INTRODUCTION
Quantum
Mechanics
SECONDEDITION
DAVID J. GRIFFITHS
FundamentalEquations
Schrodinger
equation:
9* = //*
ih\342\200\224
dt
equation:
Timeindependent
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 1031kg
Massof proton:
mp
= 1.67262
x 10\"27kg
x 10\"I9C
e = 1.60218
Chargeof proton:
Chargeof electron:
e
Permittivity of space: eo
x 1019C
1.60218
= 8.85419
x 10'2
C2/Jm
Boltzmannconstant: kg = 1.38065
x 10~23J/K
HydrogenAtom
Finestructureconstant:
or
1/137.036
47t\302\243ohc
Bohrradius:
Bohrenergies:
Bindingenergy:
a =
En
Rydberg constant:
mee2
amec
y/jta^
EX = 2m
ea2
x 1011m
5.29177
4 (n= 1,2,3,...)
ee4
2(47te0)\302\2762
m
h2
Groundstate:
Rydberg formula:
fl2
4jT\342\202\254o
a~mec~
= 13.6057
eV
e rja
l ~
X
ny
2nhc
nj
= 1.09737
x 107/m
Introductionto
QuantumMechanics
SecondEdition
DavidJ. Griffiths
ReedCollege
^^^KiiH PearsonEducationInternational
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CONTENTS
PREFACEvii
PARTI THEORY
1 THE WAVE FUNCTION1
1.1 The SchrbdingerEquation1
1.2 The Statistical
2
Interpretation
1.3 Probability5
1.4 Normalization12
1.5 Momentum 15
1.6 The Uncertainty Principle18
2 TIMEINDEPENDENT
SCHRODINGER
EQUATION24
2.1 Stationary States24
2.2 The InfiniteSquareWell 30
2.3 The HarmonicOscillator40
2.4 The FreeParticle59
2.5 The DeltaFunction
Potential68
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
160
5 IDENTICALPARTICLES201
5.1 TwoParticle
Systems201
5.2
Atoms
5.4
Mechanics
230
Quantum Statistical
210
5.3 Solids218
PARTII APPLICATIONS
6 TIMEINDEPENDENT
THEORY249
PERTURBATION
6.1 Nondegenerate
Perturbation
Theory 249
6.2 Degenerate
Perturbation
Theory 257
6.3 The FineStructure of Hydrogen266
8 THEWKBAPPROXIMATION
315
8.1 The \"Classical\"
Region316
8.2 Tunneling320
8.3 The Connection
Formulas325
9 TIMEDEPENDENT
PERTURBATION
THEORY340
9.1 TwoLevelSystems341
of Radiation348
9.2 Emission
and Absorption
9.3 Spontaneous
Emission355
10 THEADIABATICAPPROXIMATION
368
10.1 The AdiabaticTheorem368
10.2 Berry'sPhase376
Contents
11 SCATTERING394
11.1 Introduction394
11.2 Partial Wave Analysis 399
11.3 PhaseShifts405
11.4 The BornApproximation
408
12 AFTERWORD420
12.1 The EPR Paradox421
12.2 Bell'sTheorem423
12.3 The NoCloneTheorem428
12.4 Schrodinger's
Cat 430
12.5 The Quantum ZenoParadox431
APPENDIX LINEARALGEBRA435
A.l Vectors435
A.2 InnerProducts438
A.3 Matrices441
A.4 ChangingBases446
A.5 Eigenvectors
and Eigenvalues
449
A.6 Hermitian
455
Transformations
INDEX459
PREFACE
UnlikeNewton'smechanics,
or Maxwell's
or Einstein's
electrodynamics,
relativity,
was
not
even
one
definitivelypackaged\342\200\224by
quantum theory
and it retainsto thisday someof the scarsof its exhilarating
but traumatic
as to what itsfundamentalprinciples
are,how
youth.Thereis no generalconsensus
be taught, or what it really \"means.\"
can \"do\"
it should
Every competent
physicist
but the storieswe tellourselves
aboutwhat we are doingare
quantum mechanics,
and almostas implausible.
NielsBohrsaid,
asvariousasthe talesof Scheherazade,
then you haven'treally understood
\"If you are not confused
by quantum physics
\"I think I can safely say that nobodyunderstands
it\"; Richard Feynman remarked,
created\342\200\224or
individual,
quantum mechanics.\"
from someessential
in Chapter1,the deeperquasiphilosophical
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..McGrawHill,New York (1992).
vii
for example,
instructors,
may wish to treat timeindependent
perturbationtheory
after Chapter2.
immediately
Thisbookis intendedfor a onesemester
or oneyearcourseat the junioror
seniorlevel.A onesemester
coursewill have to concentrate
mainly on Part I;
a fullyearcourseshouldhave roomfor supplementary
material beyondPart II.
The readermust be familiar with the rudimentsof linearalgebra(assummarized
in the Appendix),
complexnumbers,and calculusup through partial derivatives;
with Fourieranalysisand the Diracdeltafunctionwouldhelp.
someacquaintance
mechanics
is essential,
of course,and a littleelectrodynamics
Elementary classical
would be usefulin places.
As always, the morephysicsand math you know the
easierit will be, and the moreyou will get out of your study.But I would like
to emphasize
that quantum mechanics
that flows
is not, in my view, something
an
smoothlyand naturally from earliertheories.On the contrary, it represents
ideas,callingforth a wholly new
abrupt and revolutionarydeparturefrom classical
and radicallycounterintuitive
way of thinking aboutthe world.That, indeed,is
what makesit sucha fascinating
subject.
We
At first glance,
thisbookmay strikeyou as forbiddinglymathematical.
encounterLegendre,Hermite,and Laguerrepolynomials,
sphericalharmonics,
and
Hankel
and
Bessel,Neumann,
functions,
Airy functions, even the Riemann
to mentionFouriertransforms,
zeta
Hilbertspaces,hermitian
and Lagrangemultipliers.
Is all thisbaggage
ClebschGordan
coefficients,
really necessary?
Perhapsnot, but physicsis likecarpentry:Usingthe right tool
makesthe job easier,notmoredifficult,and teaching
without
quantum mechanics
the appropriate
mathematical equipmentis likeaskingthe studentto dig a
with a screwdriver.
(On the otherhand,it can be tediousand divertingif
the instructor
feelsobligedto give elaboratelessonson the properuse of each
tool.My own instinctis to hand the studentsshovelsand tellthem to start
blistersat first, but I stillthink thisis the mostefficient
digging. They may develop
and excitingway to learn.)At any rate,I can assureyou that there is no deep
mathematics
in thisbook,and if you run intosomething
unfamiliar, and you don't
find my explanation
aboutit, or lookit up.
by allmeansask someone
adequate,
Thereare many goodbookson mathematical
particularly recommend
2nded.,Wiley, New
Methodsin the PhysicalSciences,
Mary Boas,Mathematical
York (1983),
or GeorgeArfken and HansJurgen
Methods
Weber,Mathematical
for
But
5th
Academic
O
rlando
whatever
don't
Press,
(2000).
Physicists, ed.,
you do,
let the mathematics\342\200\224which, for us,is only a tool\342\200\224interfere with the physics.
Severalreadershave notedthat there are fewer worked examples
in thisbook
and that someimportantmaterial is relegated
than is customary,
to the problems.
Thisis no accident.
I don'tbelieveyou can learn quantum mechanics
without doing
foryourself.Instructors
shouldof coursego overasmany problems
many exercises
in classas timeallows,but students
shouldbe warned that thisis not a subject
aboutwhich anyonehas natural intuitions\342\200\224you're developinga whole new set
of muscleshere,and there is simplyno substitute
for calisthenics.
Mark Semon
function\342\200\224not
operators,
foundation
methods\342\200\224I
Preface
ix
*
an essentialproblemthat every readershouldstudy;
** a somewhat moredifficultor moreperipheral
problem;
** * an unusually challenging
that
take
overan hour.
problem, may
(No starsat all means fast food:OKif you'rehungry, but not very nourishing.)
Mostof the onestarproblems
appearat the endof the relevant section;mostof
the threestar
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 finitedimensional
at thislevel
to the Appendix.I have addedsomeexamples
are already comfortable)
relegated
of raisingand loweringoperators
in Chapter2 (and fixed the awkward definition
In laterchaptersI have madeas few changesas I
for the harmonic oscillator).
and equations,
where possible.
could,even preservingthe numberingof problems
The treatment is streamlined
in places(a betterintroduction
to angular momentum
a simplerproofof the adiabatictheoremin Chapter
in Chapter4, for instance,
10,and a new sectionon partialwave phaseshiftsin Chapter11).Inevitably,the
secondeditionis a bit longerthan the first, which I regret,but I hopeit iscleaner
and moreaccessible.
I have benefitedfrom the comments
and adviceof many colleagues,
who
readthe originalmanuscript,
(orerrors)in the first edition,
pointedoutweaknesses
in the presentation,
and supplied
I
improvements
interesting
suggested
problems.
JeffDunham (Middlebury),
JohnEssick(Reed),Gregg
GregElliott(PugetSound),
Franklin (Carnegie
Mellon),Henry Greenside
(Duke),Paul Haines(Dartmouth),
J. R. Huddle(Navy), Larry Hunter(Amherst), David Kaplan(Washington), Alex
Kuzmich (GeorgiaTech),PeterLeung(PortlandState),Tony Liss(Illinois),
Jeffry
J
ames
McTavish
James
Mallow(Chicago
(Miami),
Loyola),
(Liverpool), Nearing
Powell
K
rishna
(
(Reed),
Johnny
Rajagopal MIT),Brian Raue (Florida
RobertReynolds(Reed),KeithRiles(Michigan),Mark Semon(Bates),
Herschel
StavrosTheodor(Lewisand Clark),JohnTaylor(Colorado),
Snodgrass
akis (Cyprus),A. S.Tremsin (Berkeley),Dan Velleman (Amherst), Nicholas
Wheeler (Reed),ScottWillenbrock
William Wootters (Williams),
Sam
(Illinois),
International),
Introductionto
QuantumMechanics
PARTI THEORY
CHAPTER
1.1THESCHRODINGEREQUATION
to move alongthe xaxis,subjectto
Imaginea particleof massw, constrained
somespecifiedforce F(x.t)(Figure1.1).
The programof classicalmechanics
is to determinethe positionof the particleat any given time:x(t). Oncewe
know that, we can figure out the velocity(v = dx/dt), the momentum (p =
mv), the kineticenergy (T = (l/2)mv2),or any otherdynamical variable of
interest.And how do we go aboutdeterminingx(/)? We apply Newton's
second law: F = ma. (For conservative
only kind we shall
systems\342\200\224the
consider, and, fortunately, the only kind that occurat the microscopic
force can be expressed
as the derivative of a potentialenergy function,1F =
and Newton'slaw readsmdrxjdt1=
This,togetherwith
(typically the positionand velocityat t = 0),
appropriateinitialconditions
level\342\200\224the
\342\200\224dV/dx.)
\342\200\2243V/3.V,
x{t).
determines
thissameproblemquitedifferently.In this
Quantum mechanics
approaches
casewhat we'relookingfor is the particle'swave function,W(x, f), and we get
it by solvingthe Schrodinger
equation:
9vj/
fi1 dH
at
2m
assumethroughout
this
let'snot
,,,
axil
worry
A]
(,i\302\273
<SC
c).
o n
r{X,t)
X
x(t)
1.1:
A \"particle\"
to movein onedimension
FIGURE
constrained
underthe influence
of a specified
force.
\342\200\2241,
and h
\342\200\224
2tt
is Planck's
constant\342\200\224or
rather, hisoriginal
= 1.054572
x 10~34J
s.
[1.2]
The Schrodinger
to Newton'ssecond
equationplays a rolelogicallyanalogous
law: Givensuitable
initialconditions
(typically,ty{x, 0)),the Schrodinger
equation
Newton's
determines
mechanics,
ty(x,t) for all future time,just as,in classical
law determines
x(t) for allfuture time.2
1.2THE STATISTICAL
INTERPRETATION
But what exactly is this\"wave function,\"
and what doesit doforyou onceyou've
at a point,whereas the wave
got it?After all,a particle,by its nature, is localized
function(asits name suggests)
is spreadout in space(it'sa functionof x, for any
the stateof a particle'?
The answer
given time /). How can suchan objectrepresent
is providedby Bom'sstatistical
interpretationof the wave function,which says
that \\^(x, t)\\2 givesthe probabilityof finding the particle
at pointx, at time
moreprecisely,3
t\342\200\224or,
J.a
\\V(x\\t)\\2dx=
[1.3]
Section1.2:The Statistical
Interpretation 3
*M2
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.
story\342\200\224some
information
...
found
in
\342\200\242'Bernard
p.
165).
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:
discontinuously
collapses.9
1.3PROBABILITY
DiscreteVariables
1.3.1
Because
of the statistical
interpretation,
probability
playsa centralrolein quantum
soI digressnow for a briefdiscussion
of probability
mechanics,
theory.It is mainly
and I shalldo it in the
a question
of introducingsomenotationand terminology,
contextof a simpleexample.
fourteenpeople,whoseagesare asfollows:
Imaginea roomcontaining
onepersonaged14,
onepersonaged 15,
three peopleaged 16,
JThe role of measurement in quantum mechanics is so critical and so bizarre that you may
well be wondering what preciselyconstitutes a measurement. Doesit have to do with the interaction
between a microscopic(quanlum) systemand a macroscopic
(classical)measuring apparatus (as Bohr
insisted),or is it characterized by the leaving of a permanent \"record\" (as Heisenbergclaimed),or does
it involve the intervention of a conscious
\"observer\" (as Wigner proposed)?I'llreturn to this thorny
issue in the Afterword: for the moment let'slake the naive view: A measurement is the kind of thing
that a scientistdoes in the laboratory, with rulers, stopwatches,Geigercounters, and so on.
peopleaged24.
peopleaged25.
