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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

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

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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
9.2 Emission
and Absorption

9.3 Spontaneous
Emission355

368
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
12.2 Bell'sTheorem423
12.3 The No-CloneTheorem428
12.4 Schrodinger's
Cat 430
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
quantum mechanics,
and almostas implausible.
NielsBohrsaid,
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
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
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
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:

*
** 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
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
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.
who
(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
Snodgrass
akis (Cyprus),A. S.Tremsin (Berkeley),Dan Velleman (Amherst), Nicholas
Wheeler (Reed),ScottWillenbrock
William Wootters (Williams),
Sam
(Illinois),
International),

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 =
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

assumethroughout

this

let'snot

,,,
axil

worry

A]

(,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'?
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 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

theory.

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

C.4Question:Where was the particle
There
are three plausible
and they serveto characterize
the main
schoolsof thoughtregardingquantum indeterminacy:
1.The realistposition:Theparticlewas at C.Thiscertainly seemslikea
sensible response,
and it is the oneEinstein
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
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).

## 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
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
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:
one
\"Oneshouldno more rack one'sbrain aboutthe problemof whether something
of
how many angelsare ableto siton the pointof a needle.\"7
thiswas the
to
the
\"fall-back\"position
of mostphysicists:
They'dtry sellyou
but if you were persistent
the
retreat
to
and
they'd
agnostic
response, terminatethe
conversation.
Untilfairly recently,allthree positions(realist,orthodox,
and agnostic)
their partisans.
But in 1964JohnBellastonished
the physics
communityby showing
that it makes an observable
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
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
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
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
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,
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

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

[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
the ageprofile
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

## 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)

\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,
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

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

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

## 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

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

## 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

[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>

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),
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.
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
interpretation,
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

## 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

## 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
energy (by \"constant\"
I mean independent
of x as well as /). In classical
thisdoesn'tchange
mechanics
Showthat the wave functionpicks
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
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
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
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]

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.)
measurements, momentum measurements
yield precise
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

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

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
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
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.
(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
(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.
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,

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

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

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

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]

## value (the distribution

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
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.

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,

## 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

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

2.19).

31

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

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

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

= 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]
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
|

the magnitude
of A, but it

so

\\A\\2

-.
a

## 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

\\

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

)/

\\

\\

\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
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

1961),
p. 126.

35

## (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

the actual coefficients:

guarantees

that

c\342\200\236

J-

sin
(\342\200\224Jc)

*(-v.0)dx.

[2.37]

## 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

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

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

V(x.t).

^(x, 0)

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^

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(\\-22). and M) = -22)\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\\ + ab24- - + 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 dd<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:

[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.

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,
\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

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
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.

## 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.

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

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
Problem4.25If the electronwere a classical
re =

e2
\342\200\224

4jr6o7wcz

[4.138]

classical
(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
(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]

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

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
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

## 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-=

[4>179fj

## 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

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
(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
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
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).

\\si

## 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

[4.196]

192

(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)

(c)

## Use0(p)to calculate(p2),in the groundstateof hydrogen.

value of the kineticenergy in thisstate?Express
What is the expectation
with the
virial theorem
(Equation4.191).

(d)

Problem4.43
Constructthe spatialwave function(VO for hydrogenin the staten 3,
I = 2, m
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
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)

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,
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

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
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

## 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)

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
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;

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.

,,

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
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,

## 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
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) =-1/7in(\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. The2integralis 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

(b)

## Use your resultin (a) to estimatethe electroninteraction

energy in the
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
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

shellinfe-space.

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

## 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
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

[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,
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[Amk{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

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]

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

## 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
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.

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)?
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

/N\\
,AV

AH

\\)

\342\200\224

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\\)

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
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)

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.
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.

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,

+ (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
\342\200\242

(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.

+ 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
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:
energy of an electron
is
this isn'tvery realistic,but it the simplestmodel,and it will
give us the right orderof magnitude.
\342\200\224e1/{Aneob)\\

AE
\342\200\224~

= A(b/a)\".

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]

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

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
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.
(a)

* * *Problem
6.34 ProveKramers'relation:25

## - (25+ l)a(rx-1)+ -U21

= 0,
+ 1)2- s2]a2(rs-2)
'~{rs)
4
n1
01

6.103while

working

[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)).
(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
closeto the exactvalue.Here'show it works:Pick any normalized
function\\j/
whatsoever;I claimthat
\302\243\"gs,

\302\243gs,

\302\243gs

[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

= ^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.

is unchanged.

293

294

## Chapter7 The VariationalPrinciple

Since\\j/ is normalized,
1=

(ifr\\ilr)

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.

## 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'

(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>-

ma)

(\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).

/2/?-.As
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

\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.

