of ca belonging to the cigen value CA. 3. Show that, if u is an eigenfunction of a belonging to the eigenvalue a, and if P(a) is a polynomial in the operator a, then u is an eigenfunction of P(a) belonging to the eigenvalue P(a). 4. Show by means of an example that a wellbehaved operand u may satisfy the equation (af3  {fo)u = 0 without being an eigenfunction of either a or f3. 6. Inspect the commutator of x and ia /ax, and show (without reference to their explicit eigenfunctions) that these operators have no eigenfunctions in common. 6. Show that, if a and f3 commute, and if u is an eigenfunction of a belonging to the eigenvalue X, then the operand f)u, if wellbehaved, 1s also an eigenfunction of a belonging to the eigenvalue X.
31
MATHEMATICAL PRELIMINARIES
§6
7. Let a, 13, and 'Y be operators satisfying the equations a{j  {ja = 'Y, 'Yf3 = a, and 'Ya  ar = /3. Show that, if u is a simultaneous eigenfunction of any two of these operators, then it is also an eigenfunction of the third, and the eigenvalues of a, /3, and 'Y belonging to u are all zero. 8. Show that, if a, (3, and 'Y satisfy the commutation rules of Exercise 7, fhen each of these operators commutes with a 2 + /3 2 1 2•
f3'Y 
+
7. Degenerate Eigenvalues It was shown in Exercise 33 that, if ui is an eigenfunction of a linear operator a belonging to the eigenvalue Ai of a, then Cui , where C is an arbitrary constant, is also an eigenfunction of a belonging to the same eigenvalue, so that to every eigenvalue of a linear operator a there belongs an infinite set of eigenfunctions. In this connection, we must distinguish two cases: (a) when every eigenfunction of a be]onging to Ai can be obtained from any other such eigenfunction by multiplying the latter by a constant (we then call Ai a nondegenerate eigenvalue of a); and (b) when not all eigenfunctions of a belonging to Ai have the form Cui , where ui is one of these eigenfunctions (w·e then call Ai a degenerate eigenvalue of a). To illustrate: the eigenvalue O of the operator 2 2 d /dx is nondegenerate, because, as shown in §3, all eigenfunctions of  d2/ dx 2 belonging to this eigenvalue are constants, so that every one of them can be obtained from any other by multiplying the latter by a constant; on the other hand, every eigenvalue of  d2/ dx 2 greater than O is degenerate, because, when A > 0, this operator has such eigenfunctions as i~Jx u = Ae
(1)
ixlz u = Be ,
(2)
and
which cannot be converted into each other by a multiplication by a constant. A set of n functions, Ji , !2 , · · · , f n, is said to be linearly independent if it is impossible to choose n constants c1, c2, ... , Cn, not all of which are zeros, in such a way that the equation (3)
holds for all values of the arguments of the f's; otherwise the f's are said to be linearly dependent. The multiplicity, or the degree of degeneracy, of an eigenvalue of an operator is now defined as
32
§7
MATHEMATICAL PRELIMINARIES
follows: if the aggregate of the eigenfunctions belonging to Ai contains n, and not more than n, linearly independent eigenfunctions (that is, if the explicit general expression for the eigenfunctions belonging to Ai contains just n essentially arbitrary constants), then the degeneracy of Ai is said to be nfold (except· that Ai is said to be nondegenerate when n = 1). For example, the degeneracy of each eigenvalue A > 0 of d2/dx 2 is twofold, since the functions (1) and (2) are linearly independent, and since, when A > O, Equation 53 possesses no solutions that are not linear combinations of (1) and (2). Exercises 1. Show that the three functions 1, cos2 x, and sin2 x are linearly dependent, and that the three functions 1, cos x, and sin x are linearly independent. 2. Show that none of the three operators ia/ax, x, and a 2 /ax 2 x2 has any degenerate eigenvalues. Show that the single eigenvalue of the operator c is degenerate to an infinite degree. 3. Show that, if a and (3 commute, if u is an eigenfunction of a belonging to a nondegenerate eigenvalue of a, and if {3n is wellheha ved, then u is also an eigenfunction of (3. 4. Show that if "'X is real the function A eiXx is an eigenfunction of every differential operator that commutes with ia /ax.
+
8. Orthogonal Sets of Functions The eigenfunctions of some of the operators of quantum mechanics form socalled discrete orthogonal sets, and we shall now make a few remarks concerning such sets. We shall deal, in general, with complex functions of real variables, and shall employ the following terminology and notation. If f1 and /2 are real numbers or real functions of real variables, and
f =Ji+ i/2'
(1)
where i 2 =  1, we call f~ the real part off, call f2 the imagi·nary part off, and write
f1 = Ref, and /2 = Im/; (2) for example, since /x = cos x + i sin x, the real part of /x is
cos x, the imaginary part of i,; is sin x, and we write Re ix = cos x, and Im /x = sin x. The function f 1  i/2 , which we denote by J, is called the complex conjugate off; for example, if f = iX, then f = eix. The complex conjugate of a given function is obtained
§8
MATHEMATICAL PRELIMINARIES
33
from the function itself by reversing the algebraic sign of i wherever i appears in the given function; it is unnecessary first to rewrite the function in the form (1). The function +Vii + which we denote by Ii I, is called the modulus, or the absolute value, of i; for example, if i = /X, then Ii I = 1. The principal value of arc tan (!2/fi) is called the phase of i The product of f and its complex conjugate, that is, the square of the modulus of i, 2 will be denoted by Ji or by Ii j • If Imi = 0, so that i is real, the complex conjugate of i is j itself, and Ji = /. The product of a function g and the complex conjugate j of a function i will be written in the form Jg, rather than in the equivalent form gJ; the convenience of this convention will become apparent when we come to quantum mechanics. If the product of a function u 1 (x) and of the complex conjugate u2(x) of a function 1t2(x) vanishes when integrated with respect to x over the interval a < x < b, that is, if
n,
[
u2(x)u1(x) dx = 0,
(3)
then ui(x) and u2(x) are said to be mutually orthogonal, 19 or, simply, orthogonal in the interval (a, b). If every two functions contained in the set (4)
are mutually orthogonal in the interval (a, b) of x, that is, if
lb
Um(x)un(x) dx = 0 when n ¥ m and n, m = 1, 2, 3, ... ,
(5)
then the set (4) is said to be orthogonal in the interval (a, b) of x. For example, the infinite set 1, cos x, cos 2x, cos 3x, · · · )
sin x, sin 2x, sin 3x, · · ·
J
(6)
is orthogonal in the interval (  1r, 1r) of x because the integral of the product of any member of (6) and the complex conjugate 20 of any other member of the set vanishes when the limits of inteSome of the definitions given here differ from those usually employed in discussions restricted to real functions of real variables. 20 Since every member of (6) is real, the words complex conjugate may be omitted in the present case. 19
34
MATHEMATICAL PRELIMINARIES
§8
gration are 1r and 1r; the set (6) is in fact orthogonal in any interval of x of length 21r. The set (6) is of great interest in mathematical physics because 21 a large class of functions of x can be expressed in an interval of length 21r as linear combinations 22 of members of (6), so that a large class of periodic functions having the period 21r can be expressed in this manner in the infinite interval (  oo , oo). When a function is expressed as a linear combination of the members of (6), it is said to be expanded into its Fourier series. Certain Fourier series are encountered in elementary trigonometry; for example, the right side of the familiar identity • 2 sm x
=
1 2 
1
2
cos 2x
(7)
2
is the Fourier series of the function sin x. The Fourier expansion (that is, the Fourier series) of a given function, if it exists, can sometimes be found in several superficially distinct ways; for example, the expansion (7) can be carried out by trigonometric or by equally elementary algebraic methods. But a general method exists for finding the Fourier expansion of a given function by means of integration; this method applies equally well to orthogonal sets other than (6), and we shall now present it for the general case. If it can be shown that in the interval (a, b) the function f(x) admits of an expansion
in terms of the set U 1 , U2 , U3 , • • • ,
(9)
which is orthogonal in the interval (a, b) then the expansion coejficients, 23 that is, the e's in (8), can be evaluated as follows: 1) write (8) with the e's undetermined; 21 Only highly discontinuous functions (not satisfying the Dirichlet
conditions discussed in mathematical books) cannot be expanded into Fourier series in a finite interval. 22 By a linear combination of the functions u1 , u2 , ua , · · · , we mean an expression of the form c1u1 + c2u2 + caua + · ·· , where the e's are constants. 23 Expansion coefficients are sometimes called Fourier coefficients, even when sets other than (6) are concerned.
35
MATHEMATICAL PRELIMINARIES
2) multiply (8) through by Uk/= C1UkU1
Uk ,
§8
getting
+ C2UkU2 + C3UkUa + · · · + CkUkUk +
(10)
3) integrate (10) term by term over the interval (a, b); in view of the orthogonality of the u's, all terms on the right side of (10) except that involving UkUk will vanish, and hence (11)
so that k = 1, 2, 3, . . . . (12)
Note that (12) was derived on the assumptions that f(x) does admit of an expansion of type (8), and that a termbyterm integration of the right side of (10) is permissible; hence the fact that the e's given by (12) can be computed for a given f(x) and a given orthogonal set (9) does not guarantee that the expansion (8) exists; and therefore the use of the method of integration for the evaluation of expansion coefficients should be accompanied by an investigation of the question whether the series so obtained converges to the values of f(x) for the value of x under consideration. If a computation presumes the convergence of series or integrals without proving the validity of this presumption for the case on hand, we call it a formal computation. Incidentally, the fact that the e's are given by (12) if the expansion (8) exists shows that the expansion of a given function in terms of a given orthogonal set, if it exists, is unique. In the case of some of the more important orthogonal sets, general conditid'ns have been set up that enable us to determine, prior to a formal evaluation of the expansion coefficients, whether or not the expansion is possible; for example, it is known that every continuous 21 periodic function of period 21r can be expanded in terms of the set (6). If every function of a certain type admits of an expansion in terms of a given orthogonal set, the set is said to be complete with respect to functions of this type; for example, the set (6) is complete with respect to continuous periodic functions of period 21r.
36
MATHEMATICAL PRELIMINARIES
§8
To illustrate the use of (12), let us obtain the Fourier series of the function f(x), shown in Fig. 6 and defined as follows: 2
(x
+ 1r)
for
7r
sxs
!1r
for
!1r
sxs
!1r
for
!1r
sxs
1r,
h/41r; similarly, devices intended primarily for the measurement of Px render the knowledge of x inexact. These matters are discussed very lucidly by Heisenberg in his book cited in footnote 13. With regard to contention (b) given above in support of the Heisenberg principle, we can but reiterate that the Heisenberg inequalities are, as we have seen, deducible from the fundamental assumptions of the quantum theory, and that hence the theory does not permit the translation into its mathematical terms of just the kind of information that, in the light of the Heisenberg principle, is to be regarded as not physically obtainable. All deductions from the quantum theory are thus bound to be in accord with the demands of this principle. Exercise
1. Why cannot a correction for the alteration in P.c of the particle observed by means of a microscope be made, without affecting the accuracy of the knowledge of x, by measuring the wave length of the light coming out of the microscope at the instant to, and then computing the angle through which the photon was deflected?
26. Kennard Packets We shall next determine the form that the Schroedinger function it,, must have at a given instant of time in order that ~z~p have at that instant its smallest possible value h/41r. The replacement of > by = in 1323 is permissible if and only if it is permissible in 623 , that is, if and only if t/; satisfies the equation
it,,'
+
(ax
+ /3 + io)y;
=
0,
(1)
THE SCHROEDINGER METHOD
126
§25
whose general solution is
VI
= Aeiax2(,s+io>x.
