Modern Quantum Mechanics

J.J.Sakurai

RevisedEdition

Modern QuantumMechanics RevisedEdition
Late, University of California,LosA ngeles

/./. Sakurai
University

San Fu Tuan, Editor
of Hawaii, Manoa

Reading,Massachusetts MenloPark, California New York DonMills,Ontario Wokingham, England Amsterdam Bonn Sydney SingaporeTokyo Madrid San Juan Milan Paris
\342\200\242 \342\200\242 \342\200\242 \342\200\242 \342\200\242 \342\200\242 \342\200\242 \342\200\242 \342\200\242 \342\200\242 \342\200\242

Addison-Wesley Publishing ompany C

Editor: Stuart W. Johnson Sponsoring Assistant Editor: Jennifer Duggan
P Senior roduction Coordinator: Amy
Manufacturing

Willcutt

Manager:Roy Logan

Library

of Congress Cataloging-in-Publication

Data

Sakurai, (Jun John), 1933-1982. Sakurai Modern quantum mechanics /

J.J.

J.J.

; San

Fu Tuan,

editor.\342\200\224

Rev. ed. p. cm.

and index. Includes bibliographical references ISBN 0-201-53929-2 Quantum theory. Tuan, San Fu, 1932-

1994 QC174.12.S25
530.1'2\342\200\224dc20

1.

I.

. II. itle. T
93-17803

CIP

Copyright All rights a retrieval

\302\251

1994 by

Addison-Wesley Publishing

Company,

stored in publication may system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior written permission of the publisher. Printed in the United States of America.

reserved. No part of this

Inc. be reproduced,

5 6 7 8 9 1O-MA-9695

Foreword
welcomeguest here at CERN,for he was one of those rare theorists to whom the experimental facts are even more interesting than the theoretical game itself. Nevertheless, he delighted in theoretical physicsand in its teaching, a subject on which he held strong opinions.He thought that much theoretical physicsteaching was both too narrow and too remote from application: \"...we a number of sophistisee yet uneducated, theoreticians who are conversant in the LSZ forformalism of the Heisenberg field operators, ut do not know why an excited b atom radiates, or are ignorant of the quantum theoretic derivation of Rayleigh's law that accounts for the bluenessof the sky.\" And he insisted that the student must be able to usewhat has beentaught: \"Thereaderwho h has read the book but cannot do the exercises as learned nothing.\" Heput these principles work in his fine book Advanced Quantum to Mechanics A967) and in Invariance Principles and Elementary Particles A964), both of which have beenvery much usedin the CERNlibrary. This new book, Modern Quantum Mechanics,should be used even more, by a larger and less specialized group. The book combinesbreadth of interest with a thorough practicality. Its readerswill find here what they need to know, with a sustained and successfuleffort to make it intelligible. J.J. Sakurai'ssuddendeath on November 1982 this book left unfinished. Reinhold Bertlmann and I helped Mrs. Sakurai sort out her husband'spapers at CERN.Among them we found a rough, handwritten version of most of the bookand a large collectionof exercises. Though only three chaptershad beencompletelyfinished, it was clear that the bulk of the creative work had beendone.It was also clear that much work remained to fill in gaps,polishthe writing, and put the manuscript in order. That the bookis now finished is due to the determinationof Noriko Sakurai and the dedication of San Fu Tuan. Upon her husband'sdeath, Mrs. Sakurai resolved immediately that his last effort should not go to waste.With great courage and dignity shebecamethe driving force behind the project, overcoming all obstacles and setting the high standards to be maintained. San Fu Tuan willingly gave his time and energy to the editing to work. Perhaps only others close the hectic and completion of Sakurai's field of high-energy theoretical physicscan fully appreciate the sacrifice involved. For me personally, J.J. had long been far more than just a particuIt distinguished colleague. saddensme that we will never again laugh at physicsand physicists and life in general, and that he will not together seethe successf his last work. But I am happy that it has beenbrought to o
sophisticated,

J. J.Sakurai was always a very

1,

particularly

fruition.

S.Bell Geneva CERN,
John
in

Prefaceto the Revised Edition
Since1989 Editor has enthusiastically pursued a revised edition of the ModernQuantum Mechanicsy his late great friend J.J.Sakurai,in order b to extend this text'susefulnessinto the twenty-first century. Much conconsultation took placewith the panel of Sakuraifriends who helpedwith the original edition, but in particular with ProfessorYasuo Hara of Tsukuba University and ProfessorAkio Sakurai of Kyoto Sangyo University in Japan. Thereare three important additions and/or changesto the revisededition, T include which otherwise preservesthe original version unchanged. hese 5.2 a reworking of certain portionsof Section on time-independent erp perturbation c by theory for the degeneratease ProfessorKenneth Johnsonof M.I.T., into accounta subtlepoint that has not beenproperlytreated taking
by

The major motivation

for

this

i projects to

revise the main

text.

a number of texts on quantum mechanics in this country. Professor RogerNewton of Indiana University contributed refinements on lifetime broadeningin Stark effect, additional explanations of phase shifts at resT a resonances, the optical theorem, nd on non-normalizablestate. hese appear P note\" in the revised edition. roas \"remarks by the editor\" or \"editor's Thomas Fulton of the JohnsHopkinsUniversity reworkedhis CouProfessor so 7.13) that it now appears as a Scattering contribution (Section w shortertext portion emphasizingthe physics, ith the mathematical details to relegated AppendixC. Though not a major part of the text, some additions were deemed in necessaryto take into account developments quantum mechanics that To have becomerominent since November 1982. this end, two supp I are includedat the end of the text.Supplement is on adiabatic supplements and geometrical phase (popularized M. V. Berry since 1983) by change and is actually an English translation of the supplementon this subject version of Modern written by ProfessorAkio Sakurai for the Japanese Mechanicscopyright Yoshioka-Shotenublishing of Kyoto). Quantum P ( II h Supplement is on non-exponential decayswritten by my colleague ere, ProfessorXerxesTata, and read over by ProfessorE.C.G.Sudarshanof the University of Texast Austin. Though non-exponential decayshave a a long history theoretically, experimental work on transition rates that tests Introduction of additional indirectly such decayswas done only in 1990. material is of coursea subjective matter on the part of the Editor; the w Thanks to Proreadersill evaluate for themselves its appropriateness. Akio Sakurai,the revisededition has been \"finely toothcombed\" Professor for misprint errors the first ten printings of the original edition. My of ProfessorSandipPakvasa, provided overall guidance and encolleague, this process revision. of encouragement to me throughout
Coulomb

1,

\302\251

IV

Preface

to the Revised Edition

computer graphic assisThe Department of Physics and Astronomy and particularly the High Energy PhysicsGroupof the University of Hawaii at Manoa provided again both the facilities and a conducive atmospherefor me to carry out I wish to express y gratitude to Physics (and my editorial task. Finally m SeniorEditor, Stuart Johnson,and his Editorial Assistant, sponsoring) P Jennifer Duggan,as well as Senior roduction Coordinator Amy Willcutt, of Addison-Wesleyfor their encouragement and optimism that the revised edition will indeed materialize.
term
assistance.

In addition to the acknowledgments above, my former studentsLi Shi Xiaohong,and Yasunaga Suzuki provided the sounding board Ping, for ideas on the revisededition when taking my graduate quantum methe spring of Suzuki mechanics course the University of Hawaii during at of the initial translation from Japanese Supplement as a course provided

paper.Dr. Andy Acker provided me with

1992. I

San Fu TUAN Honolulu,Hawaii

J.J. Sakurai1933-1982

VI

In Memoriam
Jun

John Sakuraiwas born in 1933 Tokyo and came to the United States in as a high schoolstudent in 1949. studied at Harvard and at Cornell, He i where he received his Ph.D.n 1958. was then appointed assistant He of Physics at the University of Chicago, and became a full professor when he moved to the He professorin 1964. stayed at Chicago until 1970 of California at LosAngeles,where he remained until his death. University of a During his lifetimehe wrote 119rticles in theoreticalphysics elementary as well as several books and monographs on both quantum and particles particle theory. The disciplineof theoretical physicshas as its principal aim the formulation of theoreticaldescriptionsf the physicalworld that are at once o conciseand comprehensive. Becausenature is subtle and complex, the pursuit of theoretical physics requiresbold and enthusiastic ventures to the frontiers of newly discoveredphenomena. This is an area in which Sakurai reigned supremewith his uncanny physical insight and intuition and also his ability to explain these phenomena in illuminating physical terms to the One on unsophisticated. has but to read his very lucid textbooks Invariance and Elementary Particles and Advanced Quantum Mechanicsas Principles well as his reviewsand summer schoollectures to appreciate this. Without I could say that much of what I did understand in particle exaggeration physicscame from these and from his articles and private tutoring. When Sakurai was still a graduate student, he proposed what is now known as the V-A theory of weak interactions, independently of (and simultaneously with) Richard Feynman, Murray Gell-Mann, Robert in I he S Marshak,and George udarshan.n 1960 published Annals of Physics a propheticpaper,probably his singlemost important one.It was concerned with the first seriousattempt to construct a theory of strong interactions based on Abelian and non-Abelian (Yang-Mills)gauge invariance. This seminal work inducedtheorists to attempt an understanding of the mechaof massgeneration for gauge(vector)fields,now realizedas the Higgs mechanism.Above all it stimulated the search for a realistic unification of forces under the gauge principle, now crowned with successin the celcelebrated Glashow-Weinberg-Salam of weak and electromagnetic unification forces. On the phenomenological side, Sakurai pursued and vigorously advocated the vector mesons dominancemodel of hadron dynamics.He was the first to discussthe mixing of o) and meson states.Indeed,he made numerous important contributions to particle physics phenomenologyin a
mechanisms
<f>

Vll

Vlll

In Memoriam

much more general

activities.

to sense,as his heart was always close experimental

I knew Jun John for more than 25 years, and I had the greatest admiration not only for his immense powersas a theoretical physicist but also for the warmth and generosityof his spirit.Though a graduate student himself at Cornellduring 1957-1958, time from his own pioneering he took researchin K-nucleon dispersion relations to help me (via extensivecorreB with my Ph.D.thesis on the same subject at Berkeley. oth correspondence) with one of his last Sandip Pakvasa and I were privilegedto be associated once more his papers on weak couplings of heavy quarks, which displayed infectious and intuitive style of doing physics. t is of coursegratifying to us I in retrospect that Jun John counted this paper among the score of his publishedworksthat he particularly enjoyed. The physicscommunity suffered a great loss at Jun John Sakurai's I death. The personal senseof loss is a severe one for me.Hence am to edit and complete his manuscript thankful for the opportunity profoundly for on Modern Quantum Mechanics publication.In my faith no greater gift can be given me than an opportunity to show my respectand love for Jun John through meaningful service.

San Fu

Tuan

Contents
Foreword Preface In Memoriam
iii

iv
vii

1 FUNDAMENTALCONCEPTS

1.1The Stern-Gerlach xperiment E 1.2 Kets,Bras,and Operators 1.3BaseKetsand Matrix Representations 1.4 Measurements, and Observables, the Uncertainty Relations 1.5Change of Basis
1.6 Position, Momentum,
1.7 Wave
Problems
and Translation Functions in Positionand Momentum Space

1 10
2

17
23 36

41
60 68 68 80 89

51

2 QUANTUM DYNAMICS 2.1 Time Evolution and the SchrodingerEquation P 2.2 The Schrodinger Versus the Heisenberg icture 2.3 SimpleHarmonicOscillator

2.4 Schrodinger's Wave
Problems

2.5 Propagators Feynman and

2.6 Potentials and Gauge Transformations

Equation Path Integrals

109 123
143

97

3 THEORYOF ANGULAR MOMENTUM Rotations and Angular Momentum Commutation Relations 3.2 Spin1/2Systemsand Finite Rotations 3.3 SOC), UB),nd Euler Rotations a S 3.4 Density Operatorsand Pure VersusMixedEnsembles 3.5 Eigenvaluesand Eigenstatesof Angular Momentum 3.6 Orbital Angular Momentum 3.7 Addition of Angular Momenta 3.8 Schwinger's scillatorModelof Angular Momentum O 3.9 SpinCorrelationMeasurementsand BelPsInequality

3.1

152 152 158
174

168

187
203

195
217
223 232 242 248 248

TensorOperators 3.10 Problems

4 SYMMETRY QUANTUMMECHANICS IN 4.1 Symmetries,ConservationLaws,and Degeneracies 4.2 Discrete Symmetries,Parity, or SpaceInversion 4.3 Lattice Translation as a Discrete Symmetry 4.4 The Time-ReversalDiscrete Symmetry

251
266 282
IX

261

Problems

Contents

5 APPROXIMATION METHODS

5.1Time-Independent Perturbation

285 Theory: 285 298 304

5.2 5.3 5.4 5.5 5.6
5.7

C Nondegenerate ase Perturbation Theory: Time-Independent The Degenerate ase C A Hydrogenlike toms: Fine Structure and the Zeeman Effect Variational Methods Potentials:The Interaction Picture Time-Dependent Perturbation Theory Time-Dependent to Interactions with the Classical Applications Radiation Field
Energy
Shift

313 316
325 335

5.8

Problems

and Decay Width

341
345 357 357

PARTICLES 6 IDENTICAL 6.1 Permutation Symmetry 6.2 Symmetrization Postulate 6.3 Two-ElectronSystem 6.4 The Helium Atom 6.5 Permutation Symmetry and Problems
7

361
363 366 370
377

Young

Tableaux

SCATTERING THEORY

7.1 The Lippmann-Schwinger quation E
7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9

The Born Approximation OpticalTheorem Eikonal Approximation Free-Particle Plane Waves Versus Spherical aves States: W Methodof Partial Waves Low-EnergyScatteringand Bound States Resonance Scattering IdenticalParticlesand Scattering 7.10 in Symmetry Considerations Scattering 7.11 Formulation of Scattering Time-Dependent 7.12 InelasticElectron-AtomScattering 7.13 Coulomb Scattering

410 418
421
422 424 429 434

379 379 386 390 392 395 399

Problems

441
446 456 458 464

Appendix A Appendix B Appendix C SupplementI Adiabatic Change and Geometrical Phase SupplementIINon-Exponential Decays Bibliography

481
487

Index

491

Modern QuantumMechanics

CHAPTER1

FundamentalConcepts

The revolutionary change in our understanding of microscopichenomena p the first 27 years of the twentieth century is that took place during in Not unprecedented the history of natural sciences. only did we witness severe limitations in the validity of classicalphysics, but we found the alternative theory that replacedthe classicalphysical theories to be far richer in scopend far richer in its range of applicability. a The most traditional way to begin a study of quantum mechanicsis radiation law, the Einsteinto follow the historical developments\342\200\224Planck's matter waves, Debye theory of specificheats, the Bohr atom, de Broglie's with careful analyses of some key experimentssuch and so forth\342\200\224together as the Compton effect, the Franck-Hertz experiment, and the Davissonexperirtient. In that way we may come to appreciate how Germer-Thompson the physicistsin the first quarter of the twentieth century were forced to of abandon, little by little, the cherishedconcepts classical hysicsand how, p despiteearlier false starts and wrong turns, the great masters\342\200\224Heisenberg, in a succeeded formulating Schrodinger, nd Dirac, among quantum mechanicsas we know it today. However, we do not follow the historical approach in this book. Instead,we start with an example that illustrates, perhapsmore than any other example,the inadequacy of classical oncepts a fundamental way. in c We hope that by exposing reader to a \"shock the treatment\" at the onset, he
others\342\200\224finally

l

2

Fundamental

Concepts

or she may be attuned to what we might call the \"quantum-mechanical ay w of thinking\" at a very early stage.

THE E 1.1. STERN-GERLACHXPERIMENT
The example we concentrate on in this section is the Stern-Gerlachxperie and originally conceivedby O.Stern in 1921 carried out in Frankfurt This by him in collaboration with W. Gerlach in 1922. experimentillustrates in a dramatic manner the necessity for a radical departure from the conceptsof classicalmechanics. In the subsequent sectionsthe basic forin mechanicsis presented a somewhataxiomaticmanner formalism of quantum but always with the exampleof the Stern-Gerlachxperimentin the backof e our minds.In a certain sense,a two-state system of the Stern-Gerlach type m is the least classical, ost quantum-mechanicalsystem.A solidunderstandof problems involving two-state systemswill turn out to be rewarding to seriousstudent of quantum mechanics.It is for this reason that we refer any this book. repeatedly to two-state problems throughout
experiment,
understanding

which

atoms are heated in an oven.The ovenhas a small hole through which some of the silver atoms escape. shown in Figure As the beam goesthrough a collimator and is then subjectedto an inhomogeneous magnetic field o producedby a pair of polepieces, ne of which has a very sharp edge. We must now work out the effectof the magnetic field on the silver atoms. For our purposethe following oversimplifiedmodel of the silver atom suffices.The silver atom is made up of a nucleus and 47 electrons, where 46 out of the 47 electronscan be visualizedas forming a spherically symmetrical electroncloud with no net angular momentum. If we ignore the nuclear spin,which is irrelevant to our discussion, see we that the atom as a whole does have an angular momentum, which is due solely to the intrinsic as opposedto orbital\342\200\224angular momentum of the single 47th Es) electron. 47 electrons are attached to the nucleus, which is ~ 2x105 The times heavier than the electron; as a result, the heavy atom as a whole possessesa magnetic moment equal to the spin magnetic moment of the I 47th electron.n other words, the magnetic moment of the atom is

of Description the Experiment We now presenta brief discussion the Stern-Gerlachxperiment, of e is discussed almost any bookon modern physics.* in First, silver (Ag)

1.1,

spin\342\200\224

|i

* For an

elementary

but enlightening

discussion of the Stern-Gerlach experiment,

seeFrench

and Taylor A978,

432-38).

1.1. Stern-Gerlach The

Experiment

z-axis

Beam direction

Oven
To detector

B -field

Shaped .
magnet

Collimating Slit

FIGURE

1.1. Stern-Gerlach experiment. The
jiocS,

(polepieces)

proportional to the electron spin S, where the

A.1.1)

preciseroportionalityfactor turns out to be e/mec(e < 0 in this p book)to an accuracy of about 0.2%. Becausethe interaction energy of the magnetic moment with the t magnetic field is just |i-B,he z-component of the force experiencedy b the atom is given by
\342\200\224

A.1.2)
where we have ignored the components of B in directions other than the z-direction. ecausethe atom as a whole is very heavy, we expectthat the B classical onceptof trajectorycan be legitimately applied,a point which can c be justified using the Heisenberg uncertainty principle to be derived later. With the arrangement of Figure 1.1, ju,z > 0 (Sz< 0) atom experiences a the downward force, while the ju,z < 0 (Sz>0)tom experiences n upward a a force. The beam is then expected get split according to the values of ju,z. to In other words,the SG (Stern-Gerlach) apparatus \"measures\" the z-compoz-component

of or, equivalently, the z-component of S up to a proportionality factor. The atoms in the oven are randomly oriented; there is no preferred direction for the orientation of p,. If the electron were like a classical spinning object,we would expectall valuesof ju,z to be realizedbetween T and ||x|. his would lead us to expecta continuous bundle of beams out of the SG apparatus, as shown in Figure 1.2a. Instead,what we coming
\342\200\224

|i

||i|

Fundamental

Concepts

Screen

Screen

FIGURE

B 1.2. eams

(a)
from

(b)
from

the SGapparatus; (a) is expected

classical physics, while (b)

is actually observed.

In other experimentally observe is more like the situation in Figure words,the SG apparatus splitsthe original silver beam from the oven into two distinct components, a phenomenon referred to in the early days of To the extent that can be quantum theory as \"spacequantization.\" identified within a proportionality factor with the electron spin S, only two possiblevalues of the z-componentof S are observed to be possible,Sz up and Sz down, which we call Sz + and Sz The two possiblevalues of Sz are multiples of somefundamental unit of angular momentum; numerically it turns out that Sz = h /2 and h /2,where -27 h= 1.0546X10

1.2b. |i

\342\200\224.

\342\200\224

*\"erg-s

= 6.5822 '16eV-s X10
This
\"quantization\"

A.1.3)

of the electron spin angular momentum is the first feature we deducefrom the Stern-Gerlachxperiment. important e t Of course,here is nothing sacredabout the up-down directionor the z-axis. e could just as well have applied an inhomogeneous field in a W in horizontal direction, say in the jc-direction, ith the beam proceeding the w I the ^-direction. n this manner we could have separated beam from the oven into an Sx + component and an S component.
\342\200\224

Sequential Stern-GerlachExperiments Let us now considera sequential Stern-Gerlachxperiment. By this e we mean that the atomicbeam goesthrough two or more SG apparatusesn i The sequence. first arrangement we consideris relatively straightforward. We subjectthe beam coming out of the oven to the arrangement shown in where SGz stands for an apparatus with the inhomogeneous Figure 1.3a, magnetic field in the z-direction,as usual. We then blockthe Sz compo\342\200\224

1.1. Stern-Gerlach The

Experiment

S2+comp. S2-comp.
(a)

S2+comp. No S2-comp.

S2+beam.
Oven

SGz

V\\

SGx

Sx+beam.

- beam.
(b)

Sx-beam.

Sz+beam.
Oven

Sx+beam.

SGz Sz-beam.
FIGURE

-Sz+beam. -Sz-beam.

Sx-beam.
(c)
Stern-Gerlach experiments.

1.3.equential S
first

the Sz + one beam component coming out of the second This is perhapsnot so surprising; after all if the atom spinsare component.
apparatus\342\200\224just

to component be subjected another SGz apparatus.This time

nent coming out of the

SGz apparatus and let the

remaining

there is only
that

Sz +

spinsbetweenthe first and the secondSGzapparatuses. A little more interesting is the arrangement shown in Figure 1.3b. Herethe first SGapparatus is the same as before but the secondone (SGx) has an inhomogeneous magnetic field in the ^-direction.The Sz + beam that entersthe second i apparatus (SGx)s now split into two components,an + componentand an Sx component, with equal intensities.How can Sx we explain this? Does mean that 50% of the atoms in the Sz + beam it out of the first apparatus (SGz)are made up of atoms characterized coming by both Sz + and Sx +,while the remaining 50%have both Sz + and Sx ? It turns out that such a picture runs into difficulty, as will be shown below. We now considera third step, the arrangement shown in Figure
\342\200\224 \342\200\224

up, the

they

are expectedto remain so, short of

any

external field

rotates

which 1.3(c), most dramatically illustrates the peculiarities of quantummechanical systems.This time we add to the arrangement of Figure 1.3b yet a third apparatus, of the SGz type. It is observed experimentallythat two componentsemerge from the third apparatus, not one; the emerging beams are seento have both an Sz + component and an Sz component. This is a completesurprisebecauseafter the atoms emerged from the first
\342\200\224

Fundamental

Concepts

apparatus, we made sure that the Sz component was completelyblocked. Howis it possible the Sz componentwhich, we thought, weeliminated that earlier reappears? The model in which the atoms entering the third apparaare visualizedto have both Sz + and Sx + is clearly unsatisfactory. This example is often used to illustrate that in quantum mechanics we cannot determineboth Sz and Sx simultaneously.Moreprecisely, can we say that the selectionof the Sx+ beam by the secondapparatus (SGx) completely destroysany previous information about Sz. It is amusing to compare this situation with that of a spinning top in classicalmechanics, where the angular momentum
\342\200\224

-

apparatus

L = /co

A.1.4)

can be measuredby determining the components of the angular-velocity vector to. By observinghow fast the object is spinning in which directionwe can determine cox, coy, and coz simultaneously. The moment of inertia / is computable if we know the mass density and the geometric shape of the spinning top, so there is no difficulty in specifyingboth Lz and Lx in this classicalsituation. It is to be clearly understood that the limitation we have encountered in determining Sz and Sx is not due to the incompetence of the experiexperimentalist. By improving the experimentaltechniques we cannot make the disappear.The Sz component out of the third apparatus in Figure 1.3c us by the experiment of quantum mechanicsare imposed upon peculiarities itself. The limitation is, in fact, inherent in microscopichenomena. p
\342\200\224

Analogy

with

Polarizationof Light

Becausethis situation looksso novel, some analogy with a familiar classicalsituation may be helpful here.To this end we now digressto considerthe polarization of light waves. Considera monochromaticlight wave propagating in the z-direction.
A linearly

the .x-direction,which we call for short an x-polarizedlight, has a space-time field dependentelectric oscillatingin the ^-direction

polarized (or plane polarized) light

with

a polarization vector in

E = E0xcos(kzcot).

-

A.1.5

Likewise,we may considera ^-polarizedlight, also propagating in the z-direction, E = Eoy cos( z k

- cot).
90\302\260

A.1.6

Polarized light beamsof type A.1.5) r A.1.6) an be obtained by letting an c o unpolarized light beam go through a Polaroid filter. We call a filter that selectsonly beams polarized in the x-direction an x-filter. An jc-filter, of b a about the propagation (z) course, ecomes y-filter when rotated by

1.1. Stern-Gerlach The

Experiment

7

No

beam
No light

x filter

/filter (a)

100%

x filter
D5\302\260

x'filter diagonal) (b)

y filter

FIGURE

1.4. Light

beams subjected to Polaroid

filters.

direction.t is well known that when we let a light beam go through an I x-filter and subsequently let it impinge on a j>-filter, no light beam comes out provided,of course,we are dealing with 100% efficient Polaroids;see Figure 1.4a. The situation is evenmore interesting if we insert between the x-filter and the jy-filter yet another Polaroid that selectsonly a beam polarized in makesan angle of the direction\342\200\224which we call the x '-direction\342\200\224that in This 1.4b. time, there is a with the x-direction the xy plane; see Figure beam coming out of the j>-filter despitethe fact that right after the light beam went through the jc-filter it did not have any polarization component in the ^-direction. other words,once the x'-filter intervenesand selects In the .x'-polarized beam, it is immaterial whether the beam was previously The selectionof the x'-polarized beam by the secondPolaroid x-polarized. information on light polarization. Notice that this destroys any previous situation is quite analogousto the situation that we encounteredearlier with the SG arrangement of Figure 1.3b, provided that the following correspon45\302\260 correspondence

is made:

Sz

\302\261

atoms <-> jc-, j>-polarized light atoms <->jc'-, '-polarized y light,

A.1.7)

Sx\302\261

where the x'-and the j>'-axesre definedas in Figure a Let us examine how we can quantitatively describethe behavior of beams(x'-and y '-polarized 45\302\260-polarized beams)within the framework of

1.5.

8

Fundamental

Concepts

\\ \\ \\ \\ \\ \\ \\

\\ \\ \\ \\

FIGURE

1.5.Orientations

of the

xf- and

y'-axes.

classical lectrodynamics.UsingFigure e Eox'cos(kz cot) = Eo
\342\200\224

1.5 obtain we
\342\200\224 \342\200\224

.

\342\200\224

v2

= xcos(kz cot)+ 2 yco$(kz
v
\342\200\224

cot)
\342\200\224

E0y'cos(kzcot) = Eo
\342\200\224

v/2

xcos(kz cot)+--=rycos(kz

cot)

A.1.8
1.4b

In the triple-filter arrangement of Figure the beam coming out of the first Polaroid is an x-polarized beam, which can be regardedas a linear combination of an x'-polarized beam.The second beam and a y '-polarized Polaroid selectsthe x '-polarized beam, which can in turn be regardedas a linear combination of an x-polarized and a ^-polarized beam.And finally, the third Polaroid selects y-polarizedcomponent. the from the sequential Stern-Gerlach A Applying correspondence .1.7) to the triple-filter experiment of Figure experiment of Figure that suggests we might be able to represent the spin state of a silver atom by some kind of vector in a new kind of two-dimensionalvector space, an abstract vector space not to be confused with the usual two-dimensional Just a (xy) space. as x and y in A.1.8) re the basevectors usedto decompose the polarization vector of the x'-polarizedlight, it is reasonableto represent the Sx + state by a vector, which we call a ket in the Dirac notation to be developedfully in the next section. e denote this vector by W

1.3c,

1.4b

x'

1.1. Stern-Gerlach The
\\SX;
\342\200\224

Experiment

+) and write it as a linear combination of two base vectors, + ) and \\SZ; ), which correspond the Sz + and the Sz states, respectively. to So we may conjecture
\\SZ\\
\342\200\224

The next question of immediate concern is, How are we going to representthe Sy states? Symmetry arguments suggest that if we observe an Sz beam going in the x-direction and subject it to an SGyapparatus, the resulting situation will be very similar to the casewhere an Sz beam is to T going in the ^-direction subjected an SGxapparatus. he ketsfor Sv shouldthen be regardedas a linear combination of \\SZ; ), but it appears that from A.1.9) we have already used up the available possibilities in How can our vector space formalism distinguish writing states from SY + states? An analogy with polarized light again rescues here. his time we us T consider a circularly polarized beam of light, which can be obtained by letting a linearly polarized light passthrough a quarter-waveplate.When we pass such a circularly polarized light through an jc-filter or a j>-filter, we beam or a jy-polarizedbeam of equal again obtain either an x-polarized intensity. Yet everybody knows that the circularlypolarized light is totally different from the 45\302\260-linearly polarized (x'-polarizedy '-polarized) or light. Mathematically, how do we representa circularlypolarized light? A right circularly polarized light is nothing more than a linear combinationof an x-polarizedlight and a j>-polarizedlight, where the oscillation of the electric for the j>-polarized field out of phasewith that of component is
\302\261 \302\261 \302\261 \302\261 \302\261

from emerge

analogy with using the general formalism of quantum mechanics. Thus the unblocked component coming out of the second(SGJc) is of apparatus of Figure 1.3c to be regardedas a superposition Sz + and in the sense of A.1.9a). for this reason that two components It is Sz
\342\200\224

in

A.1.9a) j=r\\Sz;+)+j= j\\Sz;+)+j=r\\Sz;-) A.1.9b) \"> = -> +>+ j=\\Sz\\ Later A.1.8). we will show how to obtain these expressions
\\SX\\

?

-^;

the

third

(SGz)apparatus.

1^;+).

Sv\302\261

90\302\260

the

x-polarized component:*
\342\200\224

iot)+ Jo 2/ F) .V2 V2 2/J It is more elegant to use complexnotation by introducing as follows:
\342\200\224

xcos(kz

\342\200\224=ycos|

kz

\342\200\224

cot

+

\342\200\224

I

V \\

\342\202\254

Re(\342\202\254)

= E/Eo.
in the definition

A.1.11
of right versus left circularly

* Unfortunately, there is no unanimity polarized light in the literature.

10

Fundamental

Concepts

Fora right

circularlypolarized light, we can then
* i(kz-ut)
Lv/2
i

write

* i(kz-ut)
v/2

A.1.12

where we have used i = el7r/2. We can make the following

atoms:

analogy with the spin states of silver
circularly polarized beam,

Sv + atom Sv
Applying
\342\200\224

<->

right

atom

<->

left circularly polarized beam.

A.1.13

we see this analogy to A.1.12), that if we are allowed to make the coefficientspreceding basekets complex,there is no difficulty in accommothe Sv atoms in our vector spaceformalism:
accommodating
\302\261

A.1.14
are obviously different from A.1.9). thus seethat the two-dimenWe vector spaceneededto describethe spin states of silver atoms must be a complex vector space;an arbitrary vector in the vector spaceis written as a linear combinationof the basevectors \\SZ; + ) with, in general,complex coefficients.The fact that the necessity of complex numbers is already apparent in such an elementaryexample is rather remarkable. The reader must have noted by this time that we have deliberately avoided talking about photons.In other words, we have completelyignored the quantum aspectof light; nowheredid we mention the polarization states of individual photons.The analogy we worked out is between kets in an abstract vector spacethat describeshe spin states of individual atoms with t the polarization vectors of the classical lectromagneticield. Actually we e f could have made the analogy even more vivid by introducing the photon conceptand talking about the probability of finding a circularly polarized photon in a linearly polarized state, and so forth; however, that is not neededhere.Without doing so,we have already accomplished main goal the of this section:o introduce the idea that quantum-mechanicalstates are to t be represented vectorsin an abstract complexvector space.* by
which
two-dimensional

1.2. KETS,BRAS,AND
In the

OPERATORS

precedingsection we showed how analyses of the Stern-Gerlach I experiment lead us to considera complex vector space.n this and the
*The reader

a

careful

study

who is interested in grasping the basic concepts of quantum mechanics through of photon polarization may find Chapter 1 of Baym A969) extremely

illuminating.

1.2. Bras, and Operators Kets,

11

following section we formulate the basic mathematics of vector spacesas used in quantum mechanics.Our notation throughout this book is the bra and ket notation developedby P.A. M. Dirac.The theory of linear vector had, of course,been known to mathematiciansprior to the birth of spaces has many quantum mechanics,but Dirac'say of introducing vector spaces w from the physicist's oint of view. advantages,especially p

Ket Space
We consider complexvector spacewhosedimensionality is specified a according to the nature of a physical system under consideration. In Stern-Gerlach-typexperiments where the only quantum-mechanicaldee degree of freedom is the spin of an atom, the dimensionality is determined by the number of alternative paths the atoms can follow when subjected a to SG apparatus; in the case of the silver atoms of the previous section, the to values Sz can dimensionality is just two, corresponding the two possible assume.* Later, in Section 1.6, e consider the case of continuous w example, the position (coordinate) or momentum of a particle the number of alternatives is nondenumerably infinite, in which case the vector space in question is known as a Hilbert space after D. Hilbert, who studiedvector spacesin infinite dimensions. In quantum mechanicsa physical state, for example, a silver atom with a definite spin orientation, is represented a state vector in a complex by vector space. Following Dirac, we call such a vector a ket and denote it by This state ket is postulated to contain complete information about the physical state; everything we are allowed to ask about the state is contained in the ket. Two kets can be added:
spectra\342\200\224for
\342\200\224where

|a).

A-2.1)
The sum |y) is just another ket. If we multiply \\a) by a complexnumber c, the resulting product c\\a) is another ket. The number c can stand on the left or on the right of a ket; it makesno difference:
c\\a)
In

= \\a)c.

A-2.2)

the particular casewhere c is zero, the resulting ket is said to be a null ket. One of the physics postulates is that \\a) and with c=?0, the same physical state. In other words, only the \"direction\" in represent vectorspaceis of significance. athematiciansmay prefer to say that we are M here dealing with rays rather than vectors.

c|a),

is *For many physical systems the dimension of the state space denumerably infinite. While t we will usually indicate a finite number of dimensions, /V, of the ket space,he results also hold infinite dimensions. for denumerably

12
An

Fundamental

Concepts

observable, such as momentum and spin components, can be by represented an operator, such as A, in the vector spacein question.Quite generally, an operator acts on a ket from the left,

A.2.3)
which

later.

is yet another ket. There will be more on

multiplication

operations

In general, A\\a) is not a constant times However, there are o particular ketsof importance,known as eigenkets f operator A, denotedby

|a).

\\a'),\\a\9\\a'\")9...")
with

A.2.4) A.2.5)
A

the property

where a\\ a'\\

the just reproduces same ket apart from a multiplicative number. The set of is more compactly denotedby {a'}, calledthe numbers {a\\a'\\ set of eigenvalues of operator A. When it becomesnecessaryto order a may be used in place eigenvaluesin a specificmanner, {a{l\\{2\\ a{3\\

...

A\\a')

= a'\\a')9A\\a\") = a\"\\a\9...")

are just numbers. Notice that applying

to an eigenket

a'\",...},

of

The physical state corresponding an eigenket is called an eigento state. In the simplest aseof spin \\ systems,the eigenvalue-eigenket c relation is as A.2.5) expressed
SZ\\SZ;

{a'9a\"9a'\"9...}.

...}

+) = f |SZ; +>, z,
\\SZ'9

SZ\\SZ;

->= - f |SZ; ->, z,
\302\261h/2.

A.2.6)

where \\SZ; ) are eigenketsof operator Sz with eigenvalues Herewe + ) in conformity with the notation \\a'), couldhave usedjust \\h/2) for where an eigenket is labeledby its eigenvalue,but the notation \\SZ; +), already used in the previous section, is more convenient here becausewe alsoconsidereigenketsof Sx:
\302\261

\\S)
experiments.

A.2.7)

We remarked earlier that the dimensionality of the vector spaceis determined by the number of alternatives in Stern-Gerlach-type xperie More formally, we are concernedwith an TV-dimensional vector spacespannedby the TV eigenkets of observable A. Any arbitrary ket \\a) can be written as

a'
with

A.2.8)

a\\ up to a(N\\ where ca, is a complex coefficient.The question of the uniqueness f such an expansionwill be postponed o until we prove the of eigenkets. orthogonality

a\",...

1.2. Bras, and Operators Kets,
Bra Space Inner Products and

13

The vector spacewe have been dealing with is a ket space. now We introduce the notion of a bra space,a vector space\"dual to\" the ket space. We postulate that correspondingto every ket \\a) there existsa bra, denoted in this dual, or bra, space. The bra spaceis spannedby eigenbras by There is a one-to-one {(a'\\]which correspondto the eigenkets b correspondenceetweena ket spaceand a bra space:

(a|,

{|#')}.

DC
\\a)
<->

(a\\

~ \\a'),\\a\9...") (a%(a\"\\9...
DC

DC

A.2.9)

where DC standsfor dual correspondence. w Roughly speaking, e can regard the bra spaceas somekind of mirror image of the ket space. The bra dual to c\\a) is postulated to be c*(a|,not c(a\\, which is a very important point. More generally,we have
DC

written

define the inner product of a bra and a ket.* The product is as a bra standing on the left and a ket standing on the right, for example,
We now
<j8|a>=\302\253j8|)-(|a\302\273.

bra (c) ket

A.2.11

This product is, in general, a complex number. Notice that in forming an inner productwe always take one vector from the bra spaceand one vector
from the ket space. We postulate two fundamental

propertiesof inner products.First,

(C\\a)= (a\\p)*.

A.2.12)

In other words, (P\\ot) and (a\\fi) are complex conjugates of each other. Notice that even though the inner product is, in some sense,analogous to the familiar scalarproduct ab,(fi\\a) must be clearly distinguished from (ol\\P); the analogous distinction is not neededin real vector spacebecause a-b is equal to ba.UsingA.2.12) e can immediately deducethat (a\\a) w must be a real number. To prove this just let (/?|-> (a\\.
* In the literature an inner product is often referred to as a scalar product because it is in analogous to a-b in Euclidean space; this book, however, we reserve the term scalar for a space. quantity invariant under rotations in the usual three-dimensional

14 The secondpostulate on inner productsis

Fundamental

Concepts

<a|a>>0,

A.2.13)

where the equality sign holds only if \\a) is a null ket. This is sometimes known as the postulate of positive definite metric. From a physicist's point of view, this postulate is essential for the probabilistic interpretation of quantum mechanics,as will become apparent later.* Two kets |a)and |/?) are said to be orthogonal if
<\302\253|j3>

= 0,

A.2.14)

even though in the definition of the inner product the bra (a\\ appears.The a orthogonality relation A.2.14)lso implies,via A.2.12), Given a ket where
which

|a),
with

A.2.15) <j8|a>= 0. is not a null ket, we can form a normalizedket

the property

(a|a)=l.
|a|

A.2.17)

Quite generally, ]/(ot\\a) is known as the norm of analogous to the Because and magnitude of vector /a-a = in Euclideanvector space. \\a) representthe same physical state, we might as well require that the kets c\\a) we use for physical states be normalized in the senseof A.2.17).*

|a),

Operators
components

we remarked earlier, observableslike momentum and spin comare to be represented operators that can act on kets. We can by considera more general class of operators that act on kets; they will be denotedby X, 7, and so forth, while A, B, and so on will be used for a restrictive classof operators that correspond observables. to An operator acts on a ket from the left side,
As

= X-(\\a)) X\\a),
and the resulting product is another ket. OperatorsX and equal,
Y

A.2.18)
are said to be

X=Y9
shall not

A.2.19)

*Attempts to abandon this postulate led to physical theories with \"indefinite metric.\" We be concerned with such theories in this book. f For eigenkets of observables with continuous spectra, different normalization conventions will be used; seeSection

1.6.

1.2. Bras, and Operators Kets,
if X\\a)

15

= Y\\a)

A.2.20)
is said to be

for an arbitrary ket in the ket spacein question. Operator X we have the null operator if, for any arbitrary ket
X\\a)

= 0.

|a),

A.2.21)

Operatorscan be added;addition operations are commutative and associaassociative:

X+Y=Y+X, (Y+Z) = (X+Y)+Z.
With

A.2.21a A.2.21b
A.2.22)
side

in the single exception of the time-reversaloperator to be considered Chapter 4, the operators that appearin this book are all linear, that is,

+ X(ca\\a) cp\\P)) = caX\\a) + cpX\\fi).
An

operator X always acts on a bra from the

right

((a\\)-X=(a\\X,

A.2.23)
(a\\X

and the resulting product is another bra. The ket X\\a) and the bra are, in general, not dual to each other. We define the symbol X^ as
X\\a)
\302\253

(a\\XK

A.2.24)

The operatorX^ is called the Hermitian adjoint, or simply the adjoint, of X.
An

operatorX is said to be Hermitian

if

X=X\\
Multiplication

A.2.25)

OperatorsX and
in

Y

can be multiplied. Multiplication operations are,
that

general, noncommutative,

is, XY*YX.

A.2.26) A.2.27)

Multiplication operations are, however,associative:

X(YZ) = (XY)Z= XYZ.
We

also have
X(Y\\a))

= (XY)\\a)= XY\\a),

((P\\X)Y= @\\(XY) = (fi\\XY. A.2.28) A.2.29)

Noticethat

16

Fundamental

Concepts

because
XY\\a)

= X(Y\\a)) DC{(a\\Y*)X* = (a\\Y*XK ~
following

A.2.30)

So far, we have considered the
(ol\\X, and XY. Are and multiply

|)8)

there other products we are allowed to form? Let us (a|,in that order.The resulting product
|

products: (j8|a), \\a), X

A.2.31)

We will emphasizein a is known as the outer product of |p) and henceit is fundais moment that |p)(a| to be regarded as an operator; which is just a number. different from the inner product (p|a), fundamentally There are also \"illegal products.\" e have already mentioned that W an operator must stand on the left of a ket or on the right of a bra. In other words, \\a)X and X(a\\ are examples of illegal products.They are neither P kets, nor bras, nor operators;they are simply nonsensical. roducts like

(a|.

a are |a)|j8)nd (a|(j8| also illegal when

\\a)

and

(bra) vectors belongingto the same ket (bra) space.*
The AssociativeAxiom

|/?) ((a\\

and

(/?|)are ket

As is clearrom A.2.27), f multiplication operations among operators are associative.Actually the associativeproperty is postulated to hold quite generally as long as we are dealing with \"legal\" multiplications among kets, bras, and operators.Dirac calls this important postulate the associative axiom of multiplication. To illustrate the power of this axiom let us first consideran outer productacting on a ket:

(|j8><a|).|Y>.

A.2.32)
A-2-33)

of Because the associativeaxiom, we can regard this equally well as where (cc\\y) is just a number. So the outer product acting on a ket is just can another ket; in other words, |j8)(a| be regarded an operator.Because as are A.2.32)and A.2.33) equal, we may as well omit the dots and let stand acting |j8)(a|y) for the operator |j8)(a| on |y) or, equivalently, the number (a|y) multiplying |/?).(On the other hand, if A.2.33)s written as i we ((a|y))-|/J), cannot afford to omit the dot and bracketsbecausethe
in the book we will encounter products like which are more appropriately vector and |/?) always refer to kets from different but in such cases |a)\302\256|/?), For spaces. instance, the first ket belongs to the vector spacefor electron spin, the second ket to for the vector space electron orbital angular momentum; or the first ket lies in the vector space of particle the second ket in the vector space particle 2, and so forth. of written

* Later

as

|a)

|a)|K),

1,

1.3. Kets and Matrix Base
resulting

Representations

17

expressionwould look illegal.) Notice that the operator rotates |y) into the directionof |/?).It is easy to see that if

|/?)(a|

X=\\P)(al
then

A.2.34) A.2.35)

X*=\\aXP\\,
which that
\302\253i8|).(Jf|a\302\273

is left as an exercise. In a secondimportant illustration

of the associativeaxiom, we note
\302\253i8|Jr).(|a\302\273.

=

bra

ket

bra might

ket

A.2.36)

Becausethe
notation

two

sidesare equal, we

as well use the more compact

A.2.37)
to stand for either sideof A.2.36). Recall now dual to X\\a), so
that (a\\X^

is the bra that is

A.2.38)
addition to the associative axiom, we used the fundamental where, For of the inner product A.2.12). a Hermitian X we have property
in

. 13.BASEKETSAND
MATRIX

A.2.39)

REPRESENTATIONS

operator

of Eigenkets an Observable Let us considerthe eigenketsand eigenvaluesof a Hermitian operA. We use the symbol A, reservedearlier for an observable,because in mechanics Hermitian operators of interest quite often turn out to begin by
stating

be the operatorsrepresentingsome physical observables.
We

quantum

an important

theorem:

Theorem. The eigenvalues of a Hermitian operator A are real; to a eigenketsof A corresponding different eigenvalues re orthogonal Proof First, recall that
A\\a')

the

= a'\\a').

A.3.1)

18
A Because is Hermitian, we also have = a\"\\a'\\

Fundamental

Concepts

where are eigenvaluesof A. If we multiply b (a\"\\ on the left, both sidesof A.3.2) y \\a') on the obtain

a\\a\"...

A.3.2) both sidesof A.3.1) y b
right,

and subtract, we

Now

to be the same; we half of the theorem)

choose them

a' and a\" can be taken to be either the same or different. Let us first
then

= 0. (tf'-tf\"*)<tf>')

A.3.3)
first

deducethe reality condition (the

a'=a'*, a'
\342\200\224

A.3.4)

wherewe have usedthe fact that \\a') is not a null ket. Let us now assume and a\" to be different. Because the just-proved reality condition, the of difference i a\"* that appearsin A.3.3)s equal to a'\\ which cannot The inner product (a\"\\a') ust then vanish: m vanish, by assumption.

a'

a'

\342\200\224

= (a\"\\a') 0,
which

(a'*a\,")

A.3.5)

proves the
We

orthogonality

property (the secondhalf of the theorem).

?

expecton physicalgrounds that an observablehas real eigenvalthat will becomeclearer in the next section,where measurein quantum mechanics will be discussed. he theorem just proved T the reality of eigenvalueswhenever the operator is Hermitian. guarantees in That is why we talk about Hermitian observables quantum mechanics. It is conventional to normalize \\a') so the {\\a')} form a orthonormal
eigenvalues,

a point

measurements

set:

= (a\"\\a') 8a,,a,.
We may

A.3.6)

logicallyask,Is this set of eigenketscomplete?Sincewe started our discussion asserting that the whole ket spaceis spannedby the eigenkets by of A, the eigenkets A must therefore form a complete set by construction of of our ket

space.*

as Eigenkets BaseKets We have seen that the normalized eigenkets A form a complete of A in orthonormal set. n arbitrary ket in the ket spacecan be expanded terms
already familiar with wave mechanics, may point out that the completeof eigenfunctions we use can be proved by applying the Sturm-Liouville theory to the Schrodinger wave equation. But to \"derive\" the Schrodinger wave equation from our fundapostulates, the completeness of the position eigenkets must be assumed.
fundamental

* The astute reader,

completeness

1.3. Kets and Matrix Base

Representations

19

of the eigenkets A. In other words, the eigenketsof A are to be used as of baseketsin much the same way as a set of mutually orthogonal unit vectors is usedas base vectors in Euclidean space. Given an arbitrary ket \\a) in the ket spacespannedby the eigenkets of A, let us attempt to expand it as follows: a'
Multiplying (a\"\\ on the left and using the orthonormality we can immediately find the expansion coefficient,

A.3.7)
property A.3.6),

ca,=(a'\\a).
In other words,we have

A.3.8)
A-3-9)
in

? a'
V=Ie,(e,.V),

which

is analogous to an expansion of a vector V

(real) Euclidean space:

A.3.10)

where {e,} form an orthogonal set of unit vectors. We now recall the associativeaxiom of multiplication: \\a')(a'\\a) an be regarded either as the c number (a'\\a) multiplying \\a') or, equivalently, as the operator \\a')(a'\\ Because\\a) in A.3.9)s an arbitrary ket, we must have i acting on

|a).

a'

A.3.11

where the 1 on the right-hand side is to be understood as the identity is known as the completeness relationor closure. operator.Equation A.3.11) Given It is difficult to oveiestimatethe usefulnessof A.3.11). a chain of kets, operators,or bras multiplied in legal orders,we can insert, in any place at our convenience, the identity operator written in form A.3.11 f Consider, or example (oc\\a); by inserting the identity operator between (a\\ and we obtain

|a),

a a

A.3.12)
\\a)

This, incidentally, shows that if coefficientsin A.3.7) ust satisfy m a'

is normalized, then the expansion

a

A.3.13)

20

Fundamental

Concepts

Since Let us now look at \\a')(a'\\ that appearsin A.3.11). this is an outer product,it must be an operator.Let it operate on \\a):

= \\a')(a'\\a) ca\\a')= A.3.14) ('|)\302\273 We seethat \\a')(a'\\ selectsthat portion of the ket |a)parallel to \\a'), so \\a')(a'\\ is known as the projectionoperator along the base ket \\a') and is denotedby A/
The completenesselation A.3.11) r
a a, = \\a')(a'\\. can now be written

A.3.15)
as

A.3.16)

Matrix Representations
Having specified the base kets, we now show how to representan twice, we write the operator,say X, by a square matrix. First, using X as operator

A.3.11)

a There are altogether N2 numbers of form (a\"\\X\\a')9 where N is the W dimensionality of the ket space. e may arrange them into an iVxiV squarematrix such that the column and row indicesappearas follows:
a\"

= L E \\a\{a\"\\X\\a'){a'\\.")

A.3.17)

(a\"\\X row

\\a')
column

A.3.18

Explicitly we may

write

the matrix as

X=
where the symbol

(aB)\\X\\a(l))

(aA)\\X\\aB))

A.3.19

we UsingA.2.38), can write
(a\"\\x\\a')

= standsfor \"is represented * by.\" = (a'lX^a\*.")

A.3.20

At

has last, the Hermitian adjoint operation, originally defined by A.2.24), been related to the (perhapsmore familiar) concept of complexconjugate I transposed.f an operator B is Hermitian, we have
{a\"\\B\\a')

= {a'\\B\\a\*.

A.3.21

the equality sign here because the particular form of a matrix representation depends on the particular choice of basekets used. The operator is different from a representaof the operator just as the actress is different from a poster of the actress.
representation

* We do not use

1.3. Kets and Matrix Base
The
conformity

Representations

21

into a square matrix is in conforway we arranged (a\"\\X\\af) the usual rule of matrix multiplication. To seethis just note that the matrix representation of the operator relation
with

Z= XY
reads
(a\"\\Z\\a')

A.3.22)

= (a\"\\XY\\a')
a

Z(a\"\\X\\a'\(a'\"\\Y\\a')
identity

A.3.23)
in form

Again, all

between A.3.11), X and

we have done is to insert the
Y\\

operator, written

Let us now examine how the ket relation

can be represented using can be obtainedby multiplying

A.3.24) |y) = X|a> our base kets. The expansion coefficientsof |y)
(a'\\

on the left:

(a'\\y) = (a'\\X\\a)
a

A.3.25)

But this can be seen as an application of the rule for multiplying a square matrix with a column matrix representingonce the expansion coefficients of and |y) arrange themselvesto form column matricesas follows:

|a)

Wl)\\y) W2)\\y)

A.3.26)

Likewise, given

A.3.27)
we can regard a

A.3.28)

So a bra is represented a row matrix as follows: by

e,...).

A.3.29)

Note the appearanceof complexconjugationwhen the elementsof the column matrix are written as in A.3.29). he inner product (p|a) can be written as T

22

Fundamental

Concepts

product of the row representing\\a):
the a

matrix

representing (/?| with the column matrix

(aw\\a) A.3.30)
If we
preceding

multiply

representing|/?), then we obtain just the complexconjugate of the precedw expression, hich is consistent with the fundamental property of the inner product A.2.12). Finally, the matrix representation of the outer product \\fi)(a\\ *s easily seento be

the row matrix representing (a\\

with

the column matrix

'

(aA)\\p)(aB)\\a)*

A.3.31
The matrix representation of an observable A becomes particularly of simpleif the eigenkets A themselvesare usedas the basekets. First, we have

= E E \\a\(a\"\\A\\a')(a'\\.") a\" a'
But the

A.3.32) A.3.33)

squarematrix

(a\"\\A\\a')

{a\"\\A\\a')

is obviously diagonal, = (a'\\A\\a')8a,a,, a'SaV,,

-

so
a a

A.3.34)

Spin \\ Systems It is here instructive to considerthe specialcase spin \\ systems. of The basekets used are which we denote,for brevity, as | + ).The simplestoperatorin the ket spacespanned by | + ) is the identity operator, to can which, according A.3.11), be written as 1= | + ><+|+| A.3.35) to A.3.34), must be able to write Sz as we According
\\SZ\\
\302\261),
\342\200\224><\342\200\224

|.

.

A.3.36)

1.4.Measurements,

Observables, and the Uncertainty

Relations

23

The eigenket-eigenvalue relation

=
\302\261)

\302\261{h/2)\\\302\261)

A.3.37)

immediately follows from the orthonormality property of It is also instructive to look at two other operators,

|+).
A.3.38)

= h\\ + >(-|,
which
\342\200\224 |\342\200\224

S_ = h\\-)(+l

are both seen to be non-Hermitian.The operator S+, acting on the spin-down ket | ), turns ) into the spin-up ket |+) multiplied by h. On a the other hand, the spin-up ket when acted upon by S+, becomes null ket. So the physical interpretation of S+ is that it raises the spin component by one unit of h\\ if the spin component cannot be raisedany S_ further, we automatically get a null state. Likewise, can be interpreted as an operator that lowers the spin component by one unit of h. Later we will show that S x can be written as Sv + iSv. , x y In constructing the matrix representationsof the angular momentum operators,it is customary to label the column (row) indicesin descending order of angular momentum components,that is, the first entry corresponds to the maximum angular momentum component, the second, the next highest, and so forth. In our particular caseof spin \\ systems,we have

|+),

\342\200\224

(i-3-39a)

A.3.39b)
We
will come back to these explicit expressions hen we discuss w the Pauli two-componentformalism in Chapter 3.

AND 1.4. MEASUREMENTS, OBSERVABLES,

THE UNCERTAINTYRELATIONS Measurements

Having developed the mathematicsof ket spaces,we are now in a This position to discussthe quantum theory of measurement processes. is not a particularly easy subject for beginners,so we first turn to the wordsof the great master, P. A. M. Dirac, for guidance (Dirac 1958, 6): \"A 3 measurement always causesthe system to jump into an eigenstate of the dynamical variable that is being measured.\"What does all this mean? We w interpret Dirac's ords as follows:Beforea measurementof observableA is

24

Fundamental

Concepts

made, the system is assumed to be represented some linear combination by
a
When the

a
into\"

A.4.1)
one of

the

measurement is performed, the system is \"thrown s eigenstates,ay \\a') of observableA. In other words,
,

.

A measurement

\\a)

-\\a').

,

..

A.4.2)

,. .

_x

Forexample, a silver atom
into either
\\SZ;

with

an

SGz.Thus a measurement usually when the state is already in one of the eigenstates of the observable being i measured,n which case
with further. When the measurement causes certainty, as will be discussed to change into \\a'), it is said that A is measured to be It is in this sensethat the result of a measurementyields one of the eigenvaluesof the

+) or

|SZ;

\342\200\224

)

when

subjectedto a SG apparatus of type changesthe state. The only exception is

arbitrary

spin orientation will change

|a)

a'.

observable beingmeasured. Given A.4.1), hich is the state ket of a physical system before the w measurement, we do not know in advance into which of the various |fl')'s the system will be thrown as the result of the measurement. We do postulate,however, that the probability for jumping into some particular \\a') is given by
Probabilityfor a'=|<tf'|a>|2, A.4.4) provided that |a)is normalized. we have been talking about a single physical system, to Although determine probability A.4.4)empirically,we must considera great number of measurements performed on an is, a identically preparedphysicalsystems,all characterizedby the same ket \\a). Such an ensemble known as a pure ensemble.We will say more about is ( ensemblesin Chapter 3.) As an example, a beam of silver atoms which with the Sz survive the first SGz apparatus of Figure component blockedis an example of a pure ensemble becauseevery member atom of + ). is the ensemble characterizedby The probabilisticnterpretation A.4.4)for the squaredinner product i is |(tf'|a)|2one of the fundamental postulates of quantum mechanics,so it cannot be proven. Let us note, however,that it makes goodsensein extreme cases. upposethe state ket is \\a') itself even before a measurement is S more made; then according to A.4.4),the probability for getting for being thrown into the result of the measurement is precisely, predictedto be which isjust what we expect. measuring A once again, By
ensemble\342\200\224that collection\342\200\224of

1.3

\342\200\224

\\SZ\\

a'\342\200\224or,

1,

\\a')\342\200\224as

1.4.Measurements,

Observables, and the Uncertainty

Relations

25

we, of course, et \\a') only; quite generally,repeatedmeasurementsof the g in same observable successionield the same result.* If, on the other hand, y we are interestedin the probability for the system initially characterizedby \\a') to be thrown into some other eigenket \\a\") with an'?=a\\ then A.4.4) between \\a') and \\a\.") From the gives zero becauseof the orthogonality of view of measurementtheory, orthogonal kets correspond mututo point exclusivealternatives; for example,if a spin \\ system is in \\SZ; + ), it is not in > with certainty. Quite generally, the probability for anything must be nonnegative. m Furthermore, the probabilities for the various alternative possibilities ust add up to unity. Both of these expectations are met by our probability postulate A.4.4). We define the expectationvalue of A taken with respectto state \\a) as
mutually
\342\200\224

\\S2\\

A.4.5)
the notation (A)a is To make sure that we are referring to state sometimesused.Equation A.4.5)is a definition; however,it agreeswith our it intuitive notion of averagemeasuredvalue because can be written as

|a),

a' a'

a\"

a'
I

\\<a'\\\302\253)

measured

value

a'

probability

for obtaining

a'

It is very important not to confuse eigenvalueswith expectation values.For example,the expectationvalue of Sz for spin \\ systemscan assume any real in value between h/2and + h/2, ay 0.273/i; contrast, the eigenvalueof s only two values, h/2 and h/2. Sz assumes To clarify further the meaning of measurements in quantum meIn mechanics we introduce the notion of a selectivemeasurement,or filtration. Section we considered Stern-Gerlach arrangement where we let only a one of the spin components pass out of the apparatus while we completely blockedthe other component. More generally,we imagine a measurement processwith a device that selectsonly one of the eigenketsof A, say and rejectsall others; seeFigure This is what we mean by a selective measurement; it is also called filtration because only one of the A eigenkets the ordeal.Mathematically we can say that such a selective filters through
\342\200\224 \342\200\224

1.1

1.6.

|a'),

* Heresuccessive measurements must be carried out immediately afterward. This point becomeclear when we discuss the time evolution of a state ket in Chapter 2.

will

26

Fundamental

Concepts

\\a>

Measurement

FIGURE

1.6.elective measurement. S

measurement amounts to applying the projectionoperator Ka. to \\a):

A.4.7)
based on a thorough examination of selectivemeasurements.Heintroduces a measurement symbol M(a') in the beginning, which is identical to Aa, or in our notation, and deduces number of properties M(a')(and a of also of M(b\\a') which amount to \\b')(a'\\) by studying the outcome of various Stern-Gerlach-typexperiments. this way he motivates the entire In e mathematics of kets,bras, and operators.In this book we do not follow Schwinger'spath; the interested reader may consult Gottfried'sbook.

J. Schwinger has

developed a formalism of quantum

mechanics

|a')(a'|
(Gottfried

1966, 192-9).

O Spin \\ Systems, nceAgain
Before proceeding with a general discussion observables, once of we consider spin \\ systems.This time we show that the results of again sequential Stern-Gerlach experiments,when combined with the postulates of quantum mechanicsdiscussed far, are sufficient to determine not only so the Sxy eigenkets,\\SX; + ) and \\Sy\\ + >, but also the operatorsSx and Sy themselves.
First, we recall that when the Sx + beam is subjected an apparatus to of type SGz, the beam splitsinto two components with equal intensities. This means that the probability for the Sx + state to be thrown into \\SZ; + >, simply denotedas | + ), is \\ each; hence,

A.4.8)
We can therefore construct the

Sr + ket as follows:

&
with dx

A.4.9)

(common to both | + > and

real.In writing A.4.9)we have used the fact that

|-

\302\273

the overall phase of a state ket is immaterial; the coefficient

1.4.Measurements,

Observables, and the Uncertainty

Relations

27

of | + ) can be chosento be real and positive by convention.The Sx ket must be orthogonal to the Sx + ket becausethe Sx + alternative and Sx alternative are mutually exclusive.This orthogonality requirement leads to
\342\200\224

-

A-4.10)
where we have, again, chosenthe coefficientof | + ) to be real and positive by convention. We can now construct the operator Sx using A.3.34)as follows:

+ \\)-{\\Sx; j[{\\Sx;+)(Sx-

must

Noticethat the Sx we have constructed is Hermitian, just as it similar argument with Sx replaced S leadsto by

be.A

1' '
\302\246

l

*

A.4.12)

A.4.13) Is there any way of determining 5X and S2?Actually there is one wehave a beam of spin \\ of information we have not yet used.Suppose piece a atoms moving in the z-direction.We can consider sequentialStern-Gerlach experiment with SGJcfollowedby SG>\\ The results of such an experiment are completely analogous to the earlier caseleading to A.4.8):
A.4.14)
which

is not surprising in view of the invarianceof physical systems under we into rotations. Inserting A.4.10)nd A.4.12) A.4.14), obtain a
v2

A.4.15)

which

is satisfied only if

A.4.16) tt/2 or -tt/2* I We thus see that the matrix elementsof Sx and Sv cannot all be real. f the Sx matrix elements are real, the Sy matrix elements must be purely imagin(and vice versa).Just from this extremelysimpleexample, the introducof complexnumbers is seen to be an essential feature in quantum mechanics.t is convenient to take the Sx matrix elements to be real* and I
imaginary introduction

|-). be

always be done by adjusting arbitrary phase factors in the definition of | + ) and This point will become clearer in Chapter 3, where the behavior of under rotations will discussed.
|\302\261)

* This can

28

Fundamental

Concepts

the positive jc-axiswould be oriented direction.The secondphaseangle 52 must then be 77/2 or opposite tt/2.The fact that there is still an ambiguity of this kind is not surprising. We have not yet specifiedwhether the coordinate system we are using is right-handed or left-handed; given the x- and the z-axesthere is still a twofold ambiguity in the choiceof the positive >>-axis. Later we will discuss angular momentum as a generator of rotations using the right-handed coordinatesystem; it can then be shown that 82 = 77/2 is the correct choice. To summarize,we have

set 8X

= 0;if we were to choose8X = tt,

in

the

-

^ ^
and

??
\302\261

A.4.17a) A.4.17b)

A.4.18a
\302\261 \302\261

A.4.18b

The Sx and Sy eigenketsgiven here are seen to be in agreement with a based our earlier guesses A.1.9)nd A.1.14) on an analogy with linearly and in this comparison, that only the relative circularly polarizedlight. (Note, components is of physical significance.) phase between the |+) and | c Furthermore, the non-Hermitian S operatorsdefined by A.3.38)an now
\342\200\224)

be written as

= Sx\302\261iSv.
x\302\261iSv

A.4.19)
A.4.20)

The operators Sx and Sv, together with Sz given earlier, can be readily shown to satisfy the commutation relations ] and the anticommutation relations

!
,

A.4.21)

where the commutator [ , ] and the anticommutator { , } are defined by

A.4.22a) [AyB]= AB-BAy =AB + BA. A.4.22b) {A,B} The commutation relations in A.4.20)will be recognized as the simplest
significance
anticommutation

realization of the angular momentum commutation relations, whose signifiIn in will be discussed detail in Chapter 3. contrast, the anticommutain A.4.21) turn out to be a special relations property of spin \\ systems.

1.4.Measurements,
We

Observables, and the Uncertainty

Relations

29

can also define the operator

SS,or S2 for short, as follows:
\\

A.4.23)

of this Because A.4.21), operator turns out fo be just a constant multiple of
the
identity

operator

We

obviously have

S2=(|)/i2. [S2,S,]=0.
Chapter 3, for

A.4.24) A.4.25)
longer a

As will

be shown

in

multiple of the

identity

spinshigher than \\, S2 is no operator; however,A.4.25)still holds.

CompatibleObservables
now to the general formalism, we will discuss compatible Returning A versus incompatible observables. Observables and B are defined to be compatiblewhen the correspondingperators commute, o

[A9B]= 09
and incompatiblewhen
[A9B]\302\2610,

A.4.26) A.4.27)

For example,S2 and Sz are compatible observables, while Sx and Sz are observables. incompatible Let us first considerhe case compatible observablesA and B.As of t usual, we assumethat the ket spaceis spannedby the eigenketsof A. We may also regard the same ket spaceas being spanned by the eigenketsof B. We now ask, How are the A eigenkets related to the B eigenketswhen A and B are compatible observables? Before answering this question we must touch upon a very important point we have bypassed conceptof degeneracy.Supposethere are two (or more) linearly independent eigenkets of A having the same eigenvalue; then the eigenvalues of the two eigenkets are said to be In degenerate. such a case the notation \\a') that labelsthe eigenket by its f eigenvaluealone doesnot give a completedescription;urthermore, we may recall that our earlier theorem on the orthogonality of different eigenkets Even worse, the whole was proved under the assumption of no degeneracy.
earlier\342\200\224the

concept that the ket space is spanned by {\\a')}appears to run into difficulty when the dimensionality of the ket spaceis larger than the number
of distinct eigenvaluesof A. Fortunately,
quantum

i that mechanics,t is usually the case

of some other commuting

practical applications in quansuch a situation the eigenvalues observable, say B, can be used to label the

in in

degenerate eigenkets.

30

Fundamental

Concepts

Now we are ready to state an important theorem. Theorem. Suppose A and B are compatibleobservables,and the that eigenvaluesof A are nondegenerate.Then the matrix elements(a\"\\B\\af) are all diagonal. (Recall ere that the matrix elementsof A are alreadydiagonalif h are usedas the basekets.) Proof The proof of this important theorem is extremely simple. we of Usingthe definition A.4.26) compatible observables, observe that
(a\"\\[A9

= B]\\a')= (a\" a'){a\"\\B\\a')0. = unless a'' a'\\
which

-

A.4.28)

So{a\"\\B\\a')
We

must vanish

proves our assertion.

?

can write the matrix elementsof B as

A.4.29) Soboth A and B can be represented diagonal matrices with the same set by of basekets. UsingA.3.17)nd A.4.29)we can write B as a

= E \\<*\(<*\"\\B\\<*\"){<*\"{")
a\"

A.4.30)

Supposethat

this

operator acts on an eigenket of A:

B\\af) But this
with

= E \\a\(a\"\\B\\a\")(a\"\\a')")
other
than

= ((a'\\B\\a'))\\a'). A.4.31)
B

is nothing

the eigenvalueequation for the operator

eigenvalue

b'={a'\\B\\a').
simultaneous

A.4.32)

The ket \\a') is therefore a simultaneous eigenketof A and B.Just to be w impartial to both operators, e may use \\a\\b') to characterizethis simulta-

eigenkets.

eigenket. We have seen that compatible observables ave simultaneouseigenh Even though the proof given is for the case where the A eigenkets re a the statement holds even if there is an nondegenerate, degeneracy, that is,
\302\253-fold

A\\a'(i))

= a'\\a'(i)) for i =1,2,..., n

A.4.33)

where \\a'(l)) are n mutually orthonormal eigenkets f A, all with the same o To seethis, all we need to do is construct appropriate linear eigenvalue combinations of |<z'(z)) that diagonalize the B operator by following the in to diagonalization procedure be discussed Section

a'.

1.5.

1.4.Measurements,
A

Observables, and the Uncertainty

Relations

31

simultaneous eigenket of

A

and

B, denotedby

\\a\\b')9

has the

property

a\\b')= a'\\a\\b')>
= B\\a\\b') b'\\a\\b').
When
it

A.4.34a) A.4.34b)

there is no degeneracy,this notation is somewhatsuperfluousbecause f that is clearrom A.4.32) if we specifya\\ we necessarilyknow the b' that T appearsin \\a'9b'). he notation \\a\\b') is much more powerful when there A are degeneracies. simpleexample may be used to illustrate this point. of Even though a complete discussion orbital angular momentum will not appear in this book until Chapter 3, the reader may be familiar
from his

or her earlier training in elementary wave mechanics that the eigenvaluesof L2 (orbital angular momentum squared)and L, (the z-component of orbital angular momentum) are h 1A + 1)and m/ft, respectively, with / an integerand m/= + /. To characterize an orbital i to momentum state completely,t is necessary specify both I and angular For example, we just say /=1, mz value can still be 0, if the or mh if we just say m/= / can be 2,3,4, and so on. Only by specifying both I and mz do we succeed uniquely in characterizing the orbital angular momentum state in question.Quite often a collective index K' is used to stand for (a\\ br), so that
\342\200\224/,

\342\200\224/+1,...,

-1;

1,

1,

+1,

|X\">

= |<i',fc'>.

A.4.35)

We can obviously generalizeour considerations a situation where to there are several (more than two) mutually compatible observables, namely,

= = [A,B] [B,C] [AX]= =0.
\342\200\242\342\200\242\342\200\242

A.4.36)

that we have found a maximal set of commuting observables; that we cannot add any more observables our list without violating A.4.36). to is, The eigenvaluesof individual operatorsA, may have degeneracies, but if we specify a combination @', then the corresponding simultaneous eigenket of A, B, is uniquely specified. can again use We a collectiveindex K' to stand for (a\\b\\c\\...). orthonormality relaThe

Assume

C,...

6',c',...),

B,C,...

relation

for

') = \\a\\b\\c\\...)
reads
t,

A.4.37)

...,

A.4.38)

while the

c r completenesselation, or closure, an be written as a'
W

K'

c'

'--\\<t',b\\c\\...Xa\\b\\c\\...\\=l. A.4.39)

32

Fundamental

Concepts

compatible

Subsequently,

follows from our measurement formalism that the third measurement algives with certainty, that is, the second(B) measurementdoes not destroy the previous information obtained in the first (A) measurement. This is rather obvious when the eigenvaluesof A are nondegenerate:
always

We now consider measurementsof A and B when they are compatiobservables. upposewe measure A first and obtain result a\\ SubseS we may measure B and get result b'. inally we measureA again. It F

a'

A measurement,

,
\\a',

b')

f

/v

B measurement,

, , /x

~\\a\\

b')

A

measurement, , ~\\a\\

, b').
/v

A.4.40)
first

When there is degeneracy,the argument goes as follows: After the (A) measurement, which yields a\\ the system is thrown into some
n

linear combination

A.4.41)
where n is the degreeof degeneracyand the kets \\a\\ b(l))all have the same The eigenvalue as far as operator A is concerned. second(B) measureselectust one of the terms in the linear combination A.4.41), say, may j the third (A) measurement applied to it still yields \\a\\ 6G)), but Whether or not there is degeneracy,A measurementsand B measurements do not interfere. The term compatibleis indeeddeemedappropriate.

a'

measurement

a'.

IncompatibleObservables
We now turn to incompatibleobservables, which are more nontrivial. The first point to be emphasized is that incompatible observables o not d have a completeset of simultaneouseigenkets. o show this let us assume T the converse to be true. There would then exist a set of simultaneous with property A.4.34a) nd A.4.34b). learly, a eigenkets C
AB\\a\\

b') = Ab'\\a'9 b') = a'b'\\a\\
V)

b').

A.4.42) A.4.43)
A.4.44)

Likewise,
BA\\a\\

= Ba'\\a\\ b') = a'b'\\a'9 b');
b') = BA\\a\\ b')9

hence,
AB\\a\\

contradiction to the assumption. So in general, does not make sensefor incompatible observables. There is, how\\a\\ b') an interestingexception;it may happen that there existsa subspace of the ket spacesuch that A.4.44) holdsfor all elementsof this subspace, ven e though A and B are incompatible.An example from the theory of orbital and
thus in
however,

= [A,B] 0

1.4.Measurements,

Observables, and the Uncertainty

Relations

33

an we S angular momentum may be helpful here. uppose consider / = 0 state do not commute, this state is a simultaE (s-state). ven though Lx and Lz eigenstate of Lx and Lz (with eigenvaluezero for both operators).
simultaneous

in The subspace this caseis one-dimensional. with We already encountered some of the peculiarities associated Stern-Gerlachexobservables when we discussed sequential incompatible We now give a more general discussionof experiments in Section of the experiments of that type. Consider sequence selectivemeasurements some particular \\a') and The shown in Figure 1.7(a). first (A) filter selects second(B) filter selectssome particular \\b') and rejects all others, the rejects all others, and the third (C) filter selects some particular \\c') and rejectsall others.We are interested in the probability of obtaining |c'> when the beam coming out of the first filter is normalized to unity. Because a the probabilities re multiplicative, we obviously have

1.1.

A.4.45) |<c'|Z>'>|2|<Z>V>|2. the Now let us sum over b' to consider total probability for going through all possible b' routes. Operationally this means that we first record the probability of obtaining c'with all but the first b' route blocked,then we a with all but the secondb' blocked, nd so on; then we repeat the procedure at sum the probabilities the end and obtain A.4.46)
b'
We now
filter

is absent(ornot operative); seeFigure

compare this

with

a

different

1.7b. Clearly, the probability is
\\c'>

arrangement, where the B

\\b'>

B

(a) b'
\\C'>

(b)
FIGURE

1.7.Sequential

selective measurements.

34

Fundamental

Concepts

just

which |(c'|tf')|2,

can also be written as follows:
b'
b\"

= IE l<cK>l2 <c'\\b')<b'\\a')\\2 = LL(c'\\b')(b'\\a')(a'\\b\(b\"\\c')
b'

A.4.47)
Notice that expressions .4.46)and A.4.47)are different! This is remarkA in because both casesthe pure \\a') beam coming out of the first (A) filter can be regardedas being made up of the B eigenkets
remarkable

IO = X>'><^K>,
b'

A.4.48)

where the sum is over all possible valuesof The crucial point to be noted is that the result coming out of the C filter dependson whether or not B measurements have actually been carried out. In the first case we experiascertain which of the B eigenvaluesare actually realized; in the w secondcase, e merely imagine \\a') to be built up of the various |ft')'s in the senseof A.4.48). in another way, actually recording the probabilities Put of going through the various b' routes makes all the differenceeven though we sum over b' afterwards. Herelies the heart of quantum mechanics. Under what conditions do the two expressions ecomeequal? It is b for left as an exercise the reader to show that for this to happen, in the of it absence degeneracy, is sufficient that
experimentally

b'.

= [A,B] 0
In other

or

= [5,C] 0.

A.4.49)

words, the peculiarity we have illustrated is characteristic of incompatible observables.
The Uncertainty Relation The last topic to be discussedin this section is the relation. Given an observableA, we define an operator
uncertainty

= A -(A),

A.4.50)

where the expectation value is to be taken for a certain physical state under consideration. expectationvalue of (&AJ is known as the dispersion The of A. Because have we

the

dispersion.Sometimes the terms variance and mean square deviation are vanishes when the state used for the same quantity. Clearly, the dispersion t of in question is an eigenstate of A. Roughly speaking, he dispersion an observable characterizes \"fuzziness.\" For example, for the Sz + state of a

= + <(A^J> = <(^2-2^(^><^>2)> </J2>-<^>2, A.4.51 last line of A.4.51) of may be taken as an alternative definition

1.4.Measurements,
spin

|

Observables, and the Uncertainty

Relations

35

of system, the dispersion Sx can be computed to be

A.4.52)
sharp\"\342\200\224a Sz\342\200\224while

In contrast the dispersion (ASZJ)obviously vanishesfor the Sz + state. So, for for the Sz + state, Sz is \" vanishing dispersion Sx
We now state the uncertainty relation, which is the generalizationof in Let the well-known x-p uncertainty relation to be discussed Section A and B be observables. Then for any state we must have the following

is fuzzy.

1.6.

inequality:

({bAf)({UiJ)>\\\\([A,B])\\2.
To prove this we first state three lemmas. Lemma
which

A.4.53)

1.TheSchwarzinequality
<a|a></3|/?>>|<\302\253|/?>|2,

A.4.54) A.4.55)

is analogousto

|a|2|b|2>|a-b|2
in

real Euclidian

space.
+ X|/?>)>0, a|+X*</?|).(|a>

Proof. First note

A.4.56)
X

where X can be any complexnumber. This inequality set equal to -<j8|a>/<j8|j8>:

must hold when

is

> 0, (a\\a)(P\\P) |<a|?>|2
which

-

A.4.57)

is the sameas A.4.54).
Lemma

?

real.

2. The expectationvalue
trivial\342\200\224just

of a Hermitian operator is

purely

Proof. The proof is

useA.3.21).

?
operator, de-

Lemma 3. The expectationvalue of an anti-Hermitian
defined

by

C = C+, is purely
\342\200\224

imaginary.

Proof The proof is also trivial.

?
A.4.58)

uncertainty

Armed with these lemmas, we are in a position to prove the uncerrelation A.4.53). UsingLemma 1with

36

Fundamental

Concepts

where the blank ket | ) emphasizesthe fact that our consideration may be appliedto any ket, we obtain

A.4.59)
where the Hermiticity of A A and w right-hand side of A.4.59), e note
AZ?

has been used. To evaluate the

^
where the commutator [A^4,AZ?], anti-Hermitian
which

A.4.60)

is equal to [A, B]9 is clearly

([A,B])f = (AB
=
\\

-

BA)f

= BA

-

AB

= -[A, ]. B

A.4.61
A.4.62)

In contrast, the anticommutator {A^4, AZ?}
purely imaginary

is obviously Hermitian, so
purely real

([A, B])+ \\ <{HA,AZ?}> ,

becomes

where Lemmas 2 and 3 have beenused.The right-hand

sideof A.4.59)ow n

A2?>|2= \\\\({A, B])\\2 + \302\261\\<{\\A,M})\\2.

A.4.63)

The proof of A.4.53)s now complete becausethe omission of the second i c (the anticommutator) term of A.4.63)an only make the inequality relation Applications of the uncertainty relation to spin \\ systemswill be left as exercises. come back to this topic when we discussthe fundamental We commutation relation in Section 1.6. x-p
* stronger.

1.5. CHANGE BASIS OF
Transformation Operator
A Supposewe have two incompatible observables and B.The ket or spacein question can be viewedas being spannedeither by the set {|tf')} For by the set {\\b')}. example, for spin \\ systems may be used as our base kets; alternatively, \\SX may be used as our basekets.The two W different sets of base kets, of course,span the same ket space. e are interestedin finding out how the two descriptions re related.Changing the a
\\SZ\302\261)
\302\261)

*In
written

the literature

as &A AS > \\\\([A, B])\\. In this not A.4.50)], numbers. operators [see

most authors use hA for our y ((A4) ) so the uncertainty relation is book, however, A A and AS are to be understood as

1.5. Change of Basis

37

set of base kets is referred to as a change of basis or a change of is representation. The basisin which the base eigenketsare given by {\\a')} called the A representation or, sometimes, the A diagonal representation to becausethe squarematrix corresponding A is diagonal in this basis. Our basic task is to construct a transformation operator that conthe old orthonormal set {\\a')} and the new orthonormal set To this end, we first show the following.
connects

{|?')}.

Theorem. Given

two

sets of base kets, both
unitary

satisfying

orthonormality

and completeness,there existsa

operator U such that

A.5.1)
By

a

unitary

operator we mean an operatorfulfilling

the conditions

A.5.2)
as well as = 1/1/* 1.
Proof We prove
that this

A.5.3)

theorem by explicit construction. We assert

the

operator

A.5.4)
will

do the joband we apply

this

U to

|#(/)).Clearly, A.5.5)
Furthermore, {|tf')}\342\200\224

is guaranteed by the orthonormality
k
I

of

U
\342\200\224

is unitary:

2^\\a k

)\\a

I

1*

vi.^.oj

where we have used the orthonormality of {\\b')} the completeness and of We i {\\a')}. obtain relation A.5.3)n an analogousmanner. TransformationMatrix
in

?

the

It is instructive to study the old {|tf')} We have basis.
\\U

matrix

representation of the U operator
\\U

|L/|u /

\342\200\224

\\u

>,

yi

/ .J.J

which

is obvious from A.5.5). other words, the matrix elementsof the U In operator are built up of the inner productsof old basebras and new base kets.We recall that the rotation matrix in three dimensionsthat changesone set of unit base vectors (x,y,z)into another set (x^y^z')can be written as

38 for 128-37, example) (Goldstein1980, XX /
A A

Fundamental

Concepts

xy /
A A

xz/
A A

AA/ AA/ zx

yy

A

A

/

yz /
A A

z-y

AA/

AA/ zz

A.5.8)

The squarematrix made up of (a(/c)|[/|a(/)) referred to as the transformais
transformation

matrix from the

Given an
known in the

basis basis. {|tf')} to the {\\b')}
ket
\\a)

old basis,

arbitrary

whose expansion coefficients(a'\\a) are

a how can we obtain

answer is very simple:Just avoid confusion) by (b(k)

(b'\\a),the expansion coefficientsin the new basis?The A.5.9)(with a' replacedby a(/) to multiply

A.5.10)
basis can be obtained just by matrix in the old basis:
In matrix notation, A.5.10)tates that the column matrix for \\a) in the new s applying the square matrix ?/* to the column

(New) = (t/+)(old). A.5.11 The relationships between the old matrix elements and the new matrix elements are also easy to obtain:
(bik)\\X\\b(i))

? =?
=
m m

^(bik)\\aim))(aim)\\X\\ain))(ain)\\b(l))
n

Y,Wk)\\U^\\a{m))(a(m)\\X\\a{n))(a{n)\\U\\a{l))
n

A.5.12)
This is simply the well-known formula for a matrix algebra,
similarity

transformation

in

' = U*XU.

A.5.13)

elements:

The trace of an operator X is defined as the sum of diagonal

a

A.5.14)
definition,

Even though

a particular set of basekets is used in the

1.5. Change of Basis
turns

39

out to

be independent of representation, as shown:

= L{\"'\\X\\a')
a

I Z Z<aW)(b>\\X\\b\(b\"\\a')
a'
W
b\"

=V
b' b'
b\"

= Z<b'\\X\\b').
We

A.5.15)

can also prove

tr(XY) = tr(YX),
tr(\\a')(a\"\\)

= 8aW,,

A.5.16a A.5.16b A.5.16c

Diagonalization So far we have not discussedhow to find the eigenvalues and basis of eigenkets an operator B whose matrix elements in the old {|tf')} are assumedto be known. This problem turns out to be equivalent to that of finding the unitary matrix that diagonalizesB.Even though the readermay in already be familiar with the diagonalizationprocedure matrix algebra, it is worth working out this problem using the Diracbra-ket notation. We are interested in obtaining the eigenvalue b' and the eigenket with the property \\b')
B\\b')

= b'\\b').

A.5.17)

First, we rewrite this as a
When \\b') in A.5.17)tands for the /th s in matrix notation as follows: A.5.18)

A.5.18
eigenketof operator B, we can write

(Bu Bu u
B2l B22
with

Bu
c2(/)

A.5.19

A.5.20a)
and
C{/)=(\302\253(A:)|/>(/>>,

A.5.20b)
As space.

where i,

j,k run

up to

iV,

the dimensionality of the ket

we know

40 from linear

Fundamental

Concepts

characteristic equation

algebra,nontrivial solutions for C^ are possibleonly

if

the

det(?- XI)

=0

A.5.21

is satisfied.This is an Nth order algebraicequation for X, and the TV roots obtained are to be identified with the various />(/)'swe are trying to determine. nowing />(/) we can solve for the corresponding (k!)'s to an up K C overall constant to be determined from the normalizationcondition. Comwe w A.5.20b) ith A.5.7), see that the Cfci)9s are just the elementsof Comparing ~* the unitary matrix involved in the change of basis {\\a')} {\\b')}. For this procedure Hermiticity of B is important. For example, the T o consider S+ defined by A.3.38) r A.4.19). his operator is obviously non-Hermitian. The corresponding atrix, which readsin the Sz basisas m

cannot be diagonalized by any unitary matrix. In Chapter 2 we will encounter eigenketsof a non-Hermitian operator in connection with a coherent state of a simple harmonic oscillator. uch eigenkets, S however,are known not to form a completeorthonormal set, and the formalism we have in developed this sectioncannot be immediately applied.
Unitary Equivalent

Observables

We
unitary

transform of an

concludethis section by discussing remarkabletheoremon the a observable.

Theorem. Consideragain two sets of orthonormal basis{\\a')} and Knowing U, we may construct by {\\b')} connected the U operator a unitary transform of A, UA U~ then A and UA U~ are saidto be unitary
The equivalent observables. eigenvalueequationfor A,
A\\a^)

;

A.5.4).

= <i<V>>,
=
a(l)U\\a(l)).

A-5-23)

clearly implies that
UAU~lU\\a{l))

A.5.24) A.5.25)

But

this

can be rewritten

as
{UAU~l)\\b{l))

= a(/)|fe(/)>.

This deceptivelysimple result is quite profound. It tells us that the of are eigenkets UAU~l with exactly the same eigenvaluesas the A

1.6. Position, Momentum,
spectra.

and Translation

41

eigenvalues. In other words, The eigenket |Z>(/)>, by

unitary definition,

equivalent

observableshave identical

satisfiesthe relationship

A.5.26)
we A.5.26), infer that B and UAU1aresimulA diagonalizable. natural questionis, is UAU1the sameas B itself?The answer quite often is yes in cases f physical interest. ake,or o T f and Sz.They are related by a unitary operator, example,Sx which, as we will discuss Chapter 3,is actually the rotation operator around the y-axis in it/2. In this case itself is the unitary transform of Sz.Because by angle Sx we know that Sx and Sz exhibit the same set of eigenvalues\342\200\224namely, + h/2 and see that our theorem holds in this particular a Comparing A.5.25)nd
simultaneously

-

h/2\342\200\224we

example.

AND 1.6. MOMENTUM, POSITION,

TRANSLATION

Continuous Spectra

so c The observables onsidered far have all been assumed to exhibit discrete eigenvalue spectra. In quantum mechanics, however, there are w observables ith continuous eigenvalues.Take, for instance, pz, the z-comof momentum. In quantum mechanicsthis is again represented a by ponent
Hermitian In operator.
\342\200\224

contrast to Sz, however, the eigenvaluesof pz (in can assume any real value between oo and oc. appropriate units) The rigorous mathematics of a vector spacespannedby eigenkets that exhibit a continuous spectrum is rather treacherous.The dimensionality is of .sucha space obviously infinite. Fortunately, many of the results we worked out for a finite-dimensionalvector spacewith discreteeigenvalues can immediatelybe generalized.In placeswhere straightforward generalizado not hold, we indicate danger signals. We start with the analogue of eigenvalueequation A.2.5), hich, in w i the continuous-spectrumcase,s written as
generalizations

A.6.1
where ? is an operator and is simply a number. The ket is, in other words, an eigenket of operator ? with eigenvalue just as \\a') is an eigenketof operatorA with eigenvalue the In pursuing this analogywe replace Kronecker symbol by Dirac's 8-f sum discrete over the eigenvalues by an integral over the

?'

a'.

?',

|?')

unction\342\200\224a

{a'}

42
continuous

Fundamental

Concepts

variable

i~'\342\200\224so

(\,")
-1,
\302\253>

A.6.2a) A.6.2b)

\302\253>

= E ifl'

=1
a
{a\"\\A\\a')

-

/#'|<*'|\302\253>|2

A.6.2d)

= a'&a.a..

-

= fdf < j8|O<*1\302\253>.

(l.6.2e

(t\"\\t\\V)

= S'8(t\"

-

?')\342\200\242

(l.6.2f)

a A.6.2c) nd A.6.2e).

Noticein particular how the completeness i relation A.6.2b)s usedto obtain
Position Eigenkets Position Measurements and
In Section 1.4 we emphasized that a measurement in quantum To mechanics is essentiallya filtering process. extend this idea to measureof observablesxhibiting continuous spectrait is best to work with a e To specific example. this end we consider the position (or coordinate) operatorin one dimension. The eigenkets o |jc') f the position operator x satisfying
measurements

x\\x')

are postulatedto form a complete set. Here x' is just a number with the dimension of length 0.23 for example,while x is an operator.The state cm, ket for an arbitrary physical state can be expanded terms of in

= x'\\x')

A.6.3)

/oo dx'\\x')(x'\\a). -oo
We now

A.6.4)

considera highly idealized selective measurement of the we observable. uppose placea very tiny detectorthat clicksonly S position at when the particle is precisely x' and nowhere else.mmediatelyafter the I detectorclicks,we can say that the state in question is represented \\x'). by In other words,when the detector clicks,\\<x) abruptly \"jumps into\" \\x') in much the same way as an arbitrary spin state jumpsinto the Sz + (or Sz state when subjected an SG apparatus of the Sz type. to In practicethe best the detectorcan do is to locate the particle within a narrow interval around x'.A realistic detector clickswhen a particle is observedto be located within some narrow range A/2,jc'+ A/2).
\342\200\224)

(jc'\342\200\224

1.6. Position, Momentum,
When

and Translation

43

a count is registeredin such a detector, the state ket changesabruptly as follows:
i \\

\\a)

j )(x /V+A/2, |x,,v , = / ox//i|x//w m|o>measurement I ox )(x Jx'-H/2
f\302\260\302\260

\\

-*

\342\200\236

\342\200\236

* |o). A.6.5)
v
/-%

c\\

\342\200\242'-oo

Assuming that (x\"\\a) does not change interval, the probability for the detector to
\\(x'\\a)\\2dx\\

clickis given by

appreciably within

the narrow

A.6.6)

for where we have written dx' for A. This is analogous to |(tf'|a)|2 the for \\a) to be thrown into \\a') when A is measured.The probability probability of recording the particle somewherebetween oc and oc is
\342\200\224

given by
/\342\200\242OO

/
\342\200\242'-oo

dx'\\(x'\\a)\\\\

A.6.7)

which

is normalized to unity

if

\\a)
/\342\200\242OO

is normalized:

<a|a>=l=> dx'(a\\x')(x'\\a)=l. /
\342\200\242'-oo

A.6.8)

f The readeramiliar with wave mechanics may have recognized by time that (x'\\a) the wave function for the physical state represented is We will say more about this identification of the expansioncoefby with the jc-representation of the wave function in Section The notion of a position eigenket can be extendedto three dimenIt is assumedin nonrelativistic quantum mechanics that the position The are complete. state ket for a particle with internal degrees eigenkets of freedom, such as spin, ignored can therefore be expandedin terms of
this
I

a).

coefficient

1.7.

dimensions.

|x')

a {|x')}s follows:

A.6.9)
where x' stands for x\\ y\\ and z';in other words, |x\") is a simultaneous x eigenketof the observables , y, and z in the senseof Section

1.4:

A.6.10a
y\\K')

= y'\\&')9

= A z|x') z'|x'>. .6.10b

To be able to consider such a simultaneouseigenketat all, we are implicitly assuming that the three componentsof the position vector can be measured of simultaneously to arbitrary degrees accuracy; hence, we must have where xv

A.6.11
x2,and jc3 stand
for
x>

y, and z, respectively.

44

Fundamental

Concepts

Translation
We now introduce the very important concept of translation, or spatial displacement. upposewe start with a state that is well localized S an around x'.Let us consider operation that changes this state into another with everything else(for well-localized state, this time around example,the spin direction)unchanged. Such an operation is defined to be an infinitesimal translation by dx\\ and the operator that does the job is

x'+dx'

denotedby

T(dx'):

= 3T(dx')\\x') \\x'+
where a possiblearbitrary
that with
infinitesimal

dx'),

A.6.12

phasefactor is set to unity by convention.Notice is sideof A.6.12) again a position eigenket,but this time is O eigenvaluex'+ dx'. bviously |x') not an eigenket of the infinitesitranslation operator.
the right-hand
By

we eigenkets can examine the effectof infinitesimal translation on
\\a)

expanding an

arbitrary

state ket

\\a)

in

terms of the position
\\<x):

= -> ^(dx')\\a)

^(dx')jd3x'\\x')(x'\\a) jd3x'\\x'+dx')(x'\\a).
sideof A.6.13)s a

=

A.6.13
We

also write the

right-hand

= dx')(x'\\a) jd3x'\\x')(x'dx'\\a) jd3x'\\x'+
because the integration is over all space and
\342\200\224

A.6.14

x' is just

an integration

variable.This showsthat the wave function of the translated state ^(dx')\\a) is obtained by substituting x' dx'for x' in There is an equivalent approach to translation that is often treated in the literature. Instead of considering an infinitesimal translation of the a physical system itself, we consider change in the coordinate system being used such that the origin is shifted in the opposite direction, dx'. Physically,in this alternative approach we are asking how the same state ket would look to another observer whose coordinate system is shifted by dx'.In this book we try not to use this approach.Obviously it is important that we do not mix the two approaches! We now list the properties the infinitesimal translation operator of The ^~{dx'). first property we demand is the unitarity property imposedby probability conservation. It is reasonable to require that if the ket \\a) is normalized to unity, the translated ket ^(dx')\\a) also be normalized to

(x'|a).

\342\200\224

\342\200\224

unity,

so

(a\\a)= (a\\^{dx'KT{dx')\\a).

A.6.15

This condition is guaranteedby demanding that the infinitesimal translation

1.6. Position, Momentum,
be unitary:

and Translation

45

A.6.16)
Quite generally, the norm of a ket is preserved under unitary transformawe t infinitesForthe secondproperty, suppose considerwo successive translations\342\200\224first by dx'and subsequently by dx'\\ where dx' and dx\" neednot be in the samedirection. We expectthe net result to be just a so single translation operation by the vector sum dx'+dx\", we demand
transformations. infinitesimal

that

= x\^(dx')")iT(dx'+dx\.")

A.6.17)

For the third property, supposewe considera translation in the opposite translation to be the same as the direction; we expectthe opposite-direction inverseof the original translation:

- dx')= y~\\dx').
lim

A.6.18)
translation

For the fourth property, we demand that as operation reduceto the identity operation

the dx'->0,

y~(dx')=l
identity

A.6.19)
operator be of first
translation

and

that

order in

dx'.
be

and the differencebetween 3T{dx') the

We now

demonstrate that if we take the infinitesimal

operator to

^(Jx/)=1-/K-Jx/,

A.6.20)

where the components of K, Kx9 Ky, and Kz, are Hermitian operators, then all the propertieslisted are satisfied. The first property, the unitarity of i ^(dx'),s checkedas follows:

= dx')^(dx') A + i?J-dx')(liK-dx')

where terms of

secondorder in dx'have been ignored for an infinitesimal translation. The secondproperty [A.6.17)] also be proved as follows: can

-1,

A.6.21)

=A dx\^(dx')") - /K-dx\{\\") iK-dx')

A.6.22) The third and fourth properties obviously satisfiedby A.6.20). are t Accepting A.6.20)o be the correct form for 3T(dx'),we are in a
position to derive an extremely fundamental relation between the K oper-

46

Fundamental

Concepts

ator and the x operator.First, note that

= dx') A.6.23a) x^{dx')\\x') x|x'+ = (x'+dx')\\x'+ dx')
and

= = dx')\\ F{dx')x\\x') x'F{dx')\\x') x'|x'+
hence,
\\x') dx') dx'\\x'), [x,f(dx')] = dx'\\x'+
\302\253

A.6.23b) A.6.24)

is where the error made in writing the last line of A.6.24) of secondorder in a dx'.Now |x')can be any position eigenket,and the position eigenkets re known to form a complete set. We must thereforehave an operator identity

[x,^(dx')]=dx\\
or

A.6.25) A.6.26)

- /xK-dx'+ /K-dx'x=

dx\\

where on the right-hand sidesof A.6.25)nd A.6.26) x'is understood to a d be the number dx' multiplied by the identity operator in the ket space spannedby |x'). y choosing dx'in the direction of xy and forming the B scalarproductwith x,., e obtain w
[*\342\200\236*,]=

id,,,
identity

A.6.27)
operator.

where again 6/y is understood to be multiplied by the
Momentum

J. Schwinger,lecturing on quantum mechanics,onceremarked, for fundamental propertieswe will borrow only names from classical physics.\"In the present case we would like to borrow from classical mechanics the notion that momentum is the generator of an infinitesimal translation. An infinitesimal translation in classicalmechanics can be reregarded as a canonical transformation,
Xnew

as a Generatorof Translation i Equation A.6.27)s the fundamental commutation relation between the positionoperatorsx, y, z and the K operatorsKx, K,Kz. Remember that so far the K operator is definedin terms of the infinitesimal translation What is the physicalsignificancewe can attach to K? operatorby A.6.20).

\"...

= X = X+ JX,

pnew

= P = p,

A.6.28)

obtainable from the generating function

395 1980, and 411) (Goldstein F(x,P)= x-P+ p-Jx, A.6.29) where p and P refer to the corresponding omenta. m This equation has a striking similarity to the infinitesimal translation in operatorA.6.20) quantum mechanics,particularly if we recall that x-Pin

1.6. Position, Momentum,

and Translation

47

i A.6.29)s the generating function for the identity transformation (X = x,P = p).We are thereforeled to speculate that the operator K is in some sense
related to the momentum operator in quantum mechanics. Can the K operator be identified with the momentum operator itself? Unfortunately the dimensionis all wrong; the K operator has the dimension But of I/lengthbecauseK*dx' ust be dimensionless. it appearslegitimate m
to

set

K=

universal constant with the dimensionof action

'

A.6.30)

From the fundamental postulates of quantum mechanicsthere is no way to determine the actual numerical value of the universal constant. Rather, this constant is neededhere because, istorically, classical hysicswas developed h p before quantum mechanics using units convenient for describing macrocircumferenceof the earth, the mass of 1ccof water, quantities\342\200\224the the duration of a mean solar day, and so forth. Had microscopic hysics p been formulated before macroscopic physics,the physicists would have almost certainly chosen the basic units in such a way that the universal constant appearing in A.6.30) would be unity. T An analogy from electrostaticsmay be helpful here. he interaction energy between two particles of charge e separatedat a distance r is proportional to e2/r\\ in unrationalizedGaussianunits, the proportionality factor isjust but in rationalizedmks units, which may be moreconvenient for electrical engineers,he proportionality factor is \\/Atneo. t The universal constant that appearsin A.6.30)urns out to be the t same as the constant h that appearsin L. de Broglie's relation, written in
macroscopic

1,

1924,

>

A.6.31

where X is the wavelength of a \"particle wave.\" In other words, the K t operator is the quantum mechanicaloperator that correspondso the wave is, 277 times the reciprocalwavelength, usually denotedby k. With this identification the infinitesimal translation operator ^~(dx')reads
number\342\200\224that

f(dx')=l-iydx'/h9
where p is the momentum operator. The commutation

becomes

A.6.32) relation A.6.27)ow n A.6.33)

= [x,,pJ] ih8lJ.
px
impossible

The commutation relations A.6.33) imply, for example, that x and It (but not x and pv) are incompatibleobservables. is therefore impossito find simultaneous eigenkets of x and px. The general formalism of

48

Fundamental

Concepts

1.4 Section can be appliedhereto obtain the position-momentum unceruncertainty

relation of W.

Heisenberg:

A.6.34)
Someapplications of A.6.34) appear in Section1.7. will Sofar we have concerned ourselveswith infinitesimal translations. A finite translation\342\200\224that is, a spatial displacement by a finite be obtainedby successively compoundinginfinitesimal translations. Let us considera finite translation in the jodirection by an amount Ax':
amount\342\200\224can

= ^(Ajc'x)|x'> |x'+Ajc'x).
AT

A.6.35)

By compounding infinitesimal translations, each of which is characterized a by a spatial displacement kx'/N in the ^-direction, nd letting AT ->oo, we

obtain

=

Urn

1

N

\342\200\224

Nh

= exp

h function

A.6.36)
of the operator px,

Hereexp(-pxkx'/h)is understood to be a i generally, for any operator X we have

2!
in

A.6.37)

A fundamental property of translations is that successive translations different directions, ay in the x-and ^-directions, commute.We see this s in shifting from A and B it does not matter whether clearly in Figure we go via C or via D.Mathematically,

1.8;

A y'y)

=
B

A.6.3o)

D

Ay'y

A

Ax'*
FIGURE

1.8.uccessive translations S

in different directions.

1.6. Position, Momentum,

and Translation

49

This point is not so trivial as it may appear;we will show in Chapter 3 that rotations about different axesdo not commute.Treating Ajc' and Ay' up to secondorder, we obtain

1

ipyAy' h

P2y(Ay')

/\\2 ipA*' P2A^') h 2h

(Ax')(Ay')[Py,Px]
h2

A.6.39) A.6.40)

Ajc' Because and

A>>'

are arbitrary,

or requirement A.6.38),

immediately

leads to

A.6.41)
or, more generally,

A.6.42)
This commutation relation is a direct consequencef the fact that translao in different directionscommute.Whenever the generators of transforcommute, the corresponding group is said to be Abelian. The translation group in three dimensionsis Abelian. Equation A.6.42) implies that px, py, and pz are mutually compatiW observables. e can therefore conceiveof a simultaneous eigenket of
translations

transformations

compatible

Px>Py>Pz>

namely,

A.6.43a)

')= /^Ip')'PvIp') = /^Ip')*
is instructive to eigenket:
It

Pz\\p'y

= A'Ip')-

A.6.43b)

work out the

effect of

o ?T{dx') n

such a momentum
/
\\

1
We

\342\200\224

z'p#</xM h

h

A-6.44)

seethat the momentum eigenketremains the sameeven though it suffers a slight phase change, so unlike |xr),|p') is an eigenket of ^(dxf), which we anticipated because

=0. [pt&idx')]

A.6.45)

i Notice, however, that the eigenvalue of J7~(dx')s complex;we do not

50

Fundamental

Concepts

expect a real eigenvalue here because
Hermitian.

though

unitary,

is not

The CanonicalCommutation Relations
We summarize the commutator

relations we inferred by

studying

the

propertiesof translation:

= [x,,xj]0,

[/>\342\200\236

Pj]

= 0,

[xi9Pj] = ihStJ.

A.6.46)

These relations form the cornerstone of quantum mechanics; in his book, P. A. M. Dirac calls them the \"fundamental quantum conditions.\"More
often they are known as the canonicalcommutation relations, or the fundacommutation relations. showed that the who, in 1925, Historically it was W. Heisenberg combination rule for atomic transition lines known at that time could best be understoodif one associated arrays of numbers obeying certain multiplirules with these frequencies.Immediatelyafterward M. Born and P. Jordan pointed out that Heisenberg's ultiplication rules are essentially m those of matrix algebra, and a theory was developed based on the matrix which is now known as matrix mechanics.* analogues of A.6.46), Also in 1925, A. M. Dirac observed that the various quantumP. mechanical relations can be obtained from the corresponding classical relations just by replacing classicalPoissonbracketsby commutators, as follows:
fundamental
multiplication

[ , ]
classical

ih

A.6.47)

where we may recall that the classicalPoissonbracketsare defined for functions of q 'sand p 'sas

[A(q,p),B(q,p)] = y
classical
i>

'

8A

8B

3A

3B . A.6.48) dqs)

Forexample, in classical echanics,we have m
Pj J j Jclassical

A.6.49)

which

in quantum

and quantum-mechanicalcommutators satisfy similar algebraic properIn particular, the following relations can be proved regardlessof whether [ , ] is understood as a classical oisson P bracket or as a quantumbrackets properties.

Dirac'sule A.6.47)is plausiblebecausethe classical oissonbrackr P

mechanicsturns into A.6.33).

*

Appropriately, pq

\342\200\224

qp = h /2mi is inscribed on the gravestone of M. Born in Gottingen.

1.7.Wave

Functions

in Position and Momentum

Space

51

mechanicalcommutator:

=0

A.6.50a) A.6.50b)

(c isjust

a number)

A.6.50c) = [A9C]+ [B,C] A.6.50d) = + [A,BC] [A,B]C B[A,C] A.6.50e) + + [A9[B9C]] [B9[C9A]] [C9[A9B]]=09 A.6.50f)
where the last relation is known as the Jacobiidentity.* However,there are P bracket important differences.First, the dimensionof the classical oisson differs from that of the quantum-mechanicalcommutator becauseof the differentiations with respect to q and p appearing in A.6.48). econd, S the Poissonbracketof real functions of and is purely real, while the commutator of two Hermitian operators anti-Hermitian (seeLemma 3 of is To take care of these differencesthe factor ih is inserted in Section

q's

p's

A.6.47).
the

1.4).

We have deliberatelyavoided exploitingDirac'snalogy in obtaining a canonical commutation relations. Our approach to the commutation relations is based solely on A) the propertiesof translations and B) the identification of the generator of translation with the momentum operator modulo a universal constant with the dimensionof action. We believe that this approachis more powerful because can be generalizedto situations it where observables ave no classical nalogues. or example, the spin-anguh F a we encounteredin Section 1.4 spin-angular-momentum having nothing to components do with the and q'sof classicalmechanics; yet, as we will show in Chapter 3, the spin-angular-momentum commutation relations can be dederived using the propertiesof rotations just as we derived the canonical commutation relations using the properties translations. of

p's

W 1.7. AVE

AND MOMENTUM SPACE IN FUNCTIONS POSITION Function

Wave Position-Space wave
return

In this section we present a systematic study of the propertiesof For functions in both position and momentum space. simplicity let us The to the one-dimensionalcase. baseketsusedare the position kets
mechanics is much easier to prove than

*It is amusing that the Jacobi identity in quantum its classical analogue.

