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TO

INTRODUCTION

Quantum

Mechanics
SECONDEDITION

DAVID J. GRIFFITHS

FundamentalEquations
Schrodinger
equation:

9* = //*

ih\342\200\224

dt

equation:
Time-independent
Schrodinger
Hty

*= fe~iEt/h

= Ef,

Hamiltonian
operator:
2m
Momentum operator:

p = -ihV

value:
Time dependence
of an expectation

^->\342\200\242\302\253>-(\302\245:

Generalized
uncertainty principle:

gaob> \\:
U, B])
LI
Heisenberg
uncertainty principle:

oxOp> h/2

Canonical
commutator:

[x,p] = ih
Angular momentum:

[L,,Lv] = ihLz,
Pauli matrices:

P
a, = '0
0
A

[Lv,Lz) = ihLx,

'0

-i'

^=/ 0 I

[L-,Lx]
a~ =

FundamentalConstants
= 1.05457
x 1(T34J s

Planck'sconstant:

Speedof light:

c = 2.99792x 108m/s

Massof electron:

me

= 9.10938
x 10-31kg

Massof proton:

mp

= 1.67262
x 10\"27kg

x 10\"I9C
e = 1.60218

Chargeof proton:
Chargeof electron:

-e

Permittivity of space: eo

x 10-19C
-1.60218

= 8.85419
x 10-'2
C2/Jm

Boltzmannconstant: kg = 1.38065
x 10~23J/K

HydrogenAtom
Finestructureconstant:

or

1/137.036
47t\302\243ohc

Bohrradius:
Bohrenergies:
Bindingenergy:

a =
En

Rydberg constant:

mee2

amec

y/jta^

-EX = 2m
ea2

x 10-11m
5.29177

-4 (n= 1,2,3,...)

ee4
2(47te0)\302\2762
m

h2

Groundstate:
Rydberg formula:

fl2

4jT\342\202\254o

a~mec~

= 13.6057
eV

e -rja

l ~
X

ny

2nhc

nj
= 1.09737
x 107/m

Introductionto
QuantumMechanics
SecondEdition

DavidJ. Griffiths
ReedCollege

^^^KiiH PearsonEducationInternational

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CONTENTS

PREFACEvii

PARTI THEORY
1 THE WAVE FUNCTION1
1.1 The SchrbdingerEquation1
1.2 The Statistical
2
Interpretation
1.3 Probability5
1.4 Normalization12
1.5 Momentum 15
1.6 The Uncertainty Principle18
2 TIME-INDEPENDENT
SCHRODINGER
EQUATION24
2.1 Stationary States24
2.2 The InfiniteSquareWell 30
2.3 The HarmonicOscillator40
2.4 The FreeParticle59
2.5 The Delta-Function
Potential68

2.6 The FiniteSquareWell

78

3 FORMALISM93
3.1 HilbertSpace93
3.2 Observables96
3.3 Eigenfunctions
of a HermiiianOperator100

iii

3.4 Generalized
Statistical
Interpretation106
3.5 The UncertaintyPrinciple110
3.6 DiracNotation118
4 QUANTUMMECHANICSIN THREEDIMENSIONS131
4.1 Schrodinger
Coordinates
131
Equationin Spherical
4.2 The HydrogenAtom 145

4.3

Angular Momentum

4.4 Spin 171

160

5 IDENTICALPARTICLES201
5.1 Two-Particle
Systems201
5.2

Atoms

5.4

Mechanics
230
Quantum Statistical

210
5.3 Solids218

PARTII APPLICATIONS
6 TIME-INDEPENDENT
THEORY249
PERTURBATION
6.1 Nondegenerate
Perturbation
Theory 249
6.2 Degenerate
Perturbation
Theory 257
6.3 The FineStructure of Hydrogen266

6.4 The Zeeman Effect 277


6.5 Hyperfine Splitting283

THE VARIATIONAL PRINCIPLE293


7.1 Theory 293
7.2 The GroundStateof Helium299
7.3 The HydrogenMolecule
Ion 304

8 THEWKBAPPROXIMATION
315
8.1 The \"Classical\"
Region316

8.2 Tunneling320
8.3 The Connection
Formulas325

9 TIME-DEPENDENT
PERTURBATION
THEORY340
9.1 Two-LevelSystems341
of Radiation348
9.2 Emission
and Absorption

9.3 Spontaneous
Emission355

10 THEADIABATICAPPROXIMATION
368
10.1 The AdiabaticTheorem368
10.2 Berry'sPhase376

Contents

11 SCATTERING394
11.1 Introduction394
11.2 Partial Wave Analysis 399
11.3 PhaseShifts405
11.4 The BornApproximation
408
12 AFTERWORD420
12.1 The EPR Paradox421
12.2 Bell'sTheorem423
12.3 The No-CloneTheorem428
12.4 Schrodinger's
Cat 430
12.5 The Quantum ZenoParadox431
APPENDIX LINEARALGEBRA435
A.l Vectors435
A.2 InnerProducts438
A.3 Matrices441
A.4 ChangingBases446
A.5 Eigenvectors
and Eigenvalues
449
A.6 Hermitian
455
Transformations
INDEX459

PREFACE

UnlikeNewton'smechanics,
or Maxwell's
or Einstein's
electrodynamics,
relativity,
was
not
even
one
definitivelypackaged\342\200\224by
quantum theory
and it retainsto thisday someof the scarsof its exhilarating
but traumatic
as to what itsfundamentalprinciples
are,how
youth.Thereis no generalconsensus
be taught, or what it really \"means.\"
can \"do\"
it should
Every competent
physicist
but the storieswe tellourselves
aboutwhat we are doingare
quantum mechanics,
and almostas implausible.
NielsBohrsaid,
asvariousasthe talesof Scheherazade,
then you haven'treally understood
\"If you are not confused
by quantum physics
\"I think I can safely say that nobodyunderstands
it\"; Richard Feynman remarked,
created\342\200\224or

individual,

quantum mechanics.\"

of thisbookisto teachyou how todo quantum mechanics.


The purpose
Apart

from someessential
in Chapter1,the deeperquasi-philosophical
background
are savedfor the end.I do not believeonecan intelligently
questions
discusswhat
meansuntil onehas a firm senseof what quantum
quantum mechanics
does.But if you absolutelycannotwait, by all meansread the Afterword
mechanics

immediately
followingChapter1.
Not only is quantum theory conceptually
rich,it is alsotechnically
difficult,
and exactsolutions
to allbut the mostartificialtextbookexamples
are few and far
between.It is thereforeessential
to developspecialtechniques
for attacking more
realisticproblems.
thisbookis dividedintotwo parts;'Part I covers
Accordingly,
the basictheory, and Part II assembles
an arsenalof approximation
with
schemes,
illustrativeapplications.
Although it is important to keepthe two parts logically
it is not necessary
to study the material in the orderpresented
here.Some
separate,
'Thisstructure was inspiredby David Park'sclassictext, Introduction to the Quantum Theory,
3rd ed..McGraw-Hill,New York (1992).
vii

for example,
instructors,
may wish to treat time-independent
perturbationtheory

after Chapter2.
immediately
Thisbookis intendedfor a one-semester
or one-yearcourseat the junioror
seniorlevel.A one-semester
coursewill have to concentrate
mainly on Part I;
a full-yearcourseshouldhave roomfor supplementary
material beyondPart II.
The readermust be familiar with the rudimentsof linearalgebra(assummarized
in the Appendix),
complexnumbers,and calculusup through partial derivatives;
with Fourieranalysisand the Diracdeltafunctionwouldhelp.
someacquaintance
mechanics
is essential,
of course,and a littleelectrodynamics
Elementary classical
would be usefulin places.
As always, the morephysicsand math you know the
easierit will be, and the moreyou will get out of your study.But I would like
to emphasize
that quantum mechanics
that flows
is not, in my view, something
an
smoothlyand naturally from earliertheories.On the contrary, it represents
ideas,callingforth a wholly new
abrupt and revolutionarydeparturefrom classical
and radicallycounterintuitive
way of thinking aboutthe world.That, indeed,is
what makesit sucha fascinating
subject.
We
At first glance,
thisbookmay strikeyou as forbiddinglymathematical.
encounterLegendre,Hermite,and Laguerrepolynomials,
sphericalharmonics,
and
Hankel
and
Bessel,Neumann,
functions,
Airy functions, even the Riemann
to mentionFouriertransforms,
zeta
Hilbertspaces,hermitian
and Lagrangemultipliers.
Is all thisbaggage
Clebsch-Gordan
coefficients,
really necessary?
Perhapsnot, but physicsis likecarpentry:Usingthe right tool
makesthe job easier,notmoredifficult,and teaching
without
quantum mechanics
the appropriate
mathematical equipmentis likeaskingthe studentto dig a
with a screwdriver.
(On the otherhand,it can be tediousand divertingif
the instructor
feelsobligedto give elaboratelessonson the properuse of each
tool.My own instinctis to hand the studentsshovelsand tellthem to start
blistersat first, but I stillthink thisis the mostefficient
digging. They may develop
and excitingway to learn.)At any rate,I can assureyou that there is no deep
mathematics
in thisbook,and if you run intosomething
unfamiliar, and you don't
find my explanation
aboutit, or lookit up.
by allmeansask someone
adequate,
Thereare many goodbookson mathematical
particularly recommend
2nded.,Wiley, New
Methodsin the PhysicalSciences,
Mary Boas,Mathematical
York (1983),
or GeorgeArfken and Hans-Jurgen
Methods
Weber,Mathematical
for
But
5th
Academic
O
rlando
whatever
don't
Press,
(2000).
Physicists, ed.,
you do,
let the mathematics\342\200\224which, for us,is only a tool\342\200\224interfere with the physics.
Severalreadershave notedthat there are fewer worked examples
in thisbook
and that someimportantmaterial is relegated
than is customary,
to the problems.
Thisis no accident.
I don'tbelieveyou can learn quantum mechanics
without doing
foryourself.Instructors
shouldof coursego overasmany problems
many exercises
in classas timeallows,but students
shouldbe warned that thisis not a subject
aboutwhich anyonehas natural intuitions\342\200\224you're developinga whole new set
of muscleshere,and there is simplyno substitute
for calisthenics.
Mark Semon
function\342\200\224not

operators,

foundation

methods\342\200\224I

Preface

ix

Guide\"to the problems,


that I offera \"Michelin
with varying numbers
suggested
of starsto indicatethe levelof difficulty and importance.
This seemedlikea good
idea(though,likethe quality of a restaurant, the significance
of a problemis partly
a matter of taste);I have adoptedthe followingrating scheme:

*
an essentialproblemthat every readershouldstudy;
** a somewhat moredifficultor moreperipheral
problem;
** * an unusually challenging
that
take
overan hour.
problem, may
(No starsat all means fast food:OKif you'rehungry, but not very nourishing.)
Mostof the one-starproblems
appearat the endof the relevant section;mostof
the three-star
are at the endof the chapter.
A solution
manual is available
problems
(to instructors
only) from the publisher.
In preparingthe secondeditionI have triedto retain as much as possiblethe
spiritof the first.The only wholesale
changeis Chapter3, which was much too
material
rewritten, with the background
longand diverting;it hasbeencompletely
vectorspaces(a subjectwith which moststudents
on finite-dimensional
at thislevel
to the Appendix.I have addedsomeexamples
are already comfortable)
relegated
of raisingand loweringoperators
in Chapter2 (and fixed the awkward definition
In laterchaptersI have madeas few changesas I
for the harmonic oscillator).
and equations,
where possible.
could,even preservingthe numberingof problems
The treatment is streamlined
in places(a betterintroduction
to angular momentum
a simplerproofof the adiabatictheoremin Chapter
in Chapter4, for instance,
10,and a new sectionon partialwave phaseshiftsin Chapter11).Inevitably,the
secondeditionis a bit longerthan the first, which I regret,but I hopeit iscleaner
and moreaccessible.
I have benefitedfrom the comments
and adviceof many colleagues,
who
readthe originalmanuscript,
(orerrors)in the first edition,
pointedoutweaknesses
in the presentation,
and supplied
I
improvements
interesting
suggested
problems.

wouldliketo thank in particular


P. K. Aravind (Worcester
Polytech),
GregBenesh
Burt Brody(Bard),Ash Carter(Drew),Edward
(Baylor),David Boness(Seattle),
PeterCollings(Swarthmore),Richard Crandall(Reed),
Chang (Massachusetts),

JeffDunham (Middlebury),
JohnEssick(Reed),Gregg
GregElliott(PugetSound),
Franklin (Carnegie
Mellon),Henry Greenside
(Duke),Paul Haines(Dartmouth),
J. R. Huddle(Navy), Larry Hunter(Amherst), David Kaplan(Washington), Alex
Kuzmich (GeorgiaTech),PeterLeung(PortlandState),Tony Liss(Illinois),
Jeffry
J
ames
McTavish
James
Mallow(Chicago
(Miami),
Loyola),
(Liverpool), Nearing
Powell
K
rishna
(
(Reed),
Johnny
Rajagopal MIT),Brian Raue (Florida
RobertReynolds(Reed),KeithRiles(Michigan),Mark Semon(Bates),
Herschel
StavrosTheodor(Lewisand Clark),JohnTaylor(Colorado),
Snodgrass
akis (Cyprus),A. S.Tremsin (Berkeley),Dan Velleman (Amherst), Nicholas
Wheeler (Reed),ScottWillenbrock
William Wootters (Williams),
Sam
(Illinois),
International),

Wurzel (Brown),and JensZorn (Michigan).

Introductionto
QuantumMechanics

PARTI THEORY
CHAPTER

THE WAVE FUNCTION

1.1THESCHRODINGEREQUATION
to move alongthe x-axis,subjectto
Imaginea particleof massw, constrained
somespecifiedforce F(x.t)(Figure1.1).
The programof classicalmechanics
is to determinethe positionof the particleat any given time:x(t). Oncewe
know that, we can figure out the velocity(v = dx/dt), the momentum (p =
mv), the kineticenergy (T = (l/2)mv2),or any otherdynamical variable of
interest.And how do we go aboutdeterminingx(/)? We apply Newton's
second law: F = ma. (For conservative
only kind we shall
systems\342\200\224the
consider, and, fortunately, the only kind that occurat the microscopic
force can be expressed
as the derivative of a potentialenergy function,1F =
and Newton'slaw readsmdrxjdt1=
This,togetherwith
(typically the positionand velocityat t = 0),
appropriateinitialconditions
level\342\200\224the

\342\200\224dV/dx.)

\342\200\2243V/3.V,

x{t).

determines

thissameproblemquitedifferently.In this
Quantum mechanics
approaches
casewhat we'relookingfor is the particle'swave function,W(x, f), and we get
it by solvingthe Schrodinger
equation:

9vj/

fi1 dH

at

2m

Magnetic forces are an exception,but

assumethroughout

this

let'snot

,,,
axil

worry

A]

about ihem just yet. By the way. we shall

book that the motion is nonrelalivislic

(,i\302\273

<SC

c).

Chapter1 The Wave Function


m

o n

r{X,t)
X

x(t)

1.1:

A \"particle\"
to movein onedimension
FIGURE
constrained
underthe influence
of a specified
force.

Herei is the squarerootof


constant(/?) dividedby 2tt:

\342\200\2241,

and h

\342\200\224

2tt

is Planck's

constant\342\200\224or

rather, hisoriginal

= 1.054572
x 10~34J
s.

[1.2]

The Schrodinger
to Newton'ssecond
equationplays a rolelogicallyanalogous
law: Givensuitable
initialconditions
(typically,ty{x, 0)),the Schrodinger
equation

Newton's
determines
mechanics,
ty(x,t) for all future time,just as,in classical
law determines
x(t) for allfuture time.2

1.2THE STATISTICAL
INTERPRETATION
But what exactly is this\"wave function,\"
and what doesit doforyou onceyou've
at a point,whereas the wave
got it?After all,a particle,by its nature, is localized
function(asits name suggests)
is spreadout in space(it'sa functionof x, for any
the stateof a particle'?
The answer
given time /). How can suchan objectrepresent
is providedby Bom'sstatistical
interpretationof the wave function,which says
that \\^(x, t)\\2 givesthe probabilityof finding the particle
at pointx, at time
moreprecisely,3
t\342\200\224or,

J.a

\\V(x\\t)\\2dx=

probabilityof finding the particle


betweena and /?, at time t.

[1.3]

isthe areaunder the graph of \\ty |2.Forthe wave functionin Figure1.2,


Probability
in the vicinity of pointA, where |4>|2
you wouldbe quitelikelyto find the particle
is large,and relatively mh likelyto find it near pointB.
^For a delightful first-hand account of the origins of the Schrodingerequation seethe article by
FelixBloch in PhysicsToday. December1976.
= ***
wave function itself is complex,
but |*|2
(where ** is the complex
conjugate of
is
real
a
and nonnegalivc\342\200\224as
*)
probability, of course,must be.
\342\200\242'The

Section1.2:The Statistical
Interpretation 3

*M2

FIGURE1.2: A typicalwave function.


The shadedarea represents
the probability
of
the
b
etweena
and
b.
The
w
ould
be
to
be
found
particle
relativelylikely
rinding
particle
near A, and unlikely tobe found near B.

The statistical
introduces
a kind of indeterminacy
into
interpretation

for even if you know everything the theory hasto tellyou about
mechanics,
the particle(to wit: its wave function),stillyou cannotpredictwith certainty the
outcomeof a simpleexperiment
to measureits
quantum
has to offer is statisticalinformationaboutthe possibleresults.This
has been profoundlydisturbingto physicistsand philosophers
alike,
indeterminacy
quantum

position\342\200\224all

mechanics

and

it

is natural to wonder whether it is a

fact of nature, or a defectin the

theory.

SupposeI do measurethe positionof the particle,and I find it to be at point


C.4Question:Where was the particle
There
justbeforeI made the measurement?
are three plausible
answers to thisquestion,
and they serveto characterize
the main
schoolsof thoughtregardingquantum indeterminacy:
1.The realistposition:Theparticlewas at C.Thiscertainly seemslikea
sensible response,
and it is the oneEinstein
advocated.Note,however,that if thisis
true then quantum mechanics
is an incomplete
theory,sincethe particlereally was
was unableto tellus so.To the realist,
at C, and yet quantum mechanics
is nota fact of nature, but a reflection
of our ignorance.
As d'Espagnat
put
o
f
never
was
but
it, \"the position the particlewas
indeterminate,
merely unknown
to the experimenter.\"5
additional
Evidently 4> is not the whole
as
to
(known a hiddenvariable)isneeded providea complete
description
of the particle.
2. The orthodoxposition:Theparticlewasn 7 really anywhere. It was the act
of measurement
that forcedthe particleto \"takea stand\" (thoughhow and why it
decidedon the pointC we darenotask).Jordansaidit moststarkly:\"Observations
not only disturbwhat is to be measured,
We compel(the
they produceit
indeterminacy

story\342\200\224some

information

...

found

4Of course,no measuring instrument is perfectly precise:


what I mean is that the particle was
the vicinity of C.to within the tolerance of the equipment.

in

\342\200\242'Bernard

p.

165).

d'Espagnat,\"The Quantum Theory and Reality\" (ScientificAmerican.November 1979.

Chapter1 The Wave Function


This view (the so-calledCopenhagen
particle)to assumea definiteposition.\"6
it
with Bohr and his followers.
Among physicists
interpretation),is associated
has always beenthe mostwidely acceptedposition.Note,however,that if it is
aboutthe act of measurement\342\200\224something
correctthere is something
very peculiar
littleto illuminate.
that overhalf a century of debatehasdoneprecious
3. The agnosticposition:Refuse to answer.Thisis not quiteas silly as it
aboutthe status
sounds\342\200\224after all,what sensecan there be in making assertions
when the only way of knowing whether you
of a particlebeforea measurement,
were right is precisely
in which casewhat you get is no
to conducta measurement,
(in the pejorativesenseof the
longer\"beforethe measurement?\"It is metaphysics
that cannot,by its nature, be tested.Pauli said:
word) to worry aboutsomething
one
\"Oneshouldno more rack one'sbrain aboutthe problemof whether something
of
cannotknow anything aboutexistsall the same,than aboutthe ancientquestion
how many angelsare ableto siton the pointof a needle.\"7
Fordecades
thiswas the
to
the
\"fall-back\"position
of mostphysicists:
orthodoxanswer,
They'dtry sellyou
but if you were persistent
the
retreat
to
and
they'd
agnostic
response, terminatethe
conversation.
Untilfairly recently,allthree positions(realist,orthodox,
had
and agnostic)
their partisans.
But in 1964JohnBellastonished
the physics
communityby showing
that it makes an observable
differencewhether the particlehad a precise(though
or not.Bell'sdiscoveryeffectively
unknown) position
priorto the measurement,
eliminated
as a viableoption,and made it an experimental
agnosticism
question
whether 1 or 2 is the correctchoice.I'll return to thisstory at the endof the book,
when you will be in a betterposition
to appreciate
Bell'sargument;for now, suffice
it to say that the experiments
have decisively
confirmedthe orthodox
A particle
simplydoesnothave a precisepositionpriorto measurement,
any
morethan the rippleson a ponddo;it is the measurementprocessthat insistson
oneparticular
result,limited
number, and thereby in a sensecreatesthe specific
only by the statistical
by the wave function.
weighting imposed
What if I madea secondmeasurement,
immediately after the first? Would I
new
get C again,ordoesthe act of measurementcoughup somecompletely
eachtime?On thisquestion
A repeated
measurement
everyone is in agreement:
(on the sameparticle)must return the samevalue.Indeed,it would be toughto
if this couldnot
provethat the particlewas really found at C in the first instance,
beconfirmedby immediaterepetition
of the measurement.
How doesthe orthodox
interpretation:8

number

\"Quoted in a lovely article by N. David Mennin. \"Is the moon there when nobody looks?\"
(PhysicsToday. April 1985.
p. 38).
Mermin
(footnote 6). p. 40.
7Quolcdby
8This statement is a little loo strong:There remain a lew theoretical and experimental loopholes,
some of which I shall discuss in the Afterword. There exist viable nonlocal hidden variable theories
(notably David Bohm's).and other formulations (such as the many worlds interpretation) that do not
fit cleanly into any of my three categories.
But 1 think it is wise, at least from a pedagogicalpoint of
view, to adopt a clearand coherent platform at this stage,and worry about the alternatives later.

Section1.3:
Probability

tM2

1.3:

of the wave function:graph of |>P|2immediatelyafter a


FIGURE
Collapse
measurementhas found the particle
at pointC.

accountfor the fact that the secondmeasurement


is boundto yield
interpretation
the value C? Evidently the first measurement
radicallyaltersthe wave function,
so that it is now sharply peakedaboutC (Figure1.3).We say that the wave
to a spikeat the pointC (it soonspreadsout
collapses,
uponmeasurement,
with the Schrodinger
equation,so the secondmeasurement
again,in accordance
kindsof physical
must bemadequickly).Thereare,then, two entirely distinct
processes:\"ordinary\"ones,in which the wave functionevolvesin a leisurely
fashion
in which ^ suddenlyand
under the Schrodinger
equation,and \"measurements,\"
function

discontinuously
collapses.9

1.3PROBABILITY
DiscreteVariables
1.3.1
Because
of the statistical
interpretation,
probability
playsa centralrolein quantum
soI digressnow for a briefdiscussion
of probability
mechanics,
theory.It is mainly
and I shalldo it in the
a question
of introducingsomenotationand terminology,
contextof a simpleexample.
fourteenpeople,whoseagesare asfollows:
Imaginea roomcontaining
onepersonaged14,
onepersonaged 15,
three peopleaged 16,
JThe role of measurement in quantum mechanics is so critical and so bizarre that you may
well be wondering what preciselyconstitutes a measurement. Doesit have to do with the interaction
between a microscopic(quanlum) systemand a macroscopic
(classical)measuring apparatus (as Bohr
insisted),or is it characterized by the leaving of a permanent \"record\" (as Heisenbergclaimed),or does
it involve the intervention of a conscious
\"observer\" (as Wigner proposed)?I'llreturn to this thorny
issue in the Afterword: for the moment let'slake the naive view: A measurement is the kind of thing
that a scientistdoes in the laboratory, with rulers, stopwatches,Geigercounters, and so on.

Chapter1 TheWave Function


two peopleaged22,
two
five

peopleaged24.
peopleaged25.

If we let N(j) represent


the number of peopleof age j, then

N(U) = 1,
N(15)= 1,
N(16)= 3,
N(22)= 2,
N(24)= 2,
N(25)= 5,

is zero.The totalnumber of peoplein the roomis


while N(17),for instance,
00

tf = X>c/).

[1.4]

7=0

of course,N = 14.)Figure1.4is a histogram


of the data.The
(In the example,
onemight askaboutthisdistribution.
followingare somequestions
Question If you selectedoneindividualat randomfrom thisgroup,what
is the probabilitythat thisperson'sage would be 15?Answer: One chancein
14,sincethere are 14possiblechoices,allequallylikely,of whom only onehas
that particularage.If P(j) is the probability
of gettingage j, then P(14)=
1/14,P(15)= 1/14,P(16)= 3/14,and soon.In general,

1.

P(j) =

N(j)

[1.5]

N(J) I

j
J
L
10 11 12 13 14 1516 17 18 19 20 21 22 23 24 25 26 j
i

FIGURE1.4: Histogramshowing the number of people,


NO),with age

1.3.1.

in Section
distribution

;, for the

Section1.3:
Probability 7
Noticethat the probabilityof gettingeither14or 15is the sum of the individual
the sum of all the probabilities
is
(in thiscase,1/7).In particular,
probabilities
certainto getsomeage:
1\342\200\224you're

oo

= i.
En/)
7=0

[1.6]

2. What is the mostprobableage?Answer: 25,obviously;five


Question
peoplesharethisage,whereas at mostthree have any otherage.In general,the
mostprobablej is the j for which P(j) is a maximum.
3. What is the medianage?Answer: 23,for 7 peopleare younger
Question
the medianis that value of j suchthat the
than 23,and 7 are older.(In general,
probabilityof gettinga largerresultis the sameas the probabilityof gettinga
smallerresult.)
4. What is the average(or mean)age?Answer:
Question
(14)+ (15)+ 3(16)+ 2(22)+ 2(24)+ 5(25) 294 = 21.
14
14
In general,the average value of j (which we shallwrite thus:(/'))is

0\ =

\342\200\224jv\342\200\224

= 1^,j nj).

[1.7]

7=0

Noticethat there neednotbe anyone with the average ageor the median
the average
thisexamplenobodyhappensto be 21or 23.In quantum mechanics
is usually the quantity of interest;in that contextit hascometo be calledthe
age\342\200\224in

value.It'sa misleading
that thisis the outcome
term, sinceit suggests
expectation
a
{that would
you would be mostlikelyto get if you made singlemeasurement
be the mostprobablevalue, not the average
I'm afraid we'restuck
value)\342\200\224but

with

it.

5. What is the average of the squaresof the ages?Answer: You


Question
couldget 142= 196,with probability1/14,or 152= 225,with probability1/14,
or 16~= 256,with probability3/14,and soon.The average,then, is
00

U2) = ^J2PU)-

[1.8]

7=0

In general,the average value of somefunctionof j is given by

[1.9]

Chapter1 The Wave Function


Nil) i

N(j) A

123456789
10/ 123456789
10/
i

>

>

1.5:

Two histograms
with the same median,same average,and same most
FIGURE
but
differentstandard
deviations.
probablevalue,

Beware:
(Equations1.6,1.7,and 1.8are,if you like,specialcasesof thisformula.)
The average of the squares,(j2),is not equal,in general,to the squareof the
average,(./)2.For instance,if the roomcontainsjust two babies,aged 1 and 3,
then (x1)= 5, but (x)2= 4.
difference
betweenthetwo histograms
in Figure1.5,
Now, thereisa conspicuous
even thoughthey have the samemedian,
the sameaverage,the samemostprobable
Thefirst issharplypeakedaboutthe average
value, andthe samenumberofelements:
the ageprofile
isbroadand flat. (Thefirst might represent
value, whereasthe second
the second,
for studentsin a big-cityclassroom,
schoolperhaps,a rural one-room
measureof the amount of \"spread\"in a distribution,
house.)We needa numerical
with respectto the average.The mostobviousway to do thiswouldbeto find out
how far eachindividual
deviatesfrom the average,
Aj =

j-{j),

[l.io]

computethe average of Aj. Troubleis,of course,that you get zero,since,by


the nature of the average,Aj is as oftennegativeas positive:
and

(aj) = J2u u))pu)= J2Jpw u)

\302\243

p(j)

= U) (j) = o.
doesnot changeas you go from onememberof
(Notethat (j) is
the sampleto
the summation.)
it can be taken outside
To avoidthis
irritating problemyou might decideto average the absolutevalue of Aj. But
absolutevaluesare nasty to work with; instead,we get around the signproblem
by squaringbeforeaveraging:
constant\342\200\224it

another\342\200\224so

a2 = ((Aj)2).

[1.11]

Section1.3:
Probability 9

Thisquantity is known as the varianceof the distribution;


a itself(the square
rootof the average of the squareof the deviationfrom the

average\342\200\224gulp!)

is

calledthe standarddeviation.The latter is the customary measureof the spread


about(j).

There is a usefullittletheoremon variances:

a2 = ((Aj)2)= \302\243(A/)2P(./)=
=
\302\243

j2P(j)

\302\243(./

- (j))2P(j)

- 2U)^jP(j)+ U)2J2P{j)

+ U)2= U2)-U)2.
U2)-2U)(j)

Takingthe squareroot,the standarddeviationitselfcan be written as


\302\260

= y/(J2)~ U)2-

[1.12]

In practice,thisis a much fasterway to get a: Simplycalculate(/2) and (j)2,


I warned you a moment ago that
subtract,and take the squareroot.Incidentally,
{j~) is not, in general,equalto (j)~. Sincea~ is plainly nonnegative(from its
definitionin Equation1.11),
Equation1.12impliesthat

[i.i3]

(r)>0*)2,

and the two are equalonly when a = 0, which is to say, for distributions
with no
spreadat all (every memberhaving the samevalue).

1.3.2ContinuousVariables
So far, I have assumedthat we are dealingwith a discrete
is,one
that can take on only certainisolatedvalues(in the example,
j had to be an
to
integer,sinceI gave agesonly in years).But it is simpleenoughto generalize
If I selecta randompersonoff the street,the probability
distributions.
continuous
that her age is precisely16years,4 hours,27 minutes,
and 3.333 seconds
is
zero.The only sensiblething to speakaboutis the probabilitythat her age liesin
someinteryal\342\200\224say, between 16and 17.If the interval is sufficiently short,this
to the lengthofthe interyal.
Forexample,
the chancethat
is proportional
probability
her age is between 16and 16plustwo days is presumably twice the probability
I suppose,there was some
that it is between 16and 16plusone day. (Unless,
which casewe
extraordinary baby boom 16years ago,on exactly that
have simplychosenan interval too longfor the ruleto apply.If the baby boom
variable\342\200\224that

...

day\342\200\224in

The Wave Function

lastedsix hours,we'lltake intervals of a secondor less,to be on the safe side.


we'retalking aboutinfinitesimal
Thus
intervals.)
Technically,
probabilitythat an individual(chosen 1
I

at

..
j/
random) liesbetweenx and
\\

,\342\200\242

,.,

j x \\=p{x)dx.
(a* + ax)

...

r,
,
[1.14]

The proportionality
factor,p(x),is oftenlooselycalled\"the probabilityof getting
a betterterm isprobability
A',\" but thisis sloppy
density.Theprobability
language;
that x liesbetweena and b (a.finiteinterval) is given by the integralof p(x):

= /I P(x
Pah=
P(x)dx,
Ja

[1.15]

and the ruleswe deduced


for discretedistributions
translate in the obviousway:

p(x)dx,
/+oo
-oc

[1.16]

xp(x)dx,
/+oo
-oo

[1.17]

f(x)p(x)dx,

[1.18]

[1.19]

/+0C
-oo
a2 ee <(Aa-)2)= (x2) (a)2.

1.1

Example SupposeI dropa rockoff a cliffof heighth. As it falls.I snapa


millionphotographs,
On eachpictureI measure the dssUince
at randomintervals.
That rs
the rockhasfallen.Question:
What is the averageof all thesedistances'
to say, what is the time averageof the distancetraveled?10
Solution:The rockstartsout at rest,and picksup speedas it falls;it spendsmore
time near the top, so the average distancemust be less than h/2. Ignoringair
the distance
x at time t is
resistance,
1

*(')= J*'9

\342\200\242

Thevelocityisdx/dt = gt, and the totalflight time is T = y/2h/g.Theprobability


that the camera flashesin the interval dt

is dt/T, so the probabilitythat a given

l0A statistician will complain that


am confusing the average of a finite sample (a million, in
this
with the \"true\" average (over the whole continuum). This can be an awkward problem for
the experimentalist, especiallywhen the sample
of
is small, but here I am only
with the true average, lo which the sampleaverage is presumably a good approximation.

case)

size

concerned, course,

Section1.3:
Probability

11

P(x)\"

1.1:
p(x)= l/(2</hx).

FIGURE1.6:The probability
densityin Example

photographshowsa distancein the corresponding


range dx is

dt _ dx

jg _ 1 dx.
T~~giy2h~27n=x
density(Equation1.14)is
Evidently the probability
1

p(x) =

2Vhx

(0 < x < h)

(outsidethisrange,of course,the probabilitydensity is zero).


We can checkthisresult,usingEquation1.16:

I
0

ly/hx

dx =

1
2Vh

l.

The averagedistance(Equation1.17)is

Jo

iVte

1 /2 r3/2
2Vh \\

3'

which is somewhatlessthan /?/2,as anticipated.


Figure1.6showsthe graph of p(x).Noticethat a probabilitydensitycan
be infinite,though probabilityitself(the integralof p) must of coursebe finite

(indeed,lessthan or equalto 1).

12

Chapter1 The Wave Function

1.1

of agesin Section1.3.1:
*Problem For the distribution
Compute(./2)and (j)2.
(b) Determine
Ay for eachj, and use Equation1.11to computethe standard
(a)

(c)

deviation.
Useyour resultsin (a) and (b) to checkEquation1.12.

Problem1.2
(a)

1.1.

in Example
Findthe standarddeviationof the distribution

(b) What

is the probabilitythat a photograph,selectedat random,wouldshowa

distancex morethan onestandarddeviationaway from the average?

*Problem1.3Consider
the gaussiandistribution
p(x) = Ae-k{x~a)\\

a, and k are positivereal constants.


(Lookup any integrals
you need.)
UseEquation1.16to determine
A.

where A,
(a)

Find (x),{x2),and er.


(c) Sketchthe graph of p(x).

(b)

1.4NORMALIZATION
of the wave function(Equation1.3),
return now to the statistical
interpretation
which says that \\ty(x, t)\\2 is the probability
densityfor finding the particleat point
must be 1 (the
x, at time t. It follows(Equation1.16)that the integralof
We

|^|2

particle'sgotto be somewhere):

\\V(x,t)\\2dx
/+oo
-co

l.

[1.20]

wouldbe nonsense.
this,the statistical
interpretation
shoulddisturbyou:After all,the wave functionis
However,thisrequirement
to be determinedby the Schrodinger
can'tgo imposing
supposed
equation\342\200\224we
^
on without checking
that the two are consistent.
an extraneous
condition
Well, a
Without

Section1.4:Normalization

13

sotoois A^U, /), where


glanceat Equation1.1revealsthat if ^(jc,f) isa solution,
constant.What we must do, then, is pickthisundetermined
A is any (complex)
factorso as to ensurethat Equation1.20is satisfied.
Thisprocess
multiplicative
is callednormalizingthe wave function.For somesolutionsto the Schrodinger
factoris goingto
equationthe integralis infinite;in that caseno multiplicative
=
0. Suchnon-normalizable
make it 1.The samegoesfor the trivial solution
vj/
solutionscannotrepresentparticles,and must be rejected.Physicallyrealizable
to the square-integrable
solutions
to Schrodinger's
statescorrespond
equation.11
I have normalized
But wait a minute!
the wave functionat time t = 0.
Suppose
How doI know that it will stay normalized,
astime goeson,and ^ evolves?
(You
the wave function,for then A becomes
can'tkeep^normalizing
a functionof t,
and you no longerhave a solutionto the Schrodinger
Fortunately,the
equation.)
hasthe remarkablepropertythat it automatically
the
Schrodinger
equation
preserves
normalization
of the wave function\342\200\224without thiscrucialfeature the Schrodinger
with the statistical
and the whole
interpretation,
equationwould be incompatible
theory would crumble.
Thisis important,so we'dbetterpausefor a careful proof.To beginwith,
+oc a

+0O

dt;_oo l*(*,t)\\2d

-oo dt

\\V(x,t)\\2dx.

[1.21]

(Notethat the integralis a functiononly of t, so I usea totalderivative (d/dt)


in the first expression,
but the integrand
is a functionof x as well as r, so it'sa
partialderivative (d/dt) in the secondone.)By the productrule,
9
= 9 (vi/*vi/) = ijr 9* + 8V* vl/.
|vl/|2
[1.22]
dt
dt
dt
dt
\342\200\224

\342\200\224

Now the Schrodinger


equationsays that

9^ iti d2V
dt

2m

dx-

[1.23]

and hencealso(taking the complex


conjugateof Equation1.23)

9**
dt

ih d2V*
2m dx1

[1-24]

ft

so

9,-,=

\342\200\2241*1

dt

92vl>*

Im \\
2m.
\342\200\236

dx2

\\

9x2 1

9*

9
dx 2m

\\

dx

8V*
*
dx

[1.25]

oo.Incidentally, normalization
t) must go to zero faster than \\/y/[x],as |.v|
'Evidently *(.v.
as we shall see,the latter
fixes
of
A:
the
remains
undetermined.
However,
the
modulus
phase
only
carriesno physical significance anyway.
1

\342\200\224*\342\226\240

TheWave Function
The integralin Equation1.21can now beevaluatedexplicitly:

d f+00 w
J = ^ /\"t*9^ 9Vr * +00
|vl/(.r,r)|~</.r
/
af J.qo
2m \\
3jc
3x

(**But *!>(*.
f) must go to zeroasx goesto (i)
m\">

\342\226\240

\342\200\224

\342\200\224

\342\200\224

infinity\342\200\224otherwise

[1.26]

\342\200\22400

the wave function

wouldnotbe normalizable.12
It followsthat

=
dt J_oo \\V(x,t)\\2dx 0,
of time);if
and hencethat the integralis constant(independent
for all future time. QED
at t = 0, it stays normalized
f+\302\260\302\260

[1.27]

\342\200\224

^ is normalized

Problem1.4At time t = 0 a particleis represented


by the wave function

A-,
a
V(x,0) =

\342\200\242

(b x)

(b-a)

0.

if 0 < x < a,
if a < x < b,
otherwise,

a, and b are constants.


Normalize (that is,find A, in terms of a

where A,
(a)

vj>

and /?).

SketchW(x, 0), as a function of x.


mostlikelyto be found,at t = 0?
(c) Where is the particle
of finding the particleto the left of al Checkyour
(d) What is the probability
(b)

resultin the limitingcasesb = a and b = 2a.

(e) What

value of x?
is the expectation

^Problem1.5Consider
the wave function
where A, k, and co are positive
real constants.
(We'llseein Chapter2 what potential
sucha wave function.)
(V) actually produces

in

(a)

Normalizevj>.

(b)

the expectation
Determine
valuesof x and x2.

,2A goodmathematician can supply you with pathological counterexamples,


but
physics;for us the wave function always goesto zero at infinity.

they

do not arise

Section1.5:
Momentum
(c)

15

Find the standard deviationof x. Sketchthe graph of \\W\\2, as a function


of a\", and mark the points((x)-f- er) and {(x) er),to illustrate
the sensein
which er represents
the \"spread\"in x. What is the probability
that the particle
wouldbe foundoutsidethisrange?
\342\200\224

1.5MOMENTUM
For a particlein statevj>, the expectation
value of x is

[1.28]

x\\V(x,t)\\2dx
/+oo
-00

doesnot mean that


What exactly doesthismean?It emphatically

if you measure
the position
of oneparticleoverand overagain, x\\^\\2dx is the average of the
resultsyou'llget.On the contrary:The first measurement(whoseoutcome
is
the wave functionto a spikeat the value actually obtained,
indeterminate) will collapse
and the subsequent
measurements
(if they'reperformedquickly)will simplyrepeat
that sameresult.Rather, (x) is the average of measurements
performedon particles
allin the state^, which meansthat eitheryou must find someway of returning the
or elseyou have to preparea
particleto its originalstateafter eachmeasurement,
wholeensemble
of particles,
of
eachin the samestate^, and measure
the positions
all of them:(x) is the average of theseresults.(I liketo picturea row of bottleson
a shelf,eachcontaining
a particle
in the state^ (relativeto the centerof the bottle).
A graduate studentwith a ruler is assigned
to eachbottle,and at a signalthey all
measurethe positions
of their respective
a histogram
We then construct
particles.
of the results,which shouldmatch |vl>|2,and computethe average,which should
agreewith (x).(Ofcourse,sincewe'reonly usinga finite sample,we can'texpect
In
but the morebottleswe use,the closerwe oughtto come.))
perfectagreement,
value is the averageof repeated
measurements
on an
short,the expectation
on
of identically
preparedsystems,not the average of repeatedmeasurements

ensemble

oneand the samesystem.


Now, as time goeson, (x) will change(becauseof the time dependence
of ^), and we might be interested
in knowinghow fast it moves.Referring to
Equations1.25and 1.28,we seethat13
d{X)

dt

\342\200\242-\"

dt

---

- J'--\"'--- - -dx.

2m

dx

\\

dx

dx

To keep things from gelling too cluttered. I'llsuppressthe limits of integration.

[1.29]

The Wave Function


can be simplified
Thisexpression
usingintegration-by-parts:14

d(x)
dt

ih

/.,3^ 9^*

2m /(*\342\200\242?

dx

\342\226\240*

dx.

[1.30]

(I usedthe fact that dx/dx= 1,and threw away the boundary term, on the ground
that
goesto zeroat ( + ) infinity.) Performinganotherintegrationby parts,on
vj>

the secondterm, we conclude:

d(x) =
dt
\"velocity\"

V*
dx
cix
J/
\342\200\224

[1.31]

What are we to make of thisresult?Notethat we'retalkingaboutthe


of the expectation
value of A', which is not the samething as the velocityof

the particle.
the velocity
Nothing we have seenso far wouldenableus to calculate
of a particle.
If the
It'snoteven clearwhat velocitymeansin quantum mechanics:
neitherdoesit
particledoesn'thave a determinate
position(priorto measurement),
ask for is the probabilityof
have a well-defined
All we couldreasonably
velocity.
the probability
gettinga particularvalue.We'llseein Chapter3 how to construct
for our presentpurposesit will sufficeto
densityfor velocity,given
that the expectation
value of the velocityis equalto the time derivative of the
value ofposition:
expectation

^;

postulate

,(v) = d{x)
\\

dt

[1-32]

(v) directlyfrom ^.
Equation1.31tellsus,then, how to calculate
Actually, it is customary to work with momentum(p = mv), rather than
velocity:

[1.33]
14The

product rule says that

d.f,
ax
from which it

,.dg df
ax

dx

follows that

Underthe integral sign.then, you can peel a derivative off one factor in a product, and slap it onto the
cost you a minus sign, and you'll pick up a boundary term.

other

one\342\200\224it'll

Section1.5:
Momentum

17

Let me write the expressions


for (.v) and (p) in a moresuggestiveway:
(a-) = J

ty*(x)Vd.x,

(p)=Jv*(j^)vdx.

[1.34]

[1.35]

the operator15
x \"represents\"
position,and the operator(/?//)(3/3.v)
to calculate
valueswe
momentum,in quantum mechanics;
\"represents\"
expectation
\"sandwich\"the appropriate
operatorbetween^* and ^, and integrate.
That'scute,but what aboutotherquantities?
The fact is,allclassical
in terms of position
and momentum.
Kineticenergy,
variablescan be expressed

We say that

dynamical

for example,
is

l 2=
rT = -mv
2

P2
\342\200\224,

2m

and angular momentum is

L = r x m\\ = r x p
To calculate
(the latter,of course,doesnot occurfor motionin onedimension).
the expectation
value of any suchquantity, Q{x,p), we simply replaceevery p
insertthe resulting
by (fi/i)(d/dx),
operatorbetween^* and ^, and integrate:

(Qix.p))= J**Q(x,~^Vdx.

[1.36]

Forexample,
the expectation
value of the kineticenergy is
(T) =

W*a^
a2*

I1371

the expectation
value of any dynamical
Equation1.36isa recipeforcomputing
quantity, for a particlein state^; it subsumes
Equations1.34and 1.35as special
cases.I have tried in thissectionto make Equation1.36seemplausible,given
Bom'sstatistical
but the truth is that thisrepresents
sucha radically
interpretation,
new way of doingbusiness
that it'sa good
(ascomparedwith classical
mechanics)
ideato get somepracticeusingit beforewe comeback(in Chapter3) and put it
if you preferto think of it as
on a firmer theoretical
foundation.
In the meantime,
an

axiom,that'sfine with me.

'-''An \"operator\" is an instruction lo do something lo the function that follows it. The position
operator lellsyou lo multiply by .v: Ihe momentum operator tells you to differentiate with respect lo
.v (and multiply
the result by
ih). In this book all operators will be derivatives (d/clt,ch/clt~.
or combinations of these.
a-/i)xciy.etc.)or multipliers (2. x~.etc.).
\342\200\224

i.

18

Chapter1 The Wave Function

Problem1.6Why can'tyou do integration-by-parts


directlyon the middle
in Equation
the time derivative overontox, notethat dx/dt = 0,
and conclude
that d(x)/dt = 0?
expression

1.29\342\200\224pull

^Problem1.7Calculate
d{p)/dt.Answer:

of 1.33)and 1.38are instancesof Ehrenfest's


laws.
valuesobeyclassical
theorem,which tellsus that expectation
Equations1.32(or the

first part

Problem1.8Suppose
Vo to the potential
you adda constant
energy (by \"constant\"
I mean independent
of x as well as /). In classical
thisdoesn'tchange
mechanics
Showthat the wave functionpicks
anything, but what aboutquantum mechanics?
What effectdoesthishave on
up a time-dependent
phasefactor:
the expectation
value of a dynamical variable?
exp(\342\200\224iV^t/h).

1.6THEUNCERTAINTYPRINCIPLE
Imaginethat you'reholdingone end of a very longrope,and you generatea
wave by shakingit up and down rhythmically (Figure1.7).If someone
askedyou
where is that wave?\" you'dprobablythink he was a littlebit nutty: The
\"Precisely
wave isn'tprecisely
any
spreadout over50 feet or so.On the other
hand,if he askedyou what its wavelength is, you couldgive him a reasonable
answer:It lookslikeabout6 feet.By contrast,
if you gave the ropea suddenjerk
(Figure1.8),you'dgeta relatively narrow bump traveling down the line.Thistime
where\342\200\224it's

the first question


is the wave?) is a sensibleone,and the second
(Where precisely
so how
(What is its wavelength?) seemsnutty\342\200\224it isn'teven vaguely periodic,
can you assigna wavelength to it? Of course,you can draw intermediate
cases,in
which the wave isfairly well localized
and the wavelength isfairly well defined,
but there is an inescapable
trade-offhere:The moreprecisea wave'spositionis,
the lesspreciseis its wavelength, and viceversa.16
A theoremin Fourier
analysis
makesall thisrigorous,
with the qualitative
but forthe moment I am only concerned
argument.
That's why a piccolo
player must be right on pitch, whereasa double-bassplayer can afford to
wear garden gloves.For the piccolo,
a sixty-fourth
note contains many full cycles,and the frequency
(we'reworking in the time domain now, instead of space)is well defined, whereasfor the bass, at a
much lower register,the sixty-fourth
note contains only a few cycles,and all you hear is a general sort
of \"oomph,\" with no very clearpitch.

Section1.6:The UncertaintyPrinciple 19

50 x (feet)
FIGURE1.7: A wave with a (fairly) well-definedwavelength, but an ill-defined

position.

10

AH30

20

40

50 x (feet)

but an ill-defined
FIGURE1.8:A wave with a (fairly) well-definedposition,
wavelength.

Thisapplies,of course,to any wave phenomenon,


and hencein particularto
wave
the quantum mechanical function.
Now the wavelengthof ^ isrelatedto the
momentumof the particleby the de Broglieformula:17
P

l
h

= litft

[1.39]

Thus a spreadin wavelengthcorresponds


to a spreadin momentum,and ourgeneral

determineda particle'spositionis,
observationnow says that the moreprecisely
the lessprecisely
is its momentum.Quantitatively,

[1-40]
is the standard deviationin x, and ap is the standarddeviationin /?.
Thisis Heisenberg's
famousuncertaintyprinciple.
(We'llproveit in Chapter3,
where ax

I wanted to mentionit right away, so you can testit out on the examples
in
Chapter2.)
Pleaseunderstandwhat the uncertainty principlemeans:Likeposition
measurements, momentum measurements
yield precise
\"spread\"here
refersto the fact that measurements
on identically
preparedsystemsdo not yield
identicalresults.You can,if you want, constructa statesuchthat repeated
will be very closetogether
measurements
(by making ^ a localized
\"spike\,
but you will pay a price:Momentum measurements
on thisstatewill be widely
Or you can preparea slatewith a reproducible
scattered.
momentum (by making
but

answers\342\200\224the

position

course.Many

authors lake the de Broglie formula as an axiom, from


this is
with the operator (h/i)(B/dx).
Although
a conceplually cleanerapproach, il involves diverting mathematical complicationslhal I would rather
save for later.
l7I\"ll

which

prove

they then

this in

due

deducethe associationof momentum

20

Chapter1 The Wave Function

^ a longsinusoidal
measurements
will be widely
wave), but in that case,position

scattered.
And, of course,if you'rein a really badmoodyou can createa statefor
which neitherposition
normomentum is well defined:
Equation1.40is an
and there'sno limiton how big ax and ap can
make ^ somelong
structure.
and no periodic
wiggly linewith lotsof bumpsand potholes
be\342\200\224just

inequality,

*Problem1.9A particleof massm is in the state

V(x,t)= Ae-al(mx2/ti)+i'\\
where A and a are positive
real constants.

FindA.
(b) For what potential
energy functionV(x) does^ satisfy the Schrodinger
(a)

(c)
(d)

equation?
Calculate
the expectation
values of x, x~, p, and p .
with the uncertainty principle?
Findax and ap. Is theirproductconsistent

FURTHERPROBLEMSFORCHAPTER1
the first 25 digitsin the decimal
Problem1.10
Consider
of tt (3,1,4,
expansion

1,5,9,...).

onenumberat random,from thisset,what are the probabilities


If you selected
of gettingeachof the 10digits?
(b) What is the mostprobabledigit?What is the mediandigit?What is the
(a)

average value?

(c)

Findthe standarddeviationfor thisdistribution.

1.11

Problem
The needleon a brokencar speedometer
is free to swing,and
bouncesperfectlyoff the pinsat eitherend,so that if you give it a flick it is
equallylikelyto cometo restat any anglebetween0 and tt.
is the probabilitydensity,p(0)?Hint:p(6)d6is the probabilitythat
the needlewill cometo restbetween9 and (0+d0).
Graphp(0) as a function
of 6, from
to 3tt/2.(Ofcourse,
so p
part of thisinterval is excluded,
is zerothere.)Make surethat thetotalprobabilityis 1.

(a) What

\342\200\224tt/2

Further Problems
for Chapter1

21

Compute(6), (0-),and a, for thisdistribution.


(c) Compute(sin#),(cos#),and (cos20).

(b)

We consider
the samedeviceas the previousproblem,
but thistime
Problem1.12
we are interested
in the .*-coordinate
of the needle
is, the \"shadow,\"
or \"projection,\"
of the needleon the horizontal
line.
(a) What is the probability
densityp(.r)?Graph p(x) as a functionof ,v, from
to +2/-,where r is the lengthof the needle.Make surethe total
is 1.Hint:p(x)dxis the probabilitythat the projection
liesbetween
the probability
that 9 is in
x and (x + dx).You know (from Problem1.11)
a given range;the questionis, what interval dx corresponds
to the
point\342\200\224that

\342\200\2242r

probability

interval

(b)

dOl

Compute(x),(x2),and a, for thisdistribution.


Explainhow you couldhave
obtainedtheseresultsfrom part (c)of Problem

1.11.

**Problem1.13
Buffon'sneedle.A needleof length/ is droppedat random ontoa
sheetof paperruledwith parallellinesa distanceI apart.What is the probability
that the needlewill crossa line?Hint:Refer to Problem1.12.
Let Pab(t) be the probabilityof finding a particlein the range
Problem1.14
(a < x < h), at time t.
(a) Showthat
**J\302\260\302\261

dt

= j(a.t)-J(b.t),

where

J(x.t)=

(4/ dV
[V^^-V*
2/7/
3,v
dx
dx
ift

\342\200\224

2\302\273r

\342\200\224

V
\\

of J(x.t)l Comment:J iscalledthe probabilitycurrent,


becauseit tellsyou the rate at which probabilityis \"flowing\"pastthe point
then moreprobability
x. If Pc,b(t)is increasing,
is flowing intothe regionat
oneendthan flows out at the other.
current for the wave functionin Problem1.9.(This is
(b) Findthe probability
I'm afraid;we'llencounter
not a very pithy example,
moresubstantial
ones
in duecourse.)
What are the units

The Wave Function

*Problem1.15
Supposeyou wanted to describean unstableparticle,that
with a \"lifetime\" In that casethe total probabilityof
spontaneously disintegrates
but shoulddecreaseat
finding the particlesomewhereshouldnot be constant,

t.

(say) an

rate:
exponential

'+00

\\V(x,t)\\2dx=

Pit)

e-'tT.

/-t-oo
-00
A crudeway of achievingthisresultis as follows.
In Equation1.24we tacitly
but it
assumedthat (the potentialenergy) is real.That is certainly reasonable,
in Equation1.27.
What if we
of probability\"
enshrined
leadsto the \"conservation
assignto V an imaginary part:
V = Vo-iT,
V\"

real constant?
is the true potential
energy and r is a positive
Showthat (in placeof Equation1.27)we now get

where Vq
(a)

dt
(b)

Solvefor P(t), and find the lifetimeof the particlein terms of F.

Problem1.16
Show that
d

/ **vj/, dx = 0
dt y_oo
two (normalizable)
to the Schrodinger
solutions
ty\\ and vi/2.
equation,
f\302\260\302\260

\342\200\224

for any

Problem1.17
A particle
is represented
(at time t = 0) by the wave function

A(a2-x2]
otherwise.
I o.
f

(a)
(b)
(c)
(d)

Determine
the normalization
constantA.
What is the expectation
value of .v (at time t = 0)?
What is the expectation
value of p (at timet = 0)? (Note that
Why not?)
get it from p = md{x)/dt.
Findthe expectation
value of x2.

value of p2.
(e) Findthe expectation
(f) Findthe uncertainty in .v (ax).

you

cannot

Further Problems
forChapter1

23

Findthe uncertainty in p (crp).


with the uncertainty principle.
(h) Checkthat your resultsare consistent
(g)

is relevant when the de Broglie


Problem1.18
In general,quantum mechanics
size
wavelength of the particlein question
(h/p) is greaterthan the characteristic
at (Kelvin)temperature 7\\ the average
of the system(d).In thermal equilibrium
kineticenergy of a particleis

p- = 3
-kBT
2
2/77

\342\200\224

so the typicalde Brogliewavelength is


constant),
(where ks is Bol'tzmann's

v/3/77/V/jr

The purpose
of thisproblemis to anticipate
which systems
will have to be treated
and which can safely be described
classically.
quantum mechanically,
(a)

Solids.The latticespacingin a typical solidis around d = 0.3nm. Findthe


in a solidare quantum
temperaturebelowwhich the free18electrons

Belowwhat temperature are the nucleiin a solidquantum mechanical?


(Usesodiumas a typicalcase.)Moral:The free electronsin a solidare

mechanical.

the nucleiare almostnever quantum


always quantum mechanical;
The samegoesfor liquids(forwhich the interatomic
spacingis roughly
the same),with the exception
of helium below4 K.

mechanical.

(b)

Gases.For what temperaturesare the atomsin

an idealgas at pressureP
Hint:Usethe idealgaslaw {PV= NkgT) to deduce
quantum mechanical?

interatomic
spacing.Answer: T < (I/ ks)(h2/3m)*/5P2^5.Obviously
(forthe gasto showquantum behavior)we want m tobe assmallas possible,
and P as largeas possible.
Put in the numbers for heliumat atmospheric
Is hydrogen in outerspace(where the interatomic
pressure.
spacingis about
1 cm and the temperature is 3 K) quantum mechanical?
the

l8In a solid Ihe inner electronsare attached to a particular nucleus,and for them the relevant
size would be the radius of the atom. But the outermost electronsare not attached, and for them the
relevant distanceis the lattice spacing.This problem pertains to the outer electrons.

CHAPTER2

TIME-INDEPENDENT
SCHRODINGEREQUATION

2.1STATIONARYSTATES
In Chapter1 we talkeda lot aboutthe wave function,and how you use it to
of interest.
calculate
variousquantities
The time hascometo stopprocrastinating,
How do you get ^(x,t) in the
and confrontwhat is,logically,
the priorquestion:
first place?We needto solvethe Schrodinger
equation,
9vl/
/ft\342\200\224=

dt

-2mh1 92*
dx\342\200\224\342\200\224+

V\302\245.

[2.1]

for a specified
V(x,t). In thischapter(and mostof thisbook)I shall
potential1
assumethat V is independent
of t. In that casethe Schrodinger
equationcan be
first lineof attack
solvedby the methodof separationof variables(the physicist's
on any partial differential
We lookforsolutions
that are simple
equation):
products,

V(x.t)= f{x)<p(t).

[2.2]

is a functionof .v alone,and <p is a functionof t alone.On


(lower-case)
its face,thisis an absurdrestriction,
and we cannothopeto get morethan a tiny
where xj/

'It is tiresome to

keep saying \"potential energy function.\" so most peoplejust call V the


even though this invites occasionalconfusion with electricpotential, which is actually
potential energy perunit charge.
\"potential.\"

24

Section2.1:
StationaryStates

25

in thisway. But hang on,because


the solutions
subsetof allsolutions
we do obtain
of
outto
be
interest.
Moreover
is
the
case
turn
with separation
(as typically
great
of variables)we will be ableat the endto patchtogetherthe separable
solutions
in sucha way as to construct
the mostgeneralsolution.
For separable
solutions
we have

9*
dt

dtp

d2V

dt

dx2

=^
d2yfr

now), and the Schrodinger


(ordinaryderivatives,
equationreads

d2f
2m dxh2

Or, dividingthrough by

yfr<p:

h2

in

\342\200\224

<p

dt

d2ir + V.

2m \\f/ dx2

[2.3]

Now, the left sideis a functionof t alone,and the right sideis a functionof
x alone.2The only way this can possiblybe true is if both sidesare in fact
constant\342\200\224otherwise,
by varying t, I couldchangethe left sidewithout touching
the right side,and the two would no longerbe equal.(That'sa subtlebut crucial
argument, so if it'snew to you,besureto pauseand think it through.)Forreasons
that will appearin a moment,
constantE. Then
we shallcallthe separation

=
//2--7dt
.\342\200\236ld<p

\302\243.

<p

or

iE

d<p

[2.4]

~dt=~ h
and

1 d2xj/
+v
2m \\j/ dx2
h2

--=

E.

or

d2i/
2m dx1
h2

ordinary

Ef.

[2-5]

ofvariableshasturned a partialdifferential
intotwo
equation
Separation
2.4and 2.5).The first of these(Equation2.4)
differential
equations
(Equations
-Notethat

this

would not

be true if

were a function of t as well as .v.

Schrodinger
Equation
Time-Independent
the generalsolution
is
is easy to solve(justmultiply through by dt and integrate);
C into\\j/ (sincethe quantity
C exp(\342\200\224i.Et/Ii),but we might aswell absorbthe constant
of interestisthe productyjr<p). Then
(p(t) =

e-[Et^.

[2.6]

The second(Equation2.5)is calledthe time-independent


Schrodinger
equation;
we can go no further with

it

until the potential


V(x)

is specified.

The rest of this chapterwill be devotedto solvingthe time-independe


Schrodinger
equation,for a variety of simplepotentials.But beforeI get to

that you have every right to ask: What's so great aboutseparablesolutions?


to the (time dependent)
After all,mostsolutions
Schrodinger
equationdo not
and one
take the form \\Jf(x)<p(t).I offerthree answers\342\200\224two of them physical,

mathematical:
1.They are stationarystates.Althoughthe wave functionitself,

y(x,t) = xl/(x)e-iE'/n,

[2.7]

does(obviously)dependon t, the probabilitydensity,


|vi/(X;t)\\2

= ***= ^e+iEt'hi;e-iE,'h
= |i/r(x)|2,

[2.8]

cancelsout.3The samething happensin


time-dependence
the expectation
value of any dynamical variable;Equation1.36reduces
to

does

not\342\200\224the

calculating

(Q(X,p)) =

^*Q L

l\302\261\\^djCt

[2.9]

in time;we might as well dropthe factor<p(t)


value isconstant
expectation
use
in
it is common
and simply \\j/ placeof ^.(Indeed,
to refer to as
altogether,
\"the wave function,\"but thisis sloppylanguagethat can be dangerous,
and it is
to
t
hat
the
true
function
t
hat
wave
always carries exponentia
important remember
I
n
is
factor.) particular,{x) constant,and hence(Equation1.33)
time-dependent
(p) = 0. Nothingever happensin a stationary state.
2. They are statesof definitetotalenergy.In classical
thetotal
mechanics,
is
called
the
Hamiltonian:
pluspotential)
energy (kinetic

Evety

\\Jf

P2

+ V(x).
H(x,p)= ^2m
3For normalizable solutions,E must

be real (seeProblem 2.1(a)).

[2.10]

Section2.1:
StationaryStates

2.7

The corresponding
Hamiltonianoperator,obtainedby the canonical
substitution

p -> (h/i)(d/dx),is therefore4


H=

---^+
ox- V(x).
92

h2

[2.11]

2m

Thus the time-independent


equation(Equation2.5)can be written
Schrodinger

Hf = Ejfr,
and the expectation
value of the totalenergy is

(H)= f f*Hirdx= E

\\yj/\\2

[2.12]

dx = E f \\V\\2dx = E.

[2.13]

of *I/ entailsthe normalization


of \\j/.) Moreover,
(Noticethat the normalization

H2ir= H(Hir) = H{Ef) = E(Hf) = E2i/,


and hence

(H2)= f yj/*H2yj/dx= E2 j \\^\\2dx = E2.


So the variance of H is
ajd =
But remember,
if a =

(H2)-(H)2= E2-E2=0.

[2.14]

0, then every memberof the samplemust sharethe same

value (the distribution


haszerospread).Conclusion:
A separable
solutionhasthe
of the totalenergy iscertainto return the value
propertythat every measurement
E. (That'swhy I chosethat letterfor the separation
constant.)
3. The generalsolutionis a linearcombinationof separablesolutions.As
we'reaboutto discover,
the time-independent
equation
(Equation2.5)
Schrodinger
an
infinite
eachwith
collection
o
f
solutions
yields
(ijfi(x),xj/jix),
its associated
value of the separation
constant(E\\,Ei, \302\2433,...);thus there is a
different wave functionfor eachallowedenergy:

foix),...),

*i(x,t) = xl/{(x)e-iEi'/h,

vi/2(A%

t)

....

= if2(x)e-iE2^h,

(as you can easilycheckfor yourself)the (time-dependent)


Schrodinger
of solutions
equation(Equation2.1)hasthe propertythat any linearcombination5
Now

I'll

4Whenever confusion might arise. put a \"hat\" C) on the operator, to distinguish it from the
dynamical variable it represents.
5A linearcombinationof the functions f\\ (z)./2(2)
is an expressionof the form

where

...

q.ct.

/U) = n/iU)+ Q/2(<-)+ ---

are any (complex)


constants.

\342\200\242

Time-Independent
Schrodinger
Equation

is itselfa solution.Oncewe have found the separablesolutions,


then,we can
of the form
a much moregeneralsolution,
construct
immediately
CO

t)

\302\245(*.

= J^cMx)e-',E\"'/h-

[2.15]

11=1

It so happensthat every solutionto the (time-dependent)


Schrodinger
equation
can be written in this
is simplya matter of finding the right constants
to
fit
initial
the
conditions
for the problemat hand.You'llsee
soas
(cj, ci,
and in Chapter3 we'll
in the following
how all thisworks out in practice,
sections
but the main pointis this:Onceyou'vesolved
put it intomoreelegantlanguage,
the ti me-in dependentSchrodinger
done;gettingfrom
equation,
you'reessentially
there to the generalsolutionof the time-dependent
Schrodinger
equationis, in

...)

form\342\200\224it

simpleand straightforward.
principle,
A lot has happenedin the last four pages,so let me recapitulate,
from a
somewhatdifferent perspective.
You'regiven a (timeHere'sthe genericproblem:
potentialV(x),and the startingwave function^(.v,0);your job is
independent)
to find the wave function,^(x,t), for any subsequent
timet. To do thisyou must
The strategy6 is
solvethe (time-dependent)
Schrodinger
equation(Equation2.1).
first to solvethe time-in
equation(Equation2.5);thisyields,
dependentSchrodinger
in general,
an infinitesetof solutions
(\\j/\\ (x),\\j/2(x),1^3CO,.. eachwith itsown
To fit ^(a-,0)you write down the general
associated
Ei, \302\2433,...).
energy
linearcombination
of thesesolutions:
\342\226\240),

(\302\2431,

00

vI/(x,0)= ]Tc,,iMa-):

[2-16]

...

the miracleis that you can always match the specified


initialstateby appropriate
choiceof the constants
. To constructW(x, t) you simplytack onto
c\\, ci, C3,
eachterm itscharacteristic
time dependence,
exp(\342\200\224/\302\243,,///2):

00

V(x.0--

CO

r%(-V

-iE\342\200\236t/tt

,if\342\200\236(x)e

\302\273=1

0.

\302\273=1

The separable
solutions
themselves,

%(x,t)= ifn(x)e-iE\"'/r\\
separation

[2.18]

\"Occasionallyyou can solve the time-dependent Schrodingerequation without recourseto


for instance.Problems2.49
But such casesare extremely rare.
of
and 2.50.
variables\342\200\224-see.

Section2.1:
StationaryStates

29

and expectation
allprobabilities
valuesare
of time,but thispropertyis emphatically
not sharedby the general
independent
solution(Equation2.17);the energiesare different,for different stationary states,

are stationarystates,in the sensethat

and the exponentials


do not cancel,when you

calculate|^|2.

of just two
Example2.1 Supposea particlestarts out in a linearcombination
stationary states:
*(*.0) = cifi (x)+ cifiix).
(To keepthingssimpleI'll assumethat the constants
cn and the states\\j/n(x) are

times?Findthe probability
real.)What is the wave function*I>(a\\ t) at subsequent
itsmotion.
density,and describe
Solution:The first part is easy:
= c\\f\\{x)e-iE^fh
+ c2i/o(*)<?\"'\"
vl/(A% t)
\302\2432'//!,

Ei are the energiesassociated


with \\f/[ and xj/j.It followsthat
|y(.v,Ol2= (cifieiE^^+c2f2eiE2/h)(ciirie-iEi,/'1
+C2f2e~iE2/l1)

where E\\ and

= c\\fl + c\\\\lrl

H-2cic2^i^2Cos[(\302\243:2E\\)t/fi].

(I usedEuler'sformula,expIB cosB -f- i sinB, to simplifythe result.)Evidently


the probability
at an angularfrequency (E2 Ei)/h;
densityoscillates
sinusoidally,
thisis certainly not a stationary state.But noticethat it tooka linearcombination
to producemotion.7
of states(with different energies)
\342\200\224

\342\200\224

^Problem2.1Provethe followingthree theorems:


the separation
constantE must be real.Hint:
solutions,
(a) For normalizable
Write E (in Equation2.7)as
+ 'T (with Eq and F real),and show that
if Equation1.20is to holdfor allt, T must be zero.
wave function\\j/(x) can always be taken to be real
(b) The time-independent
This doesn'tmean that every
(unlikety(x.t), which is necessarily
complex).
solutionto the time-independent
Schrodinger
equationis real;what it says
as a linear
is that if you'vegot onethat is not,it can always be expressed
combination
of solutions
(with the sameenergy) that are.So you might as
well stickto i/r's that are real.Hint:If i/(x) satisfies
Equation2.5,for a
and hencealsothe reallinear
given E, sotoodoesits complex
conjugate,
combinations
(i/r + \\f/*) and i(if/ if/*).
\302\243o

\342\200\224

'Thisis

nicely illustrated
quantum/deepwellmain.html.

by

an applet

at

the Web site http://lhorin.adnc.com/~topquarky

30

Schrodinger
Chapter!Time-Independent
Equation
(c)

= V(x))then \\j/(x) can always


If V(x) is an even function(that is,
be taken to be eithereven or odd.Hint:If yfr(x) satisfiesEquation2.5,for
a given E, so toodoes
and hencealsothe even and odd linear
V(\342\200\224x)

combinations
yfr(x) +

\\f/(\342\200\224x),

\\fr(\342\200\224x).

*Problem2.2 Show that E must exceedthe minimum value of V(x),for every


normalizable
solutionto the time-independent
Schrodinger
equation.What is the
classical
Hint:Rewrite Equation2.5in the form
analogto thisstatement?

d2i/
dxl

2m

tr

if E < Vmin, then \\j/ and itssecondderivative always have the same
that sucha functioncannotbe normalized.

sign\342\200\224argue

2.2 THE INFINITE SQUAREWELL


Suppose
V(x)

0.

ifO<A'<\302\253,

oo. otherwise

[2.19]

A particle
in thispotential
is completely
free,exceptat the two ends
(Figure2.1).
A classical
(x = 0 and x = a), where an infinite forcepreventsit from escaping.
modelwouldbe a cart on a frictionless
horizontalair track, with perfectlyelastic
justkeepsbouncingbackand forth forever.(This potentialis
of course,but I urge you to treat it with respect.Despiteits simplicity\342\200\224or
rather, preciselybecauseof its simplicity\342\200\224it servesas a wonderfully
testcasefor all the fancy machinery that comeslater.We'llrefer backto it
frequently.)
bumpers\342\200\224it
artificial,

accessible

V(x)i

->- FIGURE2.1:Theinfinite squarewellpotenx tial (Equation


2.19).

Section2.2:The InfiniteSquare Well

31

Outsidethe well, ij/(x) = 0 (the probabilityof finding the particlethere is


zero).Insidethe well,where V = 0, the time-independent
Schrodinger
equation
reads
(Equation2.5)

d2ir =

h2

2m dxy

or

d2^ =
dx1
\342\200\224=-

1^ ,

u
where
/:r =

\342\200\224k-d/,

[2.20]

Ex//,

^2m\302\243
\342\200\224-\342\200\224.

mil
[2.21]

in this way, I have tacitly assumed


that E > 0; we know from
Problem2.2that E < 0 won't work.)Equation2.21is the classical
simple
(By writing

harmonic

it

oscillator
the generalsolution
is
equation;
\\//(x) =

s'mkx+ B coskx,

[2.22]

where A and B are arbitrary constants.


are fixed by the
Typically,theseconstants
boundaryconditionsof the problem.What are the appropriateboundary
conditions for i/f(x)?Ordinarily,
both yj/ and d\\J//dx are continuous,
but where the
(I'llprovetheseboundary
potential
goesto infinity only the first of theseapplies.
and account
for the exception
when V = oo,inSection2.5;for now I
conditions,
hopeyou will trust me.)
that
Continuityof \\//(x) requires

^(0) = \\/r(a) = 0,

[2.23]

soas to joinontothe solutionoutsidethe well.What doesthis tellus aboutA and

5?Well,

t/K0) =

so B = 0, and hence
Then \\j/(a) =

Asin0+ ficos0= fi,

i/r(x) =

Asmkx.

[2.24]

Asinka,so eitherA = 0 (in which casewe'releft with the


}Jr(x) = 0), or elsesinka = 0, which means

trivial\342\200\224non-normalizable\342\200\224solution

that

ka

= 0,

\302\261tt,

\302\2612tt,

\302\2613tt,

...

[2.25]

But k = 0 is no good (again,that would imply yj/(x) = 0), and the negative

=
solutionsgive nothingnew, since
are
minussignintoA. Sothe distinctsolutions
sin(\342\200\2240)

= mt
\342\200\224.

k\342\200\236

with

\342\200\224

sin(0)and we can absorbthe

= 1,2,3.

...

[2.26]

Schrodinger
Equation
Time-Independent

Vi(*)|

V|/2(X) A

\302\2453W-

FIGURE2.2: Thefirst threestationarystates


oftheinfinitesquarewell (Equation2.28).

A,

at x = a doesnot determine
the constant
Curiously,the boundary condition
but rather the constant
valuesof E:
k, and hencethe possible

[2.27]
In radicalcontrastto the classical
case,a quantum particlein the infinite square
well cannothave justany old
hasto be oneof thesespecialallowed
energy\342\200\224it

values.8
To find

A, we normalize
\\}/:

=
|A|2sm2(kx)dx = A\\22 1,
Jfo
|

This only determines


the magnitude
of A, but it

so

\\A\\2

-.
a

issimplestto pickthe positivereal

root:A = *J2/a(the phaseof A carriesno physicalsignificance


anyway). Inside
the well, then,the solutions
are

tyn

(X)

= J~

v!sin(T*)-

[2.28]

Schrodinger
equationhas deliveredan
promised,the time-independent
infinite setof solutions
(onefor eachpositiveintegern). The first few of theseare
plottedinFigure2.2.They lookjustlikethe standingwaves ona stringof lengtha;
the lowestenergy,is calledthe groundstate,the others,whose
\\J/\\, which carries
increase
in proportion
to n2,are calledexcitedstates.As a collection,
the
energies
functions
have someinteresting
and important properties:
1.They are alternately evenand odd,with respectto the centerof the well:
t/^i is even,\\j/2 is odd,1//3 is even,and soon.9
As

^\342\200\236(x)

8Nolicelhal the quantization of energy emergedas a rather technical consequence


of the
conditions on solutions to the time-independent Schrodingerequation.
9To make this symmetry more apparent, some authors center the well at the origin (running it
a to
from
The even functions are then cosines,
and the odd ones are sines.SeeProblem 2.36.
boundary

\342\200\224

+\302\253)\342\200\242

\\

Section2.2:The InfiniteSquare Well

2. As

33

statehas onemorenode(zerogo up in energy,eachsuccessive


don'tcount),fa hasone,fa has two, and
crossing):
\\f/i hasnone(the end points
you

soon.

3. They are mutually orthogonal,in the sensethat


[jfm(xrfa(x)dx= 0,

whenever m

[2.29]

^ n. Proof:

-/

I fat(x)*fa(x)dx =

\\

Ttx

\342\200\224\342\200\224

(m

\342\200\224

il

n)Tt
n)it

. (m
sin
\\

\342\200\224

\342\200\224

,
cosfm+n Ttx \\~| dx

/J

\\

. (m + n Ttx \\\\
sin
\\

\\

Ttx

dx

(\342\200\224x)

(\342\200\224\342\226\240*)

rrcos(m-n
-1
a
Jo I

= 1

sin

sin

\342\200\224

(in + n)Tt

)/

\\

\\

sin[(w n)rt] sin[(w+ n)7t] = 0.


\342\200\224

(m

\342\200\224

(m + n)

n)

Notethat thisargument doesnot work if m = n. (Canyou spotthe pointat which


it fails?)In that casenonnalization
tellsus that the integralis 1.In fact, we can
combineorthogonality
and normalization
intoa singlestatement:10

/ fa,(x)*fa(x)dx = 5,,,,,,

[2.30]

where 5,,,,,
Kroneckerdelta)is definedin the usualway,
(the so-called

0, if iw
5\"\"'-j1. \\fm=n.

the \\J/'s are orthonormal.


4. They are complete,in the sensethat any
as a linearcombination
of them:
expressed
We say that

oo

fix) = ]T

c\342\200\236fa(x)

n=\\

In

idea to get

case

this
the
in the habit

[231]

#\302\253;

nr

otherfunction,./(.*),can be

oo

J- ]T

c\342\200\236

/7=1

sin
(\342\200\224.vj

[2.32]

Vr's-arereal,sothe * on rjrm is unnecessary,but for future purposesit'sa good


of putting it there.

Schrodinger
Equation
Time-Independent
of the functionssin(tmx/a),but if you've
I'm notabouttoprovethe completeness
studiedadvancedcalculusyou will recognize
that Equation2.32is nothingbut the
Fourierseriesfor f(x), and the fact that \"any\" functioncan be expandedin this
calledDirichlet's
theorem.11
way is sometimes
a methodI call
The coefficients can be evaluated\342\200\224for a given
of {\\//n}: Multiply
Fourier'strick, which beautifully exploitsthe orthonormality
bothsidesof Equation2.32by \\//m(x)*,and integrate.
f(x)\342\200\224by

c\342\200\236

oo

,\342\200\236\302\253./(*)*

oo

E,/\302\253-v\302\273V,W*
/1=1
/1 =

\302\243>,\342\200\236\342\200\236

= cm.

[2.33]

(Noticehow the Kroneckerdeltakillsevery term in the sum exceptthe onefor


in the expansion
which n = m.)Thus the nth coefficient
of f(x) is12

\342\226\240n

= / fnOx)*f(x)dx.

[2.34]

are extremely powerful,and they are not peculiar


to the
Thesefourproperties
infinite squarewell.The first is true whenever the potential
itselfis a symmetric
of the shapeof the potential.13
function;the secondis universal,regardless
isalsoquite
show you the proofin Chapter3. Completeness
holdsfor allthe potentials
but the proofstendto be
you are likelyto encounter,
and
I'm afraid mostphysicists
nasty and laborious;
simplyassumecompleteness,
hopefor the best.
The stationary states(Equation2.18)of the infinite squarewell are evidently
general\342\200\224I'll

Orthogonality

e-'V-*/2'-2)'.

=
*,,(.,.,)
y|sin

(\342\204\242x)

[2.35]

I claimed(Equation2.17)that the mostgeneralsolutionto the (time-dependent)


of stationary states:
Schrodinger
equationis a linearcombination
\302\245(*.

t)

=
Y,c\302\273yJ-

/7 =

''See,

sin
(\342\200\224A\")

e-''(\"~V/?/W)'.

[2.36]

2d cd.(New
for example,Mary Boas, Mathematical Methodsin the Physical Sciences,
York: John Wiley,
,/'(.v) can even have a finite number of finite discontinuities.
p.
doesn'tmatter whether you use m or n as the \"dummy index\" here (as long as you are
consistent on the two sides of the equation, of course):whatever letter you use.it just stands for \"any
positive integer.\"
1*
See.for example,John L. Powell and Bemd Crasemann, Quantum Mechanics (Addison-

1983),313;

'-It

Wesley, Reading. MA,

1961),
p. 126.

35

Section2.2:The InfiniteSquare Well

(If you doubtthat thisis a solution,by all meanscheckit!)It remainsonly for


me to demonstrate
that I can fit any prescribed
initialwave function,^(.v.0),by
choiceof the coefficients
appropriate
c\342\200\236:

^-,0)=

CO

^,,^).

/1=1

The completeness
of the \\j/'s (confirmed
in thiscaseby Dirichlet's
theorem)

I can always express^(.v,0)in this way, and their orthonormality


licensesthe useof Fourier'strick to determine
the actual coefficients:

guarantees

that

c\342\200\236

J-

sin
(\342\200\224Jc)

*(-v.0)dx.

[2.37]

That doesit: Given the

initialwave function,^(.v.0),we first computethe


coefficients usingEquation2.37,and then plugtheseintoEquation2.36
expansion
toobtainvl>(.\\\\ t).Armed with the wave function,we are in a position
to computeany
in Chapter1.And thissame
of interest,usingthe procedures
dynamical quantities
ritual appliesto any potential\342\200\224the only thingsthat changeare the functional
form
of the 1^'sand the equation
for the allowedenergies.
c\342\200\236,

Example2.2

particlein the infinite squarewell has the initialwave function

V(x.0) = Ax (a x). (0 < -v < a).


for someconstantA (seeFigure2.3).Outsidethe well,of course,^ = 0. Find

V(x.t).

^(x, 0)

FIGURE2.3: The startingwave functionin Example2.2.

Time-Independent
Schrodinger
Equation

Solution:Firstwe needto determine


A, by normalizing
vl>(.v, 0):
= |A|2 fax2(a-x)2dx= \\A\\2^
1= r|\302\245(jr,0)|2</jc
M
Jo

JO

SO

A=

/?\302\260.

a5

The /7th coefficient


is (Equation2.37)

\342\200\236=^r,n(-v)/lo,(a_.v)rf,
a Jo
a / a3
\\

. Inm v dx I x 2 sin
. I//77T \\ dx
= 2v/l5 T /fa .v sin
v a
\\ a
I
J _
a* L Jo
Jo
ax /nn \\\\
//77T \\
\\/ a \\2
= 2\\/l5(
sin
\\ a
V a
/ /J7T cos!\342\200\224a)
ai \\a
[ 1_V/77T/
/J 0
\342\200\224

<:/

\342\200\224=\342\200\224

\342\200\224x

\342\226\240

\342\200\224x

\342\200\224\342\200\224

f\342\200\224)

\342\200\236/

a
\342\200\224

. (nit
sin
\\

\\2
I .v

\342\200\224a*

V/77r/

2v^l5

o3

a-

/77T

f\342\200\224x)

(nitx/a)- 2 cos/tut
a
{nitay
\342\200\224

\\

/J

\\

-2
:
(nity

3(/77T)2=

C0S(/77T)+ a1

4</l5r
-=; [COS(0)
(mty

\342\200\224x

=\342\200\224

COS(/77T) CT

\\

/J
=- COS(0)

(nity

COS(/77T)]

if /7 iseven.
8vT5/(/7tt)3.if /7 is odd.

10,

Thus (Equation2.36):

\\izJ
*-? 773
x 7 //=1.3.5...

V fl

in vl/.\"
that is contained
Looselyspeaking, tellsyou the \"amountof
Somepeopleliketo say that
is the \"probability
of finding the particlein the
/7th stationary state,\"but thisis bad language;
the particleis in the state4>, not
to be in a particular
ty,,, and,anyhow, in the laboratory
you don't\"find a particle
and what you get is a number.As we'll
measuresomeobseivable,
seein Chapter3, what
tellsyou is the probabilitythat a measurement
of the
c\342\200\236

yjf\342\200\236

|c\342\200\236|2

state\"\342\200\224you

|c\342\200\236|2

Section2.2:The InfiniteSquare Well

37

measurement
will always return one
(a competent
energy wouldyieldthe value
of the \"allowed\"values\342\200\224hence the name\342\200\224and
is the probabilityof getting
the particularvalue
Of course,the sum of theseprobabilities
shouldbe 1,
E\342\200\236

\\c\342\200\236\\2

E\342\200\236).

[2.38]
of vj/ (the
are independent
of time,
Indeed,thisfollowsfrom the normalization
=
soI'm goingtodo the prooffort 0;if thisbothersyou,you can easilygeneralize
c\342\200\236's

the argument to arbitrary t).

\\

/ CO

\\

1
(CO
oc oc

m=\\

EC'\302\273C\302\273

n=\\

/ fm(x)*fn(x)dx
CO

CO CO

J21lc\302\273>c\"8\302\273\"'

lt=l111=1

= J2\\c\"\\2\302\273=1

deltapicksout the term m = n in the summationoverm.)


(Again, the Kronecker
value of the energy must be
Moreover,the expectation
CO

[2.39]
n=\\

and thistoocan be checked


directly:The time-independent
Schrodinger
equation

(Equation2.12)says

Hfn =

[2.40]

E\342\200\236Vo,.

so
(H) =

J V*HVdx= J
=E
/
Ec'\302\273c\302\273\302\243\302\273

H
(]Tc\342\200\236,Vo\342\200\236)*

*\302\243*\302\273dx

dx
(][>\"V0,)

ic\302\273i2\302\243\302\273-

of gettinga particularenergy is independent


of time,and
Noticethat the probability
value of H. This is a manifestation
of conservation
so,a fortiori,isthe expectation
of energyin quantum mechanics.

Schrodinger
Equation
Time-Independent

Example2.3 In Example2.2the startingwave function(Figure2.3)closely


that \\c\\ should
resemblesthe groundstate (Figure 2.2).This suggests
dominate,
\\2

yfr\\

and in fact

The restof the coefficients


make up the difference:14

* J n=TT.5....n
\\
,,=
is
The expectation
value of the energy,in thisexample,
1

480/?2

J_ _ 5/32
7T4ma2 fr1^ n4
,,=1.3.5.... ma2

y^

onemight expect,it isvery closeto E\\ = 7T2h~/2ma2\342\200\224slightly larger,because


of the admixture of excitedstates.
As

Problem2.3 Show that there is no acceptable


solutionto the (time-independent)
equationfor the infinite squarewell with E = 0 or E < 0. (This is a
Schrodinger
specialcaseof the generaltheoremin Problem2.2,but thistime do it by explicitly
and showingthat you cannotmeetthe boundary
solvingthe Schrodinger
equation,
conditions.)
^Problem2.4 Calculate
(x),(x~), {p),(p2),ax,and ap,forthe /ith stationarystate
of the infinite squarewell.Checkthat the uncertainty principle
issatisfied.
Which
statecomesclosestto the uncertainty limit?
*Problem2.5A particlein the infinite squarewell has asitsinitialwave function
an even mixture of the first two stationary states:
*U.0)= A[ylr\\(x) + f2(x)l
1

You

can look up

the

series
J_ +

_ 7T6
j_ +\"\"~

and

3^

56

H
in

math

%()

111

lfl

tables,under

\"Sums

34

54

\342\226\240
\342\226\240
\342\226\240

jr4
\342\200\224

96

of ReciprocalPowers\"or \"Riemann Zela Function.\"

Section2.2:The InfiniteSquare Well

39

Normalize^(x,0).(That is, find A. Thisis very easy,if you exploitthe


of
and yfri. Recallthat, having normalized^ at t = 0,
orthonormality
you canrestassuredthat it stays normalized\342\200\224if you doubtthis,checkit
after doingpart (b).)
explicitly
functionof
(b) Find ty(x,t) and \\ty(x,t)\\2. Expressthe latter as a sinusoidal
=
time,as in Example2.1.To simplifythe result,let a> jr-ft/2ma-.
in time.What is the angular frequency
(c) Compute(x).Noticethat it oscillates
of the oscillation?
What is the amplitude
of the oscillation?
(Ifyour amplitude
is greaterthan a/2, go directlyto jail.)
(d) Compute(p).(As PeterLorrewouldsay, \"Doit ze kveek vay, Johnny!\
(a)

%f/\\

what valuesmight you get,and


the energy of thisparticle,
If you measured
of gettingeachof them? Findthe expectation
value
what is the probability
of H. How doesit comparewith E\\ and

(e)

\302\2432?

Problem2.6 Although the overallphaseconstantof the wave function is of no


a measurable
outwhenever you calculate
(it cancels
quantity),
physicalsignificance
in Equation2.17doesmatter. For example,
the relative phaseof the coefficients
supposewe changethe relative phaseof and \\j/2 in Problem2.5:
\\f/\\

W{x,0)= A[\\lrax)+ ei*\\lr2{x)],


is someconstant.Find ^(x,t), \\ty(x,t)\\-,and (,r),and compareyour
resultswith what you got before.Study the specialcases<p = tt/2 and $> = tt.
of thisproblemseethe appletin footnote7.)
(Fora graphicalexploration
where (p

*Problem2.7A particlein the infinite squarewell hasthe initialwave function15

-x - a/2<
nx o); = fJ Ax<
A(a-x). a/2<x <a.
\302\260

(a)

A.
SketchW(x, 0), and determine
the constant

(b)

FindV(x.t).

is no restriction in principle on the shape of the starting wave function, as long


as il is normalizable. In parlicular, ty(.v.O) need nol have a conlinuous
facl, il
doesn't even have to be a conlinuous function. However, if you iry 10 calculate (H) using
f ty(.v. 0)*//ty(.v-.0)dxin such a case,you may encounter technical difficulties, becausethe second
derivative of #(x. 0) is ill-defined. Il works in Problem 2.9becausethe discontinuities occurat Ihe end
you'll seehow to manage caseslike
points, where ihe wave function is zero anyway. In Problem 2.48
1

\342\200\242'There

derivative\342\200\224in

Problem 2.7.

40

Chapter2 Time-Independent
Schrodinger
Equation
(c) What

is the probabilitythat

a measurement of the energy would yieldthe

value E\\ ?
(d)

Findthe expectation
value of the energy.

Problem2.8 A particleof massm

in the infinite squarewell (of width a) starts


out in the left half of the well,and is (at t = 0) equallylikelyto be foundat any
pointin that region.

is itsinitialwave function,vJ/(a',0)?(Assumeit is real.Don'tforget


to normalize
it.)
What is the probabilitythat a measurement
of the energy would yieldthe

(a) What
(b)

value 7T2/72/2ma2l

value of
Problem2.9 For the wave functionin Example2.2,find the expectation
H, at time t = 0, the \"oldfashioned\"
way:

(H) = I V(x.0)*HV(x,0)dx.
of
in Example2.3.Note:Because
(H) is independent
Comparethe resultobtained
=
time,there is no lossof generalityin usingt 0.

2.3 THEHARMONICOSCILLATOR
The paradigmfor a classical
is a massm attachedto a spring
harmonic oscillator
of forceconstant
k. The motionis governedby Hooke'slaw,

Fv =

i
\342\200\224kx

d2x
= m --^

dt-

is
and the solution
(ignoringfriction),
x(t) = A sin(atf)+ B cos(atf),
where
co =

JV

[2.41]

is the (angular)frequency of oscillation.


The potential
energy is
V(x) =

itsgraph is a parabola.

^kx2;

[2.42]

Section2.3:The HarmonicOscillator 41
V(X)A

in
FIGURE2.4: Parabolicapproximation
(dashedcurve) to an arbitrary potential,
ofa localminimum.
the neighborhood

Of course,there'sno suchthing as a perfectharmonic

you

oscillator\342\200\224if

stretchit too far the springis goingto break,and typically Hooke'slaw fails
longbeforethat pointis reached.But practicallyany potentialis approximately
of a localminimum (Figure2.4).Formally,if we
in the neighborhood
parabolic,
expandV(.v) in a Taylorseriesaboutthe minimum:
V(x)

= V(x0) + V'(xo)(x

a-o)+ iV\"(jto)(* *o)2+

\342\226\240 \342\200\242 \342\200\242

subtractV(xo) (you can add a constantto V(a\") with impunity, sincethat doesn't
that V'(xo)= 0 (since
a'o is a minimum),and dropthe
changethe force),recognize
as longas (x .vo) stays small),we get
terms (which are negligible
higher-order
\342\200\224

V(x)

^V\"(x0)(x-x0)2,

which describes
(aboutthe pointxo),with an effective
simpleharmonic oscillation
That'swhy the simpleharmonicoscillatoris so
springconstantk = ^\"(a-o).16
as
motionis approximately
simpleharmonic,
important:Virtually any oscillatory
longas the amplitudeissmall.
The quantum problemis to solvethe Schrodinger
equationfor the potential
*
2 2
t//
V(x)\\ = -mcox

[2.43]

in favor of the classical


the springconstant
iscustomary to eliminate
frequency,
A
s
we
have
it
to
suffices
solve
the
seen,
2.41).
time-independent
usingEquation
(it

Schrodinger
equation:

tr d2xj/ -mco
1
2 2 =
x f
+
Ef.
pj2m ax1 2

[2.44]

\342\226\240-

l6Note that V\"(.vo) > 0.sinceby assumption xq is a minimum. Only in


is the oscillation not even approximately simpleharmonic.

the

rare caseV\"(.vo)

=0

Time-Independent
Schrodinger
Equation
In the literatureyou will

to thisproblem.
find two entirely different approaches

The first is a straightforward \"bruteforce\"solutionto the differentialequation,

usingthe power seriesmethod;it has the virtue that the samestrategy can be
appliedto many otherpotentials(in fact, we'lluse it in Chapter4 to treat the
Coulombpotential).
The secondis a diabolically
cleveralgebraic
using
technique,
so-called
ladderoperators.I'll showyou the algebraic
methodfirst, becauseit is
quickerand simpler(anda lot morefun);17if you want to skipthe powerseries
methodfor now, that'sfine, but you shouldcertainly plan to study it at some

stage.

2.3.1AlgebraicMethod
To beginwith,

form:
let'srewrite Equation2.44in a moresuggestive
\342\200\224

2/7/

= Ef.
[p2+ {mcox)2]^

[2.45]

where p = {h/i)d/dx is,of course,the momentum operator.


The basicideais to
factorthe Hamiltonian,

H=

\342\200\224[p2

2m

+ {mcox)2].

[2.46]

If thesewere numbers,
it wouldbe easy:

it + v~ = {in+

v){\342\200\224iu

+ v).

Here,however,it's notquiteso simple,becausep and x are operators,and


do not,in general,commute{xp is not the sameas px). Still,thisdoes
motivate us to examine
the quantities

operators

^=^(^+^)
(the factorin front isjustthere to make the final
Well, what is the producta-ci+7

a~a+ =

{ip+

2ft mco

mcox){\342\200\224ip

[2.47]

resultslooknicer).

+ mcox)

+
Inmco[p2 {mcox)2 imco{xp px)].

\342\200\224

17We'llencounter some of the same strategiesin the theory of angular momentum (Chapter 4).
and the technique generalizesto a broad class of potentials in super-symmetric
quantum mechanics
f
or
W.
New
Section
Richard
Robinett. Quantum Mechanics.(Oxford
York. 1997).
(see. example.

U.P.,

14.4).

Section2.3:The HarmonicOscillator 43

there'san extra term, involving (xp px).We callthisthe


anticipated,
of how badly they fail to commute.
In general,
commutator of X and p; it is a measure
A and B (written with squarebrackets)
the commutator
of operators
is
[A, B] = AB BA.
[2.48]

As

\342\200\224

In

thisnotation,
CI-CI+=

-)

-'

ol.m co IP' + (ma>x)~]


2ft
->

\342\200\224

2ft

[a\\

p].

[2.49]

needto figure out the commutatorof a- and p. Warning: Operatorsare


notoriouslyslipperyto work with in the abstract,and you are boundto make
mistakesunlessyou givethem a \"testfunction,\"f(x), to act on.At the end you
can throw away the testfunction,and you'llbeleftwith an equationinvolving the
alone.In the presentcasewe have:
operators
We

[Jr,p]f(x) =

ft

d
dx

ft
\342\200\236

d
dx

\\
n
df
( df -X\342\200\224-f)=
=T
Iftf (A\.
i V dx
dx
J
X\342\200\224

[2.50]

Droppingthe testfunction,which hasservedits purpose,

[x,p] = ih.

[2.51]

Thislovelyand ubiquitous
resultis known as the canonicalcommutation
relation.18

With

this,Equation2.49becomes

a-a+=

1
-.

+2

-\342\200\224//

ftCD

[2.52]

or
H = ftcD a-a+

[2.53]

\342\200\224

doesnotfactorperfectly\342\200\224there's that extra


on the
Evidently the Hamiltonian
right.Noticethat the orderingof a+ and a- is importanthere;the sameargument,
with a+ on the left,yields
\342\200\2241/2

a+a-=
In particular,

1
\342\200\236

\342\200\224H

ftCD

[a-,a+]= 1.

1
.
2

[2.54]
[2.55]

18Ina deepsenseall of the mysteries of quantum mechanicscan be traced to the fact that position
and momentum do not commute. Indeed,some authors take the canonical commutation relation as an
axiom of the theory, and use it to derive p =

(h/i)d/dx.

Schrodinger
Equation
Time-Independent
can equallywell be written
Sothe Hamiltonian
1

H = hco a+a-+

[2.56]

In terms of

a\302\261,

for the harmonicoscillator


takes
then,the Schrodinger
equation19

the form
\302\261-)f=

hco

[2.57]

Ef

(\302\253\302\261*F\302\261i)

readthe uppersignsallthe way across,or elsethe lower

likethisyou
(in equations
signs).

the Schrodinger
Now, here comesthe crucialstep:I claimthat if \\j/ satisfies
equationwith energy E, (that is:H\\j/ = E\\j/), then a+\\j/ satisfiesthe Schrodinger
Proof:
equationwith energy (E + hco):H(a+\\f/) = (E + hco){a+\\}/).

H(a+\\j/)= hco

a+ci-+ - 1 (a+xf/) = hco a+a-a++ -a+ J


I

= hcoa+lci-d++

-)

\\f/

= a+

if/

a+a-+ 1+ -1^

hco I

= a+(H + hco)\\j/= a+(E + ftco)\\j/ = (E + hco)(a+\\j/).


(I usedEquation2.55to replacea~a+ by a+a- + 1, in the secondline.Notice
and
that whereas the orderingof a+ and a- doesmatter, the orderingof
a\302\261

any

constants\342\200\224such

as h, co, and

constant.)

By the sametoken,a-\\f/

H(ci-\\j/)= hco

= a-

a-a+

\342\200\224

E\342\200\224does

with
not;an operatorcommutes

is a solutionwith energy (E hco):


\342\200\224

- ] (fl-VO= hcoci- a+ci- -

hco I a-a+

any

- 1- - j

\342\200\224

= a-(H

\342\200\224

\\j/

\\f/

hco)\\j/= a-(E hco)\\j/


\342\200\224

= (E hoj)(a-i/).
with higherand
Here,then, is a wonderful machinefor generatingnew solutions,
to get started!We call
lower
we couldjust find one solution,
ladderoperators,becausethey allow us to climbup and down in energy;a+ is
the raisingoperator,and a- the loweringoperator.The \"ladder\"of statesis
illustrated
in Fisure2.5.
energies\342\200\224if

19I'm
getting

the

context which

a\302\261

tired of writing ''time-independent


Schrodingerequation,\"
one I mean. just call it the \"Schrodinger
equation.\"

I'll

so when

it'sclearfrom

Section2.3:The HarmonicOscillator 45

FIGURE2.5: The \"ladder\"ofstatesfor the harmonicoscillator.

But wait! What if I apply the loweringoperatorrepeatedly?Eventually I'm

to the general
goingto reach a statewith energy lessthan zero,which (according
theoremin Problem
2.2)doesnot exist!At somepointthe machinemust fail.
How can that happen?We know that ci-\\j/ is a new solutionto the Schrodinger
but thereis no guarantee
that it will be normalizable\342\200\224it might be zero,
equation,
orits square-integral
In practiceit is the former:Thereoccursa
might be infinite.
\"lowestrung\" (callit

\\j/o)

suchthat

a-i,0= 0.
We

[2.58]

can usethisto determine


\\j/q(x):

ltd

\\

+ m(0X )fo = 0.
,
[h-r
ax
J
s/lhmco
\\

Schrodinger
Equation
Time-Independent

or
mco

dxf/Q

Xf0dx
h
Thisdifferentialequationis easy to solve:

/ to

so

,In

mco

d\\[/o

= mco -, + constant.
\342\200\224x\"

2/J

/.V\342\200\236.V

xj/0(x)= Ae
We

,
y/Q

_ into A 2
2ft

it right away:
might as well normalize

\\

\\A\\2

(\302\260\302\260

e-'\"\302\273x2/hdx

J-oo
so A1 = y/mco/jrh,and hence

= \\A\\\\[^V m cc

[2.59]
To determine
the energy of thisstatewe plugit intothe Schrodinger
equation(in

theform of Equation2.57),hco(a+ci+ 1/2)^0= Eofa,and exploitthe fact that


a-xj/o= 0:
=
[2.60]
\\hco.

\302\243o

ourfootnow securely
plantedon the bottomrung (the groundstateof the
we simplyapply the raisingoperator
to generate
quantum oscillator),
(repeatedly)
With

the excitedstates,20
the energy by hco with
increasing

eachstep:

[2.61]
is the normalization
constant.
By applyingthe raisingoperator
to t/tq, then,we can (in principle)
constructall21the stationary statesof

where
(repeatedly)

A\342\200\236

20In the

caseof the harmonic oscillatorit is customary, for somereason,to depart from the usual
the states starting with n
0,instead of n = 1.Obviously, the lower limit on the

practice,and number

\342\200\224

a formula such as Equation 2.17


should be altered accordingly.
-lNotethat we obtain all the (normalizable) solutions by this procedure.For there were some
other solution, we could generate from it a secondladder, by repeatedapplication of the raising and
and
lowering operators.But the bottom rung of this new ladder would have to satisfy Equation 2.58,
sincethat leads inexorably to Equation 2.59,
the bottom rungs would be the same, and hence the two
sum

in

it\"

ladderswould

in

fact

be identical.

Section2.3:The HarmonicOscillator 47
we have
hamionicoscillator.
Meanwhile,without ever doingthat explicitly,
the allowedenergies.
determined
the

Example2.4 Findthe first excitedstateof the harmonicoscillator.

Solution:UsingEquation2.61,
i/i(x) = A\\a+\\j/0 =

' e u' i
d
(-^3-+m(i)X
(mo)\\1/4

A\\

_>mo

\\

)\\\342\200\224T

/ma>\\' lima)

=AiU

[2.62]
_w<jdl.2

v\342\200\224~

it \"by hand\":
We can normalize

so,as it happens, = 1.
A\\

the raisingoperator
I wouldn'twant to calculate
xf/so thisway (applying
fifty
times!),but never mind:In principleEquation2.61doesthe job\342\200\224exceptfor the

normalization.

You can even

footwork,so watch closely.We know that

a\302\261\\f/n

it

\\j/n\302\261\\,

= fn+\\, a-fn = dn

a+\\lfn

but what are the

takes somefancy
isproportional
to

but
get the normalization
algebraically,

c\342\200\236

factors, and
proportionality
c\342\200\236

d\342\200\236'l

functionsf(x) and g(x),

[2-63]

VOi\342\200\224i

First notethat for \"any\"22

/\302\2730O

=
f*(a\302\261g)dx

/00
-co

[2.64]

(aTf)*gdx.
\302\253/\342\200\224CO

(In the languageof linearalgebra,a^ is the hermitianconjugateof a

\302\261.)

Proof:
/ f*(ct\302\261g)dx
J-cc
-~0f course,the
\302\261oo.

/ f*(Th\342\200\224+
dx
V
y/lhmo)J-oo

integrals must exist, and

this

means

that

max)gdx..
J

/(.v) and g(x) must go to zero

at

Time-Independent
Scbrodinger
Equation
and integration
by partstakesf f*(dg/dx)dxto J(df/dx)*gdx(the boundary
terms vanish, for the reasonindicated
in footnote22),so
\342\200\224

/00
-co

\302\261g)dx

-I*

1
dx

y/2hm(D J-oQl_\\

+ mcox)f gdx=

(a^fTgdx,
/OO
-oc
<

QED
In particular,
/\302\273CO

(fl

/OO
-co

\302\261

^/i)

(A

\302\261

^/i)

= / (flTfl
J-oc

^A\"

VOi)

\302\261

*
VOi

^A'

\342\200\242

But (invokingEquations2.57and 2.61)

a+a-fn=

a-a+f\342\200\236

mjr\342\200\236,

[2.65]

(n+l)f\342\200\236.

so
/\302\2730C

J-oc

|T/r\342\200\236+I|2c/A\"

/OO
-co

\302\273oo

(/1+

/\302\273CO

/\302\273CO

= K|2 /
(\302\253_^,)*(\302\253-^)^

/OO
-OO

|^,-i|2\302\253/jr

=n /

\302\253/\342\200\224oo

But since

\\j/\342\200\236

and

+_

^r\342\200\236

\\

and hence
a+f\342\200\236

l^nl2^1)/
./-co
llM2*/*.