(2)
If we choose A so as to normalize (2), the resulting VI may be written as i'Y
if; = e
¥ [ 2( a ; exp

1 ~

v 1ax
+ y';:; {3 )2 
J
. iOx ,
(3)
where 1' is real and independent of x, but otherwise arbitrary. A computation of avx ( = Xa), avp ( = Pa), and ~x for the state (3) shows that these quantities are related to a, {3, and othrough Equations 1023 , so that (3) can be written as i"'(
VI=
~XXa) ..
+ i PaX
e__ e  ~ ,;
{/21r~i
(4)
The distributioninx corresponding to the amplitude (4) is the Gauss distribution _ if;if; =
1
~x
v21r
_ txxa) 2 e
2Ai
(5)
and has a maximum at x = Xa ; hence Xa is not only the average of x but also its most probable value. The distributioninp for the state (4) is (§27) 1
(6)
where ~p
h = 41r~}
(7)
the distribution (6) is also Gaussian, so that Pa is the average and also the most probable value of p. The Schroedinger function (4) thus represents a state for which the most probable value of x is Xa , the most probable value of p is Pa, and for which ~x~p has its least possible value h/41r. In specifying the state of a onedimensional system by the function (4) we consequently come, so to speak, as near to the specification of precise initial conditions of the motion (to which we are accustomed in the classical theory) as is possible to do in quantum mechanics. For this reason, states that at some instant of time have the form (4) are of special interest; we shall call such states
127
§25
INTRODUCTORY PROBLEMS
onedimensional Kennard packets. 14 The packet 121 , for example, is a Kennard packet having xo for the most probable value of x, zero for the most probable value of p, and a/ V2 for 11x . The manner in which a Kennard packet varies with the time depends of course on the dynamical system under consideration, because the time dependence of a Schroedinger function is determined by the equation Hi/; = ihaf /at, whose solutions depend on the explicit form of the Hamiltonian. In a linear restoring field, the Kennard packet 121 was found to vary with the time as shown by 1921 ; in another field, the behavior of the packet would be different. The fact that the Hamiltonian must be known in order that the behavior of a Kennard packet (for that matter, of any Schroedinger function) may be determined corresponds to the fact that in classical theory the force field ;must be known before the motion of a particle can be calculated. Quantum theory does not provide for us an opportunity for employing in a strict sense the mental picture of a moving particle cultivated by daily experience and also by classical mechanics, the picture that associates with the particle a definite position and momentum at every instant of time and allows us to follow mentally the motion of the parti
0,
(3)
so that the eigenvalue spectrum of our Hamiltonian consists of all positive numbers, zero included. We conclude that (when Vo = 0)
FURTHER PROBLEMS
145
§28
any positive value of the energy, zero included, is a possible value of the energy of a free particle, and that no other values are possible. This result is in agreement with the corresponding result of the classical theory of a free particle: the energy of a free
particle is not quantized. The eigenfunctions of H belonging to the eigenvalue E have the form a exp ( i ~ x) + b exp (i'VKE x), that is, ae iy2mB xi h
+ beiy2mE xi h ,
(4)
where a and b are independent of x, but are otherwise arbitrary; (4) is the general solution of (2), except when E = 0. To compute the properly timedependent Schroedinger function for a free particle of energy E, we substitute (4) into the second 16 Schroedinger equation 1 ( which in the case of an energy state reduces to Et/; = ihatf; /at), and find that this function, to be denoted by t/; E , is ,I,
_
'YE 
A eiyf;;,,E xlh eiEt/h
+ B eiy2mE xlh eiEt/h,
(5)
where A and B are independent of both x and t, but are otherwise arbitrary. Every nonvanishing positive value of E is a doubly degenerate eigenvalue of H, since the two special eigenfunctions iy2;;,,E xlh
Ae
eiEt/h
(6)
and iy2mE xlh iEt/h
Be
e
,
(7)
of which (5) is a linear combination, are linearly independent when E ~ 0. The energy spectrum of a free particle is continuous and degenerate, and the eigenfunctions of H are not quadratically integrable; for these reasons, the theory of a free particle is in some respects more involved than the theory of a linear harmonic oscillator. 27 Comparison of (6) and (7) with 4 shows that each of these functions, besides being an eigenfunction of our H, is simultaneously an eigenfunction of p, and that (6) belongs to the eigenvalue V2mE of p, while (7) belongs to the eigenvalue V2mE of p; the values ± V2mE of p (corresponding, respectively, to rightward and leftward motion) are just the possible values of p of a classical free particle of energy E. The general energy state (5) of a free particle is thus a superposition of two momen
THE SCHROEDINGER METHOD
146
§28
tum states; in fact, the possible results of a precise measurement of the momentum of a free particle whose state is specified by the Schroedinger function (5) are V2mE and V2mE, the respective relative probabilities of these results at any time being I AeiEt/h 12 and I BeiEt/h 12, that is, I A 12 and I B 12 • The distributioninx, :;hVIE, for the state (5) is stationary and has the general form . F.1g. 27 2i . shown m vVe saw in §18 that the knowledge of the energy of a linear harmonic oscillator with certainty leaves the Schroedinger function specifying the state of the oscillator undetermined only to the extent of an arbitrary multiplicative constant, and that consequently the condition that the energy of the oscillator is a certainty constitutes a maximal set of conditions on the oscillator: if the statement that the energy of the oscillator is a certainty is made, no relevant information, not already implied in this statement, can be added to it. In the case of a free particle, the situation is different on account of the degeneracy of the energy spectrum: the knowledge that the energy of a free particle is a certainty does imply that the Schroedinger function is (5), yet it leaves both A and B in (5) arbitrary. This means that the condition that the energy of a free particle is certainly E does not constitute a maximal set of, conditions when E > 0, and can be supplemented by further information concerning the particle. For example, the statement that the energy of a free particle is certainly E, E > 0, may be accompanied by the statement that the momentum is also a certainty and equals + V2mE; in this case the Schroedinger function has the form (6) and is undetermined only to the extent of an arbitrary multiplicative constant: these conditions that both E and p be certainties constitute a maximal set of conditions on a free particle. In fact, the condition that the momentum of a free particle be a certainty constitutes a maximal set, since if the momentum is certainly p the energy is 2
necessarily certainly ~ p • The iffunction (5) can be written as 2 . '¥E = sm V2mE h x + D cos V2mE h x ) eiEt/h ; b u t th•1s expression
., (c .
does not display VIE as an explicit superposition of momentum states, and the form (5) is usually preferable. 7 N onstationary states. We consider next how the Schroedinger 7
C. G. Darwin, Proc. Roy. Soc., 117A, 258 (1927).
147
FURTHER PROBLEMS
§28
function y; describing the state of a free particle at the instant t can be found if it is known to be y;° at t = 0; in the fieldfree case, 16 the second Schroedinger equation 1 has the form
a ax 2 i/1 = at i/;,
ih a2 2m
(S)
so that, stated in mathematical terms, our problem is to fihd that solution of (8) which at t = 0 reduces to the given i/;°. If vi is an eigenfunction of H belonging to the eigenvalue E, then, as has been shown, VI is simply Vlo eiEt/h; but, if the energy of the particle is not a certainty, VI is more complicated. In §16 we found that the solution of the corresponding problem for the case of an oscillator can be obtained by first resolving Vlo in terms of the eigenfunctions of H referring to t = 0, and then attaching the appropriate time factor to each term in the summation. Essentially the same procedure can be used in the present case, except that: (a) since to all but one eigenvalue of H there belong two linearly independent eigenfunctions, the simultaneous eigenfunctions of H and p, rather than the eigenfunctions of H alone, are to be used in the expansions; and (b) integrals must be employed instead of sums. The functions that will play a fundamental part in our calculation are thus the functions (6) and (7), which all have, apart from a multiplicative constant, the form .I, 'YP
=
ipx/h ip2 t/2mh
e
e
,
(9)
where p is the numerical value of the momentum (positive, negative, or zero) and where VIP is used for brevity instead of the more explicit symbol VIE,p . For t = 0, the functions (9) become ./,0 _ 'Yp 
ipx/h
e
.
(10)
We now proceed formally in a manner parallel to that of §16. First, we expand the given l/;0 in terms of the (continuous) set (10):
,{;°
=
f
Cpijt~
dp;
(11)
16
Equation (11) is analogous to 13 • Secondly, we substitute if;p, given by (9), for VI~ in (11), and denote the resulting function of x and t by if;:
(12) Equation (12) is analogous to 1416 • ·More explicitly, according to
148
THE SCHROEDINGER METHOD
§28
(10), 3027 , and 31 27 , Equation (11) is
iJ;° while (12) is if; = h1
f [!
if} eipx/h dx
1: [L: if;°
J
= h1
eipx/h dx
J
eipx/h
dp,
/Pxlh eip2t/2mh
(13)
dp.
(14)
At t = 0, the right sides of (14) and (13) are the same, and consequently it remains only to show that (14) satisfies (8). Now, differentiation of (14) once with respect to t under the. integral sign introduces the factor ip2/2mh in the integrand of the integral with ,respect top; differentiation8 of (14) twice with respect to x under the integral sign introduces the factor (ip/h) 2 in the integrand of the integral with respect to p; and, since (ih/2m) (ip/h) 2 = ip 2/2mh, (14) is a solution of (8). Our problem has been solved: if the Schroedinger function describing the state of a free particle is if} at t = 0, then it is (14) at the instant t. The case when i/;0 is a discrete superposition of momentum states, that is, has the form (15) y;O = c1 eip'x/h + c2 eip"x/h + ca eip'"x/h + · · · , is a special case of the continuous superpositions considered above; but it can be treated without reference to (14), since we can readily verify that the function r = c1 eip'x/h eiE1 t/h + c2 eip"x/h eiE2 t/h + ca eip"'x/h eiE3 t/h + · · · , (16)
.I,
where E1 = (p')2 /2m, E2 = (p")2 /2m, and so forth, satisfies (8) and reduces to (15) at t = 0. Constancy of p. According to classical mechanics, the momentum of a free particle is a constant of motion, so that if it is certainly p (that is, if it certainly has the numerical value p) at the instant t = 0, then it will continue to be certainly p for all time; or, if the momentum of a classical free particle at t = 0 is nof a certainty, then the distributioninp at any subsequent time is the same as it is at t = 0. The situation is similar in quantum mechanics. In the first place, if the momentum of a free particle at t = 0 s Note that the bracketed part of (14) is independent of x.
149
FURTHER PROBLEMS
§28
is certainly p, then the Schroedinger function at t  0 is a constant multiple of (10), and the timedependent Schroedinger function is a constant multiple of (9); and, since (9) is at any time an eigenfunction of momentum belonging to the eigenvalue p, it follows that, if the momentum of a free particle is certainly p at t = 0, it will continue to be certainly p for all time. "Secondly, if the momentum of a free particle at t = 0 is not a certainty, so that the Schroedinger function for the instant t has 27 the general form (14), then by inversion (Exercise 2 ) we get
[JVJ°
eir,x/h
dx
J
J
eip2 t/2mh =
if;eipx/1,
dx.