52 satisfying

Fundamental

Concepts

normalized in such a way
We

that

x\\x') = x'\\x'), the orthogonality condition reads

A.7.1)
A.7.2)

have already remarked that the ket representing a physical state can be expandedin terms of |jc'),

a) = fdx'\\x')(x'\\a)9
and
that

A.7.3)
way that

the expansion coefficient(x'\\a)is interpreted in such a

A.7.4)
is the probability for the particle to be found
in a narrow interval dx' around In our formalism the inner product (x'\\a) is what is usually referred to as the wave function 4>a(x')or state \\a): f

x'.

coefficient

In elementary wave mechanics the probabilistic interpretations for = (a'\\a))and for the wave function i/'aC*') the expansioncoefficientca* ( are often presentedas separate postulates.One of the major (= of our formalism, originally due to Dirac,is that the two kinds advantages of probabilistic interpretations are unified; \\pa(x') is an expansion coeffiin [see A.7.3)] much the same way as ca* By following the footsteps of Dirac we come to appreciate the unity of quantum mechanics. Considerthe inner product o Usingthe completenessf

(jc'|a))

is.

we have

(j8|a).

|jc'),

=

jdx'((S\\x')(x'\\a)
A.7.6)

two wave functions. Note as the overlap integral; the identification of defining (fi\\a) w postulate for (/?|a)ith the overlap integral follows from our completeness The more general interpretation of (fi\\ct), independent of representa\\x'). is that it representshe probability amplitude for state \\a) to be found t in state \\fi). This time let us interpret the expansion that

so (fi\\ot) characterizes the overlap between the
we are not

representations,

la) = 2* \\a

)\\a la>
multiply

A-7.7)
both sidesof A.7.7)

using the language of wave functions.We just

1.7. ave W
by

Functions

in Position and Momentum

Space

53

the

positioneigenbra (x'\\ on the left. Thus
a

In the usual notation of wave mechanicsthis

is recognizedas

a' where we have introduced an eigenfunction of operator A

a':

with

eigenvalue

ua,(x')= (x'\\a').
Let us now examine how (fi\\A\\a) can functions for \\a) and |/3).Clearly, we have
(P\\A\\a)

A.7.9)
be written
using

the wave

= =

(P\\x')(x'\\A\\x\(x\"\\a) jdx'jdx\"

A.7.10) jdx'jdx\"mx')(x'\\A\\x\^a{*\")'")

So to be able to evaluate (fi\\A\\a)9 we must know the matrix element which is, in general, a function of the two variables x' and x\". (x'\\A\\x\,") An enormous simplification takes placeif observableA is a function of the positionoperator x. In particular, consider
A which
oscillator

= x2,

A.7.11)

actually appearsin the Hamiltonian for the simple harmonic oscillain problemto be discussed Chapter 2.We have

= ((x'\\)-(x\022\\x\=x'2S(x'-x\9") A.7.12)
where we have used A.7.1) nd A.7.2). he doubleintegral A.7.10)s now a i T reducedto a single integral:
(P\\x2\\a)

=

jdx'(f}\\x')x'2(x'\\a)

A.7.13)
In general,

=

jdx'+$(x')f{x')+a(x').

A.7.14)

Note that the f(x) on the left-hand sideof A.7.14) an operator, while the is on the right-hand sideis not an operator. f(x')

54
Momentum

Fundamental

Concepts

jc-basis\342\200\224that

Operator in the Position Basis We now examine how the momentum operator may look in the is, in the representationwhere the position eigenketsare used as base kets. Our starting point is the definition of momentum as the generator of infinitesimal translations:

1-ipkx'

\\

= = = =

fdx'\\x'+Lx')(x'\\a)

fdx'\\x')(x'-bx'\\a)
J
/\"rfx/|jc/>(<jc/|a>\342\200\224
\\

Ajc/-^-<Jc/|a>).A.7.15) dx' I

of Comparison both sidesyields
p\\a)

fdx'\\x')

ih

dx

A.7.16)
A.7.17)

or
(x'\\p\\a)

= -ih\342\200\224-(x'\\a),
dx

where we have used the orthogonality property A.7.2).For the matrix element p in the jc-representation, e obtain w
OX

A.7.18)

From A.7.16) e get a very important identity: w

(P\\p\\a)=
d -ihdx')
\\

A.7.19)

we can also obtain

In our formalism A.7.19)s not a postulate; rather, it has been derived i using the basic propertiesof momentum. By repeatedly applying A.7.17),

dx
n

A.7.20)

1.7. ave W

Functions

in Position and Momentum

Space

55

Momentum-SpaceWave Function So far we have worked exclusivelyin the x-basis.There is actually a from occasional minus signs complete symmetry between x and we can infer from the canonicalcommutation relations.Let us now work in the /?-basis,hat is, in the momentum representation. t The For simplicity we continue working in one-space. baseeigenkets in the /?-basis specify
p\342\200\224apart \342\200\224which

A-7-22)
and

A.7.23)
The momentum eigenkets {\\p')} span the ket spacein much the same way as the positioneigenkets An arbitrary state ket \\a) can therefore be expandedas follows:

(|x')}.
=

jdp'\\p')(P'\\a).

A.7.24)

We

can give a probabilistic interpretation for the expansion coefficient (p'\\a)\\ the probability that a measurementof p gives eigenvalue within a narrow interval dp' is \\{p'\\a)\\2dp'. It is customary to call (p'\\ot) the wave function; the notation 4>a(p')is often used: momentum-space

p'

If

|a)is normalized, we obtain

j?
and the

A-7-26)

Let us now establish the connection between the ^-representation We ^-representation. recall that in the caseof the discretespectra, the change of basis from the old set {|fl')} the new set {\\b')} to is characterizedby the transformation matrix A.5.7). ikewise, expectthat we L the desiredinformation is contained in (x'\\p'), hich is a function of x' w and usually called the transformation function from the ^-representation to the /^-representation.To derive the explicit form of (x'\\p'), irst recall f we A.7.17); letting \\a) be the momentum eigenket |/?'), obtain

p',

or

ax

56

Fundamental

Concepts

The solution to

this differential

equation for (x'\\pf)is

ip'x'^
h

A.7.29)

where N is the normalization constant to be determined in a moment. Even is though the transformation function {x'\\pf) a function of two variables, x' and p\\ we can temporarily regard it as a function of x' with fixed.It can then be viewedas the probability amplitude for the momentum eigenstate specifiedby /?' to be found at position x';in other words, it is just the wave function for the momentum eigenstate |/?'),ften referred to as the o momentum eigenfunction(still in the x-space). A.7.29)imply says that So s the wave function of a momentum eigenstateis a plane wave. It is amusing that we have obtained this plane-wave solution without solving the Schrodinger quation (which we have not yet written down). e To get the normalization constant N let us first consider

p'

=

jdp'(x'\\p')(p'\\x\.
right-hand

A.7.30)

The left-hand sideis just 8(x' x\;")the using the explicit form of {x'\\p')\\
\342\200\224

side can be evaluated

h

= 27rh\\N\\28{x'-x\.
= <*'!/>'>

A.7.31)
A.7.32)

ChoosingN to be purely real and positive by convention, we finally have

l

exp

ip'x'
h

We can now demonstrate how the position-space ave function is w related to the momentum-spacewave function. All we have to do is rewrite

=
and

jdp'(x'\\p')(p'\\cL)

A.7.33a) A.7.33b)

=
as
*\302\253(*')

jdx'(p'\\x')(x'\\a)
exp
ip x

=
=

A.7.34a)

and

1

*\302\253(/>')

I Jx'exp

ip'x\"
+\302\253(*')

A.7.34b)

1.7. ave W

Functions

in Position and Momentum

Space

57

inversion This pair of equations is just what one expectsfrom Fourier's theorem.Apparently the mathematicswe have developedsomehow\" knows\" w Fourier's ork on integral transforms.

Gaussian Wave Packets
It is instructive to look at a physicalexample to illustrate our basic formalism. We considerwhat is known as a Gaussian wave packet, whose x-spacewave function is given by
<*'!<*>

=

l

exp ikx'

X

\342\200\224

Id

A.7.35)

This is a planewave with wave number k modulated by a Gaussianprofile centeredon the origin. he probability of observing the particle vanishes T ver rapidly for \\x'\\ > d; more quantitatively, the probability density a)|2 a Gaussianshapewith width d. |2 has We now compute the expectation values of x, x2, p, and p2. The expectation value of x is clearly zero by symmetry: /OOdx'(a\\x')x'(x'\\a)\\ -oo For x2 we obtain '2 2)= (x2)= -oodx'x'2\\(x'\\a)\\ ( I 00

=

/\342\200\242OO

0. dx'\\(x'\\a)\\2x'= A.7.36)

\342\200\242'-oo

r
2

\342\200\224

X

1'

A.7.37)

which

leads to

A.7.38) 2 T for the dispersion the position operator. he expectationvaluesof p and of can alsobe computed as follows: p2

(p)= hk
Id
which

A.7.39a) A.7.39b)

The is is left as an exercise. momentum dispersion therefore given by

Id

A.7.40)

58 Armed
with

Fundamental

Concepts

in relation A.6.34);

w a A.7.38)nd A.7.40), e can checkthe Heisenberg uncertainty
this

casethe

uncertainty

product is given by
2

4~'
equality this

A.7.41)

independentof d, so for a Gaussian wave packet we actually have an

For

relation rather than the more general inequality relation A.6.34). reason a Gaussian wave packetis often called a minimum uncer-

uncertainty

wave

packet.
now

We

integration\342\200\224just

go to momentum space. By a straightforward obtain completingthe square in the
exponent\342\200\224we

l
exp

1

dx' /OO exp
-oo 2h

/2
/j

\\

2d2) A.7.42)

-(p'-hkfd

This momentum-space wave function provides an alternative method for w obtaining (/?) and (p2), hich is also left as an exercise. is The probability of finding the particle with momentum Gaussian(in momentum space)centered on hk, just as the probability of (in position space)centered on zero. finding the particle at x' is Gaussian are Furthermore, the widths of the two Gaussians inversely proportional to eachother, which is just another way of expressing constancy of the the T uncertainty product ((AjcJ)(A/?J) explicitly computed in A.7.41). he wider the spreadin the /?-space, narrower the spreadin the x-space, the and vice versa. As an extreme example, supposewe let d->oo. position-space The wave function A.7.35) becomes plane wave extending over all space; then a the probability of finding the particle is just constant, independent of In contrast, the momentum-space wave function is 5-function-like and is extreme,by letting d -> 0, we obtain a sharply peakedat hk. In the opposite w position-space ave function localizedlike the 5-function, but the momenwave function A.7.42) just constant, independent of is momentum-space We have seenthat an extremelywell localized(in the x-space) state is to be regardedas a superpositionof momentum eigenstateswith all possible values of momenta. Even those momentum eigenstateswhose momenta are m Howcomparableto or exceed e must be included in the superposition. at such high valuesof momentum, a description basedon nonrelativistic quantum mechanics is bound to break down.*Despitethis limitation

p'

x'.

p'.

However,

*It

more intricate

1967,

118-19).

turns out that the concept of a localized state in relativistic quantum mechanics is far because the possibility of \"negative energy states,\" or pair creation (Sakurai of

1.7. ave W

Functions

in Position and Momentum

Space

59

of our formalism, based on the existence the position eigenket wide domain of applicability. Generalizationto Three Dimensions

has |jc'), a

for section we have worked exclusivelyin one-space if we have donecan be generalizedto three-space, the necessary changes are made. The basekets to be used can be taken as either the positioneigenketssatisfying
in this

So far

simplicity, but everything

= x|x/> x/|x/>
or the momentum eigenketssatisfying

A.7.43)
A-7.44)

P|p'>= P'lP'>.
They obey the normalization conditions

= <x'|x\"> 63(x'-x\")
and
<P'|P\">

A.7.45a) A.7.45b)

= S3(p'-p\,")

where 83 stands for the three-dimensional5-function

= 8(x'-x\8(y'-y\")8(z'-z\").") A.7.46)
The completenesselationsread r

J</V|x'><x'|=l
and

A.7.47a)

/</V|p'><p'|=l,
which

A.7.47b)

can be used to expand an
\\a)

arbitrary

state ket:

=

jd\\'\\x')(x'\\a),

A.7.48a) A.7.48b)

The expansioncoefficients(x'|a) and (p'|a)re identified with the wave a functions ^a(x') and </>a(p') in position and momentum space,respectively. The momentum operator, when taken between \\fi) and |a>, ecomes b

A.7.49)

60

Fundamental

Concepts

The transformation function

i analogous to A.7.32)s

1
3/2

exp

A.7.50)

so that

B-nh)
and

3/2

exp

A.7.51a)
/p'-xM

i
3/2

I d3x' xp e

*ft(x'). A.7.51b)

It is interesting to check the dimension of the wave functions. In one-dimensional roblemsthe normalization requirement A.6.8)implies p that |(jc'|a)|2 the dimension of inverse length, so the wave function has

itself must have the dimension of (length) ~1/2.In contrast, the wave function in three-dimensional problems must have the dimension of integrated over all spatial volume must be (length)~3/2 because |(x'|a)|2
unity

(dimensionless).

Problems

1.Prove

[ AB, CD] = AC{D,B } + A { C, } D C{ A } + { C,^ } 2)B. 2. Supposea 2x2matrix X (not necessarily Hermitian, nor unitary) is written as Y n -i- a a = a0 A- rfna, where a0 and tfli2,3 are numbers. a. How are a0 and ak (k = 1,2,3) to tr(X) and tr(a^X)? related b. Obtain an and 0. in terms of the matrix elements 3. Show that the determinant of a 2x2matrix a*a is invariant under

-

5

-

i), ?

I,

<va -> a*a

= exp

cvaexp

Find a'k in terms of ak when h is in the positive z-direction and interpret your result. 4. Usingthe rules of bra-ket algebra,prove or evaluate the following: a. tr(XY) = tr(YX), where X and Y are operators; b.(XY)^= Y^X*, where X and Y are operators; = c. exp[//(^4)] ? in ket-bra form, where A is a Hermitian operator whose eigenvaluesare known;

dV .

7 ify^ 1 L-i a'*Y n'\\ Y
ale

I

/

/\\

I / //\\ 1 / /I ^**^-^^ I I/ /111; a\\I V 1 U/nPFP T a'VV /1 = / V /7 j
if/
/\\
\342\200\224

/\\

)\">

\\

/\"

\\

Problems

61 and and |/?). Suppose(a'\\a), (a\"\\a),...

5. a. Consider two kets \\a)
(a'\\ft)9

form a where \\a'), set of base kets. Find the matrix representation of the complete
known,

(a\"|/?),...

are all

|fl\,...")

6.

7. Considera

answer. of spacespanned by the eigenkets (|fl')} a Hermitian A. There is no degeneracy. operator a. Prove that
your

= \\a) and |/?) be \\sz down explicitly the square matrix \\sx in the usual (sz diagonal) basis. that corresponds to and \\j) are eigenkets of some Hermitian operator A. Suppose |/) that Underwhat conditioncan we conclude |/) + \\j) is also an eigenket

b.We

in operator |a)(/?| that basis. now consider spin \\ system and let a

and

= h/2),espectively.Write r

h/2)

|a)(/?|

of A! Justify

ket

a

b.What

is the

null

is the significanceof

operator,

(A-a\
.// a\"*

8.Usingthe orthonormality
where

c. Illustrate (a) and (b) using

of

set equal to Sz of a spin prove |+) and t t2 h
A
|\342\200\224), \302\253,.,

\\

system.

9.Construct|S*h;+> such that

where h is characterizedby the angles shown in the figure. Express your answer as a linear combinationof |+) and | ). [Note: The answer is
\342\200\224

cos
But do not just verify that this answer satisfies the above eigenvalue eigenvalue equation. Rather, treat the problem as a straightforward

62

Fundamental

Concepts

n

problem.Also do not use rotation operators,which we will introduce later in this book.] 10. he Hamiltonian operator for a two-state system is given by T
where a is a number with the dimension of energy. Find the energy ( eigenvaluesand the correspondingnergy eigenketsas linear combinae of and |2)). A two-state system is characterizedby the Hamiltonian
combinations

11.

|1)

= Hn\\l)(l\\ + H22\\2)B\\ + Hn[\\l)B\\
where 22 and 12 are real numbers with the dimension of and and |2) are eigenketsof someobservable Find energy, the energy eigenkets and correspondingnergy eigenvalues.Makesure e that your answer makes good sensefor Hl2 = 0.(You need not solve this problem from scratch.The following fact may be used without

|1)

(#//).

proof:

(S-ft)|ft;+>= -|ft;
with

|h;

+ ) given by

where ft and a are the polar and azimuthal angles, respectively,that characterize ft.) 12. spin \\ system is known to be in an eigenstateof S*ft with eigenvalue A h /2,where ft is a unit vector lying in the xz-plane that makes an angle y with the positive z-axis.

Problems

63

in b. Evaluate the dispersion

W a. SupposeSx is measured. hat is the probability of getting + h/2?

Sx,that is,

(For your
A 13.

beam of spin \\ atoms goes through a seriesof Stern-Gerlach-type measurementsas follows: a. The first measurementacceptssz = h/2atoms and rejectssz = h/2

cases = 0, tt/2, and y
atoms.

own

peace of
tt.)

mind

check your answers for the special

-

b.The secondmeasurement acceptssn = h/2atoms and

atoms, where sn is the eigenvalueof the operator S h, with h making an angle /? in the xz-plane with respectto the z-axis. c.The third measurement acceptssz = h/2atoms and rejectssz =
\342\200\242 \342\200\224

-h/2

rejectssn =

we orient the secondmeasuring apparatus if we are to maximize the of the final sz = h/2beam? intensity A 14. certain observablein quantum mechanicshas a 3 X 3 matrix represenas follows:
\342\200\224

beam when the sz = intensity of the final sz beam surviving the first measurementis normalizedto unity? How must
What

h/2atoms.
is the

=

\342\200\224

h/2

h/2

representation

v/2

/0 1 0\\ 1 0 1 [0 1 0,
this

a. Find

eigenvalues.Is there any degeneracy? corresponding b.Give a physicalexamplewhere all this is relevant. 15. et A and B be observables. L the Suppose simultaneouseigenketsof A and B {\\a\\ b')} form a completeorthonormal set of basekets. Can we always concludethat
If your answer is yes, prove the assertion. f I counterexample.

the normalized eigenvectorsof

observable and the

corre-

your

answer is no, give a

16. wo Hermitian operators anticommute: T {A,B}=AB Isit possibleto have a simultaneous(that is, common) eigenket of A and BlProve or illustrate your assertion.
17.Two observables Ax
known not

and A2,

which

do not

involve time explicitly,

are

to commute,

64 yet we alsoknow
that Ax

Fundamental

Concepts

and

A2

both commute with the Hamiltonian:

[Al9H]= 0,

[A29H]=

Are Prove that the energyeigenstatesare, in general, degenerate. there As an example,you may think of the central-forceproblem exceptions? H = p2/2m+ K(r),with Ax -> L2,A2 -> Lx. 18. . The simplestway to derive the Schwarz inequality goesas follows. a First, observe
X choose

for

any

complex number
the

\\;

then

in

such a

way that

the

b. Show that
with that
X

preceding inequality holdsif the

reducesto the Schwarzinequality, equality sign in the generalized uncertainty state in question satisfies

relation

c. Explicit calculations using
the wave
function

purely imaginary.

the usual rules of wave mechanics show for a Gaussian wave packetgiven by

l/4 satisfies the minimum

exp

\302\253p)x'

Ad

uncertainty

relation

=h
\"

2*

Prove that the requirement
(x'\\hx\\a)
with

= (imaginary number)(.x'|A/?|a)

is indeed satisfied for such a Gaussianwave packet,in agreement

19.a. Compute
where the expectation value is taken for the Sz + state. Usingyour result, checkthe generalizeduncertainty relation

(b).

b.Check the uncertainty relation with A -> Sx,B -> S for the Sx + state. 20.Find the linear combinationof | + ) and | ) kets that maximizesthe
\342\200\224

with

A

-> Sx9 B -> Sy.

Problems

65

uncertainty product

explicitly that for the linear combination you found, the uncer relation for Sx and S is not violated. 21. valuate the x-p uncertainty product ((AjcJ)((A/?J) for a one E dimensional particle confinedbetween two rigid walls
Verify tainty

oo

forO , otherwise.

22.Estimate the rough

Do this for both the ground and excited states.

order of magnitude of the length of time that an ice can be balancedon its point if the only limitation is that set by the pick uncertainty Heisenberg principle.Assume that the point is sharp and that the point and the surfaceon which it restsare hard.You may make approximations which do not alter the general order of magnitude of the result.Assume reasonablevalues for the dimensions and weight of it the icepick. Obtain an approximate numerical result and express in

If 23.Considera three-dimensionalket space. a certain set of orthonormal usedas the basekets,the operators A |2), |1>, and
kets\342\200\224say, |3)\342\200\224are

seconds.

and B are represented by

A= 0
with
Z>

a

0 ib 0 \\0 a and both real. a. Obviously^4 exhibits a degeneratespectrum. DoesB also exhibit a degenerate spectrum? b. Show that A and commute. c. Find a new set of orthonormal ketswhich are simultaneouseigenkets of both A and B.Specifythe eigenvaluesof A and B for each of the three eigenkets. oes your specificationof eigenvaluescompletely D characterizeeach eigenket? 24. a. Prove that (l/vT)(l + iox) acting on a two-componentspinor can be regardedas the matrix representation of the rotation operator about the x-axisy angle tt/2. (The minus sign signifies that the rotation b

-a

0

-a)

0 0

b
7

0 o

0 0

-ib

0

5

\342\200\224

representation of Sz when the eigenkets of S are usedas basevectors. 25.Someauthors define an operator to be real when every member of its matrix elements (b'\\A\\b\") is real in some representation({\\b')} asisin b this case). this concept representation independent, that is, do the Is

b.Construct the matrix

is clockwise.)

66
matrix

Fundamental

Concepts

26.Construct the transformation
general relation

used?Checkyour assertion using (seeProblem 24) or x and px.

is elements remain real even if some basis other than (|/>')} familiar operatorssuch as Sv and Sz
matrix that

to the Sx diagonal basis.Show that

connects the Sz diagonal basis your result is consistent with the

27. a. Supposethat f(A) is a function of a Hermitian operator A with the property A a')= a'\\a').Evaluate (b\"\\f(A)\\b') when the transforma\\

b.

matrix from the Usingthe continuum
transformation

a' basisto the b' basisis known,

analogue of the result obtained in (a),evaluate

r is your expressionas far as you can. Note that + y2 + z2,where x9 y, and z are operators. ]jx2 28.a. Let x and px be the coordinate and linear momentum in one P bracket dimension. valuate the classical oisson E
Simplify
classical [x>F(px)\\
*

b. Let x and
this

px

time. Evaluate the commutator

be the corresponding uantum-mechanicaloperators q

;c,expiPxa\\ i. h

c. Usingthe result obtained in

(b), prove that
'>-*'!*'\302\273

is an eigenstateof the coordinate operator x.What is the correspond-

29.a. On page 247, Gottfried A966) states that
can be \"easily derived\" from the fundamental commutation relations for all functions of F and G that can be expressed power seriesin as their arguments. Verify this statement. b. Evaluate [x29p2]. Compare your result with the classicalPoisson

corresponding

eigenvalue?

bracket[*2, Jp2]classical.

Problems

67

30.The translation operator for a finite
where p is the momentum operator. a. Evaluate

(spatial) displacementis given by
h

exp

b. Using(a) (orotherwise),demonstrate how the expectationvalue (x)
the behavior of expectation values (x) and (p) under infinitesitranslation. Using A.6.25), .6.45),and |a) ^(dxf)\\a) only, A prove (x) -> (x) + dx\\ (p) (p) under infinitesimal translation. for and 32.a. Verify A.7.39a) A.7.39b) the expectation value of p and p1 wave packet A.7.35). from the Gaussian b. Evaluate the expectation value of p and p2 using the momentumspacewave function A.7.42). 33.a. Prove the following:
study
infinitesimal
-\302\273 -\302\273

I 31.n the main text we discussed effectof 3T(dx')on the position and the momentum eigenketsand on a more general state ket |a). e can also W

changesunder translation.

(i) (ii)

dp
(p\\x\\a)

=
dp

where <t>a(p') = (p'\\ol) and <t>p(p')= (p'\\fi) are momentum-space wave functions, b.What is the physicalsignificanceof
expf

where x is the position operator and H is some number dimension of momentum? Justify your answer.

with

the

CHAPTER2

QuantumDynamics

how So far we have not discussed physicalsystemschange with time. This chapter is devoted exclusivelyto the dynamic development of state kets and/or observables.In other words, we are concernedhere with the or quantum mechanical analogue of Newton's (or Lagrange's Hamilton's) equations of motion.

2.1. EVOLUTION TIME AND

THE SCHRODINGER EQUATION

The first important point we should keep in mind is that time is just a parameter in quantum mechanics,not an operator.In particular, time is not in an observable the language of the previous chapter.It is nonsensical to talk about the time operator in the same senseas we talk about the position Ironically, in the historical developmentof wave mechanicsboth operator. L. de Broglie and E. Schrodinger were guided by a kind of covariant analogy between energy and time on the one hand and momentum and position (spatial coordinate) on the other. Yet when we now look at quantum mechanics in its finished form, there is no trace of a symmetrical The treatment between time and space. relativistic quantum theory of fields doestreat the time and spacecoordinateson the same footing, but it doesso only at the expenseof demoting position from the status of being an observable to that of being just a parameter.
68

2.1. Evolution Time

and the Schrodinger Equation

69

Operator Our basic concern in this section is, How does a state ket change with time? Supposewe have a physical system whose state ket at t0 is At later times, we do not, in general, expectthe system by represented to to remain in the same state \\a). Let us denote the ket corresponding the state at somelater time by

Time Evolution

|a).

|<M0;/>,(t>to)9

B.1.1)

wherewe have written a, t0 to remind ourselvesthat the system used to be in state |a)at someearlierreferencetime /0.Because time is assumed be to a continuous parameter, we expect
lim

= \\a9t0;t) \\a)

B.1.2)

and we may

as well use a shorthand notation, = B.1.3) l<Mo;'o> l<Mo>> for this. Our basic task is to study the time evolution of a state ket:
time evolution

Put in another way, we are interested in asking how the state ket changes under a time displacement t0 -* /. As in the case translation, the two kets are related by an operator of which we call the time-evolution operator /0):
\302\260U(t,

|>
,

.

.x B.1.4)
//H
_

= |a,/0;/>^(/,/0)|a,/0>.
What
time-evolution

B.1.5)

are someof the properties would like to ascribeto the time-evoluwe operator? The first important property is the unitary requirement for ^(/, /0) that follows from probability conservation.Supposethat at t0 the state ket is expandedin terms of the eigenketsof some observableA: a'
at Likewise, somelater time, we have a

B.1.6)

>
individual

B.1.7)
expansion

In general, we do not expect the modulus of the coefficientto remain the same:*

.
For instance, considera spin
* We later show, however,
equal to \\

B.1.8)
its spin magnetic moment

system

with

that if the Hamiltonian

commutes with A, then

|<v@|is indeed

|<v(fo)|.

70

Quantum

Dynamics

subjectedto a uniform magnetic field in the z-direction. To be specific, supposethat at t0 the spin is in the positive jc-direction;that is, the system is found in an eigenstate of Sx with eigenvalue h/2.As time goeson, the in spin precesses the xy-plane, as will be quantitatively demonstrated later in this section. his means that the probability for observing Sx + is no T at t > /0; there is a finite probability for observing Sx as well. longer unity Yet the sum of the probabilities for Sx + and Sx remains unity at all we and times.Generally, in the notation of B.1.6) B.1.7), must have

-

\342\200\224

a'

a'

S for the individual expansioncoefficients. tated another way, despite if the state ket is initially normalizedto unity, it must remain normalized to unity at all later times:

B.1.8)

(a,to\\a9
As

/0> = =>

1 (a,/0; t\\a,

t0; t)

= 1.

B.1.10

in the translation case, this property is guaranteed if the time-evolution operatoris taken to be unitary. For this reason we take unitarity,

&(t9t0)V(t9t0)=l9
to

B.1.11

be one of the

coincidence that
property:

fundamental many authors

probability conservation. Another feature we require of the
>

operator. It is no propertiesof the regard unitarity as being synonymous with
\302\260U

<%

operator is the composition
(>2 > >i

'o)= #('2>>i W>i> >o),
t2\342\200\224a

> >o).

B.1.12

This equation says that if we are interested in obtaining time evolution from t0 to /2, then we can obtain the same result by first considering time evolution from t0 to tl9 then from tx to reasonable requirement.Note that we read B.1.12) right to left! from It also turns out to be advantageous to consideran infinitesimal time-evolutionoperator ^(/0 + dt, /0):
\\a9 to\\

t0

+ dt) = <tt(t0 + dt9 to)\\a910).

B.1.13

must

Because continuity [seeB.1.2)],infinitesimal time-evolutionoperator of the reduceto the identity operator as dt goesto zero, lim #(fo + <//,/o)=l, B.1.14
O

and as in the translation case,we expectthe differencebetween^(/0 + dt, t0) and 1to be of first order in dt. We assertthat all these requirementsare satisfiedby
,

i to)=l-Qdt9

B.1.15

Time 2.1. Evolution

and the Schrodinger Equation

71

where Q, is a Hermitian operator,*
With

^ = ?2.

the B.1.15)infinitesimal

B.1.16

time-displacementoperator satisfiesthe com-

composition

property

<%(t0

+ dtx + dt2, t0) = <%(t0 + dtx + dt2, t0 + dt^^itQ 4- dtl9t0);
unitarity

B.1.17
it differs from the identity operator by a term of order dt. The as property can alsobe checked follows: <&*(t0 + dt, to)V(to+ dt, t0) = A + i&dt)(l /Q A) ~*>

-

B.1.18

to the extent that terms of order or higher can be ignored. The operator fi has the dimension of frequency or inverse time. Is there any familiar observable with the dimension of frequency?We recall that in the old quantum theory, angular frequency co is postulated to be related to energy by the Planck-Einsteinrelation

{dtJ

E = ho>. B.1.19 Let us now borrow from classical echanicsthe idea that the Hamiltonian m is the generator of time evolution (Goldstein 1980, It is then natural 407-8).
to relate

2 to the Hamiltonian

operator H\\

^.
n

B.1.20
as
,

To sum up, the

infinitesimal

time-evolution operator is written

B.1.21

to where //, the Hamiltonian operator, is assumed be Hermitian.The reader ask whether the h introducedhere is the same as the h that appearsin may This question can be the expressionfor the translation operator A.6.32). answered by comparing the quantum-mechanicalequation of motion we derivelater with the classical quation of motion. It turns out that unless the e two /i's are taken to be the same, we are unable to obtain a relation like

^
dt

m

B.1.22
v y

l as the classicalimit of the correspondinguantum-mechanicalrelation. q

The Schrodingerquation E
We are now in a position to derive the fundamental differential equation for the time-evolution operator ^(/, t0). We exploit the composiIf the fl

operator depends on time explicitly, it must

be evaluated

at t0.

72

Quantum

Dynamics

B.1.12):

tion property of the time-evolution operator by

letting

tl

-\302\273t,

t2

t

+ dt

in

iHdt

B.1.23
where the time differencet
<%(t which
\342\200\224

+ dt, t0)
in

-

tn o

neednot be infinitesimal.

\302\260U{t,

(H\\ t0) = i -r- \\dt

-

We have

,'o)>

C2-1-24)

can be written

differential equation form:

B.1.25
This is the Schrodingerquation for the time-evolution operator. Everything e that has to do with time development follows from this fundamental equation. Equation B.1.25) immediately leadsto the Schrodingerequation for a state ket. Multiplying both sidesof B.1.25) /0) on the right, we by obtain

|a,

9t0)\\a9t0)= H<&(t9t0)\\a9t0).
But \\ot,t0)

B.1.26

does not dependon /, so this is the same as

= 'a9t0;t) H\\a9t0;t)9

B.1.27)

where B.1.5) beenused. has If we are given t0) and, in addition, know how W(t, /0) acts on the initial state ket it is not necessary bother with the Schrodinger to /0), for the state ket B.1.27). we have to do is apply <%(t, t0) to All equation /0); in this manner we can obtain a state ket at any /. Our first task is therefore to derive formal solutionsto the Schrodingerequation for the time There evolution operator B.1.25). are three casesto be treated separately: Case The Hamiltonian operator is independent of time. By this we mean that even when the parameter / is changed, the H operator remains unchanged. The Hamiltonian for a spin-magnetic moment interwith a time-independentmagnetic field is an example of this. The in such a caseis given by solution to B.1.25)

|a,

\302\260U(t,

|a,

1.

interacting

-^C-'o)
h

B.1.28
h

To prove this let us expand the exponential as follows:

exp

-iH(t-t0) 1 M(t-to) h

B.1.29

2.1. Evolution Time
\302\246

and the Schrodinger Equation

73

Becausethe time derivative of this expansion is given by
dt

exp

-iH(t- -iH ' (-/J 'o)\"
h h

H
2\\ h

2

obviously satisfies differential expressionB.1.28) reducesto the condition is also satisfiedbecause / -> /0, B.1.28) as boundary An alternative way to obtain B.1.28)to compound is identity operator. infinitesimal time-evolutionoperators successively just as we did to obtain

B.1.30 The equation B.1.25).

f A.6.36)or finite translation:
lim

1-

N

-/0) = exp -M(t-t0). B.1.31 h
N

//'s at

Case 2. The Hamiltonian operator H is time-dependent but the different times commute. As an example, let us consider the to spin-magnetic moment subjected a magnetic field whose strength varies with time but whose direction is always unchanged. The formal solution to in B.1.25)this caseis

B.1.32
This can be proved in a similar way. We simply replaceH(t t0) in and B.1.30)jt[dt'H(t'). by
\342\200\224

B.1.29

The Z/'s at different times do not commute. Continuing Case the exampleinvolving spin-magnetic moment, we suppose,this time, the magnetic field direction also changes with time: at / = tx in the a at x-direction, t = t2 in the ^-direction, nd so forth. Because and Sv do Sx d not commute, H(tx)and H(t2),which go like S*B, o not commuteeither. The formal solution in such a situation is given by
with that 00

3.

E
which

\342\200\224

I

n
\302\246 \302\246 \342\200\242 \302\246 \302\246 \302\246

j'dtljhdt2 f-ldtnH(tx)H(t2) H(tn), B.1.33
*0 *0 *0

a is sometimesknown as the Dyson series, fter F. J. Dyson, who developeda perturbation expansion of this form in quantum field theory. We do not prove B.1.33) becausethe proof is very similar to the one now presentedin Chapter 5 for the time-evolutionoperator in the interaction picture. In elementary applications,only case1is of practical interest. In the remaining part of this chapter we assume that the H operator is time-indetime-independent.

We

will

encounter time-dependentHamiltonians in Chapter 5.

74

Quantum

Dynamics

on w B.1.28)a general initial ket|a), e must

Eigenkets To be able to evaluate the effect of the time-evolution operator
Energy
first know

how

it

acts on the

base ketsused in expanding \\a). This is particularly baseketsused are eigenketsof A such that

straightforward

if the

= [A,H] 0;

B.1.34)

then the eigenkets A are also eigenkets of H, calledenergy eigenkets, of whose eigenvaluesare denoted by Ea>\\

= Ea,\\a').
We can now expand the time-evolution operator Taking t0 = 0 for simplicity, we obtain
in

B.1.35)
terms of \\a'){a'\\.

a' a'

a\"

The time-evolution operator written in this form enablesus to solve any initial-valueproblemonce the expansionof the initial ket in terms of {\\a')} is known. As an example,supposethat the initial ket expansion reads
\">

>o

=
a' a'

We then have
I^Y

/

==n./\\==exn

I2U_

1^ f = 0\\ = V
a7

|/7'\\//7'|/y

B.1.38)
In other words,the expansion coefficientchanges with time

as

= 0) -> ca.{i)ca,(t= =
with

0)exp(

\342\200\224f^)

B.1.39)

componentsdo
different.
A

its modulus unchanged.Notice that the relative phasesamong various vary with time because the oscillation frequencies are

of

itself. {K>} We

specialcaseof interest is where the initial state happensto be one
have

B.1.40)

2.1. Evolution Time
initially,

and the Schrodinger Equation

75

and at a later time

~Vr
\342\200\224

B.1.41

so if the system is initially a simultaneouseigenstateof A and H< it remains so at all times. The most that can happen is the phase modulation, exp( iEa4/h).It is in this sensethat an observable compatible with H is a [seeB.1.34)] constant of the motion. We will encounter this connection onceagain in a different form when we discussthe Heisenberg equation of
motion.
In the foregoing discussion basic task in quantum dynamics is the finding an observable that commutes with H and evaluating its eigenvalues. Once that is done, we expand the initial ket in terms of the o eigenkets f that observableand just apply the time-evolutionoperator.This last step merely amounts to changing the phase of each expansion coeffias indicatedby Even though we worked out the case where there is just one observA that commutes with //, our considerationsan easily be generalized c a when there are several mutually compatible observablesll also commuting

reducedto

coefficient,

B.1.39).

observable

with

H:

[A, H]= [B9 H]= [C,

w Usingthe collectiveindex notation of Section1.4 [seeA.4.37)], e have

0 #]=...=.

=0,

B.1.42

B.1.43
where EK, is uniquely specifiedoncea\\b\\c\\...re specified.t is thereI a set of fundamental importance to find a complete of mutually compatible observablesthat also commute with H. Oncesuch a set is found, we express the initial ket as a superpositionof the simultaneouseigenkets f A, B, o and H.The final stepisjust to apply the time-evolutionoperator, written as In this B.1.43). manner we can solve the most general initial-value problem a time-independent H. with
therefore

C,...

Time Dependence f ExpectationValues o

is instructive to study how the expectation value of an observable that as a function of time. Suppose at t = 0 the initial state is one of changes the eigenstates an observableA that commuteswith H, as in B.1.40). of We now look at the expectation value of someother observable B, which need not commute with A nor with H. Because a later time we have at
It

B.1.44)

76

Quantum

Dynamic^

for the state ket,

(B)is given

by

iE.t
= (a'\\B\\a')9
which

B.1.45)

is independent of t. So the expectation value of an observable taken with respect to an energy eigenstate does not change with time. For this reasonan energy eigenstateis often referred to as a stationary state. The situation is more interesting when the expectation value is taken with respect to a superposition of energy eigenstates, r a nonstationary o state. Supposethat initially we have
a
We

B.1.46

easily compute the expectationvalue of B to be

B
a

?
a

<Vexpl

\342\200\224

h

K>

-i{Ea..-Ea.)t
a'
a\"

h

B.1.47)

So this

time the expectation value consists of oscillating terms whose angular frequenciesare determined by N. Bohr'sfrequency condition
h

B.1.48

Spin Precession It is appropriate to treat an examplehere. e consider extremely W an simple system which, however, illustrates the basic formalism we have developed.
We start with

moment

c to eh/1m subjected an external magnetic field B: TJ _ S-B mec

a Hamiltonian of a spin

\\

system with magnetic

B.1.49)

(e < 0

for the electron). Furthermore, we take B to be a static, uniform magnetic field in the z-direction.We can then write H as

H=BecauseSz and H differ just by a

eB )

mec,
multiplicative

B.1.50
constant,
they

obviously

2.1. Evolution Time

and the Schrodinger Equation

77

commute. The Sz eigenstates are also energy eigenstates, and the energy eigenvaluesare corresponding

corre-

^
=

2mec

forSz\302\261.

B.1.51
the differencein the
two

It is convenient to define co energy eigenvaluesis /zco:

in

such a

way that

CO

mec as

We

can

then

rewrite the

H operator simply

H=uSz.
All

B.1.53)
z

the information

on time development is contained in the time-

evolution

operator
(
~l\302\260t

t

B.1.54)
|\342\200\224

We

apply this to the initial state. The basekets we must use in expanding ket are obviously the Sz eigenkets, and ), which are also that at / = 0 the system is characterized by energy eigenkets. uppose S
the
initial

|+)

B.1.55) |a> = c+|+ ) + c_|->. we Upon applying B.1.54),see that the state ket at some later time is
c_exp
where we have used

->, B.1.56)

B.1.57)
Specifically,let us supposethat the initial ket \\a) representsthe spin-up (or,more precisely, z +) state | + ), which means that S

c+=l,
At

c_ = 0.

B.1.58)

Next, let us supposethat initially the system is in the Sx + state. with we Comparing A.4.17a) B.1.55),seethat

this surprisebecause is a stationary state.

a later time,

tells B.1.56) us that

it

is still

in

the spin-up state, which is no

.
It

B.1.59)

is straightforward to work out the probabilitiesfor the system to be found

78

Quantum

Dynamics

in

the Sv

\302\261

state at somelater time

t:

\\(Sx\302\261\\a,to

= 0;

2_

(

1)

'1

^

]

exp
I

fit exp
exp
COS sin'

'

iwt
\302\261-exp|

T'
2
\342\200\224

for

Sr +,

for Sx

-.

B.1.60a B.1.60b

t Even though the spin is initially in the positive x-direction,he magnetic field in the z-direction causesit to rotate; as a result, we obtain a finite probability for finding Sx at some later time. The sum of the two is probabilities seento be unity at all times, in agreementwith the unitarity of the time-evolution operator. property w UsingA.4.6), e can write the expectation value of Sx as / h
\302\253n

-

h

2ICOS

B.1.61

so this

oscillates with an angular frequency corresponding the to quantity differenceof the two energyeigenvaluesdivided by h, in agreementwith our Similar exercises S and S show that with general formula B.1.47).

B.1.62a
and Physically this means that the spin precessesin the xy-plane. We will comment further on spin precession when we discuss rotation operatorsin

B.1.62b
Chapter3.

CorrelationAmplitude and the Energy-TimeUncertainty

Relation

this section by asking how state kets at different times We conclude are correlatedwith each other. Supposethe initial state ket at t = 0 of a W physical system is given by |a>. ith time it changes into f0 which we obtain by applying the time-evolution operator.We are concerned

|a,

\342\200\2240;f),

2.1. Evolution Time 0;

and the Schrodinger Equation

79

with the extent to which the state ket at a later time t is similar to the state ket at / = we thereforeconstruct the inner product between the two state kets at different times:

B.1.63
is known as the correlationamplitude. The modulus of C(t) provides measure of the \"resemblance\" between the state kets at different times. As an extreme example, considerthe very specialcase where the initial ket \\a) is an eigenketof H; we then have
which

a quantitative

-iEa.t
h

B.1.64
times\342\200\224which

so the modulus of the correlation amplitude is unity at all not surprising a stationary state.In the more general situation for initial ket is represented a superpositionof as in by
a a
As

is

where the

we {|tf')}, B.1.37),have a
h

? <>exp
a
h

B.1.65

we sum over many terms with oscillating time dependence different of frequencies, a strong cancellationis possiblefor moderatelylarge valuesof t. We expect the correlation amplitude that starts with unity at / = 0 to
in decrease magnitude with

time.

in To estimate B.1.65)a more concrete manner, let us supposethat the state ket can be regarded as a superpositionof so many energyeigenkets with similar energiesthat we can regard them as exhibiting essentially a It is then legitimate to replacethe sum by the quasi-continuous spectrum.

integral a now B.1.65) becomes

jdEP{E),

a
'a

B.1.66

where p(E) characterizes the density of energy eigenstates. xpression E

=

jdE\\g(E)\\2p(E)expi h

-iEt

B.1.67

subject to the normalization condition

jdE\\g(E)\\2p(E)=l.

B.1.68

80 In a realistic physical situation
with width

Quantum

Dynamics

A?. Writing

as B.1.67)
l

\\g(E)\\2p(E) may

be peakedaround E = Eo

C(O= expf

\342\204\242u*

-'(^-^o)' ' -'--'^\302\2462-'^--

B.1.69
we seethat as t becomes large, the integrand oscillates very rapidly unless the energy interval \\E Eo\\ is small compared with h/t.If the interval for ~ h/t holds is much narrower than width of which \\E Eo\\ of get essentiallyno contribution to C(t) because strong \\g(E)\\2p(E)\342\200\224we cancellations. characteristic time at which the modulus of the correThe amplitude starts becomingappreciablydifferent from 1is given by h \342\200\224 \342\200\224

A?\342\200\224the

correlation

'-

.70)

Even though this equation is obtained for a superposition state with a quasi-continuous energy spectrum, it also makes sense for a two-level system; in the spin-precessionroblem consideredearlier, the state ket, p = which is initially \\SX + ), starts losing its identity after ~1/co /*/(?'+E _ ), as is evident from B.1.60). To summarize,as a result of time evolution the state ket of a physical to system ceases retain its original form after a time interval of order h/&E. In the literature this point is often said to illustrate the time-energy unceruncertainty

relation

A/A?^/i.

B.1.71

However, it is to be clearly understood that this time-energyuncertainty relation is of a very different nature from the uncertainty relation between In two incompatible observablesdiscussed Section in 1.4. Chapter 5 we will in comeback to B.1.71) connection with time-dependent perturbation theory.

2.2. HESCHRODINGER T THEHEISENBERG VERSUS PICTURE
Unitary

Operators

development

In the previous section we introduced the conceptof time developthe by considering time-evolution operator that affectsstate kets; that approachto quantum dynamics is known as the Schrodinger picture. There is another formulation of quantum dynamics where observables, rather than state kets,vary with time; this secondapproach is known as the Heisenberg the in picture. Before discussing differencesbetween the two approaches detail, we digressto make some general commentson unitary operators.

2.2.The

Schrodinger Versus the Heisenberg Picture

81

in Unitary operatorsare used for many different purposes quantum I a mechanics. n this book we introduced (Section1.5)n operator satisfying with the question the unitarity property.In that section we were concerned of how the baseketsin one representation are related to those in someother The representations. state kets themselvesare assumed not to change as we switch to a different set of baseketseven though the numericalvaluesof the expansioncoefficientsfor \\a) are, of course,different in different represenwe Subsequently introduced two unitary operatorsthat actually and the change the state kets, the translation operator of Section 1.6
representations.

time-evolutionoperator of Section

2.1. have We

B.2.1)
where U may stand for ^(dx) or ^/{t,t0). HereU\\a) is the state ket to corresponding a physical system that actually has undergone translation or time evolution. It is important to keepin mind that under a unitary transformation that changesthe state kets, the inner product of a state bra and a state ket remains unchanged:

B.2.2)
operators,we can infer
(P\\X\\a)

Using the fact

that

these transformations affect the state kets but not

-

how (fi\\X\\a)

must

change:

\302\253i8|l/t).JT.(I/|a\302\273

= <j8|l/t*l/|a>.

B.2.3)
follows

We now make a very simple mathematicalobservation that from the associative axiom of multiplication:

= ((P\\Uf)-X-(U\\a))(P\\-(U*XU)-\\a).

B.2.4)

Is there any physicsin this observation?This mathematicalidentity suggests two approaches unitary transformations: to
Approach

1:
|a)-> U\\a)9 2:
X -> U^XU,
with

operatorsunchanged, state ketsunchanged.

B.2.5a)

Approach

with

B.2.5b)

In classicalphysics we do not introduce state kets, yet we talk about translation, time evolution, and the like. This is possiblebecausethese operations actually change quantities such as x and L, which are observconnection

ablesof classicalmechanics.We therefore conjecture that a closerconnecif with classical hysics may be established we follow approach 2. p A simpleexample may be helpful here. e go back to the infinitesiW in translation operator ^(dxf).The formalism presented Section 1.6 is based on approach 1; ^(dxf) affects the state kets, not the position
infinitesimal

82

Quantum

Dynamics

operator: x.
In contrast, if we follow approach 2, we obtain

B.2.6)

^x
=X + . ,
h

1

h

= x + dx'. We leave it as an exercise the reader to show that for to the same result for the expectationvalue of x:

B.2.7)
both approachesead l

B.2.8)
the

State Kets and Observable*in the Schrodingernd a Pictures Heisenberg
We now return

previous sectionwe examined how state kets evolvewith time. This means that we were following approach 1, nown as the Schrodinger k picture when to time evolution. Alternatively we may follow approach 2, known applied as the Heisenberg picture when appliedto time evolution. In the Schrodingerpicture the operators corresponding observto ableslike x, py, and Sz are fixed in time, while state kets vary with time, as indicatedin the previous section.In contrast, in the Heisenberg picture the to operatorscorresponding observablesvary with time; the state kets are fixed, frozen so to speak,at what they were at t0. It is convenientto set t0 in which is defined by /0) to zero for simplicity and work with
\302\260ll{t,

to the time-evolution operator

\302\260U(t,

t0). In

the

\302\260U(t\\

B.2.9)
observable by
Motivated by of B.2.5b) approach 2, we
A<H)(t)

define the Heisenberg picture

= W*(t)A<s>W(t)9

B.2.10

where the superscriptsH and S stand for Heisenberg and Schrodinger, At / = 0, the Heisenberg observable and the correrespectively. picture corresponding Schrodinger icture observablecoincide: p

B.2.11

2.2.The

Schrodinger Versus the Heisenberg Picture

83

The state kets alsocoincide between the Heisenberg picture state ket is frozen to

two what

pictures at / = 0;at later t the it was at t = 0:
with

B.2.12
independent of t. This is in dramatic contrast state ket, the Schrodinger-picture

K >o = 0;Os= *@K'o=
t0

\302\260>\342\200\242

B.2.13
to

The expectation value (A) is obviously the same in both pictures:

= 0;t\\A<s>\\a9t0 = 0;t)s = (a,t0 = 0\\VWs>W\\a, = H(a,t0 = 0;t\\A<H)(t)\\a910 = 0;t)H.
of Motion derive the fundamental
that

= 0>

B.2.14

The Heisenberg Equation
We now
Heisenberg

picture.Assuming

A(S)

is the
differentiating

B.2.10)]
dt

in case

most physical situations of interest, we obtain [by differentiat-

equation of motion in the Heisendoesnot dependexplicitlyon time, which

dA(H)

^r dt
in

A% + tyA

dt

in

in

r[A\\&Hty],

B.2.15

where we have used [seeB.1.25)]

B.2.16a

i
at

\\^H. in
*

B.2.16b

H Because was originally introduced in the Schrodingerpicture, we may be
tempted to define
in by

{22.11
\302\260U

accordance with

B.2.9), and
\302\260lt

H obviously commute; as a result,
write

But B.2.10).in elementaryapplicationswhere

is given

B.2.18
so it is all
right

to

as B.2.15)

[A\\H].

B.2.19

84

Quantum

Dynamics

This equation is known as the Heisenberg equation of motion. Notice that of we have derived it using the properties the time-evolutionoperator and the defining equation for A(H\\ with It is instructive to compare B.2.19) the classicalequation of bracket form. In classical hysics,or a function A of q 's f motion in Poisson p and /?'s that does not involve time explicitly, we have (Goldstein1980

405-6)
Again,

dA
\342\200\224

= [A, i/jdassical-

B.2.20

we seethat Dirac'suantization rule A.6.47)leads to the correct q was equation in quantum mechanics. Indeed, historically B.2.19) first his characteristicmodesty\342\200\224called it written by P. A. M. Dirac, the Heisenberg equation of motion. It is worth noting, however,that B.2.19 makessensewhether or not A{H) has a classical nalogue. For example, the a spin operator in the Heisenberg icture satisfies p
who\342\200\224with

dt

ih

I,

B.2.21
argue that for

which can

p's.Rather than
the ansatz,

be used to discussspin precession, ut this equation has no b classicalcounterpart becauseSz cannot be written as a function of q 'sand classicalcounterparts, the correct classicalequation quantities possessing can be obtained from the correspondinguantum-mechanicalequation via q
*L
Jclassical-

insisting

on

we Dirac'sule, A.6.47), may r

>

B.2.22
mechanics, but the

Classicalmechanics can be derived oppositeis not true.*

from quantum

FreeParticles;Ehrenfesfs Theorem
Whether we work in the Schrodingerpicture or in the Heisenberg picture, to be able to use the equations of motion we must first learn how to construct the appropriate Hamiltonian operator.For a physical system with classical nalogues,we assumethe Hamiltonian to be of the same form as in a classicalphysics; we merely replace the classicalx/s and /?/s by the W corresponding operators in quantum mechanics. ith this assumption we can reproduce correct classical quations in the classicalimit. Whenever the l e
this book we follow the order: the Schrodinger picture-* the Heisenberg picture-* the an enlightening treatment of the same subject in opposite order, classical and 109. the Schrodinger picture, see Finkelstein A973), 68-70 Heisenberg picture
\342\200\224> -\302\273

*In

F classical. or

2.2.The

Schrodinger Versus the Heisenberg Picture

85

an ambiguity arisesbecauseof noncommuting observables, attempt to we resolve it by requiring H to be Hermitian; for instance, we write the quantum-mechanical analogue of the classicalproduct xp as \\{xp + px). When the physicalsystem in question has no classical nalogues, we can a only guessthe structure of the Hamiltonian operator.We try various forms until we get the Hamiltonian that leads to results agreeing with empirical

observation. In practical applicationsit is often necessary evaluate the commuto of xt (or Pi) with functions of Xj and p-.To this end the following formulas are found to be useful:
commutator

B.2.23a
and

B.2.23b
x

where F and G are functions that can be expandedin powersof pj'sand We -'s,espectively. can easilyprove both formulas by repeatedly applying r

A.6.50e).

We are now in a position to apply the Heisenberg equation of motion to a free particle of massm. The Hamiltonian is taken to be of the same form as in classical echanics: m

\342\200\236

.?JjtgllH.
2m 2m

B.2.24
any function

We look at the observables and xi9 which are understood to be the pt momentum and the positionoperator in the Heisenberg icture even though p

we omit the

's,we have

superscript(H).Becausept commutes with

of

-

Thus for a free particle, the momentum operator is a constant of the motion, which means that pt(t) is the same as pt@) at all times. Quite that generally, it is evident from the Heisenberg equation of motion B.2.19) whenever A{H) commutes with the Hamiltonian, A{H) is a constant of the motion. Next,
dxt dt

. ih[
1

1 1 11 ih 2m ih J
Pi

d

3

dp,

E pj

P,

@) mm

B.2.26

86

Quantum

Dynamics

so we where we have taken advantage of B.2.23a), have the solution
m
which

t,

B.2.27

is reminiscent of the classicaltrajectory equation for a uniform rectilinear motion. It is important to note that even though we have

[x,@),*,@)]=0
at equal times, the commutator of the vanish; specifically,

B.2.28
times

jc/s at

different

does not

Pi@)t
m
Applying

-iht
m
this

B.2.29

the

uncertainty

relation A.4.53)to

commutator, we obtain
2

h2t2
Among

'

B.2.30

other things, this relation implies that even if the particle is well localized at f = 0, its position becomes more and more uncertain with time, a conclusionwhich can also be obtained by studying the time-evolution behavior of free-particlewave packetsin wave mechanics. We now add a potential V(x) to our earlier free-particle Hamilto-

nian:

2m

V(x).
of the

B.2.31
x-, y-, and
z-operators.

HereV(x) is to be understood as a function
UsingB.2.23b)
this

time, we obtain
dt

ihl

r'

dx V(x). El
m

B.2.32

On the other hand, we seethat

It
still

dxl

B.2.33

holds because commutes with the newly added term V(x).We can jc, use the Heisenbergquation of motion onceagain to deduce e d2x
dt2

,1?
ih dt

L,H

ih

m

m dt

'

B.2.34
obtain in vectorial form

Combining this

with

we B.2.32),finally

d2x __ = _

B.2.35

2.2.The

Schrodinger Versus the Heisenberg Picture

87

This is the quantum-mechanical analogue of Newton'ssecond law. By taking the expectation values of both sides with respectto a Heisenberg state ket that does not move with time, we obtain

This is known as the Ehrenfesttheoremafter P.Ehrenfest, who derived it in 1927using the formalism of wave mechanics.When written in this expecform, its validity is independent of whether we are using the Heisenor the Schrodinger icture; after all, the expectation values are the p is meaningI same in the two pictures. n contrast, the operator form B.2.35) if we understand x and p to be Heisenberg-picture operators. only I the have completely disappeared.t is We note that in B.2.36) /i's therefore not surprising that the center of a wave packet moves like a to classical article subjected V(\\). p
expectation
Heisenberg meaningful

Base and Transition Amplitudes Kets
So far we have avoided asking how the basekets evolvein time. A common misconception is that as time goes on, all kets move in the p Schrodinger icture and are stationary in the Heisenberg icture. This is not p the case, s we will make clear shortly. The important point is to distinguish a the behavior of state kets from that of basekets. of We started our discussion ket spacesin Section1.2 remarking by that the eigenkets observablesare to be used as basekets.What happens of to the defining eigenvalueequation
A\\a')
with

= a'\\a')

B.2.37

time? In the Schrodingerpicture, A doesnot change, so the basekets, obtained as the solutions to this eigenvalueequation at t = 0, for instance, must remain unchanged. Unlike state kets, the baseketsdo not change in the Schrodinger icture. p The whole situation is very different in the Heisenberg icture, where p the eigenvalueequation we must study is for the time-dependentoperator
From

B.2.38
evaluated at t = 0, when the two pictures coincide, e deduce w B.2.37)

B.2.39
which

impliesan eigenvalueequation for A{H):

B.2.40
If we continue to maintain the view that the eigenketsof observablesform the base kets, then {W*\\a')} must be used as the basekets in the Heisen-

88

Quantum

Dynamics

base bergpicture.As time goeson, the Heisenberg-picture kets,denotedby \\a',t)H9 move as follows:
\\a\\t)H

= ^\\a').

B.2.41)
\302\260ti

in B.2.41), the Because of the appearance of rather than basekets are seen to rotate oppositely when compared Heisenberg-picture satisfies the with the Schrodinger-picturestate kets; specifically, \\a\\t)H
\302\260ll^

\"

wrong-signSchrodingerequation\"

As

unchanged with time. This is consistent with the theorem on unitary in Notice also the following d equivalent observables iscussed Section for A^H\\t) in terms of the basekets and bras of the Heisenberg expansion

B.2.42) ihjt\\a\\t)H=-H\\a\\t)H. that for the eigenvaluesthemselves,we seefrom B.2.40) they are

1.5.

picture:
a' a'
which
Heisenberg

B.2.43)
shows that everything is quite consistent provided that the Heisenbasekets change as in B.2.41). of We see that the expansion coefficients a state ket in terms of base kets are the same in both pictures:
base bra
state ket

picture) (the Schrodinger

B.2.44a)

<V(O = ((a'\\<&)
base bra

\342\200\242

|a,t0 = 0>
state ket

p (the Heisenberg icture).B.2.44b)

Pictorially, we may say that the cosineof the angle between the state ket and the base ket is the same whether we rotate the state ket counterclockor the base ket clockwise. These considerationspply equally well to a base kets that exhibit a continuous spectrum; in particular, the wave function (x'|a)can be regarded either as A) the inner product of the stationary position eigenbra with the moving state ket (the Schrodinger picture) or as B) the inner product of the moving position eigenbra with the stationary state ket (the Heisenberg picture).We will discussthe time of the wave function in Section 2.4, where we will derive the dependence celebratedwave equation of Schrodinger. To illustrate further the equivalencebetween the two pictures, we transition amplitudes, which will play a fundamental role in Section study
counterclockwise

2.3.Simple Harmonic
TABLE

Oscillator

89
Versus the Heisenberg Picture Heisenberg picture Stationary Moving: Moving oppositely:

2.1. he Schrodinger Picture T
Schrodinger picture

State ket

Observable Baseket

Moving:
Stationary Stationary

B.1.5), B.1.27)

B.2.10), B.2.19)

B.2.41), B.2.42)

physical system prepared at t = 0 to be in an of observableA with eigenvalue At somelater time / we may eigenstate ask, What is the probability amplitude, known as the transition amplitude, for the system to be found in an eigenstateof observableB with eigenvalue A Here and B can be the same or different. In the Schrodingerpicture the state ket at t is given by W\\a')9 while the basekets \\a') and \\b') do not vary with time; so we have

2.5. uppose there is a S

a'.

b'l

?

base bra

state ket

transition amplitude. In contrast, in the Heisenberg icture the state p is stationary, that is, it remains as \\a') at all times, but the base kets S evolveoppositely. o the transition amplitude is for
this

ket

B.2.46)
base bra state ket

Obviously B.2.45)
In

and

are B.2.46) the same.They can both be written as

(b'\\W(t,0)\\a').
someloose sensethis is the
transition

B.2.47)
\"going\" from

amplitude for

state

\\a') to state \\b').

this To conclude sectionlet us summarize the differencesbetween the Table p Schrodinger picture and the Heisenbergicture; see

2.1.

OSCILLATOR HARMONIC 2.3. IMPLE S
The simpleharmonic oscillator is one of the most important problemsin F p quantum mechanics. rom a pedagogical oint of view it can be used to illustrate the basic conceptsand methods in quantum mechanics. From a practicalpoint of view it has applicationsin a variety of branchesof modern s spectroscopy, olid state physics,nuclear structure, physics\342\200\224molecular quantum field theory, quantum optics,quantum statistical mechanics, and so forth. From a historical point of view it was M. Planck'sproposalto associatediscreteunits of energy with radiation oscillators that led to the of A birth of quantum concepts. thorough understanding of the properties

90 f quantum-mechanical oscillators is indispensableor modern physics. Energy

Quantum

Dynamics

any

seriousstudent of

and Eigenkets Energy Eigenvalues We begin our discussionwith Dime's elegant operator method, which is based on the earlier work of M. Born and N. Wiener, to obtain the and energyeigenvaluesof the simple harmonic oscillator. energy eigenkets The basicHamiltonian is

H\022m+
where
co

p2

mu2x2

2

>

is the angular frequency of the classical scillator related to the o constant k in Hooke's via co = yjk/m. The operators jc and p law spring are, of course,Hermitian. It is convenient to define two non-Hermitian
mco
V

operators,
I
\\

2n

ip x + mu

\\

) J

a+ =
V

mco

/
\\

2n

x

ip

\\

,_ ^

mu>)

known
commutation

as the annihilation operator and the creation operator, respectively, for reasonsthat will become evident shortly. Usingthe canonicalcommutawe readily obtain relations,

(-i\\x d] + i[dx])=l
We

B 3 3)

also define the number operator

N=ajfa,
which

B.3.4)
to show that

is obviously Hermitian. It is straightforward
cfia =
moo
2
\\

m 2u> 2 no)

= -x

-^-,

2'

B.3.5)
v 7

so we have an important relation between the number operator and the Hamiltonian operator: + B.3.6) H=hu(N \\). BecauseH is just a linear function of N, N can be diagonalized simultawith H.We denote an energyeigenketof N by its eigenvaluen, so
simultaneously

will later show that we also have

We

n must

B.3.7) be a nonnegativeinteger. Because B.3.6) of

B.3.8)

2.3.Simple
which

Harmonic Oscillator

91

means that the energyeigenvaluesare given by

En=(n+ \\)hu.
To appreciatethe physical significanceof note that

B.3.9)
a, a\\
and
N9

let us

first

= = = + [N,a] [a*a9a] a*[a9a][a*9a]a -a9 where we have usedB.3.3). we Likewise, can derive = [N9a*] a*.
As

B.3.10

B.3.11

a result, we have

= (n+l)a*\\n)
and

B.3.12a

= (n-l)a\\n).
Theserelationsimply
eigenvalue

B.3.12b

o the B increased (decrease)f n (decreased) one. ecause increase oneamounts to the creation (annihilation) of onequantum unit of energy by h(o, the term creation operator(annihilation operator)for a*(a) is deemed

that a?\\n){a\\n)) by

o is also an eigenket f TV with eigen-

Equation B.3.12b) that implies multiplicative constant. We write

appropriate.

a\\n)

and

\\n

-1)are the same

up

to a

B.3.13 a|/i>= c|/i-l>, where c is a numericalconstant to be determined from the requirement that both \\n) and \\n be normalized.First, note that

-1)

(n\\afa\\n)

= \\c\\2.
that

B.3.14
a^a is just the

We can number

evaluate the left-hand sideof B.3.14)noting by

operator,so

h

= |c|2.
obtain

B.3.15

Taking c to be real and positive by convention,we finally

a\\n)=}[n\\n-\\).
Similarly, it

B.3.16
annihilation

is easy to show that
V

B.3.17)
the

Supposethat we keep on both sidesof B.3.16):

applying

operator a to

B.3.18

92
We

Quantum

Dynamics

can obtain numerical operator eigenkets with smaller and smaller n the sequence terminates, which is bound to happen wheneverwe start a positive integer n. One may argue that if we start with a noninteger will n, the sequence not terminate, leading to eigenketswith a negativevalue of n. But we also have the positivity requirement for the norm of a\\n)\\
until with n

= (n\\N\\n)

= ((n\\a*)-(a\\n))0, >

B.3.19

which

implies that n can never be negative! So we conclude that the sequencemust terminate with n = 0 and that the allowed values of n are nonnegative integers. the value of n is zero, the ground state of Because smallestpossible
the harmonic oscillatorhas

B.3.20) E0 = %hu. the creation operator a* to the ground state We can now successively apply we U |0). singB.3.17),obtain

B.3.21
\\n)

=

In

and

this way with

H

in we have succeeded constructing simultaneouseigenketsof energy eigenvalues

En=(n+ \\)hu,
From

w {(/?)}, e obtain the matrix elements ,,n_l, (n'\\a*\\n) =

B.3.16), B.3.17),

(/i = and the orthonormality

0,1,2,3,...)-

B.3.22

requirement for

B.3.23

Usingthese together with

x=

2mco (a

h

B.3.24
x and p operators:

we derive the matrix elementsof the

B.3.25a

B.3.25b

2.3.Simple Harmonic

Oscillator

93

Notice that neither jc nor p is diagonal in the TV-representation we are using. This is not surprising becausex and /?, like a and a\\ do not commute with N. The operator method can also be used to obtain the energy eigenfunctions
in

Let position space. us start

with

the ground state defined by

B.3.26
which, in

the jc-representation, eads r
(x'\\a\\0)

B.3.27

w Recalling A.7.17), e can regard this as a differential equation for the wave function (x'\\0): ground-state

d x'+ x0 dx'
where we have introduced
Xq
\342\200\224

\\

j

B.3.28)

ma)

B.3.29)

which

sets the

solution to

is B.3.28)

length

scaleof the oscillator.We seethat the normalized

1
0
We
evaluating

exp
I

jc,

B.3.30)

can also obtain the energyeigenfunctionsfor excited states by evaluat-

i
= (x'\\2)

' i

i

1
\302\253A<

*^

[y/2x0)

0

d

\\

dx')

B.3.31
In general, we obtain

1
x0

n X
\342\200\224

JC

0

dx'

exp

_1

x
0

2

B.3.32)

94 It

Quantum

Dynamics

is instructive to look at the expectationvaluesof x2 and p2 for the state. First, note that ground
x2 =
When we

I

)(a2+ an + a^a + aa<). \\2mo))
\\

h

yieldsa nonvanishing contribution: Likewise,

take the expectation value of

x2,only

the last term

B.3.33) in B.3.33)

(P > =
It follows
that

~2~\342\200\242

B.3.35)

the expectation values of the kinetic and the potential

a energiesre, respectively,
2m
that

?

(M1 and
it follows and B.3.25a) B.3.25b),

as expectedfrom the virial theorem. From

B.3.37)
which

alsoholds for the excited states.We thereforehave
and <(ApJ>= (p>) =

and we

see that

^,

B.3.38)

the

uncertainty

relation is satisfied in the minimum
h2

uncertainty product form:

.

B.3.39)

This is not surprising becausethe ground-state wave function has a Gausshape. In contrast, the uncertainty productsfor the excited states are
Gaussian

larger:

= ((kxJ)((kpJ) (n + \\Jh2,
as the readermay easily verify.
Time Developmentof the Oscillator

B.3.40)

So far we have not discussed time evolution of oscillator state the kets nor of observablesike x and p.Everything we have doneis supposed l to hold at someinstant of time, say at t = 0;the operatorsjc, /?, a, and eft are to be regardedeither as Schrodinger-pictureoperators(at all /) or as Heisenberg-picture operators at / = 0.In the remaining part of this section, we work exclusivelyin the Heisenberg picture, which means that x, p, a,

2.3.Simple Harmonic

Oscillator

95

and a* are all time-dependent even though we do not explicitly write a x(H)(t), nd so forth. The Heisenberg equations of motion for p and x are, from B.2.32)
and

B.2.33),

\342\200\224

dt

mco

x

B.3.41a)

and dx
dt w
w

p
m
www

B.3.41b)
two

differential equations for a and a*, namely,

This pair of coupleddifferential da
and

equations is equivalent to
\342\200\224

uncoupled

mco

icox I =

\342\200\224

icoa

B.3.42a)

da*
dt

B.3.42b)

whose solutions are

a(t)= a@)exp( iot) and
x(t)+
= x@)exp(i

B af(t) = at(O)exp(ico/). .3.43)

Incidentally, these relations explicitly show that A^ and H are time-indepenp operatorseven in the Heisenberg icture, as they must be.In terms of x and /?, we can rewrite B.3.43) as
time-independent

p(o)
mco

exp( iwt),
\342\200\224

P(O)
mco

B.3.44)
sidesseparately,

exp(icot).

Equating the Hermitian and anti-Hermitian parts of both we deduce

x(t) =
and

p(o)
mco

sin cot

B.3.45a)

p(t)=

\342\200\224

p@)coscot.

B.3.45b)

Theselook the same as the classical quations of motion. We seethat the x e and p operators\"oscillate\"just like their classical nalogues. a For pedagogical reasonswe now presentan alternative derivation of Instead B.3.45a). of solving the Heisenbergquation of motion, we attempt e
to evaluate / iHt
\\

- iHt
\342\200\224\342\200\224

B.3.46)

96

Quantum

Dynamics

To this end we recorda very useful formula:

= exp(*G\\),4exp(-/G\\) A + iX[G,A]+
\\

'ft?

2! [G,[G,A]] +
B.3.47)

ft!

.. [G\\G,[G, .

where G is a Hermitian operator and A is a real parameter. We leave the proof of this formula, known as the Baker-Hausdorfflemma as an exercise. we this formula to B.3.46),obtain Applying

exp

iHt\\ h

^

/

-iHt
h

it_

i2t2
{2\\h right-hand

\\

h

B.3.48)

Each term on the repeatedly using

side can be reduced to either x or p by

B.3.49a)
and

[H,p@)]=ihma2x@)
Thus

B.3.49b)

exp

iHt\\ h

lx@)expi

-iHt
h

P(O)
m

3!
in

tWp(o)
m

P(O) sinco/, mco
agreement with
From

B.3.50)

(x) and (p) always oscillate with angular frequency to. However, this inference is not correct. Take any energy eigenstate characterized by a definite value of n\\ the expectation value (n\\x(t)\\n) vanishes becausethe and \\n) and \\n +1)are orthogooperatorsx@) and p@) change n by This point is alsoobvious from our earlier conclusion(seeSection2.1) that the expectation value of an observable taken with respectto a stastate doesnot vary with time. To observeoscillationsreminiscentof stationary the classical scillator,we must look at a superposition of energyeigenstates o such as
\302\2611 orthogonal.

and one B.3.45a) B.3.45b), may be tempted to conclude that

B.3.45a).

B.3.51)

2.4.Schrodinger's

Wave Equation

97

p\342\200\224no

The expectation value of x(t) taken with respectto B.3.51) oscillate,as does the readermay readily verify. We have seen that an energy eigenstate does not behave like the the senseof oscillatingexpectation values for x and classical matter how large n may be.We may logically ask, How can we o construct a superpositionf energyeigenstatesthat most closelyimitates the classical scillator? In wave-function language,we want a wave packetthat o bouncesback and forth without spreading in shape. It turns out that a coherentstate defined by the eigenvalueequation for the non-Hermitian annihilation operator a,
oscillator\342\200\224in

B.3.52)
with, in

T job. he coherent general, a complexeigenvalueA doesthe desired state has many other remarkableproperties:

1.When

as expressed a superposition of energy (or N) eigenstates,

=

00
E/(\302\253)!\302\273>.

B-3.53)
n

of \\f(n)\\2 with respectto the distribution about somemean value n:

is of the Poisson type

product relation at all times. A systematic study of coherent states, pioneered by R. Glauber, is very the readeris urged to work out an exercise this subject at the on rewarding; end of this chapter.*
WAVE 2.4. CHRODINGER'S S

2. It can be obtained by translating somefinite distance. 3.It satisfiesthe minimum uncertainty

|/(n)|2=(^)exp(-n).

B.3.54)

the oscillator ground state by

EQUATION

Time-DependentWave

Equation

We now turn to the Schrodinger picture and examine the time I evolution of to\\ t) in the jc-representation. n other words, our task is to study the behavior of the wave function

|a,

= iHx',0 <x'|<M0;/>
as a function of time, where
\\a,to\\t)

B.4.1)
in

is a state ket
Scully, and Lamb

the Schrodinger

For applications to laser physics, seeSargent,

A974).

98

Quantum

Dynamics

picture at time t, and (x'|is a time-independentposition eigenbra with eigenvalue The Hamiltonian operator is taken to be

x'.

TJ

2m
in

B.4.2)

The potential V(x) is a Hermitian operator; it is also local in the sensethat
the w x-representation e have

where V(x')is a real

function of x'.Later in this book we will consider Hamiltonians\342\200\224a more-complicated time-dependent potential F(x,t)\\ a is nonlocal but separablepotential where the right-hand side of B.4.3) a replacedby vl(x\v2(x');") momentum-dependentinteraction of the form p A + A p, where A is the vector potential in electrodynamics,and so on. We now derive Schrodinger'sime-dependent wave equation. We t in the first write the Schrodinger equation for a state ket B.1.27) x-represen\342\200\242 \342\200\242

= F(x')fi3(x'-x''), <x\"|K(x)|x'>

B.4.3)

x-representation:

ih

dt

B.4.4)

in where we have used the fact that the position eigenbras the Schrodinger we picture do not change with time. UsingA.7.20), can write the kineticas energy contribution to the right-hand sideof B.4.4)

= 1m a,to;t)
As for
V(\\),

- 1m
/
h

/2

B.4.5)

we simply use
we

B.4.6)
where V(x')is no longer an operator.Combining everything,
( h2
\\

deduce

1m V '\\x'\\a,to;t)+

;'>,
B.4.7)

which we recognizeto be the

Schrodinger, usually

written

as

celebrated time-dependentwave equation of E.
h2
\\

1m
wave

B.4.8)

The quantum mechanicsbasedon wave equation B.4.8)known as is mechanics.This equation is, in fact, the starting point of many on textbooks quantum mechanics.In our formalism, however,this isjust the Schrodinger quation for a state ket written explicitly in the x-basiswhen e the Hamiltonian operator is taken to be B.4.2).

2.4.Schrodinger's

Wave Equation

99

The Time-IndependentWave
We now

Equation

eigenfunctions. We
function

derive the partial differential equation satisfied by energy that the time dependence a showed in Section2.1 of us state is given by exp( iEa,t/h).This enables to write its wave stationary

-

as

ZlfL-y

B.4.9)

where it is understood initially the system is preparedin a simultaneous that eigenstate of A and H with eigenvalues and Ea>, respectively.Let us now We substitute B.4.9) the time-dependentSchrodingerequation B.4.7). into are then led to

a'

*M
2m
}

\342\200\242'

-

B.4.10

This partial differential equation is satisfied by the energy eigenfunction (x'\\a')with energy eigenvalueEa>. Actually, in wave mechanicswhere the it is Hamiltonian operator is given as a function of x and p, as in B.4.2), not to necessary refer explicitly to observableA that commuteswith H because A x we can always choose to be that function of the observables and p with H itself. We may therefore omit reference to and which coincides as the simply write B.4.10) partial differential equation to be satisfiedby the energy eigenfunction uE(x')\\

a'

I

h2

\\

i

This is the time-independentwave equation of E. Schrodinger\342\200\224announced in the first of four monumental papers, all written in the first half of laid the foundations of wave mechanics.In the same paper he to derive the energyspectrum of the hydrogen immediately appliedB.4.11) atom. To solve B.4.11) boundary condition has to be imposed. some we with Suppose seeka solution to B.4.11)
1926\342\200\224that

E<

lim
00

F(x'),
|x'|> oo in
this

B.4.12
case is
any

where the inequality relation is to hold for appropriate boundary condition to be usedin

direction. The

-> uE(x')-> 0 as |x'| oc..
Physically
this

B.4.13)

region of

We space.

means that the particle is bound or confined within a finite know from the theory of partial differential equations

100
that

Quantum

Dynamics

condition B.4.13) allows nontrivial solufor a discreteset of values of E. It is in this sense that the only time-independent Schrodingerequation B.4.11) the quantization of yields is written, the energy levels.*Oncethe partial differential equation B.4.11) problemof finding the energy levelsof microscopic hysical systems is as p straightforward as that of finding the characteristicfrequenciesof vibrating I strings or membranes.n both caseswe solve boundary-valueproblemsin mathematical physics. A short digression the history of quantum mechanicsis in order on here.The fact that exactly soluble eigenvalue problemsin the theory of partial differential equations can also be treated using matrix methods was already known to mathematicians in the first quarter of the twentieth century. Furthermore, theoretical physicists like M. Born frequently conconsulted great mathematicians of the Hilbert and H. Weyl, in it particular. Yet when matrix mechanicswas born in the summer of 1925, did not immediately occur to the theoreticalphysicists r to the mathematio to reformulate it using the language of partial differential equations. Six months after Heisenberg's ioneering paper, wave mechanicswas prop However,a close by Schrodinger. proposed inspection of his papersshows that he was not at all influencedby the earlier works of Heisenberg, Born, and Jordan.Instead, the train of reasoning that led Schrodinger to formulate wave mechanics has its roots in W. R. Hamilton'sanalogy between optics and mechanics,on which we will comment later, and the particle-wave O hypothesis of L. de Broglie. nce wave mechanicswas formulated, many people,ncluding Schrodinger himself, showed the equivalence between i wave mechanicsand matrix mechanics. It is assumedthat the reader of this book has some experience in solving the time-dependentand time-independentwave equations. He or she should be familiar with the time evolution of a Gaussianwave packetin a force-free region; should be able to solve one-dimensionaltransmissionreflection problemsinvolving a rectangular potential barrier, and the like; should have seen derived some simple solutions of the time-independent wave particle in a box, a particle in a squarewell, the simple harmonic oscillator, the hydrogen atom, and so should also be familiar with some general propertiesof the energy eigenfunctions and energy eigenvalues, such as A) the fact that the energy levels exhibit a discreteor continuous spectrum dependingon whether or not B.4.12) is satisfied and B) the property that the energy eigenfunction in one dimenis sinusoidalor damped depending whether E V(x')is positive or on In this book we will not cover these topics.A brief summary of negative. in elementary solutions to Schrodinger's equations is presented Appendix A.
solutions day\342\200\224D.
mathematicians

B.4.11) to boundary subject

equation\342\200\224a

on\342\200\224and

dimension

-

*Schrodinger's paper
Eigenwertproblem

(Quantization

that announced is appropriately as an Eigenvalue Problem).

B.4.11)

entitled

Quantisierung

als

2.4.Schrodinger's

Wave Equation

101

Interpretations of the Wave Function o We now turn to discussions f the physical interpretations of the we wave function. In Section 1.7 commentedon the probabilisticnterpretai as that followsfrom the fact that (x'|a, t) is to be regarded of /0; in terms of the position eigenkets an expansioncoefficientof t0; t) The quantity p(x', ) defined by /
interpretation

\\\\p\\2

{|x')j.

|a,

p(x',) = + (x'9t)\\2 = |<x'|a, t)\\2 t t0;
\\

B.4.14)

is therefore regardedas the probability density in wave mechanics.Specifiwhen we use a detector that ascertains the presenceof the particle the probability of recording within a small volume element d3x'around a positive result at time t is given by In the remainder of this section we use x for becausethe position operator will not appear.UsingSchrodinger'sime-dependent wave equat it is straightforward to derive the continuity equation
Specifically,

p(x'9t)d3x'.

x',

x'

equation,

? ^

B.4.15)
j(x,t), known
as the
probability

where p(x,/) standsfor
flux,

\\\\p\\2

is given by

as before, and

B.4.16
The reality of the potential V (or the Hermiticity of the V operator) has played a crucial role in our obtaining this result. Conversely,a complex o account for the disappearance f a parpotential can phenomenologically such a potential is often used for nuclear reactions where incident particlesget absorbedby nuclei. We may intuitively expectthat the probability flux j is related to momentum. This is indeedthe case for j integrated over all space. rom F we obtain B.4.16)
particle;

B.4.17)
where (p), is the expectationvalue of the momentum operator at time t. is Equation B.4.15)reminiscentof the continuity equation in fluid that characterizesa hydrodynamic flow of a fluid in a source-free, dynamics sink-free region. ndeed,historically Schrodingerwas first led to interpret I as the actual matter density, or as the actual electric charge If we adopt such a view, we are led to face some bizarre consedensity.
e\\\\p\\2

\\\\p\\2

consequences.

102

Quantum

Dynamics

An

A typical argument for a position measurementmight go as follows. atomic electron is to be regarded as a continuous distribution of matter filling up a finite region of spacearound the nucleus; yet, when a measureis made to make sure that the electron is at some particular point, this continuous distribution of matter suddenly shrinks to a pointlike particle of with no spatial extension. he more satisfactory statistical interpretation T |\\^|2 as the probability density was first given by M. Born. To understand the physical significanceof the wave function, let us write it as
measurement

'S(x'r)
h with

B.4.18

S real and p > 0, which can always be donefor any complexfunction of x and /. The meaning of p has already beengiven. What is the physical interpretation of SINoting
we can write the probability as [seeB.4.16)]
m We now

B.4.19)
flux

B.4.20)
\\p

2 there is more to the wave function than the fact that | |2 is the probability density; the gradient of the phaseS contains a vital piece f o information. From B.4.20) see that the spatial variation of the phase of we the wave function characterizesthe probability flux; the stronger the phase variation, the more intense the flux. The direction of j at some point x is seento be normal to the surfaceof a constant phasethat goesthrough that point. In the particularly simple example of a plane wave (a momentum eigenfunction)

seethat

,

/ /px 0 a exp^-^
x

iEt
\342\200\224

\\

J,

B.4.21
operator.All
this

,_

.

..
is

where p stands for the eigenvalueof the momentum evident because

VS=p.
Moregenerally, it is tempting to regard vS/m as somekind of
m
\"

B.4.22)
velocity,\"

B.4.23)

and to write the

continuity

as equation B.4.15)

B.4.24)
just as in
fluid

dynamics. However, we would like to caution the reader

2.4.Schrodinger's

Wave Equation

103

against a too literal interpretation of j as p times the velocity defined at every point in space, becausea simultaneous precisionmeasurement of position and velocity would necessarilyviolate the uncertainty principle.
L The Classical imit We now discussthe substitute written in form wave equation. Straightforward
\\p

into B.4.18) both

classicallimit of wave mechanics. First, we sidesof the time-dependent
differentiations lead to

2m
X

= ih

dt

\\h

B.4.25)

So far everything has been exact. us supposenow that h can, in some Let sense,be regardedas a small quantity. The precisephysical meaning of this approximation, to which we will come backlater, is not evident now, but let us assume
-, and so forth. We can then collect terms in B.4.25) do not explicitly that contain h to obtain a nonlinear partial differential equation for S:
2m
We

B.4.26)
B 4 21)

1 \\\\7S(x,

t)\\2

, + V(x)-\\
\342\200\224\302\273

dS(x t) = 0
at

0 limit, classicalmechanics is function. So, ot surprisingly, in the h n interWe wave contained in Schrodinger's mechanics. have a semiclassical of the phase of the wave function: h times the phaseis equal to interpretation Hamilton'sprincipal function provided that h can be regardedas a small
quantity.

t e recognizehis to be the Hamilton-Jacobi quation in classicalmewhere S(x,t)standsfor Hamilton'sprincipal first written in 1836, mechanics,

S is separable:

Let us now look at a stationary state with time dependence This i iEt/h). time dependences anticipated from the fact that for a classical ystem with a constant Hamiltonian, Hamilton's s principal function
exp(\342\200\224

= S(x,t) W(x)-Et,

B.4.28)

where W(x) is called Hamilton's characteristic function (Goldstein1980, A 445-46). s time goeson, a surface of a constant S advances in much the

104
optics\342\200\224a

Quantum

Dynamics

\342\200\224advances.

\"wave front\" same way as a surfaceof a constant phasein wave H The momentum in the classical amilton-Jacobitheory is given

by
w is consistent ith our earlier identification of vS/m with some kind m of velocity. In classical echanics the velocity vector is tangential to the particle trajectory, and as a result we can trace the trajectory by following continuously the direction of the velocity vector. The particle trajectory is like a ray in geometric opticsbecausethe VS that traces the trajectory is normal to the wave front definedby a constant S.In this sensegeometrical m opticsis to wave opticswhat classical echanicsis to wave mechanics. Onemight wonder, in hindsight, why this optical-mechanicalanalogy in was not fully exploited the nineteenth century. The reason is that there was no motivation for regarding Hamilton's principal function as the phase of some traveling wave; the wave nature of a material particle did not t become Besides,he basicunit of action /j, which apparent until the 1920s. w into B.4.18) dimensionalreasons, as missing in the physics for must enter of the nineteenth century. which

B.4.29)

Semiclassical (WKB)

Approximation

Let us now restrict ourselves to one dimension and obtain an w approximate stationary-state solution to Schrodinger's ave equation. This s can easily be accomplishedy noting that the correspondingolutionof the b classicalHamilton-Jacobi equation is

=+

f

-Et. dx'Jlm[E-V(x')]
have

B.4.30)

Fora stationary state we must
which,

dp o ot

=0,
m

(all jc),

B.4.31

o because f the continuity

equation [seeB.4.24)] ax
\\

ax

'

implies
dW

dx

= p]/2m[E V(x)] = constant;
\342\200\224 \302\261

B.4.33)
A

hence,

VP

r=

constant
T7*

[E-V(x)]l/*

a 1
/

ft^

\342\200\242

,_ B.4.34)

.

2.4.Schrodinger's

Wave Equation

105

This makes good sensebecauseclassicallythe probability for finding the particle at a given point should be inversely proportional to the velocity. Combining everything, we obtain an approximate solution: constant

\\E-V(x)V/A
Xexp \302\261(jt)fdx'j2m[E-V(x')]
Brillouin.* Having obtained

-

iEt

B.4.35)

This is known as the WKB solution, after G.Wentzel, A. Kramers, and L.
let B.4.35),us return to the question of what we we say that h is small. Our derivation of the Hamilton-Jacobi mean when which, in oneequation from the Schrodingerequation restedon B.4.26), is equivalent to dimensional problems, d2W
dW

dx2
In terms of the to

dx

B.4.36)

de Brogliewavelength divided by 2ir, this condition amounts
h

2[E-V(x)]
\\dV/dx\\

'2m[E-V(x)]

B.4.37)

In other words, X must be small compared with the characteristicdistance t over which the potential varies appreciably. Roughly speaking,he potential must be essentially constant over many wavelengths.Thus we see that the semiclassical picture is reliable in the short-wavelength limit. has Solution B.4.35) been derived for the classicallyallowed region where E V(x) is positive. We now considerthe classically forbidden region where E V(x) is negative. The classicalHamilton-Jacobi theory s does not make sense in this case, o our approximate solution B.4.35) > V, must therefore be modified. Fortunately an which is valid for E analogous solution existsin the E < V region; by direct substitution we can
\342\200\224 \342\200\224

checkthat

constant

[V(x)-E]l/A

exp \302\261(j\\jXdx']/2m[v(x')-E] h

- iEt
to

B.4.38)
*A similar technique was used earlier by JWKB solution in some English books.

H.Jeffreys;

this solution

is referred

as the

106

Quantum

Dynamics

satisfies the wave equation provided that E) is small comwith the characteristicdistance over which the potential varies. makes sensenear the classicalurning nor Neither B.4.35) B.4.38) t point defined by the value of x for which
h/]/2m(V\342\200\224 compared

B.4.39)
becauseX (or its purely
infinite at that point, imaginary analogue)becomes In leading to a violent violation of B.4.37). fact, it is a nontrivial task to match the two solutions acrossthe classicalturning point. The standard procedureis basedon the following steps:

1.Make a
2.
turning

linear approximation to the potential V(x) near the point jc0,defined by the root of Solve the differential equation

B.4.39).

d2u dx2

2m)

B.4.40)

f exactly to obtain a third solution involving the Besselunction of order + y, valid near x0. 3.Match this solution to the other two solutions by choosing apappropriately various constants of integration. in We do not discuss these stepsin detail, as they are discussed many for 268-76, example).nstead,we content ourselvesto I places(Schiff 1968, present the resultsof such an analysis for a potential well, schematically

in Figure 2.1, with two turning points, xx and jc2.The wave function in in behave like B.4.35)region IIand like B.4.38)regions I and HI. The correct atching from region I into region II can be shown to be m

shown

must

II

III

I

FIGURE Schematic diagram for behavior of wave function with turning points xx and x2-

2.1.

uE(x) in

potential

well V{x)

2.4.Schrodinger's

Wave Equation

107

b accomplishedy choosingthe integration constants in such a way

that

1/4 [V(x)-E]

exp -(j)f*dx',l2m[V(x')-E]
COS

lE-V(x)]l/4
1

B.4.41)
f Likewise,rom region IIIinto region IIwe have

exp

/ fx \\t)\\ dx'
\\

')-E]

[E-V(x)}1/4

COS

B.4.42)
o The uniqueness f the wave function in region IIimplies that the arguments must differ at most by an integer and of the cosinein B.4.41) B.4.42) c the signs of both sidesof B.4.42) an be multiple of it [not of 2m, because I reversed].n this way we obtain a very interesting consistencycondition,

={n f 2dx]l2m[E-V(x)] +
Apart from the

\\)<nh

(n =

0,1,2,3,...). B.4.43)

differencebetween n + \\ and n, this equation is simply the condition of the old quantum theory due to A. Sommerfeld quantization as and W. Wilson, originally written in 1915

(bpdq= nh,

B.4.44)

where h is Planck'sh, not Dirac's, and the integral is evaluatedover one h whole period of classical otion, from xx to x2 and back. m for c Equation B.4.43)an be usedto obtain approximate expressions the energy levels of a particle confined in a potential well. As an example, we considerthe energy spectrum of a ball bouncing up and down over a
is *A quick way to understand the appearance of tt/4 in B.4.41)as follows. The correctly a matched pair of solutions in region I and region II, of the form B.4.38)nd B.4.35), respectively, must be related to each other by analytic continuation in a complex x-plane. An ^ excursion into the complex x-plane enables us to change the sign of ~ xx) without going through the dangerous region with x xv We now (dV/dx)xwmXi(x observe that under such an analytic continuation, the picks E]l/4 factor in B.4.38)

-

V(x)-E

up

a phase:[(dV/dx)x_Xi(x

- x^]1'4 ->

[{dV/dx)x_Xl{xx

l/[V(x)~ -

:

108 hard surface:

Quantum

Dynamics

v=(mgx, for*>0 <
I oo, for x

0,

B445)

where x stands for the height of the ball measured from the hard surface. One might be tempted to use B.4.43) irectly with d

x, = 0, 1
which that

x1= mg
\342\200\224,

?

B.4.46)

x=

problem is to considerthe
0\342\200\224of

are the classicalurning points of this problem.We note, however, t was B.4.43) derivedunder the assumptionthat the WKB wave function \"leaks into\" the x <xxregion, while in our problem the wave function must = 0.A much more satisfactory approach to this strictly vanish for x < xx
odd-parity
solutions\342\200\224guaranteed

to vanish at

a modified problem defined by

V(x)= mg\\x\\
whose turning points are
X1

(-oc< x < oc)
X9

B.4.47)
I ZnT.40 I

mg

,

mg

.

The energy spectrum of the odd-parity states for this modified problem T must clearly be the same as that of the original problem. he quantization condition then becomes

-

E/mg

= dx^2m(E-mg\\x\\) (nodd + ^7rh,

(nodd

=1,3,5,...

B.4.49)
or, equivalently,
I
E/mg

dx]J2m(E

\342\200\224

mgx)

= (n

\342\200\224

\\Orh,

(\302\253

=1,2,3,4,...).

B.4.50)
This integral is elementary,and we obtain

r

B.4.51

for the quantized energy levelsof the bouncing ball. It is known that this problem is solubleanalytically without any in approximation. The energy eigenvaluesturn out to be expressible terms the zerosof the Airy function of

Ai(-\\n) = 0

B.4.52)

2.5.Propagators

and Feynman Path Integrals

109
Energies of

TABLE

2.2. The Quantized
WKB

a Bouncing

Ball

inUnitsof(mg2/t2/2I/3
n

Exact

2
3

1

2.320 4.082

5.517

2.338 4.088

5.521

4
5 6
7

6.784 7.942 9.021 10.039

6.787 7.944 9.023

10
as

8 9

11.008 11.935
12.828

10.040
12.829

11.009 11.936

\\

21/3 (mg2h2)
j

n

The two approaches compared numerically in are energy levels.We seethat agreement is excellenteven for small valuesof n and essentiallyexact for n ~ 10. The quantum-theoreticaltreatment of a bouncing ball may appearto have little to do with the real world. It turns out, however,that a potential of type B.4.45) actually of practical interest in studying the energy is spectrum of a quark-antiquark bound system, called quarkonium. To go from a bouncing ball to a quarkonium, the x in B.4.45)s replaced the i by quark-antiquark separation distance r. The analogue of the downward gravitational force mg is a constant (that is, r-independent) force believed to be operative between a quark and an antiquark. This force is empirically estimated to be in the neighborhoodof

B.4.53) for Table 2.2 the first 10

1GeV/fm=1.6xl05 N, tons. This contrasts with which corresponds about 16 to N force of 0.98 on a ball of 0.1 kg. 2.5. ROPAGATORS AND P
FEYNMAN

B.4.54)
the gravitational

PATH INTEGRALS

Propagators in Wave Mechanics In Section 2.1 we showed how the most general time-evolution with a time-independent Hamiltonian can be solved once we problem expand the initial ket in terms of the eigenkets of an observable that

110
commutes with

Quantum

Dynamics

H.Let us translate this
with

W mechanics. e start

statement into the languageof wave

= |a,fo;/>
a
Multiplying

-iH{t-t0)

B.5.1)

(x'|on the left, we have -iEe.(t -h) t) (x'\\a,t0; = ?<x'|0')<tf'|a, to)exp
both sidesby
a
form '>

B.5.2)

which

is of the

0 = E <v(/0)iv(x')exp a
with

B.5.3)

with

standing for the eigenfunctionof operator A
that

eigenvalue

a'.Note also
the

B.5.4)

= fl1a,*0> Jd3x'(a'\\x')(x'\\a,t0),
which we recognize as the usual rule in wave mechanics for expansioncoefficientsof the initial state:

B.5.5)
getting

B.5.6)
All with

on the

can B.5.5) also be visualizedas somekind
initial

this should be straightforward

wave function

and familiar. Now together of integral operator acting to yield the final wave function:

B.5.2)

t;x', 0 = jdh'K(x\"y to) + (x',t0)

B.5.7)

Herethe kernelof the integral operator, known as the propagator in wave i mechanics,s given by
a In
any

B.5.8)

given problem the propagator dependsonly on the potential and is independentof the initial wave function. It can be constructed oncethe energy eigenfunctionsand their eigenvaluesare given. Clearly, the time evolution of the wave function is completely predictedif K(x'\\t;x\\ t0) is known and \\^(\\\\ t0) is given initially. In this

2.5.Propagators

and Feynman Path Integrals

111

sense Schrodinger's mechanics is a perfectly causal theory. The time wave of a wave function subjected some potential is as \"determinto development as anything elsein classical echanics providedthat the system is left m undisturbed. The only peculiar feature, if any, is that when a measurement
\"deterministic\"

intervenes, the wave function changes abruptly, in an uncontrollable way, into one of the eigenfunctionsof the observablebeing measured. There are two propertiesof the propagator worth recording here. First, for t > f0, AT(x\", t\\x\\ t0) satisfiesSchrodinger's time-dependentwave equation in the variablesx\" and t, with x'and t0 fixed.This is evident from because(x\"\\a')exp[ B.5.8) iEa,(t to)/h],being the wave function correto ty(t,to)\\a'), atisfiesthe wave equation. Second, s corresponding
\342\200\224

-

/-> t(
which

= S3(x\"-x'), lim#(xV;x\\/0)
-\302\273f0,

B.5.9)

B.5.8) reducesto (x\"|x'). just
function of

is also obvious; as t

of of sum because the completeness {\\a')},

of Because these two properties,he propagator B.5.8), t regardedas a at t of a particle which was x\", is simply the wave function localized precisely x' at some earlier time t0. Indeed,this interpretation at can follows,perhapsmore elegantly, from noting that B.5.8) also be written as
-<\"\302\253-<o)
,\342\200\236

B_5_10)

where the time-evolutionoperator acting on |x') just the state ket at t of a is that was localizedpreciselyat x'at time tQ ( < t). If we wish to solve system a more general problem where the initial wave function extends over a finite of space,all we have to do is multiply ^(x',t0) by the propagator region I K(x'\\t\\ x',/0) and integrate over all space(that is, over x').n this manner we can add the various contributions from different positions(x'). his T situation is analogous to one in electrostatics;f we wish to find the i electrostatic potential due to a general charge distribution p(x'), we first solve the point-chargeproblem, multiply the point-charge solution with the charge distribution, and integrate:

B.5.11
The reader familiar with the theory of the Green'sfunctions must have function recognizedby this time that the propagator is simply the Green's for the time-dependent wave equation satisfying
h
^
~\"

1m

\"'

\"x

\"

d
dt

= -ih8\\x\"-x')8(t-to K(x\",t;x',to) B.5.12

112
with

Quantum

Dynamics

the boundary condition

The delta function side of B.5.12) K because varies discontinuouslyat / = t0. o The particular form of the propagator is, of course,dependent n the to which the particle is subjected.Consider,as an particular potential example,a free particle in one dimension. The obvious observable that commutes with H is momentum; \\p') is a simultaneous eigenket of the operatorsp and H:
\342\200\22410)

K(x'\\t\\x', t0) = 0, for t < t0 is neededon the right-hand 8(t

B.5.13)

/2

\\

2m

/>'>\302\246

B.5.14)

The momentum eigenf unction is just the transformation function of Section 1.7 A.7.32)] is of the plane-waveform. Combiningeverything, we which [see have

dp'expip\\x\"-x')ip'z(t-t0) 2mh
The integral can be evaluated by completing the square in the exponent. Here simply recordthe result: we

B.5.15
im(x\"
\342\200\224

x') . B.5.16

This expression may be used,for example, to study how a Gaussianwave out as a function of time. packetspreads For the simple harmonic oscillator, where the wave function of an energy eigenstate is given by

un(x)exp

iEnt

mco \\1/4 mco

i

\342\200\224

mcox

exp|\342\200\224in

XHn
the

X

exp

- /col

n

+

\342\200\224

Ir

B.5.17)

propagatoris given by

K{x ,t\\x ,ro)=
X

T 27rihsin[co(tr to {(x\022

imco

in[co(r tQ)]

-

+ jc/2)cos[<o(/ tQ)]-2x\"x'}

-

B.5.18

2.5.Propagators

and Feynman Path Integrals

113

One way to prove this is to use

1

exp

(W2)

B.5.19
which

is found

in

Notice that

I 786). t can alsobe obtained using the a, operator method (Saxon1968, 144-45)or, alternatively, the path-integral method to be describedlater.
a1*

bookson specialfunctions (Morseand Feshbach1953,

particle initially localizedpreciselyat x' will return to its original position with certainty at 277/10 D77/10, nd so forth) later. a Certain spaceand time integrals derivablefrom K(x'\\ x',t0) are of considerablenterest. Without lossof generality we set t0 = 0 in the followi The first integral we consideris obtained by setting x// = x/ and over all space.We have integrating
t\\
following.

is a B.5.18)periodicfunction of / with angular frequencyco,the classicaloscillator frequency. This means, among other things, that a

jd*x'K(x\\t\\x'9O)
a a

- lka't

B.5.20

observethat setting x' = This result is anticipated;recalling B.5.10),we x\" and integrating are equivalent to taking the trace of the time-evolution But operator in the x-representation. the trace is independentof repreit can be evaluated more readily using the {\\a')} basis where representations; the time-evolution operator is diagonal,which immediately leads to the is just the \"sum over states,\" Now last line of B.5.20). we seethat B.5.20) In reminiscentof the partition function in statistical mechanics. fact, if we continue in the t variable and make t purely imaginary, with analytically P defined by =T
real and positive, we can identify
a
with B.5.20)

B-5.21
the partition
function

itself:

B.5.22

For this reasonsomeof the techniquesencounteredin studying propagators in quantum mechanicsare also useful in statisticalmechanics.

114

Quantum

Dynamics

transform of G(t): the Next, let us consider Laplace-Fourier

G(E)=

= -i
i\\

Too

dtG(t)exp(iEt/h)/h

|

dt

2j exp(-iEa't/h)exp(iEt/h)/h. B.5.23) a

The integrand here oscillates But we can make the integral indefinitely. meaningful by letting E acquire a small positive imaginary part:

E^E + ie.
We then

B.5.24)

obtain, in the limit e -> 0, a'

Observenow that the completeenergyspectrum is exhibitedas simple poles If of G(E) in the complex ?-plane. we wish to know the energyspectrum of of a physical system, it is sufficient to study the analytic properties G(E).

Propagator as a Transition Amplitude To gain further insight into the physical meaning of the propagator, we wish to relate it to the concept of transition amplitudes introduced in Section 2.2. ut first, recall that the wave function which is the inner B w productof the fixed position bra (x'| ith the moving state ket f0; t) can alsobe regardedas the inner product of the Heisenberg-picture position bra r (x', |, which moves \"oppositely\" with time, with the Heisenberg-picture state ket the f0), which is fixed in time. Likewise, propagator can also be written as

|a,

|a,
X\"

,

t'y' / 1=7 /Y//|/7/\\//7/lY/\\fhYn f,x,toj Z^\\X ?\\a lx /CAP
\\a

a

a

= <x\",f|x',fo>,
where
t\\

B.5.26)

are to be understood as an eigenket and an \\x\\ t0) and (xr/, eigenbraof the position operator in the Heisenberg picture.In Section2.1 we showed that (b\\ t\\a'), in the Heisenberg-picture notation, is the probfor a system originally preparedto be an eigenstate of A amplitude with eigenvalue a' at some initial time tQ = 0 to be found at a later time t in an eigenstate of B with eigenvalue b\\ and we called it the transition there is nothing amplitude for going from state \\a') to state I&').Because about the choice of the time difference t tQ is special
probability
\342\200\224

t0\342\200\224only

2.5.Propagators
relevant\342\200\224we

and Feynman Path Integrals

115

can identify (x\", t\\x\\ t0) as the probability amplitude for the particle prepared at t0 with position eigenvaluex' to be found at a later time / at x\". Roughly speaking, (x\", f|x',f0) is the amplitude for the particle to go from a space-timepoint (x',t0) to another space-time point is (x\", t), so the term transition amplitude for this expression quite apappropriate. This interpretation is, of course,in complete accord with the t;x\\ t0). interpretation we gave earlier for K(x'\\ Yet another way to interpret (x\", t\\x\\ t0) is as follows. As we emphasizedearlier, |x',0) is the position eigenket at t0 with the eigenvalue t x' in the Heisenbergpicture. Becauseat any given time the Heisenbergof picture eigenkets an observablecan be chosenas basekets,we can regard (x\", t\\x\\ t0) as the transformation function that connects the two sets of basekets at different times. Soin the Heisenberg icture, time evolution can p be viewed as a unitary transformation, in the senseof changing bases,that connects one set of base kets formed by (|x',0)} to another formed by / i p (|x\", )}. his is reminiscentof classical hysics,n which the time developt T of a classicaldynamic variable such as x(t) is viewedas a canonical (or contact) transformation generated by the classical Hamiltonian
development

1980, (Goldstein 407-8). It turns out to be convenient to use a notation that treats the space and time coordinates ore symmetrically. To this end we write (x\", t\"\\x\\ t') m in place of (x\",\\x\\t0). Because any given time the position kets in the at t form a complete set, it is legitimate to insert the identity picture Heisenberg
operator written as
jd3x\"\\x\",

r\"><x\",

t\"\\

=1
two

B.5.27
evolution from

f\";by

at any

we For place desire. example,considerthe time
dividing

the time interval

, we have

(/',t'\")

t' to
and

into

parts, (t\\t\")

, /'\" (x'\", /\"'|x','> = jd3x\"(x'\" |x\", f \"><x\", t\"\\x'91'), /
'\"

>t\">t').B.5.28

We call this the compositionproperty of the transition amplitude.*Clearly, we can divide the time interval into as many smaller subintervals as we wish. We

have
, t\"\"\\x\\ V)

=

jd3x
X

'\"

fd3x\"(x\"\"9 t\"\"\\x

'\"

,t

'\" '\{x") , t'\" |x\",

t\

<x\", t\"\\x\\

t')9

(t\"\"

> t'\"> t\" > t'),
as the

B.5.29

in *The analogue of B.5.28) probability theory is known equation, and in diffusion theory, the Smoluchowsky equation.

Chapman-KolmogoroflT

116
infinitesimal

Quantum

Dynamics

and so on. If we somehowguessthe form of (x\", t\"\\x\\ t') for an infinitesitime interval (between V and t\" = t'+dt),weshould be able to obtain the amplitude (x\",\"\\x\\ t') for a finite time interval by compounding the t appropriatetransition amplitudesfor infinitesimal time intervals in a manner This analogous to B.5.29). kind of reasoning leads to an independent formulation of quantum mechanics due to R. P. Feynman, publishedin to 1948, which we now turn our attention. Path Integrals as the Sum Over Paths Without loss of generality we restrict ourselves to one-dimensional like problems.Also, we avoid awkward expressions
N times

x'\"

the by using notation such as xN. With this notation we consider transition for a particle going from the initial space-time amplitude point (xl9 tx) to The entire time interval between tY and the final space-time point (xN, tN). equal parts: tN is divided into N
\342\200\224

1

(N-l)
Exploiting the compositionproperty, we obtain
\\xn> ^n\\xi->

B.5.30)

h) = I \"xn-iJdxN_2

J dx:

B.5.31
To visualize this pictorially, we considera space-time plane, as shown in The 2.2. initial and final space-timepoints are fixed to be (xl9 tY) and Figure (xN,tN), respectively.For each time segment, say between tn_x and tn, we are instructed to considerthe transition amplitude to go from (xn_l,tn_l) to (xn,tn); we then integrate over x2, xN_v This means that we must sum overall possible aths in the space-timeplane with the end points fixed. p Before proceeding further, it is profitable to review here how paths appear in classicalmechanics. Supposewe have a particle subjectedto a force field derivable from a potential V(x).The classicalLagrangian is written as

x39...,

^classical(*>*)

=

\342\200\224

~ H*)

\342\200\242

B.5.32

Given this Lagrangian with the end points (xl9 tx) and (xN, tN) specified,we do not considerjust any path joining (xl9 tx) and (xN, tN) in classical t O mechanics. n the contrary, there existsa unique path that correspondso

2.5.Propagators
t

and Feynman Path Integrals

117

(XN,

tN)

f/V-1

FIGURE

2.2.