N(U) = 1,
N(15)= 1,
N(16)= 3,
N(22)= 2,
N(24)= 2,
N(25)= 5,
tf = X>c/).
[1.4]
7=0
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
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]
0\ =
\342\200\224jv\342\200\224
= 1^,j nj).
[1.7]
7=0
Noticethat there neednotbe anyone with the average ageor the median
the average
thisexamplenobodyhappensto be 21or 23.In quantum mechanics
is usually the quantity of interest;in that contextit hascometo be calledthe
age\342\200\224in
value.It'sa misleading
that thisis the outcome
term, sinceit suggests
expectation
a
{that would
you would be mostlikelyto get if you made singlemeasurement
be the mostprobablevalue, not the average
I'm afraid we'restuck
value)\342\200\224but
with
it.
U2) = ^J2PU)
[1.8]
7=0
[1.9]
N(j) A
123456789
10/ 123456789
10/
i
>
>
1.5:
Two histograms
with the same median,same average,and same most
FIGURE
but
differentstandard
deviations.
probablevalue,
Beware:
(Equations1.6,1.7,and 1.8are,if you like,specialcasesof thisformula.)
The average of the squares,(j2),is not equal,in general,to the squareof the
average,(./)2.For instance,if the roomcontainsjust two babies,aged 1 and 3,
then (x1)= 5, but (x)2= 4.
difference
betweenthetwo histograms
in Figure1.5,
Now, thereisa conspicuous
even thoughthey have the samemedian,
the sameaverage,the samemostprobable
Thefirst issharplypeakedaboutthe average
value, andthe samenumberofelements:
the ageprofile
isbroadand flat. (Thefirst might represent
value, whereasthe second
the second,
for studentsin a bigcityclassroom,
schoolperhaps,a rural oneroom
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]
\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
average\342\200\224gulp!)
is
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)
= y/(J2)~ U)2
[1.12]
[i.i3]
(r)>0*)2,
and the two are equalonly when a = 0, which is to say, for distributions
with no
spreadat all (every memberhaving the samevalue).
1.3.2ContinuousVariables
So far, I have assumedthat we are dealingwith a discrete
is,one
that can take on only certainisolatedvalues(in the example,
j had to be an
to
integer,sinceI gave agesonly in years).But it is simpleenoughto generalize
If I selecta randompersonoff the street,the probability
distributions.
continuous
that her age is precisely16years,4 hours,27 minutes,
and 3.333 seconds
is
zero.The only sensiblething to speakaboutis the probabilitythat her age liesin
someinteryal\342\200\224say, between 16and 17.If the interval is sufficiently short,this
to the lengthofthe interyal.
Forexample,
the chancethat
is proportional
probability
her age is between 16and 16plustwo days is presumably twice the probability
I suppose,there was some
that it is between 16and 16plusone day. (Unless,
which casewe
extraordinary baby boom 16years ago,on exactly that
have simplychosenan interval too longfor the ruleto apply.If the baby boom
variable\342\200\224that
...
day\342\200\224in
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]
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
*(')= J*'9
\342\200\242
case)
size
concerned, course,
Section1.3:
Probability
11
P(x)\"
1.1:
p(x)= l/(2</hx).
FIGURE1.6:The probability
densityin Example
dt _ dx
jg _ 1 dx.
T~~giy2h~27n=x
density(Equation1.14)is
Evidently the probability
1
p(x) =
2Vhx
(0 < x < h)
I
0
ly/hx
dx =
1
2Vh
l.
The averagedistance(Equation1.17)is
Jo
iVte
1 /2 r3/2
2Vh \\
3'
12
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
*Problem1.3Consider
the gaussiandistribution
p(x) = Aek{x~a)\\
where A,
(a)
(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
+0O
dt;_oo l*(*,t)\\2d
oo dt
\\V(x,t)\\2dx.
[1.21]
\342\200\224
9^ iti d2V
dt
2m
dx
[1.23]
9**
dt
ih d2V*
2m dx1
[124]
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
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
A,
a
V(x,0) =
\342\200\242
(b x)
(ba)
0.
if 0 < x < a,
if a < x < b,
otherwise,
where A,
(a)
vj>
and /?).
(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.
they
do not arise
Section1.5:
Momentum
(c)
15
1.5MOMENTUM
For a particlein statevj>, the expectation
value of x is
[1.28]
x\\V(x,t)\\2dx
/+oo
00
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
dt
\342\200\242\"
dt

 J'\"'  dx.
2m
dx
\\
dx
dx
[1.29]
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]
the particle.
the velocity
Nothing we have seenso far wouldenableus to calculate
of a particle.
If the
It'snoteven clearwhat velocitymeansin quantum mechanics:
neitherdoesit
particledoesn'thave a determinate
position(priorto measurement),
ask for is the probabilityof
have a welldefined
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
[132]
(v) directlyfrom ^.
Equation1.31tellsus,then, how to calculate
Actually, it is customary to work with momentum(p = mv), rather than
velocity:
[1.33]
14The
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
ty*(x)Vd.x,
(p)=Jv*(j^)vdx.
[1.34]
[1.35]
the operator15
x \"represents\"
position,and the operator(/?//)(3/3.v)
to calculate
valueswe
momentum,in quantum mechanics;
\"represents\"
expectation
\"sandwich\"the appropriate
operatorbetween^* and ^, and integrate.
That'scute,but what aboutotherquantities?
The fact is,allclassical
in terms of position
and momentum.
Kineticenergy,
variablescan be expressed
We say that
dynamical
for example,
is
l 2=
rT = mv
2
P2
\342\200\224,
2m
L = r x m\\ = r x p
To calculate
(the latter,of course,doesnot occurfor motionin onedimension).
the expectation
value of any suchquantity, Q{x,p), we simply replaceevery p
insertthe resulting
by (fi/i)(d/dx),
operatorbetween^* and ^, and integrate:
(Qix.p))= J**Q(x,~^Vdx.
[1.36]
Forexample,
the expectation
value of the kineticenergy is
(T) =
W*a^
a2*
I1371
the expectation
value of any dynamical
Equation1.36isa recipeforcomputing
quantity, for a particlein state^; it subsumes
Equations1.34and 1.35as special
cases.I have tried in thissectionto make Equation1.36seemplausible,given
Bom'sstatistical
but the truth is that thisrepresents
sucha radically
interpretation,
new way of doingbusiness
that it'sa good
(ascomparedwith classical
mechanics)
ideato get somepracticeusingit beforewe comeback(in Chapter3) and put it
if you preferto think of it as
on a firmer theoretical
foundation.
In the meantime,
an
'''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
1.29\342\200\224pull
^Problem1.7Calculate
d{p)/dt.Answer:
first part
Problem1.8Suppose
Vo to the potential
you adda constant
energy (by \"constant\"
I mean independent
of x as well as /). In classical
thisdoesn'tchange
mechanics
Showthat the wave functionpicks
anything, but what aboutquantum mechanics?
What effectdoesthishave on
up a timedependent
phasefactor:
the expectation
value of a dynamical variable?
exp(\342\200\224iV^t/h).
1.6THEUNCERTAINTYPRINCIPLE
Imaginethat you'reholdingone end of a very longrope,and you generatea
wave by shakingit up and down rhythmically (Figure1.7).If someone
askedyou
where is that wave?\" you'dprobablythink he was a littlebit nutty: The
\"Precisely
wave isn'tprecisely
any
spreadout over50 feet or so.On the other
hand,if he askedyou what its wavelength is, you couldgive him a reasonable
answer:It lookslikeabout6 feet.By contrast,
if you gave the ropea suddenjerk
(Figure1.8),you'dgeta relatively narrow bump traveling down the line.Thistime
where\342\200\224it's
Section1.6:The UncertaintyPrinciple 19
50 x (feet)
FIGURE1.7: A wave with a (fairly) welldefinedwavelength, but an illdefined
position.
10
AH30
20
40
50 x (feet)
but an illdefined
FIGURE1.8:A wave with a (fairly) welldefinedposition,
wavelength.
l
h
= litft
[1.39]
determineda particle'spositionis,
observationnow says that the moreprecisely
the lessprecisely
is its momentum.Quantitatively,
[140]
is the standard deviationin x, and ap is the standarddeviationin /?.
Thisis Heisenberg's
famousuncertaintyprinciple.
(We'llproveit in Chapter3,
where ax
I wanted to mentionit right away, so you can testit out on the examples
in
Chapter2.)
Pleaseunderstandwhat the uncertainty principlemeans:Likeposition
measurements, momentum measurements
yield precise
\"spread\"here
refersto the fact that measurements
on identically
preparedsystemsdo not yield
identicalresults.You can,if you want, constructa statesuchthat repeated
will be very closetogether
measurements
(by making ^ a localized
\"spike\,
but you will pay a price:Momentum measurements
on thisstatewill be widely
Or you can preparea slatewith a reproducible
scattered.
momentum (by making
but
answers\342\200\224the
position
course.Many
which
prove
they then
this in
due
20
^ 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,
V(x,t)= Aeal(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,...).
average value?
(c)
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
(b)
We consider
the samedeviceas the previousproblem,
but thistime
Problem1.12
we are interested
in the .*coordinate
of the needle
is, the \"shadow,\"
or \"projection,\"
of the needleon the horizontal
line.
(a) What is the probability
densityp(.r)?Graph p(x) as a functionof ,v, from
to +2/,where r is the lengthof the needle.Make surethe total
is 1.Hint:p(x)dxis the probabilitythat the projection
liesbetween
the probability
that 9 is in
x and (x + dx).You know (from Problem1.11)
a given range;the questionis, what interval dx corresponds
to the
point\342\200\224that
\342\200\2242r
probability
interval
(b)
dOl
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
\\
*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.
/too
00
A crudeway of achievingthisresultis as follows.
In Equation1.24we tacitly
but it
assumedthat (the potentialenergy) is real.That is certainly reasonable,
in Equation1.27.
What if we
of probability\"
enshrined
leadsto the \"conservation
assignto V an imaginary part:
V = VoiT,
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)
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(a2x2]
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
p = 3
kBT
2
2/77
\342\200\224
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)
mechanical.
mechanical.
(b)
an idealgas at pressureP
Hint:Usethe idealgaslaw {PV= NkgT) to deduce
quantum mechanical?
interatomic
spacing.Answer: T < (I/ ks)(h2/3m)*/5P2^5.Obviously
(forthe gasto showquantum behavior)we want m tobe assmallas possible,
and P as largeas possible.
Put in the numbers for heliumat atmospheric
Is hydrogen in outerspace(where the interatomic
pressure.
spacingis about
1 cm and the temperature is 3 K) quantum mechanical?
the
l8In a solid Ihe inner electronsare attached to a particular nucleus,and for them the relevant
size would be the radius of the atom. But the outermost electronsare not attached, and for them the
relevant distanceis the lattice spacing.This problem pertains to the outer electrons.
CHAPTER2
TIMEINDEPENDENT
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]
'It is tiresome to
24
Section2.1:
StationaryStates
25
9*
dt
dtp
d2V
dt
dx2
=^
d2yfr
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
=
//27dt
.\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.
[25]
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
Schrodinger
Equation
TimeIndependent
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]
it
is specified.
mathematical:
1.They are stationarystates.Althoughthe wave functionitself,
y(x,t) = xl/(x)eiE'/n,
[2.7]
= ***= ^e+iEt'hi;eiE,'h
= i/r(x)2,
[2.8]
does
not\342\200\224the
calculating
(Q(X,p)) =
^*Q L
l\302\261\\^djCt
[2.9]
Evety
\\Jf
P2
+ V(x).
H(x,p)= ^2m
3For normalizable solutions,E must
[2.10]
Section2.1:
StationaryStates
2.7
The corresponding
Hamiltonianoperator,obtainedby the canonical
substitution
^+
ox V(x).
92
h2
[2.11]
2m
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]
(H2)(H)2= E2E2=0.
[2.14]
foix),...),
*i(x,t) = xl/{(x)eiEi'/h,
vi/2(A%
t)
....
= if2(x)eiE2^h,
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.
\342\200\242
TimeIndependent
Schrodinger
Equation
t)
\302\245(*.
= J^cMx)e',E\"'/h
[2.15]
11=1
...)
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 (timedependent)
Schrodinger
equation(Equation2.1).
first to solvethe timein
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):
[216]
...
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)eiE\"'/r\\
separation
[2.18]
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,
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)eiE^fh
+ c2i/o(*)<?\"'\"
vl/(A% t)
\302\2432'//!,
= c\\fl + c\\\\lrl
H2cic2^i^2Cos[(\302\243:2E\\)t/fi].
\342\200\224
\342\200\224
'Thisis
nicely illustrated
quantum/deepwellmain.html.
by
an applet
at
30
Schrodinger
Chapter!TimeIndependent
Equation
(c)
combinations
yfr(x) +
\\f/(\342\200\224x),
\\fr(\342\200\224x).
d2i/
dxl
2m
tr
if E < Vmin, then \\j/ and itssecondderivative always have the same
that sucha functioncannotbe normalized.
sign\342\200\224argue
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
31
d2ir =
h2
2m dxy
or
d2^ =
dx1
\342\200\224=
1^ ,
u
where
/:r =
\342\200\224kd/,
[2.20]
Ex//,
^2m\302\243
\342\200\224\342\200\224.
mil
[2.21]
harmonic
it
oscillator
the generalsolution
is
equation;
\\//(x) =
s'mkx+ B coskx,
[2.22]
^(0) = \\/r(a) = 0,
[2.23]
5?Well,
t/K0) =
so B = 0, and hence
Then \\j/(a) =
i/r(x) =
Asmkx.