(17)
Now, according to the transformation formula 5827 , the right side of (17) is h1 times the amplitude, (p I), of the distributioninp at the time t, while the bracket on the left side of (17) is h1 times the amplitude, (p l )0 , of the distributioninp at the instant t = 0; consequently (p I ) = (p I )o eip2t/2m\ 8)
ci
so that the amplitude of the distributioninp for any state of a free particle depends on t in a rather simple way. The distributioninp at the time t is C
I P) (p
l )
= Vo. The Schroedinger equation is now
IL
1 fJX a2 ~ + V(x)i.t 2
K
(1)
= Eif; 7
where
Vo V(x) =
{
>
for x for a for a
0
0
Vo
< a g(xo), then u"(xo)/u(xo) is negative, and hence u is concave toward the xaxis at x = xo ; similarly, if u(xo) ~ 0 and X < g(xo), then u"(xo)/u(xo) is positive, and hence u is convex toward the xaxis at x = xo . 3. If u(xo) = 0 and X ~ g(xo), then u"(xo) = 0 and u'"(xo) so that u inflects at x = Xo •
~
0,
4. If u(xo) ~ 0, X = g(xo), and g' (xo) =p 0, then u" (xo)  0 and u"' (xo) =p 0, so that u inflects at x = Xo • 5. If u' vanishes at X1 and at X2, and if X > g(x) everywhere between x1 and x2 , then u vanishes at least once between X1 and X2. {Integration of (1) between Xi and x2 gives u'(x2)  u'(xi)
1
+
x2
[X  g]udx
1
1 x2
=
0, that is,
[A  g]udx = 0, so that, if [A  gJ does not change sign
1
between x1 and x2, then u must do so.}
6. The function uu' can, at most, vanish once in a region throughout which X < g(x); for example, u cannot have two nodes, or a maximum and a node in such a region.
170
THE SCHROEDINGER METHOD
§32
{ If uu' vanishes at X1 and X2, then, by Rolle's theorem, d(uu')/dx must vanish at least once between x1 and x2 ; now, d(uu')/dx = u'u' + uu" = (u') 2 + [g  A]u 2 , and hence d(uu')/dx > 0 wherever A< g.}
7. If ?:t1 and u2 are two particular solutions of (1) then (2)
where c is a constant.
u:' and u;' by means of (1).}
{Differentiate (2) and eliminate
8. The condition c = 0 in (2) is necessary and sufficient m order that u1 and u2 be linearly dependent. {Necessity: if u1 and u2 are linearly dependent (so that u2 = const. X u1), then tbe left side of (2) vanishes. Sufficiency: set c = 0 in (2), getting u~/u1 = u;/u2 , and integrate, getting log u1 = log u2 + constant, that is, u2 = constant X u1 . }
9. Two linearly independent solutions of (1) cannot vanish at the same value of x. 10. If U1 is a particular solution of (1), then
U2
=
U1
rx ul
}xo
2
dx,
where Xo is an arbitrarily fixed value of x, is another particular solution of (1); further, u 1 and u2 are linearly independent, so that u = Au1
+ Bui }xo {"' ul
2
dx,
(3)
where A and B are arbitrary constants, is the general solution of (1).
I=
{ U2
l1X
U1
2
U1
dx
xo 2 U1U1 I
2 f U1 U1
=
I/
(theorem 8)
u1
2
£x
U1 •
u2 satisfies (1).
+ U1U1
=
I Jrx
U1
2 U1
dx = [g 
0
+ U11 ; U2I/ = U11/iX U12 dx +
x
xo 2 U1
dx
X]u1
1
u1 2
xo
dx = [g  A]
U2;
hence
xo
Substitution of u1 and u2 into (2) yields c = 1, and hence and u2 are linearly independent.}
11. If u 1 and u2 are the two particular solutions of (1) that satisfy the conditions20 u1(0) = 1,
u~(O) = 0,
u2(0) = O,
u~(O) = 1,
(4)
It is quite immaterial for our purposes whether the explicit analytic expressions for u1 and u2 are available or not. 20
FURTHER PROBLEMS
171
§32
and v is the function
Vui + u~,
v(x) 
(5)
then v'(O) = 0
v(O)  1,
(6)
and v(x)
>
(7)
0,
so that v is a nodeless function of x. {The equation
(8) holds for x = 0 and hence (theorem 7) it holds for all values of x; consequently u1 and u2 are linearly independent (theorem 8), and (7) follows from theorem 9. Fig. 42, computed numerically, shows v for X = 1, 2, and 3 when g(x) = x2.}
2
1
0
1
2 x
Fig. 42. Graphs of v(x) for the case g(x) = x 2 •
12. If u1 and u2 are the particular solutions (4), and is the function (x) = tan i
udu1 ,
(9)
then cp(O) = 0
(10)
and (11)
so that is an increasing function of x.
+
{ct/= d(tan 1 u2/u1)/dx = (uiu;  u2u~) (ui u:) 1; (11) then follows from (8) and (5). Graphs of for X = 1, 2, and 3 when g(x) = x 2 are shown
in Fig. 43, computed numerically.}
172
THE SCHROEDINGER METHOD
§32
Fig. 43. Graphs of (x) for the case g(x) = x 2 •
13. The general solution of (1) can be written in the form u = Cv(x) sin [(x)  8],
(12)
where C and 8 are arbitrary constants ;21 it is then the factor sin [(x)  8] that is responsible for the nodes of u. {Since u1 and u2 satisfying (4) are linearly independent (theorem 8), the general solution of (1) is u = A u1 + Bu2 . Using (5) and (9), we get Au1 Bu 2 = (ui + u~)i[Aui/(ui + u~)t + Bud(u~ + u~)t] = v[A cos cp B sin].= (A 2 + B 2)i v[A cos ¢/(A 2 + B 2)i + B sin ¢/(A 2 B2)l), and, introducing the constants C 2 = A 2 + B 2 and 8 =  tan 1 A/ B, we get (12).}
+
+
+
14. The function v(x) is the particular solution of the equation v"
+ [X
 g(x)]v
=
v 3
(13)
that satisfies the conditions (6)
v(O) = 1,
v'(O) = 0.
(14)
,{To verify (13), substitute (12) into (1), noting that, in view of (11), u" = C(v"  v 3 ) sin[  0) = (v"  v 3 )v 1 u.}
15. If u"
+ [X
 g(x)]u = 0,
(15)
and
U"
+ [X +
E 
g(x)]U = O,
(16)
It should perhaps be emphasized that, when g and X in (1) are given, then both v and are definite functions of x even though their analytical forms may not be available. 21
173
FURTHER PROBLEMS
§32
where E is a positive constant, then U has a node between every two nodes of u; that is, the nodes of u are separated by nodes of U. This theorem is a special case of Sturm's first comparison theorem:22 {Multiply (15) by U and (16) by u; subtract, getting Uu"  uU" = EUU, that is, d(u'U  uU')/dx = EuU; integrate this between pwo successive nodes xi and X2 of u, getting u'(x2)U(x2)  u(x2)U'(x2)  u'(x1)U(x1)
+
1 x2
u(x1)U'(x1) =
E
uUdx, that is,
1
(17) Suppose now that 'U is positive between X1 and X2 and that U is positive at and between xi and X2 ; then (Fig. 44) the left side of (17) is negative, while the right side of (17) is positive, and we have an inconsistency. We may change the sign of u, of U, or of both, and may allow U to have a node at x1 , or a node at X2 , or nodes at both xi and X2 ; but the inconsistency persists until we allow U to have a node between Xi and x2 . } Fig. 44.
The bound case. If V(x) ~ oo when I x I ~ oo, then the classical motion of a particle of given total energy does not extend outside certain values of x, and we call the motion bound. If X1 and x2 are, respectively, the smallest and the greatest roots of the equation g(x) = X in a bound g case (Fig. 45), then we use the terms left outer, inner, and right outer region to denote, respectively, the region at the left of x1 , that beXi . X2 x tween X1 and X2 , and that at the ..,._ Inner Region ~ right, of X2 • Fig. 45. A bound case. 16. In the bmind case, u has at most a finite number of nodes. {It is perhaps obvious that u has a finite number of nodes (if any) in the finite inner region; and it has at most one node in each of the two outer regions (theorem 6).} 22
E. L. Ince, Ordinary Differential Equations [hereafter cited as Ince],
page 228.
174
THE SCHROEDINGER METHOD
§32
17. In the bound case, (x) 
d,
(19)
where A is an arbitrary constant. When x ~  oo, (19) becomes oo ·O; to resolve the indeterminacy, we rewrite (19) as A sin [  1]/v 1, and replace this by the quotient of the derivatives of the numerator and denominator, that is, by A cos [ct,  d'/(v2v') = A cos[  1]/v'; the last fraction tends to zero when x ~  oo (theorem 19), and hence (19) does also. Solutions of Equation (1) pertaining to the case g = x 2 and having the form (19) are shown in Fig. 46. All of the solutions shown have the same A. The point at which a curve emerges from the inner into the right outer region is marked by a crossline. In the left portion of the figure, some curves lie too close together to be drawn separately. Note that as A increases the nodes (except that at  oo) move leftward (as is to be expected from theorem 15 when all u's under consideration have a node at  oo) and that after the rightmost node has moved into the inner region a new node forms at + oo. Note also the good behavior of the curves for A = 1 and X = 3, that is, for A's that, according to 284, are eigenvalues of Equation (1) when g = x 2 •
175
§32
FURTHER PROBLEMS u
Fig. 46. Solutions of the form (19) for the case g(x)
x2 •
Solutions of type (c) are Cv(x) sin [¢(x)  ¢2].
(20)
Solutions of type (b) are linear combinations of Bv(x) cos [¢(x)  ¢il and (19); those of type (d) are linear combinations of Dv(x) cos [¢(x)  ¢2] and (20).}
21. If u remains finite in an outer region, then it approaches zero when x recedes outward in this region. {The solutions v sin[¢  ¢2] and v cos [¢  ¢2] are linearly independent (theorem 8), so that the general solution of (1) can be written as u = Cv(x) sin [cf,(x)  21
+ Dv(x)
cos [¢(x)  ¢21,
(21)
where C and D are arbitrary constants. When x + oo, the first term in (21) approaches zero and the second term increases with out limit (theorem 20); hence u remains finite when x + oo only if D = 0; but in this case u approaches zero when x + oo. Substituting ¢1 for 2 in (21), we get the general solution in the form suitable for proving the theorem for the left outer region. A graphical argument runs as follows: Let u(xo) > 0 (Fig. 47), where Xo lies in the right outer region, so that u is convex toward the xaxis everywhere at the right of xo (theorem 2). Now (a) if u' (xo) ~ 0, then u + oo when x+ oo. If u'(xo) < 0, there are three possibilities: (b) when x+ oo, u remains positive, has a minimum at the right of xo, and then goes to oo;
176
THE SCHROEDINGER METHOD a
§32
(c) u approaches the xaxis when x ~ oo; (d) crosses the xaxis at the right of xo , inflects at the crossing (theorem 3), and then goes to  oo. Thus remains finite only in the case (c). Similar arguments apply when x 0 is in the right outer region and u(xo) < 0, and when xo is in the left outer region.} 'U
u
22. In the bound case, an eigenfunction of Equation (1) vanishes when
Ix I~ Fig. 47. Possible forms of u in the right outer region.
oo.
23. The quantity ¢2  1 is an increasing function of X and tends to oo when X) oo.
{Differentiate (1) partially with. respect to X, multiply the result by u, and substitute u" for [X  g]u, getting u"au/ax  uau" ;ax = u 2 , that is, d(u'au/ax  uau' /ax)/dx = u 2 ; substitute (12) into this, getting
. 2 [4>  O] d {( v' av v av') sm dx ax ax
. 2(4>  O] } = + ocp  + v av sm ax ax 1 
. 2 [cp  o]. v2 sm (22)
,
Choose some value of x, say xo, and set O = cp(xo); the expression in { } which vanishes at x = 0 in view of (6) and (10), then becomes acp(xo)/a>.. at x = xo , so that, integrating (22) from O to xo , we get act,(xo)
 = a>..