Paths in

xf-plane.

the actual motion of the

classical article.For example, given p

V(x) = mgx,

(xl9tx) =

(xN9 tN)

=

g

B.5.33)
where h may stand for the height of the Leaning Towerof Pisa, the classical path in the jc/-planecan only be

x
which

\342\200\224

h

\342\200\224

2

'

B.5.34)

More generally, according to Hamilton's principle, the unique path is that minimizes the action, defined as the time integral of the classical
Lagrangian:

B.5.35)
from which

Lagrange's quation of motion can be obtained. e

Feynman's Formulation The basic differencebetween classical echanicsand quantum mem mechanics should now be apparent. In classical echanicsa definite path in m the jcf-planeis associated with the particle's motion; in contrast, in quantum mechanics all possiblepaths must play rolesincluding those which do not bear any resemblanceo the classical ath. Yet we must somehowbe able to t p classical echanicsin a smooth manner in the limit h 0.How m reproduce are we to accomplish this?
-\302\273

118

Quantum

Dynamics

As a young graduate student at Princeton University, R. P.Feynman I tried to attack this problem. n looking for a possible clue, he was said to be a mysterious remark in Dirac's ook which, in our notation, b intrigued by amounts to the following statement:

exp

'h \"t ^classical VX X)
>

h

A , t correspondso (x2,/2l-x:i^

.

,

.

. h/\\

to\" Feynman attempted to make senseout of this remark. Is \"corresponds the same thing as \"is equal to\" or \"is proportional to\"? In so doing he was led to formulate a space-timeapproach to quantum mechanics based on path integrals. In Feynman's formulation the classical ction plays a very important a role. or compactness, introduce a new notation: F we

= S(n,n-l) J'\" <//Lclassicai(*,*).
\342\200\224

B.5.36)

Because 1)is defined only after a ?ciassicai is a function of x and x, S(n,n definite path is specifiedalong which the integration is to be carried out. So is even though the path dependence not explicit in this notation, it is understood that we are considering a particular path in evaluating the integral. Imagine now that we are following some prescribedpath. We
(x\302\253-i>
'\302\253)\342\200\242 \342\200\224

concentrate our attention on a small segmentalong that path, say between K-i)and (xn> Accordingto Dirac,we are instructed to associate l)/h]with that segment.Going along the definite path we are exp[/\\S(>7, n set to follow, we successively o multiply expressions f this type to obtain

n
contribution

N

iS(n,n 1) = exp h
\342\200\224

h

= S(n,n-1) exp iS(N9l) h
rather,

B.5.37)
This does not yet give (xN,tN\\xv
to
this equation is the contribuparticular path we have considered. We must still integrate over x2,x3,...,x/v_1. same time, exploiting At the the composition property, we let the time interval between tn_x and tn be for infinitesimally small.Thus our candidate expression (xN,tN\\xl9 tx) may be written, in someloosesense,as
tx)\\

(xN, tN\\xv

tx) arising from the

all paths

E

exP

h

B.5.38)

where the sum is to be taken over an innumerably infinite set of paths! Before presenting a more preciseformulation, let us see whether l considerations long this line make sensein the classicalimit. As h -> 0, the a in B.5.38) oscillates so there is a tendency for very violently, exponential cancellation among various contributions from neighboring paths. This is

2.5.Propagators

and Feynman Path Integrals

119

f for becauseexp[iS/h] some definite path and exp[iS/h]or a slightly o different path have very different phasesbecauseof the smallness f h. So most paths do not contribute when h is regardedas a small quantity. However, there is an important exception. Supposethat we considera path that satisfies

= 8S(N,l) 09

B.5.39

where the change in S is due to a slight deformation of the path with the end points fixed.This is preciselythe classical ath by virtue of Hamilton's p W principle. e denotethe S that satisfiesB.5.39)Smin. We now attempt to by deform the path a little bit from the classical ath. The resulting S is still p equal to Smin to first order in deformation. This means that the phase of d exp[iS/h]oes not vary very much as we deviate slightly from the classical even if h is small. As a result, as long as we stay near the classical path I path, constructiveinterferencebetween neighboring paths is possible.n the h the major contributions must then arise from a very narrow limit, strip (ora tube in higher dimensions)containing the classical ath, as shown p in Figure 2.3. Our (or Feynman's) guessbasedon Dirac's ysterious remark m makes good sensebecausethe classical ath gets singled out in the h -> 0 p
-\302\2730

limit.

To formulate Feynman'sconjecturemore precisely, us go back to let where the time difference tn tn_l is assumed to be (xn,tn\\xn_l, tn_l), infinitesimally small. We write
\342\200\224

1
\\Xn-> *n\\Xn-l>
'\302\253-!/
\342\200\224

exp

iS(n9n-l)
h

B.5.40

where we evaluate S(n,n 1)in a moment in the A/ -> 0 limit. Notice that we have inserted a weight factor, l/w(A/), which is assumedto depend only on the time interval tn tn_x and not on V(x).That such a factor is neededis clear from dimensional considerations; according to the way we
\342\200\224

(xN,

U) FIGURE

2.3.

Paths important

in the h

\342\200\224

0 limit.

120

Quantum

Dynamics

normalized our position eigenkets,(xn,tn\\xn_l,tn_l) must have the dimenof 1/length. We now look at the exponential in B.5.40). task is to evaluate Our the the A/ limit of S(n,n Because time interval is so small, it is legitimate to make a straight-line approximation to the path joining and (xn,tn) as follows:
dimension
-\302\2730

-1).

n,n-l)= dt\\^-v(x)
I'\"

m

T
As an tion now B.5.40) becomes

Ar

w example, e considerspecificallythe

free-particlecase, V

0.Equa-

B.5.41

exp

B.5.42)

We seethat the exponent appearing here is completelyidentical to the one The readermay in the expression for the free-particlepropagator work out a similar comparison for the simple harmonic oscillator. We remarked earlier that the weight factor l/w(Af) appearing in is assumedto be independent of V(x),so we may as well evaluate it for the free particle.Noting the orthonormality, in the senseof 6-function, of Heisenberg-picture position eigenketsat equal times,

B.5.16).

B.5.40)

Xn-\\)->

B.5.43)

we obtain
m

B.5.44)

where we have used
\302\24600

m

B.5.45a

and
lim m

exp 2/iA/

This weight factor is, of course,anticipated from the expression the for free-particlepropagator B.5.16). To summarize,as A/ we are led to
-\302\2730,

m

exp

h

B.5.46

2.5.Propagators

and Feynman Path Integrals

121
amplitude
with
\342\200\224

The final expression the for
x,

transition

tN

tx finite

is

*i)

=

lim

m
N

x jdxN_ljdxN_2-\"dx2 j
-\302\273oo

exp

iS(n9n-l)
h

B.5.47)
where the jV limit is taken with xN and tN fixed. It is customary here to define a new kind of multidimensional (in fact, infinite-dimensional)
integral

operator

JfX\"9[x(t)] v

=

N-2

jdx

B.5.48
and write

as B.5.47)

j

*n

dt

i. ^classical (x, x)
h

. B.5.49

This expression known as Feynman's path integral. Its meaning as the sum is over all possiblepaths should be apparent from B.5.47). Our steps leading to B.5.49) not meant to be a derivation. are Rather, we (or Feynman) have attempted a new formulation of quantum o mechanicsbasedon the concept f paths, motivated by Dirac's ysterious m remark.The only ideaswe borrowedfrom the conventional form of quanmechanicsare A) the superpositionprinciple (usedin summing the concontributions from various alternate paths),B) the compositionproperty of the in 0 limit. transition amplitude, and C) classicalcorrespondence the h Even though we obtained the same result as the conventional theory for the free-particle case,it is now obvious, from what we have doneso far, that Feynman'sformulation is completelyequivalent to Schrodinger's ave w mechanics.We conclude section by proving that Feynman's expression this for (xN, tN\\xl9 tY) indeedsatisfiesSchrodinger's time-dependentwave equain the variables xN9 tN, just as the propagator defined by B.5.8).
quantum
\342\200\224>

equation

We start with

=

J
00

i->

h)
h

lim\\

{xN-xN_x) /FA/
A/

\\2h)
\\

N-l> '/V-

B.5.50

122 where we have assumedtN and
\342\200\224

Quantum

Dynamics

tN_Y

to

be infinitesimal. Introducing

= xn \" xn-\\
letting xN

B.5.51
iVAt
\\

-> x and tN->t + A/, we obtain
00

(x,t+ At\\xl,tl) = iJ
As
this

2hAt

h

B.5.52)
is evident from B.5.45b), the limit At -> 0, the major contribution to in comes from the ? 0 region. It is therefore legitimate to integral expand (x ?, t\\xx, tx) in powersof ?.We also expand (x,t + At\\xv ?x and iVht/h) in powersof A/, so
\342\200\224 \342\200\224

exp(\342\200\224

(x,t\\x1, tx
lirihLt J_ oo exp
X

m

i

OO

2hAt

1-

h

(x^lx^t^ + l

?

2

\\

B.5.53)

where we have dropped a term linear in $ becauseit vanishes when integrated with respectto The (x,t\\x^ ^) term on the left-hand sidejust side because of B.5.45a) matches the leading term on the right-hand terms first order in Af, we obtain Collecting

?.

= Atj^(x,t\\xl,tl)
where we have used

m

lirihAt

j

ihAt\\3/2l d2 m 2 dx (x,t\\x1,tl)

-\\-)AtV(x,t\\xl,tl),

B.5.54)

m

B.5.55
In
this

obtainedby

seethat (x, t\\xl9
d_ dt

differentiating

time-dependent wave equation: tx) satisfiesSchrodinger's
h 2
\\

with B.5.45a) respectto A/.

manner we

2m

dx

B.5.56
Thus we can conclude that (x,t\\xv tx) constructed according to Feynman's is wave prescription the sameas the propagator in Schrodinger's mechanics.

2.6.Potentials

and Gauge Transformations

123

Feynman'sspace-timeapproach based on path integrals is not too convenient for attacking practical problems in nonrelativistic quantum mechanics. ven for the simple harmonic oscillator it is rather cumbersome E to evaluate explicitly the relevant path integral.* However,his approach is extremfely gratifying from a conceptual point of view. By imposing a certain set of sensiblerequirementson a physical theory, we are inevitably led to a formalism equivalent to the usual formulation of quantum mechanics. It makes us wonder whether it is at all possible to construct a sensible alternative theory that is equally successfulin accounting for microscopic phenomena. Methods based on path integrals have been found to be very s powerful in other branches of modern physics, uch as quantum field theory In and statistical mechanics. this book the path-integral method will appear again when we discussthe Aharonov-Bohmeffect.*

AND 2.6. OTENTIALS P

GAUGETRANSFORMATIONS

Constant Potentials
In classicalmechanics it is well known that the zero point of the potential energy is of no physical significance.The time development of dynamic variables such as x(/) and L(t) is independent of whether we use F(x)or V(x)+Vo with Vo constant both in spaceand time. The force that appears in Newton's second law depends only on the gradient of the potential; an additive constant is clearly irrelevant. What is the analogous situation in quantum mechanics? We look at the time evolution of a Schrodinger-picturestate ket subject to some potential. Let to;t)be a state ket in the presenceof s F(x),and f0; f), the correspondingtate ket appropriate for

|a,

|a,

= V(x)+V0.

B.6.1)

To be precise us agree that the initial conditions are such that both kets let coincide with \\<x) at / = t0. If they representhe same physical situation, this t can always be done by a suitable choice the phase. Recalling that the of state ket at / can be obtained by applying the time-evolution operator
reader is challenged to solve the simple harmonic oscillator problem using the path integral method in Problem 2-31. *The reader who is interested in the fundamentals and applications of path integrals may consult Feynman and Hibbs 1965.

The

Feynman

124
, t0) to the state ket at f0, we obtain
_^_

Quantum

Dynamics

F

2m

h

= exp
In other

h

B.6.2)

words, the ket computed under the influence of V has a time For d dependenceifferent only by a phase factor exp[to)/h]. iVQ(t with this means that if the time dependence computed stationary states, time dependence omc V(x) is exp[ iE(t to)/h\\ then the corresponding In other words,the use with V(x)+Vo is exp[- + V0)(t i(E computed to)/h]. of V in placeof V just amounts to the following change:

-

\342\200\224

\342\200\224

-

,

B.6.3

which the reader probably guessed immediately.Observableeffectssuch as the time evolution of expectation values of (x) and (S) always dependon the Bohr frequencies that characterize the energy differences[see sinusoidaltime dependence expectation values are the same whether we of use V(x) or V(x)+Vo. In general, there can be no differencein the expectai values of observablesf every state ket in the world is multiplied by a

B.1.47)];

expectation

common factor exp[iV0(t to)/h]. Trivial as it may seem, we see here the first example of a class of transformations known as gaugetransformations.The change in our convenfor the zero-point energy of the potential
convention

-

B.6.4)
must

be accompanied a change in the state ket by

|a,fo;f>->exp
Of course,his change implies the t

h

a,to;t).

B.6.5

following

change in the wave function:

h

B.6.6
but

Next we considerVo that is spatially uniform then easily seethat the analogue of B.6.5) is
rt dt h

dependenton time.

We

-i M')

B.6.7)

Physically, the use of V(x)+V0(t) in place of F(x)simply means that we are choosinga new zero point of the energy scaleat each instant of time.

2.6.Potentials

and Gauge Transformations

125

Interference
\302\246

region

FIGURE

2.4.

Quantum-mechanical

interference

to detect

a potential

difference.

Even though the choice of the absolute scale of the potential is are arbitrary, potential differences of nontrivial physical significanceand, in can be detectedin a very striking way. To illustrate this point, let us fact, A beam of chargedparticles considerthe arrangement shown in Figure I is split into two parts, each of which enters a metallic cage.f we so desire, we can maintain a finite potential difference between the two cages by be visualizedas a turning on a switch, as shown.A particle in the beam can wave packet whose dimension is much smaller than the dimension of the S cage. upposewe switch on the potential difference only after the wave packetsenter the cagesand switch it off before the wave packetsleave the no T cages. he particle in the cage experiences force becauseinsidethe cage the potential is spatially uniform; hence no electric field is present.Now let the us recombine two beam componentsin such a way that they meet in the of of Because the existence the potential, interference region of Figure As each beam component suffers a phasechange, as indicated by B.6.7). a result, there is an observableinterference term in the beam intensity in the

2.4.

2.4.

interference region, namely,

cos(<>!
where

-

B.6.8)

B.6.9)
no the particle experiences force, there is an has observable effect that dependson whether V2(t)-Vx(t) been applied. in the limit h -> 0, the Noticethat this effect is purely quantum mechanical; interesting interferenceeffectgetswashed out becausethe oscillationof the

So despite the fact

that

cosinebecomes infinitely rapid.*
* This gedanken experiment is

experiment

the Minkowski-rotated to be discussed later in this section.

form

of the Aharonov-Bohm experi-

126
Gravity in Quantum

Quantum

Dynamics

Mechanics

There is an experiment that exhibits in a striking manner how a Before describing we it, gravitational effect appearsin quantum mechanics. first comment on the role of gravity in both classical nd quantum mechaa
mechanics.

Considerthe classical quation of motion for a purely e
mx =

-

falling

body:

grav

= mgz.
\342\200\224

B.6.10

The massterm dropsout; so in the absence air resistance, feather and a of a la Galileo\342\200\224under the influenceof stone would behave in the same of gravity. This is, of course,a direct consequence the equality of the the B gravitational and the inertial masses. ecause massdoes not appearin m the equation of a particle trajectory, gravity in classical echanics is often said to be a purely geometrictheory. The situation is rather different in quantum mechanics. In the wave-mechanicalformulation, the analogue of B.6.10) is
way\342\200\224a f

h

2

\\

2m

grav

B.6.11

The massno longer cancels; instead it appearsin the combination h/m, so in a problemwhere h appears,m is alsoexpected appear.We can see to this also using the Feynman path-integral formulation of a falling body point based on
dt
n 1
\342\200\224

\\mx}

\342\200\224

mgz)

h

\342\200\236-/\342\200\236_!-A/-*0).

B.6.12

in Here that m appears the combination m/h. his is in sharp T again we see contrast with Hamilton's classical pproach, basedon a

8 fhdt

mx 2
\342\200\224

mgz

= 0,

B.6.13

where m can be eliminated in the very beginning. we Starting with the Schrodingerequation B.6.11),may derive the Ehrenfest theorem
dt

<x>

= gz.

-

B.6.14
appear\342\200\224in

a However, h doesnot appearhere, nor doesm. To see nontrivial quantummechanical effect of gravity, we must study effects in which h appears consequently where we expect the mass to contrast with purely gravitational phenomena in classical echanics. m
explicitly\342\200\224and

2.6.Potentials
Until

and Gauge Transformations

127

there the 1975, had beenno direct experiment that established of the w<I>grav term in B.6.11). be sure, a free fall of an To presence elementaryparticle had beenobserved,but the classical quation of motion e the Ehrenfest theorem B.6.14), h doesnot to where account for this. The famous \"weight of photon\" experiment of V. Pound and collaborators id not test gravity in the quantum domain either because d measureda frequencyshift where h doesnot explicitly appear. they On the microscopic scale,gravitational forces are too weak to be T observable. o appreciate the difficulty involved in seeinggravity in readily bound-stateproblems,et us considerthe ground state of an electron and a l neutron bound by gravitational forces.This is the gravitational analogue of the hydrogen atom, where an electron and a proton are bound by Coulomb forces. the same distance, the gravitational force between the electron At and the neutron is weaker than the Coulombforce between the electron and the proton by a factor of ~ 2 X1039. The Bohr radius involved here can be
\342\200\224or

appear\342\200\224sufficed

obtainedsimply:

a0 =

\342\200\224

e me e

>

\342\200\224

\342\200\224,

GNmemn GNmAemn

B.6.15

where GN is Newton'sgravitational constant. If we substitute numbers in the equation, the Bohr radius of this gravitationally bound system turns out to be ~1031 or ~1013 years, which is larger than the estimated cm, light radius of the universe by a few ordersof magnitude! a We now discuss remarkablephenomenon known as gravity-induced interference. A nearly monoenergeticbeam of quantum practhermal split into two parts and then brought together as shown in Figure 2.5.n actual experiments the neutron beam is split and I bent by silicon crystals, but the details of this beautiful art of neutron the interferometry do not concern us here.Because size of the wave packet can be assumedto be much smaller than the macroscopicimensionof the d loop formed by the two alternate paths, we can apply the conceptof a classicaltrajectory. Let us first supposethat path A-> B -> D and path A-* C D lie in a horizontal plane. Becausethe absolute zero of the potential due to gravity is of no significance,we can set V = 0 for any phenomenon that takes placein this plane;in other words,it is legitimate to ignore gravity altogether. The situation is very different if the plane formed by the two alternate paths is rotated around segment AC by angle 5.This time the potential at level BD is higher than that at level AC by mg/2sin5, which means that the state ket associated with path BD \"rotates faster.\" This leads to a gravity-induced phasedifferencebetween the amplitudes for the two wave packetsarriving at Z). Actually there is also a gravity-induced with phasechange associated AB and alsowith CD,but the effectscancelas we comparethe two alternate paths.The net result is that the wave packet
particles\342\200\224in
practice,

neutrons\342\200\224is

-\302\273

128

Quantum

Dynamics

Interferenceregion
B

FIGURE

2.5.

Experiment

to detect gravity-induced

quantum

interference.

arriving at

D via path ABD suffers a phasechange
\342\200\224

exp
relative to

imngl2sin8 T
h

B.6.16

that of the wave packetarriving at D via path A CD,where T is the time spent for the wave packetto go from B to D (orfrom A to C) and mn9 the neutron mass.We can control this phasedifferenceby rotating the 8 can change from 0 to tt/2, or from 0 to plane of Figure the time spent T9 or /iAwavepacket, in terms of X, the de Broglie Expressing for wavelength of the neutron, we obtain the following expression the phase

2.5;

\342\200\224

tt/2.

difference:

~ <$>acd =

h

B.6.17)

optics.

In this manner we predict an observableinterferenceeffect that dependson angle 5, which is reminiscentof fringes in Michelson-typeinterferometersin

An alternative, more wave-mechanicalway to understand B.6.17 follows. Becausewe are concerned with a time-independentpotential, the sum of the kinetic energy and the potential energy is constant:

2m

+ mgz =

?.

B.6.18

The difference in height between level BD and level AC implies a slight difference in p, or X. As a result, there is an accumulation of phase differencesdue to the X difference.It is left as an exercise show that this to wave-mechanicalapproach also leadsto result B.6.17).

2.6.Potentials

and Gauge Transformations

129

1200
3 o o c o 3 A)

1000
800

600

-30
FIGURE

-20

-10

0

10

20 8.

30

2.6.

Dependence of gravity-induced

phase on the angle of rotation

is that What is interesting about expression B.6.17) its magnitude is neither too small nor too large; it isjust right for this interesting effectto be detected with thermal neutrons traveling through paths of \"table-top\" F A dimensions. or X =1.42 (comparable to interatomic spacing in silicon) As we rotate the loop for and lxl2 =10 cm2, we obtain 55.6 rn\\glxl^K/h2. we predict the intensity in the interferenceregion to plane gradually by we should see exhibit a series of maxima and minima; quantitatively It 55.6/27T= 9 oscillations. is extraordinary that such an effecthas indeed taken from a 1975 beenobservedexperimentally;seeFigure 2.6 experiment of R. Colella,A. Overhauser, and S. A. Werner. The phase shift due to
o
90\302\260,

gravity

gets washedout. The gravitational potenhas been shown to enter into the Schrodingerequation just as expected. This experiment also shows that gravity is not purely geometric at the on the quantum level because effectdepends (m/hJ.*
h
potential

as

-*0, the interferencepattern

We

is seen to be verified to well within 1%. emphasize that this effect is purely quantum mechanicalbecause

this doesnot imply that the equivalence principle is unimportant in understandof this sort. If the gravitational mass (wgrav) and inertial mass (winert) were The fact that we could unequal, {m/h)z would have to be replaced by m grav'\" inert correctly predict the interference pattern without making a distinction between marav and grav minert shows some support for the equivalence principle at the quantum level.
understanding

* However,
an effect

//r.

130

Quantum

Dynamics

Gauge Transformationsin Electromagnetism Let us now turn to potentials that appearin electromagnetism.We consideran electric and a magnetic field derivable from the time-indepenscalar and vector potential, <?(x) and A(x):
time-independent

E = -V4>,

B = vxA.

B.6.19

The Hamiltonian for a particle of electric charge e (e < 0 for the electron) p subjectedto the electromagneticfield is taken from classical hysicsto be e4>.
<f>

B.6.20)

In quantum mechanics and A are understood to be functions of the position operator x of the charged particle. Becausep and A do not The commute, somecare is neededin interpreting B.6.20). safest procedure is to write

-) A2.
In
this

B.6.21

form the Hamiltonian is obviously Hermitian. To study the dynamics of a chargedparticle subjected <? and A, let to in We can evaluate the time us first proceed the Heisenberg picture. derivative of x in a straightforward manner as
\342\200\224

dx1 =
dt

\\xt,H\\ in
rz\342\200\224

=

(p\342\200\224

eA,/c)
m

,

, yZ.b.lZ)

which shows that the operator p, defined in this book to be the generator of translation, is not the same as mdx/dt.Quite often p is called canonical momentum, as distinguished from kinematical (or mechanical) momentum, denotedby

II:

dt

v

c

v

7

Even

though

we have

for canonical momentum, the analogous commutator does not vanish for mechanical momentum. Instead we have

as the readermay easily verify.

Rewriting

],

B.6.24

B.6.25

the Hamiltonian as

n2 H= 2m +
\342\200\224

e<f>

B.6.26

and using the fundamental

commutation relation, we can derive the quan-

2.6.Potentials

and Gauge Transformations

131

tum-mechanicalversionof the Lorentz force, namely,
m

d2x dU = e dt
dt

dt

dt

B.6.27)

This then is Ehrenfest's theorem, written in the Heisenberg picture, for the of in the presence E and B. charged particle We now study Schrodinger's wave equation with <? and A. Our first task is to sandwich H between (x'| nd a f0; f). The only term with which we have to be careful is

|a,

\\oc,t0;t)

a,to;t)
,
\302\253A(x')

(*'\\a,to;t) B.6.28)

It

is important to emphasizethat the first V' in the last line can differentiate

both

(x'|a, 0 and A(x').Combiningeverything, /0;
1
2m

we have

M(x')

-

ih

V' M(x')
d
\342\200\224

-

e<t>(x')(x'\\a, t) = ih t0;

dt

(x'\\a, 0; t). t
continuity

B.6.29)
equation

From this expression readily obtain the we
dp_

dt

B.6.30)
(x'\\a,to;t)written as
me
substitution
\\p,

where p is |^|2 as before, probability flux j we have
m
which

with

but

for the

B.6.31

is just what we expectfrom the

B.6.32)
Writing

the wave function of alternative form for j, namely,

y/p

we exp(iS/h)[see B.4.18)],obtain

an

c

B.6.33)

132
which

Quantum

Dynamics

is to be compared with B.4.20). will find this form to be We convenient in discussinguperconductivity, flux quantization, and so on.We s also note that the spaceintegral of j is the expectation value of kinematical momentum (not canonical momentum) apart from 1/m:

n.
We
transformations

B.6.34)

in

are now in a position to discussthe subject of gauge transformaelectromagnetism.First, consider

+ 4>-+4> A,
with

A-^A,

B.6.35)

X constant, that is, independent of x and f. Both E and B obviously remain unchanged. This transformation just amounts to a change in the zero point of the energy scale,a possibility treated in the beginning of this w the section; ejust replaceV by e<f>. We have already discussed accompanyneededfor the state ket [seeB.6.5)],we do not dwell on this so change transformation any further. Much more interesting is the transformation
accompanying

4>-+4>, A-^A+vA, B.6.36 where A is a function of x. The static electromagneticfields E and B are are Both and unchanged under B.6.36). B.6.35) B.6.36) specialcasesof
C ut

A->A+vA,
<9A

B.6.37

which leave E and

B, given

by

1

c ot

=V

XA,

B.6.38

unchanged, but in the following we do not considertime-dependent fields and potentials. In the remaining part of this section the term gauge transformation refers to B.6.36). In classicalphysics observable effects such as the trajectory of a chargedparticle are independent of the gauge used,that is, of the particular of choice A we happen to adopt.Considera charged particle in a uniform magnetic field in the z-direction This magnetic field may be derived from

B.6.39

or also from

Ax=-By,

A=0,

Az

= 0.

B.6.41

2.6.Potentials

and Gauge Transformations

133
first

The secondform is obtained from the

by

B.6.42)
is indeedof the form of o Regardless f which A we may use, the trajectory of the chargedparticle with a given set of initial conditions is the same;it is just a in uniform circular motion when projected the with a uniform rectilinear motion in the z-direction. jcy-plane,superposed Yet if we look at px and py, the results are very different. For one thing, px is a constant of the motion when is used but not when is
which
helix\342\200\224a

B.6.36).

used.

B.6.41)

B.6.40)

Recall Hamilton's equations of motion:
dt

dx9

dt

dy9mmmm

In general, the canonical momentum p is not a gauge-invariant quantity; its numerical value dependson the particular gauge used even when we are referring to the same physical situation. In contrast, the kinematic momenII, or mdx/dt,that traces the trajectory of the particle is a gaugeinvariant as one may explicitly verify. Because and mdx/dtare p quantity, related via B.6.23), p must change to compensate for the change in A given
momentum

by
reasonable

transformations,

We now return to quantum mechanics.We believe that it is reasonto demand that the expectationvalues in quantum mechanicsbehave in a manner similar to the corresponding classicalquantities under gauge are not to change under gauge transfortransformations, so (x) and while (p) is expected change. to of Let us denoteby \\a) the state ket in the presence A; the state ket for the same physical situation when

B.6.42).

(II)

= A+vA B.6.44) of is usedin place A is denoted by |a). ere as well as A, is a function of H A, the positionoperator x. Our basicrequirementsare
and

B.6.45a
B-6-45b)
In addition, we require, as usual, the norm of the state ket to

be preserved:

(a\\a)= (a\\a).
We must

B.6.46)

construct an operator <&

that

relates \\a) to

|a):

B.6.47)

134

Quantum

Dynamics

and Invariance properties are B.6.45a) B.6.45b)guaranteed if and
eA We

B.6.48a)
evA
eA

c

B.6.48b)

assertthat

= exp
will

he

B.6.49)

is is all do the job. irst, ^ is unitary, so B.6.46) right. Second, .6.48a) F B satisfied becausex commutes with any function of x. As for obviously B.6.48b), note that just exp

-

ieA

he

fieA pexp[ he = exp

- ieA
he
\342\200\224

p,exp \\~hc~

/ ieA

+P
ieA

= -expi

ieA he

exp

+P

B.6.50)
where we have usedB.2.23b). The invariance of quantum mechanicsunder gauge transformations can alsobe demonstrated by looking directly at the Schrodingerquation. e Let of f0; /) be a solution to the Schrodingerequation in the presence A:

|a,

(p-eA/c)
2m

e<t>

B.6.51

The corresponding of solution in the presence A must satisfy
(p\342\200\224

eA/c\342\200\224

d_

2m We

dt

. B.6.52)

seethat

if the new ket

is taken to be

in

be satisfied; all we have to note is that exp

B.6.53) will accordance B.6.49), the new Schrodingerequation B.6.52) with then

(ieA

- ieA
he

eA
applying

evA

\\

ieA

B.6.54)

which follows from

twice. B.6.50)

2.6.Potentials

and Gauge Transformations

135

w also Equation B.6.53) implies that the corresponding ave equations are related via

he

B.6.55)

where A(x') is now a real function of the position vector eigenvalue x'. into This can, of course,be verified also by directly substituting B.6.55) w by Schrodinger's ave equation with A replaced A+ vA. In terms of p and , we seethat p is unchangedbut S is modifiedas follows:
eA .

B.6.56)

This is highly satisfactorybecause seethat the probability flux given by we gauge invariant. To summarize, when vector potentials in different gauges are used for the same physical situation, the corresponding state kets (or wave functions) must necessarilybe different. However,only a simple change is needed;we can go from a gauge specified by A to another specified by A + vA by merely multiplying the old ket (the old wave function) by The exp[ieA(x)/hc] (exp[/eA(x')/#<:]). canonicalmomentum, definedas the of translation, is manifestly gauge dependentin the sensethat its generator expectation value dependson the particular gauge chosen,while the kinemomentum and the probability flux are gauge invariant. is The reader may wonder why invariance under B.6.49) called invariance.This word is the translation of the German Eichinvarianz, gauge where Eich means gauge. There is a historical anecdote that goeswith the origin of this term. Considersome function of position at x: F(x). At a neighboring we obviously have point

is B.6.33)then

kinematic

But

B.6.57) follows: supposewe apply a scalechange as we go from xtox+rfxas B.6.58) ]|atx+</x
rescale(x)as follows: F

F(x+ dx) =- F(x)+ (vF)dx.

We must then

B.6.59) [ ] instead of B.6.57). combinationV + 2 is similar to the gauge-invariant The combination

V-(?)A

B.6.60)

encountered in B.6.32) exceptfor the absenceof /. Historically, H. Weyl unsuccessfully attempted to construct a geometric theory of electromagnetism based on Eichinvarianz the scale function 2(x) in by identifying

136 and with B.6.58) B.6.59) mechanics,V.
by comparing the vector potential
A

Quantum

Dynamics

Fockand F. London realized the importance of the quantum combination B.6.60), they recalledWeyl's earlier work and gauge-invariant

itself. With the

birth

of

2 with i times A. We are stuck with the term gauge invarianceeven though the quantum-mechanicalanalogue of B.6.58)
1at x

l- ie
~hc

\\A'dx
at x+ dx

B.6.61
to

would actually

to correspond \"phase change\" rather

than

\"scale change.

The Aharonov-Bohm Effect The use of vector potential in quantum mechanics has many farW someof which we are now ready to discuss. e start reaching consequences, with a relatively innocuous-looking problem. Considera hollow cylindrical shell, as shown in Figure 2.7a. e W assumethat a particle of charge e can be completelyconfined to the interior of the shell with rigid walls.The wave function is required to vanish on the inner (p = pa) and outer (p = ph) walls as well as at the top and the bottom. It is a straightforward boundary-valueproblem in mathematical physicsto obtain the energyeigenvalues. Let us now considera modified arrangement where the cylindrical shell encloses uniform magnetic field, as shown in Figure 2.7b. pecifia S

(a)
FIGURE
magnetic

(b)
shell

2.7.
field.

Hollow cylindrical

(a)

without

a

magnetic

field,

(b)

with

a

uniform

2.6.Potentials

and Gauge Transformations

137

cally, you may imagine fitting a very long solenoidinto the hole in the The middle in such a way that no magneticfield leaksinto the region p>paconditionsfor the wave function are taken to be the same as boundary before; the walls are assumed to be just as rigid. Intuitively we may conjecture that the energy spectrum is unchanged becausethe region with to B # 0 is completely inaccessible the charged particle trapped insidethe shell. However, quantum mechanics tells us that this conjecture is not

correct.

Even though the magnetic field vanishes in the interior, the vector theoremwe can infer that potential A is nonvanishing there; using Stokes's the vector potential neededto producethe magnetic field B ( = Bz) is

A=
where 4> is the

I-^U,

B.6.62)

unit vector in the directionof increasingazimuthal angle. In to solve the Schrodingerequation to find the energyeigenvalues attempting for this new problem,we need only to replacethe gradient V by V (ie/hc)\\;we can accomplishthis in cylindricalcoordinatesby replacingthe partial derivative with respectto as follows:

-

<f>

d<}>

[he) 2 '
cylindricalcoordinates: oz

recall the expression gradient for
V

in

= p-jop

+z\342\200\224

+ <j>p

\342\200\224.

o<f>

B.6.64)

The replacement B.6.63) results in an observable change in the energy spectrum, as the reader may verify explicitly. This is quite remarkable becausethe particle never \"touches\" the magnetic field; the Lorentz force i the particle experiencess identically zero in this problem, yet the energy levelsdependon whether or not the magneticfield is finite in the hole region t inaccessibleo the particle. The problemwe have just treated is the bound-state versionof what is commonly referred to as the Aharonov-Bohm effect.* We are now in a position to discussthe original form of the Aharonov-Bohm effect itself. Considera particle of charge e going aboveor belowa very long impenetraInsidethe cylinder is a magnetic field cylinder, as shown in Figure 2.8. parallel to the cylinder axis, taken to be normal to the plane of Figure 2.8. a So the particle paths above and below enclose magneticflux. Our object is to study how the probability of finding the particle in the interferenceregion B dependson the magneticflux.
impenetrable

*After a 1959 paper by Y. Aharonov and D.Bohm. Essentially 10years earlier by W. Ehrenberg and R. E. Siday.

the

same effect was discussed

138
Even to the
though this

Quantum

Dynamics

problem can be attacked by comparing the soluSchrodinger quation in the presenceand absenceof B, for e reasonswe prefer to use the Feynman path-integral method. pedagogical Let x2 and x^ be typical points in sourceregion A and interference region m B, respectively.We recall from classical echanics that the Lagrangian in the presencef the magnetic field can be obtained from that in the absence o of the magnetic field, denotedby ^chLskai* as follows:
solutions

classical

2

\\

dt

r@) . 'classical

,

?^L.a c dt
dt

B.6.65)

The corresponding change in the action for some definite path segment going from (xw_l9 tn_x) to (xw, tn) is then given by

B.6.66)

But this

last integral can be written as i dx e ft at c /ln-l
\\

i\"

.

e
n-l

\\

B.6.67)

where ds is the differential line element along the path segment,so when we consider the entire contribution from xx to xN, we have the following

change:

Flexp
All this

h

nexp

r

exp he
\342\200\224

A-Js

B.6.68)
Fortunately, we know from the theory of electromagnetismthat the line integral JA'dsis independent of paths, that is, it is dependentonly on the end points,as long as the loop formed by a pair of different paths doesnot enclose magnetic flux. As a result, the contributions due to A =?0 to all a paths going above the cylinder are given by a common phase factor;

is for a particular path, such as going above the cylinder. We must still sum over all possible paths, which may appearto be a formidable task.

B

inteference
region
FIGURE

2.8.

The Aharonov-Bohm

effect.

2.6.Potentials

and Gauge Transformations

139

similarly, the contributions from all paths going below the cylinder are multiplied by another common phase factor. In the path-integral notation we have, for the entire transition amplitude,
above

L below (exp

h

I I

above

{)L

/V

above-

below

exp \\hc

A*ds
below
*

B.6.69
The probability for finding the particle in the interferenceregion B depends on the modulus squaredof the entire transition amplitude and hence on the phase difference between the contribution from the paths going above and of below.The phase differencedue to the presence B is just e e e A*ds Amds He He above below

)iy

/V

B.6.70
standsfor the magneticflux insidethe impenetrablecylinder.This where means that as we change the magnetic field strength, there is a sinusoidal component in the probability for observing the particle in region B with a periodgiven by a fundamental unit of magnetic flux, namely,
\302\256B

= 4.135 X10\027 Gauss-cm2.
e\\

B.6.71

emphasize that the interference effect discussedhere is purely mechanical. Classically,the mption of a charged particle is dedetermined solely by Newton's secondlaw supplemented by the force law of Lorentz. Here,as in the previous bound-state problem, the particle can never enter the region in which B is finite; the Lorentz force is identically zero in all regionswhere the particle wave function is finite. Yet there is a of or striking interference pattern that dependson the presence absence a magnetic field inside the impenetrable cylinder. This point has led some that peopleto conclude in quantum mechanicsit is A rather than B that is fundamental. It is to be noted, however,that the observableeffectsin both i examplesdepend only on 3>a, which is directly expressiblen terms of B. t Experimentso verify the Aharonov-Bohm effecthave beenperformed using a thin magnetized iron filament calleda whisker *
We quantum

*One such

1443.

recent experiment

is that of A. Tonomura et

al., Phys.

Rev. Lett.

48 A982):

140

Quantum

Dynamics

Magnetic Monopole We concludethis section with one of the most remarkable predictof quantum physics,which has yet to be verified experimentally.An astute student of classical lectrodynamicsmay be struck by the fact that e there is a strong symmetry between E and B, yet a magnetic referred to as a magnetic monopole\342\200\224analogous to electric charge is equations. The sourceof a magnetic field peculiarly absent in Maxwell's observedin nature is either a moving electric charge or a static magnetic dipole,never a static magneticcharge. Insteadof
predictions

charge\342\200\224com-

charge\342\200\224commonly

m

B.6.72

analogous to
V*E

=

B.6.73

V*B actually vanishes in the usual way of writing Maxwell's equations. Quantum mechanics doesnot predict that a magneticmonopole must exist. However, it unambiguously requires that if a magnetic monopole is ever found in nature, the magnitude of magnetic charge must be quantized in terms of e, h, and c, as we now demonstrate. Supposethere is a point magneticmonopole, situated at the origin, of strength eM analogous to a point electriccharge. The static magnetic field is then given by
MU

B.6.74)

At first sight

it may

c appearthat the magnetic field B.6.74) an be derived
A

from

=
in

^A-cosfl)
spherical coordinates:

B.6.75

Recall the expression curl for
V

xA =
d<}>

r

1
r sin 0 30 dr

(^sin0) dAr

+
But

1 0- .sin0 r
A

dr
difficulty\342\200\224it

. B.6.76

z-axisF = it). In fact, it
singularity-free

vector potential B.6.75) one has
turns

\"Gauss's law\"

is singular on the negative t out to be impossibleo construct a singularvalid everywherefor this problem. o see this we first note T potential = 4ireM

closed surface

B.6.77)

2.6.Potentials

and Gauge Transformations

141

FIGURE

2.9.

Regions of validity for the potentials

A(I) and A(II)

surface boundary enclosing the origin at which the magnetic On monopole is located. the other hand, if A were nonsingular, we would
for
any

have

V(V XA) = O
everywhere;hence,
closed surface in

B.6.78)

B'da
volume inside

B.6.79)

contradiction with B.6.77). However, one might argue that becausethe vector potential is just a devicefor obtaining B, we need not insist on having a single expression for A valid everywhere.Suppose construct a pair of potentials, we

@<7T-e)
Adi)=_
\342\200\224

B.6.80a

cosfl)

B.6.80b

such that the potential A(I) can be used everywhereexceptinsidethe cone defined by 6 = 77 e around the negative z-axis;likewise,the potential A(II) can be used everywhereexceptinside the cone6 = e around the positive for z-axis;seeFigure 2.9. ogether they lead to the correct expression B T * everywhere.
*An alternative approach to this problem uses A(I) everywhere, but taking special careof the string of singularities, known asa Dirac string, along the negative z-axis.

142

Quantum

Dynamics

Consider now what happens in the overlap region e < 6 < it e, the where we may use either A(I) or A(II). Because two potentials lead to the same magnetic field, they must be related to each other by a gauge
\342\200\224

transformation. To

find

A

appropriate for
\\

this

problem we first note

that

l6M
r sin 6

U-

B.6.81
i0S

for Recalling the expression gradient in spherical coordinates, *1dA - 1 dA dA VA = r-j~+ 4>~^-E ~5T>
A

*--?*+

r MX B.6.82

we deducethat
A will

= -2eM<}>

B.6.83

do the job. Next, we consider the wave function of an electrically charged to As particle of charge e subjected magnetic field B.6.74). we emphasized earlier, the particular form of the wave function dependson the particular gauge used. In the overlap region wherewe may use either A(I) or A(II), the wave functions are, according to B.6.55), related to each corresponding
other by

*<\302\246\342\200\242)_

expJ^jSpti)^.).
must

B.6.84

Wave

chooseparticular gauge, the expansion of

each be single-valuedbecauseoncewe the state ket in terms of the positioneigenketsmust be unique. After all, as we have repeatedly ememphasized, the wave function is simply an expansion coefficientfor the state ket in terms of the position eigenkets. Let us now examine the behavior of wave function \\p(II) on the equator 6 = 77/2 with somedefinite radius r, which is a constant. When we the increase azimuthal angle <? along the equator and go around once,say from = 0 to = 2tt, \\p(II), as well as \\p(I), must return to its original value this becauseeach is single-valued.According to B.6.84), is possible only if functions \\p(I) and
\\//(II)
<f> </>

he quantized
in units

N=

+ 0,+1, 2,....
\\e\\.

B.6.85

So we reach a very far-reachingconclusion: he magneticcharges must be T
of

2\\e

B.6.

I electronicharge.t is amusing c

The smallest magnetic charge possibleis hc/2\\e\\, where e is the that once magneticmonopole is assumed a to exist, we can use B.6.85) so to speak, to explain why the backward,

Problems

143

electric chargesare quantized, for example, why the proton charge cannot

be 0.999972 times
We

\\e\\*

that quantum mechanics does not require magnetic monopolesto exist. However, it unambiguously predictsthat a magneticcharge, if it is ever found in nature, must be quantized in units of The quantization of magnetic charges in quantum mechanics was hc/2\\e\\. first shown in 1931 P.A. M. Dirac.The derivation given here is due to by T. T.Wu and C.N. Yang.

repeat once again

PROBLEMS

1.Considerthe spin-precession in problem discussed
\302\273\342\200\224(^
\\

the text. It can also

be solved in the Heisenberg icture. Usingthe Hamiltonian p
me

write the
operators

2.Look again at the Hamiltonian
typist

time.

equations of motion for the time-dependentoperHeisenberg S Sx(t)9 Sy(t),and Sz(t). olvethem to obtain Sx^y^z as functions of of Chapter made an error and wrote H as

1,Problem 11. Supposethe
your

What

attempting to solve the most general time-dependentproblem using an illegal Hamiltonian of this kind. (You may assume Hn = H22 = 0 for

principle is now violated? Illustrate

point explicitly by

3.An

simplicity.) electron is subject to a uniform, time-independentmagnetic field of strength B in the positive z-direction.At / = 0 the electron is known to be in an eigenstateof S h with eigenvalueh /2,where h is a unit vector, lying in the jcz-plane,that makes an angle /? with the z-axis. a. Obtain the probability for finding the electron in the sx = h/2state as a function of time.
\342\200\242

b. Find
c. For

4.

the expectationvalue of Sx as a function of time. your own peace of mind show that your answers make good sensein the extreme cases(i) /? -> 0 and (ii) /? -> tt/2. Let x(t) be the coordinate operator for a free particle in one dimension in the Heisenberg picture. Evaluate

*Empirically

established to an accuracy of

the equality in magnitude between the electron charge and the proton charge is four parts in 1019.

144

Quantum

Dynamics

5. Considera particle in

one dimensionwhose Hamiltonian is given

by

By

calculating [[//,x],x] prove
h2

2\\(a\"\\x\\a')\\2(Ea,-Ea,,)=2m,

6. Considera particle in

where \\a') is an energyeigenketwith eigenvalueEa,. three dimensionswhose Hamiltonian is given by

By

H calculating [x-p, ] obtain
d
dt

^

,

'
x

\"

/ P2
\\

m

To

identify

the

analogue

of the

virial

relation with the quantum-mechanicalanapreceding theorem it is essential that the left-hand sidevanish.
this

Under what condition would
satisfies the minimum

7. Consider a free-particle wave packet
uncertainty

happen?
in

one dimension.At

t

=0

it

relation

In addition, we know
Using the Heisenbergicture, obtain ((AjcJ), as a function of t(t > 0) p when ((AxJ)r==0 given. (Hint: Take advantage of the property of is the minimum-uncertainty wave packet you worked out in Chapter

Problem 18). 8. Let \\a') and \\a\") be eigenstates of a Hermitian operator A with The Hamiltonian opereigenvalues and a'\\ respectively
operator

1,

is given by

a'

(a'^a\.")

H=\\a')8(a\"\\+\\a\8(a%
where S is just a real number. a. Clearly, \\a') and |a\")are not eigenstatesof the Hamiltonian. Write down the eigenstates of the Hamiltonian. What are their energy eigenvalues? b. Supposethe system is known to be in state \\a') at t = 0.Write down the state vector in the Schrodingerpicture for t > 0.

Problems

145

is the probability for finding the system in \\a\") for / > 0 if the system is known to be in state \\a') at / = 0? d.Can you think of a physicalsituation corresponding this problem? to 9.A box containing a particle is divided into a right and left compartment by a thin partition. If the particle is known to be on the right (left) side with certainty, the state is representedy the positioneigenket |i?)(|L)) b
where we have neglectedspatial variations within each half of the The most general state vector can then be written as
\\a)

c. What

box.

= \\R)(R\\a)+\\LXL\\a),

where (R\\ot) and (L\\ot) can be regardedas \"wave particle can tunnel through the partition; this tunneling
characterized

functions.\"

The effect is char-

by the Hamiltonian

where A is a real number with the dimensionof energy. a. Find the normalized energy eigenkets. hat are the corresponding W energy eigenvalues? b. In the Schrodingerpicture the basekets \\R) and \\L) are fixed, and the state vector moves with time. Suppose system is represented the as given above at / = 0.Find the state vector t0 = 0;t) for by t > 0 by applying the appropriate time-evolutionoperator to \\a). c. Supposeat t = 0 the particle is on the right sidewith certainty. What is the probability for observing the particle on the left side as a function of time? d.Write down the coupledSchrodingerequations for the wave func(R\\a, ^o^O; )and (L|a,0=0; ). Show that the solutions to the / / t coupledSchrodingerequations are just what you expectfrom (b). e. Supposethe printer made an error and wrote H as

|a)

|a,

functions

explicitly solving the most general time-evolutionproblem with Hamiltonian, show that probability conservationis violated. 10. sing the one-dimensionalsimple harmonic oscillator as an example, U illustrate the difference between the Heisenbergpicture and the in Schrodinger icture. Discuss particular how (a) the dynamic variables p x and p and (b) the most general state vector evolvewith time in each of the two pictures. Consider a particle subject to a one-dimensional simple harmonic oscillator potential. Suppose t = 0 the state vector is given by at
By
this

11.

where p is the momentum operator and a is some number with dimension of length. Usingthe Heisenberg picture, evaluate the expecvalue (jc) for / > 0.
expectation

146

Quantum

Dynamics

12. . Write a

down the wave

in specified

Problem

11 / = 0.You may at .2 x

function

(in

coordinate space)for the state

use

o

'

/

/

\\

l/2\\

exP

mo)

13. onsidera one-dimensionalsimple harmonic oscillator, C
a. Using
a

b.Obtain a simple expression the probability that the state is found for in the ground state at t = 0.Doesthis probability change for t > 0?
\\

a+/\"V2^

- Imi0

{

JP_\\

a^
flt|w>

\\X\302\261maJ'

b. Checkthat 14.a. Using
prove

evaluate (m\\x\\n),

(m\\p\\n), (m|{jc, p)\\n),(m\\x2\\n), and (m\\p2\\n). the virial theoremholds for the expectation valuesof the kinetic and the potential energy taken with respect to an energy

eigenstate.

= <jc'|/>'> Birh)~l/2eip'x'/h (onedimension)
/ L/ 'i\\x\\(Y> \\ = inI ( D I* / If
\\ i I -A- I
\342\200\242*

*

/ IS 'iI* \\ ( Ti /
\\
\\C\302\261

I

>

\342\200\242

b.Considera one-dimensionalsimpleharmonic oscillator. tarting S
the

with

Schrodingerquation for the state vector, derive the Schrodinger e equation for the momentum-space wave function. (Make sure to the operator p from the eigenvalue/?'.)Can you guessthe distinguish
energy eigenfunctionsin momentum space? known as the correlation function, defined by

C 15. onsidera function,

where x(t) is the position operator in the Heisenberg picture. Evaluate the correlation function explicitly for the ground state of a one-dimensimpleharmonic oscillator. 16. onsideragain a one-dimensionalsimple harmonic oscillator.Do the C following algebraically,that is, without using wave functions. a. Construct a linear combination of |0) and such that (jc) is as large as possible. b. Supposethe oscillatoris in the state constructed in (a) at / = 0.What is the state vector for t > 0 in the Schrodingerpicture? Evaluate the expectation value (x) as a function of time for t > 0 using (i) the p picture. Schrodinger icture and (ii) the Heisenberg c. Evaluate ((AjcJ) as a function of time using either picture.
one-dimensional

|1)

Problems

147

17.Show for

the one-dimensionalsimple harmonic oscillator

= exp[ &2<0|jt2|0>/2],
A 18.

-

where x is the position operator. coherent state of a one-dimensional simple harmonic oscillator is defined to be an eigenstateof the (non-Hermitian)annihilation operator

a:

where A is, in general, a complex number, a. Prove that

b. Prove the minimum

is a normalizedcoherent state.
|X>

c. Write

as

uncertainty

relation for such a state.
00

=

LfM\\n).

of \\f(n)\\2 with respectto n is of the Show that the distribution Poissonform. Find the most probablevalue of n, hence of E. d. Show that a coherent state can also be obtained by applying the translation (finite-displacement)operator e~ipl/h (where p is the momentum operator, and / is the displacement distance) to

19. et L

the ground state. (See also Gottfried

1966, 262-64.)
TV

J\302\261

= ha^a^,
\302\261

+ Jz = -z(a\\a

- a*_a_),

=

\\+

_

where a

and a\\ are the annihilation and creation operators of two the usual simple independent simple harmonic oscillator satisfying harmonic oscillator commutation relations. Prove
2_

2

N

2

+1

20.Considera particle of mass m subject to a one-dimensionalpotential of
the following form:
/

~zkx2 oo

i

for

x> 0 for x < 0.

b.What

a. What is the ground-stateenergy?

is the expectationvalue (jc2)for the ground state?

148
A 21. particle in

Quantum

Dynamics

one dimensionis trapped between two rigid walls: 0, for 0 < jc < L oo, for x < 0, x > L. At t = 0 it is known to be exactly at x = L/2with certainty. What are the relative probabilitiesor the particle to be found in various energy f
Write down the wave eigenstates?
worry function

for

t

> 0.(You need not

about absolute normalization, convergence,and other mathemati-

mathematical

22.Considera

particle in one dimension bound to a fixed center by a 5-function potential of the form V( x) = vo8 (x), (v0 real and positive). Find the wave function and the binding energy of the ground state.Are there excitedbound states? 23.A particle of massm in one dimensionis bound to a fixed center by an attractive S-functionpotential:
\342\200\224

subtleties.)

At t = 0, the potential is suddenly switchedoff (that is, V= 0 for t > 0). Find the wave function for t > 0.(Be quantitative! But you need not attempt to evaluate an integral that may appear.) 24. A particle in one dimension (\342\200\224oo<jc<oo) is subjectedto a constant

V(x)= -\\8(x),(X>0).

force derivable from

energy spectrum continuous or discrete?Write down an for approximate expression the energyeigenfunctionspecifiedby E. Also sketchit crudely. b. Discussbriefly what changes are neededif V is replacedby

a. Is the

V=\\x,

K=X|jc|. 25.Consideran
electron confined to the interior of a hollow cylindrical shell whoseaxis coincides ith the z-axis. he wave function is required T w to vanish on the inner and outer walls, p = pa and ph9 and also at the top and bottom, z = 0 and L. a. Find the energyeigenfunctions.(Donot bother with normalization.) Show that the energyeigenvaluesare given by
Imn

2m e

mn

hr_\\

\\

)

I

JL,^>,.3,...,
YYX

where kmn'\\s the

/7th

root of the transcendental equation

b. Repeat the

B = Bz for 0 < p < pa. Note

same problem when there is a uniform magnetic field that the energy eigenvalues are ininfluenced by the magnetic field even though the electron never \" touches\"the magnetic field.

Problems

149

c. Compare,in
that quantization\"

particular, the ground state of the B = 0 problem with of the B # 0 problem.Show that if we require the ground-state energy to be unchanged in the presenceof B, we obtain \"flux

lirNhc

26.Considera particle moving

in one dimension under the influenceof a can be written as potential V(x). Suppose its wave function H P t)/h]. rovethat S(x,t) satisfiesthe classical amilton-Jacobi exp[/iS(jc, equation to the extent that h can be regardedas small in some sense. Show how one may obtain the correct wave function for a plane wave H by starting with the solution of the classical amilton-Jacobiequation with V(x)set equal to zero. hy do we get the exact wave function in W this particular case? for 27. Usingsphericalcoordinates, obtain an expression j for the ground and excitedstates of the hydrogen atom. Show, in particular, that for m!=?0 states, there is a circulating flux in the sense that j is in the direction of increasing or decreasing dependingon whether ml is positive or negative. 28. Derive B.5.16) obtain the three-dimensional generalization of and
<J>,

29.Define the partition
as in

B.5.16).

function

as

=
taking

Jd3x'K(x'9r9x'90)\\fi_it/h,
the ground-stateenergyis obtained by

Showthat B.5.20)-B.5.22).

_l_dZ
Z

Illustrate this for a particle in a one-dimensionalbox. 30. The propagator in momentum spaceanalogous to B.5.26) is given by for (p\", /|p',0). Derive an explicit expression (p\", t\\p\\ t0) for the freet particle case. 31.a. Write down an expressionfor the classicalaction for a simple harmonic oscillator for a finite time interval. b. Construct (xn,tn\\xn_l,tn_l) for a simple harmonic oscillator using Feynman's prescription for tn tn_1 = A? small. Keeping only terms up to order (A/J, show that it is in complete agreement with the 0 limit of the propagator given by B.5.26). t t0 32. State the Schwingeraction principle (seeFinkelstein 1973, Obtain 155). the solution for (x2t2\\xlt1) by integrating the Schwingerprinciple and for compareit with the correspondingFeynman expression Describethe classicalimits of these two expressions. l
\342\200\224

-

-\302\273

150

Quantum

Dynamics

33.Show that
34. a. Verify

in discussed Section2.6 leadsto phase-difference also expression .6.17 B

the wave-mechanics pproach to the gravity-inducedproblem a

35.Considerthe
generated

b.Verify

j given by Hamiltonian of a spinlessparticle of charge o presence f a static magnetic field, the interaction terms can by
Poperator Poperator

and B.6.25) B.6.27). with continuity equation B.6.30)

B.6.31). e. In

the

be gener-

c

>

f where A is the appropriate vector potential. Suppose,or simplicity, that B is uniform in the positive z-direction. Prove that the magnetic field the above prescription indeedleads to the correct expression the for with the magof the orbital magnetic moment (e/2mc)L interaction field B. Show that there is also an extra term proportional to + B2(x2 y2), and comment briefly on its physical significance. 36.An electron moves in the presenceof a uniform magnetic field in the z-direction (B= Bz). a. Evaluate
magnetic

where

=P

eA

n,+
eB\\h

eA y

b. By

comparing the Hamiltonian and the commutation relation obin (a) with those of the one-dimensionaloscillator problem, show how we can immediately write the energyeigenvaluesas
obtained

2 7,2

2m

me

n

1_

2
n

where hk is the continuous eigenvalueof the pz operator and nonnegativeinteger including zero. 37. Considerthe neutron interferometer.

is a

Interference !-::; region

Problems

151
that

Prove

successive axima m

the difference in the magnetic fields in the counting rates is given by
Airhc

that

produce two

where
\342\200\224

gn

(=
in

\342\200\2241.91)

[If eh/2mnc. you

is the neutron magnetic moment in units of had solved this problem in 1967, could have you

publishedit

PhysicalReview Letters

!]

CHAPTER 3

Theory of AngularMomentum

This chapter is concerned with a systematic treatment of angular momenand related topics.The importance of angular momentum in modern A physicscan hardly be overemphasized. thorough understanding of angumomentum is essential in molecular,atomic, and nuclear spectroscopy; angular-momentum considerationsplay an important role in scattering and collisionproblemsas well as in bound-state problems.Furthermore, anguangular-momentum in nuclear have important generalizations\342\200\224isospin concepts a physics,SUC),SUB)\302\256UA) in particle physics, nd so forth.
momentum angular

3.1. AND ROTATIONS

ANGULAR MOMENTUM COMMUTATION RELATIONS

Finite Versus Infinitesimal

Rotations
30\302\260

We recall from elementaryphysics that rotations about the same axis commute, whereasrotations about different axesdo not. For instance, a rotation about the z-axisfollowedby a rotation about the same z-axis is rotation followed by a rotation, both obviously equivalent to a about the same axis. However, let us considera rotation about the rotation about the x-axis, z-axis,denotedby /?z(tt/2),followed by a denoted by RxGt/2);compare this with a rotation about the jc-axis
60\302\260 60\302\260 30\302\260 90\302\260 90\302\260 90\302\260

152

Rotations 3.1.

and Angular Momentum

Commutation

Relations

153

followed by a rotation about the z-axis. he net results are different, as T from Figure we can see Our first basictask is to work out quantitatively the manner in which rotations about different axesfail to commute.To this end, we first recall how to representrotations in three dimensions by 3x3real, orthogonal matrices.Considera vector V with components Vx, Vv, and V2. When we rotate, the three components becomesome other set of numbers, Vx, Vv\\ and V/. The old and new components are related via a 3x3orthogonal
90\302\260

3.1.

matrix

R:

v
X

\\VX

V y
\\

R
>

K
1

C.1.1a

V' / *

\\

1>W

RRT=RTR=1,

C.1.1b
V'2 + V'2 r r z y

T where the superscript stands for a transpose a matrix. It is a property of of orthogonal matrices that
K2 + vy2

+ K2 =

C.1.2)

is automatically satisfied.

>

FIGURE

3.1. xample to illustrate E

the noncommutativity

of finite rotations.

154

Theory of Angular Momentum

To be definite, we considera rotation about the z-axis by angle The convention we follow throughout this bookis that a rotation operation while the coordinate axes affects a physical system itself, as in Figure remain unchanged.The angle is taken to be positive when the rotation in question is counterclockwisein the xy-plane, as viewed from the positive If z-side. we associatea right-handed screw with such a rotation, a positive rotation around the z-axis means that the screw is advancing in the W positive z-direction. ith this convention,we easily verify that

3.1,

<j>

<j>

cos<f>
sin<f>

\342\200\224

sin<J>

0

cos<? 0 0

I,

C.1.3)

different convention, in which a physical system rethe coordinate axes rotated, this same matrix with a a rotation of the x- and >>-axes, positive would have represented clockwise when viewed from the positive z-side.It is obviously important not to mix the two conventions! Someauthors distinguish the two approachesy using b \"activerotations\" for physical systems rotated and \"passiverotations\" for the coordinateaxesrotated. We are particularly interested in an infinitesimal form of Rz: remained

Had we adopted a
fixed
but
<f>

l0

\342\200\224

e

0 0

1-2
0 o

C.1.4)

where terms of order e3 and higher are ignored.Likewise, have we

1
0 0 and

10

0 )
\342\200\224

e

1-^
0

C.1.5a

1
0

1-

0

C.1.5b
z\342\200\224that

is, may be read from by cyclicpermutations of jc, y, x y, y z, z -* x. Compare now the effectof a j-axis rotation followed by an jc-axisrotation with that of an jc-axisrotation followed by a j^-axis
which

-*

-*

C.1.4)

3.1. Rotations

and Angular Momentum

Commutation

Relations

155

rotation. Elementary matrix manipulations lead to

1Rx(e)R(s)=
\342\200\224

0

1
e

\342\200\224

e

C.1.6a

l-e

and

1R(e)Rx(s)=
\342\200\224

0 e

1-

C.1.6b

From C.1.6a) C.1.6b) have the first important result:Infinitesimal and we rotations about different axesdo commute if terms of order e2 and higher are ignored.* The secondand even more important result concernsthe manner in which rotations about different axesfail to commute when terms of order e2are kept:

= Rx(e)Ry(e)-Ry(e)Rx(e) =R
where all terms of order higher derivation. We also have
than

0 0

0 0

0 0

-1,

C.1.7)
this

e2 have been ignored throughout

C.1.8
where any stands for

as

any

rotation

axis.Thus the

final

result can be written

C.1.9
This is an exampleof the commutation relations between rotation operabout different axes,which we will use later in deducing the angularmomentum commutation relations in quantum mechanics.
operations

vector

*Actually there is a familiar example of this in elementary mechanics. The angular velocity co that characterizes an infinitesimal change in rotation angle during an infinitesimal time interval follows the usual rule of vector addition, including commutativity of vector addition. However, we cannot ascribe a vectorial property to a finite angular change.

156
Infinitesimal

Theory of Angular Momentum

Rotations in Quantum Mechanics So far we have not used quantum-mechanicalconcepts. matrix The R is just a 3 X 3 orthogonal matrix acting on a vector V written in column matrix form. We must now understand how to characterize rotations in
quantum

to the original unrotated system. Given a rotation operation R, corresponding characterized by a 3x3orthogonal matrix /?, we associatean operator in the appropriate ket spacesuch that

mechanics. Because rotations affect physicalsystems,the state ket corresponding to to a rotated system is expected look different from the state ket corre-

C.1.10
where \\a)R and |a)stand for the kets of the rotated and original system, respectively.* Note that the 3x3orthogonal matrix R acts on a column matrix made up of the three components of a classical vector, while the The operator@(R)acts on state vectors in ket space. matrix representation of @(R),which we will study in great detail in the subsequent ections, s F dependson the dimensionality N of the particular ket spacein question. or TV = 2, appropriate of a for describing spin \\ system with no other degrees freedom, @(R)is represented a 2x2matrix; for a spin 1 system, the by appropriaterepresentationis a 3 X 3 unitary matrix, and so on. To construct the rotation operator @{R),it is again fruitful to examine first its properties under an infinitesimal rotation. We can almost how we must proceedby analogy. In both translations and time guess and evolution, which we studied in Sections1.6 respectively, the infinitesimal operators could be written as appropriate

2.1,

U? with

= l-iGe

C.1.11

a Hermitian operator G. Specifically,
n

r,
IT

e-^dx'

C.1.12

for an infinitesimal and

translation by a displacement dx' in the x-direction,

G-^-r, e-*dt
rotation

C.1.13

for an infinitesimal time evolution with time displacement dt. We know from classical mechanics that angular momentum is the generator of rotain much the same way as momentum and Hamiltonian are the of translation and time evolution, respectively. We therefore generators define the angular momentum operator Jk in such a way that the operator for an infinitesimal rotation around the kth axis by angle d<$> can be Thesymbol Q) stems from
the German word Drehung, meaning

rotation.

3.1. Rotations
obtained by
in

and Angular Momentum

Commutation Relations

157

letting

-r,
With C.1.11).
d<f>

e-^d<t>

C.1.14

Jk taken to be Hermitian, the infinitesimal rotation is guaranteed to be unitary and reducesto the identity operator in operator

the limit

-> 0.More generally,we have
h,

/ d<t>)=l- ~y

d<}>

C.1.15
unit

for a rotation about the direction characterized by a
infinitesimal angle d<f>. We stressthat in this

vector h by an

bookwe do not define the angular-momentum be x X p. This is important becausespin angular momentum, to h which our general formalism also applies, as nothing to do with xt and pr Put in another way, in classical echanicsone can prove that the angular m momentum defined to be xXp is the generator of a rotation; in contrast, in quantum mechanics we define J so that the operator for an infinitesimal rotation takes form C.1.15). A finite rotation can be obtained by compounding successively infinitesimal rotations about the same axis.For instance, if we are interested in a finite rotation about the z-axis by angle <?, we consider operatorto =
lim
00

1-1

z h

\\

N

N

In order to obtain the angular-momentum commutation relations, we need one more concept. s we remarked earlier, for every rotation R A represented a 3 X 3 orthogonal matrix R there existsa rotation operator by We 3>(R)in the appropriateket space. further postulate that @(R)has the same group properties R: as Rl = rt=> @(R)\\= @(R) Identity: C.1.17a

Closure:
Inverses:

= = R3 ^ S)(Rl)9{R2) $(R3)C.1.17b l =1=* = RRl= @(R)@-\\R) \\ C.1.17c
RXR2

= = Associativity: Rl{R1R2) {RlR1)R3 RXR2R2

C.1.17d

158

Theory of Angular Momentum

Let us now return to the fundamental commutation relations for rotation operationsC.1.9) written in terms of the R matrices. Its rotation operatoranalogue would read
/

1-

h

)

2h2 ]

(1 1

iJye
r

.2

I*)
UXE

1

1-

1

h

2h2

l-

h

2h2)
Equating

n

C.1.18
order e2 on

Terms of order e automatically drop out. we obtain both sidesof

C.1.18),

terms of

[jx,Jy\\ =ihJz.
Repeating this kind of argument
known
with

C.1.19

rotations about other axes,we obtain

[ji9Jj\\=iheiJkJk,

C.1.20

as the fundamental commutation relationsof angular momentum. In general, when the generators of infinitesimal transformations do not commute, the corresponding group of operations is said to be nonthe rotation group in three dimensions is Abelian. Becauseof non-Abelian. In contrast, the translation group in three dimensionsis Abelian becausept and p- commuteeven with i # We emphasize that in obtaining the commutation relations we have used the following two concepts:

C.1.20),

j.

C.1.20

1.Jk is the generator of rotation about the /cth axis.
2. Rotations about different
It
in
dimensions.

axesfail to commute.

is no exaggeration to say that commutation relations C.1.20) summarize a compact manner all the basicpropertiesof rotations in three dimen-

3.2. PIN\\ SYSTEMSAND S

FINITEROTATIONS

Rotation Operator for Spin \\ The lowest number, N9 of dimensionsin which the angular-momencommutation relations C.1.20) realized, is N =2.The reader has are already checkedin Problem 8 of Chapter 1that the operatorsdefined by
angular-momentum

C-2.1

3.2.Spin

\\

Systems and Finite Rotations

159

with satisfy commutation relations C.1.20) Jk replacedby Sk. It is not a priori obvious that nature takes advantage of the lowest dimensional realization of C.1.20), numerous experiments\342\200\224from atomic specbut to convince us that this is to nuclear magnetic resonance\342\200\224suffice troscopy in fact the case. Considera rotation by a finite angle about the z-axis.If the ket of the ket after rotation is a spin \\ system before rotation is given by
<J>

|a),

given by
\\a\\n

= Sd (<b)\\a\\
\342\200\2247-^1-

C 2 2\

with

C.2.3)
yJ.^.H)

To seethat this operator really rotates the physical system, let us look at its effect on (Sx).Under rotation this expectation value changes as follows:
Wjc/ We must
R\\a\\^x\\a/R

\\a|-^zW J^x-^zKV )\\a/'

therefore compute

exp
I

h

C.2.5)
We C.2.1).

r For pedagogicaleasonswe evaluate this in two different ways. Derivation Herewe use the specificform of Sx given by then obtain for C.2.5)

1:

Hi

exp
i

\"~\"
h

(|-><+l)}exp h

x

\342\200\224

Svsin<t>.

C.2.5):
exp
h

Derivation 2:Alternatively

C.2.6)
we may t use formula B.3.47)o evaluate

Sxexp

h

h

V.)\\h

+ ihS.
h2S.

1 %K[sz,[sz,[s2,sx)}}
n

)

^

-+

1-2!
= Sxcos<j>
\342\200\224

y

3!

Svsin<j>.

C.2.7)

160

Theory of Angular Momentum

Notice that in derivation 2 we usedonly the commutation relations for Si9 so this method can be generalized to rotations of systems with angular
momentum

higher

than

\\.

For spin \\, both methods give (Sx)-+ R(a\\Sx\\a)R (Sx)cos<t> (Sy)sin<t>,
\302\253

-

C.2.8)

where the expectation value without subscriptsis understoodto be taken with respectto the (old)unrotated system. Similarly,

C.2.9) (Sy) -+ (Sy)cos<t>+ (Sx)sin<t>. As for the expectation value of Sz, there is no change becauseSz commutes
with

C.2.10 <S,)-+(SZ). are Relations C.2.8), and C.2.9), C.2.10) quite reasonable. hey show that T when applied to the state ket, does rotate the rotation operator C.2.3),
expectation value of S around the z-axis by angle In other words,the expectation value of the spin operator behaves as though it were a classical vector under rotation:
</>.

@2(<t>):

C.2.11
where Rki are the elementsof the 3x3orthogonal matrix R that specifies the rotation in question.It should be clear from our derivation 2 that this I property is not restricted to the spin operator of spin \\ systems.n general, we have

IXC-2.12 ??

under rotation, where Jk are the generators of rotations satisfying the Later angular-momentumcommutation relations C.1.20). we will show that relations of this kind can be further generalizedto any vector operator. So far everything has been as expected. now, be preparedfor a But We on surprise! examine the effectof rotation operator C.2.3) a general ket, a little more closely. e W

C.2.13
seethat

h>(-|a>.C.2.14
The appearanceof the half-angle <f>/2 here has an extremely interesting

consequence.

Let us considera rotation by
\\a)

2*rr. We then

have

->-|a>.

C.2.15

3.2.Spin

\\

Systems and Finite Rotations

161

So the ket for the rotated state differs from the original ket by a minus = Att) rotation to get back to the same ket (</> sign.We would need a for the expectation with a plus sign.Notice that this minus sign disappears value of S becauseS is sandwichedby |a)and (a|, oth of which change b sign.Will this minus sign ever be observable?We will give the answer to this onceagain. interesting question after we discuss spin precession
360\302\260 720\302\260

R Spin Precessionevisited
in We now treat the problem of spin precession, lready discussed a from Section2.1, a new point of view. We recall that the basicHamiltonian of the problemis given by

(
m\342\202\254c

)

,

C.2.16

where
(a)

mec The time-evolutionoperator basedon this Hamiltonian is given by

_ =

\\e\\B

C.2.17)

C.2.18
we Comparing this equation with C.2.3), see that the time-evolution operhere is precisely same as the rotation operator in C.2.3) with set the equal to cor. In this manner we seeimmediately why this Hamiltonian causesspin precession. we and C.2.9), C.2.10),obtain Paraphrasing C.2.8),
operator
<J>

(Sx\\= <Sx>,=0coscor<Sv>,=0sincor,

-

= 27r/co,the spin returns to its original direction. This set of equations can be used to discuss spin precession a the of an electronlike particle which, however, is 210 times as heavy. The muon, muon magnetic moment can be determined from other experiments\342\200\224for example,the hyperfine splitting in muonium, a bound state of a positivemuon and an be eh/lm^c,just as expectedfrom Dirac'srelativistic of spin 2 particles. We will here neglect very small correctionsthat theory ( arise from quantum field theory effects). Knowing the magnetic moment we can predict the angular frequency of precession. o C.2.19) be and, in S can has beencheckedexperimentally.In practice, as the external magnetic fact, field causes the spin precession, spin directionis analyzedby taking advantage of the fact that electrons from muon decay tend to be emitted preferentially in the direction opposite the muon spin. to
After t
electron\342\200\224to

C.2.19a C.2.19b C.2.19c

162

Theory of Angular Momentum

Let us now look at the time evolution of the state ket itself. we Assuming that the initial (t = 0) ket is given by C.2.13),obtain after
time

= a910 0;t) = e~i0)t/2
until

a)

and we must wait acquires a minus sign at C.2.20) Expression t = 47r/coto get back to the original state ket with the same sign.To sum up, the period for the state ket is twice as long as the periodfor spin precession
2tt
precession

t = 2tt/(o,

\ +l0)t/2\\-)(-\a). \\-)(-

C.2.20)

0) 0)
Study

C.2.21a
2it Rotations

state ket

C.2.21b

Neutron Interferometry Experimentto
We now

parts\342\200\224path

describean experimentperformed to detect the minus sign the universe is multiplied by a minus sign, there will be no observableeffect.The only way to detect the predictedminus sign is to make a comparison between an unrotated state and a rotated state. As in gravity-induced quantum interference, discussed in Section2.6, e rely on the art of neutron interferometry to verify this w extraordinary prediction of quantum mechanics. A nearly monoenergeticbeam of thermal neutrons is split into two A and path B\\ seeFigure 3.2.ath A always goesthrough a P magnetic-field-freeregion; in contrast, path B enters a small region where a static magnetic field is present.As a result, the neutron state ket going via where T is the time spent in the path B suffers a phase change eTlOiT/2, B =? 0 region and to is the spin-precession frequency
in

Quite C.2.15). clearly,if every state ket in

\"

= ?f-:> (g,,\302\253-i.9i)
mpc

C.2.22)

for the neutron with a magneticmoment of gneh/2mc, as we can see we if

Interference
region B
FIGURE

3.2.

Experiment to study the predicted minus sign under

a 2-n

rotation.

3.2.Spin

\\

Systems and Finite Rotations

163

which C.2.17), is appropriate for the electron with When path A and path B meet again in the eh/2mec. the interference region of Figure 3.2, amplitude of the neutron arriving via

compare this
path

with

magnetic moment

B is

*

C.2.23

while the amplitude of the neutron arriving via path A is cl9 independent of B. So the intensity observable in the interference region must exhibit a sinusoidalvariation

(^

)

C.2.24

where 8 is the phasedifferencebetween cx and c2 (B = 0). In practice, the time spent in the B # 0 region, is fixed but the precession frequencyto is varied by changing the strength of the magnetic field. The intensity in the interference region as a function of B is predictedto have a sinusoidal variation. If we call Ai5 the differencein B neededto producesuccessive maxima, we can easily show that A5 = where / is the path length.

^?,

C.2.25

In deriving this formula we usedthe fact that a Air rotation is needed for the state ket to return to the original ket with the same sign, as required of by our formalism. If, on the other hand, our description spin \\ systems were incorrect and the ket were to return to its original ket with the same value for Ai5 would be just one-half sign under a 2tt rotation, the predicted of C.2.25). Two different groups have conclusivelydemonstrated experimentally that prediction is correct to an accuracy of a fraction of a percent.* C.2.25) This is another triumph of quantum mechanics. he nontrivial prediction T in has C.2.15) beenexperimentallyestablished a direct manner.

Pauli Two-Component ormalism F Manipulations with the state kets of spin \\ systems can be convenusing the two-componentspinor formalism introduced by W. Pauli in 1926. Section In we learned how a ket (bra) can be representedby a column (row) matrix; all we have to do is arrange the expansioncoefficientsin terms of a certain specifiedset of basekets into a
conveniently

carriedout

1.3

*H. Rauch et al., Phys. Lett. 54A, 425A975); S.A. Werner et al., Phys. Rev. Lett. 35 A975), 1053.

164 column (row) matrix. In the spin
\\

Theory of Angular Momentum

casewe have

=x
4-

C.2.26)

for the basekets and bras and

C.2.27a)
and for an arbitrary state ket and the corresponding state bra. Column matrix

C.2.27b <a|-<a|+><+|+<a|-X-|-\302\253a|+>,<a|-\302\273
is C.2.27a)referred to as a two-componentspinor and is written
c
V
\"***\" N

as

where c+ and c_ are, in general,complex numbers.Forx* we have

+ The matrix elements ( + 1^1 > and ( + \\Sk\\ ), apart from h/29are to be set equal to those of 2x2matrices ak9 known as the Pauli matrices.
\342\200\224

()

C.2.28

C.2.29)

We identify

(f)
We can now write the expectation value

C-2-30 (f)\302\261.(Sk) in terms of x and (a\\a')(a>\\Sk\\a\(a\"\\a)
\302\260k

(Sk) = (a\\Sk\\a) =
h

C.2.31

where the usual rule of matrix multiplication is used in the last line. that Explicitly, we seefrom C.2.1) together with C.2.30) 0 1 0

1 Oj'

-/

1

0/'

C.2.32

where the subscripts 2, and 3 refer to x, y, and z, respectively. someproperties the Pauli matrices.First, of We record

1,

+ OjOj
where the right-hand side of

= 0,

for / #

j,

C.2.33a C.2.33b

is C.2.33a)to

be understoodas the

2x2

3.2.Spin
identity

\\

Systems and Finite Rotations

165

matrix. These two relations are, of anticommutation relations

course, equivalent to the

(a,, ,}=25,,.. a
relations
,

C.2.34)

We

also have the

commutation

C.2.35)

which we

realizations of the angularmomentum commutation relations C.1.20). and CombiningC.2.34) C.2.35) we can obtain

seeto be the

explicit 2x2 matrix

Noticealso that

OiO2

=

~~

<*2ai

= *a3

\342\200\242 \342\200\242 \342\200\242 \342\200\242

C.2.36)

o}= an det(az) = Tr(a,)= 0.

-l,

C.2.37a) C.2.37b) C.2.37c)

This We now consider a*a, wherea is a vector in three dimensions. is actually to be understood as a 2 X 2 matrix. Thus

3

_

\302\246

C.2.38)

There is also a very important

identity,

= a-b+ (o-a)(o-b) /o-(aXb).

C.2.39)
and commutation

To prove this all we need are the anticommutation and relations, C.2.34) C.2.35), respectively:

j

k

j

k

J k

= a-b+/o-(axb).
If the components a are real, we have of

C.2.40)

(a-aJ= |a|2,
where |a|is the magnitude of the vector a.

C.2.41

Rotations in the Two-Component ormalism F Let us now study the 2x2 matrix representation of the rotation

operator<S>(h,</>).

We have

exp

7\342\200\224?

= exp

ih
\342\200\224^

.

C.2.42)

166

Theory of Angular Momentum

Using

I
o*n
which

for for

n
\302\253

even,

odd,

C.2.43)

follows from

we C.2.41),can write
2

exp

0
2

+

4!

= lcosl
Explicitly,
in

\342\200\224

I

\342\200\224

\342\200\224zcvhsin!

I.

C.2.44

2 X 2 form we have

\342\200\224

cosi
iomn<t>

\342\200\224

-mzsin
cosi
\342\200\224

exp
I

2

+ mzsin|

C.2.45)
as the operator iSmh<f)/h) acts on a state ket |a),the 2x2 acts on a two-componentspinor Underrotations exp( /a*h<J>/2) we change x as follows:
Just
exp(\342\200\224

matrix

\342\200\224

x\302\253

C.2.46
On the other hand, the aks themselvesare to remain unchanged under rotations. So strictly speaking,despite its appearance,a is not to be regarded as a vector; rather, it is xtCFX which obeys the transformation property of a vector:

C.2.47)
An

explicit proof of this may be given

using

exp 2
and so on, which is the

I

axexpi

C.2.48
analogue of C.2.6).

2x2matrix

3.2.Spin

2 Systems and Finite Rotations

167

In
that

a spin \\ ket

a discussing 2<n rotation using the ket formalism, we have seen T into |a). he 2x2analogue of this statement is \\a) goes
\342\200\224

exp!
which

=

\342\200\224

1, for any

h,

C.2.49

is evident from

As an instructive application of rotation matrix let us see how we can construct an eigenspinorof a*h with eigenvalue where h is a unit vector in some specified direction. Our object is to construct x satisfying In other
representation

C.2.44).

C.2.45), +1,

C.2.50

words,we look for the two-componentcolumn matrix representa+ of |S-h; ) defined by

C.2.51
Actually
this can be solved as a straightforward eigenvalueproblem (see Problem 9 in Chapter 1),but here we presentan alternative method based on rotation matrix C.2.45). Let the polar and the azimuthal angles that characterizeh be /? and a, respectively.We start with I l ], the two-componentspinor that represents the spin-upstate. Given this, we first rotate about the >>-axis by angle /?; we rotate by angle a about the z-axis.We seethat the desired subsequently

Second
rotation

First rotation

FIGURE

3.3.

Construction of o#h eigenspinor.

168

Theory of Angular Momentum

In spin state is then obtained; seeFigure 3.3. the Pauli spinorlanguage this of operations is equivalent to applying exp(-o2fi/2)to sequence i The followedby an application of exp( io3a/2). net result is

a cosi- m3smi I a cosi- isin y 0

cosi

\342\200\224

i

io2sm\\

\342\200\224

0

0

cos. j + /

-

-

cosl- -sini 1 sinl- cosl- 0
\342\200\224

cosif
in

-/a/2

C.2.52)

completeagreement with Problem 9 of Chapter 1 if we realize that a phase common to both the upper and lower components is devoid of
physical significance. A 3.3.SOC), UB), ND EULER ROTATIONS S Orthogonal Group
We
will

now

of the operationswith

study a little which we

have

sections.

more systematicallythe group properties beenconcernedin the previous two

The most elementary approach to rotations is based on specifying the axis of rotation and the angle of rotation. It is clear that we need three real numbers to characterizea general rotation: the polar and the azimuthal anglesof the unit vector h taken in the direction of the rotation axis and the rotation angle itself. Equivalently, the same rotation can be specifiedby the three Cartesiancomponents of the vector h</>. However, these ways of characterizing rotation are not so convenient from the point of view of the group propertiesof rotations. For one thing, unless is studying infinitesimal or h is always in the same direction, we cannot add vectors of the form h</> to characterizea succession rotations. It is much easierto of work with a orthogonal matrix R becausethe effect of successive rotations can be obtained just by multiplying the appropriate orthogonal
<f> <f>

3x3

matrices.

How many independent parameters are there in a 3 X 3 orthogonal matrix? A real 3x3matrix has 9 entries, but we have the orthogonality constraint

C.3.1

3.3SOC), UB),and S
which

Euler Rotations

169

beingthe
As

number previously obtained by a more elementarymethod. The set of all multiplication operations with orthogonal matrices forms a group. By this we mean that the following four requirements are

correspondsto 6 independent equations becausethe product RRT, sameas RTR, is a symmetrical matrix with 6 independent entries. a result, there are 3 (that is, 9-6) independent numbers in /?, the same

satisfied:

1.The product of any
matrix, which

two

is satisfiedbecause holds:

orthogonal matricesis another orthogonal

2.The associativelaw 3. The identity
\342\200\224defined

= (RlR2)(R1R2)T R^RlRl-l. = Rl(R2R3) (RlR2)R3.

C.3.2) C.3.3)
C.3.4)
in

matrix
by

1\342\200\224physically

to corresponding no rotation

Rl=lR = R
sense\342\200\224defined

is a member of the classof all orthogonal matrices. 4. The inverse matrix R~l\342\200\224physically to corresponding rotation the opposite by

RR1= R~lR=l
is also a member.

C.3.5)

This group has the name SOC), here S standsfor special, standsfor w O 3 for three dimensions. ote only rotational operationsare N orthogonal, consideredere,hence have SOC)rather than OC) (which can include we h the inversion operationof Chapter4 later).
Unitary unimodular

group

In the previous sectionwe learned yet another way to characterizean that acts on matrix is, to look at the arbitrary is unitary. As a result, for the the two-componentspinor x- Clearly,
rotation\342\200\224that

c+ and c_, defined in

can write the most general unitary unimodular matrix as a C.3.7) U(atb)=[ b* a* J where a and b are complexnumbers satisfying the unimodular condition
We
\342\200\224

is left invariant. a determinant is 1, s will be shown explicitly below.

C.2.28), + |c+|2 |c_|2=l is Furthermore, matrix C.2.45)unimodular;

2x2 C.2.45)

C.2.45)

C.3.6)
that

is, its

\\

b\\

2

2

C.3.8)

170
We

Theory of Angular Momentum

can easily establish the

unitary

as property of C.3.7) follows:
a*

t = U(a9byU(a9b)

[b*

-b

a
b*

a,

a

C.3.9)

where we have used C.3.8). Notice that the number of independent real is parameters in C.3.7) again three. We can readily see that the 2x2matrix C.2.45) characterizesa that rotation of a spin \\ system can be written as U(a,b). Comparing C.2.45 with C.3.7), identify we

Re(a) = cosl

\342\200\224

y

Im(a) =
\\m(b)

=-

\342\200\224

\302\253zsin!

w^sinl

-J,

y

C.3.10

from

which

the unimodular

t is clearhat the most general unitary unimodular be interpreted as representinga rotation.

is property of C.3.8)immediate. Conversely,it matrix of form C.3.7) can

The two complex numbers a and b are known as Cayley-Klein H parameters. istorically the connection between a unitary unimodular maand a rotation was known long before the birth of quantum mechanics. In fact, the Cayley-Kleinparameters were used to characterize complicated in motions of gyroscopes rigid-body kinematics. Without appealing to the interpretations of unitary unimodular of matrices in terms of rotations, we can directly checkthe group properties multiplication operations with unitary unimodular matrices.Note in parmatrix

particular

that

U(al9bl)U(a29 = U(axa2 bxb^ axb2 + a$bx), b2) where the unimodular condition for the product matrix is
ala2 bxb2\\ Forthe inverse of U we have
\342\200\224

-

C.3.11

_ + \\axb2 + a*bx\\ 2 =1.

C.3.12

C.3.13
This group is known as SUB),where S stands for special,U for unitary, and 2 for dimensionality2.In contrast, the group defined by multiplication constrained operationswith general 2x2unitary matrices (not necessarily T to be unimodular) is known as UB). he most general unitary matrix in two dimensionshas four independent parameters and can be written as eiy (with y real) times a unitary unimodular matrix: a SUB)is calleda subgroup of UB).

U=el

-b

a

C.3.14

3.3SOC), UB),and S

Euler Rotations

171

we Because can characterizerotations using both the SOC)language and the SUB)language, we may be temptedto concludethat the groups c SOC)and SUB) areisomorphic\342\200\224that is, that there is a one-to-oneoro o This correspondence betweenan element f SOC)and an element f SUB). inference is not correct. Considera rotation by 2ir and another oneby 4tt. In the SOC)language, the matrices representing a 2tt rotation and a 4tt rotation are both 3x3identity matrices;however, in the SUB)language the times the 2 x 2 identity matrix and the identity correspondingmatricesare matrix itself, respectively. More generally, U(a,b) and U( a, b) The both correspondto a single 3x3matrix in the SOC)language. corU for a given /?, the corresponding correspondence therefore is two-to-one; is double-valued. ne can say, however, that the two groupsare locally O

-1

\342\200\224

\342\200\224

isomorphic.
Euler Rotations
that

From classicalmechanics the reader may be familiar with the fact in rigid body can be accomplished three steps, known as Euler rotations. The Euler rotation language,specifiedby three Euler angles, provides yet another way to characterize the most general rotation in three dimensions. The three steps of Euler rotations are as follows. First, rotate the rigid body counterclockwise(as seen from the positive z-side)about the s z-axisby angle Imagine now that there is a body ^-axisembedded, o to speak,in the rigid body such that before the z-axis rotation is carried out, the body>>-axis coincides ith the usual ^-axis,referred to as the space-fixed w Obviously, after the rotation about the z-axis, the body ^-axisno j;-axis. w longer coincides ith the space-fixed >>-axis; let us call the former the T >>'-axis. o seehow all this may appearfor a thin disk, refer to Figure 3.4a. We now perform a secondrotation, this time about the y '-axisby angle /?. As a result, the body z-axis no longer points in the space-fixed z-axis direction. call the body-fixedz-axisafter the secondrotation the z'-axis; We seeFigure 3.4b. third and final rotation is about the z'-axisy angle y. The b The body >>-axis now becomes >>\"-axis of Figure 3.4c. terms of 3 X 3 In the orthogonal matrices the product of the three operations can be written as
an arbitrary rotation of a

a.

C.3.15
cautionary remark is in order here.Most textbooksin classical mechanics prefer to perform the secondrotation (the middle rotation) about rather than about the body ^-axis (see,for example, the body x-axis This Goldstein1980). conventionis to be avoided in quantum mechanicsfor a reasonthat will become apparent in a moment. In C.3.15) appear Ry. and Rz>, which are matrices for rotations there about body axes. his approach to Euler rotations is rather inconvenientin T
A

172

Theory of Angular Momentum

(a)

(b)

y

(c) 3.4.
Euler rotations.

FIGURE

we f mechanics because earlier obtained simple expressionsor the space-fixed (unprimed) axis components of the S operator, but not for the body-axiscomponents.It is therefore desirableto expressthe body-axis in rotations we considered terms of space-fixedaxis rotations. Fortunately there is a very simple relation, namely,
quantum

The meaning of the right-hand side is as follows. First, bring the body Figure 3.4a (that is, the >>'-axis)back to the original fixed-space about the ^-directionby rotating clockwise(as seenfrom the positive z-side) z-axisby angle a; then rotate about the >>-axis by angle ft. Finally, return the body 7-axisto the direction of the >>'-axisby rotating about the z tells fixed-space-axis (not about the z'-axis!) angle Equation C.3.16) by us that the net effectof these rotations is a single rotation about the y '-axis by angle /?.
>>-axis of

a.

3.3SOC), UB),and S

Euler Rotations

173

To prove this assertion,let us lookmore closelyat the effectof both sidesof C.3.16)the circular disc of Figure 3.4a. learly, the orientation on C of the body >>-axis is unchanged in both cases,namely, in the y '-direction. Furthermore, the orientationof the final body z-axis is the same whether we apply Rv>(fi) or Rz(a)R (fi)Rz x(a).In both casesthe final body z-axis makesa polar angle fi with the fixed z-axis (the same as the initial z-axis), and its azimuthal angle, as measured in the fixed-coordinatesystem, is just a.In other words,the final body z-axis is the same as the z'-axisf Figure o

3.4b. Similarly, we can prove

we and UsingC.3.16) C.3.17),can now rewrite

We C.3.15).obtain

=
where in the summarize,
final

Rz(a)Ry(p)Rz(y),

C.3.18

stepwe usedthe fact that Rz(y) and Rz(a)commute.To

= R(a,0,y) R,(a)Rjfi)Rz(y),

C.3.19

where all three matriceson the right-hand siderefer to fixed-axis rotations. Now let us apply this set of operations to spin \\ systemsin quantum mechanics. orresponding the product of orthogonal matrices in C.3.19 to C there existsa product of rotation operators in the ket spaceof the spin \\ system under consideration: The 2x2matrix representation of this product is ia3a ia3y

C.3.20)
exp exp
I

exp
I

-/a/2
0

-sin 0 'cos(j8/2) .ia/2 sin(j8/2)
\342\200\242

0 0

/(a-y)/2sin(j8/2)

C.3.21

where C.2.44) used.This matrix is clearly of the unitary unimodular was form. Conversely, the most general 2x2 unitary unimodular matrix can be written in this Euler angle form. Notice that the matrix elements of the second (middle) rotation had exp( io <f>/2) are purely real. This would not have been the case we chosento rotate about the jc-axisrather than the >>-axis, as done in most
\342\200\224

174

Theory of Angular Momentum

textbooksin classical echanics.In quantum mechanics it pays to stick to m our convention because we prefer the matrix elements of the second rotation, which is the only rotation matrix containingoff-diagonalelements,
to
* be purely real.
representation

The 2x2 matrix in C.3.21) is called the = \\ irreducible representaof the rotation operator 3){a, y). Its matrix elementsare denotedby /?, a,/?, y). In terms of the angular-momentum operatorswe have

j

h

expl
higher

y=2>\342\204\242

In

Section3.5we will extensivelystudy

y-analoguesof C.3.21).

3.4. ENSITYOPERATORS AND D

PURE VERSUSMIXEDENSEMBLES
Polarized Versus UnpolarizedBeams

The formalism of quantum mechanicsdeveloped so far makes statison predictions an ensemble,that is, a collection,of identicallyprepared i physical systems.More precisely,n such an ensembleall members are A goodexample of to be characterizedby the same state ket supposed this is a beam of silver atoms coming out of an SG filtering apparatus. Every atom in the beam has its spin pointing in the same direction, namely, the direction determined by the inhomogeneity of the magnetic field of the filtering apparatus.We have not yet discussedhow to describequantum of mechanicallyan ensemble physicalsystemsfor which some,say 60%,are and the remaining 40% are characterized by some characterized by other ket |j6). of To illustrate vividly the incompleteness the formalism developed so far, let us considersilver atoms comingdirectly out of a hot oven, yet to be subjectedto a filtering apparatus of the Stern-Gerlachype. On symmet grounds we expectthat such atoms have random spin orientations; in with such an other words,there should be no preferred direction associated so ensembleof atoms. According to the formalism developed far, the most general state ket of a spin \\ system is given by
statistical

|a).

|a),

symmetry

C.4.1
generally,

*This, of course, depends on our convention Jv) are taken to be purely imaginary.

that the matrix

elements of

SY

(or, more

3.4.Density

Operators and Pure Versus Mixed Ensembles

175

a equation capableof describing collection of atoms with random characterizesa state ket spin orientations? The answer is clearly no; C.4.1) whosespin is pointing in somedefinite direction,namely, in the direction of h, whosepolar and azimuthal angles, /? and a, respectively,are obtained by
solving

Is this

^- e'asin@/2) cC\302\260s(/?/2)

;

C.4.2)

a situation of this kind we introduce the conceptof fractional population, or probability weight. An ensembleof silver atoms with completely random spin orientation can be viewed as a collectionof are silver atoms in which 50%of the membersof the ensemble characterized We specify such an ensemble by | + ) and the remaining 50% by by
|\342\200\224

seeC.2.52). To copewith

assigning

).

_=

0.5,

C.4.3)

where w+ and w_ are the fractional population for spin-up and -down, there is no preferred direction for such a beam, it is respectively. Because reasonableto expectthat this same ensemble be regardedequally well can The mathematical formalism as a 50-50 mixture of \\SX; + ) and \\SX;
\342\200\224

this neededto accomplish will appearshortly. It is very important to note that we are simply introducing here two real numbers w+ and w_. There is no information on the relative phase between the spin-upand the spin-down ket. Quite often we refer to such a situation as an incoherent mixture of spin-upand spin-down states.What we are doing here is to be clearly distinguished from what we did with a coherent linear superposition, example, for

).

{

y2 /

\\

y2 )
\342\200\224

C.4.4)

where the phase relation between | + > and | > contains vital information in on the spin orientation in the xy-plane, in this case the positive x-direction. In general, we should not confuse w+ and w_ with |c+|2 \\c_\\2. and The probability conceptassociated with w+ and w_ is much closerto that encounteredin classicalprobability theory. The situation encountered in dealing with silver atoms directly from the hot oven may be compared with that of a graduating classin which 50%of the graduating seniorsare male, the remaining 50%female.When we picka student at random, the probabilWhoever heard of a that the particular student is male (or female)is 0.5. student referred to as a coherent linear superposition male and female of with a particular phaserelation? The beam of silver atoms coming directly out of the oven is an example of a completely random ensemble;the beam is said to be unprobability

176

Theory of Angular Momentum

polarized becausethere is no preferred direction for spin orientation. In contrast, the beam that has gone through a selective Stern-Gerlach-type measurement is an example of a pure ensemble;the beam is said to be a are polarized becausell membersof the ensemble characterizedby a single common ket that describesa state with spin pointing in some definite T direction. o appreciate the differencebetweena completelyrandom ensemand a pure ensemble, us consider rotatable SG apparatus wherewe let a can vary the direction of the inhomogeneousB just by rotating the apparaWhen a completely unpolarized beam directly out of the oven is subjectedto such an apparatus, we always obtain two emerging beamsof equal intensity no matter what the orientation of the apparatus may be.In to contrast, if a polarized beam is subjected such an apparatus, the relative intensities of the two emerging beamsvary as the apparatus is rotated. For one someparticular orientation the ratio of the intensities actually becomes I to zero.n fact, the formalism we developed in Chapter 1 tells us that the relative intensitiesare simply cos2(/?/2) sin2(/?/2), and where /? is the angle between the spin direction of the atoms and the direction of the inhomogemagnetic field in the SG apparatus. A complete random ensemble a pure ensemble be regarded and can In as the extremesof what is known as a mixed ensemble. a mixed ensemble a certain the membersare characterizedby example, a state ket |a>,the remaining 30%by |/?).In such a case beam is saidto the be partially polarized. Here \\a) and |/?) need not even be orthogonal; we can, for example,have 70% with spin in the positive x-direction and 30% with spinin the negativez-direction.*
ensemble apparatus. inhomogeneous

fraction\342\200\224for

70%\342\200\224of

Ensemble Averagesand DensityOperator
We now presentthe density operator formalism, pioneered J. von by Neumann in 1927,hat quantitatively t describesphysical situations with mixed as well as pure ensembles.Our general discussionhere is not restricted to spin \\ systems, but for illustrative purposeswe return re-

pure ensemble definition is a collection of physical systems by such that every member is characterizedby the same ket \\a). In contrast, in a mixed ensemble, fraction of the memberswith relative population wx are a characterized by |aA)), some other fraction with relative population w2, by can |aB)),and so on. Roughly speaking, a mixed ensemble be viewedas a mixture of pure ensembles,ust as the name suggests.The fractional j
A
*In the literature what we call pure and mixed ensembles are often referred to as pure and mixed states. In this book, however, we use state to mean a physical system described by a definite state ket \\a).

repeatedly

to

spin \\ systems.

3.4.Density

Operators and Pure Versus Mixed Ensembles

177

populationsare constrained to satisfy the normalization condition

C.4.5)
As we mentioned previously, |aA)) and |aB)) need not be orthogonal. neednot coincide Furthermore, the number of terms in the / sum of N with the dimensionality N of the ket space; it can easily exceed . For 40% with spin in example,for spin \\ systemswith N = 2, we may consider the positive z-direction, 30% with spin in the positive x-direction, and the remaining 30% with spin in the negative ^-direction. Supposewe make a measurement on a mixed ensembleof some observable We may ask what is the averagemeasured value of A when a A. large number of measurementsare carried out. The answer is given by the ensemble average of A, which is defined by

C.4.5)

a'

C.4.6)

where \\a') is an eigenket of A. Recall that (oSl)\\A\\a{l)) is the usual quantum mechanical expectation value of A taken with respect to state tells |a(/)).Equation C.4.6) us that these expectationvalues must further be weighted by the correspondingfractional populations wr Notice how probfor conceptsenter twice; first in |(tf'|a(/))|2 the quantum-mechaniprobability for state |a(/)>to be found in an A eigenstate \\a')\\ second, in the probability factor wi for finding in the ensemble quantum-mechania state characterizedby |a(/)).* We can now rewrite ensemble average C.4.6) a more general using
probabilistic
quantum-mechanical quantum-mechanical

basis, {\\b')}:

V b\"

b'

b

The number of terms

the sum of the (b\")is just the dimensionality of the ket space,while the number of terms in the sum of the / dependson is Notice how the mixed ensemble viewedas a mixture of pure ensembles. that in this form the basicproperty of the ensemble which doesnot depend on the particular observableA is factored out. This motivates us to define the density operator p as follows:
in

b'

C.4.8)
*Quite often in the literature the ensemble average is also called the expectation value. However, in this book, the term expectation value is reserved for the average measured value when measurements are carried on a pure ensemble.

178

Theory of Angular Momentum

The elements of the correspondingensity matrix have the d
(b\"\\p\\bf)

following

form:

= ?vvz<fc''|a(/)><<*(/>'>-

C.4.9)

The density operator contains all the physically significant information we in we obtain about the ensemble question. eturning to C.4.7), can possibly R seethat the ensemble averagecan be written as
b'
b\"

= tr( pA).
using

C.4.10

Because trace is independent of representations,tr(pA) can be evaluated the is an extremely powerful any convenient basis.As a result, C.4.10)

relation. There are two propertiesof the density operator worth recording. First, the density operator is Hermitian, as is evident from C.4.8). Second, the density operator satisfiesthe normalization condition
b'

=1.

C.4.11

Because the Hermiticity and the normalizationcondition, for spin \\ of with dimensionality 2 the density operator, or the corresponding systems F density matrix, is characterizedby three independent real parameters. our
real numbers characterizea 2 X 2 Hermitian matrix. However,only three are independentbecauseof the normalization condition. The three numbers needed are [Sx],[Sy], and [Sz];the reader may verify that knowledge of these three ensemble averagesis sufficient to reconstruct the density operThe manner in which a mixed ensembleis formed can be rather involved. We may mix pure ensemblesharacterizedby all kinds of |a(/))'s c with appropriatew/s; yet for spin \\ systems three real numbers completely in T that a mixed characterize the ensemble question. his strongly suggests in into ensemble be decomposed pure ensembles many different ways. A can problemto illustrate this point appearsat the end of this chapter. A pure ensemble specifiedby wt =1for some / = n, is = 0 for all other conceivablestate kets, so the correfor wt density operator is written as corresponding
operator. |a(/)>\342\200\224with instance\342\200\224and

with

p = \\a(n))(a(n)\\ no summation. Clearly, the density operator for a pure

C.4.12
ensembleis

idempotent, that is,

C.4.13

3.4.Density

Operators and Pure Versus Mixed Ensembles

179

or, equivalently,

= p(p-l) 0.

C.4.14)

Thus, for a pure ensemble only, we have
in

addition to

ensemble zero or one, as can be seenby inserting a complete set of base are kets that diagonalize the Hermitian operator p between p and (p 1) of When C.4.14). diagonalized,the density matrix for a pure ensemblemust therefore look like
\342\200\224

The C.4.11).eigenvaluesof the density operator for a pure

tr(p2)=l.

C.4.15)

0 0 0 0 0 0

0
(diagonal form)

0

o;

C.4.16

It can be shown that tr(p2) is maximal when the ensemble pure; for a is mixed ensemble tr(p2) is a positive number less than one. Given a density operator, let us seehow we can construct the density matrix in some specifiedbasis.To this end we first corresponding recall that
I\302\253X\302\253I

b' b\" this showsthat we can form the square matrix corresponding |a(/))(a(/)| to in the senseof outer product, the column matrix formed by by combining, w w (b'\\a(l)) ith the row matrix formed by (a(/)|6\,") hich, of course,is equal to (Z>\"|a(l))*. final step is to sum such square matrices with weighting The

= E El*'X*'l\302\253X\302\253l*\"X*''l-

E?

C.4.17)

factors

wi9

as indicated in

expected.
It

The C.4.8). final

form

agreeswith

as C.4.9),
\\

is instructive to

study

a several examples, ll referring to spin

systems.
Example

1.A completelypolarized beam with
1
0 0 0

Sz

+.

C.4.18

180

Theory of Angular Momentum

Example 2. A completelypolarized beam with Sx +.

=

\\SX;\302\261)(SX;\302\261\\

= 1)
f

' 1)

1.

2

C.4.19)

The ensembles f Examples1and 2 are both pure. o Example
mixture
An unpolarized beam.This can be regardedas an incoherent of a spin-up ensembleand a spin-down ensemblewith equal

3.

weights

E0% each):

I 2
0
which

0

i 2

C.4.20

is just the identity matrix divided by 2.As we remarked earlier, the sameensemblecan also be regarded as an incoherent mixture of an Sx + and ensemble an Sx ensemble ith equal weights.It is gratifying that our w
\342\200\224

formalism automatically satisfiesthe expectation

i 2
0

0

I 2

I I 2 2 I I I 2 2 2

>

I 2 I 2

I 2 1 2
\342\200\224.

C.4.21

where we seefrom Example 2 that the two terms on the right-hand sideare with Sx + and Sx Because in the density matrices for pure ensemble p is this case just the identity operator divided by 2 (the dimensionality), we have

= = C.4.22 tx(PSx) tr(pS) tr(pSz)= 0, Thus for the ensemble where we used the fact that Sk is traceless. averageof
S we have

= [S] 0.

C.4.23

This is reasonable becausethere should be no preferred spin direction in a random ensemble spin \\ systems. of completely Example 4. As an example of a partially polarized beam, let us considera o 75-25 mixture of two pure ensembles, ne with Sz + and the other with

C.4.24

3.4.Density

Operators and Pure Versus Mixed Ensembles

181

The corresponding can be represented p by 0 0

i I 2 2

I I I
7 8 8 8 8

I I) 2 2

C.4.25)
8
that this

from which

follows

-

= [sy]=o, [sz]

C.4.26)
ensemble

leave as an exercise the readerthe task of showing for can be decomposed ways other than C.4.24). in
We

Time Evolution

of Ensembles

Howdoesthe density operator p change as a function of time? Let us supposethat at sometime t0 the density operator is given by

C-4-27)
ensembleis to be left undisturbed, we cannot change the fractional population vvz. Sothe changein p is governedsolelyby the time evolution of
If the

state ket |a(/)):
From the fact

|a(/)> at
a <'\\

to-*\\a(i\\to;t).

C.4.28)
t,\\ t\\H)

that

|a(/),0; t) satisfiesthe Schrodingerequation we obtain t

- |a('\\t0;

r><a<'\\

C.4.29)
This looks like the Heisenberg equation of motion exceptthat the sign is This is not disturbing becausep is not a dynamic observablein the wrong! Heisenberg picture.On the contrary, p is built up of Schrodinger-picture state kets and state bras which evolvein time according to the Schrodinger equation. It is amusing that C.4.29) be regarded the quantum-mechanican as of Liouville'stheorem in classical tatistical mechanics, s analogue
quantum-mechanical

^Pclassical

r
L Pclassical
>

rri
Jclassical'

dt

C.4.30)
in

where

pciassicai

T space.* hus the name

stands for the density of representative points
density

operator for the p appearing in

is C.4.29)

phase

by a single moving point in phase space at each instant of time. A classical statistical state, on the other hand, is <jy, described by such t'iat nonnegative density function at time t is pciassical probability that a system is found in the interval dpj

X,...,

*Remember, a pure classical state is one represented

/?!,..., pj) our

dqx,...,

pciassicai(9i\302\273---\302\2739/\302\273Pi\302\273---\302\273/;y\302\2730

182

Theory of Angular Momentum

indeed appropriate.The classicalanalogue of average of someobservableA is given by
A

for C.4.10)

the

ensemble

average

=/ Pclassical
q,

(^4 1\"h

where d T

standsfor a volume element in phasespace.
Generalizations

Continuum

So far we have considered density operatorsin ket spacewhere the T of base kets are labeledby the discrete-eigenvalues someobservable. he conceptof density matrix can be generalizedto caseswhere the base kets used are labeledby continuous eigenvalues.In particular, let us considerthe ket spacespannedby the position eigenkets |x'). analogue of C.4.10) The is
given by

[A] = d3x'fd3x\"(x\"\\p\\x')(x V|x\">.

j

C.4.32)

The density matrix here is actually a function

of x'and x\", namely,

C-4-33)
where
that

is the wave function corresponding the state ket |a(/)).Notice to the diagonal element (that is, = x\") of this is just the weighted sum of the probability densities. nceagain, the term density matrix is indeed O
\\pi

x'

In continuum cases,too, it is important to keep in mind that the same mixed ensemblecan be decomposed different ways into pure in For ensembles. instance, it is possibleto regard a \"realistic\" beam of particleseither as a mixture of plane-wavestates (monoenergeticfree-parstates)or as a mixture of wave-packetstates.
free-particle

appropriate.