[2.24]
trivial\342\200\224nonnormalizable\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
TimeIndependent
Vi(*)
V/2(X) A
\302\2453W
A,
at x = a doesnot determine
the constant
Curiously,the boundary condition
but rather the constant
valuesof E:
k, and hencethe possible
[2.27]
In radicalcontrastto the classical
case,a quantum particlein the infinite square
well cannothave justany old
hasto be oneof thesespecialallowed
energy\342\200\224it
values.8
To find
A, we normalize
\\}/:
=
A2sm2(kx)dx = A\\22 1,
Jfo

so
\\A\\2
.
a
tyn
(X)
= J~
v!sin(T*)
[2.28]
Schrodinger
equationhas deliveredan
promised,the timeindependent
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)
\342\200\224
+\302\253)\342\200\242
\\
2. As
33
soon.
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(mn
1
a
Jo I
= 1
sin
sin
\342\200\224
(in + n)Tt
)/
\\
\\
(m
\342\200\224
(m + n)
n)
/ fa,(x)*fa(x)dx = 5,,,,,,
[2.30]
where 5,,,,,
Kroneckerdelta)is definedin the usualway,
(the socalled
0, if iw
5\"\"'j1. \\fm=n.
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]
Schrodinger
Equation
TimeIndependent
of the functionssin(tmx/a),but if you've
I'm notabouttoprovethe completeness
studiedadvancedcalculusyou will recognize
that Equation2.32is nothingbut the
Fourierseriesfor f(x), and the fact that \"any\" functioncan be expandedin this
calledDirichlet's
theorem.11
way is sometimes
a methodI call
The coefficients can be evaluated\342\200\224for a given
of {\\//n}: Multiply
Fourier'strick, which beautifully exploitsthe orthonormality
bothsidesof Equation2.32by \\//m(x)*,and integrate.
f(x)\342\200\224by
c\342\200\236
oo
,\342\200\236\302\253./(*)*
oo
E,/\302\253v\302\273V,W*
/1=1
/1 =
\302\243>,\342\200\236\342\200\236
= cm.
[2.33]
\342\226\240n
= / fnOx)*f(x)dx.
[2.34]
Orthogonality
e'V*/2'2)'.
=
*,,(.,.,)
ysin
(\342\204\242x)
[2.35]
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
^,0)=
CO
^,,^).
/1=1
The completeness
of the \\j/'s (confirmed
in thiscaseby Dirichlet's
theorem)
guarantees
that
c\342\200\236
J
sin
(\342\200\224Jc)
*(v.0)dx.
[2.37]
Example2.2
V(x.t).
^(x, 0)
TimeIndependent
Schrodinger
Equation
JO
SO
A=
/?\302\260.
a5
\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\2362
state\"\342\200\224you
c\342\200\2362
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
\\
/ 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
[2.39]
n=\\
(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
Schrodinger
Equation
TimeIndependent
yfr\\
and in fact
* 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^
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
39
%f/\\
(e)
\302\2432?
x  a/2<
nx o); = fJ Ax<
A(ax). a/2<x <a.
\302\260
(a)
A.
SketchW(x, 0), and determine
the constant
(b)
FindV(x.t).
\342\200\242'There
derivative\342\200\224in
Problem 2.7.
40
Chapter2 TimeIndependent
Schrodinger
Equation
(c) What
is the probabilitythat
value E\\ ?
(d)
Findthe expectation
value of the energy.
(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]
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
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
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
higherorder
\342\200\224
V(x)
^V\"(x0)(xx0)2,
which describes
(aboutthe pointxo),with an effective
simpleharmonic oscillation
That'swhy the simpleharmonicoscillatoris so
springconstantk = ^\"(ao).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]
Schrodinger
equation:
tr d2xj/ mco
1
2 2 =
x f
+
Ef.
pj2m ax1 2
[2.44]
\342\226\240
the
rare caseV\"(.vo)
=0
TimeIndependent
Schrodinger
Equation
In the literatureyou will
to thisproblem.
find two entirely different approaches
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,
socalled
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]
H=
\342\200\224[p2
2m
+ {mcox)2].
[2.46]
If thesewere numbers,
it wouldbe easy:
it + v~ = {in+
v){\342\200\224iu
+ v).
operators
^=^(^+^)
(the factorin front isjustthere to make the final
Well, what is the productaci+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 supersymmetric
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
As
\342\200\224
In
thisnotation,
CICI+=
)
'
\342\200\224
2ft
[a\\
p].
[2.49]
[Jr,p]f(x) =
ft
d
dx
ft
\342\200\236
d
dx
\\
n
df
( df X\342\200\224f)=
=T
Iftf (A\.
i V dx
dx
J
X\342\200\224
[2.50]
[x,p] = ih.
[2.51]
Thislovelyand ubiquitous
resultis known as the canonicalcommutation
relation.18
With
this,Equation2.49becomes
aa+=
1
.
+2
\342\200\224//
ftCD
[2.52]
or
H = ftcD aa+
[2.53]
\342\200\224
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
TimeIndependent
can equallywell be written
Sothe Hamiltonian
1
H = hco a+a+
[2.56]
In terms of
a\302\261,
the form
\302\261)f=
hco
[2.57]
Ef
(\302\253\302\261*F\302\261i)
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
= hcoa+lcid++
)
\\f/
= a+
if/
a+a+ 1+ 1^
hco I
any
constants\342\200\224such
as h, co, and
constant.)
By the sametoken,a\\f/
H(ci\\j/)= hco
= a
aa+
\342\200\224
E\342\200\224does
with
not;an operatorcommutes
hco I aa+
any
 1  j
\342\200\224
= a(H
\342\200\224
\\j/
\\f/
= (E hoj)(ai/).
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
I'll
so when
it'sclearfrom
Section2.3:The HarmonicOscillator 45
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 squareintegral
In practiceit is the former:Thereoccursa
might be infinite.
\"lowestrung\" (callit
\\j/o)
suchthat
ai,0= 0.
We
[2.58]
ltd
\\
+ m(0X )fo = 0.
,
[hr
ax
J
s/lhmco
\\
Schrodinger
Equation
TimeIndependent
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
Joo
so A1 = y/mco/jrh,and hence
= \\A\\\\[^V m cc
[2.59]
To determine
the energy of thisstatewe plugit intothe Schrodinger
equation(in
\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
in
it\"
ladderswould
in
fact
be identical.
Section2.3:The HarmonicOscillator 47
we have
hamionicoscillator.
Meanwhile,without ever doingthat explicitly,
the allowedenergies.
determined
the
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.
a\302\261\\f/n
it
\\j/n\302\261\\,
= fn+\\, afn = dn
a+\\lfn
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
[263]
VOi\342\200\224i
/\302\2730O
=
f*(a\302\261g)dx
/00
co
[2.64]
(aTf)*gdx.
\302\253/\342\200\224CO
\302\261.)
Proof:
/ f*(ct\302\261g)dx
Jcc
~0f course,the
\302\261oo.
/ f*(Th\342\200\224+
dx
V
y/lhmo)Joo
this
means
that
max)gdx..
J
at
TimeIndependent
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 JoQl_\\
+ mcox)f gdx=
(a^fTgdx,
/OO
oc
<
QED
In particular,
/\302\273CO
(fl
/OO
co
\302\261
^/i)
(A
\302\261
^/i)
= / (flTfl
Joc
^A\"
VOi)
\302\261
*
VOi
^A'
\342\200\242
a+afn=
aa+f\342\200\236
mjr\342\200\236,
[2.65]
(n+l)f\342\200\236.
so
/\302\2730C
Joc
T/r\342\200\236+I2c/A\"
/OO
co
\302\273oo
(/1+
/\302\273CO
/\302\273CO
= K2 /
(\302\253_^,)*(\302\253^)^
/OO
OO
^,i2\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 = Vnfni
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
[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]
twice\342\200\224first
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)*{aifn)dx=
/OO
oo
(a+af,\342\200\236)*$\342\200\236
dx
J\342\200\224oc
CO
='\"/ fmfndx.
oo
c\342\200\2362
Solution:
1 tt\\ =
o/
= { mco~x~)
ma>~ I
(V)
2\"
\\js*x\\j/n
d:x.
=
2m(o (C1++CI):p /./
lima)
[2.69]
\342\200\224\342\200\224(\302\253+\342\200\224fl_).
we are interested
in .v2:
In this example
A'\"
+
+
+
2ni(o (a+)2 (a+a) (fl_fl+) (a)2
So
T *:
ft\302\256
(V)
f I*
\\j/n
dx.
Equation
Schrodinger
TimeIndependent
which is orthogonalto \\j/n, and
But (a+)2Voiis (apart from normalization)
1^,,+2,
(V)
ha)
\342\200\224
(
+ n + 1)= ha>In +
1
(n
\\\\
it
\342\231\246Problem
2.10
\342\231\246Problem
(a)
2.11
(b)
(c)
\\j/\\,
\302\243
*Problem
2.12Find(a*),(p),(x2),(p2),and (T),for the /7th stationary stateof the
harmonicoscillator,
usingthe methodof Example2.5.Checkthat the uncertainty
principleissatisfied.
Problem2.13A particlein the harmonicoscillator
startsoutin the state
potential
*(.r.O)= A[3^o(*)+4TM.v)].
FindA.
(b) Construct*(.v.r)and vI/(a\\f)2.
(a)
Section2.3:The HarmonicOscillator 51
Find (x) and (p). Don'tget tooexcitedif they oscillateat the classical
frequency;what wouldit have beenhad I specified
faix), insteadof (x)?
Checkthat Ehrenfest's
theorem(Equation1.38)holdsfor thiswave function.
what values might you get,and
the energy of thisparticle,
(d) If you measured
(c)
\\j/\\
with what
probabilities?
of gettingftcol [Answer:0.943.]
2.3.2AnalyticMethod
We
, , = Ef.
+
m(D2x2xj/
2m dx2 2
ft1 d2xj/
V
[2.70]
III
IImco
mm
[2.71]
Vfiv;
in terms of
\302\243
the Schrodinger
equationreads
i^K
d2yj/
where K
[2.72]
_ 2E
[2.73]
ftco
at very
\302\243
* *V<
Jr
d$~
very
largex),
\302\2432
[2.74]
[2.75]
TimeIndependent
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.
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.
= J2ajtJ
\342\200\242 \342\226\240
[2J9]
/=0
=0,+
+ 3a^2+
2a2\302\243
= 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
Chapter
12.
in
11).
Section2.3:The HarmonicOscillator 53
Putting theseintoEquation2.78,we find
\302\243\342\200\242''
= 0.
[2.80]
7=0
=
a;+>
J
(2j + 1K)a;.
[2.81]
(./+ 1)0+2)J
allthe evennumbered
coefficients:
Startingwith ao,it generates
a2 =
(1/0
\342\200\224^\302\253>.
\342\200\224^a{),
\342\200\224[ja2
^ = (7/0
(3K)
^^
\342\200\224g\342\200\224..
We
(5K)
(5/0(1/0
a0t
the oddcoefficients
generates
a4 =
(7/0(3/0
fl,<
120
\"\342\200\242\342\200\242\342\200\242
[2.82]
/*odd(\302\243).
where
hcvcn(Z)=
\302\2530
+ aii1+
\302\2534?4
\302\243,
/*odd(\302\243)
fli\302\243+fl3\302\2433+tf5\302\2435
+ 
/z(\302\243)
in terms of
a\\)\342\200\224which
secondorder
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
TimeIndependent
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 somenonnegative
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]
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
relation is equivalent to
found
27
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 ./^12
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
\302\253y+2
20? j)
fly(7 + 1)(7+2)
/?()(\302\243)
=flo.
and hence
V'o(\302\243)
= a0e $~12
[2.84]
\\
0 to kill /20Cid,
Schrodmger
Equation
TimeIndependent
(which,apart from the normalization,
Equation2.59).For n =
reproduces
1 we
\302\2533
\302\253o
\342\200\224
\342\200\224
2\302\253o>
\302\2532
and
7=2gives
\302\2534
h2(t)=a0(\\2$2).
and
M$) =
2$2)\302\253\"*2/2.
\302\253od
algebraic
means.)
of degree11 in involvingeven powers
In general,
will be a polynomial
only,if n is an even integer,and odd powersonly,if n is an odd integer.Apart
or a\\) they are the socalledHermitepolynomials,
from the overallfactor
the arbitrary
The first few of them are listedin Table2.1.By tradition,
factoris chosenso that the coefficientof the highestpowerof
multiplicative
is 2\".With thisconvention,the normalized30
stationary statesfor the harmonic
are
oscillator
mco 1/4 1
f/2
=
[2.85]
fn(x)
\302\243,
//\342\200\236(\302\243)
(\302\253o
#\342\200\236(\302\243).29
\302\243
:#\342\200\236($)<?
in Equation2.67.
to the oneswe obtained
(ofcourse)
algebraically
They are identical
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.
(1968).
Section2.3:TheHarmonicOscillator 57
In Figure2.7(a)I have plotted\\j/n(x) for the
first few
/?'s.The quantum
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
formulasaysthat
(a) The Rodrigues
Hn^) =
e*\\
[2.86]
(\\)\"e^(J^j
recursion
relationgivesyou
(b) The following
preceding
Hermitepolynomials:
//\342\200\236+,(\302\243)
2\302\243//\342\200\236(\302\243)
Hn+\\
[2.87]
2/7#\342\200\236_,(\302\243).
as an ensembleof
2 TimeIndependent
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 nthorderpolynomial,
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 zderivative,
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
We turn
velocity,
timeindependent
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]
course:
yjr
[2.92]
= Aeik{x^n+ BeiHx+^n.