1:ro v sm. 2
o
2 f4>(x)
 (xo)] dx.
(23)
The integrand in (23) is never negative, so that the algebraic sign of the integral is the same as that of xo ; hence, when >.. increases, cp increases for positive and decreases for negative values of x, as illustrated in Fig. 43.}
24. In order that X be an eigenvalue of Equation (1) in the bound case, it is necessary and sufficient that
n = 1, 2, 3, . · . .
(24)
{Sufficiency: if (24) holds, then v sin [4>  cpi] = v sin [ct, + n1r  2] = [4>  2], so that a solution of type (19) is also of type (20), and hence remains finite when I x I ~ oo. Necessity: if u is an eigenfunction, then u ~ 0 when I x I  t oo (theorem 22), so that both 2  8 in (12) must be integral multiples of 1r. The condition (24) is illustrated by the graphs of for X = 1 and X = 3 in Fig. 43.}
±v sin
177
FURTHER PROBLEMS
§32
25. In the bound case, Equation (I) possesses a discrete and nondegenerate eigenvalue spectrum of the form A1 , X2 , · • · , Xn , • · ·
where X1 < A2 value of g(x).
< . · · , and
(25)
where X1 is greater than the smallest
{An eigenfunction of (1) vanishes when x +  oo (theorem 22) and hence has the form (19). If A is smaller than the smallest value of g, then (19) has no nodes besides that at  oo (theorem 6); hence 2  1
THE SCHROEDINGER METHOD
= !i log I ~ I +
§34
c2 , recalling that the logarithm of a negative
function differs only by an imaginary constant from the logarithm of the absolute value of the function, and that c2 is an arbitrary constant in any case. Thus we get the approximate equation ¢(x)
1'.I
o(x)
+ !ih log I ~ I ,
. (9)
where ¢0 is given by (8) and c2 is absorbed in C1 . Substituting (9) into (2) and rearranging the result, we finally get our approximate solution in the form v,'app.
= C{2m IE V(x) l}l
exp (±{ f
V2m[E=V(x)]dx ),
(10)
where C remains arbitrary. The two solutions contained in (10) and differing in the sign of the exponent are linearly independent, and hence the approximate general solution of (1) is
Vlapp.
=
exp Gf +Bexp(kf
{2m IE  V l}t {A
v'2m[E  V] dx)
V2m[EV]dx)},
(11)
where A and B are arbitrary constants; an alternative form of (11) IS
Vlapp.
=
Cl2mJE Vl}1
cos{1L"
V2m[E V]dx+e},
(12)
where C and () are arbitrary constants. The approximate solutions (11) and (12) of the Schroedinger equation are usually called W. B. K. ffunctions, or B. W. K. ffunctions. 7 Connection formulas. Consider now the case (Fig. 51), when V is greater than E everywhere in region I lying at the left of X1 • Then set xo = X1 in (11), and recall that the precise soiutions of (1) that are of interest to us are reI X1 II quired to be wellbehaved. Writing [E  V] 1 = i [V  E] 1 and remembering that x < X1 in region Fi g. 51.
~
189
§34
APPROXIMATE COMPUTATIONS
I, we then find that as x ~  oo the Aterm in (11) increases without limit while the Bterm approaches zero. Hence, in order that (11) may approximate a solution of (1) which remains finite when x ~  oo, we must set A == 0 and adopt the function (13)
as the appropriate approximation for region I. Incidentally, at x = x1 the function (13) becomes infinite on account of the factor { }i, and hence, although (13) may be a good approximation to a precise solution of (1) for values of x lying sufficiently far to the left of x1 , it certainly departs violently from this solution when x ~ x 1 ; this departure is illustrated in Fig. 54, which presents the correct ffunction for the fifth energy state of an oscillator together with a W. B. K. approximation to this function. In region II of Fig. 51 no limitations are put on the arbitrary constants, and we may take the approximate general solution to have the form (12). Now, how should the adjustable constants in (12) be chosen in order that (12) may connect properly with (13), that is, in order that (12) may approximate in region II the same exact solution of (1) which (13) approximates in region I? A complicated computation, which we omit, gives the following answer: the approximate solution for region II that connects properly with (13) is
lf!~P
= 2B {2m[E  V]
1 {1 f 1
cos
"V2m[E  V] dx 
which is obtained from (12) by letting C = 2B, xo = X1 , and fJ =  !1r. Incidentally, from the elementary standpoint, (13) and (14) do not join at an smoothly at x1 , where both are infinite; but both are, of course, poor approximations near X1 • For the case (Fig. 52) when V is greater than E everywhere at the right of x2 , it is found that the appropriate approximation for the region III is
h},
(14)
4
t
!
Fig. 52.
(15)
§34
THE SCHROEDINGER METHOD
190
and that the function approximating in region II of Fig. 52 the same exact solution of (1) that (15) approximates in region HI is it,!~p.
= 2A {2m[E 
VW 1
cos{i i:
+ !1r}·
'V2m[E  V]dx
(16)
The bound case. We turn next to the bound case, restricting ourselves to a potential V such that V' vanishes only once, as in According to theorem 25 of §32, the energy in this case is quantized, a fact that shows up in our present approximate work as follows: On the one hand, V!'app. must have the form (13) in region I, so that in region II it must have X2 fil II I the form (14); on the other hand, ~app. must have the form (15) in Fig. 63. A bound case. region III, so that in region II it must have the form (16). Consequently, the proper connections can be made only if the functions (14) and (16) are equal to each other, that is, only if throughout region II we have Fig. 53.
B
COS
1 {h
lx x1

41 1r} = A
COS
{1h,
1·i; + 41 } 7r
x2
'
(17)
where f stands for f 'V2m[E  V] dx. Now, differentiating (17) with respect to x and canceling the factor common to both sides of the result, we get an equation precisely like (17), except that the cosines are replaced by sines; and combining this equation with (17), we get
lr~ lx
tan h
x1

1 } 4 7r
 . {~ tan h
1x + 41 } x2
7r
•
(18)
Since the period of the tangent is 1r, the arguments of the two tangents in (18) must differ by n1r, where n is an integer or zero, and we finally get x2
2
v'2m[E V(x)] dx = (n
[
+ !)h,
n
= 0, l, 2, · · · , (19)
1
where negative n's are suppressed, since the left side of (19) is positive. For a preassigned V, Equation (19) is a condition on E, and consequently only for particurar E's is it possible properly to connect our approximate 1/;'s. The rondition (19) is thus an
191
APPROXIMATE COMPUTATIONS
§34
approximate quantization rule for the energy when the potential has the form shown in Fig. 53. Examples. To illustrate the use of (19), we shall employ it to estimate the energy levels for the case of the particular potential V(x) = Kx4. The integrand in (19) is now even in x, and the claSsical limits of motion for a particle of energy E are = (E/K)1 and x2 = (E/K)l, so that (19) becomes
ri
((E/K)i
4
Jo
'V2m[E Kx4] dx = (n
+ !)h,
n = 0, 1, 2, · · · . (20)
The substitution y = Kx 4/E sends (20) into
v'2m,Ir1 E1
f
(1  y) 1 y1 dy = (n
+ !)h.
(21)
The integral in (21) is approximately8 3.50, so that, writing En for E, we finally get
En= .87(2n + l)!KJK\
n
= 0, 1, 2, · · ·
as the approximate formula for the energy levels. levels are given by (22) as
(22)
The two lowest (23)
Fig. 54. Top: a Schroedinger function. Bottom: the W.B.K. approximation to this function.
Comparison with 21 33 shows that, when V = Kx4, the formula (19) underestimates the lowest level by about 18 per cent, and the second level by about 1 per cent; this formula usually gives better results for the higher levels. The B.\V.K. it,function for the fifth energy state of a linear harmonic oscillator is shown in Fig. 54, together with a correct Schroedinger function for this state. The corresponding distributioninx, ;j;app. \f"app. , is shown in Fig. 55; note that in the inner region this distribution is a compromise between the
See, for example, H. B. Dwight, Tables of Integrals and Other Mathematical Data, formula 855.2 and table 1018; New York: The Macmillan Co., 1934. Or B. 0. Peirce, A Short Table of Integrals, formula 482 and the table of logarithms of the gamma function; Boston: Ginn and Co. 8
192
THE SCHROEDINGER METHOD
§34
classical and the correct quantummechanical distributions, both of which are shown at the top of the figure. A comparison with the Bohr theory. In the Bohr theory, the energy of a particle moving in the field shown in Fig. 53 is quantized by the WilsonSommerfeld rule, which states that 2
Fig. 66. Top: a Schroedinger distributioninx and the corresponding classical distributioninx. Bottom: the W.B.K. distributioninx for the same state.
2 [: pdx
= nh,
where p is the momen
tum of the particle at the point x, and n = 1, 2, 3, ... ; this rule can be rewritten
as2 f\!2m[EV(x)] dx = nh.
The
WilsonSommerfeld rule and the in general more accurate approximate rule (19) may be contrasted by saying that the former uses integer quantization and the latter odd halfinteger quantization. Note that the WilsonSommerfeld rule bears some resemblance to the exact formula 2632 • Exercises 1. Show that (19) yields (fortuitously) the correct energy levels for the linear harmonic oscillator. Remember Fig. 54, however. 2. Show that if V(x) = c I x I, where c is a positive constant, then the approximate energy levels given by (19) are En = [3c(n + !)h/8V2m]i. 3. Apply, in turn, the rule (19) and the WilsonSommerfeld rule to a particle in a box and compare the results with 530 • 4. Consider a region in which E > V and show that the factor {}i in (11) contributes to the approximate distributioninx, Japp .. V'app. , a factor that is just the classical distributioninx. What is the nature of the remaining factor in Japp. lfapp. ? 6. Consider a particle in a potential box with a slanting bottom, Fig. 11 17 , and show (essentially by inspection) that for the higher energies the W. B. K. method gives a result in qualitative agreement with the corresponding classical result of Exercise 14 11 • We do not stress the agreement for the lower energies, because for lower energies this method might be unreliable; but see Exercise gaa. 6. Show that our disregard for the physical dimensions of cf>~ in (7) does not invalidate (10).
193
APPROXIMATE COMPUTATIONS
§35
35. A Variation Method 9 In preparation for the next method of approximation, we shall say a word about ordinary curve fitting. If a given curve (say a trace made by a recording instrument), whose correct equation y = F(x) is either unknown or inconveniently too complicated, happens to be approximately straight, it is often expedient to write y = ax + b, to adjust the numerical values of the constants a and b so as to obtain a 'best fit' to the given curve, and then to use the linear equation as an approximation to the correct one. Similarly, if the given curve resembles a parabola, the function 2 y = ax + bx + c may be profitably fitted to it; in general, if a given curve has a shape resembling that of some simple function, it is sometimes expedient to adjust the numerical constants in this function so as to fit the given curve best, and then to use the resulting function as an approximation to the given curve. The process of curve fitting consists essentially of three steps: I, to choose a function f(x) that has the appropriate general shape and contains adjustable constants a, b, · · · , II, to decide on a criterion of 'best fit,' and III, to adjust the constants a, b, · · · , in f(x) so as to obtain the best fit. In its most elementary aspect, which alone we shall consider, the variation method for approximate solution of a onedimensional first Schroedinger equation can be viewed as essentially a process of curve fitting, consisting of the steps I, II, and III enumerated above. To be sure, in ordinary curve fitting we fit &. chosen function to a given curve, while in the variation method we fit a chosen function to an unknown solution of a given differential equation; the underlying ideas of the two types of computations have, nevertheless, much in common. In describing the method, we shall restrict ourselves to approximating the lowest eigenvalue Eo and the corresponding normalized eigenfunction i/;o of the Schroedinger equation pertaining to bound motion. I. The choice of the approximating if;. Our first step is to write down a function if; that has the same general shape as the 9
For important ramifications and extensions of this method (which, from the mathematical standpoint, is best approached through the calcuIus of variation) and for references see, for example, Pauling and Wilson, and Kemble.