Quantum Statistical Mechanics
We concludethis section with a brief discussion the connection on between the density operator formalism and statistical mechanics. Let us first recordsomeproperties completelyrandom and of pure ensembles. of

3.4.Density

Operators and Pure Versus Mixed Ensembles

183

lookslike The density matrix of a completelyrandom ensemble

1 1
N

0
1

C.4.34)

0
in any

1)
C.4.20)]. C.4.16)

This followsfrom representation [compareExample 3 with the fact that all states correspondingto the basekets with respectto which I the density matrix is written are equally populated. n contrast, in the basis where p is diagonalized, we have for the matrix representation of the density operator for a pure ensemble. two diagonal matricesC.4.34) The and both satisfying the normalization requirement cannot if look more different. It would be desirable we could somehowconstruct a

C.4.16),

C.4.11),

quantity

that characterizesthis dramatic difference. Thus we definea quantity called a by

a = tr( p In
\342\200\224

p).

C.4.35)

The logarithm of the operator p may appear rather formidable, but the is quite unambiguous if we use the basisin which p is meaning of C.4.35)

diagonal:

E^fi
iW^i=
we C.4.16) have

CA36)

we have

Becauseeach element p(^ag) is a real number between 0 and 1,a is F C necessarily ositive semidefinite. or a completelyrandom ensemble .4.34), p

C.4.37)

In contrast, for a pure ensemble

C.4.38)
where we have used
Pkk
~~

n(diag) Pkk

=

C.4.39)

for each term in We now argue that physically a can be regardedas a quantitative measure of disorder.A pure ensembleis an ensemblewith a maximum amount of order because all members are characterized by the same in quantum-mechanical state ket; it may be likened to marching soldiers a

C.4.36).

184

Theory

of Angular

Momentum

a vanishesfor such an ensemwell-regimentedarmy. Accordingto C.4.38), i On the other extreme, a completely random ensemble,n which all states are equally likely, may be likenedto drunken quantum-mechanical soldierswandering around in random directions. ccording to C.4.37),is a A indeed,we will show later that In N is the maximum possiblevalue large; for a subjectto the normalization condition
ensemble.

Ip**-1.
k

C-4-40)

In thermodynamicswe learn that a quantity calledentropy measures disorder.It turns out that our o is related to the entropy per constituent via member, denotedby S, of the ensemble

S = A:a,
mechanics.

C.4.41

where k is a universal constant identifiablewith the Boltzmann constant. In fact, C.4.41) be taken as the definition of entropy in quantum statistical may
We now show how the density operator p can be obtained for an ensemblein thermal equilibrium. The basic assumption we make is that nature tends to maximize a subject to the constraint that the ensemble value. To justify this average of the Hamiltonian has a certain prescribed would involve us in a delicate discussion how equilibrium is of assumption as established a result of interactionswith the environment, which is beyond the scopef this book.In any case, nce o o thermal equilibrium is established, we expect

ot

r0.

C.4.42

this Becauseof C.4.29), means that p and H can be simultaneously So may diagonalized. the ketsusedin writing C.4.36) be taken to be energy With eigenkets. this choice standsfor the fractional population for an pkk

energy eigenstate with energyeigenvalueEk. Let us maximize a by requiring that 8a = 0.

C.4.43

However, we must take into account the constraint that the ensemble value. In the language of statistical average of H has a certain prescribed mechanics, is identified with the internal energyper constituent denoted [H]
by

U:

In addition, we should not our basictask is to require C.4.43)ubject to the constraints s

C.4.44 So forget the normalizationconstraint C.4.40).

[H]= tr{pH)= U.

C.4.45a

3.4.Density and

Operators and Pure Versus Mixed Ensembles

185

C.4.45b)
We

can most readily accomplish this obtain
k

by using

Lagrange multipliers. We

Y]=0,
variation

C.4.46)
C.4.47)

which

for an

arbitrary

is possibly only if

The constant y can be eliminatedusing the normalization condition C.4.40), and our final result is
Pkk

exp( 0Ek) = ~ij

-

?

\302\273

C.4.48)
fxAAQ\\

directly gives the fractional population for an energy eigenstatewith that the sum is over eigenvalue Ek. It is to be understood throughout i distinct energy eigenstates;f there is degeneracywe must sum over states with the sameenergyeigenvalue. The density matrix elementC.4.48)s appropriate for what is known i in statistical mechanics as a canonical ensemble. ad we attempted to H maximizea without the internal-energyconstraint C.4.45a), would have we obtained instead
which Pkk which

= 77

>

(independent of k),

C.4.49)

is the density matrix element appropriate for a completelyrandom ensemble.Comparing C.4.48) with C.4.49), e infer that a completely w random ensemblecan be regarded as the ft limit (physically the of a canonical ensemble. high-temperature limit)
-\302\2730

We

a recognize the denominatorof C.4.48) s the
N

partition

function

Z=?exp(-/??J k
in

C.4.50)

statistical mechanics.It can also be written as

Z=tr(e-I*H).
Knowing
pkk given in

C.4.51)

the energy basis,we can write the density operator as -

C.4.52)
everything

This is the most basic equation from

which

follows. We can

186

Theory

of Angular

Momentum

immediately evaluate the ensemble average of any observableA:

N

N

C.4.53)

In particular, for the

internal

energy per constituent we obtain
N

IXexP(k
N

k

d

C.4.54)

a formula well known to every student of statistical mechanics. The parameter fi is related to the temperature T as follows:

CA55)
where k is the Boltzmann constant. It is instructive to convinceourselvesof this identification by comparing the ensembleaverage [H] of simple harmonic oscillatorswith the kT expectedfor the internal energy in the classicalimit, which is left as an exercise. have already commented that We l in the high-temperature limit, a canonical ensemble becomesa completely in random ensemble which all energy eigenstates are equally populated.In the oppositelow-temperaturelimit (/? oo), C.4.48)ells us that a canonit ensemblebecomesa pure ensemblewhere only the ground state is
-\302\273

canonical

As a simple illustrative made a example,consider canonical ensemble of spin \\ systems, ach with a magneticmoment eh/2mecubjected a e to up s uniform magnetic field in the z-direction.The Hamiltonian relevant to this Because problemhas already been given [seeC.2.16)]. H and Sz commute, is the density matrix for this canonical ensemble diagonal in the Sz basis. Thus

populated.

0 where the partition
function

C.4.56)

is just

C.4.57)

3.5.Eigenvalues
From
this

and Eigenstates of Angular Momentum

187

we compute

tanh C.4.58) [Sx] = [Sy] = 0, [Sz] = 21 2 The ensembleaverage of the magnetic moment component is just elmec T times [Sz]. he paramagnetic susceptibility x may be computedfrom
\\

- 'ti

\\mxj

[Sz] =

C.4.59)

In

this way

we arrive at Brillouin'sformula for x:
X

=

h )

2mecBi

tanh

C.4.60)

A 3.5. EIGENVALUESND

ANGULAR

EIGENSTATES F O MOMENTUM

expressionsfor

work out the eigenvaluesand eigenkets of J2 and Jz and derive the matrix elements of angular momentum operators, first obtained in a and paperby M. Born, W. Heisenberg, P.Jordan.
first

of Up to now our discussion angular momentum has been confinedexcluto spin \\ systems with dimensionality N =2.In this and subsequent sectionswe study more-generalangular momentum states.To this end we
exclusively

1926

Commutation
Everything

Relationsand the Ladder Operators

we will do followsfrom the angular-momentum commurelations C.1.20), where we may recall that /, is defined as the of infinitesimal rotation. The first important property we derive generator from the basiccommutation relations is the existence a new operator J2, of defined by
commutation

,
that

C.5.1

commutes with every one of Jk:

To prove this

=O, (?=1,2,3). let us look at the k = 3 case:

C.5.2)
y

= 0.
caseswhere k = 1 and 2 follow by

C.5.3

The proofs for the cyclic permutation B A -> 2 -> 3 ->1) of the indices. ecause Jy, and Jz do not commute with Jx,

188

Theory of Angular Momentum

each other, we can chooseonly one of them to be the observable to be diagonalized simultaneously with J2.By convention we chooseJz for this

purpose.

We now lookfor the simultaneous eigenketsof J2 and Jz. We denote the eigenvaluesof J2 and Jz by a and b, respectively:

C.5.4a) C.5.4b)
To determine the allowedvalues for a and b, it is convenient to work the non-Hermitian operators
with

J
commutation relations and

\302\261

= Jx\302\261iJy,
than with

C.5.5)
Jx

called the ladder operators, rather

and Jv. They satisfy the

= [J+,J_] 2hJz
[Jz,J\302\261]

C.5.6a)

=
\302\261hJ\302\261,

C.5.6b)

which

can easily be obtained from

Note C.1.20). also that

[j2,/\302\261]=0,

C.5.7)

is an obvious consequencef C.5.2). o What is the physicalmeaning of J To answer this we examinehow Jz acts on b):
which
\302\261?

J\302\261\\a9

Jz(J\302\261\\\302\260>b))=([Jz9J\302\261]+J\302\261Jz)\\a,b)

= (b\302\261h)(J\302\261\\a,b))

C.5.8)
J\302\2619

where we have used C.5.6b).other words,if we apply /+(/_)to a Jz In the resulting ket is still a Jz eigenket exceptthat its eigenvalueis eigenket, which now increased (decreased)y one unit of h. So now we seewhy b one step up (down) on the \"ladder\" of Jz eigenvalues,are known as the step

ladder operators. We now digressto recall that the commutation relations in

are reminiscentof some commutation relationswe encounteredin the earlier the chapters.In discussing translation operator y(l) we had
the also, in discussing simple harmonic oscillatorwe had =

C.5.6b)

C.5.9)

-a.

C.5.10

We

The seethat both C.5.9) C.5.10) a structure similar to C.5.6b). have and physical interpretation of the translation operator is that it changes the eigenvalueof the position operator x by 1 in much the same way as the

3.5.Eigenvalues

and Eigenstates of Angular Momentum

189

ladderoperator /+ changesthe eigenvalueof Jz by one unit of h. Likewise, the the oscillator creation operator a^ increases eigenvalueof the number
operator TV
by unity.
J\302\261

Even though changes the eigenvalueof Jz does not change the eigenvalueof

J2:

by

one unit of h,

it

= a(J\302\261\\a9b)),
where we have used C.5.7). summarize, To of eigenkets J2 and Jz with eigenvaluesa and b
J\302\261\\a9b)
\302\261

C.5.11
are simultaneous
may write

h. We

=

c\302\261\\a9b\302\261h)9

C.5.12

where the proportionality constant c will be determined later from the normalization requirement of the angular-momentum eigenkets.
\302\261

Eigenvaluesof J2 and Jz We now have the machinery neededto construct angular-momentum eigenketsand to study their eigenvaluespectrum. Supposewe apply /+ say successively, n times, to a simultaneouseigenketof J2 and Jz. We then obtain another eigenketof J2 and Jz with the Jz eigenvalueincreased nh, by while its J2 eigenvalue is unchanged. However, this processcannot go on indefinitely. It turns out that there exists an upper limit to b (the Jz eigenvalue)for a given a (the J2 eigenvalue):

a>b2.
To prove this assertion we first note that

C.5.13 ).

Now J +J\\

( and J\\J + must have nonnegativeexpectation values because DC DC
j\\\\a9b)

C.5.14

<-> (a9b\\j+9

J+\\a9b) <-> (a9b\\j\\\\

C.5.15

thus

(a,b\\(j2-Jz2)\\a,b)>0,
which,
in turn,

C.5.16

such that

It thereforefollowsthat there must be a bmax impliesC.5.13).

C.5.17)
Stated another way, the eigenvalueof b cannot be increased beyond bmax. Now C.5.17) implies also

C.5.18

190
But

Theory of Angular Momentum

= J2-J2-hJz.
So

C.5.19)

= 0. {32-Jz2-hJz)\\a,bmax)
Because\\a,
or
In a similar manner we argue from
^min SUch that

C.5.20)

bmax)

itself is not a null ket,
max

this

relationship is possible only if

C.5.21)
that C.5.13)

C.5.22)
there must also exist a
_

|0,^min) = U.

yi.j.23)

By
in

writing

/+ /_ as

/+ J_ = J2-Jz2 + hJz
^ = ^minv^min
\342\200\224

C.5.24)
^J.J.ZjJ

analogy with

we C.5.19),conclude that
*U *
with we C.5.22) C.5.25) infer that

By comparing
with

*>max=-?min>
6max

C.5.26)

positive, and

that

the allowedvalues of b lie within

~bmax<b<bmax.

C.5.27)

Clearly, we must be able to reach \\a9 bmax) by applying /+ successivelyto \\a9 bmin) a finite number of times. We must thereforehave where n is someinteger. As a result, we get
It

C-5.29)

with

is more conventional to bmax so that

work with

j\\

defined to be bmax/h, instead of

C.5.30)
The maximum value of the Jz eigenvalueis jh9 where is either an integer or a half-integer. Equation C.5.22) implies that the eigenvalueof J2 is given
by

j

C.5.31

3.5.Eigenvalues

and Eigenstates of Angular Momentum

191

Let us also define m so that
b = mh. If

C.5.32)

values are integers; if is a half-integer, all m values are half-integers.The allowed ra-valuesfor a given are

j

is an integer, all

m

j

m= -y,-y+

2 +1states Instead of \\a9 b) it is more convenient to denote a simultaneous eigenket of J2 and Jz by | j\\ m). The basiceigenvalueequations now read

l,...,y-l,y.

j

C.5.33)

j

J2\\j,m)= j(j + l)h2\\j,m)
and
Jz\\j\\

C.5.34a)

m) = mh\\j, m),

C.5.34b)

either an integer or a half-integerand m given by C.5.33). very It is to recall here that we have used only the commutation relations important to C.1.20)obtain these results.The quantization of angular momentum, is a manifested in C.5.34), direct consequence f the angular-momentum o commutation relations, which, in turn, follow from the propertiesof rotatogether with the definition of Jk as the generator of rotation.
with
rotations

j

Matrix Elementsof Angular-Momentum
angular-momentum

Operators

C.5.34)
and

Let us work out the matrix elementsof the various angular-momenoperators. Assuming |y, m) to be normalized,we obviously have from
(j\\m'\\J2\\j\\m)

= j(j + l)h28yj8m,m

C.5.35a)

\\ m'\\Jz\\j,

m) = mh&sjSm.m.

C.5.35b)

To obtain the matrix elementsof

(j,m\\Jl
Now

J+ \\j,

J+, we first consider m) = (j,m|(j2 // hJ,)\\j,m)

- -

be the same as |j,m +1) (normalized) up to a constant [seeC.5.12)]. Thus multiplicative
must
with Comparison

J + |j, m)

[

2-m].

C.5.36)

C.5.37)
leads C.5.36) to

C.5.38)

192

Theory of Angular Momentum

Sowe have determined c* up to an arbitrary phasefactor. It is customary 'jm to choose to be real and positive by convention. So cfm

C.5.39)
Similarly, we can derive

Finally, we determine the matrix elementsof

/.

C.5.40)
to

be

C.5.41
Representationsof the Rotation Operator Having obtained the matrix elementsof Jz and J we are now in a I positionto study the matrix elements of the rotation operator @{R). f a rotation R is specifiedby h and we can define its matrix elements by
\302\2619

<f>,

C.5.42)
These matrix elements are sometimescalled Wigner functions after E. P. Wigner, who made pioneeringcontributions to the group-theoreticalpropermechanics.Notice here that the same /-value we C.5.42);neednot considermatrix elements of 2d(R) between states with different y-values becausethey all vanish is trivially. This is because 3>(R)\\j,m) still an eigenketof J2 with the same + l)h2: eigenvalue
properties

of rotations

in quantum

appearsin

the ket and bra of

j(j

C.5.43)
which follows directly from the fact that J2 commutes with Jk (hence with any function of Jk). Simply stated, rotations cannot change the y-value, which is an eminently sensible result. Often in the literature the By + 1)X + 1) matrix formed by *s referred to as the B +1)-dimensional irreduciblerepresentation of the rotation operator @{R). his means that the matrix which correT to an arbitrary rotation operator in ket space not necessarily corresponds characterized by a single y-value can, with a suitable choice basis, be of

j

Bj

3.5.Eigenvalues

and Eigenstates

of Angular

Momentum

193

form: brought to block-diagonal

C.5.44)

\302\256m'lt

X where eachshadedsquare is a Bj +1) By +1) squarematrix formed by wi^ somedefinite value of Furthermore, each square matrix itself cannot bebrokeninto smaller blocks

j.

2y+1

-k 2/+1
2y+1-/c

2/+1

C.5.45)
choice basis. of The rotation matricescharacterizedby definite form a group.First, the identity is a member becausethe rotation matrix correspondingo no t x By + l) identity matrix. Second, the rotation D> 0) is the inverse is also a member; we simply reverse the rotation angle -> <J>) without changing the rotation axis n. Third, the product of any two
with

any

j

\342\200\224

Bj+1)

(<f>

-

194 membersis also a member;explicitly we have
m

Theory of Angular Momentum

C.5.46)
a where the product RXR2 represents single rotation. We also note that the rotation operator is rotation matrix is unitary becausethe corresponding we have unitary; explicitly

C-5-47)
To appreciatethe physical significanceof the rotation matrix let us start with a state represented \\j\\m). We now rotate it: by
\\j\\m)->\302\256(R)\\j9m). though this rotation operation doesnot change j\\ we generallyobtain states with m-valuesother than the original m. To find the amplitude for being found in m'),we simply expand the rotated state as follows:

C.5.48

Even

\\j\\

m

C.5.49
m

where, in using the completeness relation, we took advantage of the fact that connectsonly states with the same So the matrix element 2^m{R) @(R) is simply the amplitude for the rotated state to be found in m') when the unrotated state is given by \\j9m). original In Section3.3 saw how Euler angles may be used to characterize we the most general rotation. We now consider the matrix realization of for C.3.20) an arbitrary (not necessarily

j.

\\j\\

j

j):

\342\200\224

Um

'exp
h

h

exp

h

(j,m'|exp
Noticethat the
only nontrivial part which mixes different m-values. It

C.5.50
>\302\273-axis,

is the middle rotation about the is convenient to define a new
h

matrix

C.5.51
of C.3.21),

Finally, let us turn to beenworkedout in Section

3.3. the middle matrix See
cos

someexamples. he j = \\ casehas already T

(f) sin. f

-mr
cos

C.5.52

3.6.Orbital

Angular

Momentum

195

The next simplestcaseis y =1,which we considerin some detail. Clearly, we must first obtain the 3x3matrix representation of Jv. Because

/=
from the defining equation

2/
-1

C.5.53)
m'= -y/li m'= 0.
0 0
\342\200\224

to for C.5.5) /+,we can use C.5.41)obtain =1 w = 0

0
\\/2i

-\\fli
0
y/li

C.5.54)

0

Our next task is to work out the Taylor expansionof exp( iJvft/h). Unlike the case = \\, [JyJ=1)]2 independent of 1and Jvfy=1). However,it is easy is to work out

j

-1)\\3 /O= l)
h

h

C.5.55)
J,
h

for Consequently,

y

=1only,
h

it

is legitimate to replace
A
\342\200\224

exp as the readermay

cos/3)
we have
\\

sin/3,

C.5.56)

verify in

detail. Explicitly
/

1

sin

sin/3

cos

1

sin^S

C.5.57) 3.8 will we
Clearly, this
method

learn a much

becomes time-consumingfor large j. In Section easiermethod for obtaining dj^L(fi) for any j. MOMENTUM

3.6. RBITAL ANGULAR O

We introduced the concept of angular momentum by defining it to be the generator of an infinitesimal rotation. There is another way to approach the subjectof angular momentum when spin-angularmomentum is zero or can be ignored.The angular momentum J for a singleparticle is then the same as orbital angular momentum, which is defined as In
this

L = xxp. sectionwe explore the connectionbetween the

C.6.1)
two

approaches.

196

Theory of Angular Momentum

Orbital Angular Momentum as Rotation Generator note that the orbital angular-momentum operator definedas satisfies the angular-momentum commutation relations C.6.1)
We first

[Ll,LJ]=ieljkhLk Lx.Ly) = [ yPz

C.6.2)

by virtue of the commutation relations among the components of x and p. This can easily be proved as follows:

-

ZPy

\302\246

ZPx

-

XPz

yp

= ihL
Next we let act on an arbitrary position eigenket \\x\\ obtain

C.6.3) z') to examine whether it
can

C.6.4)
be interpreted as the infinitesimal rotation operator about the z-axis by angle 8<f>. Usingthe fact that momentum is the generator of translation, we
y\\

[see A.6.32)]
L

1-/

= \\x',y',z')

1-/

\\x',y\\z')

= \\x'-

C.6.5)

This is preciselywhat we expectif Lz generates an infinitesimal rotation about the z-axis. we have demonstrated that if p generates translation, So then L generates rotation. Suppose the wave function for an arbitrary physical state of a spinlessparticle is given by {x\\ y\\z'\\a).After an infinitesimal rotation about the z-axis is performed, the wave function for the rotated state is

{x\\y\\z'\\\\-i
It

L a) = (x'+y'8<}>, y'-x'H, '\\<*)z

C.6.6)

is actually more transparent to change the coordinate basis

C.6.7)
Forthe rotated state we have, according to C.6.6),
1

:

L

C.6.8)

3.6.Orbital

Angular

Momentum

197

Because(r,0,4>\\ is an

arbitrary

position eigenket,we can identify

C.6.9)
is a well-known result from wave mechanics. Even though this relation can alsobe obtainedjust as easily using the position representation of the momentum operator, the derivation given here emphasizesthe role of Lz as the generator of rotation. We next considera rotation about the .x-axis by angle 8$x.In we analogy with C.6.6) have
which

C.6.10
By
x\\ expressing y\\

and

z' in

spherical coordinates,we can show 86 -cot0cos<?

that

<x'|L\302\273

=

-i*

C.6.11

Likewise,
(x'\\Lv\\a)

=

-

If)
\\

cos<J>tt~cot6 sin<J>^7 du
d<p
\302\261

<x'|a>. C.6.12

we have

and for UsingC.6.11)C.6.12),the ladderoperator L definedas in

C.5.5),

{x'\\L
Finally,
it

\302\261\\a)

=

<9 ihe\302\261' -cot0\342\200\224

\\

d<p)
using

<x'|a>. C.6.13

is possibleto write (x'|L\\a)

C.6.14
and as follows: C.6.9), C.6.13), 1
sin20
Apart from

+

1
dd \\sm0 dd

C <x'|a>. .6.15

w 1/r2, e recognizethe differential operator that appearshere to be just the angular part of the Laplacian in sphericalcoordinates. It is instructive to establish this connectionbetween the L2 operator

and the angular part of the Laplacian in another way by looking directly at the kinetic-energyoperator. We first recordan important operator identity,
\342\200\224

L p (x*p)+/7ix*p, C.6.16 where x2 is understoodto be the operator x*x,ust as p2 stands for the j
\342\200\224x

198

Theory of Angular Momentum

operatorp#p. The proof of this is straightforward: = 2^ ?ijkXiPjelmkXlPm
ijlmk.

ijlm

L
ijlm

Pm*

= x2p2 x2p2-/7ix-pijlm

= x2p2

(x\302\273p)

+/7jx*p.

C.6.17)

Before taking the preceding between (x'| nd a expression
<x'|x\302\253p|a>

= x'=
\342\200\224

(-

\\a), first

note that

ihV

ihr'

d

. ..

'(x'\\a))

C.6.18

Likewise,

= -h
Thus

d dr

<x' x'|a>

C.6.19

d dr In terms of the kinetic energy p2/2m,we have 2m <x'
( h '2
\\

. C.6.20)

{2mjV'2<x'|a>
\\

( h2

1
2

2

2m

C.6.21
The first two terms in the last line are just the radial part of the Laplacian The last term must then be the angular part of the acting on in on (x'|a), completeagreement with C.6.15). Laplacian acting

(x'|a).

SphericalHarmonics Consider a spinlessparticle subjectedto a spherical symmetrical potential.The wave equation is known to be separablein spherical coordi-

3.6.Orbital

Angular

Momentum

199

nates and the energy eigenfunctionscan be written as

/ C.6.22) <x>,, m) = Rnl(r)Yr@,*), where the positionvector x' is specifiedby the spherical coordinates 0, r,
stands for some quantum number other than / and m, for number for bound-state problemsor the quantum for a free-particlesphericalwave. As will be made clearer in Section energy this o 3.10, form can be regarded as a direct consequence f the rotational invariance of the problem.When the Hamiltonian is sphericallysymmetriH commutes with Lz and L2, and the energy eigenketsare expectedto be eigenketsof L2 and Lz also. BecauseLk with A: =1,2,3 satisfy the
and
4>9

and

n

example,the radial

symmetrical,

angular-momentum commutation relations, the eigenvaluesof L2 and Lz are expected be /(/ + l)/i2,and mh = to + Becausethe angular dependence common to all problemswith is sphericalsymmetry, we can isolate it and consider
this point of view, by @, <j>) is the amplitude for a state characterized /, m to be found in the direction n specified 0 and by Supposewe have relations involving orbital angular-momentum eirelations involving the eigenkets. We can immediately write the corresponding harmonics. or example,take the eigenvalueequation F spherical
Y\342\204\242

[-lh,(-l l)h,...9(l-l)h9lh

<h|/,m) = Yim@, = y/\"(h), where we have defined a direction eigenketn). From |
<t>)
cf>.

C.6.23)

C.6.24)
Multiplying

(h| on the left and

using

- ih-jr-(h\\l, = m)

we C.6.9), obtain
mh(h\\l,

m).

C.6.25)

We

recognize this equation to be

^y/\"@,<?)= m/*y/\"@,4>),
which

C.6.26)
behave like
elm<t>.

implies that the ^-dependencey/\"@, t Likewise, correspondingo

<?) must

L2|/, ) = /(/ +l)/*2|/, m m>,
we have [see C.6.15)]
7^ sin
which

C.6.27)

C.6.28)
Y,m

orthogonality relation

is simply the partial differential equation satisfiedby

itself. The

C-6.29

200

Theory of Angular Momentum

leads to

f

O

-I

C.6.30)

where we have used the completeness relation for the direction eigenkets,

C.6.31
To obtain the have
which,
Y\342\204\242

themselves,we may start

with

the m

\342\200\224

I

case. e W

C.6.32)
o leads because f C.6.13), to

-ike*

= n|/,/> 0

C.6.33)

m we Remembering that the ^-dependence ust behave like e'1*, can easily show that this partial differential equation is satisfiedby

<n|/,/> = Y/@, = c^'+sin'd,
<f>)

C.6.34)
to C.6.30)be*

where c{is the normalizationconstant determined from

(-D7

2'/!

4it

C.6.35

Starting

with

we C.6.34) can use
(h\\L_\\l,m)

dd

+ icot 6

n|/,m)

C.6.36
t successivelyo obtain all Ytm with / fixed. Becausethis is done in many textbookson elementary quantum mechanics, we will not work out the detailshere. he result for m > 0 is T

(-D/ I'll
*Normalization
(\342\200\224

l\342\200\224m

l-m d(cos6)

C.6.37)
1)'is inserted
Yf\302\260

obtain
/>,(!)\302\253!

C.6.39)]. [see

of C.6.30), course, doesnot determine the phase of cf. The factor when we use the L_ operator successively to reach the state m 0, we whose phase is fixed by with the same sign as the Legendre polynomial P^cosO)
condition

so that

\302\253

3.6.Orbital

Angular

Momentum

201

and we define Yi

m

by

p Regardlessof whether m is positive or negative, the ^-dependent art of with a highest power of is [sin0]|w|times a polynomial in cos0 Ytm@,
<f>)
\342\200\224

? [}*.

C.6.38)

\\m\\.

Form = 0, we obtain

From the point of view of the angular-momentum commutation i relations alone,t might not appearobvious why / cannot be a half-integer. It turns out that several arguments can be advanced against half-integer /-values. First, for half-integer /, and hence for half-integer m, the wave function would acquire a minus sign,
e'\302\253Bw)\302\273\302\253lf

C.6.40

under a 2tt rotation. As a result, the wave function would not be singlevalued; we pointed out in Section2.4that the wave function must be of single-valuedbecauseof the requirement that the expansion a state ket in terms of positioneigenkets e unique. We can prove that if L, defined to be b x X p, is to be identified as the generator of rotation, then the wave function must acquirea plus sign under a 2tt rotation. This followsfrom the fact that the wave function for a 27r-rotatedstate is the original wave function itself with no sign change:

(x' exp
\\

5
n

I

a) = (jc'cos2tt+ y'sin27r, ^'cos2tt

\342\200\224

Jt'sin27r,

-<x1a>,

z' a) C.6.41

where we have used the finite-angleversion of C.6.6). let us suppose Next, with a half-integer / were possible. o be specific,we choose T the Y/m@,4>) / we simplestcase, = m = \\. According to C.6.34) would have From the property of
L__

C.6.42
we [seeC.6.36)]would
then

obtain

-\302\253-\302\246

+1-cot

= c1/2<r'*/2cot 0\\/sin0\\

-

C.6.43

This expression not permissible ecause is singular at 6 = 0, What is is it b it. worse,from the partial differential equation

=0

C.6.44

202

Theory of Angular Momentum

we directly obtain
in

[^,
Y\342\204\242

C.6.45)

Finally, we know from the Sturmsharp contradiction with C.6.43). with Liouville theory of differential equations that the solutionsof C.6.28) / form a complete set. An arbitrary function of 6 and <? can be integer it with integer / and m only. Forall these reasons expandedin terms of is futile to contemplate orbital angular momentum with half-integer /-val/-values.

H Spherical armonicsas Rotation Matrices We concludethis section on orbital angular momentum by discussh the spherical armonics from the point of view of the rotation matrices W introduced in the last section. e can readily establishthe desiredconnecbetween the two approaches y constructing the most general direction b eigenket|h) by applying appropriate rotation operatorsto |z),the direction eigenketin the positive z-direction.We wish to find S>(R)such that
discussing connection

\\h)

= @(R)\\z).

C.6.46
\342\200\242

We can rely on the techniqueusedin constructing the eigenspinorof a h in Section We first rotate about the >>-axis by angle 0, then around the z-axisby angle see with ft -> 0, a -> In the notation of Euler Figure

3.2.

<J>;

3.3

<f>.

angleswe have

Writing

as C.6.46)

@(R)= $(a= <t>,p = d,y = 0).
|n> =

C.6.47)

E I>(*)|/> m|z>, m)(l, m
/

C.6.48

we seethat |h), when expandedin terms of |/,m), contains all possible /-values. However, when this equation is multiplied by (l,m'\\ on the left, only one term in the /-sum contributes, namely,

(/,m'|h> = m
<f>

E#i'i,(\302\253

= 4>,fi = 0,y = 0)</,m|z>.
Y\342\204\242

C.6.49

Now (/, m\\z) is just a number; in fact, it is precisely evaluated at 6 = 0 with undetermined. At 6 = 0, is known to vanish for m # 0, which can alsobe seendirectly from the fact that |z) is an eigenket of Lz S (which equalsxpy ypx) with eigenvaluezero. o we can write
<f>)
Y\342\204\242 \342\200\224

F,

</,m|z> = Yr\\6 = 0,<? undetermined)8m0 B/+ 1)
4tt 4tt
0 cos = 1

C.6.50

3.7.Addition of Angular
Returning to

Momenta

203

we C.6.49),have

C.6.51
or

C.6.52)
Notice the
m

= 0 case, hich is of particular importance: w

C.6.53
3.7.ADDITIONOF ANGULAR
Angular-momentum
collisions. physics\342\200\224from

MOMENTA

addition has important applications in all areas of modern to atomic spectroscopy nuclear and particle colliaddition provides an Furthermore, a study of angular-momentum excellent to illustrate the conceptof change of basis,which we opportunity discussed extensivelyin Chapter

1.

o SimpleExamples f Angular-Momentum
worth

Addition

Before studying a formal theory of angular-momentum addition, it is looking at two simple exampleswith which the reader may be familiar: A) how to add orbital angular momentum and spin-angular momentum and B) how to add the spin-angular momenta of two spin \\ Previously we studied both spin \\ systemswith all quantum-mechaas position and momentum degreesof freedomother than and quantum-mechanicalparticles with the space degreesof freedom (such as position or momentum) taken into account but the internal degreesf freedom (such as spin)ignored. realistic description A of o a particle with spin must of coursetake into account both the spacedegree of freedom and the internal degrees freedom.The base ket for a spin \\ of be visualizedto be in the direct-product spaceof the infiniteparticle may dimensional ket spacespannedby the position eigenkets{|x')} the and we have two-dimensional spin spacespannedby | + ) and | Explicitly, for the base ket
quantum-mechanical

particles.

spin\342\200\224such

\342\200\224ignored

\342\200\224

).

C.7.1)
where
any operatorin

commutes with operator in the spacespannedby {|x')} the two-dimensionalspacespannedby | +

).

any

204

Theory of Angular Momentum

b The rotation operator still takes the form exp(-J-h</>//j)ut / of rotations, is now made up of two parts, namely, generator

J, the

J = L+ S.
L\302\2561

C.7.2)

It

is actually more obvious to write J=

as C.7.2) +
1\302\256S,

where the
write

L 1standsfor the identity operator in the spin space,while k the 1in 1 S standsfor the identity operator in the infinite-dimensional et the position eigenkets. L Because and S commute,we can spacespannedby
\302\256 \302\256

1in

C.7.3)

j

C.7.4)

The wave function for a particle with spin is written as The two components follows:
+

C.7.5)
\\p

are often arranged

in

column matrix form as

C.7.6)
stands for the probability density for the particle to be as the base spin up and down, respectively.Insteadof kets for the spacepart, we may use \\n, /, m), which are eigenketsof L2 and Lz with eigenvaluesh2l(l + 1)and mth, respectively.For the spin part, are eigenkets S2 and Sz with eigenvalues3h2/4 and h/29respectively. of However, as we will show later, we can also use base kets which are of In other words,we can expanda state ket of eigenkets 7Z, L2, and a particlewith spin in terms of simultaneouseigenkets f L2, S2, Lz, and Sz o where
\\\\p

found at

x' with

\302\261(x')\\2

|x')

|\302\261>

\302\261

J2,

S2.

or in terms of simultaneouseigenketsof J2,7Z, L2, and S2. e will study in W detail how the two descriptionsre related. a As a second example, we study two spin \\ two electrons\342\200\224with the orbital degreeof freedom suppressed. he total spin T operatoris usually written as
particles\342\200\224say

S = S1+S2,
x\302\256

C.7.7)

but again it

is to be understood as

1+1

\302\256

JS29

where the

1in the first (second)term standsfor the identity operator in the spin spaceof electron 2 A). We, of course,have
and so forth.
Within

C.7.8)

C.7.9)
the

space of electron

1B)we

have the usual

3.7.Addition of Angular

Momenta

205

commutation relations
and As a direct consequencef C.7.9) o

C.7.10) [Slx,Sly]=ihSlz,[S2x,S2y]=ihS2z,....
we C.7.10),have

[Sx,Sy\\=ihSz

C.7.11

and so on for the total spin operator. are The eigenvaluesof the various spin operators denotedas follows: 2 2: s(s+l)h2
Sz = Slz+ S2z

Slz
S2z
Again,
two

: mh : mxn : rn2h

C.7.12

we can expand the ket corresponding an arbitrary spin state of to electronsin terms of either the eigenketsof S2 and Sz or the eigenkets of iSlz and S2z.The two possibilitiesre as follows: a 1.The {^h,w2} representation based on the eigenkets of S^ and and
m1 = \\,

2.The {s, ) representation (or the m

where

\\-\\\342\200\224

) stands for

= m2

l-->>
\342\200\224

C-7-13)

\\,

and

so forth.

based on the eigenketsof S2 and Sz: m = \302\2611,0), \\s = 0,m = 0), \\s =1,

triplet-singletrepresentation)

where s =1(s = 0) is referred to as spin triplet (spinsinglet).

C.7.14)

between the

Notice that in each set there are four base kets. The relationship two sets of baseketsis as follows:

= 5=l,w=l> |++>, =

|-->,
)
A+->-!-+\302\273\342\200\242

\\y/2

C.7.15a C.7.15b C.7.15c C.7.15d

The right-hand side of C.7.15a) us that we have both electrons with tells W spin up; this situation can correspond only to j =1,m =1. e can obtain from C.7.15b) C.7.15a) applying the ladderoperator by
i3

= i3i

t

in

= (Slx-iSly)(S2x-iS2y) +

C.7.16)

206

Theory of Angular Momentum

write

In doing so we must remember that an electron 1 to both sidesof C.7.15a). operatorlike S\\_ affectsjust the first entry of |++), and so on. We can

+ m S_ = 1, =1)= {Sx_ S2_)|++ >
\\s

C.7.17)

as

C.7.18)
which immediately leads to Likewise,we can obtain m= once again to by applying Finally, we can obtain it to be orthogonal to the other three kets,in by requiring
\342\200\224

C.7.15b). |j=1, C.7.16) C.7.15b). C.7.15d) particular to C.7.15b). The coefficientsthat appearon the right-hand sideof C.7.15) the are

1)

coefficientsto be discussed further at a simplestexampleof Clebsch-Gordan later time. They are simply the elementsof the transformation matrix that connectsthe {mx, basis to the m2) m) basis.It is instructive to derive these coefficientsin another way. Suppose write the 4x4matrix correwe to corresponding

[s,

becausean operator
matrix that

S2 = S12+S22+2S1-S2 = S2l+S22+2SlzS2zSl+ S2_+ Sl_S2+ + C.7.19) using the (mvm2) basis. The square matrix is obviously not diagonal
\\mx, m2) basekets into the base kets. The elements of this unitary matrix are preciselythe \\s,m) Clebsch-Gordan coefficientsfor this problem.The readeris encouraged to work out all this in detail.

like Sx+ connects

|\342\200\224h)

with

diagonalizesthis matrix

carries the

|++).The unitary

Formal Theory of Angular-Momentum

Addition

Having gained some physicalinsight by consideringimpleexamples, s we are now in a position to study more systematicallythe formal theory of t angular-momentumaddition. Considerwo angular-momentum operators Jx and J2 in different subspaces. he components of Ji(J2)satisfy the usual T angular-momentum commutation relations:

C.7.20a)
and

[J2i,j2j]=iheukj2k.

C.7.20b)

3.7.Addition of Angular However, we have

Momenta

207

= [Ju,J2l]0

C.7.21)

between any pair of operators from different subspaces. 1 The infinitesimal rotation operator that affects both subspace and 2 is written as subspace

1We

Hx n5<|> h
\342\200\242

i ^ L
\\

1-

H2

\342\200\242

n8(J>

h

=, 1

-

i{tx\302\256\\

+

\342\200\242

1\302\256J2)

n

h

C.7.22)
define the total angular momentum by

JsJ^l+
as

1\302\256^,

C.7.23)

which

is more commonly

written

J = J1+J2.
The finite-angleversionof C.7.22) is

C.7.24)
~*

)- C.7.25) Notice the appearanceof the same axis of rotation and the same angle of rotation. It is very important to note that the total J satisfies the angularmomentum commutation relations
ft

~l

Uexp

I

C.7.26)
as a direct consequence C.7.20) C.7.21).other words, J is an of In and momentum in the senseof Section 3.1. angular Physically this is reasonable because is the generator for the entire system. Everything we learned in J Section example, the eigenvaluespectrum of J2 and Jz and the matrix elements of the ladderoperators\342\200\224also holdsfor the total J. As for the choice basekets we have two options. of
3.5\342\200\224for

Simultaneouseigenketsof J2,J22, Jlz,and J2z, denoted by \\j\\j2\\ mxm2). bviously the four operatorscommute with each other. O The defining equations are Option A:

I)h2\\jj2; mxm2),
m2), = hih +l)h2\\Jd2>^i^2>^ = m2h\\jj2; xm2). m
that this

C.7.27a) C.7.27b) C.7.27c) C.7.27d)

J2, Option B: Simultaneouseigenketsof J2, J22, and Jz. First, note set of operatorsmutually commute. In particular, we have

[J2,J12]=O,

C.7.28)

208
which

Theory of Angular Momentum

can readily be seenby

writing

J2 as

J2= J2+ J22 +2 J2z + /1 /2.+ Jl.J2 + + Ju
We

C.7.29)

use \\jv

j2;jm) to denote the baseketsof option B:
*\\\\j\\h\\ Ji\\JiJ2\\

Jm) = h(h + W1\\J\\h\\ Jm)> = h(h + l)*2l7i72; Mh
J\342\204\242)

2

I)h2\\jj2; jm),

j2;jm).
Quite often jl9 j2 are understood, and the basekets are written
\\j\\m).

C.7.30a) C.7.30b) C.7.30c) C.7.30d)
simply

as

It

is very

important

to note that even though

[J2,/Z]=O,
we have

C.7.31)

[J2,J1Z]*O,[J2,/2J'#O,

C.7.32)

This as the reader may easily verify using C.7.29). means that we cannot add J2 to the set of operators of option A. Likewise, e cannot add Jlz w to the set of operators of option B. We have two possible setsof and/orJ2z base kets corresponding the two maximal sets of mutually compatible to observables e have constructed. w Let us considerthe unitary transformation in the senseof Section 1.5 connectsthe two bases: that
\\j\\h\\

Jm) =

?
m

H\\hJi\\

m\\mi){kh\\

mlm2\\jj2;m), j

C.7.33)

where we have used

yV^

C.7.34)

and where the right-hand side is the identity operator in the ket space of given j\\ and j2. The elements of this transformation matrix c (JiJi*m\\m2\\J\\JT> Jm) are Clebsch-Gordanoefficients. There are many important properties Clebsch-Gordanoefficients of c that we are now ready to study. First, the coefficients vanish unless
m

= mx + m2.

C.7.35)

To prove this,
Multiplying

first

note that

(J,
(j\\j2;mlm1\\

-Jlz -J2z)\\jJ2;jm) = 0.
on the left, we obtain
mxm2\\jxj2\\

C.7.36)

m-nti-m2)(jj2;

jm) = 0,

C.7.37)

3.7.Addition of Angular
which

Momenta

209

A proves our assertion. dmire the power of the Dirac notation! It in bracket form, coefficients Dirac's to write the Clebsch-Gordan really pays as we have done. vanish unless the Second, coefficients

+ \\Ji-J2\\*J*JiJ2-

C.7.38)

This property may appear obvious from the vector model of angularmomentum addition, where we visualizeJ to be the vectorial sum of Jx and J2. However, it is worth checking this point by showing that if C.7.38) holds, then the dimensionality of the spacespannedby {\\j\\j2\\ m\\m2)} is the (ml,m2) the same as that of the spacespannedby {\\j\\j2\\ Jm)}way of counting we obtain
F\302\260r

+ C.7.39) N-Bj\\+ l)Bj2 l) becausefor given j\\ there are 2j\\ +1 possiblevalues of m x; a similar A statement is true for the other angular momentum j2. s for the (j\\m) way of counting, we note that for each j\\ there are 2j+ l states, and according to C.7.38), itself runs from jx j2 to jx + j2,where we have assumed, j without loss of generality, that j\\ > j2. We thereforeobtain
\342\200\224

j\\

+h

J\\

-h
C.7.40)

Because both ways of counting give the same TV-value, we see C.7.38) that is * quite consistent. The Clebsch-Gordan coefficientsform a unitary matrix. Furtherthe matrix elementsare taken to be real by convention.An immediate of consequence this is that the inversecoefficient(j\\j29 jm\\jlj2\\ m^m^) is the same as (j\\j29 ^\\^2\\j\\j2\\ jm) itself. A real unitary matrix is orthogoso we have the orthogonality condition
Furthermore,
orthogonal,

<JlJ2lm\\m is obvious from the orthonormality of {\\j\\j2\\ miM2)}together with the reality of the Clebsch-Gordan coefficients. ikewise, also have we L

C.7.41)
which

j m )=

Ojj'Omm>.

C.7.42)
book.
*A complete proof of C.7.38) given in Gottfried is

1966, and also in Appendix B of this 215,

210
As a

Theory of Angular Momentum

obtain

specialcaseof

this

we may set

j'=j, m'= m = ml + m2. We
M Jm)\\2 =l>

then

C.7.43)

m

which

is just the normalization condition for \\j\\j2\\ ji Some authors use somewhat different notations for the ClebschGordan coefficients. Instead of (j\\j29 mlm2\\jlj2\\ jm) we sometimes see mxm2m), Cjd^jm\\ mxm2\\ and so on. They C(jj2j; (j\\mlj2m2\\jlj2jm), can alsobe written in terms of Wigner's 3-y symbol, which is occasionally
found
in

the literature:

JJiJ
m^m0
\342\200\224

C.7.44)
Coefficients* RecursionRelationsfor the Clebsch-Gordan
With j\\, j2,and fixed, the coefficientswith different are related to each other by recursionrelations.We start with

j

mx

and m 2

C.7.45)
and we m'2) UsingC.5.39) C.5.40) obtain (with mx->m[, m2->

J2;j,
m[ m'2

m\302\261\\)

m '2)(j2 m'2
\302\261

m +1)\\jj2; [9 m'2

\302\261

Our next

mality, which

means that are possibleonly with side for the
first

(j\\j2;rn[m2\\jj2; jm). C.7.46) on step is to multiply by {Jxj^m^m^ the left and use orthonorX

nonvanishing

contributions from the

right-hand

x

C.7.47) =
m'2\302\261l

term and

C.7.48)
recoupling, and the

*More-detailed discussion of Clebsch-Gordan and Racah
like is given in A.

coefficients,

f R. Edmonds 1960,or instance.

3.7. Addition

of Angular Momenta

211
manner we obtain the

for the second term. In relations:

this

desired recursion

j2;mlm2\\jlj2;
mi

j9
mi

m\302\261\\)

i

\302\261

mi) {j\\h\\
\302\261

\\h\\

Jm)
2; jm).

1H2
\302\261

\"h, m 2

C.7.49)
It is important to note that becausethe J operatorshave shifted the condition C.7.35)or the Clebsch-Gordan f m-values, the nonvanishing coefficientshas now become [when appliedto C.7.49)]
mx

+ m2 = m

\302\2611.

C.7.50)

We can appreciate the significanceof the recursion relations by The in looking at C.7.49) an m1m2-plane. /+ recursionrelation (uppersign) tells us that the coefficient at (ml9m2) is related to the coefficientsat a L (m1 l,m2)nd (ml,m2 \\\\ as shown in Figure 3.5a. ikewise,the /_ recursion relation (lower sign) relates the three coefficientswhose m1,m2 valuesare given in Figure 3.5b. Recursion relations C.7.49),ogether with normalization condition t almost coefficients.We say ( C.7.43), uniquely determineall Clebsch-Gordan \"almost uniquely\" because conventionshave yet to be specified.) certain sign Our strategy is as follows.We go back to the m1m2-plane,again for fixed l9 j2,and j\\ and plot the boundary of the allowed region determined by
\342\200\224 \342\200\224

-

Ju

\\m2\\^J2,

seeFigure 3.6a. We
A.

-j-

mx

+ m2^ /;

C.7.51)

corner, denotedby may start with the upper right-hand Because work near A at the start, a more detailed \"map\" is in order; we

RHS

\\ \\ \\ \\ \\ \\ \\ \\ \\ \\ \\

1 I

j\\
(mi,m2-1)

\\ \\ \\ \\

i
(mi,m2)

\\ \\

RHS

(a) J+ relation
FIGURE

(b)

J-relation

relations

3.5. w1m2-plane C.7.49).

showing the Clebsch-Gordan coefficients related by the recursion

212

Theory of Angular Momentum

with

We seeFigure 3.6b. apply the J _ recursion relation C.7.49)lower sign), ( (mvm2+l) corresponding to A. Observe now that the recursion

to relation connectsA with only B becausethe site corresponding (ml+ we can obtain the ClebschAs i l,ra2)s forbidden by m1<jv a result, Gordancoefficientof B in terms of the coefficientof A. Next, we form a/+ triangle made up of A, B, and D.This enablesus to obtain the coefficient We of D oncethe coefficientof A is specified. can continue in this fashion: to E\\ knowing B and E we can get to C, Knowing B and Z>, we can get and so on. With enough patience we can obtain the Clebsch-Gordan coefficientof every site in terms of the coefficientof starting site, A. For The overall normalization we use C.7.43). final overall sign is fixed by the following example.) convention. (See As an important practical example we consider the problem of addingthe orbital and spin-angularmomenta of a single spin \\ particle.We have

= / (integer), Jl
~~

ml m2

= mh

S \"~

2

J- 2

I

C.7.52)

The allowed values of

j are given by
=0

C.7.53) Sofor each / there are two possible y-values;for example,for / = 1(p state) r where the subscript efers we get, in spectroscopicotation, p3/2 and pl/2, n is
to
particularly

this j. The m1m2-plane,or better the ra/W^plane,ofthe two rows:

and the lower row for

T simple. he allowedsitesform

m=-\\\\

ms = \\ see Figure 3.7.Specifically,we work out
only

problem

particu-

upperrow for

D

r-\342\200\224

1 1 1

>

Forbidden!
I

! J- \\\\J
J+
\342\200\224-4

\\ \\ \\

J-

^x

/77i+m2\342\200\224-/

I
m2\342\200\224-J2

c
(b)

(a)
FIGURE

3.6. Useof the

recursion relations to obtain the Clebsch-Gordan coefficients.

3.7.Addition of Angular

Momenta

213
X X \\
\302\246

4
\"

m.

X \\
I

K
i \\

m
\342\200\242 \342\200\242

FIGURE 3.7. Recursion relations used to obtain the Clebsch-Gordan coefficients for and j2 = s = \\.

jl = /

the
in

case = I + \\. Because cannot exceed we can usethe J _ recursion j' \\, ms such a way that we always stay in the upper row {m2= ms = \\), while the
one

m /-value changesby

obtain from

Suppressingj\\ = I, j2 = \\

C.7.49) sign) (lower

unit each time in writing the

we considera new J _ triangle. Clebsch-Gordanoefficients,we c
\\,

/(/
where we have used
In
this way

+ + +!)(/ i-m)(m-\\,\\\\l

,

C.7.54)

C.7.55)
by one unit:
m

we can move horizontally

1 1, 1
We

/+2'm

+

2' 2

1^

2

C.7.56

can in turn express(m + \\, \\\\l + \\, m +1)in terms of (m + f, \\\\l + j,m + 2), and so forth. Clearly, this procedurecan be continued until mt reaches/, the maximum possible value:

11
2

/+

-,

m

+2

X

5

1

-

l+m+

Z

2/ + 1

C.7.57)

214

Theory of Angular Momentum

configuration in which ml and ms / and \\, respectively.The total m = m7 + ms is / is, + which is possibleonly for = I + \\ and not for = / \\. So \\ml = /, must be equal to \\j = / + 5, m = I + \\) up to a phase factor. We ms = take this phasefactor to be real and positiveby convention.With this choice
angular-momentum

Considerthe

are both maximal,

j,

that

i)

j:

j:

\342\200\224

we have

C.7.58)
Returning to

we C.7.57), finally

obtain

1 1, 1
But this
determine

/+2'm

2/ + 1

C.7.59)
de-

is only about one-fourth of the story. We must still the value of the question marks that appearin the following:

y

=/ +

-,m) =
,m

=m

=

-

2/ + 1

1 = = m--,ms 1

-

C.7.60)
\342\204\242-2'W*=2

=

2 '\"'5
1_

We note that the transformation matrix with fixed m from the (m,,ms) basis is, becauseof orthogonality, expectedto have the basis to the form

(j,m)

cos sin a a C.7.61) a sin a cos a shows that cos is C.7.59) itself; so we can Comparisonwith C.7.60) determine sin a up to a sign ambiguity: readily
\342\200\224

sin2a =
We

1

\342\200\224

B/+ 1)
\342\200\224

(/-

#\302\273

+*

B/+ 1)

C.7.62)

all
\\j

\342\200\224

convention. So the

(m,= m + \\,ms= \\\\j = 1 + \\,m) must be positivebecause = I + \\ statesare reachableby applying the J _ operator successivelyto j I + in = I + 2)* and tne matrix elementsof J_ are always positive by
claim that

i,

2x2transformation
2/ + 1 2/ + 1

matrix

can C.7.61) be only

2/ + 1 2/ + 1

C.7.63

3.7.Addition of Angular
We

Momenta

215
in

define spin-angular functions

two-componentform as follows:
X

. C.7.64)
They are, by construction, simultaneous eigenfunctionsof L2, S2,J2,and Jz. They are also eigenfunctionsof L*Sbut L*S,being just

L-S=Q)(J2-L2-S2),
follows: 2
lh2

is not independent.Indeed, its eigenvalue can easily be computed as
hi\" j for / = /
\342\200\224

C.7.65)

?.

C.7.66)
Clebsch-Gordan Coefficientsand Rotation Matrices addition may be discussedfrom the point of Angular-momentum view of rotation matrices. Considerhe rotation operator 3)Ul)(R) the ket t in the angular-momentum space spanned by eigenketswith eigenvalue jv c T Likewise, onsider@Ul\\R). he product ^(yi)\302\256^(^) is reduciblein the sense that after suitable choice of base kets, its matrix representation can
take the following form:

O
(J1+J2-1)
(J1+J2-2)

o

C.7.67)

216
In the notation of group
theory this

Theory of Angular Momentum

is written as

C.7.68)
known as the Clebsch-Gordan series: expansion

In terms of the elements of rotation matrices, we have an important

EE j m m'
where the y-sum runs from The proof of this equation j2\\ to jx + j2. follows. First, note that the left-hand sideof C.7.69)the same as is m[m2)

1^-

,

C.7.69)

-

? {%2

C.7.70)

But the

of statesin the

samematrix element is alsocomputable by inserting a complete set b (j,m) asis.Thus

UiJ2>mim2\\@(R)\\JiJ2'> m[m2)

E E E EOiA; i^jmmxjiji* ^ Jm\\^(R)\\jJ2> j'm') j m y m' E EE
which

j' m'
right-hand

C.7.71)
sideof C.7.69). we application of C.7.69), derive an important formula for an integral involving three spherical harmonics. First, recall the connection between 3)^1 and 7/w* given by C.6.52). Letting j\\ -* /1?j2 -> we (hence m'-^O) in C.7.69), obtain, after complex /2,m(^0,m2^0 conjugation, is just the
As an interesting

/'

m'

We

both sidesby Y^XO^) and integrate over solid angles.The multiply summations drop out becauseof the orthogonality of spherical harmonics,

3.8.Schwinger's

Oscillator Model of Angular Momentum

217

and we are left

with

C.7.73)
The squareroot factor times the first Clebsch-Gordan coefficient s indepeni of orientations; that is, of m1 and m2. The secondClebsch-Gordan coefficientis the one appropriate for adding lx and l2 to obtain total /. t Equation C.7.73)urns out to be a specialcase of the Wigner-Eckart theorem to be derived in Section 3.10. formula is extremelyuseful in This matrix elementsin atomic and nuclear spectroscopy. evaluating multipole
independent

3.8. CHWINGER'S S MODELOF OSCILLATOR
ANGULAR
Angular

MOMENTUM

UncoupledOscillators There exists a very interesting connection between the algebra of angular momentum and the algebra of two independent (that is, uncoupled) n oscillators,which was worked out in J. Schwinger's otes [see Quantum Theory of Angular Momentum, edited by L. C. Biedenharn and H. Van Dam, Academic PressA965), p.229]. Let us considertwo simple harmonic w oscillators, hich we call the plus type and the minus type. We have the annihilation and creation operators, enotedby a+ and a\\ for the plus-type d w We oscillator;likewise, e have a_ and al_ for the minus-type oscillators. also define the number operators 7V+ and N_ as follows:
Momentum and

#+ = a\\ a +
We

9

N_

= ala_.

C.8.1)
TV

assumethat the usual commutation relations among a, a*, and for oscillators the same type (seeSection 2.3). of
]

hold

a_,
9

a\\ \\

\\= \\=a\\9
any

However,we assume that commute: and so forth. So it is

[N_9 of operators between different oscillators pair

al]=al.

C.8.2a) C.8.2b) C.8.2c)

= [a+,al] [a_,a\\]=0
sense that we say the
two

C.8.3)
oscillators are

in this

uncoupled.

218

Theory of Angular Momentum

BecauseJV+ and N_ commute by virtue of C.8.3), can build up we simultaneous eigenkets of iV+ and N_ with eigenvalues n+ and n_, respectively.Sowe have the following eigenvalueequations for
N\302\261:

. C.8.4)
and the complete analogy with B.3.16) B.3.17),creation and and a+, act on |w+, n_ ) as follows: operators,a\\ In
annihilation
w +,

w_+ 1),

C.8.5a)

C.8.5b)
We

can obtain the most general eigenketsof N+ and N _ and a!_ successivelyto the vacuum ket defined by

by

applying

a\\ \\

= 0, a+|0,0>
In
this way

= a_|0,0> 0.

C.8.6)

we obtain
n + , n_ >

=

C.8.7)

Next, we define and

C.8.8a)

C.8.8b)
We can readily prove that these operators satisfy the angular-momentum commutation relations of the usual form
[Jz,J\302\261]

=

\302\261

,

C.8.9a) C.8.9b)

Forexample,we prove C.8.9b)follows: as
h2[a\\a-,aLa+]= h2a 2[a\\
\342\200\224h2a!-a+a\\a-

= h2a\\\\ = h\\a\\ h\\a\\a+
Defining the total N to be

-

-h2ai(a\\a+ \\)a. 2ai(a\\ + aia-)= 2hJ2.
a+

C.8.10)

C.8.11

3.8.Schwinger's

Oscillator Model of Angular Momentum

219

we can also prove

N
which

''

C.8.12

is left as an exercise.

What are the physicalinterpretations of all this? We associate spin up (m = with one quantum unit of the plus-type oscillatorand spindown (m = j) with one quantum unit of the minus-type oscillator. If you like, you may imagine one spin \\ \"particle\" with spin up (down) with each T quantum unit of the plus- (minus-) type oscillator. he eigenvaluesn + and n_ are just the number of spins up and spins down, respectively.The is that it destroys one unit of spin down with the z-compomeaning of of spin-angular momentum and createsone unit of spin up with the z-component of the z-component of spin-angular momentum + /_ by angular momentum is therefore increased h. Likewise destroysone unit of spin up and createsone unit of spin down; the z-component of by angular momentum is therefore decreased h. As for the Jz operator, it times the differenceof n+ and /i_, just the z-component simply counts at our disposalwe can easily of the total angular momentum. With examine how and Jz act on \\n+, n_ ) as follows:

j)

\342\200\224

/+

\342\200\224

z-component

h/2

h/2;

h/2

C.8.5)

J\302\261

C.8.13a

C.8.13b

C.8.13c
t Noticethat in all these operations, the sum n+ + n_, which correspondso the total number of spin \\ particles remains unchanged. reduce to the and Observenow that and Jz operatorswe derived in Section3.5, f familiar expressionsor the provided we substitute

C.8.13a), C.8.13b), C.8.13c)
J\302\261
\342\200\224

m.

C.8.14

The squareroot factors in

and C.8.13a) C.8.13b) to change

which

are exactly the square root factors appearing in

and C.5.39) C.5.41)

220

Theory of Angular Momentum

Notice also that the eigenvalue of the J2 operator defined by changesas follows:
<h 2
\\

C.8.12

2
All this may that

+1

+ h2j(j l).

C.8.16

not be too surprising becausewe have already proved and J2 operatorswe constructed out of the oscillator operators satisfy the usual angular-momentum commutation relations. But it is inin instructive to see an explicit manner the connectionbetween the oscillator it I matrix elements and angular-momentum matrix elements. n any case, is
J\302\261

now natural to

use

7
in w_

_ =

+

)

2

>

m==
\342\200\236

+

j
into
\342\200\224

According to
\342\200\224

placeof n + and h_ to characterizesimultaneouseigenketsof J2 and /z.

means that y is unchanged and m goesinto ra Likewise, we seethat the /_ operator that changes n+ into n+ rc_ into n_ +1 lowersm by oneunit without changing y. We can now write as C.8.7) for the most general N+, N_ eigenket
+

1,which

the C.8.13a) action of /+ changes n+

f h++1,l_

m/

\\

+

}

[a~l\\0) ?

|

1;

+1.

into

w- m

C.8.18

j.

where we have used |0) for the vacuum ket, earlier denotedby |0,0). A special caseof C.8.18)of interest. Let us set m = which is for physically means that the eigenvalueof Jz is as large as possible a given We have

j,

^L ?
We

C.8.19

spins all pointing

can imagine this state to be built up of 2j spin \\ particles with their in the positive z-direction. In general, we note that a complicated object of high can be visualized as being made up of primitive spin \\ particles, + m of them with spin up and the remaining m of them with spin down.This picture is extremely convenienteven though we obviously cannot always regard an object of angular momentum literally as a composite system of spin \\ All particles. we are saying is that, as far as the transformation properties under rotations are concerned, we can visualize any object of angular as a composite momentum system of 2j spin \\ particlesformed in the manner indicatedby C.8.18).

j j

j

j

\342\200\224

j

3.8.Schwinger's

Oscillator Model of Angular Momentum

221

From the point of view of angular-momentum addition developedin the previous section,we can add the spinsof spin \\ particles to obtain As a simpleexample, we states with angular momentum j9 momenta of two spin \\ particles to obtain a total can add the spin-angular oscillator scheme, angular momentum of zero as well as one.In Schwinger's when we start we obtain only states with angular momentum however, In the language of permutation symmetry to be with spin \\ particles. in developed Chapter6, only totally symmetrical states are constructed by this method. The primitive spin \\ particles appearing here are actually bosons!This method is quite adequate if our purposeis to examine the propertiesunder rotations of states characterizedby and m without asking how such states are built up initially. The reader who is familiar with isospin in nuclear and particle physicsmay note that what we are doing here provides a new insight into one the isospin(or isotopicspin)formalism. The operator /+ that destroys unit of the minus type and createsone unit of the plus type is completely analogous to the isospinladder operator T+ (sometimes denotedby /+) that annihilates a neutron (isospin down) and createsa proton (isospin up), thus raising the z-component of isospinby one unit. In contrast, Jz is analogous to Tz, which simply counts the differencebetween the number of

j j 1, - 2,....
\342\200\224

2j

2j

j

j

protonsand neutrons in nuclei.

Explicit Formula for Rotation Matrices s Schwinger'schemecan be used to derive, in a very simple way, a closedformula for rotation matrices, first obtained by E. P.Wigner using a similar (but not identical) method. We apply the rotation operator S)(R)to In the m), written as C.8.18). Euler angle notation the only nontrivial rotation is the secondone about the j>-axis, o we direct our attention to s
\\j\\

y>

h

C.8.20

We

have

C.8.21
contributes.

Now, @(R)acting on |0)just reproduces because, y virtue of C.8.6) b |0) contribin the expansion of exponential C.8.20) only the leading term,

So

1,

- iJJ3
h

exp

h

C.8.22

222

Theory of Angular Momentum

Thus we may use formula

B.3.47). Letting
y

h in

'

C.8.23

we B.3.47), realize that
Jy

we must look at various commutators,namely,
t

+

/ I

y

Jy

h

h

'

u+

~ J at y
h

' 2/

C.8.24

and so forth. Clearly, we always obtain either a\\ or we get

at.Collectingterms,

= alcosl?)alsml?). + 3(R)ai?)-1(R)
Likewise,

C.8.25)

i?)-alsmi?).
Actually

this result is not surprising. After all, the supposedto transform as

cos

a \\

sin( j

under a rotation about the j-axis. ubstituting S and C.8.21) recalling the binomial theorem
N\\xN

|

C.8.26)

basic spin-up state is

C.8.27 and into C.8.25) C.8.26)

at

kyk

we obtain
k X

(N-k)\\k\\'

C.8.28

,

j + m- k)\\k\\{j(

7

m)\\(j-m)\\ .

. -m-/)!/! .....
o).

x[-a
\\

C.8.29
We may
with compareC.8.29)

/

a

m

')\\(j

-

m')\\

C.8.30

3.9.Spin Correlation
We

Measurements and Bell's Inequality

223

can obtain an explicit form for d^)m{^) equating the coefficientsof by and w powersof a\\ in C.8.29) C.8.30). Specifically, e want to compare a\\ with raisedto + m' in C.8.30) a\\ raisedto 2y /c /, so we identify

j

\342\200\224

\342\200\224

l=
We

j-k-m'.

C.8.31)

j

are seekingdm,m(fi) with m' fixed.The /c-sum and the /-sum in C.8.29) are not independent f each other; we eliminate / in favor of k by taking o As for advantage of C.8.31). the powersof #t_, we note that al_ raisedto m' in C.8.30) automatically matches with at raisedto k + I in C.8.29) when C.8.31) is imposed.The last step is to identify the exponents of a which are, respectively, cos(/?/2), in(/3/2), nd s
\342\200\224

(-1),
\342\200\224

k

+

j-m-l
j
m
\342\200\224

m-m',
\342\200\224

= 2k-m+ m\\ l = k m + m\\
this way

C.8.32a) C.8.32b) C.8.32c)

formula

to where we have used C.8.31)eliminate /. In for ~m +m /
X

we obtain Wigner's

(j + m /

k)\\k\\( ft
\\

cosy

ft

\\2j-2k + m-m

s^nT

j - k - m')\\{k '

-

m

+ m')\\

C.8.33)

where we take the sum over k whenevernone of the arguments of factorials in the denominator are negative.

3.9. PINCORRELATIONMEASUREMENTS S AND
BELL'S INEQUALITY
i Correlationsn Spin-Singlet States The simplestexample of angular-momentum addition we encounin Section 3.7was concerned a composite with system made up of spin In this sectionwe use such a system to illustrate one of the most \\ particles. of astonishing consequences quantum mechanics. Considera two-electronsystem in a spin-singletstate, that is, with a total spin of zero. e have already seenthat the state ket can be written as W [seeC.7.15d)]
encountered

|spinsinglet) =

/
v v

\342\200\224

1

\\

2 /

(|z+;z->-z-;z+ |
quantization

\302\273,

C.9.1)

where we have explicitly indicated the

direction. Recall that

224

Theory of Angular Momentum

example

|z + ; z ) means that electron 1is in the spin-up state and electron 2 is in the spin-down state.The same is true for ;z+ Supposewe make a measurementon the spin component of one of the electrons. Clearly, there is a 50-50chance of getting either up or down the because composite system may be in |z+ ; z ) or |z z + ) with equal if one of the components is shown to be in the spin-up probabilities.But state, the other is necessarilyin the spin-down state, and vice versa. When the spin component of electron 1 is shown to be up, the measurement a subsequent apparatus has selectedthe first term, |z+;z of C.9.1); measurement of the spin component of electron 2 must ascertain that the state ket of the composite system is given by |z+ It is remarkable that this kind of correlation can persisteven if the two particlesare well separated and have ceasedto interact provided that as there is no change in their spin states.This is certainly the they fly apart, casefor a = 0 system disintegrating spontaneously into two spin \\ particles with no relative orbital angular momentum, because angularAn momentum conservation must hold in the disintegration process. examof this would be a rare decay of the tj meson (mass549 MeV/c2)nto a i muon pair
\342\200\224

|z\342\200\224

).

\342\200\224

\342\200\224;

\342\200\224)

;z\342\200\224

).

/

C.9.2)
which, t More realistically, in proton-proton scattering at low kinetic energies,he in Pauli principleto be discussed Chapter 6 forces the interacting protons to be in lS0 (orbital angular momentum 0, spin-singlet state), and the spin states of the scattered protons must be correlated in the manner indicated distance. even by C.9.1) after they get separated a macroscopic by To be more pictorial we considera system of two spin \\ particles in O moving in oppositedirections, as in Figure 3.8. bserver A specializes measuring Sz of particle 1(flying to the right), while observer B specializes in measuring Sz of particle 2 (flying to the left). To be specific,let us assume that observer A finds Sz to be positive for particle 1. Then he or she can predict, even before B performs any measurement, the outcome of B's measurement with certainty: B must find Sz to be negativefor particle 2.On the other hand, if A makesno measurement,B has a 50-50chanceof getting Sz + or Sz This by itself might not be so peculiar. ne may say, \"It is just like O an urn known to contain one black ball and one white ball. When we blindly pick one of them, there is a 50-50chance of getting blackor white. But if the first ball we pickis black,then we can predictwith certainty that the secondball will be white.\" It turns out that this analogy is too simple.The actual quantummechanical situation is far more sophisticated than that! This is because observersmay choose measure Sx in place of Sz. The same pair of to
unfortunately,

has a branching ratio of only approximately6 X10 ~6.

-.

3.9.Spin Correlation

Measurements and Bell's Inequality

225

Particle2

Particle1
FIGURE

t

3.8.

Spin correlation in

a spin-singlet

state.

white or

\"quantum-mechanicalballs\" can be analyzed either in terms of black and in terms of blue and red! Recall now that for a single spin \\ system the Sx eigenkets and Sz are eigenkets related as follows:
x\302\261>

=
compositesystem, we can rewrite spin-singlet ket
f

C.9.3)
by C.9.1) choosingthe x-direction as the axis of quantization: Returning now to our

|spinsinglet) =
Apart from the

1

y

|x-

C.9.4)

overall sign, which in any caseis a matter of convention,we because couldhave guessedthis form directly from C.9.1) spin-singletstates Let have no preferreddirection in space. us now supposethat observer A

to can choose measure Sz or Sx of particle 1by changing the orientation of in his or her spin analyzer,while observer B always specializes measuring Sx of particle 2.If A determines Sz of particle 1to be positive, B clearly has a even though Sz of particle 2 is 50-50 chancefor getting Sx+ or Sx known to be negative with certainty, its Sx is completelyundetermined.On to that A alsochooses measure Sx;if observer the other hand, let us suppose A determinesSx of particle 1 to be positive, then without fail, observer B to will measure of particle 2 to be negative.Finally, if A chooses make no Sx measurement, B, of course,will have a 50-50 chance of getting Sx + or To sum up: Sx

-;

\342\200\224

.

A measures Sz and B measures Sx, there is a completely random correlationbetween the two measurements. 2. If A measures Sx and B measures Sx, there is a 100%(opposite sign)correlationbetween the two measurements. 3.If A makes no measurement, B'smeasurements show random

1.If

results. resultsof such measurementswhen B and A are Table 3.1 showsall possible to allowed to choose measureSx or Sz.

226
TABLE Spin component measured by A

Theory of Angular Momentum

3.1.pin-correlation Measurements S
A's result
\342\200\242+\302\246

Spin component measured by B

B'sresult

z z x x
Z

\342\200\224

\342\200\224

\342\200\224

z x z z
X X X

X
Z

+ + +
\342\200\224 \342\200\224 \342\200\224

x z z
X X

x z x
Z Z

+ +

These considerationshow that the outcome of B'smeasurement s to dependon what kind of measurementA decidesto perform: an appears
A and B can be miles apart with no possibility of communications or mutual interactions. Observer A can decide how to orient his or her

Sx measurement, an Sz measurement,or no measurement.Notice again that

measured.

I spin-analyzer apparatus long after the two particles have separated. t is as 2 \"knows\" which spin component of particle 1 is being particle though

The orthodox quantum-mechanicalinterpretation of this situation is as follows. A measurementis a selection(or filtration) process. When Sz of 1is measuredto be positive, then component |z+;z ) is selected. particle A subsequent easurementof the other particle'sSz merely ascertains that m the system is still in |z+; ).We must acceptthat a measurementon what z as appearsto be a part of the system is to be regarded a measurementon the whole system.
\342\200\224 \342\200\224

Einstein'sLocalityPrinciple and Bell's Inequality
Many
orthodox

interpretation of spin-correlation measurements. Their feelings are typified in the following frequently quoted remarks by A. Einstein, which we call Einstein'slocality principle: \"But on one supposition should, in we hold fast: The real factual situation of the system S2 my opinion, absolutely is independentof what is done with the system Sl9 which is spatially in this separatedfrom the former.\" Because problem was first discussed a

have felt uncomfortable with the preceding orthophysicists

3.9.Spin Correlation

Measurements and Bell's Inequality

227

A. Einstein, B. Podolsky, and N. Rosen, it is sometimes as the Einstein-Podolsky-Rosen aradox.* p Somehave argued that the difficulties encounteredhere are inherent in the probabilisticinterpretations of quantum mechanics and that the l dynamic behavior at the microscopicevel appearsprobabilistic only bebecause someyet unknown hidden not parameters\342\200\224so-called been specified.t is not our purposehere to discussvarious alternatives to I quantum mechanics based on hidden-variable or other considerations. d Rather, let us ask, Do such theoriesmake predictionsifferent from those of it mechanics? Until 1964, could be thought that the alternative quantum theories could be concoctedin such a way that they would give no predictions,other than the usual quantum-mechanical predictions,that to couldbe verified experimentally.The whole debatewould have belonged the realm of metaphysics rather than physics.It was then pointed out by J. S. Bell that the alternative theories basedon Einstein'slocalityprinciple actually predict a testable inequality relation among the observables of w o e spin-correlationxperimentsthat disagrees ith the predictions f quantum
known
variables\342\200\224have

1935 paper of

mechanics.

We derive Bell'sinequality within the framework of a simple model, conceived by E. P. Wigner, that incorporates the essential features of the various alternative theories. Proponents of this model agree that it is to impossible determine Sx and Sz simultaneously. However,when we have a large number of spin \\ particles, we assign a certain fraction of them to have the following property: If Sz is measured, we obtain a plus sign with certainty. If Sx is measured, we obtain a minus sign with certainty. A particlesatisfying this property is said to belong to type (z +,x Notice that we are not asserting that we can simultaneously measure Sz and Sx to be + and respectively.When we measure Sz, we do not measure Sx9 and vice versa. We are assigning definite valuesof spin components in more than one direction with the understanding that only one or the other of the can E components actually be measured. ven though this approach is fundadifferent from that of quantum mechanics,the quantum-mechanifundamentally predictionsfor Sz and Sx measurements performed on the spin-up provided there are as many particles belonging (Sz+) state are reproduced to type (z +,x +) as to type (z +,x Let us now examine how this model can account for the results of spin-correlationmeasurements made on compositespin-singlet systems.
\342\200\224).
\342\200\224, quantum-mechanical

\342\200\224).

*To be historically accurate, the original Einstein-Podolsky-Rosen paper dealt with measurements of x and p. The use of composite spin systems to illustrate the EinsteinPodolsky-Rosen paradox started with D.Bohm.
\\

228

Theory of Angular Momentum

Clearly, for a particular pair, there must be a perfect matching between particle1and particle 2 to ensure zero total angular momentum: If particle 1is of type (z +,x then particle 2 must belong to type (z x +), and so can forth. The resultsof correlation measurements,such as in Table 3.1, be reproducedif particle 1and particle 2 are matched as follows:
\342\200\224),
\342\200\224,

particle 1 particle 2

)~(z+,x-)>
+ )~(z+,x )
with

C.9.5b) C.9.5c) C.9.5d)

t equal populations,hat is, 25% each.A very important assumption is here. upposea particular pair belongsto type C.9.5a) observer and implied S A decidesto measure Sz of particle then he or she necessarilyobtains a of plus sign regardless whether B decidesto measure Sz or Sx.It is in this A sensethat Einstein'slocality principle is incorporated in this model: 's of B's result is predetermined choice to what to measure. as independently In the examples in considered far, this model has beensuccessful so the predictionsof quantum mechanics.We now consider reproducing s different more-complicatedituations where the model leads to predictions from the usual quantum-mechanicalpredictions. his time we start with T three unit vectors a, b, and c,which are, in general, not mutually orthogonal. We imagine that one of the particles belongsto some definite type, say ,b+ ,c+ ), which means that if S-ais measured, we obtain a minus sign with certainty; if S#b is measured, we obtain a plus sign with certainty; if S-cis measured,we obtain a plus with certainty. Again there must be a perfect matching in the sensethat the other particle necessarilybelongsto to ensure zero total angular momentum. In any given type (a + ,b event, the particle pair in question must be a member of one of the eight T a types shown in Table 3.2. heseeight possibilities re mutually exclusive and disjoint.The population of each type is indicated in the first column. Let us supposethat observer A finds S^ a to be plus and observer B finds S2-bto be plus also.t is clear from Table 3.2 I that the pair belong to either type 3 or type 4, so the number of particle pairs for which this situation is realized is N3 + N4. Because is positive semidefinite,we must Nt have inequality relations like

1;

(a\342\200\224

\342\200\224,c

\342\200\224)

< (N2 + N4) + (N3 + N7).

C.9.6)

Let P(a+;b+ ) be the probability that, in a random selection, observer A measuresSx-ato be + and observer B measures S2-bto be +, and so on.

3.9.Spin Correlation
TABLE

Measurements and Bell's Inequality

229

3.2.

Spin-component Matching in the Alternative Theories
Particle

Population

1

Particle

2

(a+,b+ ,c
N2
NA

(a+,b-,c + (a-,b ,

(a-,b-,c
(a-,b+,c (a+,b-,c
(a+,b+ ,

(a-,b-,c
Clearly, we have

C.9.7)
In a similar manner, we obtain

N,)
\342\200\242

C-9.8)

The positivity condition C.9.6) becomes now

;b P(a+ ;b+ ) < P(a+ ;c+ ) + P(c+
This is Bell's inequality,
Quantum
which

C.9.9)

followsfrom Einstein's locality principle.

a Mechanicsnd Bell's Inequality

We now return to the world of quantum mechanics. In quantum mechanics we do not talk about a certain fraction of particle pairs, say N3/L*N;,belonging to type 3. Instead, we characterize all spin-singlet in systemsby the same ket C.9.1); the language of Section3.4 we are concerned here with a pure ensemble.Using this ket and the rules of quantum mechanics we have developed, we can unambiguously calculate each of the three terms in inequality C.9.9). We first evaluate P(a+;b ). Suppose + observer A finds Sx-ato be positive; becauseof the 100% (oppositesign) correlation we discussed measurementof S2-awill yield a minus sign with certainty. But earlier, B's to calculate P(a+;b ) we must considera new quantization + axis b that makesan angle 9ab with a; seeFigure 3.9. According to the formalism of Section 3.2,he probability that the S2-b measurement yields + when t particle 2 is known to be in an eigenketof S2*awith negativeeigenvalueis

230

Theory of Angular Momentum

a direction
b direction

<S2>
I

FIGURE

3.9.

Evaluation

of

b P(a4-; 4-).

given by

cos
As a result, we obtain

2 )
I

C.9.10

2 where the factor
with
\\

sm-

C.9.11
initially obtaining the other two terms of

+. Using C.9.11) its generalization to and we C.9.9), can write Bell'sinequality as
\\

arisesfrom the probability of
/ /)

\\

C.9.12
plane, and let c bisectthe
We now show that inequality is not always possiblefrom of view. For simplicity let us choose b, and c to lie in a, geometricpoint
two

C.9.12)

directionsdefined by a and b:

a a

C.9.13
is then violated for Inequality C.9.12)

C.9.14)
Forexample,take 0 = 7r/4; we then
obtain
not compatible
with

< ?? 0.5000.292

C.9.15
Bell's

the senseof being experimentally inequality. There is a real verifiable\342\200\224difference between quantum mechanicsand the alternative theosatisfying Einstein's locality principle.
observable\342\200\224in
theories

So the quantum-mechanical predictionsare

3.9.Spin Correlation

Measurements and Bell's Inequality

231

Several experimentshave beenperformed to test Bell'sinequality. In one of the experiments spin correlations between the final protons in low-energy proton-proton scattering were measured.In all other experiphoton-polarization correlations between a pair of photons in a cascade transition of an excited atom (Ca,
experiments

Hg,...),

C.9.16)
or
in

measured;studying photon-polarizationcorrelationsshould be just as good
in view

the decay of a positronium (an

e+e~ bound state

in

lS0) were

* of the analogydevelopedin Section e in x-direction, Sz
H\342\200\224>

1.1:

S7

>

I
?

in in in

y-direction,
45\302\260 135\302\260

Sx Sx

H\342\200\224>

>?

diagonal direction, diagonal direction.

C.9.17)

The results of all recent precisionexperiments have conclusively established Bell's that was violated,in one case more than nine by inequality standard deviations. Furthermore, in all these experiments the inequality relation was violated in such a way that the quantum-mechanicalpredictwere fulfilled within error limits. In this controversy,quantum mechahas triumphed with flying colors. The fact that the quantum-mechanicalpredictions ave beenverified h mean that the whole subject is now a triviality. Despite the does not experimental verdict we may still feel psychologicallyuncomfortableabout many aspects of measurements of this kind. Considerin particular the following point:Right after observerA performs a measurementon particle how does particle may, in principle, be many light years away from particle to \"know\" how to orient its spin so that the remarkcorrelationsapparent in Table 3.1 realized? In one of the experiare to test Bell's inequality (performed by A. Aspect and collaborators) the analyzer settings were changed so rapidly that A'sdecision to what to as measure could not be made until it was too late for any kind of influence, traveling slowerthan light, to reach B. We concludethis section by showing that despitethese peculiarities we cannot use spin-correlationmeasurementsto transmit any useful inforinformation between two macroscopically separatedpoints.In particular, superluminal (faster than light) communicationsare impossible. A Suppose and B both agree in advance to measure Sz; then, without B knows preciselywhat A is getting. But this doesnot mean that asking A,
predictions mechanics

1,

2\342\200\224which

1\342\200\224get

remarkable

experiments

*It should be kept
realm of nonrelativistic

in mind here that by working with photons we are going outside the quantum mechanics, which is the subject of this book.

232
A

Theory of Angular Momentum

and B are communicating;B just observes random sequence positive a of and negative signs.There is obviously no useful information contained in it. B verifiesthe remarkablecorrelationspredicted quantum mechanicsonly by after he or she gets together with A and compares notes (or computer the

sheets).

measurements are completelyuncorrelated with the results of B's measureso there is no information transferred. But then, suppose suddenly A breakshis or her promise and without telling B starts measuring Sx.There are now complete correlationsbetweenA's results and B's results.However, B has no way of inferring that A has changed the orientation of his or her of analyzer. B continues to see just a random sequence + 's and 's by looking at his or her own notebook only. So again there is no information transferred.
measurements,

be thought that A and B can communicateif one of them suddenly changesthe orientation of his or her analyzing apparatus. Let us supposethat A agreesinitially to measure S29 and B, Sx.The results of A's
It might

-

3.10. TENSOROPERATORS
Vector Operator
We have been using notations such as x, p, S, and L, but as yet we their rotational properties. hey are vector have not systematicallydiscussed T under rotations? In this section we operators,but what are their properties q give a preciseuantum-mechanicaldefinition of vector operatorsbased on W their commutation relations with the angular-momentum operator. e then generalize to tensor operators with more-complicatedtransformation propand derive an important theoremon the matrix elementsof vectorand
properties

We all know that a vector in classical hysicsis a quantity with three p under a rotacomponentsthat transforms by definition like 2y/?,y V} It is reasonableto demand that the expectation value of a vector operator V in quantum mechanics be transformed like a classicalvector under rotation. Specifically,as the state ket is changed under rotation accordingto
Vf-\342\200\224>

tensoroperators.
rotation.

\\a)-+9(R)\\a),
the expectation value of V
<a|>\302\273

C.10.1

is assumed to change as follows:

-> {a\\&(R)Vt9(*)\\\302\253)
arbitrary

= E*,,<a|J\302\273.

This must be true for an

ket

T |a>. herefore,

j

C.10.2

C.10.3

3.10. Operators Tensor
must

233

hold as an operator equation, where RtJ is the 3x3 matrix that to corresponds rotation R. Let us now consider specificcase,an infinitesimal rotation. When a the rotation is infinitesimal, we have

ieJ-h
h

C.10.4

We

can now write

as C.10.3)

C.10.5
In particular, for h along the z-axis, we have

/I -e
e 0 0

1

0

1
y

C.10.6

SO

i-l: K+^[VX,JZ]=
y

C.10.7a)

C.10.7b) J ]=
the commutation relations

C.10.7c)

This means that

V must satisfy

[VnJj]=ieiJkhVk.

C.10.8)

Clearly, the behavior of V under a finite rotation is completely determined by the precedingcommutation relations; we just apply the t by-now familiar formula B.3.47)o

exp
We simply

h

C.10.9)
]]]\302\246

need to calculate

Multiple commutators keepon

C.2.7). spin case
We

giving

back to us

Vl

ox

Vk

C.10.10 (k # /, j) as in

Noticethat the

c angular-momentum commutation relationsare a special ase in which we let Vi Ji9 Vk -> Jk. Other special asesare [y, Lz]= of c ihx, [jc,Lz] = ihy, [px,Lz]= ihp , [py, Lz] = ihpx\\ these can be proved

can use C.10.8)the as
-\302\273 \342\200\224 \342\200\224

defining

property of a vector operator.

C.10.8)

explicitly.

234

Theory of Angular Momentum

Cartesian TensorsVersus IrreducibleTensors
In

classicalphysics it is customary to define a tensor
-\302\273

generalizing Vi

LjR^Vj as follows:

TiJk..m

by

rlJk... E E E
k'

- /' r

\342\200\242 \342\200\242 \342\200\242

*\302\273>*jj>-

T>>rk>...

C.10.11

under a rotation specifiedby the 3 X 3 orthogonal matrix R. The number of indicesis calledthe rank of a tensor.Such a tensor is known as a Cartesian

tensor.
component

The simplestexample of a Cartesian tensor of rank 2 is a dyadic formed out of two vectors U and V. One simply takes a Cartesian compoof U and a Cartesian component of V and puts them together:

C.10.12
Noticethat we have nine componentsaltogether.They obviously
like

C.10.11)

transform

reducible\342\200\224that

differently

under rotation. The trouble with a Cartesian tensor like C.10.12) is that it is it can be decomposed into objectsthat transform differis, under rotations. Specifically, or the dyadic in C.10.12) f we have

U-V

C.10.1
The first term on the right-hand side, U#V, is a scalar product invariant under rotation. The secondis an antisymmetric tensor which can be written as vector product ^(UxV)^. There are altogether 3 independent compowhere 1 The last is a 3 X 3 symmetric traceless tensor with 5 ( = 6 The number comesrom the traceless f condition) independent components. of independentcomponents checks:
components.
\342\200\224

1,

+ 3x3=1 3 + 5.
We

C.10.14

note that the numbers appearing on the right-hand sideof C.10.14) are the multiplicities of objectswith angular momentum / = 0, / = precisely and / = 2, respectively.This suggestshat the dyadic has beendecomposed t into tensorsthat can transform like sphericalharmonicswith / = and 2. In fact, C.10.13) simplest nontrivial example to illustrate the reducis the of a Cartesiantensor into irreduciblesphericaltensors. Before presenting the precise definition of a spherical tensor, we first give an example of a spherical tensor of rank k. Supposewe take a We have already seenthat it can be written as sphericalharmonic Yim{6, We now y/m(n), where the orientation of n is characterized by 6 and n replace by somevector V. The result is that we have a sphericaltensor of rank k (in place of /) with magnetic quantum number q (in placeof m),

1,

0,1,

reduction

<\302\273.

<t>.

3.10. Operators Tensor
namely, Specifically,in the

235

C.10.15
( replacez/r)= (h)z by Vz, and so on.
casek = 1 we take spherical harmonics with
/ = and

1

C.10.16
v/2

Obviously this can be generalizedfor higher k, for example,
y\302\2612

2

To seethe transformation of spherical tensors constructed in this transform under rotations. First, we manner, let us first review how have for the direction eigenket;
Y\342\204\242

F just ^ are irreducible, as y7m are. or this reason,working with spherical tensorsis more satisfactory than working with Cartesian tensors.

C.10.18
which defines the rotated eigenket (n'\\l* rn) would look in terms of
with
\302\256(R-l)\\l,

^(n).
m'

W In'). e wish We

to examine how Y^fi') = can easily seethis by starting

m) =

?|/, ^iPjR-1) m
C.10.18):
it

C.10.19

and contracting with (n| on the left, using
m'

C.10.20
Yfm(V)9

If there is an operator that acts like

is then reasonable expect to

C.10.21
m

where we have used the

unitarity

of the rotation operator to rewrite

C.10.21)

as components

All this work is just to motivate the definition of a spherical tensor. We now consider pherical tensors in quantum mechanics. otivated by M s we define a spherical tensor operator of rank k with
k

Bk+1)

9$\\R)T}k> q'=-k

C.10.22a

236

Theory of Angular Momentum

or, equivalently,

k

q'=-k

^^

C.10.22b

o This definition holdsregardless f whether T^k) can be written as Y^q(W)\\ for example,(Ux + iUy)(Vx + iVy) is the q = + 2 component of a spherical tensor of rank 2 even though, unlike (Vx + iVyJ, it cannot be written as more convenient definition of a spherical tensor is obtained by the namely, considering infinitesimal form of C.10.22b),
A
k q'=-

or

C.10.23
[J-n,Tf\\ = 2 r^(^'|j-n|A:<7). q'

By taking h
nonvanishing

the z- and in the matrix elements of Jz and
in

and

[z^\\q^C.10.25
J\302\261

??
(x
\302\261

C.10.24

we obtain and [seeC.5.35b) C.5.41)],

/y) directionsand using the nonvanish-

+ 1) as Thesecommutation relations can be considered a definition tensorsin placeof C.10.22).

q)(k

\302\261q

T<k\302\261\\.

C.10.25b
of spherical

Product of Tensors
We have seenhow to form a scalar, vector (or antisymmetric tensor), a tracelesssymmetric tensor out of two vectors using the Cartesian and tensor language. Of course,spherical tensor language can also be used Chapter 17),for example, (Baym 1969,

r0

@)

=

3

(Uxv)

C.10.26
_

3.10. Operators Tensor
where

237

of rank 1, Uq(Vq) is the qth component of a spherical tensor correspondingto vector U(V). The precedingtransformation properties can be checked by comparing with and remembering that {/+ = x UO -(Ux+ iUy)/yf2, U.^iUx-iUy)/)/!,= UZ. A similar checkcan be
Y\342\204\242

made for

V\302\261l

0. For instance,

where 3z2 r2 can be written as
\342\200\224

2z2+2 (x + iy) (x-iy)
hence,
is just a special aseof ToB) for U = V = r. c more systematicway of forming tensor productsgoesas follows. We start by stating a theorem:
Y2\302\260

A

kx

Theorem.Let X^l) and Z^2) be irreducible sphericaltensorsof rank and k2, respectively. hen T
It
<7l

*/i/7

I

It It

'

It si\\ \\^'

1' 2/ 7'

I

i 1(I /7 I

^2

is a

spherical{irreducible)tensor of rank k.
Proof We must show
that

accordingto C.10.22)

under rotation T^k) must transform

xk^ kq)

E
^

EE E E E
^

wherewe have usedthe Clebsch-Gordan seriesformula
preceding

becomes expression

The C.7.69). preced-

EEEE
ft'

^

238

Theory of Angular Momentum

coefficients where we have used the orthogonality of Clebsch-Gordan
Finally, C.7.42).
this

reducesto expression

q

~~q q \\~

/

im*~~qq

The foregoingshowshow we can construct tensor operators higher of or lower ranks by multiplying two tensor operators. Furthermore, the manner in which we construct tensor products out of two tensors is completely analogous to the manner in which we construct an angularmomentum eigenstate by adding two angular momentums; exactly the same Clebsch-Gordanoefficientsappearif we let kx 2 -* A,2> #1,2 m 1,2c
~~*

Matrix Elementsof Tensor Operators;he Wigner-Eckart Theorem t
the considering interactionsof an electromagneticfield with atoms it is often necessaryto evaluate matrix elements of tensor of operatorswith respectto angular-momentum eigenstates. Examples this will be given in Chapter 5. In general, it is a formidable dynamic task to calculate such matrix elements.However, there are certain propertiesof these matrix elements that follow purely from kinematic or geometric which we now discuss. considerations, there is a very simple m-selectionrule: First, In

and nuclei,

m-selectionRule
<\302\253',

j'm'\\T(k)\\a,

jm) = 0, unlessm'=q+ m.

C.10.28

we have Proof. UsingC.10.25a),

hence,
Another
T^k)\\a,

(a\\ j'm'\\Tqik)\\a, jm) = 0 unlessm'= q + m.
way that

?
property of

to see this is to note under rotation, namely, jm)
\302\256Tq(k)\\a,

transformation

jm) = 9T^&9\\a,m). j

C.10.29

If we now let

Of

stand for a rotation operator around the z-axis,we get [see

3.10.Tensor

Operators

239

and C.10.22b) C.1.16)]
, <t>)Tq(k)\\a, jm) = e'tq*e'tm*Tq(k)\\a9
which
quantum

jm),

C.10.30

unlessq + is orthogonal to \\arj'm')

m

=

t mechanics, he Wigner-Eckart theorem.

We are going to prove oneof the most important

m!.
theoremsin quan-

with

The Wigner-Eckart Theorem. The matrix elementsof tensoroperators respectto angular-momentum eigenstatessatisfy
<a\\

j'miT^la, = (jk;mq\\jk; j'm') jm)

C.10.3
where the double-barmatrix elements independentof m and m\\ and q. i Before we present a proof of this theorem, let us look at its significance.First, we see that the matrix element is written as the product of two factors. The first factor is a Clebsch-Gordanoefficientfor adding c and k to get It dependsonly on the geometry, that is, the way the t T system is oriented with respect o the z-axis. here is no referencewhatsoever to the particular nature of the tensor operator.The secondfactor does dependon the dynamics, for instance, a may stand for the radial quantum number and its evaluation may involve, for example, evaluation of radial integrals.On the other hand, it is completelyindependent of the magnetic quantum numbers m,m\\ and q, which specify the orientation of the physical system.To evaluate (<x\\ jfmf\\T^k)\\a, jm) with various combinaof m, m\\ and it is sufficient to know just one of them; all others can be related geometrically because they are proportional to ClebschGordan coefficients,which are known. The common proportionality factor is {a'j'WT^Waj), hich makes no reference whatsoever to the geometric w features. The selectionrules for the tensor operator matrix element can be immediately read off from the selectionrules for adding angular momenc f Indeed, rom the requirement that the Clebsch-Gordanoefficientbe derived we immediately obtain the m-selectionrule C.10.28) nonvanishing, before and also the triangular relation

j'.

j

combinations

q'

momentum.

Now we prove the theorem.

j-k </' </ + k.

C.10.32

we have Proof UsingC.10.25b)

jm) = hj(k + q)(k\302\261q+l) < a\\

j'm'\\T<k\302\261\\\\a9

jm),

C.10.33

240

Theory of Angular Momentum

or using

we and C.5.39) C.5.40) have

' + l)(a'9j'9m'Tl\\T\342\204\242\\a9jm)
*',j'm'\\T}k>\\a9j9m\302\261l)

{(k+ q)(k

\302\261q

+ l) <a', 'm'|7;<*\\|a, jm). 7

C.10.34
the form the same

Both and m->ml9k-+j29 q-*m2. recursion relations are of = 0,that is, first-orderlinear homogeneousequations with YtjdijXj coefficientsatj.Whenever we have

c Comparethis with the recursionrelation for the Clebsch-Gordanoefficient Note the striking similarity if we substitute j'-> m' -* m, y -* jl9 j9 C.7.49).

jjj

C.10.35
we cannot solve for the

ratios; so

Xj Xj

(or j>7)
\"J

individually

but

we can solve for the

or

x, = cyi9

C.10.36

where

c is a universal proportionality factor. Noting that recursion relation C.7.49) corresponds \\\\jlj2\\ jm) in the Clebsch-Gordan to (a\\ jW\\T^\\\\a9 jm), we seethat jm) = (universalproportionality constant independent of (a'9
j'm'\\T(\302\261\\\\a,

m,

mq\302\261l\\jk; q, and m')(jk;

j'm'),

C.10.37

which proves the theorem. Let us now look at

?

two

simple examplesof the Wigner-Eckart

theorem. Example Tensorof rank a scalaroperatorsatisfies

1.

0,that

is, scalar ro(O)= S.The matrix elementof

Thus the scalaroperator cannot change j9 m values.

(a',j'm>\\S\\a, jm) = 8jr8mJaj^J>- C.10.38 yjl] + 1 because acting on |a,m) is like adding an angular momentum of zero. S j
2. Example Vector operator which in the sphericaltensor languageis a rank so we 1 tensor.The sphericalcomponent of V can be written as rule have the selection
Vqam\302\261h09

??

Am

sm'-m = 1,0
\302\261

Ay

=

j'-j = / ^

C.10.39

3.10.Tensor

Operators

241

is forbidden. This selection rule is of In addition, the 0 transition fundamental importance in the theory of radiation; it is the dipoleselection rule obtained in the long-wavelength limit of emitted photons.*
-\302\2730

For 7 = 7' the Wigner-Eckart theorem\342\200\224when appliedto the vector a particularly simple form, often known as the projection operator\342\200\224takes theorem for obvious reasons. The Projection Theorem
/
\302\253 \342\200\242

, jm'\\V\\a9

,,t/. jm) = (a\\ J
\342\200\242

v

->

** jm\\J*\\\\a,

'(jm'\\J\\jm)9C.10.40 \\Jjm)
.

,

,

where analogous to our discussion after

we C.10.26)choose

C.10.41
Proof. Noting

(a',

ym|J\302\253V|a,

we C.10.26)have j jm) = <a',m\\(J0V0 J+lV_x

-

- J_xV+l)\\a,jm)
h
\342\200\224

= mh(a\\

jm\\V0\\a,

jm) + 2

/(j'+ m)(j-m + 1)

= cJm(aW\\\\\302\253J)
by the Wigner-Eckart theorem and V, and the matrix elements of
Ko
\302\261

C.10.42
x

where C.10.31), cjm is independent of a, a', are all proportional to the

double-barmatrix element (sometimesalso calledthe reduced matrix eleFurthermore, cjm is independent of m becauseJ*V is a scalar element). operator,so we may as well write it as cy. Because doesnot dependon V, cy holds C.10.42) even if we let V and a'~->a, that is,
-\302\273J

(a,jm\\J2\\a,
Returning

jm) = c/a/||J||a/>.
Vq (a>j\\\\\\\\\\aj)

C.10.43
C 10 44)
to these

to the Wigner-Eckart theorem appliedto
(a>Jm'\\Vq\\\302\253Jm)

and Jq, we have

?1 selection rules. dipole

^Additional

parity selection rules are discussed in Chapter

4, Section 2. They lead

242
But the right-hand

Theory of Angular Momentum

/(a,

side of
by

is just of C.10.43)
<a\\
which

jm\\J2\\a,

jm)
\342\200\242

j(j + l)h2.So
jm) = ^
\342\200\242

is j C.10.44)the same as (a',m\\J9\\\\a, jm) and Moreover, the left-hand side C.10.42) C.10.43).
v

/

/

jm'\\V\\a9

/.t/i

jm\\J*\\\\a, (<x\\ J **

\\

/. . j jm) (jm'\\J\\jm)9 1A .cv C.10.45
?

'

proves the projection theorem.
We will give

s applications of the theorem in subsequent ections.

PROBLEMS

1.Find

the eigenvaluesand eigenvectorsof

ay

=I

.

' . Supposean

electron is in the spin state If sy is measured, what is the of the result h /2? probability 2. Considerthe 2x2matrix defined by an + zo#a a0 zo#a where a0 is a real number and a is a three-dimensionalvector with real

l^j.
\342\200\224

components.

unimodular matrix represents rotation in a three dimensions. Find the axis and angle of rotation appropriate for U in terms of a09 al9 a2, and a3. 3. The spin-dependent Hamiltonian of an electron-positron system in the of a uniform magneticfield in the z-directioncan be written as presence

b. In general, a 2 X 2 unitary

a. Prove that

U

is unitary and unimodular.

me,
Supposethe spin function of the system is given by

a. Isthis
what

-> b. Sameproblemwhen eB/mc 0, A # 0. 4. Considera spin 1particle.Evaluate the matrix elementsof

value of

an eigenfunctionof H in the limit is the energy eigenvalue?If it is not,

A->\302\2479

# eB/mc 0? If it is,

x+*

^X^-

)-

HI

what

is the expectation

h)(Sz-h)and
5. Let the

+ Sx(Sx h)(Sx-h).

Hamiltonian of a rigid body be

H-1
where K is the
angular

2 T

+ J + J3
in

vl

is2\\

momentum

the body frame. From

this

Problems

243

equation of motion for K and then expressionobtain the Heisenberg limit. find Euler'sequation of motion in the correspondence 6. Let ?/ = elG*aelGll*elG*y, where (a,/?,y) are the Eulerian angles.In order that U representa rotation (a,/?,y), what are the commutation rules satisfied by the Gkl Relate G to the angular momentum operators. 7. What is the meaning of the following equation:

U~lAkU=l,RklAh
where the three componentsof A are matrices?From this equation show that matrix elements (m\\Ak\\n) transform like vectors. 8. Considera sequence Euler rotations represented of by io3a

exp

\342\200\224-\342\200\224

-io2p
e

\\

/ expf

-io3y

ei(a-y)/2

^?

of (Sv) are known. Show how we may determine the state vector. Why is it to unnecessary know the magnitude of >? of b. Considera mixed ensemble spin \\ systems. upposethe ensemble S averages [Sx], [Sv], and [Sz] are all known. Show how we may construct the 2x2density matrix that characterizesthe ensemble. 10.a. Prove that the time evolution of the density operator p (in the p Schrodinger icture) is given by

axis by an angle 0.Find 6. 9. a. Considera pure ensemble of identically preparedspin

Becauseof the group propertiesof rotations, we expect that this sequenceof operations is equivalent to a single rotation about some
\\

Supposethe expectationvalues (Sx) and (Sz) and the

systems.

sign

E

11.

a pure ensembleat / = 0. Prove that it cannot evolve into a mixed ensembleas long as the time evolution is governed by the Schrodingerequation. of Consideran ensemble spin 1 systems. he density matrix is now a T 3x3matrix. How many independent (real) parameters are neededto characterize the density matrix? What must we know in addition to [Sx]9 completely? [Sy], and [Sz] to characterizethe ensemble A 12. n angular-momentum eigenstate |y, m = mmax = is rotated by an infinitesimal angle e about the >>-axis.Without using the explicitform of the d(j)m function, obtain an expression the probability for the new for rotated state to be found in the original state up to terms of order e2.

b. Supposewe have

j)

244

Theory of Angular Momentum

13. how that S
where
momentum

the 3 X 3 matrices G, (/ =

whoseelementsare given 1,2,3)

by

and k are the row and column indices,satisfy the angular commutation relations. What is the physical(or geometric) significanceof the transformation matrix that connectsG, to the more usual 3x3representations of the angular-momentum operator Ji with taken to be diagonal? Relate your result to J3 under infinitesimal rotations. (Note: This problem may be helpful in understanding the photon spin.) 14.a. Let J be angular momentum. It may stand for orbital L, spin S, or = Jx Lfv) satisfy the usual Jtotal.) Using the fact that Jx9 Jv, commutation relations, prove angular-momentum
JZ(J\302\261
\302\261

j

b. Using (a) (or otherwise), derive the
coefficientc_
that

\"famous\"

expressionfor the

appearsin

15. he wave function T
a. Is i//

to of a particle subjected a sphericallysymmetrical potential V(r) is given by an eigenfunctionof L2? If so, what is the /-value?If not, what are the possible valuesof / we may obtain when L2 is measured? b.What are the probabilities for the particle to be found in various ml

c. Supposeit is known somehowthat \\p(x) is an energy eigenfunction with eigenvalueE. Indicate how we may find V(r). A 16. particle in a sphericallysymmetrical potential is known to be in an
respectively.

states?

eigenstate of L2 and Lz with eigenvaluesh2l(l + \\) and mh, respecProve that the expectationvaluesbetween \\lm) states satisfy

17.Supposea half-integer /-value, say
momentum. From

Interpret

this

result semiclassically.
\\,

were allowed for orbital angular

we may deduce,as usual,

Problems

245

Now try to construct Yl/2_1/2(d, by (a) applying L_ to <{>)', and (b) using L_ 71/2_i/2@,/>) = 0.Show that the two < y1/2 i/2@, lead ( procedures to contradictoryresults. This givesan argument against half-integer /-valuesfor orbital angular momentum.) 18. onsideran orbital angular-momentum eigenstate |/ = 2, m = 0).SupC this state is rotated by an angle ft about the >>-axis. Find the and +2.(The probability for the new state to be found in m = 0, harmonics for / = 0, and 2 given in Appendix A may be spherical useful.) 19.What is the physicalsignificanceof the operators
<\302\273;

Suppose

1,

\302\2611,

+

\342\200\224

v+ v_

and

s Schwinger'scheme for angular momentum? Give the nonvanishing elements of K +. and 20.We are to add angular momenta j\\ = 1and j2 =1to form j = 2,1, 0 states. Using either the ladder operator method or the recursion relation, expressall (nine) (y, m) eigenkets in terms of
in

matrix

\\j\\j2m9

Write your

answeras

21. . Evaluate a
for

where + and 0 stand for

=1,0, respectively. m12
m=

checkyour answer for

b. Prove, for any j,

any

j (integer or half-integer);then

many ways. You may, for instance, examine the rotational properties // using the spherical(irreduciof tensor language.] 22.a. Considera system with 7 =1. xplicitly write E
(irreducible)

[Hint: This can be proved in

in

3 X 3 matrix form,

b. Show that

for

j =1only,
y

it

is legitimate to replacee~lJy^/h

by

1-/ sin#-|fh

A-cos/?).