[2.93]
TimeIndependent
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.
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
..
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
_ 2E _= ^'quantum
^classical=
\\/
[2.98J
notnormalizable.
For
V];Vkdx=
/too
co
\\A\\2
r+oo
dx = A2(oo).
[2.99]
J\342\200\224oo
Section2.4:TheFree Particle
But that doesn'tmean the separable
solutionsare of no use to us, for
61
they
[2.100]
(The quantity
c\342\200\236
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
TimeIndependent
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).
/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 Ja
Jka _
IJllCl ik
1
p\342\200\224ika
2i
kJWa
,ikx
sin(ka)
k
\342\226\240s/tFci
*(jc.r)=
sin(fctf) ;a...
If00
/
m2m
\342\200\224=
Tty/la Joo
\342\200\224^\342\200\224e'^^0
dk.
\342\200\236
[2.104]
Section2.4:TheFreeParticle
63
u\302\245(x,0l2
0)
V2a
/a/n
(a)
(b)
*(*) =
'TTsinffcfl)
ka
TimeIndependent
Scbrodinger
Equation
V(x.0)
V2a
(a)
(b)
FIGURE2.il:A
\"envelope\"
\"ripples\"
wave
packet.The
Section2.4:TheFree Particle
65
particlespeed.
the groupvelocityof a wave packetwith
The problem,
then, is to determine
the generalform
P+OO
= == /
0(Jt)e'(*jr_fttf)dk.
s/2tt Joo
*(*,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 welldefined
velocity,losesits meaning.)
Sincethe integrandis negligible
exceptin the vicinity of ko, we may as well
the functionco(k) aboutthat point,and keeponly the leadingterms:
Taylorexpand
coik)= coo + co'Q(kko),
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]
Joo
= 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
ds
0(^o+ synko+sKx^n
\342\200\224e'\"<a>n'+M\302\273'>
t)
\342\200\224
= g'^^o)^^ co'0t.
0).
\"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
TimeIndependent
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
[\342\200\224a,
+a]
CO
f(x) =
2^[\302\253/i
sin(n7rx/a)+ bn
cosijmx/a)}.
n=\342\200\224OG
What
is
c\342\200\236,
in terms of
modification
of Fourier'strick) that
appropriate
C\"
(c)
ac\342\200\236.
TaLa f{x)e'mnx'adx.
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
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.
limita
67
\342\200\224>
F(k)\342\200\224have
*\342\200\242
(c)
(d)
Construct
ty(x,t), in the form of an integral.
Discussthe limitingcases{a very large,and a very small).
vl>(.v,0)= Ae\"x\\
NormalizeV(x,0).
(b) FindW(x,t).Hint:Integralsof the form
(a)
e\302\253,x+bx)
/+OC
oo
dx
= s/a[x+ (b/2a)],and
\342\200\224
/2a\\i/4 eax2/[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'
what time
68
Chapter2 TimeIndependent
Schrodinger
Equation
2.5 THEDELTAFUNCTION
POTENTIAL
2.5.1BoundStatesandScatteringStates
We have encountered
two very different kindsof solutions
to the timeindependent
\302\253.),
well\342\200\224it
IE
,,.
\342\200\236Q1
In \"reallife\" mostpotentials
go to zeroat infinity, in which casethe criterion
even further:
simplifies
IE
._
\342\200\236,
Section2.5:TheDeltaFunction
Potential 69
Classicalturning points
(a)
Classicalturning
point
V(x)k
(c)
classical
boundstate,but
Schrodinger
Equation
TimeIndependent
8(x)
_^
2.111).
(Equation
Well
2.5.2TheDeltaFunction
lltl]
^H\302\260oo.
= 1.
with
[2.111]
\302\243%*)\302\253**
\342\200\224
[2.112]
oo
[2.113]
J\342\200\224oo
\342\200\224
V(x) =
a8(x),
[2.114]
Section2.5:The DeltaFunction
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 deltafunction
h2
d2i/
Y
2m dx2
it
 a8(x)1r= Ejr;
[2.115]
d2f =
dx1
ron*!
[2.116]
zt$=k$,
\342\200\224T
ft1
where
K
^\342\200\224r
[2.117]
\342\200\242
as x
\302\273
\342\200\224oo,
so we must chooseA = 0:
\\l/{x)= BeK\\
(x<0).
[2.119]
+00),so
yj/{x) =
[2.120]
for \\j/:
is always continuous;
2.dty/dx is continuousexceptat
\\. if/
[2.121]
:%Thedelta function
energy x length.
BeKX.
itself carriesunits of
Mkngth
(x
< 0).
(seeEquation
so a has the
2.111).
dimensions
Schrodinger
Equation
TimeIndependent
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 byproductwe'llseewhy d\\f//dx is
(Equation
\\j/,
ordinarilycontinuous.
The ideais to integratethe Schrodinger
from e to +e, and then
equation,
\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
'djj_ = lim
dx
\302\273
dir
~dx
+\342\202\254
dx
lim
/r 6>o/
J = ^)
V(x)xj/(x)dx. [2.124]
J\342\202\254
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 DeltaFunction
Potential 73
is
and the allowedenergy (Equation2.117)
hK
E=
ma~
[2.127]
2m
Finally,we normalize
\\f/:
>+00
/\302\273oo
B=
Jk =
\\E\\\342\200\224
= 1,
\302\253
y/ma
[2.128]
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]
[2.131]
F + G = A + B.
The derivativesare
dxjf/dx = ik [Feikx
dif/dx= ik (Aeikx
[2.133]
Scbrodinger
Equation
TimeIndependent
GA
G
ik(F
2ma
+ B) =
(A
B),sothe
+ fl),
[2.134]
or,morecompactly,
F
where 0 =
2/\302\243).
met
[2.135]
returning
B=
ifi
lifi
A,
F=
\\ifi
[2.137]
Ae ikx
Feikx
B&
Geikx
\342\226\240ikx
FIGURE2.15:Scatteringfrom a delta
function
well.
Section2.5:The DeltaFunction
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
= TT^T1+^2
t2138]
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=
Noticethat
of E:
[2'1391
W TW
1\342\200\224and
it
is:
+ T=\\.
[2.140]
.
(2h2E/ma2)'
1
1+
T=
[2.141]
1+ (ma2/2h2E)
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
freeparticle
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
timedependent
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
TimeIndependent
Equation
= a5(x)
_._
iV(x)
barrier.
FIGURE2.16: The deltafunction
Problem2.43).
on the table,let'slookbriefly at
As longas we'vegot the relevant equations
the caseof a deltafunction
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
/0\302\260\302\260[cos(3x)
+ 2]8(x
tt)
dx.
/+1exp(.t+3)5(A2)dT.
Potential 77
Section2.5:The DeltaFunction
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
8(cx)=
[2.142]
^8(x).
\302\243<\302\243
d9/dx= 8(x).
(P1)= Ona/h)2.
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,
(squareintegrability)
Equation2.144can be extremely useful,if handledwith care.
\342\200\224
anything
\342\200\224L
\342\200\224>\342\200\242
the doubledeltafunction
^Problem2.27 Consider
potential
+ a) + 8(x a)],
V(x) = <x[8(x
constants.
where a and a are positive
78
Scbrodinger
Chapter2 TimeIndependent
Equation
(a)
Sketchthispotential.
Findthe allowedenergies,
for a =
boundstatesdoesit possess?
h~/ma and for a = n/4ma,and sketchthe wave functions.
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 deltafunction
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=K1r,
dx
where
k
[2.146]
y/\342\200\2242mE
(as
a\"
\342\200\224>
Equation2.119)is
\342\200\224oo),
exp(\342\200\224kx)
+ B exp(/CA'),but
solution(as
so the physicallyadmissible
[2.147]
FIGURE
2.17: The finite square well
2.145).
(Equation
Section2.6:TheFiniteSquare Well
In the region a < x < a, V(x) =
\342\200\224
\342\200\224Vo,
  Vof =
2m dx1
where
79
or
= 1f,
.MH.
E\\j/,
dx
\342\200\2243
[2..48]
li
\342\200\224
< 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).
Dcos(/tf).
[2.152]
IDsin(/fl).
[2.153]
KFe~Ka=
/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
TimeIndependent
Schrodinger
Equation
to Equation2.156,
FIGURE2.18: Graphical
for Zo = 8 (even states).
solution
[2.155]
\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 +
rrnn+ 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
[2.158]
k=?\342\200\224.
[2.159]
where (asusual)
n
\342\200\224
Vo>
[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
[2.164]
sin(/\302\253)
+D
cos(/\302\253)
= Feika.
[2.165]
+a requires
[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.
TimeIndependent
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
)F.
[2.167]
2ika
F=
[2.168]
cos(2/a)/^psin(2/fl)
in terms of the
The transmission
coefficient
(T = F2/A2),
expressed
original
variables,is given by
T~x = 1 +
V2
4^^0)^(1^^^)
[2.169]
+ V0)=njr,
Hy/2m(En
n
where n
[2.170]
+ 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
Section2.6:TheFiniteSquare Well
Problem2.30Normalize\\f/(x)
in
and F.
83
to determine
D
the constants
Equation2.151,
icos(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.
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 simplyF2/A2
coefficient
the barrier,the transmission
(with A the
4This is a goodexampleof tunneling\342\200\224classically
Chapter2 TimeIndependent
Schrodinger
Equation
nV(X)
V0
becausethe transmitted
incidentamplitudeand F the transmittedamplitude),
wave travels at a different speed.Showthat
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 timeindependent
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
*(.*.0) = A sin3(7TA/fl)
...
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)
(c)
4 The fact
(and
the quantum
that the
classical
and
quantum
Am.J.Phys.69,56(2001).
86
Chapter2 TimeIndependent
Schrodinger
Equation
boundstatesare there?
boundstate,what is the probabilitythat the particle
(b) In the highestenergy
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
in the harmonic
oscillatorpotential
_wm1.2
2 uncoaI <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 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
where /
is a real constant.
= A<rflA'V/v
Further Problems
for Chapter2
87
...
\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>
\\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 counterclockwise
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 TimeIndependent
Schrodinger
Equation
kV(x)
vn
occur.
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*
 2axeil0t}
\\
the timedependent
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.
is the (constant)
velocityof the well.
t)
\"^\"\"c'\302\253o\\xvr\\/H2ci\\(E+(\\/2)mv2)tmvx\\/h
h
=
Hint:Plugit
function.
is the boundstate
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),
where a
(a)
(b)
and find
Schrodinger
TimeIndependent
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.
[2.174]
Aeikx
Be'kx
^/
peikx
\\
Ge~ikx
x
^
RegionI
RegionII
RegionIII
91
Further Problems
forChapter2
B\\
fSu Sl2\\(A\\
are
coefficients
and
0, so the reflection
F2
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]
(b)
[2A75]
So
2.114)'.
Construct
the Smatrixforthe finite squarewell (Equation2.145).
Hint:This
requiresno new work, if you carefully exploitthe symmetry of the problem.
(a)
(b)
\\Gj \\M2l
Find the four elementsof the Afmatrix, in terms of the elementsof the
Smatrix,and vice versa.Express/?/, 7/, /?,,and 7) (Equations2.176and
2.177)in terms of elementsof the Mmatrix.
of two isolated
consisting
Suppose
you have a potential
pieces(Figure2.23).
is the productof the two
Show that the Mmatrix for the combination
for eachsectionseparately:
Mmatrices
M = M2Mi.
[2.179]
to any number of pieces,and accountsfor the
(Thisobviouslygeneralizes
usefulness
of the Mmatrix.)
92
Chapter2 TimeIndependent
Schrodinger
Equation
Mh
1/=0
/W.
1/=0
1/=0
FIGURE2.23: A potential
of two isolated
consisting
pieces(Problem2.53).
(c)
pointa:
(.t)= a8(xa).
from the double
By the methodof part (b),find the Mmatrix for scattering
deltafunction
V(x) = a[8(x+ a) + 8(x a)].
What is the transmission
coefficientfor thispotential?
V
(d)
\302\243.
range\342\200\224
\342\200\22410,
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 Ndimensional
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
is the complexnumber,
dimensions)
[3.2]
(ct\\P)= a\\b\\ + a$b24  + a*NbN.
Lineartransformations,
to the specified
T,are represented
by matrices(with respect
basis),whichact onvectors(toproducenew vectors)
by the ordinary rulesof matrix
multiplication:
\342\200\242 \342\226\240
(t\\\\
ljB> = T\\a)
b = Ta =
tii
t\\2
\342\200\242\342\226\240\342\226\240
/22
t\\N\\
/fli\\
hN
cn
[3.3]
I
set allsquareintegrable
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]
il.
Section3.1:
HilbertSpace
We
95
(f\\g)= / f(x)*g(x)dx.
[3.6]
If
\\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)).
[38]
<*l/>= (f\\8)*You
(/1/)=/
\\ftx)\\2dx.
[3.9]
(fm\\f,,)=Sm\342\200\236.
[3.10]
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
< (aa)(/0/3),is
space the Schwarz inequality, (ay3)proof assumesthe existenceof the inner products,which is
96
Chapter3 Formalism
ctt
[3.12]
(f\342\200\236\\f).
on the interval
(\342\200\224oo.
oo).)
Problem3.1
set of allsquareintegrable
functionsis a vectorspace(refer
to SectionA.l for the definition).
Hint:The main problemis to show that
the sum of two squareintegrable
functionsis itselfsquareintegrable.