\302\253/\342\200\224OO

are normalized,
it followsthat

\\c\342\200\236

\\~

= n +1 and

= Jn + 11/0,+1,fl-^n = Vnfn-i-

|J\342\200\236

|2 =

\302\273,

[2.66]

Thus

*=
and

71\302\260^1

VJT2

V4

,
1
\342\200\242

V4\342\200\2423

(fl+)Vo*

soon.Clearly
^/1 =

-j==(0+^^0-

which is to say that the normalization


factorin Equation2.61is An

= 1,confirmingour resultin Example2.4).


A\\
particular,

[2.67]
= 1/VhT(in

Section2.3:The HarmonicOscillator 49
As in the caseof the infinite squarewell,the stationary statesof the harmonic

are orthogonal:
oscillator

= 5,innf*fndx
/co
-oc

[2.68]

Thiscan be provedusingEquation2.65,and Equation2.64

twice\342\200\224first

a+ and then movinga_:

moving

/\302\273oo

/oo
-oo

ir*\342\200\236

(a+fl-) dx =n I tfr *
J -oo
ir\342\200\236

f\342\200\236

dx
/\302\2730O

/
{a-\\jrm)*{a-ifn)dx=

/OO
-oo

(a+a-f,\342\200\236)*$\342\200\236

dx

J\342\200\224oc

CO

='\"/ fmfndx.
oo

Unlessw = /7, then,


must be zero.Orthonomiality
means that we
when we
can againuseFourier'strick (Equation2.34)to evaluatethe coefficients,
of stationary states(Equation2.16),and
expandty(x,0) as a linearcombination
of the energy would yield the
is again the probabilitythat a measurement
value En.
f\\l/*\\f/\342\200\236dx

|c\342\200\236|2

value of the potential


energy in the /7 th state
Example2.5 Findthe expectation
of the harmonicoscillator.

Solution:

1 tt\\ =
o/
= { -mco~x~)
-ma>~ I

(V)

2\"

\\js*x-\\j/n

d:x.

There'sa beautifuldevicefor evaluating integralsof thiskind (involvingpowers


of .,v or p): Use the definition(Equation2.47)to express.v and p in terms of the
raisingand loweringoperators:
h

=
2m(o (C1++CI-):p /./

lima)

[2.69]

\342\200\224-\342\200\224(\302\253+\342\200\224fl_).

we are interested
in .v2:
In this example
A'\"

+
+
+
2ni(o (a+)2 (a+a-) (fl_fl+) (a-)2

So

-T *:
ft\302\256

(V)

f I*

(a+)~ + (a+a-)+ (fl-fl+)+ (ci-Y

\\j/n

dx.

Equation
Schrodinger
Time-Independent
which is orthogonalto \\j/n, and
But (a+)2Voiis (apart from normalization)
1^,,+2,

to i/n-2-So thoseterms drop


samegoesfor (a-)2\\f/n, which is proportional
out,and we can useEquation2.65to evaluate the remainingtwo:
the

(V)

ha)
\342\200\224

(
+ n + 1)= -ha>In +
1

(n

\\\\

value of the potentialenergy is exactly half the


happens,the expectation
total (the otherhalf, of course,is kinetic).Thisis a peculiarityof the harmonic
aswe'llseelater on.
oscillator,
As

it

\342\231\246Problem

2.10

Construct1/^2 (-0(b) Sketch\\J/o, \\j/\\, and 1/0.


of t/tq,
(c) Checkthe orthogonality
(a)

and 1/0,by explicitintegration.


Hint:If
and odd-ness
of the functions,
there is really only
you exploitthe even-ness
oneintegral leftto do.

\342\231\246Problem

(a)

2.11

Compute(x),(/?).(.v2), and (p2),for the states\\f/o (Equation2.59)and


Comment:
In thisand otherproblems
(Equation2.62),by explicitintegration.
matters if you introduce
the
involvingthe harmonicoscillatorit simplifies
\\f/\\

= s/mco/hx and the constanta = (mco/nh)x^.


Checkthe uncertainty principle
for thesestates.
Compute(T) (the average kineticenergy) and {V) (the average potential
Is their sum what you
allowed!)
energy) for thesestales.(No new integration
wouldexpect?
variable

(b)
(c)

\\j/\\,

\302\243

*Problem
2.12Find(a*),(p),(x2),(p2),and (T),for the /7th stationary stateof the
harmonicoscillator,
usingthe methodof Example2.5.Checkthat the uncertainty
principleissatisfied.
Problem2.13A particlein the harmonicoscillator
startsoutin the state
potential
*(.r.O)= A[3^o(*)+4TM.v)].
FindA.
(b) Construct*(.v.r)and |vI/(a\\f)|2.
(a)

Section2.3:The HarmonicOscillator 51
Find (x) and (p). Don'tget tooexcitedif they oscillateat the classical
frequency;what wouldit have beenhad I specified
faix), insteadof (x)?
Checkthat Ehrenfest's
theorem(Equation1.38)holdsfor thiswave function.
what values might you get,and
the energy of thisparticle,
(d) If you measured
(c)

\\j/\\

with what

probabilities?

Problem2.14A particleis in the groundstateof the harmonic oscillatorwith


classical
soto'= 2a>,
frequency a>, when suddenlythe springconstant
quadruples,
without initiallychangingthe wave function(of course,vj/ will now evolve
becausethe Hamillonian
haschanged).
What is the probability
that a
measurement of the energy wouldstillreturn the value ftco/21
What is the probability
differently,

of gettingftcol [Answer:0.943.]

2.3.2AnalyticMethod
We

return now to the Schrodinger


equationfor the harmonicoscillator,

, , = Ef.
+
-m(D2x2xj/
2m dx2 2
ft1 d2xj/
V

[2.70]

solveit directly,by the seriesmethod.Things look a littlecleanerif we


the dimensionless
variable
introduce
and

III

IImco
mm

[2.71]

Vfiv;

in terms of

\302\243

the Schrodinger
equationreads

i^-K

d2yj/

where K

[2.72]

is the energy,in unitsof (l/2)/?a>:


K

_ 2E

[2.73]

ftco

Our problemis to solveEquation2.72,and in the processobtainthe \"allowed\"


values of K (and henceof E).

large (which is to say, at


dominates
overthe constantK, so in thisregime
completely
To beginwith, notethat

at very

\302\243

* *V<
-Jr
d$~

very

largex),

\302\2432

[2.74]

which hasthe approximate


solution(checkit!)
1r(%) % Ae~t2/2+ Be+*1/2.

[2.75]

Time-Independent
Schrodinger
Equation
The B term is clearlynot normalizable
(it blowsup as |jc|-> oo);the physically
form
solutions,
then, have the asymptotic
acceptable

^(S)

-\342\226\272

)^2/2<

[2.76]

large

at

\302\243.

Thissuggeststhat we \"peeloff\" the exponential


part,
W$) = /i($)\302\253~|2/2,
remains, has a simplerfunctionalform than
Equation2.77,
Differentiating
in

hopesthat

what

/?(\302\243),

df

(dh

\\

i/r(\302\243)

[2.77]
itself.23

_ti/2

and

dH
df-

+ (f._1)/V-,V2!
/^_2^
\\df- \"s^

so the Schrodinger
equation(Equation2.72)becomes
d2h

dh

\342\200\224

-2l;\342\200\224

+ (K-\\)h=0.

[2.78]

#fd%
I proposeto lookfor solutions
to Equation2.78in the form of powerseries
in

\302\243.

h<&) = fl0 + fl|?+02^2+

= J2ajtJ-

\342\200\242 \342\226\240-

[2J9]

/=0

the seriesterm by term,


Differentiating

-=0,+

+ 3a^2+

2a2\302\243

\342\200\242 \342\200\242 \342\200\242

= V JaiSJ~
j=Q

and

d2h =
\342\200\224j

-\342\200\242'Note

follows

the

that

\302\260\302\260

2c,2+ 2

although

\342\200\242

3fl3\302\243

+3

\342\200\242

4\302\2534\302\2432

+ ---= T]U + 1)0'+ 2)aj+2^.

we invoked some approximations to motivate Equation 2.77.what


behavior is the standard first step
for example.
Boas (footnote
equations-\342\200\224see,

exact.The device of stripping off the asymptotic


power seriesmethod for solving differential
is

Chapter

12.

in

11).

-4This is known as the Frobeniusmethod for solving a differential equation. According to


as a power scries,so
Taylor's iheorem.any reasonably well-behaved function can be expressed
Equation 2.79ordinarily involves no loss of generality. For conditions on the applicability of the
method, seeBoas (footnote 11)
or GeorgeB.Arfken and Hans-Jurgen Weber, Mathematical Methods
Section8.5.
for Physicists.5th cd..Academic Press.Orlando (2000).

Section2.3:The HarmonicOscillator 53
Putting theseintoEquation2.78,we find

J2 [U + DC/+ 2)0./+2- 2jaj + (K- \\)aj]


oo

\302\243\342\200\242''

= 0.

[2.80]

7=0

It follows(from the uniqueness


of power seriesexpansions25)
that the coefficient
of eachpowerof must vanish,
\302\243

(j + 1)(7+ 2)aj+2 2jaj + (K l)aj = 0,


and hencethat

=
a;+->
J

(2j + 1-K)a;.

[2.81]

(./+ 1)0+2)J

This recursionformulais entirely equivalentto the Schrodinger


equation.

allthe even-numbered
coefficients:
Startingwith ao,it generates
a2 =

(1-/0
\342\200\224^-\302\253>.
\342\200\224^-a{),

\342\200\224[j-a2

^ = (7-/0

(3-K)

-^-^

\342\200\224g\342\200\224-..

We

(5-K)

(5-/0(1-/0
a0t

the oddcoefficients
generates

and startingwith a\\, it


\302\2533

a4 =

(7-/0(3-/0
fl,<
120

\"\342\200\242\342\200\242\342\200\242

write the complete


solutionas
/*(\302\243)=/*even(S)

[2.82]

/*odd(\302\243).

where
hcvcn(Z)=

\302\2530

+ aii1+

\302\2534?4

is an even functionof builton ao,and


=

\302\243,

/*odd(\302\243)

fli\302\243+fl3\302\2433+tf5\302\2435

+ ---

is an odd function,builton a\\. Thus Equation2.81determines

/z(\302\243)

two arbitrary constants


(ao and

in terms of

is just what we would expect,for a

a\\)\342\200\224which

second-order
differentialequation.
are normalizable.
soobtained
For at
However,not all the solutions
j, the recursionformula becomes(approximately)
c'j+2

\302\253

^Sce.for example.
Arfkcn

-aj,

(footnote 24).Section5.7.

very

large

Time-Independent
Schrodinger
Equation
with the (approximate)
solution
%
a,7

072)!

forsomeconstant
C,and this yields(at large where the higherpowersdominate)
\302\243,

'?;

^ 072)!

^j\\q

what we'retrying to
goeslikeexp(\302\2432),then \\(/ (remember
the asymptotic
calculate)
goeslikeexp(\302\2432/2) (Equation2.77),which is precisely
behaviorwe didn'twant.26 There is only one way to wiggleout of this:For
normalizable
There must occursome
solutionsthe powerseriesmust terminate.
formula spitsout an+2 = 0 (thiswill
\"highest\"j (callit /?), suchthat the recursion
truncate eitherthe series/zCvcn or the series/7 odd; the otheronemust be zerofrom
the start:ci\\ = 0 if n is even,and ciq = 0 if n is odd).For physicallyacceptable
then,Equation2.81requiresthat
solutions,
K = 2h + 1.

Now, if /7

\\f/l\342\200\224that's

for somenon-negative
integer/7, which is to say (referring to Equation2.73)that
the energy must be
E\342\200\236

= (n + -)h(o. for n

=0.1,2

[2.83]

Thus we recover,by a completely


different method,the fundamental quantization

we found algebraically
condition
in Equation2.61.
It seemsat first rather surprisingthat the quantizationof energy should
emergefrom a technicaldetailin the powerseriessolutionto the Schrodinger
equation,but let's look at it from a different perspective.
Equation2.70 has
of course,for any value of E (in fact,it hastwo linearly independent
solutions,
for every E). But almostallof thesesolutions
blow up exponentially
at
solutions
Imagine,for example,usingan E that
largex, and henceare not normalizable.
is slightlyless than one of the allowedvalues (say, 0.49/?a>),
and plottingthe
solution(Figure2.6(a));
the \"tails\"fly offto infinity. Now try an E slightlylarger
the \"tails\"now blow up in the otherdirection
As
(say,0.51/\"7a>);
(Figure2.6(b)).
from 0.49to 0.51,the tailsflip over
you tweak the parameterin tiny increments
when you passthrough
at precisely
0.5do the tailsgo to zero,leaving
a normalizable
solution.27
0.5\342\200\224only

no surpriselhal the ill-behavedsolutions are still contained in Equation 2.81:


this recursion
-\"It's
the Schrodingerequation, so it'sgot to include both the asymptotic forms we
in Equation 2.75.

relation is equivalent to
found

27

is possibleto set this up on a computer, and discoverthe allowed energies\"experimentally.\"


call it the wag the dog method: When the tail wags,you know you've just passedover an
allowed value. SeeProblems2.54-2.56.
It
You might

Section2.3:The HarmonicOscillator 55
A

1.5'-

>v

X 0.5
1

-4

-2

-0.5

4$

^ n
\\

-1

-1.5
\\

-2
(a)
j

1.5

/o.5
\"

-4 ./^1-2

-0.5
-1 ':

>

-1.5
-2
(b)

FIGURE2.6:

to the Schrodinger
Solutions
equationfor

(b)E= 0.51/1\302\253.

(a) E

= 0.49fico, and

For the allowedvaluesof K, the recursion


formula reads

\302\253y+2

-20? j)
fly(7 + 1)(7+2)

If n = 0, there is onlyoneterm in the series(we must picka


and 7=0in Equation2.84yields = 0):
\302\2532

/?()(\302\243)

=flo.

and hence
V'o(\302\243)

= a0e $~12

[2.84]
\\

0 to kill /20Cid,

Schrodmger
Equation
Time-Independent
(which,apart from the normalization,
Equation2.59).For n =
reproduces

= 0,28and Equation2.84with j = 1 yields = 0, so


M$)= <M$.
and hence
tfr,($)= a^e-^~'2
Equation2.62).For n = 2, 7 0 yields =
(confirming
= 0, so
take

1 we

\302\2533

\302\253o

\342\200\224

\342\200\224

2\302\253o>

\302\2532

and

7=2gives

\302\2534

h2(t)=a0(\\-2$2).
and

M$) =

-2$2)\302\253\"*2/2.

\302\253od

Problem2.10,where thislastresultwas obtainedby


and soon.(Compare

algebraic

means.)
of degree11 in involvingeven powers
In general,
will be a polynomial
only,if n is an even integer,and odd powersonly,if n is an odd integer.Apart
or a\\) they are the so-calledHermitepolynomials,
from the overallfactor
the arbitrary
The first few of them are listedin Table2.1.By tradition,
factoris chosenso that the coefficientof the highestpowerof
multiplicative
is 2\".With thisconvention,the normalized30
stationary statesfor the harmonic
are
oscillator
mco 1/4 1
-f-/2
=
[2.85]
fn(x)
\302\243,

//\342\200\236(\302\243)

(\302\253o

#\342\200\236(\302\243).29

\302\243

:#\342\200\236($)<?

in Equation2.67.
to the oneswe obtained
(ofcourse)
algebraically
They are identical

2.1:Thefirst few Hermite

TABLE

polynomials,

H\342\200\236(%).

H0-= 1,
Hy-=
H2== 4^2_ 2,
#3 =
\302\276.

8\302\2763

HA--=
=

H5-

16\302\2764

32\302\2765

1\302\276

48\302\2762

12,

-160^-

f120\302\276.

28Note lhal there is a completely different set of coefficients aj for each value of n.
29The Hermite polynomials have been studied extensively in the mathematical literature, and
there are many tools and tricks for working with them. A few of these are exploredin Problem
30I shall not work out the normalization constant here:if you are interested in knowing how it is

2.17.

done, seefor exampleLeonard Schiff, Quantum Mechanics,3rd ed.,McGraw-Hill,New York


Section13.

(1968).

Section2.3:TheHarmonicOscillator 57
In Figure2.7(a)I have plotted\\j/n(x) for the

first few

/?'s.The quantum

oscillatoris strikingly different from its classical


counterpart\342\200\224not only are the
but the position
have somebizarrefeatures.
For
distributions
energiesquantized,
the probability
of findingthe particleoutsidethe classically
allowedrange
instance,
is
(that is, with x greaterthan the classical
amplitudefor the energy in question)
not zero(seeProblem2.15),and in all odd statesthe probabilityof finding the
particleat the centeris zero.Only at largen do we beginto seesomeresemblance
to the classical
case.In Figure2.7(b)I have superimposed
the classical
position
=
distribution
on the quantum one(for n
out the bumps,
100);if you smoothed
the two would fit pretty well (however,in the classical
casewe are talking about
the distribution
of positions
overtime for oneoscillator,
whereas in the quantum
casewe are talkingaboutthe distribution
overan ensemble
of identicallyprepared
systems).31
Problem2.15In the groundstateof the harmonicoscillator,
what is the probability
(correctto threesignificantdigits)of finding the particleoutsidethe classically
the energy of an oscillator
allowedregion?Hint:Classically,
is E = (l/2)ka2=
So the \"classically
allowedregion\"for an
{\\/2)marar,where a is the amplitude.
oscillator
of energy E extendsfrom
to +y/2E/mco2.
Lookin a math
tableunder \"NormalDistribution\"
or \"ErrorFunction\"for the numerical
value of
the integral.
\342\200\224y/2E/mco2

Problem2.16Usethe recursion
formula (Equation2.84)to work out //5(^)and
Invokethe conventionthat the coefficient
of the highestpowerof is 2\"
to fix the overallconstant.
//g(\302\243).

\302\243

**Problem2.17In thisproblemwe explore


someof the moreusefultheorems
(stated
without proof)involving Hermitepolynomials.

formulasaysthat
(a) The Rodrigues
Hn^) =

e-*\\

[2.86]

(-\\)\"e^(J^j

Useit to deriveH$ and //4.

recursion
relationgivesyou
(b) The following
preceding

Hermitepolynomials:
//\342\200\236+,(\302\243)

2\302\243//\342\200\236(\302\243)

Hn+\\

in terms of the two

[2.87]

2/7#\342\200\236_,(\302\243).

Useit, togetherwith your answer in (a),to obtain//5 and H^.


- 'The
distribution
parallel is perhapsmore direct if you interpret the classical
oscillatorsall with the same energy, but with random starting times.

as an ensembleof

2 Time-Independent
Schrodinger
Equation

/7

=3

/7

=2

/7=1

/7

=0

(a)

r
0.20-

|Vl00(x)i20.24

0.16-

0.12

0.06

0.04

(b)

FIGURE2.7: (a) The first four stationary statesof the harmonic oscillator.
This
material is usedby permission
of John Wiley 8c Sons,Inc.;StephenGasiorowicz,
w^h l^e
QuantumPhysics,JohnWiley 8c Sons,Inc.,1974.(b) Graph of |^iool2>

classical
distribution
(dashedcurve) superimposed.

Section2.4:TheFree Particle
(c)

59

an nth-orderpolynomial,
If you differentiate
of order
you get a polynomial
in fact,
(n 1).For the Hermitepolynomials,
\342\200\224

^=2,7//,,,^).

[2.88]

Checkthis,by differentiating
H$ and H(>.
is the z-derivative,
at z = 0, of the generating
function
+
(d) Hn
of z\"/n\\ in the Taylor
2z%)\\ or, to put it anotherway, it is the coefficient
\302\273th

exp(\342\200\224z2

(\302\243)

for thisfunction:
seriesexpansion
\302\253-=2+2*

5^/^).

[2.89]

/7=0

Usethisto rederiveHq,H\\, and Hi.

2.4 THEFREE PARTICLE


next to what shouldhave beenthe simplest
caseof all:the free particle
thiswouldjustmean motionat constant
(V(x)= 0 everywhere).Classically
is surprisinglysubtleand tricky. The
but in quantum mechanics
the problem

We turn

velocity,

time-independent
Schrodinger
equationreads
h2

d2i/ =

2m dx\\

or
d~\\l/
\342\200\224L

dx-

Ef.

[2.90]

i
y/2mE
= -k2f,
vj\\ierek=.
h

[2.91]

So far, it'sthe sameas insidethe infinite squarewell (Equation2.21),where the


potentialisalsozero;thistime,however, I preferto write the generalsolutionin
form (instead
of sinesand cosines),
for reasonsthat will appearin due
exponential

course:

yjr

(x)= Aeikx + Be-ikx.

[2.92]

Unlikethe infinite squarewell, there are no boundary conditions


to restrictthe
v
alues
hence
the
of k (and
of E);
free particlecan carry any (positive)
possible
on
the
time
standard
energy.Tacking
dependence,
exp{\342\200\224iEt/h),
vl/(x, t)

= Aeik{x-^n+ Be-iHx+^n.

[2.93]

on thesevariablesin the special


Now, any functionof x and t that depends
combination
a wave of fixed profile,
(x + vt) (for someconstantv) represents
at speedv. A fixed point on the waveform (for
traveling in the :pf-direction,

Time-Independent
Schrodinger
Equation
a maximum or a minimum) corresponds
to a fixedvalue of the argument,
example,
and henceto x and t suchthat
x

+ vt = constant, or

= =fvt + constant.

Sinceevery pointon the waveform is moving alongwith the samevelocity,its


Thus the first term in Equation2.93
shapedoesn'tchangeas it propagates.
a wave traveling to the right,and the secondrepresents
a wave (of the same
energy) goingto the left.By the way, sincethey onlydiffer by the signin front of
k, we might as well write
represents

Vk{.\\\\t)=

Aei{kx-!^t\\

[2.94]

and letk run negativeto coverthe caseof waves traveling to the left:
k

y/lmE

\302\261

/j

with

..

> 0 => traveling to the right,


, ,
[ k < 0 => traveling to the left.

k
f
{ ,

r\302\253.

__.,
[2.951
J
\342\200\236

waves; their
Evidently the \"stationarystates\"of the free particleare propagating
to the de Broglie
formula (Equation1.39),
wavelengthis k = 2n/\\k\\, and,according
they carry momentum

p = hk.

[2.96]

of x) is
The speedof thesewaves (the coefficient
of t overthe coefficient

-*'*'
~ _
\342\200\224

^quantum

\342\200\224

E
w

\342\226\240
\302\253

nan
l~-\"'J

On the otherhand,the classical


speedof a free particlewith energy E is given by

E = (l/2)mir(pure kinetic,sinceV = 0), so

_ 2E _= ^'quantum-

^classical=

\\/

[2.98J

wave functiontravels at half the speedof the


Apparently the quantum mechanical
to represent!
We'llreturn to thisparadoxin a moment\342\200\224there
particleit is supposed
is an even moreseriousproblemwe needto confrontfirst:This wave functionis

notnormalizable.
For

V];Vkdx=
/-t-oo
-co

\\A\\2

r+oo
dx = |A|2(oo).

[2.99]

J\342\200\224oo

In the caseof the free particle,then,the separablesolutionsdo not represent


states.A free particlecannotexistin a stationary state;or,
physicallyrealizable
to put it anotherway, there is no suchthing as a freeparticlewith a definite
energy.

Section2.4:TheFree Particle
But that doesn'tmean the separable
solutionsare of no use to us, for

61
they

rolethat is entirely independent


mathematical
of their physical
The generalsolutionto the time-dependent
Schrodinger
equationis stilla
of separable
linearcombination
solutions
(only thistime it's an integraloverthe
variable k, insteadof a sum overthe discrete
indexn):
continuous
play a
interpretation.

[2.100]

what playsthe roleof the


l/y/ln is factoredout for convenience;
coefficient in Equation2.17is the combination
Now this
(\\/y/2n)<p(k)dk.)

(The quantity
c\342\200\236

wave functioncan benormalized


carries
(forappropriate
0(fc)).But it necessarily
a range of fc's,and hencea range of energiesand speeds.We callit a wave

packet.32
we are given ty(x, 0), and we are askedto
In the genericquantum problem,
find y(x,t).For a free particlethe solutiontakesthe form of Equation2.100;
the only questionis how to determine
0(fc) so as to match the initialwave
function:
ikx
*(jr.0) =
dk.
[2.101]
0(*)<?'\"
-co

in Fourieranalysis;
the answer isprovidedby Plancherel's
Thisisa classic
problem
theorem(seeProblem2.20):

[2.102]
F(k)is calledthe Fouriertransformof f(x)\\ f(x) is the inverseFourier
There is, of
of F(k) (the only differenceis in the signof the exponent).
on the allowablefunctions:
The integrals
have to exist}*
course,somerestriction
thisis guaranteedby the physicalrequirement
Forour purposes
that ^(.v.0) itself
transform

-^Sinusoidalwaves extend out to infinity, and they are not normalizable. But superpositionsof
such waves lead to interference, which allowsfor localization and normalizability.
necessaryand sufficient condition on f(x) is that
\\f(x)\\2dx be finite. (In that
case -3C\\F(k)\\-dk is also finite, and in fact the two integrals are equal.)SecArfken (footnote 24).
\342\226\240,3The

f^

Section15.5.

/^,

Scbrodinger
Equation
Time-Independent
to the generic
for the freeparticle,
Sothe solution
be normalized.
quantum problem,
is Equation2.100,with

[2.103]

which is initiallylocalized
in the range
Example2.6 A free particle,
=
isreleasedat time t 0:

if

A,

\342\200\224

\342\200\224a

< x < a,

a < x < a,

[ 0, otherwise,

real constants.
where A and a are positive
Findty

(x,t).

Solution:Firstwe needto normalize


4>(a\\ 0):
pa

/oo
-oo

= \\A\\2 / dx = 2a\\A\\2
|vI/(a\\0)|2c/a-

=> A =

J\342\200\224a

Next we calculate

\302\242(1(),

usingEquation2.103:
V27T

Ca

11

V2fl J-a
Jka _

IJllCl -ik
1

p\342\200\224ika

2i

kJWa

,-ikx

sin(ka)
k

\342\226\240s/tFci

Finally,we plugthis backintoEquation2.100:

*(jc.r)=

sin(fctf) ;a...
If00
/

m2m

\342\200\224=

Tty/la J-oo

\342\200\224^-\342\200\224e'^-^0

dk.
\342\200\236

[2.104]

this integralcannotbe solvedin tennsof elementary functions,


Unfortunately,
though it can of coursebe evaluated numerically (Figure2.8).(Thereare,in fact,
preciousfew casesin which the integralfor vJ/(a\\ t) (Equation2.100)can be
seeProblem2.22for a particularly beautifulexample.)
calculated explicitly;
It is illuminating
to explorethe limitingcases.If a is very small,the starting
wave functionis a nicelylocalized
In this casewe can use
spike(Figure2.9(a)).
the smallangleapproximation
to write sm(ka)% ka,and hence
<t>{k)

Section2.4:TheFreeParticle

63

u|\302\245(x,0l2

FIGURE2.8: Graph of |*(x,t)\\2 (Equation2.104)


at t = 0 (the rectangle)and at
t = ma2/h(the curve).
V(X,

0)

V2a

/a/n
(a)

(b)

FIGURE2.9: Example2.6,for smalla. (a) Graphof W(x, 0).(b) Graphof4>{k).

it'syfotf, sincethe fc's cancelledout (Figure2.9(b)).Thisis an exampleof the

If the spreadin positionis small,the spreadin momentum


uncertainty principle:
(and hencein
Equation2.96)must be large.At the otherextreme {large
and
a) the spreadin positionis broad(Figure2.10(a))
k\342\200\224see

*(*) =

'TTsinffcfl)

ka

= 0, and dropsto zeroat z = tt (which, in


thiscontext,meansk = + n/a).Sofor largea, 0(/:)is a sharp spikeaboutk = 0
Thistimeit's got a well-defined
momentum but an ill-defined
(Figure2.10(b)).
position.
Now, sinz/z hasits maximum at z

Time-Independent
Scbrodinger
Equation
V(x.0)

V2a

(a)

(b)

FIGURE2.10:Example2.6,for large a. (a) Graph of *(x,0).(b) Graphof$(&).

I return now to the paradoxnotedearlier:the fact that the separable


solution
2.94travels at the \"wrong\"speedfor the particleit
*I>it(..Y, f) in Equation
the problemevaporatedwhen we discovered
represents.
Strictly speaking,
that Wk is not a physicallyrealizable
it is of interest
state.Nevertheless,
to
discover how information
in the freeparticle
wave function
aboutvelocityiscontained
The essentialideais this:A wave packetis a superposition
of
(Equation2.100).
it consists
functionswhoseamplitudeismodulated
of
sinusoidal
by 0 (Figure2.11);
to the particlevelocity
contained
within an \"envelope.\"
What corresponds
\"ripples\"
but rather
is not the speedof the individualripples(the so-called
phasevelocity),
the speedof the envelope
(the groupvelocity)\342\200\224which, dependingon the nature
of the waves, can be greaterthan, lessthan, or equalto, the velocityof the ripples
that go to make it up.For waves on a string,the groupvelocityis the sameas the
phasevelocity.For water waves it is one-halfthe phasevelocity,as you may have
on a particularripple,
noticedwhen you tossa rockintoa pond(if you concentrate
you will seeit buildup from the rear,move forward through the group,and fade
outat halfthe speed).What
away at the front,while the groupasa wholepropagates
I needto show is that for the wave functionof a freeparticlein quantum mechanics
ostensibly

FIGURE2.il:A
\"envelope\"
\"ripples\"

wave

packet.The

travelsat the groupvelocity;the


travelat the phasevelocity.

Section2.4:TheFree Particle

65

the groupvelocityis twice the phasevelocity\342\200\224just right to represent


the classical

particlespeed.
the groupvelocityof a wave packetwith
The problem,
then, is to determine
the generalform

P+OO

= -== /
0(Jt)e'(*jr_fttf)dk.
s/2tt J-oo

*(*,t)

(In our caseco = (hk2/2m),but what I have to say now appliesto any kind
of its dispersionrelation\342\200\224the formula for a> as a
of wave packet,regardless
functionof k.) Let usassumethat 0(fc)is narrowly peakedaboutsomeparticular
value ko.(Thereis nothingillegalabouta broadspreadin k, but suchwave packets
travel at differentspeeds\342\200\224so
changeshaperapidly\342\200\224since different components
the whole notionof a \"group,\"
with a well-defined
velocity,losesits meaning.)
Sincethe integrandis negligible
exceptin the vicinity of ko, we may as well
the functionco(k) aboutthat point,and keeponly the leadingterms:
Taylor-expand
coik)= coo + co'Q(k-ko),
where co'0 is the derivative of co with respectto k, at the pointko.
Changingvariablesfrom k to s = k ko (to centerthe integralat ko),we
have
\342\200\224

vl>(.v, t)

-== /
V 2TX

At t

ds.
<j)(ko+ 5)<?'K*o+J)*-(\"o+4,J>r]

J-oo

= 0,

*(x,0) =

f+oa
-=
\\I2ti / -co
1

+ s)e'(kQ+s)xds,

0(\302\243o

J\342\200\224oo

and at

latertimes
vl/(.v.t)

r+oo

\\j2ti

J\342\200\224oo

Exceptfor the shift from x to (avi>(x,0).Thus


vJ/(a\\

ds
0(^o+ synko+sKx-^n

-\342\200\224e'\"<-a>n'+M\302\273'>

t)

\342\200\224

co0t),the integralis the sameas the onein

= g-'^-^o)^^ co'0t.
0).

phasefactorin front (which won't affect |vj/|2in


wave packetevidently movesalongat a speed(o'Q:

Apart from the

\"group

(evaluatedat

dco
= -77-

[2.105]
any event) the

[2.106]

= ko).Thisis to be contrasted
with the ordinary phasevelocity
co
\"phase

\342\200\224

\342\200\242

[2.1071

Scbrodinger
Time-Independent
Equation
Inourcase,a> = (hk2/2m),
soco/k= (hk/2m),whereas dco/dk= (ftk/m),which
is twice as great.This confirmsthat it is the groupvelocityof the wave packet,
not the phasevelocityof the stationary states,that matchesthe classical
particle
Velocity:
^classical

\342\200\224

ugroup

= 2l)phase-

[2.10oJ

Problem2.18Showthat [Aelkx+ Be~lkx]and [Ccoskx + D sinkx] are equivalent


the constants
C and D in
ways of writing the samefunctionof x, and determine
terms of A and B, and viceversa.Comment:
In quantum mechanics,
when V = 0,
the exponentials
in discussing
represent
travelingwaves, and are mostconvenient
the free particle,
to standingwaves, which
whereas sinesand cosinescorrespond
arisenaturally in the caseof the infinite squarewell.
Problem2.19Findthe probabilitycurrent, J (Problem1.14)for the freeparticle
wave functionEquation2.94.Which direction
doesthe probabilitycurrent flow?
*Problem
2.20Thisproblemis designedto guideyou through a \"proof\"of Plancherel'stheorem,by starting with the theory of ordinary Fourierserieson a finite
interval, and allowingthat interval to expandto infinity.
(a)

Dirichlet'stheoremsaysthat \"any\" functionf{x) on the interval


can be expandedas a Fourierseries:

[\342\200\224a,

+a]

CO

f(x) =

2^[\302\253/i

sin(n-7rx/a)+ bn

cosijmx/a)}.

Show that thiscan be written equivalently as


00

n=\342\200\224OG

What

is

c\342\200\236,

(b) Show (by

in terms of

modification
of Fourier'strick) that
appropriate
C\"

(c)

ac\342\200\236.

TaLa f{x)e-'mnx'adx.

in favor of the new variablesk = (nn/a) and F(k) =


Show that (a) and (b) now become

Eliminaten and
\342\200\242v/2/tt

and bnl

a\342\200\236

c\342\200\236

f(x) = -==

\302\260\302\260

V^,,^

where Afc

1 f+a
=-=
f(x)e-''kxdx,

F(k)eikxAk: F{k)

in k
is the increment

V2^J-\342\200\236-

from onen to the next.

Section2.4:TheFree Particle

oo to obtainPlancherel's
theorem.Comment:In view
of their quitedifferent origins,it is surprising
(and delightful)that the two
formulas\342\200\224one for F(k) in terms of f(x), the otherfor f(x) in terms of
sucha similarstructure in the limita oo.

(d) Take the

limita

67

\342\200\224>

F(k)\342\200\224have

-*\342\200\242

Problem2.21A freeparticlehasthe initialwave function


vl>(.T.0)= Ae~alxl,
where A and a are positive
real constants.
Normalize^(jt,0).
(b) Find<f)(k).
(a)

(c)
(d)

Construct
ty(x,t), in the form of an integral.
Discussthe limitingcases{a very large,and a very small).

*Problem2.22 The gaussianwave packet.A free particlehas the initialwave


function

vl>(.v,0)= Ae-\"x\\

where A and a are constants


(a is real and positive).

NormalizeV(x,0).
(b) FindW(x,t).Hint:Integralsof the form
(a)

e-\302\253,x-+bx)

/+OC
-oo

dx

can be handledby \"completing


the square\":
Let y
=
notethat (ax2+ hx) y2 (b2/4a).Answer:

= s/a[x+ (b/2a)],and

\342\200\224

/2a\\i/4 e-ax2/[l+ainal/m)\\
\\7r /
+(2ihat/m)

vl>(.v.D=

\342\200\224

=\342\226\240

y/\\

(c)

Find1^(.1-,
t)\\^. Express
your answer in terms of the quantity
w

=
Y

1 +(2hat/m)2'

Sketch|^|2(asa functionof x) at t = 0, and again for somevery larget.


what happensto |^|2,
astimegoeson?
Qualitatively,
(d) Find (.v), (/?), (.v2), (p2),ax, and ap. Partialanswer:(p2)= ah2, but it
may take somealgebrato reduceit to this simpleform.
(e)

Doesthe uncertainty principlehold?At


closestto the uncertainty limit?

what time

doesthe system come

68

Chapter2 Time-Independent
Schrodinger
Equation

2.5 THEDELTA-FUNCTION
POTENTIAL

2.5.1BoundStatesandScatteringStates
We have encountered
two very different kindsof solutions
to the time-independent

For the infinite squarewell and the harmonicoscillator


equation:
Schrodinger
they
are normalizahle,
and labeledby a discreteindexn; for the free particlethey are
and labeledby a continuous
variablek. The formerrepresent
non-normalizable,
statesin their own right,the latter do not;but in bothcasesthe
physicallyrealizable
to the time-dependent
generalsolution
Schrodinger
equationis a linearcombination
of stationary
the first type thiscombination
takes the form of a sum
(over whereas for the secondit is an integral(overk). What is the physical
of thisdistinction?
significance
In classical
mechanics
a one-dimensional
can give
time-independent
potential
riseto two rather different kindsof motion.If V{x) riseshigherthan the particle's
totalenergy (E) on eitherside(Figure2.12(a)),
then the particleis \"stuck\"in the
rocksbackand forth betweenthe turningpoints,but it cannot
potential
escape(unless,of course,you provideit with a sourceof extra energy,suchas
a motor,but we'renot talking aboutthat). We callthis a boundstate.If, on the
otherhand,E exceedsV(x) on oneside(or both),then the particlecomesin from
of the potential,
and returns
\"infinity,\"slowsdown or speeds
up under the influence
to infinity (Figure2.12(b)).
unlessthere issome
(It can'tgettrappedin the potential
suchas friction,to dissipateenergy,but again,we'renottalking about
mechanism,
admit only boundstates(for
that.)We callthis a scatteringstate.Somepotentials
someallow only scattering
states(a potential
instance,the harmonicoscillator);
hill with no dips in it, for example);
somepermitboth kinds,dependingon the
energy of the particle.
The two kindsof solutions
to the Schrodinger
to
equationcorrespond
precisely
boundand scattering
states.The distinction
is even cleanerin the quantum domain,
becausethe phenomenon
of tunneling(which we'llcometo shortly)allowsthe
barrier,so the onlything that matters
particleto \"leak\"through any finite potential
is the potentialat infinity (Figure2.12(c)):
states\342\200\224for

\302\253.),

well\342\200\224it

< [V(-oo) and V(+oo)]=$> boundstate,


E > [V(-oo) or V(+oo)]=> scattering
state.

IE

,,.

\342\200\236Q1

In \"reallife\" mostpotentials
go to zeroat infinity, in which casethe criterion
even further:
simplifies

< 0 => boundstate,


state.
E > 0 => scattering

IE

._

\342\200\236,

the infinite squarewell and harmonicoscillator


Because
go to infinity as
potentials
x
+oo,they admit boundstatesonly;becausethe free particlepotentialiszero
\342\200\224>

Section2.5:TheDelta-Function
Potential 69

Classicalturning points
(a)

Classicalturning

point

V(x)k

(c)

FIGURE2.12: (a) A boundstate,(b) Scatteringstates,(c) A


a quantum scattering
state.

classical
boundstate,but

In thissection(and the following


states.34
everywhere, it only allowsscattering
that giveriseto bothkindsof states.
one)we shallexplorepotentials
34If
observant, you may have noticed that the general theorem requiring
you are irritatingly
E > Vmjn (Problem 2.2) does not really apply to scattering states,since they are not normalizable
anyway. If this bothers you, try solving the Schrodingerequation with E < 0.for the free particle, and

Schrodinger
Equation
Time-Independent
8(x)

FIGURE2.13:The Dirac deltafunction

_^

2.111).
(Equation

Well
2.5.2TheDelta-Function

The Diracdeltafunctionis an infinitely high,infinitesimally


narrow spikeat the
origin,whoseareais 1 (Figure2.13):

lltl]-

^H\302\260oo.

= 1.

with

[2.111]

\302\243%*)\302\253**

it isn'ta functionat all,sinceit is not finite at x = 0 (mathematicians


Technically,
it is an extremely
callit a generalized
function,or distribution).35
Nevertheless,
in theoretical
the charge
usefulconstruct
in electrodynamics
physics.(Forexample,
Noticethat 8(x a) wouldbe a spike
densityof a pointchargeis a deltafunction.)
of area 1 at the pointa. If you multiply 8(x a) by an ordinaryfunctionf(x),
it's the sameas multiplyingby f(a),
\342\200\224

\342\200\224

f(x)8(x-a)= f{a)8{x a),

[2.112]

becausethe productis zeroanyway exceptat the pointa. In particular,


r+oo
=
8(x- a) dx = f(a).
f(x)8(x a)dx f(a)
/+0O
/

-oo

[2.113]

J\342\200\224oo

That'sthe mostimportant propertyof the deltafunction:


Underthe integralsignit
servesto \"pickout\" the value of /(.*)at the pointa. (Ofcourse,the integralneed
not go from
to -f-oo:all that matters is that the domainof integrationinclude
the pointa, so a e to a + e woulddo,for any e > 0.)
Let'sconsidera potential
of the form
\342\200\224oo

\342\200\224

V(x) =

-a8(x),

[2.114]

note thai even linearcombinations of thesesolutionscannot be normalized.The positiveenergy solutions


by themselves constitute a completeset.
-^The delta function can be thought of as the limit of a .sequenceof functions, such as rectangles
(or triangles) of ever-increasingheight and ever-decreasingwidth.

Section2.5:The Delta-Function
Potential 71

constant.36
where a issomepositive
Thisisan artificialpotential,
tobe sure(sowas
the infinite squarewell),but it'sdelightfully
simpleto work with, and illuminates
the basictheory with a minimum of analytical clutter.The Schrodinger
equation
well reads
for the delta-function
h2

d2i/
Y

2m dx2
it

- a8(x)1r= Ejr;

[2.115]

states(E > 0).


yieldsbothboundstates(E < 0) and scattering
We'lllookfirst at the boundstates.In the regionx < 0, V(x) = 0, so
2mE

d2f =
dx1

ron*!
[2.116]

zt$=k$,

\342\200\224T

ft1

where
K

^\342\200\224r

[2.117]

\342\200\242

so k is real and positive.)


The generalsolutionto
{E is negative,by assumption,
Equation2.116is
[2.118]
i/(x) = Ae-KX+BeK\\
but the first term blowsup

as x

-\302\273

\342\200\224oo,

so we must chooseA = 0:

\\l/{x)= BeK\\

(x<0).

[2.119]

In the regionx > 0, V(x) is againzero,and the generalsolutionis of the form


F exp(-Kx)+ Gexp(/c.r);
thistimeit's the secondterm that blowsup (asx ->

+00),so

yj/{x) =

Fe-KX. (x > 0).

[2.120]

remainsonly to stitchthesetwo functionstogether,usingthe appropriate


at jc = 0. I quotedearlierthe standardboundary conditions
boundary conditions
It

for \\j/:

is always continuous;
2.dty/dx is continuousexceptat
\\. if/

points where the potentialis infinite.

[2.121]

In thiscasethe first boundary condition


tellsus that F = B, so
f

:%Thedelta function
energy x length.

BeKX.

itself carriesunits of

Mkngth

(x

< 0).

(seeEquation

so a has the
2.111).

dimensions

Schrodinger
Equation
Time-Independent

FIGURE2.14: Boundstatewave function for the delta-function


potential

2.122).
tellsus nothing;
\\}/{x)is plottedin Figure2.14.The secondboundary condition
casewhere V is infiniteat the
thisis (likethe infinite squarewell) the exceptional
join,and it'sclearfrom the graph that thisfunctionhasa kink at x = 0.Moreover,
up to thispointthe deltafunctionhas not comeintothe story at all.Evidently the
the discontinuity
at x = 0.
deltafunctionmust determine
in the derivative of
I'll show you now how thisworks,and as a by-productwe'llseewhy d\\f//dx is
(Equation

\\j/,

ordinarilycontinuous.
The ideais to integratethe Schrodinger
from e to +e, and then
equation,
\342\200\224

take the limitase


-\342\200\224

\342\200\224>

0:

=E I
V(x)xj,(x)dx

-^jdx+l

f{x)dx.

[2.123]

The first integralis nothingbut d\\[//dx,evaluatedat the two end points;the last

integralis zero,in the limite


width and finite height.Thus
A

'djj_ = lim
dx

-\302\273

0, sinceit'sthe area of a sliverwith vanishing

dir
~dx
+\342\202\254

dx

lim
/r 6->o/
-J = -^)

V(x)xj/(x)dx. [2.124]

J-\342\202\254

Typically,the limiton the right is againzero,and that'swhy dif/fdxis ordinarily


continuous.
But when V(.\\') is infinite at the boundary,this argument fails.In

if V(.v) = a8(x),Equation2.113
particular,
yields
2ma
d\\J/
A
[2.125]
h2
.dxJ
For the caseat hand (Equation2.122),
df/dx = -BKe~K\\ for > 0). so d\\j//dx\\, = Bk,
df/dx = +BKe+K-\\ for (jc < 0), so d\\j//dx\\_ = +Bk.
and henceA(d\\f//dx) =
And i/r(0)= B. So Equation2.125says
= ma
\342\200\224

\342\226\240^(0).

\342\200\224

(\342\200\236y

\342\200\2242Bk.

h2

[2.126]

Section2.5:The Delta-Function
Potential 73

is
and the allowedenergy (Equation2.117)
h-K-

E=

ma~

[2.127]

2m

Finally,we normalize
\\f/:
>+00

/\302\273oo

\\i/(x)\\2dx = 2\\B\\2 / e~lKX clx =


/+oo
-oo
./0
so (choosing,
for convenience,
the positive
realroot):

B=

Jk =

\\E\\\342\200\224

= 1,

\302\253

y/ma

[2.128]

of its \"strength\"a, has exactly one


well, regardless
Evidently the delta-function
boundstate:

E=
nx)=\"/mae-'na^t'2;
h
What

reads

ma~
\"

2/72

[2.129]

aboutscattering
states,with E > 0?For.v < 0 the Schrodinger
equation
2mE ,

d2f

n-

~dx~5

/2 ,

where
k

= \\j2mE
h

[2.130]

is realand positive.The generalsolutionis


if(x) = Aeikx + Be~ikx.

[2.131]

thistimewe cannotrule out eitherterm, sinceneitherof them blowsup.


Similarly,for .v > 0,
= Feikx+ Ge~ikx.
[2.132]
yj/ (x)
The continuityof \\j/(x) at x = 0 requiresthat
and

F + G = A + B.
The derivativesare
dxjf/dx = ik [Feikx

dif/dx= ik (Aeikx

[2.133]

- Ge-'kx). for > 0), sodxj//dx\\+= i.k(F- G),


- Be-''kx), for (x < 0), sodxj//dx\\_ = ik(A - B).
(.v

Scbrodinger
Equation
Time-Independent

-G-A

and henceA{df/dx)= ik(F


+ B).Meanwhile,xf/(0) = (A +
secondboundary condition
(Equation2.125)says

-G-

ik(F

2ma

+ B) =

(A

B),sothe

+ fl),

[2.134]

or,morecompactly,
F

- G = A(l + 2ij8)- 5(1-

where 0 =

2/\302\243).

met

[2.135]

we are left with two equations


Having imposedboth boundary conditions,
if you
(Equations2.133and 2.135)in four unknowns (A, B, F, and
countk. Normalization
won't help\342\200\224this isn'ta normalizable
state.Perhapswe'd
betterpause,then, and examinethe physicalsignificance
of thesevarious
constants. Recallthat exp(ikx)gives rise (when coupled
with the time-dependent
factorexp(\342\200\224i.Et/ft)) to a wave functionpropagating
to the right,and exp(\342\200\224ikx)
leadsto a wave propagating
to the left.It followsthat A (in Equation2.131)is the
amplitudeof a wave comingin from the left,B is the amplitudeof a wave
to the left, F (Equation2.132)is the amplitudeof a wave traveling offto the
right,and G is the amplitudeof a wave comingin from the right (seeFigure2.15).
In a typicalscattering
experiment
particlesare fired in from onedirection\342\200\224let's
of the wave comingin from the right
say, from the left.In that casethe amplitude
will be zero:
G = 0, (forscattering
from the left);
[2.136]
G)\342\200\224five,

returning

is the amplitudeof the incidentwave, B is the amplitudeof the reflectedwave,


and F is the amplitudeof the transmittedwave. SolvingEquations2.133and
2.135for B and F, we find
A

B=

ifi

l-ifi

A,

F=

\\-ifi

[2.137]

from the right,set A = 0; then G is the incident


(If you want to study scattering
F is the reflectedamplitude,and B is the transmitted amplitude.)
amplitude,

Ae ikx

Feikx

B&

Ge-ikx

\342\226\240ikx

FIGURE2.15:Scatteringfrom a delta
function

well.

Section2.5:The Delta-Function
Potential 75
of finding the particleat a specified
locationis given by
Now, the probability
that an incident
|vl> |2,so the relative27probability
particlewill bereflectedbackis
&

\\B\\2

7TTT
\\A\\2

P2
= T-T-^T1+^2

t2-138]

is calledthe reflectioncoefficient.
(If you have a beam of particles,it tells
the
number that will bounceback.)Meanwhile,
you the fractionof the incoming
o
f
is given by the transmission
coefficient
probability transmission
R

T=

IFI2=

Of course,the sum of theseprobabilities


shouldbe
R

Noticethat
of E:

[2'1391

W TW
1\342\200\224and

it

is:

+ T=\\.

[2.140]

and T are functionsof /3, and hence(Equations


2.130and 2.135)
R

-.
(2h2E/ma2)'
1

1+

T=

[2.141]

1+ (ma2/2h2E)

The higherthe energy, the greaterthe probabilityof transmission


(which certainly

seemsreasonable).
Thisis all very tidy, but there is a sticky matter of principlethat we cannot
so they
wave functionsare not normalizable,
altogether
ignore:Thesescattering
don'tactually represent
to
possible
particlestates.But we know what the resolution
linearcombinations
of the stationary
thisproblemis:We must form normalizable
states,just as we didfor the free
physicalparticlesare represented
wave packets.
thisis a messy
by the resulting
Thoughstraightforwardin principle,
businessin practice,and at this point it is bestto turn the problemover to a
to createa normalizable
sinceit isimpossible
Meanwhile,
computer.38
free-particle
wave functionwithout involvinga rangeof energies,
be interpreted
R and T should
as the approximatereflection
and transmission
for particlesin the
probabilities
particle\342\200\224true

of E.
Incidentally,it might strikeyou as peculiarthat we were ableto analyze a
comesin,scattersoffa potential,
quintessentially
time-dependent
problem(particle
vicinity

-7Thisis not a normalizable wave function, so the absolute probability of finding the particle
al a particular location is not well defined:nevertheless, the ratio of probabilitiesfor the incident and
reflected waves is meaningful. More on this in the next paragraph.
38Numerical studiesof wave packetsscattering off wells and barriers reveal extraordinarily rich
su'ucture. The classicanalysis is A. Goldberg,H.M. Schey.and L. Schwartz, Am. Pliys.35, 177
more recent work can be found on the Web.
(1967);

J.

J.

Schrodinger
Time-Independent
Equation
= a5(x)

_._
iV(x)

barrier.
FIGURE2.16: The delta-function

and fliesoff to infinity) usingstationcuystates.After all,\\j/ (in Equations2.131


and 2.132)
is simplya complex,
sinusoidal
function,
time-independent,
extending
And yet, by imposing
(with constantamplitude)to infinity in both directions.
on thisfunction we were ableto determine
the
appropriateboundary conditions
wave packet)wouldbounce
probabilitythat a particle(represented
by a localized
off, or passthrough,the potential.The mathematical miraclebehindthis is, I
of statesspreadoverallspace,
the fact that by taking linearcombinations
suppose,
and with essentially
wave functionsthat
we can construct
trivial timedependence,
are concentrated
behaviorin time (see
abouta (moving)point,with quiteelaborate

Problem2.43).
on the table,let'slookbriefly at
As longas we'vegot the relevant equations
the caseof a delta-function
barrier(Figure2.16).Formally,allwe have to do is
changethe signof a. Thiskillsthe boundstate,of course(Problem2.2).On the
otherhand,the reflection
and transmission
which dependonly on a\",
coefficients,
are unchanged.
Strangeto say, the particleisjustaslikelyto passthrough the barrier
as to crossoverthe well!Classically,
of course,a particlecannotmake it overan
of itsenergy.In fact,classical
infinitelyhigh barrier,regardless
scattering
problems
are pretty dull:If E > Vmax> then T = 1 and R =
particlecertainly
=
=
ridesup the hill until
makesit over;if E < V^ax then T 0 and R
it runs outof steam,and then returns the sameway it came.Quantum scattering
problemsare much richer:The particlehassomenonzeroprobabilityof passing
even if E < Vmilx. We callthisphenomenon
tunneling;it is
through the potential
the mechanism
that makes possible
much of modernelectronics\342\200\224not to mention
advancesin microscopy.
spectacular
Conversely,even if E > Vmax there is a
that the particlewill bounce
I wouldn'tadvisedriving
possibility
off a cliffin the hopethat quantum mechanics
will save you (seeProblem2.35).
0\342\200\224the

1\342\200\224it

back\342\200\224though

*Problem2.23 Evaluate the followingintegrals:


(a)
(b)
(c)

/+'(x3 - 3a-2+ 2x - 1)5(x+ 2)dx.

/0\302\260\302\260[cos(3x)

+ 2]8(x

tt)

dx.

/+1exp(|.t|+3)5(A--2)dT.

Potential 77
Section2.5:The Delta-Function
liveunder integralsigns,andtwo expressions
Problem2.24 Deltafunctions
(D\\ (x)
and Di{x))involvingdeltafunctionsare saidto be equalif
+ 00

C+OQ

\342\200\242

/(.t)D,(x)dx = /
-CO

f(x)D2(x)dx,

J\342\200\224OQ

for every (ordinary) functionf(x).


(a) Showthat

8(cx)=

[2.142]

^-8(x).

where c is a real constant.


(Besureto checkthe casewhere c is negative.)
(b)

Let 6(x) be the stepfunction:


\342\200\242Hi

\302\243<\302\243

(In the rare casewhere it actually matters,we define0(0)to be 1/2.)Show


that

d9/dx= 8(x).

* ^Problem2.25Check the uncertainty principlefor the wave function in


Equation2.129.Hint:Calculating
(p1)is tricky, becausethe derivative of \\(/ has
at x = 0. Use the resultin Problem2.24(b).
a stepdiscontinuity
Partialanswer:

(P1)= Ona/h)2.

^Problem2.26 What is the Fouriertransform of 8(x)lUsingPlancherel's


theorem,
show that

1 f+oc
eikx dk.
8(x)= lit /
[2.144]
./-oc
mathematicianapoplexy.Although
Comment:Thisformula givesany respectable
the integralis clearlyinfinitewhen x = 0, it doesn'tconverge(to zeroor
else)when x ^ 0, sincethe integrandoscillatesforever.There are ways
to +L, and interpret
to patch it up (for instance,you can integratefrom
oo).
Equation2.144to mean the averagevalue of the finite integral,as L
The sourceof the problemis that the deltafunctiondoesn'tmeet the requirement
for Plancherel's
theorem(seefootnote33).In spiteof this,
(square-integrability)
Equation2.144can be extremely useful,if handledwith care.
\342\200\224

anything

\342\200\224L

\342\200\224>\342\200\242

the doubledelta-function
^Problem2.27 Consider
potential
+ a) + 8(x a)],
V(x) = -<x[8(x

constants.
where a and a are positive

78

Scbrodinger
Chapter2 Time-Independent
Equation
(a)

Sketchthispotential.
Findthe allowedenergies,
for a =
boundstatesdoesit possess?
h~/ma and for a = n-/4ma,and sketchthe wave functions.

(b) How many

* ^Problem2.28 Findthe transmission


in Problem2.27.
coefficient
for the potential

2.6 THE FINITE SQUAREWELL


As a lastexample,
considerthe finitesquarewell potential

V(x) =

for a<x<a,
for |.v|> a,

Vq,

\342\200\224

\342\200\224

0.

[2.145]

is a (positive)
constant(Figure2.17).Likethe delta-function
well, this
states(with E > 0).
admitsbothboundstates(with E < 0) and scattering
potential
We'lllookfirst at the boundstates.
In the regionx <
the potential
is zero,so the Schrodinger
equationreads
where Vo

\342\200\224a

h1 d1*=

E$.
2m ax-

\342\200\224\342\200\224\342\200\224T

9
or d2ir
-\342\200\224=K-1r,

dx-

where
k

[2.146]

y/\342\200\2242mE

is real and positive.The generalsolutionis \\j/(x) = A


the first term blowsup
before\342\200\224see

(as

a\"

\342\200\224>

Equation2.119)is

\342\200\224oo),

exp(\342\200\224kx)

+ B exp(/CA'),but

solution(as
so the physicallyadmissible

f(x) = BeKX, for < -a.


a\"

[2.147]

FIGURE
2.17: The finite square well
2.145).
(Equation

Section2.6:TheFiniteSquare Well
In the region a < x < a, V(x) =

and the Schrodinger


equationreads

\342\200\224

\342\200\224Vo,

- - Vof =

2m dx1
where

79

or

= -1-f,

.MH.
E\\j/,

dx

\342\200\2243-

[2..48]

li

E is negative,for boundstates,it must be greaterthan Vq, by the


oldtheoremE > Vm\\n (Problem2.2);so / is alsoreal and positive.The general
solutionis39
Although

\342\200\224

= C sin(/.r)-f D cos(/x), for

< x < a,
[2.149]
where C and D are arbitrary constants.
Finally,in the region.v > a the potential
is again zero;the generalsolutionis \\jr{x) = Fexp(-Kx)+ Gexp(/c.t),but the
secondterm blowsup (asx 00),so we are left with
[2.150]
ir(x) = Fe~K\\ for x > a.
\\f/(x)

\342\200\224

\342\200\224>

at
The next stepis to imposeboundary conditions: and difr/dxcontinuous
and +a. But we can save a littletime by notingthat thispotential
is an even
\\J/

\342\200\224a

are either
function,so we can assumewith no lossof generalitythat the solutions
The advantage of thisis that we needonly impose
even or odd (Problem2.1(c)).
the boundary conditions
on oneside(say,at +a);the othersideis then automatic,
= +\\j/(x).I'll work out the even solutions;
since
you get to do the odd
onesin Problem2.29.The cosineis even (and the sineis odd),soI'm lookingfor
of the form
solutions
Fe KX.
for .Y > a.
[2.151]
Mx) = D cos(/.v). for0 < x < a.
<
for a 0.
\\j/(\342\200\224x)

\\j/(\342\200\224x).

The continuity of \\Js(x),at x = a, says


Fe~Ka =

Dcos(/tf).

[2.152]

-IDsin(/fl).

[2.153]

and the continuity of d\\j//dx,says

-KFe~Ka=

DividingEquation2.153by Equation2.152,we find

/r=/tan(/fl).

that

[2.154]

This
can.if you like, write the general solution in exponential form (C'e'lx+ D'e~'x).
leadsto the same final result, but sincethe potential is symmetric we know the solutions will be either
even or odd. and the sine/cosine
notation allows us to exploit this directly.
\342\200\242^You

Time-Independent
Schrodinger
Equation

to Equation2.156,
FIGURE2.18: Graphical
for Zo = 8 (even states).
solution

Thisis a formula for the allowedenergies,sincek and I are bothfunctions


of E. To solvefor E, we first adoptsomenicernotation:
Let
z

= la. and zo = yJlmVo.


n

[2.155]

\342\200\224

to Equations2.146and 2.148,(k2+12)= 2mVo/li2,soxa = Jzq z1,


According
and Equation2.154reads
\342\200\224

tan z

= yjizu/z)2 1.

[2.156]

Thisis a transcendental
equationfor z (and hencefor E) as a function of zo
of the \"size\"of the well).It can be solvednumerically,
(which is a measure
using
a computer,
or graphically,by plottingtanz and yJ(zo/z)2 1 on the samegrid,
and lookingfor pointsof intersection
(seeFigure2.18).Two limitingcasesare of
specialinterest:
1.Wide,deepwell.If zo is very large,the intersections
occurjust slightly
=
belowzn hjt/2,with n odd;it followsthat
\342\200\224

En

But E +

rrn-n+ V0 =
9

[2.157]

\342\200\242

2m(2a)

is the energy abovethe bottomof the well, and on the right side
we have precisely
for a well of width 2a (see
the infinite squarewell energies,
rather, half of them, sincethisn isodd.(The otherones,of
Equation
in Problem2.29.)
So
asyou'lldiscover
course,comefrom the odd wave functions,
the finite squarewell goesoverto the infinite squarewell,as Vq
oo;however,
for any finite Vq there are only a finite number of boundstates.
2. Shallow,narrow well.As zo decreases,
there are fewer and fewer bound
states,until finally (forzo < tt/2, where the lowestodd statedisappears)
only one
It is interesting
remains.
to note,however,that there is always oneboundstate,no
matter how \"weak\"the well becomes.
Vb

2.27)\342\200\224or

\342\200\224>

81

Section2.6:TheFiniteSquare Well

You're welcometo normalizef (Equation2.151),if you're interested


states(E > 0).
(Problem2.30),but I'm goingto move on now to the scattering
=
To the left,where V(x) 0, we have

f(x) = Aeik* + Be~ikx, for (x < -a).

[2.158]

k=?-\342\200\224.

[2.159]

where (asusual)
n

Insidethe well, where V(x) =

\342\200\224

Vo>

f(x) = C sin(Zx) + D cos(/a), for (-a < x < a),

[2.160]

where, as before,

, = 2^\302\261W.
n

[2.m

there is no incoming
To the right,assuming
wave in thisregion,we have

f{x) = Feikx.

[2.162]

B is the reflected
and F is the
HereA is the incidentamplitude,
amplitude,
amplitude.40
There are fourboundary conditions:
Continuityof f(x) at a says
transmitted

\342\200\224

Ae~ika+ Beika =

continuityof dfjdx at

\342\200\224

-C

sin(/\302\253)

+ D cos(/a),

[2.163]

a gives

ik[Ae~ika

- Beika]= l[Ccos(/a)+ D sin(/a)]

[2.164]

continuityof f(x) at +a yields


C
and continuityof dfjdx at

sin(/\302\253)

+D

cos(/\302\253)

= Feika.

[2.165]

+a requires

/[Ccos(/fl) Dsin(/fl)]= ikFeika.

[2.166]

40We could look for even and odd functions, as we did in the caseof bound states, but the
scaltering problem is inherenlly asymmetric, sincethe waves comein from one side only, and ihc
exponential notation (representingtraveling waves) is more natural in this context.

Time-Independent
Schrodinger
Equation

FIGURE2.19: Transmission
coefficientasa functionofenergy(Equation
2.169).
can usetwo of theseto eliminate
C and
B and F (seeProblem2.32):

We

2
B = i.sin(2/a)
(/

2kl

\342\200\224tt-.\342\200\224

D, and solvethe remainingtwo for


\342\200\224

)F.

[2.167]

-2ika

F=

[2.168]

cos(2/a)-/^psin(2/fl)
in terms of the
The transmission
coefficient
(T = |F|2/|A|2),
expressed

original

variables,is given by

T~x = 1 +

V2

4^^0)^(1^^^)-

[2.169]

Noticethat T = 1 (the well becomes\"transparent'\")whenever the sineis zero,


which is to say, when

+ V0)=njr,
-H-y/2m(En
n
where n

[2.170]

is any integer.The energiesfor perfecttransmission,


then, are given by

+ Vo =

n~7T~n~

[2.171]

2m(2fl)2'
which happento be precisely
the allowedenergies
for the infinite squarewell.T
is plottedin Figure2.19,as a functionof energy.41
E\302\273

*Problem2.29 Analyze the odd boundstatewave functionsfor the finite square


well.Derivethe transcendental
equationfor the allowedenergies,and solveit
Examine the two limiting
cases.Is there always an oddboundstate?
graphically.
41This remarkable

phenomenonhas been observedin the laboratory, in the form of the RamsauerOxford


discussionseeRichard W. Robineii, Quantum Mechanics.

Townsendeffect. For an illuminating


U.P..1997.
Section12.4.1.

Section2.6:TheFiniteSquare Well

Problem2.30Normalize\\f/(x)

in

and F.

83

to determine
D
the constants
Equation2.151,

Problem2.31The Diracdeltafunctioncan be thought of as the limitingcaseof a


of area 1,as the heightgoesto infinity and the width goesto zero.Show
rectangle
well (Equation2.114)
is a \"weak\"potential(eventhough it
that the delta-function
is infinitely deep),in the sensethat zq 0. Determine
the boundstateenergy for
the delta-function
by treating it as the limit of a finite squarewell.Check
potential,
that your answer is consistent
with Equation2.129.
Alsoshow that Equation2.169
reducesto Equation2.141in the appropriatelimit.
\342\200\224>

Problem2.32 DeriveEquations2.167and 2.168.Hint:UseEquations2.165and

2.166to solveforC and D in terms of F:


C = sin(la)+

i-cos(la)eikaF\\
k

D = cos(la)
\342\200\224

i- sin(/tf)

eikaF.

Obtainthe transmission
coefficient,
PlugthesebackintoEquations2.163and 2.164.
and confirm Equation2.169.
* ^Problem2.33Determine
the transmission
coefficient
for a rectangularbarrier
(sameas Equation2.145,only with V(x) = +Vb > 0 in the region a < x < a).
Treat separatelythe three casesE < Vq, E = Vq, and E > Vq (notethat the
wave functioninsidethe barrieris different in the three cases).Partialanswer:For
E < V0,42
\342\200\224

the \"step\"potential:
^Problem2.34 Consider

...
.

(a)

0,

if jc <0.

V(X)=\\ V0. ifx>0.


the reflection
for the caseE <
Calculate
coefficient,

Vq,

and commenton

the answer.
(b)
(c)

the reflection
for the caseE > Vq.
Calculate
coefficient
For a potentialsuchas this,which doesnot go backto zeroto the right of
isnot simply|F|2/|A|2
coefficient
the barrier,the transmission
(with A the
4-This is a goodexampleof tunneling\342\200\224classically

the particle would bounce back.

Chapter2 Time-Independent
Schrodinger
Equation
nV(X)

-V0

FIGURE2.20: Scatteringfroma \"cliff\" (Problem


2.35).

becausethe transmitted
incidentamplitudeand F the transmittedamplitude),
wave travels at a different speed.Showthat

for E > Vq. Hint:You can figure it out usingEquation2.98,


the probability
current (Problem2.19).
elegantly, but lessinformatively\342\200\224from
What is T, for E < V01
the transmission
for the steppotential,
and
coefficient
(d) ForE > Vb, calculate
or\342\200\224more

checkthat T + R = 1.

an
Problem2.35A particleof massm and kineticenergy E > 0 approaches
abrupt potential
drop Vo (Figure2.20).
that it will \"reflect\"back,if E = V0/3?Hint:This
(a) What is the probability
isjustlikeProblem2.34,exceptthat the stepnow goesdown, insteadof up.
a cliff,but
(b) I drew the figure soas to make you think of a car approaching
back\"from the edgeof a cliffisfar
obviouslythe probabilityof \"bouncing
smallerthan what you got in
you'reBugsBunny.Explainwhy
thispotentialdoesnot correctlyrepresenta cliff.Hint:In Figure2.20the
to Vo, as it passes.t = 0;
energy of the cardropsdiscontinuously
potential
wouldthisbe true for a fallingcar?
a suddendropin
it experiences
(c) When a free neutron entersa nucleus,
electronvolts)
energy,from V = 0 outsideto around 12MeV (million
inside.Supposea neutron,emittedwith kineticenergy 4 MeV by a fission
event,strikessucha nucleus.What is the probabilityit will be absorbed,
anotherfission?Hint:You calculated
the probabilityof
thereby initiating
reflectionin part (a);use T = 1 R to get the probabilityof transmission
through the surface.
(a)\342\200\224unless

\342\200\224

\342\200\224

potential

\342\200\224

Further Problems
forChapter2

85

FURTHERPROBLEMSFORCHAPTER2
Problem2.36Solvethe time-independent
Schrodinger
equationwith
the
\"centered\"
for
infinite squarewell:V(x) = 0 (for
boundary conditions
< x < +a), V(x) = oo (otherwise).
Checkthat your allowedenergiesare
with mine (Equation
consistent
2.27),and confirmthat your \\f/'$ can be obtained
from mine (Equation2.28)by the substitution
x
(x + a)/2 (and appropriate
Sketch
three
and
solutions, compareFigure2.2.Note
renormalization). your first
that the width of the well is now 2a.
appropriate

\342\200\224a

\342\200\224>\342\226\240

Problem2.37A particlein the infinite squarewell (Equation2.19)has the initial


wave function

*(.*.0) = A sin3(7TA/fl)

(0 < .v < a).


Determine
A, find W(x. t), and calculate
(x), as a functionof time.What is the
6 can bereduced,
value of the energy?Hint:sin\"6 and cos\"
by repeated
expectation
of
the
sum
t
o
linear
combinations
of sin(w#)
application trigonometric formulas,
=
/?.
and cos(w0),with m 0.1.2,
.

...

*Problem2.38 A particleof massm isin the groundstateof the infinite squarewell


right
(Equation2.19).Suddenlythe well expandsto twice its original
wall movingfrom a to
the wave function(momentarily)undisturbed.
The energy of the particleis now measured.
(a) What is the mostprobableresult?What is the probabilityof gettingthat
size\342\200\224the

2a\342\200\224leaving

(b)
(c)

result?
What is the next mostprobableresult,and what is its probability?
What is the expectation
value of the energy?Hint:If you find yourself
confrontedwith an infinite series,try anothermethod.

Problem2.39
(a) Show that the wave functionof a

(b)

particlein the infinite squarewell returns


to its originalform after a quantum revivaltime T = Anur/nti.That is:
vl/(jr. T) = W(x. 0) for any state(notjust a stationary state).
What is the classical
revival time,for a particleof energy E bouncingback

(c)

For what energy are the two revival timesequal'?43

and forth betweenthe walls?

4- The fact
(and

the quantum

that the

classical
and

quantum

one doesn'teven depend on

Am.J.Phys.69,56(2001).

revival times bear no obvious relation to one another


the energy) is a curious paradox:seeDaniel Slyer.

86

Chapter2 Time-Independent
Schrodinger
Equation

Problem2.40 A particleof massm is in the potential


oo
(a- < 0),
-32/r/ma2 (0<x<a).
V(x) =
0
(a- > a).
\342\226\240

boundstatesare there?
boundstate,what is the probabilitythat the particle
(b) In the highest-energy
wouldbe foundoutsidethe well (x > a)?Answer:0.542,so even though it
is \"bound\"by the well, it is morelikelyto be found outsidethan inside!
(a) How many

Problem2.41A particleof mass m


(Equation2.43)startsout in the state
vI/(a,0)= AI I

in the harmonic

oscillatorpotential

_wm1.2
-2 uncoa-I <T^A
\\

/\342\200\224

for someconstantA.

is the expectation
value of the energy?
somelatertime T the wave functionis

(a) What
(b)

At

+2 /

,.2
e~^x
,
a)

(unco
1

\\

\"no

for someconstantB.What is the smallest


possiblevalue of Tl

Problem2.42 Findthe allowedenergiesof the half harmonicoscillator


vrU)~ I (1/2)w.<w2a-2,for x > 0,

for a <0.
J oo.
a springthat can be stretched,
but not compressed.)
for example,
(Thisrepresents,
Hint:This requiressomecareful thought,but very littleactual computation.
\342\200\224

* ^Problem2.43 InProblem2.22you analyzed the stationarygaussian


free particle
wave packet,
wave packet.Now solvethe sameproblemfor the traveling gaussian
starting with the initialwave function
vl/(A-,Q)

where /

is a real constant.

= A<rflA'V/v

Further Problems
for Chapter2

87

* *Problem2.44 Solve the time-independent


equationfor a centered
Schrodinger
infinite squarewell with a delta-function
barrier in the middle:
a8(x), for a < x <
,
for |jc|> a.
[ oo,

...

\342\200\224

+\302\253,

Don'tbotherto normalize
Treatthe even and oddwave functionsseparately.
them.
if necessary).
Findthe allowedenergies(graphically,
How do they comparewith
the corresponding
energiesin the absenceof the deltafunction?Explainwhy the
oddsolutions
are notaffectedby the deltafunction.
Commenton the limiting
cases
a 0 and a oo.
\342\200\224>

\342\200\224>

Problem2.45If two (or more) distinct44solutionsto the (time-independent)


Schrodinger
equationhave the sameenergy E, thesestatesare saidto be
the free particlestatesare doublydegenerate\342\200\224one solution
For example,
motionto the right,and the othermotionto the left.But we have never
representing
and thisis no accident.
encountered
Provethe
normalizable
solutions,
degenerate
In onedimension45
there areno degenerate
houndstates.Hint:
followingtheorem:
there are two solutions, and \\j/2, with the sameenergy E. Multiply the
Suppose
equationfor \\f/2 by \\f/\\,
Schrodinger
equationfor by i/^, and the Schrodinger
to show that {^/id^\\/dx \\f/\\d\\//2/dx) is a constant.
Use the fact
and subtract,
+
0 at oo to demonstrate
is
that for normalizable
solutions
that thisconstant
\\j/
of \\j/\\, and hencethat the two solutions
in fact zero.Conclude
that xj/i is a multiple
are not distinct.
degenerate.

\\j/\\

\\f/\\

\342\200\224

\342\200\224>

arounda circular
Problem2.46 Imaginea beadof massm that slidesfrictionlessly
L. (This is justlikea free particle,exceptthat \\j/(x +
wire ring of circumference
=
and the
L) t^(a')-) Find the stationary states(with appropriatenormalization)
Notethat there are two independent
solutions
for
allowedenergies.
corresponding
and counter-clockwise
eachenergy En\342\200\224corresponding to clockwise
circulation;
in view of
callthem tJ/*(x)and \\J/~(x).How do you accountfor thisdegeneracy,
the theoremin Problem2.45(why doesthe theoremfail,in thiscase)?

Thisis a strictlyqualitative
calculations
**Problem2.47Attention:
allowed!Considerthe \"doublesquarewell\"potential(Figure2.21).Supposethe
problem\342\200\224no

44If two solutions differ only by a multiplicative constant (so that, oncenormalized, they differ
only by a phasefactor e\"^).they representthe same physical slate,and in this sensethey are not distinct
solutions.Technically, by \"distinct\" I mean \"linearly independent.\"
45In higher dimensionssuch degeneracyis very common, as we shall seein Chapter 4.Assume
isolated
that the potential does not consistof isolatedpieces
separatedby regionswhere V =
infinite square wells, for instance, would give rise to degeneratebound stales, for which the particle is
either in the one or in the other.
co\342\200\224two

88

Chapter2 Time-Independent
Schrodinger
Equation
kV(x)

-vn

FIGURE2.21: The doublesquarewell (Problem


2.47).

depthVq and the width a are fixed,and largeenoughso that severalboundstates

occur.

Sketchthe groundstatewave function\\j/i and the first excitedstatet/t2,


(i) for the caseb = 0, (ii)for b % a, and (iii)for b ^> a.
how do the corresponding
(E\\ and Ei) vary, asb goes
(b) Qualitatively,
energies
from 0 to oo?SketchE\\(b) and Ejib)on the samegraph.
modelfor the potential
(c) The doublewell is a very primitive one-dimensional
in a diatomic
molecule
(the two wellsrepresent
by an electron
experienced
the attractive forceof the nuclei).If the nucleiare free to move,they will
in
of minimum energy.In view of your conclusions
adoptthe configuration
(b),doesthe electrontendto draw the nucleitogether,or pushthem apart?
but that'sa
to consider,
(Of course,there is alsothe internuclear
repulsion
(a)

separateproblem.)
Problem2.48 In Problem2.7(d)you got the expectation
value of the energy by
summing the seriesin Equation2.39,but 1warned you (in footnote15)notto try it
the \"oldfashionedway,\" (H) = f V(x.0)*HV(x.0)dx,
becausethe
first derivative of ty(x.0) renders
the secondderivative problematic.
Actually,
could
have
done
but
the
Dirac
it
delta
function
you
usingintegrationby parts,
affordsa much cleanerway to handlesuchanomalies.
the first derivative of ^(.v.O)(in Problem2.7),and expressthe
(a) Calculate
answer in terms of the stepfunction,9(x a/2),definedin Equation2.143.
the interiorregion0 < .v < a.)
(Don'tworry aboutthe end
to writethe secondderivativeof W (x,0)
(b) Exploitthe resultofProblem2.24(b)
in terms of the deltafunction.
and checkthat you get the
(c) Evaluate the integralf W(x.0)*HV(x,0)dx,
sameanswer asbefore.
discontinuous

\342\200\224

points\342\200\224just

Further Problems
for Chapter2

89

* * ^Problem2.49
(a) Show that

/ mco\\1/4

exp

mco

+
in fa+\302\243(,+,-*-)
2
m
\302\243*

- 2axe-il0t}

\\

the time-dependent
satisfies
Schrodinger
equationfor the harmonicoscillator
Here
a
is
with the dimensions
of
(Equation2.43).
potential
any real constant

length.46
the motionof the wave packet.
(b) Find \\^(x, t)\\2, and describe
theorem(Equation1.38)is
(c) Compute(x) and (p),and checkthat Ehrenfest's

satisfied.

the moving delta-function


well:
**Problem2.50Consider
V(x,t) = -aS(x-vt),
where v

is the (constant)
velocityof the well.

(a) Showthat the time-dependent


Schrodinger
equationadmitsthe exactsolution
vl/(x<

t)

\"^\"\"c-'\302\253o\\x-vr\\/H2c-i\\(E+(\\/2)mv2)t-mvx\\/h
h

=
Hint:Plugit
function.

is the bound-state
energy of the stationarydelta
in and checkit!Usethe resultof Problem2.24(b).
in thisstate,and comment
value of the Hamiltonian
on
Findthe expectation
the result.
where E

(b)

\342\200\224ma~/2tr

* * ^Problem2.51Consider
the potential
V(x)

=
m

secrr(fl.Y),

and \"sech\"standsfor the hyperbolic


is a positiveconstant,
secant.
Graphthispotential.
hasthe groundstate
Checkthat thispotential
\\j/q(x)= A sech(rtA').

where a
(a)
(b)

and find

its energy.Normalize\\J/-q, and sketchits graph.

46This rare exampleof an exactclosed-formsolution to the time-dependent Schrodingerequation


was discoveredby Schrodingerhimself, in 1926.

Schrodinger
Time-Independent
Equation
(c) Showthat the function

/ik atenh(ax)\\
fkti) = A I
ik+a JI eikx,
V
(where k = y/2niE/ti,as usual)solvesthe Schrodinger
equationfor any
as z
energy E. Sincetanhz
(positive)
fk(x) % Ae,kx. for largenegativex.
Thisrepresents,
then,a wave comingin from the left with no
wave (i.e.,no term
What is the asymptoticform
reflected
of fkix) at largepositivex? What are R and T, for thispotential?
of a reflectionless
Thisis a famous example
potential\342\200\224every incident
of its energy,passesright through.47<
particle,regardless
\342\200\224

,-;\342\200\242\"

-\302\273

\342\200\2241

-\302\273

\342\200\224oo,

exp(\342\200\224/Aw)).

accompanying

Comment:

in
Problem2.52The scatteringmatrix.The theory of scatteringgeneralizes
a pretty obviousway to arbitrary localized
potentials(Figure2.22).To the left
(RegionI), V(x) = 0, so
/2mF
[2.173]
fix) = Ae,kx + Be~iL\\ where k =
-\342\200\224-.

To the right (RegionIII), V(x) is again zero,so

f (a) = Feikx+ Ge~ikx.

[2.174]

In between(RegionII), of course,I can'ttellyou what f is until you specifythe


but because
the Schrodinger
differential
potential,
equationis a linear,second-order
hasgot to be of the form
the generalsolution
equation,

f(x) = Cfix)+ Dgix).


There
where /*(a') and g(x) are two linearly independent
particularsolutions.48
will be four boundary conditions
(two joiningRegionsI and II, and two joining
Vix)

Aeikx

Be-'kx

^/

peikx
\\

Ge~ikx

x
^

RegionI

RegionII

RegionIII

FIGURE2.22: Scatteringfrom an arbitrary localized


(Vix) = 0 exceptin
potential
Problem
2.52.
RegionII);
47R.E, Crandall and B.R. Lill.Annals of Physics.146.
458 (1983).
48Sceany bookon differential equations\342\200\224for example,J.L. Van Iwaarden.Ordinary Differential
Equationswith Numerical Techniques.Harcourl BraceJovanovich, San Diego,1985,
Chapter 3.

91

Further Problems
forChapter2

C and D, and the other


RegionsII and III).Twoof thesecan be usedto eliminate
for B and F in terms of A and G:
two can be \"solved\"
B =SUA + S\\2G. F = S2\\A + S22G.
The four coefficients
a 2x 2
S{j,which dependon k (and henceon E), constitute
matrix S, calledthe scatteringmatrix(or S-matrix,for short).The S-matrixtells
(B and F) in terms of the incoming
(A
you the outgoingamplitudes
amplitudes
and G):

B\\

fSu Sl2\\(A\\

from the left,G =


In the typicalcaseof scattering
transmission

are
coefficients

and
0, so the reflection

|F|2
I/\"!2

2
\\B\\2

G=0

For scattering
from the right,A
Rr

(a)

\\F\\2

lap 4=0

= |52iI2

[2.176]

=0,and
->

Id' A=0 =
\\B\\2

\\Sn\\2

[2.177]

Constructthe S-matrixfor scatteringfrom a delta-functionwell


(Equation

(b)

[2A75]

So

2.114)'.

Construct
the S-matrixforthe finite squarewell (Equation2.145).
Hint:This
requiresno new work, if you carefully exploitthe symmetry of the problem.

* * ^Problem2.53Thetransfermatrix.The S-matrix(Problem2.52)tellsyou the


(B and F) in terms of the incomingamplitudes
(A and
outgoingamplitudes
2.175.For somepurposesit is moreconvenientto work with the
G)\342\200\224Equation
to the right of the potential
transfermatrix,M, which givesyou the amplitudes
(F and G) in terms of thoseto the left (A and B):

(a)

(b)

\\Gj \\M2l
Find the four elementsof the Af-matrix, in terms of the elementsof the
S-matrix,and vice versa.Express/?/, 7/, /?,-,and 7)- (Equations2.176and
2.177)in terms of elementsof the M-matrix.
of two isolated
consisting
Suppose
you have a potential
pieces(Figure2.23).
is the productof the two
Show that the M-matrix for the combination
for eachsectionseparately:
M-matrices
M = M2Mi.
[2.179]
to any number of pieces,and accountsfor the
(Thisobviouslygeneralizes
usefulness
of the M-matrix.)

92

Chapter2 Time-Independent
Schrodinger
Equation

Mh

1/=0

/W.

1/=0

1/=0

FIGURE2.23: A potential
of two isolated
consisting
pieces(Problem2.53).
(c)

the M-matrix for scattering


Construct
from a singledelta-function
potential
at

pointa:

(.t)= -a8(x-a).
from the double
By the methodof part (b),find the M-matrix for scattering
deltafunction
V(x) = -a[8(x+ a) + 8(x a)].
What is the transmission
coefficientfor thispotential?
V

(d)

Problem2.54Findthe groundstateenergy of the harmonicoscillator,


to five
significant digits,
method.That is,solveEquation2.72
by the \"wag-the-dog\"
varying K until you get a wave function that goesto zeroat large In
Mathematica,
appropriateinput codewouldbe
-(x2- K)*u[x]== 0, u[0]== 1,
PIot[EvaIuate[u[x]/.NDSoIve[{u\"[x]
u'[0]== 0),u[x],{x,10\"8,
10),MaxSteps-> 10000]],
{x,a, b),
>
PlotRange {c,d}];
(Here(a,b) is the horizontal
range of the graph,and (c,d) is the vertical
=
start with a 0, b = 10,c =
d = 10.)We know that the correctsolutionis
=
K 1,soyou might start with a \"guess\"
of K = 0.9.Noticewhat the \"tail\" of the
wave functiondoes.Now try K = 1.1,
and notethat the tail flipsover.Somewhere
in betweenthosevalues liesthe correctsolution.
Zero in on it by bracketingK
tighterand tighter.As you do so,you may want to adjusta, b, c, and d, to zero
in on the cross-over
point.
numerically,

\302\243.

range\342\200\224

\342\200\22410,

Problem2.55Findthe first three excitedstateenergies(to five significantdigits)


for the harmonicoscillator,
For the first (and
by wagging the dog (Problem2.54).
==
==
0.
1.
third) excitedstateyou will needto set u[0]
\302\253'[0]

Problem2.56Findthe first four allowedenergies(to five significantdigits)for


the infinite squarewell,by wagging the dog.Hint:Refer toProblem2.54,making
Thistimethe condition
you are
appropriatechangesto the differentialequation.
lookingfor is u{\\) = 0.

CHAPTER 3

FORMALISM

3.1HILBERTSPACE
we have stumbledon a number of interesting
In the lasttwo chapters
of
properties
Someof theseare \"accidental\"
featuresof specific
simplequantum systems.
for example),
(the even spacingof energy levelsfor the harmonicoscillator,
and it wouldbe niceto provethem onceand
but othersseemto be moregeneral,
for instance,
for all (the uncertainty principle,
and the orthogonality
of stationary
states).The purposeof thischapteris to recastthe theory in a morepowerful form,
with that in mind.There is not much herethat is genuinelynew; the idea,rather,
is to make coherentsenseof what we have already discovered
in particularcases.
wavefunctions
and operators.
The
Quantumtheory isbasedon two constructs:
stateof a system is represented
are represented
by its wave function,observables
wave functionssatisfy the definingconditions
for
Mathematically,
by operators.
abstractvectors,and operatorsact on them as lineartransformations.
So the
is linearalgebra.1
natural languageof quantum mechanics
a form of linearalgebrawith which you are immediately
Butit isnot,I suspect,
to represent
a vector,\\a), by the
familiar.In an N-dimensional
spaceit is simplest
with respectto a specified
orthonormal
basis:
{a,,},
AMuple of its components,
potentials

|or>

-\302\273\342\200\242

a=

ai

[3.1]

W/
If you have never studiedlinear algebra, you should read the Appendix before continuing.

93

Formalism

The innerproduct,(a\\f$), of two vectors(generalizing


the dot productin three

is the complexnumber,
dimensions)
[3.2]
(ct\\P)= a\\b\\ + a$b24- - + a*NbN.
Lineartransformations,
to the specified
T,are represented
by matrices(with respect
basis),whichact onvectors(toproducenew vectors)
by the ordinary rulesof matrix
multiplication:
\342\200\242 \342\226\240

(t\\\\

ljB> = T\\a)

b = Ta =

tii

t\\2

\342\200\242\342\226\240\342\226\240

/22

t\\N\\

/fli\\

hN

cn

[3.3]

are (forthe mostpart)


But the \"vectors\"we encounter
in quantum mechanics

and they livein infinite-dimensional


functions,
spaces.Forthem the //-tuple/matrix
in the finitethat are well-behaved
notationis awkward, at best,and manipulations
dimensional
casecan be problematic.
(The underlying reasonis that whereas the
an integral\342\200\224may not
finitesum in Equation3.2always exists,an infinite
converge,in which casethe inner productdoesnotexist,and any argumentinvolving
inner products
is immediately
Soeven thoughmostof the terminology
and
suspect.)
notationshouldbe familiar,it pays to approachthissubjectwith caution.
The collection
of all functionsof .v constitutes
a vectorspace,but for our
purposesit is much too large.To representa possiblephysicalstate,the wave
function^ must be normalized:
\\V\\2dx = 1.
sum\342\200\224or

I
set allsquare-integrable
functions, specified
< oo.
f(x) such
f
constitutes
smaller)
3.1(a)).
space(see

The

of

on a

that

\\f(x)\\~dx

[3.4]

Mathematicians
Problem
callit Hilbertspace.3
In quantum mechanics,
then,
physicists
vector

a (much

callit Li(a.b)\\

interval,2

Wave

functionslive in Hilbertspace.

[3.5]

but we might as well keep things more


2For us.the limits (a and b) will almost always be
the
for
moment.
general
inner product space,and the collectionof square-^Technically,a Hilberlspaceis a complete
is
functions
one
of
a
Hilberl
integrable
only
example
every finite-dimensionalvector
space\342\200\224indeed,
a
Ihe
of
is
Hilberl
B
ut
since
is
arena
mechanics,it'swhat physicists
space trivially
Lj
space.
quantum
word
mean
when
\"Hilbert
Ihe
ihe
completehere means lhal any
generally
they say
way.
space.\"By
that
is alsoin the space:it has no
functions
Hilberl
a
of
in
lo
function
Cauchy sequence
spaceconverges
\"holes\" in
as
the
set
all
real
has
ihe
of
numbers
no
holes
contrast,
(by
jusl
spaceof all polynomials,
for example,like ihe set of all rational numbers, certainly doeshave holes in it). The completeness
of a spacehas nothing lo do wilh ihe completeness(same word, unfortunately)
of a set offunctions,
which is the properly lhal any oilier function can be expressed
as a linear combination of them.
\302\261oo.

il.

Section3.1:
HilbertSpace
We

95

definethe innerproductof two functions,f(x) and g(x),as follows:

(f\\g)= / f(x)*g(x)dx.

[3.6]

and g are bothsquare-integrable


(that is, if they are bothin Hilbertspace),
/
their inner
is
to exist
in
3.6
to

If

(the integral Equation converges


product guaranteed
Thisfollowsfrom the integralSchwarzinequality:5
a finite number).4

\\j f{xTg{x)dx\\<JJ,\\f{x)\\2dxj\\g{x)\\2dx.

[3.7]

cancheckforyourselfthat Equation3.6satisfies
allthe conditions
for an inner
Noticein particular
that
product(Problem3.1(b)).
[3-8]
<*l/>= (f\\8)*You

Moreover,the inner productof f(x) with itself,

(/1/)=/

\\ftx)\\2dx.

[3.9]

is real and non-negative;


it's zeroonly6when f(x) = 0.
if itsinnerproductwith itselfis 1;two
A functionis saidto be normalized
functionsare orthogonalif their inner productis 0; and a set of functions,
isorthonormalif they are normalizedand mutually orthogonal:
{/\342\200\236},

(fm\\f,,)=Sm\342\200\236.

[3.10]

Finally,a setof functionsis completeif any otherfunction(in Hilbertspace)can


be expressed
as a linearcombination
of them:
CO

f(x) = ^2cnf\342\200\236{x).

[3.11]

/7=1
4ln Chapter 2 we were obligedon occasionto work with functions that were not nqrmalizable.
Such functions lie outsideHilbert space,and wc are going to have to handle them with specialcare,as
you will seeshorlly.For the moment. 1 shall assumethat all Ihe functions we encounter are in Hilbert

space.
\342\200\242'For

a proof,

Section21.In

-a

seeF. Riesz and B.Sz.-Nagy.Functional Analysis (Unger,New York, 1955),

< (a|a)(/0|/3),is
space the Schwarz inequality, |(a|y3)|proof assumesthe existenceof the inner products,which is

finite dimensional vector

easy to prove (seeProblem A.5).But that


preciselywhat we are trying to estabiislihere.
6What about a function that is zero everywhere except at a few isolatedpoints? The integral
(Equation 3.9)would still vanish, even though the function itself does not. If this bothers you, you
should have been a math major. In physicssuch pathological functions do not occur,but in any case,in
Hilbert space two functions that have the same square integral are consideredequivalent. Technically,
vectors in Hilbert space represent equivalenceclassesof functions.

96

Chapter3 Formalism

If the functions (.v)}are orthonormal,


the coefficients
trick:
are given by Fourier's
{f\342\200\236

ctt

[3.12]

(f\342\200\236\\f).

as you can checkfor yourself.I anticipated


this terminology,of course,back
in Chapter2. (The stationary statesfor the infinite squarewell (Equation2.28)
constitute
a complete
orthonormalset on the interval (0.a);the stationary states
for the harmonicoscillator
set
orthonormal
(Equation2.67or 2.85)are a complete

on the interval

(\342\200\224oo.

oo).)

Problem3.1
set of allsquare-integrable
functionsis a vectorspace(refer
to SectionA.l for the definition).
Hint:The main problemis to show that
the sum of two square-integrable
functionsis itselfsquare-integrable.
Use
functionsa vectorspace?
Equation3.7.Is the setof allnonnalized
the conditions
for an inner
Show that the integralin Equation3.6satisfies
A.2).
product(Section

(a) Show that the

(b)

*Problem3.2
For what rangeof v is the functionf(x) = xv in Hilbertspace,on the
interval (0.1)?Assumev is real,but not necessarily
positive.
casev = 1/2,is f(x) in thisHilbertspace?What about
(b) For the specific
x/(.v)?How about(d/dx)f(x)1
(a)

3.2OBSERVABLES
3.2.1HermitianOperators
The expectation
value of an observable
<2(.\\\\ p) can be expressed
very neatly in

notation:7
inner-product

((2)= fv*QVdx = mQV).


Remember ihal Q is the operator constructed from Q by
Theseoperators arc linear,in the sensethat

the

replacement p

[3.13]
-\302\273\342\226\240

/3

s (ft/i)d/dx.

Q\\af{x)+ bg{x)]= aQf(x)+ bQg(x).


for

any

functions

(ScclionA.3) on

complexnumbers a and b.They constitute lineartransformations


space of all functions. However, they sometimescarry a function inside Hilbert

f and g and any


the

Section3.2:Observables 97
has got to be real,and so, a fortiori,is the
measurement
averageof many measurements:

of a
Now, the outcome

(Q)= {Q)*.

[3.14]

But the complex


the order(Equation3.8),so
conjugateof an inner productreverses

<*|6*>= <G*I*>.

[3-15]

this must hold true for any wave functionvj/. Thus operatorsrepresenting
have the very specialpropertythat
obsetvables
and

(f\\Qf) = (Qf\\f) for all/(.v).


We

callsuchoperators
hermitian.

Actually, mostbooksrequirean

[3.16]

ostensibly
strongercondition:

(f\\Qg)= (Qf\\z) for allfix) and all g(x).

[3.17]

But it turns out, in spiteof appearances,


that thisis perfectlyequivalentto my

definition(Equation3.16),as you will provein Problem3.3.So use whichever


you like.The essential
pointis that a hermitian operatorcan be appliedeitherto
the first memberof an inner productor to the second,with the sameresult,and

hermitian operators
becausetheir expectation
naturally arisein quantum mechanics
values are real:

Observables
are representedby hermitianoperators.

[3.18]

hermitian?
for example,
Well, let'scheckthis.Is the momentum operator,

tide =
/hdf\\* =
+
r~dX
-f*g
-do J_00[\"-f)
dx
J_oo
dx) gdx (pf\\g).

if\\pg)=

f\302\260\302\260

oo

C\302\260\302\260

\\

[3.19]

1 usedintegrationby parts,of course,and threw away the boundary term for the
usualreason:If f(x) and g(x)are squareintegrable,
they must go to zeroat ioo.8
space into a function outside it (seeProblem 3.2(b)).and
have to be restricted.

in this

casethe domain

of the operator may

1.

,s

this is not quite true. A.s 1 mention in Chapter


there exist pathological functions
Actually,
are square-integrablc but do not go to zero at infinity. However, such functions do not arise in
physics,and if you are worried about it we will simply restrict the domain of our operators to exclude
them. On finite intervals, though, you really do have to be more careful with the boundary terms,
and an operator that is hermitian on
oo) may not be hermitian on (0.co) or
n).If you're
well,
it's
safest
to
think
wave
functions
as
about
the
infinite
of
those
residingon the
wondering
square
be
infinite
to
outside
zero
(0.a).
just happen
that

(\342\200\224oo.

line\342\200\224they

(\342\200\224n,

Formalism

of i compensates
for the minus signpicked
Noticehow the complexconjugation
up from integration
by
operatord/dx (without the i) is not hermitian,
and it doesnot represent
a possible
observable.
parts\342\200\224the

*Problem3.3 Showthat if {h\\Qh) = (Qh\\h) for all functionsh (in Hilbertspace),


of
men (f\\Qg) = (Qf\\g)
all / and g (i-e-> tne two definitions
Hint:Firstlet h = f + g, and
3.16and
equivalent).
then leth = f + ig.
f\302\260r

\"hermitian\"\342\200\224Equations

3.17\342\200\224are

Problem3.4
ishermitian.
(a) Showthat the sum of two hermitian operators
(b)

and or is a complex
number.Underwhat condition
SupposeQ is hermitian,

(ona) is a Q hermitian?
hermitian?
(c) When is the productof two hermitian operators
(d) Showthat the position
operator(.v = x) and the hamiltonian
operator(H =
At

are hermitian.

Problem3.5 The hermitianconjugate(or adjoint)of an operatorQ is the


Qf suchthat
[3.20]
(f\\Qg)= (Q\\f\\g) (forall / and g).
operator

then,is equalto itshermitian conjugate:


(A hermitian operator,
Q=

Q'.)

i,and d/dx.

(a)

of ,v,
Findthe hermitian conjugates

(b)

the hermitian conjugate


of the harmonic oscillator
Construct
raisingoperator,
(Equation2.47).
Show that (<2^)f= R*Qf\302\253+

(c)

3.2.2DeterminateStates
Ordinarily,when you measurean observableQ on an ensembleof identically
preparedsystems,all in the samestate^, you do not get the sameresulteach
is the indeterminacy
of quantum mechanics.9
Question:Would it be
of Q iscertainto return
possibleto preparea statesuchthat eveiy measurement
the samevalue (callit q)l This would be, if you like,a determinatestate,for
the observableQ. (Actually, we already know oneexample:
Stationary statesare
statesof the Hamiltonian;
a measurement of the total energy,on a
determinate
time\342\200\224this

I'mtalking
and simply get

the

about competent measurements,of


wrong answer, but that's not the fault of

course\342\200\224it's

quantum

always possibleto make a mistake.

mechanics.

Section3.2:Observahles 99
\"allowed\"
particlein the stationary state%, is certainto yieldthe corresponding
energy
Well, the standard deviationof Q, in a determinate
state,wouldbe zero,which
\302\243\342\200\236.)

is to say,
o1=

~ q)V\\{Q~ <?)*> = 0. [3.21]


(Ofcourse,if every measurement
givesq, theiraverage is alsoq: (Q) = q. I also
usedthe fact that Q, and hencealsoQ q, is a hermitian operator,
to move one
factoroverto the first term in the innerproduct.)
But the only functionwhoseinner
productwith itselfvanishesis 0, so
(\302\2532

(<2\302\2732>

(*|(G

<?)2*>=

(\302\2532

\342\200\224

[3.22]

QV=qV.

Thisis the eigenvalue


of Q,
equationfor the operatorQ;^ is an eigenfunction
and q is the corresponding
Thus
eigenvalue.
of Q.
Determinate
statesare eigenfunctions

[3.23]

Measurement
of Q on sucha stateis certainto yieldthe eigenvalue,
q.
that
the
an
Note
You can
eigenvalueis a number (not operatoror a function).

with the
and it is stillan eigenfunction,
eigenfunction
by a constant,
sameeigenvalue.
Zerodoesnot countas an eigenfunction
(we excludeit by definition\342\200\224otherwise every number wouldbe an eigenvalue,
sinceQ 0 = q 0 = 0 for
Q and allq). But there'snothingwrong with zeroas an eigenvalue.
any operator
The collection
of an operatoris calleditsspectrum.
of allthe eigenvalues
two (ormore)linearly independent
sharethe sameeigenvalue;
eigenfunctions
is saidto be degenerate.
in that casethe spectrum
For example,
statesof the totalenergy are eigenfunctions
determinate
of the
Hamiltonian:
[3.24]
Hf = Eir.

multiply any

At

Sometimes

which is precisely
the time-independent
In thiscontextwe
Schrodinger
equation.
usethe letterE for the eigenvalue,
and the lowercase for the eigenfunction
(tack
on the factorexp(\342\200\224iEt/h) to make it 4>, if you like;it's stillan eigenfunction
\\j/

of//).

the operator
Example3.1 Consider

Q= i

d
\342\200\224

<

dq>

[3.25]

where 0 is the usual polarcoordinate


in two dimensions.
(Thisoperator
might arise
in a physicalcontextif we were studying the bead-on-a-ring;
seeProblem2.46.)
Is Q hermitian?
Findits eigenfunctions
and eigenvalues.

100

Chapter3 Formalism

Solution:Herewe are working with functions/(0.)on the finiteinterval 0 < 0 <


2tt, and stipulatethat

/(0 + 2tt) = /(0).

[3.26]

since0 and 0 + 2tt describethe samephysicalpoint.Usingintegrationby parts,

soQ ishermitian(thistimethe boundaryterm disappears


by virtue ofEquation3.26).
The eigenvalue
equation,

i-^-fW)=

\302\242/(0)-

[3-27]

d<$>

hasthe generalsolution

/(0)= Ac-'**.

[3.28]

Equation3.26restrictsthe possiblevalues of the q:

e-ic,2n= ,

9 = 0, +1.\302\2612,...

[3.29]

The spectrumof thisoperator


is the setof all integers,and it is nondegenerate.

Problem3.6 Considerthe operatorQ = d2/d02,where (as in Example3.1)


and the functionsare subjectto
0 is the azimuthal angle in polarcoordinates,
and eigenvalues.
Findits eigenfunctions
What is
Equation3.26.Is Q hermitian?
the spectrum
of <2? Is the spectrumdegenerate?

3.3EIGENFUNCTIONSOF A HERMITIANOPERATOR
Our attentionis thus directedto the eigenfunctions
of hermitian operators

determinate
Thesefall intotwo categories:
If the
statesof observables).
are separated
from oneanother)then the
spectrumisdiscrete(i.e.,the eigenvalues
lie in Hilbertspaceand they constitute
states.
eigenfunctions
physicallyrealizable
If the spectrumis continuous(i.e.,the eigenvalues
fill out an entirerange)then
the eigenfunctions
are not normalizable,
and they do not represent
possiblewave
of them\342\200\224involving necessarily
a spread
functions(thoughlinearcombinations
in eigenvalues\342\200\224may be normalizable).
have a discretespectrum
Someoperators
the Hamiltonian
for the harmonicoscillator),
somehave only a
only (forexample,
the free particleHamiltonian),
and somehave
continuous
spectrum(forexample,
for a
the Hamiltonian
both a discretepart and a continuous
part (for example,
(physically:

Section3.3:Eigenfunctions
ofa HermitianOperator

101

caseiseasierto handle,becausethe relevant inner


finite squarewell).The discrete
are guaranteed
to exist\342\200\224in fact,it is very similarto the finite-dimensional
products
of a hermitian matrix).I'lltreat the discretecasefirst, and
theory (the eigenvectors
then the continuous
one.

3.3.1DiscreteSpectra
of a hermitian operatorhave two
the normalizable
eigenfunctions
Mathematically,
important properties:

1:

are real.
Theorem Their eigenvalues
Proof:Suppose
Qf = qf*

of Q,with eigenvalueq),and10
(i.e.,fix) is an eigenfunction
(/1(2/)= ((2/1/)
Then
(<2 is hermitian).

ci(f\\f)=cj*(f\\f)
iq isa number,so it comesoutsidethe integral,and becausethe first function
in the inner productis complex
conjugated
(Equation3.6),sotoois the q on

the right).But (/1/)cannotbe zero(/(.y)= 0 is not a legaleigenfunction),


so q = q*,and henceq isreal. QED

If you measurean observableon a particlein a determinate


Thisis comforting:
state,you will at leastget a real number.
to distincteigenvalues
are
Theorem2: Eigenfunctions
belonging
orthogonal.