246

Theory of Angular Momentum

c. Using(b),prove
1
\\yfl

sin
)

-j(l-cos/3)
sin

sin
\\

cos
sin
in

23.Expressthe matrix

element (\302\2532j82Y2|/32|a1)81Y1)

terms of a

seriesin

24. Consider a system made up of two spin \\ particles.Observer A in specializes measuring the spin components of one of the particles and so on), while observer B measures the spin components of Eiz> six the the other particle.Suppose system is known to be in a spin-singlet state, that is, 5total = 0. a. What is the probability for observer A to obtain slz = h/2 when observer B makes no measurement?Sameproblem for slx = h/2. b. Observer B determines the spin of particle 2 to be in the s2z= h/2 state with certainty. What can we then conclude about the outcome of observer A's measurement if (i) A measuresslz and (ii) A measuresslx1Justify your answer. 25.Considera spherical tensor of rank 1(that is, a vector)
\302\261l

for Usingthe expression d(j l) given

in

Problem 22, evaluate

results are just what you expectfrom the transforVx z under rotations about the ^-axis. 26, a. Construct a spherical tensor of rank 1 out of two different vectors U= (Ux, Uy, Uz) and V= (Vx, Vy, Vz). Explicitly write in terms of Ux , and Vx b. Construct a spherical tensor of rank 2 out of two different vectors U and V. Write down explicitly ^\\ 0 in terms of Ux v z and v 27, Considera spinless particle bound to a fixed center by a central force
your
transformation

and show that

propertiesof

T\342\204\2421<0

\302\261l

potential.

Problems

247

a. Relate, as much
(n'9/',m'\\+ ~r=
y2 using

as possible,he matrix elements t
\302\261

iy)\\n,l,

m) and

(n\\

/',

m'\\z\\n,

/, m)

only the Wigner-Eckart theorem. Make sure to state under what conditionsthe matrix elementsare nonvanishing. b. Do the same problem using wave functions \\p(x) = Rnl{r)Ylm{6^) 28 a. Write xy9 xz9 and (x2 y2) as components of a spherical(irreduci\342\200\224

tensor of rank 2. b.The expectation value
(irreducible)

Q = e(a9 m

j,
\342\200\224

= j\\Cz2 r2)\\a,\\ j
moment. Evaluate

-

m

= j)

is known as the
(where

Clebsch-Gordanoefficients. c
may by taken to

29. A spin nucleus situated at the origin is subjectedto an external inhomogeneous electricfield.The basicelectric quadrupole interaction

|

quadrupole

m'= j,j
be

e(a9j9 m'\\(x2
\342\200\224

in 1, 2,...) j

- y2)\\a, j,

m

= j),

terms of Q and appropriate

eQ

d2<t>

2s(s-l)h
where
the
</>

dx

0

0

0

is the electrostaticpotential satisfying coordinateaxesare so chosenthat
y

Laplace'sequation and

Show that

dxdz o dydz o the interaction energy can be written as

and expressA and B in terms of (d2<j>/dx2H so on.Determine the and (in energy eigenkets terms of |ra),where m = \\9 + \\) and the correcorresponding energy eigenvalues.Isthere any degeneracy?
\302\261

CHAPTER4

Symmetry in QuantumMechanics

Having studied the theory of rotation in detail, we are in a position to i discuss,n more general terms, the connectionbetween symmetries, degenerand conservation laws. We have deliberately postponedthis very important topic until now so that we can discussit using the rotation symmetry of Chapter 3 as an example.
degeneracies,

4.1. CONSERVATIONLAWS, AND SYMMETRIES,
Symmetries in Classical hysics P

DEGENERACIES

We begin with an elementary review of the conceptsof symmetry I and conservation law in classical hysics. n the Lagrangian formulation of p quantum mechanics,we start with the Lagrangian L, which is a function of a generalized coordinate qt and the correspondingeneralizedvelocityqr If g L is unchanged under displacement,

then we must have

dL =
248

0.

D.1.2)

4.1. Symmetries, Conservation Laws, and Degeneracies
It then follows, by
t

249

= 0, that

virtue

of the Lagrange equation, d/dt

(dL/dqt)-

f-0.
where the canonical momentum is definedas

D.1.3)

D.1.4)
then So if L is unchanged under displacementD.1.1), we have a conserved the canonical momentum conjugate to qr quantity, i Likewise,n the Hamiltonian formulation basedon H regarded as a

function of

qt

and

pi9

we have

? ^

0

D.1.5)

whenever

4^ = 0. dqt
way quantity.

D.1.6)

So if the Hamiltonian does not explicitly dependon qt, which is another of saying H has a symmetry under qt -> qt + Sqi9 we have a conserved Mechanics

Symmetry

in Quantum

In quantum mechanicswe have learned to associate unitary opera say Sf9 with an operation like translation or rotation. It has become o customary to call S?a symmetry operator regardless f whether the physical t to system itself possesseshe symmetry corresponding Sf. Further, we have learned that for symmetry operations that differ infinitesimally from the transformation, we can write identity
operator,

G

D.1.7)

where G is the Hermitian generator of the symmetry operator in question. Let us now supposethat H is invariant under Sf. We then have

sr*HSf= H.
But this

D.1.8)

is equivalent to

= [G9H] 0.
By virtue

D.1.9)

of the Heisenbergquation of motion, we have e

= 0;

D.1.10

250

Symmetry

in Quantum

Mechanics

translation, then momentum is a constant of the motion; if H is invariant under rotation, then angular momentum is a constant of the motion. It is instructive to look at the connection between D.1.9) and conservation of G from the point of view of an eigenket of G when G commutes with H. Suppose t0 the system is in an eigenstate of G. Then at the ket at a later time obtained by applying the time-evolutionoperator

hence,G is a constant of the motion. For instance, if H is invariant under

D.1.11

In is also an eigenket of G with the same eigenvalueg'. other words,oncea ket is a G eigenket, it is always a G eigenketwith the same eigenvalue.The and proof of this is extremelysimple once we realize that D.1.9) D.1.10 also imply that G commuteswith the time-evolutionoperator, namely,

= g'[u(t,to)\\g')]. D.1.12 G[u(t,to)\\g')]=U(t,to)G\\g')
Degeneracies
Even though concept of degeneracies. the level of classicalmechanics\342\200\224for instance in discussing closed(nonprecessing) orbits in the Keplerproblem (Goldstein conceptplays a far more important role in quantum mechanics. us supposethat Let
turn

Let us now

to the

may degeneracies be discussedat
1980)\342\200\224this

= [i/,^] 0

D.1.13

for somesymmetry operator and \\n) is an energy eigenket with eigenvalue En. Then ^\\n) is also an energyeigenketwith the same energy, because

the same energy, that is, they are degenerate.Quite often Sf is characterized by continuous parameters, say A, in which case all states of the form S^(X)\\n) have the same energy. We now considerrotation specifically.Supposethe Hamiltonian is rotationally invariant, so
with

Suppose\\n)

= D.1.14 H(&\\n)) &H\\n) = En(&\\n)). and ^\\n) represent different states.Then these are two states

[@(R)9H]=Q,
which

D.1.15

necessarily implies that

= = [J,i/] 0, [J2,i/] 0.
We
\\n;

D.1.16

can then form simultaneous eigenkets of i/, J2,and /z, denotedby j\\m). The argument just given implies that all states of the form

9(R)\\n;j,m)
have the same energy. We saw
in

D.1.17
under rotation different

Chapter 3

that

4.2.Discrete

Symmetries, Parity, or

SpaceInversion

251

m-valuesget mixed up. In general, 3>{R)\\n\\ j9 m) is a linear combinationof 2y +1independent tates.Explicitly, s
m

D.1.18

w operator@{R), e can get different linear combinationsof \\n; j\\m').If all states of form 3)(R)\\n\\ j,m)with arbitrary @(R)are to have the same m must have j\\ m) with different energy, it is then essentialthat each of the same energy.So the degeneracyhere is Bj + l)-fold,just equal to the number of possiblem-values.This point is alsoevident from the fact that all states obtained by successivelyapplying which commutes with H, to
\\n\\
J\302\2619

and by changing the continuous parameter that characterizes the rotation

same energy. As an application, consideran atomic electron whose potential is Becauser and L*S are both rotationally written as V(r)+VLS(r)L*S. invariant, we expecta Bj + l)-folddegeneracyfor each atomiclevel.On the other hand, supposethere is an external electricor magnetic field, say in the z-direction. he rotational symmetry is now manifestly broken;as a result, T + l)-folddegeneracyis no longer expected states characterized and the by different m-valuesno longer have the same energy.We will examinehow this splitting arisesin Chapter 5.
\\n;

jm) have the

Bj

4.2. ISCRETESYMMETRIES, D PARITY,OR SPACEINVERSION
So far we have considered continuous symmetry operators\342\200\224that is, operthat can be obtained by applying successively infinitesimal symmetry operations.All symmetry operations useful in quantum mechanicsare not necessarilyof this form. In this chapter we consider three symmetry to operationsthat can be considered be discrete,as opposedto continuous
operations \342\200\224parity,

lattice translation, and time reversal. The first operation we consideris parity, or space inversion. The parity operation, as appliedto transformation on the coordinate system, changesa right-handed (RH) system into a left-handed (LH) system, as shown in Figure a However,in this bookwe consider transformation on state kets rather than on the coordinate system. Given |a>,we considera s space-invertedtate, assumed to be obtained by applying a unitary operator tt known as the parity operator, as follows:

4.1.

|a>->7r|a>.
require the expectation value of x taken in inverted state to be opposite sign.
We
with

D.2.1)
respect to the space-

=

\342\200\224

(a|x|a>,

D.2.2)

252
RH
LH

Symmetry

in Quantum

Mechanics

/

new

x

new y

I

FIGURE

4.1. ight-handed R

new

z

(RH) and

left-handed

(LH) systems.

if a very reasonable requirement.This is accomplished
*
Y\302\253JT

=
\342\200\224

\342\200\224

D.2.3)

or
X7T

=

7TX,

D.2.4)
must transform

where we have usedthe fact that parity? We claim that

<n

is unitary. In other words, x and m

How does an eigenket of the position operator
ir\\x'}

under

= eiS\\-x'\\

D 2 5)

where elS is a phasefactor (8 real). o prove this assertionlet us note that T
X7T|X')

= ~ 7TX|X') =
\342\200\224 \342\200\224

D.2.6)

This equation says that tt|x')is an eigenketof x with eigenvalue x',so it must be the same as a position eigenket | x')up to a phasefactor. It is customary to take elS= 1 by convention. Substituting this in we have 7T2\\x') = |x'); ence, it1 h is, we come back to the D.2.5), samestate by applying <n twice.We easily seefrom D.2.5) tt is now not that but also Hermitian: only unitary
=1\342\200\224that
\342\200\224

7T

\342\200\224

7T.

D.2.7)

Its eigenvalue can be only
What

mdx/dt,so it is natural

operator? The momentum p is like expectit to be odd under parity, like x. A more t satisfactory argument considershe momentum operator as the generator of translation. Since translation followed by parity is equivalent to parity followed by translation in the oppositedirection, as can be seenfrom Figure
to

+1or about the momentum

\342\200\224

1.

4.2.Discrete
then 4.2,

Symmetries, Parity, or

I Spacenversion

253

D.2.8)

1-ip-dx^ ~~h
from
which

D.2.9)
= -p

follows

{w,p}=0or
We can now discuss behaviorof J the momentum we clearly have angular

D.2.10

under parity. First, for orbital

[tt,L]= 0
because L = xXp,
rotation. For3x3 orthogonal matrices, we have
n (parity) n (rotation)
==

D.2.11

D.2.12

and both x and p are odd under parity. However,to show that this property also holds for spin, it is best to use the fact that J is the generator of
n (rotation) n (parity)

D.2.13

where explicitly

?
that it
operators,

(parity)

=
\\

1
0

-l
t,

D.2.14)

is, the parity and rotation operations commute.In quantum mechanics, is natural to postulate the correspondingelation for the unitary operr so

D.2.15

dx'

-dx'
FIGURE

4.2.

Translation followed by parity, and vice versa.

254

Symmetry

in Quantum

Mechanics

= where @{R) 1

\342\200\224

This together with also transforms in the same way as L. Underrotations, x and J transform in the same way, so they are both However, x (or p) is odd under vectors, or sphericaltensors,of rank and while parity [see D.2.3) D.2.10)], J is even under parity [seeD.2.16) Vectors that are odd under parity are called polar vectors, while vectors that are even under parity are called axial vectors, or pseudovectors. Let us now consider operators like S x. Under rotations they translike ordinary scalars,such as S#L or x#p. Yet under spaceinversion we have

it follows that iJhe/h.From D.2.15) = D.2.16 [tt,J] O or 77^77 = J. = L+ S) means D.2.11) that the spin operator (given by J

1.

\342\200\242

transform

x,
while for ordinary

D.2.17

scalarswe have

ff^L-Sff^ L-S
T and so on. he operator
Wave Functions

Sxis an exampleof a pseudoscalar.

D.2.18

Under Parity

be the wave function of a spinless particle whosestate ket is |a>:

Let us now look at the parity property of wave functions. First, let

= *//(x') <x'|a>.
7r|a),is

D.2.19

The wave function of the space-invertedstate, represented the state ket by

= = <x'|7r|a> <-x'|a> *H-x').
Suppose|a)is an eigenket of parity. eigenvalue of parity must be +1,so
ir\\a)

D.2.20

We

have already seenthat the

=

\302\261\\a).

D.2.21

Let us look at its corresponding ave function, w

= <x'|7r|a> +<x'|a>.
But

D.2.22

we also have

D.2.23
so the state \\a) is even or odd under wave function satisfies corresponding
parity

dependingon whether the
v

odd parity.

;;

D.2.24)

'

4.2.Discrete

Symmetries, Parity, or

SpaceInversion

255

Not all wave functions of physical interest have definite parities in f Consider, or instance, the momentum eigenket. The D.2.24). momentum operator anticommutes with the parity operator, so the to momentum eigenket is not expected be a parity eigenket. ndeed,it is I easy to seethat the plane wave, which is the wave function for a momentum eigenket, does not satisfy D.2.24). An eigenket of orbital angular momentum is expected be a parity to To see eigenket becauseL and <n commute [seeD.2.11)]. how an eigenketof L2 and Lz behaves under parity, let us examine the propertiesof its wave function under spaceinversion,
the

senseof

D.2.25)
The transformation x'-> r -> r
\342\200\224

x'is accomplishedy letting b
7T

-^ (cos0 -cos0) (eim* -> (-1)melm*).

D.2.26)

Usingthe explicit form of
m

l

/ \\m = ( i}

V

B1 +?l)(l m)l P

\342\200\242

^

(COS\302\260)e

for positive ra,
jyt

with
1

where C.6.38),
\302\246*-#

(cose)

,

_

^

\\

\"

'

I-m
,d(cos0)
sin2/6,

III

2'/! (/- m

D.2.28)

we can readily show that

D.2.29)
as 0 and
<f>

are changed, as in

D.2.26). = (-l)!\\<xjm). 7r\\ajm)
U\302\261
\302\261

Therefore, we can conclude that

D.2.30)

It is actually not necessary lookat Y(m\\ an easierway to obtain the same to result is to work with m = 0 and note that |/, m = 0) (r = must have the same parity becauseit and (L )r commute. Let us now look at the parity propertiesof energy eigenstates. We beginby stating a very important theorem.

0,1,...,/

Theorem. Suppose

[Z/,tt]= O
and
\\n)

D.2.31

is a nondegenerate eigenketof H with eigenvalue En\\
H\\n)

= En\\n);

D.2.32)

256
then

Symmetry

in Quantum

Mechanics

\\n)

is also a parity eigenket.
first noting that

Proof, We prove this theorem by

i(l\302\261iOl*>

D.2.33)
use it1 = 1). ut B

is a parity eigenket with eigenvalues+1(just this is alsoan must energy eigenket with eigenvalue En. Furthermore, \\n) and D.2.33) representthe same state, otherwisethere would be two states with the same contradiction of our nondegenerate assumption. It therefore follows that \\n), which is the same as D.2.33) to a multiplicative up constant, must be a parity eigenketwith parity
energy\342\200\224a

+1.

?

As an example, let us look at the simple harmonic oscillator (SHO). The ground state |0) has even parity becauseits wave function, being The first excitedstate, Gaussian,is even under x'->

-x'.

D.2.34)
af have an odd parity because is linear in x and p, which are both In state of the odd [seeB.3.2)].general,the parity of the nth excited simpleharmonic operator is given by ( 1)\". It is important to note that the nondegenerateassumption is essential here.For instance, considerthe hydrogen atom in nonrelativisticquantum mechanics. is well known, the energy eigenvaluesdependonly on the As principalquantum number n (for example,2pand 2s states are degenerate) Coulombpotential is obviously invariant under an energy
must
\342\200\224

\342\200\224the

parity\342\200\224yet

eigenket
cp\\2p)

+ cs\\2s)
momentum

D.2.35)
eigenket.Momentum

is obviously not a parity eigenket. As another example, considera
so\342\200\224even parity\342\200\224the

anticommutes with parity, though free-particle Hamiltonian H is invariant under momentum eigenket (though obviously an energy eigenket)is not a parity eigenket. Our theorem remains intact we because have here a degeneracybetween |p') and | p'), which have the same energy. In fact, we can easily construct linear combinations which are parity eigenkets with eigenvalues In | A/V2\(|p')\302\261") terms of wave-function language, el^'x'/hdoes not have a definite parity, but cosp'*x'//i sinp'*x'//i o. and d
\342\200\224

\342\200\224p')),

+1.

SymmetricalDouble-WellPotential
As an
invariant

double-wellpotential; see Figure

a elementarybut instructive example,we consider symmetrical 4.3. he Hamiltonian is obviously inT under parity. In fact, the two lowest lying states are as shown in

4.2.Discrete

Symmetries, Parity, or

SpaceInversion

257

FIGURE
(symmetrical)

IA> Anti-symmetric double well with the two lowest lying states \\S) (symand |A) (antisymmetrical) shown. Symmetric

IS>

4.3.

The symmetrical

w Figure 4.3, e can see by working out the explicit solutions involving sine and cosinein classicallyallowedregions and sinh and coshin the classically T forbidden region. he solutionsare matched where the potential is disconwe call them the symmetrical state |S)and the antisymmetrical state \\A). Of course,they are simultaneouseigenketsof H and m. Calculadiscontinuous;
Calculation

alsoshowsthat

which

we can infer from that the wave function of the antisymmetrical state has a greater curvature.The energy differenceis very later. tiny if the middlebarrier is high, a point which we will discuss We can form

EA>ES9 Figure 4.3 by noting

D.2.36)

D.2.37a)
and

{\\S)-\\A)).

D.2.37b)

The wavefunctions of D.2.37a) D.2.37b) largely concentratedin the and are right-hand side and the left-hand side,respectively.They are obviously not i parity eigenstates;n fact, under parity \\R) and \\L) are interchanged.Note that they are not energy eigenstates either. Indeed, they are classical states. To be precise,let us assume that the examplesof nonstationary system is represented \\R) at / = 0.At a later time, we have by
\\R,to

= 0;t) =

v2

e~lE*t/h\\A))

-Es)t/h

D.2.38)

258
At t

Symmetry

in Quantum

Mechanics

At time / = 7/2 = 2irh/2{EA Es), the system is found in pure |L). = T, we are back to pure \\R), and so forth. Thus, in general, we have an
\342\200\224

oscillation between \\R) and

\\L)
@

with

angular frequency

= (EA~ES)

D.2.39)

This oscillatory behavior can alsobe considered from the viewpoint in quantum mechanics. A particle initially confined to the tunneling side can tunnel through the classically forbidden region (the right-hand middlebarrier) into the left-hand side,then back to the right-hand side,and so on. But now let the middlebarrier become infinitely high; seeFigure 4.4. The \\S) and \\A) states are now degenerate, so D.2.37a)nd D.2.37b)re a a even though they are not parity eigenkets. nce the O also energy eigenkets system is found in \\R), it remains so forever (oscillation time between \\S) and |-4)is now oo). ecause middlebarrier is infinitely high, there is no B the possibilityfor tunneling. Thus when there is degeneracy, the physically realizable energy eigenketsneednot be parity eigenkets. have a ground We state which is asymmetricaldespitethe fact that the Hamiltonian itself is symmetrical under spaceinversion, so with degeneracy the symmetry of H is not necessarily obeyedby energyeigenstates\\S) and \\A). This is a very simple example of brokensymmetry and degeneracy. Nature is full of situations analogous to this. Considera ferromagnet. The basicHamiltonian for iron atoms is rotationally invariant, but the ferromagclearly has a definite direction in space;hence, the (infinite) number of ground states is not rotationally invariant, since the spins are all aligned along somedefinite (but arbitrary) direction. A textbookexampleof a system that illustrates the actual importance of the symmetrical doublewell is an ammonia molecule, NH3; seeFigure 4.5.We imagine that the three H atoms form the three corners of an equilateral triangle. The N atom can be up or down, where the directions up and down are defined becausethe molecule is rotating around the axis as of
ferromagnet

CO

CO

r\\
FIGURE

r\\
double well with an infinitely high middle barrier.

4.4.

The symmetrical

4.2.Discrete

Symmetries, Parity,

or Spacenversion I

259

H
N

H

H H

H

N

(a)
FIGURE

(b)
molecule, NH3, where the three H atoms
form

4.5.
of an

An ammonia

the three

corners

equilateral

triangle.

up and down positionsfor the N atom are L of the double-wellpotential. The parity and energy are o eigenstates superpositions f Figure 4.5aand Figure 4.5bin the senseof shown
in

analogous to R and

Figure

4.5.The

and D.2.37a) D.2.37b), respectively,and the
MHz\342\200\224a

energy differencebetween the simultaneous eigenstates of energy and parity correspond an oscillation to of about 1 cm, which is in the of 24,000 frequency wavelength microwave region.In fact, NH3 is of fundamental importance in maser

physics.

There are naturally occurring organic molecules, such as sugar or amino acids, which are of the i?-type (or L-type) only. Such molecules which have definite handedness re called optical isomers.n many casesthe a I oscillation time is practically the order of 104-106 i?-type moleculesremain right-handed for all practical purposes.It is amusing that if we attempt to synthesize such organic molecules in the laboratory, we find equal mixtures of R and L. Why we have a preponderof one type is nature's deepestmystery. Is it due to a genetic accident, like the spiralshell of a snail or the fact that our hearts are on the left-hand
infinite\342\200\224on years\342\200\224so
preponderance

side?

Parity-SelectionRule

Suppose|a)and |j8) are parity eigenstates

D.2.40a)

260

Symmetry

in Quantum

Mechanics

and where ea, e^ are the
\342\200\224

D.2.40b)
parity

W eigenvalues( + 1). e can show that = <j6|x|a> 0

D.2.41)

unless ea = e^. In other words, the parity-odd operator x connects states of oppositeparity. The proof of this follows:
(p\\x\\a)

= (p\\7r-l7rx7r-l7T\\a) = eaep(

-

</?|x|a\302\273,

D.2.42)

which

is impossiblefor a finite nonzero (fi\\x\\a) unless ea and e^ are oppositein sign.Perhaps the readeris familiar with this argument from

D.2.43)
if

and \\pa have the same parity. This selectionrule, due to Wigner, is of ypp radiative transitions between atomic states.As we importance in discussing will discussin greater detail later, radiative transitions take place between of states of opposite parity as a consequence multipole expansion forThis rule was known phenomenologically formalism. from analysis of spectral lines, before the birth of quantum mechanics, as Laporte'srule. It was o rule is a consequencef the parity-selecWigner who showed that Laporte's
parity-selection

basicHamiltonian H is invariant under parity, nondegenerate cannot possessa permanent [as energy eigenstates a corollary of D.2.43)] electricipolemoment: d
If the
(n\\x\\n)

rule.

= 0.

D.2.44)

This follows trivially from D.2.43), with the nondegenerateassumpbecause a and energy eigenstates re also parity eigenstates[seeD.2.32) D.2.33) For a degeneratestate, it is perfectly all right to have an electric dipole moment. We will seean example of this when we discussthe linear Stark effect in Chapter5. Our considerationsan be generalized: c Operatorsthat are odd under matrix elements only between parity, like p or S#x, have nonvanishing states of oppositeparity. In contrast, operatorsthat are even under parity connect tatesof the same parity. s
assumption,

Parity Nonconservation

The basicHamiltonian responsibleor the so-called f weak interaction of elementary particlesis not invariant under parity. In decay processes e w can have final states which are superpositions f oppositeparity states. o Observablequantities like the angular distribution of decay productscan

4.3.Lattice

Translation

as a Discrete

Symmetry

261

such as (S)#p. It is remarkable that parity depend on pseudoscalars when conservationwas believedto be a sacredprinciple until 1956, Leeand that parity is not conserved in weak interactions and Yang speculated proposed crucial experiments to test the validity of parity conservation. Subsequentexperiments indeedshowed that observableeffects do depend on pseudoscalar uantities such as correlationbetween (S) and p. Because q parity is not conserved in weak interactions, previously thought \"pure\" nuclear and atomic states are, in fact, parity mixtures. These subtle effects have alsobeen found experimentally.

4.3. ATTICE TRANSLATIONAS A DISCRETE L SYMMETRY
We now

consider another kind of discretesymmetry operation, namely, lattice translation. This subject has extremely important applications in

solid-state physics. Considera periodicpotential in one dimension, where V(x\302\261a) = V(x),as depictedin Figure 4.6. ealistically,we may considerthe motion R

(a)

(b)
FIGURE infinite.

4.6. (a)

periodic potential

Periodic potential in one dimension with periodicity a. (b) The when the barrier height between two adjacent lattice sites becomes

262

Symmetry

in Quantum

Mechanics

of an electron in a chain of regularly spacedpositive ions.In general, the Hamiltonian is not invariant under a translation represented t(/) with / by Section 1.6) arbitrary, where t(/) has the property (see

Tt(/)jcr(/)= x + /,

t(/)|jc/>= |jc'+ />. a) = V(x).

D.3.1)
under the

w However, when / coincides ith the lattice spacinga, we do have

D.3.2)

Because kinetic-energypart of the Hamiltonian H is invariant the
translation with
any

displacement,the entire Hamiltonian satisfies

= T*(a)HT(a) H.
Becauser(a) is unitary, we have [from D.3.3)]

D.3.3)

[//,r(a)]=0,
r(a) is unitary,

D.3.4)

complex number of modulus Before we determine the eigenkets and eigenvalues of r(a) and examine their physical significance,t is instructive to look at a specialcase i of periodicpotential when the barrier height between two adjacent lattice sitesis made to go to infinity, as in Figure 4.6b. is the ground state for What the potential of Figure 4.6b? Clearly, a state in which the particle is completely localized in one of the lattice sites can be a candidate for the ground state.To be specificlet us assume that the particle is localizedat the nth site and denotethe correspondinget by \\n). This is an energyeigenket k with energyeigenvalue?0, amely, H\\n) = E0\\n). Its wave function (x'\\n) n is finite only in the nth site.However,we note that a similar state localized at some other site also has the same energy ?0,so actually there are denumerably infinite ground states n, where n runs from oo to + oo. Now \\n) is obviously not an eigenket of the lattice-translation when the lattice-translation operator is appliedto it, we operator,because obtain \\n +
\342\200\224

so the Hamiltonian and r(a) can be simultaneously diagonalized.Although it is not Hermitian, so we expectthe eigenvalue to be a

1.

1):

D.3.5)
So despitethe fact that r(a) commutes with //, is an eigenket of not an eigenket of r(a). his is quite consistent with our earlier T theorem on symmetry becausewe have an infinitefold degeneracy. hen W there is such degeneracy, the symmetry of the world need not be the Our task is to find a simultaneous eigenketof symmetry of energy eigenkets. H and r(a). Herewe may recall how we handled a somewhat similar situation with the symmetrical double-well potential of the previous section.We noted that even though neither \\R) nor \\L) is an eigenket of tt, we could
\\n)\342\200\224which
H\342\200\224is

4.3.Lattice

Translation

as a Discrete

Symmetry

263

\\L)

easily form a symmetrical and an antisymmetrical combinationof | R) and that are parity eigenkets. The caseis analogous here.Let us specifically form a linear combination
00
n

=

e'\"~\\n),
\342\200\224

'\"e

oo

D.3.6)

where 6 is a real parameter with m < 6 < it. We assert that \\0) is a simultaneous eigenket of H and r(a). hat it is an H eigenket is obvious T because\\n) is an energyeigenketwith eigenvalue Eo, independent of n. To show that it is also an eigenket of the lattice translation operator we apply r(a) as follows:
\342\200\224

r(a)\\d)=
Note that
independent

n

=

?
\342\200\224

00

e'n6\\n oo

+ \\)=

n

=

?
\342\200\224

00

oo

-/0 = e-'e\\0).

D.3.7)

this simultaneouseigenket of H and r(a) is parameterized by a continuous parameter d. Furthermore, the energyeigenvalueEo is indepenof 6. Let us now return to the more realistic situation of Figure 4.6a, where the barrier between two adjacent lattice sitesis not infinitely high. We can construct a localizedket \\n) just as before with the property r(a)\\n)= However, this time we expectthat there is some leakage possible |ft into neighboring lattice sitesdue to quantum-mechanicaltunneling. In other words,the wave function (x'\\n) has a tail extending to sitesother than the A7th site. he diagonal elementsof H in the {\\n)} basisare all equal because T of translation invariance, that is,

+1).

9

D.3.8)

ft, as before.Howeverwe suspectthat H is not completely diagonal in the (|ft)} basis due to leakage.Now, supposethe barriers between adjacent sites are high (but not infinite). We then expectmatrix elementsof H between distant sites to be completely negligible. Let us assume that the only nondiagonal elements of importance connect imimmediate neighbors. hat is, T

independentof

(n'\\H\\n)*0 onlyifftr=ft
In

or
known

ftr=ft+l.
as the
tight-binding

D.3.9)
ap-

solid-statephysicsthis assumption is
Let us define

approximation.

= <ft+l|#|ft) -A.

D.3.10

Clearly, A is again independent of n due to translation invariance of the Hamiltonian. To the extent that \\n) and \\n') are orthogonal when ft # ft',

264

Symmetry

in Quantum

Mechanics

we obtain
H\\n)

=

D.3.11
00
iH$

Note that

\\n) is no longer an energy eigenket. we have done with the potential of Figure 4.6b, let us form a linear combination

As

n

\342\200\224

\342\200\224

oo

*>.

D.3.12

Clearly, \\6) is an eigenket of translation operator r(a) becausethe stepsin s D.3.7)till hold.A natural question is, is \\6) an energyeigenket?To answer this question,we apply H:

D.3.13
The big differencebetween this and the previous situation is that the energy eigenvalue now dependson the continuous real parameter 6.The degeneris lifted as A becomes of finite, and we have a continuous distribution between Eo 2A and Eo +2A. SeeFigure 4.7,wherewe energy eigenvalues visualizehow the energy levelsstart forming a continuous energy band as A
degeneracy
\342\200\224

is increasedfrom zero.
function

To seethe physical meaning of the parameter 6 let us study the wave F (x'\\0). or the wave function of the lattice-translatedstate r(a)\\0),

FIGURE

0 4.7.

A
Energy levels forming

a continuous

energy band

as A

is increased

from

zero.

4.3.Lattice we obtain
by

Translation

as a Discrete

Symmetry

265

Thus D.3.7).

letting

= D.3.14) (x'\\T(a)\\6) (x'-a\\d) But t(^) act on (jc'|. we can also let r(a) operate on \\6) and use = (x'\\r(a)\\0) e-ie(x'\\O),

D.3.15

so

)
We

?)-t$.
with

D.3.16
period a, as we can

solve this equation by setting

= eikx'uk(x')9
with

D.3.17)

0 = ka, where uk(x')is a periodicfunction easily verify by explicit substitutions, namely,

= eik<x'-a)uk(x'-a)eikx'uk(x')e-ika.

D.3.18

Thus we get the important condition known as Bloch'stheorem: The wave w function of |0), hich is an eigenketof r(a),can be written as a plane wave eikxf tjmes a periodicfunction with periodicity a. Notice that the only fact we used was that \\6) is an eigenket of r(a) with eigenvalue e~lB [see In D.3.7)]. particular, the theorem holdseven if the tight-binding approxibreaks D.3.9) down. We are now in a position to interpret our earlier result D.3.13) for is a plane wave We \\0) given by D.3.12). know that the wave function characterized by the propagation wave vector k modulated by a periodic As 6 function uk{x')[see D.3.17)]. varies from it to 77, the wave vector k varies from m/a to m/a.The energyeigenvalueE now dependson k as follows:
approximation
\342\200\224 \342\200\224

ka. E(k) = ?0-2Acos

D.3.19)

Notice that this energy eigenvalueequation is independent of the detailed shape of the potential as long as the tight-binding approximation is valid. Note also that there is a cutoff in the wave vector k of the Bloch wave = m/a.Equation D.3.19) function D.3.17) by definesa dispersion given A curve, as shown in Figure 4.8. s a result of tunneling, the denumerably infinitefold degeneracy is now completely lifted, and the allowed energy
\\k\\

values form a continuous band between ?0-2A and

the Brillouin zone. So far we have considered only one particle moving in a periodic In a more realistic situation we must look at many electrons potential. moving in such a potential. Actually the electrons satisfy the Pauli exclusion more systematically in Chapter 6, and they start principle,as we will discuss the band. In this way, the main qualitative features of metals, filling

known ?0+2A,

as

266

Symmetry

in Quantum

Mechanics

E0+2A

?o-2A

-n

Ia

o 4.8.

+

7T

a

FIGURE

Dispersion curve for E(k) versus k in the Brillouin zone \\k\\<

ir/a.

of a semiconductors, nd the like can be understood as a consequence translation invariance supplementedby the exclusionprinciple. The reader may have noted the similarity between the symmetrical double-wellproblem of Section 4.2 and the periodic potential of this we section. omparing Figures 4.3 and 4.6, note that they can be regarded C as oppositeextremes (two versus infinite) of potentials with a finite number of troughs.

T 4.4. HE TIME-REVERSALDISCRETE SYMMETRY
In this sectionwe study another discretesymmetry operator, called time reversal.This is a difficult topic for the novice, partly becausethe term time fiction.Actually what we do reversal is a misnomer; it reminds us of science in this sectioncan be more appropriately characterizedby the term reversal of motion. Indeed,that is the terminology used by E. Wigner, who forformulated time reversal in a very fundamental paper written in 1932. For orientation purposes us look at classical echanics.Suppose let m there is a trajectory of a particle subject to a certain force field; seeFigure A 4.9. t t = 0, let the particle stop and reverse its motion: p|/=0 p|/==0. The particle traverses backward along the same trajectory. If you run the motion picture of trajectory (a) backward as in (b), you may have a hard time telling whether this is the correct sequence. More formally, if x(/) is a solution to
\342\200\224 -\302\273

rax =
\342\200\224

\342\200\224

vK(x),

D.4.1)

then x( t) is also a possible solution in the same force field derivable from V. It is, of course, to note that we do not have a dissipativeforce important

4.4.The

Time-Reversal Discrete Symmetry

267

Reverse
plt=o

-p

lf=o

FIGURE

Pl/-o-* \"Pi/Co-

(a) 4.9. (a) Classical

trajectory

which stops at t

(b) = 0 and (b) reverses

its motion

move and accelerate? With a magnetic field you may be able to tell the difference.Imagine that you are taking the motion picture of a spiraling electron trajectory in a magnetic field. You may be able to tell whether the motion picture is run forward or backwardby comparing the senseof rotation with the magnetic pole labeling N and S. However, from a microscopic oint of view, B is p producedby moving chargesvia an electriccurrent; if you could reverse the current that causesB, then the situation would be quite symmetrical.In terms of the picture shown in Figure 4.10, may have figured out that N you and S are mislabeled! nother more formal way of saying all this is that the A Maxwellequations, or example, f

A block sliding on a table deceleratesdue to friction) and eventually ( stops. But have you ever seen a block on a table spontaneously start to
\"Pi/Co:.

VE = 4irp, VxB c dE dt
\342\200\224
\342\200\224

4-nj

V

xE =

c dt , D.4.2)
under

+ and the Lorentz force equation F = e[E (l/c)(vXB)]are invariant t-* t providedwe also let

E->E,

B

B

J

J

V.

D.4.3)

Let us now look at wave mechanics,where the basicequation of the w Schrodinger ave equation is

1m
Suppose\\p(x, t) is a solution. We can easily verify
\342\200\224

D.4.4)
that
\\p(x,
\342\200\224

conjugation

/) is not a solution, becauseof the appearance of the first-order time derivative. However, \\/>*(x, t) is a solution, as you may verify by complexconjugaof D.4.4). is instructive to convince ourselvesof this point for an It

268

Symmetry in Quantum

Mechanics

8
v
\"\\J
EI

ectron

traj ectory

N

FIGURE

4.10. Electron

trajectory

between the north and south poles of

a magnet.

energy eigenstate, that is, by

substituting

,t)=
into the
must

un{x)e-lE\302\273t/h,

-/) =

u*{x)e-lE\302\273t/h

D.4.5)

Thus we conjecture that time reversal e Schrodingerquation D.4.4). have something to do with complexconjugation. If at / = 0 the wave

function

is given

by

D.4.6)
state is given time-reversed then the wave function for the corresponding We will later show that this is indeed the casefor the wave by function of a spinlesssystem.As an example, may easily checkthis you point for the wave function of a plane wave; seeProblem8 of this chapter.

(x|a)*.

on Digression

Symmetry

Operations

Beforewe begin a systematictreatment of the time-reversaloperator, symmetry operations are in order. Considera symmetry operation

some general remarks on

|a>->|fi>, \\P)^\\P)One may argue that t preserved,hat is,
it

is natural

D-4-7) to require the inner product (j3|a)o be t

D.4.8)
Indeed,for
parity,
this

If is indeedthe case.

symmetry

operations such as rotations, translations, and even \\a) is rotated and |j8)is also rotated in the

4.4.The

Time-Reversal Discrete Symmetry

269

same manner, (/3|a) is unchanged. Formally this arisesfrom the fact that, t in for the symmetry operations considered the previous sections,he correis unitary, so corresponding symmetry operator
time However, in discussing reversal,we seethat requirement D.4.8) be too restrictive. Instead, we merely impose the weaker requirement that
turns

D.4.9)
out to

\\0\\a)\\

= \\(p\\a)\\.

D.4.10)
way;

But Requirement D.4.8) obviously satisfiesD.4.10). this is not the only

D.4.11
worksequally well. We
section because pursue the latter from our earlier discussion basedon the Schrodingerequation we inferred that time reversal has something to do with complexconjugation. possibility in this Definition. The transformation -> |fi> = 0\\a)9 \\a)
|j8> -> |jB> = 6\\/3)

D.4.12)

is said to be antiunitary

if

= <j8|5) </?|a>*,
d{cx\\a) +
c2|j8\302\273

= cfO\\a) + c?0|j8>.

In such a case operator 8 is an antiunitary the alone defines an antilinear operator. We now claim that an antiunitary operator can be written as 0 = UK, D.4.14)

D.4.13a D.4.13b operator.Relation D.4.13b

where U is a unitary operator and K is the complex-conjugate operator that forms the complexconjugate of any coefficientthat multiplies a ket (and stands on the right of K). Before checking D.4.13) us examine the let of the K operator. Suppose have a ket multiplied by a complex we property
number

c.We then

have
Kc\\a)

= c*K\\a).

D.4.15)

One may further ask,What happensif Under (la')}? the action K we have
a'
a

|a)is expandedin terms of basekets
a'

D.4.16)

Notice that K acting on the base ket does not change the base ket. The

270

Symmetry in Quantum

Mechanics

explicit representation of \\a') is @) 0
\\a')

=

0 0

1

D.4.17)

10/
and there is nothing to be changed by K. The reader may wonder, for instance,whether the Sy eigenketsfor a spin \\ system change under K. The answer is that if the Sz eigenketsare usedas base kets,we must change the becausethe S eigenketsA.1.14) undergo under K Sv eigenkets K
/

D.4.18)

On the other hand, if the S eigenketsthemselvesare usedas the base kets, we do not change the Sy eigenketsunder the action of K. Thus the effectof K changes with the basis.As a result, the form of U in D.4.14) depends also on the particular representation (that is, the choiceof base kets) used. Gottfried puts it aptly: \"If the basisis changed, the work of U and K has to be reapportioned.\" to 9 = UK and D.4.13), first checkproperty D.4.13b let us Returning We have
B(Cl\\a)

+ c2\\f3)) = UK(Cl\\a) + c2\\0))

D.4.19)
so D.4.13b) indeedholds. Before checking D.4.13a),assert that it is we safer to work with the action of 6 on kets only. We can figure out always how the bras changejust by looking at the correspondingets.In particular, k it is not necessaryto consider6 acting on bras from the right, nor is it to necessary define dK We have
e
a a a

D.4.20)

4.4.The
As

Time-Reversal Discrete Symmetry

271

for I/?),we have

a'
a\"

= </?!<*>*,

D.4.21)

so this checks. In order for D.4.10) be satisfied, it is of physical interest to to and antiunitary. Other considerjust two types of transformation\342\200\224unitary via are related to either of the preceding trivial phasechanges. possibilities The proof of this assertionis actually very difficult and will not be discussed
further

here (Gottfried 1966, 226-28).

Time-ReversalOperator We are finally in a position to present a formal theory of time to be distinguished reversal. Let us denote the time-reversaloperator by from 0, a general antiunitary operator.Consider

0,

where

0|a)is the time-reversedstate.Moreappropriately, 0|a)should be called the motion-reversedstate. If |a)is a momentum eigenstate |p'),we J expect to be | p') up to a possible phase.Likewise, is to be reversed 0|a)
\342\200\224

|a)->0|a),

D.4.22)

under time reversal.
operator

We now deducethe fundamental property of the time-reversalopera by looking at the time evolution of the time-reversedstate. Consider physical system represented a ket by say at / = Then at a slightly later time / = S/, the system is found in

|a),

0.

where H is the Hamiltonian that characterizesthe time evolution.Insteadof the preceding we say at / = 0, and then let equation, suppose first apply the system evolveunder the influenceof the Hamiltonian H.We then have

(iff

\\

1-\342\200\224SM|a>,

D.4.23)

0,

at 8t

1

\342\200\224

H|a>.

D.4.24a)

If motion obeys symmetry under time reversal, we expect the preceding state ket to be the same as

a,/0= 0;/=-\302\253/>

D.4.24b)

272

Symmetry

in Quantum

Mechanics

that

and J; see Figure

is, first considera state ket at earlier time t = 8t, and then reverse p
\342\200\224

4.11. Mathematically,

D.4.25
If the preceding relation is to be true for
any

ket, we must have

= -/7/0|> 0/7/|>,

D.4.26

where the blank ket | ) emphasizesthat D.4.26)s to be true for any ket. i We now argue that 0 cannot be unitary if the motion of time reversal is to make sense.Suppose0 were unitary. It would then be a legitimate to cancel the z's in D.4.26), nd we would have the operator equation

_
Consider an energy eigenket \\n)
corresponding

ZJQk

_ ?\\ ZJ

(A

A

yi\\

D.4.27),

with energy eigenvalue En. The corretime-reversedstate would be 0|w),and we would have, because of

H@\\n)

=

-

@H\\n)

=

(-En)Q\\n).

D.4.28

This equation says that 0|w) is an eigenketof the Hamiltonian with energy of eigenvalues En. But this is nonsensicaleven in the very elementarycase a free particle. know that the energy spectrum of the free particle is We T positive semidefinite\342\200\224from 0 to +oo. here is no state lower than a
\342\200\224

Momentum

beforereversal
Momentum Momentum
after

beforereversal

reversal

\342\200\224o

at
Momentum
after

f=

reversal
(b)
time reversal at time t

FIGURE

4.11. Momentum before and after

(a)

= 0 and / = + St.

4.4.The

Time-Reversal Discrete Symmetry

273

particle at rest (momentum eigenstatewith momentum eigenvaluezero); the energy spectrum ranging from oo to 0 would be completelyunacceptable. We can also see this by looking at the structure of the free-particle w Hamiltonian. We expectp to change sign but not p2; yet D.4.27) ould
\342\200\224

imply that

2

__

2

^^\342\200\224H-. 2m

D.4.29)

@/7/|> = i@H\\ > D.4.30) Now antilinear property D.4.13b). at last we can cancel the i 'sin D.4.26) by to leading, finally, via D.4.30) D 4 31) the expresses fundamental property of the Hamiltonian Equation D.4.31) under time reversal.With this equation the difficulties mentionedearlier [see to a D.4.27) D.4.29)]re absent, and we obtain physically sensibleresults. From now on we will always take 0 to be antiunitary. We mentioned earlier that it is best to avoid an antiunitary operator on bras from the right. Nevertheless,we may use acting
\302\256H=H\302\256

becomes D.4.26)

All these arguments strongly suggest that if time reversal is to be a in D.4.26) useful symmetry at all, we are not allowed to cancel the hence, had better be antiunitary. In this casethe right-hand side of

i's

\302\251

-

</?|0|a>,
which

D.4.32)

is always to be understood as
\302\253j8|).(e|a\302\273

D.4.33)

and never as
\302\253/?|@)\302\273.

D.4.34)

In fact, we do not even attempt to define This is one placewhere the Dirac bra-ket notation is a little confusing. After all, that notation was invented to handle linear operators, not antilinear operators. With this cautionary remark, we are in a position to discussthe behavior of operatorsunder time reversal.We continue to take the point of view that the operator is to act on kets

(/?|0.

0

|5>= 0|a>, |/?)= 0|/?>,
yet
it
operators\342\200\224in \342\200\224which

D.4.35)

is often convenientto talk about particular, observables are odd or even under time reversal. We start with an important
namely,
<j8|\302\256|a>

identity,

=

(al\302\251\302\2561*\302\251-1!/?),

D.4.36)

where

\302\256

is a linear operator. This identity

follows solely from the anti-

274

Symmetry

in Quantum

Mechanics

unitary

nature of

0.To prove this

let us define

D.4.37)
w By dual correspondence e have

D.4.38)
Hence,

D.4.39)
which proves the identity. In particular, for Hermitian
(P\\A\\a)

A observables we get

= (&\\@A@-l\\p).

D.4.40)

We

say whether we have the upper or lower sign in
that

observables re even or odd under time reversal according to a
~l=\302\261A.

D.4.41)

Note that
follows:

this

the matrix elements of

equation, together with D.4.40), gives a phaserestriction on A taken with respect to time reversed states as

If |/3)is identical to have

s |a),o that

D.4.42) a> = + ($\\A\\&)*. we are talking about expectationvalues,we
=
\302\261(a\\A\\a),

(a\\A\\a)

D.4.43)

where (fi|^4|fi) is the expectation value taken with respect to the timereversed state. As an example, let us look at the expectation value of p. It is reasonableto expectthat the expectation value of p taken with respectto the time-reversedstate be of oppositesign.Thus

= (a|p|a) -E|p|5),

D.4.44)

so we take p to be an odd operator, namely,
This impliesthat

= p0|p')
Equation D.4.46) eigenket with eigenvalue
with agrees
\342\200\224

\342\200\224

\302\251p\302\251\021\302\251^')

= (-p'H|p'>.
\342\200\224

D.4.46)
i 0|p')s a momentum

p'.

our earlierassertion that It can be identified with |

p') itself with a

4.4.The

Time-Reversal Discrete Symmetry

275

of suitable choice phase.Likewise,we obtain

= |x') |x')

(up to a phase)

D.4.47)
A A AO\\

from the (eminently reasonable)requirement =/~ ~

We

can now checkthe invariance of the fundamental

(ll\\
a\\x\\a)

(a|x|a).
I I \\

/ D.4.48) commutation

relation

= [xt9Pj]\\) ih8tJ\\)9
where the blank ket | ) stands for we D.4.49), have
which any

D.4.49)

ket. Applying

0 to both

sidesof

leads to, after passing0 through
fundamental

ih9

D.4.51)
Note that the
by virtue of the fact that reason for taking to

This can be given as yet another otherwise, we will be forced to o abandon either D.4.45) r D.4.47)! Similarly, to preserve

0

0 is antiunitary.
be
antiunitary;

commutation

= relation [xl9p] ih8tJ is preserved

[jt,Jj\\=ihe,jkJkt
the angular-momentum operator must

D.4.52)
time

be odd under

reversal, that is,

This is consistentfor spinless we system where J is just x X p. Alternatively, couldhave deducedthis relation by noting that the rotational operator and the time-reversaloperator commute (note the extra /!).
Wave Function

Supposeat some given time, say at / = 0, a spinlesssingle-particle system is found in a state represented \\a). Its wave function (x'|a) by appearsas the expansion coefficientin the position representation
\\a)

=

jd3x'\\K')(x'\\a).

D.4.54)

Applying

the time-reversaloperator

,

D.4.55)

where we have chosenthe phaseconvention so that

0|x')is |x')itself. We

276

Symmetry in Quantum

Mechanics

then recover the rule

D.4.56)
Y\342\204\242.

inferred earlier by looking at the Schrodinger wave equation [seeD.4.5)]. The angular part of the wave function is given by a spherical harmonic With the usual phaseconventionwe have Now YimF,4>) is the wave function we D.4.56) deduce
for

\\l,

therefore, from m) [seeC.6.23)];

0|/,m> = (-1)\"V> m).
reasonable.

D.4.58)

If we study the probability current density B.4.16) a wave function of for type C.6.22) going like R{r)Ytm, we shall concludethat for m > 0 the current flows in the counterclockwisedirection, as seen from the positive z-axis. wave function for the correspondingime-reversedstate has its t The probability current flowing in the oppositedirection becausethe sign of m
A is reversed. ll this

is very

a nontrivial consequencef time-reversalinvariance, we state an o important theorem on the reality of the energy eigenfunctionof a spinless
As

particle.
and Theorem. Suppose Hamiltonian is invariant under time reversal the energy eigenket \\n) is nondegenerate;then the corresponding energy is real {or,more generally, a real function times a phasefactor eigenfunction independentof x).
the

Proof To prove this,

first

note that

H<d\\n)
\302\256\\n)

= SH\\n)= En@\\n),

D.4.59)

so \\n) and have the same energy. The nondegeneracy assumption us to conclude that \\n) and S\\n) must representthe same state; prompts otherwise there would be two different states with the same energy En, an
obvious contradiction! Let us recall that the wave functions for and respectively.They must be the 0|ft)are
(x'|\302\253) (x'|\302\253)*>
<x'|\302\253>

\\n)

and

same\342\200\224that

is,

=

<x'|\302\253>*

D.4.60)

for all practical more precisely,hey can differ at most by a t factor independent of x. phase
purposes\342\200\224or,

?

Thus if we have, for instance, a nondegeneratebound state, its wave function is always real. n the other hand, in the hydrogen atom with / =?0, O m =? 0, the energy eigenfunctioncharacterizedby definite /, m) quantum numbers is complexbecause is complex;this does not contradict the
(\302\253,
Y\342\204\242

4.4.The

Time-Reversal Discrete Symmetry

277

theorem because\\n9l9m) and \\n,l, m) are degenerate.Similarly, the wave function of a plane wave elp'x/his complex,but it is degeneratewith e~ip-x/h We seethat for a spinless system, the wave function for the timereversed state, say at / = 0, is simply obtained by complexconjugation. In or the terms of ket \\a) written as in D.4.16)in D.4.54), 0 operator is the K itself becauseK and 0 have the same effect complexconjugate operator We when acting on the baseket \\a') (or |x')). may note, however,that the situation is quite different when the ket |a) is expandedin terms of the 0 momentum eigenket because must change |p') into | p') as follows:
\342\200\224 \342\200\224

a) =

d3p' p'X-p'|a>*. .4.61) D

It is apparent that the momentum-space wave function of the time-reversed state is not just the complex conjugate of the original momentum-space wave function; rather, we must identify </>*( p') as the momentum-space wave function for the time-reversedstate. This situation once again ilillustrates the basic point that the particular form of 0 dependson the particular representation used.
\342\200\224

Time Reversalfor a Spin \\ System The situation is evenmore interesting for a particle with in particular. We recall from Section 3.2 that the eigenket of S#h can be written as eigenvalue h/2
|h;

spin\342\200\224spin

\\,

with

+) = e-'WV'W*|+>>

D.4.62)
angles fi and

where h is characterized by the polar and azimuthal we respectively.Noting D.4.53) have
In

a,

h;

+ +) = e-lS:a/he-lSvp/h@\\) = -n\\h]
that

-).

D.4.63)

On the other hand, we can easily verify

D.4.64)
In general, we saw earlier that the product UK is an antiunitary operator. and D.4.64) with set equal to UK, and noting that K Comparing acting on the base ket | + ) gives just ), we seethat

D.4.63)

0

|+

2S y
h

K,

D.4.65)

where r\\ standsfor an arbitrary phase(a complex number of modulus unity). Another way to be convinced of D.4.65) verify that if x(n;+ ) is the is to + two-component eigenspinorcorrespondingto |n; ) [in the sensethat

278

Symmetry

in Quantum

Mechanics

a-nx(n; +) = x(n; +)],then
(note the complexconjugation!)is the eigenspinorcorrespondingto |n; again up to an arbitrary phase, seeProblem7 of this chapter.The apappearance of Sy or cjy can be traced to the fact that we are using the reprepresentation in which Sz is diagonal and the nonvanishing matrix elements of Sy are purely imaginary. Let us now note
\342\200\224),

D.4.66)

e-\302\253^/A|+^

on D.4.65), the most general spin \\ ket: Let us apply

we UsingD.4.67), are ift

= e-/^/*|-> -|+>- D.4.67) a position to work out the effectof 0,written as = + |_^

D.4.68

0 onceagain:

D.4.69
or (where operator) for any spin orientation. This is an extraordinary result. It is crucial to note here that our conclusionis completely independent of the choice of phase; D.4.70)holds no matter what phase convention we may use for 17. In contrast, we may note that two successivepplications of 0 to a spinless a state give
\342\200\224 \342\200\224

1is to be understood as 1 times the identity

02=-l,

D.4.70)

\302\2512=+l

D.4.71

as is evident from, say, D.4.58). More generally,we now prove

Thus the

f generalizesor arbitrary

D.4.72a) 02|y half-integer) = - \\j half-integer) D.4.72b) 02|y integer) = + \\j integer). W of 02 is given by ( 1JJ. e first note that D.4.65) eigenvalue
\342\200\224

j

to

Q = ne-My/hK.

D.4.73)

Fora ket

\\a)

expandedin terms of

\\j9

we m) base eigenkets, have

D.4.74)

4.4.The
But

Time-Reversal Discrete Symmetry

279

D.4.75) e-2Mv/*Umy = (_iJ^-m), as is evident from the propertiesof angular-momentum eigenstates under rotation by 277. In D.4.72b), integer) may stand for the spin state \\j D.4.76)
of a two-electron system or the orbital state |/,m) of a spinless particle.It is is an integer. Likewise,\j half-integer) may stand, important only that \ for example, or a three-electronsystem in any configuration.Actually, for a f system made up exclusivelyof electrons,any system with an odd (even) number of electrons\342\200\224regardless of their spatial orientation (for example, relative orbital angular momentum)\342\200\224is odd (even)under @2; they neednot

j

even be J2 eigenstates! We make a parenthetical remark on the phase convention. In our earlier discussion basedon the position representation,we saw that with the usual convention for spherical harmonics it is natural to choosethe arbiphase for |/,ra) under time reversal so that
arbitrary

= 0|/,m) (-1)\"V,m).
\342\200\224 \342\200\224

D.4.77)

Someauthors find

attractive to generalizethis to obtain an integer) @|y,m) = ( l)m\\j9 m)
it

refers to / or s (for an integer spin system).We may for is this compatiblewith D.4.72a) a spin \\ system when we ask, naturally visualize \\j\\ m) as being built up of \"primitive\" spin \\ objectsaccording to is Wigner and Schwinger.It is easy to seethat D.4.72a) indeedconsistent to we choose in D.4.73) be + /. In fact, in general, we can take 17 provided of regardless whether for
any

j

(j

D.4.78)

T s chapter. he reader hould be warned,however, that this is not the only convention found in the literature. See, or instance,Frauenfelder and f ( F it Henley1974.) orsomephysical applications, is more convenient to use other

j\342\200\224either

D.4.79) -m) a half-integer j or an integer /; seeProblem 10 this of
Q\\j\\m)

= i2m\\j,

elementsimpleis not the phase convention that makesthe s time-reversal operator ropertiessimple.We emphasizeonceagain that p
operator matrix

for choices; instance,the phase convention that makes the

J\302\261

op-

eigenstates Having worked out the behavior of angular-momentum under time reversal, we are in a position to study once again the expectation values of a Hermitian operator.Recalling D.4.43), obtain under time we reversal (canceling i2m factors) the

i D.4.70)s completely independentof phase convention.

<a,7, m\\A\\a9 7, m) =

\302\261

(a,y, - m\\A\\a9

7, m).

-

D.4.80)

280

Symmetry

in Quantum

Mechanics

of Now supposeA is a component of a spherical tensor T^k\\ Because the it is sufficient to examinejust the matrix elementof Wigner-Eckart theorem, I to the q = 0 component.n general, T{k) (assumed be Hermitian) is said to be even or odd under time reversal depending how its q = 0 component on satisfies the upper or lower sign in

.
for Equation D.4.80) A , j9
m\\T\342\204\242\\a9

D.4.81
j9

= T^k) becomes j9 m) = <a, j9
\302\261

-

m\\T^\\a9

- m).

D.4.82

Due to

phase.We

C.6.46)-C.6.49), next use C.10.22)

we expect for T^k\\

7, |a,j\\ m) = ^@,*r,0)|a, m) up to a which leadsto
\342\200\224

= ,77,0O^.0@,77,0)

(-

l)kT0(k)

+ (q*0components),
(\342\200\224

= where we have used @$\\0,t,O) = Pk(cos7r) t
components

D.4.83

and

|a,

1)*,and the q # 0 comgive vanishing contributions when sandwiched between (a9j9rn\\ j9 m). The net result is

a, 7, m>. D.4.84
As an

example,aking k=l9 the expectationvalue (x) taken with respectto t of eigenstates 7, m vanishes.We may argue that we already know (x) = 0 from parity inversion if the expectationvalue is taken with respectto parity But eigenstates[see D.2.41)]. note that here \\a9 7, m) need not be parity For eigenkets! example, the \\j9m) for spin \\ particlescould be cs\\s1/2)

cp\\Pi/i)Interactions with Electricand MagneticFields; ramersDegeneracy K

Considerchargedparticlesin an externalelectricor magneticfield.If we have only a static electric field interacting with the electric charge, the interaction part of the Hamiltonian is just

F(x)= e4>(x),

D.4.85
of

where <>(x) is the electrostaticpotential. Because <j>(x) is a real function the time-reversaleven operator x, we have

D.4.86
does not lead to an interesting case, D.4.86) parity conservation law. The reason is that
even if

Unlike the

breaks down. As a result, there is no such thing as the \"conservationof

D.4.87) QU(t9t0)*U(t9t0)e of holds, D.4.86) so our discussionfollowing D.1.9) Section4.1

4.4.The

Time-Reversal Discrete Symmetry

281

time-reversal quantum number.\" As we already mentioned, requirement does, reality of D.4.86) however,lead to a nontrivial phase and a nondegeneratewave function for a spinlesssystem [see D.4.59)
restriction\342\200\224the

o Another far-reachingconsequencef time-reversalinvariance is the H and 0 commute, and let \\n) and be Kramers degeneracy. Suppose the energy eigenket and its time-reversedstate, respectively.It is evident from D.4.86) \\n) and @\\n) belong to the same energy eigenvalue that = QH\\n) = EJd\\n)). The question is, Does \\n) represent the En(H@\\n) If can differ at most by a phase same state as 0|ai)? it does, \\n) and factor. Hence,
0|\302\253) 0|\302\253)

D.4.60)].

D.4.88)
Applying

+ e~iSe iS\\n); hence,

0

w again to D.4.88), e have

\302\2562\\n)

= &elS\\n) = e~lS@\\n) =

But this

so we are led to conclude that \\n) and which have the same energy, must correspond distinct to is, there must be a This of degeneracy. means, for instance, that for a system composed an odd in number of electrons an externalelectricfield E, each energy levelmust be at least twofold degenerateno matter how complicatedE may be.Consideralong this line have interesting applications to electrons in crystals where odd-electron even-electronsystems exhibit very different behavand Historically, Kramers inferred degeneracyof this kind by looking at explicit solutionsof the Schrodingerequation; subsequently,Wigner pointed out that Kramers degeneracyis a consequencef time-reversalinvariance. o Let us now turn to interactions with an external magnetic field.The Hamiltonian H may then contain terms like
always
\342\200\2241,

D.4.89) relation is impossible half-integer j systems, for which 02 is for
0|\302\253), states\342\200\224that

Considerations

behaviors.

D.4.90) (B = VXA), where the magnetic field is to be regarded external.The operators S and as p are odd under time reversal; these interaction terms therefore do lead to

SB,

p-A + A-p,

D 4 91)
a trivial example, for a spin \\ system the spin-up state | + ) and its time-reversedstate | ) no longer have the same energy in the presence of an external magnetic field. In general, Kramers degeneracy in a system containing an odd number of electronscan be lifted by applying an external magnetic field. Notice that when we treat B as external, we do not change B under time reversal; this is becausethe atomic electron is viewed as a closed quantum-mechanical system to which we apply the time-reversaloperator.
As
\342\200\224

282

Symmetry

in Quantum

Mechanics

This should not be confused with our earlier remarks concerning the invariance of the Maxwellequations D.4.2) nd the Lorentz force equation a under t -> t and D.4.3). we were to apply time reversalto the whole There world, for example, even to the currents in the wire that producesthe B field!
\342\200\224

PROBLEMS

1.Calculate the three lowest energylevels,together with

their degeneracies, massdistinguishable particles): for the following systems(assume equal a. Three noninteracting spin \\ particles in a box of length L. b. Four noninteracting spin \\ particles in a box of length L. vector 2. Let J^J denotethe translation operator (displacement d); ^(h, <?),

a. ^ and (d and d' in different directions). and ^(n',<//)h and h' in different directions). b. ( c. and d.^(h, and 3.A quantum-mechanicalstate ^ is known to be a simultaneous eigen<\302\256(h,<f>)

pairs commute? Why?

the rotation operator (h and respectively);and tt the parity

are the axis and angle of rotation, operator.Which, if any, of the following
</>

^
77.

3TA

<J>)

77.

state of two Hermitian operators A and B which anticommute,

What

can you say about the eigenvalues of A and B for state Illustrate your point using the parity operator (which can be chosento
satisfy
771\") and the momentum operator. spin \\ particle is bound to a fixed center by a sphericallysymmetrical

m

= 77 ~1=

4.

A

potential.
your result in (b) is understandable in view of the transformation propertiesof the operator S#x under rotations and under spaceinversion (parity). 5. Because weak (neutral-current)interactions there is a parity-violating of potential between the atomic electron and the nucleus as follows:

c. Show that

b. Express(o-x)#?-1/2,\"-1/2 of someQther qyUm^ in terms

a. Write

down the spin angular

function

^/J^1/2'\021^1/2.

where S and p are the spin and momentum operatorsof the electron, and the nucleus is assumed to be situated at the origin. As a result, the ground state of an alkali atom, usually characterized by \\n9l9j\\m) actually contains very tiny contributions from other eigenstates as

Problems

283

follows:

n, /, /, m)

m)
n'l'j'm'

w On the basisof symmetry considerations lone, hat can you say about a w m'), hich give rise to nonvanishing contributions? Suppose (n\\ the radial wave functions and the energy levelsare all known. Indicate

/',/',

how you may calculate

Cn>ifm*.

Do we

get

further

restrictions on

6.Considera symmetric rectangular double-well otential: p
00 V

=

0
Vo

for |jc|> a + b; for a < x < a + > 0 for x <

a.

b\\

is very high comparedto the quantized energies f o for obtain an approximate expression the energy splitlow-lying states, betweenthe two lowest-lyingstates. 7. a. Let i|/(x,) be the wave function of a spinless t particle corresponding to a plane wave in three dimensions.Showthat i|/*(x, is the wave function for the plane wave with the momentum direction
Assuming
that Vo
splitting
\342\200\224t)

answer. a 10. . What is the time-reversed corresponding 2)(/?)|y, state to m)l b.Usingthe propertiesof time reversal and rotations, prove
tify

eigenvalue of x(n) (in terms of the polar and azimuthal anglesC and 7 that characterize n) verify that -/a2x*(n) is the two-component eigenspinor ith the spin direction reversed. w 8.a. Assuming that the Hamiltonian is invariant under time reversal, prove that the wave function for a spinlessnondegenerate system at any given instant of time can always be chosento be real, b.The wave function for a plane-wave state at t = 0 is given by a complexfunction eip x/h. Why doesthis not violate time-reversal in variance? 9.Let <j)(p') be the momentum-space wave function for state that is, I 4>(p')= (p'la)-sthe momentum-space wave function for the timereversedstate or given by <|>(p'), <K~\"P')> ^(p')* ^(\"\"P')?
\342\200\242

b.Let x(n)be the two-component eigenspinor f cr n with o

reversed.

+1.Using the explicitform

|a),

0|a)

your

11. Supposea spinlessparticle is bound to a fixed centerby a potential
\342\200\224m).

2m c.Prove 917, ) = i2m\\j, m

V(x)

so asymmetrical that no energy level is degenerate. Usingtime-

284

Symmetry in Quantum

Mechanics

reversal invariance prove for any energy eigenstate. (This is known as quenching of orbital an ei If the wave function of such a nondegenerate gular momentum.) is expandedas genstate

22
/ m

,

40,

of phase restrictions do we obtain on F/m(r)? 12. he Hamiltonian for a spin 1system is given by T
what

kind

Solve this problem exactly to find the normalizedenergyeigenstatesand Hamiltonian of this kind actually apeigenvalues. (A spin-dependent in crystal physics.)Is this Hamiltonian invariant under time appears reversal? How do the normalized eigenstates you obtained transform under time reversal?

CHAPTER5

Methods Approximation

Few problems in quantum mechanics\342\200\224with either time-independent or be solved exactly. Inevitably we are Hamiltonians\342\200\224can time-dependent forced to resort to some form of approximation methods. One may argue to that with the advent of high-speedcomputers it is always possible obtain the desiredsolution numerically to the requisite degreeof accuracy; neverit remains important to understand the basic physics of the solutions even before we embark on ambitious computer approximate of calculations. This chapter is devoted to a fairly systematic discussion solutions to bound-state problems. approximate
nevertheless,

5.1. TIME-INDEPENDENT PERTURBATIONTHEORY:
NONDEGENERATECASE Statement of the Problem The approximation method we considerhere is time-independent perturbation theory\342\200\224sometimes known as the Rayleigh-Schrodinger erp a perturbation theory. We consider time-independentHamiltonian H such that it can be split into two parts, namely,

E.1.1)
285

286

Approximation Methods

where the V = 0 problem is assumed to have been solved in the sensethat both the exact energyeigenkets\\n@)) and the exact energyeigenvaluesE^0) are known:

H0\\n^)= E^\\n((\302\273).
We

E.1.2)
full

are required to find approximateeigenketsand eigenvaluesfor the Hamiltonian problem

(H0+ V)\\n) = En\\n)9

E.1.3)

where V is known as the perturbation; it is not, in general, the full-potential For operator. example, supposewe considerthe hydrogen atom in an external electricr magnetic field. The unperturbed Hamiltonian Ho is o taken to be the kinetic energy p2/2m and the Coulomb potential due to the o O presencef the proton nucleus e2/r. nly that part of the potential due to the interaction with the external E or B field is representedby the perturbation V. it is Insteadof E.1.3) customary to solve
\342\200\224

(H0+ \\V)\\n)
where

= En\\n)9

E.1.4)

X is a continuous real parameter. This parameter is introduced to keep track of the number of times the perturbation enters.At the end of the calculation we may set X ->1to get back to the full-strength case.n other I words,we assumethat the strength of the perturbation can be controlled. The parameter X can be visualized to vary continuously from 0 to 1,the X = 0 case to corresponding the unperturbedproblem and X = 1correspondcorresponding

|w\302\260>

In to the full-strength problem of E.1.3).physical situations where this we a approximation method is applicable, expectto see smooth transition of into En as X is \"dialed\" from 0 to into \\n) and The method rests on the expansion of the energy eigenvaluesand in energy eigenkets power of X. This means that we implicitly assume the of the energy eigenvaluesand eigenkets in a complex X-plane analyticity around X = 0.Of course,if our method is to be of practical interest, good approximations can better be obtained by taking only one or two terms in
E$\302\273

1.

the

expansion.
The Two-StateProblem

let us

Beforewe embark on a systematicpresentation of the basicmethod, the expansion in X might indeedbe valid in the exactly solubletwo-state problem we have encountered many times already. Sup-

seehow

5.1. Time-Independent

Perturbation

Theory: Nondegenerate

Case

287

posewe have a Hamiltonian

that

can be written as f ?f|2@>><2@>|

+ XK12|l@>><2@)|+XK21|2(O)>A(O)|, E.1.5) where |l@)) and |2@))are the energyeigenketsfor the X = 0 problem, and we considerthe case Vn = V22 = 0. In this representation the H may be by represented a square matrix as follows: H=
21

xk12
z

E.1.6)

where we have used the basisformed by the unperturbed energy eigenkets. The V matrix must, of course, e Hermitian; let us solve the casewhen Vl2 b and V2l are real:
Vn

= Vl*2,

V2l

= V2*;

E.1.7) E.1.8)

hence, by Hermiticity

= V2l.

This can always be done by adjusting the phaseof |2@))relative to that of T |l@)). he problemof obtaining the energy eigenvalueshere is completely analogous to that of solving the spin-orientationproblem, where the anais analogue of E.1.6) ' ai H = o o#a = 0 a3 E.1.9)

ao-a3

where we assumea = (ax,0, is small and ao,ava3 are all a3) eigenvaluesfor this problem are known to be just are E.1.6)
X2F12

real.The

E.1.10
By

analogy the correspondingigenvaluesfor e

E

E.1.11

Let us supposeX|F12| small compared with the relevant energy scale,the is differenceof the energyeigenvaluesof the unperturbed problem:
We

E.1.12
can then use
.
\\/l

+e

=l+-e-y+

1

e2

\342\200\242\342\200\242\342\200\242

E.1.13
presenceof

to obtain the expansion of the energy eigenvalues in the

288

Approximation

Methods

perturbation X|F12|, namely,

E.1.14)

(?f These are expressions that we can readily obtain using the general forto be developedshortly. It is also possible write down the energy formalism to in analogy with the spin-orientationproblem. eigenkets The reader might be led to believe that a perturbation expansion this is not always existsfor a sufficiently weak perturbation. Unfortunately the A necessarily case. s an elementaryexample,considera one-dimensional probleminvolving a particle of mass m in a very weak square-wellpotential of depth Vo (V=-Vo for a < x < a, V=0 for \\x\\> a). This problem

-

admits one bound state of energy,

E=
We might

-

Bma2/h2)\\XV\\2,

X

> 0 for attraction.

E.1.15)
E.1.15)

regard the square well as a very weak perturbation to be addedto the free-particle Hamiltonian and interpret result as the energy shift in the ground state from zero to |XF|2.Specifically,because is this quadratic in F, we might be tempted to associate as the energy shift of the ground state computed according to second-order erturbation theory. p if t However, this view is false because this were the case,he system would also admit an E < 0 state for a repulsivepotential casewith X negative, which would be sheernonsense. Let us now examine the radius of convergenceof seriesexpansion If we go back to the exact expression and regard it as a of function of a complex variable X, we see that as |X| is increased from zero, branch points are encountered at

E.1.15)

E.1.14).

E.1.11)

The condition for the convergenceof the seriesexpansion for the
full-strength

X

case is

=1

l If
this

@)_ ?@)

condition is not met, perturbation expansionE.1.14) is meaningless.
discussion on convergence following under E.1.44), general remarks.

Seethe

5.1. Time-Independent

Perturbation

Theory: Nondegenerate

Case

289

o Formal Development f Perturbation Expansion
We now state in more preciseterms the basic problem we wish to solve. Supposewe know completelyand exactly the energy eigenkets and energy eigenvaluesof

E.1.18
the sense that the closurerelation = holds. LJh@))(h@)| Furthermore, we assumehere that the energyspectrum is nondegenerate;n the next section we will relax this assumption. We are i interestedin obtaining the energyeigenvaluesand eigenketsfor the problem defined by To be consistent with we should write as

The set

{| @))} is complete in n
E.1.4).

1

E.1.18)

E.1.4)

(H0+ XV)\\n)x = E^\\n)x
to

E.1.19

denote the fact
As the

\\n)x

this correct but more cumbersomenotation. continuous parameter A is increased from zero, we expectthe for the nth eigenket to depart from its unperturbed energy eigenvalue En value so we define the energy shift for the nih levelas follows:

the energy eigenvalues E^X) and energy eigenkets are functions of the continuous parameter A; however,we will usually
that

dispensewith

E^\302\260\\

The basic Schrodingerquation to be solved (approximately)is e

We may
|\302\253@)).

be tempted to invert the operator Ho; however,in general, the inverse operator l/(?w@) HQ) is ill defined becauseit may act on Fortunately in our case Aw)|w) has no componentalong on the as can easily be seenby multiplying both sidesof by
\342\200\224

{) ?
\342\200\224

E.1.20

E.1.21
E.1.21)
|\302\253@)),

Ef\302\256

(XV\342\200\224

(\302\253@)|

left:

E.1.22
Supposewe define the complementaryprojectionoperator
n

E.1.23
it multiplies
<f>n

The inverse operator l/(?w@) Ho) is well defined when
the
right.

-

on

Explicitly,

1
17@)

_ ff

*,-E ^ ^

\342\200\236\302\273.'

17@)

<J*w>)<*m|. _ F@)

E.1-24

Also from

and it is E.1.22) E.1.23), evident that

(XV- bn)\\n) = 4>n(XV-

A

J|n>.

E.1.25

290
We may

Approximation Methods

therefore be tempted to rewrite

as E.1.21)

as However,this cannot be correct because X -> 0, we must have \\n) -> \\n@)) and A^->0. Nevertheless, even for X =? 0, we can always add to \\n) a solution to the homogeneous equation E.1.18), namely, cn\\n@)), so a suitable final form is
\\n)

= cn(X)\\n^) +

^(XK-Aw)|#i>,

E.1.27

where

\\imcn(X)=l.
Note that
For reasonswe will see later, usual normalization convention Rather, we set
it

E.1.28

E.1.29
is convenient to depart
from the

(n\\n)=l.

E.1.30

even for X # 0. We can always do this if we are not worried about the overall normalization because only effectof setting cn # 1is to introduce the a common multiplicative factor. Thus, if desired,we can always normalize the ket at the very end of the calculation. It is also customary to write

E.1.31

^(O)_
and similarly

E.1-32 1 1

1
so we have

E.1.33

E.1-34
We

also note from

and that E.1.22) E.1.31)

)-

Everything dependson the two equations in Our basic strategy is to expand \\n) and A^ in the powersof

E.1.35 and E.1.34) E.1.35
X

and

then

5.1. Time-Independent

Perturbation

Theory: Nondegenerate

Case

291

are E.1.35) identities which

and match the appropriate coefficients.This is justified becauseE.1.34) hold for all values of X between 0 and We

1.

beginby writing
n n

'

'

*
\342\200\224n

Substituting

powersof

and E.1.36) E.1.35) into
X,

equating the coefficientof various

we obtain

0(X2):

E.1.37)

only up to

we E.1.36),get

so to evaluate the energy shift up to order X^ it is sufficient to know when order X^\021. We now look at E.1.34); it is expandedusing

|\302\253>

X

(\\nw)

+ X\\n{1)) +

\342\200\242\342\200\242\342\200\242)\342\200\242

E.1.38

Equating the coefficientof powersof

X,

we have
**0
with \\n(l)), it

0(X):
n

where we have used ^A^I/7^) = 0.Armed

for us to go back to our earlier expression A(^ for

is now profitable [seeE.1.37)]:

E.1.40
Knowing using

as E.1.39) follows:

A(^\\

we can work out the
*\"

X2-term

in

ket equation

also E.1.38)

0(X2): |kB))=

E^H

V

E.1.41

292

Approximation

Methods

Clearly, we can continue in this fashion as long as we wish. Our operator method is very compact; it is not necessaryto write down the indiceseach time. Of course,o do practical calculations we must use at the end the t form of as given by E.1.23). explicit To seehow all this works, we write down the explicit expansion for the energy shift
<j>n

A

n

=Z7

n

\342\200\224n

W I2

where
Vnk

^(
1^
^n

142)

= (n@)\\V\\k@))

* (n\\V\\k),

E.1.43

that is, the Notice that

goesas follows:

kets. elements are taken with respect to unperturbed we apply the expansion to the two-state problem we The expansion for the perturbed ket recover the earlier expression
matrix
when

E.1.14).
Vkn

n

p @) _ p @)
rnrXkn

+ x-

^k )

I

-\".

E.1.44)

Equation E.1.44) that the nth level is no longer proportional to the says unperturbed ket \\n@)) but acquires components along other unperturbed energy kets; stated another way, the perturbation V mixes various unperenergy eigenkets. A few general remarks are in order. First, to obtain the first-order energy shift it is sufficient to evaluate the expectation value of V with of i respectto the unperturbed kets.Second,t is evident from the expression the second-order that energy shift E.1.42) two energy levels, say the zth level and the jth level,when connected by V tend to repeleach other; the lower one, say the /th level,tends to get depressed a result of mixing with as the higher th level by |^7|2/(^7@) ?,@))> while the energy of the th level of goesup by the sameamount. This is a specialcase the no-level crossing which statesthat a pair of energy levels connected perturbation theorem, by do not crossas the strength of the perturbation is varied. m Supposethere is more than one pair of levelswith appreciable atrix elements but the ket whose energy we are concerned refers to the with, for ground state; then each term in E.1.42) the second-order energy shift is This means that the second-ordernergy shift is always negative negative. e
unperturbed

j

-

j

|\302\253),

5.1. Time-Independent
mixing.

Perturbation

Theory: Nondegenerate

Case

293

for the ground state; the loweststate tends to get even lower as a result of
will is clearthat perturbation expansionsE.1.42) E.1.44) and is sufficiently \" small.\" A more specificcrite?/0))| can be given for the case in which Ho is simply the kinetic-energy p operator(then this Rayleigh-Schrodinger erturbation expansion is just the Born series): t an energy Eo < 0, the Born seriesconvergesif and only if A neither Ho + V nor Ho V has bound states of energy E < Eo (R. G.

It

converge if
criterion

|Ff//(jE/0)\342\200\224

\342\200\224

Newton 1982, 233). p.
Wave-function We

Renormalization

we see ket. Recalling the normalization conventionwe use, E.1.31), that the ket \\n) is not normalizedin the usual manner. We can renormalperturbed ize the perturbedket by defining

are

in

a position to look at the normalization of the perturbed

E.1.45
where Zn is simply a constant with left we obtain [because f o
ZY2
What

E.1.31)]

js/(n\\n)N

=

1.Multiplying

(ai@)| on

the

satisfiesthe usual norZn can be regardedas the probability for requirement the perturbed energy eigenstateto be found in the corresponding unperNoting energy eigenstate.
normalization

= (n^\\n)N. is the physical meaning of Znl Because | n)N

E.1.46

E.1.30),
N(n\\n)N

unperturbed

= Zn(n\\n)=\\,

E.1.47)

we have
\021

= (n\\n) =

+0(X3),

E.1.48a

so up to order X2, we get for the probability of the perturbed state to be found in the correspondingnperturbed state u
\342\200\2247-

E.1.48b

The second term

in

is E.1.48b)to

be understood as the probability for

294

Approximation Methods

\"leakage\"to states other than |/7@)). Notice that Zn is less than 1,as expectedon the basisof the probability interpretation for Z. It is also amusing to note from E.1.42) to order X2, Z is related that to the derivativeof En with respectto E^0) as follows:

E.1.49)
We understand, of course,that in taking the partial derivative of En with we must regard the matrix elementsof V as fixed quantities. respectto Result is actually quite general and not restricted to second-order
E^\302\260\\

E.1.49)

perturbation theory.
Elementary Examples

To illustrate the perturbation method we have developed, us look let The first one concerns simple harmonic oscillatorwhose a examples. unperturbed Hamiltonian is the usual one:
at
two

E.1.50 2 Supposethe spring constant k moo2 is changed slightly. We may represent the modification by adding an extra potential
2m
\\
\342\200\224

V={emu2x2,
\342\202\254

where is a dimensionless parameter such that e <^ From a certain point of view this is the silliestproblem in the world to which to apply perturbatheory; the exact solution is immediately obtained just by changing to as follows: eco, E.1.52 yet this is an instructive example becauseit affords a comparison between the perturbation approximation and the exact approach. We are concernedhere with the new ground-state ket |0) in the o presencef V and the ground-stateenergy shift Ao:
perturbation

1.

E.1.51

^
and
A

0)

=v + Y
K

L1MJ
/c

^0 0

+

\342\200\242 \342\200\242 \342\200\242

E 1 53b^
this

The relevant matrix elementsare (seeProblem 5 in

em^
<o<\302\260vio<\302\260>>

=

?mwM
<2^|jc2|0<\302\260>>

=

^-.
2y2

^

chapter)

E.1.54

5.1. Time-Independent
All

Perturbation

Theory: Nondegenerate

Case
that

295

other matrix elementsof form Vk0 vanish. Noting are and energy denominators in E.1.53a) E.1.53b) everything to obtain

\342\200\2242hco,

the nonvanishing we can combine

E.1.55a
and
A

=F

-

F@) =

f

E.1.55b)

Noticethat as a result of perturbation, the ground-stateket, when expanded
in

terms of original unperturbed energy eigenkets (|^@))}, cquires a a component along the secondexcited state. The absenceof a component our along the first excitedstate is not surprising because total H is invariant under parity; hence, an energy eigenstate is expected to be a parity

eigenstate. A comparison with the exact method can easily be made for the energy shift as follows:
hco
~2

hco

E.1.56)
V

in

completeagreement with

the change in the wave function. In the function is
77 1/4

As E.1.55b).for the perturbed ket, we look at

of absence

the ground-statewave

1
where
h

-x2/2x20

E.1.57)

mco

E.1.58)

Substitution

leads E.1.52) to
x0 o

1/4

'

E.1.59)

hence,

1
1/4

1/8 I/O e) exp
\\

x 1/2 A+e) 2xo
-x2/2xl ]__
8

1 1
771/4 ,/JC

-x2/2x20

.1/4

4 JC 0 V2

1^

E.1.60)

296

Approximation

Methods

where we have used

(x 2@)) = 2V2(x

1

1

x x0

'
2l

\\

1 1 1
2V2tt1/4

-x2f2xl

2 + 4

E.1.61

2. and H2(x/x0)is a Hermitepolynomial of order As another illustration of nondegenerate perturbation theory, we A one-electron discussthe quadratic Stark effect. hydrogen outsidethe closed atom or a hydrogenlike atom with onevalence electron field subjectedto a uniform electric in (sphericallysymmetrical) The the positive z-direction. Hamiltonian H is split into two parts,
atom\342\200\224the
shell\342\200\224is

2m

. V0(r)

and

V

=

-e E z
V
\342\200\224>

(e < 0 for the electron).
\342\200\224 \342\200\224 \342\200\224> o\302\260,

bound by acquire a finite lifetime. However,we can still formally use perturbation theory to calculate the shift in the energy.(The imaginary part of this shift, which we shall ignore here, would give us the lifetime of the state or the width of the corresponding resonance.)]

[Editor's Note: Sincethe perturbation

oc as z particles n Ho can, of course, scape ow, and all formerly bound states e

E.1.62)

It is assumedthat the energy eigenketsand the energy spectrum for the unperturbed problem(Hoonly) are completely known.The electron spin turns out to be irrelevant in this problem,and we assumethat with spin of n This degrees freedom ignored, o energy level is degenerate. assumption does hold for n ?^ 1levelsof the hydrogen atoms, where Vo is the pure not Coulombpotential; we will treat such casesater. he energy shift is given T l
by
^^\342\200\224 ____

0

E zkk

zkj

2

E.1.63)

where we have used k rather than n to avoid confusion with the principal to is espected be a parity quantum number n. With no degeneracy,

hence, eigenstate;

zkk

=

0,

E.1.64)

as we saw in Section4.2. Physicallyspeaking,there can be no linear Stark effect, that is, there is no term in the energy shift proportional to |E because atom possessesvanishing permanent electricipole, the the a so d shift is quadratic in | E | if terms of order 31E or higher are ignored. energy e |3 Let us now look at zkj, which appearsin where k (ory) is the collectiveindexthat standsfor (ai, /, m) and {nf, m'). irst, we recall F the selection [see rule C.10.39)]

(n',I'm'z n, Im)

=0

E.1.63), /', '/' = / 1 unless
\302\261

m

=m

E.1.65)

5.1. Time-Independent
that

Perturbation

Theory: Nondegenerate

Case

297

follows from angular momentum (the Wigner-Eckart theorem with T^l0) and parity considerations. There is another way to look at the ra-selectionrule. In the presence of F, the full spherical symmetry of the Hamiltonian is destroyed by the external electric that selectsthe positive z-direction, but V (hence the field total H) is still invariant under rotation around the z-axis;in other words, we still have a cylindrical symmetry. Formally this is reflectedby the fact
that

[F,Lz] = 0.
\342\200\224

E.1.66

of This means that Lz is still a goodquantum number even in the presence V. As a result, the perturbation can be written as a superposition of of This eigenkets Lz with the same m m = 0 in our case. statement is true for all orders, in particular, for the first-order ket. Also, because the second-order energy shift is obtained from the first-order ket [seeE.1.40)] we can understand why only the m = 0 terms contribute to the sum. The polarizabilitya of an atom is definedin terms of the energy shift of the atomic state as follows:

A=-|a|E|2.

E.1.67)

Let us considerthe specialcaseof the ground state of the hydrogen atom. Even though the spectrum of the hydrogen atom is degenerate for excited states, the ground state (with spin ignored) is nondegenerate, so the forof nondegenerate perturbation theory can be applied.The ground formalism state |0@))is denotedin the (/?, /, m) notation by A,0,0),so

y l<*|z|l,0,0)|

?

(

,

where the sum over k includesnot only all bound states \\n,l,m) (for n > 1) but also the positive-energy continuum states of hydrogen. There are many ways to estimate approximatelyor evaluate exactly the sum in E.1.68) various degrees sophistication.We present here with of the simplest f all the approaches. o the were Suppose denominator in E.1.68) constant.Then we could obtain the sum by considering
k*0

E l</c<\302\260>|z|i,o,o>|2= E
all

k

= <l,0,0|z2|l,0,0>,

E.1.69

where we have used the completeness relation in the last step. But we can evaluate (z2) for the ground state as follows: easily and using the explicit form for the wave function
we obtain

E.1.70)
where a0 stands for the Bohr radius. Unfortunately
the

expressionfor

298

Approximation

Methods

but polarizability a involves the energy denominator that dependson we know that the inequality e2 @) i /7@)> _ 17@) , ZT(O)_ @)> ^0 E.1.71) k 2a0 As holds for every energy denominator in E.1.68).a result, we can obtain an upper limit for the polarizability of the ground state of the hydrogen atom, namely,
E?\302\260\\
\342\200\224

16tf It
turns

.
E.1.68)

/ E.1.72)

due
which

to A.

we can evaluate exactly the sum in using a method and J. T. Lewis (Merzbacher 1970, 424, for example), Dalgarno with the experimentallymeasuredvalue. This gives also agrees out
that

9a3

^

43.

E.1.73)
by

We

the

obtain the same result (without using perturbation theory) Schrodinger quation exactly using parabolic coordinates. e DEGENERATECASE

solving

5.2. IME-INDEPENDENT T T PERTURBATIONTHEORY: HE
The perturbation method we developed in the previous section fails when the unperturbed energyeigenketsare degenerate. The method of the previthat there is a unique and well-defined section assumes unperturbed ket of energy Er\\0) which the perturbed ket approaches s X -> 0.With degenera present,however, any linear combination of unperturbed kets has the same unperturbed energy; in such a caseit is not a priori obvious to what linear combination of the unperturbed kets the perturbed ket is reducedin the limit X 0.Here specifyingjust the energy eigenvalueis not enough; some other observable is needed to complete the picture. To be more w specific, ith degeneracywe can take as our basekets simultaneous eigenof Ho and some other observableA, and we can continue labeling the where k now symbolizesa collective unperturbed energyeigenketby |/c@)), index that stands for both the energy eigenvalue and the A eigenvalue. When the perturbation operator V does not commute with A, the zerothorder eigenketsfor H (including the perturbation) are in fact not A
previous degeneracy
\342\200\224>

eigenkets

eigenkets.
like

and E.1.42) E.1.44) obviously runs _

From a more practical point of view, a blind application of formulas
into difficulty
17@)

because

Vnk

E.2.1)

becomessingular
must modify

if Vnk is nonvanishing and E^0) and E[0) are equal.We the method of the previous section to accommodate such a

situation.

5.2.Time-Independent

Perturbation

Theory: The Degenerate

Case

299

our Whenever there is degeneracywe are free to choose base set of kets.We should, by all means, exploit this freedom. Intuitively unperturbed we suspectthat the catastrophe of vanishing denominators may be avoided our basekets in such a way that V has no off-diagonalmatrix by choosing elements (such as Vnk = 0 in In other words, we should use the linear combinations of the degenerateunperturbed kets that diagonalizeH in the subspacespanned by the degenerateunperturbed kets.This is indeed the correct to use. procedure Supposethere is a g-fold degeneracy before the perturbation V is switched on. This means that there are g different eigenkets all with the same unperturbed energy E$\\ Let us denote these kets by {\\m@))}. In general, the perturbation removesthe degeneracyin the sensethat there will be g perturbed eigenkets all with different energies. them form a set Let As X goesto zero |/> -* |/@)>, and various |/@)> are eigenketsof Ho all with the sameenergy Ef?\\ However,the set |/@)> neednot coincide with even though the two sets of unperturbed eigenkets the same span {|m@))} degenerateubspace,which we call We can write s

E.2.1)).

{|/>}.

D.

=

2

in where the sum is over the energy eigenkets the degenerateubspace. s in Beforeexpanding X, there is a rearrangement of the Schrodinger Let t equation that will make it much easiero carry out the expansion. Po o be a projectionoperator nto the space defined by {|m@))}. define We W Pi = 1 Po to be the projectiononto the remaining states. e shall then write the Schrodinger quation for the states | /> as e 0 = (E Ho \\V)\\l)
\342\200\224

+ (E Ho- W)P1\\[). E.2.2) We next separateE.2.2) two equationsby projecting into from the left on
KV)P0\\l>

- = (E - ?g> Po and Pu

-

with E.2.2)

We

is not singular

+ (E - Ho - XPx^Pxl/)= 0. - //0 can solve E.2.4) the subspacebecause
-\\PiVPo\\t)
in in this

(E

- ?g> -

\\P0V)P0\\t)

- XPoVP^t) = 0
PX{E

E.2.3)
E.2.4)
\\PXVP^)

of P1H0P1 all different from are
l

to subspacesinceE is close E$ and the eigenvalues we E$.Hence can write

Px

E

- H0 | /)

or written

out explicitly to

orderX when

is expandedas | /) = | /@)) +

300

Approximation

Methods

To calculate Po I), we substitute

to into E.2.5) E.2.3) obtain = 0. E.2.7) lE- o

X2 that there is a term of order in E.2.7) resultsfrom the subX we shall find that it producesa term of order in the state P0\\l). to order X and eigenTo order X we obtain the equation for the energies functions to order zero,

Although
substitution,

(E

- ?g> -

\\PoVPo)(Po\\l(O)))

= 0.

E.2.8)

This is an equation in the g dimensional degenerateubspaceand clearly s of are means that the eigenvectors just the eigenvectors the g x g matrix and the eigenvalues EA) are just the roots of the secularequation P0VP0 E.2.9) det[V (E Eg>)] = 0

- -

where V = matrix of P0VP0with matrix elements(m@) | V|m'@)). Explicitly in matrix form we have
V \\2
\\ \\ \\

B@)
\\

:

E.2.10)
\\

/

\\

The rootsdeterminethe eigenvalues are g altogether\342\200\224and by them into E.2.10), can solve for (m@)|/@)) for each/ up to we substituting an overall normalization constant.Thus by solving the eigenvalueproblem, we obtain in one stroke both the first-order energy shifts and the correct zeroth-ordereigenkets. otice that the zeroth-order ets we obtain as k N X 0 are just the linear combinationsof the various | m@))'s diagonalize that the perturbation V, the diagonal elementsimmediately giving the firstA^x)\342\200\224there
\342\200\224\302\273

ordershift

A/(D

=

y

E.2.11

Note alsothat if the degenerateubspace were the whole space, would we s have solved the problemexactly in this manner. The presencef unpero \"distant\" eigenketsot belonging to the degenerateubspace n will s show up only in higher orderand higher for the energy eiand higher for the energy eigenvalues. eigenkets and secondorder looksjust like the first-order energy shift [see Expression in that case E.1.37)]the nondegenerate except herewe have to make sure that the base kets used are such that V does not have nonvanishing offu diagonal matrix elementsin the subspacespannedby the degeneratenIf unperturbed eigenkets. the V operator is already diagonal in the baseket we representation are using, we can immediatelywrite down the first-order
unperturbed orders\342\200\224first

E.2.11)

5.2.Time-Independent
shift

Perturbation

Theory: The Degenerate

Case

301

case.

by taking the

expectationvalue of

V,

just

as in the nondegenerate
the

g x g effective Hamiltonian that appearsin
we want
P0\\l)

Let us now look at
only to

To E.2.7). be safe we keepall terms in
find

order X. We

to E.2.7) order X2 although

= 0. Let us callthe eigenvaluesof the g x g matrix

E.2.12)

PqVPqVi and the eigenvectors to first order re E\\l) = E$ + Xvr We assume a The eigen energies Po|f|O))is that the degeneracy completely resolvedso that Efp E^ = X(v, We are all non-zero. can now apply non-degenerate perturbation theory vj) to E.1.39)the g x g dimensional Hamiltonian that appearsin E.2.12). to The resulting correction the eigenvectors Po\\^) is

-

-

=
or more explicitly

2
~ vi

~~ Vj

V

, F(U)

'

-2
eigenvector

vj

2 k*D

1

M. E.2.14)

?

Thus, although the third term in the effective Hamiltonian that appearsin is E.2.12)of orderX2, it is divided by energy denominators of order X in the correction the eigenvector, to which then gives terms of order forming X in the vector. If we add together E.2.6) E.2.14), get the eigenand we X. accurate to order As in the nondegenerate case,it is convenient to adopt the norand normalization convention (/@)|/)= We then have, from E.2.3) E.2.4), = A/ = XA/A) + X2Af2) + The X-term just reproduces \\(fO)\\V\\t) As for the X2-term, we obtain AzB) = </<0)| |/A)> = {f^V^f^) V + {/^M/yP). ince vectors Po|//O)>are eigenvectors of V, the corS the correction to the vector, E.2.14), no contribution to the second-order gives energy shift, so we find using E.2.6)

1.

\342\200\242\342\200\242\342\200\242.

E.2.11).

V kl

E.2.15)

Our procedure worksprovided that there is no degeneracyin the roots of secularequation E.2.9). Otherwisewe still have an ambiguity as to which linear contribution of the degenerate nperturbed kets the peru perturbed kets are reducedin the limit X 0.Put in another way, if our method is to work, the degeneracy should be removed completely in first A How order. challenge the experts: must we proceed the degeneracy for if is not removed in first order,hat is, if some of the roots of the secular t Problem 12 this chapter.) of equation are equal? (See
\342\200\224>

302

Approximation Methods

perturbation

Let us now summarize the basicprocedureof degenerateperturbatheory: and construct the perIdentify degenerateunperturbed eigenkets matrix V, a g X g matrix if the degeneracyis g-fold. perturbation 2. Diagonalize the perturbation matrix by solving, as usual, the appropriatesecular equation. 3.Identify the roots of the secular equation with the first-order energy shifts; the base kets that diagonalize the V matrix are the correct zeroth-order kets to which the perturbedkets approach in the limit X -> 0. nonde4. For higher ordersuse the formulas of the corresponding generate perturbation theory exceptin the summations, where we excludeall contributions from the unperturbed kets in the degen-

1.

degenerate

D. subspace

Linear Stark Effect

As an example of degenerate perturbation theory, let us study the effect of a uniform electric field on excitedstates of the hydrogen atom. As is well known, in the Schrodinger theory with a pure Coulomb potential with no spin dependence,he bound state energy of the hydrogen atom t on the principal quantum number n. This leadsto degeneracy dependsonly for all but the ground state becausethe allowed values of / for a given n satisfy ^4 J 0 < / < n. E.2.16) To be specific,for the n = 2 level, there is an / = 0 state called 2s and three 1 = 1 (m = As states called 2/?, all with the same energy, e2/$a0. we apply a uniform electric field in the z-direction, the appropriate per/rm

_x

\302\2611,0)

-

= -\302\253|E|, E.2.17) B which we must now diagonalize. eforewe evaluate the matrix elements in detail using the usual (nlm) basis, let us note that the perturbation has E.2.17) nonvanishing matrix elementsonly betweenstatesof opposite and / = 0 in our case. urthermore, in order F parity, that is, between1=1 for the matrix elemento be nonvanishing, the m-values must be the same t z because behaveslike a sphericaltensor of rank onewith sphericalcomV
component

perturbation

operatoris given

by

a elementsare betweenIs (m = 0 necessarily) nd 2pwith m = 0.Thus 2s 2/7 m =1 2p m = -\\ 2p m-= 0 0 0 <2s\\V\\2p, m = 0) I
\302\260

{magneticquantum number)

zero. othe only nonvanishing S

matrix

= Bp,m 0\\V\\2 s)
0 0

0 0 0

0 0 0

0 0 0

E.2.18

5.2.Time-Independent
Explicitly,

Perturbation

Theory: The Degenerate

Case

303

m <2j|K|2/>, = 0> = B/7,m =

E.2.19)
It is sufficient to concentrate our attention on the upper left-hand corner of the squarematrix. It then looksvery much like the ox matrix, and we can the energy shifts we get immediately write down the
answer\342\200\224for
V(\302\2611}

=

\302\261

3ea0 E

E.2.20)
=

where the subscripts refer to the zeroth-order that diagonalize V: kets
\302\261

\302\261)

=

1

,m= 0)

\302\261

0\302\273.

E.2.21

Schematicallythe energy levels are as shown in Figure Notice that the shift is linear in the appliedelectric strength, field hencethe term the linear Stark effect. One way we can visualize the existencef this effect is to note that the energy eigenkets .2.21) not o are E and are therefore allowed to have nonvanishing electric parity eigenstates permanent dipole moments, as we can easily seeby explicitly evaluating (z).Quite generally,for an energy state that we can write as a superposition of oppositeparity states,it is permissibleo have a nonvanishing permanent t electricipolemoment, which gives rise to the linear Stark effect. d An interesting question can now be asked.If we look at the \"real\" Due to hydrogen atom, the 25 level and 2p levelare not really degenerate. the spin orbit force, 2p3/2 is separatedfrom 2pl/2, we will show in the as next section,and even the degeneracybetween the 2sl/2 and 2pl/2 levels that persists in the single particle Dirac theory is removed by quantum electrodynamics effects (the Lamb shift). We might therefore ask, Is it realistic to apply degenerateperturbation theory to this problem? A comcomparison with the exact result shows that if the perturbation matrix elements

5.1.

A2s. m=0>-l2p,m=0\302\273

3lellf la0
No

change for

I2p,m=\302\2611>

31 IE la0 el
m (I2s. =0>+\\2p,m=0\302\273

i

FIGURE Schematic energy-level diagram degenerate perturbation theory.

5.1.

for the linear Stark

effect

as an

example of

304

Approximation

Methods

are much larger when compared to the Lamb shift splitting, then the energy shift is linear in |E| for all practical purposes and the formalism of On extreme,if the degenerate perturbation theory is applicable. the opposite matrix elementsare small compared to the Lamb shift splitperturbation then the energy shift is quadratic and we can apply nondegenerate of perturbation theory; seeProblem 13 this chapter.This incidentally shows that the formalism of degenerateperturbation theory is still useful when the energy levelsare almost degeneratecompared to the energy scaledefined by the perturbation matrix element. In intermediate cases we must work harder; it is safer to attempt to diagonalizethe Hamiltonian exactly in the spacespannedby all the nearby levels.
splitting,

AND ATOMS:FINE STRUCTURE 5.3. HYDROGENLIKE ZEEMAN

THE

EFFECT

I Spin-Orbit nteraction and Fine Structure
In this section we study the atomiclevelsof hydrogenlike atoms, that atoms with one valence electron outside the closedshell.Alkali atoms is, such as sodium (Na) and potassium(K) belong to this category. The central (spin-independent) potential Vc(r) appropriate for the valenceelectron is no longer of the pure Coulomb form. This is becausethe electrostatic potential <j>(r) that appearsin Vc(r) = e<t>(r) is no longer due just to the nucleus of electric charge \\e\\Z\\ we must take A into account the cloud of negatively charged electrons in the inner shells. form precise of <j>(r) doesnot concern us here.We simply remark that the characteristicsof the pure Coulomb potential are now removed degeneracy in such a way that the higher / states lie higher for a given n. Physically this arises from the fact that the higher / states are more susceptible the to repulsion due to the electron cloud. Insteadof studying the details of Fc.(r), which determines the gross structure of hydrogenlikeatoms, we discuss effectof the spin-orbit(L*S) the interaction that gives rise to fine structure. We can understand the existence of this interaction in a qualitative fashion as follows.Because the central of force part E.3.1), valenceelectron experiences electric field the the

E.3.1)

E.3.2)
whenevera moving charge is subjected an electric field, it to effectivemagnetic field given by
But
\"feels\"

an

(^)

E.3.3)

5.3.Hydrogenlike

Atoms: Fine Structure and the Zeeman

Effect

305

Because electron has a magnetic moment the
mec
we

|i given by
E-3.4)

suspecta spin-orbit potential VLS contribution to H as follows: = ~ V-' B
eff

1

eS mec,
1

x

dVc

mec
dr

1 1 dVc
2 2 mzecz

XI7/(-e) dr
E.3.5)

(L-S).

When this
it

seento have the correct but the magnitude turns out to be too sign, large by a factor of two. Thereis a classical xplanation for this due to e after L. H.Thomas),but we shall not spin precessionThomasprecession { bother with that (Jackson1975, example). simply treat the spinfor We
is

is with the observed expression compared spin-orbit interaction,

The

orbit interaction phenomenologicallyand take VLS to be one-halfof

correct uantum-mechanical explanation for q

await

must discrepancy the Dirac (relativistic) theory of the electron(Sakurai 1967,or f
this

E.3.5).

We are now in a position to apply perturbation theory to hydrogenic and 5.2).The atoms using VLS as the perturbation (V of Sections5.1 Hamiltonian Ho is taken to be unperturbed

instance).

E-3.6)
where the central potential Vc is no longer of the pure Coulomb form for alkali atoms.With just Ho we have freedom in choosing the basekets: Set The eigenketsof L2,LT,S2,

1:

S,.

Set 2: The eigenketsof L2,S2, Jz. J2,
eitherset is satisfactoryin the sensethat the basekets VLS (orHLS) are also energy eigenkets. With HLS addedit is far superior to use set 2 of b E.3.7) ecause L*S does not commute with Lz and S2, while it does commute with J2 and Jz. Rememberthe cardinal rule: Choose unperturbed kets that diagonalize the perturbation. You have to be either a fool or a masochist to use the Lz, Sz eigenkets[set 1of E.3.7)] the baseketsfor this as problem; if we proceededto apply blindly the method of degenerate perturbation theory starting with set 1as our basekets,we would be forced to diagonalize the VLS(HLS) matrix written in the Lz, S2 representation.The
Without

306

Approximation

Methods

resultsof this, after a lot of hard algebra, give us just the J2, eigenketsas the zeroth-order unperturbed kets to be used!
In degenerate perturbation theory, if the perturbation is already diagonal in the representation we are using, all we need to do for the first-order energy shift is to take the expectationvalue.The wave function in the two-component form is explicitly written as

/.

=
\302\256}i=l\302\261ll2<m

Rnl(r)Wr'\302\261lu'm

is the spin-angular function where For the first-order shift, we obtain

E-3.8) of Section [see 3.7 C.7.64)].
/
\\

nlj

/ 2my\\r dr j n, 2 \\ [-(/+ 1)]
^
i dV Rnl\302\261^Rnlr2dr r J0
/\342\200\242<\302\273

1 II dV\\

tf_f

, , J l+ 2
\302\246

I
1

J

2

-^A ^
\\

1 dV

r.1

E.3.9)
[seeC.7.65)]

where we have used the w-independent identity
2 hz

2

= hLi
2

2

\\-(/+ l)

l

E.3.10)
is Equation E.3.9) known as Lande'sinterval rule. To be specific, considera sodium atom. From standard atomic notation, the ground-state configuration is spectroscopy

(lsJBs)\\2pNCs).

E.3.11)

j.

The inner 10 electronscan be visualizedto form a sphericallysymmetrical electron cloud.We are interested in the excitation of the eleventh electron from 3s to a possible higher state. The nearest possibilityis excitation to 3p. Because central potential is no longer of the pure Coulomb form, 3s and the 3/7 are now split. The fine structure brought about by VLS refers to even a finer split within 3/?,between 3pl/2 and 3/?3/2, where the subscript efers to r we observe two closelyseparated as Experimentally, yellow the sodium D at 5896 A, the other at 5890 A; see Figure 5.2. Noticethat 3p3/2 lieshigher because radial integral in E.3.9)positive. the is To appreciatethe order of magnitude of the fine-structuresplitting, let us note that for Z ^
lines\342\200\224known lines\342\200\224one

f

dr I nl, /

\\

-^
a3 UQ

E.3.12)

5.3.Hydrogenlike

Atoms: Fine Structure and the Zeeman

Effect

307

Doublet or \"Fine\"
structure

3/2 3P:

1/2

/\\=5890A

/\\=5896A

becauseVc(r)

Schematic diagram of 35 and 3>p lines. The 3s and 3p degeneracy is lifted is now the screened Coulomb potential due to coreelectrons rather than pure Coulombic; Vrs then removes the 3px/1 an<^ 3P3/2 degeneracy.
FIGURE

5.2.

just on the
splitting

of the electron, the Compton wavelength of the electron, and the Bohr radius are related in the following way:
H

So basis of dimensionalconsiderations. the fine-structuresplitwhich is of order (e2/al)(h/mecJ, is to be comparedwith Balmer r It splittings of order e2/a0. is useful to recall here that the classical adius

mec where we have used

:ao::l:137:(l37J,
hc

E.3.13)

137'
then

E.3.14)
related to typical Balmer split-

Typically, fine-structure splittings
splittings

are e2 a

via
\\

1
137

~3
which

m;c

E.3.15)

explainsthe origin of the term fine structure. There are other effects t similar orders of magnitude. Specifically, he relativisticmasscorrection of from the expansion arising
2c2 is of the r
\342\200\224

2m^

8m

E.3.16)

sameorder.