Use
functionsa vectorspace?
Equation3.7.Is the setof allnonnalized
the conditions
for an inner
Show that the integralin Equation3.6satisfies
A.2).
product(Section
(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
innerproduct
the
replacement p
[3.13]
\302\273\342\226\240
/3
s (ft/i)d/dx.
any
functions
(ScclionA.3) on
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]
<*6*>= <G*I*>.
[315]
this must hold true for any wave functionvj/. Thus operatorsrepresenting
have the very specialpropertythat
obsetvables
and
callsuchoperators
hermitian.
Actually, mostbooksrequirean
[3.16]
ostensibly
strongercondition:
[3.17]
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
1.
,s
(\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
\"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.
Q'.)
i,and d/dx.
(a)
of ,v,
Findthe hermitian conjugates
(b)
(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
course\342\200\224it's
quantum
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=
(<2\302\2732>
(*(G
<?)2*>=
(\302\2532
\342\200\224
[3.22]
QV=qV.
[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 timeindependent
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]
100
Chapter3 Formalism
[3.26]
i^fW)=
\302\242/(0)
[327]
d<$>
hasthe generalsolution
/(0)= Ac'**.
[3.28]
eic,2n= ,
9 = 0, +1.\302\2612,...
[3.29]
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
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
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.
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 GramSchmidt
(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'tedimensional
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 infinitedimensional
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.
(1958).
'In some specificcasescompletenessis provable (wc know
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 squareintegrable,
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
fp(x) = jL=eipxlK
[3.32]
(fp'\\fP)=&(pp').
[333]
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 (squareintegrable)
the form
poo
==
dp.
/ c{p)eiPx'h
\\JlMn Joo
1
c{p)fp{x)dp =
/OC
oo
[3.34]
Theexpansion
coefficient
asalways, by Fourier's
(now afunction,
c(p))isobtained,
trick:
/\302\2730O
^.
P
[3.36]
13What
normalizable\342\200\224they
with
\302\261oo.
particular.
eigenfunction
imaginary
/3\342\200\224the
Section33:Eigenfunctions
ofa HermitianOperator
105
 y'). [3.38]
gy(x)= 8(xy).
[3.39]
= &(yy')
[340]
/\302\27300
gp(x)gy(x)dx=
/00
co
\\A\\2
\"
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(xy)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)
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\2362.
where
c\342\200\236
[3.43]
(f\342\200\236\\V).
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)
[345]
In the
dependingon
Section3.4:Generalized
Statistical
Interpretation 107
coefficients
are given by Fourier'strick:15
\302\273
= (/i.l*>=
[3.46]
f\342\200\2360c)*nx,t)dx.
/\342\200\236
q\342\200\236
/\342\200\236\"
c\342\200\2362.
\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\2732
[3.49]
E>\"U2
Indeed,
(Q) =
l5Noticethai
to make
this
the
lime
dependence\342\200\224which
is
not
al issue
here\342\200\224is
[3.50]
c\342\200\236(.t).
l6Again, I am scrupulously avoiding the allloocommon 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^<?/icw2. [3.51]
measurement
\342\200\224
*(jry)*(jr.r)djr
/oo
oo
[3.52]
\302\245(y.O,
c(p)= (fpm =
1
==
/
f\302\260\302\260
e\"}X/h*(x.t)dx.
[3.53]
*(p,0= i=/
v!/(a\\t)
e^WVix.Odx;
t)dp.
/ e'px/n<$>{p,
V2tt/7 700
\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]
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).
1 Vma^iEt/h
4>0>,r)=
eiPx/nema\\x\\/n2
dx =
Jz
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
+ tanl
PPO
\\P0/
p2 + pI
1 \"
_ 1 = 0.0908
4 2Jr
\342\200\224i^dp
A\302\2730
part\342\200\224or
Mathematica.
Problem3.12Showthat
n
(x) =
I<S>*(^iz\\<S>dp.
^P,
[3.57]
/**fiRs)*'x'
(Q(x.p))=
in
positionspace;
\342\200\242
I/ 0(2
9
i dp
\342\200\224r,
[3.58]
in momentum space.
pl^dp,
)
110
Chapter3 Formalism
3.5THE UNCERTAINTYPRINCIPLE
I statedthe uncertainty principle(in the form oxop > h/2), backin Section1.6,
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
[359]
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)
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
(:
<rlcri>[([lB])J
[3.62]
Chapter2 (Equation2.51):
[x.p] = ih.
So
=
>
\302\260l*\\
(\302\261itl)
g)
.
[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
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
compatible.
*Problem3.13
(a)
Provethe followingcommutator
identity:
[AB, C]=
(b) Showthat
A[B.C]+ [A.C]B.
[3.64]
[x\".p]= ihtvcn1.
[f(x),p]=01^,
ax
[3.65]
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:PhilosopherScientist,edited by P. A. Schilpp,Tudor, New York
(1949).
Section3.5:The UncertaintyPrinciple
113
oxoh >\342\200\224\\(p)l
2/77
For stationary statesthisdoesn'ttellyou
much\342\200\224why
not?
At
At
At
3.5.2TheMinimumUncertainty
Wave Packet
have twice encountered
wave functionsthat hit the positionmomentum
uncertainty limit {axap = Ii/2):the groundstate of the harmonicoscillator
(Problem2.11)and the Gaussianwave packetfor the free particle(Problem2.22).
What is the mostgeneralminimumuncertainty
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>.
(//)
*= ~
[367]
(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 minimumuncertaintywave packetis a gaussian\342\200\224and the two
we encountered
earlierwere gaussians.20
examples
and
All
uncertainly
product is minimal.
114
Chapter3 Formalism
3.5.3TheEnergyTime
UncertaintyPrinciple
The positionmomentum
is oftenwritten in the form
uncertainty principle
h
AxAp>\\
[3.69]
O 1
AtAE>.
[3.70]
functions.
Section3.5:The UncertaintyPrinciple
115
*
/9* QV)+[V dQ V +
= d
*<G> *<*'\302\253*>=
IT
dt
ih
(where H =
9* = HV
\342\200\224
dt
So
p2/2m+ V is the Hamiltonian).
1*
I dQ
\\
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
tellsus
>
aHaQn
(Wtef^HfH\342\204\242)2\342\200\224
Or, moresimply,
OhOq
d(Q)
dt
[3.72]
aQ
\\d(Q)/dt\\
[3.73]
Formalism
Then
AEAt>~,
~ 2
[3.74]
that'sthe energytime
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
oo)\342\200\224as
states\342\200\224say:
*(*,
t)\\2
E\\
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 freeparticle
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
Section3.5:The UncertaintyPrinciple
117
Ax
FIGURE
(\342\200\224
MeV
=
] (1023sec) 6 x 10~22MeV sec,
1100
1200
1300
1400
MASS (MeV/c2)
FIGURE3.2: Histogram
ofmeasurementsofthe A mass (Example3.7).
24
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.
*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 energytime
uncertainty principle
Problem2.5and the observablex, by calculating
07/,ax, and d{x)/dtexactly.
Problem3.19Testthe energytime
for the free particlewave
uncertaintyprinciple
an,ax,and d(x)/dt
packetin Problem2.43and the observable by calculating
exactly.
\342\200\236v,
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)
with
respectto
xy
axes.
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]
\\x)
momentum eigenfunctions:
= (p\\S{t))
<5>{p,t)
[3.76]
\\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,
\302\245(*./>
I
/#(>'.t)S(xy)dy
$>(p.t)
9ipx/h dp
Jhih
= J2^eiE\"r/h^n(x).
5I
[3.78]
becausethat
3.39).
any
particular basis.Indeed,when
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]
\\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
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).
the
sums arc
\"matrix\"
any
will
confusion
Section3.6:DiracNotation
121
=a\\l)+b\\2) =
(ab\\
with
\\a\\2
\\b\\2
= 1.
specificform
c o
are realconstants.
If the systemstartsout (at
what is itsstateat time tl
where g and
= 0) in state1),
Solution:The (timedependent)
Schrodinger
equationsays
ih
\342\200\224
As always, we beginby
dt \\S)
= H\\S).
Schrodinger
solvingthe timewdependent
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
(hE .
8
h
\\
\302\243
E\\
= (/7
=\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)).
exp(\342\200\224iE\342\200\236t/h):
\\4(t))
= l=[ei{h+8)t'n\\4.+)+ei(hg)t/n\\4)]
V2
122
Chapter3 Formalism
cWhl^+c\302\256/*
igt/h
= leiht/h fe.s.,.>+e>8'/n\\_
~e
eigt/H eigtltt J
icos(gtfh)
sin(gf//J)
/'
(/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
as columns,
\\a)
Cll
[3.87]
w
bra is a row vector:
the corresponding
(a\\
...
= {a*a*_
[3.88]
a*)
space\342\200\224the
socalleddual
space.
if ck) is a normalized
vector,the operator
example,
P = \\a)(ct\\
[3.89]
Section3.6:DiracNotation
123
[3.90]
(\302\253\302\253k\302\273)=8\302\273\302\273.
then
\302\243h,)<e\342\200\236l
=l
[3.91]
= \\a).
[3.92]
is a Diracorthonormalized
continuous
basis,
Similarly,if (e;)}
(e\\ez>)=8(zz'),
[3.93]
J \\ez)(ez\\dz=\\.
[3.94]
then
an
orthonormal
a)=il)22)/3),
/J)=/1)+23).
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 certaintwolevelsystemis
Problem3.23The Hamiltonian
# = 6(1)<12)(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
(ii =
Q\\e\342\200\236)=q\342\200\236\\e\342\200\236)
1,2.3,...).
)(<?\342\200\236!
]T//Hk\342\200\236
I\302\253>,
FURTHERPROBLEMSFORCHAPTER3
Problem3.25Legendrepolynomials.
Use the GramSchmidt
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 antihermitian
(orskewhermitian)
operatoris equalto minus
itshermitian conjugate:
[3.95]
Qf = Q.
value of an
(a) Show that the expectation
antihermitian
operatoris imaginary.
didn'l know
?'Legendre
what
1
at
x = 1.and we'restuck
with
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
(c)
probabilities?
of B, A is measured
Right after the measurement
again.What is the
probability
wave function
**Problem3.28 Findthe momentumspace
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'\\
\\/2n~A.
0,
otherwise,
issomepositiveinteger.Thisfunctionispurely sinusoidal
(with wavelength
\342\200\224nX
\302\253J>(/?,
>\342\200\242
Problem3.30Suppose
vl>(.\\\\
for constants
A and a.
0) = .v ay.
+
\342\200\224^
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
<\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(/?,
[3%i
i<\">=2<r>(*9'
(\302\2731*1\302\273')
+
yj^ (Vn7*,,.,,'!
V\302\273~5\342\200\236',\342\200\236i)
SeeLev Vaidman,
Am.
\342\200\242
[398]
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),
\302\253_.
Donot
assumea isreal.
(b)
energy eigenstates:
CO
Qf) =
]Pc\342\200\236/?).
//=0
coefficients
are
Showthat the expansion
Cn
(d)
= a\"
\342\200\224f=c0
Determinecq by normalizinga).Answer:exp(\342\200\224a2/2).
\\n)^eiE\"'/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
eigenvalue?
Problem3.36Extendeduncertaintyprinciple.33
The generalized
uncertainty
s
tates
that
principle(Equation3.62)
aAaB
where C =
At
^^C) '
At
i[A.B],
it can be strengthened
to read
^I>~((02+(\302\243>)2),
yy
At
At
[399]
Al
where D = AB + BA2(A)(B).Hint:
Keepthe Re(z)term in Equation3.60.
(b)
doesn'thelpmuch either).
principle
Problem3.37The Hamiltonian
for a certainthreelevel
systemis represented
by
the matrix
c ^ + b).
what
(b)
\342\200\224
is 4(/))?
what
is \\S{t))l
129
Further Problems
forChapter3
for a certainthreelevel
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
/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,
cj2+ C22+ C312
A, and
B.
(c) What
* ^Problem3.39
(a)
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 (timedependent)
show that
Schrodinger
equation,
(wherexq is any
....
generator
(b)
in time.
isany constant
time);
\342\200\224H/h
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)eifl'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 timedependent
\"Schrodinger
equation\"
(c)
0 denotesthe
{H) = (p)2/2m+ {H)q(where the subscript
and commenton this result.
gaussian),
\342\200\224
subscripton Iq.
= <*(.*.
0)11/1
{Q(t))= (*(A.r>j2l*(.v.0>
QUmx.0)).
=
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
Px
^77Pv ^77. Pc
3.v
3v
i
fl
\"*
Ad
7 7.
/
az
[4.2]
now
on.
in
131
132
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 limeindependent
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 (limedependent)
Schrodinger
equationis
^{T,t)= J2c\"^n(T)eiE\"'/r\\
[4.9]
Section4.1:Schrodinger
Coordinates 133
Equationin Spherical
*Problem4.1
commutation
of the
relationsfor components
(a) Work out allof the canonical
= v, and rz = z.
theoremfor 3dimensions:
(b) Confirm Ehrenfest's
= (p).
^(r)
at
in
and ^<p) =
at
<VV>.
[4.11]
in three dimensions.
FormulateHeisenberg's
Answer:
uncertainty principle
(c)
[4.12]
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 \\
r2sin9\\30^/
coordinates,
then,the timeindependent
Schrodinger
equationreads
spherical
h2 r
2m
1 3 / .
1
/ 23^\\
/32^
+
+
7luV ~dr~) ~r~l^9d9 \\*m0~dO) ~rh*n1~9\\WJ]
1 3
\"
<hfr\\
+ V$ = E\\lf.