Proof:Suppose

Qf = clf

and

Then (f\\Qg)=
and Q ishermitian.

Qg = q'g,

(Qf\\g),so

q'{f\\g)=q*{f\\g)
are in Hilbert
(again,the inner productsexistbecausethe eigenfunctions
But q is real (from Theorem1),so if q' ^ q it must
spaceby assumption).
be that (f\\g) = 0. QED
,()U is here ihai we
might

not

exist at all.

assumeihe eigenfunctions arc in Hilbert space\342\200\224otherwise

the

inner product

102

Chapter3 Formalism

That'swhy the stationary statesof the infinite squarewell, for example,or the
harmonicoscillator,
are orthogonal\342\200\224they are eigenfunctions
of the Hamiltonian
with distinct
But thispropertyis not peculiarto them,or even to the
eigenvalues.
Hamiltonian\342\200\224the sameholdsfordeterminate
statesof any observable.
Theorem2 tellsus nothingaboutdegenerate
states(q' = q).
Unfortunately,
sharethe sameeigenvalue,
However,if two (or more)eigenfunctions
any
combination
of them is itselfan eigenfunction,
with the sameeigenvalue
and we can use the Gram-Schmidt
(Problem3.7(a)),
orthogonalization
to
construct
witliin eachdegenerate
(ProblemA.4)
orthogonal
eigenfunctions
It isalmostnever necessary
to do thisexplicitly
but it can
(thank God!),
subspace.
Soeven in the presenceofdegeneracythe
always be donein principle.
can be chosento be orthogonal,
and in settingup the formalism
of quantum
mechanics
we shallassumethat this has already beendone.That licenses
the use
of the basisfunctions.
of Fourier'strick,which dependson the orthonormality
In a yjm'te-dimensional
vectorspacethe eigenvectors
of a hermitian matrix
have a third fundamental property:They span the space(every vectorcan be
of them).Unfortunately, the proof doesnot
expressedas a linearcombination
to the
to infinite-dimensional
generalize
spaces.But the propertyitselfis essential
we will take it
internal consistency
of quantum mechanics,
so (followingDirac11)
as an axiom (or,moreprecisely,
on the classof hermitian operators
asa restriction
that can represent
observables):
linear

procedure

eigenfunctions

of an observableoperatorare complete:
Axiom: The eigenfunctions
Any
of
function(in Hilbertspace)can be expressedas a linearcombination
them.12

Problem3.7
At

(a)

(b)

of an operatorQ, with
Supposethat f{x) and g(x) are two eigenfunctions
the sameeigenvalue
of / and g isitself
q. Showthat any linearcombination
an eigenfunction
of Q, with eigenvalueq.
Checkthat f(x) = exp(.v)and g(x) =
are eigenfunctions
of the
Construct
two linear
operatord2/dx2,with the sameeigenvalue.
on the interval
of / and g that are orthogonal
1).
eigenfunctions
exp(\342\200\224a)

combinations

(\342\200\2241.

P. A. M. Dirac. 77k' Principle!;


of Quantum Mechanics.Oxford University Press,New York

(1958).
'-In some specificcasescompletenessis provable (wc know

that the stationary states of the


square well, for example,arc complete,because of Dirichlefs theorem). It is a little
lo call something an \"axiom\" that is provable in somecases,but 1 don't know a better way to
handle it.
infinite
awkward

Section3.3:Eigenfunctions
ofa HermitianOperator

103

Problem3.8
in Example3.1are real.
Checkthat the eigenvalues
of the hermitian operator
are orthogonal.
Showthat the eigenfunctions
(fordistincteigenvalues)
in Problem
3.6.
(b) Do the samefor the operator
(a)

3.3.2ContinuousSpectra
If the spectrumof a hermitian operatoris continuous,
are not
the eigenfunctions
and the proofsof Theorems
1 and 2 fail,becausethe inner products
normalizable,
there is a sensein which the three essential
may not exist.Nevertheless,
properties
and
I
stillhold.
think
it's
best
to
(reality,orthogonality, completeness)
approach

thissubtlecasethrough specificexamples.

of the momentumoperator.
and eigenvalues
Example3.2 Findthe eigenfunctions
Solution:Let fp{x)be the eigenfunction
and p the eigenvalue:

= pfP(x).
T-^-fP(.x)
i ax

[3.30]

The generalsolution
is

fp{x)= Ae*x>h.
Thisis not square-integrable,
value of
for any (complex)
momentum
in Hilbertspace.And yet, if we restrictourselves
to
hasno eigenfunctions
real eigenvalues,
we do recovera kindof ersatz\"oithononnality.\"
Referring to
Problems
2.24(a)and 2.26,
p\342\200\224the

operator

/\302\2730O

fp(x)fp(x)dx=
/OO
-OO

\\A\\2

\342\200\224

eHP-Wdx = \\A\\227rh8(p p'). [3.31]


OO

If we pickA = X/^/lnh,so that

fp(x) = -jL=eipxlK

[3.32]

(fp'\\fP)=&(p-p').

[3-33]

then
which is strikinglyreminiscent
of true orthonormality
(Equation3.10)\342\200\224the indices
are now continuous
and the Kronecker
deltahas becomea Diracdelta,
variables,
but otherwise
it looks
justthe same.I'll callEquation3.33Diracorthonormality.

Formalism

Mostimportant,
the eigenfunctions
are complete,
with thesum (in Equation3.11)
functionf{x) can be written in
replacedby an integral:Any (square-integrable)

the form

poo
-==
dp.
/ c{p)eiPx'h
\\JlMn J-oo
1

c{p)fp{x)dp =
/OC
-oo

[3.34]

Theexpansion
coefficient
asalways, by Fourier's
(now afunction,
c(p))isobtained,

trick:

/\302\2730O

= / c(p)8(p p')dp= c(p'). [3.35]


c(p)(fP'\\fp)dp
/OC
-oo
J-oc
for
theorem(Equation2.102),
Alternatively, you can get them from Plancherel's
the expansion
(Equation3.34)is nothingbut a Fouriertransform.
The eigenfunctions
of momentum (Equation3.32)are sinusoidal,
with
wavelength

^.
P

[3.36]

Thisis the oldde Broglieformula (Equation1.39),which I promised


to proveat
the appropriate
time.It turns outtobe a littlemoresubtlethan de Broglieimagined,
becausewe now know that there is actually no suchthing as a particlewith
wave packetwith a narrow
determinate momentum.
But we couldmake a normalizable
rangeof momenta,and it is to suchan objectthat the de Broglierelationapplies.
What are we to make of Example3.2?Although noneof the eigenfunctions
of p livesin Hilbertspace,a certainfamily of them (thosewith real eigenvalues)
with a kind of quasi-normalizability.
residein the nearby \"suburbs,\"
They do not
represent
possiblephysicalstates,but they are stillvery useful(aswe have already
seen,in our study of one-dimensional
scattering).13
and eigenvalues
of the positionoperator.
Example3.3 Findthe eigenfunctions
Solution:Let gy{x)be the eigenfunction
and y the eigenvalue:
[3.37]
xgy(x)= ygy(x).
notire&l
eigenvalues?These are not merely nonFunctions in what 1 calledthe \"suburbs\" of Hilbert space
see.for example,Leslie
(the entire metropolitan area is sometimescalled a \"rigged Hilbert space\":
Ballentine'sQuantum Mechanics:A Modern Development, World Scientific, 1998)have the property
that although
they have no (finite) inner product with themselves, they do admit inner products with all
This is not true for eigenfunctionsof p with nonreal eigenvalues.In
members of Hilbert space.
I showedthat the momentum operator is hermitian forfunctions in Hilbertspace,but the argument
That term is still zero if g is an
dependedon dropping the boundary term (in Equation 3.19).
of p with a real eigenvalue (as long as is in Hilbert space),but not if the eigenvalue has an
part. In this senseany complexnumber is an eigenvalue of the operator p, but only realnumbers
are eigenvalues of the hermitian operator
others lie outsidethe spaceover which p is hermitian.

13What

about the eigenfunctions


actually blow up at

normalizable\342\200\224they

with

\302\261oo.

particular.

eigenfunction

imaginary

/3\342\200\224the

Section33:Eigenfunctions
ofa HermitianOperator

105

Here y is a fixed number (for any given eigenfunction),


but x is a continuous
variable.What functionof ,v hasthe property that multiplying it by x is the same
asmultiplyingit by the constanty? Obviouslyit'sgotto be zero,exceptat the one
pointx = y; in fact, it is nothingbut the Diracdeltafunction:
gy(x)= A8(x -y).

Thistime the eigenvalue


hastobereal;the eigenfunctions
are notsquare-integrable,
but again they admit Diracorthonormality:

- y'). [3.38]

gy(x)= 8(x-y).

[3.39]

= &(y-y')-

[3-40]

/\302\27300

gp(x)gy(x)dx=

/00
-co

\\A\\2

\"

/ 8{x y')8(x y)dx = \\A\\28(y


J\342\200\224oo

If we pickA = 1,so
then

{gy>\\gy)

Theseeigenfunctions
are alsocomplete:

/(

/\302\273oo
/\302\273oo
/\342\226\240no

c(y)g,(x)dy=
/no
-co

c{y)8(x-y)dy,

[3.41]

\302\253/\342\200\224oo

with

c{y)= /(>')

[3.42]

(trivial,in this case,but you can get it from Fourier'strick if you insist).
If the spectrumof a hermitian operatoriscontinuous
are
(sothe eigenvalues
labeledby a continuous
or y. in the examples;
in what
z, generically,
are notnormalizable,
follows),the eigenfunctions
they are not in Hilbertspaceand
the eigenfunctions
with
they donotrepresent
possiblephysicalstates;nevertheless,
variable\342\200\224p

are Diracorthonormalizable
real eigenvalues
and complete
(with the sum now an
Luckily,thisis all we really require.
integral).

Problem3.9
(a)
(b)

Citea Hamiltonian
from Chapter2 (otherthan the harmonic oscillator)
that
has only a discretespectrum.
Citea Hamiltonian
from Chapter2 {otherthan the free particle)
that has only
a continuous
spectrum.

106

Chapter3 Formalism
(c)

Citea Hamiltonianfrom Chapter2 (otherthan the finite squarewell) that


hasbotha discreteand a continuous
part to its spectrum.

Problem3.10Is the groundstateof the infinite squarewell an eigenfunction


of
momentum? If so,what is itsmomentum? If not,why not?

3.4 GENERALIZEDSTATISTICAL
INTERPRETATION
wouldbe
In Chapter1I showedyou how to calculate
the probability
that a particle
found in a particularlocation,
and how to determine
the expectation
value of any
observablequantity. In Chapter2 you learnedhow to find the possibleoutcomes
of an energy measurementand their probabilities.
I am now in a positionto state
all of thisand enables
the generalized
statistical
which subsumes
interpretation,
and their probabilities.
resultsof any measurement,
you to figure out the possible
Togetherwith the Schrodinger
equation(which tellsyou how the wave function
evolvesin time)it is the foundationof quantum mechanics.
an observable
Generalized
If you measure
statistical
Q(x,p)
interpretation:
on a particlein the stateW(x, f), you are certainto get oneofthe eigenvalues
of
the hermitian operatorQ{x.
If the spectrumof Q is discrete,
the
of gettingthe particulareigenvalueqn associated
with the orthonormalized
\342\200\224ihcl/dx).

probability

eigenfunction

f\342\200\236(x)

is

|c\342\200\236|2.

where

c\342\200\236

[3.43]

(f\342\200\236\\V).

If the spectrumis continuous,


with real eigenvalues
Diracq{z)and associated
orthonormalized
fz(x), the probabilityof gettinga resultin the
eigenfunctions
range dz is
\\c(z)\\2dz where

c(z)=

(/s|*).

[3.44]

to the corresponding
the wave function\"collapses\"
Uponmeasurement,
eigen-

state.14
The statistical
is radicallydifferentfrom anything we encounter
interpretation
in classical
physics.A somewhat different perspective
helpsto make it plausible:
The eigenfunctions
of an observable
so the wave function
operatorare complete,
can be written as a linearcombination
of them:

V{x,t)= J2c'iMx)-

[3-45]

In the

dependingon

caseof continuous speciraihe collapseis lo a narrow


the

precisionof the measuring device.

range aboul the measured value,

Section3.4:Generalized
Statistical
Interpretation 107

I'll assumethat the spectrumis discrete;it'seasy to generalize


this
(Forsimplicity,
the eigenfunctions
are orthonormal,
the
case.)Because
argument to the continuous

coefficients
are given by Fourier'strick:15
-\302\273

= (/i.l*>=

[3.46]

f\342\200\2360c)*nx,t)dx.

in vj>,\" and giventhat a


Qualitatively, tellsyou \"how much is contained
hasto retum oneof the eigenvalues
of Q, it seemsreasonable
that
measurement
the probability
the
of getting particulareigenvalue wouldbe determined
by the
in ^. But becauseprobabilities
\"amountof
are determinedby the absolute
That'sthe
squareof the wave function,the precisemeasureis actually
essentialburdenof the generalized
statistical
interpretation.16
Of course,the totalprobability(summedoverallpossibleoutcomes)
hasgot
to be one:
c\342\200\236

/\342\200\236

q\342\200\236

/\342\200\236\"

|c\342\200\236|2.

\302\243k\342\200\236l2

l.

[3.47]

and sureenough,
thisfollowsfrom the normalization
of the wave function:

= J2
c*,,c\"8\"'\"
J2
Jl
n'

c'*c\302\253=

\"

Jl

[3.48]

ic\302\273|2-

value of Q shouldbe the sum overall possible


outcomes
Similarly,the expectation
of the eigenvaluetimesthe probabilityof gettingthat eigenvalue:
<<2)=

[3.49]

E>\"U2-

Indeed,
(Q) =
l5Noticethai
to make

this

the

mQ^) = l\\Tcn'f,A Qj2c\"f\"

lime

dependence\342\200\224which

we should really wrile


explicit,

is

not

al issue

here\342\200\224is

[3.50]

carried by ihe coefficients;

c\342\200\236(.t).

l6Again, I am scrupulously avoiding the all-loo-common assertion \"\\cn\\2 is ihe probabilily lhal
The particle is in the stale
This is nonsense.
period.Rather, \\cn is
particle is in the stale
the probabilily that a measurement of Q would yield the value qn. It is true that such a measurement
ihe stale lo the eigenfunclion
so one could corrcclly say \"|c-;;l** is ihe probabilily that
will collapse
a particle which is now in the stale u'/7/ be in the stale
subsequentlo a measurement of Q\"
but that's a completely different assertion.
the

*,

f\342\200\236.\"

/\342\200\236,

J'\342\200\236

|2

...

108

Chapter3 Formalism
but

Qf\342\200\236

so

=q\342\200\236f\342\200\236,

(Q)=

^2^2c*,cHq\342\200\236(fn'\\f\342\200\236)

^2^2c*,cHq\342\200\2368\342\200\236'\342\200\236

= J^<?/i|cw|2. [3.51]

So far, at least,everything looksconsistent.


Can we reproduce,
in thislanguage,the originalstatistical
for
interpretation
real overkill,but worth checking.
A
positionmeasurements?
of x on a particlein state^ must return one of the eigenvalues
of the
Well, in Example3.3we found that every (real)number y is an
positionoperator.
is
(Dirac-orthonormalized)
eigenvalueof a\\ and the corresponding
eigenfunction
gy(x)= 5 (a- y). Evidently
Sure\342\200\224it's

measurement

\342\200\224

*(jr-y)*(jr.r)djr
/oo
-oo

[3.52]

\302\245(y.O,

so the probabilityof gettinga resultin the range dy is \\W(y, t)\\2dy, which is


the original
statistical
precisely
interpretation.
In
of
What aboutmomentum? Example3.2we foundthat the eigenfunctions
the momentum operatorare fp(x) = (l/*l/27rh~)exp{ipx/fi),
so

c(p)= (fpm =

1
-==
/

f\302\260\302\260

e-\"}X/h*(x.t)dx.

[3.53]

Thisis suchan important quantity that we give it a specialname and symbol:the


the Fouriertransform
momentumspacewave function, r). It is essentially
of the (positionspace)wave function*(x,f)\342\200\224which, by Plancherel's
theorem,
is its inverseFouriertransform:
<\302\243(/?,

*(p,0= -i=/
v!/(a\\t)

e-^WVix.Odx;

t)dp.
/ e'px/n<$>{p,
V2tt/7 7-00

\342\200\224==

[3.54]

[3.55]

the probabilitythat a
statistical
Accordingto the generalized
interpretation,
measurement of momentum wouldyielda resultin the range dp is

Mp,t)\\2dp.

[3.56]

particleof massm is boundin the deltafunctionwell V(x) =


that a measurementof its momentum wouldyield
What is the probability
a value greaterthan po = ma,/hi

Example3.4
\342\200\224cc8(x).

Section3.4:Generalized
Statistical
Interpretation 109

Solution:The (position
space)wave functionis (Equation2.129)
n

(where E =

\342\200\224ma2/2fi2).

The momentum spacewave functionis therefore

1 Vma^-iEt/h

4>0>,r)=

e-iPx/ne-ma\\x\\/n2
dx =
J-z
-co
f\302\260\302\260

y-* H ~e+

'E\"

P2 Pq

The probability,
then,is
(I lookedup the integral).

. = -i

3 I*00

(pl+ ps>

oo

+ tan-l

PPO

\\P0/
p2 + pI
1 \"
_ 1 = 0.0908
4 2Jr

\342\200\224i^dp

A\302\2730

(again,I lookedup the integral).


wave function,
in
Findthe momentum-space
Problem3.11
f), for a particle
the groundstateof the harmonic oscillator.
What is the probability
(to2 significant
of p on a particlein thisstatewould yield a value
digits)that a measurement
outsidethe classical
range (for the sameenergy)?Hint:Look in a math table
under \"NormalDistribution\"
or \"ErrorFunction\"for the numerical
use
<\302\243(/?,

part\342\200\224or

Mathematica.

Problem3.12Showthat
n

(x) =

I<S>*(-^iz\\<S>dp.
^P,

[3.57]

Hint:Noticethat x exp(ipx/h)= \342\200\224ifr(d/dp)exp(ipx/Ii).


In momentum space,then,the positionoperatoris i lid/dp.Moregenerally,

/**fiRs)*'x'
(Q(x.p))=

in

positionspace;

\342\200\242

I/ 0(2

9
i dp

\342\200\224-r-,

[3.58]

in momentum space.
pl^dp,
)

in momentum spacejust as well (though


principleyou can do allcalculations
not always as easily)asin positionspace.
In

110

Chapter3 Formalism

3.5THE UNCERTAINTYPRINCIPLE
I statedthe uncertainty principle(in the form oxop > h/2), backin Section1.6,

and you have checked


But we have never actually
it several
times,in the problems.
provedit. In thissectionI will provea moregeneralversionof the uncertainty
The argument is beautiful,but
principle,and exploresomeof its implications.
rather abstract,
so watch closely.

3.5.1
Proofof theGeneralized
UncertaintyPrinciple
For any observableA, we have (Equation3.21):
a\\
where

/ = (A

\342\200\224

((A

(A))*\\(A

- (A)m = (/|/>,

B,
(A))^.Likewise,for any otherobservable,
<7B

where 8 =

(g\\g)'

& WW-

Therefore(invokingthe Schwarz inequality,Equation3.7),


\302\26014

Now, for any

= (f\\f)(g\\g) > \\(f\\g)\\2-

[3-59]

complexnumber z,

= [Re(z)]2
=
> [Im(z)]2
+ [Im(z)]2
\\z\\2
2i
Therefore,lettingz = (f\\g),
o\\a\\ >

n2

[3.60]

.
(J;[(f\\g) (g\\f)]j

[3.61]

But
(f\\g)

= ((A (A))V\\(B (B)m= (vl/|(A (A))(B


= {V\\(AB A(B) B(A)+ (A)(B)m
= (V\\ABV) (B)(V\\AV) (A)(V\\BV) + {A){B)-(V\\V)
= (AB)-(B)(A)-(A)(B)
+ (A)(B)
= (AB)-(A)(B).

Similarly,
(g\\f)

= (BA)-(A)(B),

<*))\302\245)

Section3.5:The UncertaintyPrinciple

so
a a
</!*)\" (g\\f) = (AB)

where

[A.fl] = Afl

a a

(BA)

111

= {[A,B])t

- SA

is the commutatorof the two operators


(Equation2.48).Conclusion:
1

(:
<rlcri>[-([lB])J

[3.62]

Thisis the (generalized)


uncertaintyprinciple.You might think the i makesit
the right sidenegative'?No, for the commutator
of two hermitian
carriesitsown factorof i, and the two cancelout.17
operators
As an example,
supposethe first observableis position(A = x), and the
secondis momentum (B = (h/i)d/dx).We worked out theircommutator
backin
trivial\342\200\224isn't

Chapter2 (Equation2.51):

[x.p] = ih.
So
=

>
\302\260l*\\

(\302\261itl)

g)

or,sincestandarddeviationsare by their nature positive,


VxOp >

-.

[3.63]

That'sthe originalHeisenberg
but we now seethat it isjust
uncertainty principle,
of a much moregeneraltheorem.
oneapplication
Thereis,in fact,an \"uncertaintyprinciple\"
for everypairofobservables
whose
donotcommute\342\200\224we callthem incompatible
observables.
operators
Incompatible
donot have sharedeigenfunctions\342\200\224at least,they cannothave a
observables
set of commoneigenfunctions
(seeProblem3.15).By contrast,compatible
observables
do admit complete
setsof simultaneous
(commuting)
eigenfunctions.18

complete

l7Moreprecisely,the commutatorof two hermitian operatorsis itself anti-hermitian (Q*=


is imaginary (Problem 3.26).
l8This correspondsto the fact that noncommuting matrices cannot be simultaneouslydiagonalized
(that is, they cannot both be brought to diagonal form by the same similarity transformation), whereas
commuting hermitian matrices can be simultaneously diagonalized.SeeSectionA.5.
\342\200\224Q),

and its expectation value

Chapter3 Formalism
For example,in the hydrogenatom (as we shallsee in Chapter4) the Hamiltoof angular
nian, the magnitudeof the angular momentum, and the z component

momentumare mutually compatible


and we will construct
observables,
But there is
of all three,labeledby theirrespective
eigenfunctions
eigenvalues.
no eigenfunction
of positionthat isalsoan eigcnfunction
of momentum, because
theseoperators
are in compatible.
in quantum
Note that the uncertainty principleis not an extra assumption
of the statistical
You might wonder
theory, but rather a consequence
interpretation.
how it is enforcedin the laboratory\342\200\224why
can't you determine
(say) both the
positionand the momentum of a particle?You can certainly measurethe position
of the particle,but the actof measurement
the wave functionto a narrow
collapses
carriesa broadrange of wavelengths (hencemomenta)
spike,which necessarily
in its Fourierdecomposition.
If you now measurethe momentum, the statewill
wave, with (now) a well-defined
collapseto a long sinusoidal
wavelength\342\200\224but
the particleno longerhas the positionyou got in the first measurement.19
The
problem,then, is that the secondmeasurement rendersthe outcomeof the first
measurementobsolete.
an eigenstate
Only if the wave functionwere simultaneously
of bothobservables
wouldit be possible
to make the secondmeasurementwithout
disturbingthe stateof the particle(the secondcollapsewouldn'tchangeanything,
in that case).But thisis only possible,in general,if the two observables
are
simultaneous

compatible.
*Problem3.13
(a)

Provethe followingcommutator
identity:
[AB, C]=

(b) Showthat

A[B.C]+ [A.C]B.

[3.64]

[x\".p]= ihtvcn-1.

(c) Show moregenerallythat

[f(x),p]=01^-,
ax

[3.65]

for any functionf(x).

IJNiels Bohr was at pains to track down the mechanism by which the measurement of .v (for
instance) destroysthe previously existingvalue of p.The crux of the mailer is lhal in orderto determine
the position of a particle you have to poke it with something\342\200\224shine
light on it. say. Bui these photons
a
to
the
You
know
the position,but you no longer
now
imparl
particle momentum you cannot control.
know ihe momentum. His famous debates with Einstein include many delightful
examples,showing
in detail how experimental constraints enforce the uncertainly
principle.For an inspiredaccount see
Bohr'sarticle in Albert Einstein:Philosopher-Scientist,edited by P. A. Schilpp,Tudor, New York

(1949).

Section3.5:The UncertaintyPrinciple

113

*Problem3.14Provethe famous\"(your name) uncertainty principle,\"


relatingthe
(A = x) to the uncertainty in energy (B = p2/2m+ V):
uncertainty in position
h

oxoh >\342\200\224\\(p)l
2/77
For stationary statesthisdoesn'ttellyou

much\342\200\224why

not?

Problem3.15Showthat two noncommuting


cannothave a complete
set
operators
Hint:Show that if P and Q have a completeset of
of commoneigenfunctions.
then [P.Q]f = 0 for any functionin Hilbertspace.
commoneigenfunctions,
At

At

At

At

3.5.2TheMinimum-Uncertainty
Wave Packet
have twice encountered
wave functionsthat hit the position-momentum
uncertainty limit {axap = Ii/2):the groundstate of the harmonicoscillator
(Problem2.11)and the Gaussianwave packetfor the free particle(Problem2.22).
What is the mostgeneralminimum-uncertainty
Thisraisesan interesting
question:
wave packet?Lookingbackat the proofof the uncertainty principle,
we notethat
there were two pointsat which in equalities
cameintothe argument: Equation3.59
we requirethat eachof thesebe an equality,and see
and Equation3.60.Suppose
We

what

thistellsus about*I>.

The Schwarz inequalitybecomes


an equality when onefunctionis a

of the other:g(x) = c/(.v),for somecomplexnumber c (seeProblemA.5).


Meanwhile,in Equation3.60I threw away the real part of z\\ equality resultsif
is certainly
Re(s)= 0, which is to say, if Re(/|g)= Re(c(/|/))= 0.Now,
real,sothismeansthe constantc must be purely imaginary\342\200\224let's callit ia.The
and sufficientcondition
for minimum uncertainty, then,is
necessary
multiple

(/|/)

g(x)= iaf(x), where a isreal.


[3.66]
thiscriterionbecomes:
For the position-momentum
uncertainty principle

*= ~
[3-67]
(7Tx ~{p)) ia{x <jr))**
which is a differentialequationfor * as a functionof .v.Its generalsolution
(Problem3.16)is

V(x)= Ae-\302\260{x-{x))2/2liei{p)x/h.
[3.68]
Evidently the minimum-uncertaintywave packetis a gaussian\342\200\224and the two
we encountered
earlierwere gaussians.20

examples

-^Note thai it is only the dependenceof * on .v that is at issue


-4.a. (x).
\"constants\"
all
be
of
*
evolve
form.
and
for
thai
mailer
from
ihe
minimal
functions
lime,
may
(p) may
away
I'masserting is lhat if, at some instant, the wave function is gaussian in .v. then (al thai instant) the
here\342\200\224the

and
All

uncertainly

product is minimal.

114

Chapter3 Formalism

Problem3.16SolveEquation3.67for W(x). Notethat (x) and (p) are constants.

3.5.3TheEnergy-Time
UncertaintyPrinciple
The position-momentum
is oftenwritten in the form
uncertainty principle
h

AxAp>-\\

[3.69]

for the standard


(the \"uncertainty\"in ,v) isloosenotation(and sloppylanguage)
deviationof the resultsof repeated
on identically
measurements
preparedsystems.-1
is
with
the
3.69
often
Equation
energy-time
uncertaintyprinciple,
paired
Ajv

O 1

AtAE>-.

[3.70]

form might be thought


Indeed,in the contextof specialrelativity the energy-time
of as a consequence
of the position-momentum
version,because.v and t (or
in the position-time
while p and E (or rather,
rather, ct) go together
four-vector,
So in a relativistic
four-vector.
E/c) go togetherin the energy-momentum
theory
to Equation3.69.But we'renot
concomitant
Equation3.70wouldbe a necessary
The Schrodinger
nondoingrelativistic
quantum mechanics.
equationis explicitly
relativistic:
It treatst and .v on a very unequal footing(as a differentialequation
in x), and Equation3.70is emphatically
it isfirst-orderin t, but second-order
not
now is to derivethe energy-time
implied
by Equation3.69.
My purpose
uncertainty
and in the courseof that derivationto persuade
principle,
you that it is really an
differentbeast,whosesuperficial
resemblance
to the position-momentum
altogether
is actually quitemisleading.
uncertainty principle
After all, position,momentum, and energy are all dynamical
measurable
characteristics
of the system,at any given time.But time itselfis
not a dynamical variable (not,at any rate,in a nonrelativistic
theory):You don't
the \"time\"of a particle,
as you might itspositionoritsenergy.
go outand measure
Time is the independent
are
variable,of which the dynamical quantities
In particular,
the At in the energy-timeuncertainty principleis not the
standarddeviationof a collection
of timemeasurements;
roughly speaking(I'll
make thismoreprecisein a moment)it is the time it takesthe system to change
substantially.
variables\342\200\224

functions.

\"'Manycasual applications of the uncertainly principle are actually based(often inadvertently) on


a completely
of \"uncertainty.\" Conversely,some
sometimesquite unjustified\342\200\224measure
use
other
definitions
of
perfectly rigorous arguments
\"uncertainly.''SeeJan Hilgevoord.Am. J. Phxs.
70, 983 (2002).
different\342\200\224and

Section3.5:The UncertaintyPrinciple

115

measureof how fast the system is changing,let us computethe time


derivative of the expectation
value of someobservable,
Q(.x,p, t):
As a

*
/9* QV)+[V dQ V +
= d
*<G> *<*'\302\253*>=
IT
dt

Now, the Schrodinger


equationsays

ih
(where H =

9* = HV

\342\200\224

dt

So
p2/2m+ V is the Hamiltonian).

1-*

I dQ

= -tt{HV\\QV)+ -mQHV)+ -f-r(Q)


in
dt
in
at
\342\200\236

\\

But H is hermitian,
so (HV\\QV)= {y\\HQV),and hence

[3.71]
and usefulresultin its own right (seeProblems
This is an interesting
3.17and

In the typical casewhere the operatordoesnot dependexplicitly


on time,22
3.31).

of changeof the expectation


value is determined
by the
In particular,
commutatorof the operatorwith the Hamiltonian.
if Q commutes
it

tellsus

that the rate

and in this senseQ is a consented


H, then (Q) is constant,
quantity.
=
=
w
e
H
and
B
A
in
the
Now, suppose pick
Q,
generalized
uncertainty
and
t
hat
assume
does
not
on t:
Q
principle(Equation3.62),
dependexplicitly
with

>
aHaQn

(W-tef^HfH\342\204\242)2\342\200\224

Or, moresimply,
OhOq

d(Q)
dt

[3.72]

Let'sdefineAE = 07/, and


At

aQ
-\\d(Q)/dt\\

[3.73]

that depend explicitly on t are quite rare, so almost always 'dQ/'dt = 0. As an


of
example explicit lime dependence,consider the potcnlial energy of a harmonic oscillatorwhose
more flexible):
spring constant is changing (perhapsthe temperature is rising, so the spring becomes
=
Q (l/2)w[ft>(/)]V.
\342\200\224Operators

Formalism

Then

AEAt>~,
~ 2

[3.74]

that'sthe energy-time
But noticewhat is meant by Af,
uncertainty principle.
here:Since
d(Q)
OQ =
dt Ar,
Af represents
the amount of time it takesthe expectation
value of Q to changeby
onestandarddeviation.23
In particular,
Ar depends
entirely on what observable
and slow
(<2) you careto look
changemight be rapidfor oneobservable
for another.
must be
But if Af is small,then the rate of changeof all observables
very gradual;or,to put it the otherway around,if any observable
changesrapidly,
the \"uncertainty\"in the energy must be large.
and

at\342\200\224the

Example3.5 In the extreme caseof a stationary state,for which the energy is


valuesare constantin time(AE = 0
all expectation
uniquely determined,
Ar =
in fact we noticedsometime ago (seeEquation2.9).To make
of at leasttwo stationary
something
happenyou must take a linearcombination
=>\342\226\240

oo)\342\200\224as

states\342\200\224say:

If a, b, \\fr\\, and fa are real,

|*(*,

t)\\2

= a2d/r,(.0)2+ b2tyi(x))2+ 2ah^{x)in{x)


cos(-E2

E\\

The periodof oscillation


AE =
is r = 2ttH/(E2 E\\).Roughly speaking,
\342\200\224

and At

= t (forthe exactcalculation
seeProblem3.18),so
AE At = 27ih,

Ei

\342\200\224

E\\

which is indeed>h/2.
wave packettopassby a
Example3.6 How longdoesit takea free-particle
in Problem3.19),
point(Figure3.1)?
Qualitatively(an exactversionisexplored
Ar = Ax/v = mAx/p,but E = p2/2m,so AE = pAp/m.Therefore,
particular

AE At

= pAp mAx = AxAp,


m
-\342\200\224

which is >ft/2 by the position-momentum


uncertainty principle.

is sometimescalled the \"Mandelstam-Tamm\" formulation of the energy-time uncertainty


principle.For a review of alternative approachesseePaul Busch,Found.Phys. 20,1 (1990).
\342\200\242^This

Section3.5:The UncertaintyPrinciple

117

Ax-

3.1:A free particlewave packetapproachesthe pointA (Example3.6).

FIGURE

Example3.7 The A particlelastsabout10~23seconds,beforespontaneously


of its mass,you get
If you make a histogramof allmeasurements
disintegrating.
a kindof bell-shaped
curve centered
at 1232
MeV/c2,with a width of about120
MeV/c2 (Figure3.2).Why doesthe restenergy (mc2)sometimes
comeout higher
and sometimes
error?No,for
than 1232,
lower?Is thisexperimental
AE At

(\342\200\224

MeV

=
] (10-23sec) 6 x 10~22MeV sec,

whereas h/2 = 3 x 10-22MeV sec.So the spreadin m is aboutas smallas the


allows\342\200\224a
uncertainty principle
particlewith so shorta lifetimejust doesn'thave
a very well-defined
mass.24

1100

1200

1300

1400

MASS (MeV/c2)

FIGURE3.2: Histogram
ofmeasurementsofthe A mass (Example3.7).
24

secon a stop-watch, and in


of a fraud. You can't measure 10-23
short-lived particle is inferred from the width of the massplot, using the
uncertainty
principle as input. However, the point is valid, even if the logic is backwards.Moreover,
if you assumethe A is about the same size as a proton (~10-'*5
secis roughly the
m), then 10--3
time it takes light to crossthe particle, and it'shard to imagine that the lifetime could be much less
3.7is a bit

Example
Actually,
practicethe lifetime of such a

than that.

118

Chapter3 Formalism
Noticethe variety of specificmeanings
attaching to the term At in these
in Example3.6it'sthe time
In Example3.5it's a periodof oscillation;
examples:
it takesa particle
to passa point;in Example3.7it's the lifetimeof an unstable
particle.In every case,however,At is the time it takesfor the systemto undergo
\"substantial\"change.

It is often said that the uncertainty principlemeansenergy is not strictly


in quantum mechanics\342\200\224that you'reallowedto \"borrow\"energy AE,
conserved
as longas you \"pay it back\"in a timeAt % h/(2AE);the greaterthe violation,
the brieferthe periodover which it can occur.Now, there are many legitimate
readingsof the energy-timeuncertainty principle,but thisis not one of them.
and
Nowhere doesquantum mechanics
licenseviolationof energy conservation,
enteredintothe derivationof Equation3.74.But the
certainly no suchauthorization
is extraordinarily
robust:It can be misusedwithout leading
uncertainty principle
to seriously
are in the habitof
incorrectresults,and as a consequence
physicists
applyingit rather carelessly.

*Problem3.17
Apply Equation3.71to the followingspecialcases:(a) Q = 1;
(b) Q = H; (c) Q = x; (d) Q = p. In eachcase,commenton the result,
with particular
of energy
reference
to Equations1.27,1.33,1.38,and conservation
(comments
followingEquation2.39).
for the wave functionin
Problem3.18Test the energy-time
uncertainty principle
Problem2.5and the observablex, by calculating
07/,ax, and d{x)/dtexactly.

Problem3.19Testthe energy-time
for the free particlewave
uncertaintyprinciple
an,ax,and d(x)/dt
packetin Problem2.43and the observable by calculating
exactly.
\342\200\236v,

reducesto the \"your


Problem3.20Showthat the energy-time
uncertaintyprinciple
name\"uncertaintyprinciple
in questionis x.
(Problem3.14),when the observable

3.6DIRACNOTATION
How wouldyou
Imaginean ordinary vectorA in two dimensions
(Figure3.3(a)).
describethis vectorto someone?
The mostconvenientway is to set up
of A: Ax = f A, Ay = ./ A
axes,x and >\\ and specifythe components
Of course,your sistermight have drawn a different set of axes,
(Figure3.3(b)).
A
x' and y\\ and shewould reportdifferent components:
Ax = V A. A'y =
it with
(Figure3.3(c)).But it's all the samevector\342\200\224we're simplyexpressing
The vectoritselflives\"out there
respectto two differentbases({/\\ j} and {?',./'}).
in space,\"
of anybody's(arbitrary) choiceof coordinates.
independent
cartesian

\342\200\242

\342\200\242

\342\226\240

j'

\342\226\240

119

Section3.6:DimeNotation

(a)

(c)

(b)

FIGURE3.3: (a) Vector A. (b) Componentsof

ofA with respect


tox'y axes.
(c) Components

with

respectto

xy

axes.

The sameis true for the stateof a system in quantum mechanics.


It is

a vector,
that lives \"out there in Hilbertspace,\"
but we can
with
expressit
respectto any number of different bases.The wave function W(.v. t)
is actually the coefficient
in the expansion
of \\S) in the basisof position
representedby

\\\302\243{t)),

eigenfunctions:

V(x,t)= (x\\S(t)).

[3.75]

of .v with eigenvalue.v),25 whereas the


standingfor the eigenfunction
momentum spacewavefunction <t>(p.r)is the expansion
of \\S) in the basisof
(with

\\x)

momentum eigenfunctions:

= (p\\S{t))
<5>{p,t)

[3.76]

of /5 with eigenvalue/?).26Or we could


standingfor the eigenfunction
for simplicitythat the
expand\\S) in the basisof energy eigenfunctions
(supposing
spectrumis discrete):
(with

\\p)

[3.77]
of H)\342\200\224Equation 3.46.But it'sallthe
(with
standingfor the /7th eigenfunction
samestate;the functionsW and and the collection
of coefficients
contain
{c,,},
c\342\200\236(t)

(n\\4(t))

\\n)

\302\242,

exactly the sameinformation\342\200\224they are simplythree different ways of describing


the samevector:

\302\245(*./>

-I

/#(>'.t)S(x-y)dy

$>(p.t)

9ipx/h dp

Jhih

= J2^e-iE\"r/h^n(x).
-5I

don't want to call it gx (Equation


the whole point here is to free ourselvesfrom

[3.78]

becausethat
3.39).
any

position basis, and


defined Hilbert
was already too restrictive, committing
now to think of it as an abstract vector space,
is

its form in the

particular basis.Indeed,when

space as the set of squarc-intcgrable functions\342\200\224over


us to a specificrepresentation (the position basis).1 want
whosemembers can be expressed
with respectto any basis you like.
26In
position spaceit would be /;>(.v)(Equation 3.32).
x\342\200\224that

I first

Chapter3 Formalism
\"transform\"

are lineartransformations\342\200\224they
observables)
Operators(representing
onevectorintoanother:

= Q\\a).
Just as vectorsare represented,
with respectto a particularbasis
components,
=
with an =
with
|a>=
\\0) =

[3.79]

\\fi)

{\\e\342\200\236)},21

(e\342\200\236\\a):

b\342\200\236

][>\342\200\236k\342\200\236).

][>\342\200\236k\342\200\236),

(e\342\200\236\\fi),

by their

[3.80]

are represented
(with respectto a particularbasis)by their matrix
operators
elements28

[3.81]

{em\\Q\\en)=Q,m.
In this notationEquation3.79takesthe form

J>.ki.)= J>\302\253fik,i).

[3.82]

or,takingthe inner productwith

\\em),

=
n

and

[3.83]

\302\243fl\302\253<*i\302\253lfiki.).

\302\243M*\302\273\302\273k\302\253)

hence
\302\273

transform.
Thus the matrix elements
tellyou how the components

Later on we will encounter


systemsthat admit only a finite number (N) of
states.In that case\\S(t)) livesin an A7-dimensionalvector
linearly independent
as a columnof (N) components
(with respectto a
space;it can be represented
These
take the form of ordinary (N x N) matrices.
given basis),and operators
are the simplest
associated
with infinitequantum systems\342\200\224none of the subtleties
dimensional
vectorspacesarise.Easiestof all is the two-statesystem,which we
explorein the followingexample.

Example3.8 Imaginea system in which there are just two linearly independent
states:29
|1>=
Til assume llic basis is
replacedby integrals.

and

|2) =
(\302\260).

discrete:otherwise n becomesa continuous index and

-sThisterminology is inspired,obviously, by the linile-dimcnsional case,but the


now typically have an infinite (maybe even uncountable) number of elements.
2
Technically, the \"equals\" signs here mean \"is representedby.\" but I don't think
will arise if we adopt the customary informal notation.

the

sums arc

\"matrix\"

any

will

confusion

Section3.6:DiracNotation

121

The mostgeneralstateis a normalized


linearcombination:
\\4)

=a\\l)+b\\2) =

(ab\\

with

\\a\\2

\\b\\2

= 1.

The Hamiltoniancan be expressed


as a (hermitian) matrix; supposeit has the

specificform

-c o-

are realconstants.
If the systemstartsout (at
what is itsstateat time tl
where g and

= 0) in state|1),

Solution:The (time-dependent)
Schrodinger
equationsays
ih

\342\200\224

As always, we beginby

dt \\S)

= H\\S).

Schrodinger
solvingthe time-wdependent
equation:
H\\t) =

that

[3.85]
[3.86]

\302\243|<t);

and eigenvalues
of H. The characteristic
is, we lookfor the eigenvectors

the eigenvalues:
equationdetermines
a
det

(h-E .
8
h

\\

\302\243

E\\

= (/7

- E)2- g2= 0 - E = T8 =>


h

=\302\273

are (h + g) and (h
Evidently the allowedenergies
eigenvectors, we write

0 CO =

{h\302\2618)

CO

\342\200\224

E\302\261

=h

\302\261

g.

the
g).To determine

=
=* ha +sP = {h\302\261g)a^f}

\302\261

a.

so the normalizedeigenvectors
are
l*\302\261>

= 1

(1

\\

J2\\\302\261K

Next we expandthe

Hamiltonian:

of the
initialstateas a linearcombination
of eigenvectors

K(0))=

Q = -^(k+)+ k-)).

Finally,we tack on the standard time-dependence

exp(\342\200\224iE\342\200\236t/h):

\\4(t))

= -l=[e-i{h+8)t'n\\4.+)+e-i(h-g)t/n\\4-)]
V2

122

Chapter3 Formalism
c-Whl^+c\302\256/*

-igt/h

= le-iht/h fe-.s.,.>+e>-8'/n\\_
~e
e-igt/H eigtltt J

-icos(gtfh)
sin(gf//J)

If you doubtthisresult,by all meanscheckit:Doesit satisfy the time-dependent

Doesit match the initialstatewhen t = 0?


Schrodinger
equation?
Thisis a crudemodelfor (amongotherthings) neutrinooscillations.
In
the electronneutrino,
and |2) the muon neutrino;
if the
that case |1)represents
hasa nonvanishing
Hamiltonian
term (g) then in the courseof time
off-diagonal
neutrinowill turn intoa muon neutrino(and backagain).
the electron

to chopthe bracketnotationfor the inner product,(a|/3),into


Diracproposed
two pieces,which hecalledbra, (a|,and ket, \\/3) (I don'tknow what happenedto
the c).The latteris a vector,but what exactly is the former?It's a linearfunction
of vectors,in the sensethat when it hitsa vector(to itsright) it yieldsa (complex)
inner product.(When an operatorhitsa vector,it deliversanother
In a functionspace,the bra
vector;when a bra hitsa vector,it deliversa number.)
can be thought of as an instruction
to integrate:
number\342\200\224the

-/'

(/1
with the ellipsis
[\342\200\242

[\342\200\242\342\200\242\342\200\242]dx,

in
] waiting tobefilledby whateverfunctionthe bra encounters

\342\200\242 \342\200\242

the ket to its right.In a finite-dimensional


vectorspace,with the vectorsexpressed

as columns,

\\a)

Cll

[3.87]

w
bra is a row vector:
the corresponding
(a\\

...

= {a*a*_

[3.88]

a*)

of all bras constitutes


anothervector
The collection

space\342\200\224the

so-calleddual

space.

The licenseto treat bras as separateentitiesin their own right allowsfor


somepowerfuland pretty notation(thoughI shallnot exploitit in thisbook).For

if |ck) is a normalized
vector,the operator
example,

P = \\a)(ct\\

[3.89]

Section3.6:DiracNotation

123

picksout the portionof any othervectorthat \"liesalong\"|a):


P\\fi) = (ct\\P)\\a);

we callit the projectionoperatorontothe one-dimensional


subspace
spannedby
is a discreteorthonormal
basis,
|a).If
{\\e\342\200\236)}

[3.90]

(\302\253\302\253k\302\273)-=8\302\273\302\273.

then
\302\243h,)<e\342\200\236l

=l

[3.91]

Forif we letthisoperatoract on any vector|a),we recover


(the identity operator).
of \\a) in the {\\en)}basis:
the expansion
J2\\en)(e\342\200\236\\a)

= \\a).

[3.92]

is a Diracorthonormalized
continuous
basis,
Similarly,if (|e;)}
(e-\\ez>)=8(z-z'),

[3.93]

J \\ez)(ez\\dz=\\.

[3.94]

then

Equations3.91and 3.94are the tidiestways to expresscompleteness.


P2 = P. Determine
are idempotent:
Problem3.21Showthat projection
operators
itseigenvectors.
of P, and characterize
the eigenvalues
a three-dimensional
Problem3.22 Consider
vectorspacespannedby
basis|1),|2),|3).Kets|a) and \\fi) are given by

an

orthonormal

|a)=i|l)-2|2)-/|3),
|/J)=/|1)+2|3).
Construct{a\\ and (/31(in terms of the dual basis(1|,(2|,(3|).
(b) Find(a\\P) and (0\\a),and confirm that (0\\a) = (a\\0)*.
of the operatorA = \\a)(fi\\, in thisbasis,and
(c) Findallninematrix elements
construct
the matrix A. Is it hermitian?
(a)

124

Chapter3 Formalism

for a certaintwo-levelsystemis
Problem3.23The Hamiltonian

# = 6(|1)<1|-|2)(2|
+ |1)<2|+ |2)(1|),
|1>,|2>is an orthonormalbasisand e is a number with

the dimensions
of
and eigenvectors
of 11)and
(as linearcombinations
energy.Find its eigenvalues
H with respectto thisbasis?
|2)).What is the matrix H representing
where

Problem3.24 Let Q be an operatorwith a complete


setoforthonormal
eigenvectors:

(ii =

Q\\e\342\200\236)=q\342\200\236\\e\342\200\236)

1,2.3,...).

Showthat Q can be written in terms of its spectraldecomposition:


n

Hint:An operatoris characterized


vectors,so what
by itsactionon all possible
you must show is that
Q\\a)

)(<?\342\200\236!

]T//Hk\342\200\236

I\302\253>,

for any vector\\a).

FURTHERPROBLEMSFORCHAPTER3
Problem3.25Legendrepolynomials.
Use the Gram-Schmidt
procedure
<
the functions1, .v, x2,and x3,on the interval
A.4)to orthonormalize
x < 1.You may recognize
the
are (apart from the normalization)30
(Table4.1).
Legendrepolynomials
(Problem

\342\200\2241

results\342\200\224they

Problem3.26 An anti-hermitian
(orskew-hermitian)
operatoris equalto minus
itshermitian conjugate:
[3.95]
Qf = -Q.
value of an
(a) Show that the expectation

anti-hermitian
operatoris imaginary.

of two hermitian operators


isanti-hermitian.
How
(b) Showthat the commutator
of two fl/m-hermitianoperators?
aboutthe commutator

didn'l know
?'Legendre

all his functions would ao to

what
1

at

the best convention would

x = 1.and we'restuck

with

be:he pickedthe overall factor so that


choice.
unfortunate

his

125

Further Problems
forChapter3

An operatorA, representing
Problem3.27 Sequentialmeasurements.
A, has two normalized
ci\\ and ct2,
eigenstates and i/o, with eigenvalues
observableB, has two normalized
respectively.
OperatorB, representing
are relatedby
h\\ and bi. The eigenstates
0| and 02,with eigenvalues
f\\ = (30,+407)/5, fo = (401 302)/5.
observable

\\j/\\

eigenstates

and the value a\\ isobtained.


Observable
A is measured,
What is the stateof
after thismeasurement?
the system (immediately)
what are the possibleresults,and what are their
(b) If B is now measured,
(a)

(c)

probabilities?
of B, A is measured
Right after the measurement
again.What is the

of gettingoi? (Note that the answer would be quitedifferentif I had


of the B measurement.)
toldyou the outcome

probability

wave function
**Problem3.28 Findthe momentum-space
t) for the nth
stateof the infinite squarewell. Graph \\<&\\(p,t)\\2and \\<&2(p< t)\\2, as
stationary
attentionto the pointsp = -tnnh/a).Use
functionsof p (pay particular
t)
value of p2.Compareyour answer to Problem2.4.
to calculate
the expectation
\302\242,,(p.

\302\242,,(/7.

Problem3.29 Consider
the wave function
q/(A\\0)=
where n

_1

\342\226\240.e

il7txl'\\

-nX < x < nX.

\\/2n~A.

0,

otherwise,

issomepositiveinteger.Thisfunctionispurely sinusoidal
(with wavelength

< x < nX, but it stillcarriesa rangeof momenta,because


on the interval
do not continueout to infinity. Find the momentum spacewave
the oscillations
and
function\302\242(/7,0). Sketchthe graphsof |^(a-,0)|2
0)|2,and determine
their widths, wx and wp (the distancebetweenzeroson eithersideof the main
peak).Note what happensto eachwidth asn oo.Usingwx and wp asestimates
issatisfied.
of A.t and A/?, checkthat the uncertaintyprinciple
Warning: If you try
the problem?
calculating
ap,you'rein for a rudesuiprise.Can you diagnose
X)

\342\200\224nX

|\302\253J>(/?,

->\342\200\242

Problem3.30Suppose
vl>(.\\\\

for constants
A and a.

0) = .v- a-y.
+
\342\200\224^

(-oo< x < oo)

126

Chapter3 Formalism
(a)
(b)
(c)

Determine
A, by normalizing
ty(.\\\\0).
Find(x),(x2),and ax (at time t = 0).
Findthe momentum spacewave function

0), and checkthat

<\302\243>(/?,

it

is

normalized.

Use
0) to calculate(/?), {p2),and ap (at time t = 0).
for this state.
(e) Checkthe Heisenberg
uncertainty principle

(d)

<\302\243(/?,

*Problem3.31Virialtheorem.UseEquation3.71to show that

[3-%i

i<\">=2<r>-(*9'

is the kineticenergy (H = T + V). In a stationarystatethe left sideis


zero(why?) so
[3.97]
2(T)= Lx^-\\.
where T

Thisis calledthe virialtheorem.Use it to provethat (T) = (V) for stationary


statesof the harmonicoscillator,
and checkthat thisis consistent
with the results
2.11and 2.12.
you got in Problems
versionof the energy-time
Problem3.32In an interesting
uncertainty principle31
=
Ar
t/jt, where r is the time it takes\\j/(.v, r) to evolveinto a state
to vl/(x,0).Test this out,usinga wave functionthat is an equaladmixture
of two (orthonormal)
vj/(jt, 0) =
stationary statesof some(arbitrary) potential:
+ fo(*)].
(lA/2)Wri(jr)
orthogonal

**Problem3.33Findthe matrix elements{n\\x\\n') and {n\\p\\n')in the (orthonormal)


basisof stationary statesfor the harmonicoscillator
(Equation2.67).You already
elements = ri) in Problem2.12;usethe same
calculated
the \"diagonal\"
X and P.
case.Construct
the corresponding
(infinite)matrices,
technique for the general
in thisbasis.Are its diagonal
Showthat (l/2/n)P2+ (mar/2)X2= H is diagonal,
elements
Partialanswer:
what you wouldexpect?
(\302\273

(\302\2731*1\302\273')

+
yj^ (Vn7*,,.,,'-!

V\302\273~5\342\200\236',\342\200\236-i)

SeeLev Vaidman,

Am.

J. Phys. 60.182(1992)I'or a proof.

\342\200\242

[3-98]

Further Problems
forChapter3

127

is in a statesuchthat a measurement
Problem3.34A harmonicoscillator
of the
or (3/2)/?a>,
with equalprobability.
What is the
energy wouldyieldeither(l/2)/?a>
largestpossiblevalue of (p) in sucha state?If it assumesthismaximal value at
time t = 0, what is W(x, r)?
* * ^Problem3.35Coherentstatesof theharmonicoscillator.
Among the stationary
=
statesof the harmonicoscillator
(|/j)
Equation2.67)only n = 0 hitsthe
\\j/\342\200\236(x),

uncertainty limit(axap= h/2);in general,axap = (2h-+ l)/i/2,as you found


in Problem2.12.But certainlinearcombinations
(known ascoherentstates)also
minimize
the uncertainty product.
They are (as it turns out) eigenfunctions
of the
loweringoperator}2
a-\\a)= a\\a)
a can be any complexnumber).
(the eigenvalue
in
(x), {x2),(/?), (p2) in the state\\a). Hint:Use the technique
(a) Calculate

Example2.5,and rememberthat a+ is the hermitian conjugateof

\302\253_.

Donot

assumea isreal.

Findax and ap; show that axap = ///2.


a coherent
statecan be expandedin terms of
(c) Likeany otherwave function,

(b)

energy eigenstates:
CO

|Qf) =

]Pc\342\200\236|/?).

//=0

coefficients
are
Showthat the expansion
Cn

(d)

= a\"

\342\200\224f=c0-

Determinecq by normalizing|a).Answer:exp(\342\200\224|a|2/2).

(e) Now put in the time dependence:

\\n)^e-iE\"'/h\\n),
an eigenstate
and show that \\a(t)) remains
of a-,but the eigenvalueevolves
in time:
a(t) = e~itota.
and continues
Soa coherent
statestayscoherent,
to minimize
the uncertainty
product.
-Thereare no normalizable eigenfunctions of the raising operator.

128

Chapter3 Formalism
(f)

Is the groundstate

(|\302\253

= 0)) itselfa coherentstate?If so,what is the

eigenvalue?

Problem3.36Extendeduncertaintyprinciple.33
The generalized
uncertainty
s
tates
that
principle(Equation3.62)
aAaB
where C =

At

^^C) '

At

-i[A.B],

(a) Show that

it can be strengthened
to read
^I>~((02+(\302\243>)2),
yy

At

At

[3-99]

Al

where D = AB + BA-2(A)(B).Hint:
Keepthe Re(z)term in Equation3.60.
(b)

CheckEquation3.99for the caseB = A (the standard uncertainty principle


is trivial, in thiscase,sinceC = 0; unfortunately, the extendeduncertainty
At

doesn'thelpmuch either).
principle

Problem3.37The Hamiltonian
for a certainthree-level
systemis represented
by
the matrix

where a, b, and c are real numbers (assume


a
(a)

c ^ + b).

If the system startsout in the state

what
(b)

\342\200\224

is |4(/))?

If the system startsout in the state

what

is \\S{t))l

seeR. R. Puri, Phys.Rev. A 49, 2178(1994).


For interesting commentary and references,

129

Further Problems
forChapter3

for a certainthree-level
Problem3.38The Hamiltonian
system is represented
by
the matrix

= Ao>

/1

0 0N
0 2 0
\\0 0 2,

Two otherobservables,
A and B, are represented
by the matrices

/0

=X 1 0
\\0 0

where a>, A., and

/x

0\\

0] ,

/2 0

0N

B = /x 0 0 1

2/

V0

1 0,

are positive
realnumbers.

and (normalized)
of H, A, and B.
Findthe eigenvalues
eigenvectors
the system starts out in the genericstate
(b) Suppose
(a)

with

= 1.Findthe expectation
values (at t = 0) of H,
|cj|2+ |C2|2+ |C312

A, and

B.

is \\<8(t))1If you measuredthe energy of thisstate(at timet), what


of each?Answer the same
values might you get,and what is the probability
for A and for B.
questions

(c) What

* ^Problem3.39
(a)

For a functionf(x) that can be expandedin a Taylorseries,show that

fix+x0) = ^^/11f(x)
Forthisreason,p/h iscalledthe
constant
distance).
of translations
of an operatoris defined
in space.Note:The exponential
e& = 1 + Q + (1/2)(22+ d/3!)fi3+
by the power seriesexpansion:
If vj/(.v, r) satisfies
the (time-dependent)
show that
Schrodinger
equation,
(wherexq is any

....

generator

(b)

Vix,t + to) = e-i\"H)/hVix,t)


(where to

in time.

isany constant
time);

\342\200\224H/h

iscalledthe generatorof translations

130

Chapter3 Formalism
value of a dynamical variable Q(x,p, t), at time
(c) Show that the expectation
t + to, can be written34

= {^{x.t)\\eifl^hQ{x.p,t
+ tQ)e-ifl'ttln\\^(x,t)).
((2),+,,,
Use this to recoverEquation3.71.Hint:Let to = dt, and expandto first
orderin dt.
* ^Problem3.40
in momentum space,
(a) Write down the time-dependent
\"Schrodinger
equation\"

for a free particle,and solveit.Answer: exp(\342\200\224ip2t/2mh) 0(p,0).


(b) Find \302\242(/7,0) for the traveling gaussianwave packet(Problem2.43),and
construct t) for thiscase.Alsoconstruct|0(/?,t)\\2, and notethat it is
of time.
independent
<\302\243>(/?,

(c)

Calculate(p) and {p2)by evaluatingthe appropriateintegralsinvolving0,


and compareyour answers to Problem2.43.

0 denotesthe
{H) = (p)2/2m+ {H)q(where the subscript
and commenton this result.
gaussian),

(d) Show that


stationary

34In particular, if we set,

\342\200\224

0.and drop the

subscripton Iq.

= <*(.*.
0)11/-1
{Q(t))= (*(A-.r>|j2l*(.v.0>
QUmx.0)).
=

This says that you can calculate expectation values of Q either by


as we have always done (letting the wave functions carry
Q between ^(.v, t)* and *(.v.f),
sandwiching
or elseby sandwiching U~]QU between *(.v.0)*
and *(.v.0).
the time dependence),
letting the
is
the
called
the
lime
The
former
a
nd
the
lallcr ihe
dependence.
operatorcarry
Schrodinger
picture,
where U

exp{\342\200\224iHr/ti).

Heisenberg
picture.

CHAPTER4

QUANTUM MECHANICSIN
THREE DIMENSIONS

4.1SCHRODINGEREQUATIONIN SPHERICALCOORDINATES
is straightforward.Schrodinger's
The generalization
to three dimensions
equation
says
ili\342\200\224

at

= HV;

[4.1]

the Hamiltonian
from the classical
operator1H isobtained
energy
{-mv2+

+
\302\261-{p2.+p1x
2m

p1)+ V

by the standard prescription


(appliednow to y and z, as well as .v):
h

Px

-^77-Pv -^77-. Pc
3.v
3v
i

fl

\"*

Ad

7 7-.
/

az

[4.2]

'Where confusion might otherwise occurI have been putting

\"hats\" on operators,to distinguish


obscrvables.I don't think there will be much occasionfor
correspondingclassical
this chapter, and the hats gel lo be cumbersome,soI am going lo leave them off from

them from the


ambiguily

now

on.

in

131

132

Chapter4 Quantum Mechanicsin Three Dimensions

or

[4.3]
for short.Thus

9* =

V2

[4.4]

2m

dt

where

n2

ih\342\200\224

= a2

a2

92

9^+9v^+9?

[4.5]

is the Laplacian,
coordinates.
in cartesian

The potential
energy V and the wave function^ are now functionsof r =
of finding the particlein the infinitesimal
volume
(.v. v, z) and t. The probability

condition
reads
d3r= dxdyclzis 1^(1%t)\\2d3r,and the normalization

|2j3 1
\\V\\-d*r=

[4.6]

of time,there
with the integraltaken overallspace.If the potential
is independent
will be a complete
setof stationary states.
^\342\200\236(r.

t)

= ^,,(^-1
E\"'/fi,

satisfiesthe lime-independent
Schrodinger

spatialwave function
equation:
where the

\\fr\342\200\236

h1

V^ + Vf = Eyjt.
2m
\342\200\224

[4.7]

[4.8]

The generalsolution
to the (lime-dependent)
Schrodinger
equationis

^{T,t)= J2c\"^n(T)e-iE\"'/r\\

[4.9]

with the constants determinedby the initialwave function,4>(r,0), in the


usual way. (If the potential
admitscontinuumstates,then the sum in Equation4.9
becomes
an integral.)
c\342\200\236

Section4.1:Schrodinger
Coordinates 133
Equationin Spherical

*Problem4.1
commutation
of the
relationsfor components
(a) Work out allof the canonical

r and p: [a-,v], [x,py], [x,px],[pY.pz],and soon.Answer:


operators
in, Pj] = -lPhrj] = ihSij, [/7./7]= [phpj] = 0,
[4.10]
where the indicesstand for x, y, or z, and rx = x, ry

= v, and rz = z.

theoremfor 3-dimensions:
(b) Confirm Ehrenfest's

= -(p).
^-(r)
at
in

and -^-<p) =
at

<-VV>.

[4.11]

(Each of these,of course,standsfor three equations\342\200\224one for each


Hint:Firstcheckthat Equation3.71is valid in three dimensions.
component.)

in three dimensions.
FormulateHeisenberg's
Answer:
uncertainty principle

(c)

oxaPx > h/2,

a,alh.> h/2. aza,h> h/2,

[4.12]

but there is no restriction


on,say, axaPv.

4.1.1
Separationof Variables
is a functiononly of the distancefrom the origin.In
Typically,the potential
caseit is natural to adoptsphericalcoordinates,(r.9,
the Laplaciantakesthe form\"
coordinates
spherical

1
/\342\226\240-

In

/?3\\

9r

\\

/
9/-/ r*sm9d9\\
1

9 \\
99J

\302\242)

that

(seeFigure4.1).In

92 \\

r2sin-9\\30^/

coordinates,
then,the time-independent
Schrodinger
equationreads
spherical
h2 r

2m

1 3 / .
1
/ 23^\\
/32^
+
+
7-lu-V ~dr~) ~r~l^9d9 \\*m0~dO) ~rh*n1~9\\WJ]
1 3

\"

<hfr\\

+ V$ = E\\lf.

We

[4.14]

that are separable


intoproducts:
beginby lookingfor solutions

i/(r,0.fr= R(r)Y(O^).

[4.15]

-In principle, this can be obtained by change of variables from the cartesian expression
However, there-arc much more efficient ways of getting it; see.
for instance, M. Boas,
(Equation 4.5).
2nd ed..(Wiley. New York. 1983),Chapter 10.
Mathematical Methods in the Physical Sciences.
Section9.

134

Chapter4 Quantum Mechanicsin ThreeDimensions

FIGURE4.1: Spherical
coordinates:
radiusr, polarangle9,and azimuthalangle

\302\242.

Putting thisintoEquation4.14,we have


//2

P-dr

2/77

[! dr )

9
r2 sin0 90
R

92y

+
M J ,-2sin20 902J

sin0\342\200\224

+VRY=ERY.
Dividingby

RY

and multiplying by

it-T.
-2////-//7
->

[1d ( -ydR\\

2m/-2

^1^(,^-^1=0.

+ Y sin0 90

39 J

sin20 902

first curly bracketdependsonly on /\\ whereas the remainder


on
0
and 0; accordingly,
eachmust be a constant.
For reasonsthat
dependsonly
will appearin duecourse,3
I will write this\"separation
constant\"in the form /(/+1):

The term in the

/ -,dR\\

1 9 / .
sin0 90

[4.16]

-^--

JY\\) + 1 92y) =-/(/+ 1).


90/ sin2090:

sir\302\2730

2mr2

\342\200\224

[4.17]

Note that there is no loss of generality


this stage I couldbe any complexnumber.
Later on we'll discoverthat / must in fact be an inieger.and il is in anticipation of that result that I
expressthe separation constant in a way that lookspeculiarnow.
\342\200\242

here\342\200\224at

Section4.1:Scbrodinger
Coordinates 135
Equationin Spherical
of variablesin cartesiancoordinates
*Problem4.2 Use separation
to solvethe
in
w
ell
a
infinite cubical
(or \"particle box\:

[0.

(a)
(b)

\342\226\240

\302\243j.

\302\2432.

(c)

if .v, v. z are all between0 and a:

'
'
V(x.v. z) = { oo,
tU
otherwise.
[
Findthe stationary states,and the corresponding
energies.
in orderof increasing
Callthe distinctenergies
energy.
Find E\\.
and E&. Determine
their degeneracies
(that is, the
number of different statesthat sharethe sameenergy).Comment:In one
dimension
boundstatesdo not occur(seeProblem2,45),but in
degenerate
three dimensions
they are very common.
of
and why is thiscaseinteresting?
What is the degeneracy
\302\2433,

\302\2434.

\302\2432.

\342\200\242\342\200\242\342\200\242

\302\2433.

\342\200\242

\302\2435,

\302\24314,

4.1.2TheAngularEquation
the dependence
of on9 and 0;multiplying
Equation4.17determines
by
yp

it

becomes:

dY\\

d2Y

sin20,

sin^r^)+^=-'('+i)sin^ [418]
You might recognize
thisequation\342\200\224it occursin the solutionto Laplace'sequation
in classical
As always, we try separation
of variables:
electrodynamics.

Y(0,0) =

0(0)0(0).

[4.19]

we find:
Pluggingthis in,and dividingby
1
1 dr$
o )
+
/(/+1)51112
dO \\
0
d9
d<$>J
The first term is a functiononly of 9, and the secondis a functiononly of 0, so
eachmust be a constant.
Thistime4 I'll callthe separation
constantm2:
'
1
( J\302\256' + /(/ + 1)sin29 = m2:
sin
[4.20]
0 d9 \\ d9
0<\302\243>,

sin0\342\200\224

sin0\342\200\224

0+--^=0.
<$>

\342\200\242

\302\253d

9\342\200\224

\342\226\240

sin0\342\200\224\342\200\224

,\302\243/2*=-m'.

O dfr

[4.21]

\"'Again, there is no loss of generality here, since at this stage in couldbe any complexnumber:
a moment, though, we will discoverthat m must in fact be an integer.Beware:The letter 111 is
now doing doubleduty, as mass and as a separation constant. There is no graceful way to avoid this
confusion, since both uses are standard. Someauthors now switch to M or /i for mass, but I hate to
change notation in mid-stream, and I don*t think confusion will arise,as long as you are aware of the
in

problem.

136

in ThreeDimensions
Chapter4 Quantum Mechanics

is easy:
The 0 equation

* = -m-$
...2*=*.. ^,,,_=Jm*
e,m<p.

d2\302\256

[4.22]

\302\242(0)

[Actually, there are /wo solutions:


exp(zw0)and exp(\342\200\224?'m0), but we'llcoverthe
There couldalso be a constantfactorin
latter by allowingm to run negative.
in electrodynamics
we
front, but we might as well absorbthat into Incidentally,
would write the azimuthal function in terms of sinesand cosines,insteadof
there
becauseelectricpotentials
must be real.In quantum mechanics
exponentials,
are a lot easierto work with.]Now,
is no suchconstraint,
and the exponentials
when 0 advancesby 2rt,we return to the samepointin space(seeFigure4.1),so
that5
it is natural to require

0.

(\302\242)

\302\242(0

+ 271-)= 0(0).

[4.23]

In otherwords,exp[/m(0+ 2n)] = exp(/w0),or exp(27n'//z)= 1.Fromthis


followsthat m must be an integer:
m

=0,+1,

it

[4.24]

\302\2612

The 9 equation,

sin9^(sin0^)+ [1(1+ 1)sin29

-m2]0= 0.

[4.25]

is not sosimple.The solutionis

0(0)= A Pj\"(cos9),

[4.26]

where P\"' is the associated


Legendrefunction,definedby6

/d

f
P/\"(jr)= (1 a-2)I'\"I/2

and

\\

\342\200\224

I\"1'

P,(x).

[4.27]

definedby the Rodriguesformula:


Pi(x)is the /th Legendrepolynomial,

M-Mil1*2-1*\342\226\240\"'This

regardlessof

[4-28]

it looks.
After all. the probability density (|4>|2)is single-valued
m. In Section4.3we'll obtain the condition on in by an entirely
more

is more slipperythan

different\342\200\224and

compelling\342\200\224argument.

^Noticethat Pj~'\" Pj\".Someauthors adopt a different sign convention for negative values
of in: seeBoas (footnote 2), p. 505.
\342\200\224

Section4.1:Schrodinger
Coordinates 137
Equationin Spherical
TABLE4.1: Thefirst few Legendrepolynomials,
P/(.v):(a) functionalform,
(b) graphs.

^0 =
^1 = X

P2 =

Py//'/I

j(3.v2- 1)

- 30.v- + 3)
P*= 1(35,=
P5 1(6^ 70.v*+15.v)
P3

= M5x> 3x)

-l

//\\jN.

\"^

//

y^)N.

-l

(a)

(b)

For example,
Po(-v) =

1.
1

P\\(x) =

(d

\\

-lax{x1- 1)=.r.

~,

\342\200\224

-,

4.1.

are listedin Table


As the name
and soon.The first few Legendrepolynomials
to
(of degree/) in .v, and is even or oddaccording
P/(.v) is a polynomial
suggests,
in
a
odd
carries
it
the parity of /. But P\"'(x)is not, general, polynomial\342\200\224if m is
a factorof Vl
P,\302\260(A-)

\342\200\224

x1:

= (1-x^/2^-I(3a-2-1)=3.*V7 x= i(3A-2-l). pUx)


~
dx
2
9 r-

]f1 2 1) = 3(1-a-2).
^(.v) = (l-.v2)(\302\243)-(3a*
2

etc.(On the otherhand,what we needis Pj\"(cos9),and Vl cos29 = sin9, so


sin0.
Pj\"(cos9) is always a polynomialin cos0, multiplied\342\200\224if m is
Someassociated
Legendrefunctionsof cos#are listedin Table4.2.)
Noticethat / must be a nonnegativeinteger,for the Rodriguesformula to
make any sense;moreover,if \\m\\ > 1,then Equation4.27says Pj\" = 0. For any
valuesof m:
given /, then, there are (2/ + 1)possible
odd\342\200\224by

= 0, 1. 2.

-l.-/+1

\342\226\2401.

0. 1,

.../,

1. /. [4.29]

differential
It shouldhave two
But wait!Equation4.25is a second-order
equation:
for any
solutions,
linearly independent

old valuesof /

and m. Where are

all the

138

Chapter4 Quantum Mechanicsin ThreeDimensions


TABLE4.2: Someassociated
P\"'(cos9):
(a) functionalform,
Le'gendrefunctions,
=
(in theseplotsr tellsyou the magnitudeof the function in
(b) graphs of/* P\"'(cos9)
the direction
0;each figure shouldberotatedaboutthe z-axis).
a\"

r0 - i
p\302\260-

pV

9-1)

= ^(3 cos2

P\\

= sin 9

p!= 15sin 9(1-cos29)

P\\]

= cos9

p}= 15sin2$ cos0

Pl = 3s\\rr9
P\\

= 3 sin B cose

rh \\sin9(5cos20-1)
P{h (5 cos30- 3 cos0)

-e&p,'(^
'i.:

8-** -^

^(^

->Z

CO ^>

pV(W)

(a)

(b)

othersolutions?
A/z.yiv<?/*: They e.mf,of course,
as mathematical solutionsto the
becausethey blow up at 0 = 0
equation,but they are physicallyunacceptable,
and/or9 = n (seeProblem4.4).
in spherical
coordinates7
is
Now, the volumeelement
dyT

= r1^medrdOd(f),

[4.30]

so the normalization
condition
(Equation4.6)becomes
/\\\\lf\\2r2^\\-\\Bdrd6d(j)=
j \\R\\2r2 dr
It

\\Y\\2

sin0 d$d<j) =

is convenientto normalize
R and Y separately:
nlTt
nrt
poo
I \\R\\2r2dr=[ and / /
Jo
Jo Jo

|r|2sin0</0

7Sce.lor instance.Boas (footnote 2). Chapter 5.Section4.

d<t>

= 1.

[4.31]

Coordinates 139
Section4.1:Schrodinger
Equationin Spherical
TABLE4.3: The first few spherical
harmonics,
Yju(6.

\302\242).

y?-(i)\"2

^-(4)^(3^-1)
Yfl

'/2

=+

'/2

^
'/2
y^1 = + (^) sin 0 (5 cos20^ \" =

COS0

(ifc)

Yf- = I

~\342\200\224

(5

C\302\260S3

9~ 3

C\302\260S

1)*\302\261'*

sin-6>cosQex-\"''

sin & cosBe**

(\302\247|)

The normalized
are calledspherical
harmonics:
angular wave functions8

|)!
/(2/+l)(/-|m
V\"\"*P/\"(cos0).

1^(0,0) = g/
A/

,-mfl4

47T

(/ +

|w|)!

where e =
for m > 0 and e = 1 for ///
so
they are automatically
orthogonal,
(\342\200\2241)'\"

pin

pir

/ JO
/
JO

[4.321

,\342\200\236

< 0. As we shallprovelater on,

= 5//'5mm',
&]*[YI?(0,0)]sin0</0<ty

[4.33]

'[Yi\"{0,

In Table4.3I have listedthe first few spherical


Forhistorical
harmonics.
reasons,/

iscalledthe azimuthalquantumnumber,and /// the magneticquantumnumber.


^Problem4.3 Use Equations4.27,4.28,and 4.32,to constructFj and 7-,1.Check
and orthogonal.
that they are normalized
Problem4.4 Showthat

0(0)= Aln[tan(0/2)]

-1)

e (which is always 1 or
8Thc normalization factor is derived in Problem 4.54:
is chosen
consistencywith the notation we will be using in the theory of angular momentum: it is reasonably
standard, though someolderbooksuse other conventions. Notice that
for

y,-'\" =

i\"

(-\\)\"'{y;\
lv\302\273'\\*

140

in ThreeDimensions
Chapter4 Quantum Mechanics

satisfiesthe 6 equation(Equation4.25),for / = m = 0. Thisis the unacceptable


solution\"\342\200\224what's wrong with it?
\"second
^Problem4.5 UseEquation4.32to construct
YJ(6,0) and Y$(6. (You can take
4.27and 4.28.)
P-2 from Table4.2,but you'llhave to work out PJ from Equations
\302\242).

Checkthat they satisfy the angular equation(Equation4.18),for the appropriate


valuesof I and m.

* ^Problem4.6 Startingfrom the Rodriguesformula,derivethe orthonormality


condition for Legendre
polynomials:

\302\243\342\204\242w*=(tt
Hint:Useintegrationby parts.
\302\273//'\342\226\240

[4.34]

4.1.3TheRadialEquation
Noticethat the angularpart of the wave function,Y(9, isthe samefor all
the actual shapeof the potential,
V{r),affectsonly
symmetric potentials;
the radialpart of the wave function,R(r),which is determined
by Equation4.16:
\302\242),

spherically

odR'
(
= l(l + l)R.
-^[V(r)-E]R
dt
n~
'

d_

[4.35]

Thisequationsimplifies
if we changevariables:
Let
u{r)= rR(r),

[4.36]

so that R = u/r, dR/dr = [r(du/dr) u]/r2,(d/dr)[r2(dR/dr)]


= rd2u/dr2\\
and hence
d2u
+
2nidr7
h2

/?2

/(/ + 1)

2m

r-

= Eu.

[4.37]

Thisiscalledthe radialequation;9it is identicalinformto the one-dimensional


Schrodinger
equation(Equation2.5),exceptthat the effectivepotential,
Veff

Those w's are masses,of


equation.

course\342\200\224ihc

h2

1(1+ 1)

2/7/

r2

separation consiant m does not appear

[4.38]
in the

radial

Section4.1:Schrodinger
Coordinates 141
Equationin Spherical

containsan extra piece,the so-calledcentrifugalterm,(ti2/2m)[l(l


+ l)/r2].It
tendsto throw the particleoutward (away from the origin),just likethe
in classical
mechanics.
the normalization
condition
Meanwhile,
(pseudo-)force
(Equation4.31)becomes
centrifugal

L \\u\\2dr=\\.

[4.39]

That'sas far as we can go until a specificpotentialV{r) is provided.


the infinitesphericalwell,
Example4.1 Consider
V(r)

<
= 0, if r a:
oo, if r > a.

[4.40]

Findthe wave functionsand the allowedenergies.

Solution:Outsidethe well, the wave function is zero;insidethe well,the radial


equationsays

/-/2,, rid
n
d-u
~ r/(/ + D

,,i1

_i_

dr2

>-2

[4.41]

where
k

_ s/lmE

[4.42]

asusual.Our problemis to solvethisequation,


subjectto the boundary condition
u(a) = 0. The case/ = 0 is easy:
d2u =
k^u
dr y
\342\200\224

=$>

u(r) = A

sin(A-r)+ B cos(kr).

But remember,
the actual radialwave function is R(r) = w('*)/'\".
and [cos(kr)]/r
then
blowsup as r -> 0. So10we must chooseB = 0. The boundary condition
n.The allowedenergies
sin(/rfl) = 0, and henceka = rm, for someinteger
requires
are evidently

E\342\200\2360

n-n-n2ma2

(n

1.2.3,
...),

[4.43]

~
'^Actually, all wc require is that the wave function be nornuilizable. not that it he finite:
For a more compellingproof
I//- at the origin is normalizable (becauseof the r2 in Equation 4.31).
that B = 0.secR. Shankar.Principles
of Quantum Mechanics(Plenum. New York. 1980).
p.
/?(;\342\200\242)

351.

142

Chapter4 Quantum Mechanicsin ThreeDimensions


the sameas for the one-dimensional
infinite squarewell (Equation2.27).
u(r) yieldsA = -J2ja\\tackingon the angular part (trivial, in thisinstance,
sinceYq{0, = 1/V4~7r),we conclude
that

Normalizing

\302\242)

-j=sin(fljrr/fl)
r
1

Vr\342\200\236oo

[4.44]

\342\200\242

V27Ttf

[Noticethat the stationary statesare labeledby threequantumnumbers,/7,/,and


tn: tynimO'i #> 0).The energy, however, dependsonly on n and /:
The generalsolutionto Equation4.41(for an arbitrary integer/) is not so
\302\243\342\200\236/.]

familiar:

u(r) = Arji(kr)+ Brni(kr).

[4.45]

where ji(x)is the spherical


Besselfunctionof order/, and /?/(a)is the spherical
Neumannfunctionof order/. They are definedasfollows:
/ /1
V
;,(*)= (-*)'(\342\200\224_)
\\x ax / x

sin.y

,7/(A-) =

, /'1 d V cosa .
_(_.v)/ _
\\xax/ x

r_

,,,

[4.46]

For example,

./0(-0=

sin.Y

\302\253oCO

cosA'

;
X

A*

d /sinx\\ = sina

Mx) = (-a)a ax
\342\200\224

\\

*/

\\~

-,/1

\342\200\224

9/l

a cosa sina
a3
\\xdxj

sina

3acosx

\342\200\224

A\"

\\a-<1y/ a

3 sina

cos.y

\342\200\224

^/

\\

\342\200\224

x2 sinx

so on. The first few sphericalBesseland Neumann functionsare listedin


Table4.4.For smalla (where sinA = x a3/3!+ a5/5!
and cosa =
and

\342\200\224

\342\200\224

1-a2/2+ a4/4!

\342\200\242\342\200\242\342\200\242

),

7o(.v)%l;

/10(.0\302\276\342\200\224:

-;

*
./iCO%-:
3 /2(.v) 15
A

A2

etc.Noticethat Besselfunctionsare finiteat the origin,but Neumann functions


blowup at the origin.Accordingly,
we must have Bi = 0, and hence
R(r) = Aji(kr).

[4-47]

Section4.1:Schrodinger
Coordinates 143
Equationin Spherical
TABLE4.4: Thefirst few spherical
Besseland Neumannfunctions,
and
7/z (-v)
/i/(.v); asymptoticformsfor small.v.
sin x
./0= x

\302\2730

COS.V

sin .v

cos

cos.v

sin x

.v

x-

ji
J~= V.v3

./1

-V

./3
-

Jl

\\

\342\200\224r

2'n

sin.v

(2/+1)!A '
I

x2

(3
>h=-\\
~
Vx3

cos,v

1,
,^.(2^
2'/! x/+1

y
A-

sin .v

for.v\302\253i.

There remainsthe boundary condition,


R(a) =

suchthat

1 \\

x) cos.v

\342\200\224$

0.Evidently /: must be chosen

j,(ka)= 0:

[4.48]

is, (ka) is a zeroof the /th-ordersphericalBesselfunction.Now, the Bessel


functionsare oscillatory
(seeFigure4.2);eachonehas an infinitenumber of zeros.
that

V8

v10

\\

12V

.14

-.31Bessel
functions.
FIGURE4.2: Graphsofthe first four spherical

144

Chapter4 Quantum Mechanicsin ThreeDimensions


they are not locatedat nicesensible
points(suchas n.
or mj, or something):
At any rate,the
they have to be computednumerically.11

But (unfortunately for us)

requiresthat
boundary condition

where /3,,/is the


then, are given by

\302\253th

= -/3,,/.
a

[4.49]

zeroof the /th spherical


Besselfunction.
The allowedenergies,
E,\342\200\236

/^Ai
2mci-

[4.50]

and the wave functionsare

fnlmir.9.

\302\242)

A\342\200\236,M[}\342\200\236ir/a)Y;\"{0.

\302\242).

[4.51]

constant to be determinedby normalization.


Each energy level is
sincethere are (21+ 1) different values of m for each
(2/ 4- l)-folddegenerate,
value of / (seeEquation4.29).
with the

A\342\200\236i

Problem4.7
(a)

Fromthe definition(Equation4.46),construct
n\\(.x) and /n(-v).

formulasfor /ii(.v)and
(b) Expand the sinesand cosinesto obtainapproximate
ni(x),valid when .v <$C 1.Confirmthat they blow up at the origin.

Problem4.8

/=1.

the radial equation


with V(r) = 0 and
Checkthat Arj\\(kr) satisfies
(b) Determine
graphicallythe allowedenergiesfor the infinite sphericalwell,
Show that for large/;.,
when
+ 1/2)2.Hint:
(tl27i2/2mcr)(n
Firstshow that ./i(.v)= 0 => .v = tan .v. Plot.v and tan.v on the samegraph,
and locatethe pointsof intersection.
(a)

1=1.

=\302\276

E\342\200\236\\

eds..

Abramowiiz and Siegun.


Handbookof Mathematical Functions. (Dover.New York.
extensive
an
listing.
Chapter
provides

10.

1965).

Section4.2:The Hydrogen
Atom

145

* *Problem
4.9 A particleof massm is placedin a.finitespherical
well:
V(r)

= -Vb.

if

< a;

ifr>a.

\342\226\240

0,

Findthe groundstate,by solvingthe radialequationwith / = 0. Show that there


is no boundstateif Vocr <iz~

4.2 THE HYDROGENATOM


The hydrogenatom consistsof a heavy, essentially
motionless
proton(we may as

the origin),
of chargee, together
with a much lighterelectron
(charge
that orbitsaround it, boundby the mutual attraction
of oppositecharges(see
law, the potential
energy (in SI units) is
Figure4.3).FromCoulomb's
well put

it at

\342\200\224e)

V(r)

e2

[4.52]

and the radialequation


(Equation4.37)says
!~r cl^u
7+
2m dr2

e1
4tz\342\202\254q

/(/+1)~u = En.
5
2m r//2

1
1

[4.53]

Our problemis to solvethisequationfor u


and determine
the allowedenergies,
E. The hydrogenatom issuchan importantcasethat I'm not goingto hand you the
(/\342\226\240),

this
solutions
work them out in detail,by the methodwe usedin the
to the harmonicoscillator.
(If any stepin thisprocessis unclear,
analytical solution
you may wish to refer backto Section2.3.2for a morecomplete
explanation.)
time\342\200\224we'll

-e
(electron)

FIGURE4.3: The hydrogenatom.

146

Chapter4 Quantum Mechanicsin ThreeDimensions


the Coulombpotential
Incidentally,
(Equation4.52)admitscontinuum states(with
E > 0), describing
as well as discretebound states,
electron-proton
scattering,
the hydrogenatom,but we shallconfineourattentionto the latter.
representing

4.2.1TheRadialWave Function
Our first task is to tidy up the notation.
Let

= sJ-lmE

[4.54]

(Forboundstates,E is negative,so k is real.)DividingEquation4.53by E, we


have
1

d2u

k2 dr2

!)'

1
+ /(/ + u.
b<r) (Kr)2

we2

2n\342\202\254ofi2K

Thissuggeststhat we introduce
p = Kr, and po

me-

[4.55]

\342\200\224

27T\342\202\254qITK

so that

d2u
dp*

po T

/(/+1)
t

As p
Next we examinethe asymptoticform of the solutions.
constantterm in the bracketsdominates,
so (approximately)

d2u =
dp7

The generalsolutionis
but

ep blowsup (asp

u(p) = Ae~p + Bep.

valid for

does nol apply

caseloo).But

of variables (Equation

[4.57]

oo),so B 0. Evidently,

-\302\273

then:

that

oo, the

\342\200\224

\342\200\224>

for largep. On the otherhand,as p

'-Thisargument

\342\200\224>

u.

u(p) ~ Ae~p.
approximately,

[4.56]

4.60).

0 the centrifugalterm dominates;12

d2u

/(/+1)

dp-

p-

when
never mind: All

[4.58]

I = 0 (although the conclusion.


Equation
I am Irving lo do is provide somemotivation

4.59,is in

fact

lor a change

Section4.2:TheHydrogenAtom

147

The generalsolution(checkit!)is

u(p) = Cpl+*+Dp~!.
p,-/' blowsup (asp

but

\342\200\224>

0),so D = 0. Thus

~ Cp/+1

\302\253(p)

for smallp.
The next

functionv(p):

[4.59]

step is to peeloff the asymptoticbehavior,introducingthe


u(p) = pl+le-pv(p),

new

[4.60]

hopethat v(p) will turn out to be simplerthan u(p).The first indications


are not auspicious:
in the

du = l -p
p (/ +
p'e
dp

\342\200\224

1-p)v + p dv~
dp.
\342\200\224

and

d2u =
dp2

p'\302\253~'

-2/

- 2 + p + /(/+1)1
+ 2(/+
P .
v

dv

dp

d2v
dp2

In terms of v(p),then,the radialequation


(Equation4.56)reads
d~v

dp-

p\342\200\2247

+ 2(/+ 1

dv

ap

p)\342\200\224

+ [p0 2(/+

)]v

= 0.

[4.61]

as a power series
Finally,we assumethe solution,v(p), can be expressed

in

p:

oo

v(p) = Ylc.iPi

[4.62]

\342\226\240

7=0

the coefficients
Our problemis to determine
(co.c\\.
by

term:

dv

dp

oc
x\342\200\224v

.. ,

00

-c-^

term
co....).
Differentiating

[In the secondsummationI have renamed the \"dummy index\":


j j + 1.If this
and checkit.You may object
troublesyou,write out tlie first few terms explicitly,
\342\200\224>

148

Chapter4 Quantum Mechanicsin ThreeDimensions


the sum shouldnow beginat j
anyway, so we might as well start at
that

^
d~V

= 1,but the factor(./+ 1) killsthat term


zero.]Differentiating
again,
\342\200\224

;
+
ikv+ip'-1.
E^./
I

t\342\200\224v

InsertingtheseintoEquation4.61,we have
oc

OO

Y,j(j+ DoW+2(/+1)j^u + u<--j+\\pj


j=0

./=0

-2J2jcjpi + [p0- 2(/+ 1)]

\302\243cjpj

i=0

= 0.

7=0

of likepowersyields
Equatingthe coefficients

./(./'+ l)c;+i+ 2(/+ 1)(7+ l)c7+, 2jcj + [po 2(/+ l)]c/= 0.


or:

[ 2(,/+/+1)-/00
]
W = {(;
+1)0-+*+2)}^

[4.63]

Thisrecursion
the coefficients,
and hencethe functionu(p):
formula determines
We start with co (thisbecomes
an overallconstant,
to be fixed eventually by
and Equation4.63givesus c\\\\ puttingthisbackin, we obtainci,
normalization),
and soon.13
Now let'sseewhat the coefficients
looklikefor largej (thiscorresponds
to
In thisregimethe recursion
formula
largep, where the higherpowersdominate).
says14

2
~ 2'
Cj+[~ JuTT)Cj ~ JTiCj-

'-'You might wonder why ] didn't use the seriesmethod directly on


factor out the
asymptotic behavior before applying this procedure?Well, the reason for peelingoff p'+l is largely
aeslhelic:
Wilhoul ihis. the sequencewould begin wilh a long siring of zeros(the firsl nonzerocoefficient
The e~p factor is more
being r/+|):by factoring out p/+l we obtain a scriesthai starts out wilh
u(p)\342\200\224why

p\302\260.

critical\342\200\224if

Cj

(try

you

ii!) and

don't pull

lhal out.

you

gel a three-term recursion formula,

lhal is enormously more difficult

involving

to work wilh.

fy+2* <*/+i> and

2(/+1)-

14You might ask why


don't drop ihe 1 in +
all, I am ignoring
po in ihe
numerator, and 2/ 2 in the denominator. In ihis approximation il would be fine to drop ihe 1 as well,
but keepingil makes the argument a lillle cleaner.
and you'll seewhat I
Try doing il without the

mean.

1\342\200\224-after

1.

Section4.2:The HydrogenAtom

149

for a moment that thiswere exact.Then


Suppose

=V

Cj

so

00

V(p)

[4.64]

\342\200\224cq.

2J

=C0y 7

\342\200\224pi

= CQ(TP,

7=0

and

hence

u(p)= cQpl+[ep,

[4.65]

which blowsup at largep. The positiveexponential


is preciselythe asymptotic
behaviorwe didn'twant, in Equation4.57.(It'sno accident
that it reappears
here;
after all,it does represent
the asymptoticform of somesolutions
to the radial
in,becausethey
justdon'thappento be the oneswe'reinterested
equation\342\200\224they
aren'tnormalizable.)
There is only oneway outof thisdilemma:
The seriesmust
terminate.
There must occursomemaximal integer,./max,suchthat

cOm,v+D=0.
vanish
(and beyondwhich allcoefficients

[4.66]

automatically).
Evidently(Equation4.63)

= 0.
20\"max+/+0-/00
Defining

= ymax +/ + 1

[4.67]

(the so-called
principalquantumnumber),we have
P0 =

In.

[4.68]

E (Equations4.54and 4.55):
But po determines
E=

so the allowedenergiesare

^k ?

-^n

2m

,,,-,me4

S7t2\342\202\254^h2pl

[4.69

150

Chapter4 Quantum Mechanicsin ThreeDimensions


This is thefamousBohr

measurethe mostimportantresultin
Bohrobtainedit in 1913by a serendipitous
mixture
all of quantum mechanics.
of inapplicable
classical
a
nd
physics premature quantum theory (the Sehrodinger
d
idnot
until
come
1924).
equation
any

formula\342\200\224by

Equations4.55and 4.68,we find that


Combining

me'

K=(

\\47teo^'2/ n

[4.71]

an'

where

a = 47re0^ = 0.529x 10\"10


m

[4.72]

me\"

is the so-called
Bohrradius.15
It follows(again,from Equation4.55)that
P

= r
an

[4.73]

The spatialwave functionsfor hydrogenare labeledby three quantum numbers(n,

I, and m):

fnlm(r,0,

\302\242)

= Rnl(r) lf(0,0),

[4.74]

where (referring backto Equations4.36and 4.60)


Rnl(r) =

[4.75]

-pJ+le-pv{p),

of degree7max = n I 1 in p, whosecoefficients
are
and v(p) is a polynomial
formula
determined
factor)by the recursion
(up to an overallnormalization
\342\200\224

Cj+1

\342\200\224

2(j+l+ l-n)

[4.76]

+ 2)6,7'
(./+ 1)04-2/

The groundstate(that is,the stateoflowestenergy) is the casen =

in the accepted
we get:
values for the physicalconstants,

E\\

=-

2~l

m
2ft2

is

[4.77]

\\47T\342\202\2540i

traditional
to write the Bohr radius
to
s
o
1
leave the subscriptoff.
prefer
unnecessary,
\342\226\2405It

= -13.6
eV.

1;putting

with

a subscript:oq.But

this:

is cumbersomeand

151

Section4.2:TheHydrogen
Atom

energyof hydrogen(the amount of energy you wouldhave


Evidently the binding
to impart to the electron
in the groundstatein orderto ionizethe atom) is 13.6eV.

Equation4.67forcesI =-0,whencealsom.

0 (seeEquation4.29),so

\342\200\224

= #io(r)^(0,<a
^ioo(n#,</O

[4.78]

The recursionformulatruncatesafter the first term (Equation4.76with

yieldsC{ = 0), so v(p)is a constant(cq),and

j =0
[4.79]

a
with Equation4.31:
it, in accordance
Normalizing
i2

lC0l f
f id
i2 2 j
\\Rw\\~rdr = -^=- I e
/

2 7 =
~r/a r~dr

\342\200\224Irla

a2 Jo

11^
c0 4 1,
1

soco %1-sfa.Meanwhile, = ljy/4n, and hencethegroundstateof hydrogen


\342\200\224

Y\302\256

is

^1()0(r,0,

\302\242)

-r/a

[4.80]

VjTtf,3

If n = 2 the energy is
E2 =

-13.6
eV
= -3.4eV;

[4.81]

\342\200\224\342\200\224

thisis the first excited


rather, states,sincewe can have eitherI 0 (in
=
which casem 0) or I = 1 (with m =
0, or +1);evidently fourdifferent
statesshare thissameenergy.If I = 0> the recursion
relation(Equation4.76)gives
state\342\200\224or

\342\200\224

\342\200\2241,

ci

\342\200\224

\342\200\224Co

(usingj = 0),.. and

\302\2422

= 0 (using;'= 1).,

so v(p) cq(1 p), and therefore


\342\200\224

\342\200\224

coefficients
differentfor different
[Noticethat the expansion
{cj}are completely
=
n
1 the recursionformulaterminates
the series
quantum numbers and /.] If I
after a singleterm;v(p) is a constant,
and we find

[4.83]

4a2
(In eachcasethe constantcq is to be determined
by
Problem

4.11.)

normalization\342\200\224see

152

Chapter4 Quantum Mechanicsin ThreeDimensions


with Equation4.67)are
For arbitrary n, thepossible,
valuesof I (consistent
/

0,1,2,...,^-1,

[4.84]

andfor eachI thereare (21+ 1)possiblevaluesof m (Equation4.29),sothe total


of the energy levelE]t is
degeneracy

d(n)=

/j-i

J](21+ 1)= a2;

[4.85]

Thepolynomial
formula,Equation4.76)isa function
v.(p) (defined
by the recursion
well known to appliedmathematicians;
it canbe written
apart from normalization,

as

[4-86]

v(p) ^SLi(2a)>
where

tf-p (*>= (\"i)p(JA

[4.87]

'H<*>

and
is an associated
Laguerrepolynomial,

Lq(x)= e*(J^\\ (*\"***)

[4.88]

are listed
is the #m Laguerrepolynomial,16
(The first few Laguerrepolynomials
in
in Table4.5;someassociated
are
Laguerrepolynomials given Table4.6.The
first few radialwave functionsare listedin Table4.7,and plottedin Figure4.4.)

The normalized
hydrogenwave functionsare17

=
*\342\226\240*

O'[*->(2rH

IWi^\302\247^'m

They are not pretty, but don't complain\342\200\224this

*\342\204\242

is one of the

\302\253\342\226\240

very few

[4.89]
realistic

systemsthat can be solvedat all,in exactclosedform.Noticethat whereas the


onall three quantum numbers,
wave functionsdepend
the energies
(Equation4.70)
of the Coulombpotential;
in the
are determined
by n alone.Thisis a peculiarity
16As usual, there,are rival normalization conventions in the literature; 1 have adoptedthe most
nearly standard one.
17Ifyou want to seehow the normalization factor is calculated, study (for example),L. Schiff,
New York, 1968),
Quantum Mechanics,2nd ed.,(McGraw-Hill,
page 93.

Section4.2:TheHydrogen
Atom

153

TABLE4.5: Thefirst few Laguerrepolynomials,


Lq (x).

Lp-= 1

Lr-= -x- 1
+-

- Ax + 2
L2 =--x2h= + 9x2-18*+6
=-.\302\2763

-16^+ 72^-96^+ 24

L4 =--xA-

h~---x5+ 25X4- 200X3+ 600x2-600x+ 120


-36^+450x4 2400x3+
-4320x+ 720
L6 =
--X\302\253-

5400.\302\2762

TABLE4.6: Someassociated
Laguerre
Lp (x).
polynomials,

j 0_ 1
L,0-

L2= 2

Lf=-jc+l

L2= -6x+18

\302\243.0

= .^-4^+2

L]-l
Z.J= -2x+ 4

1^= 3x2- 18x+ 18

L|=12x2-96x+144
L3= 6

Lj= -24x+ 96

L|=60x2-600x+1200

caseof the spherical


well,you may recall,the energiesdependalsoonI
4.50).The wave functionsare mutually orthogonal:
(Equation

^nim ifti'i'm*>'2sin# drd$

#=

8ntI>8n>&mri

\342\226\240

[4,90]

Thisfollowsfrom the orthogonalityof the sphericalharmonics


(Equation4.33)
of H with distinct
and (for n, ^ nr) from the fact that they are eigenfunctions
eigenvalues.
isnoteasy.Chemists
the hydrogen
wave functions
liketodraw
Visualizing
in which the brightness
of the cloudisproportional
to \\ty\\2 (Figure4.5).
plots,\"
Morequantitative (but perhapsharderto read)aresurfaces
of constant
probability
\"density

density(Figure4.6).

^Problem4.10Work out theradialwave functions ^31,and R32,usingthe


formula (Equation4.76).Don'tbotherto normalize
recursion
them.
./\302\275>

154

Chapter4 Quantum Mechanicsin ThreeDimensions


TABLE4.7: Thefirst few radialwave functions
for hydrogen,
RiQ=2a~3/2exp{-r/d)

#2i=-f=a-312a exp (-r/2a)


\342\200\224

V24

_
/tan
^30
n

\342\200\224\342\226\240

i'-h^i&h^-^

2 a,,-3/2

-r\342\200\224\342\226\240

V27

3 a 27 \\a

-li)(^)exp (-r/3a)

R3i -\302\273_a-M(l

i?32= 4_a-3/2^a'
81V30

^4^0474(^1\302\276\302\276^^
^4]

* -3/204f4&)2)i-p^)

ltiV3

^--ih^i^uw^^
W=

\342\200\224l\342\200\224crm(\342\200\224)

768^35

exp (-r/4a)

^Problem4.11
(a)

NormalizeR20 (Equation4,82),and construct


the function^200.

(b)

NormalizeR21 (Equation4.83),and construct


.^2-11,
i'DO,and yfrji-i-

^Problem4.12
UsingEquation4.88,work out thefirst fourLaguerrepolynomials.
(b) UsingEquations4.86,4.87,and 4.88,find v(p),for the casen = 5, I = 2,
5,.I = 2), but thistimeget it from the
(c) Find v{p)again(for the casen
formula (Equation4.76).
recursion
(a)

\342\200\224

Atom
Section4.2:TheHydrogen

155

4.4: Graphsofthe first few hydrogenradialwave functions,


FIGURE
HM/(r).
*Problem4.13
(a)

Find (r) and (r2) for an electronin the groundstateof hydrogen.Express


your answers intermsof the Bohrradius.

(b)

in the groundstateof hydrogen.Hint:This


Find(x) and (x2J for an electron
requiresno new integration\342\200\224note that r2 x2 + y2 + z2, and exploitthe
symmetry of the groundstate,
\342\200\224

(c) Fmd (x2) in the staten

\342\200\224

2, =

in jc,y, z. Usex
symmetrical

/\342\226\240

\342\200\224

i, m = 1.Warning: Thisstateis not

r sitiOcos0.

156

Chapter4 Quantum Mechanicsin ThreeDimensions

(2,0,0)

(3,1,0)

(4,0,0)

(4,1,0)

(4,2,0)

(4,3,0)

FIGURE4.5: Densityplotsfor the hydrogenwave functions I, m).Imagine


each
rotated
tobe
the
P
rinted
'\"Atomin
a
axis.
about
plot
(vertical)z
by permission
using
Yon canmake your own plotsby goingto theWeb
Box,\"vl.OiS,
by DangerResearch.
(\302\253,

sitehttp://danger.com.

Problem4.14What is the mostprobablevalue of r, in the groundstateof


(The answer is notzero!)Hint:Firstyou must figure out theprobabilitythat
the electron
wouldbe foundbetweenr and r + dr.
hydrogen?

of
Problem4.15A hydrogenatom startsout in the followinglinearcombination
the stationarystatesn 2,1 1,m..=1 and n 2, / = 1,m
\342\200\224

\342\200\224

\342\200\224

\342\200\224

\342\200\2241:

1
W(r,0)= \342\200\224Ofon+^21-1).
:x/2

(a)
(b)

Construct
ty(r,t). Simplifyit as much as you can.
Findthe expectation
value of the potential
energy,(V),(Doesit dependon
t?) Give boththe formula and theactual number, in electronvolts.

Atom
Section4.2:The;Hydrogen

157

FIGURE4.6: Surfacesof constant|^|2for the first few hydrogen wave functions.


from SiegmundBrandtand HansDieterDahmen,ThePicture
Reprintedby permissipn
BookofQuantumMechanics,
3rded..Springer,
New York (2001).

4.2.2TheSpectrumof Hydrogen
if you put a hydrogenatom intosomestationary state^nim, it should
In principle,
if you tickleit slightly(by collision
with anotheratom,
stay thereforever.However,
may undergoa transitionto someother
say,orby shininglighton it),the electron
stationary
by absorbing
energy,and movingup to a higher-energy
state,or by giving off energy (typically intheform of electromagnetic
radiation),
state\342\200\224either

158

Chapter4 Quantum Mechanicsin ThreeDimensions

transitions
In practicesuchperturbations
are always present;
and movingdown.18
and
called,\"quantum jumps\")are constantlyoccurring,
(or,as they are sometimes
theresultis that a container
of hydrogengivesoff light(photons),
whoseenergy
to thedifferencein energy betweenthe initialand final states:
corresponds
Ey

= Ei -Ef = -13.6
eV [ \\

n.