The Zeeman Effect
uniform

discusshydrogen or hydrogenlike (one-electron)atoms in a Zeemaneffect,sometimescalled the anomalous magnetic Zeeman effect with the electron spin taken into account. Recall that a
We now
field\342\200\224the

308
uniform

Approximation Methods

magnetic field B is derivable from a vector potential

E.3.17)
ForB in the positive z-direction(B= 2?z), = -\\(Byx-Bxy)

E.3.18

sufficeswhere B stands for |B|. part from the spin term, the interaction A Hamiltonian is generated by the substitution
p->p~\342\200\224.

E.3.19
<5-3-20)

We therefore have

Because

it

is legitimate to replacep*A by

A*p

whenever

? [')l,

E.3.21

VA(x) = 0,
which

E.3.22

is the case the vector potential of E.3.18). for Noting

= l|B|Lz
and

E.3.23)
),

E.3.24)

we obtain for E.3.20)

To this we may add the spin magnetic-momentinteraction mec

S-B=mc

\342\200\224|B|SZ.

mec

z

E.3.26
v 7

+ >>2) The quadratic |B|2(.x2 is unimportant for a one-electron atom; the term is important for the ground state of the helium atom where analogous ?(tot> an(j ^(tot) j3Otj1 yanigh reader may come back to this problem in when he or she computesdiamagneticsusceptibilities Problems 18 and 19 of this chapter.

j^

5.3.Hydrogenlike

Atoms: Fine Structure and the Zeeman

Effect

309

To summarize,omitting the quadratic term, the total Hamiltonian is made up of the following three terms:
0 2m
~\"~

E.3.27a)
dVc(r)L-S
dr

IILS C
r

2c2 2m2ec

E.3.27b)
E.3.27c)

_

-111 (L2+2SZ). 2mec
HLS\342\200\224the

Noticethe factor 2 in front of Sz; this reflects the fact that the g-factor of the electron is 2. SupposeHB is treated as a small perturbation. We can study the our effectof HB using the eigenketsof HQ+ J2,/, basekets. Noting
eigenkets\342\200\224as

,

E.3.28)

the first-order shift can be written

as +

-e\\B
2mec

E.3.29)

The expectationvalue of Jz immediately gives mh. As for (Sz), we first recall

1
x
_1

2/ + 1 2/ + 1
=m +
\342\200\224

2'

2/-

E.3.30)
The expectation value of Sz can then easily be computed:

2
In

B/+ 1)

-ehB m
2m ec
shift

___

i

mh

E.3.31)
this

manner we obtain Lande'sformula for the energy shift (due to B
1\302\261

field),

We

seethat

the energy

understand the physical origin for

1 E.3.32) B/ of E.3.32)proportional to m. To is
we present another method for

this,

310
deriving

Approximation Methods

We E.3.31). recall that the expectation value of Sz can also be We get [see obtained using the projection theorem of Section C.10.45)

3.10.

j

=

l\302\261l/2,m

i=

mh
1/2

l\302\261

m<J2 + S

=/ 1/2
\302\261

=

mh mh

E.3.33)

is in completeagreement with E.3.31). In the foregoing discussion magnetic field is treated as a small the Paschen-Back perturbation. We now considerthe opposite a magnetic field so intense that the effect of HB is far more important than that of HLS,which we later add as a small perturbation. With Ho + HB only, the good quantum numbers are Lz and Sz.Even J2 is no good becausespherical symmetry is completelydestroyed the strong by B field that selectsa particular direction in space,the z-direction.Weare left with cylindrical symmetry is, invariance under rotation around the z-axis. the LZ,SZ eigenkets \\l,s = \\,mhms) are to be used as our So basekets.The effectof the main term HB can easily be computed:
which
extreme\342\200\224the limit\342\200\224with only\342\200\224that

~e\\B\\

2m ec

E.3.34)

The

we originally had with Ho [see is E.3.27a)] now reducedby HB to states with the same (m7) + Bm5), namely, (m/)+(l) and (ra/ + 2)+( 1). learly we must evaluate the expecC value of L*Swith respectto \\mhms)\\
m{ and ms
\342\200\224

2B/+ degeneracy in 1)

expectation

i/n

= h2mtms,
where we have used

E.3.35)

E.3.36)
Hence,
\\nLS/m,m,

= h2m,ms I 1 dVc
2mzecz
\\

r dr

E.3.37)

5.3.Hydrogenlike

Atoms: Fine Structure and the Zeeman

Effect

311

TABLE
Dominant interaction

5-1
No good
Always good

Almost good

WeakB
Strong

J2 (orL-S)
HB

B

J2 (orL-S)

L2,S2,/Z

*The exception is the stretched configuration, for example, p3/2 with m = + \\. Here Lz and Sz are both good; this is because magnetic quantum number 72, m = m{ 4- ms can be satisfied in only one way.

In many elementary books there are pictorial interpretations of the weak-fieldresult E.3.32) the strong-fieldresult E.3.34), we do not but and bother with them here. e simply summarize our results in Table 5-1, W where weak and strong B fields are \"calibrated\" by comparing their magnitudes w I*1 ehB/2mecith (l/137Je2/^o- table almost good simply means good to the extent that the lessdominant interaction could be ignored. Specifically,let us look at the level scheme of a p electron 1= 1 Pi/2)-In the weak B casethe energy shifts are linear in B, with slopes (/?3/2, determined by

^s

m

1+ 2/1 1 +
m

As we now

same
in this

increase mixing becomes B, possiblebetweenstates with
p3/2 example, with

m-value\342\200\224for

=

\302\2615

is a rank

connection note the operatorLz + 2SZ that appearsin HB[E.3.27c) 1tensoroperator T^=^ with sphericalcomponent q = 0.In the and intermediate B region simpleformulas like E.3.32) E.3.34) the for to values are not possible;is really necessary diagonalize the it expectation In appropriate2x2matrix (Gottfried 1966, 371-73). the strong B limit the energy shifts areagain proportional to as we seein E.3.34), the are determinedby m{ + 2ms. slopes

and pl/2 with m

-

the
\302\2615;

|fi|;

Van An

der Waals' Interaction

important, nice application of the Rayleigh-Schrodingerpertheory is to calculate the long-rangeinteraction, or van der Waals9 force, between two hydrogen atoms in their ground states.It is easy to show that the energy between the two atoms for large separation r is attractive and varies as r~6. Considerthe two protons of the hydrogen atoms to be fixed at a distancer (along the z-axis) with xx the vector from the first proton to its and electron r2 the vector from the secondproton to its electron; seeFigure
perturbation

312

Approximation Methods

r 2

z-axis
FIGURE 5.3. Two hydrogen atoms with their protons and their electrons at displacements r, from them.

(-)

(+) separated

by

a fixed

distance r

5.3. the Hamiltonian Then

Hcan be written as

H=H0
2 2 2 2

|r + r2 The lowest-energysolution of Ho is simply the product of the ground-state wave functions of the noninteracting hydrogen atoms r |r +

r2-ri|

E.3.39)
Now for large r the Bohr radius a0) expand the perturbation powersof r, /r to obtain
(:\302\273

V in

2

/ 1

\\

E.3.40)

The lowest-order~3-term in E.3.40) r ~3 t correspondso the interaction of two electric dipoleserl and er2 separated r. The higher-orderterms represent by higher-ordermultipole interactions, and thus every term in V involves > 0 for each hydrogen atom. Hence, or f with sphericalharmonics in E.3.40) first-order perturbation energy matrix element each term the = 0, since the ground state f/0@) wave function E.3.39) /, = 0 (and has = 0 for / and m # 0).The second-order perturbation
Y\342\204\242 /\342\200\242

^v

will

be nonvanishing. We immediately seethat this interaction varies as s it is negative. This 1/r6 1/r6; ince long-range attractive van der Waals' potential is a general property of the interaction between two
Ej\302\256>
E^\302\260\\

atoms in their ground state.*

which gives a lower and upper bound on *Seethe treatment in SchiffA968), pages 261-263, the magnitude of the van der Waals' potential from and from a variational calculation. Also note the first footnote on page 263 of Schiff concerning retardation effects.

E.3.41)

5.4.Variational

Methods

313

5.4. ARIATIONAL V

METHODS

The perturbation theory developed in the previous section is, of course,of no help unless we already know exact solutions to a problem whose Hamiltonian is sufficiently similar. The variational method we now discuss is very useful for estimating the ground state energy Eo when such exact solutions are not available. We attempt to guessthe ground-state energy EQ by considering a w T \"trial ket\" |0), hich tries to imitate the true ground-state ket |0). o this end we first obtain a theorem of great practical importance. We define H such that <0|0>
normalized.

,

E.4.1) ;
v

where we have accommodatedthe possibilitythat |0) might not be normalWe can then prove the following. Theorem.

H>E0.

E.4.2)

This means that we can obtain an upper bound to Eo by consideringvarious kinds of |0). he proof of this is very straightforward. T Proof. Even though we do not know the energy eigenket of the Hamiltonian H, we can imagine that |0) can be expanded as

P>=
A-

I |*><*|0>
00

=0

E-4.3)

where \\k) is an exact energy eigenket of H:
H\\k)

= Ek\\k).
\342\200\224

E.4.4)
Eo + Eo to evaluate H

The theorem E.4.2) followswhen we use Ek = Ek in E.4.1). have We

E
oo

E.4.5a)

I
>E0,

E0
\\<kfi)

E.4.5b)

E.4.5c)

314
\342\200\224

Approximation Methods

is where we have used the fact that Ek Eo in the first sum of E.4.5b) necessarily positive.It is alsoobvious from this proof that the equality sign t in E.4.2)olds only if |0) coincides h exactly with |0),hat is, if the coef(k\\0) all vanish for k # 0. The theorem E.4.2) quite powerful becauseH provides an upper is bound to the true ground-stateenergy. Furthermore, a relatively poor trial if ket can give a fairly goodenergy estimate for the ground state because
coefficients

?

<A:|6>~0(e)for?#0,
then from

E.4.6)
E.4.7)

we E.4.5) have

H- Eo~0(e2).

We

in a moment.Of course, he method doesnot say t about the discrepancybetween H and EQ; all we know is that H is larger than (or equal to) Eo. Another way to state the theorem is to assert that H is stationary anything with

seean exampleof this

respectto the

variation

+ S|6>; |6>-*|6>
*

E.4.8)

we commit
w\302\2732.

is, 8H= 0 when |0) coincideswith |0).By this we mean that if + 8J0) is used in placeof |6) in E.4.5)nd we calculate //, then the error a |0)
that in

estimating the

true

ground-state energy involves |0) to order

The variational method per sedoesnot tell us what kind of trial kets are to be used to estimate the ground-state energy. Quite often we must appeal to physical example, the asymptotic behavior of wave W function at large distances. hat we do in practiceis to characterize trial kets by one or more parameters Xv and compute H as a function of
intuition\342\200\224for

\\x,

We \\2,.... all the

then minimize

H by A) setting the derivative with respectto

X2,...,

parameters zero, namely,

B) determining the optimum valuesof Xl9
back to the expression for

//.

and X2,..., C) substituting

them

ground-state energy function by this method. For example, supposesomehas the foresight to guessthat the wave function for the ground state of the hydrogen atom must be of the form
somebody

If the wave function for the trial ket already has a functional form of the exact ground-state energy eigenfunction,we of courseobtain the true

<x|0>cce-r/fl,

E.4.10

where a is regarded as a parameter to be varied. We then find, upon Not the minimizing H with E.4.10), correct ground-stateenergy e2/2a0.

-

5.4.Variational

Methods

315

the minimum is achieved when a coincideswith the Bohr surprisingly, radius a0. As a secondexample,we attempt to estimate the ground state of the infinite-well (one-dimensionalbox)problem defined by 0, for |jc|< a E.4.11) > oo, for |jc|

a.

The exact solutions are, of course,well known:
(x\\0)
GTX = 1 cos
V<2

/
But suppose we did not know vanish at x = a\\ furthermore,
\302\261

h2

\\

E.4.12)
\342\200\242n2

\\2m)

\\

4a2}

the wave function must for the ground state the wave function cannot have any wiggles.The simplest analytic function that satisfiesboth requirements is just a parabola going through x =

these. Evidently

= a2
2X

- x2

\302\261

a:

E 4 13)

H where we have not bothered to normalize |6). ere there is no variational parameter. We can compute H as follows:
TJ

=

\\

fa / 2 \" 2\\ d2 / 2 u **) dx' {a2 2m) J -a
I
(\302\253

-n

-

10
It

[&a mi

-a (a2 x2J dx 2\\ = 1.0132 Eo.
JI
M.

-

E.4.14)

with such a simole trial function we can come within of the true ground-stateenergy. 1.3% A much better result can be obtained if we use a more sophisticated trial function. We try

is remarkable that

6

A\\

E.4.15)
ft

where X is now regarded as a variational parameter. Straightforward alalgebra gives

H=
which

(X

+ 1)BX + 1)

- 1) BX

[4ma

E.4.16)

has a minimum at

X.

E.4.17)

316
not far from
X

Approximation Methods

= 2 (a parabola) considered earlier. gives This
2^6
min
\\

?0^1.00298?0.

E.4.18)

Sothe variational method
within
function 0.3%\342\200\224a

used.

with E.4.15) the correct ground-stateenergy gives fantastic result considering the simplicity of the trial func-

How well does this trial function imitate the true ground-state wave function? It is amusing that we can answer this question without explicitly evaluating the overlap integral @|0).Assuming that |0) is normalized, we have [from E.4.1)-E.4.4)]

=
Ar

f0 =

\\(kfi}\\2Ek

where 9E0 is the energy of the secondexcitedstate; the first excitedstate and (k = 1)gives no contribution by parity conservation.Solving for |@|0)| we using E.4.18), have

? ()

E.4.19)

gr |@|0)|2>

77

\302\260

min

= 0.99963.

E.4.20)

Departure from
orthogonal to
then

I |0).f we are talking

unity

characterizes a component of |0) in a direction about \"angle\" 6 defined by

E.4.20)

= <O|6> cos0,
0<1.1\302\260,

E.4.21)

t correspondso

E.4.22)

so |0) and |0) are nearly \"parallel.\" One of the earliest applications of the variational method involved in the ground-state energy of the helium atom, which we will discuss Section 6.1. can alsouse the variational method to estimate the energiesof first We excitedstates; all we need to do is work with a trial ket orthogonal to the
exact, if known, or an approximate one ground-state wave function\342\200\224either obtainedby the variational method.

5.5. TIME-DEPENDENTOTENTIALS: P THE
INTERACTION PICTURE Statement of the Problem

So far

in this

book we have beenconcerned with Hamiltonians that

do not contain

explicitly. In nature, however, there are many I quantum-mechanical systems of importance with time dependence.n the
time

5.5.Time-Dependent

Potentials: The Interaction

Picture

317

remaining part of

this

chapter we show how to deal with situations
it

with two

time-dependent potentials. We considera Hamiltonian H such that
parts,

can be split into

E.5.1)
where Ho doesnot contain time explicitly.The problem V(t) = 0 is assumed to be solved in the sense that the energy eigenkets \\n) and the energy eigenvaluesEn defined by are completely known.* We may be interested in situations where initially only one of the energyeigenstatesof populated. example, with As time goes on, however,states other than |/) are populated because we are no longer dealing with \"stationary\" problems;the timeK(/)=?0 evolution operatoris no longer as simple as e~lHt/h when H itself involves time. Quite generally the time-dependentpotential V(t) can cause transito statesother than The basicquestion we addressis, What is the as a function of time for the system to be found in |/i), with probability
Ho\342\200\224for
|/)\342\200\224is transitions

E.5.2)

|/).

More generally, we may be interested in how an arbitrary state ket changes as time goeson, where the total Hamiltonian is the sum of Ho and V(t). Supposeat t = 0, the state ket of a physical system is given by
n

E.5.3)

We wish to find

cn(t)for t > 0 such that
n

E.5.4)

where the ket on the left side stands for the state ket in the Schrodinger picture at / of a physical system whose state ket at / = 0 was found to be The astute reader may have noticed the manner in which we have o The separatedthe time dependencef the coefficientof \\n) in E.5.4). factor e-iEnt/h even ^ y js absent. This way of writing the time present makesit clear that the time evolution of cn(t)is due solely to dependence the presence f V(t); cn(t) would be identicallyequal to cn@) and hence o independentof t if V were zero.As we shall see in a moment, this separation is convenient becausecn(t) satisfiesa relatively simple differenequation.The probability of finding \\n) is found by evaluating
\302\253s

differential

|c2

In

w E.5.2) e no longer use the

notation

|^@)),

Ej,\302\260\\

318 The Interaction Picture

Approximation Methods

Before we discussthe differential equation for cn(t),we discussthe we interaction picture.Suppose have a physicalsystem such that its state ket A coincideswith \\a) at t = t0, where t0 is often taken to be zero. t a later w time, we denotethe state ket in the Schrodingerpicture by \\a,to;t)s, here the subscript S reminds us that we are dealing with the state ket of the

Schrodinger icture. p
We now define

,

where | )f stands for a state ket that represents same physical situation the in the interaction picture. At t = 0, | )f evidently coincides with | )s. For in we define observables the interaction o operators(representing bservables) picture as = eiH Aj In particular,

E.5.5)

where V without a subscriptis understood to be the time-dependent potential in the Schrodingerpicture. The readermay recall here the connecbetween the Schrodingerpicture and the Heisenberg picture:
connection

The basicdifferencebetween E.5.8) E.5.9) the one hand and E.5.6) on and and E.5.7) n the other is that H rather than Ho appearsin the exponeno
exponential.

= elHt/hAse~lHt/h.

E.5.8)

E.5.9)

characterizes

derive the fundamental differential equation that charthe time evolution of a state ket in the interaction picture. Let us take the time derivative of E.5.5) ith the full H given by w
We now

E.5.1):

a,r0; t),= ih^ie'^'/^a, t)s) t0;
a, t0; t)s +
We
thus
e<\"\302\260'/*(//0

+ V)\\a, t0; t)s

see
ih
\342\200\2241\302\253,

E.5.10
'o\">

0/ = K/K'o;0/'

E.5.11

is a Schrodinger-like equation with the total H replacedby Vf. In other words to\\ t)f would be a ket fixed in time if Vf were absent.We can alsoshow for an observableA (that doesnot contain time t explicitly in the Schrodinger icture) that p
which

|a,

which

is a Heisenberg-like by equation with H replaced Ho.

^^

E.5.12

5.5.Time-Dependent

Potentials: The Interaction

Picture

319

TABLE Heisenberg picture

5.2
picture

Interaction

Schrodinger picture Evolution determined

Stateket

No change
determined by

Evolution determined

Observable Evolution

H

by H by Vj Evolution determined No change by Ho

respects,the interaction picture, or Dirac picture, is interbetweenthe Schrodingerpicture and the Heisenberg picture; This should be evident from Table 5.2. In the interaction picture we continue using \\n) as our base kets. Thus we expand | )f as follows:
In many
intermediate

n

E.5.13

With t0

the
multiplying

a position to write the differential equation for finally both sidesof E.5.11)(n\\ from the left, we obtain by cn(t).Multiplying
We

set equal to 0, we seethat the cn(t)appearing here are the same as as cn{t)introduced earlier in E.5.4), can easily be verified by multiplyboth sidesof E.5.4)y b using E.5.2).
elH\302\260t/h

are

in

ih

\342\200\224

dt (n\\a,

t0; t),= Y,(n\\V,\\m)(m\\a,
m

t0;

t),.

E.5.14

This can also bewritten and

using :n-Em)t/h

as [from E.5.13)]
eiw\"m'c m

(t)

E.5.15

where
nm

h

=

\342\200\224

co mn'

E.5.16
r t

Explicitly,

cl
ih 22
V, 33
\\

E.5.17)
I

This is the basic coupled differential equation that must be solved to obtain of finding \\n) as a function of t. the probability

320

Approximation Methods

Nuclear MagneticResonance, Time-DependentTwo-StateProblems:

most cases e have to resort to perturbation expansion to solve the w in as we differential equationsE.5.17), will discuss the next section. coupled There is, however, a problem of enormous practical importance, which can be solved two-state problem with a sinusoidal oscillatingpoten-

rare.In

Masers,and So Forth Exact solubleproblemswith time-dependent potentials are rather

exactly\342\200\224a

potential.

The problemis defined by

(E2>El)
where y and we have
to

E.5.18)

and are real and positive.In the languageof E.5.14) E.5.15),
V12

V

= V2* = ye'\"' = V =0

E.5.19)

We thus have a time-dependent potential that connectsthe two energy o eigenstates f Ho.In other words, we can have a transition between the two states |1> |2>. / =0 An exact solution to this problem is available.If the lower level is populated so that [seeE.5.3)] E.5.20) c2@)= 0, then the probability for being found in each of the two states is given by (Rabi's formula, after I. I. Rabi, who is the father of molecular beam techniques)
?\302\261

initially\342\200\224at

\342\200\224only

\\c2(t)\\2

=

sin'

11
h1

1/2
t

where

E.5.21a) E.5.21b) _(E2~E1)
h

E.5.22)

as the reader may verify by working out Problem 30 of this chapter. Let us now lookat \\c2\\2 a little more closely.We see that the probability for finding the upper state E2 exhibitsan oscillatory time dedependence with

angular frequency, two times that of
$2

=

Y

2

\\

(<o-co21)

E.5.23)

5.5.Time-Dependent

Potentials: The Interaction

Picture

321

The amplitude of oscillationis very large when
CO
\342\200\224

(O21

==

h
potential\342\200\224usually

E.5.24)

is, when the angular frequency of the externally appliedelectricor magnetic
that
therefore

due to an to the angular nearly equal is frequency characteristicof the two-state system. Equation E.5.24) thereknown as the resonancecondition. a little closely and It is instructive to look at at resonance: exactly
field\342\200\224is

E.5.21a) E.5.21b)

co

= co21
t\\

E.5.25)

as |c2(OI2 a function of seeFigure 5.4.From two-level system absorbs energy from the timedecreases from unity as |c2(O|2 grows. dependentpotential V(t); |q@|2 At / = 7r^/2y, only the upper state is populated.From t = 7rh/2y to t = irh/y, the system gives up its excess (upper)state] energy[of the excited to V(t)\\ \\c2\\2 decreases nd \\cx\\2 increases. absorption-emissionycleis This a c repeatedindefinitely, as is also shown in Figure 5.4,soV(t)can be regarded as a sourceor sink of energy; put in another way, V(t) can cause a o to |2) (absorption) r from |2) to We transition from (emission). will come ack to this point of view when we discussemissionand absorption of b radiation. The absorption-emission cycle takes place even away from resoresonance. However, the amplitude of oscillation for |2) is now reduced; doesnot go down all the way to 0.In c2(Olmax*s no longer 1and of co.This curve has a resonance Figure 5.5we plot |c2@lmaxas a peak centeredaround co = co21, and the full width at half maxima is given by
We

/ = 0 to

can plot
t

= 7rh/2y, the

and |c1(/)|2

|1)

|1)

functi\302\260n

1

0
nh

t I2Y
irk

iy =

FIGURE
S2

Emission Absorption Absorption 5.4. Plot of and \\c2(t)\\2 against time t exactly at resonance = y/h. The graph also illustrates the back-and-forth behavior between and

|q(/)|2

co

o>21

and

|1)

|2).

322

Approximation Methods

\\cz(t)\\ max

Full width

at

half

maximum

=

0)
FIGURE 5.5. Graph of |c2(/)lmax resonant frequency.

as a

function

of <o, where

<o

=

<o21

corresponds to the

4y//i. It is worth

noting that the weaker the time-dependentpotential (y small), the narrower the resonance peak.

Spin Magnetic Resonance
applications.

The two-state problem defined by E.5.18) many physical applihas As a first example,consider spin \\ a a bound electron to a /-independent uniform magnetic field in the z-direction and, in addition, a /-dependent agnetic field rotating in the jcy-plane: m
system\342\200\224say \342\200\224subjected

B
with
/-independent

+y sin<o/)

E.5.26)

Bo and Bx constant. We can treat the effectof the uniform /-indepenfield as Ho and the effectof the rotating field as V. For

mec we have
f

E.5.27)

ehB0 2m ec
ehBx

^

+ (I+X I-I-X-I)

f

^

2m ec
\302\273/(i\\

E.5.28) where we have usedthe ket-bra forms of 2Sj/h C.2.1)]. e < 0,?+ With [see has a than and we can
+ ><
>< +

-|+i|identify

|)],

higher energy

?_,
+>
\342\200\224

-\302\273

|2> (upperlevel) (lowerlevel)

>

E.5.29)

-\302\273|1>

5.5.Time-Dependent

Potentials: The Interaction

Picture

323

The to make correspondence the notation of E.5.18). angular frequency with characteristic of the two-state system is
21= which

-r^. mec
Bx = 0

E.5.30)

problem Even though the expectationvaluesof (Sx ) already treated in Section in direction (seenfrom change due to spinprecession the counterclockwise the positive z-side),|c+12 of and \\c_ remain unchangedin the absence the rotating field. We now add a new feature as a result of the rotating field: and |c+|2 \\c_\\2 do change as a function of time. This can be seen by

is just the spin-precession frequency for the Bo # 0,

2.1.

\\2

identifying

2m ec

-+Y,

co

-\302\273

co

E.5.31)

to make correspondenceo the notation of E.5.18); time-dependent our t interaction E.5.28)preciselyof form E.5.18). fact that \\c+(t)\\2 and is The vary |c_@|2 in the manner indicated by Figure 5.4 for co = co21 and the for E.5.29), example,implies that the spin \\ system undercorrespondence of a succession spin-flops, | + ) | ), in addition to spin precession. Semiclassically, spin-flopsof this kind can be interpreted as being due to the by driving torque exerted rotating B. The resonancecondition is satisfiedwhenever the frequency of the rotating magnetic field coincideswith the frequency of spin precession determined by the strength of the uniform magnetic field. We seethat the probability of spin-flopsis particularly large. In practice, a rotating magnetic field may be difficult to produce experimentally. Fortunately, a horizontally oscillatingmagnetic is just as good. o seethis, we first note that T instance, in the such an oscillating field can be decomposed a counterclockwise into compoand a clockwiseomponent as follows: c
\342\200\224

undergoes

*\302\261

field\342\200\224for

jc-direction\342\200\224

component

cot xxcos = /^(xcosco/ ysincof)+ B^xcoscot ysincof). +
\342\200\224

E.5.32)
We

can obtain the effect of the counterclockwisecomponent simply by reversing the sign of co. Supposethe resonancecondition is met for the counterclockwise component

co~co21.
Under a typical experimentalcondition,
|1\302\2531,

E.5.33) E.5.34)

324 which

Approximation

Methods

impliesfrom

that and E.5.30) E.5.31)

co21;

E.5.35)

condition is met for the counterclockas a result, whenever the resonance c completely component, the effectof the clockwiseomponent becomes s negligible,sinceit amounts to co -> to, and the amplitude becomesmall in magnitude as well as very rapidly oscillating. The resonance problem we have solvedis of fundamental importance
counterclockwise
\342\200\224

in

B experiments. y varying the frequency of oscillating field, it is possibleto make a very precisemeasurementof magnetic moment. We have basedour discussionon the solution to differential equations E.5.17); problem this can alsobe solved, perhapsmore elegantly, by introducing the rotating axis

interpreting atomic molecular beam and nuclear magnetic resonance

representationof Rabi, Schwinger,and

Van

Vleck.

Maser
us

we may recall from Section two parity eigenstates \\S) close together such that \\A) is slightly higher. Let \\iei be the electricipoleoperator of the molecule.From symmetry considerations e w d that expect \\iei is proportional to x, the position operator for the N atom. The basic interaction is like |iw#E, where for a maser E is a time-depenfield electric in a microwavecavity: E = |E|maxzcoso/. t E.5.36)
which\342\200\224as 4.2\342\200\224has

w considera maser.Specifically, e consideran ammonia moleculeNH3,
\\A) lying

As another application of the time-dependenttwo-state problem, let

and

\342\200\224

time-dependent

It is legitimate to ignore the spatial variation of E because wavelength in the the microwaveregion is far larger than molecular dimension. he frequency T co is tuned to the energy differencebetween |A) and \\S):
CO

=

~ Es)
h

E.5.37)
by

The diagonal matrix elementsof the dipoleoperator vanish

= <^l^>= <S|^/|S>0,
(S\\x\\A)

parity:

E.5.38)

but the off-diagonalelementsare, in general, nonvanishing:

= (A\\x\\S) # 0.

E.5.39)

This means that there is a time-dependentpotential that connects \\S) and earlier is now applica\\A}9 and the general two-state problem we discussed
applicable.

We are now in a position to discusshow masers work. Given a molecular beam of NH3 containing both \\S) and \\A), we first eliminate the \\S) component by letting the beam go through a region of time-independent

5.6.Time-Dependent

Perturbation

Theory

325

e field.Suchan electric separates\\S) from field inhomogeneous lectric in much the same way as the inhomogeneous agnetic field in the Sternm Gerlachexperimentseparates | +) from | A pure beam of |^4) then enters a microwave cavity tuned to the energy difference EA-ES.The dimension of the cavity is such that the time spent by the molecule just is As a result we stay in the first emission of Figure 5.4; e w (tt/2)/i/7. phase have |^4)in and \\S) out. The excessnergy of |^4)is given up to the timee dependentpotential as |^4) turns into \\S) and the radiation (microwave) field gains energy. In this way we obtain Microwave Amplification by Stimulated Emissionof Radiation, or MASER.

-).

There are many other applications of the general time-dependent two-state problem,such as the atomic clockand optical pumping. In fact, it is amusing to seethat as many as four Nobel Prizes in physics have been awarded to those who exploitedtime-dependenttwo-state systems of some form.*

5.6. IME-DEPENDENTERTURBATIONTHEORY T P
Dyson Series
like the two-leveltime-depenthe exception of a few problems of the previous section, exact solutions to the differential problem equation for cn(t) are usually not available. We must be content with obtained by perturbation expansion: approximate solutions to
With
time-dependent

E.5.17)

where c{*\\
in

c{^\\

the strength parameter of the time-dependentpotential. The iteration method used to solve this problem is similar to what we did in time-indeperturbation theory. If initially only the state / is populated, we by approximate cn on the right-hand side of differential equation c^ = 8ni (independentof t) and relate it to the time derivative of c?\\ integrate the differential equation to obtain c{*\\ plug c^] into the right-hand side [of again to obtain the differential equation for c^\\ and so on. This is how Dirac developedtime-dependentperturbation theory in 1927. Instead of working with cn(t), we propose to look at the time evolution operator Ur(t, t0) in the interaction picture, which we will define later. e obtain a perturbation expansion for Ur(t, /0),and at the very end W
time-independent

...

cnU)= c^ + c^ + c^+---,

E.6.1)

signify

amplitudesof first order,secondorder, and so on

E.5.17)

E.5.17)]

*Nobel Prize winners who took advantage of resonance in the two-level systems are Rabi A944) on molecular beams and nuclear magnetic resonance; Bloch and Purcell A952) on B
field in atomic nuclei and nuclear magnetic moments; Townes, Basov, and Prochorov A964) on masers, lasers, and quantum optics; and Kastler A966) on optical pumping.

326

Approximation Methods

we relate the matrix elementsof
solving

Ur

to

simple problemsin nonrelativistic quantum mechanics, all this might look superfluous;however,the operator formalism we develop is very powerful becauseit can immediately be appliedto more-advanced probsuch as relativisticquantum field theory and many-bodytheory. The time-evolutionoperator in the interaction picture is defined by
problems,

cn(t).If we are interested only

in

, to)\\a,

tQ\\

to)f.

E.6.2) E.6.3)

Differential equation E.5.11) the state ket of the interaction picture is for equivalent to

j;
We must solve
this

operator

differential

condition

equation subject to the

initial

First, let us note that the differential equation together with the condition is equivalent to the following integral equation:

initial

Ur(t,t0)=l-jfvr(t')U,(t'tt0)dt'.
We

E.6.5)

can obtain an approximate solution to

this

equation by iteration:

df l-j?'v,O\U,(t\",to)dl

fWv. 0
l0

v

'

\302\2530

'0

+

--+lx /'*'/'*\"
h

X /\"'\"\"

dt(n)V,{t')V,{t\") -V,{t(n))
\342\200\242 \302\246

+

\342\200\242\342\200\242\342\200\242

.

E.6.6)

This seriesis known as the Dyson series after Freeman J. Dyson, who appliedthis method to covariant quantum electrodynamics(QED).*etting S asidethe difficult question of convergence,we can compute Uf(t,t0) to any finite orderof perturbation theory.
*Note that in QED,the time-ordered product is introduced, and then this perturbation seriescan be summed into an exponential form. This exponential form im= U(t, h)U{tly t0) (Bjorken and Drell 1965,175-78). immediately gives U(t, t0)
f\">\342\200\242\342\200\242\342\200\242)

(/'>

5.6.Time-Dependent

Perturbation

Theory

327

Transition Probability

Once Uf(t,t0) is given, we can predict the time developmentof any state ket. For example, if the initial state at t = 0 is one of the energy of eigenstates //0, then to obtain the initial state ket at a later time, all we need to do is multiply by Ur(t,0):

n

E.6.7)

We E.5.13)].will

between U(t, t0) and

In fact, (n\\Uf(t,Q)\\i) is nothing more than what we calledcn(t) earlier [see say more about this later. We earlier introduced the time-evolution operator U(t,t0) in the Let us now explorethe connection picture (seeSection Schrodinger
UF(t9

t0). We note from

2.2).

t and B.2.13) E.5.5)hat

=
So we have

eiH\302\260t/hU(t9

to)e-iH\302\260'<>/h\\a9

to\\

to)F.

E.6.8)

eigenstates

= E.6.9) UF(t910) eiH*t/hU(t9 to)e'tH^/h. Let us now look at the matrix element of Ur(t910)between energy eigenof Ho:
(n\\UF(t,

to)\\i)

= e\302\253E\"'-E''oVh(n\\U(t9

to)\\i).

E.6.10

We

recall from Section that (n\\U(t9t0)\\i) is defined to be the transition 2.2 amplitude. Henceour (n\\Uf(t,t0)\\i) here is not quite the same as the transition amplitude defined earlier. However, the transition probability defined as the squareof the modulus of (n\\U(t9t0)\\i) is the same as the analogous quantity in the interaction picture
\\{n\\Uj{t, tQ)\\i)\\2

= \\(n\\U(t,

to)\\i)\\2.

E.6.11

Parenthetically, we may remark that if the matrix elementsof Ur are taken between initial and final states that are not energy example, between \\a') and \\b') (eigenketsof A and 2?,respectively), here[H09A] # 0 w have, in general, B and/or[i/0, ] #
eigenstates\342\200\224for
0\342\200\224we

as the reader may easily verify. Fortunately, in problems where the interacpicture is found to be useful, the initial and final states are usually taken to be Ho eigenstates. Otherwise,all that is neededis to expand \\a'), '),and so on in terms of the energyeigenketsof Ho.
interaction

328

Approximation Methods

physical

Coming back to (n\\Uf(t9 to)\\i), we illustrate by consideringa physiThe state situation where at t = t0, the system is known to be in state ket in the Schrodinger icture \\i, to\\ t)s is then equal to \\i) up to a phase p the factor. In applying the interaction picture, it is convenient to choose factor at t = t0 so that phase

|/).

I/ / / \\ l^ktrkktA/c
\342\200\242

= p-'E,to/*\\j\\11 /
*~

\342\200\242>

(*)f)M) I .\\J
\\ ~J
\302\273

A. ?*

which

means that

in

the interaction picture we have the simpleequation

At

a later time we have
with

i;

f

.

f\\

=TT(f

t \\\\j\\

(^ A 1d\\

Comparing this we see
We now

the expansion
\\i

tr,' t\\

=Yc (t)\\n\\

E 6 15)

E.6.16

go back to the perturbation expansion for Ur(t,t0)[see We can also expand cn(t) as in E.6.1), where c^ is first order in E.6.6)]. is secondorder in Vr(t), and so on.Comparing the expansion of Vt(t\\ c?2) we obtain [using E.5.7)] both sidesof E.6.16),
SO)

@ = **,

of (independent t)

E.6.17)

where we have used
ei(En-E,)t/h = ei<,>nitm

E.6.18
?=

The transition probability for |/) -> \\n)

with

n

i

is obtained by

---\\\\
Constant Perturbation
As an application of turned on at / =

E.6.19

0:

let E.6.17),us considera constant perturbation

x @, V(t)= \\VT; v 7

T7/

,. * * (independent of /),
A A
4\\

for / c for t

<0 ,^n > 0.

ie r E.6.20)
_.v
v y

5.6.Time-Dependent
Even
though

Perturbation

Theory

329

on the operator V has no explicit dependence time, it is, in made up of operators like x, p, and s.Now supposeat t = 0, we general, have only |/>. ith t0 taken to be zero, we obtain W
@) @

c(l)= ^
Yl

\342\200\224-V *-

e'\"\"'1 'Mil*'
\\

dt'
*\302\246 \302\273

En-E,
or

E.6.21)

|/.(l)|2s=_
4IF
sin2

2 ft

E.6.22) E.6.22)

E.6.22)

The probability of finding \\n) depends only on \\Vm\\2 but also on not the energy difference En Et, so let us try to see how looksas a function of En. In practice, we are interested in this way of looking at when there are many states with E En so that we can talk about a continuum of final states with nearly the same energy.To this end we define

-

-

h

E.6.23)
of
co

We see Figure 5.6. see that the during of the middle peak, centered around co = 0, is t2 and the width is height As is proportional to 1//. / becomes large, |c^1}@|2 appreciable only for those final statesthat satisfy
which

and plot 4sin2(co//2)/co2a as

function

for fixed

f,

the time interval

the perturbation has been on;

M

:.
\\

E.6.24)

If we call A/ the time interval during which the perturbation has been turned on, a transition with appreciable robability is possible p only if where by we mean the energy change involved in a transition with appreciableprobability. If A/ is small, we have a broaderpeak in Figure and 5.6, as a result we can toleratea fair amount of energy nonconservation. On the other hand, if the perturbation has beenon for a very long time, we have a very narrow peak,and approximateenergy conservationis required for a transition with appreciable probability. Note that this \"uncertainty relation\" is fundamentally different from the x p uncertainty relation of
?\302\261E
\342\200\224

E.6.25)

330

Approximation Methods

-An

It
o>

An

It

0)

FIGURE 5.6. Plot of 4sin2(co//2)/a>2 versus have regarded En as a continuous variable.

for

a fixed

/, where in

o>

(En

E,)/h

we

I Section There x and p are both observables.n contrast, time in nonrelativistic quantum mechanicsis a parameter, not an observable. For those transitions with exact energy conservation En = En we have
n

1.6.

-

E.6.26)
>\"\302\246

The probability of finding
in

after a time interval / is quadratic, not linear, which V has been on. This may appear during There is no causefor alarm, however.In a realistic unreasonable. intuitively situation where our formalism is applicable, there is usually a group of final states,all with nearly the same energy as the energy of the initial state |/). In other words, a final state forms a continuous energy spectrum in the of neighborhood Er We give two examples along this line. Considerfor instance, elasticscattering by some finite range potential (seeFigure 5.7), which we will consider detail in Chapter 7. The initial state is taken to be in a plane wave state with its propagation direction oriented in the positive t z-direction;he final state may also be a plane wave state of the same energy but with its propagation direction, in general, in a direction other than the A positive z-direction. nother example of interest is the de-excitationof an excitedatomic state via the emission of an Auger electron. simplest The exampleis a helium atom. The initial state may be BsJ,where both the electronsare excited;the final state may be (Is) (that is, one of the electrons still bound) of the He+ ion, while the second electron escapeswith a I positive energy E\\ see Figure 5.8.n such a case we are interested in the
\\n)

the time interval

5.6.Time-Dependent

Perturbation

Theory

331

same energy

Nearly

the

+z-direction

FIGURE

5.7.

Elastic scattering of plane wave

by

some finite

range potential.

Bs):
Is
(Is)Bs)

1
of two

One of the electronsis in 1s state and the other is in freestate

(IsJ
FIGURE

5.8. Schematic diagram
~ Et\\
is, the

electron energy levels

of helium

atom.

total

probability\342\200\224that

transition

stateswith

summed over final probabilities

En

n >En

-

E.6.27)
Ei

It

within

is customary to define the density of final states as the number of states energy interval (E,E + dE) as
as E.6.27)

We can then write V
F
=*

P(E)dE.

E.6.28)

irA>i2

F

= 4 Isin'
As /

(En-E,)t
2h

\\vm

\\En-E,
TTt

p(En)dEn. E.6.29)

-> oo, we can take advantage of
lim

1

sin'

(EH-Et)t
2h

\\En~Ei

E.6.30)

332
which

Approximation

Methods

follows from
lim

-^^ 8{x).
=
\\Vni\\2

E.6.31)

It

is now possibleto take the averageof
with

outside the integral sign and

perform the integration
lim

the S-function:
Fn = F

E.6.32)

Thus the total
t,
which

for large valuesof / is a consequence of the fact that the total transition probability is proportional to the area w under the peak of Figure 5.6, here the height varies as t2 and the width
transition

is quite reasonable. Notice that

probability is proportional to
this linearity

t

in

varies as
It
transition

the is conventional to consider transition is, the transitells E.6.32) us that the total probability per unit time. Expression transition rate, defined by
rate\342\200\224that

1//.

is constant in / for large t. Calling E.6.33) wt_+[n], where [n] stands for a
group of final states with energy similar to /, we obtain

|()
?
n

E.6.33)

E^E,

E.6.34)

independent of /, provided the first-order time-dependent perturbation theory is valid. This formula is of great practical importance; it is called Fermi's olden rule even though the basic formalism of /-dependentperg perturbation We as theory is due to Dirac* sometimeswrite E.6.34)
V,,
\342\200\224

IT/ |2W that this

17

77

\\

/c c ^c\\
with

where

it

must

be understood

expressionis integrated

jdEnP(En).

We should also understand what is meant by \\Vm\\2. If the final states form a quasi-continuum,the matrix elements Vm are often similar if \\n) \\n) are similar. However, it may happen that all energy eigenstates with the same En do not necessarily have similar matrix elements.Consider,for example,elasticscattering. The \\Vm\\2 that determines the scattering cross sectionmay dependon the final momentum direction.In such a case the *Editorial Note. Dr. Edward Teller,
in teaching

1955 which the editor was in attendance), mentioned that this was actually Fermi's golden (in rule 2. Since Teller did not subscribe to golden rule 1,he classwas not informed what rule 1 t was. However, golden rule 1 is given in E. Fermi 1950,136 148. and

a quantum

mechanics

classat

Berkeley in

5.6.Time-Dependent

Perturbation

Theory

333

group of final stateswe should considermust have not only approximately the same energy, but they must also have approximately the same momenc direction.This point becomes learer when we discussthe photoelectric effect. Let us now look at the second-ordererm, still with the constant t From we perturbation of E.6.20). E.6.17) have
momentum

\342\200\224-\\YV

t

V Ui c L vnmvmij ('dt'e^**''(*'dt\" J m
e\"*\342\204\242'

\"

dt'ftl

E-6-36)

The first term on the right-hand sidehas the same ^-dependence c^ [see as If this E.6.21)]. were the only term, we could then repeat the same argument as before and conclude that as t -> oo, the only important contribution

arisesfrom
contribution

contribution gives riseto a rapid oscillation,which doesnot give a contributo the transition probability that grows with t. With cA) and cB) together, we have
w.

En

~ Et. Indeed,when

Em

differs from

En

and

Ei9

the

second

jrni *

i

V^*

ZmJ

m

E: E p(En) F

Vnm Vmi

-

2

=F

E.6.37)

The formula has the

following physicalinterpretation. We visualizethat the transition due to the second-order term takes placein two steps.First, |/> makesan energy nonconservingtransition to |w); subsequently, \\m) makes an energy nonconservingtransition to |n), where between \\n) and |/) there is overall energy conservation.Such energy nonconserving transitions are often called virtual transitions. Energy need not be conserved for those virtual transitions into (or from) virtual intermediate states.In contrast, the first-order term Vm is often said to representa direct energy-conserving \"real\" transition. A specialreatment is needed VnmVmi ?= 0 with Em ~ Er if t The best way to treat this is to use the slow-turn-on method V->evtV, in which we will discuss Section 5.8 and Problem of this chapter. The net result is to change the energy denominator in E.6.37) follows: as

31

ie.

E.6.38)

Harmonic Perturbation

considera sinusoidally varying time-dependent potential, referred to as harmonic perturbation: commonly
We now

where i^ may

still

V(t) dependon

= re1\021 + r^e~l\"\\ x, p, s, and so on.Actually,

E.6.39)
we have already

334

Approximation Methods

^-dependenttwo-levelproblems. discussing
Again
initially.

encountered a time-dependent potential of

this

kind in

Section

5.5 in

assume that only one of the eigenstates of Ho is populated is assumed be turned on at t = 0, so to Perturbation E.6.39)

(D^Z-i (\\rmei\302\273t'+rn]e-it*t')eit*\302\253t'dt'
n

Jq

h

CO

+

CO

\342\200\224

m

co + co m

m

E.6.40)

where i^J actually stands for (ifif)nr We seethat this formula is similar to T the constant perturbation case. he only change neededis
F
co m
\342\200\224

F

h

E.6.41
\342\200\224

So as t -> oc,

\\c\\

'\\

is appreciablenly if o + co 0 or En~ Et hco ^ Et + hco co 0 or coni

\342\200\224

\342\200\224

E.6.42a E.6.42b

is important because E.6.42a), second of the and vice versa. We see that we have no energy-concondition satisfied by the quantum-mechanical system alone; rather the apparent lack of energy conservation is compensated the by \"external\" potential energy given out energy taken away In the first case(stimulated emission), V(t).Pictorially, we have Figure the quantum-mechanical system gives up energy hco to V; this is clearly possibleonly if the initial state is excited.In the secondcase (absorption), the quantum-mechanicalsystem receivesenergy h co from V and ends up as an excitedstate. Thus a time-dependentperturbation can be regarded an as
Clearly, wheneverthe
term
first term

is unimportant,

energy-conservation

to\342\200\224or

from\342\200\224the

5.9.

inexhaustible sourceor sink of energy. In complete we analogywith E.6.34),have
w. h
\302\246

n

E.6.43)
'
n

w.

h

or, more commonly,
277
\\rHl

E.6.44)

Note also that

E.6.45)

5.7. Applications

to Interactions with the Classical Radiation

Field

335

0)
ho)

00
En
\"

FIGURE
(possible

5.9. (i) Stimulated emission: Quantum-mechanical only if initial state is excited), (ii) Absorption: Quantum from V and ends up as an excited state.

system gives up hu to V (possimechanical system receives he*)

which

is a consequencef o
DC
\302\253->

E.6.46
-\302\273

we and (rememberi/~r\\n) (n\\iT), Combining E.6.43) E.6.45), have rate emission for / _ absorption rate for n [/]
-\302\273[n]

density of final states for [ n ]
in

density of final states for [ i ]

'

E.6.47)
the absorption case we let / stand for final states. Equation which expresses E.6.47), symmetry between emission and absorption, is

where
known

as detailed balancing. To summarize, for constant perturbation, we obtain appreciable transition probability for \\i) -> \\n) only if En~ Er In contrast, for harmonic transition perturbation we have appreciable probability only if En El hu or En =* El + hco (absorption). (stimulated emission)

-

\342\200\224

5.7.APPLICATIONS O INTERACTIONS T WITH THECLASSICAL
RADIATION FIELD
Absorption and Stimulated Emission
We apply the formalism of time-dependentperturbation theory to the interactions of atomic electron with the classical adiation field. By a r classical adiation field we mean the electricor magneticfield derivablefrom r a classical as opposedto quantized) radiation field. ( The basic Hamiltonian, with |A|2 omitted, is
d2

e
mec
V-A

which

is justified if

= 0;

E.7.2)

336

Approximation Methods

specifically,we work

with A

a monochromaticfield of the plane wave for

= 2^40ecosl

\342\200\224

ft-x\342\200\224

co?I

E.7.3)

where e and h are the (linear) polarization and propagation direction. b o Equation E.7.3)bviously satisfiesE.7.2) ecausee is perpendicular to the propagation direction h. We write

cos(-h-x- = co/)
and treat
in
\342\200\224

i[e'\"<\302\253A)h-x-i\302\253/

+

^-i(\302\253/c)h.x+/\302\253/]

E.7.4)

a E.7.3)s

(e/mec)Am\\>

as time-dependentpotential, where we expressA

E.7.5)
Comparingthis result
with

we E.6.39), seethat

the e~/w'-termin

mec]

\\mec

E.7.6)
is responsible absorption, while the e+/w'-termis responsible stimufor for emission. Let us now treat the absorption casein detail. We have
stimulated

eA

mec and
277

i-+n

e2
2 2 \\A0\\2\\(n\\ei{o)/c)(hx)E'p\\i)\\28(En
mLecL

n
ft

-Et-ha). E.7.8)

The meaning of the 6-functionis clear. \\n) forms a continuum, we simply If integrate with p(En).But even if \\n) is discrete,because\\n) cannot be a ground state (albeit a bound-state energy level), its energy is not infinitely sharp; there may be a natural broadening due to a finite lifetime (see Section t 5.8);here can also be a mechanism for broadening due to colliIn such cases, regard 6(co coni) as we
collisions.
\342\200\224

monochromatic;

Finally, the incident electromagneticwave itself is not perfectly monochroin fact, there is always a finite frequency width. We derive an absorption crosssection as by (Energy/unittime) absorbed the atom (/ -> n) Energy
flux

.

,

of the radiation field

Forthe energy flux

(energyper area per unit time), classical lectromagnetic e

5.7. Applications

to Interactions with the Classical Radiation

Field

337

theory gives us

where we have used
2
max

.

2 ^max
T>

\\

2 for energy density (energyper unit volume)
with

E.7.12)

at c ^A, Putting everything together, we get (remembering that absorbed by atom for each absorption process)
\302\260abs

B = VXA.

E.7.13)
h <o

= energy ab-

Et-fico) ~ huB^/h)(e2/m2ec2)\\Ao\\2\\(n\\ei(u/c)(hx)i-p\\i)\\2S(EnAir2h

p2

= has Equation E.7.14) the correct dimension [l/(M2/T)](M2L2/T2) = e2/hc 1/137 = L2 if we recognize that a and (dimensionless) 8(En Et ha)) = (l/^M(cow/ co),where 5(cowz co) has time dimension T.
\342\200\224 \342\200\224 \342\200\224 \342\200\224

ElectricDipoleApproximation
The electricdipoleapproximation (El approximation)is basedon the fact that the wavelength of the radiation field is far longer than the atomic s dimension, o that the series(remember co/c= l/X)

\"-

E.7.15)

can be approximated its leading term, The validity of this for a light by atom is as follows: First, the hco of the radiation field must be of order of atomic level spacing,so
n

1.

Kao/Z)
chR^ion

atom

This leads to c
CO

,

137/?atom

Ze2

Z

E.7.17)

In other words,

E-7.18)
for light atoms (small Z). Because matrix elementof x is of orderR atom' the

338
that

Approximation Methods

of x2, of order Rlionv and so on, we seethat the approximation of by replacing E.7.15) its leading term is an excellentone. Now we have
(n\\el(\"/c)(hx)hp\\i)-*E-(n\\p\\i).

E.7.19)
must

calculate (n\\px\\i). Using

In particular, we take e along the
\\x

W x-axis(and h along the z-axis). e

H~] = _ m

\342\200\224^L

E 120)

we have

= imwn[(n\\x\\i}.

E.7.21)

o Because f the approximation of the dipoleoperator, approximation this schemeis called the electricipole approximation.We may here recall d the rule Since [seeC.10.39)] selection for the dipolematrix element. x is

m!

a sphericaltensor of rank 1with q = we must have m1 m = = 0,1 0 0 transition). If e is along the y-axis,the sameselection /' y| (no rule applies.On the other hand, if e is in the z-direction, q = 0;hence,

-

\342\200\224

\302\2611,

\302\2611,

\342\200\224>

\342\200\224

m.

With

E.7.14)

the electric dipoleapproximation, the absorption crosssection now takes a simpler form upon using and as
\302\260abs

= 4^2\302\253^J<\"WOI25(<\302\260

E.7.19) E.7.21) ~ E.7.22)
wWi)\302\253

In other words,oabs treated as a function of co exhibits a sharp 5-functionto like peak whenever /ico corresponds the energy-levelspacing at co ^ (En Et)/h.Suppose |/) is the ground state, then coni is necessarily
\342\200\224

positive; integrating

we E.7.22), get = foab3Mdu L47r2a^m\\(n\\x\\i)\\2. n

E.7.23)
as

we In atomic physics define oscillatorstrength, fnh

.
It

E.7.24)
E-7-25)

is

then

straightforward

Reiche-Kuhnsum rule,

(consider[x,[x, o]]) to establish the ThomasH
n

In terms of the integration over the absorption crosssection, we have ^2 4w ah = 2 O l s( ) did = 2 77 C a 2m

//

\\

CO

\342\200\236

mx2

E.7.26)

5.7. Applications

to Interactions with the Classical Radiation

Field

339

Noticehow

has disappeared. Indeed,this is just the oscillation sum rule f in classical already electrodynamics(Jackson1975,or instance). this was one of the first examples of how \"new quantum Historically, mechanics\" led to the correct classicalresult. This sum rule is quite remarkable becausewe did not specify in detail the form of the Hamiltonian.
h

known

PhotoelectricEffect
We now consider the photoelectric is, the ejection of an electron when an atom is placedin the radiation field.The basicprocessis considered be the transition from an atomic (bound) state to a continuum to state E > 0.Therefore, |/) is the ket for an atomic state, while \\n) is the ket for a continuum state, which can be taken to be a plane-wavestate |ky), an approximation that is valid if the final electron is not too slow.Our earlier formula for oabs(u)can still be used, exceptthat we must now integrate 8(coni co)together with the density of final states p(En). Our basic task is to calculate the number of final states per unit energy interval. As we will see in a moment, this is an example where the matrix element dependsnot only on the final state energy but also on the momentum direction. We must therefore considera group of final states with both similar momentum directions and similar energies. To count the number of states it is convenient to use the box normalization convention for plane-wavestates.We considera plane-wave state normalized if when we integrate the square modulus of its wave function for a cubicbox of side L, we obtain unity. Furthermore, the state is assumedto satisfy the periodic boundary condition with periodicityof the side of the box. he wave function must then be of form T
effect\342\200\224that
\342\200\224

E-7-27)
where the allowed valuesof kx must satisfy
kx
with nx

=
\342\200\224r?,...,

E.7.28)
ky

kz. Noticethat as L -* oo, kx, ky, and kz becomecontinuousvariables. The problemof counting the number of states is reducedto that of We counting the number of dotsin three-dimensionallattice space. define n
such that
n2z.

a positive or negative integer. Similar restrictionshold for

and

E.7.29)

340 As

Approximation Methods

L -* oc, it is a good approximation to treat n as a continuous variable; Let in fact it is just the magnitude of the radial vector in the lattice space. us considera small-volumeelement such that the radial vector falls within n and n + dn and the solidangle element dti; clearly,it is of volume n2 dndti. The energy of the final-stateplane wave is related to kf and hence to n\\ we
have
h2k2

tf

n2B7rJ

Furthermore, the directionof the radial vector in the lattice spaceis just the direction of the final state, so the number of states in the interval between E and E + dE with direction into dQ> being k^ is (remember dE = (h2kf/me) dkf) given by*
momentum

3m

We

can now put everything together to obtain an differential crosssection for the photoelectriceffect:

expressionfor the

2\"*g f

h2B7ry

,.

E.7.32)

To be specific,let us consider ejection of a K shell (the innermost the electron causedby absorption of light. The initial-state wave function shell) is essentially the same as the ground-state hydrogen atom wave function that except the Bohr radius aQ is replacedby aQ/Z.Thus

=e
X

X

L3/2

(-i

e- Zr/a0

3/2

a0

E.7.33)
E.7.34)

Integrating by

parts, we can pass V to the left side.Furthermore,

because e is perpendicular to h. On the other hand, V acting on e~lkf'x brings down /k^, which can be taken outside the integral. Thus to evaluate E.7.33), we need to do is take the Fourier transform of the all atomic wave function with respectto
\342\200\224

E.7.35)
This is equivalent to taking one state per cube d3xd3p/B7rhK
in phase

space.

5.8.Energy

Shift and Decay Width

341

N
FIGURE

5.10. olar P

coordinate system with

e and

h along Ox and Oz, respectively,

and

The final answer is (see Problem39 of this chapter for the Fourier transform of the hydrogen atom wave function)

/

mcco
in
</>

E.7.36)
Figure

If we introduce the coordinate system shown the differential crosssectionin terms of 6 and
)
9

we 5.10, can write

using

= kjsirfdcos2^

E.7.37)

5.8. NERGY SHIFT E AND

DECAYWIDTH

Our considerationso far have beenrestricted to the question of how states s other than the initial state get populated.In other words, we have been concernedith the time developmentof the coefficientcn(t) with n # /. The w question naturally arises,What happensto ct(t) itself? To avoid the effect of a sudden change in the Hamiltonian, we propose to increasethe perturbation very slowly. In the remote past W (t -> oo) the time-dependentpotential is assumedto be zero. e then

-

342
turn

Approximation Methods

gradually

on the perturbation to its
V(t)

full

value; specifically,

= er]tV

E.8.1)

where V is assumedto be constant and tj is small and positive.At the end and of the calculation, we let tj -> 0 (seeFigure 5.11), the potential then constant at all times. becomes In the remote past, we take this time to be oc, so the state ket in Our basic aim is to evaluate the interaction picture is assumed to be ct(t). However, before we do that, let us make sure that the old formula of the goldenrule (seeSection 5.6)can be reproduced using this slow-turn-on method.Forcn(t)with n # /, we have [using E.6.17)]
\342\200\224

|/).

n
\342\200\224

7

\342\200\224

h

Vm

tj

+i

ni

E.8.2)
probability is therefore given
2-qt

To lowest nonvanishing
by

order, the

transition

\\vm

h

2

'
)

E.8.3)

or
2

~
\\

2T)t

v

E.8.4)
unity, but

We now let

tj

-\302\273

0.Clearly, it
Iim

is all

right

to

replaceevt by

note

E.8.5)
n>o

I

v(t)

FIGURE

5.11. of Plot

V(t) versus t in the adiabatic (slow-turn-on) picture.

5.8.Energy

Shift and Decay Width

343

This leads to the golden rule,

E.6.17).

Encouragedby
c@)=

this

We have

result, let us calculate cf\\

(!)
Iim

E-8-6)
cjx\\

and cp\\ again using

h
\342\200\224

cB)=

/

\\2\302\253-,

\342\200\224-\\

T\\V

I2 2r,t

/
-\\

ft

,
f

_

11/ |

\"'

-

2t,2

E-8-7)

Thus up to secondorder we have

E.8.8)
= Now considerthe time derivative of c, [dc((t)/dt cj,which we have from and letting tj E.8.8). dividing by c, (thus replacing e71'and Upon we get by unity),
-\302\2730

C:
7\"

I
n
7] m

E-8-9)

is E.8.9)formally correct up to secondorderin V. Note here that Expansion is now independent of t. Equation E.8.9) a differential is ci(t)/ci(t) equation that is to hold at all times.Having obtained this, it is convenientto = W renormalize ci so that c,@) 1. e now try the ansatz

with

consistentwith
We

A,,

constant (in time)

but

can seethe physical meaning of A, by interaction picture implies e~lA't/h~lE't/h\\i)

becausethe E.8.9)

not necessarily real.Clearly
right-hand

side of

in the noting that e~iA't/h\\i) in the Schrodingerpicture. In

is E.8.10) is constant. E.8.10)

344

Approximation Methods

other words,

?,-*?,. +A,
\342\200\242\342\200\242\302\246

E.8.11

as a result of perturbation. That is, we have calculated the levelshift using time-dependentperturbation theory. Now expand,as usual, = *?>+ *?>+ , E.8.12) Af we with and compareE.8.10) E.8.9); get to first order

.

E.8.13)

f this is just what we expectrom t-independentperturbation theory. Beforewe look at Ap\\ recall But c_*0 X
Urn
\342\200\224\342\200\224

+ IE

= Pr.- /ttS(jc). X

-

E.8.14

Thus Re(A?>)= Pr.

()

m

? -j%?\\VmMEt-Em).
from the

E.8.15a
golden rule, so we

E.8.15b

But the right-hand

can identify
m

sideof E.8.15b) is familiar

E

\"<\342\200\224=

T ^ \\VmMEi-Em)= -\\lm[^\\.E.8.16)
as E.8.10)
+

Coming back to c,(/),we can write If we define

Ct(t) = ^-('/^[^(A^n d/^InKA,).]^

E.8.17)

=
then

|lm(A,.),

?

E.8.18)

Therefore, Fz characterizesthe rate at which state disappears. It is worth checkingthe probability conservation up to secondorder in V for small /:
m

|i)

E.8.20)

where E.8.16) beenused.Thus the probabilitiesor finding the initial has f state and all other states add up to Put in another way, the depletion of state \\i) is compensated the growth of states other than \\i). by

1.

Problems

345

To summarize, the real part of the energy shift is what we usually associatewith the level shift. The imaginary part of the energy shift is, the apart from [seeE.8.18)], decaywidth. Note also

-2

h

= r,

E.8.21)

where rt is the mean lifetime of state |/) because To seewhy F, is called width, we look at the Fourier decomposition

E.8.22)

E.8.23)
Usingthe Fourier inversion
\\f(E)\\2

formula, we get
\342\200\224

a

1-\342\200\224-2

E.8.24)

Therefore, Tt has the usual meaning of full width at half maximum. Notice that we get the time-energyuncertainty relation from E.8.21)

AfA?~/i,
where we

E.8.25)

the uncertainty in the energy with Tt and the mean identify lifetime with Af. Even though we discussedthe subject of energy shift and decay width using the constant perturbation V obtained as the limit of when tj -> 0, we can easily generalize our considerationso the harmonic t in All we must do is to let discussed Section perturbation case
En(m) in

E.8.1)

-

5.6.

\" Ei ~* En(m)

Ei

\302\261

^

E.8.26)
due to

and and E.8.2), E.8.8), E.8.15), so on.The quantum-mechanicaldeof unstable states we have developedhere is originally and Weisskopf in 1930.

description

Wigner

PROBLEMS

1.A

simple harmonic oscillator (in one dimension) is subjectedto a perturbation
where b is a real constant. a. Calculate the energy shift of the ground state to lowest nonvanishing

order.

346

Approximation Methods

b. Solve this
(a).

problem exactly and compare with your result obtained in

[You may assume without proof

2. In

nondegenerate time-independentperturbation theory, what is the probability of finding in a perturbed energy eigenstate (\\k)) the correcorresponding unperturbed eigenstate (|A:@)))? Solve this up to terms of

3.Considera particle in

a two-dimensionalpotential < 0 forO <x< L,0 y < L, oc otherwise. Write the energy eigenfunctionsfor the ground and first excited states. We now add a time-independentperturbation of the form < forO <x< L,0 y < L, _ 0 otherwise. Obtain the zeroth-orderenergyeigenfunctionsand the first-orderenergy shifts for the ground and first excited states. 4. Consider an isotropic harmonic oscillator in two dimensions.The Hamiltonian is given by
\\

order g2.

P

2

P

2

wco

9

2 a. What are the energies of the three lowest-lyingstates? Is there any degeneracy? b.We now apply a perturbation
m

where 5 is a dimensionless number much smaller than unity. real Find the zeroth-order energyeigenket and the correspondingnergy e to first order[that is, the unperturbed energy obtained in (a) plus the first-order energy shift] for each of the three lowest-lyingstates. c. Solve the HQ+ V problem exactly. Comparewith the perturbation results obtained in (b). [You may use {n'\\x\\n) =yfh/2mu(Jn+18n, n + l 5. EstablishE.1.54) the one-dimensionalharmonic oscillator given by for with E.1.50) an additional perturbation V =\\emu>2x2. Show that all other matrix elements VkQ vanish. 6. A slightly anisotropicthree-dimensional harmonic oscillator has co2 = ay A chargedparticle moves in the field of this oscillatorand u>x is at the same time exposed a uniform magnetic field in the xto direction. ssuming that the Zeeman splitting is comparableto the A splitting producedby the anisotropy, but small comparedto hio, cal\342\200\224

Problems

347

order energies f the components the first excited the o of state.Discussvarious limiting cases.(From Merzbacher,Quantum 2 e, 1970. Mechanics, 1 Reprintedby permissionof Ellis Horwood,
culate to first
\302\251

Ltd.) atom 7. A one-electron whoseground state is nondegenerateis placedin a
uniform
expression

electric field in the z-direction.Obtain an approximate expresfor the induced electric dipole moment of the ground state by consideringthe expectation value of ez with respectto the perturbed can state vector computed to first order.Show that the same expression also be obtained from the energy shift A = a\\E\\2/2 of the ground state computedto secondorder.(Note:a stands for the polarizability.)
\342\200\224

8.Evaluate the matrix
any

elements(or expectationvalues) given below.If vanishes, explain why it vanishes using simplesymmetry (orother) arguments. a. (n = 2,/ = m = 0 x n = 2,/ = 0,m = 0). b.(n = 2,/ = m = 0 pz n = 2,/ = 0,m = 0). o [In (a) and (b), nlm) standsfor the energy eigenket f a nonrelativistic hydrogen atom with spin ignored.] 9 c.(Lz) for an electron a central field with /=2>m= 7 = 4. in 2>' = 0|S^e) S^e+)| = 0) for an s-state posid.(singlet,ms ms triplet,

spin. Ignore

1, 1,

-

9.A

e.(SA)*SB)) the ground state of a hydrogen molecule. for
characterizedby \\nj = 1,m = p-orbital electron spin) is subjectedto a potential V= X(x2 y2) (X = constant).
\302\2611,0)

tronium.

(ignore

-

a. Obtain the \"correct\"zeroth-orderenergyeigenstatesthat

the perturbation. You need not evaluate the energy shifts in detail, but show that the original threefold degeneracy is now completely

diagonalize

under time reversal and becausethere is no longer any degeneracy, we expect each of the energy eigenstates obtained in (a) to go into itself (up to a phasefactor or sign) under time reversal. Checkthis point explicitly. 10. onsidera spinlessparticle in a two-dimensionalinfinite square well: C < @ forO <x<a,0 y otherwise. \\ oo

b. BecauseV

removed.

is invariant

<a,

are the energyeigenvaluesfor the three lowest states? Is there degeneracy? b.We now add a potential
any

a. What

348

Approximation Methods

Taking this as a weak perturbation, answer the following: (i) Isthe energy shift due to the perturbation linear or quadratic in X for each of the three states? for (ii) Obtain expressions the energy shifts of the three lowest statesaccurate to order X. (You neednot evaluate integrals that
may

11.

(iii) Draw an energy diagram with and without the perturbation for the three energy states.Makesure to specifywhich unperturbed state is connected to which perturbed state. The Hamiltonian matrix for a two-state system can be written as
XA
XA

appear.)

Eo

(X Clearly the energyeigenfunctionsfor the unperturbed problems = 0) are given by

\\p2

Solve this problem exactly to find the energy eigenfunctions and and the energyeigenvaluesEx and E2. | Assuming that X |A | E21, solve the same problem using time-independentperturbation theory up to first order in the energy eigenfunctions and up to secondorder in the energy eigenvalues. Comparewith the exact results obtained in (a). are Supposethe two unperturbed energies \"almost degenerate,\"that
\\px
\342\200\224

\302\253:

E\302\261

is,

Show that the exact resultsobtained in (a) closelyresemble what you expect by applying degenerate perturbation theory to this set exactlyequal to E2. problemwith 12.This is a tricky problem becausethe degeneracybetween the first and ( the secondstate is not removed in first order. eealso Gottfried 1966 S T Problem 1.) his problem is from Schiff 1968, Problem 4. A 397, 295, system that has three unperturbed states can be representedby the
would
E\302\256

perturbedHamiltonian

matrix
t

Ex

0

a

0 a where E2> The quantities a and b are to be regardedas perturbaEv that are of the same order and are small compared with E2 Ev Usethe second-order ondegenerate perturbation theory to calculate n
\342\200\224

perturbations

Problems

349

13.

14.

15.

the perturbedeigenvalues. Is this procedure correct?)Then diagonalize ( the matrix to find the exact eigenvalues.Finally, use the second-order perturbation theory. Compare the three results obtained. degenerate Computethe Stark effectfor the 2Sl/2and 2Pl/2levelsof hydrogen for a field e sufficiently weak so that eea0is small compared to the fine structure, but take the Lamb shift 8 (8 = 1057 MHz)into account (that is, ignore 2P3/2 in this calculation).Show that for eea0 5, the energy shifts are quadratic in e, whereas for eea0 8 they are linear in e.(The radial integral you need is Bs\\r\\2p) = 3]/3a0.)Briefly discuss the (if consequences any) of time reversal for this problem.This problem is Problem 7-3. from Gottfried out the Stark effect to lowest non vanishing order for the n = 3 Work level of the hydrogen atom. Ignoring the spin-orbit force and relativistic correction (Lamb shift), obtain not only the energy shifts to lowest z nonvamshing orderbut also the correspondingerotk-order eigenket. Supposethe electron had a very small intrinsic electric dipolemoment analogous to the spin magneticmoment (that is, \\iel proportional to a). interaction as a small perturbation, Treating the hypothetical discussqualitatively how the energy levels of the Na atom (Z = would be altered in the absenceof any external electromagneticfield. Are the level shifts first order or secondorder? State explicitly which states get mixed with each other. Obtain an expression the energy for shift of the lowest level that is affected by the perturbation. Assume that only the valenceelectron is subjected the hypothetito throughout
\302\253: :\302\273

1966,

\342\200\224[ieimE

ll)

16. onsidera particle bound to a fixed center by C
potential V(r). a. Prove

hypothetical

interaction.

a sphericallysymmetric

for all s states, ground and excited. relation for the ground state of a three-dimensional oscillator, the hydrogen atom, and so on. isotropic (Note:This relation has actually beenfound to be useful in guessing the form of the potential betweena quark and an antiquark.) 17.a. Suppose the Hamiltonian of a rigid rotator in a magnetic field t P perpendicularo the axis is of the form (Merzbacher 1970, roblem

b. Check this

17-1)

A\\}

+ BLZ + CLy

if terms quadratic in the field are neglected. ssuming B^> C, use A perturbation theory to lowest nonvanishing orderto get approximate

energy eigenvalues.

350

Approximation Methods

b. Considerthe matrix

elements

(n'lm\\mfs\\xy\\nlm f

,m s)

of a one-electron(for example,alkali) atom. Write the selectionrules for A/, Am,, and Am5. Justify your answer. 18. ork out the quadratic Zeeman effect for the ground-state hydrogen W = atom [(x|0> (\\/pral)e~r/ao]due to the usually neglected e2A2/ in W 2mec2'tQvm the Hamiltonian taken to first order. rite the energy
shift

as

for and obtain an expression diamagnetic ing definite integral may be useful: o

susceptibility,

x- (The follow

a For 19.Merzbacher1970, Problem11.) the Hewave function, use 448, (
=2

e~arrndr =

\342\200\224'\342\200\224.

ao with Zeff as obtainedby the variational method.The meax suredvalue of the diamagneticsusceptibilityis 1.88 10 cm /mole. in Usingthe Hamiltonian for an atomic electron a magnetic field, for determine, a state of zeroangular momentum, the energy change to order if the system is in a uniform magnetic field represented B by the vector potential A = 2B x r. Defining the atomic diamagnetic susceptibility \\ by E = -?xB2, calculate \\ atom in the ground state and comparethe 21 helium result with the measuredvalue. 20.Estimate the ground-stateenergyof a one-dimensionalsimpleharmonic
\342\200\22416> f\302\260r

oscillatorusing as a trial

function

with

p to be varied. (You
00

may

use

21.Estimate the lowest eigenvalue(X) of the differential equation
dx using the variational method with for
n

1
0

= e~axxndx

n\\
\342\200\224^

a\"*

^ + (X |jc|)^= 0,

-

xp

-> 0 for

-> |jc| 00

. . } (c(a-\\x\\)9 |x|<a ((atobevaned) ^={^ Y for|jc|>a \\0,
v

Problems

351

as a trial function. (Caution: d\\p/dx is discontinuous at Numerical data that may be useful for this problem are:

x = 0.)

31/3=1.442, 51/3=1.710, 32/3= 2.080, m 2/3 = 2.145. The exact value of the lowest eigenvaluecan be shown to be 1.019. 22.Considera one-dimensionalsimple harmonic oscillator whose classical angular frequency is coo.For / < 0 it is known to be in the ground state. For/ >0 there is also a time-dependentpotential
V(t)

= F0xcoscot

for where Fo is constant in both spaceand time. Obtain an expression the expectation value (jc) as a function of time using time-dependent order. Is this procedure perturbation theory to lowest nonvanishing +1 valid for co coo? [You may use (n'\\x\\n) =]Jh/2mcoo(}/n 8n>jn + i
\342\200\224

23.A

one-dimensionalharmonic oscillator is in its ground state for t < 0. For/ >0 it is subjected a time-dependentbut spatially uniform force to in (not potential!) the jc-direction,
to first order, obtain the probability of finding the oscillator in its first excitedstate for t > 0. Show that the / -> 00 (r finite) limit of your expression indepenis of time. Is this reasonable surprising? or b. Can we find higher excitedstates? [You may use
independent

a. Using time-dependentperturbation theory

24. Considera particle bound in a simple harmonic oscillator potential. Initially (t < 0),it is in the ground state.At / = 0a perturbation of the
form

r), the system will probability that, after a sufficiently long time have made a transition to a given excitedstate. Consider final states. all 25.The unperturbed Hamiltonian of a two-state system is represented by
(t:\302\273

is switched on.Usingtime-dependentperturbation theory, calculate the

0

I

0

?2\302\260

There is, in addition, a time-dependentperturbation

V(t)={, \\Xcosco?
\302\260

v

'

XcoAs<\302\260')

0

/

(Xreal). v

'

352

Approximation Methods

a. At t = 0 the

system

is known to be in the

first

state, represented by

1 0,
E\302\256

Using time-dependentperturbation theory and assuming that for to 2 is not close + hco, derive an expression the probability that the system be found in the secondstate represented by
as a function of t (t > 0).

-

.1
\342\200\224

0

b.Why is this procedurenot valid when is closeo hcol t 26.A one-dimensionalsimpleharmonicoscillatorof angular frequencyco is
E\302\256 E\302\256
\302\261

acted upon by a spatially uniform potential)

but

time-dependent force (not

At t

probability

oo, the oscillatoris known to be in the ground state. Usingthe time-dependent perturbation theory to first order, calculate the probthat the oscillator is found in the first excitedstate at t = + oo. Challenge for experts:F(t) is so normalized that the impulse
\342\200\224

=

p

(ivr/co)

JF(t)dt
imparted to the oscillatoris always the
yet for r
negligible.

Isthis

:\302\2731/co,

is, independent of r; is essentially neglireasonable?Matrix elementof x: (n'\\x\\n) = (h/2mu)l/2 [
same\342\200\224that

the probability for excitation

27. Considera particle in one dimension moving under
corresponding

the influence of

sometime-independentpotential. The energy levelsand the correspondeigenfunctionsfor this problem are assumedto be known. We now subjectthe particle to a traveling pulserepresented a time-dependent by = A8(x-ct).
oo the particle is known to be in the ground state whose energy eigenfunctionis (jc|/)= ut(x).Obtain the probability for finding the system in some excited state with energy eigenfunc(x\\f) = uf(x) at t = + oo. b. Interpret your result in (a) physically by regarding the 5-function pulseas a superpositionof harmonic perturbations; recall
\342\200\224

potential,

a. Supposeat t =
eigenfunction

1

r\302\260\302\260

due1\"
oo

\342\200\224

Problems

353

28.A

hydrogen atom in its ground state [(/?,/, m) = A,0,0)]is placed A between the platesof a capacitor. time-dependentbut spatial uniform i electric (not potential!)s appliedas follows: field

quantum mechanicallyas long very long time.

Emphasize the role played by energy conservation,which holdseven as the perturbation has beenon for a

E= @
<

for / < >0 \\ EQe~t/T for /

0,
(Eo in the positive z-direction).
t:\302\273

Using first-order time-dependent perturbation theory, compute the r in each of the three 2p probability for the atom to be found at = or 0). Repeat the problem for the 2s state: states: (w, /, m) = B,0,0). need not attempt to evaluate radial integrals, You (w,/,m) but perform all other integrations (with respectto angles and time). 29.Considera composite F system made up of two spin \\ objects. or t < 0, the Hamiltonian doesnot dependon spin and can be taken to be zero F by suitably adjusting the energy scale. or t > 0, the Hamiltonian is

B,1,

\302\2611

given by

|H\342\200\224),

b. 30.

Find, as a function of time, > for / < the probability for being found in each of the following states and | a. By solving the problem exactly. By solving the problem assuming the validity of first-order timedependentperturbation theory with H as a perturbation switchedon at / = Underwhat condition does(b) give the correct results? Considera two-levelsystem with Ex<E2. There is a time-dependent potential that connects the two levelsas follows:

Supposethe system is in |
|\342\200\224h),

H\342\200\224

0.

):

|++),

0.

2l = ye~i0)t
At t

(y real). is,

= 0,it is known that only the lower level is *!(<>)= 1, c2@)= 0. a. Find \\cx(t)|2 and |c2@|2 ^>0by exactly solving
f\302\260r

populated\342\200\224that

the

differential equation

coupled

ihtk=

? Vkn{t)e^\"'cn,
(ii)
co

2

(A:

= 1,2).

b. Do the

same problem using time-dependentperturbation theory to lowest nonvanishing order. Comparethe two approaches small for values of y. Treat the following two cases separately:(i) co very
different from
<o21 and

closeo t

co21.

354 Answer for

Approximation Methods

(a):(Rabi'sformula)
(id

- co21O4

sin 2 7_ 2

, +

(co

~
^

1/2

1

co21)

the slow-turn-onof perturbation V W1' (see Baym 1969, contribution from the second term in E.6.36). 257) can generate 32. . Considerthe positronium problemyou solvedin Chapter3,Proba 3. In the presencef a uniform and static magnetic field B o the along the z-axis, Hamiltonian is given by
\342\200\224\302\273

31.how that S
Problem

H = i4Si-S2+

\342\200\224

\\mx)

S2z).

Solve this problemto obtain the energy levelsof all four statesusing degeneratetime-independent erturbation theory (insteadof diagonp alizing the Hamiltonian matrix). Regard the first and the second for terms in the expression H as Ho and V, respectively. ompare C resultswith the exact expressions your

E= E=
where

h2A triplet

1

\302\261

2

1+ 4

eB
\\mechAj

m for singlet

triplet m

=0 =0 =
\302\261

for triplet m {singlet)m

1,

to causetransitions (via stimulated emissionand betweenthe two m = 0 states by introducing an oscilabsorption) magnetic field of the \"right\" frequency. Shouldwe orient the magnetic field along the z-axisor along the jc- (or y-) axis?Justify (The original static field is assumedto be along the zyour choice. axis throughout.) c.Calculate the eigenvectorso first order. t 32'. Problem32 above, but with the atomic hydrogen Hamiltonian Repeat
oscillating

b.We now attempt

pure triplet

(singlet)with m

= 0 stands for the state that becomes a = 0 as B 0.
\342\200\224\302\273

H = i4Si-S2+
where
the hyperfine term S2 is the proton spin. [Note the that of the positronium case].
in

\\mx)

B
is the

ASjS^$\\

electronspin, while
than

problemherehas lesssymmetry

33. onsiderthe spontaneousemissionof a photon by an excitedtom. C a

Problems

355

to be an El transition. Supposethe magnetic number of the atom decreases one unit. What is the by quantum angular distribution of the emitted photon? Also discussthe polarof the photon with attention to angular-momentum conservafor the whole (atom plus photon) system. and 34. Consideran atom made up of an electron a singly charged(Z=1) triton CH). the system is in its ground state (ai = / = 0). Initially b Supposethe nuclear chargesuddenly increasesy oneunit (realistically an electron an antineutrino). This means that the triton and by emitting nucleus turns into a helium (Z = 2) nucleusof mass 3 CHe). btain the O for the system to be found in the ground state of the probability resulting helium ion. The hydrogenicwave function is given by

The

is process known

polarization
conservation

1,

1 ( z\\ 3/2e
V77\"

a o)

35.The

ground state of a hydrogen atom (/? =

time-dependent potential as follows:

/ 1, = 0) is subjectedto a

F(x,t) = V0cos(kz

\342\200\224

cot).

for Usingtime-dependentperturbation theory, obtain an expression the transition rate at which the electron is emitted with momentum p. Show, in particular, how you may compute the angular distribution of the ejectedelectron (in terms of 6 and defined with respectto the z-axis). Discussbriefly the similarities and the differencesbetween this problem and the (more realistic)photoelectriceffect.(Note:For the initial wave function see Problem 34.If you have a normalization problem, the final wave function may be taken to be
<f>

1
very large, but you should be able to show that the observable effectsare independent of L.) 36.Derive an expressionfor the density of free particle states in two t dimensions,hat is, the two-dimensionalanalog of
with

L

3/ mk\\

dEdQ,

.

/

p

p2

2m

Your answer should be written as a function of k (or E) times dEd<t>, where is the polar angle that characterizesthe momentum direction in two dimensions. 37. A particle of massm constrained to move in one dimension is confined
<f>

356
within

Approximation

Methods

0 < x < L by an

infinite-wall

potential

F=oc iorx<0,x>L, V=0 fovO<x<L.
for Obtain an expression the density of states (that is, the number of states per unit energy interval) for high energiesas a function of E.

38. Linearly polarized light of angular frequency co is incident on a oneelectron \"atom\" whose wave function can be approximated by the ground state of a three-dimensionalisotropicharmonic oscillator of angular frequency co0.Show that the differential cross section for the ejection of a photoelectronis given by

(Checkyour dimension!)

4ah2kj dti
m2coco o mco0

exp
\\

h

CO

mcoo

c

Xsin20cos2<J>exp
\\

cos6

provided the ejectedelectron of momentum hkf can be regardedas being in a plane-wave state. (The coordinate system usedis shown in Figure 5.10.) 39 Find the probability |<Mp')|2d3p' the particular momentum p' for the in ground-state hydrogen atom. (This is a nice exercise three-dimenFourier transforms. To perform the angular integration choose the z-axisin the direction of p.) 40. Obtain an expression rBp->ls) the hydrogen atom. Verify that for for it is equal to 1.6 10 s. X
\302\260f three-dimensional

CHAPTER6

IdenticalParticles

of This short chapter is devoted to a discussion some striking quantummechanical effects arising from the identity of particles.We also consider some applicationsto atoms more complex than hydrogen or hydrogenlike

atoms.

6.1. SYMMETRY PERMUTATION
classicalphysicsit is possibleto keep track of individual particles even they may look alike. When we have particle 1 and particle 2 though consideredas a system, we can, in principle, follow the trajectory of 1and that of 2 separately at each instant of time. For bookkeeping urposes, ou y p
In
may

blue and the other red and then examinehow the red moves and how the blue particle movesas time passes. particle In quantum mechanics,however, identical particles are truly indiswe This is because cannot specifymore than a complete set of indistinguishable. f observablesor each of the particles;in particular, we cannot commuting label the particle by coloring it blue. Nor can we follow the trajectory because would entail a position measurement at each instant of time, that which necessarily disturbs the system; in particular the two situations (a) and (b) shown in Figure 6.1 cannot be distinguished\342\200\224not even in principle. For simplicity considerust two particles.Supposeone of the parj which we call particle is characterized by |/c'}, where k' is a particles,

color ne of them o

1,

357

358

Identical

Particles

Two different paths, (a) and (b), of a two-electron system, for example, in FIGURE which we cannot assert even in principle through which of the paths the electrons pass.

6.1.

(a)

(b)

we collectiveindex for a complete set of observables. Likewise, call the ket of the remaining particle \\k\.") The state ket for the two particles can be
written in

productform,
\\k')\\k\,")

where it is understoodthat the first ket refers to particle 1 and the second ket to particle 2.We can also consider where particle
though

F.1.1)

E \\k\") and particle 2 by |/c'). ven particles are indistinguishable, it is worth noting that are and F.1.2) distinct kets for /c'=?k\". In fact, with mathematically k' =hk\", they are orthogonal to each other. Supposewe make a measurement on the two-particle system. We may obtain kf for one particle and k\" for the other. However,we do not know a priori whether the state ket is \\k')\\k\,") \\k\\\k'),") that linear combinationof the two. Put in another way, all kets of

1 is characterized by

the

two

F.1.1)

or\342\200\224for

matter\342\200\224any

form
cx\\k')\\k\")

+ c2\\k\\\k')")

F.1.3)

lead to an identical set of eigenvalueswhen measurementis performed. This is known as exchangedegeneracy.Exchangedegeneracypresentsa difficulty unlike the singleparticle case,a specificationof the eigenvalueof a because, set d complete of observablesoesnot completelydetermine the state ket.The is quite ingenious. But before proceeding way nature avoids this difficulty
further,

We

let us develop the mathematicsof permutation symmetry. define the permutation operator Pl2 by
Pl2\\k')\\k\")

= \\k\\\k>).")

F.1.4)

Clearly,
P21= P12 and

/>?=!.

F.1.5)

6.1. Permutation
having k\"

Symmetry

359

Under P12, article 1 having p

interchanging 1and 2. In practicewe often encounter an observablethat has particle labels. Forexamplein for a two-electronsystem, Sx (S2)standsfor the spin of particle1B). For simplicity we considera specificcase where operator the two-particle state ket is completely specified by the eigenvaluesof a A singleobservable for each of the particles:

becomes particle 2 having

k' becomesparticle 1 having

k'.In other words,it has the effectof

k\"\\

particle 2

Si^

Ax\\a')\\a\")

= a'\\a')\\a\") = a\"\\a')\\a\9")

F.1.6a)

and
A2\\a')\\a\") A denote the particle labels,and Ax and A2 are A observables for particles1 and 2, respectively.Applying Pl2 to we both sidesof F.1.6a),have

F.1.6b

where the subscriptson
thus

the

= PnAipi2l\\*\\\a')") = a'lOl*')-F-1/7)
This is consistentwith

F.1.6b) if only
pnAipnl = A2-

F.1.8)

m such particles.The observables, as momentum and position operators, ust necessarily appear symmetrically in the Hamiltonian\342\200\224for example,

It follows that Pl2 must change the particle labelsof observables. Let us now considerthe Hamiltonian of a system of two identical

F.1.9
Herewe have separatedthe
mutual interaction between the two particles from their interaction with some other external potential. Clearly, we have

pnHPn=H

F.1.10 F.1.5).

for H made up of observables for two identical particles.BecausePl2 we can say that P12 is a constant of the motion. The commutes with It therefore of Pl2 allowedare +1and becauseof eigenvalues follows that if the two-particle state ket is symmetric (antisymmetric) to start with, it remains so at all times. If we insist on eigenketsof P12, two particular linear combinations are selected:

i/,

-1

\\k'k\+m\302\261r(\\k')\\k\")+\\k\")\\k')),")

F.1.11a

360

Identical

Particles

and
\\k'k\_") We

=

j={\\k')\\k\-\\k\")\\k>)).

F.1.11b

s S12 Ml + Pn), A12 i(l Pn)If we apply Sl2(Al2) an arbitrary linear combination of \\k')\\k\ to and \\k\\\k'),") the resulting ket is necessarily symmetric (antisymmetric). This can easily be seenas follows:

can define the symmetrizer and antisymmetrizer

- -

as follows:

F.1.13
can to Our consideration be extended a system made up of many identical We define particles.

= \\k')\\k\>-\\kJ)\\kl+l)--\\k1).... F.1.14
Clearly, P* = \\

F.1.15
Pt

just as before, and the allowed eigenvaluesof
important to note, however,that
in

are

+1 and

\342\200\2241.

It

is

general

[PiJtPkl]*0.
\\k')\\k\\\k'\")")

F.1.16

It is worth explicitly working out a system of three identical particles. = kets of form there are 3! 6 possible First,

F.1.17

where

and k'\" are all different. Thus there is sixfold exchange that the state be totally symmetrical or totally antisymmetrical, we can form only one linear combination each. xplicitly, E we have
k\\

k\",

Y degeneracy. et if we insist

\\k'k\"k'\" >

\302\261

= -p{\\k')\\k\\\k'\"")
v6

>

\302\261

\\k\\\k')\\k'\"

\\k\\\k'\")\\k')\302\261\\k'\")\\k\")\\k') \\k'\\\k')\\k\")\302\261\\k')\\k'\")\\k\")}.")

F.1.18

We Theseare both simultaneouseigenketsof P12, P2^ and P13. remarked

6.2.Symmetrization
that

Postulate

361

there are altogether six independent state kets.It thereforefollowsthat there are four independent kets that are neither totally symmetrical nor totally antisymmetrical. We could also introduce the operator P123 by

defining

= P173(\\k')\\k\\\k'\")\\k\\\k'\")\\k').")
Note that Pl23= PuPn because

F-1.19)

F.1.20)
In writing F.1.18)assumed we that k\\ k\", and k'\" are all different. If two of the three indicescoincide,it is impossibleto have a totally antisymmetrical state.The totally symmetrical state is given by -I-

F.1.21)
where the normalization factor is understood to be cases e have a normalization factor w
more-general

For y2!/3!. more-gen-

1
2Nl

\"
>

F-1-22)
the number of times |/c(l))

where TV is the total number of particles and

occurs.

Nt

6,2, YMMETRIZATIONOSTULATE S P
nature takes advantage of totally symmetrical or totally antisymmetrical states. It turns out that systems containing TV identical particles are either totally symmetrical under the interchange of any pair, in which case the particles are said to satisfy Bose-Einstein (B-E)statistics, hence known as bosons,or totally antisymin which case the particles are said to satisfy Fermi-Dirac (F-D) known as fermions.Thus statistics,hence
antisymmetrical,

So far we have not discussedwhether

Pjj\\N Pij\\N

identicalbosons)= + \\N identical bosons) identical fermions) =
\342\200\224

|iV

identical fermions),

F.2.1a) F.2.1b)

where Ptj is the permutation operator that interchangesthe / th and the th particle, with i and arbitrary. It is an empirical fact that a mixed
symmetry

does not occur.

j

j

362

Identical Particles

Even more remarkableis that there is a connectionbetween the of a particle and the statistics obeyedby it:

spin

Half-integerspin particles are fermions; Integer spin particles are bosons.

F.2.2a) F.2.2b)
7r\302\261,7T\302\260

f Hereparticlescan be composite;or example, a 3He nucleus is a fermion just as the e~ or the proton; a 4He nucleus is a bosonjust as the

meson.

This spin-statisticsonnectionis, as far as we know, an exact law of c with no known I exceptions. n the framework of nonrelativistic quantum mechanics, this principle must be acceptedas an empirical posIn the relativistic quantum theory, however, it can be proved that postulate. half-integer spin particles cannot be bosons and integer spin particles cannot be fermions. An immediate consequence f the electron being a fermion is that o the electron must satisfy the Pauli exclusionprinciple,which states that no two electronscan occupy the same state. This follows becausea state like for s \\k')\\k') is necessarilyymmetrical, which is not possible a fermion.As is well known, the Pauli exclusionprinciple is the cornerstone of atomic and molecular physicsas well as the wholeof chemistry. To illustrate the dramatic differencesbetween fermions and bosons, let us considertwo particles, each of which can occupy only two states, characterized by k' and k\". For a system of two fermions, we have no there choice; is only one possibility: nature

Forbosonsthere are three states possible:
jjr(\\k')\\k\+\\k\")\\k')).")
In contrast, for \"classical\" articles satisfying Maxwell-Boltzmann (M-B) p statisticswith no restrictionon symmetry, we have altogether four indepenstates:
independent

F.2.4)

\\k')\\k\,")

\\k\\\k'),") in

\\k')\\k'),

\\k\\\k\").")

F.2.5)

for the fermion caseit is impossible both particles to the same state. In the bosoncase,for two out of the three allowed occupy kets, both particlesoccupy the same state. In the classical M-B)statistics ( b case, oth particlesoccupy the same state for two out of the four allowed kets. In this sensefermions are the least sociable;hey avoid each other to t make sure that they are not in the same state; in contrast, bosonsare the most sociable,they really love to be in the same state, even more so than
We

seethat

classical articlesobeying M-Bstatistics. p

6.3.Two-Electron

System

363

The differencebetweenfermionsand bosonsshow up most dramatiat low temperatures; a system made up of bosons,such as liquid 4He, exhibits a tendency for all particles to get down to the same ground state at
dramatically

c extremelylow temperatures.This is known as Bose-Einsteinondensation,a feature not sharedby a system made up of fermions.

6.3. WO-ELECTRON SYSTEM T
Let us now considerspecificallya two-electron system. The eigenvalueof the permutation operator is necessarily Supposethe basekets we use may be specified xl9 x2,msl, and ms2, where msl and ms2 stand for the by spin-magnetic quantum numbers of electron 1 and electron 2, respectively. We can expressthe wave function for a two-electron system as a of linear combination of the state ket with eigenbras xl5 x2, msl, and ms2 as follows:
\342\200\2241.

^= E TiC(msl9ms2)(xl9rnsl;x29ms2\\a).
If the Hamiltonian commuteswith

F.3.1)

?
be an eigenfunctionof S?oV and

[St2ot,//]=0,
then the energy eigenfunctionis expected to if is written as
\\p

F.3.2)

F.3.3)
triplet (symmetrical)

then the

to spin function x is expected be one of the following: /X+

\342\200\224

v2

(x+--\"X-+)

singlet (antisymmetrical),

~~ where x+- corresponds to mS2 = 2)- Notice that the triplet functions are all symmetrical; this is reasonablebecausethe ladder spin operatorSx_ + 52_ commuteswith Pl2 and the |+ + ) state is even under

F.3.4)

x^si^h

)|

We

note

2?m^x^ msl\\a). Fermi-Dirac statistics thus requires = <x2,m52;xl9msl\\a). x, m5l;x2, ms2\\a)

F.3.5)

-

F.3.6)

364

Identical

Particles

Clearly, Pl2 can be written as where p^Pace)just interchanges the position coordinate, while P$m) just interchanges the spin states.It is amusing that we can expressP$m) as

F.3.7)

F.3.8)
which follows because
h2

a

(triplet)

2= -3h2
{
\342\200\224\342\200\224

F.3.9)

(singlet)

It follows from

that F.3.3)

letting

\\a)->Pl2\\a)
amounts to

F.3.10

<J)(x1,x2)-><i)(x2,x1), F.3.11 x{rnsl,ms2)-^x{rns2,msl).
This together with F.3.6) implies that if the spacepart of the wave function is symmetrical (antisymmetrical) the spin part must be antisymmetrical (symmetrical).As a result, the spin triplet state has to be combined with an antisymmetrical space function and the spin singlet state has to be comwith a spacesymmetrical function. The space part of the wave function <J>(x1,x2) provides the usual probabilisticinterpretation. The probability for finding electron 1 in a volume element d3xx centered around xx and electron 2 in a volume element d3x2 is
combined

\\<f>(xl9x2)\\2d3x1d3x2.

F.3.12

To seethe meaning of this more closely, let us considerthe specific case where the mutual interaction between the two electrons [for example, t can x2|),S1-S2]be ignored.If there is no spin dependence,he VpaiT(\\x1 wave equation for the energyeigenfunction $ [seeF.1.9)],
\342\200\224

-h2 ,
1m

h

F.3.13

is now separable.We have a solution of the form co/1(x1)co5(x2) the times spin function. With no spin dependenceS2ot necessarily(and trivially) commutes with //, so the spin part must be a triplet or a singlet, which have definite symmetry propertiesunder Pffim\\ The space part must then be
written

as a symmetrical and antisymmetrical

combinationof co/i(x1)co5(x2)

6.3.Two-Electron

System

365

and coA(x2)oiB(xl):

i)]

F.3.14)

where the upper sign is for a spin singlet and the lower is for a spin triplet. The probability of observingelectron 1in d3xx around xx and electron2 in d3x2 around x2 is given by

d3xxd3x2. \302\2612Re[co/4(x1)co5(x2)co*(x2)co*(x1)]} The last term in the curly bracket is known as the exchangedensity. We immediately seethat when the electrons are in a spin-triplet the probability of finding the secondelectron at the same point in state, space vanishes. Put another way, the electrons tend to avoid each other when their spins are in a triplet state.In contrast, when their spinsare in a singlet state, there is enhancedprobability of finding them at the same point in spacebecause the presence the exchangedensity. of of the question of identity is important only when the exchange Clearly, density is nonnegligible or when there is substantial overlap between function coA and function coB. To seethis point clearly, let us take the extreme case where |co^(x)|2where x may refer to xx or x2) is big only in ( A and \\coB(x)\\2 is big only in region B such that the two regions are region widely separated.Now choosed3xx in region A and d3x2 in region B; see The Figure 6.2. only important term then isjust the first term in F.3.15),

F.3.15

K(Xl)|2|<ofl(x2)|2,
which

F.3.16)

is nothing more than the joint probability density expectedfor classicalparticles. In this connection, recall that classicalparticles are well necessarily localizedand the question of identity simply doesnot arise. Thus the exchange-densityterm is unimportant if regions A and B do not overlap. There is no need to antisymmetrize if the electrons are far apart

FIGURE
\\o)B(x)\\2

6.2.

is large

Two widely separated regions A and B; in region B.

^(x)!2is large

in region A while

366

Identical

Particles

and the overlap is negligible.This is quite gratifying. We never have to billion electrons, about the question of antisymmetrization with 10 nor is it necessary take into account the antisymmetrization requirement to between an electron in LosAngelesand an electron in Beijing.
worry

6A THE HELIUMATOM
F of the helium atom is rewarding for severalreasons. irst of all, it is we simplestrealistic problem where the question of identity\342\200\224which in e an important role. econd, ven though it encountered Section S is a simplesystem, the two-particleSchrodingerequation cannot be solved analytically; therefore, this is a nice placeto illustrate the use of perturbatheory and also the use of the variational method. The basic Hamiltonian is given by
A study

the

6.3\342\200\224plays

perturbation

2m

2m

rx
\342\200\224x2|;

r2

ru

= |x2|,and r12^ |xx where seeFigure 6.3. upposethe S e2/ri2\"termwere absent.Then, with the identity question ignored, the wave function would be just the product of two hydrogen atom wave functions with Z = 1changed into Z = 2. The total spin is a constant of the motion, so the spin state is either singlet or triplet. The spacepart of the wave function for the important casewhereone of the electrons is in the ground state and the other in an excited state characterizedby (nlm) is

r^lxj,

a*2

where the upper (lower) sign is for the spin singlet (triplet).We will come back to this general form for an excitedstate later. For the ground state, we need a specialtreatment. Herethe conis characterized by (IsJ,that is, both electronsin n =1,/ = 0. configuration

Electron 1 Electron 2

x2 Nucleusof charge + 2lel
Schematic diagram of the helium atom.

FIGURE

6.3.

6.4.The

Helium

Atom

367

The space function must then necessarilybe symmetric and singlet function is allowed.So we have

only

the spin

^
ITflg

F-4.3)
wave
function

with

Z

= 2.Not surprisingly,

this

\"

unperturbed\"

gives

= 2X4
for the ground-state energy, which
experimental

2a0)

F.4.4)

obtaining

is about 30%bigger than the experimenvalue. in This is just the starting point of our investigation because obtainwe the above form F.4.3), have completely ignored the last term in O that F.4.1) describesthe interactionbetween the two electrons. ne way to the problem of obtaining a better energy value is to apply approach as first-order perturbation theory using F.4.3) the unperturbed wave funcand e2/r12 the perturbation. We obtain as
function

^V

F-4.5)

To carry out the indicated integration we first note

l+

=
r22
\342\200\224

oo

/

y 2r1r2cos

E -^P/tcosy), F.4.6) i = o r>

where r> (r<) is the larger(smaller)of rx and r2 and y is the angle between integration is easily performed by expressing xx and x2. The angular P7(cosy)in terms of Ylm{Bl, (f>x) and Yjn(Q1, <J>2) using the addition theorem of sphericalharmonics:
Arrr

m

^- yrVx^^r^i^i)=
/

l

F.4.7)

The angular integration is now trivial:

1
477

(Air)8l(fim0.

F.4.8)

it The radial integration is elementary(but involves tedious algebra!); leads

to
r\\
A%

2

\"'2

\342\200\242/,

128 z5'

F.4.9)

368

Identical

Particles

Combining everything,

we have (for Z = 2)
it

ao I

128

a0

2a
Adding this

F.4.10)

energy shift to

we F.4.4), have

8+fI 2a0 = -74.8eV. 2 o~
I

F.4.11)

Comparethis

with

the experimentalvalue,

?exp=-78.8eV.

F.4.12)

This is not bad, but we can do better! We propose to use the variational method with Z, which we call Zeff, as a variational parameter. The physical reasonfor this choices that the effectiveZ seenby one of the i electronsis smaller than 2 becausethe positive charge of 2 units at the by origin (seeFigure 6.3)is \"screened\" the negatively charged cloud of in the other electron; other words, the other electron tends to neutralize the F positive charge due to the helium nucleus at the center. or the normalized trial function we use

= <Xl,x2p>
From
this

Z3

F.4.13)
+ 0
0

we obtain
2 2

H=

0

2m

2m

L

0\\- 0 Ze1 Ze10
(
g
~2\\

12

a of H is at

F.4.14)

We easily seethat the minimization

F.4.15)
This is smaller than

2,as anticipated.Usingthis = -77.5 eV,

value for Zeff we get

F.4.16)

is already very close considering the crudenessof the trial wave function. Historically, this achievement was consideredto be one of the earliestsignsthat Schrodinger's mechanicswas on the right track. We wave
which

6.4.The Helium

Atom

359

FIGURE atom.

100 6.4.
\"I\"

^1J
Cnlm

Singlet
Triplet

Schematic diagram for the energy-level

splittings

of

(ls)(nl) for

the helium

cannot get this kind of number by the purely algebraic (operator)method. The helium calculationwas first doneby A. Unsoldin 1927.* Let us briefly considerexcitedstates.This is more interesting from the point of view of illustrating quantum-mechanicaleffectsdue to identity. We consider We write the energy of this state as just
(Is)(\302\253/).

E = ?100 Enlm + A?. +
expectation

F.4.17

In first-order perturbation theory, A? value of We can write

e2/rl2.

is obtained by evaluating the expec-

rl2

F.4.18

where / and known respectivelyas the direct integral and the exchange integral, are given by

/,

\342\200\224,

12

F.4.19a

F.4.19b
Figure 6.4. The physical interpretation for this is as follows: In the singlet case the space function is symmetric and the electrons have a tendency to come closeto each other. Therefore, the effect of the electrostatic repulsion is more serious; ence, higher energy results.In the triplet case,he space a h t function is antisymmetric and the electrons tend to avoid each other. Helium in spin-singletstates is known as parahelium, while helium in spin-tripletstates is known as orthohelium. Each configuration splits into
A. Unsold, Ann. Phys.

The upper(lower)sign goeswith the spinsinglet (triplet) state.Obviously,/ is positive; we can alsoshow that J is positive.Sothe net result is such that for the same configuration, the spin singlet state lies higher, as shown in

82A927) 355.

370

Identical

Particles

S)Bp)

^
\"

Para
ortho 3P2,i,o

s)Bs)

para 1So
ortho

3Si

2

Spin singlet, necessarily\"para1
FIGURE atom.

ii

6.5.

Schematic energy level diagram

for low-lying

configurations

of the helium

the para state and the ortho state, the para state lying higher. For the ground state only parahelium is possible.SeeFigure 6.5for a schematic energy level diagram of the helium atom. It is very important to recall that the original Hamiltonian is b spin-independent ecausethe potential is made up of just three Coulomb terms.There was no S1#S2-term whatsoever.Yet there is a spin-dependent
effect\342\200\224the

from

electronswith parallel spins have a lower arises statistics. Fermi-Dirac of This explanation of the apparent spin dependence the helium The atom energy levels is due to Heisenberg. physical origin of ferromagdisof the electron spins extendedover microscopic netism\342\200\224alignment also believed to be essentially the same, but the propertiesof
energy\342\200\224that
distances\342\200\224is

ferromagnets are much harder to calculate quantitatively

from first

princi-

principles.

SYMMETRYAND 6.5. ERMUTATION P
In

TABLEAUX YOUNG

keeping track of the requirement imposedby permutation symmetry, there is an extremely convenient bookkeeping technique known as Young a tableaux, after A. Young, an English clergyman who published fundamenThis paper on this subject in 1901. section is meant to be an introduction to Young tableaux for the practical-mindedreader. do not necessarily We presentall derivations; this is one of those caseswhere the rules are simpler than the derivations. To illustrate the basic techniques involved, we consideronceagain the spin states of a two-electron system. We have three symmetric states to orientationsof the spin-triplet state and corresponding the three possible an antisymmetric state corresponding the spin singlet. The spin state of to an individual electron is to be represented a box. e use 1 for spin up W by
fundamental

6.5.Permutation
and |_2jfor
A

Symmetry

and Young Tableaux

371

tableau,CD, and an antisymmetric tableau, states of a two-electron system, ED is the Young tableau for a spin triplet, while R is the Young tableau for a spin R singlet. eturning now to jJLj and |_2j,we can build up the three-tripletstates as follows:
We define a symmetric When applied to the spin

spin down. These boxesare the basicprimitive objectsof SUB). a singlebox represents doublet.