We
[4.14]
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, therearc 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
FIGURE4.1: Spherical
coordinates:
radiusr, polarangle9,and azimuthalangle
\302\242.
Pdr
2/77
[! dr )
9
r2 sin0 90
R
92y
+
M J ,2sin20 902J
sin0\342\200\224
+VRY=ERY.
Dividingby
RY
and multiplying by
itT.
2//////7
>
[1d ( ydR\\
2m/2
^1^(,^^1=0.
+ Y sin0 90
39 J
sin20 902
/ ,dR\\
1 9 / .
sin0 90
[4.16]
^
sir\302\2730
2mr2
\342\200\224
[4.17]
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)
'
'
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 midstream, 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)
0.
(\302\242)
\302\242(0
+ 271)= 0(0).
[4.23]
=0,+1,
it
[4.24]
\302\2612
The 9 equation,
m2]0= 0.
[4.25]
0(0)= A Pj\"(cos9),
[4.26]
/d
f
P/\"(jr)= (1 a2)I'\"I/2
and
\\
\342\200\224
I\"1'
P,(x).
[4.27]
MMil1*21*\342\226\240\"'This
regardlessof
[428]
it looks.
After all. the probability density (4>2)is singlevalued
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.
\342\200\224
x1:
]f1 2 1) = 3(1a2).
^(.v) = (l.v2)(\302\243)(3a*
2
= 0, 1. 2.
l./+1
\342\226\2401.
0. 1,
.../,
1. /. [4.29]
differential
It shouldhave two
But wait!Equation4.25is a secondorder
equation:
for any
solutions,
linearly independent
old valuesof /
all the
138
r0  i
p\302\260
pV
91)
= ^(3 cos2
P\\
= sin 9
P\\]
= cos9
Pl = 3s\\rr9
P\\
= 3 sin B cose
rh \\sin9(5cos201)
P{h (5 cos30 3 cos0)
e&p,'(^
'i.:
8** ^
^(^
>Z
CO ^>
pV(W)
(a)
(b)
othersolutions?
A/z.yiv<?/*: They e.mf,of course,
as mathematical solutionsto the
becausethey blow up at 0 = 0
equation,but they are physicallyunacceptable,
and/or9 = n (seeProblem4.4).
in spherical
coordinates7
is
Now, the volumeelement
dyT
= r1^medrdOd(f),
[4.30]
so the normalization
condition
(Equation4.6)becomes
/\\\\lf\\2r2^\\\\Bdrd6d(j)=
j \\R\\2r2 dr
It
\\Y\\2
sin0 d$d<j) =
is convenientto normalize
R and Y separately:
nlTt
nrt
poo
I \\R\\2r2dr=[ and / /
Jo
Jo Jo
r2sin0</0
d<t>
= 1.
[4.31]
Coordinates 139
Section4.1:Schrodinger
Equationin Spherical
TABLE4.3: The first few spherical
harmonics,
Yju(6.
\302\242).
y?(i)\"2
^(4)^(3^1)
Yfl
'/2
=+
'/2
^
'/2
y^1 = + (^) sin 0 (5 cos20^ \" =
COS0
(ifc)
Yf = I
~\342\200\224
(5
C\302\260S3
9~ 3
C\302\260S
1)*\302\261'*
sin6>cosQex\"''
(\302\247)
The normalized
are calledspherical
harmonics:
angular wave functions8
)!
/(2/+l)(/m
V\"\"*P/\"(cos0).
1^(0,0) = g/
A/
,mfl4
47T
(/ +
w)!
where e =
for m > 0 and e = 1 for ///
so
they are automatically
orthogonal,
(\342\200\2241)'\"
pin
pir
/ JO
/
JO
[4.321
,\342\200\236
= 5//'5mm',
&]*[YI?(0,0)]sin0</0<ty
[4.33]
'[Yi\"{0,
0(0)= Aln[tan(0/2)]
1)
e (which is always 1 or
8Thc normalization factor is derived in Problem 4.54:
is chosen
consistencywith the notation we will be using in the theory of angular momentum: it is reasonably
standard, though someolderbooksuse other conventions. Notice that
for
y,'\" =
i\"
(\\)\"'{y;\
lv\302\273'\\*
140
in ThreeDimensions
Chapter4 Quantum Mechanics
\302\243\342\204\242w*=(tt
Hint:Useintegrationby parts.
\302\273//'\342\226\240
[4.34]
4.1.3TheRadialEquation
Noticethat the angularpart of the wave function,Y(9, isthe samefor all
the actual shapeof the potential,
V{r),affectsonly
symmetric potentials;
the radialpart of the wave function,R(r),which is determined
by Equation4.16:
\302\242),
spherically
odR'
(
= l(l + l)R.
^[V(r)E]R
dt
n~
'
d_
[4.35]
Thisequationsimplifies
if we changevariables:
Let
u{r)= rR(r),
[4.36]
/?2
/(/ + 1)
2m
r
= Eu.
[4.37]
course\342\200\224ihc
h2
1(1+ 1)
2/7/
r2
[4.38]
in the
radial
Section4.1:Schrodinger
Coordinates 141
Equationin Spherical
L \\u\\2dr=\\.
[4.39]
<
= 0, if r a:
oo, if r > a.
[4.40]
//2,, rid
n
du
~ r/(/ + D
,,i1
_i_
dr2
>2
[4.41]
where
k
_ s/lmE
[4.42]
=$>
u(r) = A
sin(Ar)+ 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
nnn2ma2
(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
Normalizing
\302\242)
j=sin(fljrr/fl)
r
1
Vr\342\200\236oo
[4.44]
\342\200\242
V27Ttf
familiar:
[4.45]
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
\342\200\224
\342\200\224
1a2/2+ 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
[447]
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.
suchthat
1 \\
x) cos.v
\342\200\224$
j,(ka)= 0:
[4.48]
V8
v10
\\
12V
.14
.31Bessel
functions.
FIGURE4.2: Graphsofthe first four spherical
144
requiresthat
boundary condition
\302\253th
= /3,,/.
a
[4.49]
/^Ai
2mci
[4.50]
fnlmir.9.
\302\242)
A\342\200\236,M[}\342\200\236ir/a)Y;\"{0.
\302\242).
[4.51]
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.
1=1.
=\302\276
E\342\200\236\\
eds..
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,
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]
e1
4tz\342\202\254q
/(/+1)~u = En.
5
2m r//2
1
1
[4.53]
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)
146
4.2.1TheRadialWave Function
Our first task is to tidy up the notation.
Let
= sJlmE
[4.54]
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
valid for
caseloo).But
of variables (Equation
[4.57]
oo),so B 0. Evidently,
\302\273
then:
that
oo, the
\342\200\224
\342\200\224>
'Thisargument
\342\200\224>
u.
u(p) ~ Ae~p.
approximately,
[4.56]
4.60).
d2u
/(/+1)
dp
p
when
never mind: All
[4.58]
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]
new
[4.60]
du = l p
p (/ +
p'e
dp
\342\200\224
1p)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
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
148
^
d~V
;
+
ikv+ip'1.
E^./
I
t\342\200\224v
InsertingtheseintoEquation4.61,we have
oc
OO
./=0
\302\243cjpj
i=0
= 0.
7=0
of likepowersyields
Equatingthe coefficients
[ 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
p\302\260.
critical\342\200\224if
Cj
(try
you
ii!) and
don't pull
lhal out.
you
involving
to work wilh.
2(/+1)
mean.
1\342\200\224after
1.
Section4.2:The HydrogenAtom
149
=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]
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 socalled
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
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
me'
K=(
\\47teo^'2/ n
[4.71]
an'
where
[4.72]
me\"
is the socalled
Bohrradius.15
It follows(again,from Equation4.55)that
P
= r
an
[4.73]
I, and m):
fnlm(r,0,
\302\242)
= Rnl(r) lf(0,0),
[4.74]
[4.75]
pJ+lepv{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+ ln)
[4.76]
+ 2)6,7'
(./+ 1)042/
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
Equation4.67forcesI =0,whencealsom.
0 (seeEquation4.29),so
\342\200\224
= #io(r)^(0,<a
^ioo(n#,</O
[4.78]
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
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
\342\200\224
\342\200\2241,
ci
\342\200\224
\342\200\224Co
\302\2422
= 0 (using;'= 1).,
\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
0,1,2,...,^1,
[4.84]
d(n)=
/ji
[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
[486]
v(p) ^SLi(2a)>
where
[4.87]
'H<*>
and
is an associated
Laguerrepolynomial,
[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
*\342\204\242
is one of the
\302\253\342\226\240
very few
[4.89]
realistic
Section4.2:TheHydrogen
Atom
153
Lp= 1
Lr= x 1
+
 Ax + 2
L2 =x2h= + 9x218*+6
=.\302\2763
16^+ 72^96^+ 24
L4 =xA
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
L=12x296x+144
L3= 6
Lj= 24x+ 96
L=60x2600x+1200
#=
8ntI>8n>&mri
\342\226\240
[4,90]
density(Figure4.6).
154
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_aM(l
i?32= 4_a3/2^a'
81V30
^4^0474(^1\302\276\302\276^^
^4]
* 3/204f4&)2)ip^)
ltiV3
^ih^i^uw^^
W=
\342\200\224l\342\200\224crm(\342\200\224)
768^35
exp (r/4a)
^Problem4.11
(a)
(b)
^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
(b)
\342\200\224
2, =
in jc,y, z. Usex
symmetrical
/\342\226\240
\342\200\224
r sitiOcos0.
156
(2,0,0)
(3,1,0)
(4,0,0)
(4,1,0)
(4,2,0)
(4,3,0)
sitehttp://danger.com.
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+^211).
: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
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 higherenergy
state,or by giving off energy (typically intheform of electromagnetic
radiation),
state\342\200\224either
158
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
to its frequency:
EY
= hv.
K
[4.92]
= c/v, so
[4.93]
where
R=
2
^
^ ] = 1.097 107
(
m\"1
[4.94]
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/
By its nature, this involves a unieifependent interaction, and the detailswill have to wait for
Chapter 9;for our presentpurposesthe actual mechanism involved is immaterial.
19Thephoton isa 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*
theearthsunsystemasa gravitational
Problem4.17Consider
analogto the
atom.
hydrogen
(a) What
(b) What
is the\"Bohrradius,\"
ag,for thissystem?Work outthe actualnumber.
160
in ThreeDimensions
Chapter4 Quantum Mechanics
(d)
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 =
ypzzpy,
Ly
zpx\342\200\224
xpz, Lz=xj?yypx.
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
eigerifunctions.
4.3.1Eigenvalues
in fact2The operators
L.x and Ly do not commute;
[4.97]
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] =
[4.98]
[4,99]
everything
vLsOLy >~\\(LZ)\\.
'
[4.100]
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
[4.102]
162
in ThreeDimensions
Chapter4 QuantumMechanics
or,morecompactly,
[L2,L]= 0.
[4.103]
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
\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]
=
=
L\302\261LJ
{LzL\302\261L\302\261Lz)f
\302\261hL
+ f + L^{iif)
[4.109]
({j,\302\261K](L+f%
Section4.3:Angular Momentum
163
exceeds
to reacha statefor which the zeorriporient
the total,and that cannotbe.22
L+ft = 0.
22Formally, (I1)= (L2)+ <L2)+<Lj),but (*%) =
for
L,,)\342\200\236
so.A
 (L2)+
{i\302\243)
+ ^2 > ft.
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,
I? l}z^i(ihLz),
L\302\261LT
+ L2Z^ hLz.
[4.112]
It followsthat
L2ft = (L.L++ ut+hLjfi
+1)/\342\200\236
and henee
X=h2l(l+ 1).
[4.113]
Lfh = 0.
[4.114]
[4.115]
we have
UsingEquation4.112,
and therefore
X
= /z27(7l).
[4.116]
4.113and 4.116,
we seethat 1(1f 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
\342\200\224l
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]
momenta\342\200\224in
\342\200\224
\342\200\224
(\342\200\2242,
>\342\226\240
\"trivial\"
\342\200\224
4.9\342\200\224at
I'll
f\342\204\242
Yf1\342\200\224the
(Theorem2, Section3.3.1),
eigenvalues
*Problem
unit:
4.1\302\276
[4.120]
L\302\261f{n={Af)f^\302\261\\
L\302\261
\342\226\240..
= h^(lTm)(I
Af = hy/lQ + l)m(m\302\261\\)
\302\261m
+ 1).
[4,121]
^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
\342\200\224
\342\200\224
/\302\276).
y\302\260
V\"
* ^Problem4.20
(a)
expectation
(L)= (N),
where
N = rx(VV).
(Thisis one
d(L)/dt 0 for any spherically
symmetricpotential.
\342\200\224
4.3.2Eigenfunctions
Firstof all we needto rewrite Lx, Ly, and Lz in sphericalcoordinates,
Now,
and
the
i
n
L (h/i)(rx V),
is;24
coordinates,
gradient, spherical
\342\200\224
meanwhile,r =
dr +0 r dO + r sin090;
r\342\200\224
[4.123]
0\342\200\224
rr, so
L=
9
JBr
~
r(r x r)
_
\342\226\240
\342\200\236
f
(r
y
* 9
1 9
~
(r x 0)
+
v
;W
sine90.