-~

[4.91]

n;f

the energy of a photonis


to thePlanckformula,19
Now, according
proportional

to its frequency:

EY

the wavelength is given by


Meanwhile,

= hv.
K

[4.92]

= c/v, so

[4.93]
where
R=

2
-^
-^- ] = 1.097 107
(

m\"1

[4.94]

is known as the Rydbergconstant.Equation4.93is the Rydbergformulafor the


in thenineteenth
of hydrogen;it was discovered
century, and
spectrum
empirically

for thisresult\342\200\224and
the greatest
triumph of Bohr'stheory was itsability to account
to the
of nature.Transitions
to calculateR in terms of the fundamental constants
as
groundstate(rif = he in the ultraviolet;
they are known to spectroseopists
theLyman series.Transitions
to the first excitedstate = 2) fall in the visible
to rif = 3 (the Paschen
theBalmerseries.Transitions
region;they constitute
most
series)are intheinfrared;atid soon (see.Figure4.7),(At roomtemperature,
spectrumyou must
hydrogenatomsare in the groundstate;to obtainthe emission
an electric
first populatethe variousexcitedstates;typically thisis doneby passing
sparkthroughthe gas.)
1\")

(\302\253/

atomconsistsof a singleelectronorbitinga nucleus


^Problem4.16A hydrogenic
with Z protons(Z = 1 wouldbe hydrogenitself,Z 2 is ionized
helium,Z = 3..
\342\200\224

By its nature, this involves a unie-ifependent interaction, and the detailswill have to wait for
Chapter 9;for our presentpurposesthe actual mechanism involved is immaterial.
19Thephoton is-a quantum of electromagnetic
radiation; it'sa relativistic objectif there ever was
one,and therefore outsidethe scopeof rionrelalivistic quantum mechanics.It will be useful in a lew
placesto speakof photons, and to invoke the Planck formula for their energy, but pleasebear in mind
that this is external to the theory we are developing..

Section4.2:The HydrogenAtom

159

OQ

\342\226\240

-1.0

-2.0

'v

Paschen

series

-3.0

u u u u u

-4.0

Balmer

series

-5.0
-6.0
> -7.0h
S3 -8.0
C
-9.0h
CD

LU

-10.0

-11.0
-12.0

-13.0
\342\200\242\342\200\224

\342\200\22414.0

v u u u ,r u

Lyman

series

FIGURE
inthe spectrumof hydrogen.
4.7: Energy levelsand transitions
the BohrenergiesEn(Z),the
is doublyionizedlithium,and so on).Determine
bindingenergy E\\(Z), the Bohrradiusa(Z),and theRydberg constant
R(Z) fora
of thehydrogen
your answers as appropriate
multiples
hydrogenicatom.(Express
wouldthe Lyman seriesfall,for
values.)Where in the electromagnetic
spectrum
Z = 2 andZ = 3?Hint:There'snothingmuch tocalculate
the potential
in
(Equation4.52)e2 Ze2,so allyou have to do is make the samesubstitution
allthe final results.
here\342\200\224in

\342\200\224*

theearth-sunsystemasa gravitational
Problem4.17Consider
analogto the
atom.
hydrogen

is the potentialenergy function(replacing


Equation4.52)?(Letm be
themassof the earth,and M themassof the sun.)

(a) What

(b) What

is the\"Bohrradius,\"
ag,for thissystem?Work outthe actualnumber.

gravitational\"Bohrformula,\"and, by equatingEn to the


classical
energy of a planetin a circularorbitof radiusr(j, show that n =
Fromthis,estimatethe quantum number n of the earth.

(c) Write down the


\342\226\240yJ'Toja^.

160

in ThreeDimensions
Chapter4 Quantum Mechanics
(d)

Supposethe earth madea transitionto the next lowfer level(n .1.).How


much energy (in Joules)wouldbe released?
What wouldthe wavelength of
the emittedphoton(or,morelikely,graviton) be?(Expressyour answer in
the remarkable
answer20a coincidence?)
light
\342\200\224

years\342\200\224is

4.3ANGULAR MOMENTUM
three
the
n, I, and m.The principalquantum number determines
quantum numbers:
energy of thestate(Equation4.70);asit turns out,I and m are relatedto the orbital
In the classical
angular momentum.
theory of centralforces,energy and angular
momentum are the fundamental conserved
and it is not surprising
that
quantities,
angular momentum playsa significant(in fact, even moreimportant) rolein the
As we have seen,the stationary statesof the hydrogenatomare labeledby
(\302\253.)

quantum theory.
the angular momentum of a particle(with respectto the origin)is
Classically,
given by the formula

L = r x p,

[4.95]

[4.96]

which is to say,
Lx =

ypz-zpy,

Ly

zpx\342\200\224

xpz, Lz=xj?y-ypx.

are obtained
The corresponding
quantum operators
by the standard prescription
Px

\342\200\224>

\342\200\224ihd/dx,

py

\342\200\224>

\342\200\224ihd/Byi

pt ->

\342\200\224ihd/dz-

In the followingsectionwe'll

of the angular momentum operators


obtaintheeigenvalues
by a purely algebraic
of theonewe usedin Chapter2 to getthe allowedenergies
reminiscent
technique
of the harmonic
of commutation
it isallbasedon the clever
oscillator;
exploitation
the
of determining
After that we will turn to the moredifficultproblem
relations.

eigerifunctions.

4.3.1Eigenvalues
in fact2The operators
L.x and Ly do not commute;

[Lx,Ly] = [ypz zpy,zpx xpj


= [yPz,ZPx]~ [yPz> *Pz\\ kpy, zpx\\ +[ZPy,*Pzl

[4.-97]

20ThariksLo John Meyerfor pqinling this out.


2'Notethai <ili the operators we encounter in quantum mechanics(footnote 15,Chapter 1) are
to addition: A(B + C) ~ AB + AC. In particular, [A, B + C]= [A, B~\\ +
distributive with respect
[A,

C].

Section4,3:Angular Momentum

161

Fromthe eanonieal
commutation
relations(Equation4.10)we know that the only
herethat fail to commuteare x with px,y with py, and z with pz.So
operators
the two middleterms dropOut, leaving
[LXi Ly] =

ypxipz,z] + xpylzipz] = ih{xpy ypx) = ihL-z.

[4.98]

Of course,we couldhave startedoutwith [Ly,Lz]or [Lz,Lx],butthereisnoneed


to calculate
theseseparately\342\200\224-we can getthem immediately
by cyclicpermutation
of the indices(x -> v, y -> z, z-> x):
[LXr Ly]

= ihLz; [Ly,Lz]= ihLx; [Lz,Lx]= ihLy.

[4,99]

relationsfor angular momentum;


Theseare the fundamental commutation
elsefollowsfrom them.
Noticethat LXi Ly, and Lz are incompatible
observables.
Accordingto the
generalized
uncertainty principle
(Equation3.62),

everything

vLsOLy >~\\(LZ)\\.

'

[4.100]

It wouldthereforebefutileto lookfor statesthat aresimultaneously


eigenfunctions
of Lx and Ly. On theotherhand,the squareof thetotalangular momentum,
L2=

Lxl

+ L2 + L2,

[4.101]

doescommutewith Lx:
[L2,LA = [L2X,Lx] + [L2,Lx] + [L% Lx]
= Ly[Ly,Lx]+ [Ly,Lx}Ly+Lz[Lz,
LJ+[LZJ LX]LZ
= Ly(-ihLz)+ {-ihLz)Ly+ Lz{ihLy)+ {ihLy)Lz
= .0.
notealsothat any operator
(I usedEquation3.64to simplifythe commutators;
with Ly and
commutes
with itself)It follows,of course,that L2 alsocommutes
Lz-

[L2,Z^]= 0, [L2,Ly]=0, [L^LJ^O,

[4.102]

162

in ThreeDimensions
Chapter4 QuantumMechanics

or,morecompactly,

[L2,L]= 0.

[4.103]

of L, and we canhopeto find


SoL2 is Compatible
with eachcomponent
of L2 and (say) Lz;
eigeristates

simultaneous

.L2f=kf

LJ= iif.

and

[4.104]

We'llusea \"ladderoperator\"
to the onewe appliedto
very similar
technique,
the harmonic
backin Section2.3.1.
Let
oscillator
L+

= Lr

[4.105]

\302\261iL.y

The commutator
with L7 is

[Lz,L + ] = [Lz,Lx] i[Lz,Lyl = ihLy


\302\261

\302\261
?\342\226\240(-\302\273\302\243*)

\302\261

h{Lx iLy)
yj,
\302\261

SO
[LZ,L\302\261]

And,

of course,

\302\261HL

+.

[4.1Q6]

= o.

[4.107]

[LM\302\261]

of L2andLz, soalsois
I claimthat if f is an eigenfunction
says
L2(L\302\261/)

= L\302\261(L2/) =

L\302\261(Xf)

L\302\261

/':Equation4.107

= HL\302\261f),

[4.108]

of L2,with the sameeigenvalue


4.106
soL + / is an eigenfunction
X, and Equation
says:
Lz{L\302\261f)

=
=

L\302\261LJ
{LzL\302\261-L\302\261Lz)f

\302\261hL

+ f + L^{iif)

[4.109]

({j,\302\261K](L+f%

of Lz with the new eigenvaluefi /z. We callL+


so L + f is an eigenfunction
the \"raising\"operator,
becauseit increasesthe eigenvalueof Lz by h, and L_ the
becauseit lowersthe eigenvalue
\"lowering*'operator,
by h.
For a given value of -A., then,we obtain a \"ladder\"of states,with each
of Lz (see
\"rung\"separatedfrom its neighbors
by oneunit of h in theeigenvalue
and to descend,
the
Figure4.8).To ascendthe ladderwe applythe raisingoperator,
But thisprocesscannotgo on forever:Eventually we'regoing
loweringoperator.
\342\226\240+

Section4.3:Angular Momentum

163

FIGURE4.8: The \"ladder\"ofangularmomentumstates.

exceeds
to reacha statefor which the z-eorriporient
the total,and that cannotbe.22

There must exista \"toprang,\"ft, suchthat23

L+ft = 0.
22Formally, (I1)= (L2)+ <L2)+<Lj),but (*%) =
for

L,,)\342\200\236

so.A

- (L2)+

{i\302\243)

+ ^2 > ft.

^Actually, all we can concludeis

instead of

Ihat

zero.Problem 4.18explores
this

L+ft- is not

alternative.

[4.110]
(and likewise
iffclf)= {Lxf\\Lxf)>$
normalizable\342\200\224its

norm

could be infinite,

164

in ThreeDimensions
Chapter4 Quantum Mechanics

of the letter
Let hi be the eigenvalueof Lz at thistop rung (theappropriateness
\"/'\" will appear
in a moment):

[4.111]

Lzft=hlft; L2ft=kft.
Now,

L+LT = (Lx + iLy)(Lx^iLy) = L2+ L2^i(LxLy LyLx)


\342\200\224

I? l}z^i(ihLz),

or,puttingit the otherway around,


L2=

L\302\261LT

+ L2Z^ hLz.

[4.112]

It followsthat
L2ft = (L-.L++ ut+hLjfi

- (0+ h2i2+ nH)fi-= n2w

+1)/\342\200\236

and henee

X=h2l(l+ 1).

[4.113]

of L2 in terms of themaximum eigenvalueof Lz.


This tellsus the eigenvalue

thereis also(forthe samereason)a bottomrung,j%, suchthat


Meanwhile,

L-fh = 0.

[4.114]

Let hi be the eigenvalueof Lz at thisbottomrung:


Lzfb = Hlfbi L2fh= kfh.

[4.115]

we have
UsingEquation4.112,

I>fp (L+L-+ L2-hLz)fb= (0+ h2t h2l)fb= h2J(l-\\)h,


\342\200\242=

and therefore
X

= /z27(7-l).

[4.116]

4.113and 4.1-16,
we seethat 1(1-f 1)= 7(7 1),soeither
ComparingEquations
7 = / + 1 (which is
bottomrang wouldbe higherthan the top rung!)
of else
\342\200\224

absurd\342\200\224the

7--/.

[4.117]

Section4.3:Angular Momentum

165

of Lz are mh,where m (the appropriateness


of this
Evidently the eigenvalues
letterwill alsobe cleariri a moment) goesfrom to +1in N integersteps.In
it fpllowsthat I' =
+ N, and henceI = N/2, soI must be an integer
particular,
or a half-integer.
The eigenfunctions
are characterized
by the numbersI and m;
\342\200\224/

\342\200\224l

iS-f?= HH(l+ 1)jf;

LJ\342\204\242

= hmfirin

[4.118]

where

.
1= 0, 1/2, 1,-3/2,

m=

\342\200\224

I,

\342\200\2241

+ 1,

- 1, /,

[4.119]

Fora given value of /, there are 2/ -f 1 different values of m (i.e.,11+ 1\"rungs\"


on the \"ladder\.

Somepeoplelike to illustratethis resultwith the diagramin Figure4.9


to represent
(drawn for the caseI = 2).Thearrows are supposed
possibleangular
units of h they all have the samelength*Jl(l+ 1) (in thiscase
are the allowedvaluesof m
Vfr 2.45),and theirz components
1,0, 1,
of
that
the
o
f
the
vectors
i
s
the
raditis
Notice
2).
(the
magnitude
sphere) greater
than themaximum z component!
(In general,-^/1(1+ 1) I, exceptfor the
caseI 0.)Evidently you can'tgettheangular momentum to pointperfectly
At first, thissounds
absurd.\"Why can'tIjustpickmy axes
alongthe z direction.
so that z. pointsalongthedirectionof the angular momentum vector?\"Well, to
and the
do this you would have to know all threecomponents
simultaneously,

momenta\342\200\224in

\342\200\224

\342\200\224

(\342\200\2242,

>\342\226\240

\"trivial\"

\342\200\224

43: Aiigular momentumstates(for 1= 2).


FIGURE

Chapter4 Quantum Mechanicsin ThreeDimensions


\"Well, all right,but
uncertainty principle
(Equation4.100)says that'simpossible.
along
surely oncein a while,by goodfortune,I willjusthappento aim my
the direction
of L.\"No, noI You have missedthe point.It's notmerely that you
don'tknow allthreecomponents
of L; there simply aren't three components\342\200\224a
particle
justcannothave a determinate
angular momentum vector,any morethan it
can simultaneously
If Lz hasa wellhave a determinate
positionand momentum.
definedvalue,thenLx and Ly do not.It is misleading
even to draw the vectors
in Figure
bestthey shouldbe smearedout around the latitudelines,to
indicatethat Lx and Ly are indeterminate.
I hopeyou'reimpressed:
means,startingwith the
By purelyalgebraic
fundamental
commutation
relationsfor angular momentum (Equation4.99),we have
of L2 and Lz\342\200\224without ever seeingthe eigenfunctions
determined
theeigenvalues
of constructing
the eigenfunctions,
themselves!
but
We turn now to the problem
I shouldwarn you that thisis a much messierbusiness.
lustso you know where
of
we'reheaded, beginwith the punchline: =
eigenfunctions
which we cameuponby
L2 and Lz are nothingbut theoldspherical
harmonics,
a quitedifferentroutein Section4.1.2(that'swhy I chosethe lettersI and m,
of course).And I can now tellyou why the spherical
harmonics
are orthogonal:
are
of hermitian
to distinct
(L2 and Lz) belonging
They
operators
eigenfunctions
\302\243-axis

4.9\342\200\224-at

I'll

f\342\204\242

Yf1\342\200\224-the

(Theorem2, Section3.3.1),
eigenvalues

*Problem
unit:

4.1\302\276

The raisingand loweringoperators


changethe value of m by one

[4.120]

L\302\261f{n={Af)f^\302\261\\

is someconstant.Question:What is Af, if the eigenfunctions


are to
be normalized1?
Hint:Firstshow that LT isthehermitian conjugateof
(since
Lx and Ly are observahles,
you may assume
they are herimtian . but proveit
if you like);thenuseEquation4.112.
Answer:
where Af

L\302\261

\342\226\240..

= h^(lTm)(I
Af = hy/lQ + l)-m(m\302\261\\)

\302\261m

+ 1).

[4,121]

Notewhat happensat the top andbottomof theladder(i.e.,when you apply L_|_


to fj or L_ to /\"').

^Problem
4.19
(a)

and momentum
relations
forposition
commutation
Startingwith thecanonical
(Equation4.10),work out thefollowingcommutators:

[Lz,x] = ihy,
[Lz,v] = -ihx, [Lz,z) = 0,
[Lz,px]= ihpy, [Lz,py] = -ihpx, [Lz,pz]= 0,

Section4.3;Angular Momentum

167

Usetheseresultsto obtain[Lz,L*] iHLy directlyfrom Equation4.96,


(c) Evaluate the commutators[Lz,r2] and {LA,p2] (where, of course,r2
x2 + + z2 and p2 = p2x+p$+
H = (p2/2m)+ V commutes
with all three
(d) Show that the Hamiltonian
of L, providedthat dependsonlyonr. (ThusH, L2,and Lz
components
are mutually compatible
observables.)
(b)

\342\200\224

\342\200\224

/\302\276).

y\302\260-

V\"

* ^Problem4.20
(a)

Provethat for a particlein a potentialV(r) the rate of changeof the


value of the orbitalangular momentum L is equalto the expectation
value of the torque:

expectation

|(L)= (N),
where
N = rx(-VV).

(Thisis the rotational


analogto Ehrenfesfstheorem.)
(b) Showthat

(Thisis one
d(L)/dt 0 for any spherically
symmetricpotential.
\342\200\224

form of the quantum statement


of conservation
of angularmomentum.)

4.3.2Eigenfunctions
Firstof all we needto rewrite Lx, Ly, and Lz in sphericalcoordinates,
Now,
and
the
i
n
L (h/i)(rx V),
is;24
coordinates,
gradient, spherical
\342\200\224

meanwhile,r =

dr +0 r dO + r sin090;

r\342\200\224

[4.123]

0\342\200\224

rr, so

L=

9
JBr

~
r(r x r)
_

\342\226\240
\342\200\236

f-

(r
y

* -9

1 9

~
(r x 0)
+
v
;W
sine90.
\342\226\240

61)\342\200\224

\"^GeorgeArfken and Hans-Jurgen Weber, Mathematical Methodsfor Physicists,5th


Academic

Press,Orlando (2000),Section2,5.

ed.,

168

in ThreeDimensions
Chapter4 QuantumMechanics

But (f x r) =

0, (r x 9) = 0, and (r X 0) =
/ --a -:

(seeFigure4.1),andhence

\342\200\2240

a
L=- 0--0sin0 30/
\302\273

'

\\

[4.124]

3<9

The unit vectors9 and 0 can beresolved


intotheircartesian
components:

9 = (cos9 cos

\302\242)1

\342\200\224

\342\200\224(sin0)f-f-

+ (cos9 sin0)j
(cos0)J,

Thus

[4.125]
[4.126]

\342\200\224

(sin#)\302\243;

(.-sin0i+cos0;)
\342\200\224

1 3
30_

-(eos#cos0i + cos9sin0J sin9k)sin#


\342\200\224

Evidently
Lx =

- /z

Ly

\342\200\224
\342\200\224

z'

3
3 \\
cos0eot#
69

-\302\276

\342\200\224

sin0-\342\200\224

\\

[4.127]

\342\200\224-

\302\242\302\242/

[4.128]

+CDS0V
3n sin0:eot0
I

30,

and

[4-129]
We

L+

shallalsoneedthe raisingand loweringoperators:

\342\200\224

But eos0

Lx + iLi,=

\302\261

(\342\200\224sin0

\302\261

3
d$

\342\200\224

eos0)\342\200\224-

(cos0

\302\261

sm0)cot#\342\200\224

30

+ i. so
i sin0= e*
'*,,
'

L+ =

3 +,

\342\200\224:

\302\261he\302\261ix>

3
J:

[4.130]

\342\200\224

COt\302\243

.36\302\273

30,

111
particular(Problem4.21(a))

/ 32
3
cot9
cor,
-^
+
X+L_
-^d$2
-\342\200\224h
36\302\273

32

0\342\200\224

^\302\2422+l^\302\242),

[4.131]

169

Section4,3:Angular Momentum
and hence(Problem4.21(b)):

L2 =

We are now
with

-h'

3/.9

\342\200\224

sine de \\

sin(9

_L 3*_'
m + sin20 d(j>2

\342\200\224

[4.132]

of L2,
in a positiontodetermine
//\"(#, It's an eigenfunction
\302\242).

eigenvalueh2l(l+ 1):
2
= -A\" 1
Z//f
sin
i-KfJ.

6\302\273

3/..3
sin.0

\342\200\224

9(9

96

3^

_1

sin2 302_

jf = fc2/(/ + l)//!

6\302\273

Butthisisprecisely
the \"angularequation\"(Equation4.18).
And it'salsoan
mh:
eigenfunction of Lz, with theeigenvalue
*<zf?=

j^fr=*mfr,

thisis equivalentto the azimuthal equation(Equation4.21).We have already


is the
The result(appropriately
solvedthissystemof equations:
normalized)
of
Conclusion:
harmonics
ait eigenfunctions
harmonic,
Spherical
Fjm(#>
L2 and Lz. When we solvedthe SchrOdinger
of variables,
equationby separation
in Seetion4.1,we were inadvertently constructing
of
simultaneous
eigenfunctions
thethreecommutingoperators
H, L2,and L?:
but
spherical

\302\242)-

Hlfr =

Ef,

L2iff

=h2l{l+ 1)^, Lzf = hmifr:

[4.133]

to rewrite theSehrodinger
we can useEquation4.132
equation
Incidentally,
more
4,14)
compactly:
(Equation

-2 9

2mr2

dr

+V

\\j/

-f Vifr =

Exfr.

There is a curiousfinal twist to this story, for the algebraictheory of

angular momentum permitsI (andhencealsom) to takeon ^//-integervalues


of variablesyieldedeigenfunctions
whereas separation
onlyfor
(Equation4.119),
solutions
integervalues (Equation4.29).You might supposethat the half-integer
but it turns outthat they are of profoundimportance,
are spurious,
as we shallsee

inthefollowingsections.

170

Chapter4 Quantum Mechanicsin ThreeDimensions

^Problem4.21
(a) DeriveEquation4.131from Equation4A30,Hint:Usea testfunction;
you'relikelyto dropsometerms.
Hint:Use
(b) DeriveEquation4.132from Equations4.129and 4.131.
otherwise

Equation4.112.

^Problem4.22
(a) What
(b)
(e)

is

\302\243+7/?

(No calculation
allowed!)

Usetheresultof (a),togetherwith Equation4.130and thefact that LzYf =


constant.
7/(0,0),up to a normalization
MYJ, to determine
constantby directintegration.
the normalization
Determine
Compareyour
final answer to what you got inProblem
4.5.

Problem4.23 In Problem4.3you showedthat


Y}@,0) =
Apply

-V15/87Tsinecos

\342\226\240$<?*.

theraisingoperatorto find Y%.(8,0).UseEquation4.121to getthe

normalization.

of massm are attached


Problem4.24 Two particles
totheendsof a massless
rigid
rodof lengtha. The systemis freeto rotateinthreedimensions
aboutthe center
(but the centerpointitselfis fixed).
of thisrigidrotorare
(a) Showthat theallowedenergies
En

\342\200\224-\342\200\224Y\342\200\224,

for

\302\253

= 0, 1,

2,.,.

Hint:Firstexpressthe (classical)
energy intermsof thetotalangular
momentum.

for thissystem?What is the


normalized
eigenfunctions
of thenth, energy level?

(b) What are the


degeneracy

Section4.4:Spin

171

4*4 SPIN
a rigid objectadmitstwo kindsof angular momentum:
In classicalmechanics,
with the motionof the centerof mass,and spin
orbital(L = r x p), associated
with motion
associated
aboutthecenterof mass.Forexample,
theearth
(S = 1(d),.
to its annual revolutionaroundthesun,
hasorbitalangular momentum attributable
and spinangular momentum comingfrom its dailyrotationaboutthenorth-south
axis.In the classical
contextthisdistinction
is largelya matter of convenience,
for
when you comerightdown to it, S is nothingbut the sum totalof the \"orbitaT'
angular momenta of alltherocksand dirt clodsthat go to make up theearth,as
in quantum mechanics,
they circlearoundtheaxis.Butan analogous
thing happens
is absolutelyfundamental.
In additionto orbitalangular
and herethe distinction
momentum,associated
(inthe caseof hydrogen)with themotionof the electron
aroundthenucleus(anddescribed
theelectronalso
harmonics),
by the spherical
carriesanotherformof angular momentum, which hasnothingto do with motion
in space(and which is not,therefore,described
of the position
by any function,
variablesr, 6, but which is somewhatanalogous
to classical
spin(and for which,
we usethe sameword).It doesn'tpay to pressthisanalogytoofar:The
therefore,
\302\242)

electron(asfar as we know) is a structureless


pointparticle,and its spinangular
momentum cannotbe decomposed
intoorbitalangular momentaof constituent
Sufficeit to say that elementaryparticles
4.25).25
carry intrinsic
parts(seeProblem
to their''extrinsic\"
angular momentum (L),
angular momentum (S) in addition
The algebraictheory of spinis a carboncopyof the theory of orbitalangular
with thefundamental commutation
relations:26
momentum,
beginning

[5x,Syl = ihSz, [Sy,Sz] = ihSx, [Sz:,Sx] = ihSy.


It follows(asbefore)that theeigenvectors
of 52 and

satisfy27

51\302\276

S2\\sm)= h2s(s+ l)\\sm); Sz\\sm}=


\342\226\240For

(1986).

a contrary interpretation, seeHans C.Ohanian,

\"What

[4.134]

hm\\s

m);

is Spin?\",Am.

[4.135]
J. Phys. 54, 500

26We shall take theseas


postulatesfor the theory of spin;the analogous formulas for orbital
werederivedfrom the known form of the operators (Equation 4.96).
momentum (Equation 4.99)
In
a more sophisticatedtreatment they can both beobtained from rotational invariance in three dimensions
A ModernDevelopment,World Scientific,
(see,for example,LeslieE. Ballentihe,Quantum Mechanics:
Section3.3).
Indeed,thesefundamental commutation relations apply \\a all forms of
Singapore(1998),
angular mpmentum, whether spin, orbital, or the combinedangular momentum of a compositesystem.
Which Could include somespin and some orbital.
Becausethe eigenstatesof spin are uqL functwnst I will use the \"ket\" notation for them. (I
couldhave done the samein Section4.3,writing \\lm) in placeof Yfl, but in that context the function
notation seemsmore natural.) By the way, I'mrunning out of letters,so
use m for the eigenvalue
of SV, just as I did for Lv: (someauthors write M\\ and ms at this stage,just to be absolutely clear).

angular

I'll

172

in ThreeDimensions
Chapter4 Quantum Mechanics
and

S\302\261

where S+ = Sx

\\sm) =

hy/sis+ V-miml1) \\s (m

\302\261

1)),

[4.136]

i iSy.

arenotspherical
But thistimethe eigenvectors
harmonics

(they'renotfunctionsof $ and <p at all),and thereis no a priorireasonto exclude


the half-integer
valuesof 5 and m:
.*\342\226\240

-,-..;= -s,-5+1,...s - 1,s.

1 3
= 05 -,
lr

[4.137]

It so happensthat every elementary particlehas a specificarid immutable


value of s, which we callthe spinof that particular
species:pi mesonshave spin
have spih1/2;photons
have spin1;deltas.have
0;electrons
spin3/2;gravitonshave
spin2; and so oh.By contrast,the orbitalangular momentum quantum number
I (for an electronin a hydrogenatom,say) Can take on any (integer)value you
But s
please,and will changefromoneto anotherwhen the system is perturbed.
isfixed,for any given particle,and thismakesthe theoryof spincomparatively

simple.28
solidsphere,with radius
Problem4.25If the electronwere a classical
re =

e2
\342\200\224

4jr6o7wcz

[4.138]

classical
electronradius,obtained
(the so-called
by

massis
theelectron's
assuming
formulaE = mc2),
attributable
to energystoredinitselectricfield,via the Einstein
and its angular momentum i$ (l/2)h,thenhow fast (inm/s)woulda pointon the
\"equator\"be moving?Doesthismodelmake sense?(Actually, the radiusof the
electronis known experimentally
to be much lessthan rc, but thisonly makes
matters worse.)

28Indeed,in a mathematical sense,spin 1/2is the simplestpossiblenontrivial quantum system,for


just two basis states.In placeof an infinite-dimensionalHilbcrtspace,with all its subtleties
and complications,we find ourselvesworking in an ordinary 2-dimensionalvector space;in place
it

admits

of unfamiliar

differential equations and fancy functions, we are confronted with

2x2matrices and

2-componentvectors.For this reason,some authors begin-quantum mechanicswith the study of spin.


(An outstanding exampleisJohn S.Townsend, A ModernApproach to Quantum Mechanics,University
But the priceof mathematical simplicity is conceptual absti'action,and I
Books,Sausalito,C.A, 2000.)
prefer not to do it that way.

Section4,4:Spin

173

4.4.1Spin1/2
1/2,for thisis the spinof theparticlesthat
make up ordinary matter (protons,
and electrons),
as well as allquarks
neutrons,
and allleptons.Moreover,onceyou understandspin1/2,it is a simplematter to
for any higherspin.There are justtwo eigenstates;
work out the formalism
|^
1
call
and
we
which
which we
callspindown
spinup (informally,
as
the
(4,).Usingthese basisvectors, generalstateof a spin-1/2particlecan be
as a two-element
columnmatrix (orspinor):
expressed

By far the mostimportantcaseis 5

\342\200\224

|), |j

|},

(\342\200\2245)),

(b)

= aX+ + bx-

[4-139]

with

X+=L

[4-140]

X-=

[4-141]

representing
spinup,and
V

for spindown.
become2x2matrices,
the spinoperators
which we can work out
Meanwhile,
A. 135says
by notingtheireffecton x+ and X-.Equation

S2x+= ^2X+ and

SV-^V.

[4-142]

If we write S as a matrix with (asyet) undetermined


elements,

S2 =
thenthe first equationsays

::flffl-H). so c =

and a

(3/4)/\302\2762

'c
sod = 0 and /

\342\200\224

\342\200\224

0. The secondequationsays

d\\ /0\\

(3/4)\302\276

/<T

3\342\200\2362/0\\

'

\302\260

. Conclusion:

*= l*Co

^14\302\276
?)\342\226\240

174

in ThreeDimensions
Chapter4 Quantum Mechanics

Similarly,
PzX+ =

[4.144]

-V

[4.145]

*
o
--xs?x^x+,
h

from which it followsthat

Sz =

/l

2V\302\260

Meanwhile,
Equation4..136says

s+x-= frx+, S-X+= hx-y S+x+= S-x^ -o,


so

'0

S_ = A.. '01 0^
o,

1\"

S-U=fi ,0 0,
Now

hence

= Sx iSy, so Sx = (1/2)(5++ S_) and Sy = (1/2/)(5+ 5_),and


\302\261

S\302\261

[4.146]

^ - 2 11or

bar\"2U.

[4.147]

SinceSjt,.Sy.,,and Sz allcarry a factorof hj'1,it is tidierto write S = (hj2)a,

where

'^s(l o)>

'Q
j

\302\260>

-f
0

7'

0
^^ 101 -1

[4.148]

Theseare the famousPaulispinmatrices.Noticethat Sx,Sy, S2,and S are all


Onthe otherhand,
hermitian
(asthey shouldbe,sincethey represent
observables).
S+ and S- are nothermitian\342\200\224evidently they are notobservable.
of Sz are (of course):
The eigenspinors
X+

+
eigenvalue

H'

eigenvalue

X-

J. [4.149]

If you measureSz on a particlein thegeneralstatex (Equation4.139),


you could
theseare the
with probability
\\b\\2. Since
get +/1/2,with probability|a|2,or
\342\200\224ft/2,

only

possibilities,

\\af + \\b\\2

=l

[4.150]

(i.e.,the spinormust be normalized)P


is the \"probability that the particle is in the spin-up state,\" but this
29Peopleoften say that |a.|2
is sloppylanguage; what they mean is that if you measured Sz, la]2 is the probability you'd get h/2.

Seefootnote 16in

Chapter \"3.

Section4,4:Spin

175

But what if, instead,


Sx1What are thepossibleresults,
you chosetomeasure

and what are theirrespective


Accordingto the generalized
probabilities?
we heedto know the eigenvalues
and eigenspinors
of Sx.The
interpretation,

statistical

is
characteristic
equation

-k
ft/2

/J/2 = o
-X

=>\342\226\240

r=

'W

ft

=*3t=\302\261

the possiblevaluesfor Sx are the


Not surprisingly,
are obtained
in thte usualway:
eigenspiriors

sameas thosefor Sz. The

;(?.oca-*
tew.'

=+

so ^

\342\200\224

+ a. Evidently the (normalized)


of Sx are
eigenspinors
1

/J_\\
yW

'a'

+
eigenvalue

72

ft\"
*\302\253

eigenvalue

ft'

[4.151]

72'

\342\226\240

theeigenvectors
of a hermitian
matrix, they spanthe space;the genericspinor
of them:
as a linearcombination
(Equation4.139)canbe expressed

As
X

x=

+ (<L^)xn
(^)tf
72
72

[4.152]

If you measureSx, the probabilityof getting+ft/2 is .(1/2.)[a


+ h]1,and the
is (1/2)\\a, b\\2.(You shouldcheekfor yourselfthat
probabilityof getting
theseprobabilities
addup to 1:)
\342\200\224

\342\200\224ft/2

a spin-1/2
particleisinthestate
Example4.2 Suppose
X

Wl+T

76

'2

of getting+ft/2 and
What are theprobabilities

\342\200\224ft/2,

if you measureSz and SA?

Solution:Herea = (1+ 0/76and b 2/76,sofor.S-zthe probabilityof getting


= 1/3,and the probabilityof getting-ft/2 is |2/76|2
=
+ft/2 is |(1+0/76|2
2/3. For Sx the probabilityof getting+ft/2 is (1/2)1(3+ 0/76|2 5/6, and
\342\200\224

176

Chapter4 Quantum Mechanicsin ThreeDimensions


the probabilityof getting-h/2is1(1/2)1(-1
+ 0/V6|2=
value of Sx is
expectation

5( h\\ + l{ h\\ =

6 (+2J 6

the
1/6.Incidentally,

ft

which we couldalsohave obtained


moredirectly:

I'd likenow to walk you throughan imaginary measurement


scenario

spin 1/2,becauseit servesto illustratein very concreteterms someof the


abstractideaswe discussed
backin Chapter1.Let'ssay we start out with a
of that particle's
in the statex+- If someone
asks,\"What is the z-component
we couldanswer unambiguously:
+H/2.Fora
spinangularmomentum?\",
of SV iscertainto return that value.Butif ourinterrogator
asksinstead,\"What
of that particle'sspinangular momentum?\"we are obligedto
is thex-componerit
If you measureSx,the chancesare fifty-fifty of gettingeitherh/2 or
equivocate:
If the questioner
or a ''realist\"
isa classical
(inthe senseof Section
physicist,
1.2),he will regardthisas an inadequate\342\200\224-hot to say impertinent\342\200\224-response: \"Are
On the contrary;
you tellingmethat youdon'tknow the true stateof that particle?''
I know preciselywhat the stateof the particleis: x+. \"Well, then,how comeyou
of its spinis?\"Becauseit simplydoesnot
can'ttell me what the ^-component
of spin.Indeed,it cannot,for if both Sx and Sz
x -component
have a particular
wouldbeviolated.
the uncertainty principle
were well-defined,
At thispointourchallenger
and measures
thex-component
grabsthe test-tube
of its spin;let'ssay he getsthe value +/I/2.\"Aha!\"(he shoutsin triumph), \"You
lied!Thisparticlehas a perfectlywell-defined
value of Sx:h/2,\"Well,
\"You
doesnow, butthat doesn'tproveithadthat value,priorto your measurement.
beenreduced
to splitting
hairs.And anyway, what happenedto your
have obviously
I now know both Sx and Sz.\"I'm sorry,but you do not:In
uncertainty principle?
the courseof your measurement,
you alteredtheparticle'sstate;it is now in the
statex+ and whereasyouknow the value of Sx,you nolongerknow the value pf
\"But I was extremely careful notto disturbthe particlewhen I measured
Sx\"
it
if
see
check
Measure
and
out:
don'tbelieve
what
well,
me,
Very
you
you
Sz,
be
to
if
which
will
he
course,
may get+/i/2,
embarfassihg my
get.(Of
we repeatthiswholescenario
overand over,halfthe timehe will get
To the layman, thephilosopher,
orthe classical
a statement
of the
physicist,
form \"this particledoesn'thave a well-defined
(or momentum, or xposition\"
of spinangular momentum,or whatever) soundsvague,incompetent,
component
or (worstof all)profound.It is noneof these.But its precisemeaningis, I think,
involving

particle

measurement

\342\200\224h/2.

sure\342\200\224it

>

5\302\276..

ease\342\200\224but
\342\200\224h/2.)

Section4.4;Spin

177

to convey to anyone who hasnotstudiedquantum mechanics


almostimpossible
in somedepth.If you find your own comprehension
fromtimeto time
slipping,
the problem),
cqmebackto the
(if you don't,you probablyhaven'tunderstood
spin-1/2system:It is the simplestand cleanestcontextfor thinking through the
of quantum mechanics.
paradoxes
conceptual

Problem4.26
(a)

Checkthat the spinmatrices(Equations4.145and 4.147)obeythe


commutation
relationsfor angular momentum,
Equation4.134.

fundamental

(b) Showthat

thePaulispinmatrices(Equation4.148)satisfy theproductrule
ffj<rk

= 8jk+ i 2^ ejkim*

[4-!53]

indicesstandfor x, y, or z, and
is the Levi-Civitasymbol:
=
=
+ 1 if jkl 123,231,.or 312; if jkl 132,213,or 321;0 otherwise.

where the

-1

\342\202\254jm

*Problem4.27 An electronisin the spinstate

-\"CO(a)
(b)

constantA.
Determine
the normalization
Findtheexpectation
valuesof Sx.,Sy, and Sz,

(Note:Thesesigmasare standard
(c) Findthe \"uncertainties\"crsr, a$v, and
notPaulimatrices!)
deviations,
with allthreeuncertainty principles
(d) Confirmthat your resultsare consistent
(Equation4.100and its cyclicpermutations-\342\200\224only with S in placeof L, of
course).
0\302\276.

^Problem4.28For themostgeneralnormalized
spinorx (Equation4.139),
(Sx), (Sy), (Sz), (Sj), (S2),and (S2).Check that (S2)+ (S2)+ (S2Z)
= (S2).
compute

*Problem4.29
(a)

and eigerispinors
of S
Findthe eigenvalues

in ThreeDimensions
Chapter4 Quantum Mechanics
(b)

If you measuredSy on a particlein the generalstate-, (Equation4.139),


of each?Checkthat
what values mightyou get,arid what is theprobability
theprobabilities
add up to 1.Note:a and b neednotbe real!

(c)

If you measured
Sy,.what valuesmight you get,arid with what probabilities?

jjf

* ^Problem4.30Construct
thematrix Sr representing
thecomponent
of spinangular
f. Usespherical
momentum alongan arbitrary direction
for which
coordinates,

r = sin6 cos(f>.i + sin6 sin<p j + cosB k.

[4.154]

of Sr,Answer:
Findthe eigenvalues
and (normalized)
eigenspinors
(,)

X+

/ cos(^/2)\\.'
- [j*
m(0/2)j
_

(/.) _
X~

fe-vmem}
'
cos(6/2))

^{-

Note:You'realways free to multiply by an arbitrary phase


your answer may notlookexactly the sameasmine.

factor\342\200\224say,

r415S1
J
L

el^~so

Problem4,31Constructthe spinmatrices(S*,Sy, and Sz) for a particleof


of Sz are there?Determine
theactionof Sz:,.
spin1.Hint:How many eigenstates
5+,.and SL on eachof thesestates.Followthe procedureusedin the text for
spin1/2.

4.4.2Electronin a MagneticField
a magnetic
dipole.Its magneticdipole
spinningchargedparticleconstitutes
to its spinangular momentum,
S:
moment,ji, is proportional
A

\\i

= yS;

[4.156]

the proportionality
ratio.30When a
constant,y, is calledthe gyromagnetic
fieldB, it experiences
a torque,u, x B, which
is placedin a magnetic
magnetic dipole
\"See.for example,D.Griffiths, Introduction to Electrodynamics,3rd ed.(Prentice Hall, Upper
SaddleRiver, NJ, 1999),
Classically,the gyromagnetic ratio of an objectwhosecharge--and
page 252.
where q is the charge and m is the mass.Forreasonsthai are
mass are identically distributed is q/1m,
in
fully
explainedonly relatiyistic quantum theory, the gyromagnetic ratio of the electron is (almost)
exactly twice \"the

value: y
classical

\342\200\224
\342\200\224

e/m.

Section4.4:Spin

179

tendsto lineit up parallelto the field(justlike a compassneedle).The energy


with thistorqueis31
associated
H=

-\\lB,

[4.157]

sotheHamlltonian
of a spinning
chargedparticle,at rest32in a magneticfieldB,

is

# = -yB-S.

[4.158]

Example4.3 Larmorprecession:
Imaginea particleof spin 1/2at rest in a
uniform magnetic
field,which pointsin the z-direction:
B = Bok.

[4.159]

The Hamiltonian
in matrix form,is
(Equation4.158),
H

=-yfcS,

=-*\302\247\302\243
\302\243

[4.1601

_0,).

The eigenstates
of H are the sameasthoseof Sz:
X+,

X-,

with energy E+ =
with energy E- =

-(yBQk)/2,

[4.161]

+(yBq<ft)/2.

to the field\342\200\224just
Evidently the energy islowestwhen thedipolemomentisparallel
as it wouldbe classically.
to the timethe generalsolution
is time-independent,
Sincethe Hamiltonian
equation,
dependentSchrodiriger
[4T62]

ih%\302\243-=Hx,
at

in termsof the stationary states:


can be expressed
iyBot/2 n
iyB{)t/2
(footnote 30),page 281.
32If the particle is allowedto move, there will also be kinetic energy to consider;moreover, it
will be subjectto the Lorentz force (q\\ x B), which is not derivable from a potential energy function,
show you later
arid hence does,not fit the Schrodingerequation as:we have formulated it sofar.
that
the
on how to handle this (Problem 4.59),but for the moment let's
assume
just
particle is free to
rotate, but otherwisestationary.
31Griffiths

I'll

180

Chapter4 Quantum Mechanicsin ThreeDimensions

a and b are determined


The constants
by theinitialconditions:
X-(0) =

(f) ,

I'll write a
(of course,\\a\\2 + |&|2= 1).With no essentiallossof generality33
and b = sin(a/2),where a is a fixedanglewhosephysicalsignificance
:Cos'(a/2)
will appearin a moment.
Thus
\342\200\224

,,

/cos(ar/2)ez>B\302\260'/2\\

rA..\342\200\236,

To geta feelfor what ishappeninghere*let'scalculate


the expectation
value of S,

as a functionof time:
(\302\276)

= X (OfS^X (?) = (cos(a/2)^*<\"/2


sin^)^^/2)
ft
X

\342\200\224

/0

l\\

2 (l oj

/cos(a/2)e'>B^/2\\

[4.164]

^/2),-^^/2)

-sinacos[yB[)t).

Similarly,
(Sy) =

= --sinasin()/5oO,
X(.()%X(!)

[4.165]

and

($z)= Xlrf&rt(t) = ^ cosa.


Evidently (S) is tiltedat a constant
angleql
fieldat theLarmorfrequency
co =

[4.166]

to the z-axis,and precesses


aboutthe

[4.167]

yB0,

(seeFigure4.10). No surprisehere\342\200\224Ehrenfest's
just as it would classically34
theorem(intheform derivedin Problem4.20)guarantees
that (S) evolves
laws.But it's niceto see how this works out in a specific
to the classical
context.
according

\342\226\240^This

it

doesassumethat a and b are refill you Can work

doesis add a constant to

t.

out 'the

general caseif you like, but all

34See,for instance, Tfve Feynman Lectureson Physics(Addison-Wesley,Reading, 1964),Volume


the classical
caseit is the; angular momentum vector itself, not just its
that
around the magnetic field.
expectation value,
precesses

II,Section34-3; Of course,in

Section
4.4:Spin

181

z\302\273

of
FIGURE4.10:Precession
uniformmagneticfield.

{3}in a

experiment:In an inhomogeneous
magnetic
Example4.4 TheStern-Gerlach
a
field,there is not only torque,but also& force,on a magneticdipole:35
F = VQi-.B).

[4.168]

Thisforce can be usedto separateout particleswith a particularspin


as follows.Imaginea beam of relatively heavy neutral atoms,36traveling in
which passesthrougha regionof inhomogeneous
the y direction,
magneticfield
orientation,

(Figure4,11)\342\200\224say,

h(x,y,z) = -axi+ (Bo+ az)k,

[4.169]

a describesa smalldeviation
where Bo is a stronguniform fieldand the constant
from homogeneity.
(Actually, what we'dlikeisjustthe z component^but
law V B = 0;like
that'simpossible\342\200\224it wouldviolatethe electromagnetic
it or not,an x component
comesalongfor theride.)The forceon theseatomsis
unfortunately

^Griffiths, (footnote 30), page


(Equation

4.157).

258.Note

that

F is

the negative gradient, of the energy

36We make them neutral so as to avoid the large-scale


deflection that would otherwise result
from the Lorentz force, and heavy so we can construct localizedwave packetsand treat the motion
in terms of classical
particle ti'ajeclofies.In practice,the Stern-Gerlachexperiment doesn'twork, for

example,with a beam of free electrons.

\\

182

inThreeDimensions
Chapter4 Quantum Mechanics
Zn

Spin up

Spin down
Magnet

FIGURE
4.11:The Stern-Gerlach
apparatus.
But becauseof the Larmorprecession
aboutBq, & oscillates
rapidly,and

averagesto zero;thenet forceis in the z direction:


Fz = y<xSz,

[4.170]

to the z component
of the
and the beamis deflected
up or down, in proportion
we'dexpecta smear(becauseSz wouldnot
Classically
spinangular momentum.

be quantized),
but in fact the beamsplitsinto 2s + 1 separatestreams,
the quantizationof angular momentum.(If you usesilver
demonstrating
f
or
are paired,in sucha. way that their
atoms, example,all the innerelectrons:
spin and orbitalangular momentacancel.The net spinis simplythat of the
= 1/2, and the beam splits
outermost\342\200\224unpaired\342\200\224electron, so in thiscases
in two.)
Now, that argument was purelyclassical,
up to the very final step;\"force\"
no
in
has place a properquantum calculatiori,
and you might thereforeprefer
to
thesame
fromthe
We exarriirietheprocess
the followingapproach
problem.37
of
frame that movesalongwith thebeam.In thisframe the
perspective a reference
out
starts zero,turns on for a timeT (astheparticlepassesthrough
Hamiltohian
the magnet),
arid thenturns off again:
beautifully

\342\226\240H

for t < 0,
0,
(*) = -y(Bo+ aZ)Sz, forO<f <T,
for t > T.
0,

[4.171]

of B,
reasonsindicated
(I ignorethe peskyx cornporient
irrelevant to the problem,)
Supposethe atomhas spin1/2,and startsout in the
above\342\200\224is

which\342\200\224-lot

state

ft)

= ax+ + H-, for t < 0.

9.1,

This argument follows L. Ballentine.-(footnote'26)


Section

183

Section-4.4:
Spin
While theHamiltonian
acts,x(0evolvesintheusualway:
X(t)

= ax+e~iE+!/n+ bX-e~iE-t/h,for0 < t < T,

where (from Equation4.158)


E\302\261

==py(B0+ az)-i

[4.172]

and henceit emerges


inthestate

(for i > T), The two termsnow carry momentum in the z direction(see
Equation

has momentum
3.32);the spin-upcomponent
Pz =

ayTh

-^-s

[4.174]

it movesin the plus-zdirection;the spin-downcomponent


has the
momentum,and it movesin the minus-zdirection.Thus the beam splits
in two, asbefore.(Notethat Equation4.174is consistent
with the earlierresult
=
for in thiseaseSz ft/2,and pZ/ FZT.)
(Equation4.170),
The Stern-Gerlach
hasplayedan importantroleinthephilosophy
experiment
of quantum mechanics,
where it servesboth asthe prototype:
for the preparation
of a quantum statearid as an illuminating
modelfor a certainkindof quantum
measurement.
We tendcasuallyto assume
that theinitialstateof a systemisknown
(the Schrodinger
evolves)\342\200\224but it is natural
equationtellsus how it subsequently
to wonderhow you get a systemintoa particular
statein the first place.Well, if
you Want to preparea beamof atomsin a givenspinconfiguration,
you passan
beamthrough a Stern-Gerlach
unpolarized
magnet,and selectthe outgoingstream
in (closingoff the otherswith suitablebafflesand shutters).
you are interested
if you want to measurethe z component
of an atom'sspin* you send
Conversely,
it througha Stern-Gerlach
apparatus,and recordwhich bin it landsin, I do not
claimthat thisis always the mostpracticalway todothe job,but it isconceptually
of state
very clean,and hencea usefulcontextin which to exploretheproblems
preparationarid measurement.
and

opposite

\342\200\224

Problem4.32In Example4.3:
(a)

If you measuredthe component


of spin angular momentum alongthe x
at timet, what is the probability
that you wouldget +ft/2?
direction,

184

Chapter4 Quantum Mechanicsin ThreeDimensions


(b)

Samequestion,
but for the _y\302\273comp6nent.

(c)

Same,for the z component.

* ^Problem4.33An electronis at restin an oscillating


field
magnetic
B

BQCOs(a)t)k,

\342\200\224

where Bq and xo are constants.


(a)
(b)

matrix for thissystem.


the Hamiltonian
Construct
The electronstartsout (at t
0) in the spin-upstatewith respectto the
time.Beware:
x-axis(that is:% (0) x+ Determine
x (?) at any subsequent
Thisis a time-dependent
so you cannotget /(f) in the usual
Hamiltonian,
inthiscaseyou can solvethetimeway from stationary states.Fortunately,
equation(Equation4.162)directly.
dependentSchrodinger
Findthe probabilityof getting
if you measureSx.Answer:
\342\200\224

\342\200\224

)\342\200\242

(c)

\342\200\224h(2,

sur
(d) What

\\2cd

srn(a)f)

is the minimum field(Bq)requiredto forcea complete


flipin Sx?

4.4.3Additionof AngularMomenta
theelectronand
now that we have two spin-1/2
Suppose
particles\342\200\224for example,
Eachcan have spinlipor spindown,
the protoninthegroundstate38of hydrogen.
sothereare four possibilities
in all:39

tt. U, It, 44,

[4.175]

arid thesecondto theproton.Question:


where thefirst arrow refersto the electron
What is the totalangular momentum of the atom?Let

S = S<?)+ S(2),

[4.176]

3^l put them in the ground stale so there won't be any orbital angular momentum to worry about.
39Moreprecisely,each particle is in a linearcombination of spin up; and spin down, and the
compositesystemis in a linearcombinixtion of the four stateslisted.

Section4.4:Spin
of
Eachof thesefour composite
statesis an eigenstate
simplyadd:

Sz\342\200\224the

185

components

sf

szxiX2= (si{)+ )xiX2= (sPxi)xi+ xiisfhi)


= (hmiXx)X2+ X] (AOT2X2) = ft(m.i+ wii)xtxa,
(notethat S^ actsonly on xi?and S(2^ actsonlyon xi\\ thisnotationmay notbe
elegant,but it. doesthe job).So m (the quantum number for the composite
system)
isjustmi + mi;

ff:

l;

f|:m

0;
0;

If: m

-1.

44,^ m

to advancein integer
first glance,thisdoesn'tlookright:m is supposed
there is an \"extra\"state
steps,from $ to +s, so it appearsthat s 1
is to apply the loweringoperator,
with m = 0. Oneway to untanglethisproblem
S_ = s!P+ 5l2)to the stateft,Equation4.146:
At

\342\200\224

\342\200\224

\342\200\224but

usin\302\247

s_(tt) = (S- t) t +1 t)
=.(*^) t + r i) mt + u>.
(s\302\256

(\302\276

Evidently the threestateswith

in)

s 1 are (inthenotation\\sm)):
\342\200\224

-tt

110) =\302\261tu+ m.

<

= 44
..11-1)

= 1 (triplet).

[4-177]

|1

to 0);what shouldyou get?See


applyingthe loweringoperator
for the obviousreason.
Problem4.34(a).)Thisis calledthe tripletcombination,
the orthogonal
statewith m = 0 carriess 0:
Meanwhile,
(As a check,try

\342\200\224

{|00)

i(U - W}

= 0 (singlet).

[4.178]

(If you apply the raisingor loweringoperatorto this state,you'llget zero.See

Problem4.34(b).)

186

in ThreeDimensions
Chapter4 Quantum Mechanics

I claim,then, that thecombination


of two spin-1/2particlescancarry a total
spinof 1 or 0, dependingon whether they occupythe tripletor the singlet
To confirm this,I needto provethat the tripletstatesare eigenvectors
of
S2 with eigenvalue
of S2 with eigenvalue
2h2,and the singletis an eigenvector

configuration.

0. Now,

S2-=

(S(1)+ S(2)) . (S(1)+ SC2>)_ (S(l)f+ (vS(2))2+ 2S(1). s(2)_

[4>179fj

UsingEquations4,145and 4.147,we have

s(1) smm)= (sp t)(sf $.+ismtxsf ^) + $n t)(^2)i).


\342\200\242

h2
-(24t-H)-

Similarly,

n- it)-

sP .s^(w= ^-(2
It followsthat
S<\" .S(#|i
o) =

,2

fc2

\" +2
=
^--^,(2
4 0),
4 V2 If t4- f4- W ^-IJ

[4.180]

and
fe2 i

S^ . S^IOO)= -j

4rt
jj=C2

3^2
- t4- -2 n + ;t)- -^100).
[4.181]

that
we conclude
Returning to Equation4.179(andusingEquation4.142),
0
S2\\\\

- /sn2 + 3h2

0}

\342\200\224

H2\\

\342\200\224

+2\342\200\224

9
|10)= 2/72|10),

[4.182]

of S~ with eigenvalue2k, and


so 110)is indeedan eigenstate

3h:, ...0,
-r- z-r-

,3k1+ 3h2

=[

S2\\Q0)

|0.Q>

[4.183]

0.(I will leaveit for youto confirm


so |00)is an eigenstate
of S2 with eigenvalue
of S2,with the appropriateeigenvalue\342\200\224see
that |11) and
1) are eigenstates
|.l\342\200\224

Problem4,34(6)*)

Section4.4:Spin,

187

What we have just done(combining


spin1/2with

spin1/2to get spin1 and


If you combinespins\\ with
spin0) is the simplestexampleof a largerproblem:
what totalspinss can you get?4\"The answer41is that you get every spin
spins.2.,.
from (s-i + 52) down to (s\\
i'l),if >
integersteps:
\342\200\224

\342\200\224

.\302\276)\342\200\224of

(\302\276

\302\2532

\302\2431\342\200\224in

[4.184]
highesttotalspinoccurswhen the individualspinsare
alignedparallelto oneanother,and the lowestoccurswhen they are antiparallel.)
if you packagetogethera particleof spin3/2with a particleof spin
For example,
ontheconfiguration.
2,you couldgeta totalspinof 7/2,5/2,3/2,or1/2,depending
Another example:
If a hydrogenatom is inthestateijfnim, the net angular
of the electron(spinplusorbital)is I + 1/2or I 1/2;if you now throw in
spinof the proton,the atom'stotalangular momentum quantum number is / + 1,
I, or I 1 (andI can be achievedin two distinctways, dependingon whether the
electronaloneisin the/ + 1/2configuration
ortheI 1/2configuration).
The combined
state\\s m) with totalspins arid z-Component
m will be some
linearcombination
of thecomposite
states|^i mi)
the
(Roughly speaking,

\342\200\224

momentum

\342\200\224

\342\200\224

1\302\276

\\s

m)

C%%n1*1
\302\2731

\302\243

m.\\

\302\25322):

>

1\302\276

[4.185]

\302\253a>

-\\-m2=m

the z components
statesthat contribute
arethose
add,the only composite
(because
for which mi + m.2 in):Equations4.177and 4,178are specialcasesof this
generalform,with si = s% = 1/2 (I usedthe informalnotationt = It \\)-> ^
The constants
coefficients.
A few
Cs,n^m2m ar? calledClebsch-Gotdan
(-5)).)of the simplest
of
the shadedcolumn
casesare listedin Table4.8.42For example,
the 2x1tabletellsus that
\342\200\224

\342\200\224

1\302\276

|30}= -L|21)|1-1)+

y\302\247

+ -^|2-1)|11).
|20)|10}

In particular,
if two particles(ofspin2 and spin1)are at restin a box,and the total
of S% couldreturn the
is 0, then a measurement
spinis 3, and its z component
value h (with probability1/5),or 0 (with probability
3/5),or (with probability
\342\200\224h

I say spins, for

simplicity, but either one (or both) could just as Well be orbital angular
(for which, however, we would use the letter I).
41For a
proof you must look in a more advanced text; see,for instance, ClaudeCohen-Tannoudji,
BernardDiu, and Franck Laloe,:
Quantum Mechanics,(Wiley, New York, 1977),Vol. 2, Chapter X.
The general formula isderived in Arno Bohm,Quantum Mechanics:
Foundations and
2nd ed.,(Springer,1986),
p. 172.
momentum

Applications,

18:8 Chapter4

Quantum Mechanics,in ThreeDimensions


TABLE4.8: Clebsch-Gordan
coefficients.
for
(A squarerootsignisunderstood
the radical.)
every entry;the minussign,if present,
goesoutside

addup to 1 (the sumof the squaresof any column


1/5).Noticethat the probabilities
on\"the Clebsch-Gordan
tableis 1).

Thesetablesalsowork the otherway around:


\\si

= V C%$ \\sm)^
Ml)\\s2m1)

[4.186]

Forexample,
the shadedrow in the 3/2 x I tabletellsus that

itlUirv,-ft\\il\\+ /X|3I\\ /I|1I\\


If you put particlesof spin3/2 and spin 1 in the box, and you know that the

= 1/2 and the secondhas mi Q (so m is necessarily


1/2),and
you measurethe total spin,5, you couldget 5/2 (with probability3/5),or 3/2
or 1/2(with probability1/3).Again, the sum of the
(with probability1/15),
of eachrow on the Clebsch-Gordan
table
probabilities is 1 (the sum of the squares
first has mi

is 1).

\342\200\224

I don'tblame
If you think thisis startingto soundlikemysticalnumerology,
tablesmuch in the rest of the
you. We will not be Using the Clebsch-Gordan
book,but I wanted you to know where they fit intothe schemeof things,in case
them lateroil.In a mathematical sensethisis all appliedgroup
you encounter
of thedirectproductof
we aretalkingaboutis the decomposition
theory\342\200\224what

Section4.4:Spin

189

two irreducible
of the rotation
representations
groupintoa directsum of irreducible
representations
yourfriends).
(you canquotethat, to impress

^Problem4.34
(a) Apply S_ to 110)(Equation4-177),and confirmthat you
(b) Apply

S\302\261

(c) Showthat

get V2h\\l

-1).

and confirmthat you getzero,


to )00}(Equation4.178),

|11)and 11-1)(Equation4.177)areeigenstatesof S2,.with the

eigenvalue.
appropriate

tomake a baryon
Problem4.35Quarkscarry spin1/2.Threequarksbindtogether
(suchas the protonor neutron);two quarks (or morepreciselya quark and an
to make a meson(suchasthepionor the kaoh).Assume
antiquark) bindtogether
the quarks are in the groundstate(sothe orbitalangular momentum is zero).
(a) What
(b) What

for baryons?
spinsare possible
spinsare possiblefor mesons?

Problem4.36
particleof spin1 and a particleof spin2 are at restin a configuration
suchthat the totalspinis 3, and its z component
is h. If you measuredthe
of the angular momentum of the spin-2particle,what values
z component
of eachone?
might you get,and what is theprobability
with spindownis in the state^510of the hydrogenatom.If you
An electron
couldmeasurethe totalangular momentum squaredof the electronalone
the protonspin),what valuesmightyou get,and what is:the
{notincluding
probabilityof each?

(a) A

(b)

of S2with s|1}(where S = S<1}+ S(2)).


Problem4.37Determine
the commutator
Generalize
your resultto show that

x S(2)).
[S2,S{1)]= 2ifc(S(1)

[4.187]

Comment;
BecauseS% doesnotcommutewith S2,,we cannothopeto find states
of 52 we
of both.In orderto form eigenstates
that are simultaneous
eigenvectors

190

in ThreeDimensions
Chapter4 Quantum Mechanics

of . Thisisprecisely
of eigenstates
what the Clebschneedlinearcombinations
dofor us.On theotherhand,it followsby
Gordancoefficients
(in Equation4..185)
from Equation4.187
that the sum S^ +SC9doescommutewith
obviousinference
we already knew (seeEquation4.103).
S2,which is a specialcaseof something
5\302\276

FURTHERPROBLEMSFORCHAPTER4
for which
*Problem4.38 Considerthe three-dimensional
harmonicoscillator,
the potential
is
Vir) = -mco2r2.
[4.188]
of variablesin cartesiancoordinates
turns thisinto
separation
and exploityour knowledgeof thelatter
threeone-dimensional
Oscillators,
to determine
theallowedenergies.
Answer:

(a) Show that

EA

(b)

= (n+3/2)h(D.

[4.189]

the degeneracy
Determine
d(n) of En-

** ^Problem4.39Because
thethree-dimensional
harmonicoscillator
potential
the
i
s
c
an
equation be handledby
4.188) spherically
symmetric, Schrodinger
as well ascartesiancoordinates.
of variablesin sphericalcoordinates,
separation
Findthe recursion
formula
Usethe powerseriesmethodtosolvethe radialequation.
theallowedenergies.
forthe coefficients,
Checkyour answer against
and determine
Equation4.189.
(Equation

**Problem4.40
(a)

vi'rialtheorem:
Provethethree-dimensional

2{T)= (t*VV)

[4.190]

(forstationary states).Hint:Refer to Problem3.31,


tothecaseof hydrogen,and showthat
(b) Apply thevirial theorem
(T) =

-En; (F)=2EW.

[4.191]

191

Further Problems
forChapter4

tothethree-dimensional
oscillator
harmonic
(e) Apply the virial theorem
4.38),and showthat in thisease
(Problem

(T) = (V) = En/2.

[4.192]

* ^Problem4.41[Attempt this problemonly if you are familiar with vector


of
calculus.]Definethe (three-dimensional)
probabilitycurrentby generalization

\342\226\240*\342\226\240\342\226\240

Problem1.14:

J = 2m (vl/ vm*
(a) Showthat J

W*

W) .

[4.193]

thecontinuityequation
satisfies

-|-|*|2,

V-J = at

[4.194]

It follows(from the
expresseslocalconservationof probability.
that
theorem)
divergence
which

f J~d*=

[4.1.95]
(it Jy
Inwords:The flow
where V is a (fixed)volumeand S isitsboundary surface.
of probabilityoutthroughthe surfaceis equaltothedecrease
in probability
of findingtheparticlein the volume.
FindJ for hydrogenin the staten-:=2, I 1,m 1..Answer:

Js

(b)

\342\200\224

(c)

~ [ |*fd3r,
\342\200\224

:re-r/asm0$.

If we interpretmj as the flow of mass,theangular momentum is


L = m / (r x J) d?r.
and comment
on the result.
Usethisto calculateLz for thestate#2.11,

**.^Problem4.42 The (time independent)


momentumspacewave functionin three
of Equation3.54:
dimensions
is definedby the natural generalization

^(P) \" Tldm Ie\"i<Pf)/S*W<?*\342\226\240

[4.196]

192

Chapter4 Quantum Mechanicsin ThreeDimensions


(a)

Findthe momentum spacewave functionfor the groundstateof hydrogen


coordinates,
settingthe polaraxisalong
(Equation4.80).Hint:Usespherical
thedirection
of p. Do the 0 integralfirst.Answer:

**)=

/o

\\

3/2

;f(t)

[4197]

[i + iaP,nn-

(b)

Checkthat 0(p) is normalized.

(c)

Use0(p)to calculate(p2),in the groundstateof hydrogen.


value of the kineticenergy in thisstate?Express
What is the expectation
with the
your answer as a multipleof Ei, and checkthat it is consistent
virial theorem
(Equation4.191).

(d)

Problem4.43
Constructthe spatialwave function(VO for hydrogenin the staten 3,
I = 2, m
1. Expressyour answer as a functionof r, 0, and a (the
Bohrradius)
othervariables(p,z,etc.)orfunctions
(Y, v, etc.),or
constants
allowed{n is okay,and e, and 2, etc.).
(A, cq,etc.),or derivatives,
(b) Checkthat this wave functionis properlynormalized,
by carrying out the
integralsoverr, 0, and
appropriate
value of rs in thisstate.For what rangeof s (positive
(c) Findthe expectation
and negative)istheresultfinite?
(a)

\342\200\224

\342\200\224

</>,

only\342\200\224no

\302\242.

Problem4.44
Construct
thewave functionfor hydrogeninthestaten 4,-./ = 3,m = 3.
coordinates
r, 6..,and
Expressyour answer as a functionof the spherical
value of r in thisstate.(As always,lookup any nontrivial
(b) Findthe expectation
integrals.)
(c) If you couldsomehowmeasurethe observableL2 + L2, on an atomin this
state,what value (or values)couldyou get,and what is the probabilityof
each?
(a)

\342\200\224

<fi.

in the groundstateof
that an electron
Problem4.45What istheprobability
will be foundinsidethe nucleus?
hydrogen

(a)

the exactanswer, assuming


Firstcalculate
the wave function(Equation4,80)
is correctallthe way downto r = 0.Let b be the radiusof the nucleus.

193

Further Problems
forChapter4
(b)

(c)

Expandyour resultas a powerseriesin the smallnumber e = 2b/d,and


term is the cubic:P
showthat thelowest-order

Thisshould
(4/3)(fr/a)3.
be a suitableapproximation,
providedthat h <^a (which it is).
constantover the
Alternatively, we mightassumethat ^.(r) is essentially
so that P (4/3)nb3\\f(0)\\^.
Checkthat you
(tiny) volumeof the nucleus,
get the sameanswer thisway.
Useb ^ 10-15m and a ~ 0.5x 10_10mto geta numerical
estimate
for P.
the \"fractionof its time that the electron
Roughly speaking,thisrepresents
spendsinsidethe nucleus.\"
\302\253*

-\302\276

(d)

Problem4.46
(a)

formula (Equation
Usethe recursion
4.76)to confirm that when I
theradialwave functiontakestheform

p,

, _ Nnr
a!

^n(f?-i)

vn\342\200\224^0\342\200\224rjna

\342\200\224

\342\200\224

\342\200\224

and determine
the normalization
constantNn by directintegration.
'(b) Calculate
(r) and (r2) for statesof the form ifn{n-\\)m(c) Show that the \"uncertainty\"in r (oy) is (r)l\\/2n+ 1 for suchstates.Note
with increasing
that the fractionalspreadin r decreases,
n (in thissensethe

to; lookclassical,\"
with identifiable
for large
circular\"orbits,\"
system\"begins
this
n). Sketchthe radialwave functionsfor severalvaluesof n, to illustrate

point.
Problem4.47 Coincidentspectrallines.43Accordingto the Rydberg formula
(Equation4.93)the wavelength of a linein the hydrogenspectrumis determined
by the principal
quantum numbersof theinitialand final states.Findtwo distinct
that yieldthe sameX. Forexample,
{6851,
6409}and {15283,
11687}
pairs{n,,n/}
will do it, but you'renotallowedto usethose!
the observables
A = x2 and B = Lz.
Problem4.48 Consider
(a)
'(b)
(c)

theuncertainty principle
for <jaGbConstruct
Evaluate <jb in the hydrogenstate\\//nim.
What can you conclude
about(xy) in thisstate?

4^ISfichplasWheeler, \"CoincidentSpectralLines\" (unpublished ReedCollege


report, 20Q1).

in ThreeDimensions
Chapter4 Quantum Mechanics

Problem4.49 An electronis in the spinstate

(a)
(b)
(c)
(d)

the constant
A by normalizing
Determine
xIf you measured
what valuescouldyou get,and what is
Sz on this electron,
theprobabilityof each?What is the expectation
value of S^?
If you measured
what valuescouldyou get,and what is
S'x:on this; electron,
the probabilityof each?What is the expectation
value of Sx-?
If you measured
what values couldyou get,and what is
Sy on thiselectron,
theprobabilityof each?What is the expectation
value of Sy?

* * ^Problem4.50Suppose
two spin-1/2
areknown tobe inthesinglet
particles
of the spinangular momentum
Let
bethe component
(Equation4.178).
of particlenumber 1 in thedirectiondefinedby the unit vectora. Similarly,let
of 2's angular momentum in the direction
b. Showthat
$1 be the component
configuration

.\302\276

\342\226\240

(S^sf)= -jcosB,

[4.198]

where 8 is theanglebetweena and b.

** ^Problem4.51
(a) Work
anything.

for the cases\\ = 1/2,


out the Clebsch-Gofdari
coefficients
A and B in
Hint;You'relookingfor the coefficients

\342\200\224

.\302\276

Ism)

A\\\\

1)1\302\276

(m

- i)>+

B\\\302\261

(-^))1\302\276(m

+ |)),

of S2.Usethe method;of Equations4.179


is an eigenstate
(2)
doesto ma),
(forinstance)
through4.182.If you can'tfigure outwhat
referbackto Equation4.136and the linebeforeEquation4.147.Answer:

suchthat

\\sm)

5\302\243

2*2+ l

2^2+1

= S2 1/2.
Checkthisgeneralresultagainstthreeor fourentriesin Table4.8.
where the signsare determined
by

(b)

1\302\276

s\342\226\240

195

Further Problems
forChapter4

Problem4.52Findthe matrix representing


Sx for a particleof spin3/2(using,as
to determine
of S^), Solvethe characteristic
always,the basisof eigenstates
equation
the eigenvalues
of S*.
for arbitrary spins,generalizing
* * ^Problem4.53Work outthe spinmatrices
spin1/2
(Equations4.145and 4.147),spin1 (Problem4,31),and spin3/2 (Problem4.52).
Answer:

S,=h

\342\200\224
\342\200\224

s-2

0
0

~s)

hs

0
0

bs-2

,or

0\\

--1

0
0

^
/0
h

*s

0
0
;
\342\226\240I

^-1

bS-\\

^-2 0

S,= 2

\\o

ibs
0 ibs~]
0

'.

0
0

0
0

-ih-1

ibs~2
;

\342\200\242

0
0

b~s+i

b-s+i
0
0

-th-2

..

0
0

\342\200\242\342\200\242\342\200\242

0
\342\226\240

0
0

\342\200\242

...

\\

'.

;\342\226\240

where

0
0
0

fc

/0 -ihs
0
H

0
0
o
0

)
0
0
0

\\

0
\342\200\242\342\226\240

0
-ik-s+i
i-fe-j+1 0

bj = V^ + ,/)Cy+l-7)

*.* ^Problem4.54Work out the normalization


as
factorfor the spherical
harmonics,
we know that
follows.FromSection4.1.2
Yff

= B?t?m*PFiGQs6y,

the factorB\\n (which I quoted^ but did not derive,


the problemis to determine
in Equation4.32).Use Equations4.120,4.121,and 4.130to obtaina recursion

196

Chapter4 Quantum Mechanicsin ThreeDimensions

relationgivingB^ in terms of *Z?zm. Solveit by induction


on m to get up to
an overallconstant,
CQ).Finally,usethe resultof Problem4.22to fix the constant.
You may find the followingformulafor the derivative of an associated
Legendre
functionuseful:
B\342\204\242

dPm
(1 x1) dx = Vl-x2^1 mxP'r.
\342\200\224l-

[4.199]

Problem4.55The electronin a hydrogenatomoccupiesthe combined


spinand
positionstate
R2l

(7i/33fx++ VV3YU-)

\342\226\240

(a)

If you measured
the orbitalangular momentum squared(L2),what values
ofeach?
might you get,and what is the probability

(b)

Samefor the z component


of orbitalangular momentum (Lz).

(c)

Samefor the spinangular momentum squared(S2).

(d)

Samefor the z component


of spinangular momentum
Let J L + S be the total angular momentum.

(\302\276).

\342\226\240=

(e)

If you measured
J2, what valuesmight you get,and what isthe probability
of each?

(f)

Samefor Jz.
If you measured
the positionof the particle,what is the probabilitydensity

(g)
(h)

*\342\226\240

for findingit

at

r, &, (p?

from the
If you measured
boththe z component
of thespinand the distance
is
what
the probability
observables),
origin(notethat theseare compatible
densityfor findingthe particlewith spinup and at radiusr?

* ^Problem4.56
(a)

For a function

/\342\226\240(#')

is an arbitrary angle).For thisreason,Lz/h is calledthe


of rotationsaboutthe 2-axis,Hint:Use Equation4.129,and referto

(where tp
generator

that can be expandedin a Taylorseries,show that

Problem3.39.

Further Problems
for Chapter4

197

aboutthe direction
Moregenerally,L h/h isthe generatorof rotations
n, in
the sensethat exp(zL n<p/h) effectsa rotation
through angle (inthe righthand sense)aboutthe axisft. In the caseof spin,the generatorof rotations
is S h/h. In particular,
for spin1/2
\342\226\240

\342\200\242

<p

\342\200\242

= ei\302\253x^2x

X,

[4-200]

tellsus how spinorsrotate.


(b)

the (2 x 2) matrix representing


rotationby
aboutthe jc-axis,
Construct
and show that it converts\"spinup\" (x+) into \"spindown\"
^s
wouldexpect.
rotationby 90Q aboutthe y-axis,and check
Construct
the matrix representing
what it doesto x+.
Construct
the matrix representing
rotationby
aboutthe z-axis.If the
discussits implications.
answer is not quitewhat you expected,
180\302\260

(x\342\200\224)\302\273

(c)
(d)

y\302\260u

,360\302\260

(e) Showthat

ei(a-h)<p/2=.Gos^/2)+ i(b ff)


\342\200\242

[4.201]

sin(<p/2).

The fundamental commutation


relationsfor angular momentum
**Problem4.57

But for
(as well as integer)eigenvalues.
(Equation4.99)allowfor half-integer
orbitalangular momentum only the integervaluesoccur.There must he some
in the specific
form L f x p that excludes
values.44
extra constraint
half-integer
constant
with thedimensions
Let a besomeconvenient
of length(the Bohrradius,
say, if we'retalkingabouthydrogen),and definethe operators

=\342\226\240

q\\

-L

[*+ (a2/H)py]; Pi =

s 7![x ~

12

(a2(hyPy\\

P2 =

-\302\276

[px (fi/a^y];

7i [px.+ (hia2)y\\

\342\226\240

[qi,qz\\= [pi,Pi\\ = 0; [q\\}p\\\\ = [qo,P2~] = ih. Thus the


commutation
for positionand
relations
q's and the p'ssatisfy the canonical
with thoseof index2.
and thoseof index1 are compatible
momentum,

(a) Verify that

(b) Showthat
h

fl2

+ ^(/>i-H)L*= ^t-\342\202\254)
\342\226\240

-2.,

This problem is based on an argument in Ballenline(footnote 26),page 127.

198

Chapter4 Quantum Mechanicsin ThreeDimensions


(c)

for a harmonic
Checkthat Lz = Hi H2,where eachH is the Hamiltonian
oscillator
with massm h/a2 and frequency,co 1.
of the harmonicoscillatorHamiltonianare
We know that the eigenvalues
2.3.1
(n + \\/2)hcd,where n 0,1,
(Inthe algebraic
theory of Section
thisfollowsfrom the.form of the Hamiltonian
commutation
anci the canonical
Usethisto conclude
of Lz must be integers.
that the eigenvalues
relations).
\342\200\224

\342\200\224

(d)

\342\200\224

2,...

\342\200\224

Problem4.58Deducethe condition
for minimum uncertainty in Sx and Sy (that
is, equality in the expression
osr(7sy ~> (h/2)\\{Sz)\\), for a particleof spin1/2in
we can pick
Answer: With nO lossof generality
the genericstate(Equation4.139).
a to be real;then the conditionfor minimum uncertainty is that b is eitherpure
realorelsepure imaginary.
** ^Problem4.59In elassical
the force on a particleof chargeq
electrodynamics
movingwith velocityv throughelectricand magneticfieldsE and B is given by
the Lorentzforcelaw:

F = <7(E+ vxBj.

[4.202]

Thisforcecannotbe expressed
asthe gradientof a scalarpotential
energy function,
and thereforethe Schrodinger
cannot
equationin its originalform(Equation1.1)
accommodate
it. But in the moresophisticated
form

[4.203]

dt

thereis no problem;
the classical
is
Hamiltonian45
H=

1 --(p
qAY +
2m
9

q<pt

[4.204]

is the vectorpotential(B V x A.) and is the scalarpotential(E =


equation(making the canonicalsubstitution
dA/ftt), sothe Schrodinger
p -> (h/i)V) becomes

where A

\342\200\224

<p

\342\200\224

\342\200\224V<p

[4.205]

45.See,for

Mechanics,3rd
example,H.Goldstein,C.P. Poole,and J.L. Safko, Classical

(Prentice Hall, UpperSaddleRiver, Nj, 2002),page 342.

ed.,

199

Further Problems
for Chapter4
(a) Showthat

=
~^
m
at -<(p-?A)}.

[4,206]

we identify d(r)fdtwith (v). Showthat


(b) As always (seeEquation1.32)

xB-Bxp))-%x
B)).
m

=
{(p
m^P2mat q(E)+ ^(c)

[4.207]

if thefieldsE and B are uniform overthevolumeof the wave


In particular,

packet,show that

at

m\342\200\224p-

= q(E + (v) x B),

[4.208]

value of (v) movesaccording


sothe expectation
to the Lorentzforcelaw, as
we wouldexpectfrom Ehrenfesfs theorem.

* * ^Problem4.60 [Refer to Problem4.59for background.]


Suppose
A: =

-y(xJ

-A

and

cp

= Kz2,

where Bq and K are constants.


(a)

Findthe fieldsE and B.

(b)

Findthe allowedenergies^for a particleof massm and chargeq, in these

fields.Answer:
E(nu n2) =

(\302\253i

+ j)hm +

(/\302\276

+ j)hm, (m, n2 = 0,1,2,

...),[4.209]

=
where ca\\ = qBo/mand
Comment:If K' 0 thisis the
motion;xd\\ istheclassical
cyclotronfrequency,
quantum analogto cyclotron
The allowedenergies, + \\)hco\\,
and it'sa free particlein the z direction.
are calledLandauLevels.46
\342\200\224

<\302\2732

\342\226\240s/lgKjm..

(\302\2531

.\342\226\240*

In classical
^Problem4.61[Refer to Problem4.59forbackground.]
A and p are hotuniquelydetermined;47
the physicalquantities
the potentials
are the fields,E and B.
electrodynamics

11.3.
10.1.2,

46For further discussionseeBallentine (footnote 26) Section


47See,for example,Griffiths (footnole 30) Section

200

Chapter4 Quantum Mechanicsin ThreeDimensions


(a) Showthat

thepotentials
\302\242/

=
0-.-,
at
9A

A'

+ VA

[4.210]

is an arbitrary realfunctionof positionand time)yieldthe same


fieldsas tp and A.Equation4.210is calleda. gaugetransformation,
and the
theory is saidto be gaugeinvariant..
(where A

(b)

In quantum mechanics
the potentials
play a moredirectrole,and it is of
interestto know whether the theory remainsgaugeinvariantShowthat

W'=e'>A/%

[4.211]

the Schrodinger
satisfies
equation(4.205)with thegauge-transformed
M*'
cp' and A'.Since differsfrom ^ onlyby a phasefactor,it represents
the samephysicalstate,48and the theory is gaugeinvariant (seeSection
10.2.3
for further discussion).

potentials

48That is to say, (r)* d(r)/dt,etc.are unchanged. Because


A dependson position,(p) (with p
representedby the operator (ft/i)V) doeschange, but as we found in Equation 4.206,
p does not
representthe mechanical momentum (mv) in this context (in lagrangian mechanics it is so-called

canonicalmomentum).

CHAPTER5

IDENTICALPARTICLES

5.1TWO-PARTICLE
SYSTEMS
For a singleparticle,^(r,i) is a functionof the spatialcoordinates,
r, and the
The stateof a two-particle
time,t (we'llignorespin,for themoment).
system is
of particleone(n),the coordinates
of particletwo
a functionof the coordinates

(ra),and thetime:

*(ri,r2,^.

[5.1]

Its timeevolutionis determined


(asalways) by the Schrodinger
equation:

9* =

tf\342\200\224

where H

H%

[5.2]

is the Hamiltonianfor the wholesystem:

H = -^-V? ^-V22+ V(ri,r2,t)

[5.3]

with respectto the coordinates


of
subscripton V indicatesdifferentiation
carries
particle1 or particle2, asthe casemay he).The statistical
interpretation
overin the obviousway:

(the

I^Cn.ta.oi^riAs

[5.4]

is the probabilityof findingparticle1 in the volume($y\\ and particle2 in the


in sucha way that
volumed3i2\\evidently *!> must benormalized

/ \\^(rur2,t)\\1d3r}d3T2=l.

[5.5]
201

202

Particles
Chapter5 Identical
For time-independent
set of solutionsby
we obtaina complete
potentials,
of variables:
separation

*(ri,r2f 0 = f(r\\, Y2)e'iEt/h,

[5,6]

Schrodinger
spatialwave functionOft) satisfiesthe time-independent
equation:
[5.7]
-7T-Vh~ ~-^if + Vj, = Ef,

where the

2mi

and E

Imi

is the totalenergy of the system.

* *Problem5.1Typically^ theinteraction
potentialdependsonly on the vectorr
In that casethe SchrQdinger
ri r2 betweenthe two particles.
equationseparates*
if we changevariablesfrom r\\, r2 to r and R = (mir\\ + m.2T^/{jn\\_+ m.2) (the
centerof mass).
=\342\226\240

\342\200\224

(a) Showthat
Vn,

rj

\342\200\224

+ (/z/mi)f,r2 = R

V2 = (li/mi)VR V,-,where

\342\200\224

(/x/miir,and Vi

\342\200\224

(/x/m2)VR +

= mim2
mi+m2
\342\226\240

/tt

[5,8]

is thereducedmassof the system.


(b) Showthat

becomes
the (time-independent)
Schrodinger
equation
h2

-v\\f
2(mi+m2)

- ^-vff +.V(r)f = Ef.


h2

2fjt

(c) Separatethe variables,


lettingi/f(R, r) = ^jtr (R)-^,-(r).Notethat ^r satisfies
in
the one-particle
Schrodinger
equation,with the totalmass(mj +
the one-particle
zero,and energy Er, while \\frr satisfies
placeof ra, potential
equationwith the reducedmassin placeof m, potentialV(r),
Schrodinger
and energy Er.The totalenergy is the sum:E = Er + Er.What thistells:us
is that the centerof massmoveslikea free particle,and the relativemotion
2 with respectto particle1)is the sameas if
(that is,the motionof particle
we had a singleparticlewith thereducedmass,subjectto the potential
V.
it reduces
occursin classicalmechanics;1
Exactly the samedecomposition
the two-bodyproblem
to an equivalentone-bodyproblem.
\302\27322)

See,for example,
Dynamics of Particles
Jerry B.Marion and StephenT.Thornton, Classical
and Systems,4th ed,,Saunders,Fort Worth, TX (1995),
Section8.2.

Section5.1:
Two-B'article
Systems

203

Problem5.2In view ofProblem5.1,we cancorrectforthe motionof the nucleus


in hydrogenby simplyreplacing
the electronmasswith the reduced
mass.
Find (to two significantdigits)the percenterrorin the bindingenergy of
hydrogen(Equation4.77) introduced
by ouruseof m insteadof \\x.
in wavelength betweenthe redBalmerlines(n 3
(b) Findthe separation
=
n
2) for hydrogenand deuterium.
(c) Findthebindingenergy of positronium
(in which the protonis replaced
by
a positron\342\200\224-positrons have thesamemassas electrons,
but opposite
charge).
of muonichydrogen*in which
(d) Suppose
you wanted to confirmtheexistence
the electron
is replacedby a muon(samecharge,hut 206.77timesheavier).
line
Where (i.e.,at what wavelength) would you lookfor the 'Xyman-o:\"
=
=
->
n
1)?
(n 2
(a)

\342\200\224

-\302\273

Problem53 Chlorine
hastwo naturally occurring
isotopes,CI35and CI3'7.Show
that the vibrational
with
spectrumofHC1shouldconsistof closelyspaceddoublets,
a splitting
givenby Av 7.51x 10_4u,where v is the frequency of theemitted
with co s/k/jji,where jjl is
oscillator,
photon.Hint:Think of it as a harmonic
the reduced
mass(Equation5,8)and k is presumablythe sameforbothisotopes.
\342\200\224

\342\200\224.

BosonsandFefmions
5.1.1
stateifa(x),and particle2 is in the state
Suppose
particle1 is in the (one-particle)
In that easeVKrl> ri) is a
I'mignoringspin,for the moment.)
ifb(r).(Remember:
simpleproduct'?
[5.9]
fin, r?) %(n)^b(^2)-

Of course,this; assumes
that we cantellthe particles
apart\342\200\224otherwise it wouldn't
make any senseto claimthat number 1 isin state andnumber 2 is in stateyj/y,
allwe couldsay is that oneof them is in the state\\j/a and the otheris in state^/,,
this
but we wouldn'tknow which is which.If we were talkingclassical
mechanics
You canalways tellthe particles
wouldbe a sillyobjection:
apart, inprinciple\342\200\224just
\\jjra

2It is emphatically not truelhat every two-partiele wave function is a product of two one-particle
wave functions. There exist so-called
this way. However:
entangledstatesthat cannot be decomposed
If particle 1 is in state a and particle 2is in state b, then the two-partiele state is a product.I know
what you're thinking:
\"How couldparticle 1not bein some staxe, and particle 2 in some other state?''
can'ttell you the state of
The classicexampleis the singlet spin configuration (Equation
partiele 1 by itself, becauseit is \"entangled\" (Sehrodinger's
lovely word) with the state of particle 2.
If 2 is measured,and found to be spin up, then 1 is spin down, but if 2 is spin down, then 1is spin up.
4.178)\342\200\224I

204

Particles
Chapters Identical
numberson
paintoneof them red and the otheroneblue,or stamp identification
to followthem around.But in quantum mechanics
them,orhireprivate detectives
the situation
is fundamentally different:You can'tpaintah electronred,or pin a
labelon it, and a detective's
observations
alter
will inevitablyand unpredictably
its state,raisingdoubtsas to whether the two had perhapsswitchedplaces.The
fact is,all electrons
in a way that no two classical
are utterly identical,
objectscan
is which; God
ever be.It's notjust that we don'thappento know which electron
doesn'tknow which is which,becausethere is no suchthing as \"this\" electron,
or
all we canlegitimately
\"that\" electron;
speakaboutis \"art\" electron.

of particlesthat are
the existence
Quantum mechanics
neatly accommodates
in principle:
a wave functionthat is nonWe simplyconstruct
indistinguishable
committedasto which particleis in which state.There are actually two ways to

do it:

f+ (ri,r2)= A\\^a{Yx)ifb{t2)

\302\261

#6(1-,)^0\302\276)].

[5.10]

Thus thetheory admitstwo kindsof identical


bosons,for which we use
particles:

theplussign,and fermions,for which we usethe minussigh.Photonsarid mesons


are bosons;
It sohappensthat
are fermions.
protonsand electrons

allparticleswith integerspinare bosons*and


allparticleswith halfintegerspinare fermions.

,,

betweenspinand statistics(aswe shallsee,bosonsand fermions


This connection

have quite different statistical


canbe proved in relativisticquantum
properties)
inthenonrelativistic
mechanics;
theory it is taken as an axiom.3
that two identical
It follows,in particular,
fermions(for example,two
then
electrons) cannot
occupythe samestate,Forif

^ ^,
\342\200\224

iMri,r2) = A[faft\\)fa(Y2)- fa(n)fa(ri)]= 0,


and we are left with no wave functionat all.4Thisis thefamousPauliexclusion
a weirdad hocassumption
It isnot(asyou may have beenledtobelieve)
principle.
of therulesfor constructing
but rather a consequence
applyingonlyto electrons,
wave functions,
fermions.
two-particle
applyingto all identical
I assumed,
for the sakeof argument, that oneparticlewas in the statei/a
and the otherin state\\f/-y, but thereis a moregeneral(andmore sophisticated)
\342\226\240^It

seemsbizarre that

relativity

should have

anything

to do

with

it,

and there has beena lot

of discussionrecently as to whether it might be possibleto prove the spin-statisticsconnection in


Ian Duck and
Robert C.Hilborn,Am. J, Phys. 63,298(1995);
other (simpler)ways. See,for example,
E. C.G.Sudarshan, Pauli and the Spin-StatisticsTheorem, World Scientific, Singapore(1997).
this bothers you (after all, a spmlessferrnion
4I'mstill leaving out the spin, don't
assume
in
the
same spin state. I'llincorporate spin explicitlyin a
is a contradiction in terms),
they're
forget\342\200\224if

moment.

Section5.i:Two-Particle
Systems

205

to formulatethe problem.Let us definethe exchangeoperator,P, which


thetwo particles:
interchanges
[5-12]
Pf(*UT2)= f{T2,T\\).

way

of P are
Clearly,P2 = 1,and it follows(proveit for yourself)that the eigenvalues
+ 1.Now, if the two particlesare identical,
the Hamiltonian
must treat them the
same:mi mi and V(r\\, t-z) V(r%, f i).It followsthat P and H are compatible
\342\200\224

observables,

\342\200\224

[P,H] = 0,

[5.13]

and hencewe canfind a complete


setoffunctionsthat aresimultaneous
eigenstates
of both.That is to say, we canfind solutionsto the Schrbdingerequationthat
are eithersymmetric (eigenvalue+1) of antisymmetric (eigenvalue
under
\342\200\2241)

exchange;
TA(ri,r2)=

[54.4]

\302\261tA(r2,ri).

Moreover,if a systemstarts out in sucha state,it will remainin sucha state.The


isthat foridentical
new law (Hi callit the symmetrization
requirement)
particles
the wave functionis not merely allowed,but requiredto satisfy Equation5.14,
with the plussignfor bosons,
aridthe minussignfor fermions.5
Thisisthe general
of which Equation5.10is a specialcase.
statement,
we have two noninteracting\342\200\224they passrightthroughone
Example5;1 Suppose
another never mindhow you wouldsetthisup in practice!\342\200\224particles, bothof
statesare
massm, intheinfinite squarewell (Section2.2).The one-particle

,..

/2 . /nn

fn(x) =-1/7$in(\342\200\224*)> En=irK


\\

If the particles
are distinguishable,
with
forconvenience),
(where K = jr2h2/2ma2,
#1 in staten\\ and #2 instateni,:the composite
wave functionis a simpleproduct:

is sometimessuggested,that the symmetrization requirement (Equation 5.14)


is-forcedby
P and H commute. This is false:It is perfectly possibleto imagine a system of two
distinguishableparticles(say, an electron and a positron)for which the Hamiltonian is symmetric, and
yet there is no requirement that the: wave function be symmetric (or antisymmetric). But identical
particleshave to occupy symmetric or antisymmetric states,and this is a completely new fundamental
a .par,logically,with Schrodinger?s
equation and the statistical interpretation. Of course,there
didn't have to be any such things as identical particles;it could have been thai every single particle
in nature was distinguishable from every other One. QuanlUm mechanicsallowsfor the possibilityof
identical particles, and nature (being lazy) seized the opportunity^
(But I'mnot complaining\342\200\224this
makesmatters enormously simpler!)
-\"'It

the fact

law\342\200\224on

that

206

Particles
Chapter5 Identical
the groundstateis
For example,

2..
2,.

smty-xz/a), E\\\\
a sin(KXi/a)
the first excitedstateis doublydegenerate:

\342\200\224

\342\200\224

\\jt\\\\

\342\200\224

\342\200\224

4r\\2

- sin(7r:xi/a) sin(271x2/0),En-

\342\200\224

^21=
#21='\342\200\224Sin(2jrxi7a)sin(7rx2/d0-,
a

2a;
5K,
5\302\243;

are identical
and so on.If the two particles
bosons,the groundstateis unchanged,
but the first excitedstateis nondegenerate:

a/2 r
-,
+
sm(jtx\\/a)
sm(7Txz/.a)
sin(27rx?/a)
sin(27rxi/tf)
a

-\342\200\224

there is no state
(stillwith energy 5K).And if the particlesare identical
fermions,
with energy 2K\\ the groundstateis

V2r

sm(2jrx2/fl)
a sin(jrjci/d)
and its energy is 5K.
\342\200\224

\342\200\224\342\226\240\342\226\240sin(2^jci/a)

-,

sin(7rx2/a),

^Problem5.4
If tya and are orthogonal,
A in
and bothnormalized,
what is theconstant
Equation5.10?
what Is A? (Thisease,of course,occurs
(b) If
i//t> (and it is normalized),
only for bosons.)
(a)

1/\302\276

\342\200\224

%ffa

Problem5.5
for two noninteraeting
identical
(a) Write downtheHarniltonian
particlesin the
infinitesquarewell.Verify that the fermiongroundstategiveninExample5.1
is an eigenfunction
of H, with the appropriate
eigenvalue.
(b)

Findthe next two excitedstates(beyondthe onesin Example


functionsand energies\342\200\224foreachof the three eases(distinguishable,
identical
5.1)\342\200\224wave

bosons,identical
fermions).

5.1:Two-ParticleSystems
Section

207

5.1.2ExchangeForces
To giveyou somesenseof what thesymmetrizationrequirement
actually does,Fm

example.Supposeoneparticleis in
goingto work out a simplebhe-dimensional
and the otheris in statefh(x),and thesetwo statesare orthogonal
state:yjra(x),
andnumber1 is the one
and normalized.
If the two particlesaredistinguishable,
in state-^, then the combined
wave functionis

ir(xi,x2)= fa to)in?to);

15]

[5>

if they areidentical
5.4for
wave functionis (seeProblem
bosons,the composite

thenormalization)

+ fhto)fato)\\\\
f+to,x2)= \342\200\224~[irato)ih,to)

[5.1.6]

ir-to,x2)= \342\200\224^[fato)fbto)- itbtowato)]-

[5-17]

V2
it is
and if they are identical
fermions,

theexpectation
Let'scalculate
value of the squareof the separation
distance
betweenthe two particles,

(to

-x2)2)= <xf}+ (xf) - 2(xix2),

[5.18]

1:

Case Distinguishable
particles.For the wavefunctionin Equation5.15,
(Xi) =

x\\\\faix\\)\\2dx\\

= (x2}a
/ \\ifbto)\\2dx2

value of x2 in the one-particle


statefa),
(the expectation
(xf)

/ \\if-a(xi)\\2dxi

xl\\fb{X2)\\24X2 = (X2)b,

and
(xiX2) =

In thiscase,then,

= {x)a{x)b.
/ xi\\fato)\\2dxi/ X2\\fhto)\\2dx2,

{(xi x2)2)d= (x% + (x2)b 2(x)a{x)h.

[5.19]

the answer would,of course,be the sameif particle1 had beenin


(Incidentally,
statefb, andparticle2 in statex(ra.}

208

Particles
Chapter5 Identical

5.16and 5.17,
Case2:Identicalparticles-Forthewave functionsinEquations

.(*?)=

/ xi\\fa(xi)\\2dxi/

\\\\ftb(xz)\\2dxi

+ / *i2|W*T)|2^'l
/ \\ta(x2)\\2dx2

\302\261

/ xfira(Xi)*fb(X\\)dXi
/ fb(X2)*fa(X2)dx2

\302\261

/ X2\\Jtb(x\\)*ifa(xi)dxi Vkto)V&(*2)'#>B.
/

0 0] =
2 [<*2 + (^2}i
\302\261

\302\261

>\302\253

((x2)\302\273

+ <x2)fi) .

Similarly,

(*i) =
(Naturally, (xj) =

\\

{&2)b+

\342\200\242

<*2)\302\253)

(x2),sinceyou can'ttellthem apart.)But

(x1x2)=

-\\
+/
\302\261

dxi x2\\fb(x2)\\2dx2

x\\\\x(ra(xi)\\2

xi\\irb(xi)\\2dx\\ x2\\%(x2)\\2dx2

^#ir^(^i)^i/ ^2^(^2)^^(^2)^2

+ xifb(xi)*ita(xi)dxi/ xifa(x2)*fb(x2)dx2
= -({X)a(x)b
+
= (x)a{x)b
\302\261\\{x)ab\\2,

<xMx)\302\253

\302\261(x)afc<x)ta \302\261(*>&a(*)fl&)

where
(x)ab =
Evidently

((A

x2)2)\302\261

Xljfa

{x)*-fb(x)dx.

= {x2}*+ {x2)b 2{x)a{x)b


T 2|{*W|2.

[5.20]

[5.21]

Comparing
Equations5.19and 5.21,we seethat the differenceresidesin the

final term:

+ = ((Ax)2)d
^ 2\\ (x)abI2.
{(Ax)2)

[5.22]

Section5.1:
Two-Particle
Systems

0^4

209

\342\200\242\342\200\224^0

(b)

5.1:

Schematicpictureof the covalentbond:(a) Symmetricconfiguration


FIGURE
attractiveforce,(b) Antisymmetricconfiguration
repulsiveforce.
produces
produces

Identical
bosons(the uppersigns)tendtobesomewhatclosertogether,
and identical
fermions(the lowersigns)somewhatfarther apart, than distinguishable
particles
in the sametwo states.Noticethat (x)ab vanishesunlessthe two wave
actually overlap[if ira(x)is zerowherever ^(#) is nonzero,the integral
in Equation5.20is zero].So if \\(ra represents
an electron
in an atomin Chicago,
an electronin an atom in Seattle,it's not goingto make any
and ifb represents
differencewhether you antisymmetrize the wave functionor not.As a practical
wave
it's okay to pretendthat electronswith nohoveflapping
matter, therefore,
functionsare distinguishable.
(Indeed,thisis the only thing that allowsphysicists
and chemists
to proceedat all,for in principleevery electronin the universe is
linkedto every otherone,via the antisymmetrizationof theirwave functions,
and
if thisreally muttered,you wouldn'tbe ableto talk aboutany oneunlessyou were
preparedto dealwith them allVj
The interesting
caseis when thereis someoverlapof the wave functions:
The systembehavesas thoughthere were a \"forceof attraction\"betweenidentical
between
bosons,pullingthem closertogether,and a \"forceof repulsion\"
that we are for the momentignoring
fermions,
pushingthem apart (remember
spin).We callit an exchangeforce,althoughit's not really a forceat
rather, it is a purely geometrical
physicalagencyis pushingontheparticles;
It is alsoa strictlyquantum mechanical
of the symmetrization
requirement.
with no classical
it hasprofound
Nevertheless,
phenomenon,
counterpart.
the hydrogenmolecule
for example,
consequences. Consider,
Roughly speaking,
the groundstateconsists
in theatomicgroundstate(Equation
of oneelectron
4:80)
centeredon nucleus1, and oneelectronin the atomicgroundstatecenteredat
nucleus2. If electronswere bosons,the symmetrization
(or,if you
requirement
the electronstoward the
like,the \"exchangeforce\")would tend to concentrate
middle,betweenthe two protons(Figure5.1(a)),and the resultingaccumulation
of negativechargewould attract theprotonsinward, accounting
for the covalent
and thismeans
bond,6Unfortunately,
electronsaren'tbosons,they'refermions,
that theconcentration
of negativechargeshouldactually be shiftedto the wings
tearingthe molecule
apart!
(Figure5.1(b)),
functions

identical

all\342\200\224no

consequence

(\302\276).

6A covalent bond occurswhen sharedelectrons


congregate between the nuclei, pulling the atoms
It
7.3we'll encounter a.covalent bond with just
not
involve
two
Section
need
together.
one electron.
electrons\342\200\224in

210

Particles
Chapter5 Identical

stateof the electron


But wait! We have beenignoringspin.The complete

the
includesnot only its positionwave function,but alsoa spinor,describing
orientation
of its spin:7
[5-23]
1r(r).xl*)>
When we put togetherthe two-electron
state,it is the whole works,notjust the
Now, a glance
spatialpart,that hasto be antisymmetricwith respectto exchange.
4.177and 4.178)
hack at the composite
revealsthat the singlet
spinstates(Equations
combination
is antisymmetric(and hencewouldhave tobejoinedwith a symmetric

spatialfunction)whereasthe threetripletstatesare allsymmetric(andwouldrequire


an antisymmetric spatialfunction).
Evidently,then,the singletstateshouldleadto
to
anti
Sureenough,
thechemists
tellusthat covalent
bonding.
bonding,and thetriplet
the
the
electrons
to occupy singletstate,with totalspinzero.8
bondingrequires two
j

^Problem5.6Imaginetwo npninteraeting
eachof massm, in the infinite
particles,
squarewell.If oneis in the state-tyn (Equation2.28),and the otherin state^
{I 7^ n), calculate{(x{ -xi)2),assuming(a) they are distinguishable
particles,
identical
are
are
and
identical
fermions.
bosons, (c)they
(b) they
\342\200\224

Problem5,7 Supposeyou had threeparticles,onein state^(i),onein state


and oneinstatet/tc(x).
and are orthonomnal,
construct
Assuming
states(analogous
thethree-particle
to Equations5.15,
5.16,and 5.17)representing
bosons,and(c)identicalfermions.
(b) identical
(a)distinguishable
particles,
Keep
in mind that (b) must be completely
under
of
interchange any pair of
symmetric,
and (e)must be completely
in the samesense.Comment:
antisymmetric,
particles,
There'sa cutetrick for constructing
antisymmetric wave functions:
completely
Formthe Slaterdeterminant,whosefirst row is ^(x\\),.^bixi),tycCxi), etc.,
whosesecondrow is.ira{x2)i (#2),i^i-ixi),etc.,and so on (thisdeviceworks
for any number of particles).

^,^,

\342\226\240fibix),

^\302\276

^/\302\276

5-2ATOMS
neutral atom,of atomicnumber Z, consistsof a heavy nucleus,with electric
(massm and charge e). The Hamiltonian
chargeZe, surrounded
by Z electrons

\342\200\224

'Inthe

absenceof coupling betweenspin and position,we are free to assumethat the state is
its
separable spin and spatial coordinates.This just says that the probability of getting spin up is
of coupling,the general state would take
independent of the location of the particle.In the presence
the form of a linear combination: ^+ (r)x+ #-(r)x-\302\273 as in Problem
in

4.55.