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\\'

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
Bohr
o
r
1.3
A
value
is
2.4
1.06A). The
(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,
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

## * *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

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)

*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

**Problem7.12
(a)

Generalize

310

\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)\"

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,
-\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
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.
where \\i

## Problem7.15Supposeyou'regiven a quantum system whoseHamiltonian

\\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
parameter.Note:Writing the linearcombination
thisway isjusta neat way to guarantee that i/r is normalized.
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
second-order
theory.
perturbation
find the variational principle
boundon
the groundstateenergy.
(a)

## * * ^Problem7.17Although the Schrodinger

equationfor helium itselfcannotbe
solvedexactly,there exist\"helium-like\"

312

## Chapter7 The VariationalPrinciple

is \"rubber-band
helium,\"in which the Coulombforcesare
simpleexample15
replacedby Hooke'slaw forces:
A

n2

H=

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).

(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
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
Surprisingly,
boundstate.18
(a) Showthat the lowestenergy that can propagateoffto infinity

\302\243

threshold

\342\200\224

is

8ma2'

= 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\\

--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
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

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

## 8.7 Use the WKB approximation

to find

\342\231\246Problem

harmonicoscillator.

## Problem8.8 Considera particleof massm

harmonicoscillator
(angularfrequency a>).

## 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

(.v>.v2).

[8.52]

## Do not assumeC = 0. Calculatethe tunnelingprobability,T = \\F\\2/\\A\\2,

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

\\

E\342\200\236

=a

(\302\253

3' (&)

\" 1/2)/2,

[8.53]

+

## * *Problem8.12Usethe WKB approximation

to find the boundstateenergy for the
in Problem2.51.
potential

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

## 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
\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]

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

(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.
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
(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
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
\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
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

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

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,
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
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
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
(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
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

(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
theory, and no assumption
the field.
approximation

(a)

## SolveEquation9.13in the rotatingwave approximation

(Equation9.29),for
=
=
the usual initialconditions:
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

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
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).
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
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,
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

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
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
emission)
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
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
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,

## 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,

9.2.3IncoherentPerturbations
wave is10
The energy densityin an electromagnetic
u

where Eq

jEl

[9.37]

## 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

= (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

## The term in curly bracketsis sharply peakedabout

(Figure9.2),whereas
as well replacep(a))by p(a>o),and take
a\302\273o

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
=
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

\\p.

it

- |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

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

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
stimulated

(A)\342\200\224which

for\342\200\224in

3<?o\302\253\"

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
rate.CompareEquation9.56.
without

...

emission

Section9.3:Spontaneous
Emission 357

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
energy states,\\j/Cl, i//fM, \\f/ay....).
.
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'
must be lower than n\\ forour purposes,
then.

and the
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
oscillator
Not surprisingly,
at the classical
frequency.
transition
rate (Equation9.56)is
A

-1

= nq~orv

[9.63]

of the ;?th stationary stateis

^^

*=

(9.64]

nq^co-

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,
oscillator
with the sameenergy.According
to classical
the power
electrodynamics,
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 =

(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

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).

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,
calledforbidden
transitions

transitions
emission.
(Problem9.21),or by multiphoton

\342\231\246Problem

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?
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
When there is morethan onedecay route
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

*(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.

## 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),

## 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
interpretation.
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
essential
this:
How
the
processes.
question
are
final statedifferfrom the initialstate,if the parametersin the Hamiltonian
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
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.

\"amplitude:\"

amplitude,\"

ti\\

## of 0,and both are complex

numbers.I'mnow
of course)height of a sinusoidalwave.

is the
talking

\"partial

## 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.

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)

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]

notation,

G(r)=
=

seisr

oo

se

\342\200\224isr

-ds

-ds

+ k)
/oo
-oo (s-k)(s

^h~h)-

[11.61]

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

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

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]

is
cross-section
(independent

m2 ~ /2//?%'
dQ
3/r
da

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
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

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.

\342\231\246Problem

in Problem11.4,
11.13
For the potential

(a)

(b)

## calculatef(6) for arbitrary energies,

in the Bomapproximation;

in the

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
corrections,
The integralform of the Schrodinger
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+

. [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
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.

\342\200\224

(2mVbrt3/3/T)[l(4mVQa2/5h~)].
\342\200\224

11

FURTHERPROBLEMSFORCHAPTER

11.16
Schrodinger

** *Problem

## the integralform (analogous

to Equation11.67).
and useit to construct
equation,
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
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

=
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
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
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
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

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
foundations
of the theory.
conceptual

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
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

\342\200\224

(a

## .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
spinup (and the positronspin down) from the moment they were created
it'sjust that quantum mechanics
view
holdsthat neitherparticlehad eitherspin up or spin down until the act of
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 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
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)>.

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
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
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

+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
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.

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
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

## < 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),
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

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

## If they are right,then notonly isquantum

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.
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^
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
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
doesnot carry any energy;norcan it transmita messagefrom onepointtoanother
on the screen.A personat pointX cannotcauseanything to happenat pointY by
manipulating
fasterthan lightwould
On the otherhand, a causalinfluencethat propagated
Foraccording
to specialrelativity there existinerimplications.
carry unacceptable
tial frames in which sucha signalpropagatesbach\\>ardin
effect
(You could,for
preceding the
logicalanomalies.
Not a goodidea!)
The question
is,
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

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
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