194
THE SCHROEDINGER METHOD
§35
unknown fo and contains some adjustable constants a, b, · · · . This step is feasible because the theorems of §32 enable us at once to enumerate several important features of the unknown y;0 • Thus Ylo , being the lowest eigenfunction for a bound motion, can be taken as real, vanishes when I x I ~ oo , has no nodes at finite values of x so that it can be taken as everywhere positive, and has one maximum and no minima; if V(x) happens to be even in x, then Ylo is also even in x. A person familiar with the shapes of YIfunctions in a variety of special cases could perhaps infer additional information about Ylo by inspecting the given V(x) more closely. We shall take it for granted in the sequel that YI is normalized. To illustrate: If V = Kx 4, say, then t/;o vanishes when I x I+ oo, has no nodes at finite values of x, is even in x, and, if taken as positive, has a maximum at x = 0. Several simple functions of this general shape come to mind, among them the function VI = N(l + a 2x2)2, where N is the normalizing factor and a is a single adjustable constant that we shall take to be positive; written out in detail, this function is 
,t, 
4
l
a 
51r (1
1 + a2x2)2'• ( 1)
graphs of (1) for three values of a are shown in Fig. 56. Thus, for example, in dealing with the case V = Kx4, we may adopt (1) as the function to be fitted 10 (by an adjustment of a) to the unknown Vlo . x 2 1 0 1 Fig. 56. Graphs of the function (1).
Extraordinary coincidences excepted, the approximating YI chosen in this manner is of course not precisely equal to the unknown y;0 even for special values of the adjustable constants; 10 Incidentally, the function (1) would be a rather bad approximating VI when V = Kx4, because it does not decrease sufficiently fast when I x I grows large. Indeed, for large values of I x I, Equation 133 becomes if;" rv KKx4if;; for large values of I x I, approximate solutions of the latter equation are xPe±qx3, where pis arbitrary and 9q 2 = KK; the function (1), on the other hand, behaves for large values of I x I as x 4 •
195
APPROXIMATE COMPUTATIONS
§35
instead, VI is a superposition of the various unknown instantaneous Schroedinger eigenfunctions of H. But, since VI has substantially the same shape as 1/;0 , i/;0 appears in this superposition particularly prominently; in other words, the approximating VI represents instantaneously a state for which the energy of the system is not a certainty, but is particularly likely to be Eo . II. The criterion of best fit used in approximating the lowest eigenfunction by the variation method can be set up as follows: Let Eo be the lowest energy level of the system (that is, the lowest possible result of a precise measurement of the energy of the system). Let av Ebe the expected average of the energy (that is, the probabilityweighted arithmetic average of the possible results of a precise energy measurement) of this system for some state that is either the normal state, or a higher energy state, or, in general, a superposition of the various energy states. It is then 11 perhaps obvious (if not, recall Exercise 17 ) that av E > Eo . If the state in question is specified by a Schroedinger function VI, so that we may replace the symbol av E by avt E, this result takes the form
(2) The = sign in (2) applies if and only if VI is the Schroedinger function i/;o specifying the normal state of the system. Now, if if; is normalized, then, according to the Schroedinger 18 expectation formula 2 , av1,
E
= f if;Hif., ax,
(3)
where His the Hamiltonian operator of the system; and, combining (3) with (2), we conclude that
J if;Hif., dx > Eo,
(4)
whenever if; is normalized. The relation (4) holds, of course, whether if; is an instantaneous or a timedependent i/;function. The relation (4), taken together with its special case
f if!oHY'o ax =
Eo,
(5)
suggests the following criterion of good fit, adopted in the variation method: of two normalized f's, the one for which the integral f if;Hy; dx has the lesser numerical value is the better approximation
to Vlo •
196
§35
THE SCHROEDINGER METHOD
III. Adjustment of the constants in if;. Substitution of the
approximating if; into f ij;Hif; dx yields a number involving the adjustable constants a, b, ... , appearing in if;. According to the criterion quoted above, to make t/; fit the unknown 1/;0 best, we must choose these constants so as to make ff Hif; dx as small as possible. Thus our problem reduces to that of minimizing a function of a, b, .. · , so that, to determine the best values of a, b, , we need only to solve simultaneously the equations a
aa
J
if;Htf; dx
=
0
a ab
'
J
i/;Htf; dx = O, · · · .
(6)
To illustrate, we return to the potential V = Kx 4 and to the approximating function (1). We have
f =
;jH,t, dx
f [4II f +
2
(1 +a2x
= I6a 51r
[4a2 (1
2 ) ]
[  : :;.
a2 x2)a  24a4 x2(1
K
+ Kx4
J[41
: (1 5
+ a•x2)}x
+ a2 x2)6 + Kx4(1 + a2 x2)4] dx, (7)
K
and evaluation of the integral yields
f Thus d da

7a 2 fH.f; dx = 
5K
f
tf;Hif; dx
+ 5aK · 4
= 14a  4K  5, 5"
5a
(8)
(9)
so that the value of a that minimizes f ;j;H.f; ax satisfies the equation 14a/5"  11K/10a5 = 0, whose positive solution is
(10) Substitution of (IO) into (1) now yields that function which, among all functions of the form (1) with a positive a, is (according to the criterion adopted above) the best approximation to 1/;o for the case V = Kx 4 ; when just two significant figures are kept in the numerical coefficients, this function is .91K1ll2K1!12
t/;
=
(1
+ .66K!Ktx 2) 2 .
(11)
The approximate value of E o· Since the relation
(4)
Eo
l + 1,
(27)
so that the following n values of l are compatiblle with a prescribed value n of the principal quantum number: (28)
l = 0, 1, 2, · · · , (n  1).
Now, there are 2l + 1 values of mz which are compatible with a prescribed value l of the azimuthal quantum number, and therefore there are [20
+ 1] + [21 + 1] + [22 + 1] + .. · + [2.(n 
1)
+ 1]
= n 2 (29)
463
§80
MOTION IN THREE DIMENSIONS
distinct pairs of values of l and mz which arc compatible with a prescribed value n of the principal quantum number. And, since the energy formula (18) involves only n, it fol1ows that in the
Coulomb case the degeneracy of the nth quantum state is n 2fold. The continuous energy spectrum of the hydrogen atom (that is, the spectrum consisting of all positive values of E) is also degenerate. But a discussion of this dPgeneracy lies outside the scope of this book. Concluding remarks. A particle moving classically in a central field remains in a plane that is perpendicular to the orbital angular momentum L; consequently, shou]d we expect the motion to exhibit any symmetry at all, this Rymmetry wou]d be with respect to an axis having the direction of L and thus inclined to the zaxis at an angle whose cosine is Lz/ L. To determine the direction of L it is of course necesAary to know all the three quantities Lz, L 11 , and Li. Now, quantum mechanically, the knowledge of L% and Ly is incompatible with that of Lz (except for sstates), and consequently, quantum mechanical]y, the direction of L is never known. For state~ for which both Lz and L are known and L ¢. 0, we may, however, picture Las lying somewhere on a cone that makes with the zaxis the angle whose cosine is Lz/ L. It then follows that states with known Lz and L, if they should exhibit any symmetry at all, should exhibit it with respect to the 78 zaxis. This is indeed the case: note, recalling 12 , that our basic ifv/s are independent of cp and, recalling Exercise 278 , that the probability currents associated with the basic y;'s are also independent of cp. A particle moving classically in a central field may remain in the equatorial plane (the xyplane); this case arises when L is directed along the zaxis, so that Lz has the largest value consistent with the value of L, that is, the value Lz = L. According to quantum mechanics, the largest value of Lz consistent with the value v'l(l 1) h of Lis lh, and consequently the smallest angle that L can make with the zaxis has the cosine l/v'l(l 1). This cosine approaches 1 for large values of l, and we may therefore expect by classical analogy that, for a state having a large l and having as large an mz as is consistent with this l, namely, mz = l, the particle should be very likely to be near the equatorial plane. It will be shown in Exercise 5 that this is so. If L = 0, the classical motion of a particle in a central field
+
+
464
THE SCHROEDINGER METHOD
§80
takes place along a st.raight line, passing through 0, whose direction can be ascertained as soon as the initial conditions of the motion are known; but if all we know is the energy of the system and the fact that L = 0, then the direction of this line is entirely indeterminate, and hence the distributioninposition of the particle is spherically symmetric about O. Since states for which L = 0, that is, sstates, are described by spherically symmetric f's, the situation is quite analogous in quantum mechanics. For the basic polar states, the possible orientations of L with respect to the zaxis (not the orientations of L in space, which are never known) can be pictured by vector diagrams. Thus the first diagram of Fig. 106, which refers to the case l = 1, shows the vector L of length L = Vi ·2 h in the three positions corresponding to the respective p States possible values  h, 0, and h of its zcomponent Lz ; d States the second diagram refers Fig. 106. Vector diagrams for L. in a similarwaytodstates. Exercises 1. Consider the normal state (26) of a hydrogen atom and show that: (a) the most probable value of r for this state is ao; (b) av100 r 1 = a 01 ; (c) av100 r 2 = 2a 02 ; (d) if k = 1, 2, 3 · · · , then av100 rk = (k + 2) !a~/2k+l; (e) av100 Pi = h2 /3a5 ; (f) av100 V(r) = e 2 /a 0 ; (g) the average potential energy equals twice the total energy; (h) the average kinetic energy equals minus the total energy. 2. The state of a hydrogen atom is specified at t = 0 by the ffunction (8  p sin fJ eii1>)eP1 2 ; compute the distributioninE, the distributionin£, and the distributioninLai ; and set up the timedependent f. 3. An electron moves in the fixed Coulomb field Ze 2 /r 2 as though a nucleus of charge Ze were permanently located at 0. Show by inspection that the energy levels of this system 35 and the various f's pertaining to it 35 This system is of interest in connection with the socalled hydrogenic or hydrogenlike atoms which, like the deuterium atom, the singly ionized helium atom, and so forth, consist of a nucleus and a single electron.
465
:MOTION IN THREE DIMENSIONS
§80
can be obtained from the corresponding results of this srntion by merely replacing e2 by Ze 2 ; this means, in particular, that, in results expressed entirely in terms of a o , a o is to be replaced by a o/ Z. 4. An electron moving in the fixed Coulomb field of Exercise 3 is in the normal state. Show that then the average electrostatic potential in space due to both the fixed field and the fie] d of the electron itself 2Zr
is e(Z  1)/r + (eZ/ao + e/r)eao. 5. Recall 7874 and show that for a basic polar state with l large and ·vith m 1 = l the particle is very likely to be near the equatorial plane. 6. Note that the motion of a spatial isotropic harmonic oscillator is central, and compute the energy levels 5276 using the constants of motion H, L, and Lz , that is, using polar quantization. 7. Show that the functions RT 1 1, RT~ , and RTf of Exercise 1077 are the basic polar f's of the isotropic oscillator belonging to the first excited state. 8. Show on physical grounds that, if a basic Cartesian if; of an isotropic oscillator (that is, a t/; of the form 4876 ) belonging to the nth energy level is expanded in terms of the basic polar tf;'s of the oscillator (that is, t/;'s of the form 1278 ), then only the polar tf;'s belonging to the nth level will appear in the expansion. The expansions of Exercise 1077 illustrate this result, the converse of which is of course also true.