\"In casual language; it is often said that the electronsare \"oppositelyaligned\" (one with spin
the other with spindown).This is something of an oversimplification,sincethe, same couldbe
and
up,
said of the m
statement is that they are in the singlet configuration.
triplet state. The precise
\342\200\224

Section5.2:Atoms

211

for thissystemis9

[5.24]

/-1

The term in curly bracketsrepresents


the kineticpluspotential
energy of the ,/th

electron,in the electricfieldof the nucleus;the secondsum (which runsover


allvaluesof / and k exceptj = k) is the potentialenergy associated
with the
mutual repulsion
of theelectrons(the factorof 1/2in front correctsfor the fact
that the summation
countseachpairtwice).The problemis tosolveSchrodinger's
equation,
Ha//

=\342\226\240

Ef,

[5,25]

for the wave function\\Ki*i,i\"2>,..


are identical
, tz).Becauseelectrons
fermions,
state
are acceptable:
however,not allsolutions
onlythosefor which the complete
and spin),
(position

, rz)x(si,
s2,...,
f(ti,r2,...
sz),

is antisymmetricwith respectto interchange


of any

[5.26]

In particular,
no
two electrons.

two electrons
can occupythe samestate.
the Schrodinger
in Equation5.24
Unfortunately,
equationwith Hamiltonian
cannotbesolvedexactly (at any rate,it hasn'tbeen)*exceptfor the very simplest
case,Z = 1 (hydrogen).In practice,onemust resortto elaborateapproximation
methods.
Someof thesewe shallexplorein Part II; for now I planonlyto sketch

somequalitativefeaturesof thesolutions,
obtained
theelectron
by neglecting
In Section5.2.1we'llstudy the groundstateand excitedstates
term altogether.
the groundstatesof higheratoms.
of helium,and in Section5.2.2we'llexamine
repulsion

ti,....,

Problem5.8Suppose
(t/r(ri,
tz)) to the
you couldfind a solution
equation(Equation5.25),for the Hamiltonianin Equation5.24.Describe
how you wouldconstruct
from it a completely
symmetricfunctionand a completely
which alsosatisfy theSchrodinger
with the same
antisymmetricfunction,
equation,
Schrodinger

energy.
assuming the nucleus is stationary. The trick ofaccounting for nuclear motion by using the
worksonly for the ftw-body problem;fortunately, the nucleus is so much
reducedmass (Problem 5.1)
more massive than the electronsthat the correction is extremely small even in the easepi\" hydrogen
(seeProblem5.2(a)),and it is smaller still for the heavier atoms. There are moreinteresting effects,
due to magnetic interactions associatedwith electron spin,relativistic corrections,
and the finite sizeof
the nucleus.
We'll lookinto these in later chapters,but all of them are minute correctionsto the \"purely
coulombie\"atom describedby Equation 5.24.
\342\226\240\"\342\226\240I'm

212

Particles
Chapter5 Identical

5,2.1Helium
After

hydrogen,the simplestatomis helium(Z 2)- The Hamiltonian,


\342\200\224

, h2
1

2m

1 2e2
Arteo

r\\

h2 1 le1
V2
'i~
2m
47reo ri

e2

\"\342\200\224'\342\200\224

47T60

[n

t2\\

[5.27]

consistsof two hydrOgenicHamiltonians


(with nuclear
charge2e),onefor electron
1 and onefor electron2, togetherwith a final term describing
of the
the repulsion
two electrons.
It isthislastterm that causesallthe trouble.If we simplyignoreit,
canbe written asproductsof
the Schrodinger
and the solutions
separates,
equation
hydrogenwave functions:
\342\226\240f

(ri,r2) = fnim(ri)Vv/'m'(ri),

[5.28]

onlywith half the Bohrradius(Equation4:72),and four timestheBohrenergies


The total
you don't see why, refer backto Problem4...16.
(Equation
energy wouldbe
E = 4(En+ En>),
[5.29]
4.70)\342\200\224if

where En

\342\200\224

\342\200\22413.6/n2

eV'.'Inparticular,
the groundstatewouldbe

= -^e~1{r{+n)la,
Mri,r2)=^ii\302\253.(ri)^iDD(ra)
Trar

[5.30]

(seeEquation4.80),and its energy wouldbe


EQ =

eV.
8(-13.6
eV) = -109

[5.31]

Becauset/^q is a symmetricfunction,
the spinstatehasto be antisymmetric,sothe
with the spins
groundstateof heliumshouldbe a singletconfiguration,
The actual groundstateof heliumis indeeda singlet,but the
aligned.\"
determined
eV, so the agreementis not very
experimentally
energy is
which is
We ignoredelectron
good.But thisis hardly surprising:
repulsion,
It is clearlypositive(seeEquation5.27),which is
contribution.
certainly not a small
it bringsthe totalenergy up from
to
eV (see
comforting\342\200\224evidently
\"oppositely

\342\200\22478.975

\342\200\224109

\342\200\22479

Problem5.11).

The excitedstatesof heliumconsistof oneelectron


in the hydrogenicground

state,and theotherin an excitedstate:

fnlmfWQ-

[5:32]

[If you try to put both electronsin excitedstates,oneirnmediately dropsto the


groundstate,releasingenoughenergy to knockthe otherone into the
(E > 0), leavingyou with a heliumion (He+) and a free electron.This
continuum

Section5.2:Atoms

is an interestingsystemin its own

right\342\200\224see

Problem

5.9\342\200\224but

it

213

is not our

We can construct
both symmetric and antisymmetric
presentconcern.]
the formergo with the antisymmetricspin
in theusualway (Equation5.10);
and they are calledparahelium,
whilethe latterrequire
(the singlet),
configuration
a symmetric spinconfiguration
(the triplet),and they are known asorthohelium.
The groundstateis necessarily
the excitedstatescomein bothforms.
parahelium;
closertogether(aswe
Becausethe symmetric spatialstatebringstheelectrons
we expecta tagherinteraction
discoveredin Section
5.1.2),
energy in parahelium*and
confirmedthat the paraheliumstateshave somewhat
indeed,it is experimentally
(seeFigure5.2).
higherenergy than theirorthohelium
counterparts
combinations,

Parahelium

1j

1]

4S.T 4P-- AD- 4F

3S
>
3-

o) ~J
^.

Orthohelium

3p

3D

4S 4P-- 40- 4F

3P 3D1-

..

3P 3D1-

3S

2p\302\261

UJ

2P-L

-4 2S

2S1-

Sat -24.5
eV)

5.2: Energy level diagram for helium (the notationis explainedin


FIGURE
are uniformlyhigher than their
Notethat paraheliumenergies
Section5,2.2).
The
numericalvalues
on
the verticalscaleare relativeto the ground
counterparts.
eV = -54.4eV;to getthe totalenergyof
stateofionizedhelium (He+):4 x (--13.6}
5
4.4
the state,subtract eV.

orthohelium

214

Particles
Chapter5 Identical

Problem5.9
(a)
(b)

in a heliumatomintothen 2 state;what
Supposeyou put bothelectrons
wouldtheenergy of the emittedelectron
be?
of the heliumion,He+.
Describe
(quantitatively)thespectrum
\342\200\224

Prpblem5.10Discuss(qualitatively)the energy levelschemefor hehum if


were distinguishable
were identical
bosons,and (b) if electrons
(a) electrons
and
Pretend
the
these
stillhave spin
same
mass charge).
\"electrons\"
(but with
are thesingletand thetriplet.
1/2,so the spinconfigurations

particles

* *Prpblem5..11
(a)

Calculate
rjjl)}for the state (Equation530),Hint:Do the
{{\\f\\t\\
and settingthepolaraxisalongrj,
coordinates,
integralfirst,usingspherical
sothat
|ri r2]= y r\\ + r\\-InncosB2.
The $2integralis easy,but be carefulto take the positiveroot.You'llhave
to breaktheti integralintotwo pieces,onerangingfrom 0 to r\\, theother
\342\200\224

-0\302\276

^3\302\276

^\342\200\224

from r\\ to co.Answer: 5/4a.


(b)

Use your resultin (a) to estimatethe electroninteraction


energy in the
groundstateof helium.Expressyour answer in electronvolts,and add it
to Eq (Equation5.31)to geta corrected
of the groundstateenergy.
estimate
value, (Of course,we'restillworking with an
Comparethe experimental
wave function,sodon'texpectperfectagreement.)
approximate

5.2.2ThePeriodicTable
The groundstateelectron
forheavieratomscan bepiecedtogetherin
configurations
much thesameway. To first approximation
(ignoringtheirmutual repulsion

the individualelectrons
occupyone-particle
hydrogenicstates(n,I, m),
calledorbitals,in the Coulombpotentialof a nucleuswith chargeZe. If
electrons
were bosons(or distinguishable
particles)
they wouldall shakedown to the
are
groundstate(.1,0,0),.and chemistrywouldbe very dullindeed.But electrons
altogether),

fact identicalfermions,subjectto the Pauli exclusion


principle,so only two
can occupyany givenorbital(onewith spinup, and one with spin
moreprecisely,
in the singletconfiguration).
There are n2 hydrogenicwave
(allwith the sameenergy En) for a givenvalue of n, so the n = 1 shell
2 shellholds8, n = 3 takes 18,and in
hasroomfor 2 electrons,
the n
the nth shellcan accommodate
2n2 electrons.
the horizontal
Qualitatively,
rowson the PeriodicTablecorrespond
to fillingout eachshell(if thiswere the.
in

down\342\200\224or,

functions

\342\200\224

general

215

Section5.2;Atoms

whole story,they would have lengths2, 8, 18,32,50,etc.,insteadof 2, 8, 8,


throws the
18,18,etc.;we'llseein a momenthow theelectron-electron
repulsion

countingoff).

helium,the n.= \\ shellis filled,so the next atom,lithium(Z 3),has


to put oneelectroninto the n 2 shell.Now, for n 2 we can have / = 0 of
/ = 1; which of thesewill the third electron
choose?In theabsenceof electronelectroninteractions,
depend
they bothhave the sameenergy (theBohrenergies
on h, remember,
but noton /). But the effectof electron
is to favor the
repulsion
lowestvalue of /, for the followingreason.Angular momentum tendsto throw
the electronoutward, and the farther out it gets,the moreeffectivelythe inner
theinnermost
screenthenucleus(roughly speaking,
electron\"sees\"the
electrons
full nuclearchargeZe,but the outermost
electronseesan effectivechargehardly
thestatewith lowestenergy (which
greaterthan e).Within a givenshell,therefore,
is to say, the mosttightly boundelectron)
is I = 0,.and theenergy increases
with
/. Thus the third electronin lithiumoccupiesthe orbital(2,0,0). The
increasing
next atom (beiyllium,
with Z
4) alsofits intothis state(onlywith \"Opposite
1.
butboron(Z 5) hasto make useof
spin\,")
=
Continuingin thisway, we reachneon(Z 10),at which pointthe n = 2
shellis filled,and we advance to the next row of theperiodictableandbeginto
with
then 3 shell.Firstthereare two atoms(sodiumand magnesium)
populate
0, and then thereare sixwith
(
(aluminum through argon).Following
=
be 10atomswith n 3 and I = 2;however,by thistimethe
argonthere\"should\"
effectis so strongthat it overlapsthe nextshell,so potassium
(Z 19)
screening
=
=
=
and calcium(Z 20)choosen
to n 3, I 2. After
4, I 0, in preference
=
that we dropbackto pickup the
3, I 2 stragglers
(scandiumthrough zinc),
=
followedby n 4,1 1 (gallium
throughkrypton),at which pointwe againmake
a prematurejump to thenext row (n = 5),and wait until laterto slipin the 1 2
For detailsof thisintricatecounterpoint
I
and I = 3 orbitalsfrom the
A shell.
referyou to any bookon atomicphysics.10
I would be delinquent
if I failedto mentionthe archaicnomenclature
for
atomicstates,becauseallchemists
and mostphysicists
useit (and the peoplewho
make up the GraduateRecordExam lovethiskindof thing).For reasonsknown
I = 0 iscalleds (for\"sharp\,")I = 1 isp
bestto nineteenth
century spectroscopists,
I =2hd (\"diffuse\,")
after that I
and I = 3 is f (\"fundamental\;")
(for\"principal\,")
becauseit now continues
guessthey ran outof imagination,
(g,h, /,
alphabetically
The stateof a particular
electron
butskip
to beutterly perverse,
k, /, etc.).ll
is represented
by the pairnl,with n (the number) givingthe shell,and / (the letter)
With

\342\200\224

\342\200\224

\342\200\224

\342\200\224

\342\200\224

/\342\200\224

/-1

\342\200\224

\342\200\224

\342\200\224

\342\200\224

\342\200\224

n.\342\200\224

\342\200\224

\342\200\224

n\342\200\224

/\342\200\224just

10

See*for example,U. Fano

York

(1959),
Chapter 18,or the

arid L. Fario, Basic


-Physicsof Atoms and Molecules,Wiley, New
classicby G'f Herzberg,Atomic Spectraarid Atomic Structure, Dover,

New York (1944).


The shells themselves are assignedequally arbitrary nicknames,stalling (dori'lask hie why)
wilh K:The K. shell is n = 1,the L shell is n
2, M is n = 3, and so on (at least they're in
alphabetical order).
\342\200\224

216

Particles
Chapters Identical
the magnetic
quantum numberm is not
specifyingtheorbitalangular momentum;
that occupythe
listed,but an exponentis usedto indicatethe number of electrons
Thus the configuration
statein question.

[5,33]

(lsf.Qs?Q.p)2

in the orbital(1,0,Q), two in theorbital(2,0,0),


tellsusthat thereare two electrons
and two in some'combination
.ofthe orbitals(2,1.,1),.(2, 1,0),.and (2,1,
This
happenstobe the groundstateof carbon.
In that example
with orbitalangular momentum
there are two electrons
number 1,.sothe totalorbitalangular momentum quantum number,L (capital
L, insteadof /^ to indicatethat thispertainsto the total,notto any oneparticle)
couldbe 2, 1,or 0. Meanwhile,the two (Is) electronsare lockedtogetherin the
but the two
singletstate,with totalspinzero,and so are the two (2s)electrons,
couldbe in the singletconfiguration
So
or the tripletconfiguration.
(2p)electrons
the totalspinquantum number 5 (capital,
again,becauseit'sthe total)couldbe 1
or 0. Evidently the grand total(orbitalplusspin),J, couldbe 3,2, 1,or 0. There
existrituals,known as Hund'sRules(seeProblem5.13)for figuring out what
atom.The resultis recorded
thesetotalswill be, for a particular
as the following
hieroglyphic:
[5.34]
2S+iLj,
\342\200\2241).

quantum

and L the letter\342\200\224capitalized,


(where S and J are thenumbers,

thistime,because
we'retalkingaboutthe totals).The groundstateof carbonhappensto be 3Pq:
the totalspinis 1 (hencethe 3), the totalorbitalangular momentum is 1 (hence
the P), and the grand totalangular momentum is zero(hencethe 0).In Table5.1
the individualconfigurations
and the total angular momenta (in the notationof
Table.12
Equation5,34).are listed,for the firstfourrows of the Periodic
^Problem5.12
(inthe notationof Equation5.33)for
Figureout theelectronconfigurations
the first two rows of thePeriodic
Table(up to neon),and checkyour results
againstTable5.1.
totalangular momenta,in thenotationof
'(b) Figureout the corresponding
for boron,
Listallthe possibilities
5-34,for the first fourelements.
(a)

Equation

carbon,

and nitrogen.

-After krypton\342\200\224element
situation
gets more complicated(fine structure starts to play
a significant role in the ordering of the states)soit is not for want of space that the table terminates
36\342\200\224the:

there.

Section$.2:Atoms
TABLE5.1:.-Groundstateelectron
forthe first four rows ofthe Periodic
configurations

Table,

Element
1 H

2 He
3 Li
4 Be
5

9 F

10
11
12
13

Ne
Na
Mg
Al

14 Si

Corrfiguratior
L

(lj)

2Sm

i\\s)2

(He)(2s)
(He)(2s)2

%/2

(mm2(2p)

2Pm
3Po

(He)(2s)2(2p)2
(He)(2s)2(2p)3
(He)(2s)2(2p)4
(He)(2s)2(2p)5

(He)(2s)2(2#
(Ne)(35)

(Ne)(3s)2
(Ne)(3s)2(3p)
(Ne)(3s)2(3\302\243)2

15

16

(Ne)(3s)2(3p)3

(Ne)C3s)2(3p)4
(Ne)(3^)2(3^)5

17 CI

18

Ar

19 K
20 Ca
21 Sc
22 Ti
23 V
24 Cf
25 Mn
26 Fe
27 Co
28 Ni
29 Cu
30 Zri

31 Ga
32
33
34
35
36

Ge
As

Se
Br
Kr

(Ne)@s)20p)6

%/2.
3P2

2Pm

2c

V
%/2
P\\I2

3P2

2Pm
lSo

(Ar)(4s)
(Ar)(4j)2
XAt){4s)20d)

%/2

(kr){4s)2W)2

3?2
*Fm

(Ax)(4s)2{3df
(Ar)(4s)(3rf)5
(Ar)(4s)2(3d)5
(At)(4s)2(3d)6
(Ar)(4s)2(3tf)7

2D3n

%/2

%/2

{M)(4s)2{3df

(Ar)(4s)(3<f)10

2SV2

(Ar)(4.s)2(3d)10 %
(Ar)(4i')2(3^)10(4p) 2Pl/2
3d
(Ar)(4.s)2(3tf)10(4p)2 0
(Ar)(4s)2(3d)10(4p)3 S3J2
(Ar)(4^2(3d)1()(4p)4 3P2
(Ar)(4s)2(2dj[V(4p)5 2Pm
(AT)(4s)H3d)l0(4pj6 %

217

218

Particles
Chapters Identical

**Problem5.13
(a)

(b)

(c)

with the Pauliprinciple,


thestatewith
Hund'sfirstrule says that, consistent

thehighesttotalspin(S)will have thelowestenergy.What wouldthispredict


in the caseof the.excitedstatesof helium?
Hund'ssecondrulesaysthat, for a given spin,the statewith thehighesttotal
with overallantisyrnmetrization,
orbitalangular momentum (L),consistent
will have the lowestenergy.Why doesn'tcarbonhave L = 21Hint:Note
that the \"topof the ladder\"(Ml = L) is symmetric.
Hund'sthird rule says that if a subshell(n, I) is no morethan halffilled,
if it ismorethan halffilled,then
then thelowestenergy levelhasJ
/ L.+ hasthe lowestenergy.Usethisto resolvethe boronambiguity
in Problem
5.12(b).
\342\200\224

\\L\342\200\224S\\;

\342\226\240=

(d)

5\"

UseHund'srules,togetherwith thefact that a symmetric spinstatemust go


with an antisymmetric positionstate(andvice versa) to resolvethecarbon
inProblem5.12(b).
and nitrogen
Hint:Always go to the.\"topof
ambiguities
theladder\"to figure out the symmetry of a state.

Problem5.14The groundstateof dysprosium(element


66,in the 6throw of the
PeriodicTable)islistedas5/8.What are thetotalspin,totalorbital,and grand total
for
angular momentum quantum numbers?
Suggesta likelyelectronconfiguration
dysprosium.

5.3SOLIDS
in each
In the solidstate,a few of thelooselyboundoutermost
valenceelectrons
no longersubject ]
and roamaroundthroughout
atom become
the material,
detached,
fieldof a specific
but rather to thecombined
only to theCoulomb
\"parent\"nucleus,
of theentirecrystallattice.In thissectionwe will examine
two extremely
potential
which ignoresall
primitivemodels:first,the electrongas theory of Sommerfeld,
as free 'M
forces(exceptthe confiningboundaries),
treatingthe wandering electrons
particlesin a box (the three-dimensional
analogto an infinite squarewell);and
a periodic
the elee- jfl
second,Bloch'stheory,which introduces
potential
representing
tricalattractionof the regularly spaced,positivelycharged,
nuclei(but stillignores m
electron-electron
Thesemodelsare nomorethan the first haltingsteps m
repulsion).
toward a quantum theory of solids,but already they revealthe criticalrole of m
thePauliexclusion
in accounting
for \"solidity,''
and provideilluminating
principle

1
1
1

\342\226\240

\342\226\240

SectionS3:Solids 219

semi-conductors,
insightintothe remarkableelectricalpropertiesof conductors,
and insulators.

53.1TheFreeElectronGas
lXi ly> lz,
Supposethe objectin questionis a rectangularsolid,with dimensions
inside
ho
and imaginethat an electron
experiences forcesat all,exceptat the
walls:
impenetrable

k'
V(x,y,z)=\\
-7
I co, otherwise.
<X <

\302\260'

'>'and < Z \" k]

\302\260<y<

[5.35]

\302\260

if,\302\260

The Schrodinger
equation,
h2

=
2mV2f Ef,
in cartesian
with
coordinates:
ijr(x.,y, z) X(x)Y(y)Z{z),
separates,

^_

h2 d2X _
*^X'X\\
x '
2m dx2
and E = Ex + Ey

\342\200\224

2ra dy2
Z\342\200\2247y

\342\200\224

h2 d2Z _
^
1m dz2

'
tLyl\\
y

\342\200\224

&zA->

+ Ez-.Letting
_ s/2mEx

_ yjTmEy'
*~
/i

\342\226\240'

/z

y/2mEz
h

we obtainthegeneralsolutions

X(x) Ax sm(kxx) + Bxcos(&xx),Y(y) = Ay


Z(z)= Az sin(^z)+ Bz cosfe).
The boundaryconditions
requirethat Z(0)
Bz = Q, and X(lx)= Y(ly)
kxlx
where eachn

\342\200\224

Y(G)

sm(kyy)

\342\200\224

ny7i,

kzlz

\302\24208(\302\276

Z(0) 0, so Bx =

\342\200\224

= ZQZ) = Q, sp that

nx7i, kyly

-f By

nz7t,

\342\200\224

y),

By

[5.36]

is a positiveinteger:

nx

.
3,...^ = 1,2,3,..., 1,2,3,...
[5.37]

1,2,

nz

\342\200\224

The (normalized)
wave functionsare

*\302\253*=-' sin

u^z

{irx)sin(ify)sin(ifz)'

[5,38]

220

Particles
Chapter5 Identical
and the allowedenergies
are
2

\":*%\302\253.-

where k

Jl

h\302\2437t

2m

\"1+ *l + nl
11
%
l2y

2
hzk

2m

[539]

is the magnitudeof the wave vector,k ^ (kx, ky, kz).

...,

If you imaginea three-dimensional


space,with axeskxi ky, kz, and planes

drawn in at kx
and at kz

.,.,

= (tt/Ix),(27t/lx),(3tt/Ix), at ky = (jt/ly),Qjji'/ly),On/ly),
eachintersection
(tt/Q,(27t/lz),(3;7r/lz)r...,
pointrepresents
\342\200\224

*-K

FIGURE
5.3:Free electrongas.Each intersection
a stationary
on the gridrepresents
one\"block\";
there isonestatefor every block.
state.Shadingindicates

Section5.3:Solids 221

distinct(one-particle)
stationary state(Figure5.3).Eachblockin thisgrid,and
hencealsoeachstate,occupies
a volume
a

71

7t

[5.40]

Ixlyk

= lxlylz is the volumeof the objectitself.Supposeour


samplecontainsN atoms,and eachatom contributes
q free electrons.
(In
the
N will be enormous\342\200\224on
orderof Avogadro'snumber,for an object
of macroscopic
or 2, typically,)If
size\342\200\224whereas q is a small
were bosons(or distinguishable
particles),they would all settledown to
But electronsare in fact identical
the groundstate,.i/nii-13
fennions,subject
to the Pauli exclusionprinciple,so only two of them can occupyany given
state.They will fill up one octantof a spherein A-space,14
whoseradiu$jkf,
is determined
by the fact that eachpair of electrons
requiresa volumen3/V

of \"A-space,\"where

practice,

number\342\200\2241

electrons

(Equation5,40):

Thus
kF

\342\226\240=

[5.41]

(3p7T2)1/3,

where
P=

Nq
~

[5.42]

is ih&freeelectrondensity(the numberof freeelectrons


perunit volume).
and unoccupied
The boundary separating
is called
states,in
occupied
the Fermisurface(hencethe subscript
F).The corresponding
energy iscalledthe
Ferriiienergy,Ep\\ for a freeelectrongas,
\302\243-space,

h2

EF = \342\200\224(3pir2)2/3>
2m

[5.43]

The total energy of the electrongas can be calculated


as follows:A shellof

dk (Figure5.4)contains;
a volume
thickness
1

\342\200\242>

o
'3I'massumingthere is no appreciablethermal excitation, or other disturbance, to lift the solid
youlike, I'mtalking about a \"cold\" solid,though (as you will show

out of its collective ground state. If

Problem 5.16(c)),
typical solids arc still \"cold,\" in this sense,far above room temperature.
iV is such a huge number, we need not worry about the distinction betweenthe actual
of
jaggededge the grid and the smooth sphericalsurface that approximates it.
in

'\342\226\240^Because

222

Particles
Chapters Identical

\342\226\240*-kv

FIGURE5.4: Oneoctantof a spherical


shellinfe-space.

sothe number of electronstatesin theshellis


V l2
2[(l/2)7tk2dk]
_= -^kL
dk.

~\"m^

(7t3/V)

Eachof thesestatescarriesan energy H2k2/2m(Equation5.39),sothe energy of

theshellis

dE =

[5.44]

^kzdk,

\342\200\224

2m tc2

and heneethetotalenergy is

=
Em.
tot
\342\200\224

.^.
~

\302\253

dk =

/I

Jo

1/
V

k4 ClK=
K

[5.45]

Thisquantum mechanical
to the internal
energy playsa rolerather analogous
thermalenergy (U) of an ordinary gas.In particular,
it exertsa pressureonthe
walls,forif thebox expandsby an amount dV, the totalenergy decreases:

dRtot

_2^y
3

107t2m

and this showsup as work doneon the


pressureP. Evidently

=2
3

y_5Pdv = _2

\302\243tot

=2
3

JVV

outside(dW = P dV) by the quantum

^\302\276
1071\302\275

= (3jt2)2/3^2
P5/3
5m

[5.46]

Section5.3:Solids 223

Here,then,is a partialanswer to the questionof why a coldsolidobjectdoesn't


internalpressure,
Thereis a stabilizing
having nothingto do with
simplycollapse:
or thermal motion(which we
electron-electron
(which we have ignored)
repulsion
have excluded),
and derivesultimately from
but is strictly quantum mechanical,
theantisymmetrization
forthe wave functionsof identical
It
fermions.
requirement
is sometimes
calleddegeneracy
pressure\"
pressure,though\"exclusion
might be a
betterterm.15
Problem5.15Findthe average energy perfree electron(EXot/Nq),as a fraction
of the Fermienergy.Answer: (3/'5)Ef.

Problem5.16The densityof copperis 8.96gm/cm3,and its atomicweight is


63.5gm/mole.
--.
the Fermienergy for copper(Equation5.43).Assume
(a) Calculate
q = 1,and
giveyour answer in electronvolts.
electronvelocity?Hint:SetEp = (l/2)mv2.Is
(b) What is the corresponding
it safeto assume
the electrons
in copperare nonrelativistic?
thermal energy (ksT,where ks
(c) At what temperaturewouldthecharacteristic
is the Bpltzmannconstantarid T is the Kelvintemperature)
equalthe Fermi
Thisis calledthe Fermitemperature.As
energy,for copper?Comment:
belowtheFermitemperature,
is substantially
longas the actualtemperature
the materialcanbe regardedas \"cold,\"
with mostof the electrons
in the
state.Sincethe meltingpointof copperis 1356K, solid
lowestaccessible
copperis always cold.
the degeneracy
(d) Calculate
pressure(Equation5.46)of copper,in the electron
gasmodel.
Problem5.17The bulkmodulusof a substance
is the ratioof a smalldecrease
in pressureto the resultingfractionalincreasein volume:
B=

dP
-V\342\200\224-.

dV

Show that B =

(5/3)P, in the free electrongas model,and use your resultin


to estimatethe bulkmodulusof copper.Comment:The observed
Problem5.16(d)
value is 13,4x 1010N/m2, but don'texpectperfectagreement\342\200\224after all,we're
15\\Ye

derived Equations 5.41,


5.43,5.45,and 5.46for the specialcaseof an infinite rectangular
hold for containers qf any shape,as long as:the number of particlesis extremely large.

well, but they

224

I'articles
Chapter5 Identical
all electron-nucleus
forces!Actually, it is rather
and\" electron-electron
neglecting
that thiscalculation
comesas closeasit does.
surprising

5.3.2BandStructure
the forces
We'renow goingto improveoh the free electronmodelby including
exertedon the electronsby the regularly spaced,positivelycharged,essentially
stationary nuclei.The qualitativebehaviorof solidsis dictatedto a remarkable
isperiodic\342\200\224its actualshapeis relevant
degreeby themerefact that thispotential
Toshowyou how it goes,I'm.goingto developthe simplest
only to the finer details.
of evenly spaceddelta
DiraCcomb,consisting
possiblemodel:a one-dimensional
But first I needto introduce
functionspikes(Figure5.5).16
that
a powerfultheorem
the analysisof periodic
potentials.
vastly simplifies
is onethat repeatsitselfafter somefixeddistancea:
A periodic
potential

V(x..+a) = V(jp).

[5.47]

to theSehrodinger
Bloch'stheoremtellsus that for sucha potentialthe solutions

equation,
h2

d2is

02m dxL2+V(x)f= Ef>

[5.48]

can be taken to satisfythe condition

f(x + a) =eiKa\\ff(x),

[5.49]

of x\\ it may well


for someconstantK (by \"constant\"I meanthat it is independent
dependon E).
kV{x)

-2a

2a

3a

4a

5a

6a

FIGURE5.5iThe Diraccomb,Equation5.57.

so

'\"It would bemorenatural to let the delta functions go;down, as to representthe attractive force
of the nuclei.But then there would be negative energy solutions as well as positive energy solutions,
Sinceall we'retrying to do here
and that makes- the calculations more cumbersome(seeProblem
to
t
he
of
it
is
this
lessplausibleshape;if it .comforts
is explore consequences periodicity,
simpler adopt
as
think
of
the
nuclei
at
you,
residing

5.20).

+#/2,+3a/2,+5a/2,

Section5-3:Solids

225

Proof:Let D bethe \"displacement\"


operator:
BfOc)= f(jc+a).

[5.50]

For a periodicpotential
D commutes
with the Hamiltonian:
(Equation5.47)*.

W, H] = 0,

[5.51]

of H that are simultaneously


and hencewe are freetochooseeigenfunctions

of D: D\\Js
eigenfunctions

\342\200\224

kx//, or

ir{x+ a) = \\4r(x).
Now, A

all

[5.52]

Equation5.52holdsfor
obtain\\j/(x) =0, which is not a permissible
wouldimmediately

is certainly notzero(if it were,

x\342\200\224we

then\342\200\224since

likeany nonzerocomplexnumber, it can be expressed


as an
eigenfunction);
exponential:
[5.53]
k=eiKft,
for someconstantK. QED

thisstageEquation5.53:
is just a strangeway to write the eigenvalueA.,.
but in a momentwe will discoverthat K is in fact real,so that although\\(r(x)
itselfis notperiodic,| f(x) \\2 is:
At

\\tt* + a)\\2 = \\f{x)\\2,

[5.54]

as onewouldcertainly expect.17
Of course,no real solidgoeson forever,and the edgesare goingto spoil
of V(x),and renderBloch?s
the periodicity
theoreminapplicable.
However,for
on the orderof Avogadro'snumber
any macroscopic
crystal,containing
something
that edgeeffectscansignificantly
influence
the
of atoms,it is hardly imaginable
behaviorof electrons
deepinside.Thissuggeststhe followingdeviceto salvage
theorem:We wrap the x-axisaroundin a circle,and connectit ontoits
.Bloch's
tail,after a largenumberN ~ 1023of periods;formally,we imposethe boundary
condition
[5.55]
f(x + Na) = f(x),
It follows(fromEquation5.49)that
eiNKcfi/(x)= xf/{x),
argument, starting with Equation 5,54,as a way
It
for
doesn't
of proving Bloch's
theorem.
work,
Equation 5.54alone would allow the phase factor in
to
be
a
function of
Equation 5,49
\342\226\240

Indeed,you

might

be tempted to reversethe

x.

226

Particles
Chapters Identical
so eiNKa = 1,orNKa = 2jzn,and hence
K=

2jrn
-\342\200\224,

TVa

(n

= 0,

., ...-

\302\261

1,

\302\261

2,

[5-56]

In particular^for this arrangement K is necessarily


real.The virtue of Bloch's
theoremis that we needonlysolvethe Sehrodinger
Equationwithin a singlecell
of Equation5.49generates
(say,on the interval 0 < x < a); recursiveapplication
the solution
everywhere else.
thepotentialconsistsof a longstringof delta-function
Now, suppose
spikes
Dirac
(the
comb):

N-l
7=0

(InFigure5.5you must imaginethat the Jt-axishasbeen\"wrappedaround,\"so


No onewouldpretendthat thisis a
the JVth spikeactually appearsat x
that concerns
us
it is only the effectof periodicity
realisticmodel,but remember,
here;the classicstudy18useda repeatingrectangularpattern,and many authors
In the region0 < x < a thepotential
is zero,so
stillpreferthat one.19
\342\200\224

\342\200\224a.)

h2

d2f

1mdx2
or
= -*v,
*%
dx
where
k

[5.58]

^-\342\200\224,

asusual.
The generalsolution
is
Vr(jc)

\342\200\224

Asin(&x) + B cos(^x), (0 < x

< a),

[5.59]

to the
Accordingto Bloch'stheorem,the wave functionin the cellimmediately
left of theoriginis

$(x)= e~iKa[A$mk{x+ a) + B cosk{x+ a)], (-a< x < 0).

[5.60]

499 (1930).
l8R.de L. Kronig and W. G.Penney, Proc.R. Soc.Land.,ser.A, 130,
McGraw-HilljNew
See,for instance, t). Park, Introduction to the Quantum Theory, 3rd

ed\342\200\236

York

(1992).

Section5.3:Solids 227
At

\342\200\224

so
0, mustbe continuous,
iff

B = e~iKa[Asin(fca)+ B c6s,(\302\243a)];

[5.61]

itsderivativesuffersa discontinuity
to the strengthofthe deltafunction
proportional
(Equation2.125,with the signof ql switched,sincetheseare spikesinsteadof
wells):
=
kA
e~iKak[A
[5.62]
cos(ka) B sin(fca)]
h

-^B.

SolvingEquation5.61for Asm(ka)yields

- - cos(ka)]B.

sin(jfco)

[5.63]

[eiKa

thisintoEquation5.62,and cancelling
kB,we find
Substituting

- cos(fca)][1-

[eiKa

<TiKacos(ka)]
+ e~ilCasin2(ka)=

\342\200\224-

frk

sin(\302\243\302\253),

to
which simplifies
mcx

+ sin(ka).
[5.64]
cos(Ka) cos(fca)
h2k
Thisisthe fundamentalresult,from which allelsefollows.Forthe Kronig-Penney
but it sharesthe
potential(seefootnote18),the formula is morecomplicated,
qualitativefeatureswe are aboutto explore.
the possiblevaluesof k, arid hencethe allowed
Equation5.64determines
To simplifythe notation,
let
energies.
\342\200\224

z = ka,

'-=\342\200\224

arid

ft

YYMXQ

[5.65]

/r

\342\200\224~\342\200\224,

so the rightsideof Equation5.64canbe written as

f{z)= co&(z)+

sinfz^

[5.66]
z
The constant
measureof the\"strength\"of the deltafunction.
/3 is a dimensionless
In Figure5.6I have plottedf(z), for the case$ = 10.The importantthingto
noticeis that f(z) strays outsidethe range
+1),and in suchregionsthere is
no hopeof solvingEquation5.64,since\\cos(Ka)\\,of course,cannotbe greater
than 1. Thesegapsrepresent
forbiddenenergies;they are separated
by bands
of allowedenergies.Within a givenband,virtually any energy is allowed,since
to Equation5.56Ka ~ litn/Nt where N is a hugenumber^ and n can
according
be any integer.You might imaginedrawing N horizontal
lineson Figure5.6,at
valuesof cps(2nn/N)rangingfrom +1 (n 0) down to (n N/2),and back
thispointthe BlochfactorelKarecycles,so no
almostto +1 (n = N
0\342\200\224^-.

(\342\200\2241,

\342\200\224

\342\200\224

\342\200\224

1)\342\200\224at

\342\200\2241

228

Chapter5 IdenticalParticles

\342\226\240\\

n
U

-1

1i

2tt

3tt

4tt

FIGURE5.6: Graph of f (z) (Equation


5.66)for /? = 10,showing allowedbands
(shaded)
by forbidden
separated
gaps(where\\f(z)\\ > 1).

Ei
band

\342\226\240

gap
band

\342\226\240

\342\226\240gap

band

FIGURE5.7: The allowed energiesfor a


bands.
potentialform essentiallycontinuous

periodic

of eachof
n. The intersection
solutionsare generatedby further increasing
theselineswith f(z) yieldsan allowedenergy.Evidently thereare N statesin each
we canregardthem as fonninga
band,so closelyspacedthat for mostpurposes
new

continuum(Figure5.7).
Sofar, we'veonly put oneelectronin our potential.
In practicethere will be
of
Nq of them, where q is againthe number of \"free\"electrons
peratom.Because
the Pauliexclusion
can occupya givenspatialstate,
only two electrons
principle,
so if q = 1,they will half fill the first band,if q = 2 they will completelyfill the
first band,if q = 3 they half fill the second
the groundstate.
band,and so
the band structure may
and with morerealisticpotentials,
(In three dimensions,
on\342\200\224in

Section5.3:Solids 229
be morecomplicated,
but the existence
of allowedbands,separated
by forbidden
gaps,persists\342\200\224band structureis the signatureof a periodicpotential.)
Now, if a band is entirely filled,it takesa relatively largeenergy to excite
an electron,
sinceit has to jump acrossthe forbiddenzone.Suchmaterialswill
be electrical
On the otherhand, if a band is only partly filled,it takes
insulators.
and suchmaterials
are typically
very littleenergy to excitean electron,
If you dopean insulator
with a few atomsof largeror smallerq, this puts
some\"extra\"electronsinto the next higherband,or createssomeholesin the
previouslyfilledone,allowingin eithercasefor weak electriccurrentsto flow;
In the free electron
suchmaterialsare calledsemiconductors.
modelall solids
shouldbe excellentconductors,
sincethere are no largegaps in the spectrumof
allowedenergies.
It takesthe band theory to accountfor the extraordinaryrange
in nature.
of electrical
conductivities
exhibited
by the solids
conductors.

Problem5.18
(a)

UsingEquations5.59and 5.63,show that the wave functionfor a particlein


the periodic
deltafunctionpotential
can be written in the form
tA(x) =

(b)

C[sin(fa)+ e~iKa sink(a x)], (0 < x < a).

the normalization
constantC.)
(Don'tbotherto determine
There is an exception:
At the top of a band,where z is an integer
multiple
=
of n (Figure5.6),(a) yields\\//(x) 0. Find the correctwave function for
this case.Notewhat happensto yj/ at eachdeltafunction.

Problem5.19Find the energy at the bottomof the first allowedband,for the


casefi = 10,correctto three significantdigits.For the sakeof argument, assume
a/a = 1 eV.
* *Problem5.20Suppose
we usedeltafunctionwells,instead
ofspikes(i.e.,switchthe
the analogto Figure5.6.
signof a in Equation5.57).
Analyzethis case,constructing
Thisrequiresno new calculation,
for the positiveenergy solutions
(exceptthat ft is
usefi = 1.5forthe graph),but you do needto work outthe negative
now negative;
and z =
for E < 0).How many states
(letk =
energy solutions
are there in the first allowedband?
\342\200\224

y/\342\200\2242mE/h

\342\200\224tea,

Problem5.21Show that mostof the energiesdeterminedby Equation5.64are


What are the exceptional
cases?Hint:Try it for N = I, 2,3,
doublydegenerate.
to seehow it goes.What are the possiblevaluesof cos(Ka)in eachcase?

4,...,

230

Particles
Chapter5 Identical

5.4 QUANTUMSTATISTICAL
MECHANICS
At

absolutezero,a physicalsystemoccupiesits lowestallowedenergy

As we turn up the temperature,


randomthermal activity will beginto populate
the excited
If we have a largenumber
states,and this raisesthe followingquestion:
N of particles,
in thermal equilibrium
at temperature T, what is the probability
that

configuration.

particle,selectedat random,would be foundto have the specificenergy,


in question
has nothingto do with quantum
Note that the \"probability\"
thesamequestionarisesin classicalstatistical
mechanics.
The
reasonwe must be contentwith a probabilistic
answer is that we are typically
dealingwith enormousnumbers of particles,and we couldnot possiblyexpect
to keeptrack of eachoneseparately,
whether or not the underlying mechanics
is
deterministic.
The fundamentalassumptionof statistical
mechanicsis that in thermal
equilibriumevery distinctstatewith the sametotalenergy,E, is equally
Random thermal motions
constantlyshiftenergy from oneparticleto another,
and from oneform (rotational,
kinetic,vibrational,etc.)to another,but (absent
external influences)
the totalis fixed by conservation
of energy.The assumption
redistribution
of
(and it's a deepone,worth thinking about)is that this continual
energy doesnot favor any particularstate.The temperature,T, is simplya
of the totalenergy of a system in thermal equilibrium.
The only new twist
hasto do with how we countthe distinctstates
introducedby quantum mechanics
(it'sactually easierthan in the classical
theory, becausethe statesare generally
discrete),and this dependscriticallyon whether the particlesinvolvedare
The arguments are relatively
bosons,or identicalfermions.
distinguishable,identical
straightforward, but the arithmetic
getspretty dense,so I'm goingto beginwith
an absurdly simpleexample,
so you'llhave a clearsenseof what is at issuewhen
we cometo the generalcase.
a

\302\243/?

indeterminacy\342\200\224exactly

probable.

measure

5.4.1An Example
particles(allof massm) in the oneSupposewe have just three noninteracting
dimensional
infinite squarewell (Section
2.2).The totalenergy is
E = EA + EB + EC =

2/-2

^-^
2ma1

(n2A

+ n\\ + n\\)
c

[5.67]

Now suppose,
for
(seeEquation2.27),where n&, ns, and nc are positiveintegers.
which is to say,
the sakeof argument, that E = 363(7T2h2/2ma2),

=363.
n2A+n2B+n2c

[5.68]

of three positiveintegers,the sum


There are, as it happens,13 combinations
of whosesquaresis 363:All three couldbe 11,two couldbe 13 and one 5

Section5.4:Quantum Statistical
Mechanics 231

onecouldbe 19and two 1 (again,three


(which occursin three permutations),
or onecouldbe 17,one 7, and one 5 (sixpermutations).
Thus
permutations),
(/7,4,ns, nc) is oneof the following:

(11,11,11).
(13,5,13),(5,13,13).
(13.13,5).
(1,1.
I), (19,1.
19),(1.19.
1).
(5,7,17),
(5,17,7).
(17,7,5).
(7,5.17),
(7,17.5).
(17,5,7),
a distinct
If the particles
are distinguishable,
eachof theserepresents
quantum
of statistical
mechanics
state,and the fundamentalassumption
says that in thermal
in knowing which
equilibrium20
they are all equallylikely.But I'm not interested
i
s
in each
state,only the totalnumberof particles
particle in which (one-particle)
of all
occupationnumber, for the state\\//n. The collection
numbers for a given 3-particle
statewe will callthe configuration.
If all
in
three are \\//\\ \\, the configuration
is
state\342\200\224the

N\342\200\236,

occupation

0....).

(0.0,0,0.0,0,0.0.0,0,3,0,0,0.0,0,0.
(i.e.,

N\\\\

configuration

is

= 3, all otherszero).If two are in

and

\\j/\\3

oneis in ^5, the

0....),

(0,0,0,0.1.0,0,0.0,0,0.0.2,0.0.0.
(i.e.,N5 = 1, N\\3 = 2, all otherszero).If two

[5.69]

are in

\\J/\\

and oneis in

[5.70]
\\j/\\g,

the

is
configuration

0....),

0,0,0,0.0,0,0,0.0,0. 1,
(2,0,0,0,0,0,0.0.

[5.71]

(i.e., = 2, N\\9 = 1,allotherszero).And if there is oneparticlein ^5,onein


N\\

\\J/j,

and onein

\\J/\\j,

is
the configuration

0,...).

(0.0.0,0.1,0.1.0,0,0,0,0.0.0,0,0.1.0,

[5.72]

(i.e.,N5 = N-j = N\\j = 1,allotherszero.)Of these,the lastis the mostprobable

becauseit can beachievedin sixdifferent ways, whereas the middle


configuration,
two

occurthree ways, and the first


-l)Howthe particlesmaintain

only

one.

really don*t interact at all. is a problem


up (beingcareful not
of energy is caused
to add or remove any energy).In real life, of course,the continual redistribution
between
the
Jet there
interactions
so
if
don't
of
divine
intervention
particles,
you
approve
preciselyby
be extremely weak interactions\342\200\224sufficient
to thermalize the system (at least, over long time periods),
stales and the allowed energiesappreciably.
but loo small to alter the stationary

I'drather

not worry

about\342\200\224maybe

thermal equilibrium, if they

God reachesin periodically and stirs things

232

Chapter5 IdenticalParticles
if we selectoneof thesethree particles
Returning now to my original
question,
at random,what is the probability
of gettinga specific(allowed)energy
the
The only way you can getE\\ isif it'sin the third configuration
(Equation5.71);
chancesof the system beingin that configuration
are 3 in 13,and in that
configuration
the probabilityof gettingE\\ is 2/3, so Pi = (3/13)x (2/3) = 2/13.
2 (Equation5.70)\342\200\224chances 3 in
You couldget E$ eitherfrom configuration
13\342\200\224with probability
4 (Equation5.72)\342\200\224chances 6
1/3,or from configuration
=
in 13\342\200\224with probability1/3,so P$
(3/13)x (1/3)+ (6/13)x (1/3)= 3/13.
You can only get E-j from configuration
4: Pi = (6/13)x (1/3)= 2/13.
comesonly from the first configuration
E\\\\
(Equation5.69)\342\200\224chances 1 in
=
13\342\200\224with probability
1:Pn (1/13).
Similarly,P13= (3/13)x (2/3)= 2/13,
Pn = (6/13)x (1/3)= 2/13,and P,9 = (3/13)x (1/3)= 1/13.As a check,
(P\342\200\236)

\302\243\342\200\236?

Likewise,

notethat

12

= 1.
+ Pl7 + Pl9
P|+P5
* + P7 + Pll+Pn
n
l =
13 13 13+ 13 13+ 13 13
1

\342\200\224(-

\342\200\224H

1\342\200\224

\342\200\224h\342\200\224

If in fact they are identical


That'swhen the particlesare distinguishable.
the antisymmetrizationrequirement
fermions,
(leavingasidespin,forsimplicity\342\200\224or
the first three
assuming
they are allin the samespinstate,if you prefer)excludes
worsestill,three\342\200\224particles to the same
(which assign
configurations
(seeProblem5.22(a)).
state),and there isjustonestatein the fourth configuration
For identicalfermions,
then, P5 = P-j = Pn = 1/3 (and again the sum of the
is 1).On the otherhand,if they are identicalbosonsthe symmetrizaprobabilities
tionrequirement
allowsfor onestatein eachconfiguration
(seeProblem5.22(b)),
so Pi = (1/4)x (2/3) = 1/6, P5 = (1/4)x (1/3)+ (1/4)x (1/3) = 1/6,
P7 = (1/4)x (1/3)= 1/12,Pn = (1/4)x (1)= 1/4,Pl3= (1/4)x (2/3)= 1/6,
Pn = (1/4)x (1/3)= 1/12,and Pl9 = (1/4)x (1/3)= 1/12.As always, the
sum is 1.
The purposeof thisexamplewas to show you how the countingof states
In onerespectit was actually more
dependson the nature of the particles.
than the realistic
in which N is a huge number.For as N grows,
situation,
the mostprobableconfiguration
(in thisexample,
N$ = N-j = Nn = 1,for the case
of distinguishable
becomes
particles)
ovenvhelminglymorelikelythan its
we can afford to ignorethe othersaltogether:21
sothat, for statistical
purposes,
The distribution
at equilibrium,
is simply their
of individualparticleenergies,
in the mostprobable
distribution
(If this were true for N =
configuration.
wouldconclude
that P$ = Pi = Pn = 1/3for the case
obviously,it is
of distinguishable
I'll return to thispointin Section5.4.3,but first we
particles.)
needto generalize
the countingprocedure
itself.
two\342\200\224or,

complicated

competitors,

3\342\200\224which,

not\342\200\224we

-'Thisis an astonishing and counterintuitive fact about the statistics of large numbers. For a good
discussionseeRalph Baicrlein,Thermal Physics.CambridgeU.P.(1999).
Section2.1.

Section5.4:Quantum Statistical
Mechanics

233

*Problem5.22
(a)

Constructthe completely
for
antisymmetric wave function^/{xa-xb,xc)

(b)

Constructthe completely
for three
symmetric wave function^{xa-xb^xq)
if
all
three
are
in
if
state\\}/\\\\, (ii) two are in state
identicalbosons,(i)
in
if
and oneis state1/^9,and (iii) oneis in the state1^5,onein the statefa,

three identical
onein the statefa, onein the state1^7,and onein
fermions,
the state\\j/\\-j.

\\}/\\

and onein the state1/^7.

*Problem5.23Supposeyou had three (noninteracting)


in thermal
particles,
in a one-dimensional
harmonicoscillatorpotential,with a total energy
equilibrium,
E = (9/2)hco.
(a) If they are distinguishable
particles(but allwith the samemass),what are
the possible
and how many distinct
(threeconfigurations,
occupation-number
particle)statesare there for eachone?What is the mostprobable
If you pickeda particleat randomand measured
itsenergy,what values
might you get,and what is the probabilityof eachone?What is the most
configuration?

probableenergy?
fermions(ignoringspin,as we did in
(b) Do the samefor the caseof identical
(c)

Section5.4.1).
bosons(ignoringspin).
Do the samefor the caseof identical

5.4.2TheGeneralCase
an arbitrary potential,
forwhich the one-particle
are E\\, E2,
Now consider
energies
d\\, di,
(i.e.,thereare distinctone-particle
\302\2433...., with degeneracies
stateswith energy
Supposewe put N particles(allwith the samemass)into
we are interested
in the configuration
thispotential;
for which
(N\\.N2,
there are N\\ particleswith energy E\\, N2 particleswith energy Ej, and so on.
Question:How many different ways can this be achieved(or, moreprecisely,
to thisparticularconfiguration)?
The answer,
how many distinctstatescorrespond
identical
Q(N\\, Afa. Afy.
dependson whether the particlesare distinguishable,
or identical
fermions,
bosons,sowe'lltreat the three casesseparately.22
How many ways are there to
First,assumethe particlesare distinguishable.
the N\\ to be placedin the first \"bin\"?
select(from the N availablecandidates)

dj,....

d\342\200\236

E\342\200\236).

N^....),

\342\200\242

\342\200\242.),

presentation here follows closely that of Amnon Yariv,


Applications of Quantum Mechanics.Wiley. New York (1982).
\342\200\224The

An

Introduction to Theory and

234

Chapter5 IdenticalParticles

chooseN\\,\"

'W
Answer: the binomialcoefficient,

/N\\
,AV

AH

N\\\\(N

[5.73]

Ni)\\

Forthere are N ways to pickthe first particle,leaving (N

soon:

N(N

- -2)...(N
-N{+
\\)(N

\\)

\342\200\224

1)for the second,and

AH

(N-Ni)l

of the N\\ particles,


However,thiscountsseparatelythe N\\! differentpermutations
whereas we don'tcarewhether number 37 was pickedon the first draw, or on
the 29thdraw; so we divideby N\\\\, confirming
Equation5.73.Now, how many
be arranged within the first bin?Well, there
different ways can thoseN\\ particles
are d[ statesin the bin,soeachparticlehas d\\ choices;
evidently there are (d\\)N]
in all.Thus the number of ways to put N\\ particles,
selectedfrom a
possibilities
of A^, intoa bin containing
totalpopulation
d[ distinctoptions,is
N\\d?1

Nil(N -N\\)\\
The samegoesfor bin 2, of course,exceptthat there are now only (N

\342\200\224

N\\)

leftto work with:


particles

N-.

(N-N{)ldp
N2\\(N

N\\

-N2)\\

and soon.It followsthat

Q(N{.N2.N3

,...)
N{\\(N
N\\

(N-Ni)ld* (N--NX--N2Yd^
N2\\(N --N{ -N2YN3\\(N -Ni -N2-N3Y

N\\Y

,N-i
d, 'a,
2 -d-,
3

\342\226\240

oo

,N%

,N\\
l

\342\226\240

\342\200\224

NilNY.N^l

=N

,N\342\200\236

[5.74]

iTT\342\200\224\342\200\242

//=1

in Section
5.4.1
(You should
pauseright nowand checkthisresult,forthe example

\342\200\224

seeProblem5.24.)
The problemis a lot easierfor identical
Becausethey are
fermions.
are in which
it doesn'tmatter which particles
antisymindistinguishable,
metrizationrequirementmeansthat there is just one N-particlestatein which a
statesare occupied.
Moreover,only oneparticlecan
specificset of one-particle
occupyany given state.There are
states\342\200\224the

Section5.4:Quantum Statistical
Mechanics
ways

to choosethe

N\342\200\236

235

statesin the nth bin,23so


occupied

,,

CO

0(^^^.-)=11^1^,.

[5.75]

in Section
5.4.1\342\200\224see
Problem5.24.)
(Checkit for the example
The calculation
is hardestfor the caseof identicalbosons.Again, the symmetrizationrequirementmeansthat there is just one N-particlestatein which a
statesare occupied,
but thistime there is no restriction
specificsetof one-particle
on the number of particlesthat can sharethe sameone-particle
state.For the nth

How many different ways can we assignNn identical


bin,the questionbecomes:
particlesto different slots?There are many tricksto solvethis combinatorial
an especially
clevermethodisasfollows:Letdotsrepresent
and
problem;
particles
=
so that, for example,
crossesrepresent
if dn 5 and Nn 7,
partitions,
d\342\200\236

\342\200\224

\342\200\242

\342\200\242x*x***x*x

wouldindicate
that there are two particles
in the first state,onein the second,
three

third,onein the fourth, and nonein the fifth. Notethat there are Nn dots,
and
the dotsinto dn groups).
If the individualdots
1) crosses(partitioning
and crosseswere labeled,
there wouldbe (Nn +
1)!different ways to arrange
the dotsare allequivalent\342\200\224permuting them
them.But forourpurposes
ways)
doesnotchangethe state.Likewise,the crossesare all equivalent\342\200\224permuting them
in the

\342\200\224

(d\342\200\236

\342\200\224

d\342\200\236

(N\342\200\236!

\342\200\224

((d\342\200\236

1)!ways) changesnothing.So there are in fact


(Nn + dn

(Nn+d\342\200\236-\\)l

distinctways of assigning
the
that
bin,and we conclude
\"
Q{NX.Afc,
1

N\342\200\236

particlesto the

d\342\200\236

\\\\

statesin the /7 th
one-particle

'11

tf,....)
' = TT {Nn+?\"~l)[

[5.77]

N\342\200\236\\(d\342\200\236-l)\\

\302\253=l

(Checkit for the Examplein Section5.4.1\342\200\224seeProblem5.24.)

*Problem5.24CheckEquations5.74,5.75,and 5.77,for the examplein


Section

5.4.1.

**Problem5.25ObtainEquation5.76by induction.
The combinatorial
questionis
this:How many different ways can you put N identical
ballsintod baskets(never
2;,This should be zero, of course,if
negative integer to be infinite.

N\342\200\236

>

d\342\200\236,

and

it

is, provided we considerthe factorial of a

236

Chapter5 IdenticalParticles
mindthe subscript
n for thisproblem).
You couldstickallN of them intothe third
basket,or all but onein the secondbasketand onein the fifth, or two in the first
and three in the third and all the restin the seventh,etc.Work it out explicitlyfor
the casesN = I, N =2, N = 3, and N = 4; by that stageyou shouldbe ableto
deducethe generalformula.

5.4.3TheMostProbableConfiguration
In thermal equilibrium,
every statewith a given totalenergy E and a given particle
number N is equally likely.So the mostprobableconfiguration
(N\\, N2, N3,...)
is the onethat can be achievedin the largestnumber of different
is that
for which Q(N\\,N2, N3,...)
is a maximum, subjectto
particularconfiguration
ways\342\200\224it

the constraints

00
\302\243>,,

= \",

[5.78]

[5.79]

\302\273=1

and

00
\302\243.

\302\243>\342\200\236\302\243\342\200\236

11=1

The problemof maximizing a functionF(xi.X2,

of severalvariables,
x$,...)
=

= 0, /2(^1,X2, X3,...) 0, etc.,is


mostconveniently
handledby the methodof Lagrangemultipliers.24
We introduce

f\\ {x\\ ,^2.^3


subjectto the constraints

the new function

G(.Y|..T2.A-3

= F + Xif\\ +X2f2+
A.i.A.2....)

[5.80]

and setall its derivatives


equalto zero:

dG =

0;

dG =

0.

[5.81]

dx\342\200\236

In our caseit's a littleeasierto work with the logarithmof Q, insteadof


turns the productsinto sums.Sincethe logarithmis a monotonic
Q
functionof its argument, the maxima of Q and ln(<2)occurat the samepoint.So
itself\342\200\224this

we let

00

G = \\n(Q)+a

\"-\302\243w\302\273

00

+ P E-YjNnEn

Mathematical Methodsin
24See.for example,Mary Boas.

New York

(1983),
Chapter 4.Section9.

[5.82]

n=\\

\302\273=1

the

2nd ed..
PhysicalSciences,
Wiley.

Mechanics
Section5.4:Quantum Statistical

237

where or and ft are the Lagrangemultipliers.


Settingthe derivativeswith respect
to a. and ft equalto zeromerely reproduces
the constraints
(Equations5.78and
5.79);it remains,then,to setthe derivative with respectto Nn equalto zero.
are distinguishable,
then Q is givenby Equation5.74,and we
If the particles
have

- MAT*!)]

oo

G = ln(AH) + J2

[N\302\253

lnW\342\200\236)

[5.83]

oo

+ ot

+P

*-\302\243>\342\200\236

E-J^N\342\200\236E\342\200\236

n=l
n=i
numbers (Nl})are large,we caninvokeStirling's
Assumingthe relevant occupation

-z

approximation:25

ln(z!)% zln(z)

for z

1,

\302\273

[5.84]

to write
oo

lnW ~
G^Y,
=I
W\302\253

N\302\273

ln^\302\273>

+ N\" ~

aN\302\273

pe\302\273n\302\273i

+ ln(A^!)+aA^+
It followsthat

dG =

[5.85]

^\302\243.

[5.86]

\\n(d\342\200\236)-MN\342\200\236)-a-PE\342\200\236.

we conclude
that the mostprobable
Settingthisequalto zero,and solvingfor
for distinguishable
are
numbers,
particles,
occupation
N,\342\200\236

= dl}e-(a+^E\"].

N\342\200\236

[5.87]

If the particlesare identical


fermions,then Q is given by Equation5.75,and
we have

- WW,!)-

CO

G = J2 0nM>0

\\n[(d\342\200\236

N\342\200\236)!]}

\302\253=i

00

+ a N-J^Nn + fi
H

=I

[5.88]

00
\302\243-\302\243>\342\200\236\302\243\342\200\236

H=l

approximation can be improved by including more terms in the Stirlingseries,but


suffice for our purposes.SeeGeorgeArfken and Hans-Jurgen Weber. Mathematical
Academic Press,Orlando (2000).Section10.3.
If the relevant occupation
MethodsforPhysicists,5th ed..
in Section
numbers are not
statisticalmechanics simply doesn'tapply.The whole
point is to deal with such enormous numbers that statistical inference is a reliable predictor.Of course,
there will always be one-particle statesof extremely high energy that are not populated at
fortunately.
Stirling'sapproximation holdsalso for z = 0.1 use the word \"relevant\" to excludeany stray statesright
at the margin, for which Nn is neither huge nor zero.
\"\342\200\242'Stirling's

the

first

two

will

large\342\200\224as

5.4.1\342\200\224then

all:

238

Particles
Chapter5 Identical

Thistime we must assumenot onlythat Nn is large,but alsothat dn


that Stirling's
approximation
appliesto bothterms.In that case

oo

\302\253

J2[\\n(dn!)
n=l

ln(JV\342\200\236)

N\342\200\236

- (d\342\200\236

N\342\200\236

dG =

mi

\\n(d\342\200\236

Mm26 so

N\342\200\236)

[5.89]
+ ocN+ 0E,

(d\342\200\236-N\342\200\236)-aN\342\200\236-/3E\342\200\236N\342\200\236

so

N\342\200\236)

;\302\247>

\\n(N\342\200\236)

Settingthisequalto zero,and solvingfor


fermions:
numbersfor identical

[5.90]

0E\342\200\236.

N\342\200\236)

we find the mostprobable


occupation

N\342\200\236,

N\342\200\236

- -a-

]n(d\342\200\236

[5.91]

d\342\200\236

\"

e(a+pE\342\200\236)

_j_

are identical
bosons,then Q is givenby Equation5.77,
Finally,if the particles

and we have

- 1)!]- ln(tfn!)-

oo

G=J2
n=i

M(N\342\200\236

d\342\200\236

*-!>.

+p

Nn

^>

[5.92]

e-^2n\342\200\236e\342\200\236

11=1

Assuming(asalways) that

- 1)!]}

oo

00

+a

\\n[(d\342\200\236

n=\\

I, and usingStirling's
approximation:

- 1)ln(M,+ -1)tl - - - +
+aN + /3E,
1)!]
oo

*Ym, +
N\342\200\236

so

dn

d\342\200\236

\\n[(d\342\200\236

aN\342\200\236

dG =
ln(M,+

(N\342\200\236

+d\342\200\236-\\)-

N\342\200\236

\\n(N\342\200\236)

[5.93]

PE\342\200\236N\342\200\236}

d\342\200\236

-1)-

\\n(N\342\200\236)

[5.94]

-a-0E\342\200\236.

9N\342\200\236

26In one dimension the energiesare nondegenerate (seeProblem 2.45),but in three dimensions
So
dn typically increases
rapidly with increasing n (for example,in the caseof hydrogen, dn
it is not unreasonable to assume that for most of the occupiedstates
On the other hand.
dn is certainly not much greater than Nn at absolutezero, where all states up to the Fermi level are
Hereagain we are rescuedby the fact that Stirling'sformula holdsalso for
filled, and hencedu =
=
0.
z
\342\200\224

d\342\200\236

N\342\200\236.

:\302\247>

1.

;r).

Mechanics
Section5.4:Quantum Statistical

239

Settingthisequalto zero,and solvingfor Nn, we find the mostprobableoccupation


bosons:
numbersfor identical
N\"

I5'95!

e^tlLy

with the approximation


(Forconsistency
already invokedin the caseof fermions,
we shouldreally dropthe 1 in the numerator, and I shalldo so from now on.)

Problem5.26Usethe methodof Lagrangemultipliers


to find the rectangleof
largestarea,with sidesparallelto the axes,that can be inscribedin the ellipse
(x/a)2+ (y/b)2= 1.What is that maximum area?
Problem5.27
(a)

Findthe percenterrorin Stirling's


for z = 10.
approximation

(b) What

is the smallestintegerz suchthat the errorislessthan 1%?

5.4.4PhysicalSignificance
of a andft
associated
The parametersa. and ft cameinto the story as Lagrangemultipliers,
with the total number of particles
and the totalenergy,respectively.
the occupation
numbers (Equations
5.87,
they are determined
by substituting

Mathematically,

5.91,and 5.95)backintothe constraints


(Equations5.78and 5.79).To carry out

the summation,
and their
however, we needto know the allowedenergies
in question.
As an example,
I'll work out the
(dn), for the potential
degeneracies
caseof an ideal
allwith the same
largenumber of noninteracting
particles,
infinitesquarewell.Thiswill motivate the physical
mass,in thethree dimensional
of a and ft.
interpretation
In Section
5.3.1we foundthe allowedenergies(Equation5.39):
(E\342\200\236),

gas\342\200\224a

Ek =

where
k

= nnx

r-

^-k2,
2m
7tnY

[5.96]

jtnz

before,we convertthe sum intoan integral,


variable,
treating k as a continuous
with onestate(or,for spins, 25+ 1 states)pervolumett3/V of &-space.
Taking

As

240

Particles
Chapter5 Identical
shellsin the first octant(seeFigure5.4),the
as our \"bins\"the spherical
(that is,the number of statesin the bin) is
\"degeneracy\"

= \\47tk2dk
=
=

, dk.
,

5.97]
J
In1
For distinguishable
particles(Equation5.87),the first constraint
(Equation5.78)
dk

8 (7t3/V)

\342\200\224Tr

becomes

N=

\342\200\224,e~a

27T2

Jo

e-^2kl/2mkl
dk = ye-a

\\

3/2

te&h1

so

e-\302\253M^\\\\
m
V

The secondconstraint
(Equation5.79)says

f00 _RMn
2m Jo
h2

2tt2
or,putting

in

[5.98]

\\

.. 20
3V

_\342\200\236(

\\3/2

Inph1

Equation5.98for e~a:
E=

3N

[5.99]

(If you includethe spinfactor,2s+ 1,in Equation5.97,it cancelsoutat thispoint,


soEquation5.99iscorrectfor allspins.)
Thisresult(Equation5.99)is reminiscent
of the classical
formula for the
average kineticenergy of an atom at temperature 7:27
E
3
= -kBT.
[5.100]
N
2
that ft isrelated
where ks is the Boltzmann
constant.
Thissuggests
to the
\342\200\224

temperature:

= T^fkBT

[5-101]

To provethat thisholdsin general,and not simplyfor distinguishable


particles
infinite squarewell,we would have to demonstrate
that
in the three-dimensional
in thermal equilibrium
with oneanotherhave the samevalue of
differentsubstances
in many books,28
it
but I shallnot reproduce
ft. The argument issketched
as the definitionof T.
will simplyadoptEquation5.101
here\342\200\224I

David Halliday. Robert Resnick.and Jearl Walker. Fundamentals of Physics.


-7See.for example.

5th

Section20-5.
ed..Wiley. New York (1997).

28See.
Yariv
for example.

(footnote 22).Section15.4.

Section5.4:Quantum Statistical
Mechanics

241

It is customary to replacea (which, as is clearfrom the specialcaseof


chemicalpotential,
Equation5.98,is a functionof T) by the so-called

fi(T)= -akBT,

[5.102]

and rewrite Equations5.87,5.91,and 5.95as formulasfor the mostprobable


numberofparticlesin a particular(one-particle)
statewith energy e (to go from
the number of particleswith a given energy to the number of particlesin a
particularstate with that energy,we simplydivideby the degeneracyof the

state):
MAXWELL-BOLTZMANN

e-(\342\202\254-H)/kBT

\302\253(0

1
\342\200\242

e(\342\202\254-H)/k/]T

_j_

_
e{e-H)/kBT

FERMI-DIRAC

[5.103]

BOSE-EINSTEIN
\\

The Maxwell-Boltzmann
distributionis the classical
result,for distinguishable
and the Bosethe Fermi-Dirac
distributionappliesto identical
particles;
fermions,
Einsteindistributionis for identicalbosons.
The Fermi-Dirac
distribution
has a particularly simplebehavioras T -> 0:

0, if 6 < (1(0),
oo, if e > fi(0).

Ae-H)/kBT

so

[5.104]

n(e)

statesare filled,up to an energy /i(0),and noneare occupied


forenergies
above
the
this(Figure5.8).Evidently the chemical
potentialat absolutezerois precisely

All

Fermi energy:
At(0)

= EF.

[5.105]

\"softens\"
the cutoff,as
As the temperaturerises,the Fermi-Dirac
distribution

Figure5.8.
Returning now to the specialcaseof an idealgas,for distinguishable
particles
we foundthat the totalenergy at temperature T is (Equation5.99)

indicated

by the roundedcurve in

E = -NkBT.
2

[5.106]

242

ChapterS IdenticalParticles
n(e)

EF= (i(0)

for T = 0 and for T somewhatabovezero.


distribution
FIGURE5.8: Fermi-Dirac
while (from Equation5.98)the chemical
is
potential

fx(T) = kBT

\\Vj

[5.107]

\\mkBT

formulasfor an idealgas of identical


1wouldliketo work out the corresponding
fermionsand bosons,usingEquations5.91and 5.95in placeof Equation5.87.The
first

constraint
(Equation5.78)becomes
N

k2

2^-Jo
0

e\\(h'ki/2m)-n\\lkBT+

dk.

[5.108]

and the secondconstraint


and minus for bosons),
(with the plussignfor fermions

(Equation5.79)reads

tr

r\302\260\302\260

In1 2m Jo

kA

+
e\\.(hlk-/2m)-n\\lkBT

dk.

[5.109]

The first of thesedetermines


fi(T),and the seconddetermines
E(T) (from the

the heat capacity:


C = dE/dT).Unfortunately,
these
latter we obtain,for instance,
and I shallleaveit
cannotbe evaluatedin terms of elementary functions,
integrals
for you to explorethe matter further (seeProblems
5.28and 5.29).

Problem5.28Evaluate the integrals(Equations5.108and 5.109)for the caseof


zero.Compareyour resultswith Equations5.43and
identical
fermionsat absolute
5.45.(Notethat for electronsthere is an extra factorof 2 in Equations5.108and
to accountfor the spindegeneracy.)
5.109,

Section5.4:Quantum Statistical
Mechanics

243

* * *Problem5.29
for bosonsthe chemical
potentialmust always be lessthan the
minimum allowedenergy.Hint:n{e)cannotbe negative.
for the idealbosegas,/i(T) < 0 for allT. Showthat in this
(b) In particular,
case(J.(T)monotonically
as T decreases,
N and V are
increases
assuming
heldconstant.
Hint:Study Equation5.108,
with the minus sign.
occurswhen (aswe lowerT) /i(T)hits
(c) A crisis(calledBosecondensation)
zero.Evaluate the integral,for /i = 0, and obtainthe formula for the critical
Belowthe criticaltemperature,the
temperature Tc at which thishappens.
crowdintothe groundstate,and the calculational
deviceof replacing
particles
the discretesum (Equation5.78)by a continuous
integral (Equation5.108)
losesitsvalidity.29
Hint:
(a) Show that

xs~l

<*>

where T

ex

dx = r(j)f(j),

[5.110]

is Euler'sgammafunctionand is the Riemannzetafunction.


\302\243

Lookup the appropriatenumerical values.


is
(d) Find the criticaltemperature for 4He.Its density,at this temperature,
value of the criticaltemperature
0.15gm/cm3.Comment:The experimental
in 4Heis2.17K. The remarkable
of 4Hein the neighborhood
of
properties
in the reference
citedin footnote29.
Tc are discussed

5.4.5TheBlackbodySpectrum
Photons(quanta of the electromagnetic
bosonswith spin1,but
field)are identical
and henceintrinsically
becausethey are massiessparticles,
they are very special,
relativistic.
We can include
them here,if you are preparedto acceptfourassertions
that do not belongto nonrelativistic
quantum mechanics:

1.The energy of a photonis relatedto its frequency by the Planckformula,


E = hv = lico.

2. The wave number k is relatedto the frequency by k = 2n/X w/c, where


c is the speedof light.
3. Only two spinstatesoccur(the quantum number m can be +1 or but
not 0).
\342\200\224

\342\200\2241,

SeeF. Mandl.StatisticalPhysics.Wiley.

11.5.

Section
London (1971).

244

Particles
ChapterS Identical

4. The number of photonsis not a conserved


quantity; when the temperature
rises,the number of photons(perunit volume)increases.

In view of item 4, the first constraint


(Equation5.78)doesnot apply.We
can take accountof thisby simplysettinga -> 0, in Equation5.82and
that follows.Thus the most probableoccupation
number, for photons,is
(Equation5.95):
Nw
.
j
l[5.111]
ehto/ki;T_ 1

everything

=\342\200\224\342\200\224L

Forfreephotonsin a boxof volumeV, dk is given by Equation5.97,30


multiplied
of
i
n
of
k
2
for
and
terms
co
instead
(item 2):
by
spin(item 3), expressed
d^

= V- ,a>2 dco.

[5.112]

where
So the energy density,N^hco/V,in the frequency range dco,is p(co)dco,

Pico)=

^3

(eha>/kBT

[5.113]

l)'

Thisis Planck'sfamousformula for the blackbodyspectrum,givingthe energy


fieldin equilibrium
at
perunit volume,perunit frequency,for an electromagnetic
in Figure5.9.
temperature T. It is plotted,for three different temperatures,
Problem5.30
(a)

the energy densityin the wavelengthrange


UseEquation5.113
to determine
=
elk.Hint:Set p(co)dco p(X) d\\, and solvefor p(X).

(b)

Derivethe Wien displacement


law for the wavelength at which the blackbodyenergy densityis a maximum:

2.90xlO\"3mK
Vu =
j.

rcilill
[5.114]

\342\200\242

Hint:You'llneedto solvethe transcendental


equation(5 x) = 5e~x,
or a computer;
answer accurate
to three
get the numerical
usinga calculator
\342\200\224

significantdigits.

wc have no business using this formula, which camefrom the (nonrclativistic)


Schrodingerequation: fortunately, the degeneracyis exactly the same for the relativistic case.See
Problem 5.36.
-,0In

truth,

245

Further Problems
forChapter5

1.8
1.6
1.4
77

1.2

X
P3

e 1.0

in

o 0.8
Q.

0.6
0.4
0.2
0

6
Hz]
Frequency[1014
4

5.113.

FIGURE5.9: Planck'sformulafor the blackbody


spectrum,
Equation

formulaforthe totalenergy density


Problem5.31Derivethe Stefan-Boltzmann
in blackbody
radiation:
n
- = \\15/rV/
V

T4 =

(7.57x 10-16Jm_3K-4)
/ T4.
V

Hint:UseEquation5.110
to evaluate the integral.Notethat

\302\243(4)

[5.115]

= tt4/90.

FURTHERPROBLEMSFORCHAPTER5
eachof massm, in the oneProblem5.32Imaginetwo noninteracting
particles,
dimensional
harmonicoscillator
potential(Equation2.43).If oneis in the ground
state,and the otheris in the first excitedstate,calculate((.V| xi)1),assuming
bosons,and (c)they are
(a) they are distinguishable
(b) they are identical
particles,
\342\200\224

246

Particles
Chapter5 Identical
identicalfermions.
Ignorespin(if thisbothersyou, just assumethey are both in
the samespinstate).
Problem5.33Supposeyou have three particles,and three distinctone-particle
How many different three-particle
states(^/(,(x), (.v), and \\f/c(x))are available.
statescan be constructed,
(a) if they are distinguishable
particles,(b) if they are
identicalbosons,(c) if they are identicalfermions?
(The particlesneednotbe in
are
wouldbe onepossibility,
if the particles
different states\342\200\224^(^1)^0(^2)^(^3)
distinguishable.)
1/\302\276

Problem5.34Calculate
the Fermi energy for noninteracting
electronsin a twodimensional
infinite squarewell.Let a be the number of free electrons
per unit
area.
* * *Problem5.35Certaincoldstars(calledwhite dwarfs)are stabilized
against
o
f
their
electrons
gravitational
the
degeneracypressure
collapseby
(Equation5.46).
as
Assuming constant
density,the radiusR of suchan objectcan be calculated

follows:

total electronenergy (Equation5.45)in terms of the radius,the


number of nucleons
per
(protonsand neutrons)N, the number of electrons
nucleonq, and the massof the electronm.
the gravitationalenergy of a uniformly densesphere.
(b) Lookup, or calculate,
Expressyour answer in terms of G (the constantof universal gravitation),
Notethat the gravitationalenergy is
R, N, and M (the massof a nucleon).
(a) Write the

negative.
(c) Findthe radiusforwhichthe totalenergy,(a) plus(b),isa minimum.Answer:
GmM2N1'3

as the totalmassincreases!)
Put in the actual
(Notethat the radiusdecreases
=
a bit
numbers,foreverything exceptN, usingq 1/2(actually,q decreases
as the atomicnumber increases,
but thisis closeenoughforour purposes).

= 7.6x 1025AT1'3
m.
of a white dwarf with the massof the
the radius,in kilometers,
(d) Determine
sun.
the Fermi energy,in electronvolts,for the white dwarf in (d),
(e) Determine
and compare
it with the restenergy of an electron.
Note that thissystem is
relativistic
(seeProblem5.36).
gettingdangerously
Answer: R

Further Problems
forChapter5

247

* * *Problem5.36We can extendthe theory of a free electrongas (Section


to
5.3.1)
the relativistic
domainby replacing
the classical
kineticenergy, E p2/2m,with
the relativistic
formula,E = >Jp2c2+m2c4 mc1.Momentum is relatedto the
wave vectorin the usual way: p = ftk. In particular,
in the extreme relativistic
limit,E pc = hck.
\342\200\224

\342\200\224

=\302\276

(a)

hck,
Replaceh k-/2min Equation5.44by the ultra-relativistic
expression,
and calculate

\302\243tot

(b)

in

thisregime.

electron
gas.
Repeatparts(a) and (b) ofProblem5.35forthe ultra-relativistic
Noticethat in thiscasethere is no stableminimum, regardless
of R; if the
totalenergy ispositive,
forcesexceedgravitational
forces,and the
degeneracy
star will expand,whereas if the totalis negative,gravitationalforceswin out,
and the star will collapse.
Findthe criticalnumber of nucleons,
Nc, suchthat

occursfor N > Nc. Thisiscalledthe Chandrasekhar


gravitationalcollapse
limit.Answer: 2.04x 1057.What is the corresponding
stellarmass(give
of the sun'smass).Starsheavier than thiswill not
your answer as a multiple
are right)
form white dwarfs, but collapsefurther, becoming
(if conditions

neutronstars.
(c)

n + v, converts
extremely high density,inversebetadecay,e~ + p+
of
all
the
a
nd
electrons
intoneutrons
neutrinos,
virtually
protons
(liberating
which carry off energy, in the process).
Eventually neutron degeneracy
the
as
stabilizes collapse,
just electrondegeneracydoesfor the white
dwarf (seeProblem5.35).
Calculatethe radiusof a neutron star with the
massof the sun.Alsocalculatethe (neutron)Fermi energy, and compare
it to the rest energy of a neutron.
to treat a neutron star
Is it reasonable
At

\342\200\224\302\273

pressure

nonrelativistically?
* * *Problem5.37
(a)

Findthe chemical
and the totalenergy for distinguishable
in
potential
particles
the three dimensional
harmonicoscillator
(Problem4.38).Hint:The
potential
sumsin Equations5.78and 5.79can be evaluatedexactly,in this
needto usean integralapproximation,
as we didfor the infinite squarewell.
the geometric
Notethat by differentiating
series,
case\342\200\224no

1 =

\342\200\224

\302\243>\".

\342\226\240

\342\200\236=G

you can get

J:
d_

H=l

[5-116]

248

Particles
Chapter5 Identical
and similarresultsfor higherderivatives.
Answer:

3
+
E = -Nfico(\\ e-hulkBT\\.

(b)
(c)

\\i-e-hw/kBTJ
\342\200\224-\342\200\224j\342\200\224j-^r

[5.117]
J

Discussthe limitingcaseksT <& fico.


Discussthe classical
in the light of the equipartition
limit,ksT
How many degreesof freedomdoesa particlein the three
theorem.31
dimensional
harmonicoscillator
possess?
\302\273

/ia\302\273,

See.l'or example,Halliday and Resnick(footnote 27).Section20-9.

PART II APPLICATIONS
CHAPTER6

TIME-INDEPENDENT
PERTURBATIONTHEORY

6.1NONDEGENERATEPERTURBATIONTHEORY
6.1.1
GeneralFormulation
Schrodinger
equationfor some
Supposewe have solvedthe (time-independent)
infinite squarewell):
potential(say, the one-dimensional
H\302\260*!

= E,W

[6-1]

setof orthonormal
obtaininga complete
eigenfunctions,
i/r^,

{fnWl)=^,n-

[6.2]

and the corresponding


eigenvalues Now we perturb the potential
slightly(say,
We'dlike to find
by putting a littlebump in the bottomof the well\342\200\224Figure 6.1).
and eigenvalues:
the new eigenfunctions
E\302\256.

H-ilrn

E\342\200\236yjr\342\200\236,

[6.3]

unlesswe are very lucky, we'renot goingto be ableto solvethe Schrodinger


potential.Perturbationtheory is a
equationexactly,for this morecomplicated
forobtainingapproximate
solutions
to the perturbedproblem,
systematic
procedure
to the unperturbedcase.
by buildingon the known exactsolutions
but

249

250

Perturbation
Chapter6 Time-Independent
Theory
V(x)k

^\\

FIGURE6.1:Infinite squarewellwith smallperturbation.

To beginwith we write the new Hamiltonian


as the sum of two terms:

H=

H\302\260

+ XH',

[6.4]

where H' is the perturbation


0 always identifies
the unperturbed
(the superscript
quantity). For the moment we'lltake X to be a smallnumber; laterwe'llcrank it
as power
Next we write i/o, and
up to 1,and H will be the true Hamiltonian.
\302\243\342\200\236

seriesin X:

En

= En + XEn + X~E~ +

[6.5]
[6.6]

\342\200\242 \342\200\242 \342\226\240

HereEj, isthe first-ordercorrectionto the nth eigenvalue,


and i/r,J is the first-order
correction
to the ;?th eigenfunction;
E2 and ^/2 are the second-order
corrections,
and soon.PluggingEquations6.5and 6.6intoEquation6.3,we have:

+ XH')[f*+ Xfl + X2tf + ]


=
+ XEJ}+X2E2
+ owrJ+A^+AV?+
\342\200\242 \342\200\242 \342\200\242

(H\302\260

(E\302\260

\342\226\240\342\226\240\342\226\240].

or (collecting
likepowersof X):

hV,?+ m#V,!+ #>,?)+ *2(#V,?+ #>,!)+


=
+ M\302\243M +
+
+ EM +
\342\200\242 \342\200\242 \342\200\242

\302\243,\302\2760

\302\243>,?)

*2(\302\243,fy,7

\302\243^\302\260)

Section6.1:Nondegenerate
Perturbation
Theory

To lowestorder1
thisyields
6.1).To first order(X1),
(X\302\260)

H\302\256iJ/\302\256

251

which is nothingnew

Efy\302\256,

(Equation

HV,!+ //>,?=

\302\243>,!

+ EM.

[6.7]

To secondorder(X2),

J/V,?+ H'ti = EM + EM + Elfl


was just a
and so on. (I'm donewith X,
different orders\342\200\224so crank it up to 1.)
now\342\200\224it

[6.8]

deviceto keep track of the

6.1.2First-OrderTheory
Takingthe inner productof Equation6.7with

\\J/\302\256

(that

is, multiplying by

(if/\302\256)*

and integrating),

= eMwI)+ ejmM)+ <vo?itf>,?>


<v,?i#V,!>
But

//\302\260

is hermitian,
so

(^1^)= 1,so2

and thiscancelsthe first term on the right.Moreover,

\302\243i

(^|HU\302\260).

[6.9]

Thisis the fundamental resultof first-orderperturbationtheory;as a practical


It
matter, it may well be the most important equationin quantum mechanics.
to the energy is the expectation
value of the
says that the first-ordercorrection
in the unperturbedstate.
perturbation,
Example6.1 The unperturbedwave functionsfor the infinite squarewell are
(Equation2.28)

*!m= JIHtx)2.

As always (Chapter footnote 25) the


the coefficientsof like powersare equal.
1

uniquenessof power seriesexpansionsguarantees that

2In this context it doesn'tmatter whether we write (^\\H'ir^) or (if^\\H'\\-i//jj)


(with the extra
vertical bar), becausewe are using the wave function itself to \"label\" the stale.But the latter notation
is preferable, becauseit frees us from this specificconvention.

252

Perturbation
Theory
Chapter6 Time-Independent
V{x),
k

Vo

FIGURE6.2: Constantperturbation
overthe wholewell.
we perturb the systemby simplyraisingthe \"floor\"of the well a constant
Suppose
correction
to the energies.
amount (Figure6.2).Findthe first-order
Solution:In thiscaseH' = Vq, and the first-ordercorrection
to the energy of the
/?th stateis
= <V0? W,?>= VoWflV\302\260> = V0.
E\\
Vfo

= + Vfo they are simplyliftedby the


The corrected
energy levels,then, are
amount Vq. Of courselThe only surprising
thingis that in this casethe first-order
E\302\256

\302\243\342\200\236

allthe higher
theory yieldsthe exactanswer.Evidently for a constantperturbation
corrections
extendsonly half-way
vanish.3On the otherhand,if the perturbation
acrossthe well (Figure6.3),then

rl = 2V0 If/2 sin2/\"* I ax


, =
\\

\342\200\242

\"

a Jo

E\342\200\236

\342\200\224x

^0

\342\200\224.

In thiscaseevery energy level is lifted by Vq/2.That'snot the exactresult,


but it doesseemreasonable,
as a first-orderapproximation.
presumably,
to the energy;to find the first-order
Equation6.9is the first-ordercorrection
correction
to the wave functionwe first rewrite Equation6.7:
(H\302\260

\302\243j)^

- EM.

= -{W

nothing here dependson the specificnature of the


holds for any potential, when the perturbation is constant.
\342\226\240'Incidentally,

infinite

[6.10]
square

well\342\200\224the

same

Section6.1:Nondegenerate
Perturbation
Theory

253

V(x)\342\200\236

Vo

>-

overhalf the well.


FIGURE6.3: Constantperturbation

Theright sideisa known function,sothisamountsto an inhomogeneous


differential
a complete
set,
equationfor i/r,}.Now, the unperturbedwave functionsconstitute
as a linearcombination
so i/r,} (likeany otherfunction)can be expressed
of them:

ri = Ec\"V\302\260.

[6.11]

m = n in the sum,forif i/r,| satisfies


Thereis no needto include
Equation6.10,so

toodoes(i/r,,1 + ai/r,?),for any constanta, and we can usethisfreedomto subtract


the coefficients
off the i/r,? term.4If we coulddetermine
f,(/,'\\ we'dbedone.
Well, puttingEquation6.11intoEquation6.10,and usingthe fact that the \\j/m
satisfiesthe unperturbed
Schrodinger
equation(Equation6.1),we have

Taking the innerproductwith i/^0,

- Ey^i^Wl)= -W?\\H'\\*2)+ *J W/VJ?>-

\302\243(\302\243\302\260

be pulled out and combinedwith the


as the coefficient of

\\jrfj

in

M(^il l^,?>+ (i>?M>u))+


the

first term

6.5reveals thai

a glance at Equation

Alternatively,

is 1 and

[if/,]

Equation
*

\342\226\240

*\342\226\240\"('

\\\\[/\302\256)

first

term. In fact, the

6.5\342\200\224is

\342\200\242

any

component in

ty\302\256

choice

c\342\200\236

normalized (to

first

might

\\f/,\\

= 0 ensuresthat

order in

A):

(if,,\\i(/\342\200\236)

as well

\\j>\342\200\236\342\200\224with

= (^?l^i?)+

the orthonormality of the unperturbed states means that


= 0, as long as has no i(/jj component.

but

(^1^,))

\\j/}t

254

Perturbation
Chapter6 Time-Independent
Theory
If / = n, the left sideis zero,and we recoverEquation6.9;if I ^ n, we get
(\302\2430_\302\243J)cW=_^0|WU0>f

or
fO _ fO
SO

[6.13]
with m = n) as
Noticethat the denominator
is safe (sincethere is no coefficient
But if two different
longas the unperturbedenergy spectrumis nondegenerate.
statessharethe sameenergy,we'rein serioustrouble(we dividedby
unperturbed
zeroto getEquation6.12);in that casewe needdegenerateperturbationtheory,
which I'll cometo in Section6.2.
That completes
first-orderperturbationtheory:The first-ordercorrection
to
the energy,EJ}, is given by Equation6.9,and the first-ordercorrection
to the
wave function,xfr*, is given by Equation6.13.I shouldwarn you that whereas
accurateenergies(that is, + E\\ is
perturbation
theory oftenyieldssurprisingly
the wave functionsare notoriously
quitecloseto the exactvalue
poor.
E\302\256

\302\243\342\200\236),

*Problem6.1Supposewe put a delta-function


bump in the centerof the infinite
squarewell:

H' = oc8(x-a/2),
where a

is a constant.

Findthe first-order
to the allowedenergies.
correction
Explainwhy the
are not perturbedfor even n.
(b) Find the first three nonzeroterms in the expansion
(Equation6.13)of the
correction
to the groundstate,\\j/\\.
(a)

energies

*Problem6.2 For the harmonicoscillator[V(x)= (l/2)kx2],the allowed


energies

are

E\342\200\236

= (n + \\/2)h(o,

(n

= 0. 1.2,

...),

= ^Jk/m is the classical


frequency.Now supposethe springconstant
increases
(1+ e)k.(Perhapswe coolthe spring,so it becomesless
slightly:k
flexible.)
where co

\342\200\224\302\273

Section6.1:Nondegenerate
Perturbation
Theory

255

Findthe exactnew energies


(trivial,in thiscase).Expandyour formula as a
powerseriesin 6, up to secondorder.
the first-order
in the energy,usingEquation6.9.
(b) Now calculate
perturbation
What is H' here?Compareyour resultwith part (a).Hint:It is not
a singleintegralin doingthis
fact,it is notpermitted\342\200\224to calculate
(a)

necessary\342\200\224in

problem.
Problem6.3 Two identicalbosonsare placed in an infinite square well
(Equation2.19).They interact weakly with oneanother,via the potential
V(x\\,X2)=
(where Vo is a
the well).
(a)

\342\200\224

aVo8(xi

\342\200\224

X2)

constantwith the dimensions


of energy,and a is the

width

of

betweenthe particles,find the groundstate


First,ignoringthe interaction
and the first excited
the wave functionsand the associated
energies.
Use first-orderperturbationtheory to estimatethe effectof the particleon the energiesof the groundstateand the first excited
particleinteraction
state.
state\342\200\224both

(b)

6.1.3Second-Order
Energies
as before,we take the inner productof the secondorder equation
Proceeding
(Equation6.8)with
if/\302\256:

= B%w*n\\*i) + ElwM)+ ElwM)+ <v,?i#V,!>


<v,?i#V,2>
Again,we exploitthe hermiticity of

H\302\260:

so the first term on the left cancelsthe first term on the right.Meanwhile,
(^0?1^0?)= 1' anc* we are left with a formula for E}}:

El = {^\\H'Wl)-El{^\\fl).
But

[6.14]

256

Perturbation
Theory
Chapter6 Time-Independent

so
the sum excludes
m = n, and allthe othersare orthogonal),
(because

E\302\260

E\302\260

or, finally.

3 E
=

0|r//u/,0\\i2
/rO _ c-0

[6.15J

m-fin

Thisis the fundamental resultof second-order


theory.
perturbation
We couldgo on to calculate
to the wave
correction
the second-order
(^), the third-ordercorrectionto the energy,and so on, but in practice
Equation6.15is ordinarilyas far as it is usefulto pursuethismethod.5
function

*Problem6.4
Find the second-order
correctionto the energies(E2.)for the potential
in Problem6.1.Comment:You can sum the seriesexplicitly,
obtaining
for oddn.
the second-order
to the groundstateenergy
for the
correction
(b) Calculate
with the exact
potentialin Problem6.2.Checkthat your resultis consistent
(a)

\342\200\2242m{a/7ihn)2

(\302\243q)

solution.

* *Problem6.5 Consider
a chargedparticlein the one-dimensional
harmonic
so that the potential
potential.
Supposewe turn on a weak electricfield
energy is shiftedby an amount H' =
oscillator

(\302\243),

\342\200\224qEx.

sIn the short-hand notation


to the

Hth

V,\342\200\236\342\200\236

energy are
it

_ i/

ir2

V^

~f

rti^tii

Vim

= (rlr^lH'lif/fj).A,,,,, =

|1
I~

p^ _ V^

T\302\273

IF

^ii/V/m

\302\243^

E\302\256,

IF
^1\302\273))

*\342\200\224*

the

first

V^

/.1115=11

It/

Mmi

,\">
l~

*\342\200\224

AWA\342\200\236\342\200\236,

A\342\200\236\342\200\236,

three corrections

1117=11

An,,,
'\"\"

The third order correction is given in Landau and Lifschitz, Quantum Mechanics:
Non-Relativistic
the fourth and fifth orders (together with a
Theory. 3rd ed..Pergamon. Oxford (1977).page 136:
powerful general technique for obtaining the higher orders) are developed by Nicholas Wheeler,
Higher-Order
SpectralPerturbation (unpublished Reed Collegereport. 2000).
Illuminating
formulations of time-independent perturbation theory include the Delgarno-Lewismethod and
the closely related \"logarithmic\"
theory (see.for example,T.Imbo and U.Sukhatme.
perturbation
for DelgarnoAm. J. Phys. 52.140
(1984),for LPT. and H. Mavromatis. Am. J.Phys. 59,738 (1991),
alternative

Lewis).

Section6.2:Degenerate
Perturbation
Theory

257

is no first-orderchangein the energy levels,and calculate


the second-order
correction.
Hint:SeeProblem3.33.
can be solveddirectlyin thiscase,by a changeof
The Schrodinger
equation
variables:
x' = x (qE/mar).Findthe exactenergies,and show that they
with the perturbation
are consistent
theory approximation.

(a) Show that there


(b)

\342\200\224

6.2 DEGENERATEPERTURBATIONTHEORY
If the unperturbedstatesare degenerate\342\200\224that is, if two (or more)distinctstates
and
sharethe same
ordinary perturbation
theory fails:ca
(Equation6.12)and E\\ (Equation6.15)blow up (unless,perhaps,the numerator
that will be importantto us lateron).In the
vanishes,
loophole
{^\\H'\\\\j/^})=
there is no reasonto trust even thefirst-ordercorrection
case,therefore,
degenerate
to the energy (Equation6.9),and we must lookfor someotherway to handlethe

(^

energy\342\200\224then

\\j/\302\256)

0\342\200\224a

problem.

6.2.1Two-FoldDegeneracy
Supposethat
H\302\260tf

with i/r^ and

= EPtf,

H\\l = E\\l

^ bothnormalized.Note

that any

t\302\260=atf

is stillan eigenstate
of

H\302\260,

<V\302\253V,?>=0,

[6.16]

linearcombination
of thesestates,

+ Ml

[6.17]

with the sameeigenvalue

E\302\260:

H\302\260x}/0

= E0x}/0.

[6.18]

As we
Typically,the perturbation(//') will \"break\"(or \"lift\") the degeneracy:

increaseX (from 0 to 1),the commonunperturbedenergy


splitsinto two
when we turn off the perturbation,
the
(Figure6.4).Goingthe otherdirection,
of
and i/r^, and the
\"upper\" statereducesdown to one linearcombination
to someorthogonal
linearcombination,
\"lower\"statereduces
but we don'tknow a
will be.Forthisreasonwe can'teven
linearcombinations
prioriwhat these\"good\"
don'tknow what unperturbed
calculate
the first-orderenergy (Equation
statesto use.
For the moment,therefore,let'sjust write the \"good\"unperturbedstatesin
We want to solvethe
genericform (Equation6.17),keepinga and fi adjustable.
Schrodinger
equation,
[6.19]
Hxlr= Ex}/,
\302\243\302\260

6.9)\342\200\224we

258

Perturbation
Theory
Chapter6 Time-Independent
E

Eo

FIGURE6.4: \"Lifting\"of a degeneracyby a perturbation.


with

H=

H\302\260+XH'

E=E\302\260

and

+ \\E1+\\2E2+ ->-,

yjr

ifr\302\260

+ Xifr1 + X2x}/2+

\342\200\242 \342\200\242 \342\200\242

[6.20]

likepowersof X (as before)


Pluggingtheseinto Equation6.19,and collecting
we find

#V\302\260

+ M#

But /f0!//0=

\302\243\302\260i/f0

V\302\260

+ #V) +

\342\200\242 \342\200\242 \342\200\242

E\302\260\\lr\302\260

+ X(E

V\302\260

+ ^V) +

\342\200\242 \342\200\242 \342\200\242


\342\200\242

(Equation6.18),so the first terms cancel;at orderX] we have

tfV

+#>\302\260

\302\243V

\302\243

V\302\260.

[6-21]

Taking the innerproductwith i/r^:

Because is hermitian,the first term on the left cancelsthe first term on


the right.Putting in Equation6.17and exploiting
the orthonormality
condition
//\302\260

(Equation6.16),we obtain

=aEl.

*{^a\\H'\\fQa)+0{tf\\H'\\1,$)

or, morecompactly,

aWaa+0Wab=aEl,

where
W-,j

= Wf\\H'\\tf). (/,j = a.b).

[6.22]
[6.23]

Section6.2:Degenerate
Perturbation
Theory
Similarly,the inner productwith

259

yields

\\J/\302\256

aWba+pWhh= PE]

Fs

[6.24]

Noticethat the
are just the \"matrix
are (in principle)
to the unperturbed
wave functions and i/r^.
elements\" of H', with respect
/3 Wab, we find:
Equation6.24by Wab, and usingEquation6.22to eliminate

known\342\200\224they

Multiplying

aiWabWba

- (El - Waa)(El -

Wbh)]

= 0.

[6.25]

If a is not zero,Equation6.25yieldsan equationfor El:

(E1)2 El(Waa + Wbb) + (WaaWhb

WahWba)

= 0.

Invokingthe quadraticformula,and noting(from Equation6.23)that

[6.26]
Wba

that
we conclude

E\\=-

Waa

+ Wbb

\302\261

J{Waa

Whh)2

+ 4\\Wab\\*

W*b,

[6.27]

This is the fundamental resultof degenerate


perturbationtheory;the two roots

to the two perturbedenergies.


correspond
But what if a is zero?In that case/? = 1, Equation6.22says Wab = 0,
in the generalresult
and Equation6.24givesEl = Wbb. This is actually included
to a = 1,/? = 0).
(Equation6.27),with the minus sign(the plussigncorresponds
What'smore,the answers,

4=

Waa

W\302\260|ff'Wr\302\260),

El = Wbb = Wjlff'l^).

what we wouldhave obtained


are precisely
theory
usingnon degenerate
perturbation
(Equation6.9).We have simply beenlucky:The states and \\frf were already
linearcombinations.
the \"good\"
Obviously,it would be greatly to our advantage
if we couldsomehowguessthe \"good\"statesright from the start\342\200\224then we could
go aheadand usenon degenerate
perturbation
theory.As it turns out,we can very
oftendo thisby exploiting
the followingtheorem:
\\(r\302\256

with
and H'.
Theorem: Let A be a hermitian operatorthat commutes
are alsoeigenfunctions
If \\j/^ and (the degenerate
of
eigenfunctions
of A, with distincteigenvalues,
H\302\260

if;\302\256

H\302\260)

A^,=fi^r Afl = virl andM/v.

260

Perturbation
Theory
Chapter6 Time-Independent
then

Wab

= 0 (and hence and


\\J/\302\256

i/r\302\243

are the \"good\"


statesto usein

theory).

perturbation

Proof:By assumption,
[A,H'] = 0, so

= {AfQa\\H'ff))-{fQa\\H'vfl)
= (At v){^a\\H'fl)= (M \" \"Wab.

But fi

v,

so

W\342\200\236/,

= 0. QED

Moral:If you'refacedwith degenerate


states,lookaroundforsomehermitian

statesones
with
and H'\\ pickas your unperturbed
operatorA that commutes
that are simultaneously
of and A. Then useordinaryfirst-order
eigenfunctions
perturbationtheory.If you can't find suchan operator,you'llhave to resortto
Equation6.27,but in practicethis is seldomnecessary.
H\302\260

H\302\260

Problem6.6 Let the two \"good\"unperturbed


statesbe

where
Equation

ot\302\261

and

fi\302\261

are determined
(up to normalization)
by Equation6.22(or

that
6.24).Showexplicitly

(a)

f% are orthogonal

(b)

W\302\243|ff'Wr\302\243)=0;

(e)

{\\j/\\\\H'\\fQ\302\261)

= 0);

\302\253i/rj|i/r\302\260)

=
El\302\261,

with
El\302\261

given by Equation6.27.

Problem6.7 Consider
a particleof massm that is free to move in a
regionof lengthL that closeson itself(for instance,a bead that slides
on a circularwire of circumference
L, as in Problem2.46).
frictionlessly

one-dimensional

(a) Showthat the stationary statescan be written in the form

tM-v)= -!-e27Tinx/L,(-L/2< x < L/2).

Section6.2:Degenerate
Perturbation
Theory
where n

= 0, +1,+2,

...,

261

and the allowedenergies


are

= 2 fmth\\

E\342\200\236

\\

of the groundstate =
Notice
the exception
doublydegenerate.
that\342\200\224with

(\302\273

0)\342\200\224these

are all

the perturbation
we introduce
(b) Now suppose

H' = -V0e-x2/a\\
L. (Thisputsa little\"dimple\"in the potential
at x = 0,as though
where a
to
we bentthe wire slightlyto make a \"trap.\")Findthe first-order
correction
usingEquation6.27.Hint:To evaluate the integrals,
exploitthe fact that
after all,H' is essentially
a <$C L to extendthe limitsfrom +L/2 to
zerooutside < x < a.
<\302\243

\302\243\342\200\236,

\302\261oo;

\342\200\224a

for this problem?


of and
(c) What are the \"good\"linearcombinations
Show that with these states you get the first-ordercorrectionusing
\\(r\342\200\236

Equation6.9.
(d) Find a hermitian operatorA that

i/r_\342\200\236,

of the theorem,and
requirements
of
and A are precisely
show that the simultaneous
the ones
eigenstates
you usedin (c).
fits the

H\302\260

6.2.2Higher-OrderDegeneracy
In the previoussectionI assumedthe degeneracywas two-fold,but it is easy to
seehow the methodgeneralizes.
Rewrite Equations6.22and 6.24in matrix form:

ff:

\302\243)6)=^6)-

of the W-matrix;Equation6.26
Evidently the El'sare nothingbut the eigenvalues
is the characteristic
equationfor this matrix, and the \"good\"linearcombinations
of W.
of the unperturbedstatesare the eigenvectors
we lookfor the eigenvalues
In the caseof n-folddegeneracy,
of the n x n
matrix
Wij

= W?\\H'\\rf).

[6.29]

In the languageof linearalgebra,finding the \"good\"unperturbed


wave functions
a basisin the degenerate
the
amounts to constructing
that diagonalizes
subspace

262

Perturbation
Theory
Chapter6 Time-Independent
A that commutes
with H',
matrix W. Onceagain,if you can think of an operator
and use the simultaneous
of A and
then the W matrix will
eigenfunctions
and you won't have to fuss with solvingthe
automaticallybe diagonal,
from 2-fold
(If you'renervous aboutmy casualgeneralization
equation.6
to /?-folddegeneracy,
work Problem6.10.)
degeneracy
H\302\260,

characteristic

the three-dimensional
infinite cubicalwell (Problem4.2):
Example6.2 Consider

0, if 0 < x < a.0 < v < a. and 0 < z < a:

.
V(\\\\y.z) = oo
otherwise.

[6.30]

The stationary statesare


n
>'\342\200\242

<\342\200\236,\342\200\236(-V,

z)

. /nx7T \\ sin(nsiz \\ sin /iutz \\ .


= /2V sin
(-i-x) (-L-y)

(-^-z)

(^-J

[6.31]

where nx,ny, and nz are positive


The corresponding
allowedenergies
are
integers.

+ nh.
<nvn: = ^(\302\273l+nl

[6.32]

Noticethat the groundstate(\\J/\\ 11)is nondegenerate;


its energy is
\302\2430\302\260

- 3^.
a1
2m

[6.33]

But the first excitedstateis (triply) degenerate:


^0

= ^112. fb = ^121.and \\j/c = f2\\\\,

all sharethe sameenergy

E?

- 3^:.
ma1

[6.34]
[6.35]

Now let'sintroduce
the perturbation

H' =

< all and 0 < y < a/2;


0. otherwise.

V0. if 0 < x

[6.36]

\"Degenerateperturbation theory amounts to diagonalization of the degeneratepart of the Hamiltonian. The diagonalization of matrices (and simultaneous diagonalizability of commuting matrices) is

discussedin

the

Appendix

(SectionA.5).