\342\226\240
61)\342\200\224
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= 00sin0 30/
\302\273
'
\\
[4.124]
3<9
9 = (cos9 cos
\302\242)1
\342\200\224
\342\200\224(sin0)ff
+ (cos9 sin0)j
(cos0)J,
Thus
[4.125]
[4.126]
\342\200\224
(sin#)\302\243;
(.sin0i+cos0;)
\342\200\224
1 3
30_
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
[4129]
We
L+
\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$2
\342\200\224h
36\302\273
32
0\342\200\224
^\302\2422+l^\302\242),
[4.131]
169
Section4,3:Angular Momentum
and hence(Problem4.21(b)):
L2 =
We are now
with
h'
3/.9
\342\200\224
sine de \\
sin(9
_L 3*_'
m + sin20 d(j>2
\342\200\224
[4.132]
of L2,
in a positiontodetermine
//\"(#, It's an eigenfunction
\302\242).
eigenvalueh2l(l+ 1):
2
= A\" 1
Z//f
sin
iKfJ.
6\302\273
3/..3
sin.0
\342\200\224
9(9
96
3^
_1
sin2 302_
jf = fc2/(/ + l)//!
6\302\273
Butthisisprecisely
the \"angularequation\"(Equation4.18).
And it'salsoan
mh:
eigenfunction of Lz, with theeigenvalue
*<zf?=
j^fr=*mfr,
\302\242)
Hlfr =
Ef,
L2iff
[4.133]
to rewrite theSehrodinger
we can useEquation4.132
equation
Incidentally,
more
4,14)
compactly:
(Equation
2 9
2mr2
dr
+V
\\j/
f Vifr =
Exfr.
inthefollowingsections.
170
^Problem4.21
(a) DeriveEquation4.131from Equation4A30,Hint:Usea testfunction;
you'relikelyto dropsometerms.
Hint:Use
(b) DeriveEquation4.132from Equations4.129and 4.131.
otherwise
Equation4.112.
^Problem4.22
(a) What
(b)
(e)
is
\302\243+7/?
(No calculation
allowed!)
V15/87Tsinecos
\342\226\240$<?*.
normalization.
\342\200\224\342\200\224Y\342\200\224,
for
\302\253
= 0, 1,
2,.,.
Hint:Firstexpressthe (classical)
energy intermsof thetotalangular
momentum.
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 dailyrotationaboutthenorthsouth
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)
satisfy27
51\302\276
(1986).
\"What
[4.134]
hm\\s
m);
is Spin?\",Am.
[4.135]
J. Phys. 54, 500
angular
I'll
172
in ThreeDimensions
Chapter4 Quantum Mechanics
and
S\302\261
where S+ = Sx
\\sm) =
\302\261
1)),
[4.136]
i iSy.
arenotspherical
But thistimethe eigenvectors
harmonics
1 3
= 05 ,
lr
[4.137]
simple.28
solidsphere,with radius
Problem4.25If the electronwere a classical
re =
e2
\342\200\224
4jr6o7wcz
[4.138]
classical
electronradius,obtained
(the socalled
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.)
admits
of unfamiliar
2x2matrices and
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 spin1/2particlecan be
as a twoelement
columnmatrix (orspinor):
expressed
\342\200\224
), j
},
(\342\200\2245)),
(b)
= aX+ + bx
[4139]
with
X+=L
[4140]
X=
[4141]
representing
spinup,and
V
for spindown.
become2x2matrices,
the spinoperators
which we can work out
Meanwhile,
A. 135says
by notingtheireffecton x+ and X.Equation
SV^V.
[4142]
S2 =
thenthe first equationsays
::flfflH). 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
Sz =
/l
2V\302\260
Meanwhile,
Equation4..136says
'0
S_ = A.. '01 0^
o,
1\"
SU=fi ,0 0,
Now
hence
S\302\261
[4.146]
^  2 11or
bar\"2U.
[4.147]
where
'^s(l o)>
'Q
j
\302\260>
f
0
7'
0
^^ 101 1
[4.148]
+
eigenvalue
H'
eigenvalue
X
J. [4.149]
only
possibilities,
\\af + \\b\\2
=l
[4.150]
Seefootnote 16in
Chapter \"3.
Section4,4:Spin
175
statistical
is
characteristic
equation
k
ft/2
/J/2 = o
X
=>\342\226\240
r=
'W
ft
=*3t=\302\261
;(?.oca*
tew.'
=+
so ^
\342\200\224
/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]
\342\200\224ft/2
a spin1/2
particleisinthestate
Example4.2 Suppose
X
Wl+T
76
'2
of getting+ft/2 and
What are theprobabilities
\342\200\224ft/2,
176
5( h\\ + l{ h\\ =
6 (+2J 6
the
1/6.Incidentally,
ft
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
Problem4.26
(a)
fundamental
(b) Showthat
thePaulispinmatrices(Equation4.148)satisfy theproductrule
ffj<rk
= 8jk+ i 2^ ejkim*
[4!53]
indicesstandfor x, y, or z, and
is the LeviCivitasymbol:
=
=
+ 1 if jkl 123,231,.or 312; if jkl 132,213,or 321;0 otherwise.
where the
1
\342\202\254jm
\"CO(a)
(b)
constantA.
Determine
the normalization
Findtheexpectation
valuesof Sx.,Sy, and Sz,
(Note:Thesesigmasare standard
(c) Findthe \"uncertainties\"crsr, a$v, and
notPaulimatrices!)
deviations,
with allthreeuncertainty principles
(d) Confirmthat your resultsare consistent
(Equation4.100and its cyclicpermutations\342\200\224only with S in placeof L, of
course).
0\302\276.
^Problem4.28For themostgeneralnormalized
spinorx (Equation4.139),
(Sx), (Sy), (Sz), (Sj), (S2),and (S2).Check that (S2)+ (S2)+ (S2Z)
= (S2).
compute
*Problem4.29
(a)
and eigerispinors
of S
Findthe eigenvalues
in ThreeDimensions
Chapter4 Quantum Mechanics
(b)
(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,
[4.154]
of Sr,Answer:
Findthe eigenvalues
and (normalized)
eigenspinors
(,)
X+
/ cos(^/2)\\.'
 [j*
m(0/2)j
_
(/.) _
X~
fevmem}
'
cos(6/2))
^{
factor\342\200\224say,
r415S1
J
L
el^~so
4.4.2Electronin a MagneticField
a magnetic
dipole.Its magneticdipole
spinningchargedparticleconstitutes
to its spinangular momentum,
S:
moment,ji, is proportional
A
\\i
= yS;
[4.156]
the proportionality
ratio.30When a
constant,y, is calledthe gyromagnetic
fieldB, it experiences
a torque,u, x B, which
is placedin a magnetic
magnetic dipole
\"See.for example,D.Griffiths, Introduction to Electrodynamics,3rd ed.(Prentice Hall, Upper
SaddleRiver, NJ, 1999),
Classically,the gyromagnetic ratio of an objectwhosechargeand
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
\\lB,
[4.157]
sotheHamlltonian
of a spinning
chargedparticle,at rest32in a magneticfieldB,
is
# = yBS.
[4.158]
Example4.3 Larmorprecession:
Imaginea particleof spin 1/2at rest in a
uniform magnetic
field,which pointsin the zdirection:
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 timeindependent,
Sincethe Hamiltonian
equation,
dependentSchrodiriger
[4T62]
ih%\302\243=Hx,
at
I'll
180
(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,
as a functionof time:
(\302\276)
\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
[4.166]
[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
t.
out 'the
II,Section343; 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 TheSternGerlach
a
field,there is not only torque,but also& force,on a magneticdipole:35
F = VQi.B).
[4.168]
(Figure4,11)\342\200\224say,
[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
4.157).
258.Note
that
F is
\\
182
inThreeDimensions
Chapter4 Quantum Mechanics
Zn
Spin up
Spin down
Magnet
FIGURE
4.11:The SternGerlach
apparatus.
But becauseof the Larmorprecession
aboutBq, & oscillates
rapidly,and
[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\224lot
state
ft)
9.1,
183
Section4.4:
Spin
While theHamiltonian
acts,x(0evolvesintheusualway:
X(t)
==py(B0+ az)i
[4.172]
(for i > T), The two termsnow carry momentum in the z direction(see
Equation
has momentum
3.32);the spinupcomponent
Pz =
ayTh
^s
[4.174]
opposite
\342\200\224
Problem4.32In Example4.3:
(a)
184
Samequestion,
but for the _y\302\273comp6nent.
(c)
BQCOs(a)t)k,
\342\200\224
\342\200\224
)\342\200\242
(c)
\342\200\224h(2,
sur
(d) What
\\2cd
srn(a)f)
4.4.3Additionof AngularMomenta
theelectronand
now that we have two spin1/2
Suppose
particles\342\200\224for example,
Eachcan have spinlipor spindown,
the protoninthegroundstate38of hydrogen.
sothereare four possibilities
in all:39
[4.175]
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
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
in)
s 1 are (inthenotation\\sm)):
\342\200\224
tt
110) =\302\261tu+ m.
<
= 44
..111)
= 1 (triplet).
[4177]
1
\342\200\224
{00)
i(U  W}
= 0 (singlet).
[4.178]
Problem4.34(b).)
186
in ThreeDimensions
Chapter4 Quantum Mechanics
configuration.
0. Now,
S2=
[4>179fj
h2
(24tH)
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)= 2/7210),
[4.182]
3h:, ...0,
r zr
,3k1+ 3h2
=[
S2\\Q0)
0.Q>
[4.183]
Problem4,34(6)*)
Section4.4:Spin,
187
\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 zComponent
m will be some
linearcombination
of thecomposite
states^i mi)
the
(Roughly speaking,
\342\200\224
momentum
\342\200\224
\342\200\224
1\302\276
\\s
m)
C%%n1*1
\302\2731
\302\243
m.\\
\302\25322):
>
1\302\276
[4.185]
\302\253a>
\\m2=m
the z components
statesthat contribute
arethose
add,the only composite
(because
for which mi + m.2 in):Equations4.177and 4,178are specialcasesof this
generalform,with si = s% = 1/2 (I usedthe informalnotationt = It \\)> ^
The constants
coefficients.
A few
Cs,n^m2m ar? calledClebschGotdan
(5)).)of the simplest
of
the shadedcolumn
casesare listedin Table4.8.42For example,
the 2x1tabletellsus that
\342\200\224
\342\200\224
1\302\276
30}= L21)11)+
y\302\247
+ ^21)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
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, ClaudeCohenTannoudji,
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
= V C%$ \\sm)^
Ml)\\s2m1)
[4.186]
Forexample,
the shadedrow in the 3/2 x I tabletellsus that
is 1).
\342\200\224
I don'tblame
If you think thisis startingto soundlikemysticalnumerology,
tablesmuch in the rest of the
you. We will not be Using the ClebschGordan
book,but I wanted you to know where they fit intothe schemeof things,in case
them lateroil.In a mathematical sensethisis all appliedgroup
you encounter
of thedirectproductof
we aretalkingaboutis the decomposition
theory\342\200\224what
Section4.4:Spin
189
two irreducible
of the rotation
representations
groupintoa directsum of irreducible
representations
yourfriends).
(you canquotethat, to impress
^Problem4.34
(a) Apply S_ to 110)(Equation4177),and confirmthat you
(b) Apply
S\302\261
(c) Showthat
get V2h\\l
1).
eigenvalue.
appropriate
tomake a baryon
Problem4.35Quarkscarry spin1/2.Threequarksbindtogether
(suchas the protonor neutron);two quarks (or morepreciselya quark and an
to make a meson(suchasthepionor the kaoh).Assume
antiquark) bindtogether
the quarks are in the groundstate(sothe orbitalangular momentum is zero).
(a) What
(b) What
for baryons?
spinsare possible
spinsare possiblefor mesons?
Problem4.36
particleof spin1 and a particleof spin2 are at restin a configuration
suchthat the totalspinis 3, and its z component
is h. If you measuredthe
of the angular momentum of the spin2particle,what values
z component
of eachone?
might you get,and what is theprobability
with spindownis in the state^510of the hydrogenatom.If you
An electron
couldmeasurethe totalangular momentum squaredof the electronalone
the protonspin),what valuesmightyou get,and what is:the
{notincluding
probabilityof each?
(a) A
(b)
x S(2)).
[S2,S{1)]= 2ifc(S(1)
[4.187]
Comment;
BecauseS% doesnotcommutewith S2,,we cannothopeto find states
of 52 we
of both.In orderto form eigenstates
that are simultaneous
eigenvectors
190
in ThreeDimensions
Chapter4 Quantum Mechanics
of . Thisisprecisely
of eigenstates
what the Clebschneedlinearcombinations
dofor us.On theotherhand,it followsby
Gordancoefficients
(in Equation4..185)
from Equation4.187
that the sum S^ +SC9doescommutewith
obviousinference
we already knew (seeEquation4.103).
S2,which is a specialcaseof something
5\302\276
FURTHERPROBLEMSFORCHAPTER4
for which
*Problem4.38 Considerthe threedimensional
harmonicoscillator,
the potential
is
Vir) = mco2r2.
[4.188]
of variablesin cartesiancoordinates
turns thisinto
separation
and exploityour knowledgeof thelatter
threeonedimensional
Oscillators,
to determine
theallowedenergies.
Answer:
EA
(b)
= (n+3/2)h(D.
[4.189]
the degeneracy
Determine
d(n) of En
** ^Problem4.39Because
thethreedimensional
harmonicoscillator
potential
the
i
s
c
an
equation be handledby
4.188) spherically
symmetric, Schrodinger
as well ascartesiancoordinates.
of variablesin sphericalcoordinates,
separation
Findthe recursion
formula
Usethe powerseriesmethodtosolvethe radialequation.
theallowedenergies.
forthe coefficients,
Checkyour answer against
and determine
Equation4.189.
(Equation
**Problem4.40
(a)
vi'rialtheorem:
Provethethreedimensional
2{T)= (t*VV)
[4.190]
En; (F)=2EW.