11 12
2 2
We
symmetry

F.5.1)

when we put boxes do not consider 2 1 because symmehorizontally, is understood.So we deducean important rule: Doublecounting is avoided if we require that the number (label)not decrease going from the

left to the right. As for the antisymmetric

spin-singletstate,

F.5.2)
is the only symmetric

C possibility. learly

requirement of antisymmetry;

state.Furthermore,

m is discardedto avoid doublecounting.To
1

becauseof the are impossible for a vertical tableau we cannot have a
and

1

eliminate the unwanted symmetry states,we therefore requirethe number (label)to increaseas we go down. We take the following to be the general rule. In drawing Young tableau, going from left to right the number cannot decrease; going down the number must increase. deducedthis rule by considering the spin We states of two electrons, ut we can show this rule to be applicable the b to construction of any tableau. Considernow three electrons. e can construct totally symmetric W
spin

statesby the

following

rule:

111 112 12 2
2 2 2

F.5.3)

This method gives four states altogether. This is just the multiplicity of the = 2 state, which is obviously symmetric as seenfrom the m = f case, where all three spins are aligned in the positive z-direction. What about the totally antisymmetric states? We may try vertical tableau like

1 1 1

or

1

2 2

372

Identical

Particles

But these are illegal, becausethe numbers must increaseas we go down. for This is not surprising becausetotal antisymmetry is impossible spin states of three electrons;quite generally, a necessary (but, of course,not sufficient) condition for total antisymmetry is that every state must be we different. In fact, in SUB) cannot have three boxesin a vertical column. We now define a mixed symmetry tableau that lookslike this: Such a tableau can be visualized as either a single box attached to a or symmetric tableau [as in Equation F.5.4a)] a single box attached to an antisymmetric tableau [as in Equation F.5.4b)].
_

I

.
1

F.5.4a)
I
1

m

F.5.4b)

i If the spin function for three electronss symmetric in two of the to neither of them can be antisymmetric with respect a third index. indices, For example,
satisfies symmetry under 1 2,but it is neither symmetric nor antisymto with respect 1 3 (or2 3).We may try to enforce antisymmetry with 1 and 3 under 1 3 by subtracting the same thing from F.5.5)
<-\302\273

antisymmetric

<-\302\273

<-\302\273

\302\253\302\246\302\273

interchanged:
/2
~~

/3 \"~

+ /31 /

/2

\"\"

/3 \"~

/3

+/

F.5.6)

This satisfies antisymmetry under 1<-> 3, but we no longer have the original the dimensionality of -^ is 2;that is, symmetry under 1<-> 2.In any case = j).We can seethis by noting that such a tableau it represents doublet (j a to and a corresponds the angular momentum addition of a spin doublet spin triplet ( OH ). We have used up the totally symmetric quartet so the remainder must be a doublet.Alternatively, we may attach a doublet the ) to a singlet ( pj ) as in F.5.4b); net product is obviously a doublet. So no matter how we considert, must represent doublet. But this is a i in what the rule gives.If the number cannot decrease the horizonprecisely direction and must increase the vertical direction, the only possibilities in are

(?)

\342\200\224'

horizontal

and

F.5.7)
must

Because there are only two possibilities, Noticethat we do not consider

to correspond a doublet.

6.5.Permutation

Symmetry

and Young Tableaux

373

addition

s We can considerClebsch-Gordaneriesor as follows:

angular-momentum

ad-

Bx2= 3 + 1) Cx2= 4 + 2) F.5.8)

1 = (Note: is impossible; x2 2.)
We now extend our consideration to three primitive objects. box A can assumethree possibilities:
\342\200\242 \342\200\242

1

2

3

F.5.9)
77\302\260,

The labels 2, and 3 may stand for the magnetic quantum numbers of <n~, or the u, /?-orbitalsin atomic physicsor charge states of the pion 77+, and s quarks in the SUC)classificationof elementary particles.We d, assume that the rule we inferred using two primitive objects can be generalized and work out such conceptsas the dimensionality; we then

1,

checkto seewhether
1 1

everything

is reasonable.

3 :dimensionality 3 1
dimensionality

3

(in

3 SUC)* is
from

used to distinguish
Antisymmetry
\342\200\242 \342\200\242

.)

\\

1 2 3

only one

(Totally antisymmetrical.)

F.5.10)
1 1
Symmetry

12

1 3

2 2 1 1 3 2 2 3 1 3 2 2 3 3

2 3 12 2 2 3 3 1 1 3

3 3 : dimensionality 6 12 3 3 3 3 : dimensionality

1 1 1 1 33 1 1 2
\342\200\242 \342\200\242

1 1 2 2 22 12 2 2 2 3

10

1 2 3

Mixed symmetry

|

13 3

>: dimensionality

8

374

Identical

Particles

to Thesetableaux correspond representationsof SUC). in Xx boxes first row X 2 boxes second in row X 3 boxes third row in

For the purposeof figuring the dimensionality,
\342\200\242

it

is legitimate to strike

F.5.11
out

t

\342\200\242

\342\200\242 \342\200\242\342\200\242

F.5.12)

\342\200\242\342\200\242\342\200\242

a \"singlet\" at the left-hand sideof
to

be

We F.5.11).can show the dimensionality

l9

A2,

@.3.13

where p = Xx
In the

7=1state.

and q = A2 ~~ t SUC)language,a tableau correspondso a definite irreducible of SUC). n the other hand, when each boxis interpreted to O representation to mean a = 1 object,then a tableau does not correspond an irreducible of the rotation group. Let us discussthis point more specifirepresentation a w We start with putting together two boxes, hereeach box represents
\342\200\224

X2

j

specifically.

_ _

Cx3= 6 + 3)

F.5.14

The horizontal tableau has six states;the tableau is to be broken down into 7 = 2 (multiplicity 5) and 7 = 0 (multiplicity 1),both of which are symmettensor out In fact this is just how we construct a symmetric second-rank to of two vectors. The vertical tableau fl corresponds an antisymmetric 7=1state behaving like a X b. To work out the addition of three angular momenta with j\\ = j2 = j3 = let us first figure out
symmetric.

1,

+ Fx3= 10 8)

= Cx3 8+1)

F.5.15

To see how breaks down, we note that it must contain 7 = 3. + this is not the only totally symmetric state; a(b*c)+b(c#a) c(a#b) However, is also totally symmetric, and this has the transformation property of 7=1. Sorm contains both 7 = 3 (seven states) and 7=1(three states).As for -^ with eight possibilities ltogether, the argument is more involved, but a we note that this 8 cannot be broken into 7+1 because 7 is totally symmetric, while 1is totally antisymmetric when we know that 8 is of mixed other words 7 = 2 symmetry. So the only other possibility is 8 = 5 + and 7=1.
3\342\200\224in

6.5.Permutation

Symmetry

and Young Tableaux

375

Finally, therefore, we must have

3X3 X3 =
In terms of angular-momentum 7) 7 = 3 (dimension once

10
7+3
T

8
5+3
T

8
5+3
T

+1

F.5.16)

states, we have
(totally symmetric)

5) 7 = 2 (dimension twice 3) 7=1(dimension

(both mixed symmetry)

three times (one totally symmetric, two mixed symmetry) 1) (totally antisymmetric) 7 = 0 (dimension once

F.5.17)

t That the 7 = 0 state is unique correspondso the fact that the only product which is necessarily of a, b, and c invariant under rotation is a-(bxc), We can also look at the 7=1 states using the tensor antisymmetric. approach.We have three independent vectorsconstructed from a, b, and c: F a a(b*c),b(c*a), nd c(a*b). rom these we can construct only one totally combination, symmetric

+ a(b-c)+b(c-a)c(a-b).
We

F.5.18

can apply this consideration to the BpKconfiguration of the There are alnitrogen atom, N (Z=7, shell structure (lsJBsJBpK).
altogether

The space function have /tot = 3, is it because must be combined with a totally antisymmetactually impossible spin function. Remember
antisymmetric

6* 6-5-4 \" 3!3! 3-2 = 20 states. behaving like rm, which would

F.5.19

where each box standsfor spin up or down, is impossibleor spin states of f In three electrons. contrast the totally antisymmetric spacefunction

with

= 0 is perfectly allowableif combinedwith a totally symmetric spin /tot function which has total spin angular momentum \\; we have 4S3/2 for this configuration. The mixed-symmetry spacefunction ^p (/tot = must be combined with a mixed-symmetry spin function, necessarilya spin doublet So we have 2D5/23/2and ^3/2,1/2- counting of states The

rm,

2,1)

[p.

376

Identical

Particles

leads to the following:
7=2

=i y

6 states

J; = 1

i

4x3states
\342\200\224

2 states 20 states

F.5.20)

This agreeswith the other way of counting. H Finally, we consider pplicationsto elementaryparticle physics. ere a we apply SUC)considerationsto the nonrelativisticquark model, where the primitive objects are w, d, s (up, down, and strange, where up and down refer to isospin up and isospin down). A box can now stand for w, d, or s. We look at the decuplet epresentation rrn A0): r
+'Of

dddudduuduuu ddls wds ww5

I=

\302\247,

F.5.21

sss
where / stands for isospin. Now all ten states are

known to be spin \\ objects. is safe to It assumethat the spacepart is in a relative S-state for low-lying states of three quarks.We expecttotal symmetry in the spin degreeof freedom.For instance, the j = \\, m = \\ state of A can be visualized to have quark spins all aligned. But the quarks are spin \\ objects;we expect total antisymmetry because f Fermi-Dirac o statistics. et Y

Quark label(now called flavor): symmetric

Spin:

symmetric symmetric

F.5.22)

Space:
for the
this

becauseother aspectsof the nonrelativisticquark model were embarrassing so successful. The way out of this dilemma is to postulate that there is actually an additional degree freedom called color (red, blue, or yellow) and posof

the j = \\ decuplet.But as is evident from F.5.22), total symmetry in case even! This led to the \"statisticsparadox,\"which was especially is

Problems

377

J= j+ statesconsidered are color singlets here) 1 + +

tulate

that

the observed hadrons (strongly interacting

particles,including

(|RBY> |BRY> |BYR> |YBR> |YRB>

-

-

-

|RYB\302\273.

F.5.23)

This is in completeanalogy with the unique

The a totally antisymmetric combinationin color space. statistics of F.5.10), problemis now solved because

p =

p(flavor)

p(spin)

p(space) (color) p

/? 5 24)

this is a cheap way to get out of the dilemma. other piecesof evidencein favor of color, such Fortunately, there were also and the crosssection for electron-positronannihilaas the decayrate of into hadrons.In fact, this is a very good example of how attempts to overcome difficulties lead to nontrivial prediction of color.
77\302\260 annihilation

One might argue that

PROBLEMS
to \\ particles are subjected a one-dimensionalsimple harmonic oscillator potential. What is the ground-stateenergy?What is the Fermi energy? b. What are the ground state and Fermi energiesf we ignore the mutual i interactions and assume N to be very large? 2. It is obvious that two nonidenticalspinl particleswith no orbital angular momenta (that is, s-statesfor both) can form y = 0, y=l, and y = 2. Suppose,however, that the two particlesare identical.What restrictions do we get? 3.Discusswhat would happen to the energy levelsof a helium atom if the electron were a spinless boson.Beas quantitative as you can. 4. Three spin 0 particles are situated at the corners of an equilateral triangle. Let us define the z-axis to go through the center and in the direction normal to the plane of the triangle. The whole system is free to rotate about the z-axis. singstatistics considerations, obtain restrictions U on the magnetic quantum numbers corresponding to

1.a. N identical spin

/.

378

Identical

Particles

5. Considerthree weakly interacting, identical spin 1particles. a. Supposethe spacepart of the state vector is known to be symmetric

under interchange of any pair.Usingnotation | + )|0)|+for particle ) 1in ms = +1,particle 2 in ms = 0, particle 3 in ms = +1,and so on, construct the normalizedspin states in the following three cases: (i) All three of them in |+ (ii) Two of them in |+), one in |0). (iii) All three in different spin states. What is the total spin in each case? b. Attempt to do the same problem when the spacepart is antisymmetric under interchange of any pair. 6. Supposethe electron were a spin particle obeying Fermi-Dirac statisWrite the configuration of a hypotheticalNe (Z = 10)atom made up of such \"electrons\" Show that [that is, the analog of (lsJBsJBpN]. the configuration is highly degenerate. hat is the ground state (the W lowest term) of the hypothetical Ne atom in spectroscopic notation where S, L, and stand for the total spin, the total orbital B5+1L7, when angular momentum, and the total angular momentum, respectively) exchange splitting and spin-orbit splitting are taken into account? 7. Two identical spin \\ fermions move in one dimension under the ininfluence of the infinite-wall potential V= oc for x < 0, x > L, and V= 0 for 0 < x < L. a. Write the ground-state wave function and the ground-state energy when the two particles are constrained to a triplet spin state (ortho

).

\302\247

statistics.

/

b. Repeat (a)when

state).

c. Let us now supposethat
Assuming

are in a singlet spin state (para state). the two particles interact mutually via a very short-range attractive potential that can be approximated by
they

V=-\\8(xl-x2)(A>0).
that perturbation theory is valid even with such a singular potential, discuss semiquantitatively what happensto the energy levels obtained in (a) and (b).

CHAPTER7

Theory Scattering

This last chapter of the book is devoted to the theory of scattering and, more generally, collision processes.is impossible overemphasizethe It to of this subject. importance

7.1. HE LIPPMANN-SCHWINGER T EQUATION
We We begin with a time-independentformulation of scattering processes. assume that the Hamiltonian can be written as

+ H=H0 V
where Ho stands for the kinetic-energyoperator

G.1.1

In the would
scattering

absenceof a scatterer, V would be zero, and an energy eigenstate of be just a free particle state |p).The presence V causesthe energy eigenstate to be different from a free-particlestate.However,if the scatterare interested is, no change in processis to be
elastic\342\200\224that energy\342\200\224we

in

obtaining a solution to the full-Hamiltonian Schrodingerequation with be the energyeigenket l the same energy eigenvalue.More specifically,et
\\<f>)

379

380

Scattering

Theory

of

Ho:

G.1.3)
(We

use |<f>) here rather than |p) becausewe may later be interested in wave rather than plane-wavestates; may stand for either.) free-spherical The basicSchrodingerquation we wish to solve is e
\\<f>)

G.1.4)
Both Ho and Ho + V exhibit continuous energy spectra.We look for a solution to G.1.4) that, as F-> we have |\\//) -> |<J>),where |<J>) is the such 0, with solution to the free-particle Schrodingerequation [G.1.3)] the same energy eigenvalue. It may be argued that the desiredsolution is

It/

~F

t - Ho M r / ~M9/>
7F~

1

^/.l.jj

apart from complications arising from the singular nature of the operator 1/(E Ho).We can seethis by noting that E Ho applied to G.1.5 is The immediately gives the correct equation, G.1.4). presenceof reasonable because must reduceto as V vanishes.However,without prescriptionsfor dealing with a singular operator, an equation of type has G.1.5) no meaning.The trick we usedin time-independentperturbation the complimentary projection operator, and so on (see theory\342\200\224inserting Section not work well here becauseboth |<f>) and exhibit continuous eigenvalues. Instead, this time the solution is specified by
\\<j>)

-

-

\\\\p)

\\<f>)

5.1)\342\200\224does

\\\\p)

making

E

slightly

complex:

Edistances.

Ho\302\261

ie

G.1.6)
(x|\\//(\302\261))

This is known as the Lippmann-Schwinger equation. The physical meaning of + is to be discussedin a moment by looking at at large The Lippmann-Schwinger quation is a ket equation independentof e We particular representations. now confine ourselves to the position basis by multiplying (x| from the left. Thus

E-

Ho\302\261

ie

This is an integral equation for scattering becausethe unknown ket appears under an integral sign.If |<J>) stands for a plane-wave state with momentum p, we can write 3/2

7.1. he Lippmann-Schwinger T

Equation

381

is, [Editor'sNote:In contrast to bound states, the plane-wave state G.1.8) of course, normalizable and not really a vector in Hilbertspace. not Dealing with such statesis oneof the inconveniencesof time-independent scattering is theory. The \"normalization\" in G.1.8)such that = j</3jt<p'|x><x|p> 8C)(p

- p').
is written
ie

G.1.9)]
using

If, on the other hand, the Lippman-Schwinger equation the momentum basis, we obtain
<p We

=

<pl<t>>

+

1 - (pz/2m) E

\302\261

G.1.10

shall come 7.2. back to this equation in Section Let us considerspecificallythe positionbasisand work with G.1.7) To make any progresswe must first evaluate the kernel of the integral equation defined by
h2

E
We

i - Ho
x
\342\200\224

\302\261

ie

G.1.11

claim that

G\302\261(x,

x') is given by
G\302\261(x,

x') =
h

-

\302\261ik\\x-x'

x

G.1.12

where E
2m

= h21^l2m. show this, To
E

we evaluate

as follows: G.1.11)

-1

\302\261

ie

x' =

2m -

d3p'

x p E
where Ho acts on <p' Now use

1 - (p'2/2m)

\302\261

ie

.

G.1.13
1
Jf
\302\261

E

- (p'2/2m)
p') =

ie
372

sC)(p' p\ E (p'72m) ie

-

-

\302\261

(x

'

<P\"

G.1.14

The right-hand side of
2m

becomes G.1.13)
*

[E (p'2/2m) ie]
\302\261

-

G.1.15

382

Scattering Theory

Now write E = h2k2/2m and set pr= hq. Equation
f
d<f>
t I ?M \\

becomes G.1.15)
\342\200\224x'lcosfl

I'll^

W~t

I

\302\247s

/|q||x

J-i

kz-qz\302\261ie

i\\x-x'\\'-co
e
477 'x

q2
V

/!
\342\200\224x

.
that

G.1.16
the
integrand

In the last step we used the method of residues, oting n has polesin the complex g-plane at

=

\302\261k\302\261ie'.

G.1.17

The reader may recognize that G + is nothing for the Helmholtz equation,
( V72 Armed
-I-

more than Green's function
\342\200\224

k2\\(l

(v

v^ = ^^3)^v v^
in

/7 1 1fi\\ we G.1.12), can use

G.1.11)

with

the explicit form of G+ as to write Equation G.1.7) as

Equation

\342\200\224

x
Notice that the wave
written

lk\\\\

Xr|
\302\261}>.

47r|x-x|

G.1.19

of the scatterer is function (x|^(\302\261)) in the presence as the sum of the wave function for the incident wave (x|<f>) and a term that represents effectof scattering.As we will see the explicitly later, at of large distancesthe spatial dependence the second term is sufficiently provided that the potential is of finite range. This means that the t positive solution (negativesolution) correspondso the plane wave plus an outgoing (incoming) spherical wave. In most physical problemswe are interestedin the positive solution becauseit is difficult to preparea system satisfying the boundary condition appropriate for the negative solution. To seethe behavior of (x|^(\302\261)) more explicitly,let us considerthe where V is a local is, a potential diagonal in the specificcase Potentials that are functions only of the position operator x-representation. x belongto this category. In preciseterms V is said to be local if it can be written as
e\302\261lkr/r potential\342\200\224that

G.1.20

7.1. he Lippmann-Schwinger T
As

Equation

383

a result, we obtain

)) =

j

d3x\"(x'\\V\\x\(x\"\\xP(\302\261))

G.1.21
The integral equation G.1.19) simplifies as now

x

\342\200\224

G-1.22)

Let us attempt to understand the physics contained in this equation. The to towards the observationpoint at which vector x is understood be directed the wave function is evaluated.For a finite range potential, the region that In gives rise to a nonvanishing contribution is limited in space. scattering we are interested in studying the effectof the scatterer (that is, the processes finite range potential) at a point far outside the range of the potential. This is quite relevant from a practical point of view becausewe cannot put a O detectorat short distance near the scattering center. bservation is always made by a detectorplacedvery far away from the scatterer at r greatly larger than the range of the potential. In other words, we can safely set
|x|\302\273|x'|,

G.1.23)

as depictedin Figure 7.1. Introducing
r

= |x|

r'=lx'l
and a = z(x,x'), P

G.1.24)

G.1.25)
Observation point

k

=
point P is where the wave to the integral in Equation G.1.22) less than the range of the potential, as depicted by the shaded region of the figure.
\302\261

FIGURE function

7.1.Finite-range

is for

|x'|

(x\\\\p{

*) is to be evaluated,

scattering

potential. The

observation

while the contribution

384

Scattering Theory

we have for r

\302\273

r',
Ix
\342\200\224x'l

= vr2 2/r'cosar' +
\342\200\224

=r , 1
\342\200\224

r 2r'cosa+ /2 -

\\

1/2

G.1.26)

~ r vx
where
^^

G.1.27) k' representsthe
then x

Also define

k'=kr.
x. We
obtain
x|_

G.1.28
propagation

The motivation for this definition is that vector for waves reaching observationpoint
e\302\261iK\\x

e\302\261itcre+iK

for large r. It is legitimate to replace Furthermore, to by just rid of the /Ts in expressionsuch as 1/Bt7^K/2,t is convenient to use i s get |k) rather than |pz), where
\342\200\224xr|

l/|x

G.1.29)

1/r.

Because|k) is normalizedas
we have

k=^.
= 5C)(k-k/)
<x|k> = 3/2

G.1.30)

G.1.31

G.1.32

So,finally,

1 2m
4tt

elkr
\342\200\224

f

1 B*)3/2

ikr

G.1.33 /(k',k) iven by g
This form makes it very clear that we have the original plane wave in propagation direction k plus an outgoing spherical wave with amplitude

1 2m
4tt

\342\200\224

/k'*x'

3/2

G.1.34

7.1. he Lippmann-Schwinger T
Similarly,

Equation

385

correspondsto the original plane wave in propagation direction k plus an incoming sphericalwave with spatial dependence e~lkr/r and amplitude

we can readily show from

that and G.1.22) G.1.29) (x|i//(])

To obtain the differential cross sectiondvldil, we may considera large number of identicallypreparedparticlesall characterized by the wave function G.1.32). can then ask, what is the number of incident particles We to crossinga planeperpendicular the incident direction perunit areaper unit time? This is just proportional to the probability flux due to the first term on the right-hand side in we Likewise may ask, what is the number of scattered particles going into a small area da subtending a differential solid-angle d element Ct? Clearly, do number of particles scattered into dQ, per unit time unit area per unit time dSl number of incident particles crossing

-(I/477)B7rKBm//i2X-k'|F|i//-)>.
G.1.33).

__

Jincid

Hence the

differential

crosssection is

d2
Wave-Packet Description
formulation

do_

G.1.36)

The readermay wonderhere whether our time-independentformulaof scattering has anything to do with the motion of a particle being

(a)

(b)

FIGURE 7.2. (a) Incident wave packet approaching scattering center initially, (b) Incident wave packet continuing to move in the original direction plus spherical outgoing wave front (after a long time duration).

386

Scattering Theory

bouncedby a scattering center. The incident plane wave we have used is infinite in extent in both spaceand time. In a more realistic situation, we the that considera wave packet(a difficult subject!) approaches scattering

center.* After a long time we have both

the original wave packet moving in the original direction plus a sphericalwave front that moves outward, as in Figure 7.2.Actually the use of a plane wave is satisfactory as long as the dimension of the wave packet is much larger than the size of the scatterer

(orrange of V).

7.2.THE BORNAPPROXIMATION
is Equation G.1.34)still not directly useful in computing the differential for crosssectionbecausein the expression /(k',k)the unknown ket |^(+ )) If the effectof the scatterer is not very strong, we may infer that it appears. is not such a bad approximationto replace(x'|\\//(+)) (which appearsunder the integral sign) by is,
(x'|<f>)\342\200\224that

we Because treat the for We then obtain an approximateexpression potential V to first order, the approximate amplitude so obtained is known as the first-orderBorn amplitude and is denotedby /A):

/(k',k).

f^(k\\k) = ^^^jd3x'e^k-k/^V(x').
\342\200\224

G.2.2)

In other words,apart from the Bm/4iTh2), first-order amplitude is just the three-dimensionalFourier transform of the potential V with respectto q =k
\342\200\224k'.

For a

|k

\342\200\224k'|,

spherically symmetric potential, /A)(k',k)is a = given by (remember |k'| k by energyconservation) 6

function

of

sin;

G.2.3)

seeFigure 7.3. e W

can perform the angular integration explicitly to obtain

9ml
h

-

/ q Jo

rV(r)sinqrdr.

G.2.4)

*For a fuller account of the wave-packet approach, seeM. L. Goldberger and K. M. R Watson, Collision Theory, Chapter 3 (New York: John Wiley, 1964); . G.Newton, Scattering Theory of Waves and Particles, Chapter 6 (New York: McGraw-Hill, 1966).

7.2. The

Born Approximation

387

k'

FIGURE

7.3.

Scattering through angle

9, where

q=

k-k'.
Yukawa

An

example is now

in

order. Considerscattering by a

potential

V(r) =

fir

G.2.5)
\302\273

in where Vo is independent of r and 1/ju, corresponds, a certain sense,to the range of the potential. Notice that V goesto zero very rapidly for r 1/ju,. For this potential we obtain [from G.2.4)]

G.2.6)
where we have used
/\342\200\242OO

Im

G.2.7)
Noticealso that
q2 =

= 2k2 -cos0). 2k2(l

G.2.8)

the first Born approximation, the differential cross section for scattering by a Yukawa potential is given by

So, in

do

-cos

G.2.9)
fixed\342\200\224for

It is amusing to observehere that as /t -* 0, the Yukawa potential is reduced to the Coulomb potential, provided the ratio V0/n is the limiting process. seethat the first Born We example,to be differential cross sectionobtained in this manner becomes
ZZ'e2\342\200\224in

da\\

)~

BmJ(ZZ'e2J
h4

1

16A:4sin4@/2)

G.2.10)

388 Even the
h

Scattering Theory

if disappears

hk

s is identified as |p|, o

d?l I where

16

juke

sin4(9/2)

'

= \\p\\2/2m; this is preciselythe Rutherford scattering cross EKE sectionthat can be obtained classically. Coming back to G.2.4),the Born amplitude with a spherically
symmetric potential, there are several general remarks we can make if first Born amplitude, the corresponding

/(k/,k) can be approximated by

1.do/dQt,or /@), is a function
2A:2(l-cos0).
k

of q only; that is, fF) dependson the energy (h2k2/2m)and 6 only through the combination

4. Forsmall

2. fF) is always real. 3. do/dQ* is independent of the sign of V.
(q necessarilysmall),

5. f@) is small for large q due to rapid oscillationof the integrand.
Let us now discuss validity of the first-orderBorn approximation. the is clear from the derivation that if the Born approximation is to be + applicable, x|^( )) should not be too different from (x|<J>) insidethe range ( of is, in the region where V(x) is appreciable. therwise,it O is not legitimate to replace|^(+))by |<J>).In other words,the distortion of the incident wave must be small. Going back to the exact expression we G.1.22),note that the condition that (x|^(+)) be not too different from at the center of the scatteringpotential x ~ 0 is seento be (x|<J>)
It
potential\342\200\224that

involving

a volume integral independent of

0.

2m

1

f

d 3x,

Jkr e

1.
<\302\253

G.2.12)

We now considerwhat the specialcase the Yukawa potential in of is legitimate is, for small k (k may imply. At low to replaceelkr by So we must have

G.2.5)

1.

energies\342\200\224that

/x)\342\200\224it

n

jtr

This requirement may be compared with the condition for the Yukawa potential to develop a bound state, which we can show to be
h

n

|KO|>2.7

G.2.14)

7.2. The
with Vo

Born Approximation

389

negative. In other words, if the potential is strong enough to develop a bound state, the Born approximation will probably give a misleading result. In the oppositehigh &-limit, the condition that the secondterm in is small G.1.22) can be shown to imply
/*/
As k

G.2.15)
energies.

the Born approximation tends to get better at higher

becomes this larger,

inequality

is more easily satisfied.Quite generally,

The Higher-Order orn Approximation B
it Let us now considerhe higher-orderBorn approximation.Here, is t F more compact to use the symbolicapproach. or the transition operator 7, we define T such that

V\\^) =
Multiplying V

T\\<j>).

G.2.16) G.1.6) V, we obtain by

the Lippmann-Schwinger quation e

\302\273.,P7W-

G.2.17)

This is supposed to hold for |<J>) taken to be any plane-wave state; T furthermore, we know that these momentum eigenketsare complete. herewe must have the following operator equation satisfied:
Therefore,

T=V+ VE = /(k'.k) -

\342\200\224

Ho + ie
^r\342\200\224\342\200\224

T. as [using

G.2.18)

The scattering amplitude of G.1.34) now be written can with the |<J>) as momentum eigenkets]

G.2.16

^ ^B7rK<k'|T|k>.
E Ho + ie E Ho + ie
\342\200\224 \342\200\224

G.2.19)
operator T.
V

Thus to determine /(kr,k),it is sufficient to know the transition We can obtain an iterative solution for T as follows:
V

+V

E

\342\200\224

Ho + ie

V

+V

V

+

G.2.20)
we Correspondingly, can expand as follows:
00

/

G.2.21)

390

Scattering Theory

FIGURE

7.4.

Physical interpretation

of the higher-order Born term /B)(k',k) V

where n is the number of times the

operator enters.We have
3

4tt

-V\\k) E-Ho + ie

G.2.22

If an explicit form

is required for /B), we can write

it

as

1 2m
Air

Btt)

x/x' E-Ho + ie x\F(x\")<x\"|k>
1 2m
X

(k''xV(x')

2m

V(x\elk'
is G.2.23)given
x\"\342\200\224which

G.2.23
for
the

A

physical interpretation of incident wave interacts at
V(x\\342\200\224and")

in Figure 7.4, where the explains the appearance of

then

Helmholtz equation G.1.18); subsequently,a secondinteraction occursat xr the wave is scattered into the of the appearance finally, to direction k\". In other words, /B) corresponds scattering viewed as a a likewise,/C) is viewedas a three-step process, nd so on. two-step process;
\342\200\224thus

propagatesfrom

x\"

to xr via

Green'sfunction

K(xr)\342\200\224and,

7.3 OPTICALTHEOREM
Thereis a very famous relationship popularly attributed to Bohr,Peierls,
Placzek [Editor's Note: This relationship is in fact due to Eugene see Feenberg* (Phys. Rev. 40, 1932); R. G. Newton (Am. J. Phys. 44,
and
*As pointed out by Newton in his Review (c.f.Ref.8 therein), Feenberg's paper is also with a receipt date stated as remarkable for the fact that it was published on 1 April 1932, 8 September violating causality!
1932\342\200\224thus

7.3.Optical

Theorem

391

w c for the 639,1976) historical background.] alledthe optical theorem, hich =

relatesthe imaginary part of the forward scattering amplitude fF the total crosssectionatot, as follows:
Optical Theorem

0) to

G.3.1
where
the

G.3.2)
setting of k'= k imposesscatteringin
da_ the

forward direction, and

dtt

dQ

G.3.3)

we Proof. From G.2.19)have

G.3.4)
We next evaluate Im(k|r|k) using

G.2.16), and the hermiticity G.1.6),

of

V:

= Im
Now we use the well-known relation

E-H0-ie
= Pr.
\342\200\224

1

G.3.5)

E
to reduce the

\342\200\224

Ho ie

E-H, i<n8(E-H0) o
form

right-hand

sideof G.3.5) the to

'E
The

o

G.3.6)
of
V

G.3.6) - H0)]V; hence G.3.6) becauseof the reducesto FPr.[l/(?
first

two terms of

vanish

hermiticity

and

G.3.7)
Again,

we can recastG.3.7)sing u

= H0)T\\k) Im(k|r|k> ir(k\\T*8(E= d3k 3k'

-

and G.2.16) |^>)= |k) as

-j
7T

E- hlk 2m

2/,/2

\\

mk

G.3.8)

392

Scattering Theory

where we have used d3k'=k'dE(dk'/dE)dti\\the 5-function constraint E = h2k'2/2m [hence dE = (ti1k'/m)dk'\\ k'= k. From and we G.3.4) G.3.8), have
and\342\200\224finally\342\200\224

where in the last stepwe have usedG.1.36), and G.2.19), G.3.3).

?

We can appreciate the physical significanceof the optical theorem after we discussshadow scattering.

7.4.EIKONALAPPROXIMATION

This approximation coversa situation in which K(x) varies very little over a distanceof orderof wavelength X (which can be regardedas \" small\.") Note that V itself need not be weak as long as E h |K|; ence the domain of here is different from the Born approximation. Under these condivalidity the semiclassical concept ecomes pplicable, nd we replacethe b a path a exact wave function \\// + ) by the semiclassical wave function [seeB.4.18) and B.4.22)], namely,
\302\273

conditions,

\\

G.4.1)

This leads to the Hamilton-Jacobiequation for S,
2m

G.4.2)

as discussedin Section 2.4. e proposeto compute S from G.4.2)by W the further approximation that the classicalrajectory is a straightmaking t line path, which should be satisfactoryfor small deflectionat high energy.* Considerthe situation depictedin Figure 7.5,where the straight-line trajecis along the z-direction.Integrating G.4.2) e have w
trajectory

1/2

dz'+ constant.
that

G.4.3)

The additive constant is to be chosenin such a way

Tkz
n

as V-+0
this

G.4.4)
zero-potential
would

so that the plane-waveform for
*Needless to say, solution of
forbidding

is G.4.1)reproducedin
determine

to G.4.2)

the classical trajectory

be a

task in general.

7.4.Eikonal
limit. We

Approximation

393

can then

write

Equation r
m

a G.4.3) s

T = kz +
= kzwhere for E
:\302\273

S

,

Im

-k dz'
'2)dz'
~k
mV h2k

h2k * oo

-

G.4.5)

V,

we have used

k2- 2m
at
high

E = hzkl/2m. o S
ZTL)

=s

1
Btt)
3/2

\342\200\224

im

h'k J-oo

/

G.4.6)
have the correct asymptotic form appropriatefor an incident plussphericaloutgoing wave (that is, it is not of form e + and indeedrefers only to motion along the original direction), f(Q)(elkr/r) it can neverthelesstill be usedin G.1.34) s to obtain an approximate expresto wit, for/(k',k),
expression

does Though G.4.6) not

+ za)e^' -^^Jd3x'e-ik''*'v()lb2 Xexp Note that
integration

im

G.4.7)
G.4.7) [...], isjust like the first-order

without

Born amplitude in
in

We G.2.2). perform the three-dimensional(d3x') integraG.4.7) y introducing cylindricalcoordinates d3x'= b bdbd$hdz' (see

the last factor, exp

z-direction

Scatteringregion

FIGURE
straight

7.5.

line trajectory

Schematic diagram of eikonal approximation scattering where the classical is along the z-direction, |x| = /*, and b = |b| is the impact parameter.

394

Scattering Theory

Figure 7.5)and

noting

that

where we have used k and (k k')-z~ O@2),which can be ignored for small deflection 6.Without loss of generality we choose scattering to be in the xz-planeand write
\342\200\224

(k-k')-x'=(k-k')-(b+z'z)--k'-b, G.4.8)
\302\261b

= (ksin0x+
The expression for

kcosdz)\342\200\242

(bcos

bsin<j>hy)

^

kbdcos<}>h.

G.4.9)
/(k',k)becomes 1 2m 00bdb /(k\\k) =
4tt

f
\342\200\224

\342\200\224

ikbO

cos<j>h

/-oo
We next

+ 00 dz Kexp

im

hLk

fJ-ooVdz'
J

G.4.10

use the

following

identities:
d<t>he-'khecos't'\302\273

= 2irJ0(kbd)

G.4.11
Z

and

/-oo

+ 00 dz Kexp
\342\200\224

Vdz'
oo

ih2k m

\342\200\224

exp

im

h2k * oo
\342\200\224

r

= + 00 =
\342\200\224

Vdz'

oo

G.4.12
the where, of course, contribution from z

=

\342\200\224

oo on

vanishes in the exponent. o,inally of G.4.12) S f

the right-hand side

f(k\\k) = -ik
where
\342\200\224

/\342\200\242OO

dbbJ0(kbd)[e2'Hh)
00
i

-I],

G.4.13

V{]/b 2kh2 /+ -oo

m

dz.

G.4.14
\342\200\224

In G.4.14)fix the impactparameter b and integratealong the straight-line we T path z, shown in Figure 7.5. here is no contribution from [ell^h) X] in if G.4.13)b is greater than the range of V. It can be shown in a straightforward manner that the eikonal This approximation satisfies the optical theorem G.3.1). proof plus some interesting applications\342\200\224for example,when V is a Gaussian potential A F) becomes in in the literature (Gottfried Gaussian discussed For 1966). the casewhere V is a Yukawa potential, seeProblem 7 in this
b-space\342\200\224are

chapter.

7.5.Free-Particle

States: Plane Waves Versus Spherical Waves

395

7.5.FREE-PARTICLETATES: LANE WAVES VERSUS P S
SPHERICAL WAVES
In consideringscattering by a spherically symmetric potential, we often examine how states with definite angular momenta are affected by the scatterer.Such considerationslead to the method of partial waves, to be the discussedin detail in Section 7.6.However, before discussing angular o momentum decompositionf scattering states, let us first talk about freeparticle states,which are also eigenstatesof angular momentum. For a free particle the Hamiltonian is just the kinetic-energyoperwhich obviouslycommuteswith the momentum operator.It is for this reasonthat in Section7.1we also took |<J>), an eigenket of the free-particle Hamiltonian, to be a momentum eigenket or a plane-wavestate |k), where the eigenvalueof the momentum operator is h k. We note, however,that the free-particle Hamiltonian also commuteswith L2 and Lz.Thus it is possible to considera simultaneouseigenketof Ho, L2, and Lz. Ignoring spin,such a state is denotedby \\EJ,m),often called a spherical-wave state. More generally, the most general free-particlestate can be regarded as a superposition \\EJ,m) with various E, /, and m in much the same of as way as the most general free-particlestate can be regarded a superposiof |k) with different k, different in both magnitude and direction. Put in another way, a free-particle state can be analysed using either the or basis {\\E, /, m)}. plane-wave basis (|k)} the spherical-wave We now derive the transformation function (k\\E9 /, m) that connects the plane-wave basiswith the spherical-wave basis.We can also regard this as the momentum-spacewave function for the spherical wave quantity characterized by E, /, and m. We adopt the normalization convention for the spherical-waveeigenketas follows:
operator,
superposition

/, E'). (E\\ /',m'|?, m) = 8ir8mm,8(EIn analogy with the angular w position-space ave function, we may

G.5.1)
guessthe

dependence:

G.5.2)
To prove this rigorously,we proceedas follows.First, consider momenthe is, a plane-wavestate whose propagation direction eigenket is along the positive z-axis. n important property of this state is that it has A no orbital angular-momentum component in the z-direction:
momentum

\\kz)\342\200\224that

Lz\\kz)

= (xpy

-

ypx)\\kx

= 0,ky = 0,kz = k) = 0.

G.5.3)

T Actually this is plausible from classicalconsiderations: he angularmomentum component must vanish in the directionof propagation because

L*p= (xXp)*p= 0. Becauseof

G.5.3)\342\200\224and

since (E\\ /',m'\\kz) = 0 for

396
must
\\kz)

Scattering Theory

0\342\200\224we

be able to expand \\kz) as follows: = ',/',m'= \\ /',m'= 0\\kz).

r

G.5.4)
<J>,

W Noticethat there is no m' sum; m' is always zero. e can obtain the most

general momentum
from

and Figure 3.3

\\kz)

by just applying

C.6.47)]:

eigenket, with the direction of k specifiedby 0 and the appropriate rotation operator as follows[see

G.5.5)
Multiplying

G.5.5) (E,/, m\\ on the left, we obtain by
v

= X(E'J\\m'

X8U,8(EE')(E',l',m'=0\\kz) = 0,y = ,/,m = 0|A:z>
No^v

G.5.6 oi

(E, [, m =

is independentof the orientation
cj)\342\200\224and

independentof 6 and
we can write, using

we may as well call it

hi +

i

k\342\200\224that

is,

/\342\200\224^\342\200\224

g*E{k).

So

C.6.51),
= <k|?,/,m>
gIB

(k)

YT

(k)

G.5.7)

Let us determine giE(k). irst, we note that F

= 0. (Ho-E)\\E,l,m)
But
\342\200\224

G.5.8)

we also let Ho E operate on a momentum eigenbra (k| as follows:

= (k\\(H0-E)
Multiplying with G.5.9)
\\E,

'h2k2
2m
right,

G.5.9)
we obtain

I, m) on the

( h2k 2k2

G.5.10
only

This means that (k\\E,l,m)can be non vanishing we must be able to write g/E(k) as
h2k2

if

2/, 2 E = hlkL/7.m;so

1m E

G.5.11

7.5.Free-Particle

States: Plane Waves Versus Spherical Waves

397

To determine N we go back to our normalization convention G.5.1). We obtain

',/',

m'\\E,

/, m)

, /, m>

=

j

k\022dk

\"

'h2k\022
\342\200\224~

2m

E'

x8'h2k 2m
k\022dE'

-E
(fi2k 2m

dE\"/dk

-E

xy;
// = fe2/,//2 where we have defined E\" _ h k\" /2m to change ^\"-integration into we E\"-integration. omparing this with G.5.1), seethat N = h/yfrnk will C suffice.Therefore, we can finally write

G.5.12)

h

{mk

>h2k2 2m

-E

G.5.13

hence
h

{mk

'h2k2 E 2m

-

G.5.14

the plane-wavestate |k) can be expressed a as of free spherical-wavestates with all possible/-values; in superposition particular,

From

we G.5.14) infer that

/

m

, /, m)(E,/, m|k>
h h2k2/2m
\\

oo

E E \\E,l9m) = 1=0 m=-l

ymk

y/\"*(k) -

G.5.15

Becausethe transverse dimension of the plane wave is infinite, we expect that the plane wave must contain all possible valuesof impact parameter b the impact parameter b^lh/p).rom this point of view it F (semiclassically, is no surprisethat the momentum eigenstates|k),when analyzedin terms of valuesof /. spherical-wavestates,contain all possible
We

have derived the wave

function

for

w Next, space. we considerthe corresponding ave function

\\E,l,m) in
in

momentum

position space.

398

Scattering Theory

From wave mechanics, the readershould be familiar with the fact that the wave function for a free spherical wave is y/(A:r)Y/w(f), where ji(kr) is the sphericalBesselfunction of order / (seeAppendix A). The secondsolution n^kr), although it satisfiesthe appropriate differential equation, is inadmisbecauseit is singular at the origin. So we can write
inadmissible

(x\\E9

/, m) = ctjt(kr)Ytm(t).

G.5.16)

To determine ch all we have to do is compare

= -^777 = E E
B^K/2
I

i~m

I, jdE(x\\E, m)(E,I,
h h2k2\\

m

fdEcjAWW-^slE ^HlTXk) ymk

+ {2l 1)PlQL.f)-1!L=rcljl(kr), 4* 'K 'JmJ 7
where we have used the addition theorem
in the last

G.5.17)

N step. ow (x|k)= e;k'x/Bv7\"K/2

can also be written as

which

can be proved by

using

the

following

integral representation for

Ji(kr): = ji(kr)
with Comparing G.5.17)
\342\200\224.

G.5.19) (*lelkrcosePl(cos0)d(cos6).
'\"

we G.5.18),have

P^.
E- 2m
h

G.5.20)

To summarize, we have
h

8

ymk

G.5.21a

G.5.21b

These expressionsare extremely useful in developing the partial-wave in expansiondiscussed the next section. We concludethis section by applying G.5.21a) decay process. to a Supposea parent particle of spin j disintegratesinto two spin-zeroparticles A (spin j) B (spin0)+C (spin0).The basicHamiltonian responsibleor f
-*\302\246

7.6.Method of Partial

Waves

399

such a decayprocessis, in general,very complicated. However,we do know that angular momentum is conserved becausethe basic Hamiltonian must be rotationally invariant. So the momentum-spacewave function for the final state must be of the form G.5.21a), / identified with the spin of with the parent particle.This immediately enablesus to compute the angular distribution of the decay product because momentum-spacewave functhe is nothing more than the probability amplitude for finding the decay productwith relative momentum direction k. As a concrete example from nuclear physics,let us considerthe of an excitednucleus,Ne20*: decay
function

+ Ne20*->O16He4.

G.5.22

the Both O16and He4 are known to be spinless S particles. uppose magnetic number of the parent nucleus is +1,relative to some direction z. quantum Then the angular distribution of the decay product is proportional to = C/877-)sin20, here @,<t>) are the polar angles defining the w \\Y1\302\2611F,(j>)\\2 relative direction k of the decay product.On the other hand, if the magnetic the decay angular quantum number is 0 for a parent nucleus with spin = C/4t7-)cos20. distribution varies as Fora general spin orientation we obtain

1,

\\Y\302\256@,<j>)\\2

m=

-1

-

G-5.23

Foran
an

unpolarized nucleus the various w(m) are all equal, and we obtain this is not surprising because there is no preferred direction if the parent particle is unpolarized. For a higher spin object,the angular distribution of the decay is more involved; the higher the spin of the parent decaying system, the of the decay products. greater the complexity of the angular distribution Quite generally, through a study of the angular distribution of the decay products,it is possibleto determine the spin of the parent nucleus.

isotropicdistribution;

7.6.METHODOF PARTIAL WAVES
Partial-Wave Expansion Let us now come back to the case V # 0. We assume that the potential is sphericallysymmetric, that is, invariant under rotations in three dimensions.t then followsthat the transition operator T, which is given by I commutes with L2 and L. In other words, T is a scalar operator. G.2.20), It is now useful to use the spherical-wave basisbecausethe WignerEckart theorem [see C.10.38)], to a scalar operator, immediately applied

400

Scattering Theory

gives

/ <?',',

m'\\T\\E9

/, m) = Ti(E)8ir8mm,.

G.6.1)

In other words, T is diagonal both in / and in m\\ furthermore, the (nonvanishing) diagonal element dependson E and / but not on m. This leads to an enormous simplification, as we will see shortly. Let us now look at the scattering amplitude

G.2.19):

/

m

I' m'
Ylm(kf)YlmXk)

X{E'l'm'\\T\\Elm){Elm%)
mk
Ait2
I

m

E = h2k2/2m

k

I

.

m

t,(e)

G.6.2)

z-direction. e W

To obtain the angular dependence f the scatteringamplitude, let us choose o the coordinatesystem in such a way that k, as usual, is in the positive
then

have

[seeC.6.50)]

0,

G.6.3)

= hence only the terms ra = 0 contribute. where we have used P7(l) 6 to be the angle between k' and k, we can write Taking

l;

G.6.4)
It

is customary hereto define the partial-wave amplitude ft{k) as follows:

G-6.5)
ForG.6.2) then we
have
00

G.6.6)
where fF)

still dependson k (or the incident energy) even though k is suppressed. To appreciatethe physical significanceof //(A:), let us study the behavior of the wave function (x|\\//( +)) given by G.1.33 large-distance Using the expansionof a plane wave in terms of spherical waves [G.5.18

7.6. Method of Partial and
that

Waves

401

noting

(AppendixA)
j{kr-(t*l2))

large r

ji

_ e~i{kr-{M2))

2ikr

(/' = eiGr/2)l) G.6.7)

and

that

fF) is given
]arger

by 3/2

we G.6.6), have
ikz ikr

3/2

l)P,(cos0) likr
ikr

_ -i(kr-lw)

\\

1
Brr)
3/2
When the scatterer is absent, we can The physicsof scattering is now clear. analyze the plane wave as the sum of a sphericallyoutgoing wave behaving like elkr/r and a spherically incoming wave behaving like e~l{kr~l7r)/r for each /. The presence the scatterer changes only the coefficientof the of outgoing wave, as follows:
\342\200\224

G.6.8)

G.6.9)
The incoming wave is completelyunaffected.
Unitarity

and

PhaseShifts

We now
unitarity.

o examine the consequencesf probability conservation, or In a time-independentformulation, the flux current density j must

satisfy

v-j

dt

= 0.

G.6.10)

Let us now considera spherical surface of very large radius. By Gauss's theorem, we must have
spherical surface

G.6.11
The particles. and Physically G.6.10)
outgoing

mean G.6.11) that
flux must

of because angular-momentum

there is no sourceor sink of equal the incoming flux. Furthermore, conservation,this must hold for each partial

402

Scattering Theory

I wave separately. n other words, the coefficientof elkr/r must be the same in magnitude as the coefficientof e~lkr/r. Defining Sj(k) to be

+ S/(?)=l 2/A//(fc),
this that means [from G.6.9)]

G.6.12)

G.6.13)
that is, the most that can happen is a change in the phase of the outgoing is known as the unitarity relation for the /th partial wave. Equation G.6.13) as wave. In a more advanced treatment of scattering, S^k) can be regarded the /th diagonal elementof the S operator, which is required to be unitary as a consequence probability conservation. of We thus seethat the only change in the wave function at a large distance as a result of scattering is to change the phase of the outgoing wave. Calling this phase28i (the factor of 2 here is conventional),we can

write
S7 = e2/\\
with 67

G.6.14)
/\342\200\236

do

G.6.12)]

real.It is understood here that 8i is a function not explicitly write 5, as 5/(A:). Returning to

or, explicitly in terms of
f/

8h

^
?
V

of k even though we we can write [from

G-6.15
kcot

=

2ik
full

\302\253,

-

ik

whicheveris convenient.For the
=o

scattering amplitude we have

= T L Bl+ l)el8fsin8lPl(cos6) k
i

o

G.6.17)

for f@) rests on the twin principlesof 67 real.This expression rotational invarianceand probability conservation.In many bookson wave mechanics, .6.17) G is obtained by explicitly solving the Schrodingerequawith a real, sphericallysymmetric potential; our derivation of G.6.17) may be of interest becauseit can be generalized to situations when the in potential described the contextof nonrelativisticquantum mechanicsmay fail. The differential crosssection do/dSl can be obtained [seeG.1.36) To by just taking the modulus squaredof G.6.17). obtain the total cross
with
equation

7.6. Method of Partial

Waves

403

sectionwe have

kz Jo
X

/

/'

^'sinS/e-'

G.6.18)
We

can checkthe optical theorem G.3.1), we obtained earlier using a which that more general argument. All we need to do is note from G.6.17)
0= 0

/

sin6/'

G.6.19)

is the sameas G.6.18) for Air/k. except As a function of energy, 8, changes; hence ft(k) changes also.The relation of G.6.13) restriction on the manner in which f, can is a unitarity vary. This can be most conveniently seenby drawing an Argand diagram for kf/. We plot kft in a complexplane, as shown in Figure 7.6,which is
which

FIGURE

7.6.

eachradii

the magnitude of Argand diagram for kfh = of length on the unitary circle; angle OCP 257.
\\

0 OP is

Re (kf,)
kfh

while

COand CP are

404

Scattering Theory

self-explanatoryif we note from

that G.6.16)

21*'-

G-6-20) as the
unitary

Notice that there is a circle of radius
which
kft must We can

important features from Figure 7.6. uppose is S 57 It near the bottom of the circle. may be positiveor negative, but fl is almost purely real:

small.Then fl

lie. seemany

\\, known

circle, on

must stay

ft- e^sinS,= (l k

+ i8l)8l=
k

\302\2537

k.

G.6.21)

On the other hand, if 5, is near tt/2, kft is almost purely imaginary, and the magnitude of kfi is maximal. Under such a condition the /th partial wave in a may be in resonance, concept to be discussed somedetail in Section7.8. crosssection Note that the maximum partial

l)
is achieved [see when G.6.18)]

G.6.22)

^

Connectionwith the Eikonal Approximation The eikonal approximation discussed 7.4is valid at high energies in (X range R); hence many partial wavescontribute. We may regard / as a continuous variable. As an aside we note the semiclassical argument that / = bk (becausengular momentum lh = bp, where b is the impact paramea and momentum p = hk).We take
\302\253: parameter

lmax

= kR;

then we make the
max

following

substitutions

in

G.6.23) G.6.17): expression
6

smalln n

where lmax
We

= kR

G.6.24)
implies that

have

= = e2i8'-l e2i^h)-l0 for/>/max.

G.6.25)

=

-ikjdbbJ0(kb6)[e2iA(h)-l]. G.6.26)

The computation of 8, can be done by using the explicit form for given by G.4.14) Problem 7 in this chapter). (see

7.6. Method

of Partial Waves

405

Determinationof Phase Shifts
how we may actually determine the phaseshifts Let us now consider a potential V. We assume that V vanishes for r > R, R being the given range of the potential. Outside (that is, for r > R) the wave function must be that of a free spherical wave. This time, however, there is no reason to The excludent(r) becausethe origin is excludedfrom our consideration. wave function is therefore a linear combination of j/(kr)P/(cos6)and ni(kr)Pi(cosd)or, equivalently, h(jl)Pl and h^P^ where h^ and h{^] are the sphericalHankelfunctions defined by

-in,',
thesehave the asymptotic behavior (seeAppendix A)
r
large

G.6.27)
ikr

-t(kr-(lir/2))

ikr

. G.6.28

The full-wave

function

at

any

r can

then

be written as:

1 3/2 B*)
Forr > R
we have (for the radial-wavefunction)

. G.6.29

G.6.30
where the coefficient that multiplies A, in G.6.29)chosenso that, for is coincideswith j)(kr) everywhere. Using G.6.28), can we A,(r) the behavior of the wave function for large r given by G.6.29) and compare
V\342\200\2240,

with G.6.30)

1 B*)3/2
Clearly, we must have

2ikr

2ikr

G.6.31

a)-ip2,s,

rB) _ 2 Cl ~

I

G.6.32
is,just

So the radial-wave function for r > R is now written as A,(r) = e/8'[cos 6/7/(A:r)-sin V/(?>\] Usingthis, we can evaluate the logarithmic derivative at r = R outsidethe range of the follows:
potential\342\200\224as

G.6.33
that

r dA, A, dr r= R

= kR

)sin n',{kR 8, jl(kR)cos8l nl(kR)sin8l
\342\200\224 \342\200\224

kR [{ )cos6/

G.6.34
kr

where j/(kR) stands for the derivative of

j, with

respectto

evaluated at

406
kr

Scattering Theory

Conversely, knowing the logarithmic derivative at R, we can obtain the phase shift as follows:
tan

= kR.

5, =

\342\200\224^

; HlJ/y kRj,'(kR)-p,j,(kR)
the

kRn](kR)-filnl(kR)
phase shift is

-.
reducedto

G.6.35
that

The problem of determining obtaining /?,.
We now
\342\200\224that

thus

of

potential, we can solve the Schrodingerequation in three dimensions by looking at the equivalent one-dimensionalequation
d2U/ dr 2m

look at the solution to the Schrodingerequation for r < R is, inside the range of the potential. For a spherically symmetric

r2

G.6.36)

where

G.6.37)
subjectto the boundary condition
u

G.6.38 0.
equation\342\200\224if

We

to r = R, starting at r = In this way we obtain numerically\342\200\224up logarithmic derivative at R. By continuity we must be able to match logarithmic derivative for the insideand outside solutions at r = R: Pi
inside solution
~~

integrate

this

one-dimensional Schrodinger

necessary,
the the

Pi

outside solution'

V

' -O-

where the left-hand sideis obtained by integrating the Schrodingerequation in up to r = R, while the right-hand sideis expressible terms of the phase shifts that characterize the large-distance behavior of the wave function. This means that the phaseshifts are obtained simply by substituting /?7 for the inside solution into tanS7 [G.6.35)].an alternative approach it is For possibleto derive an integral equation for A^r), from which we can obtain phase shifts (seeProblem 8 of this chapter).

Hard-Sphere Scattering
Let us work out a specificexample. e consider W scatteringby a hard, or rigid, sphere
F=(\302\260\302\260

\\0

{(OTr<* for r>R.

G.6.40
v y

In this problemwe neednot even evaluate /?7 need to know is that the wave function must

(which is actually oo). All we vanish at r = R becausethe

7.6. Method of Partial

Waves

407

Therefore, sphereis impenetrable.

G.6.41)
or, from or
tan 67

G.6.33),

= y/(A:/?)cos6/ nl(kR)sin8l 0
\342\200\224

G.6.42)

=
n,(kR)m

G.6.43)

Thus the phase shifts are now known for any /. Notice that no approximahave been made so far. To appreciatethe physical significanceof the phase shifts, let us considerthe / = 0 case (S-wave scattering) specifically.Equation G.6.43) for becomes, / = 0,
approximations

tan

On

=

k -cosR /kR

sin kR /kR

=

-

tan

kR,
el8\302\260

G.6.44)
omitted varies as

or 60 =

\342\200\224

kR. The radial-wavefunction
sin At

with G.6.33) 1. coskr .

80).

G.6.45

Therefore, if we plot rAl=0(r) as a function of distance r, we obtain a to sinusoidal ave, which is shifted when compared the free sinusoidalwave w amount R; see 7.7. by Figure

R=-60/k
FIGURE 7.7. Plot of rA^0{r) versus r (with the factor removed). The dashed curve for V 0 behaves like sin At, while the solid curve is for S-wave hard-sphere scattering, shifted by from the caseV= 0.

= = -80/k

elS\302\260

408

Scattering Theory

Let us now study the low and high energy limits of tan 5,. Low Appendix A) energy means kR small, kR <c We can then use(see

1.

(kr)'

G.6.46)
to obtain

tanS,=

{B/ l)[B/l)!!]2}

It is therefore all right to ignore 5, with / =?0. In other words, we have for iS-wave scattering only, which is actually expected almost any finite-range o potential at low energy. Because = kR regardless f whether k is large 50 or small, we obtain

??
^^
~

\342\200\224.

G.6.47)

^
It

dQ

do = sin250 \342\200\224-^^R2
k2

forkR<zl.

G.6.48)

is interesting that the total crosssection, given by do
ottot

-f%<*-*'#<

<7-6-49>

is four times the geometriccrosssection ttR2. By geometriccrosssection we mean the area of the disc of radius R that blocksthe propagation of the plane wave (and has the same crosssection area as that of a hard sphere). Low-energyscattering, of course,means a very large wavelength scattering, and we do not necessarilyexpecta classicallyreasonable result. One might conjecture that the geometric crosssection is reasonable to expectfor high-energy scattering becauseat high energies situation the look similar to the semiclassical situation. At high energiesmany might /-values contribute, up to /max ~kR,& reasonableassumption. The total cross sectionis therefore given by
TT k
But using

/_o

E B/ +

l)sin2\302\253/.

G.6.50)

we G.6.43),have

l + tan2S,

[ i.lkRW1!\\n.(kR\\\\2

sir?(kR 2
1
\\

-

G.6.51)

7.6. Method

of Partial Waves

409

wherewe have used

n,(kr)
We
90\302\260

~\342\200\224

t~cos kr kr
\\

1

2
\342\200\224

seethat 57 decreases y each time / increases y one unit. Thus, for b b = an adjacent pair of partial waves, sin2^+ sin25/+1 sin25z + sin2E/ it/2) = sin25/ 4-cos25, and with so many /-valuescontributing to = it is legitimate to replacesin26/ by its average value, \\. The number of terms in all the the /-sum is roughly kR, as is the average of 2/ + Putting

1,

G.6.50),

becomes ingredients together, G.6.50)

1.

1
which

= 2'nR2,

G-6-53)

is not the geometriccrosssection ttR2 either! To seethe origin of the into factor of 2, we may split G.6.17) two parts:
kR

.

kR

~ /reflection
In evaluating

\"*\"

/shadow

\342\200\242

(/

.0. j j4

the /|/refl|2dl2, orthogonality of the /^(costfysensuresthat there is no interference amongst contributions from different /, and we obtain the sum of the square of partial-wavecontributions:
max

/

-.

^

m

G.6.55) 1

Turning our attention to /shad, we note that it is pure imaginary. It is = particularly strong in the forward direction becauseP^cosO) for 6 = 0, and the contributions from various /-values all add up coherently\342\200\224that is, W with the same phase,pure imaginary and positive in our case. e can use to the small-angleapproximation for P( [seeG.6.24)] obtain

o

bdbJ0(kb6)

.
But this

G.6.56)
in

isjust the

formula for

Fraunhofer diffraction

opticswith a strong

410

Scattering Theory

peakingnear 6

\342\200\224

0.Letting ? = kR6 and

di~/i~=

w dd/d, e can evaluate

/
o ^ Finally, the interferencebetween /shad and
T\"*

J(cosfl)

G.6.57)
/refl
/\"v

vanishes:
/ ^7
v
\342\200\224

/
\\

/* jit
\342\200\242/

/*
\342\200\242/

dllctu.

1C11

t becausehe phaseof /refl oscillates 8/+1= 287 B
averaging

/

\\

^\"

^O

\\

/

to zero, while

/shad

is pure imaginary. Thus
tot

77), approximatelyaverag-

t
arefl

T
ashad

G.6.59)

The secondterm (coherent contribution in the forward direction) is w called a shadow becausefor hard-sphere scattering at high energies, aves with impact parameter less than R must be deflected. So,just behind the scatterer there must be zero probability for finding the particle and a shadow must be created.In terms of wave mechanics,this shadow is due to destructive interference between the original wave (which would be there even if the scatterer were absent) and the newly scattered wave. Thus we need scattering in order to create a shadow. That this shadow amplitude must be pure imaginary may be seen by recalling from G.6.8) the that coefficientof elkr/2ikr for the /th partial wave behaves like 1+ likf^k), where the 1 would be present even without the scatterer; hence there must be a positive imaginary term in ft to get cancellation. In fact, this gives a physical interpretation of the optical theorem, which can be checkedexexplicitly. First note that
4*77

TIm/@) TIm[/shad@)]
we obtain

= 4*77
.

r

i

G.6.60

becausem[/refl@)] veragesto zero due to oscillatingphase.UsingG.6.54), a I

= /shad @)
which

kR

= 2ttR2 G.6.61

is indeedequal to ator

7.7.LOW-ENERGYSCATTERINGAND BOUNDSTATES
At

low

energies\342\200\224or,

larger
unimportant.

than

the range This point may

R\342\200\224partial

more precisely, hen X=l//c is comparable to or w waves for higher / are, in general, unimbe obvious classicallybecausethe particle cannot

7.7. Low-Energy

Scattering and Bound States

411

penetrate the centrifugal barrier; as a result the potential inside has no effect. In terms of quantum mechanics, the effectivepotential for the /th partial wave is given by

unless the potential is strong enough to accommodate / ?= 0 bound states near E =^ 0, the behavior of the radial-wavefunction is largely determined by the centrifugal barrier term, which means that it must resemble jj(kr). to Morequantitatively, it is possible estimate the behaviorof the phaseshift
using

the integral equation for the partial wave
^

(seeProblem 8 of

this

chapter):

J J,(kr)V(r)A,(r)r2dr.

G.7.2)

If At{r) is not too different from j)(kr) and \\/k is much larger than the range of the potential, the right-hand side would vary as kll\\ for small Sh the left-hand side must vary as 8t/k. ence,the phaseshift k goesto zero H as
Oj

~K
finite

\\

/./.J)

for small k. This is known as threshold behavior. It is therefore clear that at low energies with a S-wave scattering is important.

range potential,

Rectangular Well or Barrier To be specificlet us consider S-wavescattering by
} attractive v otherwise finite Many of the featureswe obtain here are common to more-complicated range potentials. and We have already seenthat the outside-wavefunction [seeG.6.33) must G.6.45)] behave like
\\ \\

is

( *o = constant

for r

<R

10

(

\\

>0 Vo < 0
Vo

repulsive

' G74)
*

8 /o(*r)cos0

-no(kr)sm 80] h2k'2 E~K~,

g*m^r+8\302\260>.
Vo

G.7.5)

The insidesolution can also easily be obtained for
u with

a constant:

k' determined by

= Avl/==0(r)

a sin kV,

G.7.6)

(\".7)
= 0 at r = 0.In other words,

where we have used the boundary condition u

412

Scattering Theory

the insidewave function is also sinusoidalas long as E > Vo. The curvature of the sinusoidal ave is different than in the free-particlecase; s a result w a the wave function can be pushedin E0> 0) or pulled out E0< 0) dependon whether Vo < 0 (attractive) or Vo > 0 (repulsive),as shown in Figure 7.8. oticealso that G.7.6)and G.7.7)hold even if Vo > provided we N understand sin to mean is, the wave function behaveslike
depending

?,

sinh\342\200\224that

u(r) ocsinh[/cr],
where
2m

G.7.6')
G.7.7')

No potential

curvature

bigger

Vo<0

(b)

u(r)
<5o//c

Vo>O

iyf
0
sinh function
if

\\ \\l

(c)

V0>E
Plot

FIGURE

7.8

with the wave function

of u(r)

(solid line) pulled out.

versus r. (a) For V = 0 (dashed line), (b) For Vo < 0, 60 > 0 (solid line) pushed in. (c) For Vo > 0, 60 < 0 with the wave function

7.7. Low-Energy

Scattering and Bound States

413

We now concentrate on the attractive caseand imagine that the a Increasedttraction will result in a wave magnitude of Vo is increased.
function with

a larger curvature. Supposethe attraction is such that the o w [0, ] just accommodatesne-fourth cycle of the sinusoidal ave. R 1 in the low energy kR<t: limit, the phase shift is now 80 = tt/2, Working and this results in a maximal 5-wave crosssectionfor a given k because the sin280 is unity. Now increase well depth Vo even further. Eventually w the attraction is so strong that one-half cycle of the sinusoidal ave can be fitted within the range of the potential.The phase shift 80 is now it; in other words, the wave function outsideR is out of phasecompared to the free-particle-wave function. What is remarkableis that the partial crosssectionvanishes (sin 80 = 0), G.7.8) a/=0= 0, despitethe very strong attraction of the potential.In addition, if the energy is low enough for / ?^ 0 waves still to be unimportant, we then have an almost-perfect transmission of the incident wave. This kind of situation, known as the Ramsauer-Townsend effect, is actually observedexperimenfor scattering of electronsy such rare gasesas argon, krypton, and b xenon.This effect was first observedin 1923 to the birth of wave prior mechanics and was considered be a great mystery. Note the typical to ~8 kinetic energy of order parametershereare R 2 x 10 cm for electron ~ 0.324. O.leV, leadingto kR
interval
180\302\260 experimentally
\342\200\224

r

> R and for / = 0, the outside radial-wavefunction satisfies

Zero-Energy Scattering and Bound States Let us considerscattering at extremely low energies (k ~ 0). For

The obvious solution to G.7.9)s i u (r) = constant( r a), just a straight line!This can be understood as an infinitely limit of the usual expression the outside-wavefunction for
\342\200\224

^

G.7.9)

G.7.10
long wavelength a [seeG.6.37)nd

G.6.45)],
which

lim sin(/cr c-0 + 80)

= lim
8n

k-+0

sin

*i,+|
o r

G.7.11

lookslike G.7.10). have We
u u

= kcoi

Setting r = 0 [even though at r we obtain
A:->0

k^i =
-\302\273

\\

1
\342\200\224

a
true

G.7.12
wave function],

is 0, G.7.10)not the
a

lim/:cot(S0

.

G.7.13

414 The quantity

Scattering Theory

sectionas k

-\302\273

a is known as the scatteringlength. The limit of the total cross 0 is given by [seeG.6.16)]

1
k cot 80 ik
\342\200\224

G.7.14)

Even though a has the same dimensionas the range of the potential R, a and R can differ by orders of magnitude. In particular, for an for attractive potential, it is possible the magnitude of the scattering length to be far greater than the range of the potential. To see the physical meaning of a, we note that a is nothing more than the intercept of the outside-wave function. For a repulsive potential, a > 0 and is roughly of order of R, as seenin Figure 7.9a. owever,for an attractive potential, the H I intercept is on the negative side(Figure 7.9b).f we increase the attraction, the outside-wave function can again cross the r-axis on the positive side

7.9c). (Figure

The sign change resulting from increased attraction is related to the we note from development of a bound state. To seethis point quantitatively, Figure 7.9cthat for a very large and positive, the wave function is with essentially flat for r > R. But G.7.10) a very large is not too different N from e~Kr with k essentially zero. ow e~Kr with k 0 is just a boundstate-wave function for r > R with energy E infinitesimally negative. The inside-wave function (r < R) for the = 0+ case (scattering with zero kinetic energy) and the E = 0 case(bound state with infinitesimally small in binding energy) are essentiallythe same because both casesk' in sin k 'r is [G.7.6)] determined by
\342\200\224

?

\342\200\224

2m
with

-= F

\342\200\224

V

^

\\V

I

A 7

IS\"!

E

infinitesimal

of the bound-state-wave function kinetic-energyscattering,

Because inside-wavefunctions are the same for the two physical the situations (E = 0 + and E = 0 we can equate the logarithmic derivative
\342\200\224),

(positiveor negative).
with that

of the solution involving

zero

1
r =r
\\

r

\342\200\224

a

r= R

G.7.16

or, if R

\302\253:

a,
*\302\253-.

a

G.7.17) iw1\"\". 9' Jr\" 2ma

The binding energy satisfies
BE

^boundstate

G.7.18

7.7. Low-Energy

Scattering and Bound States

415
(b)

(a)

R

a<0 a>0

(c)

a>0

FIGURE

7.9.

deeperattraction. The intercept a shown for eachof three cases.

Plot of u(r) versus r for (a) repulsive potential, (b) attractive potential, and (c) of the zero-energy outside-wave function with the /--axis is

and we have a relation between scattering length and bound-state energy. This is a remarkable result.To wit, if there is a looselybound state, we can infer its binding energy by performing scattering experiments near zero kinetic energy,provided a is measured to be large compared with the range R of the potential. This connection between the scattering length and the bound-stateenergy was first pointed out by Wigner, who attempted to apply
to G.7.18)^-scattering.
that

is, the deuteronwith

of Experimentally, the Sj-state the np-system has a bound state,
EBE

=

2.22 eV. M

G.7.19

416 The scattering length is measured to be
* triplet

Scattering Theory

= 5.4X1O\0213 cm,

G.7.20)

leading to the binding-energyprediction 2[ia2
\"\342\200\242

mNa

-m^j*

S^0

\302\253\342\200\242

mNca

= (938MeV)B'1Xl\302\260\"^Cm) MeV =1.4

\\5.4xl(r13cm/

G.7.21)

where /x is the reducedmass approximated by mnp/2. The agreement i between G.7.19) G.7.21)not too satisfactory.The discrepancys due is and to the fact that the inside-wavefunctions are not exactly the same and that R is not really such a good approximation for the deuteron. A a triplet better result can be obtained by keeping the next term in the expansion of k cot S as a function of k,
\302\273

kcotS0=

+ yr0A:2,

G.7.22)

where r0 is known as the effectiverange (see, or example,Preston 1962, f 23). Bound Statesas Poles f 57(/r) o

concludethis section by studying the analytic propertiesof the where and amplitude Si(k) for / = 0.Let us go back to G.6.8) G.6.12), the radial wave function for / = 0 at large distance found to be proportional was
We

to

S,-0(k)Comparethis
with

ikr

p-ikr
\342\200\224.

G.7.23)

the wave

function

for a bound state at large distance,

e'Kr

G.7.24)

The existenceof a bound state implies that a nontrivial solution to the v Schrodinger quation with E < 0 existsonly for a particular (discrete) alue e of k. We may argue that e~Kr/r is like elkr/r,exceptthat k is now purely imaginary. Apart from k being imaginary, the important differencebetween and i G.7.23) G.7.24)s that in the bound-state case, ~Kr/r is presenteven e without the analogue of the incident wave. Quite generallyonly the ratio of the coefficientof elkr/r to that of e~lkr/ris of physical interest, and this is given by S^k). In the bound-state case we can sustain the outgoing wave (with imaginary k) even without an incident wave. So the ratio is oo, which means that S!=0(k), variable k, has a regarded as a function of a complex

7.7. Low-Energy

Scattering and Bound States

417

Imk

pole

k>0(real) Region of physical scattering

Re*

FIGURE

7.10. he complex fc-plane T

with bound-state

pole at k = +/k.

For seeFigure 7.10. k real and positive, we have the region of physical Herewe must require[comparewith G.6.14)] scattering. 5/-o = e2*0 G.7.25) with 80 real.Furthermore, as k k cot 80 has a limiting value \\la 0,
\342\200\224\302\273

pole at k = ik.Thus a bound state impliesa pole(which can be shown to be a simplepole)on the positive imaginary axis of the complex/c-plane;

[G.7.13)],

which

is finite, so 80 must behave as follows:

0, 80-*
-\302\273

\302\261

ir,

Hence = Sl=0

as k Now let us attempt to construct a
e2ib\302\260

-* 1

0.

....
ik ik

\342\200\224

G.7.26)
satisfying:

2. |S/=ol= 1for > 0 real (unitarity).
A:

1.Poleat k

= ik

simplefunction o (existencef bound state).

3. Sl=0 = 1at k = 0 (thresholdbehavior).
that
\342\200\224

G.7.27)

The simplext function

is satisfies all three conditions of G.7.27)
k k
\342\200\224 \342\200\224

G.7.28)

for is [Editor'sNote:Equation G.7.28) chosen simplicity rather than as a realisticexample. reasonableotentials (not hard spheres!) For physically p the phase shift vanishes as k An assumption implicit in choosingthis form is that there is no other that is important apart from the bound-state We singularity pole. can then use G.6.15)obtain, for fi=0(k), to
\342\200\224> \302\260\302\260.]

/#-o = Comparing this
with

^rf^ = 1 .-,, 2ik
\342\200\224

k

ik

G-7.29)

G.6.16),
//=o

=

1
\342\200\224

k cot 80

ik'

G.7.30)

418 we seethat
lim

Scattering Theory

= A:cot50

=

- k,

G.7.31

the precisely relation betweenbound state and scattering length [G.7.17)] It thus appearsthat by exploiting unitarity and analyticity of S in the /c-plane,we may obtain the kind of information that can be secured by solving the Schrodingerequation explicitly.This kind of technique can be very useful in problems where the details of the potential are not known.

7.8.RESONANCE SCATTERING
In atomic, nuclear, and particle physics,we often encounter a situation where the scattering cross section for a given partial wave exhibits a with the dynamics of such a pronouncedpeak. This section is concerned

resonance.
We

continue to consider finite-rangedpotential V(r).The effective a for the radial wave function of the /th partial wave is potential appropriate V(r) plus the centrifugal barrier term as given by G.7.1). SupposeV(r) itself is attractive. Because secondterm, the
h2 1A

+ 1)
r2

2m

is repulsive, we have a

where the effective potential has an situation a attractive well followedby a repulsivebarrier at larger distances, s shown in Figure for Supposethe barrier were infinitely high. It would then be possible to be trapped inside, hich is another way of saying that we expect w particles bound states,with energy E > 0.They are genuine bound states in the sense that they are eigenstates of the Hamiltonian with definite values of E. In other words,they are stationary states with infinite lifetime.

7.11.

Quasi-boundstate
barrier

(or Vior?=0)

= V(r) + (h2/2m)[l(l+ FIGURE Ve(( + to (h2/2m)[l(l 1)A2];for / = 0 barrier must

7.11.

l)/r2]versus r. For / * 0 the
be due
to V itself.

barrier can

be due

7.8.Resonance

Scattering

419

L particle leaks through the barrier to the outsideregion. et us call such a it state quasi-bound state because would be an honest bound state if the

finite barrier, the particle can be but it cannot be trapped forever. Sucha trapped state has trapped inside, a finite lifetime due to quantum-mechanical tunneling. In other words,a

In the more realistic caseof a

barrierwere infinitely high. The corresponding scattering phase shift 8/ rises through the value it/2 as the incident energy risesthrough that of the quasi-bound state, and at the same time the correspondingpartial-wave cross section passes its maximum possiblevalue 4ttB/ + 1)//^.[Editor'sNote: Such through a sharp rise in the phaseshift is, in the time-dependent chrodinger quaS e o associatedwith a delay of the emergencef the trapped particles, for rather than an unphysical advance, as would be the case a sharp decrease
equation,

through

It
known
resonance

is instructive to verify this point with explicit calculationsfor some potential. The result of a numerical calculation showsthat a resfor behavior is in fact possible /1^0 with a spherical-well potential.
287T

tt/2.]

res

(a)
<53(k)

n

ttI

V*
FIGURE

k res

(b) = D7r/k^)X7 2&7r/k2cs
2mV0R2/h2

7.12.Plots
=

of (a)

= 77/2 and a/=3 = a/==3 versus k, where at resonance 83(Arcs) and (b) S3(k) versus k. The curves are for a spherical well with

420

Scattering Theory

To be specificwe show the results for a sphericalwell with 2mV0R2/h2= 5.5 The w and / = 3 in Figure 7.12. phaseshift (Figure 7.12b), hich is small at extremely low energies,starts increasing rapidly past k=\\/R, and goes through 77/2 around k =1.3//?. Another very instructive example is provided by a repulsive 5-shell potential that is exactly soluble (seeProblem 9 in this chapter):

G.8.1)
Here resonances re possible / = 0 because 5-shellpotential itself can for the a
trap the particle in the region 0 < r < R. For the seriesof bound states in the region r < R with
kR
this

case y = oo, we expecta

= ir,2ir9... ;
function

G.8.2)
given by

r

= 0 but also at r = R

is becausethe radial wave
\342\200\224

in this

for / = 0 must vanish not only at F case. or the region r > R, we simply have

hard-sphere scattering with the 5-wave phaseshift, = -kR.
With
y

G.8.3)
problemsbecausethe

wall at r

The situation is more interesting with a finite barrier, as we can show behaviorwhenever explicitly.The scatteringphaseshift exhibitsa resonance
^incident

= oo, there is no connectionbetween the = R cannot be penetrated.
F

two

= ^quasi-bound F

state

\342\200\242

G -u '8
V

\342\200\242

Moreover, the larger the y, the sharper the resonance peak.However,away
from the

Thus we have a situation in which a resonance o behavior is superimposedn a smoothly behaving background scattering. This serves as a model for neutron-nucleus scattering, where a series of sharp resonancepeaks are observedon top of a smoothly varying crosssection. of d s Coming back to our general iscussion resonancecattering,we ask how the scattering amplitudes vary in the vicinity of the resonance energy.If we are to have any connection between07 beinglarge and the states, 8/ must go through tt/2 (or 3tt/2, .) from below,as quasi-bound discussed above. In other wordscot 8/ must go through zerofrom above. Assuming that cot 8/ is smoothly varying near the vicinity of resonance,

resonance50 looks very

much like the

hard-sphere phase shift.

..

that

is,

G.8.5)
we may attempt to expand cotS7 as follows: cot
\302\2537

= cot

fi7|?.Er 0

- c(E- Er)+ 0[(E- Erf\\.

G.8.6)

7.9. Identical

Particles and Scattering

421

This leads to

1 //(*)= k cot 81

1
ik

1
,

\342\200\224

k

r/2
where we have defined the
width

G.8.7)

T

by

d(cot8,)
d~E

2
*\302\246

E=Er

G.8.8)

Notice that T is very small

if cot 8, varies rapidly. If a simple resonance dominates the /th partial-wave cross section, we obtain a one-level resoresonance formula (the Breit-Wigner formula):

\"

(E-ErJ+T2/4

ignored.

So it is legitimate to regard T as the full width at half-maximum, provided the resonanceis reasonably narrow so that variation in 1/k2can be

7.9.IDENTICAL PARTICLES AND
As an

SCATTERING

exampleto illustrate the phase of the scattering amplitude, let us considerthe scattering of two identical spinlesscharged particles via the Coulombpotential (which we discussfurther in Section 7.13). spaceThe wave function must now be symmetric, so the asymptotic wave function must look like
e ik'x
\342\200\224 \302\253r

- 0)]

ik
\342\200\224,

where x = xx x2 is the relativeposition vector between the and 2.This results in a differential crosssection,

two

G.9.1) particles 1

da _
The crosssectionis enhanced through constructiveinterferenceat 6 ~ 77/2. In contrast, for spin \\ spin \\ scattering with unpolarizedbeam and V independent of spin, we have the spin-singlet scattering going with function and the spin triplet going with space-antisymspace-symmetrical metrical wave function (seeSection 6.3). the initial beam is unpolarized, If
\342\200\224

422

we have the statistical contribution

hence

\\

for spin singlet and

|

Scattering Theory

for spin

triplet;

)].
In other

G.9.3)

fact, beenobserved.

words,we expectdestructiveinterference at 0

\342\200\224

it/2.This has, in

IN SYMMETRY CONSIDERATIONS SCATTERING 7.10.

SupposeV and Ho are both invariant under some symmetry operation. We may ask what this implies for the matrix elementof T or for the scattering
If the symmetry operator is unitary (for example, rotation and Usingthe explicit form of T as parity), everything is quite straightforward. we see that given by

amplitude /(k',k).

G.2.20),

UH0U*

= H0,
under

UVUf
U\342\200\224that

=V is,

G.10.1

impliesthat T is also invariant
We

UTU*= T. define
jk>

G.10.2)
= ?/|k').

= f/|k>,

jk'>

G.10.3)

Then

= <k'|:r|k>(k'\\UWTUW\\k)
= (k/|r|k>.
As an

G.10.4

the example,we consider specificcasewhere U stands for the
77|k>

parity operator

= = |\"k>, 77|-k> |k>.
V

G.10.5

Thus invariance of Ho and

under

parity

would mean

= <-k'|r|-k><kr|r|k>.
Pictorially,we have the situation
We

G.10.6
7.13a.

illustrated

in

Figure

o exploitedthe consequence f angular-momentum conservation when we developed method of partial waves.The fact that T is diagonal the in the \\Elm) representation is a direct consequence f T being invariant o under rotation. Notice also that (kr|r|k) depends only on the relative orientation of k and k', as depicted Figure 7.13b. in When the symmetry operation is antiunitary (as in time reversal),we must be more careful. First, we note that the requirement that V as well as

7.10. Symmetry

Considerations in Scattering

423

a

k' -k

k'
rotated

/

-k'
(a)
FIGURE
Equality

7.13.(a)
of

(b)
Equality

T

elements between k matrix elements under rotation. of
matrix

T

-\302\273

k'

and

-k-\302\273\342\200\224k'.

(b)

Ho be invariant under time reversalinvariance requires that This is becausethe
antiunitary

G.10.7) 1
in

operator changes
into

+ E-Ho ie
We G.2.20). alsorecall that

.

1
\342\200\224

E Ho ie
\342\200\224

G.10.8)

for an

antiunitary

operator [seeD.4.11)],

G.10.9
where

a) = 0|a)
Let us consider
then

and

G.10.10

G.10.1
= d) = er|k> becomes G.10.9)
(k
Notice that the

^Ik) =

G.10.12
As a result

= |i|k) (

\342\200\224k|i|

\342\200\224k

).

G.10.13

and [G.10.13)]parity [G.10.6)]: . under e under <k'|r|k) = <that is, from G.2.19) G.2.22) have and we

initial and final momenta are interchanged, in addition to the fact that the directionsof the momenta have been reversed. It is also interesting to combine the requirements of time reversal

G.10.14

G.10.15

424 which results in

Scattering Theory

is known as detailedbalance. Equation G.10.16) It is more interesting to look at the analogue of G.10.14) we when have spin. Here may characterize the initial free-particle by | we ket and we exploitD.4.79) the time-reversal portion: for
(k'9m's\\T\\k,ms)

= r2\"^2\"v <-k, ms\\T\\-k',

-

m

T\\k\\

- m's).

-

mfs)

G.10.17

Forunpolarized initial
by

states.We

Bs+1);

if the

then

states, we sum over the initial spin states and divide polarization is not observed,we must sum over final obtain detailed balance in the form
final

G.10.18
i to mean that where we understand the bar on the top of do/dttn G.10.18) we average over the initial spin states and sum over the final spin states.

TIME-DEPENDENTORMULATIONOF SCATTERING 7.11. F
Our discussion scattering so far has beenbasedon the time-independent of formulation. It is also possibleto develop a formalism of scattering based on the time-dependentSchrodingerequation. We show that this formalism leads to the same Lippmann-Schwinger quation, G.1.6). e In the time-dependent formulation we conceiveof a scattering proas a change in the state ket from a free-particle ket to a state ket influenced by the presence the potential V. The basicequation of motion of
process

is

/

o

\\

G.11.1

where t) is the time-dependentSchrodinger ket in the presenceof V. The boundary condition appropriate for the scattering problem is that in the remote past (t -* oo), the particle was free. This requirement is if automatically accomplished we turn on the potential adiabatically\342\200\224that in Section 5.8: is, very
\\\\p;
\342\200\224

slowly\342\200\224as

V-+ lim
Just

Ve*.

G.11.2

as the partial differential equation with an inhomogeneous term is solved by introducing a Green'sfunction [see G.1.18)], operator the

7.11. Time-Dependent
, t') satisfying

Formulation

of Scattering

425

is solved o Schrodinger quation G.11.1) by introducing the Green's perator e
/#-7 izq \\Lr+\\t,
t

) = Oyt

\342\200\224

t

).

\\IAl.5)

The causality requirement we imposeon G+ is that the interaction of a particle at has an effectonly for t > We therefore imposethe retarded boundary condition = 0 iort<t\\ G.11.4

t'

t'.

We

claim that the solution to G+ (/,t') =

is and G.11.3) G.11.4)
n

- U{t- t')e-lH^'-t>)/h.

G.11.5

For t > a constant times e-l/foC-'')/*clearly satisfies the differential the because 8-function on the right-hand sideis inoperequation because For t < t\\ we obviously have the desiredcondition G.11.4) G+(t,t')hereis identically zero.At t = t\\ we note that there is an extra of the 0-function that just balances contribution due to the discontinuity the right-hand side of

t', G.11.3)

inoperative.

G.11.3):
full

d mdt

=
+ 00
oc

8(t-t').
+

G.11.6

The solution to the

problem can now be written as follows:

/
where and the upper limit of the t. As G+ vanishes for

\342\200\224

G+(t,t')V\\+< );t')dt\\

G.11.7)

G.11.8
required;this is becauseG+(/,t') vanishesas t -> oo for any finite value of t'. To seethat G.11.7) satisfies the /-dependentSchrodingerequation +
\342\200\224

t'>

in integration t oo, + );
\342\200\224 -\302\273

with |^( t) coincides

may G.11.7)

as well be t because t) just as
|</>;

we G.11.1),merely
|<f>;

by means of which the Ho] acting on G+ just gives 8(t + integration is immediately evaluated to be K|^( ); t). So far we have not even required |^(+ ); t) to be an energyeigenket. If it is, we can separate time dependences usual: the a
[ih(d/dt)\342\200\224

t)

ket

makes no contribution; as for its effect on the second term,

apply the operator

[ih(d/dt)\342\200\224

Ho] to

|\\//

);/).The

-1'),

Herethere is

the implicit assumption that

E does not change if

V

is

426

Scattering Theory

switched on adiabatically according to evaluated at t = 0, now yield G.11.7),
\342\200\224

and G.11.2). Equations G.11.5)

oo

G.11.10

The integral may appearto oscillateindefinitely. However,we recall that V is really to be understood as Vevt. As a result, the time integration is straightforward:
h t,. _

_

r\302\260A'e\302\253c/o
Jt\302\273

1
Ho E o
\342\200\224

t\"

\"

--

iff

oo

G.11.1
oc, this is just the Lippmann-Schwinger quation G.1.6). e The reader should note carefully how the ie prescription appearsin the two formalisms. Earlier, using the time-independentformalism we saw of that the choice positive sign of the ic-term (seeSection 7.1)corresponds to the statement that the scatterer affects only outgoing spherical waves. In the r-dependent ormulation presented f here, the presenceof ie (e= t)h) in arisesfrom the requirementthat the particle was free in the remote
But

as f\"

-\302\273

\342\200\224

G.11.11)
past.

on One may argue that the slow switch-onof the potential which we have relied is somewhat artificial. But let us supposethat we are scattering.When the wave packet using a wave-packetformalism to describe is well outside the range of the potential, it does not matter whether the potential is zero or finite. In particular, V may be zero in the remote past, which then leads to no difficulty.

G.11.2)

G.11.1), G.11.1).

ConnectionWith Time-DependentPerturbation Theory Inasmuch as scattering can be discussed using the time-dependent formulation, which is based on the time-dependent Schrodingerequation we should be able to apply an approximation scheme based on In particular we should be able to deploy the methods of timedependent perturbation theory developed earlier in Section 5.6 to the scattering problem\342\200\224provided, of course,the potential can be regardedas weak in somesense. First we will show how the golden rule can be appliedto compute do/dti,eading to the results of the Born approximation of Section 7.2. l We assumein the remote past that the state ket is represented a by momentum eigenket |k). When the interaction is slowly switched on, as in momentum G.11.2), example, eigenkets other than
|k)\342\200\224for

|k')\342\200\224are

7.11. Time-Dependent

Formulation

of Scattering

427

t populated.As we have seen(seeSection5.6),he transition probability is (to first order) evaluated in the following manner. First we write

r
where Vtf) = eiHQt'lhVe-iHot'lhe^ and Ek = at of finding |k') time t is then
probability

(k'\\Vr(t')\\k)dt',

G.11.1
prob-

T tftfllm. he transition

G.11.1
As
Tj

rule:

-> 0 (t finite), the transition
\"

rate isjust

what

we expectfrom the golden

-

2*

-

-,), G.11.U

where we have used E.8.5). that the right-hand side of G.11.14) Note is independentof /. It is important here to review the normalization conventionsusedfor we plane-wave states.In Section 1.7 used the 5-function normalization

= SC)(k-k').
The completenesselation is then r
written

G.11.1

as

1=

[ d3A;|k)<k|.

G.11.1

In applying /-dependent erturbation theory to scattering processes,t is i p more helpful to use box normalization,

G.11.17
where the allowed values for k are given
by

*, V,

The wave function is given

by

<xlk>

=

~jhe'k'X

G.11.1

insteadof [l/B7rK/2]elk'x. completeness The relation is

l=I>><k|, k
but

G.11.20
v

for a very large box we

might

as well treat the variables kx

, as

428

Scattering Theory

continuous, so

G.11.21
This lookslike G.11.16) for the presence (L/2ttK. very useful of A except relation that enablesus to go from the 5-functionnormalizationconvention to that of box normalization is
box
normalization normalization

G.11.22

as the reader may easily verify

by inserting

a complete set of states in the

positionrepresentation. The box normalization is very convenient for evaluating the density of states.Forthis reason it is used more often in a treatment of scattering based on time-dependentperturbation theory. Thus if we are interested in scattering into the solidangle dQ,,the relevant formula is

2ir)

G.11.23

[see E.7.31)].

Coming backto scattering,which we view as a transition rate w from into a group of states element dti, we subtending the solid-angle |k) have w given by (for elastic scattering k''= k)

|k')

277

h
from the

G.11.24
be equated to

goldenrule

This and E.6.34) G.11.14).must

(Incidentflux)
1

X

-rpr du

dti.
hk

G.11.25

As for the incident flux, we obtain [from j = (h/m)lm(\\p
/k-x A Im e~lk'x e V

m

mL

G.11.26
every-

Alternatively,
everything

incident
( mL3 hk
\\

flux

= velocity/volume= hk/mL3. Putting
( km
277

together

do

1 2m
But this

G.11.27
a similar manner.

Born [G.2.22)]. Higher-order terms can be obtainedin

is preciselythe result of the first-order Born approximation

7.12. Inelastic

Electron-Atom Scattering

429

To sum up, the time-dependent formulation based on the timeenables dependentSchrodinger quation [G.11.1)] us to derive easily the e results we obtained earlier using the time-independent formalism\342\200\224the Lippmann-Schwingerequation, the Born approximation, and so on. FurFurthermore, it turns out that the time-dependent formalism is more suitable for discussing o more-generalreaction processes ther than elastic scattering. As a concretexample to illustrate this point, we now turn to a discussion f o e the inelastic scattering of electrons by atoms.

7.12. INELASTIC ELECTRON-ATOMSCATTERING
in

Let us considerthe interactionsof electron beamswith atoms assumed to be their ground states.The incident electron may get scattered elastically with final atoms unexcited:

e~+atom (ground state) e~+atom (ground state).
\342\200\224>

G.12.1

This is an exampleof elasticscattering.To the extent that the atom can be regarded as infinitely heavy, the kinetic energy of the electron does not
I for change.t is also possible the target atom to get excited: e~ + atom (ground state) e'+atom (excited state).
\342\200\224>

G.12.2

In this case talk about inelastic scattering becausethe kinetic energy of we the final outgoing electron is now less than that of the initial incoming the electron, differencebeing usedto excite the target atom. The initial ket of the electron plus the atomic system is written as

|k,0>

G.12.3

where k refers to the wave vector of the incident electron and 0 stands for the atomic ground state. Strictly speaking G.12.3) should be understood as the direct product of the incident electron ket |k) and the ground-state atomic ket |0). he correspondingwave function is T
x

L3/2

G.12.4

where we use the box normalization for the plane wave. We may be interested in a final-stateelectron with a definite wave vector k'.The final-state ket and the corresponding ave function are w
and

-^^k\"x^(x1,...,xz), G.12.5

where n

w Assuming that time-dependentperturbation theory is applicable, e can immediately write the differential cross section, as in the previous

= 0 for elastic scattering and n + 0 for inelastic scattering.

430

Scattering Theory

section:

In

da

1
(hk/meL )

2tt h

(k'n V

kO)

,2i

L_

k'm(

G.12.6)
is similar, including the cancellationof terms such as L3, with Everything is one important exception: /c'=|k'| not, in general, equal to fc = |k| for inelastic scattering. The next question is, What V is appropriate for this problem? The to incident electron can interact with the nucleus,assumed be situated at the So origin; it can also interact with each of the atomic electrons. V is to be written as 7p
x
\342\200\224

x

G.12.7)

Herecomplications may arise because of the identity of the incident electron with one of the atomic electrons;to treat this rigorously is a nontrivial task. Fortunately, for a relatively fast electronwe can legitimately there is little overlap between ignore the question of identity; this is because We the bound-stateelectron and the incident electron in momentum space. when explicitly writmust evaluate the matrix element (k'/7|F|k0), which,
written,

is

= <k'w|F|kO>

\\ Id3xeiq'x(n\\L

x x
\342\200\224

P>

Ze

+E

G.12.8
with
\342\200\224

Let us seehow to evaluate the matrix element of the first term, F Ze2/r,where r actually means |x|. irst we note that this is a potential between the incident electron and the nucleus, which is independent of the atomic electron coordinates. it can be taken outside the integration So

q =k

\342\200\224

k'.

n/
in

we G.12.8); simply

obtain
this

G.12.9)
for the remainder. In other words,
term

contributes

only

to the

Inelastic 7.12.

Electron-Atom Scattering

431

case, where the target atom remains unexcited. In the elastic-scattering elasticcase must still integrate eiq'x/rwith respectto x,which amounts we be done because already evaluated in Section7.2the Fourier transform we of the Yukawa potential [seeG.2.6)conjunction with G.2.2)]. in Hence
to taking the Fourier transform of the Coulomb potential; this can readily

= Urn
q
As

G.12.10

x

l/|x + We x,|.
\342\200\224

for the secondterm in G.12.8), evaluate the Fourier transform of we can can accomplish this by shifting the coordinate variables
x x ,-:

-\302\273

J
Notice that
this

IX

Xf-|

. J

|X|

ql .

T eiq'x-

A

12 11)

is just the Fourier transform of the Coulomb potential the Fourier transform of the electron density due to the multiplied by atomic electronssituated at

x.:

G.12.12
We customarily define the form factor Fn(q) for excitation

follows:

|0) to

\\n)

as

G.12.13
which

is made of
relationcontributions

coherent\342\200\224in

the

ships
have

from the various

sense of definite phase relationelectrons. otice that as q 0, we N
\342\200\224>

for n = 0;hencethe form factor approaches unity in case.For n # 0 (inelastic scattering), Fn(q)-+0as q

the elastic-scattering
-\302\2730

between \\n) and

|0).

by orthogonality

We

can then

write

the matrix element in

as G.12.8)

Ze2

2 x-x,

G.12.14
section We are finally in a positionto write the differential cross for inelastic(orelastic) cattering of electronsy atoms: b s

da
@->\302\253)

=
\\kj

2me 4>nZe2 r
2
h

+
\\kj

Fn

(q)

G.12.15

432

Scattering Theory

Forinelastic scattering the S^-termdoesnot contribute, and it
to write the differential
h

crosssection in terms of the Bohr radius,

is customary

G.12.16
1

as follows:

do

0

G.12.17

Quite often do/dq is usedin placeof do/d&;using q2 = and dq =
\342\200\224

= |k-k'|2k2 + k'2-2kk'cos6 do ~ lirq do
__

G.12.18

we can d(cos0)kk'/q, write dq

kk'

G.12.19

stopping

The inelastic crosssection we have obtained can be used to discuss energy loss of a charged particle as it goes through matter. A number of people,including H. A. Bethe and F. Bloch, have discussedthe quantum-mechanicalderivation of stoppingpower from the point of view of the inelastic-scatteringcrosssection.We are interested in the energy loss of a charged particle per unit length traversed by the incident charged particle.The collisionrate per unit length is No, where N is the number of atoms per unit volume; at each collisionprocessthe energy lost by the charged particle is En Eo. So dE/dxis written as
power\342\200\224the
\342\200\224

dE
dx
n

da @ dq

\342\200\224>

n)

dq

ax

dq

J

q min

G.12.20

There are many paperswritten The upshot of all this is to formula for stopping power,

justify

on how to evaluate the sum in G.12.20) quantum mechanically Bohr's 1913
In

dE
dx

4-rrNZe4

Bm v

G.12.21
A966) and

where

/

is a semiempiricalparameter related to the average excitation
elementary

*For a relatively
Jackiw A968).

discussion,

seeK. Gottfried

H. A. Bethe and R. W.

7.12. Inelastic

Electron-Atom Scattering

433

energy (En Eo). If the charged particle has electric charge + ze,we just Z replace e4 by z2Ze4.It is also important to note that even if the projectile is still the is not an electron, me that appearsin G.12.21) the electron mass, o S not the massof the charged particle. o the energy lossis dependent n the charge and the velocity of the projectile but is independent of the mass of This the projectile. has an important application to the detectionof charged
\342\200\224

particles.

Quantum mechanically,we view the energy lossof a chargedparticle At as a seriesof inelastic-scatteringprocesses. each interaction between the chargedparticle and an atom, we may imagine that a \"measurement\" of the position of the charged particle is made. We may wonder why particle tracks in such media as cloud chambers and nuclear emulsionsare nearly is sharply straight. The reasonis that the differential crosssection G.12.17) t peaked at small q\\ in an overwhelming number of collisions, he final direction of momentum is nearly the same as the incident electron due to the rapid falloff of q~4 and Fn(q) for large q. Nuclear Form Factor
q

or Fn(q) drop off very rapidly.

~109 to 1010 If q is too large, the contributionsdue to F0(q) cm\021 cm\021.
At

The excitation of atoms due to inelastic scattering is important for

Coulombpotential due to the point nucleus must now be replacedby a Coulombpotential due to an extended object,

~ l^12cm~\\the structure of the nucleus becomesmportant. The 1/-R i nucieus

extremelyhigh q, where q is now of order

Ix-x
where N(r) is a nuclear charge distribution, normalized so that

jd3x'N(r')=l.
The pointlike nucleus can now be regarded as a specialcase, ith w

G.12.23

N(r') = 8C)(r').
We can evaluate the Fourier transform of the

analogy with

as follows: G.12.10)
n v

right-hand

G.12.24 in sideof G.12.22)
r
r
\\

//\342\200\242

J

I

d3x'Piq'xN( = /p r'}
\342\200\224

r

'x

\342\200\224

xr|

J

I

n vp

\"

A/i

J

I

r

--F
9

nucleus VM/

(a)

A\\2 25) '
V
\342\200\242XA--^--//

434

Scattering Theory

where we have shifted the coordinates x

-\302\273

x+

x' in

the

first

step and

G.12.26
We

obtain the deviation from the Rutherford formula due to the of the nucleus, size
thus
Rutherford

finite

where (da/dfl)Rutherford is the differential cross section for the electric of electrons a pointlike nucleusof charge Z\\e\\. For small q we scattering by have
(

/q-x-|<? V(q-rJ

G.12.28
vanishes becauseof spherical symmetry, and in the ^r2-term The we have used the fact that the angular averageof cos20(where 6 is the angle between q and r) is just \\:
q\302\253x-term

H G U I COS I
z~f
/-\302\273/'~\\c

H ItOo i7 ^^ l/^/^xo
\342\200\224

\342\200\224\342\200\224

.

III) .VL.Ljj
I /
1vJ 1

The quantity
In

is possible \"measure\" the sizeof the nucleus and also of the to as doneby R. Hofstadter and coworkers. the proton casethe spin In proton, effect is also important. (magnetic moment)
this way it

</2)nucieus *s known

as the mean square radius of the nucleus.

7.13. OULOMBSCATTERING C
This last sectionwas not written even in preliminary form by Professor Sakurai,but it was listedas an item he would like to considerfor Modern Thomas Fulton of The JohnsHopkinsUniProfessor Quantum Mechanics. notes on Coulomb University graciously offered to contribute his own lecture in honor of ProfessorSakurai's memory. The scattering for this section this gestureof friendship.However,the reader editor deeplyappreciates needs be alertedthat there couldbe stylistic and even notational changes to herefrom the rest of the book. In this revisededition, the material is somewhat reorganized; the resultspreviously obtainedare still given in the main text, while principal the mathematical detailsare now presentedin Appendixes and C.2. C.I Much of this material is a slightly expandedversion of Gottfried's treatment (Gottfried 1966, and pp.148-153) uses the notation of thi?

7.13. Coulomb

Scattering

435

text.The

for example, Bohm 1951, Schiff 1968) y dealing directly with the and b is the asymptotic forms. The differential equation G.13.7) standard form, which can alsobeobtainedby separating variables in parabolic coordinates. It can be recognizeds the differential equation for the confluent hypera function,* and so the properties of this function (including geometric t H asymptoticforms) can be appliedto analyse this case. owever,he present alternative approach can pass directly to the asymptotic limit by using variable techniques C.I Laplacetransforms and complex (seeAppendixes and C.2), thus avoid referring to the detailedproperties the confluent of and hypergeometric function. Clearly, this simplerapproach, which can be understood without any reference material outsidethe presenttextbook, to losesinformation about the scattering wave function at the origin. Thus, for example, wecan say nothing about the Gamowfactor? which is relevant for the study of many nuclear reaction rates.The interested reader is therefore encouraged supplement is knowledge to herewith reading from h other texts (e.g., t Schiff 1968)hat deal with the behavior of the Coulomb wave function at the origin via power series expansionof the associated confluent hypergeometricunction. f Scattering Solutionsof the Hamiltonian of the Coulomb Interaction
We start
Coulomb

treatment of Coulombpartial waves is original. The present of discussion Coulombscattering differs from the standard treatment (see,

with

the three-dimensional Schrodingerquation with Coue

potential
V(r)

=

ZlZ2??

G.13.1
a -Z2e, s follows:

for a collision betweenparticlesof chargesZxe and

_h
or

v2

ZxZ2e

V2

+

k2

+

\342\200\224

]i|/(r) = 0

G.13.2b

where m is the reduced massm = mxm2i'(ffij + m2) for the particlesZxe
instance, E. T. Whittaker and G. N. Watson, A Course of Modern Analysis, Cambridge University Press,1935), Chapter XVI. fG. Gamow, Z. Phys. Vol. 57, no. 204A928); R. W. Gurney and E.U.Condon, Phys. Rev. Vol. 33,no. 127 A929).

*See,for

4th

ed.(London:

436

Scattering Theory

and
yk

The -Z2e. yk

in

is given G.13.2b) by
i Z2c

= -+
ft

or

v

a=

he

1 137.03608 G.13.3)

to Note that 7 > 0 corresponds attraction. As long as we are interestedin a pure Coulombfield, it is possibleto write our solution v|ik(r) to G.13.2)

as

u

=

\342\200\224

ikr{\\

cos6) =

ik(r

\342\200\224

z) =

ikw

G.13.4)

r

= kz.
<j>

The separationof variables for i|>k(r) in G.13.4) is plausibleif we recognize of A) that the solution will not involve the azimuthal angle because the axial symmetry of the problemand B) sincei)>k(r) represents complete the Coulomb-wave function (incident plus scatteredwave), terms must exist in its dominant asymptotic form that contain e*'rand r~lelkr. We will demonstrate shortly [seeEquations G.13.9a), and G.13.14) of that, with the choice independentvariables we areabout to make, this will indeedbe the case. of (Another argument for our particular choice variables is given by Gottfried 1966, 148.) Let us choosendependentvariables (z, w, X) where w = r z i and X can be taken to be cj), on which the solution v|ik( r) does depend. not In changing our Cartesiancoordinates(jc, y, z) to (z, h>, X),

G.13.13),

-

use\342\200\224for

example\342\200\224such

as expressions
dw

d dw d

dx

dx
X

dz d dx dz

dk d

dx dk

ax

d

r

dw

dx dk

G.13.5)
*
\302\246

Note that because elkzx(u) is independentof X, the operationd/dk makes no contribution. The reader ill readily verify that, operating on e w

1
dx

2\\

r2 dw2
y_

r3, r3,
w _d_ dw

By

r2 dw2
w2

G.13.6)
2w d2 r dzdw

d2
dw2

r2

72

2) _d_

73, dw

+

W
\342\200\224^

d
dw

r

+

d

dz

^

7.13.Coulomb

Scattering

437

in G.13.2),have we UsingG.13.4H7.13.6) d2 , d + (l-u)\342\200\224-iy
u\342\200\224^

du

du

X(u)

=

0.

G.13.7)

case\342\200\224that

considers asymptotic the Our first attempt at the solution of G.13.7) is,solutionsfor large r z (away from the forward direction, cos6) = 0 for 6 = 0). Let us try two types of since r z = r(l ~ wx and B) x ~ e\". solutions,A) x The first type of solution requires G.13.8) (-X i7)iix 0, or X = -17
\342\200\224 \342\200\224 \342\200\224

-

-

and, hence,
X(u)

- u'h- e'h -

ln

k(r~z)

In _ ^/[k.r-7 k(r-z)]

G.13.9a G.13.9b

T clearly representsthe incomingplane-wave piece. he Equation G.13.9b) second type of solution, x ~ eu, manifestly satisfies u(d2x/du2) features u(dxldu) = 0,so heuristically we try for a solution that combines of both solutions in productform,

-

X(u)

ukeu,

G.13.10
X

and substitute into The coefficient of ux+leu obviously vanishes, while the coefficient of the wV-term leads to the following relation:
2X

G.13.7).
A

+

- X)
\302\253

17

=

0,

or

=

-1+ 17.

G.13.1

Hence,
X(M)

fLL
U

\302\253

ACl

J

V

Z,

)

en m kir-z)

G.13.12

and
J[kr + y
In

k(r-z)]
,
two

i|i(r)

G.13.13
solution
\342\200\224

clearly an
by

normalizedwave

G.13.9) G.13.13) linearly noting = 2r sin2(8/2)while ln[2Ar sin2(8/2)]= lnBfcr)
and and
function

outgoing

sphericalwave. Combining the
that

r

z

+ 2 In

sin

as

F/2),we write the
ln

= r(l

piecesgiven cos 6)
\342\200\224

1
Btt)
3/2

J[k.r-yln(fcr-kr)] ,

G.13.14

Thereareextra phase effects at large r, which is due to the long range of
the Coulombinteraction.

438

Scattering Theory

Now we must find the Coulombscattering amplitude fc(k, 0). Inz): Interestingly, asidefrom a factor of y/k, the magnitude is just from (r But we (l/2k sin 8/2),which appears in the asymptotic form have to work hard to get the Because detailshere arequite involved to the first-time readers encouraged i mathematically Appendix focus only on the final results summarized below. The physical basis of
\342\200\224

(c.f.

it!

G.13.13).

C.I),

our resultsarediscussed later on in this section. For the normalized i|ik(r) we obtain

1
Bir)
3/2

i[kz-y

In

k(r-z)] ,

51 1/
V

gl(y) 2k sin2F/2)

?