81. The Bohr Formula for the Hydrogen Atom; Free Nucleus We now proceed to remove the physica1ly unsatisfactory condition that the nucleus of our hydrogen atom be held fixed, and turn to the problem of an electron (mass m, charge  e) and a proton (mass M, charge e) moving nonrelativisticaJly in each other's field and free from external influences. As we have seen in a number of instances, the quantummechanical study of a dynamical system is made quite systematic as soon as the constants of motion of the system are identified. And since the constants of motion of a classical system, which are usually identified rather easily, are certain to be constants of motion of a corresponding nonrelativistic quantummechanical system, we begin with a few remarks on the classical theory of our present system. The coordinates and the components of the linear momentum of the electron will carry the subscript 1, those of the proton the subscript 2. The distance between the two particles is then [ (x1  x2)2 + (Yi  y2)2 + (z1  z2)2]i, their mutual electric potential energy when they are at this distance apart is
466
§81
THE SCHROEDINGER METHOD
e2/[(x1  x2)2 + (Yi  Y2) of the system is
2 + (z1  z2)2]\ and the Hamiltonian
H = 2m l (Px1 2 + PY1 2+2 l(2 Pz1 ) +2M Px2+ 2 PY2+ 2 Pz2) e2
(1)
Since the forces exerted by the proton on the electron, and conversely, are directed along the straight line joining the proton and the electron, and since there are no external forces, it is perhaps obvious that the center of gravity of the two particles, whose coordinates are
X
= mx1
+ Mx2
y =
my1
+ MY_~
m+M'
m+M'
z=
Mz2 m+M '
mz1 +
(2)
will move uniformly in a straight line, while the electron and the proton revolve about their center of gravity as though this center were at rest. Hence we may expect a simplification if we replace the six coordinates of the electron and proton by the three coordi· nates (2) and by three additional internal coordinates describing the internal configuration of the system; for the latter we choose the three coordinates Y
=
(3)
Y1  Y2,
of the electron with respect to the proton. Rewriting (1) in terms of the new variables (2) and (3) and the quantities Px = (m
+
M)X,
P 11
=
(m
+ M)Y,
P:= (m
+ M)Z
(4)
and Px
= µx,.
py = µiJ,
Pz = µz,
(5)
where µ, defined as µ=
mM m+M'
(6)
is called the reduced mass of the system, we get
H =He+ H\
(7)
467
MOTION IN THREE DIMENSIONS
§81
where
He
=
2(m
~ M)
(P!
+ P! + P!)
(8)
and i
H =
1 (
2µ
2
e Px + P11 + Pz  r ' 2
2
2)
(9)
r being the distance between the electron and the proton. The term He in (7) refers to the motion of the center of gravity and is the Hamiltonian of a free particle of mass m + M; the term Hi refers to the internal motion and is the Hamiltonian of a particle of massµ moving in a fixed Coulomb field with V = e2/r; He and Hi have no variables in common, so that the motion of the center of gravity and the internal motion are independent of one another. The total energy E of the system has the form · {10) here Ee is the translational kinetic energy (P; + P; + P;)/ 2(m + M), computed as though the total mass m + M were concentrated at the center of gravity; and Ei is the internal energy, that is, the energy of the electron and the proton moving under each other's influence about their center of gravity as though this center were at rest, or, if we use the particular internal coordinates (3), the energy of a particle of reduced mass µ and charge  e moving about a fixed nucleus of charge e. Insofar as the motion of the center of gravity is concerned, the quantities Px, Pu, and Pz are constants, and since this motion is independent of the internal motion the P's are constants of motion of the complete system; similarly, the constants of the internal motion are also constants of motion of the complete system. Schroedinger theory. In the present problem we encounter for the first time the task of identifying the Schroedinger operators to be associated with the coordinates and the components of linear momentum of two interacting particles. The procedure (which can be justified by a study of Poisson brackets relating to a system containing two particles) is a direct extension of that for the case of a single particle: with the variables X1 , Y1 , Z1 , Px 1 , Pu 1 , and Pz 1 pertaining to the electron we associate.~ the respective operators X1, Y1, Z1, ih a/ax1, ih a/ay1, and ih a/az1; and
468
THE SCHROEDINGER METHOD
§81
with the variables X2 , Y2 , z2 , Pz 2 , py 2 , and Pz 2 pertaining to the proton we associate the respective operators x2 , Y2 , z2 ,  ih a/ ax2 , ih a/ay2, and ih a/az2. The operands of these operators are wellbehaved functions of the six variables X1 , Y1 , z1 , x2 , Y2 , and z2 ; good behavior36 is now defined by a direct generalization of the definition of §7 4. The Schroedinger operator associated with the Hamiltonian (1) is h2 ( H=  2m
a2 a2 +a2) +~ axi ayr azr h2 ( a2 a2 a2) 2M ++ax~ ay~ az~
r
(11)
The classical procedure suggests that we introduce the new coordinates defined by (2) and (3), and the new momentum operators
Px
=
.h i
a
ax'
Py
=
ih _!_
P. = ih a~ (12)
aY'
and Px =
.h  a
i
ax'
PY=
.h a,
1,
ay
Pz=i.h a.
az
(13)
In terms of these, the operator (11) becomes H =He+ Hi,
(14)
where
(15) It should perhaps be emphasized that the two particles· unqer consideration hereelectron and protonare distinguishable. In the case of identical particles, the ffunctions must not only be wellbehaved but must also satisfy certain symmetry conditions (to put it roughly, the additional conditions take care of the experimental impossibility of detecting an interchange of two indistinguishable particles); this extremely 1mportant point lies outside the scope of this book. Incidentally, in the case of two particles, the configuration space referred to in the general Schroedinger expectation formula 117 is a fictitious 6dimensional space; its axes refer to the six coordinates Xi , Yi , z1 , x2 , y1, and z2, so that every configuration of the two particles in 3space is represented by a single point in the configuration space. 36
469
MOTION IN THREE DIMENSIONS
§81
and
Hi
= 
h2 2µ
(
a2
Ox 2
+
a2 Oy 2
+
a2 )
e2
az2
T.

(16)
The commuting dynamical variables
(17)
H, Px' Py' Pz
are among the constants of motion of our system, and we begin by determining the form of their simultaneous eigenfunctions. The simultaneous eigenfunctions of the P's are .I, _ 'Y 
u ( x, y, z) ei(Pfx+P11 y+P~z) /h ,
(18)
where the P"s are arbitrary real constants and u(x, y, z) is an arbitrary wellbehaved function of the internal coordinates. Now, if we operate on (18) with H and write 2(m
1 [P'2 + p'2 + p'2] + M) u x
z
= ·
EC '
(19)
we get
(20) so that if (18) is to satisfy the Schroedinger equation H l/; = El/; we must have
(21) When (18) is explicitly substituted into (21) the exponential factor cancels out, and we are left with
Ecu(x, y, z)
+ Hiu(x, y, z)
=
Eu(x, Y, z).
(22)
If we finally write (23)
Equation (22) becomes
Hiu(x, y, z)
=
Eiu(x, y, z).
(24)
We therefore conclude that the simultaneous eigenfunctions of the variables (17) have the form (18) where u(x, y, z) is a wellbehaved function satisfying (24), and (since the values of the P"s remain unrestricted) that the quantity EC, which we may call the translational energy of our system, is not quantized.
470
THE SCHROEDINGER METHOD
§81
Now, in view of (16), Equation (24) is just the Schroedinger equation for a single particle of mass µ moving in the fixed Cou2 lomb potential e /r, and consequently the possible values of the parameter Ei in (24), that is, of the internal energy of our system, can be obtained from the results of the preceding section by writing µ for m. The conclusion is that all positive values of the internal energy are possible, while its possible negative values are 2
Eni = 
21r µe h2n 2
4
n
,
= 1, 2, 3, . . . .
(
25 )
Exercise 1. Compare the energy levels of the internal motion of the hydrogen atom, the deuterium atom, and a singly ionized helium atom of mass 4.
82. The Fine Structure of the Hydrogen Levels When the spectrum of atomic hydrogen is studied with apparatus of moderate resolving power, the discrete energy levels are found to be just those given by the Bohr formula
(1880)
En
=

2
2
21r me4/ n h2,
(1)
provided this formula is corrected for nuclear motion, 37 as we have done in §81. But when high resolution is employed it is found that the levels which the Bohr formula requires to be singlets are, in fact, with the exception of the lowest level, very narrow multiplets. The fine structure of the l.ower portion of the hydrogen energy 38 spectrum is shown schematically in Fig. 107. The long thin lines mark the positions of the singlet levels required by the Bohr formula; these levels are shown as equally spaced, although their separations, in fact, decrease with increasing n. The short thick lines show the actual levels. The displacement of each member of the nth multiplet below the nth Bohr level, measured in terms of the unit 4 (2) me8/2c2h4n, In the remainder of our work with the hydrogen atom we shall disregard the corrections for nuclear motion. 38 By permission of The Cambridge University Press and The Macmillan Company, publishers, our energylevel diagrams for hydrogen are patterned after Fig. 25 of Condon and Shortley. 37
471
MOTION IN THREE DIMENSIONS
is indicated by the number at the right of the corresponding short line. Since the unit {2) decreases with n, the diagram exaggerates the widths of the higher multiplets; it also exaggerates the separations of the members a multiplet compared to the separations of the Bohr levels. The formula that gives the levels correctly 39 was obtained ~n 1915 by Sommerfeld, who extended Bohr's quantization rules to an electron moving in a Coulomb field according to the laws of Einstein's theory of relativity, rather than the laws of Newtonian mechanics. Sommerfeld's finestructure formula is
of
E nk
2]i = me [1 + ( ) nk+~ a
2
where the principal takes on the values
quantum
n
=
§82 1
q}13
115
~
13 1
M3 II
~
9
N} II
~....5
4
111 ~
(3)
number n
Fig. 107. Fine structure of hydrogen levels.
(4)
1, 2, 3, · · · ,
and the auxiliary quantum number k takes on, for a prescribed value of n, the n values (5)
k = 1, 2, · · · , n. The symbol c denotes the speed of light, while a, defined as
e2
(6)
a= 
ch
and called the Sommerfeld finestructure constant, is a pure number whose value is approximately d7 . Since a 2 is very small compared to k2, the term k in (3) is almost canceled by the radical following this term, and ther~fore the levels having the same n but different k's lie very close together compared with levels having different n's; the formula (3) thus describes a series of narrow multiplets. To re ea] their structure more clearly we expand the right side of (3) into a power series 11
39
A. Sommerfeld, Annalen der Physik, 61, 1 (1916).
472
THE SCHROEDINGER METHOD
§82
in a and then drop the terms containing 1/ c4, 1/c6, and so on. The resulting high]y accurate approximation is
E
= nk
E _ n
I En4n2I ci
(4nk _3) + me ' 2
(7)
"There En is given by (1) and the factor I En I a 2/n 2 is just the quantity (2). The term mc 2 in (7) is called the relativistic rest energy of the electron. The levels computed by means of (7), with the rest energy left out, and their Sommerfeld classification in terms of the quantum numbers n and k are shown on the k 1 k = 2 k = 3 k = 4 right side of Fig. 108; the left part of this figure is a reproduction of Fig. 107 (Fig. 107 has, in fact, been computed from Equation (7) 13 rather than from experimental data). 1 So far, our quantummechanical '; 3 f: computations concerning the hy9 drogen atom have led to the Bohr formula; but since Som.merfeld's, rather than Bohr's, formula agrees N 1 II with experiment, we should expect f: 5 the theory to yield Sommerfeld's formula or one much like it. Our study is thus as yet incomplete; ........ and, guided by the fact that Som111 ~ merfeld's computations invoked the Fig. 108. Finestructure theory of relativity, we proceed to levels of hydrogen, and their investigate the relativity corrections Sommerfeld classification. to our quantumII?echanical result. Exercises 1. Deduce (7) from (3). 2. Extend Fig. 108 through n
=
5.