Section6.2:Degenerate
Perturbation
Theory

263

Zy

//
a/2

a//r

/
/
/ /

'a

increases
the potential
FIGURE6.5: The perturbation
by an amount Vq in the shaded
sector.

Thisraisesthe potential
by an amount Vq m onequarter of the box(seeFigure6.5).
The first-order
correction
to the groundstateenergy is given by Equation6.9:
Ek =

Wiu\\H'\\fni)
3

(!)
i

v\302\260

rct/2

1'sin2(r)dx

= -V0.

sin2

(fy)dy [sin2(r)rfz
[6.37]

which is pretty much what we wouldexpect.


Forthe first excitedstatewe needthe full machineryof degenerate
perturbation
T
he
first
is
to
construct
the
W.
The
e
lements
are the
matrix
theory.
step
diagonal
sameas for the groundstate(exceptthat the argument of one of the sinesis
doubled);
you can checkfor yourselfthat
waa = wbh

= wcc = ]-v0.
4

The off-diagonal
elements
are moreinteresting:
Wab

(^)
x /

[\302\2532

V0

f\" sin2

(^.r) dx

. (ii
.
sin
(
v ) sin(In
v

\342\200\224

\342\200\224y

\\
I

dy

. (In
IJ\" sin
I

\342\200\224z

\\

. (n
sin
(

\342\200\224z)

dz.

264

Perturbation
Chapter6 Time-Independent
Theory
But the z integralis zero(asit will bealsofor Wac), so

= Wac = 0.

W\342\200\236b

Finally,
Whc

sin

[\"sin(Vv)sin&)

Thus
W

Vo

\342\200\224.v

dy

ax

=
*
(^)
fsin2

0N

/f

,0

5\302\276Vo-

[6.38]

(8/3;r)2^ 0.7205.
The characteristic
equationfor W (or rather, for 4W/ Vq, which is easierto

where /c =

work with)

is

(1-w)3 -k2{\\-u>) =0.


and the eigenvalues
are
W\\

= 1;

iy2

= 1+

\302\253
\302\253

1-705; iw3 =

-*

*\302\253

0.2795.

To first orderin A, then,

+ XVo/4,
+ A.(l+K)Vb/4.
Ef + A.(l-^)Vo/4.

E^
\302\243iW=

\342\200\242

\302\243\302\260

[6.39]

where
is the (common)unperturbedenergy (Equation6.35).The perturbation
liftsthe degeneracy,
splitting intothree distinctenergy levels(seeFigure6.6).
Noticethat if we had naively applied/20/2degenerate
perturbationtheory to this
that the first-order
we wouldhave concluded
correction
problem,
(Equation6.9)is
the samefor allthree states,and equalto Vb/4\342\200\224which is actually correctonly for
the middlestate.
the \"good\"
of the form
statesare linearcombinations
Meanwhile,
unperturbed
\302\243^

E\302\256

rlr\302\260

where the coefficients


(\302\273,

ft,

= ctxlra + P1,h+ yxlrc,

and y) form the eigenvectors


of the matrix W:

1 0 0\\ /a\\
/a\\
0 1 k) \\fi]=w\\fi\\.

,0

1/ Kyi

\\y)

[6.40]

Section6.2:Degenerate
Perturbation
Theory

265

5(X)A

FIGURE6.6: Lifting of the degeneracyin Example6.2(Equation


6.39).

For w = 1 we get a = 1,ft = y = 0; for if = 1 + k we get a = 0, ft = +y


them as I went along.)Thus the \"good\"
statesare7
1/V2.(I normalized

t\302\260

fa-

[6.41]

(^ - 1M/a/2.

Problem6.8 Supposewe perturb the infinite cubicalwell (Equation6.30)by


putting a deltafunction\"bump\"at the point(a/4,a/2,3a/4):

H' = a3V08(x a/4)5()- a/2)8(z 3a/4).


to the energy of the groundstateand the (triply
Find the first-ordercorrections
first excited
states.
degenerate)

have guessedthis result right from the start by noting that the operator Fvv. which
interchanges x and y, commutes with H'.Its eigenvalues are +1(for functions that are even under the
(for functions that are odd).In this case^/0 is already even. (\\J/i, + \\Jrc) is even,
interchange), and
and (^/, tyc) is odd. This is not quite conclusive,sinceany linear combination of the even states
would still be even. But if we also use the operator Q, which takes z to a z, and note that ^ru is
an eigenfunction with eigenvalue
whereas the other two are eigenfunctions with eigenvalue +1,
the ambiguity is resolved.Here the operators Fvv and Q together play the role of A in the theorem of
7We might

\342\200\2241

\342\200\224

\342\200\224

\342\200\224I,

Section6.2.1.

266

Perturbation
Theory
Chapter6 Time-Independent

*Problem6.9 Considera quantum system with just three linearly independent


in matrix form,is
states.Supposethe Hamiltonian,
H

where Vq

'(1-6)0
0
0

V0 I

0^

e 2,

is a constant,and e is somesmallnumber (e <$C 1).

and eigenvalues
of theunperturbedHamiltonian
(a) Write down the eigenvectors

(e = 0).

(b)

Solvefor the exacteigenvalues


of H. Expandeachof them as a powerseries
in 6, up to secondorder.

(c) Use first- and second-order


nondegenerate
perturbationtheory to find the
approximateeigenvaluefor the statethat grows out of the nondegenerate
of
Comparethe exactresult,from (a).
eigenvector
to the
(d) Usedegenerate
perturbationtheory to find the first-ordercorrection
two initiallydegenerate
Comparethe exactresults.
eigenvalues.
H\302\260.

to an /?-fold
Problem6.10In the text I assertedthat the first-ordercorrections
of the W matrix, and I justifiedthisclaimas
energy are the eigenvalues
degenerate
the \"natural\"generalization
of the casen = 2. Proveit, by reproducingthe steps
in Section
6.2.1,starting with
7=1

(generalizing
Equation6.17),and ending by showing that the analog to
for the matrix W.
Equation6.22can be interpretedas the eigenvalueequation

6.3 THE FINE STRUCTUREOF HYDROGEN


to be
In our study of the hydrogenatom (Section
4.2)we tookthe Hamiltonian
\302\253

=-^-^
2m

47T60 r

[6.42]

(electronkineticenergy pluscoulombic
potentialenergy).But this is not quite
the whole story.We have already learnedhow to correctfor the motionof the

Section6.3:TheFineStructureof Hydrogen

267

TABLE6.1:Hierarchyof corrections
to the

of hydrogen.
Bohrenergies

?
Bohrenergies:oforder
Finestructure: oforder 4 5
Lambshift: oforder aDmc~
Hyper fine splitting: oforder (m/mp)a4mc^
~>

Moresignificantis
nucleus:Just replacem by the reducedmass(Problem5.1).
the so-called
fine structure,which is actually dueto two distinctmechanisms:
a
relativisticcorrection,and spin-orbit
coupling.
Comparedto the Bohrenergies
(Equation4.70),fine structure is a tiny perturbation\342\200\224smaller by a factorof or2,
where
47t\342\202\2540hc

137.036

is the famousfinestructureconstant.Smallerstill(by anotherfactorof a) is the


Lambshift,associated
with the quantization
of the electricfield,and smallerby
yet anotherorderof magnitudeis the hyperfinestructure,which is due to the
betweenthe dipolemomentsof the electronand the proton.
magneticinteraction
in Table6.1.
In the presentsectionwe will analyze
Thishierarchy is summarized
of time-independent
the fine structure of hydrogen,as an application
perturbation
theory.

Problem6.11
(a)
(b)

Expressthe Bohrenergiesin terms of the fine structure constantand the rest


energy (mc2)of the electron.
the finestructureconstant
Calculate
from first principles
(i.e.,without recourse
The fine structure
to the empirical
valuesof e-> ^ and c).Comment:
isundoubtedly
the mostfundamentalpure(dimensionless)
number in all
of physics.It relatesthe basicconstants
of electromagnetism
(the chargeof
the electron),
(Planck's
relativity(the speedof light),and quantum mechanics
If you can solvepart (b),you have the mostcertainNobelPrize
constant).
in historywaiting for you.But I wouldn'trecommend
a lotof time
spending
on it right now; many smart peoplehave tried,and all (sofar) have failed.
\342\202\254$\342\226\240>

constant

6.3.1TheRelativisticCorrection
The first term in the Hamiltonian
is supposed
to represent
kineticenergy:

T=lmv2=P
2
2m

[6.44]

268

Perturbation
Theory
Chapter6 Time-Independent
and the canonical
substitution
p

{h/i)Vyieldsthe operator

\342\200\224>

r = -\302\243v2.
2m
But Equation6.44is the
formula is

[6.45]

for kineticenergy;the relativistic


classicalexpression

mc
mc
[6.46]
~
(v/c)2
<J\\
The first term is the total relativistic
energy (not countingpotentialenergy,
which we aren'tconcerned
and the secondterm is the rest
with at the moment),
to motion.
differenceis the energy attributable
We needto express
T in terms of the (relativistic)
momentum,
T=

\342\200\224

energy\342\200\224the

P=

mv

[6.47]

y/l-(v/c)2'

insteadof velocity.Noticethat
c2,
4-m 2c4 =
p222

m2v2c+tn2c4[l (v/c)2]
l (v/cy

\342\200\224

2,.4
nrc
, = (T -\\-tnc2)2.

- (v/c)

so
T=

[6.48]

y/p2c2+m2c4-mc2.

Thisrelativistic
equationfor kineticenergy reduces(of course)to the classical
result(Equation6.44),in the nonrelativistic
limitp <$c mc;expandingin powers
of the smallnumber (p/mc),we have
T = mc

(A)2.,=mc2 1+'(M2_'(A)4..._!
2 \\mc/
o \\mc/

+ \\mc/
r.4

2m

[6.49]

8;??3c2

The lowest-order8
correction
to the Hamiltonian
is evidently
relativistic
P4
8m

[6.50]

10

kinetic energy of the electron in hydrogen is on the order of


eV.which is miniscule
to
its
rest
so
the
atom
is
eV),
energy
compared
hydrogen
basically nonrelativistic. and we
can afford to keep only the lowest-ordercorrection.
In Equation
p is the relativistic momentum
not
the
momentum
mv.
It
is
the
we now associatewith the
classical
former
that
(Equation 6.47),
//}
in
V,
operator
quantum
Equation
\302\260Thc

(511.000

\342\200\224

6.50.

6.49.

Section6.3:The Vine StructureofHydrogen 269

expectation

In first-orderperturbation
to En is given by the
theory, the correction
value of H' in the unperturbed
state(Equation6.9):
E\\

= {H'r)= -\342\200\224L^|pV>
=

--^(^1^). [6.51]

Now, the Schrodinger


states)says
equation(forthe unperturbed
p\"\\fr

and hence9

*;=

V)2)
-^((\302\243
2mc-

= 2m(E
=

\342\200\224

V)\\fr,

- 2E(V)+ (V2)].
-^[E2
2mc-

[6.52]
[6.53]

in hydrogen,
Sofar thisis entirely general;but we'reinterested
for which V(r)=

-(l/4Tre0)e2/n
V=

2mc2

[6.54]

\302\242-^)(3-(\302\276\302\276\302\276

is the Bohrenergy of the statein question.


To complete
the job,we needthe expectation
valuesof 1/r and 1/r2,in the
state
The first is easy (seeProblem6.12):
(unperturbed)
(Equation4.2.1).

where

E\342\200\236

\\[r\342\200\236im

[6.55]

where a is the Bohrradius(Equation4.72).The secondis not so simpleto derive


(seeProblem6.33),but the answer is10

1
(/ + 1/2)/7\302\275

3\342\200\2362-

[6.56]

It followsthat

*;=

2mc-.2

E\302\273

2\302\243\"

+
{4jre0)n2a \\4jteo) (I + 1/2),7\302\2752

somesleight-of-hand in

maneuver, which exploitsthe hermiticity of p- and of


and
(E V). In truth, the operator p4 is not hermitian for states with / = 0 (seeProblem 6.15),
the applicability of perturbation
is therefore calledinto question (for the case
theory to Equation 6.50
I = 0). Fortunately, the exact solution is available; it can be obtained by using the (relativislic) Dirac
equation in place of the (nonrelativistic) Schrodingerequation, and it confirms the results we obtain
here by less rigorous means (seeProblem 6.19).
l0The general formula for the expectation value of any powerof r is given in HansA. Betheand
Edwin E. Salpeter,Quantum Mechanicsof One-and Two-ElectronAtoms, Plenum, New York (1977),
9There is

\342\200\224

p. 17.

this

270

Perturbation
Theory
Chapter6 Time-Independent
a (usingEquation4.72)and expressing
or, eliminating
everything in terms of En

(usingEquation4.70):

E' =

<*\302\253>'

-3

An

[6.57]

Imc1 L/+1/2

correctionis smallerthan
by a factorof about
Evidently the relativistic
En/mc2=2x 10\"5.
You might have noticed
that I usednon degenerate
theory in this
perturbation
calculation
(Equation6.51),in spiteof the fact that the hydrogenatomis highly
with
But the perturbation
is spherically
so it commutes
degenerate.
symmetrical,
L2 and L-.Moreover,the eigenfunctions
of theseoperators
(taken together)have
distincteigenvalues
for the n2 stateswith a given En. Luckily,then, the wave
functions
are the \"good\"statesfor thisproblem(or,as we say, n, I, and
m are the goodquantumnumbers),so as it happensthe useof nondegenerate
perturbation
theory was legitimate
(seethe \"Moral\"to Section6.2.1).
\302\243\342\200\236,

\\frni,\342\200\236

*Problem6.12Usethe virial theorem(Problem4.40)to proveEquation6.55.


the expectation
value of rs in the
Problem6.13In Problem4.43you calculated
Checkyour answer for the specialcases
state1^321.
(trivial),s = 1
(Equation6.56),and s =
(Equation6.55),s =
(Equation6.64).Comment
=
on the cases

5=0

\342\200\2242

\342\200\224

\342\200\2243

\342\200\2247.

* *Problem6.14Findthe (lowest-order)
to the energy levelsof
relativistic
correction
in Example2.5.
the one-dimensional
harmonicoscillator.
Hint:Usethe technique
* * *Problem6.15Show that p2 is hermitian,
but p4 is not,for hydrogenstateswith
I = 0. Hint:For suchstates is independent
of 9 and 0, so
\\fr

r2 dr

\\

dr J

Usingintegrationby parts,show that


(Equation4.13).
(/1,\302\276

= -4nh2

+ <P2/I*>L2ffr-r2gd-\302\243
o

Checkthat the boundary term vanishesfor

i/0i00\302\273

which goeslike

1
VOiOO

-=-\342\200\224-^expi-r/na)
^/71(nayl1

Section6.3:TheFineStructureof Hydrogen

271

near the origin.Now do the samefor p4, and showthat the boundary terms do not

vanish.In fact:

8/i4(/?
{fnW\\Ptnm)= a4

m)

+ {P fnOOl^mOO)'

(nm)5/-

6.3.2Spin-Orbit
Coupling

in orbitaroundthe nucleus;
from the electron's
Imaginethe electron
pointof view,
the protonis circlingaroundit (Figure6.7).Thisorbitingpositivechargesetsup
a magneticfieldB, in the electronframe, which exertsa torqueon the spinning
of the field.
electron,
tendingto alignits magneticmoment (ft) alongthe direction
The Hamiltonian
(Equation4.157)is
H = -fi-B.
[6.58]

To beginwith, we needto figure out the magneticfieldof the proton(B) and the

dipolemoment of the electron(fi).

The magneticfieldof the proton.If we picturethe proton(from the


electron's perspective)
as a continuous
current loop(Figure6.7),its magneticfieldcan
be calculated
from the Biot-Savart
law:
B=

2r
with an effectivecurrent I = e/T, where e is the chargeof the protonand T is
the periodof the orbit.On the otherhand, the orbitalangular momentum of the
electron(in the restframe of the nucleus)is L = rmv = 2Tcmr-/T.Moreover,B
and L pointin the samedirection
(up,in Figure6.7),so
B=

(I usedc =

L.

47reomc2r3
no in favor of
1/v^OMO to eliminate

[6.59]

\342\202\254q.)

B, LA

FIGURE6.7: Hydrogen

electron's
perspective.

atom, from the

272

Perturbation
Chapter6 Time-Independent
Theory

Themagneticdipolemomentoftheelectron.The magneticdipolemoment
of a spinningchargeis relatedto its (spin)angular momentum; the proportionality
in Section
factoris the gyromagnetic
ratio(which we already encountered
4.4.2).
a
Let'sderiveit, thistime,usingclassical
Consider
first
electrodynamics.
charge
o
ut
around
a
ring of radiusr, which rotatesaboutthe axiswith period
q smeared
T (Figure6.8).The magneticdipolemoment of the ring is definedas the current
(q/T)timesthe area (nr2):
fJ-

= qitr

If the massof the ring is m, its angular momentum is the moment of inertia(mr2)
timesthe angular velocity(2tt/T):
S=

2jrmr-

The gyromagnetic
ratiofor thisconfiguration
is evidently fi/S = q/2m.Notice

of (and T).If I had somemorecomplicated


it is independent
object,such
as a sphere(all I requireis that it be a figure of revolution,rotatingaboutits
axis),I couldcalculatefi and S by choppingit into littlerings,and addingup
theircontributions.
As longas the massand the chargeare distributed
in the same
manner (sothat the charge-to-mass
ratiowill
ratiois uniform),the gyromagnetic
be the samefor eachring,and hencealsofor the objectas a whole.Moreover,the
directions
of fi and S are the same(oropposite,
if the chargeis negative),so
that

;\342\200\242

2m

H\302\243)\302\273

That was a purely classical


calculation,
however;as it turns outthe electron's
value:
magneticmoment is twice the classical

fie =
jit,

S.

[6.60]

Sii

FIGURE6.8: A ring of charge,rotating

aboutitsaxis.

Section6.3:TheFineStructureofHydrogen 273
The \"extra\"factorof 2 was explained
by Dirac,in hisrelativistic
theory of the

electron.11

we have
Putting all thistogether,

\\4)reo/w-e~rJ
I did the analysisin the restframe
But there is a seriousfraud in thiscalculation:

of the electron,but that'snotan inertial


as the electron
accelerates,
orbitsaround the nucleus.You can get away with thisif you make an appropriate
known as the Thomasprecession.12
In thiscontextit throws
kinematiccorrection,
in a factorof 1/2:13
system\342\200\224it

so

(\342\200\224)
\\

\342\200\224

8;reo/m2c2r3

Thisis the spin-orbit


interaction;apart from two corrections
(the modifiedgyrocoincifactor\342\200\224which,
magneticratiofor the electronand theThomasprecession
dentally,exactly canceloneanother)it isjustwhat you wouldexpecton the basis
of a naive classical
model.Physically,it is dueto the torqueexertedon the
dipolemoment of the spinningelectron,
by the magneticfieldof the proton,
in the electron's
restframe.
instantaneous
In the presenceof spin-orbitcoupling,the
Now the quantum mechanics.
Hamiltonianno longercommutes
with L and S, so the spinand orbital
conserved
momenta are not separately
(seeProblem6.16).However,H^a does
commutewith L2, S2 and the totalangular momentum
magnetic

angular

J = L + S,

1'We have already noted that

[6.62]

it can be dangerousto picture the electron as a spinning sphere(see


and it is not too surprising that the naive classicalmodel gets the gyromagnetic ratio
Problem 4.25),
wrong. The deviation from the classical
expectation is known as the g-factor:fi = #(<y/2//i)S.Thus
the ^-factorof the electron, in Dirac'stheory, is exactly 2.But quantum electrodynamics
reveals tiny
correctionsto this: ge is actually 2+{a/n)
+ = 2.002 The calculation and measurement (which
anomalousmagneticmoment of the electron were among
agreeto exquisiteprecision)of the so-called
the greatest achievements of twentieth-century
physics.
'-Oneway of thinking of it is that the electron is continually steppingfrom one inertial system to
another; Thomas precessionamounts to the cumulative effect of all these Lorcntz transformations. We
could avoid the whole problem,of course,by staying in the lab frame, in which the nucleus is at rest.
In that casethe field of the proton is purely electric,
and you might wonder why it exerts any torque
on the electron.Well, the fact is that a moving magnetic dipoleacquiresan electricdipole moment,
and in the lab frame the spin-orbit coupling is due to the interactionof the electricfield of the nucleus
with the electricdipole moment of the electron.Because
this analysis requires more sophisticated
electrodynamics,it seemsbest to adopt the electron's
perspective,where the physical mechanism is
more transparent.
l3Morc precisely, Thomas precession subtracts 1 from the g factor. See R. R. Haar and
L. J. Curtis, Am. J.Phys., 55. 1044(1987).

...

274

Perturbation
Chapter6 Time-Independent
Theory
and hencethesequantities
are conserved
(Equation3.71).To put it anotherway,
the eigenstates
of Lz and 5- are not \"good\"statesto usein perturbationtheory,
but the eigenstates
of L2, S2,J2, and Jz ore.Now

J2 = (L + S) - (L + S) = L2+ 52+ 2L S,
\342\226\240

so

L-S=-(J2-L2-S2),

[6.63]

and thereforethe eigenvalues


of L S are
\342\226\240

r-

j[j(j+ D-Id +D-5(5+1)].


In thiscase,of course,s = 1/2.Meanwhile,the expectation
value of 1/r* (see
is
Problem6.35(c))

/(/ +1/2)(/+l)n-V

V\"3/

and we conclude
that
1

_l_
Fiso =(H>*
* so>

(fl2/2)L/(y+1)-/(/+1)-3/4]

Sireom2c2

it all in terms of
or,expressing

s0 =

/(/

+ 1/2)(/+1)/1\302\2753

\302\243,,:14

+ 1)-/(/+ 1)-3/4]
(^ 1,,^/(/+1/2)(/+1)
j
mc2 (

the totally different physicalmechanisms


It is remarkable,considering
are of the same
correction
and the spin-orbit
involved,that the relativistic
coupling
order(E2/mc2).Adding them together,
we get the complete
fine-structure
formula
(seeProblem6.17):
\302\243.

ls

.
=^(3--+^-)
1/2/
2mc2\\

[6.66)
J
L

l4Onceagain, the case/ = 0 is problematic, sincewe are ostensiblydividing by zero.On the


other hand, the numerator is alsozero,sincein this case =
so Equation 6.65is indeterminate.
On physical grounds there shouldn't be any spin-orbit couplingwhen I = 0.One way to resolve the
Darwin term(sec.for instance, G.K. Woodgate, Elementary
ambiguity is to introduce the so-called
Atomic Structure, 2nd ed.,Oxford (1983).
p. 63).Serendipitouslv,even though both the relativistic
correction (Equation 6.57)and the spin-orbit coupling (Equation 6.65)
arc questionablein the case
I = 0.their sum (Equation 6.66)is correct for all I (seeProblem 6.19).

j s.

Section6.3:TheFineStructureofHydrogen

275
= 7/2
= 5/2

n =4

= 3/2
= 1/2
n=

= 5/2

= 3/2

\342\226\240^

= 1/2
n=

^:

= 3/2

7=1/2

n=-\\

7= 1/2

/=0
(S)

=1

/=2

/=3

(P)

(D)

(F)

fine structure (notto scale).


FIGURE6.9: Energy levelsofhydrogen,
including

Combiningthiswith the Bohrformula,we obtainthe grand resultfor the energy


levelsof hydrogen,with fine structure included:

[6.67]
Finestructure breaksthe degeneracyin I (that is,for a given n, the different
allowedvaluesof I donotallcarry the sameenergy),but it stillpreserves
fororbitaland spinangular
in j (seeFigure6.9).The ^-component
eigenvalues
and ms) are no longer\"good\"
momentum
stationary
quantum
of stateswith different valuesof thesequantities;
the
statesare linearcombinations
\"good\"
quantum numbers are n, /, s, ,/, and trij.15

degeneracy

(;\302\253/

'-Towrite \\jm/) (for given

I and s) as a linear combination of


Clcbsch-Gordan
c
oefficients
(Equation 4.185).
appropriate

numbers\342\200\224the

we would use the


|/;;i/)|5//i.;)

276

Perturbation
Theory
Chapter6 Time-Independent

Problem6.16Evaluate the followingcommutators:


(a) [L S,L], (b) [L S,S],
(c) [L S,J], (d) [L S,L2],(e) [L S,S2],(f) [L S,J2].Hint:L and S satisfy
the fundamental commutation
relationsfor angular momentum (Equations4.99
and 4.134),
but they commutewith eachother.
\342\226\240

\342\200\242

\342\226\240

\342\200\242

\342\200\242

\342\200\242

*Problem6.17Derivethe fine structureformula (Equation6.66)from the relativistic correction


(Equation6.57)and the spin-orbit
coupling(Equation6.65).Hint:
and you'll
Note that j = I + 1/2;treat the plussignand the minus signseparately,
find that you get the samefinal answer eitherway.
* *Problem6.18The mostprominentfeature of the hydrogen spectrum
in the visible
n = 3to n = 2.Firstof all,
regionisthe redBalmerline,comingfrom the transition
the wavelength and frequency of thislineaccording
determine
to the Bohrtheory.
Finestructure splitsthislineintoseveralcloselyspacedlines;the questionis:How
how many sublevels
Hint:Firstdetermine
the
many, and what is theirspacing'?
n = 2 levelsplitsinto,and find E{f$ for eachof these,in eV.Then do the samefor
from n = 3
n = 3. Draw an energy leveldiagram showingallpossible
transitions
to n = 2.The energy released
+ the first
(in the form of a photon)is
(dueto fine structure) varying from
part beingcommonto allof them, and the
onetransition
to the next.Find
(in eV) for eachtransition.
Finally,convert
the spacing
lines(in
betweenadjacentspectral
to photonfrequency,and determine
the frequencyinterval betweeneachlineand the unperturbedline(which
but the frequency interval betweeneachlineand the
is,of course,unobservable),
next one.Your final answer shouldtake the form:\"TheredBalmerlinesplitsinto
(1)
(???)lines.In orderof increasing
frequency,they comefrom the transitions
=
=
=
=
The
to
to
j (???) j (???),(2) j (???) j (???),
frequency spacing
betweenline(1)and line(2)is (???)Hz,the spacingbetweenline(2)and line(3)
is (???)Hz, .\"
\342\200\224

(\302\2433

\302\2432)

A\302\243,

A\302\243

A\302\243

Hz)\342\200\224not

....

...

Problem6.19The exactfine-structure
formula for hydrogen(obtainedfrom the
Diracequation
to perturbation
without recourse
theory) is16
'

E\342\200\236j

= mc~

1
\\n

yr1/2
- (./+ 1/2)+ ^-+1/2)2-0,2/

Expand to ordera4 (notingthat a. <$c 1),and showthat you recoverEquation6.67.


Betheand Salpeter(footnote 10).
page 238.

Section6.4:TheZeemanEffect

277

6.4 THE ZEEMANEFFECT


When an atom is placedin a uniformexternal magneticfieldBext,the energy levels

isknown asthe Zeemaneffect.Fora singleelectron,


are shifted.
Thisphenomenon
the perturbation
is
[6.68]
H'z = -(fi,+ fis.) -Bext,
where

--S

fis = m

[6.69]

is the magneticdipolemoment associated


with electron
spin,and

fi, = --^L
2m

[6.70]

is the dipolemoment associated


with orbitalmotion.17
Thus

+ 2S).Bexl.
/^ = -^(L
2m

[6.71]

on the strength of the


The nature of the Zeeman splittingdependscritically

with the internalfield (Equation6.59)that givesrise


comparison
If
and H'z can
to spin-orbit
<$c Bint, then fine structure dominates,
coupling.
whereas if Bext^> B\\m, then the Zeeman effect
be treatedas a smallperturbation,
and fine structure becomes
the perturbation.
In the intermediate
zone,
dominates,
we needthe full machinery of degenerate
where the two fieldsare comparable,
the relevant portionof the
to diagonalize
perturbationtheory,and it is necessary
sectionswe shallexploreeachof these
Hamiltonian
\"by hand.\"In the following
regimesbriefly, for the caseof hydrogen.

external fieldin

\302\243cxl

Problem6.20 Use Equation6.59to estimatethe internal fieldin hydrogen,and


characterize
quantitatively a \"strong\"and \"weak\"Zeemanfield.
ZeemanEffect
6.4.1Weak-Field
dominates(Equation6.67);the \"good\"quantum
numbersare n, /, j, and nij (but not and /niV,
the presence
of spinand S are not separately
Infirst-order
orbit
conserved).18
perturbation
If

Bext <C Bjru, fine structure

/\302\253/

because\342\200\224in

coupling\342\200\224L

value
The gyromagnetic ratio for orbital motion is just the classical
is only for
\"extra\"
factor
of
2.
spin that there is an
In this problem we have a perturbation
(Zeeman splitting) piled on top of a perturbation (fine
this
structure). The \"good\" quantum numbers are those appropriate to the dominant perturbation\342\200\224in
casethe fine structure. The secondaryperturbation (Zeeman splitting) lifts the remaining degeneracyin
which plays here the role of the operator A in the theorem of Section
Technically. Jz does
not commute with H'y. but it does in the time average senseof Equation 6.73.
1

(q/lin)\342\200\224it

/;,

6.2.1.

278

Perturbation
Theory
Chapter6 Time-Independent

FIGURE6.10:In the presence


of spin-orbit
and
S
L
are
not
separatelyconserved;
they
coupling,
aboutthe fixedtotalangularmomentum,J.
precess

to the energy is
theory,the Zeemancorrection

=
4 = (nljmj\\H'z\\nljmj)

\342\200\224Bext

\342\200\242

(L + 2S).

[6.72]

we donot immediately
Now L + 2S = J + S.Unfortunately,
know the expectation
value of S. But we can figure it out, as follows:The total angular momentum
J = L + S is constant(Figure6.10);L and S precessrapidly aboutthis fixed
the (time)averagevalue of S is justits projection
vector.In particular,
alongJ:
Save =

^j^ J-

- S,so L2 = J1 + 52- 2J S, hence


S J = i(72+ 52 - L2)= [./(./+ 1)+ 5(5 + 1)-/(/+ 1)].
y

But L = J

\342\200\242

[6.73]

and

[6.74]

from which it followsthat


<L +

2S)=/(\\+

^)j\\

+ 1)+3/4+ ./(./+1)-/(/
(J). [6.75]
2./(7+ 1)

The term in squarebracketsis known as the Landeg-factor,gj.


We may as well choosethe <:-axis
to lie alongBcxl;then

_ fJ.BgjBcx[mj.
Ez =
l

\342\200\242

where

eh

[6.76]

^5 eV/T
liB= 2m = 5.788x 10-0
[6.77]
Bohrmagneton.The totalenergy is the sum of the fine-structure
is the so-called
part (Equation6.67)and the Zeemancontribution
(Equation6.76).For example,
\342\200\224

Section6.4:TheZeemanEffect
the groundstate

(\302\273

levels:

279

= I, = 0, j = 1/2,and thereforegj = 2) splitsinto two


I.

-13.6
eV(l+ a2/4)

with the plussignfor mj =

\302\261

[6.78]

(XBB^

1/2,and minus for nij =

plotted(asfunctionsof Bcx[)in Figure6.11.

\342\200\2241/2.

Theseenergiesare

the (eight)n = 2 states,\\2ljnij).


Findthe energy of each
*Problem6.21Consider
construct
a
and
state,under weak-fieldZeemansplitting,
diagram likeFigure6.11
show
how
the
as
Label
eachlineclearly,and
to
energiesevolve Bex[increases.
indicateits slope.

ZeemanEffect
6.4.2Strong-Field
If #ext ^>

B'mi, the

with Bex{in the z direction,


Zeemaneffectdominates;19
the

\"good\"
quantum numbersare now n, I, mi,and ms (but not j and mj

because\342\200\224in

of the external torque\342\200\224the totalangular momentum is notconserved,


the presence
is
whereas L- and S- are).The ZeemanHamiltonian
H'z= 2m

\342\200\224Bexl(Lz

+ 2Sz),

eV
-13.6(1+e^/4)

/77/

= -1/2

Weak-fieldZeeman splittingof the groundstate of hydrogen;the


6.11:
=
=

FIGURE

upperline(ntj
In this

1/2)has slope1,the lowerline(mj

regime the Zeeman effect is also known as the

\342\200\2241/2)

has slope

Paschen-Back
effect.

\342\200\2241.

280

Perturbation
Theory
Chapter6 Time-Independent
and the \"unperturbed\"energies
are
Enm,ms =

13.6eV
n-7

HBBexdmi+ 2m,).

[6.79]

But we can do better.


That'sthe answer,if we ignorefine structure completely.
Infirst-order
to theselevelsis
correction
perturbation
theory the fine-structure

4=

(nl mi ms\\(H'r+ J4)|/i/m, ms).

[6.80]

The relativistic
is the sameasbefore(Equation6.57);forthe spin-orbit
contribution
term (Equation6.61)we need

(S L) = (SX)(LX)+ (Sy)(Ly) + (Sz)(Ly)= h2mims


\342\200\242

[6.81]

of 5- and L-).Putting
(notethat (Sx) = (Sy) = (Lv) = <LV) = 0 for eigenstates
allthistogether(Problem6.22),we concludethat
,

E^=

...-,

13.6
..6eV

7 f
\\

,4\342\200\236

+ 1)-mimx
L/(/ + 1/2)(/+ 1)J
/(/

[6.82]

for I = 0; itscorrectvalue in this


(The term in squarebracketsis indeterminate
caseis
Problem6.24.)The toted energy is the sum of the Zeeman part
1\342\200\224see

(Equation6.82).
(Equation6.79)and the fine structure contribution

Problem6.22 Startingwith Equation6.80,and usingEquations6.57,6.61,6.64,


and 6.81,deriveEquation6.82.

* *Problem6.23 Consider
the (eight)n = 2 states,|2/m/m.v).Findthe energy of
eachstate,under strong-field
Zeemansplitting.
Expresseachanswer as the sum of
three terms:the Bohrenergy,the fine-structure
to or),and the Zeeman
(proportional
how
contribution
to /j.bBcx1).
If you ignorefine structure altogether,
(proportional
many

distinctlevelsare there,and what are their degeneracies?

Problem6.24 If / = 0, then / = s, mj = tuu and the \"good\"statesare the same


l
Determine
(\\n m.v)) for weak and strongfields.
Elz (from Equation6.72)and the
fine structure energies
(Equation6.67),and write down the generalresultfor the
/ = 0 Zeeman effect\342\200\224regardless of the strengthof the field.Showthat the strongfieldformula (Equation6.82)reproduces
thisresult,providedthat we interpret the
indeterminate
term in squarebracketsas 1.
\342\200\242

Section6.4:TheZeemanEffect

281

ZeemanEffect
6.4.3Intermediate-Field
In the intermediate
and we must treat the
regimeneitherH'z nor H'{% dominates,
two on an equalfooting,as perturbations
to the BohrHamiltonian
(Equation6.42):

H' = H'z+ H'is.

[6.83]

I'll confinemy attentionhereto the casen = 2, and useas the basisfor

by /, j, and my.20 Usingthe


perturbationtheory the statescharacterized
Clebsch-Gordan
coefficients
(Problem4.51or Table4.8)to express\\jnij) as a
linearcombination
of \\Imi)\\sms),we have:
degenerate

=0

^x

= \\{\\) =|00)|\302\261I).
-I = 100)11^),
-I
= 11
14^)
I

\342\200\224

3 3
to = IH)
I

^4

=1

=111)1**).
1

11^)= 11-l)|i=^),

l!i> =V273|10)|ii)+VT73|1l)|i^),
+ V273|l1)11^i),
*6 = lH> =-vT73|10)|H)
Tfc

^7^11^)= 71/311-1)1^)
+v^73|io>ii^>,

^ = li =^) = -72/311

i> + Vl73|10)|i
^-).
In this basisthe nonzeromatrix elementsof H{s are all on the diagonal,
and given by Equation6.66;H'zhas four off-diagonal
and the complete
elements,
is (seeProblem6.25):
matrix
\\
0
0
0
0
0
0
I 5y 0 0
0 5y + 0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0 y+2f} 0
0
0
0
0
0
0
0 Y-\\P
0
0
0
0
0
0
0
0
5y \\fl
0
0
0
0
0
0
Y + \\P
0
0
0
0
0
0
5y +
\\
J
\342\200\2241>!i

\342\200\224W

i\302\243

makesthe matrix elementsof H'z easier,but


-\"You can use /, m/. mx states if you
those of H{.s more difficult; the W matrix will be more complicated,but its eigenvalues (which are
independent of basis) are the same either way.
prefer\342\200\224this

282

Perturbation
Theory
Chapter6 Time-Independent
where
y

= (a/8)213.6
eV and

\302\243

= nBBexl.

are already displayedalongthe diagonal;


The first four eigenvalues
it remains
only
of the two 2x2 blocks.The characteristic
for the
to find the eigenvalues
equation
first

of theseis

k2

X(6y

-0)+Uy1

-l\302\261yp\\

= 0,

and the quadratic formula givesthe eigenvalues:

+ (P/2)
k\302\261=-3y

\302\261

y/V + Q/3)yP+

(\302\2432/4).

[6.84]

of the secondblockare the same,but with the signof fi reversed.


The eigenvalues
are listedin Table6.2,and plottedagainstBcx[in Figure6.12.
The eightenergies
In the zero-field
limit(ft = 0) they reduceto the fine-structure
values;for weak
fields(fi <$c y) they reproduce
what you got in Problem6.21;for strongfields
to five
(P ^5> y) we recoverthe resultsof Problem6.23(notethe convergence
in Problem6.23).
distinctenergy levels,at very high fields,as predicted

/\"8eext

FIGURE6.12: Zeeman splittingof the


and strongfieldregimes.
intermediate,

= 2 statesof hydrogen, in the weak,

Section6.5:HyperfineSplitting 283
TABLE6.2: Energy levelsfor the n =2 statesof
hydrogen,with fine structureand Zeemansplitting.
= \302\2432-5y+jS
= E~2-5y-p
= E2-y+2/3
=
e4
E2-y-2p
= E2 3y+f}/2
+ V4y2 + (2/3)yff + fi2/4
H = E2 3y+p/2 V4y2 + (2/3)yff + ff2/4
= E2 3y- p/2+ V4y2 (2/3)yfi+ fi2/4
+
*8 = E2 3y- ^/2 V4y2
\342\202\254l

\342\202\2542

\342\202\2543

\342\202\2545

\342\202\2547

(2/3)y\302\243

Problem6.25Work out the matrix elementsof /f^


W-matrix given in the text, for n = 2.

\302\2432/4

an^

#iv

anc*

constructthe

* * *Problem6.26 Analyze the Zeemaneffectfor the n = 3 statesof hydrogen,in the


fieldregimes.
Constructa tableof energies
weak, strong,and intermediate
to Table6.2),plotthem as functionsof the external field(asin Figure6.12),
and checkthat the intermediate-field
resultsreduceproperlyin the two limiting
(analogous

cases.

6.5 HYPERFINESPLITTING
a magnetic
The protonitselfconstitutes
dipole,thoughits dipolemoment is much

smallerthan the electron'sbecauseof the massin the denominator


(Equation6.60):

[6.85]
made up of three quarks,and itsgyromagnetic
structure,
(Theprotonis a composite

ratiois not as simpleas the electron's\342\200\224hence the explicitg-factor(gp),whose


value is 5.59,
asopposedto 2.00for the electron.)
measured
Accordingto classical
a dipole/i setsup a magneticfield-1
electrodynamics,
B=

2'ifyou are unfamiliar

the

dipole as a spinning

goesto

infinity

(with

ft

, +. 2/zo
~.~
r,,,
r)r
[3(^
-fi]
4tt/

with

Mo

\342\200\242

the delta function

^, .

\342\200\224-fi8\\r).

term in Equation

6.86,you can derive it by

[6.86]
treating

charged sphericalshell, in the limit as the radius goesto zero and the charge
held constant). SeeD. J. Griffiths. Am. J. Phys.. 50.698(1982).

284

Perturbation
Theory
Chapter6 Time-Independent

Sothe Hamiltonian
of the electron,
in the magneticfielddueto the proton's
dipolemoment,is (Equation6.58)
magnetic

IJ-ogpe2[3(S/;r)(Se=r) Sp Se] h Hogpe2


nhi- =
5>p
\342\200\242

\342\226\240

\342\200\236,

\342\200\242

\342\200\242

r-

5>t-d

,(r).

[6.87]

3mpme
Accordingto perturbationtheory, the first-ordercorrectionto the energy
value of the perturbingHamiltonian:
(Equation6.9)is the expectation
67tmpme

MQgpg2

/3(Sj, r)(Se r) Sp Se
\342\200\242

\342\200\242

\342\226\240

r3

M~S7tmpme\\

\\

[6.88]

f*Q8Pe2lo v..rm|2
3mpme
In the groundstate(orany otherstatefor which / = 0) the wave functionis
and the first expectation
value vanishes(seeProblem6.27).
symmetrical,
= l/ina3),so
from Equation4.80we find that 1^100(0)12
Meanwhile,
,

\302\253

spherically

JMpf_{S sy
37rmpmea*

E,

[6g9]

in the groundstate.Thisis calledspin-spin


coupling,becauseit

involvesthe dot
which involvesS L).
productof two spins(contrast
spin-orbit
coupling,
In the presenceof spin-spin
coupling,the individualspinangular momenta
of the totalspin,
are no longerconserved;
the \"good\"
statesare eigenvectors
\342\200\242

S = St> + SP.
As

[6.90]

before,we squarethisoutto get


S\342\200\236-S,

i(S2-S2-S2).

[6.91]

But the electronand protonboth have spin 1/2,so S2 = S2 = (3/4)/?2.In the


the totalspinis 1,and henceS1= 2h2;in the singlet
tripletstate(spins\"parallel\")
statethe totalspinis 0, and S2= 0. Thus
i

Eur
M

\342\200\224

Wj4

+ 1/4. (triplet):

Im^y-a* -3/4. (singlet).

breaksthe spindegeneracy
of the groundstate,liftingthe
Spin-spin
coupling
and depressing
the singlet(seeFigure6.13).The energy gap
tripletconfiguration

is evidently

AE

4gph4 . = 5.88x 10\"6eV.


,K/?, ,
ipm]c

3m\342\200\236m-c-cr

[6.93]

Section6.5:HyperfineSplitting 285
Triplet
i

Unperturbed
AE
\\
\\
\\
\\
\\
\\

Singlet

'

in the groundstateof hydrogen.


FIGURE6.13:Hyperfinesplitting

The frequency of the photonemittedin a transition


from the tripletto the singlet

stateis

A\302\243
\342\200\224-

= 1420MHz.

[6.94]

= 21cm, which fallsin the microwave


lineisamongthe mostpervasiveand ubiquitous
region.Thisfamous21-centimeter
forms of radiationin the universe.
and the corresponding
wavelength is c/v

Problem6.27 Let a and b be two constantvectors.Showthat

(a r)(b - r) sm0d0d<$> =
\342\200\242

is overthe usual range:0 < #


(the integration

to demonstrate
that

for stateswith /

(a

\342\200\242

b)

[6.95]

< tt, 0 < 0 < 2tt).Usethisresult

'3(S\342\200\236.r)(Se-r)-S\342\200\236-Sc

,-3

4tt
\342\200\224

= 0.

= 0.Hint:r = sin#cos0f+ sini9sin0,/


+ cosQk.

of the hydrogen formula, determine


Problem6.28 By appropriatemodification
the hyperfine splittingin the groundstateof (a) muonichydrogen(in which a
but 207timesthe
chargeand ^-factoras the electron,
for the electron),(b) positronium(in which a positron\342\200\224same massand
^-factoras the electron,but oppositecharge\342\200\224substitutes for the proton),and
(c)muonium(in which an anti-muon\342\200\224same massand g-factoras a muon,but
for the proton).Hint:Don'tforgetto usethe reduced
charge\342\200\224substitutes
opposite
the \"Bohrradius\"of theseexotic\"atoms.\"
mass(Problem5.1)in calculating
the answer you get for positronium
(4.82x 10-4eV) is quitefar from
Incidentally,
is due to pair
the experimental
value (8.41x 10~4eV);the largediscrepancy
-^
an extra (3/4)A\302\243\\ and doesnot
annihilation
(e+ + e~
y + y), which contributes
occur(of course)in ordinary hydrogen,muonichydrogen,or muonium.
muon\342\200\224same
mass\342\200\224substitutes

286

Perturbation
Chapter6 Time-Independent
Theory

FURTHERPROBLEMSFORCHAPTER6
to the groundstateenergy of hydrogendue
Problem6.29 Estimatethe correction
to the finite sizeof the nucleus.
Treat the protonas a uniformly chargedspherical
insidethe shellisconstant:
shellof radiusb, sothe potential
energy of an electron
is
this isn'tvery realistic,but it the simplestmodel,and it will
give us the right orderof magnitude.
Expandyour resultin powersof the small
parameter(b/a),where a is the Bohrradius,and keeponly the leadingterm, so
\342\200\224e1/{Aneob)\\

your final answer takesthe form

AE
\342\200\224~

= A(b/a)\".

Your business
is to determinethe constantA and the powern. Finally,put in
b % 10-15
m (roughly the radiusof the proton)and work out the actual number.
with fine structure and hyperfine structure?
How doesit compare

Problem6.30Considerthe isotropicthree-dimensional
harmonic oscillator
(Problem4.38).Discussthe effect(in first order)of the perturbation

H' = Xx2yz
(forsomeconstant
X) on
(a) the groundstate;
(b) the (triply

degenerate)first excitedstate.Hint: Use the answers to

2.12and 3.33.
Problems

* * *Problem6.31Van derWaalsinteraction.
R apart.
Consider
two atomsa distance
Becausethey are electrically
neutral you might suppose
there would be no force
there is in fact a weak attraction.
betweenthem, but if they are polarizable
To
modelthissystem,pictureeachatom as an electron(massm, charge e) attached
k) to the nucleus
by a spring(springconstant
(charge+e),as in Figure6.14.We'll
The Hamiltonian
assumethe nucleiare heavy, and essentially
motionless.
for the
systemis
unperturbed
\342\200\224

w\302\260

*1

i\"'+ ^v' + ipi+ ^x2

atoms(Problem6.31).
FIGURE6.14: Two nearbypolarizable

[6-961

FurtherProblems
forChapter6

287

The Coulombinteraction
between the atomsis

H', =

e
R-X\\

(e~

47T\342\202\2540\\R

(a)

e~

R+X2

e~

\\

R-X\\+X2/

[6.97]

ExplainEquation6.97.Assumingthat |,Y||and |.\\\"2| are bothmuch lessthan


R, show that

H' ^ -

'

[6.98]

\342\200\236V

(b) Showthat the totalHamiltonian


(Equation6.96plusEquation6.98)separates

intotwo harmonicoscillator
Hamiltonians:
H=

2.1(,

_\302\2431_\\

.)*?
'

+ r^-P+ ^U+
2 \\ 2^c0/?3
2m

[6.99]

under the change


t>v of variables
,\342\226\240*\342\226\240+

\342\200\224pUi

V2

which entailsp+ =

\302\261.v?),

\342\200\224p(pi

V2

i /??).

[6.100]

is evidently
(c) The groundstateenergy for thisHamiltonian
\302\243

= -n(co++ o>_), where a>+ = J


2

[6.101]

Without the Coulombinteraction


it wouldhave beenEq = /?a>o, where a>o =
show that
y/k/m.Assumingthat k 3> (e2/27teoR:i),
AV

(d)

\302\243

\302\2430

1-^

\\7T\342\200\224)

-n-

[6-102]

There is an attractive potential


betweenthe atoms,proportional
Conclusion:
Thisis the van der Waals
to the inversesixth powerof their separation.
interactionbetweentwo neutral atoms.
Now do the samecalculation
usingsecond-order
perturbation
theory.Hint:
The unperturbedstatesare of the form ^,,,Ui)^,,,(ai), where 1/0,(.1:)
is a
oscillator
wave functionwith massm and springconstant
k; AV
one-particle
to the groundstateenergy,for the perturbation
isthe second-order
correction
correction
is zero).
in Equation6.98(noticethat the first-order

* *Problem
6.32 Supposethe HamiltonianH, for a particularquantum system,is
a function of someparameterX; let En{X) and 1/0,(^.) be the eigenvalues
and

288

Perturbation
Theory
Chapter6 Time-Independent
of H(k).The Feynman-Hellmann
theorem22
statesthat
eigenfunctions

iH*\"1?1*1)

[6-1031

are
eitherthat En is nondegenerate, degenerate\342\200\224that the
(assuming
the \"good\"
linearcombinations
of the degenerate
eigenfunctions).
Hint:UseEquation6.9.
theorem.
(a) Provethe Feynman-Hellmann
harmonicoscillator,
(i) usingk = co (this
(b) Apply it to the one-dimensional
value of V), (ii)usingk = h (thisyields
yieldsa formula for the expectation
(T)),and (iii)usingk = m (thisyieldsa relationbetween {T) and
Compareyour answers to Problem2.12,and the virial theorempredictions
or\342\200\224if

i//\342\200\236's

(V'\302\273.

(Problem3.31).

* *Problem
6.33 The Feynman-Hellmann
theorem(Problem6.32)can be usedto
determine
the expectation
valuesof 1//-and 1//-2for hydrogen.23
The effective
for the radial wave functionsis (Equation4.53)
Hamiltonian
h1 d1 h2 /(/+1) e2 1
2m drl 2m r2
Aticq r
and the eigenvalues
in terms of /)24 are (Equation
4.70)
(expressed
E\342\200\236

me4

/+l)2'

+
32^2602/?2(./max

Use k = e in the Feynman-Hellmann


theoremto obtain(1//-).Checkyour
resultagainstEquation6.55.
(b) Usek = 1to obtain(1/r2).Checkyour answer with Equation6.56.
(a)

* * *Problem
6.34 ProveKramers'relation:25

- (25+ l)a(rx-1)+ -U21


= 0,
+ 1)2- s2]a2(rs-2)
'~{rs)
4
n1
01

\"Feynman obtained Equation

6.103while

working

on his undergraduate

[6.104]
thesis at MIT

Hcllmann'swork was publishedfour years earlier in


(R. P. Feynman. Phys. Rev. 56.340.1939);

an

obscureRussian journal.
23C.Sanchezdel Rio.Am. J. Phys. 50.556(1982);
H.S.Valk. Am. J.Phys. 54, 921(1986).
In part (b) we treat I as a continuous variable: n becomes
a function of I, accordingto
Equation 4.67,becausejmax, which must be an integer, is fixed. To avoid confusion, 1 have eliminated
n, to reveal the dependenceon I explicitly.
25This is also known as the (second)Pasternack
relation.SeeH. Bcker,Am. J.Phys. 65, 1118
For a proof basedon the Feynman-Hellmanntheorem (Problem 6.32).
seeS.Balasubramanian,
(1997).
Am.

J. Phys. 68.959(2000).

Further Problems
forChapter6

289

which relatesthe expectation


valuesof r to three different powers(s, s 1,and
s 2), for an electronin the state1/0,/,,,of hydrogen.Hint:Rewrite the radial
equation(Equation4.53)in the form
\342\200\224

\342\200\224

11

= 7(/ + 1)

r-

ar

n-a- u.

useit to expressf(urxu\dr")in terms of (rv), (r* '),and (rv 2). Then use
integrationby parts to reducethe secondderivative.Show that f{ursu')dr =
and J{u'rsu')dr= -[2/(5+ l)]f(u\"rx+lu')dr.
Take it from
-(5/2)(/-^1),
there.
and

Problem6.35
relation(Equation6.104)
(a) Plugs = 0, s = 1,.9 = 2, and jr = 3 intoKramers'
toobtainformulasfor (r-1),(r),(;-2),and (r3).Notethat you couldcontinue
to find any positivepower.
indefinitely,
however, you hit a snag.Put in $ = 1, and show
(b) In the otherdirection,
that all you get is a relation
between(r-2) and (r-3).
(c) But if you can get {r~2)by someothermeans,you can apply the Kramers'
relationtoobtainthe restof the negativepowers.UseEquation6.56(which is
derivedin Problem6.33)to determine
(/--3),and checkyour answer against
\342\200\224

Equation6.64.

* * *Problem6.36When an atom is placedin a uniform external electricfieldEcxl,


the energy levelsare
known as the Starkeffect(it is the
phenomenon
electrical
analogto the Zeemaneffect).In thisproblemwe analyze the Stark effect
=
for the n
Let the fieldpointin the z direction,
1 and n = 2 statesof hydrogen.
so the potential
is
energy of the electron
shifted\342\200\224a

H's= eEexlz =

<?\302\243\"cxt>*cos0.

Treat thisas a perturbationon the BohrHarailtonian(Equation6.42).(Spinis

so ignoreit, and neglectthe fine structure.)


irrelevant to thisproblem,
(a) Show that the

in
groundstateenergy is not affectedby thisperturbation,

order.
The first excitedstateis 4-folddegenerate:
tJ/iqq, ^21i> ^210.
^21-1-Using
first-order
determine
t
he
to the
c
orrections
degenerate
perturbationtheory,
energy.Intohow many levelsdoes split?
What are the \"good\"
wave functionsfor part (b)?Findthe expectation
value
of the electricdipolemoment (p^ = er) in eachof these\"good\"states.
first

(b)

\302\2432

(c)

\342\200\224

290

Perturbation
Chapter6 Time-Independent
Theory
Noticethat the resultsare independent
of the appliedfield\342\200\224evidently

its first excitedstatecan carry a permanentelectricdipolemoment.


Hint:There are a lotof integralsin thisproblem,but almostallof them are
zero.Sostudy eachonecarefully,beforeyou do any calculations:
If the integral
there'snot much pointin doingthe r and 9 integrals!
Partialanswer:
vanishes,
=
=
all otherelements
are zero.
W13
W31
hydrogen

in

\302\242

\342\200\2243eaEC\\[\\

* * *Problem
6.37 Considerthe Stark effect(Problem6.36)for the n = 3 statesof
states,1^3/,,, (neglecting
hydrogen.There are initiallynine degenerate
spin,as
before),and we turn on an electricfieldin the z direction.
the perturbingHamiltonian.
Partial
(a) Constructthe 9 x 9 matrix representing

-3^,

= -3y[6a,<310|z|320)
=
answer:<300|z|310)

(31\302\261l|z|32\302\261l>

-(9/2)\302\253.

(b)

Findthe eigenvalues,
and their degeneracies.

of the photonemitted
Problem6.38 Calculatethe wavelength, in centimeters,
under a hyperfine transition
in the groundstate (n = 1)of deuterium.Deuterium
is \"heavy\"hydrogen,with an extra neutron in the nucleus;the protonand neutron
bindtogetherto form a deuteron,with spin1 and magneticmoment

gde*

\342\226\240

2m,i
the deuterong-factoris 1.71.

* * *Problem6.39 In a crystal,the electricfieldof neighboring


ionsperturbsthe energy
levelsof an atom.As a crudemodel,imaginethat a hydrogenatom is surrounded
as shown in Figure6.15.
(Spinis irrelevant to this
by three pairsof pointcharges,
so ignoreit.)
problem,
that r <$Cd\\, r
di, and r <& dj,,show that
(a) Assuming

<\302\243

H' =

V0

3(\302\243i.v2

+ fry1 + foz1)

(\302\2431

+ #> + fo)r2,

where
Pi =

~^\342\200\224%.

and

Vb

= 2(jM?+/M? + fod\\).

4n\342\202\254odf

Findthe lowest-order
correction
to the groundstateenergy.
the first-ordercorrections
to the energy of the first excitedstates
(c) Calculate
=
(/?
2).Into how many levelsdoesthisfour-folddegenerate
system split,
=
=
(i) in the case of cubicsymmetry,/J]
fii
^3; (ii) in the caseof
=
tetragonalsymmetry,fi\\ fin ^ #3;(iii)in the generalcaseof orthorhombicsymmetry(allthree different)?

(b)

Further Problems
for Chapter6

FIGURE6.15:Hydrogenatom surrounded
by
Problem6.39.
crystallattice);

291

sixpointcharges(crudemodelfor a

* * *Problem6.40 Sometimes
it is possible
to solveEquation6.10directly,without
wave functions(Equation6.11).
having to expandi/r,) in terms of the unperturbed
Hereare two particularly niceexamples.
(a)

Starkeffectin the groundstateof hydrogen.


to the groundstateof hydrogenin the
(i) Find the first-ordercorrection
of a uniform external electricfieldEcn (the Stark
presence
Problem6.36).Hint:Try a solutionof the form
effect\342\200\224see

(A

+ Br + Cr2)e~r/acos9;

your problem is to find the

constantsA, B,

and

that

solve

Equation6.10.
correctionto the
the second-order
(ii) Use Equation6.14to determine
is zero,as you found in
groundstateenergy (the first-ordercorrection
Problem6.36(a)).
Answer: ~m(3a~eEeKl/2h)~.
(b) If the protonhad an electricdipolemoment p, the potential
energy of the
electronin hydrogenwouldbe perturbedin the amount
= epcos6

H'

(i)

Ajreor

SolveEquation6.10for the first-ordercorrection


to the groundstate
wave

function.

292

Perturbation
Theory
Chapter6 Time-Independent
(ii) Showthat the totalelectric
dipolemoment of the atom is (surprisingly)

zero,to thisorder,

(iii)

Use Equation6.14to determinethe second-order


correctionto the
correction?
groundstateenergy.What is the first-order

CHAPTER 7

THE VARIATIONALPRINCIPLE

7.1THEORY
the groundstateenergy,
for a system described
Suppose
you want to calculate
by the HamiltonianH, but you are unableto solvethe (time-independent)
The variationalprinciple
will get you an upperboundfor
Schrodinger
equation.
which is sometimes
allyou need,and often,if you'recleveraboutit, very
closeto the exactvalue.Here'show it works:Pick any normalized
function\\j/
whatsoever;I claimthat
\302\243\"gs,

\302\243gs,

\302\243gs

< mm*)= (H).

[7.1]

That is,the expectation


value of H, in the (presumably
statex}/ iscertain
incorrect)
the groundstateenergy.Of course,if \\j/ just happensto be one
to overestimate
of the excitedstates,then obviously{H) exceeds the pointis that the same
\302\243gs;

holdsfor any whatsoever.


of H form a complete
set,we can
Proof:Sincethe (unknown) eigenfunctions
of them:'
express\\J/ as a linearcombination
\\f/

\\ff

'ifthe Hamiltonian

as well as a sum. but the

= ^2 ^\"'
c\302\273

with

//

\\j/\342\200\236

E\342\200\236

admits scattering states,as well as bound

argument

\\j/\342\200\236.

states,then we'llneed an integral

is unchanged.

293

294

Chapter7 The VariationalPrinciple

Since\\j/ is normalized,
1=

(ifr\\ilr)

= [Y^cm\\lf,n Y^c'^n) = YlYlc\302\273ic\"W\">W\"S) = Yl lc\"l2'


m

HI

have beenorthonormalized: |i/0i)


the eigenfunctions
themselves
(assuming
(i/o\342\200\236

Meanwhile,
5.,,,,,).

hi

\302\2731

But the groundstateenergy is,by definition,


the smallesteigenvalue,
so
and hence

(//)>\302\243gs\302\243>n|2

<
\302\243gs

E\342\200\236,

\302\243gs.

which is what we were trying to prove.

Example7.1 Supposewe want to find the groundstateenergy for the oneharmonicoscillator:


dimensional
H=

tr

d~

2m dx2
\342\226\240=

77

H\342\200\224mco~x'

Of course,we already know the exactanswer, in thiscase(Equation2.61): =


(1/2)/Jco;but thismakes it a goodtestof the method.We might pickas our\"trial\"
\302\243gs

wave function the Gaussian,

xj/(x) = Ae-hx\\

where b

[7.2]

is a constant,and A is determined
by normalization:

l-IAPjT.-^-^IAP/J^A-d)\"4.[7.3,
Now
where, in

(H) = (T) + (V).

thiscase,

[7.4]

Section7.1:Theory

295

and

/m
{V) =

2,Al2

j_j
f\342\204\242

-2mco\\A\\

, = tna>2
*dx

-2/7.Y- 2

so

mco~

fl~b

Accordingto Equation7.1,thisexceeds
bound,let'sminimize (H):

\302\243gs

h~

\342\200\224

mu>-

for any b: to get the tightest


ma)

Putting thisbackinto (H), we find


(\302\273>min

[7-7]

lho>.

In thiscasewe hit the groundstateenergy right on the nose\342\200\224because (obviously)


I \"just happened\"to pick a trial functionwith preciselythe form of the actual
is very easy to work with, so it's a
groundstate(Equation2.59).But the gaussian
to the true groundstate.
populartrial function,even when it bearslittleresemblance

Example7.2 Supposewe'relookingfor the groundstateenergy of the deltafunction potential:


H=

d1
-2mh1ax\342\200\224

\342\200\224^-a8(x).

Again, we already know the exactanswer (Equation2.129): =


/2/?-.As
trial function(Equation7.2).We've already determined
before,we'llusea gaussian
the normalization,
and calculated
(T):all we needis
\342\200\224ma~

\302\2432S

{V) = -a\\A\\2

~bx

J-OG

8{x)dx=

-aj

\342\200\224

Tt

Evidently

and we know that

thisexceeds for allb. Minimizingit,


\302\243gs

d ;m = ^2
db (H) 2m

\342\200\224

'

\302\253

J2icb

= n0 => b, =

2//7\302\2752

nti4

;\342\200\224.

296

Chapter7 The VariationalPrinciple

So
(#)min =
which is indeedsomewhathigherthan

\302\243\342\200\236s,

ry<
jttr

[7

sincen > 2.

I saidyou can useany (normalized)


trial function\\(/ whatsoever,and this
true in a sense.However,for discontinuous
functionsit takessomefancy footwc
to assigna sensiblemeaning to the secondderivative (which you need,in order
calculate(T)).Continuous
functionswith kinks in them are fair game,howevi
as longas you are careful;the next exampleshowshow to handlethem.-

Example7.3 Find an upper boundon the groundstateenergy of the on


dimensional
infinite squarewell (Equation2.19),usingthe \"triangular\"trial wa
function(Figure7.1):3

Ax,

A(a--.v).

0.
where A
1

if
if

0 < x < a/2.

a/2 < x < a.

[7.1i

otherwise,

is determined
by normalization:

=|A|2

./0

x2dx+l (a
Jail

V(x)

\342\200\224

[7.i:

x)2dx

\"

FIGURE7.1: Triangulartrial wave function for the infinite square well (Equa

tion7.10).

Mci,Int. J.Edttc. Sci.Tech.30.513(1999


is no point in trying a function (such as the gaussian)that \"leaks\" outside the well
becauseyou'll get (V) = oo.and Equation 7.1tells you nothing.

-Fora collectionof interesting examplesseeW.

\342\200\242^Therc

N.

Section7.1:Theory
dvj//dx

297

a/2

-AFIGURE7.2: Derivativeof the wave function in Figure7.1.


In

thiscase

df

if 0 < ;c < a/2,


if a/2 < x < a,
otherwise,

A,
\342\200\224A.

~dx

0,

in Figure7.2.Now, the derivative of a stepfunctionis a deltafunction


asindicated
(seeProblem2.24(b)):

d2f = A8(x) 2A8(x a + A8(x a),


12)
'dxT
and

[7.12]

hence
(H) =

h2A

2m
h2A

2m

{a/D+ (a)]=

[if; (0)-2xff

Theexactgroundstateenergy is
works (12> 7T2).

f[8(x) 28(x-o/2)+8(x aM(x)dx


yjr

2m

I2h2
2ma-

[7.13]

= Ti-tr1/2ma2
(Equation2.27),sothe theorem
\">

\302\243gs

h2A2a

\302\273.2

is extraordinarilypowerful,and embarrassingly
The variational principle
easy

to use.What a physicalchemistdoesto find the groundstateenergy of some


molecule
is write down a trial wave functionwith a largenumber of
complicated
calculate(H), and tweak the parametersto get the lowest
parameters,
adjustable
to the true wave function,you
possiblevalue.Even if \\j/ has littleresemblance
accuratevaluesfor
oftenget miraculously
Naturally, if you have someway
of guessinga realistic\\f/, so much the better.The only troublewith the method
\302\243gs.

Chapter7 The VariationalPrinciple

is that you never know for surehow closeyou are to the


you can be
certainof is that you'vegotan upperbound.4Moreover,as it stands,the technique
appliesonlyto the groundstate(see,however, Problem7.4).5
target\342\200\224all

*Problem7.1Use a gaussiantrial function(Equation7.2)to obtainthe lowest


V(x) =
upperboundyou can on the groundstateenergy of (a) the linearpotential:
or|.v|;(b) the quartic potential:V(x) = otx4.
* *Problem7.2 Findthe bestboundon
for the one-dimensional
harmonic
usinga trial wave functionof the form
\302\243gs

oscillator

where A

and b is an adjustable
is determinedby normalization
parameter.

Problem7.3 Findthe bestboundon

for the delta-function


potentialV(x)
usinga triangular trial function(Equation7.10,onlycenteredat the
Thistime a is an adjustable
parameter.
\302\243gs

\342\200\224ct8{x),

origin).

Problem7.4
Provethe followingcorollaryto the variational principle:
If (i/M^gs) = 0,
then (H) >
where
is the energy of the first excitedstate.
to the exactground
Thus,if we can find a trial functionthat is orthogonal
state,we can get an upperboundon the firstexcitedstate.In general,it's
we don't
difficultto be surethat \\j/ is orthogonalto ^gs,since(presumably)
know the latter.However,if the potentialV(x) is an even function of x,
then the groundstateis likewiseeven,and henceany odd trial functionwill
meet the condition
for the corollary.
automatically
harmonic
stateof the one-dimensional
(b) Findthe bestboundon the first excited
(a)

\302\243yc,

\302\243fc

oscillator
usingthe trial function

\\f/(x)

= Axe~bx\\

4In practice this isn't much of a limitation, and there are sometimesways of estimating the
for
accuracy.The ground state helium has been calculated to many significant digits in this
A
Drake
et
A
or
Vladimir
I.
66.
G.
W.
P
hvs.
Rev.
0
54501
Phvs.
Rev.
65.
Korobov,
(2002)
example

024501(2002).
\342\200\242'For

energies

way\342\200\224see

a!..

a systematic extension of

sec.tor example.Linus Pauling

the

and

variational principleto the calculation of excited


state
to
With
Introduction
Mechanics,
Wilson,
Quantum

E. Bright

Applications to Chemistry. McGraw-Hill.New York

Section26.
(1935.
paperbackedition 1985).

Section7.2:The GroundState of Helium

299

Problem7.5
to provethat first-ordernon-degenerate
(a) Usethe variational principle
the
(orat any rate never underestimates)
theory always overestimates
groundstateenergy.
correction
to the
(b) In view of (a), you would expectthat the second-order
groundstateis always negative.Confirmthat this is indeedthe case,by
perturbation

examiningEquation6.15.

7.2 THE GROUNDSTATEOF HELIUM


in orbitaround a nucleus
The heliumatom (Figure7.3)consistsof two electrons

two protons(alsosomeneutrons,
which are irrelevant to our purpose).
containing
The Hamiltonian
forthissystem(ignoringfine structureand smallercorrections)
is:

H=

_\302\273l(vf

2w

i-r-!-;|.
i)

+
V?)-^-(l
\\n

+ -

47T6Q

t\"2

|l*l

\342\200\224

T2|

[7.14]

Our problemis to calculate


the groundstateenergy,
Physically,this
the amount of energy it would take to stripoffboth electrons.
(Given
\302\243gs.

represents

\302\243gs

is easy to figure out the \"ionization


energy\"requiredto removea single
Problem7.6.)The groundstateenergy of heliumhas beenmeasured
to
in the laboratory:
great precision

it

electron\342\200\224see

Egs =

eV (experimental).
-78.975

[7.15]

Thisis the number we wouldliketo reproduce


theoretically.
It is curious
that sucha simpleand important problemhas no known exact
solution.6
The troublecomesfrom the electron-electron
repulsion,
v^

+2e*
helium,

= e2
-a\342\200\224;

r-

[7-16]

FIGURE7.3: The heliumatom.

\"There do exist exactly solublethree-body problemswith many of the qualitative features of


but using non-coulombic potentials (seeProblem 7.17).

300

Chapter7 The VariationalPrinciple

H splitsintotwo independent
If we ignorethisterm altogether,
hydrogen Hamiltonians(only with a nuclearchargeof 2e,insteadof <?); the exactsolutionis just
the productof hydrogenic
wave functions:

[?]7]
TMri,r2) = ^iooOtiWioote)= Tier^0-1+^
eV (Equation5.31).7
and the energy is 8E| =
Thisis a long way from
eV, but it'sa start.
To get a betterapproximation
for Egs we'llapply the variational principle,
choicebecause
using\\(/q asthe trial wave function.Thisis a particularlyconvenient
of mostof the Hamiltonian:
it's an eigenfunction
+ Vee)x!f0.
[7.18]
Hiiro =
\342\200\224109

\342\200\22479

(8\302\243|

Thus

[7-19]

(ff)=8\302\243,+(Vee).

where8

e2

8 \\2

f_4(''i+'-)/u,

\\4^6o/ W'3/ J |n -r2|


I'll do the r2 integralfirst;for thispuiposen is fixed,and we may as well orient
the r2 coordinate
system so that the polaraxisliesalongn (seeFigure7.4).By
the law of cosines,

|n - r2| = yj'j + r2 - 2ri/-2cos02.

[7.21]

and hence

h= J/

d3n= /

lri~r2l

rfsinfo/W/fr./ty,.[7.22]
\"

y/rj + rl-ZnncosOi

The 02integralis trivial (2jt);the #2 integralis

fn
/

'
-

sin07
,

=clQ1

Jr2 + r2

2r\\n cos#2

/-|/-2

Jrj + tj 2rincos02

7Here is the ordinary Bohr radius and

\342\200\224

eV is the nth Bohr energy:recall


for a nucleus with atomic number Z.
The spin
and a
(Problem
with
7.17
will
be
associated
configuration
Equation
antisymmetric (the singlet).
8 You can.if
as first-order perturbation theory, with
like,
7.20
Vee.
you
interpret Equation
However.I regard this as a misuseof the method, sincethe perturbation is comparable in sizeto the
unperturbed potential. I prefer, therefore, to think of it as a variational calculation, in which we are
looking for an upper bound on
\302\253

that

En

\342\200\22413.6/ir

\342\200\224>

-\302\273\342\226\240

E\342\200\236

Z-\302\243\342\200\236

\302\253/Z

4.16).
H'

\302\243es.

\342\200\224

Section7.2:The GroundState of Helium

301

Z2n
Kr

f\\

^1

M A

/^-

--,^

y2

<t>2

x2

ofcoordinates
for the r2-integral
FIGURE7.4: Choice
(Equation7.20).

' r\\ + r\\ + 2rin

>V\"2

,
\\
[('\"1+
/\">)

xi

\342\200\224

/*1

\342\200\224

\342\200\224

y/rf

>2 ]

+ r\\

2r\\

\\

if'\"2<
= {I 2/''''
~,
-c

rl\302\273

[7.23]

Thus
/?

= 4tt

(i f'

ita3 |\\

re-AnJar2dn\\
^-4r2/i7/-22^r2+

/.

2n\\

[7.24]

,-4r,/\302\253l

It followsthat (Vee) is equalto

<r4riAVisin0i
dr\\dQ\\d<$>\\,
The angular integrals
are easy (4tt),and the r\\ integralbecomes

,-8r/<i rfr = 5<r

/;[--*'-(-\302\245)
Finally,then,

(y-> =
and

therefore

(H) =

( e1

\\

128

4^(4^)=-2\302\243l=34eV'

-109eV + 34 eV = -75eV.

Not bad (remember,


the experimental
value is

\342\200\22479

[7-25]

[7.26]

eV).But we can do better.

302

Chapter? The VariationalPrinciple


needto think up a morerealistictrial functionthan (which treatsthe
asthough they didnotinteract at all).Rather than completely
two electrons
ignoring
e
achelectron
the influenceof the otherelectron,
on
the
letus say that,
average,
a
so that
cloud
of
which
shields
the nucleus,
represents
negativecharge
partially
the otherelectronactually seesan effective nuclearcharge(Z) that is somewhat
lessthan 2.Thissuggeststhat we usea trial functionof the form
We

1/\302\276

Z3

iMri.r?)= \342\200\224-e-Z{n+ri)/a.
na5

[7.27]

We'lltreat Z asa variational


H. (Please
parameter,
pickingthe value that minimizes
notethat in the variational methodwe never touchthe Hamiltonian
Hamiltonian
for helium is,and remains,
Equation7.14.But it'sfine to think about
the Hamiltonian
as a way of motivatingthe choiceof the trialwave
approximating
function.
Thiswave functionis an eigenstate
of the \"unperturbed\"Hamiltonian
electronrepulsion),
onlywith Z, insteadof 2, in the Coulombterms.With this
in mind,we rewrite H (Equation7.14)as follows:
itself\342\200\224the

(neglecting

H=

-2mh1(Vf1+ vf) 9
L

\342\200\224

- -n.J

e1 /Z Z\\
+
An
e0 \\n

_S_ /(Z-2)+ (Z-2)+


Ane0

/'1

_j_y
|ri-r2|/

The expectation
value of H is evidently

(H) = 2Z2E{+ 2(Z

2) (

jfM/1
1-)+ (VM).
-^-\\

k47T60

[7.29]

Here(1/r) is the expectation


value of l/r in the (one-particle)
ground
hydrogenic
statet/tioo (but with nuclearchargeZ); according
to Equation6.55,
=

-.

[7.30]

The expectation
value of Vee is the sameas before(Equation7.25),exceptthat
insteadof Z = 2 we now want arbitrary
we multiply a by 2/Z:
Z\342\200\224so

5Z / e1 \\

5Z

we find
Putting allthistogether,

(H) = \\2Z2 AZ(Z

-2)-(5/4)Z

E\\

= [-2Z2+ (27/4)Z]\302\243i.

[7.32]

Section7.2:The GroundState of Helium

303

thisquantity exceeds forany value


Accordingto the variationalprinciple,
of Z. The lowestupperboundoccurswhen (H) is minimized:
\302\243gs

4={H)= [-4Z+ (27/4)]\302\243i = 0f


from which it followsthat

Z=

^16= 1.69.

[7.33]

Thisseemsreasonable;
it tellsus that the otherelectron
the nucleus,
partially screens
reducingits effectivechargefrom 2 down to about1.69.Putting in thisvalue for
Z, we find
[7.34]
<*>-i j Ex = -77.5eV.
The groundstateof helium has beencalculated
with great precision
in this

with more and more


trial wave functions,
usingincreasinglycomplicated
the
But we'rewithin 2% of
correctanswer, and,frankly,
adjustable
parameters.9
at thispointmy own interest
in the problembeginsto wane.10
way,

Problem7.6 Using =
eV for the groundstateenergy of helium,
calculate the ionization
energy (the energy requiredto removejust one electron).
Hint:Firstcalculate
the groundstateenergy of the heliumion,He+,with a single
electronorbitingthe nucleus;then subtractthe two energies.
\342\200\22479.0

\302\243gs

7.7 Apply

Sectionto the H~ and Li+ ions(each


hastwo electrons,
likehelium,but nuclearchargesZ = 1 and Z = 3,respectively).
Findthe effective(partially shielded)
the bestupper
nuclearcharge,and determine
for eachcase.Comment:In the caseof H~ you shouldfind that
boundon
that there is no boundstateat
eV, which would appearto indicate
(H) >
favorablefor oneelectronto fly off, leaving
all,sinceit would be energetically
behinda neutral hydrogenatom.This is not entirely surprising,
sincethe electrons
are lessstronglyattracted to the nucleusthan they are in helium,and the electron
tendsto breakthe atom apart.However,it turns outto be incorrect.
With
repulsion
a moresophisticated
trial wave function (seeProblem7.18)it can be shown that
<
eV, and hencethat a boundstatedoesexist.It's onlybarelybound,

\342\231\246Problem

the techniques
of this

\302\243gs,

\342\200\22413.6

\342\200\22413.6

\302\243gs

yThe classic
C.L. Pckeris,Phys.Rev.
studiesare E. A. Hyllcraas,Z Phys. 65.209(1930);

For more recent work seefootnote 4.


1216
(1959).

115.

l0The first excitedstate of helium can be calculated in much the same way. using a trial wave
Quantum Mechanics.Princeton U.P.,
orthogonal to the ground state. SeeP.J. E. Peebles,
Princeton. NJ (1992).
Section40.

function

304

Chapter7 The VariationalPrinciple

so H~ has no discretespectrum
however, and there are no excitedboundstates,11
are to and from the continuum).
As a result,it is difficult to study
(alltransitions
in the laboratory,
althoughit existsin great abundanceon the surfaceof the sun.12

7.3 THE HYDROGENMOLECULEION


Another classic
of the variationalprinciple
isto the hydrogenmolecule
application
ion, H^~, consistingof a singleelectronin the Coulombfieldof two protons
(Figure7.5).I shallassumefor the momentthat the protonsare fixedin
a specified
distanceR apart, althoughoneof the mostinteresting
byproducts
of the calculation
is goingto be the actual value of R. The Hamiltonian
is
position,

H=

\342\200\224

Vz

_ +_

[7.35]

where ;*i and /\"2 are the distances


to the electronfrom the respective
protons.As
trial wave function,and invoke
always, our strategy will be to guessa reasonable
the variational principle
to get a boundon the groundstateenergy.(Actually, our
main interestis in finding out whether thissystembondsat all\342\200\224that is,whether
its energy is lessthan that of a neutral hydrogenatom plusa free proton.If our
trial wave function indicates
that there is a boundstate,a bettertrial functioncan
only make the bondingeven stronger.)
To construct
the trial wave function,imaginethat the ion is formedby taking
a hydrogenatom in its groundstate(Equation
4.80),

Mr) = -^=e-'/(>,

[7.36]

bringingthe secondprotonin from \"infinity,\"and nailingit down a distanceR


wave function
away. If R is substantially
greaterthan the Bohrradius,the electron's
isn't
much.
B
ut
we
would
liketo
treat
the
two protonson
probably changedvery

-e

+e

+e FIGURE7.5: Thehydrogenmolecule
ion,H+

\"RobertN. Hill. J.Math. Phys. 18,2316


(1977).
'-Forfurther discussionseeHans A. Bethe and Edwin E. Salpeter,Quantum Mechanicsof Oneand Two-ElectronAtoms. Plenum. New York (1977).Section34,

Section73:The HydrogenMolecule
lorn

JOS

an equalfooting,so that the electron


has the sameprobability
of being
with eitherone.Thissuggests
that we consider
a trial functionof the fotm

JjJSL.

^ = Ar>o(n)+ iMr2)].
callthisthe LCAOtechnique,
becausewe are exp:
(Quantum chemists
molecularwave functionas a linearcombination
of atomicorbitals.)
Our first taskis to normalize
the trial function:
\\=

jm1d*r=\\A\\1\\^j\\^{rx)\\1d7,r

+ f

\\^o(r2)\\2d\\+ 2

f fo(ri)^o(ri)d^r

are 1 (sincei^o itselfis normalized);


The first two integrals
the third is more tricky.
Let

=
I ee (ifo(ri)litota))

e-^W\"dh.
A
na* J[

[7.39J

so that proton1 is at the originand proton2 is on the z axis


Pickingcoordinates
at the pointR (Figure7.6),we have
r\\

=r

and r2 = y/r1+ R2 -2rRcos6.

[7.40]

and therefore

I=

-L
(
no* J

e->lae-Jr2+R2-1>R\342\204\2420l\302\253r2sin6d
rd6d<t>.

<.

2<

rz=Jrz+R2-2rRcosQ

..0y A\\

=r

\\

1
y

FIGURE7.6:

Coordinates
oil(Equation7.39).
for the calculation

[7.41]

306

Chapter7 The VariationalPrinciple

let
The 0 integralis trivial (2;r).To do the 6 integral,
v

= Vr2 + R2-2rRcos$. so that d(y2)= 2.ydy = 2rRsin6d6.

Then

_l'R

1 f+R
/Cn e-y/r-+R2-2rRcoSe/as[nedg
/
=
r~->

JO

g-.v/\302\253v</v

J\\r'\\r-R\\

+ R + a) e^r-R^a(\\r-R\\+a)].
\\e-{r+R)/a(r

-\342\200\224

The r integralis now straightforward:

2 r
CR
/ = -^- -e~R,a/ (r + R + a)e-lrlar
dr + e~Rla / (rt
a*Rl
C\302\260\302\260

Jo

Jo

+ eR/a f

- r + a)rdr

{r-R+a)e-lrlardi^.

we find (after somealgebraic


Evaluating the integrals,
simplification),

I = e-Rla

'\342\231\246(JH(S)\"

[7.42]

I is calledan overlapintegral;it measures


the amount by which i/o(t'\\) overlaps
ijfoiri)(noticethat it goesto 1 as R -> 0, and to 0 as R -> oo).In terms of I,the
normalization
factor(Equation7.38)is

|A|'=2(1'+ /)

[7.43]

Next we must calculate


value of H in the trial statex}/.
the expectation
Noting

that

r2m
(where E\\

samewith rn

4tt\342\202\254o

t'i

eV is the groundstateenergy of atomichydrogen)\342\200\224and the


in placeof r\\
have
\342\200\22413.6

H\\f/

\342\200\224we

=A

l
\342\226\240V2-

47reo v'l

2m

\\

Wo(n)+ fo(r2)]

t'i
i

\342\204\242

= E,^-A(-^\342\200\224)-^0(/-1)
+ -^00-2)
\\4^6o/

\342\200\242

|_>\"2

>-I

Section7.3:The HydrogenMolecule
Ion

307

It followsthat
(H)= Ei-2\\A\\'

(Ifo(ri) n ^o(ri)>+ (^o(n)

47T60,

^o(ri))

[7.44]

I'll let you calculatethe two remainingquantities,


the so-called
directintegral,
1

n lfo(ri)>.

[7.45]

= a(i/fo(ri) 1 foO'i)).

[7.46]

and the exchange


integral,
X

The results(seeProblem7.8)are

[7.47]
and

X=

(i +

-U

[7.48]

-/?/\302\253

and recalling
4.70and 4.72)that
(Equations
Putting all thistogether,
we conclude:

E\\

\342\200\224(e-/47T\342\202\254o)(I/2a),

(H) =

+ X)
1+2(D
Ei.
(1+ /) J

[7-49]

the groundstateenergy islessthan (H).Of


Accordingto the variational principle,

course,thisis only the electron'senergy\342\200\224there isalsopotential


energy associated
with the proton-proton
repulsion:
V

vpp

-= ^ - -= --^1.
2aF
l

47T60 R

Thus the totalenergy of the system,in unitsof

\342\200\224E\\,

of x = R/a, is lessthan

F{x)=

-1+

[7.50]

and expressed
as a function

+ (l+x)e-2n
i(\\-(2/3)x2)e-*
I

l+(l+:c+ (l/3)jrV-*

j\"

Thisfunctionis plottedin Figure7.7.Evidently bondingdoes occur,for there


that the energy isless
existsa regionin which the graph goesbelow 1,indicating
than that of a neutral atom plusa freeproton
eV).It'sa covalentbond,with
the
the electron
sharedequallyby
two protons.
The equilibrium
of the
separation
i
s
about
Bohr
o
r
1.3
A
value
is
2.4
1.06A). The
radii,
(the experimental
protons
\342\200\224

(\342\200\22413.6

308

Chapter7 The VariationalPrinciple


F(x)

-0.5

-1
-1.2
of a bound
FIGURE7.7: Plotof the functionF(x),Equation
7.51,showingexistence
state(x isthe distance
betweenthe protons,
in units of the Bohrradius).
value is 2.8eV (the
calculated
bindingenergy is 1.8eV, whereas the experimental
as always, overestimates
the groundstate
hence
variational principle,
never mind:The essential
underestimates
the strength of the
pointwas
to seewhether bindingoccursat all;a bettervariational functioncanonly make
the potential
well even deeper.
energy\342\200\224and

bond\342\200\224but

7.8 Evaluate D and X (Equations7.45and 7.46).Checkyour


againstEquations7.47 and 7.48.

\342\231\246Problem

answers

* *Problem7.9 Supposewe used a minus sign in our trial wave function


(Equation7.37):

f = AWo(n) toin)].

[7.52]

find F(x) (the analogto Equation7.51)for this


doingany new integrals,
of bonding.13
the graph.Showthat there is no evidence
case,and construct
(Since
the variationalprinciple
an
t
hisdoesn't
that
only gives upperbound,
prove bonding
cannotoccurfor sucha state,but it certainly doesn'tlookpromising).
Comment:
Actually, any functionof the form

Without

ir^A[ir0(ri)+ ei4,ifoOl)]'-Bondingoccurswhen
But the

[7.53]

the electron \"prefers\" to be between the protons, attracting


them inward.
odd linear combination (Equation 7.52)has a node at the center, soit'snot surprising that this

configuration drives the protons apart.

Further Problems
for Chapter7

309

desiredpropertythat the electronis equallylikelyto be associated


with
eitherproton.However,sincethe Hamiltonian(Equation7.35)is invariant under
P: r\\ -o-n, itseigenfunctions
can be chosento be simultaneously
the interchange
of P. The plussign(Equation7.37)goeswith the eigenvalue+1,
eigenfunctions
and the minus sign(Equation7.52)with the eigenvalue nothingis tobe gained
the ostensibly
more generalcase(Equation7.53),though you're
by considering
welcometo try it, if you'reinterested.
has the

\342\200\2241;

* * *Problem7.10The secondderivative of F{x),at the equilibrium


point,can be
usedto estimatethe natural frequency of vibration(a>) of the two protonsin the
ion(seeSection2.3).If the groundstateenergy (hco/2)of this
hydrogen molecule
oscillator
exceedsthe bindingenergy of the system,it will fly apart.Showthat in
fact the oscillator
energy is smallenoughthat thiswill not happen,and estimate
how many boundvibrational
levelsthere are.Note:You'renot goingto be able
to obtainthe positionof the minimum\342\200\224still lessthe secondderivative at that
Do it numerically,
on a computer.
point\342\200\224analytically.

FURTHERPROBLEMSFORCHAPTER7
Problem7.11
(a)

Usea trial wave functionof the form

*rU) ~

< x < a/2),


Acos(7rx/fl),if
0
otherwise
(\342\200\224a/2

harmonic
toobtaina boundon the groundstateenergy of the one-dimensional
oscillator.
What is the \"best\"value of a? Compare{H)m[nwith the exact
derivative)
energy.Note:Thistrial functionhas a \"kink\" in it (a discontinuous
at +fl/2;do you needto take account
of this,as I did in Example7.3?
(b) Use \\f/(x) = Bsm(jrx/a)on the interval (~a,a)to obtaina boundon the
first excited
state.Comparethe exactanswer.

**Problem7.12
(a)

Problem7.2,usingthe trial wave function


Generalize

,4W. N. Mei, Int.

J. Educ.Scl.Tech.27, 285 (1996).

310

Chapter7 The VariationalPrinciple

for arbitrary n. Partialanswer:The bestvalue of b is given by


\342\200\224

\"n(4\302\253

2(2//+ 1)

ma)
(b)

~l1/2
1)(4/7-3)

Findthe leastupperboundon the first excitedstateof the harmonicoscillator


usinga trial functionof the form
Bx
=

'

tf (JO

(A'2

+ b2)\"

Partialanswer:The bestvalue of b is given by


b2 =
(c)

mco

/7(4\302\253

-5)(4/7-3)117

2(2//+ 1)

Noticethat the boundsapproachthe exactenergiesas n


oo. Why is
that? Hint:Plot the trial wave functionsfor n = 2, n = 3, and n = 4, and
comparethem with the true wave functions(Equations2.59and 2.62).To do
it analytically,
start with the identity
-\302\273

'

lim (l + ~)
ez= >!->-oo
z\\\302\273

\\

Problem7.13Findthe lowestboundon the groundstateof hydrogenyou can get


trial wave function
usinga gaussian
i//(r)= Ae'
where A

is determined
and b is an adjustable
Answer:
by normalization
parameter.

-11.5eV.

* *Problem7.14If the photonhad a nonzeromass(mY


wouldbe replaced
by the Yukawa potential,
?

V(T) =
4tt\342\202\254q

/ 0),

the Coulombpotential

_ fir

[7.54]

= myc/h.With a trial wave functionof your own devising,


estimatethe
Assume \\ia <C 1,and
bindingenergy of a \"hydrogen\" atom with thispotential.
giveyour answer correctto order(fj.a)2.
where \\i

Problem7.15Supposeyou'regiven a quantum system whoseHamiltonian


admitsjust two eigenstates,
\\l/a (with energy Eu), and t/^ (with energy Ei,).
They
/\302\276

Further Problems
for Chapter7

311

are orthogonal,
and nondegenerate
normalized,
(assumeEa is the smallerof the two
Now we turn on a perturbation
H', with the followingmatrix elements:
energies).

(TMff'M.)=

Wb\\H'\\i/h) =

0: OMff'liM= OMff'hM

=/\302\273\342\200\242

17.55]

issomespecified
constant.
of the perturbedHamiltonian.
Findthe exacteigenvalues
Estimatethe energies
of the perturbedsystem usingsecond-order
perturbation

where /?
(a)
(b)

theory.
(c) Estimatethe groundstateenergy of the perturbed
system usingthe variational
a
trial
with
functionof the form
principle,
\\jf

= (cos0)^,+ (sin

\302\242)1(/1,.

[7.56]

where 0 is an

(d)

in
adjustable
parameter.Note:Writing the linearcombination
thisway isjusta neat way to guarantee that i/r is normalized.
Compareyour answers to (a),(b),and (c).Why is the variational principle
so accurate,
in thiscase?

Problem7.16As an explicitexampleof the methoddevelopedin Problem7.15,


consideran electronat restin a uniform magneticfieldB = Bzk, for which the
Hamiltonian
is (Equation4.158):
eBH0=\342\200\224^SZ.

The eigenspinors,
Xa &nd Xb*

[7.57]

the corresponding
Ea and Eh, are given
energies,
in Equation4.161.
in the form of a uniform field
Now we turn on a perturbation,
in the .t direction:
find

H'=C-^SX.
m

[7.58]

of H', and confirm that they have the structure of


Findthe matrix elements
Equation7.55.What is hi
find the new groundstateenergy,in
(b) Usingyour resultin Problem7.15(b),
second-order
theory.
perturbation
find the variational principle
boundon
(c) Usingyour resultin Problem7.15(c),
the groundstateenergy.
(a)

* * ^Problem7.17Although the Schrodinger


equationfor helium itselfcannotbe
solvedexactly,there exist\"helium-like\"
systemsthat do admit exactsolutions.

312

Chapter7 The VariationalPrinciple

is \"rubber-band
helium,\"in which the Coulombforcesare
simpleexample15
replacedby Hooke'slaw forces:
A

n2

H=

+ V2) + -mar(r2+ rf)


2m (Vf
,\342\200\236,

(a) Showthat the changeof variablesfrom


u

- -ma>2\\ri- Ti]2.

[7.59]

n, T2, to

-=(ri+r2).
v=\342\200\224(n-n),
V2
V2

[7.60]

harmonic
turns the Hamiltonian
three-dimensional
intotwo independent
oscillators:

H=

\"

2m

\342\200\242\342\200\224V\342\200\236

V72

2 2
u
+
+, -ma)
2

-(1-X)marv2

-V2 +
2
2m
\"

[7.61]

is the exactgroundstateenergy for this system?


If we didn'tknow the exactsolution,we might be inclinedto apply the
form (Equation7.59).
in itsoriginal
methodof Section7.2to the Hamiltonian
Do so (but don'tbotherwith shielding).
How doesyour resultcomparewith
the exactanswer?Answer: (H) = 3hco(\\ A./4).

(b) What
(c)

\342\200\224

* * *Problem7.18In Problem7.7 we foundthat the trial wave functionwith


(Equation7.27),which worked well for helium,is inadequateto confirm the
useda
existence
of a boundstatefor the negativehydrogenion.Chandrasekhar16
trial wave functionof the form
shielding

+ ^2(n)^i0\"2)].
^r(ri,r2)= A[\\f/i (ri)^2(/\"2)

[7.62]

where

Mr) =

Z3
Tta-

=
and \\j/2(r)_

Z3
^2

\342\200\236-Z->r/a

na~

[7.63]

is
In effect,he allowedtwo different shielding
that oneelectron
factors,suggesting
are
and the otheris farther out.(Because
electrons
relatively closeto the nucleus,
identicalparticles,
the spatialwave functionmust be symmetrized with respectto
The spin
is irrelevant to the calculation\342\200\224is evidently
interchange.
state\342\200\224which

'-Tora more sophisticatedmodel, seeR. Crandall.R. Whitncll.

438(1984).
I6S.Chandrasekhar.Astrophys. J. 100.176(1944).

and R.

Bcttcga,Am.

J.Pins.52,

FurtherProblems
for Chapter7

313

Showthat by astutechoiceof the adjustable


antisymmetric.)
parametersZ\\ and Zi
eV. Answer:
you can get (H) lessthan
\342\200\22413.6

usedZ\\ = 1.039(since
2<s/Z\\Z~2.Chandrasekhar
as an effectivenuclearcharge
thisis largerthan 1,the motivating interpretation
but never mind\342\200\224it's stillan acceptable
trial wave function)
cannotbe sustained,
and Z2 = 0.283.
where x

Z\\

+ Z2 and v =

nuclearfusionis getting
Problem7.19The fundamental problemin harnessing
closeenoughtogetherfor the attractive (but
the two particles
(say, two deuterons)
nuclearforceto overcomethe Coulombrepulsion.
The \"bulldozer\"
short-range)
methodis to heat the particles
and allow the random
up to fantastic temperatures,
to bringthem together.A more exoticproposalis muoncatalysis,in
collisions
a \"hydrogenmolecule
in placeof
which we construct
ion,\"only with deuterons
protons,and a muon in placeof the electron.Predictthe equilibrium
separation
in sucha structure,
distancebetweenthe deuterons
and explainwhy muonsare
for thispurpose.17
superiorto electrons
* * *Problem7.20Quantumdots.Considera particleconstrained
to move in two
dimensions
in the cross-shaped
regionshown in Figure7.8.The \"arms\"of the
iszerowithin the cross,and infinite in
outto infinity. The potential
crosscontinue
this configuration
the shadedareasoutside.
admitsa positive-energy
Surprisingly,
boundstate.18
(a) Showthat the lowestenergy that can propagateoffto infinity

\302\243

threshold

\342\200\224

is

8ma2'

solutionwith energy lessthan that has tobe a boundstate.Hint:Goway


out onearm (say, x ^$> a), and solvethe Schrodinger
equationby separation
of variables;
if the wave functionpropagatesoutto infinity, the dependence
on x must take the form exp(ikxx)with kx > 0.
any

l7The classic
330(1957):for a
paperon muon-catalyzed fusion is J.D.Jackson.Phys.Rev. 106,
more recent popular review, seeJ. Rafelski and S.Jones,ScientificAmerican, November 1987,
page 84.
l8This model is taken from R. L. Schult el
In the presence
Phys. Rev. B 39.5476 (1989).
a
bound
state
becomes
this
the
of quantum tunneling
is
reverse:A classically
unbound;
classically
state is quantum mechanically bound.
al\342\200\236

i;\302\273bound

314

Chapter? The VariationalPrinciple

-a
---a

FIGURE7.8: The cross-shaped


regionfor Problem7.20.

to showthat the groundstatehas energy less


(b) Now usethe variationalprinciple
than ^threshold- Usethe followingtrial wave function(suggested
by Krishna
Rajagopal):

l/r

(*,>>)=

(1 \\xy\\/a2)e a, \\x\\ < a and \\y\\ < a


(1 \\x\\/a)e-a^a, \\x\\<a and |v| > a
(1 \\y\\/a)e-aM/a, \\x\\ >a and |v| <a
elsewhere.
0.

value of H.
Normalizeit to determineA, and calculatethe expectation
Answer:

3h2 /or2+ 2a+ 3'


(H) = ma'
6+llor
Now rninimize with respectto a, and show that the resultis less than
^threshold- Hint:Take full advantage of the symmetry of the problem\342\200\224you
only needto integrateover 1/8of the openregion,sincethe other7
will be the same.Notehowever that whereas the trial wave functionis
integrals
at x = 0, y = 0,
its derivativesare not\342\200\224there are\"roof-lines\"
continuous,
x =
a, and y = a, where you will needto exploitthe techniqueof

i 7.3. i

Example

CHAPTER 8

THE WKB APPROXIMATION

The WKB (Wentzel, Kramers,Brillouin)1


methodis a technique
for obtaining

to the time-independent
solutions
in one
approximate
Schrodinger
equation
idea
can be appliedto many otherdifferential
and
(the samebasic
equations,
in
to the radialpart of the Schrodinger
It is
equation three dimensions).
i
n
boundstateenergies
and tunnelingratesthrough potential
useful calculating
dimension

particularly

barriers.
ideaisasfollows:Imaginea particleof energy E movingthrough
The essential
a regionwhere the potentialV(x) is constant.
If E > V, the wave functionis of

the form

f(x) =

Ae\302\261ikx,

with

= y/2m(E V)/h.

is traveling to the right,and the minus sign


The plussignindicates
that the particle

means it is goingto the left (the general


of course,is a linearcombination
solution,
with fixed wavelength(X = In/k) and
of the two).The wave functionisoscillatory,
that V(x) is notconstant,
but variesrather
(A). Now suppose
unchanging
amplitude
in
to
over
a
slowly comparison X, so that
regioncontaining
many full wavelengths
is
it
isreasonable
the potential essentially
constant.
Then
to suppose
that xf/ remains
t
hat
and
practicallysinusoidal,
except the wavelength the amplitudechangeslowly
with x.Thisis the inspiration
In effect,it identifies
behindthe WKB approximation.
two different levelsof A'-dependence:
modulatedby gradual
rapid oscillations,
variation in amplitudeand wavelength.
In

Holland it'sKWB. in France it'sBWK. and

in

England it'sJWKB (for Jeffreys).

315

316

Chapter8 The WKB Approximation


By the sametoken,if E

ir(x) =
And
solution

< V (and V is constant),


then

\\j/

is exponential:

with* = ^2m(V-E)/h.

Ae\302\261KX.

if V(x) is not constant,


but varies slowlyin comparison
with \\/k, the

remainspracticallyexponential,
exceptthat

functionsof x.

and k are now slowly-varying

Now, there isoneplacewhere thiswholeprogramis boundto fail,and that is


in the immediate
turningpoint,where E % V. ForhereX (or
vicinity of a classical
\\/k) goesto infinity, and V(x) can hardly be saidto vary \"slowly\"in comparison.
As we shallsee,a properhandlingof the turning pointsis the mostdifficult aspect
of the WKB approximation,
though the final resultsare simpleto stateand easyto

implement.

8.1THE \"CLASSICAL\"
REGION
The Schrodinger
equation,

h1 d2xl/
Y
2m dx2

+ V(x)\\f/ = Exf/,

can be rewritten in the followingway:


d2\\f/

p2

dxl

hl

where

p(x) = y/7m[E V(x)]

[8.2]

is the classical
formula for the momentum of a particlewith totalenergy E and
potentialenergy V(x).For the moment,I'll assumethat E > V(x),so that p(x)
is real;we callthisthe \"classical\"
region,for obviousreasons\342\200\224classically the
particleis confinedto this range of x (seeFigure8.1).In general, is some
\\j/

function;we can expressit in terms of itsamplitude,


A(x),and itsphase,
complex
0(x)\342\200\224bothof which are real:

f(x) = A{x)ei(f>(x).

[8.3]

Usinga primeto denotethe derivative with respectto x, we find:


WW/

dx
and

=
d\"%
dx

[A\"

= (A'+ /A0V0.

+ 2iA'4>'+ iA4>\" A(0')V*.

[8-4]

Section8.1:The \"Classical\"
Region

317

V(x)k

E--

Classical
region
the particleis confinedto the regionwhere
FIGURE8.1:Classically,

\302\243

> V(x).

Putting thisintoEquation8.1:
A\"

+ 2iA'<t>'+ /A0\" A(0')2= ~A.

[8.5]

one for the real part and one for the


This is equivalentto two real equations,
imaginary part:
A\"

-A{<t>'Y=

-^A,

or

A\"

=A

(0)

- TT
h~

[8.6]

and
2A'4>'+ A4>\"

= 0. or

(a20')'= 0.

[8.7]

Equations8.6 and 8.7 are entirely equivalentto the originalSchrodinger

The secondoneis easilysolved:


equation.

A20'= C2. or

[8.8]

is a (real)constant.The first one (Equation8.6)cannotbe solvedin


here comesthe approximation:
We assume
that the amplitudeA varies
we assumethat A\"/A
(Moreprecisely,
slowly, so that the A\" term is negligible.
is much lessthan both(0')2and p2/h~.)In that casewe can dropthe left sideof

where C

general\342\200\224so

Equation8.6,and we are left with

318

Chapter8 The WKB Approximation


and therefore
0(-v)

-*{/p(x)dx.

[8.9]

constants
can be absorbed
(I'llwrite thisas an indefiniteintegral,for
intoC, which may thereby becomecomplex.)
It followsthat
now\342\200\224any

[8.10]
solutionwill be a linearcombination
of two such
general(approximate)
terms,onewith eachsign.
and the

Noticethat

W(x)\\2 =

[8.11]

p(x)

which says that the probability


of finding the particleat point.v is inversely
to its (classical)
momentum (and henceits velocity)at that point.Thisis
proportional
doesn'tspendlongin the placeswhere
exactly what you wouldexpect\342\200\224the particle
it is moving rapidly,so the probability
of gettingcaught there issmall.In fact, the
is sometimes
WKB approximation
derivedby starting with this\"semi-classical\"
The
insteadof by droppingthe A\" term in the differentialequation.
observation,
latterapproachis cleanermathematically,but the former offersa moreplausible

physicalrationale.

Example8.1 Potentialwell with two verticalwalls.Supposewe have an


infinite

squarewell with a bumpy bottom(Figure8.2):


V(x) _

somespecified
function, if 0 < x < a,
otherwise.
oo.

V(x)i

a
FIGURE8.2: Infinite squarewellwith a bumpy bottom.

[8.12]

Section8.1:The \"Classical\"
Region

319

Insidethe well (assuming


E > V(x) throughout)
we have
ir(x) =

1
-==
\\c+emx)+ C-e-W**

or, moreconveniently,
M*) =

[C\\ sin0(x)+ Cj cos0(x)],

TpU)

[8-131

where (exploiting
the freedomnotedearlierto imposea convenient
lowerlimiton
the integral)
1 fx

0U) =

Now \\j/(x) must go to zeroat x =


\\fr(x) goesto zeroat x = a, so

- Jo/ p{x')dx>.

[8.141

0,and therefore(since0(0) = 0) Ci = 0. Also,

\302\242(0)=1171 (/7

1,2.3,...)-

[8.15]

Conclusion:
x)dx = rnih.