~

G.13.15
This exhibitsexplicitly all the r- and ^-dependentphasesand leads to the identification from G.13.14) that + j[eG) ln sin(e/2)]

^'

=

2\302\253y

\302\260^

2k sin2F/2)

eie(y)

=

Thus, as in

the sectionis G.1.36), differential cross

G.13.
where y is given by G.13.3)\342\200\224and we areback to the Rutherford formula of Forthe aficionados, e remind the reader f Hankel's w o formula

G.2.11).

rB)
(which

G.13.18

checks z = 1and T(l) = 0!= for

T 1). hus

Partial-Wave Analysis for the CoulombCase
We can rewrite i|>(r) from

and as G.13.4) (C.I.5)

c euttly-\\l

- t)ndt

7.13.Coulomb

Scattering

439

=A
=

J e*-V*(r-z)'(l t)d(t, y)dt
y)dt

AJceik\"eik\302\2531-<\\:

- t)d{t,

G.13.20

where

-iy-l G.13.21 d(t, 7) = We perform the partial-wave expansionof the plane wave analogous to as G.5.18)
oo

=
\302\253l\302\27300

E B/ + 1=0

9)A?kr),

G.13.22

where

A^kr) = A JI
Now, //

- t)](l - t)d(t, y)dt.
1
i

G.13.23
*

= 2(MX) +

(seeAppendixA

where the htp aresphericalHankel functions h\\^*)y and Whittaker and Watson 1935), = ?/(p)elp/p, /i/(p) 0

?/(p)

+5i

li
hi

G.13.24

we and, asymptotically, ?/(p) = (~/)/+1+ 0(P l)- Hence, write Aikr) = A\\l\\kr) + A\\2\\kr), G.13.25 where A\\1^ and A\\2^ correspondto the contributions from
respectively.

and hf,

re-

C.2 leads to the following results and
and

The explicit evaluation of A^\\kr) and A\\2){kr) is given in Appendix

=0
A?\\kr)

G.13.26

x
+ fe-i[kr-(M2)y
In

2kr]

_

In 2A:r

]i

G.13.27

where we have optimistically introduced a real phase i)i(k):

G.13.28

440

Scattering Theory

Note that we write T)t(k) because dependson k 7
t\\i(k)

Let us look briefly at some simpleexamplesto demonstrate is indeed a real phase.For / = 0,

[seeG.13.3)].
that

= 1,

2mg3(y) =

= 2itigt(y) =

2iri

ry)'

For/ =

1,

fy)' we have

G.13.29
Ef 2i
^

1-

-s
s
Ids

1\342\200\224s/2L

1

=

\342\200\224

2m
\342\200\224

1

rB

rB +

ry)

[A

+ 17) 2] =

-

rB + 17) rB + 17) Thus for a general/, we The same pattern repeats for / = 2,3,
conjecture

17) TB

-

17) 17)
ry)

G.13.30

....
- iy)

G.13.31
As a final summary we remark that the Coulombpartial-wavediffers from the general artial-wave case (seeSection scattering case p 7.6) only through the modification J(kr-(M2)) 2ikr 2i^ J(kr-(M2)+ y
In

2kr)

2ikr

G.13.32

=

Let us note
wave function,
written G.1.33),

the asymptotic form of the Coulombscattering is different from that which appearsin Eq. Eq. for large r as
that

G.13.15),
jkz

Jkr

G.13.33

The latter form is valid only for short-range forces, hile the Coulomb w force is a long-range one.The form is modified as followsfor the Coulombinteraction: The first term on the right-hand side of G.13.15

G.1.33')

Problems

441
elkz

but as in G.13.33), also a modifying, the factor e~nln *(r~z).Hence, coordinatedependent,multiplicative phase of how far away the incident plane wave is slightly distorted,irrespective term on the right-hand A particle is from the origin. nalogously, the second to the outgoing sphericalwave, contains side of G.13.15), corresponding i the r dependentphasefactor en In 2kr. Nevertheless,n spiteof these longeffects leading to phase factors that vary with distance,we can still range the define a scattering crosssection for short-range forces because disalter physically observablequantities (e.g., terms, although they distorting l the mean current), ead to alterations that vanish as r goesto infinity.

contains not only the factor

PROBLEMS

1.The Lippmann-Schwingerformalism
potential,

can also be applied to a onedimensional transmission-reflection problem with a finite-rangepotenV(x)?= 0 for 0 < |x|< a only. a. Supposewe have an incident wave coming from the left: (x\\(j>) = How must we handle the singular \\/{E HQ)operator if we are to have a transmitted wave only for x > a and a reflected wave and the original wave for x < Is the E -> E + ie prescripstill correct? Obtain an expression for the appropriate Green's function and write an integral equation for (x\\\\p(*]). b. Considerthe specialcaseof an attractive 5-function potential

^n.

\342\200\224

\342\200\224

a]

prescription

V= lyh2
\342\200\224

2m

)\302\253(*)

(y>0).

one)bound state for any value of y. Show that the transmission and reflection amplitudes you computed have bound-state poles at the expected positions when k is regarded as a complex variable. 2. Prove
only
'tot

C 52. amplitudes. heckyour results with Gottfried 1966, c. The one-dimensional5-functionpotential with y > 0 admits one (and

Solve the integral equation to obtain the transmission and reflection

-

m2 r
mn

.?

J

r /,/v J
.\302\246>

.....,
x_., r

sin2k\\\\-\\'

k

|x-x

in

cross section computed using the first-order Born approximation. b. By applying the optical theorem to the forward-scatteringamplitude in the second-order Born approximation.[Note that /@)is real if the first-order Born approximation is used.] 3. Considera potential V = 0 for r > R, V = Fo = constant for r < 7?,

a. By

each of the

following ways. the differential integrating

442

Scattering Theory

where Vo may be positive or negative. Using the method of partial E = h2k2/2m and kR 1 the differential waves, show that for crosssectionis isotropic and that the total crosssection is given by
\302\253: \\VQ\\\302\253\302\253

2

can

Supposethe energyis raisedslightly. Show that the angular then be written as

distribution

Bcosv.
for Obtain an approximate expression B/A. 4. A spinlessparticle is scattered by a weak Yukawa potential
V

=
fir in

where ju > 0 but Vo can be positive or negative.It was shown that the first-order Born amplitude is given by

the

text

a. Using f{X){6)and assuming
terms of a

15/1

function of the secondkind, Legendre

[2A:2(l-cos0) for <zl,obtain an expression 5/ in

b. Use the expansion formula 1-3-5 B/+ 1)
\342\200\242\342\200\242\342\200\242

X

(/ + l)(/+ 2)(/ + 3)(/ + 4)^_
+ + 2-4-B/ 3)B/ 5)
f/+5
to prove each assertion. (i) 8/ is negative (positive) when the potential
(attractive).

???
2B/+ 3)

\\

/

( ' Vl

is repulsive(attrac-

(ii) When the de Brogliewavelength is much longer than the range of the potential, 5/ is proportional to k2l+l.Find the proportionalproportionality

constant.

Problems

443

5. Checkexplicitly the x

relation for the ground state of px uncertainty for a particle confined inside a hard sphere: F=oo r > a, V=0 for r < a. (Hint: Take advantage of spherical symmetry.) 6. Considerthe scattering of a particle by an impenetrable sphere
\\

-

oo

for r

< a.

a. Derive an expression for

b.

the s-wave (/ = 0) phase shift. (You need not know the detailed properties the spherical Bessel unctions to of f be able to do this simple problem!) What is the total crosssection o [o = dQ,]in the extreme limit k -> 0? Compare your answer with the geometric low-energy crosssection 7ra2. You may assume without proof:

j(do/d?l)

d\302\260=\\f(ey2

7. Use8,=k(b)\\h^l/k to obtain the phaseshift 8, for scattering at high a energies (a) the Gaussian potential, V = by r2/a2), nd (b) the Yukawa potential, V= Foexp( jur)//xr.Verify the assertion that 5, kR, where goesto zero very rapidly with increasing I (k fixed) for
Foexp(\342\200\224
\342\200\224

/:\302\273

R

is the

8. a. Prove

G.4.14)].

\"range\"

of the potential. [The formula for A(&) is given

in

\342\200\224

lip. T\" IE u

I

,

m

b. For sphericallysymmetric
\\Elm(

where r< (r>) stands for the smaller (larger) of r and r\\ potentials, the Lippmann-Schwinger qua e tion can be written for spherical waves:

+ )) = \\Elm)+
in

Using (a), show that this equation, written leads to an equation for the radial function,
2mik
h 00
X

the x-representation,

A((k\\r),

as follows:

/

jl(kr<)h(j1\\kr>)V(r')Al(k;r')r'2dr'

444
By taking

Scattering Theory

r very large, also obtain sin 8,

.
{

Bm)
h2

L o

9. Considerscattering by
h

a repulsive 5-shellpotential:

2ra

ti I
1

(y>o)

a. Set up

b.

an equation that determines the s-wave phase shift 80 as a function of k (E = h2k2/2m). Assume now that y is very large,

to Show that if tan/:/? is not close zero, the s-wave phase shift in resembles hard-sphereresult discussed the text. Show also that the for

to (but not exactly equal to) zero, resonance tan kR close behavior is possible;that is, cot50 goes through zero from the D positive side as k increases. etermine approximately the positions of the resonances keeping terms of order 1/y;compare them with the bound-stateenergiesfor a particle confined inside a spherical wall of the same radius,

K=0, r<R;
\"

F=oo, r>R.

Also obtain an approximate expression the resonancewidth T for defined by

-2

[d(cot80)/dE]\\E=Er
and notice, in particular, that the resonances ecome b extremelysharp as y becomeslarge. (Note: For a different, more sophisticated who discusses approachto this problem seeGottfried 1966, the analytic properties the /^-function defined by A{ = Ji/Dt.) of A 10. spinlessparticle is scattered by a time-dependentpotential

131-141,

y(r,t) = F(r)cosco/.
Show that if the potential is treated to first order in the transition or amplitude, the energy of the scattered particle is increased decreased hco. Obtain do/dQ,.Discuss qualitatively what happens if the by higher-order terms are taken into account. Show that the differential crosssection for the elastic scattering of a fast

11.

Problems

445
by

electron by the ground state of the hydrogen atom is given

do

Am2e

16

\\2 I

12. et the L
functional

the (Ignore effectof identity.)

energy of a particle moving in a central field be E(JlJ2J3), where (JVJ2,J3) the three action variables. How does the funcare form of E specializefor the Coulomb potential? Usingthe recipe of the action-angle method, compare the degeneracyof the central field and the Coulomb problems relate it to the vector A. and
If the Hamiltonian is
2/x

how are these statements changed? o Describe corresponding the degeneracies f the central field and Coulombproblemsin quantum theory in terms of the usual quantum numbers (n, /, m) and also in terms of the quantum numbers (k, m, n). Herethe secondset, (k, m, n), labelsthe wave functions ^^n(a/3y). How are the wave functions 2^n{afiy) related to Laguerre times

sphericalharmonics?

APPENDIXA

Brief Summary of ElementarySolutionsto Wave Equation Schrodinger's

wave Here summarize the simple solutions to Schrodinger's equation for we a variety of solublepotential problems.

A.I.FREEPARTICLES 0) (F=
The plane-wave,or momentum, eigenfunctionis

B*)
where

h'
and our normalization is

h

2mh

2m

I The superposition plane waves leads to the wave-packetdescription.n of the one-dimensionalcase,

-00 For |A(k)| sharply peaked near
446

k^k0,the

wave

packet moves with a

A.2. Piecewise

Constant Potentials In

OneDimension

447

group velocity
hk o
g
*

dk J k0

m

(A.1.5)

The time evolution of a minimum wave packet can be described by 1/4 hk2 2w where 1/2

'

(A.I.6)

Xexp{

\342\200\224

hkot/m) 2(Ax)l\\l + (h2t2/4rn )(AxH
\342\200\224

.

(A.1.7)

So the

width

of the wave packet expandsas

(AjcH at f =

1+

1/2

4m

at/>0. (A.I.8)

CONSTANTPOTENTIALS ONEDIMENSION IN A.2. PIECEWISE The basic solutions are:

E>V=V0:

\342\200\224

ikx

k

, = \\l,2m(E-V0) .(A.2.1)
y\342\200\224~\342\200\224\342\200\224

E < V = Vo (classicallyorbidden region): f
c_e~KX,

2m(V0-E)

(A.2.2)

(c

be set equal to 0 if x = oo is included in the domain under discussion).
must
\302\261 \302\261

Rigid-Wall

Potential (One-dimensional ox) B

Here
y
\342\200\224

0
oo

otherwise.

forO<*<L,

(A.2.3)

448

Brief Summary of Elementary

Solutions to Schrodinger's Wave Equation

The wave functions and energy eigenstatesare = , 2 (rvnx\\
\\l
\342\200\224

sinl

.

-j-

I,

\302\253

=1,2,3...,
(A.2.4)

2mL Square-WellPotential The potential V is

v=

@
rz

for c

Ijcl

>a

\\\\

a,
for for

n\\

(A.2.5)

,

The bound-state < 0) solutions are: (E

~ { coskx (even parity))
sin A:x
\342\200\242#

|x|>
(A.2.6)
\\x\\<a>

^ (oddparity)
^
\342\200\242\302\246

\\

J

where

The allowed discretevaluesof energy E =
by solving ka
tan

- h2K2/2mare to be determined
, ,

ka cot ka
YYl

= Ka (even parity) = Ka (oddparity).

-

Note also that

k and

A:

are related by
V r\\Cl
2\342\200\224

=

h

(A.2.9)

A.3. TRANSMISSION\342\200\224REFLECTION PROBLEMS
In this discussion define the transmission coefficientT to be the ratio of we the flux of the transmitted wave to that of the incident wave. We consider

thesesimpleexamples. SquareWell
T=

(V-0for |jc|> a, V= - Vo for 1
(A:'2

\\x\\

< a.)

- k2J/4k2k'2]sin22k'a
1
(A.3.1)

+ V0)/h [vo2/4E(E+ F0)]sin2Ba/2m(?

A.3.

Transmission\342\200\224Reflection

Problems

449

where

Note that resonances occur whenever
. 2a\\l

2m(E+ V0) =mr,
h

n

=1,2,3,....
\\x\\

(A.3.3)

Potential Barrier (F=0for

Case1:E <V0.

> |:t| a, F= Fo >0for

< a.)

[VO2/4E(VO

- ?)]sinh2Ba/2m(F0E)/h
V
V

1

.

(A.3.4)

with Case 2: E > VQ. This case the same as the square-wellcase is replacedby Vo.
\342\200\224

Vo

Potential Step (V

-0 for x < 0, drk *kk

Fo

for
\302\260

x >0,and E > Fo.)

Twith

,=

4)I(E-VO)E

,

(A.3.5)

2mE

,

^' kd 2m(E-V0) .

(A.3.6)

MoreGeneralPotentialBarrier [V(x) >E for a < x <b, V(x)<E outside range (a,b].] The approximate JWKB solution for T is = exp
-2jVxy\342\200\224

'-^' \"' },

(A.3.7)

where a and b are the classicalurning points. t
JWKB stand for Jeffreys-Wentzel-Kramers-Brillouin.

450

Brief Summary of Elementary

Solutions to Schrodinger's Wave Equation

A.4. SIMPLE HARMONIC OSCILLATOR

Here potential is the
V(x)=

2 2

(A.4.1)
X.

and we introduce a dimensionless variable
h

(A.4.2) (A.4.3)
(A.4.4)

The energy eigenfunctionsare 1/4 and the energy levelsare

E = hco\\

n

+

\342\200\224

I,

w

=

0,1,2,....
properties:

The Hermite polynomialshave the

following

'oc

Hn
n

=0

= 24,
//4D) = 16C4 4842 +

(A.4.5)

-

2,H 12

A.5. THE CENTRALFORCEPROBLEM [SPHERICALLY SYMMETRICALOTENTIAL F* F(r).l P

Here basic differential the

equation is

\\d
2m
d<j>

1
r2sin6

sin^

do

(A.5.1)
where our spherically symmetrical potential V(r) satisfies

limr2F(r)->0. r-*0

(A.5.2)

A.5.The Central ForceProblem

451

The method of separation of variables,

= R{x)Y

(A.5.3)
8

leads to the angular equation

l

d i .

sin0 30

sin0

d

1
sin20

(A.5.4) (A.5.5)

d<}>

h where the spherical armonics
satisfy
m

(A.5.6)

and

Ytm{d,

<f>)

have the following properties:

w)!
YrF,<t>)=

'
for m

(-

> 0,

form<0, dm m/2 f P,(cosd) orw>0, d(cos0)
m

^'(l-cos20) p,(cose)= -1)' 2'/! d{cosd)' 1
2a\\>
Y\302\260

4tt

(A.5.7)

\302\260

=
1673-

Ccos20-l),

y2 _
\302\2612

l/

32tt

Forthe radial piece (A.5.3), us define of let = rR(r).

(A.5.8)

452

Brief Summary of Elementary

Solutions to Schrodinger's Wave Equation

Then the radial equation is reduced to an equivalent one-dimensional

problem,namely,
H2

d2u

2m

V(r)

\\)h

2mr

uE

= EuE
(A.5.9)

subjectto the boundary condition

Forthe caseof free particles [V(r)= 0] in our sphericalcoordinates: R(r) = clj,(p)+c2nl(p) = 0 if the origin is included.)(A.5.10) (c2
where p is a dimensionless variable
p = kr, k

= 2mE

(A.5.11

We need to list the commonly usedproperties the Bessel unctions of f and sphericalBesseland Hankel functions. The sphericalBesselfunctions are

2p

-/-1/2
Jo(p) =
smp
sin p

cosp
p

cosp

cosp

sin p

(A.5.12)

Ji(p)=

P,

I) smp
cosp

cosp,
3

. rsinp.
p-0

Forp ->0, the leading terms are
where

p-oB/+ 1)!!'
1

B/-1)!! (A.5.13 7+1
(A.5.14)

In the large p-asymptotic limit, we have

7/(p)p->00 p cos P
w/(p) p-100 p
>

i

(/ + l)ir\"
2

1sin

P

(/ + 1)tt'
2

(A.5.15)

A.5. The

Central Force Problem

453

of Because constraints (A.5.8)and (A.5.9), must be finite at R(r) = 0;hence,from (A.5.10) (A.5.13) seethat the /t/(p)-term must we and be deleted because its singular behavior as p 0.Thus R{r) = C///(p) of in the notation of Chapter VII,Section 7.6, t(r) = R(r) = C///(p)][or, A For a three-dimensional p (with square-well otential, V = -V{)fovr<R Vo > 0), the desiredsolution is
r
\342\200\224\302\273

R(r) = At{r)= constant j/(ocr),
where a = 2m(V0-\\E\\)
h2

(A.5.16) (A.5.17)

1/2

r<R.

in discussed G.6.30),exteriorsolutionfor r > R, where V = 0, can be the written as a linear combination of spherical Hankel functions. Theseare defined as follows:

As

(A.5.18)
which, from have (A.5.15), the asymptotic forms for p -> oo as follows:
oo

p
oo

(A.5.19)

If we are interested in the bound-state energy levels of the threedimensional square-wellpotential, where V(r) = 0, r > R, we have
uA

/

W r) = rAA r) = constant e -KrA j\\
X X

\342\200\224

1

1/2

(A.5.20)

To the extent that the asymptotic expansions, f which (A.5.19) the o give leadingterms, do not contain terms with exponent of oppositesign to that r> desiredsolution from (A.5.20): given, we
have\342\200\224for
R\342\200\224the

At(r) = constant /^(//cr) = constant [y7(iKr)+ in7(//cr)], (A.5.21)
where the
first

three of these functions are

1 ... 1
K2r2)
K2r2

(

1

(A.5.22)

Kr

454

Brief Summary of Elementary

Solutions to Schrodinger's Wave Equation

[V(r)= 0] to

E-Vo. = J2m(V0-E)/h2.

Finally, we note that in considering the shift from free particles the case of the constant potential V(r) = V0, we need only to a the by replace E in the free-particle solution [see (A.5.10)nd if E < Vo, h^2\\iKr)is to be used with k Note, though, that

(A.5.11)

A.6. HYDROGEN ATOM

Herethe potential is
V(r) =

- Ze
1/2

(A.6.1)

variable and we introduce the dimensionless
8me E P = h

(A.6.2)

The energy eigenfunctionsand eigenvalues(energy levels)are

' 2Z
En =
2n2ao

(n

{na0 2n[{n +

-/-I)! 1/2
(A.6.3)
h

(independent of / and m)

0 = Bohr radius =
n

mee

>

2Zr
na o

The associated Laguerrepolynomialsare defined as follows
dpq
where\342\200\224in

(A.6.4) (A.6.5)

particular

dp
and the normalization integral satisfies

(A.6.6)

A.6. Hydrogen Atom

455
n

The radial functions for low

are:
3/2
2e~Zr/a\302\260

f

Z ) 3/2

2ao) 2ao
The radial integrals are

B-Zr/ao)e-Zr/2a\302\260

(A.6.7)

( Z ) 3/2 Zr

-Zr/2a0

[3n2 [5n

-

1)] 1)] (A.6.8)

APPENDIXB

Proof of the Angular-Momentum AdditionRule
Given by EquationC.7.38)

addition rule from It will be instructive to discussthe angular-momentum the quantum-mechanical point of view. Let us, for the moment, label our This we can always From Equation angular momenta, so that j\\ ;> the C.7.35), maximum value of m, mmax is

j2.

do.

max

=

(B.l.l)

that corresponds the eigenvaluemmax, whether the to descriptionis in terms of \\j\\j2> mim2) or \\j\\J2> Jm)- ^n other words, w choosingthe phasefactor to be 1, e have = \\JlJ2> JJl) \\j\\h\\ h + J2, h + Jl)(B.1.2

There is only one ket

j

In the \\JiJ2\\rnlm2) basis, there are two kets that correspondto the m 1 and m2 = mmax eigenvalue mmax namely, one ket with ml = mmax = mmax and m1 = mmax and one ket with m, There is thus a twofold in degeneracy this basis; therefore, there must be a twofold degeneracyin the \\jij2, jm) basisas well. From wherecould this come? Clearly, mmax 1 is a possible m-value for = ji + j2- It is a possible m-value for = j\\ + j2 Soj\\, j2 can add fact, the maximum m-value for this to of j\\ + j2 and jx + j2 We can continue in this way, but it is clear that the degeneracy cannot increase indefinitely. Indeed, for mmin = j\\ j2, there is once + again a single ket. The maximum degeneracyis Bj2 l)-fold,as is apparent
\342\200\224

1,

\342\200\224

\342\200\224

1.

\342\200\224

j

als\302\260

\342\200\224

1\342\200\224in

j's

-1.

j.
\342\200\224

\342\200\224

456

Proof

of the

Angular-Momentum Addition Rule Given

by

Equation

C.7.38)

457

TABLE

B.I.Special Examples of Values
3

h = 2, j2 = 1 and h = 2J2 = \\' 2
A,

of m, mx, and m2 for the Two Cases
Respectively

h = 2, h = l
m

1

0

\342\200\224

1

\342\200\224

3

(ml9m2)

B,1) 1
2
5

B,0)
2
3

1)

B 1) A,-1)
3
1
2

@, A, 0)

1)

(-1,1)
@,0)
3
2
1

2,1) 1,0)
@,

(-2, -1) (-1,-1) -1)
2
5

(-2,0)

Numbers of States

3
\342\200\224

1

= 2, h = 2 J\\
m

2 A,

3

2 A

2

(m1(m2)
Numbers of States

B.1)
1

i)
A

@,

%

h (-l,i) 12) -i) -1)(-1, (-2,-2-)
@,

1

from Table

for
the

+ 2j2 l states j:

j\\

= 2,

f B.Iconstructed for two specialexamples:or j\\ = 2, j2 =1and = 2- This Bj2 l)-fold degeneracy must be associatedwith + j2

h
If we lift the restriction j\\

>---> ~ J2 Ji we obtain C.7.38). ;> j2,

APPENDIXC

Detailsof Coulomb cattering Mathematical S Formalism
C.I. THE COULOMBSCATTERINGAMPLITUDEfc{k,6)
Let us go back to the differential equation G.13.7). theory of differThe tellsus that the only singularity in the finite u-plane is at equations u = 0.* We (We want the solution that is regular at u = 0.) examine x(w) in the Laplacetransform space, t:
differential

X(m)

=
\342\200\224\302\273t2

J U eutf(t)dt,

P

(C.I.I)

where the path of integration t\\ in the complex f-plane will be decided later.If we substitute x(u)given by (C.I.I) G.13.7), obtain into we
f'2 J tx [ui1

- u)t -

i
emdt

/

- h)f- Jt[t(tevidently it

eutdt

= 0,

(C.I.2)

where we have integrated by parts. If we assumethat surface terms vanish,

- iy)f(t) -jt[(t-i)tf(t)] = 0' t)

(C.1.3

and we can easily obtain the solution for f(t) as
~h

(C.1.4 where A is someconstant.As an interim summary we have [from (C.I.I)] = A ' d\"F-r(\\- t)~iydt, f . (C.1.5 J Jf c c
X(\302\253)

I

tx

^

*For the

mathematical

of Modern
458

Analysis, 4th

background, seeE. T. Whittaker and G. N. ed. (Cambridge, London: 1935), Chapter XVI.

Watson, A Course

The C.I. Coulomb Scattering

Amplitude fc

(k, 8)

459

has branch Now we must choose Note that the integrand in For the surface seeFigure in the complex at t = f-plane; points to vanish, we require that the t at the end points contain term in u an imaginary part that goesto +00.This is because = ik(r z) = ikr
A

- cos0) =

(C.1.2)
ik

0,1

C

C.I.

(C.1.5)

and k

> 0.Hence,

-

h>

0.

and surface terms vanish. But there arelots of ways of reaching t = a + will give the correct The choice C indicated in Figure of asymptotic forms, as the actual calculations show [see(C.I. and we will adopt 10)],
i\302\260\302\260\\

C.la

this

specificcontour. Let s = ut. Then

becomes (C.1.5) iy-1
_
U
\342\200\224e
\342\200\224

S

-a

u

-a\\_dsessa Jc
x(\302\253)

l

(u

\342\200\224

s)

-a

(c.1.6)

We where C is the s-planecontour depictedin Figure C.2a. require that is regular at u = 0;in fact, it is because

x@) =

(-l)-'\\4 \\_-ds= (o\302\260\342\200\224the

(C.1.7)
limit\342\200\224and

We now evaluate for u -^> asymptotic the correctorm is obtained. For the curve Cx in Figure f

(C.1.6)
\302\261

fixed s, s
k
\342\200\224\302\273

(s0 ie) and slu = (s0 ie)/ik,but this is small for oo. So, e can expand(u w s) in powersof slu. For the curve C2 in

=

C.2b for a and

show that

\342\200\224

\342\200\224

\302\261

\342\200\224

/-plane

0

1
(a)

1

FIGURE and simple straight-line branch cut between (a) Branch point at t = distorted\" branch cut between @, 1) and a possible @, 1) in /-plane, (b) \"Rubber-band contour C for

C.I.

0,1

(b)

(C.1.5).

460

Mathematical

Details of Coulomb Scattering Formalism

s-plane

s=u=ikrA-cos 6)

(a)

s-plane

u

C,
(b)
FIGURE C.2, (a) .s-plane contour C into Q plus C2.

C for

Equation

(C.1.6). Rubber-band (b)
\342\200\224

distortion

of

so s s Figure C.2b, = s0 + j(k e); hence, /m = 1 (^0 /e)/kk-^1, we can not expandin powersof slu.However,if we change variables s sf here, is where = s u, then expansionabout s'lu possible. Hence, the contour C is now replacedy the contour given in Figure C.2b and, b takes C2 further, s
\342\200\224 \302\261 \302\261 \342\200\224\302\273 \342\200\224\302\273

s' s'

\342\200\224

\342\200\224\302\273

&

-

Q:

f

ds +

J C2

\\

c ds
5 =

J Cx 5' +
M

ds +

I

ds'

(C.I.8)

and
m) xO

-

A

\\ J cx

\"

~ s)iy]ds

(C.I.9)

C.I.he Coulomb Scattering T
Here(s' +
compactly

Amplitude fc

(k, 8)

461
and\342\200\224since

u)n is clearly expandablein s'/u, integration variable for the Q-contour\342\200\224we may write

sr

as

more (C.I.9) com-

is a dummy

-17
X(u)

= A u-a f ^nr-1 J
{

Cx

uj

ds

17-1
+
Note
euuiy

e5

1

s'nds. (C.I. 10)

that

G.13.12),
then

the coefficients of the two integrals in (C.I. u l and 10), ( 1) l7, do have the correctasymptotic forms [see G.13.9) and G.13.14)] for Coulombscattering. The leading terms in 10)are obtainedwhen we let s/u 0;
\342\200\224

(C.I.

\342\200\224>

X(M)

xdj

(C.I.11

2G) =
for Integrating the expression 2mg2(y) by parts, we have

)cx
Noting
that
\342\200\224

\342\200\224

00

\342\200\224

(C.I. 12)
u

= u*, =

we find

X(\")

.

,

= 2mAu~hgl(y)
where we have noted that

' ''ry

\342\200\224

(C.I. 13)
(C.I. 14)

Using

= (-if[k(r

- z)f =

(C.I.15

462

Mathematical

Details of Coulomb Scattering Formalism

we obtain the in going from x [multiplication by e as in G.13.4)], normalized asymptotic ita(r),which is given by Eq.
\342\200\224>

*l>

G.13.15).

C.2.EVALUATIONOF A\\l)
Let us note that
ikrt

FOR (kr) AND A\\2) (kr) NECESSARY OF THE PARTIAL WAVE ANALYSIS COULOMB SCATTERING

eikrt

w e-ikr{ \\-i) = ^-1 ^

(C.2.1

so that
A\\l\\kr)

= Aeikr
\342\200\224

f
\\cEl\\kr{\\

- t)]d(t,y)dt.
0,

(C.2.2)

from Et when the f-plane arebranch pointst = 0,1and possiblepoles its argument Ar(l the contour C in the manner t) vanishes, we close shown in Figure This leads at onceto
in
\342\200\224

0 -2 Since d(t,y) ~ t for large f and Et~ v ~ \\ and the only singularities

C.lb.

A\\l\\kr)
since\342\200\224thinking

=

(C.2.3

unit

sphere\342\200\224the

exterior

of a stereographic of projection the complexplane on the contour C can be viewed as surrounding the regionexto it, where thereareno poles. For A$2\\kr), we have

A?\\kr) =

Ae~ikr f
\342\200\224\342\200\224

ET

[kr(l

-

t)]e2ikrtd{t,

y)dt.

(C.2.4

We play the same game as we did between t = (u , where u = 2ikr; then t = slu and

1
\342\200\224

and Let (C.1.5) (C.1.6). s =
\342\200\224

\342\200\224

s)lu, so
\342\200\224

A)

aA\\/i

}(kr)=
\\

miZ,

I

t:,__v.-.m

1

U

3\\

lU

S\\ US

u

u

2/

-,
u

(C.2.5
\342\200\224u,

where C is like Figure C.2a that except now the ends of the branch point in the S-planeare s = 0 and s = 2ikr.We recallhat u* = t and therefore
A\\2)(kr)

= iAe -u/2
= iAe -u/2
fy

T7

\"=\\-/7-l

17* u

\342\200\224

s s

ds

1(u s)
\342\200\224

-iy-l

u

\342\200\224

2/ )

C.2.Evaluation

A) B) of A)lf (kr) and AT (kr)

463

ds
I
\\

iA u

-M/2--

1
2A:r
\342\200\224s

Ef

ds

\\2i

(C.2.6)
=
u

where in the last equation we have used the asymptotic form in for Ef (TU2i) as given in G.13.24). Note next that e~W2 u~h f
eW2e-i(kr+yin2kr).

()

becomes

(kr)

- - Ae

ity/2

2ikr

(C.2.7)
where

(C.2.8) ds.
Note giG) and g3(y) areused in and Eq.G.13.28),indeedlead to a real

phase tj/(A;).

I SUPPLEMENT

Phase Adiabatic Changeand Geometrical
When
this the author died in 1982, book was left in manuscript form; in there have beensome new developments quantum mesubsequently, mechanics. The most important development is a definitive formulation of The geometrical phases,introduced by M. V. Berryin 1983. phasefactors in a are accompanyingadiabatic changes expressedconcisend elegant forms and have found universal applications in various fields of physics,thus giving

a new viewpoint to quantum theory. We review here the physical of consequences these phases,which have in fact beenused unconsciously t version of in somecases lready,by adding a supplement o the Japanese a

in the text.(Here the new English edition of ModernQuantum Mechanics o we are providing a translation from Japanese f this supplement, repared p by ProfessorAkio Sakuraiof Kyoto Sangyo University for the Japanese T version of the book. he Editor deeplyappreciatesProfessorAkio Sakurai's guidance on an initial translation provided by his student,Yasunaga here Suzuki,as a term paper for the graduate quantum mechanics course at the University of Hawaii\342\200\224Manoa.)

ADIABATICTHEOREM Let us first considera spinwith magnitude 5 in a uniform time-independent with the spin, the magnetic field.Due to the magnetic moment associated

levels. he state T energy levels of this quantized system are split into 25+1 ket \\n) with the nth energy eigenvalue En undergoes change in phase a factor as (for a Hamiltonian constant in time)

of the stationary state. e next change the direction of the magnetic field W very slowly. Following the slowly varying magnetic field, the direction of the spin changesalso.We keepits component in the direction of the
n

n)-+e-iEJ* \\n) (S.I) in time evolution, as we learnedin Chapter2.This is the time development

magnetic field constant in time, however. Thus the initial quantum number does change at all with the changing magnetic field.This is a typical not exampleof the adiabatic theorem in quantum mechanics. Generallyspeaking,the adiabatic theorem assertsthat there should be mechanical invariants under the slow variation exertedxternally on a e mechanical system. The entropy in thermodynamic systemsand action m integral in classical echanical systemsare,like the quantum numbers in quantum mechanical systems,examplesof adiabatic invariants. Herewe

464

Berry's Phase

465

regard an adiabatic change as a time change that is very slow comthe time for proper motion in eachsystem (suchas periodsof compared We oscillation).+ do not discusshow slow change can be regardedas an N adiabatic change (seeA. Messiah,Quantum Mechanics, ew York: InOur problemis to discusshow the state terscience, ChapterXVII). 1961, ket \\n) of a quantum mechanical system changesunder adiabatic changes. there is another We find that apart from the simpleextensionof (S.I), The factor dependentupon the path of an adiabatic process. general phase was clearly given by Berry (M. V. Berry, Proceedings the of expression V Royal Societyof London. ol. A392 A984),p.45) in his seminal paper.
simply
with

BERRY'SPHASE
We
time-dependent

nth
equation

t considerhe Hamiltonian of the system with an external time-depenparameterR(t) by denoting it as H(R(t)).The ket \\n(R(t))) of the to c energy eigenstateorresponding R(t) satisfiesthe eigenvalue equaat time

(S.2) n(R(t))) H(R(t))\\n(R(t))) = En where the ket \\n(R(t))) has already beennormalized. et us make R evolve L in time from R@) = Ro.Suppose that the state ket is \\n(R0), t0 = 0;t)at
time t. The is

time-dependent chrodinger quation that the state ket obeys S e

H(R(t))\\n(R0),

t0; t)

=

ih

ot

\\n(R0),

t0; t)

(S3)

where t0 = 0.When the change of R(t) is slow enough, e expectrom f w the adiabatic theorem that \\n(R0), t0; t) would be proportional to the nth i energy eigenket\n(R(t))) of H(R(t))at time t. Thus we representt as \

n(R0),t0;
up all

t)

= exp

-

En

(R(t'))dt'

The first factor on the

phasechangesin

by substituting

to be determinedby

(S.4)into

r.h.s. the usual dynamical phasefactor summing is On stationary states [c.f. .6.7)]. the other hand, B
the (S.3), second factor exp(ryw(f)) phase

is shown

adiabatic

invariants

seeS.Tomonaga,

in classical periodic systems and Ehrenfest's adiabatic

Quantum

Mechanics

I.(Amsterdam:

hypothesis,

North-Holland

Press,1962).

466

Adiabatic Change and Geometrical

Phase

VRn(R(t)))jtR(t).

(S.5)
\342\200\224)

Therefore, is representedy a path integral in the parameter (R yn(t) b

space:

o

VRn(R(t')) )

dR(t')

(S.6)

where the path C of integration is that of the adiabatic processs the a external parameterR changesfrom Ro to R(t). We can seethat 7^ is a real number by differentiating with respecto R both sides of the nort
normalization

condition:

<\302\273(Jt(O)

\\n(R(t)))

=

(S.7)

contains the derivative the {{n VRn) is pure imaginary.) Since integral (S.6) of the eigenstate | VRn), the practical evaluation here might be to a However,if R describes closed expected be complicated. loop in parameter space returning to the starting point after time interval T (the periodicity),as is in the caseof R(T) = Ro, the path integral becomes w F t greatly simplified. irst applying the Stoke'sheorem, e transform the line integral along the closed C to a surface integral over the surface loop S(C)enclosed the closed C: by loop
I

yn

(C) = (R) =
Im

(n(R) VRn(R))dR
I

=

-

\\

5(C)

Vn(R)-dS, (S.8)

Vn

x (n(R) VRn(R)) = Im (VRn(R) x | VRn(R)) = Im m(R))x(m(R)\\VRn(R)),
VRn
\\

I

(S.9)

where we have used the vector identity:

x

(S.10)

Then,even Suppose|n(R))is modified by somephase factor exp[/x(K)]if the integrand of line integral (S.8)changesas
(n(R)VRn(R))
Vn(R)

^ (n(R)VRn(R)) + iVRX(R),
2.6

(S.ll)

Vx change because F\\ = 0 (seeSection on gauge inWe have omitted the term m = n in the last line of (S.9) because variance).

doesnot

Degeneracy

Point and Solid Angle\342\200\224Geometrical

Phase Factor

467

is purely imaginary. On the other hand, the off-diagonal matrix a element (m\\ VRn) is representeds follows. Multiplying (m\\ from the left to the equation
(n\\VRn)

(VRH(R)) \\n(R)) + H(R) (VR \\n(R)))

= (VRE(R)) \\n(R)) + En(R) \\VRn(R))
to obtainedby differentiating the eigenvalue equation (S.2)with respect the external parameter/?, we get (m(R) \\VRH(R) (m(R)| VRn(R)) = Fn Fm
\342\200\224

\\n(R))

(S.13)
by

Therefore the integrand of the surface integral (S.8)is given
Vn{R)

= Im

(n(R) \\VRH(R) \\m(R))x(m(R) \\VRH(R)
(Em(R) En(R))

-

\\n(R))

(S.14)

onecompleteturn is expressed as
to

Herewe notice that the vector Vn(R) passing through the surface of 2 the integral S(C)is expressed the differential form of degree of the by Hamiltonian H(R). Knowledge the state ket \\n(R)) itself is usually not of to needed calculate Vn as we shall seelater. o sum up, the state ket after T = 0;T) = exp(/7rt(C))exp
n(R0)),
S(C)

(S.15) (S.16)

--//

Vn{R)-dS.

f Here,yn(C) is called the Berry's phase,and comesrom the adiabatic We change of the external parameter. shall next show that this phase is determinedby the geometricpropertiesin parameterspace.

DEGENERACYPOINT AND SOLID ANGLE\342\200\224GEOMETRICAL PHASEFACTOR
w Supposethat the nth energy eigenstate\\n(R)) is degenerateith the mth eigenstate\\m(R)) for an external parameter/?*. lthough the degeneracy A

468

Adiabatic Change and Geometrical

Phase

point /?* in the parameterspaceis by no means on the path of the actual o t adiabatic change,he existence f/?* is essentialfor the value of yn(C). t This is becausehe integrand Vn(R) of yn(C) is singular at/?*,asis evident
from

the Let us continue our discussion taking as an example, problem by of the spin in a magnetic field mentioned earlierspin magnitude 5, and ( magnetic moment g\\jS/h.t When the magnetic field B(t)slowly changesits direction while keepingits magnitude constant, we denote the spin com= mh (m = S, , +S) along the direction of the component as Sz> magnetic field at eachinstance (taking this to be the positive direction of the z'-axis). Writing the Hamiltonian of this system as
\342\200\224

(S.14).

...

H(B) =
the energy eigenvalue is
Em

-

= -g^mB =

(S.18)

and
VBH(B)

-gpS/h.

(S.19)

B The degeneracy point is at the origin of the parameterspace, = 0,where When fold degeneracies. we rotate the direction of the there are 2S+1 magnetic field B keepingits magnitude constant and bring it back to the around the closed on a sphere initial direction again, the vector Bgoes loop from as of radius B.Then the vector Vm(B) can be expressed (S.14)
Slh\\m'(B))x{m'(B)\\Slh\\m(B)) (s-20)
(mf

- m)

\342\200\242

In order make the calculation easier, us take the z-axisof spin space to let to be the direction of the magnetic field (z'-axis irection). Since the d only terms with m! = contribute to the intermediate states, we use the for o expressionC.5.41) the matrix element f the spin operator:
m\302\261\\

E, m 1 SJh 5, m) = 2
\302\261

(S.

m\302\261\\

Sylh

5, m) =

-hi

By

substituting

Vm(B)

as follows:

into we (S.21) (S.20), obtain the componentsof the vector

(Vm{B))x>

=

0,{Vm(B)\\. = 0,{VJB))Z.= ^.
of ft,
while vector

(S.22)

fHere spin magnitude

Sis in

unit

S has dimension of h.

Experimental

Verification

469

A round

adiabaticchange

t-space

A round

adiabaticchange

ff Degeneracypoint
FIGURE External parameter if-space. the adiabatic change ofone turn along the For closed C, the geometrical phase is given by the surface integral of the vector V(R) loop penetrating through the surface S(C)surrounded by C (right). This is proportional to the solid angle that the closed loop C subtends at the degeneracy point R* (left).

S.I.

Thus the vector V(B) is parallel to the magnetic field B and penetrates Hence phase the normally through the sphericalsurface of the il-space. 7m(C) is given by
m

(C) =

-ml 5(C)B

dB =

-ml,

(S.23)

circuit C subtendsat the i where 11(C)s the solid angle which the closed for This simpleexpression 7m(C) is dependentneither point. degeneracy on the magnitude of the magnetic field nor on the spin which determines the dynamics of the system,but exclusivelyon the dimensionlessuantum q accomnumber m and the solidangle H(C).The phasefactor exp(rym(C)) the adiabatic change along the closed loop is regardedas a geowith the degeneracy geometrical point that is singular. phasefactor associated S.Iillustrates this integral for the geometricalphasein the parameter Figure
accompanying

the According to (S.23), state ket changesits sign if mll(C) = after oneround trip of an adiabatic process. notice that this is the case We not only for fermions with m = half integer but alsofor bosonswith m =
\302\261tt

space.

integer.
EXPERIMENTAL VERIFICATION
The experimentto verify (S.23) beenperformedby letting polarized has neutrons passthrough a coil which producesa spiral magnetic field inside. The neutrons, having passed through one completeperiod of the spiral

470

Adiabatic Change and Geometrical

Phase

T field after time interval T, feel the samefield as the initial ones. he solid c of on the r.h.s. (S.23) an be continuously changedby changing the angle ratio of the magnitude of the spiralfield to the magnitude of another field L appliedalong the direction of the spiralaxis. et us assumethat the initial of neutrons is in a mixed state of two eigenstates: parallel and antispin to the field. Under an adiabatic change the ratio of the numbers parallel The of these two statesis preserved. neutrons passingthrough the inside to w of the coil proceed hile rotating their spinsin the planeperpendicular After the field whose direction changesalong the course[seeC.2.20)]. passingthrough one period of the spiralfield, the Berry'sphase +ft/2 is to to parallelor added according (S.23) the phasesof the spineigenstates twice as many of 3.2, anti-parallel to the field. As mentioned in Section value. Therethem contribute to the rotational angle of the spinexpectation from geometrical the phase besidesthe dynamicalphase, contribution is added in the total angle of spin rotation, <J>, during one period of the field. To wit, = g\\iBTIh + ft. (S.24) d>
Therefore,

The value of is obtainedfrom the measurement of the neutron polarwith ft The measuredvalue of A<J> = g\\xBT/h closelyagrees condition (the ratio of the fields for two determinedby the experimental f Thus, directions). the validity of (S.23)or the Berry'sphasewasconfirmed was This experiment performed T.Bitterand D.Dubbers by Fig. (see S.2).
<J>

polarization.

<(>

-

in

1987.

CO

Q.

c co c o
o
-e< Theory prediction

SolidangleQ (steradian)
FIGURE Experimental data showing the existence of the geometrical phase.The shift that have passedthe spiral magnetic field is Ac}) in the rotation angle of the spin of neutrons almost equal to the solid angle ft determined by the applied fields. The solid line is the prediction of the theory.

S.2.

General Consideration of Two-Level Crossing

471

OF GENERALCONSIDERATION TWO-LEVEL CROSSING

= For general ases ith external parameter/? (*,)>, the samesituation c w z), as the above exampleof spin in the field can be realizedaround the delevels.ChoosingR* as the degeneracy point R* if there are some crossing w of the parameter space, e suppose that the energy eigenstates origin + (/?))and | (/?))are degeneratet R* = 0.Taking eacheigenvalue to a be such that E+(R) > E-(R),we measureenergy from the degeneracy point. We expandthe Hamiltonian H{R)around the origin up to the first orderin R, and perform an appropriatelinear transformation. Then the H by general amiltonian connecting the two levels is expressed a 2 x 2 Her-

-

mitian matrix;

Z H(R) = \\ [X+iY
E\302\261(R)

X-iY

-Z
\342\200\224

(S.25)

= The energy eigenvalues are and the two levels conically cross the degeneracypoint. VRH(R) is equal to 1&-Theseexpressions at are the same as those of the casem for the spin in the field. Therefore, integrating over surface S by
\302\261jR
\302\2611 V\302\261

(R) =

R
\302\261

(S.26)

the geometrical factor for generalwo-level crossingis obtainedas: t
exp(ry\302\261(C))

= exp J J S(C)V\302\261(R)-dS

-'II

= exp

i

.

(S.27)

As before, 1(C)s the solid angle of the closed i 1 loop (adiabaticpath) at the degeneracy poiat We notice here that the expression(S.26) the vector for

/?*.

C,
is

V\302\261(R)

equivalent to the magnetic field B.6.74) producedby a magnetic monopole T at the origin. he singularity of the degeneracy placed point in the paramis structurally the same as that of a magnetic monopole, and space the magnetic field by a magnetic monopoleis regardedas determining the geometrical phase.We can exploit further the analogy to the magnetic in field; for example, comparing the two following relations
parameter

B(r) =
V{R)

V

x A{r)
(n(R)
VRn(R)),

(S.28) (S.29)

472

Adiabatic Change and Geometrical

Phase

we can interpret (n(R) | VRn(R)) as a kind of vector-potential causedby this the singularity at the degeneracy point. As we have shown in to is gauge dependent,but V(R), which corresponds the magnetic quantity flux density, B,is gauge-invariant.

(S.ll),

AHARANOV-BOHM EFFECTREVISITED
In

the phase factors. Among them the effect of electrics well as a gravitational fields gives rise to dynamical phase factors. On the other hand, the Aharanov-Bohm effect due to the magnetic field can be shown to be just a consequence a geometrical phase factor. of e Let a small box confining an electron (charge <0) make oneturn
determine

Section we studiedsomeexampleswhere integrals along paths de2.6

along a closed loop C,which surroundsa magnetic flux line <bB (seeFig. We S.3). take as R the vector connecting the origin fixed in the spaceand a reference point in the box.In this casethe vector R is an external parameterin the real space itself. By using the vector-potential A to dein describe the magnetic field U, the nth wave function of the electron the box (positionvector r) is written as
(r\\n(R))

= exp '

(S.30)

at where ita(r')is the wave function of the electron the r' position coorof the box in the absence magnetic field. Then,in the presence of coordinates

Magnetic

flux line

FIGURE
magnetic

S.3. The Aharanov-Bohm
flux

Effect. Electron in

a

box takes

one turn

around

a

line.

Complex System and Adiabatic Potential

473

with

of magnetic field, we can easily calculatethe derivativeof the wave function to respect the external parameterto obtain

(n(R) | VRn(R)) =

*

(r-R)
ieA(R) he

x

TA{R)l?n{rnc

te

(S.31)
box.

in The secondterm under the integral vanishes for the electron the we From (S.6)and (S.31) seethat the geometrical phase is given by

\302\246Y\302\273(C)

e = T-\302\273A'dR = e
he

- \\\\B(R)-dS -**.
he J J s(C)

=

he

(S.32)

This result is just the expressionB.6.70) the Aharanov-Bohm effect of

obtainedearliern Chapter2. i

COMPLEXSYSTEMAND ADIABATICPOTENTIAL
R that changesadiabatically is an external paquantity more interesting question is to treat quantum mechanically somecomplexsystem made up of two constituent systems,where an adiadiabatically changing quantity is contained in the system as an internal dyof how the appearance the Berry'sphase dynamical variable. We shall discuss influencesthe other constituent in oneof the constituent systems reversely that moves slowly. he former can respondquickly to an adiabatic change T F causedby the latter. orbackground,let us first considerthe problemof a of a a polyatomic moleculehich is composed electronsnd nuclei, typical w exampleof a complexsystem.When calculating the energy levels of rowe rotation and vibration of a molecule, shall apply a method that has been used for many years. we of Considerthe case a diatomic molecule; write the Hamiltonian of the complexsystem as

Up to now, the
parameter. A

HT = HN(R) + Hel (#-!,

. . . , rN)

+ V(R, ru

. . . , rN),

(S.33)

where R is the relative position coordinatebetweenthe two nuclei, ru r2, and of , rN the Af-electron coordinates, the center massof the molecule is chosen at the origin. The first, second, and third terms of the Hamiltonian correspondto the kinetic energy of nuclei,he energy of the t electron and the interaction energiesmong nuclei themselves and system, a betweennuclei and electronsespectively. Since nuclei with heavy mass the r move relatively slowly and electrons ith light massmove quickly, we can w use an adiabatic approximation here. e first fix the position of the nuclei W

...

474

Adiabatic

Change and Geometrical

Phase

t of and determinethe eigenstate electrons\n(R)) correspondingo the fixed \ of the nuclei configuration {Hel(#-!,

. . . , rN)

+ V(R, ru

. . . , rN)} \\n(R))
= Un(R)
\\n(R)),

(S.34)

We where Un(R) is the energy of the nth eigenstate. next approximate the state ket of the complexsystem in the form of a product of the nucleus ket ket \\A) and the electron

= |i4) \\n(R)).
Substituting this

(S.35)

system,we obtain

into the Schrodinger quation e

H^ =

E*V

of the complex

(HN(R) + Un(R)) \\A)

\\n(R))

=

En \\A) \\n(R)).

(S.36)

SinceH^R) is the differential operator with respecto coordinatesof t the nuclei /?, it will operate both the nucleus state ket \\A) and the on electron state ket \\n(R)). However,we can ignore the derivative term of electron ket with respect /?, as long as the amplitude of the relative state to motion of the two nuclei is small comparedto the equilibrium distance between them. This approximation is the so-calledorn-Oppenheimer B t approximation. Equation (S.36)hen leadsto a simpleeigenvalueequation that involves only the coordinates the nuclei, s follows: of a
Un(R)) \\A)

= En\\A>-

(S-37)

that determinesthe motion of the nuclei is called adiabatic potential. It is the sum of the Coulombrepulsive force betweennuclei and the energy of electronsor f fixed R. Un(R) is obtained for each level of the electronsystem. The minimum Un(R) gives approximately the equilibrium distancebetween nuclei about which the moleculeibrates and rotates. he corresponding T v levels are given approximately by energy

In the above equation the effective potential Un(R)

En
iV

= ho*n(N +
U,X,^,
\342\200\242 \342\200\242

2)
\342\200\242 \342\200\242

T LL

(S.38)

where standsfor the angular frequency determinedby the curvature at If the minimum of Un(R) and In is the moment of inertia of the molecule. the two nuclei are identical,L is further limited to be an even or odd number by permutation symmetry.
<*>\342\200\236

Dynamical Jahn-Teller Effect

475

DYNAMICAL JAHN-TELLEREFFECT
Our objects to investigate the roleof the geometrical phasein a complex i in To this end, let us considerthe case which the electronictates s system. t f aredegenerateor a certain spaceconfiguration /?* of the nuclei;hat is, for a case such that the adiabatic potentials satisfy
Un(R*)

=

Um(R*)

(S.39)

that and cross another at /?*. et us remember an adiabatic change L one of one turn around the degeneracy causesa geopoint R* in the /?-space where the geometrical phase.Thus for the caseof the diatomic molecule distanceassociatedwith the nuclei is a singleone-dimensional parameter in determining the electron state, this is not enough to discussthe Berry's o W (ions) r a group of atoms phase. e needto considertri-atomic molecules in a crystal. Herewe use the latter one as an example for discussion s purpose. enerallyin crystalsthe electronictatesin the crystal fields (e.g., G in a pair of d-orbital states)are often degenerate energy for certain atomic the configurations of high symmetry. Then,in most cases, crystal becomes slightly distorted to assume a lower symmetric configuration, and thus moves in a more stable state by lowering its electronicnergy.This phee phenomenon is what is calledthe Jahn-Tellerffect. To make the argument e s simpler,considerthe electronictate of the central ion surroundedby four atoms in a plane. Supposethat the four atoms are placed in a square states |a)and | b) extending their orbitals configuration, for which electronic The in different directions respectively are degenerate. deformation of the of lattice then removes the two-folddegeneracy. isplacements atoms from D the squarelattice points, are expressed the equilibrium position,taken on in terms of the normal modes of vibration. Among the several possible normal modes, look at the two independentmodesA and B as shown we with the degenerate lectronic tates. uppose e in Fig. S.4, hich couple w s S that A and B have the same eigenfrequency, o>, and we denote their normal coordinatesas Qa and Qb,respectively^On the other hand, the

FIGURE

modes, Qa and Qb, are shown.

S.4. Distortion

of lattices

causing dynamical

Jahn-Teller effect. Two normal

fOur explanation for the Jahn-Teller effect is not exact but conceptual.

476

Adiabatic Change and Geometrical

Phase

electron system isdescribedby a linear-combinationof the two degenerate
levels

a) = Ca a) + Cb b).
Then the effective Hamiltonian of the normal vibration, with the electron system,can be written in the form of
which

(S.40)
couples

Pi + p a
2|x

|X@

~Qa

Qb Qb Qa)

(S.41)

where Pa and Pb are the conjugate momenta to Qa and Qb,respectively; jjl is the effective massof the normal vibration and K is the strength of the The and lattices. matrix that representsthe coupling between electrons o state vector (Cfl).We have expressed interaction operatesn the electron the interaction by the first order terms of the normal coordinates, and Qa i Qb, assuming that the vibration of the atomic displacements small. For
normal

coordinateswritten as Qa = p cos6,Qb = p sin

6,
/
\\

(S.42)

o 8 the eigenenergy and the eigenket f the electron system are obtainedby
solving

-Kp
as

-cose
sin

sin 01
\302\2511

e cos

= 8
Q
\\cb

(S.43)

e

=

\302\261Kp

(S.44)

0 cos- a)

.

6

b)

0 e - @)) = sin - a) + cos- b).
From and (S.44) adiabatic potential for the normal the is given by the two-valued function

(S.45)
coordinates

(S.41)

(P) =

(S.46)

If one illustrates the surface of the adiabatic potential as a function of Qa The and Qb,a \"Mexicanhat\" shapelikeFig.S.5 emerges. potential consists of two axially-symmetricsurfacesand assumesa minimum value at p0 =

Dynamical Jahn-Teller Effect

477

ad

Q,
FIGURE

S.5.Adiabatic potential surface related to dynamical Jahn-Teller effect (S.46). state Herewe notice that the electron kets (S.45)change sign for rotation by 2tt around the symmetry axis: = 0)). = 2ir)> = (-1) (S.47)
\302\261F

|\302\261F

Formally, this is the sameas the rotation of the spin with S = j discussed in Section o s 3.2,incethe sinusoidaldependencef the ket on the rotation in (S.45) given by just one half of the rotation angle, 6/2.Naturally, in is i our case,t is the orbital state ket of the electron system that has changed on the r.h.s. and thus has nothing to do with spins.The factor sign the i of (S.47)s easily shown to be just the Berry'sphasefactor. Here origin is When the of the QaQb-p\\ane a degeneracy of the electron system. point vector (QaiQb)describingthe state of the lattice deformation circulates \"solid angle\" amounts to 2tt. oncearound this origin, the corresponding f Therefore,rom the generalexpression(S.27)the electronstate ket is = It is to be multiplied by the geometrical phase factor exp(+/2Tr/2) this noted that as early as in 1963, kind of Berry'sphasewas already taken and H.C. Longuetinto account in a very natural way by G.Herzberg w Higgins, hen they solvedthe problemof a coupledsystemwith degeneracy while studying poly-atomic molecules. As shown here, or such an electron-lattice f system in which degena electronictatescoupleto two lattice vibrational modes, minimum s of the adiabatic potential doesnot form a well but a continuous valley. adiThus, the dynamical deformation of the lattice and the corresponding adiabatic state change of the electron This system are both incorporated. is the so-called e dynamical Jahn-Tellerffect. Now, let us considerthe dydynamical motion of the normal coordinates(Qa,Qb)(that is, (p,6))under the adiabatic potential (S.46) and find the influence of the Berry'sphase on the dynamics. he two-dimensionalSchrodinger's T equation to be solved

(-1)

-1.

degenerate

is

<d2
2\\x

l

a2

\\

,e),

(s.48)

478

Adiabatic Change and Geometrical

Phase

where the wave function ^(p,6) is expressed the product of the nucleus by and the electron state ket piece
<t>\302\261(p,6)

,e) = 4>+(P,e)l+(e)> +

4>-(p>\302\273)

I-(\302\273)>\342\200\242

(s.49)

The adiabatic potential written as V*d *n (S.48)is to be understoodas is acting on c|>+ in ^(p,6) for V^d and on c|>- for V~d. Since(S.48) a difdifferential with separablevariables we can solve it by choosing the equation nucleus wave function as
4>\302\261(P,\302\273)

= U (p) eij\\

(S.50)

Herethe

most important point is that the state function ^(p,6), which describesthe whole coupled system consisting of electrons lattices, and must remain a singlevalued function. The state ket of the electron system in t changessign when 6 is rotated by 2tt. Therefore, orderto cancelhis must change its sign as well to preservethe singlesign change, valued nature of ^(p,6)! rom this requirement we conclude that F = that is exp(i/2ir) / = (/ + 2) = half integer,(/ = integer). (S.51
c|>\302\261(p,6)

-1,

of The presence the Berry'sphasehas changedthe quantum number that t characterizeshe motion of atoms, from the usual integer number to half integer one.1 If two adiabatic levels are well separated, are allowed to solve we the equation (S.48)by ignoring the mixing between c|>+(p,6)| +@)) and Then the low energy excitations in the potential valley is (|>_(p,6)| approximately expressed by

-F)).

tLnj

= \\n + 2)^^

10

1

\342\200\242

\342\200\224^\342\200\2242\342\200\224

(S.52) 7 (n:integer, : half integer) The result is just the sum of the energies vibration along the radial of direction and thoseof rotation in the plane of the normal modecoordinates term comes from the electron (The factor 4 in the numerator of the second In the picture of lattice deformation they arethe energieselated r system.)
2^\302\260

to oscillation of the magnitude of the atomic displacement nd transfora of the deformation patterns, respectively. hesekinds of energy T levels have beenwell analyzed experimentally through spectralmeasurefor ionsin crystals and poly-atomicmolecular gases alsothrough and o in several physical measurements n matter. Soscientists these fields have
transformation
measurements

method and action in H. Kuratsuji and S. Iida, Prog. Theor. Phys. 74 A985), p. 439concerning how Berry's phase modifies the quanquantization condition of dynamical variables.
fA general discussion is given using path integral

Universality

of Geometrical

Phase

479

beenfamiliar

with the half-integerquantization which appearsin rotational levels for sometime. After Berry'spaper,he precisepectralexperiment t s on a tri-atomic molecular gas,Na3 was repeated and again in 1986, the was reconfirmed by G.Delacretazal. et half-integer quantization

PHASE UNIVERSALITY GEOMETRICAL OF However,let us notice quantum-mechanical systemsas example. the Planck's onstant is lost in the general xpression c e giving the phase In i (S.27). this respectt is totally different from the dynamical factor in discussed Chapter2.Therefore, although the original derivation B.6.7) by Berry is based on quantum mechanics,the geometrical phase factor to of itself is expected be universal, regardless quantum-mechanicalsystems or classical-mechanical ones.The questionis then, where can we find a phase in a classical ystem effected by an adiabatic change? geometrical s Detection the Berry'sphasehas beendone for light, which is on of the one hand very quantum-mechanical and relativistic, but on the other
taking
that in

Sofar we have discusseda geometrical phase calledthe Berry'sphase by

alsodescribable classical lectrodynamics. letting linearly poe By by the insideof a spirally-twistedoptical fiber, one light pass through observesthe rotation of its polarization plane.According to quantum thea photon is a particle with spin one,and the spin in an eigenstateis either parallelto the direction of propagation or anti-parallel to it.(This E leads to the helicity eigenvalue being +1or 1 respectively.) ach eiis a circularly polarizedlight with a rotational direction opposite eigenstate to eachother. hen the linearly-polarized light, which is a combination W of these two states, passes through the inside of a once-twisted optical
hand
polarized
theory
\342\200\224

fiber, the propagation vector (the relevant quantity for an adiabatic change a circuit. (At the same time the spin also rotates.) here)describesclosed As a result the different Berry'sphase is added to eachcomponent of the I combination state, so that the polarization plane of light rotates.n the 1986xperimentperformedby Chiao,Wu, and Tomita, the agreement e betweenthe rotational angle of the polarization plane and the solidangle determinedby the degree f twist of the optical fiber was confirmed. On o the other hand, the effectcan alsobe explained classical lectrodynamics by e as a result of integration of continuousparalleltransformation of the electric field vector insidethe optical fiber. Although the directionsof light at the entrance and the exit are parallel, a difference betweenthe polarization planesis producedfor the optical fiber which is twisted in the middle. even Furthermore, for a classical-mechanical system a geometrical a when phasefactor emerges we oscillate conical pendulum on the revolving earth.Seenfrom the rest coordinatesystem the time neededfor change

480

Adiabatic Change and Geometrical

Phase

much

direction at a certain place on the revolving earth is very larger the periodof the conical pendulum.That is, the direction of the gravity acting on the pendulum adiabatically changesas the earth rotates. us take the rotational angular velocity of the pendulum in the Let orbital planeto be co.In the total rotational angle 6 of the conical pendulum after oneday (earth periodof revolution = T) a deviation by A6 from the i That is, simply predictedvalue coT,a dynamical angle, s realized. 6 = 0O+ A8. (S.53)
in

the

gravity

than

The shift

is dependenton the latitude of the measurement point but is independentof the gravity and the length of the string which govern the motion of the pendulum.This is after all a geometrical phase and is gencalledthe Hannay'sangle. generally So the phenomenonis quite similar to the rotation of a quantum for spin in a varying magnetic field. Let us comparethe two expressions the total rotational anglesin these two cases,S.24) and (S.53). may We ( T speculatethat A6 = ft. For the conical pendulum, this is the case. he Hannay'sangle is equal to the solid angle subtendedat the centerof the
A6

earth by the closedircuit which the gravity vector acting on the pendulum c draws following the rotation of the earth.This is a geometrical phase in classicalmechanics corresponding the Berry's phase in quantum meto
mechanics.

this way geometrical phasesaccompanyingadiabatic changes apvarious systemssuch as oscillating systems,optical systems,spin of a m systems, olecular systems, nd so on,regardless whether we are dealing In or with classical quantum mechanics. solid state physics,this kind of argument has also beenused to explain the quantum Hall effect besides above.Lastbut not leastBerry's effect discussed the dynamicalJahn-Teller phase has also impacted field theory. Without prior knowledgeof the b geometrical phase,it has nevertheless eenpossibleto accommodate such if a phase naturally into theories one treats preciselySchrodinger's equaNewton's equation, Maxwell'sequations, and the path-integrals. However,we can concludeby saying that our understanding of quantum of since the existence geometrical phases mechanics has been deepened was explicitly revealed.

In

appear

in

equation,

II SUPPLEMENT

Decays Non-Exponential
Radioactive nuclei furnish us with one of the best known examplesof T unstable,or decaying, ystems. he assumption that the radioactive decay s of any nucleus is a random process, furthermore, that even in a large and, leadsto the familiar exponential sampleeachnucleus decaysindependently, decay law,
N(t)

= N(to)e-k(t-to\\

(T.la)

where N(t) is the number of nuclei that have not decayedafter a time t, and X is a constant determinedby the propertiesof the individual nucleus. Since fluctuations in (T.la) small only when the number of nuclei the are is large,we can rephrasethe radioactive decaylaw as a probabilistictates The probability that any particular nucleus will not undergoa decay in a time interval betweent0 and t is given by
statement:

P(t)

= <rx('-'o),t > t0

(T.lb)

The quantity P(t) may be called the survival probability. Notice that that the nucleus under P(t0) = this is the statement of our knowledge examination had not decayedat t = t0. Here, e investigate the form of w T because ithin the w P(t) for quantum mechanical systems. his is necessary framework of quantum mechanics, robabilities derived from fundaare p probability amplitudes,so that it is not a priori obvious that the c assumptions leading to (T.I) an be consistently incorporated. In keepingwith our intuitive notions,we will say that a quantum system is in an unstable state if the survival probability for that state reduces to zero If monotonically with time.1 the state vector of the system at time t is given by \\qh t) (here, denote all quantum numbers necessaryto qt specify the state), the survival probability P{i)is given in terms of the survival amplitude (c.f.he analogous discussion Chapter2 of text), in t

1;

fundamental

a(t)
by

=

(q\302\273

*o\\<!h

*)

= (ih *o U(t,
\\a(t)\\2.

t0) qh t0),

(T.2) (T.3)

P(t) =

tIt is important to stress the requirement of monotonicity, since it is possible to find Rabi examples where the survival probability exhibits an oscillatory behavior (see, 5 oscillations, Sec. .5 of text. Notice that the oscillatory behavior persists even when the external potential is time independent).

e.g.,

481

482

Non-Exponential

Decays

For an isolatedsystem,the Hamiltonian is time independent,and the unitary operator U(t, t0) in (T.2)that evolvesthe statesfrom an initial time t0 to a later time t is given by U(t, t0) = e-gH^-t^thm We thus seethat if \\qh t) is a normalized stationary state so that it has a definite value of energy,a(t) is a pure phase and P(t) = an unstable state of a quantum mechanical system cannot Although be represented one of the energy eigenkets,he assumption of comas t of the eigenketsf the Hamiltonian tellsus that we can represent o completeness the unstable state as a linear superposition over these eigenketsith timew independentcomplexcoefficients; that is,

1.

qht) =

SE\\z,t)(E\\qht0).

(T.4)

Here,S denotesa summation (integration) over the discrete(continuous) part of the spectrumof H.We can thus write (T.2)as,
(T.5) a(t) = SBe-u\302\253-W*\\(B\\qi9td\\2. It is reasonableto supposethat the unstable states are orthogonal to the (normalizable) discreteeigenstates the Hamiltonian which, as we of assumethat unstable states argued above,cannot decay.We will, therefore, are associatedwith the continuum states of the Hamiltonian. This is in with our intuitive expectation from the fact that an unstable particle keeping decaysonly to continuum states; that is,the unstable state has non-vanprojections only on continuum statesinto which it can decay.In this the survival amplitude in (T.5)can be written as the Fourier transcase,
non-vanishing

transform,

a{i) = J dee ^p(e),
of a real non-negative function

where (for later convenience) have set t0 we 0. Notice that (e|g,) just the wave-functionfor the decaying state in is the energy representation,so that p(e)is just the probability density that an energy measurement of this state yieldsa value 8.If p(e)has the familiar Breit-Wigner form,

||

(T.6) (T.7)

|2,
=

Pw(s) = (r/2ir)/[(e

- e0J+ T2/4],

(T.8a)

of to we leave it to the reader t (c.f.he discussionE.8.21)E.8.24) text) has the form to show that the corresponding survival probability

W) = e-r\"-*\"\\

(T.8b)

so that the decayof the state is indeeddescribedby the exponential decay
law.

Non-Exponential

Decays

483

somevery reasonableassumptions, Eq. system. In particular, we will show that for very long times,the survival probability must decrease a rate that is slowerthan exponential. seethis, we at To
We
will

now show that

with

c (T.lb) an never be exact regardlessof the nature of the quantum

remark that any interacting quantum-mechanicalsystem must have a t s ground state; that is, here is a state |e0),with H\\e0) = eo|eo)uch that e0 is the smallest igenvalue of H.If this was not the case,t would be possible i e to extract arbitrarily large amounts of energy from the system by interinteractions that send it to eigenstates increasingly lower energy.The exisof of the ground state obviously impliesthat the probability density function p(e)introducedvia (T.7)above vanishes if 8 < e0. To proceed further, we introduce a theorem due to Paley and Wieand N. Wiener, \"FourierTransforms in the ComplexDo(R. Paley Am. Math. Soc. ub. Vol. XIX, 1934), hich can be stated as w P Domain,\" follows: If a(t) and p(e)are Fourier transforms of eachother such that p(e) = 0 for e < e0 and pi*dt\\a{i)\\2 is finite, then pln dt\\\\n\\a(t)\\\\/(l + t1) is also finite. We will seebelow(wherewe follow essentially the argument of L. A. Khalfin, Sov. Phys.JETP Vol. 6,pg. 1053, that this remarkable 1958) result strongly constrains long time behavior of the survival probability. the so First, we note that the fact that p(e)is real impliesa*(t) = a{-t) that if the survival probability decays sufficiently fast for large times, df|a(f)|2is finite, and the Fouriertransform pair a{t) and p(e) in (T.6) indeed satisfies the conditions for the Paley-Wiener theorem. Thus, for s times,|ln|a(f) is requiredto increaselowerthan linearly, and hence large the exponentialbehavior for \\a{t)\\ is precluded. We point out that while our general rgument impliesthat the long a i time behavior of the survival probability cannot be exactly exponential,t doesnot shed any light on when the non-exponential behavior sets in or on how much the survival probability deviates from the exponential form. o The former requiresthe specificationof a time scalether than the lifetime, and so is probablydependenton the detailsof the dynamics that causes the decay. We also remark that the Breit-Wigner form p#w(8) in (T.8a) is (which led to the exponential form for the survival probability (T.8b)) non-vanishing for all values of e,and so violates the conditions of appliof the Paley-Wiener theorem. Physicallythis form of p(e)violates our assumption of the existence f a ground state, so that the resulting o a exponential behavior can be,at best, n approximation to the real situation. that if we cut off the It will be left as an exercise the readero check t for Breit-Wigner form of p, the survival probability P(t) decaysaccording to a powerlaw for large times. We stress herethat the fact that we have not seendeviations from a the exponentialdecay law at large times does not vitiate our general rfirst
existence Wiener
/\"\302\253

||

applicability

484

Non-Exponential

Decays

that do not tell us when the non-exponential behavior sets in. It could be that non-exponential decay occursonly after many lifetimes in which case would be very difficult to observe. it Thereare,however, equally that imply deviations from the exponential decay law general rguments a for very short times (definedpreciselybelow)which we turn to now. We begin by noting (our discussion essentially follows that of B. t Misra and E. C.G. Sudarshan,J. Math. Phys. Vol. 18, 56,1977)hat 7 the time derivative of the survival amplitude (T.6),

guments

daldt

= de(-ie/ft)e\"iel/*p(e), J
further

(T.9)
assume (as is

is a well defined, continuous function of t if we
that
expectation

the decaying state has a finite energy expecphysically reasonable) value. We can,therefore, valuate the rate of change of the survival e probability,

= [da*(r)/dt]a(r)
where we have useda*{t) = a{ and the dot denotes ifferentiation with d to the argument. We thus seethat, respect

-1)

dP(t =0)/dt =
which
exponential

0,

(T.ll)

of coursemeans that the survival probability cannot be an expoWe remind the readerhat in (T.6), = 0 was defined at t = 0! t t as the latest instant of time when we knew that the system had not yet decayed.This impliesthat t = 0 is also the time when the system was last observedor, in Dime'serminology, the time of preparationof the state t of the system.We remark that while our argument clearly precludesthe possibility of exponentialdecay at t = 0,it sets no limitations on when exponential decaymay set in. s obTaking this analysis a step further, we can consider uccessive observations of a system.As discussed must hold after each above, of theseobservations. he implicationsof this are schematicallyillustrated T in Fig. The survival probability for a system prepared at t = tx is shown by the curve labeled 1 in Fig. Notice that, in keepingwith the slopeof the curve is zeroat t = tx. If this system is allowed to evolve undisturbed, he survival probability will followthe first curve which t f for may rapidly take an exponential orm (of course, very large values of t, not shown in the figure, we have seenthat the decaywill be slowerthan The exponential). sizeof the flat region at t = tx is not determinedby our general rguments and must be dependenton dynamical details. a If, however, an observation is made on this system at t = t2, our must hold at t = t2, so that the system arguments above imply that

(T.ll)

T.I. (T.ll),

T.I.

(T.ll)

Non-Exponential

Decays

485

CL

A schematic of the short time behavior of the survival probability P(t) of a FIGURE state of a quantum mechanical system prepared at t = tx is illustrated by the curve labeled The curves labeled 2, 3, 4 show how P(t) is modified by observations of the state at times t2, t3, t4. Notice that each successivemeasurement increases the survival probability from what it would have been had the system not been disturbed by that measurement.

T.I.

t

1.

now followsthe curve labeled Successive bservations at t = t3, t = o would make the system evolve along the other curves in the figure. observations is to We seethat the qualitative effect of these successive increase survival probability of the system beingobservedfrom what the it would have beenif the system was allowed to evolve undisturbed after its preparationat t = tv This inhibition of the decayappearsto be a feature

etc.,

2.

observations

of quantum mechanics, ncewe grant that eachobservation of the system o to the preparation of the quantum mechanical state. corresponds Thesearguments imply that it shouldbe possibleto slow down the of a quantum mechanical system by making successiveapid obserdecay r on it.In the limit of continuous observation (providedthat this can be operationally defined),an unstable system would not decay.This has beenreferred to as the quantum Zenoeffect. Deviations from the exponential decay law have never been obof observed for radioactivenucleior for the well measured KLmesons particle Rev. Vol. A41, 2295, 990, howW. M. Itano et 1 have Phys. physics. recently demonstratedthat the rate for transitions betweentwo dismeadiscrete levels of a quantum system is indeed inhibited by successive shown measurements of the state of the system.Theseauthors have further w increasesith the frequency with which the that the amount of inhibition is monitored. argue that their resultsare completelyconsistent They system with the expectationfrom quantum mechanics assuming, as usual, that eachmeasurement is effectively equivalent to preparingafresh the state

al,

however

486

Non-Exponential

Decays

of the system.This servesto bring home the fact that while this inhibition of transitions may be somewhat surprising,it is a consequencef the o structure of quantum mechanics. At this point, it is fair to warn the reader that we have only touched of the basic question in our discussion the quantum Zeno effect. upon Thereisconsiderable somewhat controversial) literature on the phys(and implications of this result.It is not our purposehereto discussthese in detail,nor is it our purposeto enterinto various subtleties (both physical and philosophical) f the issuesinvolved. Forthis, we refer the readero t o the original literature. To sum up, we have presentedvery general rguments to demona that the decayof any quantum mechanical state must deviate from the familiar exponential decaylaw, both for very long and for very short times asmeasured of from the instant of preparation the state of the system. Thesedeviations have not beenexperimentally observedfor systemsthat exhibit (at least approximately) exponential decay.Since these arguments refer only to asymptoticallylong and short times,they do not precludethe possibility that a decaying quantum mechanical system may exhibit (es(essentially) exponentialdecay over most of its lifetime. Indeed by making suitable approximations, exponential decaylaw has beenderived (see, the Merzbacher[1970], Chapter 18)for modelsystemswhosedecaycan be describedin perturbation theory. It is instructive to study these apapproximations and trace why they areinvalid for very long and very short times (as they must be in view of our general onsiderations). c
physical demonstrate

e.g.,

Bibliography

The literature in quantum mechanics is very large and very diverse. We in presenthere a bibliography of those booksto which we refer specifically our text as well as a referencesectionof more-elementarytexts in quantum mechanics (generally at the undergraduate level) that provide the backto our book (addressed background primarily to the first-year graduate student). Since many bookshave beenwritten about elementaryquantum mechanics, the list in this referencesection is, of course, ot meant to be complete. he T n editor has studied some of the suggested books,read others, glanced at a few, and likely missedothers.The editor apologizesin advance if, as is all too probable, there are glaring omissions.Throughout the book little attempt has been made to quote original papers; the few that have been^ quoted are noted in the footnotes or the text itself. This we believe to be appropriatein a bookwhoseprimary purposeis to serveas the textbook to a basic beginning graduate course. Baym, G. Lectureson Quantum Mechanics, New York: W. A. Benjamin, 1969.
Bethe, H. A.,
and R. W. Jackiw. Intermediate York: W. A. Benjamin, 1968.
Quantum

Mechanics, 2nd

ed.,New

and H.Van Dam. (eds)Quantum Theory of Angular Momentum, Biedenharn, L. New York: Academic Press,1965. and S.D.Drell, Relativistic Quantum Fields, New York; McGraw-Hill, Bjorken, 4th Dirac,P.A. M. Quantum Mechanics,

C,

Bohm,

D. Quantum

1965.

J.D.,

Theory,

Englewood Cliffs, NJ: Prentice-Hall,

1951. L ed., ondon:OxfordUniv. Press,1958.
487

488

Bibliography

Dirac,P. A. M. Quantum Mechanics, 4th ed.,London:Oxford Univ. Press,1958.
Edmonds, A. R. Angular Momentum
Princeton

in Quantum Mechanics, Princeton, NJ: PrinceUniversity Press,1960. Fermi, E. Nuclear Physics, Chicago: niversity of Chicago Press,1950. U and A. R. Hibbs. Quantum Mechanics and Path Integrals, New Feynman, R.

P., 1964. Finkelstein, R. J. Nonrelativistic Mechanics, Reading, MA: Frauenfelder, H.,and E. M. Henley. Subatomic Physics,
York: McGraw-Hill,

W. A. Benjamin,
Englewood Cliffs,

1973.
NJ:

French, A. P.,and E. F. Taylor. An Introduction to Quantum Physics, New York: W. W. Norton, 1978. M Goldberger, . L.,and K. M. Watson. Collision Theory, New York: Wiley, 1964. Goldstein,H. Classical echanics, 2nd. ed.,Reading, MA: Addison-Wesley, 1980. M Gottfried, K. Quantum Mechanics, vol. I, New York: W. A. Benjamin, 1966. New York: Wiley, 1975. Jackson,J. D. Classical lectrodynamics, 2nd E and E. M. Lifschitz. Quantum Mechanics, Landau, L. Reading, MA: AddisonWesley, 1958. N 2nd E Merzbacher, . Quantum Mechanics, ed., ew York: Wiley, 1970. 1 New York: Interscience, 961. A Messiah, . Quantum Mechanics, Morse,P. M., and H. Feshbach.Methods of Theoretical Physics, B vols.), New York: McGraw-Hill, 1953.
Newton,

1974. Prentice-Hall,

D.;

ed.,

R. G. Scattering Theory of Waves and Particles, 2nd. ed., New York: McGraw-Hill, 1982. Preston, M. Physics of the Nucleus, Reading, MA: Addison-Wesley, 1962.

Sakurai, Sargent

Addison-Wesley, 1974. 1968. Saxon,D.S. Elementary Quantum Mechanics. San Francisco: olden-Day, H 3 N Schiff, L. Quantum Mechanics, rd. ed., ew York: McGraw-Hill, 1968. S I Tomanaga, . Quantum Mechanics ,Amsterdam: North-Holland, 1962. Whittaker, E. T.,and G.N. Watson. A Courst of Modern Analysis, New York:

III, .,M. O. Scully, M

J.J. Advanced

Quantum

and W.

Mechanics, Reading, MA: Addison-Wesley, 1967. E. Lamb, Jr. LaserPhysics, Reading, MA:

Cambridge University

Press,1965.

REFERENCE SECTION
Dicke,R. H.,and
Addison-Wesley,
few

A very topics,notably

J. P. Wittke, Introduction to Quantum Mechanics, Reading, MA: 1960. readablebut terse book at the junior or senior level. It discusses a
quantum statistics, not usually treated in textbooks at this

level.

Feynman, R. P.,R. B. Leigh ton, and M. Sands, The Feynman Lectures vol. 3, Quantum Mechanics, Reading, MA: Addison-Wesley, 1965.

on Physics,

This is an introduction to quantum mechanics that from the viewpoint of state vectors,an approach that\342\200\224together
\342\200\224greatly

t approacheshe subject with Dirac'sclassic

stimulated

book.The many

with a discussed

the spirit and substance of the earlier chapters of our own fascinating examples(for example, the Stern-Gerlachxperiment) e minimum of formalism are to be noted in particular. Physics, New York: Wiley

S. Gasiorowicz, Quantum

1974.

Reference Section

489

This book is at a level comparable to that of Dicke and Wittke 1960. i Gasiorowiczs known to be a very effective teacher, who makes difficult concepts areasof particle theory. Henceit is not simple and cleareven in advanced research

enhancesthe
Mandl,

surprising

that

his quantum physics readability of the book.

book

reflects

that clarity

of purpose

that

F.Quantum

Mechanics, London:Butterworths

Scientific Publications,

1957.
and

This book contains a clearand compact presentation

of the

foundation

book.

mathematical principles of wave mechanics at a level comparable to
Matthews,

Gasiorowicz's

P.T. Introduction

1974.

to Quantum

Mechanics, 3rd

ed.,London:McGraw-Hill,

This third edition is lucid, concise,self-contained, and addressedto the It is a mathematically oriented introduction to development in wave undergraduate. and matrix mechanics,basedon clearly defined postulates.
Mott, N.

1952.

F. Elements
but

of

Wave

Mechanics,
treatment

London:Cambridge
of

University

Press,

A short

theoretical level by one of the pioneers.
Park,

delightful

wave mechanics at an elementary

D. Introduction 1974.

to the Quantum

Theory,

2nd. ed.,New York: McGraw-Hill,

Intended for advanced
outstanding

applications to
theory.

has pedagogue a general
various

use the
Pauling,

The applications book as a reference.

this attractive book by an outstandundergraduates, introduction to quantum theory, followed by selected branches of physics, illustrating different aspectsof the appearto require little teaching, and hence students can Introduction to Quantum

1935. McGraw-Hill, Though one of the older texts, it is still well worth studying. Thereis a treatment of the hydrogen atom and harmonic oscillator from surprisingly complete
the wave Rojansky,

L., and E. B. Wilson,

Mechanics, New York:

mechanics viewpoint.
V. Introductory

1938.

Quantum

Mechanics, Englewood Cliffs, NJ: Prentice-Hall,

its

detailed coverage the of

Despiteits

t vintage, this book remains a classicalext, especiallyvaluable for fundamental principles of wave and matrix mechanics.

Index

Abelian, definition of, 49 Absorption, in classical radiation

Angular

Absorption-emission cycle,321-22 Adiabatic potential, 474 complex system and, 473-74 Adiabatic theorem, 464-65 Aharonov-Bohm effect, 136-39, 472-73
Airy function,

335-37

fields,

momentum addition, examples of, 203-206
formal theory

203-17

of, 206-210

Angular

momentum addition rule, proof of, 456-57 Angular momentum commutation relations, ladder operators and, 188-89 rotations and, 152-58 matrix realizations, 165 Angular momentum operator, 156-157 Angular momentum operator, matrix elements of, 191-92 Angular velocity vector, angular momentum and, 6 Annihilation 1 operator, 90-91, 47,218 Anomalous Zeeman effect, 307 Anticommutation relations, 28 Antilinear operator, 269,273 states, 257 Antisymmetrical operator, 269,273, 277, Antiunitary

187-89

108-9

Algebra, bra-ket, 60 Alkali atoms, fine structure and, 304-7 Angular frequency, Planck-Einstein relation and, 71 Angular integration, helium atom and, 367 Angular momentum vector and, 6 angular-velocity eigenvalues and eigenstates of, 188-95 orbital, 195-203 eigenvalues of, 31 parity eigenket of, 255 rotation generation and, 196-98 spherical harmonics and, 198-203 Schwinger's oscillator model of, 217-23 of silver atoms, 2 uncoupled oscillators and, 217-21
quenching

2x2

of, 284

422-23

Argand diagram, 403 Argon, Ramsauer-Townsend effect and,

413

Associative axiom

of multiplication,

16-17
491

492

Index

Atomic spectroscopy, Axial vectors, 254

159

Central

Baker-Hausdorff formula, 96 Baimer splittings, fine structure splittings and, 307 Basekets change of basis in, 36-37 eigenkets as, 18-20 spin 1/2systems and, 22 transition amplitudes and, 87-89
Baym,

forceproblem, Schrodinger wave equation and, 450-54 Classicalphysics, symmetry in, 248-49 Classicalradiation fields, absorption and stimulated emission, 335-37 Clebsch-Gordan coefficients, 206,238-40 properties of, 208-10 recursion relations for, 210-15 rotation matrices and, 215-17 2 Clebsch-Gordan series, 16 Clebsch-Gordan series formula, 237
Closure, 19 Collectiveindex, 31,296 Colorsinglets, 377
Commutation relations,
Commutativity,

Bell'sinequality,

2 G., 36

229-32

quantum

mechanics and,

Bethe, H.A., 432

Berry, M. V., 464,465 Berry's phase, 465-80 and polarized light, 479-80 Bessel functions, properties of, 452-53

28
momentum

152-58

angular

and,

217 Biedenharn, L. Bitter, T., 470 Bloch, F.,432 Bloch's theorem, 265 Bohr, N., 76, 391,432 Bohr atom, 1 Boltzmann constant, 184 Born, M., 50,90, 100, 02, 87 1 1 Born amplitude, first-order, 386,393,442, 446
Born approximation, 386-90, 426,428,441 Born-Oppenheimer approximation, 474 Bose-Einstein condensation, 363 Bose-Einstein statistics, 361

C,

Commutators, 66, 86 Poisson brackets and, 50-51 Completeness relation, 19 Complex conjugate transposed, 20 Complex numbers, quantum mechanics and, 27-28 Complex systems, adiabatic potential and,

473-74

Complex vector

space,pin states and, 10 s Compton effect, 1 Constant potentials, gauge transformations
Continuous spectra, 41-42 Correlation amplitude, energy-time uncertainty relation and, 78-80 Correlation function, 146 Coulomb case, artial-wave analysis and, p

and,123-25

Bosons, 361-63
Bound states

438-41

low-energy scattering and, 410-18 quasi-, 419 zero-energy scattering and, 413-16 Bra, matrix representation of, 21 Bra-ket algebra, 60

Bra space, 3 1
Brillouin, Brillouin

Breit-Wigner form, 482,483 Breit-Wigner Formula, 421

Coulomb interaction, Hamiltonian of, scattering solutions of, 435-38 Coulomb scattering, 433-41 Coulomb scattering amplitude, 458-62 Coulomb scattering formalism, details of, 458-63 mathematical Creation operator, 90-91, 47,218 1 Dalgarno, A., 298 Davisson-Germer-Thompson

L.,105 zone,265

Canonical commutation relations, Canonical ensembles, 185-87 Canonical momentum, 130, 35 1 definition of, 249 Cartesian tensors, 234-36 Cayley-Klein parameters, 170

50-51

L., deBroglie, 47,68, 100

experiment,

1

de Broglie's matter waves, 1 Decaywidth, energy shift and, 341-45 Decays,non-exponential, 481-86 Degeneracy, 29, 61,250-51 exchange, 358
Kramers,

281

Index

493

Degeneracy point, geometrical phase factor and, 467-69

Delacretaz, .,479 G Density matrix, 178 of completely random ensemble, 183
continuum

generalizations and,

182

Density operator definition of, 177

ensemble averages and, 176-81 Hermitian, 178 pure vs. mixed ensembles and, 174-87 time evolution of, 243 Detailed balance, 335,424 6 Diagonalization, 39-40, 6, 90
Diamagnetic

Eigenspinors, 277-78 Eigenstates, 12 angular momentum, 188-95 time reversal and, 279-80 Wigner-Eckart theorem and, 239 energy, parity properties of, 255-56 zeroth-order, 347 Eigenvalues, 12 angular momentum, 188-95 degenerate, 29 energy, simple harmonic oscillator and,

90-94

350 susceptibility, Dicke,R. H.,488 Differential crosssection, 385 Dipoleoperator, 338 Dirac8 function, 41 8 Dirac,P. A. M., 23-4,50-52, 4, 143, 25,332 3 107,
Dirac bra-ket notation, 273 Diracnotation, 8 Clebsch-Gordan coefficients and, Dirac picture, 319 Direction eigenkets, 199 Dispersion, 34 Double-bar matrix element, 239 Dual correspondence, 13 470 Dubbers, Dyadic tensors, 234 73, 326 Dyson, F. 7 Dyson series, 3, 325-26

expectation values and, 25 Hermitian operators and, 17 orbital angular momentum squared and,

energy eigenkets and,

74

31

1,11, 118-19,

209

D.,

J.,

Eikonal approximation, 392-94 partial waves and, 404 Einstein, A., 226-27 Einstein-Debye theory, 1 Einstein-Podolsky-Rosen paradox, 277 Einstein's locality principle, 226-29 Elastic scattering, 444-45 Electric dipole approximation, 337-39 Electric fields, charged particles in, 280-81 Electromagnetic fields, polarization vectors of, kets and, 10 Electromagnetism, gauge transformations in, 130-36 Electron spin, magnetic moment and, 2-4 Emission, in classical radiation fields,

335-37

87 Ehrenfest, 1 Ehrenfest's theorem, 87, 126, 31
Eichinvarianz,

P.,

eigenkets, 74-75 simple harmonic oscillator and, 90-94 Energy eigenstates, parity properties of,
Energy

255-56

135

Eigenbras, eigenkets and, 13 Eigenfunctions, 53 Eigenkets, 12 angular momentum, 189-91 as base kets, 18-20 direction, 199 eigenbras and, 13 energy, 74-75 simple harmonic oscillator and, Hermitian operators and, 61 observables and,

90-94

17-18

parity,

255

position, 42-43 simultaneous, 30 zeroth-order, 298

eigenvalues, simple harmonic oscillator and, 90-94 Energy shift, decay width and, 341-45 Energy-time uncertainty relation, correlation amplitude and, 78-80 Ensemble average definition of, 177 density operator, 176-81 Ensembles canonical, 185-87 completely random, 175 density matrix of, 183 mixed, 176 pure, 24, 176 time evolution of, 181-82 Entropy, 184
Energy

494 Equation of motion Euler, 243 9 Heisenberg, 83-84, 5,243,249
Euclidian

Index

Gaussian wave packets, 57-59, 4, 67, 6

112

100,

Euler angle notation, 221 243 Euler rotations, 171-74, Exchange degeneracy, 358 Exchange density, 365 Expectation values, 25, 160 Hermitian operators and, 35 time dependence of 75-76 Experimental verification geometric phase of, 469-70

3 space, 5

Gauss'slaw, 140 Gauss'stheorem, 401
experimental verification, 469-70 universality of, 479-80 Geometrical phase degeneracy point and, 467-69 solid angle and, 469 Gerlach, W.,2 Goldstein, 38, Gottfried, K., 26, 147, 348,349 Gravity, quantum mechanics and, 126-29

Geometric phase

H., 171,250

Feenberg, Eugene, 390 Fermi-Dirac statistics, 361, 76, 378 3 Fermions, 361-63 Fermi's golden rule, 332 Feshbach, H.,113

Green'sunction, f Green's perator, 425 o

311, 111, 441 390,424,

488 Feynman, R. 117-23 Feynman's formulation, 138 Feynman's path integral, 121-23, Filtration, 25-26 Fine structure, spin-orbit interaction and,

P.,116, 118,

Hamilton, W. R., 100 3 Hamilton-Jacobi equation, 149, 92 Hamilton-Jacobi theory, 103 of Coulomb interactions, Hamiltonian,

435-38
348

Hamiltonian Hamiltonian

matrix, for two-state systems, operator,

304-7

Finite rotations infinitesimal rotations and,

152-55

143-45

71,90,98,99,

of, spin 1/2systems and,
noncommutativity Finkelstein,

153

R.

Form factor, 431 Fourier decomposition, 345 Fourier inversion formula, 345 Fourier transform, 431, 82,483 4 Fractional population, 175 Franck-Hertz experiment, 1 279 Frauenfelder, Free-particle states, scattering and, 395-99 Free particles Heisenberg equation of motion and, 85 Schrodinger wave equation and, 446-47

J.,149

158-68

H.,

time-dependent, 73 time-independent, 72-73 two-state systems and, 62 Hamilton's characteristic function, 103-4 4 Hankel functions, 405,439, 53 Hankel's formula, 438 Hannay's angle, 480 Hard-sphere scattering, 406-10 Harmonic oscillator, seealsoSimple harmonic oscillator isotropic, 346 Harmonic perturbation, 333-35 1 48,50, 100, 87 Heisenberg, W., 9 Heisenberg equation of motion, 83-84, 5,

1,

243,249

Fulton, Fundamental

4 T., 34

Heisenberg picture,

commutation relations,

50-51

488-89 Gasiorowicz, Gauge invariance, 135-36 Gauge transformations constant potentials and, 123-25 electromagnetism and, 130-36 Gaussian potential, 443

S.,

basekets and, 87-89 state kets and observables and, Heisenberg uncertainty principle, Helium atom, 366-70 Helmholtz equation, 390 Henley, E. M., 279 Hermite polynomials properties of, 450 Hermitian adjoint, 15

318-19 181,

80, 114-15, 143-44,

82-83
3, 58

Index

495

Hermitian

operator, 27, 45,66,71,85,90, 274, 178-79, 1 96,98, 144, 56-57,

Kets,

8-9

base
change of basis in, 36-37 eigenkets and, 18-20 spin 1/2systems and, 22 transition amplitudes and, 87-89 definition of, electromagnetic field polarization vectors and, 10 normalized, 14

279
anticommute, 63 eigenvalues of, 17 expectation values of,
Hermiticity,

477 Herzberg, 100 Hilbert, Hilbert space,

D.,11,

G.,

35 40, 178,391

11

Hooke'saw, 90 l

11

null,

Hydrogen atom ground state of polarizability of, linear Stark effect and, 302-4 Schrodinger wave equation and, Hydrogen-like atoms fine structure and, 304-7 Zeeman effect and, 307-11

298

454-55

particles, scattering and, 421-22 Identity operator, 19,29 spin 1/2systems and, 22 Incoherent mixtures, 175 Inelastic scattering, 429-34 nuclear form factor and, 433-34 Inertia, moment of, computation of, 6 Infinitesimal rotation operator, 156-57, 196 Infinitesimal rotations
Identical

Kramers, H.A., 105 Kramers degeneracy, 281 Kronecker symbol, 41 Krypton, Ramsauer-Townsend effect and,

vacuum, 218 Khalfin, A.,483 Kinematic momentum,

operators and, 14 spin, 160-61 orbital state, 477 perturbed, normalization of, 293-94 state Schrodinger and Heisenberg pictures and, 82-83 time and, 69-71

11

130,135

413

mechanics and, 156-58 vector operator and, 233 Infinitesimal time-evolution operator, 70 Inner products, 13-14 Integral equation, 380 Interaction picture, 318-19 Irreducible tensors, 234-36 Isospin, 221 Itano, W. M.,486
quantum

of, 155 commutativity finite rotation and, 152-55

Ladder operators, angular momentum commutation relations and, 187-89 Lagrange equation, 249 138 Lagrangian, classical, Laguerre polynomials, 454 Lamb shift, 303,349 Lande'sinterval rule, 306 Laplace-Fourier transform, 114 Laplacetransform, 435 4 Laplacetransform space, 58 Laporte'srule, 260 Lattice translation, as discrete symmetry,

116-17,

3 Jackson, J.D., 39 Jacobi identity, 51

261-66

Jahn-Teller effect, 475-79, 480 1 Jordan, 50, 100, 87

P.,

Lattice translation operator, Legendre function, 442 Leighton, R. B.,488 Lewis, T., 298

262-64

J.

Ket equation, 380 Ket space, bra space and, 13 operators and, 14-15 and, 65 orthonormality

Light circularly

11-12

polarized, mathematical representation of, 9-10 polarized and Berry's phase, 479 Polaroid filters and, 6-10 x-polarized, y-polarized, 6-10

6-10

496

Index

Linear Stark effect, Liouville's theorem,
Lippmann-Schwinger Lippmann-Schwinger

302-4 181
equation, formalism,

Multiplication

389,424,426,447
477 Longuet-Higgins, H. Lorentz force, 139 equation of, 267

379-86,
4 441, 43

associative axiom of, noncommutative, Muons, spin precession of,

15-16

16-17
161

C, 131,

Magnetic fields charged particles in, 281-82 Stern-Gerlach experiment and, 2-4 Magnetic flux, fundamental unit of, 139 Magnetic moment electron spin and, 2-4 Magnetic monopoles, 140-43 489 Mandl,

Masers, 324-25
Matrices,
Matrix elements

F.,

Neutron interferometer, 150 Neutron interferometry 2tt rotations and, 162-63 1 Newton's secondlaw, 87, 123, 39 Non-Abelian, definition of, 158 Non-exponential decays, 481-86 states, 76, 257 Nonstationary Norm, 14 Nuclear form factor, inelastic scattering and, 433-34 Nuclear magnetic resonance, 159 Null kets,

11

seespecific type
Observables, 12
compatible, 29-32 eigenkets of, 17-18 incompatible, 29, 32-34 transformation operator and, 36-37 matrix representation of, 22 Schrodinger and Heisenberg pictures and, 82-83
unitary equivalent,

operators, 191-92 double bar, 239 reduced, 241 tensors, 238-42 Matrix mechanics, 50 Matrix representations, 20-22 Matter waves, de Broglie's, 1 Matthews, P. T., 489 Maxwell-Boltzmann statistics, 362 Maxwell's equations, 140, 67 2 Mean square deviation, 34 Measurements quantum theory of, 23-26
angular-momentum

40-41

selective, 25-26

298,347, 349,350 Merzbacher, Messiah, A., 465 Minimum uncertainty wave packets, 58 484 Misra, Momentum 1 canonical, 130, 35 definition of, 249 definition of, 54 1 kinematic, 130, 35 translation generation and, 46-50 Momentum operator, 59-60, 7 6 position basis and, 54 Momentum-space wave function, 55-57,

E.,

B.,

Operator equation, 233 Operator identity, 46 seealsospecific type Operators, 12, definition of, 34, 65-66 time reversal and, 273-75 trace of, 38 Optical isomers, 259 Optical theorem, 390-92 Orthogonal matrices operations with, 169 multiplication Orthogonal groups, 168-69 Orthogonal matrices, 153-55

14-15.

Orthogonality,

spherical harmonics and, Orthohelium, 369-70
Orthonormality,

14,17,27, 52,54,209,431 216 18,19,23,30, 37, 61,120,

209

ket

146 Morse, P. M., 113
95,243,249

Oscillation

Motion, Heisenberg equation of, Mott, N.

83-84,

F.,489

strength, definition of, 338 Oscillators, seealso Simple harmonic oscillator uncoupled, angular momentum and,

and, space 65

217-21

Index

497

Outer products, matrix representation of,

22

Paley, R., 483 theorem, 483 Paley-Weiner 369-70 Parahelium, Parity, 251-54 wave functions under, 254-56 Parity nonconservation, Parity operator, 251

260-61

Parity-selection rule, 259-60 Park, D.,489 Partial-wave amplituted, 400
Partial-wave

Polarized light and Berry's phase, 479 Polaroid filters light and, 6-10 Polyatomic molecules as complex systems, 473-74 Position eigenkets, 42-43 Position-momentum uncertainty relation, 48 Position-space wave functions, 51-53 Positive definite metric, 14 Potassium atom, fine structure and, 304-7 Potentials, Schrodinger wave equation and, Preston,

447-48 M., 416 101

for Coulomb case, 38-41 4 Partial-wave expansion, 399-401 Paschen-Back limit, 310
Pauli, W., 163 Pauli exclusion principle, 265,362 Pauli matrices, 164-65 Pauli two-component formalism, 163-65

analysis

Probability Probability Probability

conservation, 402 density, wave mechanics and,
flux,

101
20

Projection operator, Projection theorem, Propagators

241

rotations in,

165-68

transition amplitude and, wave mechanics and, 109-14

114-16

Pauling, Permutation operator, definition of, Permutation symmetry, 357-61 Young tableaux and, 370-77

L.,489

358

Pseudoscalar, examples of, Pseudovectors, 254 Pure ensembles, 24

254

Pertubation, 286 constant, 328-33 harmonic, 333-35 Pertubation expansion, formal development of, 289-93 Perturbation theory 353,355 time-dependent, 325-35, scattering and, 426-29 time-independent 354 degenerate, 298-304, nondegenerate, 285-98 variational methods in, 313-16 Phase shifts determination of, 405-6 unitarity and, 401-4 Photoelectric effect, 339-41 Planck, M.,89, 107 Planck-Einstein relation, angular frequence and, 71 Planck's constant, 479 Planck's radiation law, 1 227 Podolsky, Poisson bracket, 66, 84 commutators and, 50-51 Polar vectors, 254 Polarized beams, 174-76

Quadratic Stark effect, 296 Quantum electrodynamics, covariant, Quantum Hall effect, 480 Quantum interference, gravity-induced,

326

127-28

Quantum

mechanics and, 229-32 complex numbers and, 27-28 gravity in, 126-29 infinitesimal rotations and, 156-58 symmetry in, 249-50 tunneling in, 258 Quantum statistical mechanics, 182-87 Quantum Zeno effect, 485,486 Quarkonium, 109 Quenching, 284

Bell'sinequality

B.,

Rabi, 320,324 Rabi's formula, 320 Radial integration, helium atom and, 367 Radiation law, Planck's, 1 Ramsauer-Townsend effect, 413 Rayleigh-Schrodinger perturbation theory,

I.I.,

285,311

498

Index

Recursion relations, Clebsch-Gordan coefficients and, 210-15 Reduced matrix element, 241 4 Resonance, 321, 18 spin magnetic, 322-24 Resonance scattering, 418-21 Rigid-wall potential, Schrodinger wave equation and, 447-48 Rojansky, V., 489 Rosen, N., 227 Rotation generation, orbital angular momentum and, 196-98 Rotation matrices Clebsch-Gordan coefficients and, 215-17 formula for, 221-23 spherical harmonics and, 202-203 Rotation operator, 156-58 effect on general kets, 160-61 irreducible representation of, 174 representations of, 192-95 matrix representation of, 165-66 Rotational in variance, 402 Rotations, seealsospecific type and, 162-63 2tt, neutron interferometry angular momentum commutation relations and, 152-58

resonance,
symmetry
Schiff,

and, 422-24 time-dependent formulation

418-421

68,99, 101 Schrodinger, 1 1 Schrodinger equation, 56, 71-73, 26, 29, 425,435

L.,106

of,

424-29

E.,1,

138,181, 299,366,406,424, 281,

complex systems and, 474 time-dependent, 426,429,465 Schrodinger picture, 80, 144-45,

state kets and observables in, 82-83 Schrodinger wave equation, 97-109,

327, 318-19, 343 basekets in, 87-89 2 134, 67

181, 131,

Feynman's path integral and, 121-23 semiclassical (WKB) approximation of,

104-9

2x2

finite vs. infinitesimal, 152-55 Pauli two-component formalism and,

165-68

Rutherford formula, 434,438 Rutherford scattering, 388 Sakurai, Akio, 464 305,434 Sakurai, Sands, M., 488 113 Saxon, D. Scattering length, 414 Scattering processes Born approximation and, 386-90 Coulomb, 434-41 eikonal approximation and, 392-94 free-particle states and, 395-99 hard-sphere and, 406-10 identical particles and, 421-22 inelastic electron-atom, 429-34 Lippmann-Schwinger equation and,

J.J.,
S.,

solutions to, 446-55 time-dependent, 97-98 time-independent, 99-100 Schrodinger wave function, 276 interpretations of, Schrodinger's equation two-dimensional, 477 Schwartz inequality, 35, 64 3 26,46,217,221, 24 Schwinger, Schwinger action principle, 149 Selective measurement, 25-26 Silver atom beams, polarized vs. unpolarized, 174-76 Silver atoms spin states of and, 10 complex vector space representation of, 8-10 Stern-Gerlach experiment and, 2-4 Similarity transformation, 38 1 Simple harmonic oscillator, 89-97, 45,

101-3

J.,

146,188

energy eigenkets and eigenvalues of,

90-94
350

ground state of, 92 one-dimensional, ground-state energy of,

low-energy, bound states and, 410-18 low-energy, rectangular well/barrier, optical theorem and, 391-92 partial waves and, 399-410

379-86

411-13

345-46 perturbation and, 294-96, Schrodinger wave equation and, 450 time development of, 94-97 Simultaneous eigenkets, 30 Singlets, 354,377 Sodium atoms, fine structure and, 304-7 Sodium D lines, 306

parity properties of,

256

Index

499

Solid angle geometrical phase factor and, Sommerfled, A., 107 inversion, seeParity Space

469

Stoke'stheorem, 137
Stopping power, inelastic-scattering and,

sequential,

4-6

432

Space quantization,

4

Sturm-Liouville

Spatial displacement, seeTranslation Specific heats, Einstein-Debye theory of, 1 Spherical harmonics helium atom and, 367 Laguerre times, 445 orbital angular momentum and, 198-203 of, 216 orthogonality Spherical tensors, 234-36 Spherical-wave states, 395 Spin 1/2particles, spin operator for, 204-5 6 2 Spin 1/2systems, 22-23, 6-29, 1 anticommutation relations and, 28 canonical ensembles and, 186-87 dispersion in, 35 eigenvalues-eigenket relations in, 12 rotations of, 158-68 matrix and, 170 spin precession and, 76-78 time-evolution operator and, 69-70 time reversal for, 277-80 Spin-angular functions, definition of, 215 Spin correlations, spin-singlet states and,

theory, 202 484 Sudarshan, E.C. Suzuki, Yasunaga, 464 Symmetrical double-well potential, 256-59 Symmetrical states, 257 Symmetrization postulate, 361-63

G.,

Symmetry in classical physics,

248-49
as, 261-66

discrete
lattice translation

time-reversal, 266-82 perm