83. Relativity Corrections for Hydrogen In relativity theory, the Newtonian relation E  V = (p; + p; + p;)/2m between the kinetic energy E  V and the
473
MOTION IN THREE DIMENSIONS
§83
Cartesian components Px, Pu, and Pz of the linear momentum of a particle is replaced by the relation 1 ( 2 c
E  V
)2
=
2
Px
+ PY + Pz + m c 2
2
2 2
,
(1)
where c is the speed of light and m is the socalled rest mass of the particle, that is, mass as determined by an observer with respect to whom the particle is at rest. In the case of a free particle at rest, or, more precisely, in the case V = 0 and Px = py = Pz = 0, Equation (1) reduces to E 2 = m2c4 and yields for the energy of the particle the positive value
Eo
=
rnc
2
(2)
and the negative value mc2• The second alternative is of no interest in classical relativity, while (2) is interpreted to mean that, even when at rest, the particle possesses a mass energy or 2 rest energy of the amount mc • According to relativity theory, a Cartesian component of the linear momentum of a particle may have any va]ue between  oo and oo , while the speed of the particle cannot exceed the speed of light c; hence the relativistic relation (Px = mx/Vl  v2/c 2 , and so on) between linear momentum and velocity, which we need not discuss here, is more complicated than the corresponding Newtonian relation. The fundamental problem of the relativistic quantum mechanics of a single particle, namely, the construction of the operator H that should replace the Schroedinger Hamiltonian operator when the Newtonian energy equation is replaced by the relativistic equation (1), will be taken up in §91. For the present we shall employ a somewhat indirect procedure that avoids the use of the explicit form of the operator H; critical comments on this procedure will be made in §91. We consider a state y; for which the total energy of the system is certainly E, rewrite (1) as 1 (E  V)2  Px2  Pu2  Pz2 =m2c2 , 2c
(3)
and find that the Schroedinger operator associated with the quantity on the left side of (3) is
.!_2 (E  V)2
c
+h
2
(~ 2
ox
+~ + !_) ay oz 2
2
(4) '
474
§83
THE SCHROEDINGER METHOD
where E is the numerical value of the total energy and V is the Schroedinger operator associated with the potential energy. Now, according to (3), the quantity on the left side of (3) is simply the 2 2 number m c ; we interpret this fact to mean quantum mechanically that the Schroedinger function y; describing an energy state of energy Eis an eigenfunction of the operator (4) belonging to the 2 2 eigenvalue m c of (4), and write
The energy levels of the system can now be found by computing the numerical values of E for which (5) has wellbehaved solutions. Recalling the steps from 178 to 378 , we may rewrite (5) as 2
[
2 _
Pr
L r2
+ (E
 V) c2
2
J., =
76
'Y
2 2.,,
m c 'Y
,
(6)
77
where L 2 and Pr arc the operators 65 and 24 • Let us now consider central fields, when V in (6) has the form V(r). The straightforward mathematical procedure for studying (6) in this case is to try separating the variables by assuming that i/; has the form R(r)e(8)t1>) if;(m) = ( A2(r, o)i '
(8)
where the values of m are those given in (7) and where A 1 (r, 0) and A2(r, 0) are arbitrary wellbehaved functions of r and O, except that one of them can be taken as zero. The simultaneous eigeny;'s of lz and L 2• Since the eigen2 values of L are known to be l(l l)h2, with l = 0, 1, 2, we write the eigenvalue equation for L 2 from the outset as
+
(9)
This equation splits up into the two Schroedinger eigenvalue equations 2 2 J £ 1/;1 = zcz + 1)h f1 (10) 2 2 £ 1/;2 = l(l + l)h 1/;2,
l
and it follows from
¥11
=
6i4 that (11)
R1 T(l, m'),
or, more explicitly (we absorb the factor (21r )i of the T's in the R's), Y12
= R 28lm'' eim''t/>,
(12)
where R 1 and R 2 are arbitrary wellbehaved functions of r, and m' and m" are integers, zero included, such that I m' I < l and
Im" I < z.
Comparison of (11) with (8) now shows that to get a y; [we denote such a if; by if;(lm)] that is simultaneously an eigenl/; of J. belongfog to the eigenvalue mh of Jz and an eigeny; of L 2
493
§87
PAULI'S THEORY OF SPIN
belonging to the eigenvalue l(l and m'' = m + !, so that
+ 1) h
2
2
of L we must set m'
=m !
!))
R1 T(l, m if;(l m) = ( R{f(l, m + !) ·
(13)
The wellbehaved radial factors R1 and R2 remain undetermined and unrelated, except that at most one of them can be taken as zero. The simultaneous eigenfunctions of lz, L 2, and J2. We finally proceed to adjust (13) so as to make it an eigenfunction of J 2 ; that is, writing the eigenvalues of J 2 in the form j(j + l)h2, wj.th j as yet undetermined, we proceed to force (13) to satisfy the eigenvalue equation
Tf) = j(j + 1) h2 (R1 Tf)
J2 ( R1 f3 R2Ti
[j
(14)
'
R2Tz
where we have used the temporary abbreviations a
~
= m  !,
= m + !.
(15)
Using J 2 in the form 4286 , we find that (14) splits up into the two equations 10
(L
2
+ hLz + !h2)R1Tf + h(L:r; 
( h(L:r: + iLy)R1Tf
+ (L
2
iL 1J&T1 = j(j + l)h R1Tf 2
hLz + !h )R2T1 = j(j + l)h R2Tt 2

2
(16)
which, in view of Equations 1~ to 15A, reduce to
+ 1) + a + !] R1 Tf + Hf R2Tf = j(j + l)R1 Ti ( Gf R1T1 + [l(l + 1)  ~ + !]R2T1 = j(j + l)R2T'f [l(Z
where, according to 10\
H1
=
Gf
=
·y(l +
!)
2 
m2 •
(17)
(18)
The angle factors in each of the equations (I 7) cancel out, and we get [l(l
+ 1) 
( V(l 10
+ !)
2
j(j + 1) 
+ m + l]R1 + V(l + !)2  m R2 = 0 (19) m R1 + [l(l + 1) j(j + 1)  m + i]R2 = 0. 2
2
We restrict ourselves to the case when both T's in (13) are different from zero, but write our final results in completed form; see Exercises land 3.
494
PAULI'S THEORY OF SPIN
§87
Thus in an eigeny; of J 2 the radial factors R1 and R2 are no longer unrelated. · Equations (19) can be made consistent by a proper choice . of the quantum number j, called the inner quantum number, which so far has been undetermined. Inspection of (19) shows that the condition for the vanishing of the determinant of the coefficients is [l(l
+ 1)
 j(j
+ 1) + tJ2
l(l
+ 1)
 j(j
+ 1) + i
=
(l
+ !)2,
(20)
+ !).
(21)
that is, = ±(l
Taking the lower sign, we get the possibility j(j
+ 1)
= l(l
+ 1) + (l + t) + i
= (l
+ !)(l + t).
(22)
One root of this equation is
= l
j
+ !,
l = 0, 1, 2, ... ,
(23)
and the second root is l!; but, since j appears in (19) only in the combination j(j + 1), the second root adds nothing new. Similarly, the upper sign in (21) yields j(j
+ 1)
l(l
=
+ 1)
 (l
+ !) + !
=
(l  !)(l
+ !),
(24)
so that J.
= l 
1
2,
l=123···
' ' '
(25)
'
while the second root of (24) adds nothing new. The inclusion of l = 0 in (23) and its omission in (25) are justified by a special consideration of the case l = O, to be taken up in Exercise 3. Substituting (23) into (19), we find that Ri/R2 = Vl ! m/ Vl + !  m, that is,
+ +
R1
=
Vz + ! + mR,
R2 =
vz + !  mR,
(26)
where R is an arbitrary (wellbehaved) function of r. The result of substituting (26) into (13) will be denoted by i/;(l, j = l + !, m):
i/;(l,j = l
+ !,m)
!)),
= (Vz + ! + mRT(l, m Vz + !  mRT(l, m + !)
(27)
l = 0, 1, 2, . · · .
The expression (27) is one form of the simultaneous eigeny;'s of J,, L2, and J 2•
495
§87
PAULI'S THEORY OF SPIN 2
To get the remaining simultaneous eigenf's of Jz, L , and J2, which we denote by t/;(l, j = l  !, m), we substitute (25) into (19) and find that
R1 =
Vz + ! 
mR,
R2 = 'Vl
+ ! + mR,
(28)
and that hence tf;(l,j
=
= l  !, m)
Vz + !  mRT(l, m  !) ) ( Vz + ! + mRT(l, m + !) '
l
= 1, 2, 3, ... ,
(29)
where the radial factor R need not be related to that in (27). Exercises 1. Set m = l + ! in (13) and show that the corresponding simultaneous eigenf of J z , L 2 , and J 2 is included in (27); show that (29) does not provide for the case m = l + ! and explain why this is to be expected on intuitive physical grounds. Consider in a similar way the case m = l  i. 2. Show that, if m = ± (l + !), then the simultaneous eigenf's of J z, L 2 , and J 2 are also eigenf's of Lz and Sz , and explain why this is to be expected on intuitive physical grounds. 3. Use the result of Exercise 1 to justify the inclusion of l = 0 in (27) and its omission in (29). 4. Verify that for a state of the form (27) wt have: J ,: certainly mh L 2 : certainly l(l + l)h 2 J 2 : certainly j(j + l)h 2 = (l + !)(l + f)h 2 2lmh {possible values: (m  !)h (m + i)h L,: av L, = 2l + 1; rel. probabilities: (l + i + m) (l + i  m)
{possible values: !h ih Sz: av ' = rel. probabilities: (l + i + m) (l + !  m). 6. Consider states of the form (29) along the lines of Exercises 4 and show that the differences between the new and the former results are consistent with the fact that now J 2 < L 2 , while formerly J 2 > L 2 • 6. Show that (27) and (29) are eigenf's of the operator 8
mh 2l + 1;
which is usually denoted by L·s, and that in fact L·sf(l, j = l
+ i,
m) = !lh 2f(l, j = l
+ t,
m)
(30)
i, m).
(31)
and
L·sf(l, j = l 
i, m) = !(l +
l)h 2f(l, j
=l

496
PAULI'S THEORY OF SPIN
§88
88. SpinOrbit Interaction and the Spin Correction We now proceed to set up the Pauli Hamiltonian for an electron in a central electrostatic field described by a potential function V (r). The total energy of the electron now consists of three parts: the kinetic energy, the potential energy, and the energy due to the interaction of the spin magnetic moment es/me with the orbital magnetic moment eL/2mc; the latter energy is called the spinorbit interaction energy. The kinetic and potential energies are quantities with which we are familiar; but new considerations are required for the spinorbit interaction. Now, the case of two bar magnets suggests that the spinorbit interaction energy should be proportional to the respective magnitudes of the orbital magnetic moment and the spin magnetic moment, and to the cosine of the angle between the two moments; that is, because of the proportionality of the orbital magnetic moment to L and the proportionality of the spin magnetic moment to s, we may expect the spinorbit interaction energy to contain the factor L. s, that is, Lxsx + LySy + LzSz . Further, we would expect this energy to depend on the distance of the electron from the center of the field. The interaction energy would thus be expected to have the form (1)
Hr)Ls,
where Hr) is a function of r whose form depends on the potential field. The intricate problem of evaluatipg the spinorbit interaction energy was considered in the light of classical analogy by Thomas 11 and by Frenkel ;11 and both concluded that this energy is given by (1) with
Hr)
=
_1_
! dV(r).