Jo

[8.16]

Thisquantization
condition
determines
the (approximate)
allowedenergies.
For instance,
if the well has aflatbottom(V(x)= 0),then p(x) = y/2mE (a
and Equation8.16sayspa = nnti,or
constant),
E\342\200\236

= n-TT-rr
2ma

->

is the old formula for the energy levelsof the infinite square well
yieldsthe exactanswer (the
(Equation2.27).In thiscasethe WKB approximation
so droppingA\" costus nothing).
amplitudeof the true wave functionis constant,
which

*Problem8.1Use the WKB approximation


to find the allowedenergies

(\302\243\"\342\200\236)

an infinite

of

squarewell with a \"shelf,\"of height Vq extendinghalf-way across

(Figure6.3):

V(x) =

V0.
\342\200\242

if 0 < x < a/2.


if a/2 < x < a,

0,
oo, otherwise.

320

Chapter8 The WKB Approximation

= {rnrhr/lmcr(the nth allowed


> Vo, but do
energy for the infinite squarewell with no shelf).Assume that
notassumethat En ^> Vo- Compareyour resultwith what we got in Example6.1
usingfirst-orderperturbation
theory.Notethat they are in agreementif eitherVo is
very small(the perturbation
theory regime)or n is very large(the WKB\342\200\224semiExpressyour answer in terms of

Vo

and

E\342\200\236

E\302\256

classical\342\200\224regime).

* *Problem8.2 An illuminatingalternative derivationof the WKB formula


in powersof H. Motivatedby the free(Equation8.10)is basedon an expansion
=
+
particlewave function,\\(/ Aexp( ipx/ti),we write
xf/(x) =

where f(x)
here\342\200\224any

eif{x)/tl,

is somecomplexfunction.(Notethat

there is no lossof generality

nonzerofunctioncan be written in this way.)

(a) Put this

intoSchrodinger's
(in the form of Equation8.1),and show
equation

that

ihf\"-(f')2+ p2 = 0.
(b) Write

f(x) as a powerseriesin fi:


fix) = fo(x)+ fr/i (x)+ h2f2(x)+

\342\200\242 \342\200\242 \342\200\242

likepowersof h, show that


and,collecting

(fi)2= P2, ifo=2fif{. ifl' = 2fifi + (f;)2, etc.


(c)

Solvefor /o(.v)and /i(.v),and show


Equation8.10.

that\342\200\224to

first

orderin

Note:The logarithmof a negativenumber is definedby


where n is an odd integer.If thisformula is new to you,
sides,and you'llseewhere it comesfrom.

h\342\200\224you

recover

= ln(z)-f inn,
both
exponentiating

ln(\342\200\224z)

try

8.2TUNNELING
Sofar, I have assumed
that E > V, so p{x)isreal.But we can easilywrite down
the sameas
the corresponding
resultin the new classical
region(E <
V)\342\200\224it's

Section8.2:Tunneling

321

before(Equation8.10),onlynow p(x) is imaginary'?

f(.x)=

[8.17]

,\302\261};f\\p<x)\\dx

VlpOOl

for example,
the problemof scattering
from a rectangularbarrier
Consider,
with a bumpy top(Figure8.3).To the leftof the barrier(x < 0),

f(x) = Aeik* + Be~iLx,

[8.18]

is the incidentamplitude,
B is the reflected
and k = ^JlinE/h
amplitude,
(seeSection2.5).To the right of the barrier{x > a),

where A

\\}/(x)=

[8.19]

Feikx;

F is the transmitted amplitude,


and the transmission
probabilityis

r = IFI2
o'

[8.20]

In the tunnelingregion(0 < x < a), the WKB approximation


gives

is(x)=

IhtiMx'Kdx'
/\342\200\242\342\226\240>-

-UalPix'Hdx'

V\\pixT\\

V\\P(xT\\

[8.21]

V(x),i

E
*\342\226\240

c1

FIGURE8.3: Scatteringfrom a rectangularbarrierwith a bumpy top.

-Inthis casethe
necessarilyfrom

Equation

wave function

8.5,although

derivation in Problem 8.2.

is real,and the analogs to Equations 8.6and 8.7do not follow


they

are still sufficient.If this bothers you,

study

the alternative

322

Chapter8 The WKB Approximation

1 ^^^^^^^^^-^

/l\\

'

1'
A\\

/
I1

^^

\342\226\240

\342\200\224

1
1

\\

\302\260

-JL- -**:

/ \\ / \\
\342\200\224

\342\200\224

from a high,
FIGURE8.4: Qualitativestructure of the wave function,for scattering

broadbarrier.

If the barrieris very high and/orvery wide (which is to say,if the probability
is small),then the coefficient
of tunneling
of the exponentially
term (C)
increasing
must be small(in fact, it would be zero if the barrier were infinitely broad),and
the wave functionlookssomething
of the
like3Figure8.4.The relativeamplitudes
incidentand transmittedwaves are determined
of
essentially
by the totaldecrease
the exponential
overthe nonclassical
region:

so that

_]
T=e~2y. withy =
^h

rJo

[8.22]

\\p(x)\\dx.

Example8.2 Gamow'stheoryof alphadecay.4In 1928,GeorgeGamow(and,


Condonand Gurney) usedEquation8.22to providethe first
independently,
of alphadecay (the spontaneous
emission
of an alpha-particle\342\200\224two
explanation
certainradioactivenuclei).5
Sincethe alpha particle
protonsand two
carriesa positivecharge(2e),it will be electrically
repelledby the leftovernucleus
(chargeZe), as soonas it getsfar enoughaway to escapethe nuclearbinding
force.But first it has to negotiate
a potential
barrierthat was already known (in the
caseof uranium) to be morethan twice the energy of the emittedalphaparticle.
Gamow approximated
the potential
energy by a finite squarewell (representing
the attractive nuclearforce),extendingoutto ?-| (the radiusof the nucleus),
joined
successful

neutrons\342\200\224by

heuristic argument can be made more rigorous\342\200\224see Problem


4For a more complete discussion, and alternative formulations,
\342\200\242This

(1996).
Am.J.Phys.64, 1061
Tunneling,\"

8.10.
see Barry

R. Holstein.

5For an interesting brief history seeEugen Mcrzbacher,\"The Early History of Quantum


PhysicsToday. August 2002.
p. 44.

Section8.2:Tunneling

323

/(0.,

x.

Coulombrepulsion

E\302\273-

/i

r2

Nuclearbinding

\342\200\224

V0

FIGURE8.5: Gamow'smodelfor the

nucleus.
radioactive

potentialenergy of an alpha particlein a

to a repulsivecoulombic
tail(Figure8.5),and identifiedthe escapemechanism
as
quantum tunneling(thiswas, by the way, the first timethat quantum mechanics
had beenappliedto nuclearphysics).
If E is the energy of the emittedalphaparticle,the outerturning point(/-2) is

determined
by

2Ze~ =

,,
[8.23]
r

\342\200\236

\302\243.

The exponent
8.22)is evidently6
y (Equation
n
Y
ft

1 2Ze2

'2m

J,

\342\200\236\\

Cff-

>'

k47ren

- E \\dr = y/2mE
h

The integralcan be doneby substitution


(letr = /'2sin\"

\302\253),

Typically,/-i
approximation

<\302\243

Vm

\"

\342\200\224

\342\200\224

V2

sin

'

\342\200\224

\\dr.

and the resultis

-\\/ri(r2-ri)

[8.24]

n, and we can simplify this resultusingthe smallangle

(sine= e):
y

= y/lmE [TT
\342\200\224-\342\200\224

y-n 2VnnJ =

K\\\342\200\224-

Kiy/Zn

[8.25]

6In this casethe potential does not drop to zero on the left side of the barrier (moreover. Liu's is
is all \\vc really
really a three-dimensional problem),but the essentialidea, contained in Equation 8.22.

need.

324

Chapter8 The WKB Approximation


where
Ki

^-

(-^-)

= 1.980MeV'/2,

[8.26]

and

Kl=(jL\\'2^= j.485fin\"1/2.

[8.27]

[Onefermi (fm) is 10-15m, which is aboutthe sizeof a typical nucleus.]


If we imaginethe alphaparticlerattlingaroundinsidethe nucleus,with an
with the \"wall\"is about
average velocityv, the average time between\"collisions\"
is v/2r\\. The probabilityof escapeat
2r\\/v, and hencethefrequencyof collisions
eachcollision
of emission,
is e~ly,sothe probability
perunit time,is (v/2r\\)e~ly,
and hencethe lifetimeof the parent nucleus
is about
T

[8.28]

\342\200\224ely.

it hardly matters,
for the exponential
factor
Unfortunately,we don'tknow
as we go from
varies over a fantasticrange (twenty-five ordersof magnitude),
one radioactivenucleusto another:relative to this the variation in v is pretty
if you plotthe logarithmof the experimentally
In particular,
measured
insignificant.
lifetimeagainst1/n/E,the resultis a beautifulstraight line(Figure8.6),7just as
8.25and 8.28.
you wouldexpectfrom Equations
v\342\200\224but

*Problem8.3 UseEquation8.22to calculatethe approximatetransmission


a finite squarebarrierof height
for a particleof energy E that encounters
Vq > E and width la.Compare
your answer with the exactresult(Problem2.33),
to which it shouldreducein the WKB regimeT <^\\.
probability

the lifetimes
of U238and Po212,
**Problem8.4 Calculate
usingEquations8.25and
8.28.Hint:The densityof nuclearmatter is relatively constant(i.e.,thesamefor
all nuclei),so (ri)3 is proportional
to A (the number of neutronsplus protons).

Empirically,

n =(1.07fm)A1/3.

[8.29]
cd.,

(1992);

McGraw-Hill
it was
7Ffom David Park. Introduction to the Quantum Theory, 3rd
O.
Vol.
and
Rasmussen,\"Alpha Radioactivity,\" Encyclopedia Physics.
42,
adapted from Pcrlman
This material is reproducedwith permissionof The McGraw-HillCompanies.
Springer(1957).

I.

J.

of

Section8.3:The Connection
Formulas

'

'

'

'

'

l_l

1_1

325

1_L

[MeV]

FIGURE8.6: Graph of the logarithm of the lifetimeversus 1/VjE(where is the


for uraniumand thorium.
energyof the emittedalphaparticle),
\302\243

The energy of the emitted


can be deduced
formula
by usingEinstein's
alphaparticle

(E = me1)-.

E = m pc~ m(]C~ mac~.


\342\200\224

\342\200\224

[8.30]

where mp isthe massof the parent nucleus,


mj is the massof the daughternucleus,
To
and ma is the massof the alphaparticle(which is to say, the He4nucleus).
is,notethat the alphaparticlecarriesoff two
figure out what the daughternucleus
so Z decreases
by 2 and A by 4. Lookup the relevant
protonsand two neutrons,
nuclearmasses.To estimatev, use E = (l/2)mair:
thisignoresthe (negative)
and surely underestimates
v, but it's aboutthe
energy insidethe nucleus,
potential
bestwe can do at thisstage.Incidentally,
the experimental
lifetimesare 6 x 109
yrs and 0.5/zs,respectively.

8.3 THECONNECTIONFORMULAS
In the discussion
so far I have assumedthat the \"walls\"of the potentialwell (or

the barrier) are vertical,


so that the \"exterior\"solutionis simple,and the boundary
trivial.As it turns out,our main results(Equations8.16and 8.22)are
conditions
reasonablyaccurateeven when the edgesare not so abrupt (indeed,in Gamow's
it is of someinterest
theory they were appliedto just sucha case).Nevertheless,
to study morecloselywhat happensto the wave function at a turning point(E =
V), where the \"classical\"
regionjoinsthe \"nonclassical\"
region,and the WKB

326

Chapter8 The WKB Approximation

| jt^|

Linearized
potential

/^--~

Turning
point nJ

>

Patching
region
X

Classical

Nonclassical

region

region

FIGURE8.7: Enlargedview of the right-handturning point.

itselfbreaksdown.In this sectionI'll treat the boundstateproblem


approximation
(Figure8.1);you get to do the scattering
problemfor yourself(Problem8.10).8
let'sshift the axesover so that the right-handturning point
For simplicity,
=
we have
occursat .v 0 (Figure8.7).In the WKB approximation,
1

Mx) =

+ Ce-^uw]t ifx<Qt

Vpm [2teUV*w

[8.31]

if .v > 0.

De-Uu\\P^')\\dx\\
J\\p(xj\\

the positive
(AssumingV(x) remainsgreaterthan E for all x > 0, we can exclude
oo.)Our task is to jointhe
exponentin this region,becauseit blowsup as x
two solutions
at the boundary.
But there is a seriousdifficulty here:In the WKB
0).The true
\\j/ goesto infinity at the turning point(where p(x)
approximation,
the WKB
wave function,of course,has no suchwild
anticipated,
methodsimply failsin the vicinity of a turning point.And yet, it is precisely
the
at the turning points
that determine
the allowedenergies.
What
boundaryconditions
i
s
WKB
we needto do,then, splicethe two
solutions
together,
usinga \"patching\"
\342\200\224>

\342\200\224\302\273

behavior\342\200\224as

wave function that straddles


the turning point.
Sincewe only needthe patchingwave function(\\j/p) in the neighborhood
of
the origin,we'llapproximate
the potential
by a straightline:
V(x) =
'Warning: The following argument

reading.

E+V'(0)x,

is quite technical, and

[8.32]
you

may wish to

skip it on a

first

Section8.3:The Connection
Formulas
for this
and solvethe Schrodinger
ft2

2m

327

linearized
V:

d2^P

=
ax1 + [E + V{0)xwP Etp,

\342\200\224-rr

or

d2ifrp

[8.33]

tf.v-

where

a=

1/3

[8.34]

ft-

The a'scan be absorbed


intothe independent
variable by defining
z

= ax.

[8.35]

so that

(Ftp =

~aW

[8.36]

**'\342\226\240

This is Airy'sequation,and the solutions


are calledAiry functions.9
Sincethe
there are two linearly
differentialequation,
equationis a second-order
Ai(z)and Bi(z).
independent Airy functions,
Airy

TABLE8.1:Someproperties
ofthe Airy functions.
Differential Equation:

\342\200\224'-

= zv.

LinearcombinationsofAiry Functions,/1/(.-)and Bi(z).

dissolutions:

IntegralRepresentation: Ai{z) =

\342\200\224

cos

(t+\302\253)*

Asymptotic Forms:

Ate)--7\302\275^
- -M2

z\302\2730:

\302\253

0.

yjn;

1/4

Classically,a linear potential means a constant force, and hence a constant acceleration\342\200\224the
It is ironic that
simplestnontrivial motion possible,and the starting point for elementary mechanics.
the same potential in quantum mechanics gives rise to unfamiliar transcendental functions, and plays
only

a peripheral role in the theory.

328

Chapter8 TheWKB Approximation


2.0- /

B/(z)|

1.8
1.6
1.4

rV
A

0.5

0.4
0.3 A
0.2
0.1

1.2- /
1.0

-a!
-0.2tM /
-0.3V

.8

'
/\\-8/\\
r6 V3
/
/

^^

'

-0.4

\\l

\\

/l
/~7 \\-5/
y

\\l
\\

-4

-0.5
i

'

.6

-.4

/ -.2
/
-2/-1 12
--.2
--.4
--.6
--.8
I

3\302\275

--1.0

FIGURE8.8: Graphofthe Airy functions.


are
They are relatedto Besselfunctionsof order1/3;someof their properties
listedin Table8.1and they are plottedin Figure8.8.Evidently the patchingwave
of Ai(z)and Bi(z):
function is a linearcombination
yf/,,{x)=

aAi{ax)+ bBiiptx).

[8.37]

for appropriate
constants
a and h.
wave function in the neighborhood
Now \\J/p is the (approximate)
of the origin;
ourjob i.sto match it to the WKB solutions
in the overlapregionson eitherside
(seeFigure8.9).Theseoverlapzonesare closeenoughto the turning pointthat the
linearized
to
potentialis reasonablyaccurate(sothat \\j/p is a goodapproximation
the true wave function),and yet far enoughaway from the turning pointthat the
WKB approximation
is reliable.10
In the overlapregionsEquation8.32holds,and
therefore(in the notationof Equation8.34)

p(x) = y/2m{E-E-V'(O).v) = flayi^/^x.

[8.38]

In particular,
in overlapregion2,
I \\p(x')\\dx'= Hay2Jo
I V?dx' = -h(ax)3/1,
3
Jo
This is a delicatedoubleconstraint, and it is possibleto concoctpotentials so pathological that
no such overlap region exists.
SecProblem
However, in practical applications this seldomoccurs.

8.8.

Section8.3:The Connection
Formulas 329

VWKB

\302\245WKB

-Vp-

Turning
point

Overlap 1

overlap2

Patching
region

FIGURE8.9: Patchingregionand the two overlapzones.


and thereforethe WKB wave function(Equation8.31)can be written as
V'tv)

e-W\\

*>

[8.39]

V7k*3/4vl/4

Meanwhile,using the large-zasymptoticforms11of the Airy functions(from


Table8.1),the patchingwave function(Equation8.37)in overlapregion2 becomes

2, \\V>
2^W(ax)1/4\"
we seethat
Comparingthe two solutions,
iM-v)=

a=

Alt

ah

.1\342\200\224D,

b
'

and

J*(ax)1/4

e$lax)\302\273\\

= 0.

[8.40]

[8.41]

Now we go backand repeatthe procedure


for overlapregion1.Onceagain,
/>(a) is given by Equation8.38,but thistime x is negative,so

j p{x')dx'= ^h{~ax)^

[8.42]

and the WKB wave function (Equation8.31)is

W = -^^71
HI \\Ber^-a^'2+ Ce-'V-ax)y'2'
^a-V4(-A-)i/4
L

[8.43]

'At first glance it seemsabsurd to use a laige-zapproximation in Ihis region, which after all is
supposedto be reasonably closeto the turning point at z 0 (so that the linear approximation to the
and if you study the matter carefully (see
potential is valid). But notice that the argument here is
Problem 8.8)you will find that there is (typically) a region in which ax is large, but at the same time
it is reasonableto approximate V(.v) by a straight
line.
1

\342\200\224

ax.

330

Chapter8 The WKB Approximation


Meanwhile,usingthe asymptoticform of the Airy function for largenegativez
(Table8.1),the patchingfunction(Equation8.37.with h = 0) reads

+4
tp(x) V^(-ffA-)1/4sin -(-axy12
3
=5

_ e-i:r/4g-i'j(-ar.t)-. [8.44]
iTr/A^^-ax)-'''L
,*.V2'

;2/_\302\273^.V2

yi\"(-ff.v)'/42/

the WKB and patchingwave functionsin overlapregion1,we find


Comparing

fL_,'*/4=
Hy/jt

or,putting

in

JL
'ha

fL,-'>/4= _^.

and

'ha

Hy/jT

Equation8.41for a:
B=

-ie'\"/4D.and

C = ie~i7T/4D.

[8.45]

at either
Theseare the so-called
connection
formulas,joiningthe WKB solutions
sideof the turning point.We'redonewith the patchingwave function
only purposewas to bridgethe gap.Expressing
everything in terms of the one
normalization
constantD, and shiftingthe turning pointbackfrom the originto an
arbitrary pointxi, the WKB wave function (Equation8.31)becomes
now\342\200\224its

if .v

fix) =

d
r
-===exp

-l

fx
/

< xi:

[8.46]
\\p(x')\\dx'

if x > xi.

Example8.3 Potentialwell with oneverticalwall. Imaginea potentialwell


that has onevertical side(at .v = 0) and onesloping
side(Figure8.10).In this
=
case^-(0) 0, so Equation8.46says
/
JQ

= tin.
p(x)dx+4
\342\200\224

(/?

= I.2.

3,...),

or

[8.47]

Formulas
Section8.3:The Connection

331

well with oneverticalwall.


FIGURE8.10:Potential

considerthe \"half-harmonicoscillator,\"
For instance,

, -morx~. if x > 0,

V(x) = I 2

[8.48]

otherwise.

0.

In thiscase

= mcoJxj;
p(x) = J2m[E (\\/2)mto-x-]
\342\200\224

\342\200\224

,v

where
\342\226\240-

is the turning point.So

-f(o V

x2dx =
p(x)dx = mco I y.v|
4
jo
jo v \"
and the quantization
condition
(Equation8.47)yields
I

\342\200\224

\342\200\224mtox}

-=

\342\200\224

22co

[8.49]
In thispai-ticularcasethe WKB approximation
the exactallowed
actually delivers
the odd energies
of theJulI harmonicoscillator\342\200\224see
(which are precisely
energies
Problem2.42).

332

Chapter8 The WKB Approximation


the
Example8.4 Potentialwell with noverticalwalls.Equation8.46connects
WKB wave functionsat a turning point where the potentialslopesupward
the samereasoning,
(Figure8.11(a));
turning point
appliedto a downward-sloping
(Figure8.11(b)),
yields(Problem8.9)

d'

r l rxi

m\"*r*Llp{x')ldx'. if

yfipl-

Mx) =

2D'
sin
sfpW U

/v,

p{x')dx'+

it

.v

< .vi:

[8.50]

if j > .V|.

if we'retalking abouta potentialwell (Figure8.11(c)),


In particular,
the wave
function in the \"interior\"region(.vi < x < xi) can be written eitheras

2D
sin62(x), where 9i(x) =
Mx) =

.Vt

p{x')dx'+-.
4
M-ij\302\243

(Equation8.46),or as

-2D' sin

9\\

(x). where 6\\ (.v) =

--1

C*

7T

p{x')dx' 4
A Jxi
/

(Equation8.50).Evidently the argumentsof the sinefunctionsmust be equal,


Ti-}16i = 6\\ + /?7r, from which it followsthat

modulo

[8.51]

iV(x)

(a)

(b)

(c)

and downward-sloping
8.11:Upward-sloping
turning points.

FIGURE

l~Not

lit\342\200\224an

overall minus sign can be absorbedinlo the normalization factors D and

D'.

Formulas
Section8.3:The Connection

333

Thisquantization
condition
determines
the allowedenergies
for the \"typical\"
caseof a potentialwell with two slopingsides.Noticethat it differsfrom the
formulasfor two verticalwalls (Equation8.16)or oneverticalwall (Equation8.47)
only in the number that is subtractedfrom n (0, 1/4,or 1/2).Sincethe WKB
is
works bestin the semi-classical
(largen) regime,the distinction
approximation
than in substance.
In any event, the resultis extraordinarily
morein appearance
allowedenergies
without ever
(approximate)
powerful,for it enablesusto calculate
solvingthe Schrodinger
equation,by simplyevaluating one integral.The wave
functionitselfhas droppedoutof sight.
* *Problem8.5Consider
the quantum mechanical
analogto the classical
problemof
a ball (massm) bouncingelastically
on the floor.13
(a) What is the potential
energy, as a function of heightx abovethe floor?(For
ballcan'tget there at all.)
is
negative.v, the potential
(b) SolvetheSchrodinger
equationfor thispotential,
expressing
your answer in
terms of the appropriate
Airy function(notethat Bi(z)blowsup for largez,
and must thereforebe rejected).
Don'tbotherto normalize
\\J/(x).
(c) Usingg = 9.80m/s2 and m = 0.100
kg, find the first four allowedenergies,
in joules,correct
to three significant
digits.Hint:SeeMiltonAbramowitzand
Irene A. Stegun,Handbookof Mathematical
Dover,New York
Functions,
(1970),page478;the notationis definedon page450.
(d) What is the groundstateenergy,in eV, of an electronin thisgravitational
on the average?Hint:Use
field?How high off the groundis thiselectron,
the virial theoremto determine
{x).
infinite\342\200\224the

\342\231\246Problem

8.6 Analyze the bouncingball (Problem8.5)usingthe WKB

approximation.

Findthe allowedenergies, in terms of m, g, and h.


and compare
the
(b) Now put in the particularvalues given in Problem8.5(c),
WKB approximation
with the \"exact\"results.
to the first fourenergies
(c) About how largewould the quantum number n have to be to give the ball
an average heightof, say, 1 meter abovethe ground?
(a)

\302\243\342\200\236,

For more on the quantum

\342\226\240

Am.
bouncing ball seeJ. Gea-Banacloche,

and
J. Phys. 67,776(1999)

N. Wheeler. \"'Classical/quantumdynamics in a uniform gravitational field.\" unpublished Reed College


report (2002).This may sound like an awfully artificial problem, but the experiment has actually been
done, using neutrons (V. V. Nesvizhevsky et ai.Nature 415,297 (2002)).

334

Chapter8 The WKB Approximation

8.7 Use the WKB approximation


to find

\342\231\246Problem

harmonicoscillator.

Problem8.8 Considera particleof massm


harmonicoscillator
(angularfrequency a>).

the allowedenergiesof the

in the nth stationary stateof the

Findthe turning point,*2.


(b) How far (d) couldyou go abovethe turning pointbeforethe errorin the
linearized
potential(Equation8.32,but with the turning pointat xi) reaches
l%?Thatis,if
(a)

V{X2+ d)-Vlia(x2+d)
=

V(x2)

what

0.01,

is dl

(c) The asymptoticform of Ai{z)is accurateto 1%as longas z > 5.For the d
in part (b),determine
the smallest
n suchthat ad > 5.(Forany n larger than
thisthere existsan overlapregionin which the linearized
potentialis good
to 1% and the large-zform of the Airy function is goodto 1%.)
* *Problem8.9 Derive the connectionfonnulasat a downward-sloping
turning
a
nd
confirm
8.50.
point,
Equation
* * *Problem8.10Use appropriateconnection
formulasto analyze the problemof
from a barrier with slopingwalls (Figure8.12).Hint:Beginby writing
scattering
the WKB wave functionin the form
1

+ Be-b^P^'],(x < X])

sfW) {AeU^P^^'
1 '
Ce*f**
+ d<T*\302\243i lp(x')ldx
V(a-) =
TLpCx)\\
1

17\302\276)L

l\302\273(x')Ulx'

Fej&PlW

(A'l

< A' < a*2):

(.v>.v2).

[8.52]

Do not assumeC = 0. Calculatethe tunnelingprobability,T = \\F\\2/\\A\\2,


and show that your resultreducesto Equation8.22in the caseof a broad,high

barrier.

Further Problems
for Chapter8

^_^

V(x)k

^s^

I
\342\200\242\342\200\224\"\"\"^

__

335

*1

X2

FIGURE8.12: Barrierwith sloping


walls.

FURTHERPROBLEMSFORCHAPTER8
**Problem8.11
Use the WKB approximation
to find the allowedenergiesof the
generalpower-lawpotential:
V(A-)=<*|.vf\\
where v

is a positivenumber.Checkyour resultfor the casev = 2.Answer:14


\\

E\342\200\236

=a

(\302\253

3' (&)

\" 1/2)/2,

[8.53]

2ma /j_ 1>


+

* *Problem8.12Usethe WKB approximation


to find the boundstateenergy for the
in Problem2.51.
potential
Comparethe exactanswer.Answer: -[(9/8) (1/V^)]

h~a2/m.

Problem8.13For spherically
we can apply the WKB
symmetrical potentials
to the radial part (Equation4.37).In the case/ = 0 it isreasonable15
approximation
to useEquation8.47in the form

r'a
JO

p{r)dr=

(\302\253

- 1/4)jt/L

[8.54]

always, the WKB result is most accurate in the semi-classical


(large /?) regime.In particular,
=
for
the
state
S
ee
W.
N.
Mei.
Am. J. Phys. 66,541 (1998).
1).
very good
Equation
ground
^ Application of the WKB approximation to the radial equation raisessomedelicateand subtle
problems,which I will not go into here.The classicpaper on the subjectis R. Langer.Phys. Rev.
'\"'As

8.53is not

669(1937).

(\302\253

51,

336

Chapter8 The WKB Approximation

is the turning point (in effect,we treat r = 0 as an infinite wall).


the allowedenergies
of a particlein the logarithmic
Exploitthisformula to estimate
potential
where

/\302\276

V(r)

= V0\\n(r/a)

between
(for constants
Vb and a).Treat only the caseI = 0.Showthat the spacing
the levelsis independent
of mass.Partialanswer:
\302\243,,+1-

E\342\200\236

'n+3/4\"

Vftln

kn

- 1/4,

**Problem8.14Usethe WKB approximation


in the form

p(r)dr= (n - \\/2)jrfi

[8.55]

to estimate
the boundstateenergies
for hydrogen.
Don'tforgetthe centrifugalterm
in the effectivepotential
(Equation4.38).The followingintegralmay help:

V^)2.
-J(x-a)(b-x)dx -(y/h2
J/a x
=

Note that you recoverthe Bohrlevelswhen

Enl =
\342\200\236

\302\273

and n

\302\273

[8.56]

/2. Answer:

eV
-13.6
+ VWTT)]2
[n -(1/2)

[8.57]

* * *Problem8.15Consider
the caseof a symmetrical doublewell, suchas the one
We are interested
in boundstateswith E < V(0).
picturedin Figure8.13.

> xi, (ii) .V| < x < .\\'2,


and (iii)0 < x < x\\. Imposethe appropriate
connection
formulasat .vi and
xi (thishas already beendone,in Equation8.46,for you will have to

(a) Write down the WKB wave functionsin regions


(i) x

.\302\276

work out a'i for yourself),to show that

D
<Ap(xT\\

VU) =

exP \\-T
L

*L_

\\p(x')\\dx'

2D
id
ri rx>
sin - / p{x')dx'+
;
Sp(
P(x) [h Jx

= bcose*^'
L

p(x)\\

WW + sin^-^v'WW

(i)
(ii)

(iii)

Further Problems
for Chapter8

337

V(x)i

FIGURE8.13:Symmetricaldoublewell;Problem
8.15.
where

X-i

[8.58]

9-if/, p(x)dx.
(b)

BecauseV(x) is symmetric,we needonly considereven (+) and odd


wave functions.
In the former case1/^(0) = 0, and in the latter caset/t(0) = 0.
Show that thisleadsto the followingquantization
condition:
(\342\200\224)

tan0=
where

[8.59]

\302\2612e0.

0=-JrV| \\p(x')\\dx'.
l

[8.60]

the (approximate)
allowedenergies(notethat E
Equation8.59determines
comesinto.vi and .\\'2, so 9 and 0 are bothfunctionsof
in a high and/orbroadcentralbarrier,in which
(c) We are particularly interested
case0 is large,and e^ is huge.Equation8.59then tellsus that 9 must be
very closeto a half-integer
multipleof n. With this in mind,write 9 =
where
1,and show that the quantizationcondition
(n + 1/2)jt
\302\243\.

+\342\202\254,

becomes

(d)

|e|
9^ (n + 1)ttt
\\e~^.
2
2
<\302\243

[8.61]

Supposeeachwell is a parabola:16
-ma)-(x

+\302\253)\",

V(.v) =

if x < 0.

[8.62]

\342\200\242

-)\302\273r(.v

\342\200\224

ay, if a- > 0.

'\"Even if V'(.v) is not strictly parabolic in each well, this calculation of 0.and hence the result
in the sensediscussedat the beginning of Section2.3,
(Equation 8.63)will be approximately correct,
=
to
with
\\/V\"(.X())/m. where xq is the position of the minimum.

338

Chapter8 The WKB Approximation


find 9 (Equation
Sketchthispotential,
8.58),and show that
,\302\261

_ /

hco

1 \\

[8.63]

Comment:If the centralbarrierwere impenetrable


oo),we would
(0
harmonicoscillators,
and the energies, = (n +
simplyhave two detached
sincethe particlecouldbe in the left
1/2)//0),wouldbe doublydegenerate,
well or in the right one.When the barrier becomes
finite(putting the two wells
the degeneracy
into \"communication\,")
is lifted.The even states(i}/t~}~) have
slightlylower energy,and the odd ones(\\ir~) have slightlyhigherenergy.
in a
the particlestartsout in the right
moreprecisely,
(e) Suppose
stateof the form
\342\200\224>

\302\243\342\200\236

well\342\200\224or,

0)=-^(^++^-).

*(x,

the phasesare pickedin the \"natural\"way, will be


which, assuming
in the right well.Show that it oscillates
backand forth betweenthe
wells,with a period
concentrated

r =

\342\200\224e*.

CO

(f)

[8.64]

Calculate
in part (d),and show that for V(0)
0, for the specificpotential
~
0 mcocr/h.

\302\273

E,

Problem8.16Tunneling
in theStarkeffect.When you turn on an external
the atom.
tunnel out,ionizing
field,the electronin an atom can,in principle,
We can
Question:Is this likely to happenin a typical Stark effectexperiment?
estimatethe probabilityusinga crudeone-dimensional
model,as follows.Imagine
a particlein a very deepfinite squarewell (Section
2.6).
(a) What is the energy of the groundstate,measured
up from the bottomof the
well?AssumeVb ~3>
Hint:Thisis just the groundstateenergy of
electric

fi2/\302\273ia2.

the infinite squarewell (of width 2a).


(for an electronin an electric
(b) Now introducea perturbationH' =
=
=
fieldE
Ecx[i we wouldhave a. eECK[).Assume it is relatively weak
(aa tr/mcr).Sketchthe total potential,and note that the particlecan
now tunnel out,in the direction
of positivex.
\342\200\224ax

\342\200\224

<\302\243

(c)

Calculatethe tunnelingfactor y (Equation8.22),and estimatethe time


it would take for the particleto escape(Equation
8.28).Answer: y =
J%mV*/3ah,x = (%ma2/jrh)e2Y.

339

Further Problems
for Chapter8

somereasonable
numbers:Vq = 20 eV (typicalbindingenergy for an
=
outerelectron),
a 10-10m (typicalatomicradius), = 7 x 106V/m
(stronglaboratoryfield),e and m the chargeand massof the electron.
Calculate t, and compare
it to the age of the universe.

(d) Put in

\302\243cx,

Problem8.17About how longwouldit take for a can of beerat roomtemperature


to toppleoverspontaneously,
as a resultof quantum tunneling?
Hint:Treat it as a
uniform cylinderof massm, radius/?,and lengthh. As the can tips,let,v be the
heightof the centeraboveits equilibrium
position(h/2).The potentialenergy is
ingx, and it toppleswhen x reachesthe criticalvalue .vo = >/R2 + (h/2)2 h/2.
Calculate
the tunnelingprobability
(Equation8.22),forE = 0.UseEquation8.28,
with the thermal energy ((l/2)mir= (1/2)^7)to estimate
the velocity.Put in
reasonable
numbers,and giveyour final answer in years.17
\342\200\224

R. E, Crundall, ScientificAmerican, February

1997,p. 74.

CHAPTER 9

TIME-DEPENDENT
PERTURBATIONTHEORY

Up to thispoint,practicallyeverything we have donebelongsto the subjectthat


in which the potential
energy function is
might properlybe calledquantumstatics,
independent
oftime:V(r,t) = V(r).In that casethe (time-dependent)
Schrodinger

equation,
HV =
can be solvedby

a*
ih\342\200\224.

dt

of variables:
separation

where \\j/(r) satisfies


the time-m
dependentSchrodinger
equation,

Hir =

E\\fr.

Becausethe time dependence


of separable
solutionsis carriedby the exponential
factor(e~'Et/n),
which cancels
the physically
relevant quanoutwhen we construct
valuesare constantin time.By forming
and expectation
tity |vl>|% all probabilities
of thesestationary stateswe obtainwave functionswith more
linearcombinations
time dependence,
valuesof the energy,and
but even then the possible
interesting
their respective
are constant.
probabilities,
If we want to allowfor transitions(quantumjumps,as they are sometimes
called)betweenoneenergy leveland another,we must introducea time-dependent
There are precious
few exactly solvable
problems
(quantumdynamics).
potential
340

Section9.1:Two-LevelSystems

341

quantum dynamics.However,if the time-dependent


portionOf the Hamiltonian
issmallcomparedto the time-independent
part,it can be treatedas a perturbation.
in this chapteris to developtime-dependent
perturbation
My purpose
theory,and
the emission
or absorption
of radiationby
study its mostimportant application:
in

an

atom.

9.1TWO-LEVELSYSTEMS
To beginwith, letus supposethat there are just two statesof the (unperturbed)
of the unperturbed
Hamiltonian,
system, and 1/7,.They are eigenstates
H\302\260:

\\jfa

H\302\260xfia

= Eafa, and

and they are orthonormal:


(V/\302\253IV//,>

Any

HQ^h

= Ehfh.

[9.1]

= <W.

[9.2]

statecan be expressed
as a linearcombination
of them;in particular,

W) = caylfa+cbtb.

[9.3]

The states\\j/a and i/f/, might be position-space


wave functions,
or spinors,or

more
doesn'tmatter; it is the time dependence
that concerns
something
us here,so when I write ^(t),I simplymean the stateof the systemat time t.
In the absenceof any perturbation,
eachcomponent
evolveswith itscharacteristic
factor:
exponential
exotic\342\200\224it

\302\245(f)

= car/fae-iE\"t/n+ chirhe-iEht/n.

[9.4]

is the \"probability
that the particleis in state
which
we really mean the probability
that a measurement
of the energy wouldyieldthe
value E(l.Normalization
of ^ requires,
of course,that

We say that

\\ca\\2

^r\342\200\236\"\342\200\224by

k\302\253|2

+ |cfc|2=l.

[9.5]

9.1.1
ThePerturbedSystem
Now suppose
we turn on a time-dependent
H'(t).Since\\j/a and i/f/,
perturbation.
a complete
constitute
as a linear
set,the wave functionty(t) can stillbe expressed
of them.The only differenceis that ca and c/, are now functions
combination
oft:

+ ch(t)irbc-iEh,/r'.
*(0= ca(t)irae-iE\"'/ri

[9.6]

factorsinto ca(t) and ci,(t),and somepeople


(I couldabsorbthe exponential
preferto do it this way, but I think it is nicerto keep visiblethat part of the

342

Perturbation
Theory
Chapter9 Time-Dependent
The whole
timedependence
that wouldbe present
even without the perturbation.)
the particle
ca and cb,as functionsof time.If, for example,
problemis to determine
= 1.cb(0)= 0),and at somelatertime t\\ we find
startedout in the state\\J/a
that ca(t\\) = 0, cb(t\\) = 1,we shallreportthat the system underwenta transition
(c\302\253(0)

from i/fa to tAv,.

We solveforca(t)and cb(t)by

that ty(t) satisfy the time-dependen


demanding

Schrodinger
equation,

HV=ih

r) Vl/

where H =

\342\200\224.

dt

H\302\260

+ H'(t).

[9.7]

FromEquations9.6and 9.7,we find:

+ cb[H'fb}e-iE*\"h
+cb[H%}]e-iE\"\"h
+ca[H'x};fl]e-iE\"'/r'

cfl[ffVfl>-'\302\243\"'/A

= ih\\cafae-iE\"'lh
+ch1rhe-iEht/r'

of Equation9.1,the first two terms on the left cancelthe lasttwo terms


on the right,and hence
In view

CalH'Me-'W+cWMe-'W^h

[9.8]

\342\200\242

[tfl^\302\253f-'\302\243-^+c^tf\"'\"\302\243*,/A]

To isolateca,we usethe standardtrick:Takethe inner productwith

of
exploitthe orthogonality

\\fra

and

and \\frb (Equation9.2):

For short,we define


H'u

mH'Wj):
=

notethat the hermiticity of H' entails


we conclude
that:
\342\200\224(i/h)e'E\"'/n,

//'\342\226\240

\\}/a,

h L

Similarly,the inner productwith

\"\"

\\j/b

[9.9]

(A//,-)*. Multiplyingthrough by

[9.10]

\"/j

picksout cb:

= ihcbe-iEht/n.
+ cb^b\\H'\\ifb)e-iEkt'h
cflM,|ff'lfci>*~'\302\243','//'
and hence
cft

-i[^,,+

caH'baei(E<>-E\302\253\302\273l*}

[9.11]

Section9.1:Two-Level
Systems

343

ca(t) and c^{t)\\ taken together,they are


Equations9.10and 9.11determine
to the (time-dependent)
fora two-level
Schrodinger
completely
equation,
equivalent
of H' vanish (seeProblem9.4for
system.Typically,the diagonalmatrix elements
the generalcase):

Ka = Kb=V-

[9-12]

If so,the equations
simplify:
ca

\342\200\224

Jnabe

cb*

where
\302\243/;

CO()-

(I'llassumethat

E/, >

cb

\342\200\224

Jjl Jux\\t,.
~ftHbae

c\302\253<

-. Ea

[9.13]

[9.14]

Ea,so a>o > 0.)

9.1A

electricfieldE =
hydrogenatom is placedin a (time-dependent)
H'..of the perturbation
H' = eEzbetween
allfour matrix elements
E(t)k.Calculate
the groundstate(n = 1)and the (quadruplydegenerate)
first excited
states(/? = 2).
Alsoshow that H'u = 0 for allfive states.Note:There is only oneintegral to be
donehere,if you exploitoddnesswith respectto z: onlyoneof the n = 2 states
is \"accessible\"
of thisform,and therefore
from the groundstateby a perturbation
the systemfunctionsas a two-stateconfiguration\342\200\224assuming
transitions
to higher
excitedstatescan be ignored.

\342\231\246Problem

9.2 SolveEquation9.13for the caseof a time-independent


perturbation,
=
=
+ k/,(r)|2= 1.
assumingthat ca(0) 1 and c/,(0) 0. Checkthat

\342\231\246Problem

|c\342\200\236(DI2

thissystem oscillates
between\"pure\\fra\" and \"somei/f/,.\"
Comment:Ostensibly,
Doesn'tthiscontradict
that no transitions
occurfor timemy generalassertion
No,but the reasonis rather subtle:In thiscase and
independent
perturbations?
of the Hamiltonian\342\200\224a measurement
of the
i/f/; are not,and never were,eigenstates
In time-dependent
perturbation
theory we typically
energy neveryieldsEa or
for a while,and then turning it off again,
contemplate
turning on the perturbation
in orderto examine
the system.At the beginning,and at the end,\\}/a and if/i, are
and only in thiscontextdoesit make sense
of the exactHamiltonian,
eigenstates
to say that the systemunderwenta transition
from oneto the other.Forthe present
problem,then, assumethat the perturbationwas turned on at time t = 0. and
off againat time
doesn'taffect the calculations,
but it allowsfor a more
of the result.
sensibleinterpretation
\\fra

\302\243/,.

t\342\200\224this

* *Problem9.3 Suppose
the perturbation
takesthe form of a deltafunction(in time):

H' = U8(t):

344

Perturbation
Theory
Chapter9 Time-Dependent

= 1 and
= 0, and let Uai, = U*Hl = a. If
= 1.What is
and c/,(/),and checkthat \\ca(t)\\2+ |c/,(/)|2
the net probability(Pa-*i>for t
occurs?Hint:You might
oo)that a transition
of rectangles.
want to treat the deltafunctionas the limit of a sequence
Answer:
Pa-+h= s\\n2(\\a\\/h).

assumethat Ua(l =
Cb(-oo)= 0, find

ca(\342\200\224oo)

\302\242//,/,

c\342\200\236(t)

-\302\273

9.1.2Time-Dependent
Perturbation
Theory
So far, everything isexact:We have madeno assumption
aboutthe sizeof the
of
perturbation.
But if H' is \"small,\"
we can solveEquation9.13by a process
as follows.Supposethe particlestartsout in the lowerstate:
approximations,

successive

cfl(0)=l. cfr(0) = 0.

[9.15]

If there were no perturbation


at all,they wouldstay this way forever:

ZerothOrder:

l,

[9.16]
40)(O= O.
in parentheses
to indicatethe orderof the approximation.)
(I'llusea superscript
values
To calculate
the first-orderapproximation,
we insertthe zeroth-order
on the right sideof Equation9.13:
40)(/)=

FirstOrder:
dr{(l)
ac\302\253

'\"
dcb(1) _
=
dt

u'

!:

_ 1.
,<l)/,x=
= 0 =>#'(')
\302\253

\342\226\240

J(0()l_v
-? J1)=

\342\200\224rHLne,an'=*c
baK
Lb

[9.17]

-J Jof H;}a(t')eic*>''dt'.
n

insertthese expressions
on the right, to obtain the .second-order
approximation:
Now we

SecondOrder:
dc(2)~

dt

i
ah

j^)

H'ha(t')e^''dt'^

['

[9.18]

= l ~ To Ki>(t')e~i0H)'' H'ha{t\eh^\"dt\"dt'.
-S2)('>
rr Jo
Jo
while ci,is unchanged(c;, (/) = ch
(Noticethat cy, (/) includesthe zerothorderterm; the second-order
wouldbe the integralpart alone.)
correction
'(/))\342\200\242

Section9.1:Tivo-LevelSystems

345

we couldcontinuethis ritual indefinitely,


the
In principle,
always inserting
into the right sideof Equation9.13,and solvingfor the
nth-orderapproximation
no factorsof //', the first-order
(n + l)th order.The zerothordercontains
one factorof //', the second-order
correction contains
correctionhas two factors
in
is evident in the
of //',and so on.1The error the first-orderapproximation
fact that \\ca (t)\\2 + \\c(h (t)\\2 # 1 (the exactcoefficients
must, of course,obey
Equation9.5).However,IcJ/V)!2+ \\c((}l)(t)\\2 is equalto 1 tofirstorderin H\\
which is all we can expectfrom a first-order
And the samegoes
approximation.
for the higherorders.

* *Problem9.4 Suppose
you don7 assumeH'aa =

H'bh

= 0.

=
Findca(t) and ci,(t)in first-orderperturbation
theory, lor the case
1, c,,(0)= 0. Show that \\clal\\t)\\2 + |4U(0I2= 1,to first orderin //'.
Let
(b) There is a nicerway to handlethisproblem.
(a)

c\342\200\236(0)

da = e'*&

H'\302\253\302\253l,'wca,

dh

= e*& H'i*{,')dt'cb.

[9.19]

Show that
da =
where

dh = --e^H^e1^
da.
-'-e^H^e-^'d,,:

0(0= J'[Ka(t') H'hh(t')]dt'.

[9.20]
[9.21]

in structure to Equation9.13
So the equations
for da and dh are identical
(with an extra factore'^ tackedontoH').
(c) Usethe methodin part (b) toobtainca(t)and ci,(t)in first-order
perturbation
and
to
Comment
on
answer
(a).
compareyour
theory,
any discrepancies.

\342\231\246Problem

9.5 SolveEquation9.13to secondorderin perturbationtheory, for the

generalcaseffl(0)= a, q,(0)= h.

**Problem9.6 Calculate
ca(t) and ct,(t),to secondorder,for a time-independent
(Problem9.2).Compareyour answer with the exact result.
perturbation
'Noticethat
if the perturbation
the two states.
true

c\342\200\236

is modified in cvciy even order, and q, in every odd order; this would not be
included diagonal terms, or if the system started out in a linear combination of

346

Perturbation
Chapter9 Time-Dependent
Theory

9.1.3Sinusoidal
Perturbations
has sinusoidal
time dependence:
Supposethe perturbation
H'(rft)= V(r)cos(a>t).
so that
Kb = Vabcos(o)t),

[9.22]

[9.23]

where

[9.24]

before,I'll assumethe diagonalmatrix elementsvanish, sincethisis almost


To first order(from now on we'llwork exclusivelyin
always the casein practice.)
first order,and I'll dispense
with the superscripts)
we have (Equation9.17):
(As

iVt

dt' =

cb(t)= ~Vba
f
*

1)(1

cos(cot')eko\302\273''

Jo

Vba

ei(o)o+o))t_

2h

CPQ+CO

2h

ei(i\302\273o-o))l

i;y

(w()+w)l' ei(on)-(o)t
i

\342\226\240]*\342\200\242

[9.25]

CO

\342\200\224

COQ

to work with. Thingssimplify


That'sthe answer,but it's a littlecumbersome
(a>) that are very
substantiallyif we restrictour attentionto driving frequencies
closeto the transitionfrequency(coq),sothat the secondterm in the squarebrackets
we assume:
dominates;
specifically,
coq

+ co

|a>o

;\302\273

[9.26]

\342\200\224co\\.

Thisis not much of a limitation,


have
sinceperturbationsat other frequencies
a negligible
anyway.\" Droppingthe first term,
probabilityof causinga transition
we have

Chit) =

Vba

eS

{can\342\200\224co)i/2

2/J
,

coq

\342\200\224

co

((o0-(o)l/2_ -i((0()-(o)t/

2]

sin[(aj0 co)t/2]^l{oM)_(o)l/1

Vbg

COQ

\342\200\224

CO

[9.27]

The transitionprobability\342\200\224the probabilitythat a particlewhich startedout in


the statetya will be found,at time t, in the state
\\j/b\342\200\224is

Pa--+b(t) =

/ \\.7

\\Cb(T)\\-

\\Vab\\2

h2

- co)t/2]'

sin2[(&>o-

(coq-coy\342\226\240

[9.28]

2In the followingsectionswe will be applying this theory to the caseof light, for which to ~ 10.1*5
so the denominator in both terms is huge, except(for the secondone) in the neighborhood of o)q.

Two-LevelSystems
Section9.1:

347

PMI

9.1:

FIGURE
Transition
as a functionof time, for a sinusoidal
probability
(Equation9.28).
perturbation

The mostremarkablefeature of this resultis that, as a functionof time,the

transition
probabilityoscillatessinusoidally
(Figure9.1).After risingto a
of \\Vab\\2/h-{coo-co)2\342\200\224necessarily
much lessthan 1.elsethe assumption
that the perturbation
is \"small\"would be
dropsback down to zero!
= 2htc/\\cdq co\\, where n =
the particleis certainto
At times
be back in the lower state.If you want to maximize your chancesof provoking
a transition,
on for a longperiod;you do
you shouldnot keep the perturbation
betterto turn it off after a time tt/\\coq a>|,and hopeto \"catch\"the systemin
the upperstate.In Problem9.7 it is shown that this \"flopping\"is not an artifact
of perturbation
occursalsoin the exactsolution,though the flopping
frequencyis modifiedsomewhat.
of a transitionis greatestwhen the driving
As I notedearlier,the probability
in Figure9.2,
coq.Thisis illustrated
frequency is closeto the \"natural\"frequency,
where P,,-^/,isplottedasa functionofco.The peakhas a height of (| Va/}\\t/2ti)2and
a width 4n/t; evidently it getshigherand narrower as time goeson. (Ostensibly,
the maximumincreases
without limit.However,the perturbation
breaks
assumption
maximum

invalid\342\200\224it

1,2,3....,

\342\200\224

t\342\200\236

\342\200\224

theory\342\200\224it

P(co)A

(co0 27t/f)

(co0+ 2n/t)

FIGURE9.2: Transition
asa functionofdrivingfrequency(Equation9.28).
probability

348

Perturbation
Theory
Chapter9 Time-Dependent

getscloseto 1,sowe can believethe resultonlyfor relatively small


t. In Problem9.7 you will seethat the exactresultnever exceeds1.)

down beforeit

* *Problem9.7 The first term in Equation9.25comesfrom the ell0'/2part of cos(co/),


and the secondfrom e~uo'/2.Thus droppingthe first term is formally equivalent
which is to say,
to writing H' = (V/2)e~'M',

jji

\"ha

-Uol

Hha--^~e

\342\200\242

Tit

Hab

-_

vab
\342\200\224e

TO ?Q1

\\i0\\

l9-29J

\342\226\240

matrix hermitian\342\200\224or,
(The latter is requiredto make the Hamiltonian
prefer,

if you

to Equation9.25
to pick out the dominantterm in the formula analogous

for ccl(t).)Rabi noticedthat if you make this so-called


rotatingwave
at the beginningof the calculation,
Equation9.13can be solvedexactly,
with no needfor perturbation
aboutthe strength of
theory, and no assumption
the field.
approximation

(a)

SolveEquation9.13in the rotatingwave approximation


(Equation9.29),for
=
=
the usual initialconditions:
ca(0) 1.c/,(0) 0. Expressyour results(c(,(t)
and Cb(t)) in terms of the Rabi floppingfrequency,
(Or =
\\

[9.30]

+ (Wab\\/h)2.
yJ(oJ-CO0)2

never exceeds

(b)

the transition
Determine
probability,Pa~*h(0,and show that
= 1.
1.Confirmthat \\ca(t)\\2+ |c/,(Y)|2

(c)

Checkthat Prt_>/,(f)reducesto the perturbation


theory result(Equation9.28)
is \"small,\"and statepreciselywhat smallmeansin
when the perturbation
this context,
as a constraint
on V.

(d)

At

it

what time doesthe system first return to itsinitialstate?

OF RADIATION
9.2 EMISSIONAND ABSORPTION

9.2.1Electromagnetic
Waves
wave (I'll refer to it as \"light,\"though it couldbe infrared,
electromagnetic
consists
ultraviolet,
microwave,X-ray, etc.;thesedifferonly in their frequencies)
electricand magneticfields
of transverse (and mutually perpendicular)
oscillating
of a passinglightwave, responds
(Figure9.3).An atom,in the presence
primarily
to the electriccomponent.
If the wavelength is long(comparedto the sizeof the
An

Section9.2:Emission
andAbsorption
of Radiation 349
Electric
field

Magneticfield

FIGURE9.3: An electromagnetic
wave.

atom),we can ignorethe spatialvariation in the field;3the atom,then,is exposed


to a sinusoidally
electricfield
oscillating

E=

[9.31]

Eocos(wr)\302\243

and polarized
(forthe moment I'll assumethe lightis monochromatic,
alongthe z
is4
The perturbingHamiltonian
direction).

H' = -qEozcos(cot).
where q

[9.32]

is the chargeof the electron.5


Evidently6
HL = -pEocosicot).where p = q(\\j/h\\z\\i/a)-

[9.33]

Typically,\\j/ is an even or odd functionof z\\ in eithercasez|iAI2 is odd,and

to zero(seeProblem9.1for someexamples).
Thislicensesour usual
integrates
that the diagonalmatrix elements
of H' vanish.Thus the interaction
of
assumption
3For visible light

is reasonable:
but
the field.

it

A.

would

~ 5000A.while the
not

diameter of an atom is around 1 A. so this approximation


be for X-rays.Problem 9.21explores
the effect of spatial variation of

4The energy of a charge q in a static field E is c//E dr.You may well object to the use of
an electro.s7w//c-formula for a manifestly time-dependent field. I am implicitly assuming that the period
of oscillation is long comparedto the time it takes the charge to move around (within the atom).
As usual, we assumethe nucleus is heavy and stationary: it is the wave function of the electron
\342\200\224

\342\200\242

\342\200\242^

that

concernsus.

6Thc letter p is supposedto remind you of electric


dipolemoment (for which, in
the letter p is customarily
this context it is renderedas a squiggly p to avoid confusion
with momentum). Actually,
p is the off-diagonal matrix element of the component of the dipole
moment operator, c/r. Becauseof its associationwith electric
dipole moments, radiation governed by
is calledelectricdipoleradiation:it is overwhelmingly the dominant kind, at least in
Equation
the visible region.SeeProblem
for generalizations and terminology.
used\342\200\224in

electrodynamics,

9.33

9.21

350

Perturbation
Chapter9 Time-Dependent
Theory
we
the kind of oscillatory
lightwith matter is governedby precisely
perturbation
with
studiedin Section9.1.3,

Vba

= -pE0.

[9.34]

9.2.2Absorption,StimulatedEmission,andSpontaneous
Emission
If an atom starts out in the \"lower\"state\\j/a, and you shinea polarized
beamof lighton it, the probabilityof a transition
to the \"upper\"statexj/i, is
given by Equation9.28,which (in view of Equation9.34)takesthe form
monochromatic

= (\302\2532
M(\"o-\302\253)'/2i,
[9.35]
ft
\\
/
(coo-co)~
In thisprocess,the atom absorbsenergy
E(l = hcoQ from the electromagnetic
field.We say that it has\"absorbed
a photon\"(Figure9.4(a)).(As I mentioned
the word \"photon\"really belongs
to quantumelectrodynamics
[the quantum
field],whereas we are treating the fielditself
theory of the electromagnetic
But thislanguageis convenient,
as longas you don'treadmoreintoit than
is really there.)
I could,of course,gobackand run the wholederivationfor a system that starts
offin the upperstate(crt(0) = 0, c/,(0)= 1).Doit for yourself,if you like;it comes
outexactly the same\342\200\224except that thistime we'recalculating
Pb-*a= \\ca (OI-,the
down to the lower level:
probabilityof a transition
,._,<\342\200\236

\342\200\224

\302\243/,

earlier,

classically.

JWO = ({J^)~
h
J

p.36]

\"\342\226\240*(\302\253.-\302\253*/2]_

\\

(coo-co)~

we'redoingisswitchinga b,which substitutes


(Ithasto comeoutthis
for a>o. When we get to Equation9.25we now keep the first term, with
and the restis the sameas before.)But when you
+ co in the denominator,
result:If the particleis in the
stopto think of it, thisis an absolutelyastonishing
to the lower state,
upperstate,and you shinelighton it, it can make a transition
and in fact the probability
of sucha transition
is exactly the sameas for a transition
<-\302\273

way\342\200\224'-all

\342\200\224coo

\342\200\224coo

which was first


upward from the lower state.This process,

iscalledstimulatedemission.

(a) Absorption

(b) Stimulatedemission

predicted
by Einstein,

emission
(c) Spontaneous

FIGURE9.4: Three ways in which light interacts with


emission.
(b) stimulatedemission,
(c) spontaneous

atoms:(a) absorption,

and Absorption
Section9.2:Emission
of Radiation

351

In the caseof stimulated


emission
the electromagnetic
fieldgainsenergy ftcoo
from the atom;we say that onephotonwent in and two photonscame
originalonethat causedthe transition
plusanotheronefrom the transitionitself
out\342\200\224the

for if I had a bottle


of amplification,
(Figure9.4(b)).Thisraisesthe possibility
of atoms,all in the upperstate,and triggeredit with a singleincidentphoton,a
chainreactionwouldoccur,with the first photonproducing2, these2 producing
number of photons
4, and soon.We'dhave an enormous
comingout,all with the
samefrequency and at virtually the sameinstant.Thisis,of course,the principle
behindthe laser(lightamplification
emission
of radiation).
Notethat
by stimulated
it is essential
(for laseraction)to get a majority of the atomsintothe upperstate
becauseabsorption(which costsonephoton)
(a so-called
populationinversion),
with stimulated
emission(which producesone);if you startedwith an
competes
even mixture of the two states,you'dget no amplification
at all.
Thereis a third mechanism
and stimulated
(in additionto absorption
emission)
radiation
which
with
it
is
emission.
Herean
interacts matter; calledspontaneous
by
atom in the excited
statemakesa transition
of a photon,
downward,with the release
but without any applied
fieldto initiatethe process(Figure9.4(c)).
electromagnetic
Thisis the mechanism
that accounts
for the typicaldecay of an atomicexcited
state.At first sightit is far from clearwhy spontaneous
emissionshouldoccur
at all. If the atom is in a stationary state(albeitan excited
one),and there is no
externalperturbation,it shouldjust sit there forever.And so it would,if it were
the
However,in quantum electrodynamics
really free of all external perturbations.
fieldsare nonzeroeven in the ground
as the harmonic oscillator
(for
wit:
i
n
can
has
its
state.
Y
ou
turn
out
example) nonzeroenergy (to
lico/2)
ground
all the lights,and coolthe roomdown to absolutezero,but there is stillsome
radiationpresent,and it is this\"zeropoint\" radiationthat serves
electromagnetic
to catalyze spontaneous
emission.
When you comeright down to it, there is really
no suchthing as truly spontaneous
it'sall stimulated
emission.
The only
emission;
distinction
to be made is whether the fieldthat doesthe stimulating
isonethat you
put there,or onethat God put there.In thissenseit is exactly the reverseof the
radiative process,
in which it'sall spontaneous,
and there is no suchthing
classical
state\342\200\224just

asstimulated
emission.
is beyondthe scopeof thisbook,7but there is a
Quantum electrodynamics
which interrelates
the three processes
lovelyargument, dueto Einstein,8
stimulated
Einsteindid not identify
emission,and spontaneous
emission).
the mechanism responsible
for spontaneous
emission(perturbation
by the groundstateelectromagnetic
enableus to calculatethe
field),but hisresultsnevertheless
(absorption,

'Foran accessible
treatment seeRodney Loudon, The Quantum

(Clarendon

Press,Oxford. L983).
^Einstein'spaperwas publishedin

electrodynamics

from

comesinto

1900.

1917,

Theoiyof Light. 2nd ed.

well before the Schrodingerequation. Quantum


which
the argument via the Planck blackbodyformula (Equation

5.113),

dates

352

Perturbation
Theory
Chapter9 Time-Dependent

emission
rate,and from that the natural lifetimeof an excitedatomic
spontaneous
of an atom
the response
state.9Beforewe turn to that, however, we needto consider
waves comingin
incoherent
to non-monochromatic,
electromagnetic
unpolarized,
if it were immersed
for instance,
from all directions\342\200\224such as it wouldencounter,
in thermal radiation.

9.2.3IncoherentPerturbations
wave is10
The energy densityin an electromagnetic
u

where Eq

jEl

[9.37]

is (asbefore)the amplitudeof the electricfield.So the transition

to the energy densityof


proportional
(Equation9.36)is (notsurprisingly)

probability

the fields:

Ph^a(t)=

-^

[9.38]

(wo a>r
eotr
wave, at a singlefrequency co.In many
But thisis for a monochromatic
waves at a whole range of
the system is exposedto electromagnetic
where p{co)dco
is the energy densityin
frequencies; in that caseu -> p(co)da),
the frequency rangedco,and the net transition
probabilitytakes the form of an
integral:11
\342\200\224-\\p,\\-

applications

2
Pb^a(t)=

sin2[(o>oco)t /2] dco.

\342\200\224

f\302\260\302\260

\342\200\224rl^l2

P(CO)

9For an interesting alternative derivation


Problem 9.9.

using

(coq

tt>)2

quantum
\"scat-.of-the-pants\"

[9.39]

see
electrodynamics,

Introduction to Electrodynamics, 3rd ed.(Prentice Hall.UpperSaddleRiver. NJ.


In general, the energy per unit volume in electromagnetic fields is
Section
9.2.3.
1999).

I0D.Griffiths.

For electromagnetic waves, the

= (e0/2)E2+(\\/2na)B2.

electricand
n

magnetic contributions are equal, so

= (qE~=

\302\2530^5

cos\"(to/).

sincethe average of cos-(or sin-) is 1/2.


cycle is
'Equation9.39assumesthat the perturbations at different frequencies are independent, so that
the total transition
probabilities.If the different components
probability is a sum of the individual
then wc should add amplitudes (c/,(/)).not probabilities(|c/,(/)|-).
are coherent(phase-correlated),
For the applications we will consider the perturbations arc always
and there will be cross-terms.
and the average over a
1

incoherent.

full

(<?o/2)\302\243^.

and Absorption
Section9.2:Emission
of Radiation 353

The term in curly bracketsis sharply peakedabout

(Figure9.2),whereas
as well replacep(a))by p(a>o),and take
a\302\273o

p(co)is ordinarilyquitebroad,so we may


it

outsidethe integral:

Pb^aiO=

o
;(o>o cor

/
Jo

\342\200\224-^-P(too)
\342\202\254Qtr

do).

\342\200\224

[9.40]

Changingvariablesto x = (a>o a>)t/2,extendingthe limitsof integrationto


x = +oo (sincethe integrandis essentially
zeroout there anyway), and looking
up the definiteintegral
00 sin2,v
\342\200\224

Loo

dx=n.

[9.41]

^fp(w0)r.

[9.42]

\342\200\224

we find

Pb^aif)=

60\302\253\"

Thistime the transitionprobabilityis proportionalto t. The bizarre \"flopping\"


of a monochromatic
phenomenoncharacteristic
perturbationgets \"washedout\"
when we hit the system with an incoherent
In particular,
the
spreadof frequencies.
=
transitionrate {R dP/dt)is now a constant:
Rh^a = -^\\p\\2p(o)0).
[9.43]
\342\202\254on~

So far, we have assumedthat the perturbingwave is comingin alongthe y


direction(Figure9.3),and polarizedin the z direction.
But we are interested
in
the caseof an atombathedin radiationcomingfrom all directions,
and with all
the energy in the fields(p(a>)) is sharedequallyamongthese
possible
polarizations;
different modes.What we need,in placeof \\p\\2, is the averageof \\p, -h\\2, where
[9.44]
fi = qWhMa)
and all
(generalizing
Equation9.33),and the average is overallpolarizations
directions.
The averaging can be carriedout as follows:Choosespherical
coordinates
suchthat the directionof propagation(k) is alongx, the polarization
(/7) is along
s, and the vectorp, definesthe spherical
angles9 and 0 (Figure9.5).12(Actually,
incident

'-I'lltreat p.as though


\\p.

it

were real,even though

- |Re(/i)-n +
-;}|'

i\\m(p.)

n\\~

\342\200\242

in

general it

will

be complex.
Since

= \\Rc(p.) n\\2 + \\lm(p.)


\342\200\242

n\\2

\342\226\240

we can do the whole calculation for the real and imaginary parts separately, and simply add the results.
In Equation
9.47the absolute value sign is doing double duty, signifying both the vector magnitude
and to the complexamplitude:
lA|2

l/\302\273.r|2

+ l/Iv|2+

l/\302\273;|2.

354

Perturbation
Chapter9 Time-Dependent
Theory

Za
n

^.0

FIGURE9.5: Axesfor the averagingof

^^

\\

|/i h\\2.
\342\200\242

with
p. isfixedhere,and we'reaveraging overallk and n consistent
is to say, overall9 and 0.But it'sreally the coordinate
system,not the vectorp,,
kA.fi\342\200\224which

that

is changing.)
Then

p.-n= pcos9.

[9.45]

and
1/\302\273-\"

\"lave

4^: /

d9d<l>
l/*|-cos-0sin0

cos39
An

(2tt)=

-|/l|2.
1

[9.46]

Conclusion:
The transition
rate for stimulated
emission
from state to statea,
under the influenceof incoherent,
is
from alldirections,
unpolarized
lightincident
\302\243>

[9.47]
where p. is the matrix element
of the electricdipolemoment betweenthe two states
(Equation9.44),and p(coo)is the energy densityin the fields,perunit frequency,

evaluatedat

is a

'\342\200\242^This

says that the


and to the

coq =

\342\200\224

(\302\243/,

Ea)/hP

specialcaseof Fermi'sGoldenRule for time-dependent perturbation theory, which


rate is proportional to the square of the matrix clement of the perturbing potential

transition

strength

of

the perturbation

at

the

transition

frequency.

Section9.3:Spontaneous
Emission 355

9.3 SPONTANEOUSEMISSION

9.3.1Einstein'sA andB Coefficients


of atoms,Na of them in the lowerstate(^,),and Ni, of them in
Picturea container
the upperstate(i/f/,). Let A be the spontaneous
emission
rate,14so that the number
of particlesleavingthe upperstateby thisprocess,per unit time,is Ni>A.15The
as we have seen(Equation9.47),is
transition
rate for stimulated
emission,
field:BiHlp(ojo);
the number of
to the energy densityof the electromagnetic
particlesleaving the upperstateby thismechanism,
per unit time,is Ni}Bhap(coo).
rate is likewiseproportional
it Bahp(coo)\\the
The absorption
to
of particles
All
per unit time joiningthe upperlevelis thereforeN(IB(1i,p(coq).
proportional

p(cdq)\342\200\224call

number

told,then,

^
at

= -NhA

NhBhf,p(coQ)+ NtlBllhp(co()).

[9.48]

with the ambient field,so that


theseatomsare in thermal equilibrium
Suppose
in eachlevelis constant.
In that casedN^/dt = 0, and it
the number of particles

followsthat

P(coo)=

xp
(Na/Nh)Bah

[9.49]

\342\200\224.

Blm

On the otherhand, we know from elementary statisticalmechanics16


that the

in thermal equilibrium
at temperature T, is
number of particleswith energy
to the Boltzmann
factor,expi-E/ksT),so
proportional
\302\243\",

^=

Ff,

and hence

p(coo)=

\342\200\236

[9.50]

r=eh(^k\302\253r.

...,.

[9.51]

\342\202\254\302\273\302\253*\"<*'Bah-Bba

But Planck'sblackbodyformula (Equation5.113)


tellsus the energy density

of thermal radiation:

p((o)=

-^- . ..a?_
h

[9.52]

we conclude
that
Comparingthe two expressions,
Bab = Bba
'\"'Normally

I'd use R

Einstein's notation in
^Assume that

this

for a

transition

context.

rate,

but out

[9.53]
of deferenceto

dcrAlic

everyone follows

N(, and N/, are very large, so we can treat them as continuous functions of time
and ignore statistical fluctuations.
Charles Kittel and Herbert Krocmcr.Thermal Plnsirx.2nd ed. (Freeman.
l6See,for example.
New York. 1980),Chapter

3.

356

Perturbation
Theory
Chapter9 Time-Dependent
and
A

[9.54]

-^1Bha.

Equation9.53confirmswhat we already knew: The transitionrate for


But it was an astonishing
result
emissionis the sameas for absorption.
in
in 1917\342\200\224indeed, Einsteinwas forcedto \"invent\" stimulated
emission order
to reproducePlanck'sformula.Our presentattention,however, focuseson
emission
rate
is what
Equation9.54,for thistellsus the spontaneous
terms of the stimulated
emission
rate (BiHlp((oo))\342\200\224which
we are looking
we already know.FromEquation9.47we readoff
stimulated

(A)\342\200\224which

for\342\200\224in

3<?o\302\253\"

and it followsthat the spontaneous


emission
rate is

[9.56]

for downward transitions,


emission
Problem9.8 As a mechanism
spontaneous
emission
with thermally stimulated
emission
for which black(stimulated
competes
bodyradiationis the source).Showthat at roomtemperature (T = 300K) thermal
forfrequencies
well below5 x 1012
stimulation
dominates
Hz,whereas spontaneous
emissiondominates
for frequencies
well above5 x 10 Hz. Which mechanism
dominates
for visiblelight?
rate (Equation9.56)
emission
Problem9.9 You couldderivethe spontaneous
A and B coefficients
if you knew the ground-state
the detourthrough Einstein's
field,pq(co),for then it would simplybe a
energy densityof the electromagnetic
caseof stimulated
emission(Equation9.47).To do this honestlywould require
but if you are preparedto believethat the groundstate
quantum electrodynamics,
consistsof onephotonin eachmode,then the derivationis very simple:
(a) ReplaceEquation5.111
(Presumably this
by N0J = ck, and deducepo(co).
elsethe total\"vacuumenergy\"would
formula breaksdown at high frequency,
be infinite but that'sa story for a different day.)
with Equation9.47,toobtainthe spontaneous
(b) Useyour result,together
rate.CompareEquation9.56.
without

...

emission

Section9.3:Spontaneous
Emission 357

9.3.2TheLifetimeof anExcitedState
rate for spontaneous
Equation9.56is ourfundamentalresult;it givesthe transition
emission.
now, that you have somehowpumpeda largenumber of atoms
Suppose,
intothe excitedstate.As a resultof spontaneous
thisnumberwill decrease
emission,
as time goeson; specifically,
in a time interval dt you will losea fractionAdt
of them:
dNb =

-ANhdt,

[9.57]

there is no mechanism
to replenishthe supply).17
(assuming
Solvingfor Nb(t),
we find:

Nh(t)

= Nh(0)e-A';

[9.58]

with
evidently the number remainingin the excitedstatedecreases
exponentially,
a time constant
r =
[9.59]

j.
A

callthisthe lifetimeof the state\342\200\224technically, it is the time it takesfor Ni,(t)


to reach\\/e ^ 0.368of itsinitialvalue.
I have assumedall along that there are only two statesfor the system,
but this was just for notationalsimplicity\342\200\224the spontaneous
emissionformula
rate for i///,
of what other
^ra regardless
(Equation9.56)givesthe transition
statesmay be accessible
(seeProblem9.15).
Typically,an excitedatom has many
different decaymodes(that is:\\j/i, can decay to a largenumber of different lowerIn that casethe transition
ratesadd,and the net
energy states,\\j/Cl, i//fM, \\f/ay....).
lifetimeis
.
r =
[9.60]
A\\ +A2 + A3 +
We

\342\200\224>

...

to
a chargeq is attachedto a springand constrained
Example9.1 Suppose
alongthe .v-axis.
Say it startsout in the state\\n) (Equation2.61),and decays
emission
to state\\n'). FromEquation9.44we have
by spontaneous
oscillate

p, = q{n\\x\\n')i.
You

the matrix elements


of x backin Problem3.33:
calculated
<w|.v|/i'>=

+
y^^ (vW,.,,'-!

y/nS\342\200\236>.\342\200\236-\\)

l7This situation is not to be confused with the caseoi* thermal equilibrium, which we considered
previous section.We assumehere that the atoms have been lifted out of equilibrium, and arc in
the process
of cascadingback down to their equilibrium levels.
in the

358

Perturbation
Theory
Chapter9 Time-Dependent
where co is the natural frequency of the oscillator.
(I no longerneedthisletterfor
the frequency of the stimulating
son'
But we'retalking aboutemission,
radiation.)
must be lower than n\\ forour purposes,
then.

and the
occuronly to statesonesteploweron the \"ladder,\"
Evidently transitions
frequency of the photonemittedis
coq =

E\342\200\236-E\342\200\236>

(n +

\\/2)lico-(n'+\\/2)hco
= (/7
h

\342\200\224

)co =

co.

L9.62J

the systemradiates
The
oscillator
Not surprisingly,
at the classical
frequency.
transition
rate (Equation9.56)is
A

-1

= nq~orv

[9.63]

and the lifetime


of the ;?th stationary stateis

^^

*=

(9.64]

nq^co-

Meanwhile,eachradiatedphotoncarriesan energy hco, so the powerradiatedis


Ahco:
->

\342\226\240>

q~co07T

C\302\260

\342\202\254()111

in the ;?th stateis E = (n + /2)hco,


or, sincethe energy of an oscillator
1

P= /JC0\\ \\E--haA.

[9.65]

This is the average powerradiatedby a quantum oscillator


with (initial)
energy E.

For comparison,
let'sdeterminethe average powerradiatedby a classical
oscillator
with the sameenergy.According
to classical
the power
electrodynamics,
radiatedby an accelerating
chargeq is given by the Larmorformula:18

p = crcr_
OJTfQC-

[966]

Fora harmonicoscillator
with amplitude
and the acceleration
.\\'o. v(/) = xq cos(cot),
is a = \342\200\224xoco2cos(cot).Averagingovera full cycle,then,
~>

p=

.1 4

<r*o\302\253>

\\2rreoc3

isSec,for example.
Griffiths (footnote 10).
Section 11.2.1.

Section9.3:Spontaneous
Emission 359
But the energy of the oscillator
is E =

soXq = 2E/mar,and hence


(l/2)mar.\\-Q,

->

This is the average powerradiatedby a classical


oscillator
with energy E, In the

and quantum formulasagree;19


0) the classical
however,
the groundstate:If E = (l/2)/?o>
the quantum formula (Equation9.65)protects
the
oscillator
doesnot radiate.

classical
limit (h

\342\200\224>

Problem9.10The half-life(t\\/2) of an excitedstateis the time it wouldtake for


half the atomsin a largesampleto make a transition.
Findthe relationbetween
of the state).
t\\/2 and r (the \"lifetime\"

9.11

* * *Problem
Calculatethe lifetime(in seconds)for eachof the four n = 2
statesof hydrogen.Hint:You'llneedto evaluate matrix elementsof the form
and so on. Rememberthat .v = r sin6cos0,y =
(^luokl^oo)'(^iool.vl^ii).
r sin9 sin0, and z = rcosO.Mostof theseintegrals
are zero,soscanthem before
Answer: 1.60x 10-9secondsfor all except\\J/200, which
calculating.
is infinite.

you start

9.3.3SelectionRules
of spontaneous
emissionrateshas beenreducedto a matter of
The calculation
of the form
evaluating matrix elements

workedProblem9.11(if you didn't,go back


are very oftenzero,and it wouldbe helpful
right now and do so!),thesequantities
if you
As you will have discovered

to know in advance when thisis goingto happen,so we don't waste a lot of


in systems
time evaluating unnecessary
like
integrals.
Supposewe are interested
is spherically
In that casewe
hydrogen,for which the Hamiltonian
symmetrical.
may specifythe stateswith the usualquantum numbers /?, /, and m, and the matrix

elements
are

(n'l'm'\\r\\nlm).
I9ln fact, if wc
identical.

expressP in

terms of

the

energy above the ground state, the

two

formulas arc

360

Perturbation
Chapter9 Time-Dependent
Theory
Cleverexploitation
of the angular momentum commutation
relationsand the heron
mitieity of the angular momentum operatorsyieldsa setof powerfulconstraints

thisquantity.

of LSelectionrulesinvolvingm and m': Considerfirst the commutators


with x, v, and z, which we workedout in Chapter4 (seeEquation4.122):

[Lz,x]= ihy, [L-,y]= -ihx, [L-,z]= 0.


Fromthe third of theseit followsthat

[9.68]

= (n'l'm'\\(LzzzL:)\\nlm)
0 = (n'l'm'\\[Lz.
z\\\\nlm)
= {n'l'm'\\[(m'h)zz(mh)]\\nlm)=
\342\200\224

Conclusion:

Eitherm' = m,

(//2'

\342\200\224

m)h(ril'm'\\z\\nlm).

or else{ril'm'\\z\\nlm)= 0.

[9.69]

Sounlessm' = //?, the matrix elements


of z are always zero.
of L- with .v we get
Meanwhile,from the commutator

= {n'l'm'\\{Lzx-xLz)\\nlm)
(/i7'//?'|[L-,.v]|/i/w>
= ih{n'l'm'\\y\\nlm).
= (in m)h{n'l'm'\\x\\nlm)
\342\200\224

Conclusion:

(m' m)(n'l'm'\\x\\nlm)= i{n'l'm'\\y\\nlm).

So you never have to computematrix elementsof


from the corresponding
of .v.
matrix elements
of Lz with y yields
Finally,the commutator

v\342\200\224you

[9.70]

can always get them

{n'l'm'\\[Lz,
y]\\nlm) = {n'l'm'\\(LzyyLz)\\nlm)
= \342\200\224ih{n'l'm'\\x\\nlm).
= (//j' m)h{n'l'm'\\y\\nlm)
\342\200\224

Conclusion:
(in

= -i(n'I'm'\\x\\nlm).
-m)(n'l'm'\\y\\nlm)

[9.71]

In particular,
combining
Equations9.70and 9.71,

(m' m)~Oi'l'tti'\\x\\nlm)= /(m' m)(n'l'm'\\y\\nlm)= (ri1'm\\x\\nlm),


\342\200\224

and hence:

Either

(//\302\273'

\342\200\224

- m)2 = 1,

or else(\302\25377/i'|A-|/i/m> =

(\302\2537'm'Lv|/i///0

= 0. [9.72]

Section9.3:Spontaneous
Emission 361
FromEquations9.69and 9.72we obtainthe selectionrule for in:
No transitions
occurunlessAm

= +1 or 0.

[9.73]

if you rememberthat the photoncarriesspin


This is an easy resultto understand,

1,and henceits value of m is 1,0, or

of (the z component
;20conservation
of)
momentum
t
hat
the
atom
whateverthe
takes
away.
angular
requires
giveup
photon
\342\200\224

Selectionrulesinvolving/ and /': In Problem9.12you are askedto derive


the followingcommutation
relation:
=
[L\\[L\\r] 2h2(rL2+ L2r).

[9.74]

between(n'l'm'\\and \\nlm) to derivethe


before,we sandwichthiscommutator
selection
rule:
= 2h2(n'l'm'\\(rL2
+ L2v)\\nlm)
<\302\2537V|[Z,2. [L2,r]]\\nlm)
As

= 2/?4[/(/+ 1)+I'd'
+ \\)](n'l'm'\\r\\nlm)= (n'l'm'\\(L2[L2.
r] [L2.r]L2)\\nlm)
= h2[l'(1'
1(1+ l)](/i'/V|[L2.
r]\\nlm)
= h2[l'(l'+1)-/(/
+ \\)]{n'l'm'\\(L2rrL2)\\nhn)

+1)-

+1)-1(1+ l)]2</7'/V|r|/7/m).

= H4[l'(l'

[9.75]

Conclusion:

+1)-1(1+ 1)]:

Either2[/(/+ 1)+ /'(/' + 1)]= [/'(/'


or else (n'l'm'\\v\\nlm)= 0.

[9.76]

But

+
[I'(l'+l)-l(l

\\))

= (l' + l+\\)(l'-I)

and

so the first

2[/(/+1)+/'(/' + 1)]= (/'+/ + 1)2+ (/' -I)2-I,


condition
in Equation9.76can be written in the form
= 0.
[(/'+/+1)2-!][(/'-/)2-l]

[9.77]

20When the polar axisis along the direction of propagation, the middle value does not occur,and
if you are only interested in the number of linearly independent photon states,the answer is not
However, in this casethe photon need not be going in the - direction, and all three values are possible.

2.

3.

362

Perturbation
Chapter9 Time-Dependent
Theory
/

=0

=1

=2

=3

n =4

n=

n =2

n=1
FIGURE9.6: Alloweddecaysfor the first four Bohrlevelsin hydrogen.

=
loopholeis closedin
Problem9.13),so the condition
to I' = I + 1.Thus we obtainthe
simplifies
rulefor /:
No transitions
occurunlessA/ = +1.
[9.78]

The first factorcannotbe zero(unless/' =

0\342\200\224this

selection

thisresult(thoughfar from trivial to derive)is easy to interpret:The


photoncarriesspin1,so the rulesfor additionof angular momentum wouldallow
/' = / + 1,/' = /, or /' = / 1 (for electricdipoleradiationthe middle
of angular momentum\342\200\224does not occur).
permittedby conservation
Again,

\342\200\224

possibility\342\200\224though

to lower-energy
statescan proceedby spontaneous
Evidently not all transitions
someare forbiddenby the selection
rules.The schemeofallowed
emission;
for the first fourBohrlevelsin hydrogenis shown in Figure9.6.Notethat the
25 state(1^200)is \"stuck\":It cannotdecay,becausethere is no lower-energy
state
with /= 1.It is calleda metastablestate,and itslifetime
is indeedmuch longer
than that of, for example,
the IP states(1^211,
states
^210^ and 1^21 1)-Metastable
do eventually decay,by collisions,
or by what are (misleadingly)
calledforbidden
transitions

transitions
emission.
(Problem9.21),or by multiphoton

\342\231\246Problem

9.12Provethe commutationrelationin Equation9.74.Hint:Firstshow

that

- -

[L2,z] = 2ih{xLy yL, ihz).


Use this,and the fact that r L = r (r x p) = 0, to demonstrate
that
[L2.[L2,z)]= 2h2(zL2+ L2z).
The generalization
from z to r is trivial.
\342\200\242

\342\200\242

Further Problems
for Chapter9

363

in Equation9.78by showingthat if /' = / = 0


Problem9.13Closethe \"loophole\"

then {n'l'm'\\x\\nlm)=0.

**Problem9.14An electronin the n = 3, / = 0, m = 0 stateof hydrogendecays


of (electricdipole)transitions
to the groundstate.
by a sequence
(a) What decay routesare opento it? Specifythem in the followingway:
> |100).
|300)-> \\nlm) -+ \\n'l'm')
If you had a bottlefull of atomsin thisstate,what fractionof them would
decay via eachroute?
What is the lifetime
of thisstate?Hint:Onceit's made the first transition,
it's no longerin the state|300),so only the first stepin eachsequenceis
relevant in computing
the lifetime.
When there is morethan onedecay route
rates add.
open,the transition
-\302\273

(b)
(c)

FURTHERPROBLEMSFORCHAPTER9
**Problem9.15Developtime-dependent
perturbationtheory for a multilevel
of Equations9.1and 9.2:
system, starting with the generalization
=
= <W
[9.79]
H01r\342\200\236

At

time t

(a)

{ty\342\200\236\\ty,n)

E\342\200\2361r\342\200\236,

= 0 we turn on a perturbationH'(t),so that the totalHamiltonian


is
// = //0 + H'(t).
[9.80]

Generalize
Equation9.6to read

*(0=

\302\243cII(f)iM~/\302\243,,,/A.

[9.81]

and show that


n

where
H'm\342\200\236

(b)

= Wm\\H'Wn).

[9.83]

If the system starts out in the statei/r/v, show that (in first-order
perturbation
theory)
C'N

(0 =

H'NN(t')dt'.
1-7/
Jo
n

[9.84]

364

Perturbation
Chapter9 Time-Dependent
Theory
and
cm{t) =
(c)

--Jof H'mN(t')ei{E'\"-EN),'lh
dt'.
\"

(m

# AT).

[9.85]

For example,
supposeH' isconstant(exceptthat it was turned on at t = 0,
and switchedoffagain at somelatertime t). Findthe probability
of transition
from stateN to stateM (M ^ N), as a function of t. Answer:

m^ (en -

|2 sin2[(E,y EM)t/2ti)

[9-86]

\342\200\242

EMy-

sinusoidal
functionof time:H' = V cos(cot).
Making
the usual assumptions,
occuronly to stateswith energy
show that transitions
Em = E^ + ftco, and the transition
probabilityis

H' is a
(d) Now suppose

Pn^m =

\\Vmn\\2

/,,J

Em + ftco)t/2ft]

,-,
(EN - EM
\342\200\224

sin2[(\302\243w

\302\261

nco)-

[9.87]

a multilevel
in incoherent
(e) Suppose
system isimmersed
electromagnetic
Section
9.2.3
that
the
transition
as
a
s
how
rate for
Using
guide,
stimulated emission
is given by the sameformula (Equation9.47)as for a twolevelsystem.
radiation.

Problem9.16For the examplesin Problem9.15(c)and (d),calculatecm(/),to


first order.Checkthe normalization
condition:
= 1.
[9-88]
X>\302\273,(/)|2
HI

and commenton any


of remaimng in the

the probability
you wanted to calculate
discrepancy.
Suppose
or
originalstate\\}/n: would you do betterto use |c^'(/)|2,

MOI2?
Problem9.17A particlestartsout (at time = 0) in the A/th stateof the infinite
!-\302\243\342\200\236**

squarewell.Now the \"floor\"of the well risestemporarily (maybe water leaks


in, and then drainsout again),so that the potentialinsideis uniform but time

V0(t), with V0(0) = V0(T) = 0.


dependent:
(a) Solvefor the exact
usingEquation9.82,and show that the wave
functionchangesphase,but no transitions
occur.Find the phasechange,
c,\342\200\236(t),

0(T),in terms of the functionVo(t).

(b) Analyze the

sameproblemin first-orderperturbationtheory, and compare

your answers.

Comment:The sameresultholdswhenever the perturbationsimplyadds a


constant(constant
in x, that is,not in t) to the potential;
it hasnothingto do with
the infinite squarewell,assuch.CompareProblem1.8.

FurtherProblems
for Chapter9

365

9.18A particleof massm is initiallyin the groundstateof the (one-

\342\231\246Problem

infinite squarewell.At time /=0a\"brick\"is droppedintothe well,


dimensional)
so that the potentialbecomes
if 0 < x < a/2,
Vb.
V(x) = 0, \\fa/2<x<a.
oo, otherwise,
<

E\\. After a time T, the brick is removed,and the energy of the


Find the probability(in first-orderperturbationtheory) that
particleis measured.
the resultis now E->.
where

Vq

<\302\243

Problem9.19We have encountered


stimulated
emission,
(stimulated)
absoiption,
no
such
as
and spontaneous
How comethere is
emission.
thing spontaneous
absorption

ratio
* * *Problem9.20 Magneticresonance.A spin-1/2
particlewith gyromagnetic
at the Larmor frequency a>o =
y, at restin a staticmagneticfieldB$k,precesses
yB{) (Example4.3).Now we turn on a smalltransverse radiofrequency (if) field,
sin(a)t)J],so that the totalfieldis
\302\243rf[cos(a>01
\342\200\224

B = Brrcos(fltf)
i
Br(s'm(a)t)j + B0k.

[9.89]

(a)

Constructthe 2 x 2 Hamiltonian
matrix (Equation4.158)
for thissystem.

(b)

If x(0 = I w

() is the spinstateat time f, show that

a = - kleUotb+ woo):

(c)

= '- (sie~io)'a
.
[9.90]
coQb}
where Q = yBr( is relatedto the strength of the rf field.
Checkthat the generalsolutionfor a(t) and b(t), in terms of their initial
valuesoq and ]?q, is
a{t)=

+
\\a0 cos(a)'t/2)

\342\200\224f

+
b(t) = 1b0cos{co't/2)
where
O)

\342\200\224f

[botto-

[fl0(wo <o) + b0Q]sin(w'r/2)ei(0,/2


a)0) + aQQ]sin(o>'r/2)e~ito,/2

= y/(a)-a)o)2+ n2-

[9.91]

366

Perturbation
Theory
Chapter9 Time-Dependent
(d)

If the particlestarts out with spinup (i.e.,ciq = \\, bo = 0), find the
probabilityof a transitionto spindown, as a function of time.Answer:

P(t) = {S22/[((ocoq)2+ ^2]}sin2(a)'t/2).


(e) Sketchthe resonancecurve,
P(co)=

Q2\342\200\224

(co coq)2+ Q

\342\200\224r-^7,

\342\200\224

(f)

[9.92]

as a functionof the driving frequency co (forfixed coq and Q).Note that the
maximum occursat co = coq.Findthe \"full width at half maximum,\"Aa>.
to
Sincea>o = yBq,we can usethe experimentally
observedresonance
the magnetic
dipolemoment of the particle.In a nuclearmagnetic
the g-factorof the protonis to be measured,
resonance(nmr) experiment
using
a staticfieldof 10,000
gaussand an rf fieldof amplitude0.01gauss.What
will the resonantfrequency be?(SeeSection
6.5for the magneticmoment
curve.(Giveyour answers
of the proton.)Find the width of the resonance
in Hz.)
determine

* * *Problem9.21In Equation9.31I assumed


that the atom issosmall(in comparison
to the wavelength of light) that spatialvariationsin the fieldcan be ignored.The
true electricfieldwouldbe

E(r.0 = E0cos(k r cot).


\342\200\242

If the atom is centeredat the origin,then k r


\342\200\242

[9.93]

over the relevant volume

(|k|= 2tt/\\, so k r ~ r/X 1),and that'swhy we couldafford to dropthis


term.Supposewe keepthe first-ordercorrection:
+ (k r) sin(cot)].
E(r, t) = E0[cos(cot)
[9.94]
<\302\243

\342\226\240

<\302\243

\342\200\242

we considered
The first term givesriseto the allowed(electricdipole)transitions
in the text;the secondleadsto so-called
forbidden(magneticdipoleand electric

quadrupole)transitions
(higherpowersof k r leadto even more \"forbidden\"
associated
with highermultipole
transitions,
moments).21
\342\200\242

(a)

rate for forbiddentransitions


Obtainthe spontaneous
emission
(don'tbother
and propagation
to average overpolarization
directions,
though thisshould
the calculation).
Answer:
really be doneto complete
2 5

. r)(k
Rb^a = J-^\\{a\\(H
-1For a systematic treatment

to the Quantum Theory, 3rd

\342\200\242

r)\\b)\\2.

[9.95]

(including the role of the magneticfield) seeDavid Park, Introduction


ed.(McGraw-Hill,New York. 1992).
Chapter 11.

367

Further Problems
for Chapter9

oscillator
the forbiddentransitions
(b) Show that for a one-dimensional
go from
level n to level n

and k)

is

\342\200\224

2, and the transitionrate (suitablyaveragedover h

fiq-con(n 1)
t9-%J
R=-TZ
15jreoni2c*
Find the
(Note:Hereto is the frequency of the photon,not the oscillator.)
rate to the \"allowed\"rate,and commenton the
ratio of the \"forbidden\"
terminology.
(c) Show that the 25 -> \\S transitionin hydrogen is not possibleeven by a
\"forbidden1'
transition.
(As it turns out,thisistrue for all the highermultipoles
aswell;the dominantdecay is in fact by two-photon
and the lifetime
emission,
is abouta tenth of a second.22)

4^-\342\200\224

* * *Problem9.22 Showthat the spontaneous


rate (Equation9.56)for a
emission
from /?,/ to //, /' in hydrogenis
transition

+ 1 if /' = /+1,
2/ + 1
{
/

e-arl- x

12/-1 if

I' =

[9.97J

1-1.

where

1=Jo/

[9.98]

r3R\342\200\236i(r)R\342\200\236r(r)dr.

value of m, and it goesto any of the states///'


(The atom startsout with a specific

Noticethat the answer


with the selection
rules:m' = m + 1.m.or ///-1.
consistent
allthe nonzeromatrix elements
of .v, y,
is independent
of///.)Hint:Firstcalculate
and z between\\nlm) and \\n'l'm')for the case/' = / + ].Fromthese,determine
the quantity

\\{n'J+l,m + l|r|n/m)|2+ |(n'./+1.m\\r\\nhn)\\2 + \\{n'.I + 1,/// l|r|//////)|2.


Then do the samefor 1'= I 1.
\342\200\224

Masataka Mizushima. Quantum Mechanicsof Atomic Spectraand Atomic Structure.


New York (1970).
Section

\342\200\224Sec

Benjamin.

5.6.

CHAPTER

10

THE ADIABATICAPPROXIMATION

10.1THE ADIABATICTHEOREM
10.1.1
AdiabaticProcesses
backand
oscillating
Imaginea perfectpendulum,with no frictionor air resistance,
forth in a vertical plane.If you grabthe supportand shakeit in a jerky manner the
bob will swing aroundchaotically.
But if you very gently and steadilymove the
to swing in a nicesmoothway,
the
support(Figure10.1), pendulumwill continue
in the sameplane(or oneparallelto it), with the sameamplitude.
This gradual
a
n
defines adiabatic
Noticethat there are
process.
changeofthe externalconditions
the motion
two characteristic
timesinvolved:7), the \"internal\"time,representing
of the systemitself(in thiscasethe periodof the pendulum's
and Tc,
oscillations),
o
ver
which
the
the \"external\"time,
the parameters
of system changeappreciably
(if
the pendulumwere mountedon a vibrating platform,forexample,
would
be
the
Te
i
sone
for which Te ^> 7).1
periodof the platform'smotion).An adiabaticprocess
for
an
adiabatic
is
The basicstrategy
process first to solve the
analyzing
problemwith the external parametersheldconstant,and only at the end of the
calculation
allowthem to vary (slowly)with time.Forexample,
the classical
period
of a pendulumof (fixed)lengthL is In-jLjg; if the lengthis now gradually
changing,the periodwill presumably be 2nx/L(t)/g.A more subtleexample
ion(Section7.3).We began
occurredin our discussion
of the hydrogenmolecule
1

For an interesting

Phys. 58.337 (1990).

368

secFrank
discussionof classicaladiabatic processes,

S.Crawford. Am. J.

Section10.1:
TheAdiabatic
Theorem

369

10.1:Adiabatic motion:If the caseis

FIGURE

transported
very gradually,the penduluminside
keeps
with
the sameamplitude,
in a planeparallel
swinging
to the originalone.
that the nucleiwere at rest,a fixed distance
R apart, and we solved
assuming
for the motionof the electron.Oncewe had foundthe groundstateenergy of
the systemas a function of R, we locatedthe equilibriumseparation
and from
the curvature of the graph we obtained
the frequency of vibrationof the nuclei
(Problem7.10).In molecular
physicsthistechnique
(beginningwith nucleiat rest,
electronic
wave functions,
and usingtheseto obtaininformation
about
calculating
the positions
is known as the
and\342\200\224relatively
sluggish\342\200\224motion of the nuclei)
Born-Oppenheimer
approximation.
In quantum mechanics,
the essential
contentof the adiabaticapproximation
can be castin the form of a theorem.
changesgradually
Supposethe Hamiltonian
theoremstates
from someinitialform H' to somefinal form H1.The adiabatic
that if the particlewas initiallyin the nth eigenstate
of W, it will be carried
of H*.(I assumethat the
intothe nth eigenstate
(underthe Schrodinger
equation)
throughoutthe transitionfrom H' to H1,
spectrumis discreteand nondegenerate
so there is no ambiguity aboutthe orderingof the states;theseconditions
can be
for \"tracking\"the eigenfunctions,
but I'm not
relaxed,given a suitableprocedure
goingto pursuethat here.)
Forexample,
supposewe preparea particlein the groundstateof the infinite

by

squarewell (Figure10.2(a)):

*'M= Jl\342\204\242&)

[10.1]

If we now gradually move the right wall outto 2a,the adiabatic


theoremsaysthat
the particlewill end up in the groundstateof the expandedwell (Figure10.2(b)):

*'M=

\302\243*>&)\342\200\242

[10.2]

370

Chapter10 TheAdiabaticApproximation
V(x)

\\ri
a

i|/'(x)

y'(x)

2ax

2ax

(a)

2ax

(c)

(b)

FIGURE10.2: (a) Particlestarts outin the groundstateofthe infinite squarewell, (b)


the wall movesslowly,the particleremainsin the groundstate,(c) If the wall moves
rapidly,the particleis left (momentarily)in itsinitialstate.

If

from a phasefactor).Noticethat we'renot talking abouta small


(apart, perhaps,
(as in perturbationtheory)\342\200\224this oneis huge.All we
changein the Hamiltonian
here:Whoever is moving
requireis that it happenslowly.Energy is not conserved
the wall is extractingenergy from the system,just like the pistonon a slowly
if the well expandssuddenly,the resulting
expandingcylinderof gas.By contrast,
stateis still\\}/} (x) (Figure10.2(c)),
linearcombination
of
which is a complicated
of the new Hamiltonian
(Problem2.38).In thiscaseenergy isconserved
eigenstates
value is);as in thefreeexpansion
of a gas(intoa vacuum)
(at least,itsexpectation
when the barrieris suddenlyremoved,no work is done.

* * *Problem10.1
The caseof an infinite squarewell whoseright wall expandsat a
setof solutions
is
constantvelocity(v) can be solvedexactly.2A complete
\302\242,,(.,.

,) s

/I^

\\

(\342\204\242x)

\\

^^-2/^,,)/2^

[10.3]

where w(t) = a + vt is the (instantaneous)


width of the well and E'n =
n~n~h /2nur is the /?th allowedenergy of the originalwell (width a).The general
solutionis a linearcombination
of the O's:
CO

^i(x.t)=

J2c\342\200\236<i>\342\200\236(x.t):

[10.4]

the coefficients are independent


of t.
c\342\200\236

(a)

Checkthat Equation10.3satisfies
the time-dependent
Schrodinger
equation,
with the appropriate
boundary conditions.
2S.W. Doescherand M. H.Rice.Am. J. Plm. 37, 1246
(1969).

Section10.1:
TheAdiabaticTheorem
(b)

371

Supposea particlestartsout (t = 0) in the groundstateof the initialwell:

*(,.0)= /|sin(^).
Show that the expansion
coefficients
can be written in the form
c\342\200\236

= 2 /r7 e-'01-'sin(/u)sin(z)dz.
* JO
\342\226\240

\342\226\240>

[10.5]

where a = mva/2TC2his a dimensionless


measureof the speedwith which
the well expands.
(Unfortunately,thisintegralcannotbe evaluatedin terms
of elementary functions.)
(c) Supposewe allow the well to expandto twice its originalwidth, so the
\"external\"time is given by w{Te)= 2a.The \"internal\"time is the periodof
the time-dependent
factorin the (initial)groundstate.Determine
exponential
to a <$c 1,so that
Te and 7), and show that the adiabatic
regimecorresponds
= 1 overthe domainof integration.
Usethisto determine
the
exp(\342\200\224iaz\")
coefficients, Construct^(x,t), and confirm that it isconsistent
expansion
with the adiabatic
theorem.
c\342\200\236.

(d) Showthat the phasefactorin

*(.t.t) can be written in the form

$(0=

--(Ei(t')dt'.
fi

[10.6]

Jo

= n'-jr2h~/2mw-is the instantaneous


at time t.
eigenvalue,
Commenton thisresult.
where

E\342\200\236(t)

10.1.2
Proofof theAdiabaticTheorem
but
The adiabatic
theoremis simpleto state,and it soundsplausible,

to prove.3If the Hamiltonian


is independent
of time,then
out in the /7th eigenstate,4

is not easy
a particlewhich starts
it

\\fr\342\200\236,

Hfn =

E\342\200\2361r\342\200\236.

[10.7]

in early versions
theorem is usually attributed to Ehrcnfcst. who studied adiabatic processes
theory. The first proof in modern quantum mechanics was given by Bom and Fock,
165(1928).
Other proofs will be found in Messiah,Quantum Mechanics,Wiley. New
Zeii.f. Physik
Vol. II.Chapter XVII.Section 12,J-T Hwang and Philip Pechukas.J. Chenu Phys. 67.
York (1962).
4640.1977.and Gasiorowicz,Quantum Physics.Wiley. New York (1974).Chapter 22.Problem 6.The
argument given here follows B.H. Bransden and C.J.Joachatn. Introduction to Quantum Mechanics.
2nd cd.,Addison-Wesley.Boston.MA (2000).Section9.4.
in this argument only the time
4I'llsuppressthe dependenceon position (or spin, etc.):
\342\226\240*The

of

the quantum

dependence

is

at

51.

issue.

372

Chapter10 TheAdiabaticApproximation

remainsin the nth eigenstate,


simplypickingup a phasefactor:

%(t) =

[10.8]

ifr\342\200\236e-iEnt/h.

are
If the Hamiltonian
and eigenvalues
changeswith time,then the eigenfunctions

themselves
time-dependent:

HMW) = EnWn{t).
but they

[10.9]

stillconstitute
set
(at any particularinstant) an orthonormal

(iMOIlMO)=*!,,,,.

[10-10]

and they are complete,


so the generalsolutionto the time-dependent
Schrodinger

equation

ih V{t)= H(t)V(t)
at
can be expressed
as a linearcombination
of them:

[10.11]

\342\200\224

\302\242(0

^,,(0^,,(0^,

[10.12]

where

0,,(0= -7En(t')dt'
n f

[10.13]

Jo
the \"standard\"phasefactorto the casewhere
varies with time.
generalizes
it in the coefficient
(As usual,I couldhave included
cn(t),but it is convenientto
factorout thisportionof the time dependence,
sinceit wouldbe presenteven for
\302\243\"\342\200\236

a time-mdependent
Hamiltonian.)

we obtain
Substituting
Equation10.12intoEquation10.11

ih Y, [cntn+

c\342\200\236ir\342\200\236

ew\"

=
Y^c\342\200\236(Hf\342\200\236)ei0\"

ic\342\200\2361r\342\200\2360\342\200\236]

[10.14]

(I usea dot to denotethe time derivative).In view of Equations10.9and 10.13


the lasttwo terms cancel,leaving
J2c\342\200\236fnew\"

Taking the inner productwith


instantaneous

= -5>,iMf*'.
n

\\f/m,

of the
and invokingthe orthonormality

eigenfunctions
(Equation10.10),

[10.15]

Section10.1:
TheAdiabaticTheorem
or

^,(/)= -^^(^1^)^^-0^.
Now, differentiating
Equation10.9with

+ H\\j/n =

Hyjr\342\200\236

373
[10.16]

respectto timeyields

Enyjr\342\200\236

\302\243,,1/0,.

and hence(againtaking the inner productwith i/o,,)

[10.17]

EnOmn

=
Exploitingthe hermiticityof H to write (1/0,,|//11/0,)
for n ^ m
=

(Vo\342\200\236|//|i/o,>

(\302\243\342\200\236

\302\243,\342\200\236{i/o\342\200\236|i/o,),

it

[10.18]

\302\243,\342\200\236)(i/o\342\200\236|i/o,>.

that the
remember,
Putting this into Equation10.16(and assuming,
we conclude
that
nondegenerate)
cm\302\253)

= -c<fc|*\302\253>

\302\243

followsthat

energiesare

[10.19]
c,(*-l^l\302\273',>g'-WJi^\",'-^'',\302\273^.