2m2 c2 r
For example, in the case of the Coulomb potential spinorbit interaction energy is computed to be
e2
(2)
dr
1
e2/r,
the
Ls. ~ 2m c 3 r
(3)
L. H. Thomas, Nature, 117, 514 (1926). 37, 243 (1926). Kemble, Section 58d.
J. Frenkel, Zeits. f. Physik,
11
§88
PAULI'S THEORY OF SPIN
497
Recalling 378 , we now write our complete Hamiltonian operator as 1 2 1 2 H = m Pr + mr 2 L V(r) Hr)Ls, (4) 2 2 where
+
+
Pr =  ih
(iar + !) .
(5)
r
Constants of motion and the two radial equations. The operators (6)
which, according to Exercise 986 , commute with each other, do not involve the operators r or ajar and consequently commute with operators involving only r and ajar. Further, since J 2 = 2 2 2 2 (L + s) = L + s2 + 2(Lx8x + LySy + Lzsz) = L + !h + 2L·S, so that 2 2 (7) 2L·s = J  L  £h2, the operators (6) also commute with the operator Ls. Hence Jz, L 2 , and J 2 commute with every term in the Hamiltonian (4) and, as already mentioned in §87, constitute a set of commuting constants of motion in the Pauli theory of an electron in a central field. In computing the eigenvalues of (4) we therefore may, according to the expansion theorem, restrict ourselves to y;'s that 2 2 are ~imultaneous eigeny;'s of Jz, L , and J , that is, to y;'s of the forms 27 87 and 29 87 • In other words, instead of treating the eigenvalue equation Hi/; = Ei/; in its generality, we may restrict ourselves to the simpler problem of studying separately the two equations Hi/;(l, j = l
+
!, m) = Ei/;(l, j = l
+ i, m)
(8)
and
Hw(l, i
=
l 
!, m) =
Et/;(l, j = l 
!, m).
(9)
Now, Hif;(l, j = l
+ !, m) =
[2~ p;
+ 2~r2 L2
+ V(r) + J;(r)Ls
J
if;(l,j = l
+ t, m),
(10)
498
PAULI'S THEORY OF SPIN
§88
87
so that, in view of 3_Q and the fact that our y,, is an eigeny,, of L 2 belonging to the eigenvalue l(l + 1) h2,
H·',(l , . = l 'Y 'J
+ .1
2'
m
) =
[___!_ 2 2m Pr
+ l(l 2+ l)h "
2
rnrM
+ V(r) + !lh t(r) 2
J
=l
lp(l, j
+ !, m).
(11)
The bracketed operator in (11) is free from matrices and hence does not mix the two components of y,,. Therefore, when we introduce the explicit form 2i7 for y,,, and (8) splits up into two equations, the angle factors cancel out in each equation and both equations reduce to the same radial equation, namely,
_!__ p; [ 2rn
2
+ l(l 2rnr + l)h + V(r) + !lh Hr)]R 2
2
= ER.
+
j = l ! { l = o, 1, 2, · · · .
(12)
Treating (9) in a similar way, we get another radial equation, namely,
[ _!_ p; 2rn
2
+ l(l 2mr + l)h + V(r) 2
i(l
+ l)h t(r)] R 2
= ER
j = l ! { l = 1, 2, 3, · · · .
(13)
The energy levels of our system are thus the values of E which yield wellbehaved solutions of (12) and also the values of E which yield wellbehaved solutions of (13). Apart from the terms in Hr), Equations (12) and (13) are both identical with the Schroedinger radial equation [
__!__
2rn
Pr2
+ l(l + l)h2 + V( r )JR= ER . 2mr2
(14)
Since spin effects are known to be small, we may consider the terms in Hr) as pertlirbing potentials and may handle {12) and (13) by perturbation methods. The spin corrections for hydrogen. If 1/;(n l mz) is the nor
499
PAULI'S THEORY OF SPIN 80
malized Schroedinger eigenfunction 25 12 hydrogen, then
f
ij;(nlmi)
§88
of the Hamiltonian of
:3 if;(nlmz) dr = n3l(l + ~)(l + 1)
:r 2
80
(15) 2 2
where ao is the Bohr radius 21 • For hydrogen, Hr) = e /2m c r3, so that for the hydrogen state y,,(n l mz) the average value of the quantity }lh2 Hr), that is, of the perturbing potential in (12); is 2
1
e2
zlh · 2m c n l(l 2 2•
3
+
1 !)(l
+ l)ai
=
I En I cl 4n
2 
4n
(2l
+ 1) (l + 1)'
(
16)
where En is the nth Bohr level 1880 and a is the finestructure 82 constant 6 • Similarly, for the hydrogen state i/;(n l mz), the 2 average value of HZ+ l)h Hr), that is, of the perturbing potential in (13), is
I En Ia 2
4n
4n 2
l(2l
(17)
+ 1) ·
Now, in threedimensional perturbed motion, just as in the onedimensional case treated in §36, the firstorder energy correction for a nondegenerate perturbed level equals the average of the perturbing potential for the corresponding unperturbed state. A closer study shows that this simple result holds in our present case in spite of the degeneracy of the Bohr levels; and consequently the eigenvalue of (12) which belongs to the state i/;(n, l, j = l + !, m) and which we denote by E(n, l, j = l + !) 13 can be obtained in the hydrogen case to the first approximation by adding the quantity (16) to the energy En of the Schroedinger state y,,(n l m 1). Treating (13) in a similar way, we get our final results:
, l ·_ l
rE( n,
Il
E(
,J 
1)
+2
_

E n
l . l 1) E n, 'J =  2 = n
+
I En I a7 4n 2
I En I a2 
4n2
(2l
4n
+ I)(l + 1)
4n l(2l 1) .
+
(l 8 ) a
( 18b)
The levels (18) are shown in Fig. 111, the left portion of which 82 is a reproduction of Fig. 107 • The values of j are indicated at 12 13
Condon and Shortley, page 117. Here 'to the first approximation' means 'correctly to terms in 1/c2 .'
500
PAULI'S THEORY OF SPIN s l=O
p
l=l
d l=2
f l=3
,1/2
.• ; •
I
• I I I
., •
!
, 1/2 13
.•
r3f2 ........ s12 _1/2
iI
I ........ 3/2
5/2
i.....112
' : ': : I
1 ('t) 3 II ~
9
.
N1
~II
........ l/2
5
: 1/2 :
Fig. 111. Spin corrections for hydrogen. The Sommerfeld levels are shown at the left. The odd halfintegers are the values of j.
§88
the right of the levels; the vertical lines connect the sublevels with their parent Bohr levels. Note that each slevel is raised and each of the other levels is split up into a doublet; each sublevel is of course degenerate with respect to m . The arrangement of the levels is different from that required by experiment, and their number is almost twice too great. The spin corrections alone are thus insufficient to bring agreement with experiment; but we shall, see in the next section that we do get the desired results when the spin corrections are combined with the relativity corrections.
The slevels. The quantity L · s is zero whenever L = O, so that the spinorbit interaction energy (3) is zero whenever L = 0. Since L = 0 for sstates, the formula (3) thus implies that the spinorbit interaction energy is zero for sstates, that is, that the spin causes no displacement in slevels. This conclusion is borne out by (12), which becomes identical with the Schroedinger radial equation (14) whenever l = 0. Yet (18a) gives a nonvanishing ·spin correction even when l = O; and, what is more, the correction it gives when l = 0 is correct. Two questions therefore arise: Why does (18a) give a nonvanishing correction when l = O? And why does (18a) give the correct nonvanishing correction when l = O? The answer to the first question lies in the fact that the average value of ra given by (15) contains the factor l in the denominator, and that in getting the correction ( 16) we have canceled this l with the l
501
PAULI'S THEORY OF SPIN
§88
that multiplies Hr) in (12). To the second question there is perhaps no satisfactory answer, and we may summarize the situation as follows: the Pauli method fails when applied specifically to an sstate; but, perhaps fortuitously, the correct spin correction for an sstate can nevertheless be found by extrapolating to the case l = 0 the Pauli results computed for l > 0. Exercises 1. Derive the radial equation (13). 2. Extend Fig. 111 through n = 5.
89. The SpinandRelativity Correction for Hydrogen We now turn to a Pauli electron moving relativistically in a Coulomb field. One way of treating this problem is to replace the nonrelativistic Pauli Hamiltonian 488 by the appropriate relativistic Pauli Hamiltonian and to compute the eigenvalues of the 14 latter. But the simpler way, which we shall follow, is merely to combine the relativity corrections for the Schroedinger hydrogen atom, found in §83 to be
_ I En Ia? ( ~ 4n2 l +!
3) + me' 2
(1)
with the Pauli spin corrections for the Schroedinger hydroge~ 1ttom computed in §88. In the case j = l + !, the spin correction is
IEn Ia 2 4n
2
4n
(2Z
(2)
+ l)(l + If
The Rum of (1) and (2) is
_IEnla 2 4n
that is, since j
3) + me'
~ • + i
3) + me.
l
+1
2
(3)
= l + !,
_ I En I a 4n2
14
(~ _
2
2 (
J
2
_
2
Compare C. G. Darwin, Proc. Roy. Soc., 116A, 227 (1927).
(4)
502
§89
PAULI'S THEORY OF SPIN
In the case j = l  !, the sum of the relativity correction (1) and ·the spin correction given by 18b88 is
_ I En Ia? 4n2
(4nl _3) +
mc2
(5)
'
that we get the expression (4) once again. Thus the spinandrelativity corrections depend only on j and, except for the limitations that the value of l places on the values of j, are independent of Z. Adding (4) to Bohr's En and denoting the resulting energy levels by Eni, we finally get
80
E,.i = En 
I EnnIa:2 ( j 4n +! 4 2
3
)
+ mi: . 2
(6)
Since j = !, !, {, · . · , this formula is identical with the Sommerfeld formula 782 , in which k = 1, 2, 3, . . . . We conclude that, when the Schroedinger theory of the isolated hydrogen atom is corrected to terms in 1/c2 for both the relativity effects and the spin effects, its results are in agreement (to terms in p s d I l=2 l=O l=l l=3 1/c2) with experiment inso1 far as the possible energies 112 2 3 ak of the atom are concerned. The energy levels required by (6) are shown, 131/22 apart from the term mc , s, in Fig. 112, whose left por1  3 / 2  .,2 u3 ~ion is a reproduction of ~ 91/2Fig. 107. Comparing this figure with Fig. 111, we note, in particular, that the 1 312 relativity corrections shift II . ~5  I k adjacent spin doublets in such a way as to reduce the number of levels to that required by the Sommerfeld II  1 112 formula; but the number ~ Fig. 112. Spinandrelativity correc of basic states is still almost tions for hydrogen. The Sommerfeld twice as great as in the levels are shown at the left. The halfSommerfeld theory, so that odd integers are the values of j.
J ~ CV)

('\J

=¥ =
503
PAULI'S THEORY OF SPIN
§89
our present hydrogen atom responds to external p2rturbing fields somewhat differently from the Sommerfeld hydrogen atom. Exercises
1. Extend Fig. 112 through n = 5. 2. Show that the operators L · s + ih 2 (where L • s = Lxsx + LySy + Lzsz) and d·P (=