Thisresultis e.vad'/.Now comesthe adiabaticapproximation:


Assumethat H
is extremely small,and dropthe secondterm,5 leaving
=
[10.20]
C,\342\200\236(t)

with the solution

-C,\342\200\236(l/r,\342\200\236|l/r,\342\200\236),

cm(f) = \302\242,,(0)^^,

where6
y\342\200\236,(t)

=i

[10.21]

j Um{t')^xlf,n{t')\\dt'.

[10.22]

In particular,
if the particlestarts out in the nth eigenstate
(which is to say,
= 1,and
= 0 for m # n), then (Equation10.12)

if

c,\342\200\236(0)

c\342\200\236(0)

vi/,,(/) =

e''^'V>''(,)iMO,

[10.23]

so it remainsin the nth eigenstate


(of the evolvingHamiltonian),
pickingup only
a coupleof phasefactors. QED
-\"'Rigorous

955(2000)!
(V/mlV/,\302\273}

justification of this step is

not

trivial.

SecA. C.Aguiar

6Notiec that y is real,since the normalization of


= 2Re
1^,,))= 0.
(M\342\200\236

yjfw

entails

Pinto et

ai.Am. J. Phys. 68.


\342\200\224

((l/tlt)(if\342\200\236i\\',l'm}

Milium)+

374

Chapter10 TheAdiabaticApproximation

Example10.1Imaginean electron(charge mass m) at rest at the origin,


in the presence
of a magneticfieldwhosemagnitude(Bq)is constant,
but whose
directionsweepsout a cone,of openinganglea, at constantangular velocityco
\342\200\224e,

(Figure10.3):

+ sina s'm(cot)j
+ cosctk}.
B(r)= Botsma cos(cot)i

[10.24]

The Hamiltonian
(Equation4.158)is

H(t) =

e
\342\200\242

\342\200\224B

m
fico\\

S = ehBg

+ sinasin(o>0^v
+ coscm-]

\342\200\224\342\200\224[sinacos(\302\243t\302\273/)fTx

2m

/ cosa

2 \\e,co'sina

lcot

sincv'

cosa

\342\200\224

where
co\\

= eB0
m

[10.25]
[10.26]

of H{t)are
The normalized
eigenspinors

cos(cy/2)\\ '
X+IO_ (\\ico,

[10.27]

sin(ff/2)\\
_
X-{T)-cos(a/2)y;

[10.28]

sin(a/2))

and
(e~h\302\260'

\\

they
direction

alongthe instantaneous
represent
spinup and spindown,respectively,
are
ofB(t)(seeProblem4.30).The corresponding
eigenvalues
E\302\261

tico]
\302\261

[10.29]

(0

Bl

-e

FIGURE10.3:Magnetic field sweepsaroundin a


cone,at angular velocity o> (Equation10.24).

Section10.1:
TheAdiabaticTheorem

375

Supposethe electronstarts out with spinup,alongB(0):7

'
sin(a/2)J

/cos(\302\253/2A

[10.30]

The exactsolution
to the time-dependent
Schrodinger
equationis (Problem10.2):

-i
\\cos(Xt/2)

^ sin(A//2)lcos(a/2)e-ico,/+ ^ sin(A//2)lsin(a/2)e+i(0,/1

Tcos(X//2) i{C0]

X(0 =

{c\302\260l

[10.31]

where

= Jco2+ r^ 2coco\\cosa.
it as a linearcombination
of x+ and x~
Or, expressing
A

[10.32]

\342\200\224

co cosa) . (Xt
(co\\
-icol/7x+it)
X(0 = cos(Xt\\ -'\342\200\224i\342\200\224sinIt

+i

co
\342\200\224

\342\200\224

.
. a sin
sin
V

Xt\"

[10.33]

2 , e+ico,/2X-(t).

\342\200\224-

to spindown (alongthe current


(exact)probabilityof a transition
of B) is
direction

Evidently the

=
|<x(/)lx-(\302\273)l2

co
\342\200\224

. a sin
. (Xt
sin

-\\2

[10.34]

\342\200\224

\\2

The adiabatictheoremsaysthat thistransition


shouldvanish in the limit
probability
timefor changesin the Hamiltonian
Te ^S> Tj, where Te is the characteristic
(in this
time for changes
in the wave function
case,l/co)and 7) is the characteristic
(in this
=
means co <$C (o\\\\
case,
\\/co\\).Thus the adiabatic
approximation
The fieldrotatesslowly,in comparison
with the phaseof the (unperturbed)
wave
functions.
In the adiabaticregimeX = co\\, and therefore
\342\200\224

/?/(\302\243*+

\302\243_)

Kx(/)lx-(/))l2=

co
\342\200\224

. a sin
. (Xt
sin

-,\">

0.

\342\200\224

[10.35]

\\2
as advertised.
The magneticfieldleadsthe electronaroundby its nose,with the
if co co\\ then X = co,and
of B.By contrast,
spinalways pointingin the direction
the system bounces
backand forth betweenspinup and spindown (Figure10.4).
co\\

\302\273

up

7This is essentiallythe same as Problem 9.20.


exceptthat now the electron starts
along B, whereasin Equation 9.20(d)it started out with spin up along z.

out with

spin

376

Chapter10 TheAdiabaticApproximation

2n/l

4n/k

6k/X

8n/X

FIGURE10.4: Plotofthe transition


in the wowadiabatic
probability,
Equation10.34,
(o>
regime
u>\\).
\302\273

* *Problem10.2Checkthat Equation10.31
satisfies
the time-dependent
Schrodinger
Also
and
f
or
the
Hamiltoiiian
10.25.
confirm
in
Equation10.33,
equation
Equation
is 1,asrequiredfornormalization.
showthat the sum of the squares
ofthe coefficients

10.2BERRY'SPHASE
10.2.1Nonholonomic
Processes
to developthe notion
Let'sgo backto the classical
modelI used(in Section10.1.1)
of an adiabaticprocess:
a perfectlyfrictionless
pendulum,whosesupportiscarried
that as longas the motionof the supportis
around from placeto place.I claimed
to the periodof the pendulum(sothat the pendulumexecutes
very slow,compared
beforethe supporthas movedappreciably),
it will continue
to
many oscillations
swing in the sameplane(or oneparallelto it), with the sameamplitude(and,of
course,the samefrequency).
But what if I tookthisidealpendulumup to the North Pole,and setit
in the direction
For the moment,pretendthe
of Portland(Figure10.5).
I carry it down the
earth is not rotating.
Very gently (that is,adiabatically),
longitude linepassing
through Portland,to the equator.At this pointit is swinging
north-south.
Now I carry it (stillswingingnorth-south)
part way aroundthe
And finally, I take it backup to the North Pole,alongthe new longitudeline.
swinging\342\200\224say,

equator.

Section10.2:Berry'sPhase

377

Pendulum

FIGURE10.5:Itineraryfor adiabatictransportof
a pendulumon the surfaceof the earth.

It is clearthat the pendulumwill no longerbe swingingin the sameplaneas it


the new planemakes an angle0 with the oldone,
was when I set
where 0 is the anglebetweenthe southbound
and the northbound
longitudelines.
As it happens,
0 is equalto the solidangle(Q)subtended
(at the centerof the
For thispath surroundsa
earth) by the path aroundwhich I carriedthe pendulum.
=
fraction<3/2ttof the northern hemisphere,
soitsarea is A = (1/2)(\302\251/2tc)4ttR2
&R1(where R is the radiusof the earth),and hence
out\342\200\224indeed,

0 = A/R2 = Q.

[10.36]

Thisis a particularly niceway to expressthe answer, becauseit turns out to be


of the shapeof the path (Figure10.6).8
independent
the Foucaultpendulumis an example
this sortof
of precisely
Incidentally,
adiabatictransportarounda closedloopon a
thistimeinsteadof me
sphere\342\200\224only

FIGURE10.6:Arbitrary path on the surface of a


a solidangleft.
sphere,subtending
8 You can
prove this for yourself, if you are interested.Think of the circuit as being made up of
on the sphere):the pendulum makesa fixed angle with each
tiny segmentsof great circles
(geodesies
geodesic
segment,so the net angular deviation is related to the sum of the vertex anglesof the spherical

polygon.

378

Chapter10 TheAdiabaticApproximation
2A

in
FIGURE10.7: Path of a Foucaultpendulum,
ofoneday.
the course

carrying the pendulumaround,I let the rotation


of the earth do the job.The solid
is
anglesubtended
by a latitudeline (Figure10.7)
6\302\276

Q= sin6

d6d\302\242

= 2n(-cos6)$
=2tt(\\-cos60).

[10.37]

Relative to the earth (which has meanwhile turned through an angleof 2n), the
of the Foucaultpendulumis In cos
resultthat is ordinarily
daily precession
obtainedby appealto Coriolisforcesin the rotatingreference
frame,9 but is seen
in thiscontext
to admit a purely geometrical
interpretation.
A systemsuchas this,which doesnot return to its original
statewhen
arounda closedloop,is saidto be nonholonomic.
(The \"transport\"in
transported
questionneednot involvephysicalmotion:What we have in mind is that the
parametersof the system are changedin somefashionthat eventually returns them
to theirinitialvalues.)Nonholonomic
systemsare ubiquitous\342\200\224in a sense,every
device:At the end of eachcyclethe car has
cyclicalengineis a nonholonomic
movedforward a bit,or a weight hasbeenliftedslightly,or something.
The idea
has even beenappliedto the locomotion
of microbes
in fluidsat low Reynolds
number.10
My projectfor the next sectionis to study the quantum mechanics
of
nonholonomic
The
is
does
adiabatic
essential
this:
How
the
processes.
question
are
final statedifferfrom the initialstate,if the parametersin the Hamiltonian
carriedadiabatically
around someclosedcycle?
6\302\276\342\200\224a

See,for example,Jerry B.Marion and StephenT.Thornton, Classical


Dynamics of Particles
and Systems,4th ed..Saunders.Fort Worth. TX (1995).
10.5.
Geographersmeasure latitude
Example
=
so
A..
from
the
rather
than
down
from
the
sin
(X) up
equator,
pole, cos%
l0The pendulum exampleis an application of Hannay's angle,which is the classical
analog to
a
o
f
For
collection
on
both
see
Alfred
and
Frank
Wilczek,
eds..
Berry'sphase.
papers
subjects,
Shapere
GeometricPhasesin Physics.World Scientific, Singapore(1989).

Section10.2:Berry'sPhase

379

10.2.2GeometricPhase
In Section10.1.2I showedthat a particlewhich startsout in the /?th eigenof H(t),
in the /?th eigenstate
stateof #(0) remains,under adiabatic
conditions,
its wave functionis
phasefactor.Specifically,
pickingup only a time-dependent
(Equation10.23)

[10.38]

ty\342\200\236(t)=ei{e\"lt)+y,'u)]\\lrn(t).

where

B\342\200\236(t)

-jJof En(t')dt'

[10.39]

fi

to the case

the usualfactor
is the dynamicphase(generalizing
is a functionof time),and
where

exp(\342\200\224/'\302\243\"\342\200\236///?)

E\342\200\236

yn(t)

f Unit')

=i

dt'

[10.40]

\302\243;M')\\

is the so-called
geometricphase.
on t becausethere issomeparameter R(t) in the HamilNow \\frn(t) depends
tonianthat is changingwith time.(In Problem10.1,R(t) would be the width of
the expandingsquarewell.)Thus
d\\frn

~aT

dR
~dR~d7'

[10.41]

3i/f\342\200\236

so

d^\"^dR,
8R

[10.42]

if the
where /?/ and Rf are the initialand final values of R(t). In particular,
=
Hamiltonianreturns to its originalform after time T, so that Rf
R;, then
yn{T)=

therel
interesting
that there is only oneparameter
in
However,I assumed(in Equation10.41)
the Hamiltonian
that is changing.
there are N of them:R\\(t), Ri(t)
Suppose
RnO);in that case
JUL
dt
3i/f\342\200\236

0\342\200\224nothing

d\\lf,}

dR\\

JUL\342\200\224L

dRi

dt

very

d\\l/n

+
dt +...

dRi

JUL\342\200\224-

where R = (R\\, Rn
Thistimewe have

dR2

d\\l/n

dRu =

dR

JUL\342\200\224H.

dRN

dt

KV\"

(VRi/\342\200\236)

dt

[10.43]
J
L

/?#),and V/? is the gradientwith respectto these

parameters.

Yn(t)

=i
JR,-

M,|VtfM.</R.

[10.44]

380

Chapter10 TheAdiabaticApproximation
form after a time T,the net geometric
and if the Hamiltonian
returns to itsoriginal

phasechangeis

= i&WH\\VR1rn).dR.

if

Y\342\200\236(T)

[10.45]

and it is not, in
Thisis a lineintegralaround a closedloopin parameter-space,
and
general,zero.Equation10.45was first obtainedby MichaelBerry,in 1984,11
only on the path taken,
Yn(T) iscalledBerry'sphase.Noticethat y,,(T)depends
noton how fast that path is traversed (provided,of course,that it is slow enough
to validatethe adiabatichypothesis).
the accumulated
dynamic phase,
By contrast,

en(T)= -1En{t')dt'.
h f
Jo

on the elapsedtime.
dependscritically
We are accustomed
to thinking that the phaseof the wave functionis
involve |^|2,
and the phasefactorcancelsout.For this
quantities
reason,mostpeopleassumeduntil recently that the geometric
phasewas of no
conceivable
physicalsignificance\342\200\224after all,the phaseof \\fr,,(t) itselfis arbitrary.
It was Berry'sinsightthat if you carry the Hamiltonian
around a closedloop,
bringingit backto its originalform, the relativephaseat the beginningand the
endof the processisnot arbitrary, and can actually be measured.
For example,
supposewe take a beamof particles(allin the statevf), and
changingpotential,
splitit in two, sothat onebeampassesthrough an adiabatically
the total wave
while the other doesnot.When the two beamsare recombined,
arbitrary\342\200\224physical

functionhas the form


vj/

1
vi/0

1 T
+ _vi/0e'r,

[10.46]

where ^o is the \"direct\"beamwave function,and F is the extra phase(in part


to the varying H.
acquiredby the beamsubjected
dynamic, and in part geometric)

In thiscase

M2 =
=

d*ol2(lWr)(l + *-'T)
\\m\\2{\\

+cosD= |vI>0|2cos2(r/2).

[10.47]

So by lookingfor pointsof constructive


and destructiveinterference
(where T is
an even or oddmultiple
onecan easilymeasureF. (Berry,and
of tt, respectively),
'M.V. Berry.Pwc.R. Soc.Loud. A 392.45 (1984).
reprinted in Wilczek and
in
It
t
hat
this
is
result
10). astonishing, retrospect,
escapednotice for sixty years.
1

(footnote

Shapere

Section10.2:Berry'sPhase

381

FIGURE10.8: Magnetic flux through a


surfaceS boundedby the closed
curve C.

otherearly writers,worriedthat the geometric


phasemight be swampedby a larger
to arrange thingsso as to separateout
dynamic phase,but it has provedpossible
the two contributions.)
When the parameter spaceis three dimensional,
R = (R\\, Ri,R3),Berry's
is reminiscent
of the expression
formula (Equation10.45)
for magneticflux in
A. The flux,
terms of the vectorpotential
through a surfaceS boundedby a
is
curve C (Figure10.8),
= /f B
Bda.
da.
[10.48]
\302\242,

\302\242=

If we write the magneticfieldin terms of the vectorpotential(B =


apply Stokes'theorem:

3>

/ (V x A)

\342\200\242

da

-/,\342\226\240

Thus Berry'sphasecan be thought of as the

-i

\"flux\"

\342\200\242

x A), and

dr.

[10.49]

of a \"magneticfield\"

= /V*x<iMV*iM,

\"B\"

[10-50]

To put it the otherway


through the (closedloop)trajectory in parameter-space.
caseBerry'sphasecan be written as a surface
around,in the three-dimensional

integral,
Yn(T) =

x (fn\\VRfn)]-da.
[10.51]
J[VR
The magneticanalogycan be carriedmuch further, but for our purposes
for yn(T).
Equation10.51is merely a convenientalternative expression
\342\231\246Problem

10.3

the geometric
(a) UseEquation10.42to calculate
phasechangewhen the infinite
from width w\\ to width u>2- Commenton
squarewell expandsadiabatically
thisresult.

382

Chapter10 TheAdiabaticApproximation

If the expansion
occursat a constantrate (clw/dt= v), what is the dynamic
phasechangefor this process?
back to its originalsize,what is Berry'sphasefor
(c) If the well now contracts

(b)

the cycle?

Problem10.4The deltafunctionwell (Equation2.114)supportsa singlebound


state(Equation2.129).Calculatethe geometric
phasechangewhen a gradually
from ct\\ to ai.If the increase
rate (da/dt = c),what
increases
occursat a constant
is the dynamic phasechangefor thisprocess?
Problem10.5Show that if 1/0,(/)is real, the geometricphase vanishes.
10.3and 10.4are examplesof this.)You might try to beat the rap by
(Problems
(but perfectlylegal)phasefactorontothe eigenfunctions:
tackingan unnecessary
where 0,,(R)is an arbitrary (real)function.
Try it.You'llget a
^/,(/) = e'^'Tj/nit),
nonzerogeometric
phase,allright,but notewhat happenswhen you put it backinto
And for a closedloopit giveszero.Moral:FornonzeroBerry's
Equation10.23.
phase,you need(i) morethan onetime-dependent
parameter in the Hamiltonian,
and (ii) a Hamiltonian
that yieldsnontrivially complex
eigenfunctions.
Example10.2 The classicexampleof Berry'sphaseis an electronat the
to a magneticfieldof constantmagnitude but changingdirection.
subjected
case(analyzed in Example10.1)in which B(0 precesses
Consider
first the special
around at a constant
angular velocityo>, making a fixed anglea with the z axis.
The exactsolution
(foran electronthat startsout with \"spinup\" alongB) is given
In the adiabaticregime,w\302\253wi,
by Equation10.33.
origin,

\342\200\224

co\\xjl\342\200\224

2\342\200\224cosff+(
co\\

cosa) =

= a>\\ ( 1

\\co\\J

co\\

\\

co\\

\342\200\224

cocosa,[10.52]

and Equation10.33
becomes
X(t)

= e-imtl2eii^o,a)tiie-io,t/ix+{l)

+i

CO
\342\200\224

. I(CO\\t
. a sin
sin
V

co\\

e+'0)t/2x-(t).

[10.53]

0 the secondterm dropsout completely,


and the resultmatches
the
adiabatic
The dynamic phaseis
form (Equation10.23).
expected
As (o/co\\

\342\200\224>

MO =

-j./0/ E+{t>)dt' = -^r2


A

[10-54]

Section10.2:Berry'sPhase

383

so the geometric
(where E+ = hu>\\/2, from Equation10.29),
phaseis
y+(t)

= (cosff-1)cot
\342\200\224.

[10.55]

For a complete
cycleT = 2tt/co,and thereforeBerry'sphaseis
y+(T)= n(cosa 1).
\342\200\224

[10.56]

the moregeneralcase,in which the tip of the magneticfield


Now consider
vectorsweepsout an arbitraryclosedcurve on the surfaceof a sphereof radius
= Bo (Figure10.9).
The eigenstate
representing
spinup alongB(/) has the fonn
/\342\200\242

(seeProblem4.30):

'
I ,-,cos(0/2)
.

\\

X+=

\\eiq>

sin(0/2)J

[10.57]

coordinates
of B) are now bothfunctionsof time.
where 9 and 0 (the spherical
we find
coordinates,
Lookingup the gradientin spherical
Vy+
A+

= dy+ * + 1 dv+ + 1 dx+ v0


dr
r 89
/-sin(9 90
\342\200\224f

\342\200\224

\342\200\224\342\200\2249

0
-(1/2)sin(0/2) \\.+ 1 /
I
0.
r l(l/2)*'\"*cos(0/2)]rsinfl y<?'\"*sin(0/2),

_\\_
~

[10.58]

Hence
1

(x+|vx+)= x27

'

(0/2)
-sin(0/2)cos(0/2)9 + sin(0/2)cos(0/2)0 + 2/sin2sin0
0

*
= .sin2(0/2)
0,

[10.59]

/\\sin0
r-^\342\200\224

FIGURE10.9: Magneticfieldofconstant
but changingdirection
sweepsout a closed
magnitude

loop.

384

Chapter10 TheAdiabaticApproximation
For Equation10.51we needthe curl of this quantity:
x (x+|VX+)=

sin9

/-sin0 d$

i sin2(9/2)
r sin9

r=2S-r

[10.60]

then,
Accordingto Equation10.51,

l r
y+(T) _ _

~~2J ^

da.

[10.61]

The integralis over the area on the sphereswept out by B in the courseof the
that
cycle,so da = r2dQr,and we conclude

y+(T) =

1 f
dn =

--J

1
--n.

[10.62]

at the origin.This is a delightfully


where Q is the solidanglesubtended
simple
of the classical
result,and tantalizinglyreminiscent
problemwith which we began
the discussion
pendulumaround a closedpath on the
(transportof a frictionless
surfaceof the earth).It saysthat if you take a magnet,and leadthe electron'sspin
aroundadiabatically
in an arbitrary closedpath,the net (geometric)
phasechange
will be minus one-halfthe solidangleswept out by the magneticfield vector.
In view of Equation10.37,this generalresultis consistent
with the specialcase

as of courseit had to be.


(Equation10.56),

* * *Problem10.6Work out the analogto Equation10.62for a particleof spin 1.


Answer:
for spins the resultis
(Incidentally,
\342\200\224Q.

\342\200\224sQ.)

10.2.3TheAharonov-Bohm
Effect
In classical
the potentials
(<p and A)12 are not directly
electrodynamics
are the electricand magnetic
physicalquantities
fields:
measurable\342\200\224the

E=-V<z>

3A

dt

B = VxA.

[10.63]

12,
\"It is customary in

mechanics to use the letter V for potential energy, but in


quantum
letter
same
is
electrodynamics
ordinarily reservedfor the scalar potential. To avoid confusion I use
the scalar potential. SeeProblems4.59.
4.60,and 4.61for background to this section.
the

<p

for

Section10.2:Berry'sPhase

385

The fundamentallaws (Maxwell's


and the Lorentzforcerule)make no
equations

referenceto potentials,
which are (from a logicalpoint of view) no more than
convenientbut dispensable
theoretical
constructs.
Indeed,you can with impunrcy
changethe potentials:

<p^xp'=

OA
<p--\342\200\224.

at

A-*A'= A + VA.

[10.64]

and time;thisiscalleda gaugetransformation,


where A is any functionof position
and it hasnoeffecton the fields(asyou can easilycheckusingEquation10.63).
In quantum mechanics
the potentials
play a more significantrole,for the
is expressed
in terms of cp and A, not E and B:
Hamiltonian

H=

I/I\342\200\224

\\

\342\200\224

[10.65]

ijV-qA) +cJ<P.

Nevertheless,the theory is still invariant under gauge transformations


(see
a
nd
for
Problem4.61),
a longtime it was taken for grantedthat there couldbe
no electromagnetic
morethan
influences
in regionswhere E and B are
there can be in the classical
showedthat
theory.But in 1959Aharonovand Bohm13
the vectorpotential
can affect the quantum behaviorof a chargedparticle,even
when it is moving through a regionin which the fielditselfis zero.I'll work out a
effect,and finally indicate
simpleexamplefirst, then discussthe Aharonov-Bohm
how it allrelatesto Berry'sphase.
to move in a circleof radiusb (a beadon a
Imaginea particleconstrained
wire ring, if you like).Alongthe axisruns a solenoid
of radiusa < b, carrying
a steady electriccurrent I (seeFigure10.10).
If the solenoidis extremely long,
the magneticfieldinsideit is uniform, and the fieldoutsideiszero.But the vector
potentialoutsidethe solenoidis not zero;in fact (adoptingthe convenientgauge
zero\342\200\224any

V
condition

\342\200\242

= 0),14

2kr 0.

A=r\342\200\224

(r>a),

[10.66]

= na2B is the magneticflux through the solenoid.Meanwhile,the


solenoiditselfis uncharged,so the scalarpotentialip is zero.In this casethe
becomes
Hamiltonian
(Equation10.65)
where O

H=

-i- [-/?2V2+ q2A2+ litiqA v] .


\342\200\242

[10.67]

For a significant precursor,see


D. Bohm. Pltys. Rev. 115.
485 (1959).
Soc.
8 (1949).
London B62.
Elircnberg and R. E. Siday.Proc.Phys.
l4See.for instance. D.J. Griffiths. Introduction to Electrodynamics.
3rd ed..
Prentice Hall. Upper
SaddleRiver. NJ (1999).
Equation 5.71.
'\342\200\242'Y.

W.

Aharonov

and

386

Chapter10 TheAdiabaticApproximation

FIGURE10.10:Chargedbeadon a circular ring through which a longsolenoid

passes.

But the wave functiondepends


only on the azimuthal angle

\302\242{9

so V

A*

\342\200\224\302\273

reads
and the Schrodinger
equation
(0//))(^//^/0),
1

/r dr

2m

/?2 J02

/ <r/3>\\2

\\2^J

+ ' 7T/)2
.tig\302\256

d
V(0)=
rf0

= n/2 and r = /?),

\302\243^(0)-

[10.68]

Thisis a lineardifferentialequationwith constantcoefficients:

d2f

^.0df

#T-^+^

\302\260'

10.69]

where

\"-ha and
Solutions
are of the form

es~-\"-\342\200\242

f = AeiX(i>.

[10.70]
[10.71]

with
X

Continuityof i/f(0),at

= p\302\261y/p2 + e =P\302\261-V2^E.

0 = 2;r,requiresthat
/?

be an integer

+ -s/lmE= ;?.
/i

[10.72]

[10.73]

Section10.2:Berry'sPhase

387

and it followsthat
En

-^-^[n-^\\.

=0,

(\302\253

\302\2611.

\302\2612

).

[10.74]

liftsthe two-folddegeneracy
Thesolenoid
ofthe bead-on-a-ring
(Problem2.46):

Positiven, representing
a particletraveling in the samedirection
as the current in
the solenoid,
has a somewhatlowerenergy (assuming
than negative/?,
q is positive)
a particle
direction.
Moreimportant,
the allowed
describing
traveling in the opposite
even though thefieldat the
energies
clearlydependon the fieldinsidethe solenoid,
locationof the particleiszerol15
Moregenerally,supposea particleis moving through a regionwhere B is
zero(so V x A = 0), but A itselfis not.(I'll assumethat A is static,although
the methodcan be generalized
to time-dependent
The (time-dependent)
potentials.)
Schrodinger
equation,

iO -

with

<4'+**= //? dt

[10.75]

\342\200\224.

an electrical
contribution
potential
energy
may or may not include
be simplified
by writing
V\342\200\224which

qcp\342\200\224can

V=ei8V'.
where

g(r) =

[10.76]

l Jof A(r')dr'.

[10.77]

and O issome(arbitrarily chosen)


reference
point.Notethat this definitionmakes
senseonly when V x A = 0 throughout the regionin question\342\200\224otherwise the line
integralwoulddependon the path taken from O to r, and hencewouldnotdefine
a functionof r. In terms of *I>\\ the gradientof *I> is

V* = eig{iVgW+
but Vg

= {q/h)A,so

l-V-q\\

e''\302\253(VvI>');

* = t^VV.

[10.78]

'-Ut is a peculiar properly of superconducting


rings that the enclosedflux is quantized: * =
where is an integer. In that casethe effect is undetectable,since = (/\"r /2mb~')(n+n')~.
(Inhlq))}1',
and
+ is just another integer. (Incidentally, the charge q here turns out to be twice the charge of
an electron;the superconducting electronsarc lockedtogether in pairs.)However, flux quantization is
enforced by the superconductor(which inducescirculating currents to make up the difference), not by
the solenoidor the electromagnetic field, and it does not occurin the (nonsupcrconducting) example
\302\253'

E\342\200\236

(\302\273

\302\273')

consideredhere.

388

Chapter10 TheAdiabaticApproximation
and it followsthat

TV-^A)

4f

= -ftV*vV.

[10.79]

and cancelling
the commonfactore's,we are left
Putting thisintoEquation10.75,
with

=
\342\226\240vV+^'

2m

i\302\253

[10.80]

\342\200\224.

dt

satisfiesthe Schrodinger
equationwithout A. If we can solve
vectorpotentialwill
for the presence
of a (curl-free)
Equation10.80,correcting
be trivial:Just tack on the phasefactore'g.
Aharonov and Bohmproposed
an experiment
in which a beamof electrons
is splitin two, and passedeithersideof a longsolenoid,
beforebeingrecombined
The beamsare kept well away from the solenoiditself,so they
(Figure10.11).
encounter
is
only regionswhere B = 0. But A, which is given by Equation10.66,
not zero,and (assuming
the two beamsarrive with
V is the sameon bothsides),
Evidently

iffevent

phases:

-l!

A-rfr =

=
7jth /(\302\276M d<t>)

q<$>

[10.81]

\302\261

~2h~

The plussignappliesto the electrons


as
traveling in the samedirection
is to say, in the samedirection
The beamsarrive out
asthe current in the solenoid.
A\342\200\224which

Beam
recombined

Solenoid

10.11:

FIGURE
The Aharonov-Bohmeffect: The electron
beam
passingeither sideof a longsolenoid.

splits,with half

Section10.2:Berry'sPhase

389

(r-R)

FIGURE10.12:Particleconfinedto a box,by a potential


V(r R).

of phaseby an amount proportional


to the magneticflux their pathsencircle:

phasedifference=

[10.82]

interference
which has been
Thisphaseshift leadsto measurable
(Equation10.47),
confirmedexperimentally
and others.16
by Chambers
As Berry pointedout in his first paperon the subject,
the Aharonov-Bohm
effectcan be regardedas an exampleof geometric
phase.Supposethe charged
particleis confinedto a box(which iscenteredat pointR outsidethe solenoid)
by
a
a potentialV(r
moment
we're
to
10.12.
(In
Figure
going transport
the boxaroundthe solenoid,
soR will becomea function of time,but for now it is
of the Hamiltonian
are determined
by
just somefixed vector.)The eigenfunctions
\342\200\224

R)\342\200\224see

1
2m
We

-,->

+ V(r-R)
-V-gA(r)
i

ifr\342\200\236

= E,,1//,,.

[10.83]

have already learned


how to solveequations
of thisform:Let
yjr\342\200\236

where17
g

= e,gyjr'n.

l fA(r')

[10.84]
[10.85]

\342\200\242</!\342\200\242'.

l6R.G.Chambers,Phys.Rev. Lett. 5, 3 (I960).


l7It is convenient to set the reference point O at the center of the box, for this guarantees that we
If you use a
recover the original phaseconvention when we complete the journey around the solenoid.
in
fixed
f
or
have
to
the
at
the
far
because
hand,\"
end,
space, example,you'll
point
readjust
phase \"by
the path will have wrapped around the solenoid,circling regionswhere the curl of A does not vanish.
This leadsto exactly the sameanswer,but it'sa crude way to do it. In general, when choosingthe phase
convention for the eigenfunctions in Equation 10.9.
T) = ^-,,(.v, 0).
you want to make sure that
so that no spuriousphasechangesare introduced.
^\302\273(.v.

390

Chapter10 TheAdiabaticApproximation
and i/r' satisfies
the sameeigenvalue
only with A
equation,
It2

2m

\342\200\224>

0:

, + V(r-R)

[10.86]

V2

is a functiononly of the displacement


(r R), not (like of r
and R separately.
the process
Now let'scarry the boxaroundthe solenoid
(in thisapplication
doesn'teven have to be adiabatic).
To determine
Berry'sphasewe must first
Noticethat

\342\200\224

\\fr'lt

\\fr\342\200\236)

evaluate the quantity (i/OilV/ji/r,,).


Notingthat
V/?V0,

= V*

[V-V/,(r R)]

= -i

- R).

|A(R)^^(r R) + <r*V*#,(r

we find

=
=

J e-^lf',,(r-R)]V* -/|A(R)^(r- R) + V/^tr - R)

- jw'n{r - R)]*V^(r-

-\302\273|a(R)

R) d3r

d\\
[10.87]

The V with no subscript


denotesthe gradientwith respectto r, and I usedthe
=
fact that V/?
when actingon a functionof (r R). But the lastintegralis
\342\200\224

\342\200\224V,

i/ft timesthe expectation


value of momentum, in
\342\200\224(/?2/2/h)V2

of the Hamiltonian
eigenstate
+ V, which we know from Section2.1is zero.So
an

[10.88]

that
we conclude
Putting thisintoBerry'sformula (Equation10.45),
YniT)

-f

A(R)

\342\226\240dR=j

j{VxA)-da=

q<$>

[10.89]

which neatly confirmsthe Aharonov-Bohm


result(Equation10.82),and reveals
that the Aharonov-Bohm
effectisa particularinstanceof geometric
phase.18
What are we to make of the Aharonov-Bohm
effect?Evidently our
effectsin
are simplymistaken:
There can be electromagnetic
preconceptions
regionswhere the fieldsare zero.Notehowever that thisdoesnot make A itself
classical

'^Incidentally,in

is almost

an identity:

casethe analogy between Berry'sphaseand magnetic flux


= (cj/tl)B.

this

\"B\"

(Equation 10.50)

Further Problems
for Chapter10
the enclosed
flux
remainsgaugeinvariant.

measurable\342\200\224only

391

comesinto the final answer, and the theory

Problem10.7
DeriveEquation10.67from Equation10.65.
(b) DeriveEquation10.79,
stallingwith Equation10.78.
(a)

FURTHERPROBLEMSFOR CHAPTER10
* * *Problem10.8A particlestarts out in the groundstateof the infinite squarewell
(on the interval 0 < .v < a).Now a wall is slowlyerected,slightlyoff-center:19
V{x) =

f(t)8 (x

- - e) .
\302\260-

where f(t) risesgradually from 0 to oo.Accordingto the adiabatictheorem,


the
particlewill remain in the groundstateof the evolvingHamiltonian.

Find(and sketch)the groundstateat t -> oo.Hint:Thisshouldbe the ground


stateof the infinite squarewell with an impenetrable
barrier at a/2 + e. Note
that the particleis confinedto the (slightly)larger left \"halfof the well.
at
(b) Findthe (transcendental)
equationfor the groundstateof the Hamiltonian
(a)

time t. Answer:

sinz = T[cosz cos(zS)].


\342\200\224

= kcu T = mcif{t)/tr,S = 2e/cuand k = -JlmE/h.


for z< and show that the smallest
z goesfrom
Setting5 = 0,solvegraphically
jt to 2rr as T goesfrom 0 to oo.Explainthisresult.
Now set8 = 0.01and solvenumerically for z, using7 = 0, 1,5,
20, 100,
where z

(c)
(d)

and

1000.

Find the probabilityP,- that the particleis in the right \"halfof the well,
=
as a function of z and 8. Answer: Pr = 1/[1+ (/4.//-)],where

(e)

I\302\261

sin(,-(1+5))]sin2[-(l=f 5)/2].Evaluate
[1\302\2615-(1/-)

numerically for the

this

T's in part (d).Commenton your results.

expression

^Julio Gea-Banaclochc,
Am. J. Pliys. 70.307 (2002)usesa rectangular barrier:the delta-function
version was suggestedby M. Lakner and J. Peternelj.
Am. J. Phyx. 71.519
(2003).
1

392

Chapter10 TheAdiabaticApproximation
(f)

Plotthe groundstatewave functionfor thosesamevalues of T and S.Note


how it getssqueezed
intothe left half of the well,as the barriergrows.20

** *Problem10.9Supposethe one-dimensional
harmonicoscillator(massm,
to a driving forceof the form F(t) = mco-fit),where fit)
frequency co) is subjected
is somespecified
function(I have factoredout mar for notationalconvenience;
is
of length).The Hamiltonian
fit) hasthe dimensions
\302\253-2

pj2

H(t) = 2m ax1
[10.90]
^ + -rnarx1 mar.xf(t).
2
Assume that the forcewas first turned on at timet = 0: fit) = 0 for t < 0.
mechanics
Thissystemcan be solvedexactly,both in classical
and in quantum
mechanics.21
\342\200\224

(a)

the classical
it startedfrom
Determine
assuming
positionof the oscillator,
restat the origin(.\\v(0)= a>(0)= 0).Answer:

xcit)= a)f

Jo

fit')sin[a)it-t')]dt'.

[10.91]

to the (time-dependent)
(b) Showthat the solution
Schrodinger
equationfor this
it startedout in the /7th stateof the undriven oscillator
oscillator,
assuming

(^(.v.0)= ifn(x) where

\\ff\342\200\236(x)

as

,1,/^
q>ix,t)= ,t

yrnix

\342\200\224

is given by Equation2.61),can be written

x Ji\\-(n+k)hcol+mxAx-^)+'-^
- f^' fU')xA'')di']
J. nn
[10,92]
xc)e\"i

of Hit) are
and eigenvalues
(c) Show that the eigenfunctions

-/): Enit)= (n + i) - l-morf2.

iMJt.0 = 1M*

hco

[10.93]

adiabaticapproximationthe classical
position
10.91)reducesto xdt) = fit). State the precisecriterionfor adiaon the time derivative of Hint:
baticity,in thiscontext,as a constraint
Write sin[<w(r t')] as il/o))id/dt')cos[coit
t')] and use integration

(d) Show that in the

/.

(Equation

by

parts.

20Gea-Banaclochc
(footnote 19)discussesthe evolution of the wave function

the adiabatic theorem, and confirms these results in


21SeeY.
64
Am.

Nogami,

J. Phys. 59.

adiabatic limit.
(L991),and referencestherein.
the

without

assuming

Further Problems
for Chapter10
(e) Confirmthe adiabatictheoremfor thisexample,
by
and (d) to show that

*(a\\ t) =

393

usingthe resultsin (c)

t)ei0\"{,)eiY\"^.
[10.94]
Is the
Checkthat the dynamic phasehas the correctform (Equation10.39).
geometric
phasewhat you wouldexpect?
i/\342\200\236(x,

The adiabatic
can be regardedasthe first term in an
Problem10.10
approximation
adiabaticseriesfor the coefficients
cm{t) in Equation10.12.
Supposethe system
startsout in the /7th state;in the adiabaticapproximation,
it remains
in the nth
state,pickingup only a time-dependent
):
geometric
phasefactor (Equation10.21

(a)

thisintothe right sideof Equation10.16to obtainthe \"first


Substitute
correction\" to adiabaticity:
cm(t) =

(b)

c,\342\200\236(0)

- jf' U,n{t')A^|l(r')\\^('')e'(*-(r')-fl\302\253tf'))
,/,'. po.95]

in the nearly adiabatic


Thisenablesus to calculatetransition
probabilities
we wouldinsertEquation10.95
correction,\"
regime.To developthe \"second
and soon.
on the right sideof Equation10.16,
to the driven oscillator
As an example,
(Problem10.9).
apply Equation10.95
transitions
are possible
Showthat (in the near-adiabatic
approximation)
only
to the two immediately
adjacentlevels,for which

cH-i(t)= J^y/mf
f{t')e-^'dt'.
2h
V

Jo

are the absolute


(The transition
probabilities
squaresof these,of course.)

CHAPTER

11

SCATTERING

11.1
INTRODUCTION
11.1.1
Classical
Scattering
Theory
on somescattering
center(say, a protonfired at a heavy
Imaginea particleincident
It comesin with energy E and impactparameter/?, and it emergesat
nucleus).
somescatteringangle
(I'llassumefor simplicitythat the
Figure
is azimuthally symmetrical,so the trajectory remains in oneplane,and that
the target is very heavy, so the recoilis negligible.)
The essentialproblemof
classical
calculatethe
theory is this:Given the impactparameter,
scattering
of course,the smallerthe impactparameter,the greater
scattering angle.Ordinarily,
9\342\200\224see

11.1.

target

the scattering
angle.

Scatteringcenter

11.1:

FIGURE
Theclassical
scattering
problem,showingthe impactparameterb and
the scattering
angle6.

394

11.1:
Introduction

Section

395

FIGURE11.2:Elastichard-sphere
scattering.

11.1Hard-spherescattering.Supposethe target is a billiardball,

Example

of radius R, and the incidentparticleis a BB, which bouncesoff elastically


(Figure11.2).In terms of the anglea, the impactparameteris b = Rsina,and
the scattering
angleis 9 = ix 2a, so
\342\200\224

= Rsml

V2

= R cos

12,
\342\200\224

[11.1]

Evidently

6=

2 cos\"1
(b/R). \\fb<R,
if b > R.
0,

[11.2]

More generally,particlesincidentwithin an infinitesimalpatch of crosssolidangledQ


sectionalarea da will scatterinto a corresponding
infinitesimal
The largerda is,the biggerdQ will be;the proportionality
factor,
(Figure11.3).

D{6)= da/dQ,iscalledthe differential(scattering)cross-section:1

To my ear.the
'Thisis terrible language: D isn't a differential, and it isn't a cross-section.
would attach more naturally to da.But I'm afraid we'restuck with
words \"differential cross-section\"
this terminology. I should also warn you that the notation
D($) is nonstandard: Mostpeoplejust call it
a
11.3
l
ook
makes
like
da/dQ\342\200\224which
tautology. I think it will be less confusing if we give
Equation
the differential cross-section
its own symbol.

396

Chapter11 Scattering

da

*
I

\302\243

'-',

11.3:Particlesincidentin the area da scatterintothe solidangledSl.

FIGURE

da = D(0)dQ.

[11.3]

In termsof the impactparameter and the azimuthal angle0, da = bdbd<pand


dQ.= sin0d#d4>, so
db
=

D{9) sing d$

[11.4]

(Since6 is typically a decreasingfunctionof b, the derivative is actually


the absolute
value sign.)

negative\342\200\224hence

Example11.2Hard-spherescattering(continued).In the caseof hard-sphere


scattering
(Example11.1)
db

so
(

. /e\\

ficos(0/2)/*sin(g/2)\\= &
2
sing V
) 4

[11.5]
[11.6]

of 6.
Thisexampleis unusual,in that the differentialcross-section
is independent
The totalcross-section
is the integralof D(6),overall solidangles:

D(6)dQ;
\342\200\242-/

[11-7]

11.1:
Introduction

Section

397

it is the totalarea of incident


beamthat
roughly speaking,
in the caseof hard-sphere
For example,
scattering,

isscattered
by the target.

a = (R2/4)J

dQ = jiR2,

[11.8]

which is just what we would expect:It's the cross-sectional


area of the sphere;
BB'sincidentwithin thisarea will hit the target,and thosefarther out will missit
But the virtue of the formalismdevelopedhereis that it applies
justas
completely.
well to \"soft\"targets(suchas theCoulombfieldof a nucleus)
that are not simply

\"hit-or-miss.\"
with uniform intensity
Finally,supposewe have a beam of incident
particles,
as particlephysicists
callit)
(or luminosity,
= number of incidentparticlesper unit area,perunit time.
[11.9]
\302\243

into solidangle
The number of particlesenteringarea da (and hencescattering

dQ),per unit time,is dN = Cder= C D(0)dQ,so

--.

^) = 1dN

[11.10]

Thisis oftentaken as the definitionof the differentialcross-section,


becauseit
If the detector
makesreference
only to quantities
easilymeasuredin the laboratory:
a
acceptsparticlesscatteringinto solidangledQ, we simplycountthe number
recorded,per unit time,divideby dQ, and normalizeto the luminosityof the
incidentbeam.

11.1

* * *Problem
Rutherfordscattering.An incident
ofcharge<?| and kinetic
particle
offa heavy stationaryparticleof chargeqj.
energy E scatters
(a)

Derivethe formula relatingthe impactparameterto the scattering


angle.\"

= (qiqi/SjteoE)cot(6/2).
the differential
cross-section.
Determine
Answer:
scattering

Answer: b
(b)

qm

D(0)=
J6tt\342\202\2540E

sin2{9/2).

[11.11]

for Rutherford scattering


is infinite.We say
(c) Showthat the totalcross-section
has \"infinite range\";you can'tescapefrom a Coulomb
that the \\/r potential
force.
-This isn't easy, and

B.Marion
Fort

Worth,

and

you

might

want

to refer to a

book on classical
mechanics,such as Jerry

and Systems.4th ed.,Saunders,


Dynamics of Particles
StephenT.Thornton. Classical

TX

Section9.10.
(1995).

398

Chapter11 Scattering

FIGURE11.4:Scatteringof waves;incoming
outgoing
planewave generates
wave.
spherical

11.1.2
QuantumScattering
Theory
we imaginean incident
In the quantum theory of scattering,
planewave, i/r (z) =

a scattering
which encounters
direction,
potential,
to
That is, we lookfor solutions
an outgoingsphericalwave (Figure11.4).3
the Schrodinger
equationof the generalform
Ae'kz, traveling in the z

producing

ik:+ f{6)
ir(r.O)% A \\elK-

Jkr

[11.12]

for larger.

thisportionof 1^|2 must go


wave carriesa factorof 1//-,because
(The spherical
like I//-2 to conserve
The wave numberk is relatedto the energy of
probability.)
the incident
particlesin the usual way:
k

= y/2wE

[11.13]

in the moregeneral
before.I shallassumethe target isazimuthallysymmetrical;
casethe amplitudef of the outgoingsphericalwave coulddependon 0 as well

As

as0.

3For the moment, there'snot much quantum mechanics in this: what we'rereally talking about
particles* and you could even think of Figure 11.4
scattering of waves, as opposedto classical
as a picture of water waves encountering a rock, or (better, sincewe'reinterested in three-dimensional
scattering) sound waves bouncing off a basketball.In that casewe'dwrite the wave function in the real
is

the

form
A

and

/(0)would representthe

+
[cos(Jkz)+ /(0)cos{kr

S)/r].

amplitude of the scattered sound wave in the direction

9.

Section11.2:
PartialWave

Analysis

399

vdt

11.5:The volume dV of incidentbeam that passesthrough area da in

FIGURE
time dt.

the scatteringamplitudef(6); it tells


The whole problemis to determine

of scattenngin a given direction9, and henceisrelatedto the


you the probability

differential
cross-section.
Indeed,the probabilitythat the incident
particle,traveling
at speedv, passes
the
area
in
time
is
infinitesimal
da,
dt,
(seeFigure11.5)
through

dP =
But

\\tinc\\<icni\\2dV

= \\A\\2(vdt)da.

thisis equalto the probabilitythat the particlescattersintothe corresponding

solidangledQ:

dP =

^scattered|2dV =

from which it followsthat

\\A\\2\\

f\\2

r*
\\J

(vdt)r2dQ.

da = \\f\\2dQ,and hence
D(9)=

= \\f(9)\\2.
^d\\l

[11.14]

(which is the quantity of interestto the


Evidently the differentialcross-section
is equalto the absolutesquareof the scattering
experimentalist)
amplitude(which
In the followingsectionswe
is obtainedby solvingthe Schrodinger
equation).
the scattering
for calculating
will study two techniques
amplitude:
partialwave
analysisand the Bornapproximation.
and
Constructthe analogsto Equation11.12for one-dimensional
Problem11.2
two-dimensional
scattering.

11.2PARTIALWAVE ANALYSIS
11.2.1
Formalism
As we foundin

for a spherically
Chapter4, the Schrodinger
equation
symmetrical

solutions
potentialV(r) admitsthe separable
= R{r)Y;n{9.4>),
t{r.9.$)

[11.15]

400

Chapter11 Scattering

is a spherical
the
harmonic(Equation4.32),and u(r) = rR(r) satisfies
radialequation(Equation4.37):
h1 /(/ +
drii
it = Eu.
V(r) +
[11.16]
where Yj\"

/J\"

2m dr2

At

very

negligible,

2m

r2

!)'

is
large the potential
goesto zero,and the centrifugalcontribution
/\342\200\242

so

d2u

, -,

dr
The generalsolution
is
the first
one\342\200\224for

u{r)= Ceikr+ De~ikr\\


tennrepresents
an outgoingspherical
wave, and the secondan incoming
the scattered
wave we evidently want D = 0. At very large then,
/\342\200\242,

R{r)

eikr
,
r

as we already deduced(on physical grounds) in the previous section


(Equation11.12).

That'sfor very larger (moreprecisely,


for kr
1; in opticsit would be
calledthe radiationzone).As in one-dimensional
theory, we assume
scattering
that the potential
is \"localized,\"
in the sensethat exterior
to somefinite scattering
zero(Figure11.6).In the intermediate
regionit isessentially
region(where V can
be ignoredbut the centrifugalterm cannot),4the radialequationbecomes
;\302\247>

dhi /(/+1)
-ii -k2lL

[11.17]

dr

Radiation

zone

(*r\302\2731)

FIGURE11.6:Scatteringfrom a localized
the scattering region(darker
potential:
shading),the intermediate
region(lighter shading),and the radiationzone(where
fcr\302\273l).

follows does not apply to the Coulomb potential, since \\fr goesto zero more slowly
than
as
oo.and the centrifugal term does not dominate in this region.In this sensethe
Coulomb potential is not localized,and partial wave analysis is inapplicable.
What

\342\200\224>

;\342\200\242

1/;\342\200\224.

Section11.2:
PartialWave

11.1:
Hankelfunctions,
Spherical

TABLE
no

(x) and h,

hri

'

nQ

-'

Analysis

401

(x).

4V\"

^=(f44>-

44>*
\"l

\"/

A\"

for

\302\273

(,-)/+1^-/.1-

and the generalsolution


of spherical
Bessel
(Equation4.45)is a linearcombination

functions:

\302\253(/\342\226\240)

= Arjiikr)+ Bm,{kr).

[11.18]

However,neitherji (which is somewhat like a sinefunction)nor /?/ (which is a

cosinefunction)represents
an outgoing(or an incoming)
sortof generalized
wave.
What we needare the linearcombinations
to e'kr and e~tkr\\ theseare
analogous
known as spherical
Hankelfunctions:

/iJV) = Mx) + in,(x): h^U)= J!(X) in,(x).


Hankelfunctionsare listedin Table
The first few spherical

[11.19]

11.1.large
At

(i),(kr)
/i|
.(2),
/\\

(the \"Hankelfunctionof the first kind\") goeslike e'kr/r, whereas h)~'{kr)(the


\"Hankelfunctionof the secondkind\") goeslikee~'kr/r; for outgoingwaves, then,
we needspherical
Hankelfunctions
of the firstkind:

R{r)~~hl,l){kr).

[11.20]

Thus the exactwave function,outsidethe scattering


region(where V(r) =

0), is

0,0)= A eik'+ J2Ci,nh{,i)(kr)Yl\"(9^)

i/r(/-,

[11.21]

l.m

coefficients
The first term is the incident
planewave, and the sum (with expansion
the scattered
wave. But sincewe are assumingthe potentialis
represents
Ci,,\342\200\236)

the wave functioncannotdependon 0.5Soonly terms with


symmetric,
spherically

of course,becausethe incoming plane wave defines


-'There'snothing wrong with 0 dependence,
a z direction, breaking the sphericalsymmetry. But the aziinuthal symmetry remains; the incident plane
wave has no dependence,and there is nothing in the scattering process
that could introduce any
dependencein the outgoing wave.
<j>

<p

402

Chapter11 Scattering
m

= 0 survive (remember,Y!\" ~ e\"\"^).Now (from Equations4.27and 4.32)

/2/+ 1
=
y>.0)
n

y-^/>,(cos0).

[11.22]

is the /th Legendrepolynomial.


It is customary toredefinethe expansion
=
coefficients,
+ !)<://:
lettingC/.o i,+lk*/47r(2l
where P/

yjr{r.9)=

\342\200\242

eikz+ k

il+[(21+ 1)a,/i,(1)(kr) P,{cosd)


J2
1=0

[11.23]

You'llseein a moment why thispeculiarnotationis convenient;


the
a\\ is called
/th

partialwave amplitude.
Now, for very

so
11.1),

larger the Hankel functiongoeslike (\342\200\224i)l+[e'kr/kr (Table


ik:+ f(e)

Jkr 1

[11.24]

\\l/{}\\9)*xA\\e'KZ

where

CO

/(0)= 2^(2/+l)tf,P,(cos0).

[11.25]

/=()

Thisconfinnsmore rigorouslythe generalstructure postulated


in Equation11.12,
and tellsus how to computethe scattering
/(0),in terms of the partial
amplitude,
wave amplitudes The differential
is
cross-section
(\302\253/).

D(0)=

+ l)aiai'^/(cos#)P/'(cos0).[11.26]
|/(0)|2= J2Yl{2l+i){2l'

r
and the totalcross-section
is
i

CO

a=47tJ2(2l+ D\\oi\\2.

[11.27]

/=0

of the Legendrepolynomials,
(I usedthe orthogonality
Equation4.34,to do the
angular integration.)

11.2.2
Strategy
remainsis to determinethe partialwave amplitudes, for the potential
in
Thisis accomplished
by solvingthe Schrodinger
question.
equationin the interior
solution
and matchingthisto the exterior
region(where V(r)isdistinctlynon-zero),
The onlyproblemis
(Equation11.23),
boundary conditions.
usingthe appropriate
All that

\302\253/,

PartialWave
Section11.2:

Analysis

403

that as it standsmy notationis hybrid:I usedspherical


coordinates
for the scattered
for the incident
wave. We needto rewrite the wave
wave, but cartesiancoordinates
function in a moreconsistent
notation.
the Schrodinger
Of course,e'kz satisfies
equationwith V = 0. On the other
hand, I just argued that the generalsolutionto the Schrodinger
equationwith
V = 0 can be written in the form

Y, [A,.mj,(kr)+ BLm n,(kr)]Yjn(6t

\302\242).

I.m

In particular,
to expresse'kz in thisway. But e'kz is finite
then, it must be possible
at the origin,so no Neumann functions
are allowed(ni(kr)blowsup at r = 0),
and sincez = r cos9 has no dependence,
onlym = 0 terms occur.The explicit
of a planewave in terms of spherical
waves is known as Rayleigh's
expansion
\302\242

formula:6

oo

eikz =

\302\243Y

(2/+ 1).//(kr)P,(cos9).

[11.28]

/=0

entirely in
Usingthis,the wave functionin the exteriorregioncan be expressed
terms of r and 9:
oo
\\j/{i\\

9) = A

\302\243\\''(2/

/=0

+ 1)\\ji(kr) + ika,h)l)(kr)\\
P,(cos9).

Example11.3Quantumhard-spherescattering.Suppose
oo, for < a,
V(r) =
0, for r > a.
/\342\200\242

[11.29]

[11.30]

The boundary condition,


then, is

ir(a,6)=0.
so

[11.31]

oo
\302\243V(2/

/=0

+ 1)\\ji(ka) + ika,/iJ'^Jta)]Pi(cos9)= 0

[11.32]

for all 9, from which it follows(Problem11.3)that

ji(ka)
01=1-=-77- .
khy\\ka)

[11.33]

6For a guide to the proof, seeGeorgeArfken and Hans-Jurgen Weber, Mathematical Methods
Academic Press,Orlando (2000).Exercises
12.4.7
and 12.4.8.
for Physicists.5th ed..

404

Chapter11 Scattering

In particular,
is
the totalcross-section
oo

a = TT \302\243(2/+1) jl(ka)
[11.34]
hf\\ka)
/=0
so let's considerthe
That'sthe exactanswer, but it's not terribly illuminating,
limitingcaseof low-energyscattering:ka <$C 1.(Sincek = 2tt/X,this amounts to
Referring
saying that the wavelengthis much greaterthan the radiusof the sphere.)
to Table4.4,we notethat ni(z)is much largerthan ji(z),for smallz, so
ji(z)
Ji(z)
.//(2)
nt(z)
ji(z)+ ini(z)

f2;/!1\",2/+1

2'/!z'/(2/+l)!

-(2/)1^-/-1
/2'/!

2/ + 1 (20!

[11.35]

and hence

Ait

^-^

7T
*> Z^

T2'/r4

^2/+1L(2/)!J

4/+2

(*\302\253)

the low
1, so the higherpowersare
=
the scattering
is dominatedby the / 0 term.(This means
energy approximation
cross-section
of 6,justas it was in the classical
that the differential
is independent

But we'reassuming

A-\302\253

case.)Evidently

<$C

negligible\342\200\224in

a^Ajta2.

[11.36]

the scattering
cross-section
is
for low energy hard-sphere
scattering.
Surprisingly,

areaofthe
cross-section\342\200\224in fact, a is the totalsurface
fourtimesthe geometrical
of long-wavelength
scattering
sphere.This\"largereffectivesize\"is characteristic
in
as
in
a
t
hese
waves
\"feel\"
t
heir
would
be
true
sense,
(it
way around
optics, well);
the whole sphere,whereas classical
particlesonly seethe head-oncross-section.
Hint:Exploit
ProveEquation11.33,
Problem11.3
starting with Equation11.32.
with
the orthogonality
of the Legendrepolynomials
to show that the coefficients

vanish.
different valuesof I must separately

from a spherical
the caseof low-energy
delta**Problem11.4Consider
scattering

functionshell:

V(r)

=a8(r-a),

the scattering
Calculate
where a and a are constants.
amplitude,
/(0),the
cross-section,
D{6),and the totalcross-section, Assume ka 1,so that

differential

a.

<\302\243

Section11.3:
PhaseShifts

405

(To simplify matters,throw out all


only the / = 0 term contributes
significantly.
/ ^ 0 terms right from the start.)The main problem,
of course,is to determine
Expressyour answer in terms of the dimensionless
quantity /3 = Imaoc/h1.

\302\253o-

Answer: a = 4jta2p2/(l+ ft)2.

11.3PHASESHIFTS
Consider
first the problemof one-dimensional
from a localized
scattering
potential
=
<
on
the
a
jc
half-line
0
I'll
\"brick
wall\"
at
x
0, so a
V(x)
(Figure11.7). put
wave incident
from the left,
\\jfiix) =

is entirely reflected

Jkx (x

AelKA

<-a)

\\l/r{x)= Be~ikx {x <

[11.37]

-a).

[11.38]

Whatever happensin the interaction


region < x < 0), the amplitudeof the
wave has got tobe the sameas that of the incident
reflected
wave, by conservation
of probability.But it neednot have the samephase.If there were no potential
at
=
=
all (justthe wall at x 0), then B
sincethe totalwave function(incident
must vanish at the origin:
plusreflected)
(\342\200\224a

\342\200\224A,

V^o(a')=

(eikx

- e~ikx)

(V(x)= 0).

isnot zero,the wave function(forx <


If the potential

\342\200\224a)

[11.39]

takesthe form

ir(x) = A (eikx e^2S-kxA (V(x)^ 0).

[11.40]

FIGURE11.7:One-dimensional
froma localized
scattering
potentialboundedonthe
an
infinite
wall.
right by

406

Chapter11 Scattering
the phase
The whole theory of scattering
reducesto the problemof calculating

1 8 a functionof and henceof the


0 0
for a
shift'
k,
(as
energy E = h-k~/2m),

We do this,of course,
by solvingthe Schrodinger
potential.
equationin the
< x < 0), and imposingappropriateboundary conditions
scattering
region
The virtue of working with the phaseshift (asopposedto the
(seeProblem11.5).
the physics(because
of conservation
complexamplitudeB) is that it illuminates
of probability,
all the potentialcan do is shift the phaseof the reflected
wave) and
a
the mathematics
real
(tradinga complex
simplifies
quantity\342\200\224two
singlerealquantity).
Now let's return to the three-dimensional
case.The incidentplanewave
carriesno angular momentum in the z direction(Rayleigh's
formula
no terms with m ^ 0),but it includesallvaluesof the totalangular
Becauseangular momentum is conserved
(/ = 0, 1, 2,
(by a spherically
eachpartialwave (labelled
symmetric potential),
by a particular/) scatters
with (again)no changein amplitude8\342\200\224only in phase.If there is no
independently,
potentialat all,then = Ae'kz, and the /th partial wave is (Equation11.28)
= Ai'(2I+ \\)ji{kr)P,(cos9) (V(r)= 0).
[11.41]
specified

{\342\200\224a

numbers\342\200\224for

...).

contains
momentum

yf/Q

^\302\260

But (from Equation11.19and Table 11.1)


**
+
j,(x)= I [h(l)(x)+ />}2)(jc)]
yx [(-')/+V\"* i'+lc~lx]

(Jf

\302\273

D- H1-42]

Sofor larger
~ (-I)'e\"'*rl
=
tf % &{2l^l)
\
\e'kr
J Pi(cos6) (V(r) 0).
I
2ikr

[11.43]

The secondterm in squarebracketsrepresents


an incoming
wave; it is
spherical
when we introduce
the scattering
The first term is the outgoing
unchanged
potential.
wave; it
\302\2420)

picksup a phaseshift 5/:


_
^ A(2/+ 1)
L
2/kr \\enkr+2S,)

(_!/<,-<*>\342\200\242]

J pt(COse) (V(r)# 0).

[11.44]

wave (dueexclusively
to the /7, component
Thinkof it as a converging
spherical

e'kz),which is phaseshifted25/ (seefootnote7) and emergesas an outgoing


wave (the hj part of elkt as well as the scattered
wave itself).
spherical
in

7The 2 in front of S is conventional. We think of the incident wave as being phase shifted once
on the way in, and again on the way out: by
we mean the '\"one way\" phase shift, and the total is
<5

therefore 2<5.

8Onereasonthis subject can be so confusing is that practically everything is called an

\"amplitude:\"

/(0)is the '\"scattering

amplitude,\"

ti\\

of 0,and both are complex


numbers.I'mnow
of course)height of a sinusoidalwave.

is the
talking

\"partial

about

but the first is a function


the (real,
the original sense:

wave amplitude.\"
\"amplitude\"

in

Section11.3:
PhaseShifts

407

In Section11.2.1
the wholetheory was expressed
in terms of the partial wave
it in terms of the phaseshifts5/. There
a\\\\ now we have formulated
amplitudes
must be a connection
betweenthe two. Indeed,comparingthe asymptotic
(large
form of Equation11.23
;\342\200\242)

(2/+1)

*(/)

+ (~ + ^K'MpKcosfl) [11.45]

[^-(-1)^-^

likr

with the generic


in terms of 8/
expression
<*

we find9
(Equation11.44),

k (^ - 0 = \\*sinW-

[11.46]

It followsin particular(Equation11.25)
that

oo

/(0)= - J2(2I+ l)ei&>sin(5/)P,(cos0)

[11.47]

/=0

and

(Equation11.27)

CO

Art

a = ~J2(2l+ l)sm2(8,).

[11.48]

/=0

Again, the advantage of working with phaseshifts(as opposedto partial wave


is that they are easierto interpretphysically,and simpler
amplitudes)
of angular momentum to
phaseshift formalismexploitsconservation
reducea complex
quantity ai (two real numbers) to a singlereal one5/.
mathematically\342\200\224the

A particle
of massm and energy E is incident
from the left on the
Problem11.5
potential
0,
(x <
V(.v) = -V0. (-a<x<0).
oo. (a- > 0).
\342\200\224a).

\342\200\242

(a)

If the incomingwave isAe'kx (where k = -JlmE/h),find the reflected


wave.

Answer:

Ae -lika

/~\\i
k-ik'col(k'a)
e~ikx\\ where k' = y/2m(E+V0)/h.

+ ik'cot(k'a)

1 used the asymptotic form of the wave function to draw the connection between
Both of them are constants
nothing approximate about the result (Equation
means
in
the
of
and
the
shift
Sj
asymptotic region (where the Hankclfunctions
(independent
phase
have settleddown to <?^Although

\302\253/

11.46).

and (5/. there is


;\342\200\242).

/kr).

408

Chapter11 Scattering
wave has the sameamplitude
asthe incidentwave.
(b) Confirmthat the reflected
(c)

Find the phaseshift 8 (Equation11.40)for a

Answer: 8

very

deepwell {E <$C Vo)-

\342\200\224ka.

What are the partial wave phaseshifts(5/) for hard-sphere


Problem11.6
scattering

(Example11.3)?

Problem11.7
Findthe 5-wave (/ = 0)partial wave phaseshift 8o(k)forscattering
from a delta-function
shell(Problem11.4).Assumethat the radialwave function
u(r) goesto 0 as r oo.Answer:
2maa
cot l co\\(ka)+
where p =
\342\200\224\302\273

h2

/8sin2(fc\302\253)J

11ATHE BORNAPPROXIMATION

11.4.1
Equation
IntegralFormof the Schrodinger
The time-independent
Schrodinger
equation,
~\342\200\224V2^

2m

+ Vf = E^.

[11.49]

as
can be written moresuccinctly
(V2+A'2)V=
where

k^^l
h

and

<2-

Qm*lv+.
tr

[11-50]

[,,.51]

Thishas the superficialform of the Helmholtzequation;note,however, that the


term {Q)itselfdepends
on \\j/.
\"inhomogeneous\"
Supposewe couldfind a functionG(r) that solvesthe Helmholtzequation
with a deltafunction\"source:\"
(V2 + fc2)G(r)=

S3(r).

[11.52]

Then we couldexpressi/r as an integral:

tf3r0.
^(r) = f G(r 1-())0(1-0)

[11.53]

Section11.4:
The BornApproximation 409
For it is easy to show that thissatisfiesSchrodinger's
equation,in the form of
Equation11.50:
(V2 + k2)f(r) =

[(V2+ k2)G(r r0)] G(r0)d3r0

f 83(r-r0)Q(r0)d*ro=Q(r).

G(r) is calledthe Green'sfunctionfor the Helmholtzequation.


(In general,the
Green'sfunctionfor a lineardifferentialequationrepresents
the \"response\"
to a
delta-function
source.)
Our first task10isto solveEquation11.52
for G(r).Thisismosteasily
transform, which turns the differentialequationinto
by taking the Fourier
an algebraicequation.
Let
accomplished

[11.54]

G(r)=^W/^(s)^sThen
(V2 + k2)G(r)=

But

j [(V2+ *V*r]*(s)

d2

-^3/2

vVsr = -5VST,

[11.55]

53(r)= -1-3feisrd\\

[11.56]

and (seeEquation2.144)

so Equation11.52says

It follows1'that

(2jt)-V2(*2-52)'
we find:
Putting thisbackintoEquation11.54,
\302\253(s)

G(r)
10

Warning:

(2;r)3J

skip straight

[11.

are approaching two pages of heavy analysis, including contour inte^

answer.Equation 11.65.
'This is clearly sufficient, but it is also necessary,as you can show by combining the i
a single integral, and using Planchercl's
theorem. Equation 2.102.

you wish,
into

You

d's.
(k2 - s2)

[11.571

to the

410

Chapter11 Scattering

FIGURE
11.8:Convenientcoordinates
for the
in
11.58.
integral Equation

isfixed,as far as the s integrationis concerned,


so we may as well choose
coordinates
(s,6, with the polaraxisalongr (Figure11.8).Thens r =
spherical
srcosO,the 0 integralis trivial (2^-), and the 6 integralis
Now, r

\342\200\242

\302\242)

Jo

eisrCose
sin(9 d$ =

,isrcos9

2sin(sr)

isr

[11.59]

sr

Thus

1 2 f00 s sin(sr)
(2* 2 Jo k2 s2

;\342\226\240

f\302\260\302\260

s sin(5r)

Anh- J_*>

k2-s2ds.

[11.60]

The remainingintegralis not so simple.It pays to revert to exponential


notation,

and factorthe denominator:

G(r)=
=

seisr

oo

se

\342\200\224isr

-ds

8jr2r [J-oo (s-k)(s+ k)

-ds

+ k)
/oo
-oo (s-k)(s

^h~h)-

[11.61]

Thesetwo integralscan beevaluatedusingCauchy'sintegralformula:

f(z) dz =
2jrif(zo),

/ - zo)
(z

[11.62]

if zo lieswithin the contour(otherwisethe integralis zero).In the presentcase


the integration
is alongthe real axis,and it passesrightover the polesingularities
at +/:.We have to decidehow to skirt the
go over the one at
and under the oneat +k (Figure11.9).(You'rewelcometo choosesomeother
conventionif you
winding seventimesaroundeach
get
a different Green'sfunction,but, as I'll show you in a minute,they'reall equally
poles\342\200\224I'll

like\342\200\224even

\342\200\224k

pole\342\200\224you'll

acceptable.)
For eachintegralin Equation11.61we must \"closethe contour\"in sucha
at infinity contributes
way that the semicircle
nothing.In the caseof I\\, the factor

Section11A: The BornApproximation


A

411

lm(s)

= +k
s^7

s=-k

Re(s)

FIGURE11.9:Skirting the polesin the


contourintegral(Equation11.61)

eisrgoesto zerowhen 5 hasa jargepOSitive imaginary part;for thisonewe close


above(Figure11.10(a)).
The contourencloses
only the singularity at s = +k, so
isr
1
seisr
se
= meikr
ds = lixi
/l
[11.63]
s+k
s + k s=k

.f

s-k

In the caseof h, the factore~'srgoesto zerowhen s hasa largenegative


thistime the contourenclosesthe
part,so we closebelow(Figure11.10(b));
so we pick
(and it goesaround in the clockwisedirection,
singularity at s =
imaginary

\342\200\224k

up a minus sign):

h=

se -isr

-j S-k

s+k

ds =

se -isr
\342\200\224Ini

S-k

= meikr
\342\200\224

s=-k

[11.64]

Conclusion:
G(r)=

Jkr
=
ik [(\"\"*) (-\"\"\"')] 4JIT

[11.65]

This,finally, is the Green'sfunctionfor the Helmholtzequation\342\200\224the solution


to Equation11.52.
(If you got lostin all that analysis,you might want to check
the resultby directdifferentiation\342\200\224see Problem11.8.)
Or rather, it is a Green's
functionfor the Helmholtzequation,
for we can addto G(r) any functionGo(r)
that satisfies
the homogeneous
Helmholtzequation:
= 0;
(V2 + fc2)G0(r)
[11.66]

(a)

(b)

11.10:
11.63and 11.64.
Closingthe contourin Equations

FIGURE

412

Chapter11 Scattering

Thisambiguity
clearly,the result(G + Go) stillsatisfiesEquation11.52.
different choice
to the ambiguity in how to skirt the
corresponds precisely
amountsto pickinga different functionGo(r).
the generalsolution
to the Schrodinger
equation
Returning to Equation11.53,
poles\342\200\224a

takesthe form

i/f(r)

where \\j/q

= V/o(r)

- 2nh2J/ -|r
\342\200\224\342\200\224j

\342\200\224

-V(r0)\\J/(r0)d3ro,
r0|

[11.67]

satisfiesthe free-particleSchrodinger
equation,
(V2+fc2)Vo= 0.

[11.68]

Equation11.67is the integralform of the Schrodingerequation;it is entirely


equivalentto the morefamiliar differentialform.At first glanceit lookslike an
explicitsolutionto the Schrodinger
equation(for any potential)\342\200\224which is too
There'sa \\J/ under the integralsignon the
goodto be true.Don'tbe deceived:
right hand side,so you can'tdo the integralunlessyou already know the solution!
the integralform can be very powerful,and it is particularly well
Nevertheless,
suitedto scattering
aswe'llseein the followingsection.
problems,

Problem11.8
Checkthat Equation11.65satisfies
by direct
Equation11.52,
=
substitution. Hint:V2(l/r)
-4jrS3(r).12
**Problem11.9
Show that the groundstateof hydrogen(Equation4.80)satisfies
the integralform of the Schrodinger
for the appropriateV and E (note
equation,
=
that E is negative,so k = ik, where k
*s/\342\200\2242mE/ft).

11.4.2TheFirstBornApproximation
aboutro = 0 (that is,the potential
SupposeV(ro)islocalized
dropsto zerooutside
somefinite region,asis typicalfor a scattering
and we want to calculate
problem),
center.Then |r|^> |ro|for all points
i/r(r) at pointsfar away from the scattering
that contribute
to the integralin Equation11.67,
so

|r- r0|2= r2 + r2 - 2r

and hence

\342\200\242

r0 = r2 (l

|r-r0|= r-r-r0.

- 2^).

[11.69]
[11.70]

'-See,for example,D.Griffiths. Introduction to Electrodynamics, 3rd ed.(Prentice Hall. Upper


SaddleRiver, NJ, 1999).
Section1.5.3.

Section11.4:
The BornApproximation

413

Let
k = kr:
then

^ eikre-ikro

^/A-|r\342\200\224r0|

and therefore

[11.71]

,'A-|r-r0| Jkr

|r-ro|

e -ik-ro

[11.72]
[11.73]

we can afford to make the more radicalapproximation


(In the denominator
|r ro| = r; in the exponentwe needto keep the next term. If this puzzles
of the denominator.
What we
you,try writing out the next term in the expansion
in powersof the smallquantity (rn/r),and droppingallbut
are doingis expanding
the lowestorder.)
we want
In the caseof scattering,
\342\200\224

\\fro(r)

Jkz
= Ae'

[11.74]

an incident
planewave. For larger, then,
representing
eikr
m
ik:
/ e-'kroV(ro)iMro)d3ro.
[11.75]
f{r) = Ae,K~ 2-ntt
Thisis in the standardform (Equation11.12),
and we can readoff the scattering
amplitude:
[11.76]
f<6<*) = -^7T7 e-ik'ri)V(ro)xlf(r0)d\\0.
2nhlA

[\342\226\240

\342\200\224

J
So far, thisis exact.Now we invokethe Bornapproximation:
Supposethe
alteredby the potential;then it makes
incomingplanewave is notsubstantially
senseto use
[11.77]
If(ro)% fo (ro)= Aetkzo =
Ae''k''r\302\260,

where

k' = kz,

[11.78]

insidethe integral.(Thiswouldbe the exactwave function,if V were zero;it is


a weakpotentialapproximation.13)
In the Bornapproximation,
then,
essentially

/(0,0) =

Inn*

f ei{k'~k)-r0
V(r0)d3r0.

[11.79]

13Generally,partial wave analysis is useful when the incident particle has low energy, Cor then
only the first Few terms in the seriescontribute significantly; the Born approximation applieswhen the
potential is weak, comparedto the incident energy, so the deflection is small.

414

Chapter11 Scattering

k=kr

^e

k'= kz

= k'-k

Two wave vectors in the Born


11.11:
k'
the

FIGURE

approximation:pointsin

direction.
the scattered

in

k
incidentdirection,

of k' and k, they bothhave magnitude


(Incaseyou have losttrack of the definitions
of the incident
k, but the former pointsin the direction
beam,while the latter points
toward the detector\342\200\224see Figure
transferin
/?(k k') is the momentum

11.11;

\342\200\224

the process.)

for low energy(longwavelength) scattering,the exponential


In particular,
factoris essentially
constant
overthe scattering
region,and the Bornapproximation
to
simplifies
m

/(0.0)=

,l

2nh

V(r)d r, (low energy).

[11.80]

on r, sincethereis no likelihood
of confusion
at thispoint.)
(I droppedthe subscript

scattering.14
Suppose
Example11.4 Low-energysoft-sphere
V0. if /* < a.
V(r) =
0. if r > a.
In thiscasethe low-energy
amplitudeis
scattering

[11.81]
[11.82]

of 9 and 0),the differential


is
cross-section
(independent

m2 ~ /2//?%'
dQ
3/r
da

and the totalcross-section


is

a=4,T

' 2m

Voa

\\

[11.83]

3\\2

[11.84]

.~3fV

l4You can't apply the Born approximation to hard-spherescattering (Vq =


integral
blows up. The point is that we assumedthe potential is weak, and doesn'tchange the wave function
much in the scattering region.But a hard spherechangesit radically\342\200\224from Ae'kz to zero.
oo)\342\200\224the

The BornApproximation
Section11.4:

415

For a spherically
not necessarily
symmetrical
potential,V(r) =
Bornapproximation
low
again reducesto a simplerform.Define
V(r)\342\200\224but

at

energy\342\200\224the

*r

= k'-k,

[11.85]

and let the polaraxisfor the ro integrallie alongk, so that

(k'-k)

= Kr0coseo.

[11.86]

eiKr\302\260c\302\260se^(ro)rtsm60drod6odfo.

[11.87]

\342\226\240r0

Then

--^y

f(6) = 27r/r Jf

integralis one we have encountered


on r, we are left with
before(seeEquation11.59).
Droppingthe subscript

The 0o integralis trivial (2n), and the

/(0)

2w

f\302\260\302\260

/
h~K Jo

=\342\200\224\342\200\224

6\302\276

rV(r)sin{Kr)dr, (spherical
symmetry).

of
The angular dependence

[11.88]

we seethat
/ iscarriedby /c; in Figure11.11
k

= 2&sin((9/2).

[11.89]

Example11.5Yukawa scattering.The Yukawa potential(which is a crude


has the form
modelfor the bindingforcein an atomicnucleus)

V(r)=ft r

[11.90]

The Bornapproximation
where ft and \\i are constants.
gives

= -,,2^, .
-=^I e-^smbcndr
Ptk Jo
0
fi2(fl2+K2)
(You get to work out the integralfor yourself,in Problem11.11.)

~
f(6) =

2mft

\342\200\242oo

[11.91]

Example11.6Rutherfordscattering.If we put in ft = qxqi/^neo,M = 0,


reducesto the Coulombpotential,describing
the electrical
the Yukawa potential
of two pointcharges.
interaction
Evidently the scattering
amplitudeis
4jteoft-K-

416

Chapter11 Scattering

or (usingEquations11.89and

11.51):

/((9)=

q\\qi

__.

[11.93]

ll\"\"2
sin2(0/2)
167re0E

-\342\200\224

is the squareof this:


The differential
cross-section
da
dQ

q\\qi

-,2

[11.94]

16^e0^sin2(^/2)

11.11).

which is precisely
It happensthat for
the Rutherford formula (Equation
the Coulombpotential,
classical
the Bomapproximation,
and quantum
mechanics,
fieldtheory all yieldthe sameresult.As they say in the computer
business,the
Rutherford formula is amazingly \"robust.\"

\342\231\246Problem

in the Bomapproximation,
forsoft11.10
Findthe scattering
amplitude,

spherescatteringat arbitrary energy. Show


limit.
Equation11.82in the low-energy

that your formula

reducesto

11.11

to confirmthe expression
Problem
Evaluate the integralin Equation11.91,
on the right.

**Problem11.12
for scatteringfrom a Yukawa
Calculatethe total cross-section
potential,in the Bom approximation.
Expressyour answer as a functionof E.

\342\231\246Problem

in Problem11.4,
11.13
For the potential

(a)

calculatef(6), D(6),and a, in the low-energyBomapproximation;

(b)

calculatef(6) for arbitrary energies,


in the Bomapproximation;

in the
with the answer toProblem11.4,
(c) showthat your resultsare consistent

appropriate
regime.

11.4.3
TheBornSeries
is similarin spiritto the impulseapproximationin
The Bom approximation

classical
we beginby pretending
theory.In the impulseapproximation
scattering

Section11.4:
The BornApproximation

417

Actual

trajectory

Scatteringcenter

11.12:

FIGURE
Theimpulse
undeassumes
that the particlecontinues
approximation
the transversemomentumdelivered.
flected,and calculates
and computethe
particlekeepsgoingin a straight line (Figure11.12),
transverseimpulsethat wouldbe deliveredto it in that case:
that

the

-I

[11.95]

F\302\261dt.

If the deflection
is relatively small,thisshouldbe a goodapproximation
to the
transversemomentum impartedto the particle,and hencethe scattering
angleis
6 = tan-1(I/p),

[11.96]

is the incidentmomentum.
Thisis, if you like,the \"first-order\"
impulse
-order
is
what
with:
no
we
started
deflection
at all).
zeroth
(
the
approximation
the incident
Bornapproximation
Likewise,in the zeroth-order
planewave passes
and what we explored
in the previoussection
is really the
by with no modification,
to this.But the sameideacan be iteratedto generatea series
first-ordercorrection
of higher-order
which presumably convergeto the exactanswer.
corrections,
The integralform of the Schrodinger
equationreads
where p

V(r) = Vo(r)+
where \\}/o

J r0)V(r0)f(ro)d3r0,
g{v

[11.97]

is the incidentwave,
m elkr
g{r)= 27th2 r

[11.98]

-\342\200\224f

the factorIm/ti1,for
is the Green'sfunction(intowhich I have now incorporated
and V is the scattering
convenience),
Schematically,
potential.

^ = ^()+ f gVf.
for \\j/, and plugit
Supposewe take thisexpression

f = ^+

gV^o +

[11.99]
in under the integralsign:

JJ gVgVf.

[11.100]

418

Chapter11 Scattering

=
\302\245o

11.13:
ofthe Bornseries(Equation11.101).
Diagrammaticinterpretation

FIGURE

we obtaina formal seriesfor \\J/:


Iteratingthisprocedure,
jjf

= t0 +

gV^o +

J J gVgV^o+ J J J gVgVsVifa+

\342\200\242 \342\200\242 \342\200\242

. [11.101]

In eachintegrandonly the incidentwavefunction(\\(/o) appears,


togetherwith more
the seriesafter the
and morepowersof gV.Thefirst Bornapproximation
truncates
the higher-order
secondterm, but it is pretty clearhow onegenerates
corrections.
The Bornseriescan berepresented
diagrammaticallyasshown in Figure11.13.
In zerothorder\\j/ is untouchedby the potential;
in first orderit is \"kicked\"once,
and then \"propagates\"
outin somenew direction;
in second
orderit iskicked,
to a new location,
is kickedagain,and then propagates
out;and soon.In this
propagates

contextthe Green'sfunction issometimes


calledthe propagator\342\200\224it tellsyou how
the disturbance
oneinteraction
and the next.The Bornseries
propagatesbetween
was the inspiration
for Feynman's
formulation
of relativistic
quantum mechanics,
which is expressed
(g),
entirely in terms of vertexfactors(V) and propagators
in
connected
together Feynmandiagrams.
Problem11.14
Calculate
0 (asa functionof the impactparameter) forRutherford
in the impulse
Show that your resultis consistent
with
scattering,
approximation.
the exactexpression
in the appropriate
limit.
(Problem11.1(a)),

11.15
Findthe scattering
forlow-energy
scattering
soft-sphere
amplitude

* * *Problem

in the secondBornapproximation.
Answer:

\342\200\224

(2mVbrt3/3/T)[l(4mVQa2/5h~)].
\342\200\224

11

FURTHERPROBLEMSFORCHAPTER

Find the Green'sfunctionfor the one-dimensional


11.16
Schrodinger

** *Problem

the integralform (analogous


to Equation11.67).
and useit to construct
equation,
Answer:
xjf(x) = jjf0(x)

- trk J-oo
/
irn

\342\200\224

C\302\260\302\260

eik\\x-x\302\273W(x0)x!/(xo)dx0.

[11.102]

Further Problems
for Chapter11

419

to developthe Bom
Useyour resultin Problem11.16
11.17

* *Problem

for one-dimensional
(onthe interval oo< x < oo,with no \"brick
scattering
wall\" at the origin).
That is,choose^o.(*)= Ae'*x,and assumeijf(xo)= i^oC^o)
Showthat the reflection
to evaluate the integral.
coefficient
takesthe form:
\342\200\224

approximation

^(\302\243)1/1^--

[11.103]

Bornapproximation
Problem11.18
Usethe one-dimensional
to
(Problem11.17)
coefficient(T = 1 R) for scattering
from a delta
computethe transmission
\342\200\224

function (Equation2.114)
and from a finite squarewell (Equation2.145).
Compare
a
nswers
results
w
ith
the
exact
2
.141
and
2.169).
your
(Equations

Provethe opticaltheorem,which relatesthe total cross-section


Problem11.19
to the imaginarypart of the forward scattering
amplitude:

a = ^Im(/(0)).

[11.104]

AT

Hint:UseEquations11.47and 11.48.
to determine
the totalcross-section
Problem11.20
Usethe Bomapproximation
for scattering
from a gaussian
potential
V(x) =

Ae\"^'1.

A, /a, and m (the massof the incident


Expressyour answer in terms of the constants
=
and k y/2mE/li,where E is the incident
energy.
particle),

CHAPTER

12

AFTERWORD

Now that you have (I hope)a soundunderstanding


of what quantum mechanics
of what it means\342\200\224continuing the story
says,I wouldliketo return to the question
begunin Section1.2.The sourceof the problemis the indeterminacy associated
with the statistical
of the wave function.For ty (or,moregenerally,
interpretation
the quantum
couldbe a spinor,for example)doesnot uniquely
the outcome
of a measurement;
distribution
of
allit providesis the statistical
Didthe physicalsystem\"actually
possibleresults.This raisesa profoundquestion:
have\"the attribute in question
realist
priorto the measurement(the so-called
or did the act of measurement itself\"create\"the property,limitedonly by
viewpoint),
the statistical
constraint
(the orthodoxposition)\342\200\224or
by the wave function
imposed
can we duckthe question
entirely,on the groundsthat it is \"metaphysical\"(the
state\342\200\224it

determine

agnosticresponse)?
to the realist,quantum mechanics
is an incomplete
According
theory,for even
if you know everything quantummechanics
hasto tellyou aboutthe system(towit:
its wave function),
stillyou cannotdetermine
allof itsfeatures.Evidently there is
someotherinformation,
which (together
with ty)
external to quantum mechanics,
is requiredfor a complete
of physicalreality.
description
The orthodoxposition
forif the act of
raiseseven moredisturbingproblems,
measurement forcesthe systemto \"takea stand,\"helpingto createan attribute
that was not there previously,1
aboutthe
then there is something
very peculiar
is not mystical, as somepopularizers would like to suggest.
which Niels Bohr elevated to the status of a cosmicprinciple
(complementarity),makeselectronssound like unpredictable adolescents,who sometimesbehave like

The

This may be strange,but

it

so-called
wave-particle duality,

420

TheEPR Paradox
Section12.1:

ro

421

FIGURE12.1:Bohm'sversion of the
EPRexperiment:
A
at restdecaysinto
7r\302\260

an electron-positron
pair.

measurement process.
Moreover,in orderto accountfor the fact that an
yieldsthe sameresult,we are forcedto assumethat
repeatedmeasurement
the act of measurement
the wave function,in a manner that is
collapses
t
o
the
at best, reconcile
with
normal evolutionprescribed
by the Schrodinger
immediately

difficult,

equation.

In lightof this,it is no wonderthat generations


of physicists
retreatedto the
theirstudents
notto waste time worrying aboutthe
agnosticposition,and advised
foundations
of the theory.
conceptual

12.1THE EPR PARADOX


the famousEPR paradox,
In 1935,Einstein,Podolsky,and Rosen2published
which was designed
to prove(onpurely theoretical
grounds)that the realistposition
is the only sustainable
one.I'll describea simplified
versionof the EPR paradox,
the decay of the neutral pi mesoninto an
introduced
by David Bohm.Consider

electronand a positron:

Assumingthe pionwas at rest,the electronand positronfly off in opposite


of angular
Now, the pionhas spinzero,soconservation
(Figure12.1).
requiresthat the electronand positronare in the singletconfiguration:

directions

momentum

-4oM+
i-U)V2

[12.1]

If the electronis foundto have spinup, the positronmust have spindown, and
can'ttell you which combination
viceversa.Quantum mechanics
you'llget,in
will be
any particularpiondecay,but it doessay that the measurements
and you'llget eachcombination
half the time (onaverage).Now suppose
correlated,

adults, and sometimes,for no particular reason,like children.I prefer to avoid such language. When I say
that a particle doesnot have a particular attribute
before its measurement. I have in mind, for example.
an electron

in

the spin state

could return the value h/2.or

\342\200\224

(a

):a measurement of the

.v-component of its angular momentum


value -///2,but until the measurement is

(with equal probability) the


made it simply doesnot have a well-definedvalue of 5V.
2A. Einstein.B.Podolsky.and N. Rosen.Phys. Rev. 47. 777

(1935).

Chapter12 Afterword

let the electronand positronfly way


meters,in a practical
then you measurethe spinof the
or, in principle,10 light
electron.Say you get spinup. Immediatelyyou know that someone20 meters
(or 20 light years) away will get spin down, if that personexaminesthe
positron.
To the realist,there'snothingsurprising
in
electronreally had
spinup (and the positronspin down) from the moment they were created
it'sjust that quantum mechanics
didn'tknow aboutit. But the \"orthodox\"
view
holdsthat neitherparticlehad eitherspin up or spin down until the act of
measurement intervened:Your measurement
of the electroncollapsed
the wave
the spinof the positron20meters(or
function,and instantaneously
\"produced\"
20 light years) away. Einstein,Podolsky,and Rosenconsidered
such\"spooky
action-at-a-distance\"
(Einstein'swords) preposterous.
They concludedthat
the electronand positronmust have had
the orthodoxpositionis untenable;
well-definedspinsall along,whether quantum mechanics
can calculatethem
ornot.
The fundamental assumption
on which the EPR argument restsis that no
influencecan propagatefasterthan the speedof light.We call this the
of locality.You might be temptedto proposethat the collapseof the wave
functionis not instantaneous,
but \"travels\"at somefinite velocity.However,this
would leadto violations
of angular momentum conservation,
for if we measured
the spin of the positronbeforethe news of the collapsehad reachedit, there
of finding bothparticleswith spinup.Whatever
would be a fifty-fifty probability
one might think of sucha theory in the abstract,the experiments
are
No suchviolation
of the spinsis perfect.
(anti-)correlation
of the wave function\342\200\224whatever its ontological
Evidently the collapse
instantaneous.
we

experiment,

off\342\200\22410

years\342\200\224and

this\342\200\224the

...

principle

unequivocal:

occurs\342\200\224the

status\342\200\224is

Problem12.1
Entangledstates.The singletspinconfiguration
(Equation12.1)
is the classicexampleof an entangled
statethat cannotbe
two-particle
as the productof two one-particle
states,and for which, therefore,one
expressed
cannotreally speakof \"the state\"of eitherparticleseparately.
You might wonder
whether thisis somehowan artifact of bad notation\342\200\224maybe somelinear
of the one-particle
the system.
Provethe following
stateswoulddisentangle
theorem:
state\342\200\224a

combination

= 8,-,-.
a two-levelsystem,|0H)and |0/,),with (0,-|0y)
Consider
(Forexample,
state
might represent
spinup and |0/,)spindown.)The two-particle
|0\342\200\236)

+
a|0,,(l))|0,,(2))

\302\243|0/;(1))|0\342\200\236(2))

Section12.2:Bell'sTheorem
(with

or

423

as a product
# 0 and ft ^ 0) cannotbe expressed
llMD>hM2)>.

for any one-particle


states

\\\\ff-r)

Hint:Write

\\\\j/r)

and

\\iffs).

and |i/ry) as linearcombinations


of 10,,,)and

10/\302\276).

12.2BELL'STHEOREM
is correct,
Einstein,Podolsky,and Rosendid notdoubtthat quantum mechanics
of physical
as far as it goes;they only claimedthat it is an incomplete
description
other quantity, X, is
reality:The wave functionis not the whole
the stateof a system fully.We callX
needed,in additionto ^, to characterize
the \"hiddenvariable\"because,at thisstage,we have no ideahow to calculate
or measureit.3Over the years,a number of hiddenvariable theorieshave been
to supplement
and
they tendto be cumbersome
proposed,
quantum mechanics;\"*
but never
1964the programseemedeminently worth
implausible,
But in that year J. S.Bellprovedthat any localhiddenvariable theory
pursuing.
with quantum mechanics.5
is incompatible
Bellsuggested
a generalization
of the EPR/Bohm
Insteadof
experiment:
and positrondetectors
he allowed
orienting the electron
alongthe samedirection,
the component
The first measures
of the electron
them to berotatedindependently.
of a unit vectora, and the secondmeasures
the spinof the
spinin the direction
b (Figure12.2).For simplicity,
let'srecordthe spins
positronalongthe direction
in unitsof h/2\\ then eachdetector
the value +1 (forspinup) or
registers
(spin
the
direction
i
n
A
f
or
tableof
results, many
down),along
question.
decays,
look
like
this:
might
story\342\200\224some

mind\342\200\224until

\342\200\2241

7r\302\260

electron positron product

+1
+1

-1

+1

-1
-1

-1
-1

+1
+1

-1
-1
-1
+

3The hidden variable could be a


single number, or it couldbe a whole collectionof numbers:
to
A.
is
be
in
some
future theory, or maybe it is for some reason of principle
calculated
perhaps
incalculable.It hardly matters. All 1 am asserting is that there must be something\342\200\224if only a list of the
with the system prior to a measurement.
outcomesof every possibleexperiment\342\200\224associated

4D. Bohm.Phys. Rev. 85.166.180(1952).


and
original paper(Physics1.195(1964))is a gem:brief, accessible,
\342\200\242'Bell's

beautifully

written.

424

Chapter12 Afterword

7t\302\260

FIGURE12.2: Bell'sversionof the EPR-Bohmexperiment:


detectors
independently
a and b.
orientedin directions

Bellproposed
to calculate
the averagevalue of the productof the spins,for
a given setof detector
are
orientations.
Callthisaverage P(a,b). If the detectors
=
in thiscaseoneis
parallel(b a), we recoverthe originalEPRB configuration;
spinup and the otherspindown,so the productis always 1,and hencesotoois
\342\200\224

the average:

P(a,a)= -1.

(b =
By the sametoken,if they are anti-parallel

\342\200\224a),

[12.2]
then every productis +1,so

P(a,-a)= +l.

[12.3]

For arbitrary orientations,


quantum mechanics
predicts

P(a,b)= -a b

[12.4]

with
is that thisresultis incompatible
(seeProblem4.50).What Belldiscovered
any

localhiddenvariabletheory.

The argument is stunningly simple.Suppose


that the \"complete\"
stateof the

X (X varies,in
electron/positron
systemis characterized
by the hiddenvariable(s)
someway that we neitherunderstandnorcontrol,from onepiondecayto the next).
of
is independent
Supposefurther that the outcomeof the electronmeasurement
the orientation
(b) of the positrondetector\342\200\224which may, after all,be chosen
by the
at the positron
endjustbeforethe electron
is made,and
measurement
experimenter
hencefar toolate for any subluminal
messageto get backto the electrondetector.
Then there existssomefunctionA (a,X) which
(This is the localityassumption.)
and someotherfunctionB(b,X) for
givesthe resultof an electronmeasurement,
the positron
measurement.
Thesefunctionscan only take on the values+ 1:6
A(a,A.) = + l; B(b,X)=
[12.5]
\302\261l.

6This already concedes


far more than a classical
determinist would be prepared to allow, for it
abandons any notion that the particlescould have well-defined angular momentum vectors with
argument is to demonstrate
simultaneously determinate components.But never
point of Bell's
that quantum
mechanics is incompatible with any local deterministic
one that bendsover
backwardsto be accommodating.
mind\342\200\224the

theory\342\200\224even

Section12.2:Bell'sTheorem

425

When the detectors


the resultsare perfectly(anti)-correlated:
are aligned,

A(a,X) =

for all X.

-B(a,X).

[12.6]

is
Now, the average of the productof the measurements

-/

P(a.b)=/ p(X)A(a.X)B(b.X)dX.

[12.7]

is the probabilitydensityfor the hiddenvariable.(Likeany probability


and satisfies
the normalization
condition
density,it is nonnegative,
f p(X)dX = 1,
but beyondthis we make no assumptions
aboutp(X);different hiddenvariable
theorieswould presumably deliverquitedifferent expressions
for p.) In view of
B:
Equation12.6,we can eliminate
where p(X)

P(a.b) =

- I p(X)A(a.

X)A(b, X) dX,

[12.8]

If c is any otherunit vector,

- A(a,X)A(c,X)]dX.[12.9]
= - I p(X)[A(a.X)A(b.X)
P(a,b)-P(a.c)
1:
Or, since[A(b,X)]2=
= - p(X)[l- A(b.X)A(c,X)]A(a,X)A(b,X)dX.
[12.10]
P(a,b)-P(a,c)
J
But it followsfrom Equation12.5that

> 0, so
p(X)[l A(b,X)A(c.X)]

\342\200\2241

< [A(a.X)A(b. X)] < +1;moreover

< p(X)[\\ - A(b,X)A(c,X)]dX,


|P(a.b)-P(a.c)|
J

[12.11]

or, moresimply:

|P(a.b)-P(a.c)|< 1 + P(b.c).

[12.12]

This is the famousBellinequality.It holdsfor any localhiddenvariable theory

of Equations12.5and 12.6),
for we have
(subjectonlyto the minimal requirements
whateveras to the nature or number of the hiddenvariable(s),
made no assumptions
ortheirdistribution
(p).
But it is easy to showthat the quantum mechanical
(Equation12.4)
prediction
with Bell'sinequality.
three
Forexample,
a
ll
vectorsliein
is incompatible
suppose

426

Chapter12 Afterword

FIGURE12.3: An orientation
of the detectors
that
violations
of
Bell's
quantum
inequality.
demonstrates

a plane,and c makes a 45'anglewith a and b (Figure12.3);


in this
mechanics
says

casequantum

P(a,b)= 0. P(a,c)= P(b.c)= -0.707.


which is patently inconsistent
with

0.707

\302\243

With

Bell'sinequality:
1

- 0.707= 0.293.

Bell'smodification,
far more
then, the EPR paradoxprovessomething

If they are right,then notonly isquantum


radicalthan itsauthors imagined:
it is downright wrong.On the otherhand, if quantum mechanics
incomplete,
is right,then no hiddenvariable theory is goingto rescueus from the nonlocality
considered
sopreposterous.
Einstein
Moreover,we are providedwith a very simple
to settlethe issueonceand for all.
experiment
to testBell'sinequalitywere performedin the '60'sand
Many experiments
'70's,culminatingin the work of Aspect,Grangier,and Roger.7The detailsdonot
concernus here (they actually usedtwo-photon
atomictransitions,
not piondecays).
the remotepossibility
that the positron
\"sense\"
Toexclude
detector
might somehow
the orientation
were setquasi-randomly
of the electrondetector,
bothorientations
after the photonswere already in flight.The resultswere in excellent
agreement
and clearlyincompatible
with Bell's
with the predictions
of quantum mechanics,
mechanics

inequality.8
cameas
the experimental
of quantum mechanics
confirmation
Ironically,
of a shockto the scientific
But notbecause
it spelled
the demise
community.
had longsinceadjustedto this (and for thosewho
of \"realism''\342\200\224most physicists
couldnot, there remainedthe possibility
of nonlocalhiddenvariable theories.
something

G.Roger.Phys. Rev. Lett. 49.91(1982).


For more recent
Rev.
et
Lett.
5
039
(1998).
Phys.
sBell*stheorem involves averages and it is conceivablethat an apparatus such as Aspect's
out a nonrcprcsentative sample,thus distorting
contains somesecretbias which selects
the average. In
an improved version of Bell's
1989.
theorem was proposed,in which a single measurement suffices
to distinguish between the quantum prediction and that of any local hidden variable theory. SeeD.
and N. David
(1990)
Grecnberger,M. Home.A. Shimony.and A. Zollinger.Am. J. Phy.s. 58, 1131
Mermin. Am. J. Phys. 58.731(1990).
7A.

experiments

Aspect.P. Grangier.and

seeG.Weihs

al.

81.

Section12.2:Bell'sTheorem

427

'Y

U
r\342\200\224/

Projector

Bug

Screen^
FIGURE12.4: Theshadowofthe bug movesacross
the screenat a velocityt/ greater
than c, provided
the screenisfar enoughaway.

to which Bell'stheoremdoesnot apply9).The real shockwas the


that nature itselfis fundamentally nonlocal.
Nonlocality,in the form of the
instantaneous
collapseof the wave function(and for that matter alsoin the symmetrizationrequirementfor identicalparticles)
had always beena feature of the
but beforeAspect'sexperiment
it was possible
orthodoxinterpretation,
to hope
that quantum nonlocality
was somehowa nonphysical
artifact of the formalism,
with no detectable
That hopecan no longerbe sustained,
and we
consequences.
are obligedto reexamine
our objection
to instantaneous
action-at-a-distance.
so squeamish
aboutsuperluminal
influences?
After all,
Why are physicists
there are many things that travel fasterthan light.If a bug fliesacrossthe beam
of a movieprojector,
the speedof its shadow is proportional
to the distanceto
the screen;in principle,
that distance
canbe as largeas you like,and hencethe
shadowcan move at arbitrarily high velocity(Figure12.4).However,the shadow
doesnot carry any energy;norcan it transmita messagefrom onepointtoanother
on the screen.A personat pointX cannotcauseanything to happenat pointY by
the passingshadow.
manipulating
fasterthan lightwould
On the otherhand, a causalinfluencethat propagated
Foraccording
to specialrelativity there existinerimplications.
carry unacceptable
tial frames in which sucha signalpropagatesbach\\>ardin
effect
thisleadsto inescapable
(You could,for
preceding the
logicalanomalies.
Not a goodidea!)
The question
is,
arrange tokillyour infant grandfather.
example,
demonstration

time\342\200\224the

cause\342\200\224and

are the superluminal


influences
and detected
predicted
by quantum mechanics
by

yIt is a curious twist of fate that the EPR paradox, which assumed locality in order to prove
outcome (as
realism, led finally to the demiseof locality and left the issueof realism undecided\342\200\224the
Mermin put it) Einstein would have liked least.Most physiciststoday considerthat if they can't have
localrealism,there'snot much point in realism at all, and for this reason nonlocal hidden variable
theories occupy a rather peripheral place.Still,some authors\342\200\224notably Bell himself, in Speakahleand
Unspeakablein Quantum Mechanics(CambridgeUniversity Press.1987)\342\200\224argue that such theories
offer the best hope of bridging the conceptual gap between the measured s-ystem and the measuring
of the wave function.
apparatus, and for supplying an intelligible mechanism for the collapse

428

Chapter12 Afterword

Aspectcausal,in this sense,or are they somehowetherealenough(likethe motion


of the shadow)to escapethe philosophical
objection?
Bell'sexperiment.
Doesthe measurementof the electron
Well, let'sconsider
of the positronmeasurement?
Assuredlyit does\342\200\224otherwise
influencethe outcome
for the correlation
of the data.But doesthe measurementof the
we cannotaccount
Not in any ordinary sense
electroncausea particularoutcomefor the positron?
of the word.There is no way the personmanning the electrondetectorcoulduse
to senda signalto the personat the positrondetector,sincehe
hismeasurement
doesnot controlthe outcomeof his own measurement
(he cannotmake a given
electroncomeout spinup, any morethan the personat X can affect the passing
shadowof the bug).It is true that he can decidewhether to make a measurement
accessonly to data at hisendof
at all,but the positron
monitor,
having immediate
or not,for the listsof data
the line,cannottellwhether the electron
was measured
are completely
random.It is only
at the two ends,considered
separately,
compiled
the two listslaterthat we discover
the remarkable
correlations.
when we compare
In anotherreferenceframe the positronmeasurements
occurbeforethe electron
and yet this leadsto no logical
observedcorrelation
measurements,
whetherwe
isentirelysymmetricalin itstreatment,and it is a matter ofindifference
the measurementof the positron,
of the electroninfluenced
or
say the observation
kindof influencewhoseonly
the otherway around.This is a wonderfully delicate
is a subtlecorrelation
betweentwo listsof otherwiserandom data.
manifestation
two types of influence:
the \"causal\"variety,
We are led,then, to distinguish
in somephysicalpropertyof the receiver,
actual changes
detectable
which produce
on that subsystemalone,and an \"ethereal\"kind,which do not
by measurements
is a correlation
and for which the only evidence
transmit energy or information,
which by its
in the data taken on the two separatesubsystems\342\200\224a correlation
cannot
nature cannotbe detected
eitherlistalone.Causalinfluences
by examining
reasonwhy etherealones
propagatefaster than light,but there is no compelling
with the collapse
associated
of the wave functionare of
shouldnot.The influences
the latter type,and the fact that they \"travel\"fasterthan lightmay be surprising,
but it is not,after all,catastrophic.10
paradox\342\200\224the

12.3THE