[4.191]
191
Further Problems
forChapter4
tothethreedimensional
oscillator
harmonic
(e) Apply the virial theorem
4.38),and showthat in thisease
(Problem
[4.192]
\342\226\240*\342\226\240\342\226\240
Problem1.14:
J = 2m (vl/ vm*
(a) Showthat J
W*
W) .
[4.193]
thecontinuityequation
satisfies
*2,
VJ = at
[4.194]
It follows(from the
expresseslocalconservationof probability.
that
theorem)
divergence
which
f J~d*=
[4.1.95]
(it Jy
Inwords:The flow
where V is a (fixed)volumeand S isitsboundary surface.
of probabilityoutthroughthe surfaceis equaltothedecrease
in probability
of findingtheparticlein the volume.
FindJ for hydrogenin the staten:=2, I 1,m 1..Answer:
Js
(b)
\342\200\224
(c)
~ [ *fd3r,
\342\200\224
:rer/asm0$.
[4.196]
192
**)=
/o
\\
3/2
;f(t)
[4197]
[i + iaP,nn
(b)
(c)
(d)
Problem4.43
Constructthe spatialwave function(VO for hydrogenin the staten 3,
I = 2, m
1. Expressyour answer as a functionof r, 0, and a (the
Bohrradius)
othervariables(p,z,etc.)orfunctions
(Y, v, etc.),or
constants
allowed{n is okay,and e, and 2, etc.).
(A, cq,etc.),or derivatives,
(b) Checkthat this wave functionis properlynormalized,
by carrying out the
integralsoverr, 0, and
appropriate
value of rs in thisstate.For what rangeof s (positive
(c) Findthe expectation
and negative)istheresultfinite?
(a)
\342\200\224
\342\200\224
</>,
only\342\200\224no
\302\242.
Problem4.44
Construct
thewave functionfor hydrogeninthestaten 4,./ = 3,m = 3.
coordinates
r, 6..,and
Expressyour answer as a functionof the spherical
value of r in thisstate.(As always,lookup any nontrivial
(b) Findthe expectation
integrals.)
(c) If you couldsomehowmeasurethe observableL2 + L2, on an atomin this
state,what value (or values)couldyou get,and what is the probabilityof
each?
(a)
\342\200\224
<fi.
in the groundstateof
that an electron
Problem4.45What istheprobability
will be foundinsidethe nucleus?
hydrogen
(a)
193
Further Problems
forChapter4
(b)
(c)
Thisshould
(4/3)(fr/a)3.
be a suitableapproximation,
providedthat h <^a (which it is).
constantover the
Alternatively, we mightassumethat ^.(r) is essentially
so that P (4/3)nb3\\f(0)\\^.
Checkthat you
(tiny) volumeof the nucleus,
get the sameanswer thisway.
Useb ^ 1015m and a ~ 0.5x 10_10mto geta numerical
estimate
for P.
the \"fractionof its time that the electron
Roughly speaking,thisrepresents
spendsinsidethe nucleus.\"
\302\253*
\302\276
(d)
Problem4.46
(a)
formula (Equation
Usethe recursion
4.76)to confirm that when I
theradialwave functiontakestheform
p,
, _ Nnr
a!
^n(f?i)
vn\342\200\224^0\342\200\224rjna
\342\200\224
\342\200\224
\342\200\224
and determine
the normalization
constantNn by directintegration.
'(b) Calculate
(r) and (r2) for statesof the form ifn{n\\)m(c) Show that the \"uncertainty\"in r (oy) is (r)l\\/2n+ 1 for suchstates.Note
with increasing
that the fractionalspreadin r decreases,
n (in thissensethe
to; lookclassical,\"
with identifiable
for large
circular\"orbits,\"
system\"begins
this
n). Sketchthe radialwave functionsfor severalvaluesof n, to illustrate
point.
Problem4.47 Coincidentspectrallines.43Accordingto the Rydberg formula
(Equation4.93)the wavelength of a linein the hydrogenspectrumis determined
by the principal
quantum numbersof theinitialand final states.Findtwo distinct
that yieldthe sameX. Forexample,
{6851,
6409}and {15283,
11687}
pairs{n,,n/}
will do it, but you'renotallowedto usethose!
the observables
A = x2 and B = Lz.
Problem4.48 Consider
(a)
'(b)
(c)
theuncertainty principle
for <jaGbConstruct
Evaluate <jb in the hydrogenstate\\//nim.
What can you conclude
about(xy) in thisstate?
in ThreeDimensions
Chapter4 Quantum Mechanics
(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 spin1/2
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]
** ^Problem4.51
(a) Work
anything.
\342\200\224
.\302\276
Ism)
A\\\\
1)1\302\276
(m
 i)>+
B\\\302\261
(^))1\302\276(m
+ )),
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
S,=h
\342\200\224
\342\200\224
s2
0
0
~s)
hs
0
0
bs2
,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
ih1
ibs~2
;
\342\200\242
0
0
b~s+i
bs+i
0
0
th2
..
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
iks+i
ifej+1 0
bj = V^ + ,/)Cy+l7)
= B?t?m*PFiGQs6y,
196
dPm
(1 x1) dx = Vlx2^1 mxP'r.
\342\200\224l
[4.199]
(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)
(c)
(d)
(\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(#')
(where tp
generator
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,
[4200]
(x\342\200\224)\302\273
(c)
(d)
y\302\260u
,360\302\260
(e) Showthat
[4.201]
sin(<p/2).
But for
(as well as integer)eigenvalues.
(Equation4.99)allowfor halfinteger
orbitalangular momentum only the integervaluesoccur.There must he some
in the specific
form L f x p that excludes
values.44
extra constraint
halfinteger
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
(b) Showthat
h
fl2
+ ^(/>iH)L*= ^t\342\202\254)
\342\226\240
2.,
198
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]
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
ed.,
199
Further Problems
for Chapter4
(a) Showthat
=
~^
m
at <(p?A)}.
[4,206]
xBBxp))%x
B)).
m
=
{(p
m^P2mat q(E)+ ^(c)
[4.207]
packet,show that
at
m\342\200\224p
[4.208]
y(xJ
A
and
cp
= Kz2,
(b)
fields.Answer:
E(nu n2) =
(\302\253i
+ j)hm +
(/\302\276
...),[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,
200
thepotentials
\302\242/
=
0.,
at
9A
A'
+ VA
[4.210]
(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 thegaugetransformed
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
canonicalmomentum).
CHAPTER5
IDENTICALPARTICLES
5.1TWOPARTICLE
SYSTEMS
For a singleparticle,^(r,i) is a functionof the spatialcoordinates,
r, and the
The stateof a twoparticle
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]
9* =
tf\342\200\224
where H
H%
[5.2]
[5.3]
(the
I^Cn.ta.oi^riAs
[5.4]
/ \\^(rur2,t)\\1d3r}d3T2=l.
[5.5]
201
202
Particles
Chapter5 Identical
For timeindependent
set of solutionsby
we obtaina complete
potentials,
of variables:
separation
[5,6]
Schrodinger
spatialwave functionOft) satisfiesthe timeindependent
equation:
[5.7]
7TVh~ ~^if + Vj, = Ef,
where the
2mi
and E
Imi
* *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]
becomes
the (timeindependent)
Schrodinger
equation
h2
v\\f
2(mi+m2)
2fjt
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:
TwoB'article
Systems
203
\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 (oneparticle)
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 twopartiele wave function is a product of two oneparticle
wave functions. There exist socalled
this way. However:
entangledstatesthat cannot be decomposed
If particle 1 is in state a and particle 2is in state b, then the twopartiele state is a product.I know
what you're thinking:
\"How couldparticle 1not bein some staxe, and particle 2 in some other state?''
can'ttell you the state of
The classicexampleis the singlet spin configuration (Equation
partiele 1 by itself, becauseit is \"entangled\" (Sehrodinger's
lovely word) with the state of particle 2.
If 2 is measured,and found to be spin up, then 1 is spin down, but if 2 is spin down, then 1is spin up.
4.178)\342\200\224I
204
Particles
Chapters Identical
numberson
paintoneof them red and the otheroneblue,or stamp identification
to followthem around.But in quantum mechanics
them,orhireprivate detectives
the situation
is fundamentally different:You can'tpaintah electronred,or pin a
labelon it, and a detective's
observations
alter
will inevitablyand unpredictably
its state,raisingdoubtsas to whether the two had perhapsswitchedplaces.The
fact is,all electrons
in a way that no two classical
are utterly identical,
objectscan
is which; God
ever be.It's notjust that we don'thappento know which electron
doesn'tknow which is which,becausethere is no suchthing as \"this\" electron,
or
all we canlegitimately
\"that\" electron;
speakaboutis \"art\" electron.
of particlesthat are
the existence
Quantum mechanics
neatly accommodates
in principle:
a wave functionthat is nonWe simplyconstruct
indistinguishable
committedasto which particleis in which state.There are actually two ways to
do it:
f+ (ri,r2)= A\\^a{Yx)ifb{t2)
\302\261
#6(1,)^0\302\276)].
[5.10]
,,
^ ^,
\342\200\224
seemsbizarre that
relativity
should have
anything
to do
with
it,
moment.
Section5.i:TwoParticle
Systems
205
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\\, tz) V(r%, f i).It followsthat P and H are compatible
\342\200\224
observables,
\342\200\224
[P,H] = 0,
[5.13]
exchange;
TA(ri,r2)=
[54.4]
\302\261tA(r2,ri).
,..
/2 . /nn
If the particles
are distinguishable,
with
forconvenience),
(where K = jr2h2/2ma2,
#1 in staten\\ and #2 instateni,:the composite
wave functionis a simpleproduct:
the fact
law\342\200\224on
that
206
Particles
Chapter5 Identical
the groundstateis
For example,
2..
2,.
smtyxz/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)
bosons,identical
fermions).
5.1:TwoParticleSystems
Section
207
5.1.2ExchangeForces
To giveyou somesenseof what thesymmetrizationrequirement
actually does,Fm
example.Supposeoneparticleis in
goingto work out a simplebhedimensional
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]
[517]
V2
it is
and if they are identical
fermions,
theexpectation
Let'scalculate
value of the squareof the separation
distance
betweenthe two particles,
(to
[5.18]
1:
Case Distinguishable
particles.For the wavefunctionin Equation5.15,
(Xi) =
x\\\\faix\\)\\2dx\\
= (x2}a
/ \\ifbto)\\2dx2
/ \\ifa(xi)\\2dxi
xl\\fb{X2)\\24X2 = (X2)b,
and
(xiX2) =
In thiscase,then,
= {x)a{x)b.
/ xi\\fato)\\2dxi/ X2\\fhto)\\2dx2,
[5.19]
208
Particles
Chapter5 Identical
5.16and 5.17,
Case2:IdenticalparticlesForthewave functionsinEquations
.(*?)=
/ xi\\fa(xi)\\2dxi/
\\\\ftb(xz)\\2dxi
+ / *i2W*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)
(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.
[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:
TwoParticle
Systems
0^4
209
\342\200\242\342\200\224^0
(b)
5.1:
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).
210
Particles
Chapter5 Identical
the
includesnot only its positionwave function,but alsoa spinor,describing
orientation
of its spin:7
[523]
1r(r).xl*)>
When we put togetherthe twoelectron
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
^Problem5.6Imaginetwo npninteraeting
eachof massm, in the infinite
particles,
squarewell.If oneis in the statetyn (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
^,^,
\342\226\240fibix),
^\302\276
^/\302\276
52ATOMS
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
=\342\226\240
Ef,
[5,25]
, rz)x(si,
s2,...,
f(ti,r2,...
sz),
[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 ftwbody 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
, 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]
(ri,r2) = fnim(ri)Vv/'m'(ri),
[5.28]
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]
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).
fnlmfWQ
[5:32]
Section5.2:Atoms
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]
3S
>
3
o) ~J
^.
Orthohelium
3p
3D
4S 4P 40 4F
3P 3D1
..
3P 3D1
3S
2p\302\261
UJ
2PL
4 2S
2S1
Sat 24.5
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
particles
* *Prpblem5..11
(a)
Calculate
rjjl)}for the state (Equation530),Hint:Do the
{{\\f\\t\\
and settingthepolaraxisalongrj,
coordinates,
integralfirst,usingspherical
sothat
ri r2]= y r\\ + r\\InncosB2.
The $2integralis easy,but be carefulto take the positiveroot.You'llhave
to breaktheti integralintotwo pieces,onerangingfrom 0 to r\\, theother
\342\200\224
0\302\276
^3\302\276
^\342\200\224
5.2.2ThePeriodicTable
The groundstateelectron
forheavieratomscan bepiecedtogetherin
configurations
much thesameway. To first approximation
(ignoringtheirmutual repulsion
the individualelectrons
occupyoneparticle
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),
down\342\200\224or,
functions
\342\200\224
general
215
Section5.2;Atoms
countingoff).
\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
York
(1959),
Chapter 18,or the
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
quantum
thistime,because
we'retalkingaboutthe totals).The groundstateof carbonhappensto be 3Pq:
the totalspinis 1 (hencethe 3), the totalorbitalangular momentum is 1 (hence
the P), and the grand totalangular momentum is zero(hencethe 0).In Table5.1
the individualconfigurations
and the total angular momenta (in the notationof
Table.12
Equation5,34).are listed,for the firstfourrows of the Periodic
^Problem5.12
(inthe notationof Equation5.33)for
Figureout theelectronconfigurations
the first two rows of thePeriodic
Table(up to neon),and checkyour results
againstTable5.1.
totalangular momenta,in thenotationof
'(b) Figureout the corresponding
for boron,
Listallthe possibilities
534,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)
\\L\342\200\224S\\;
\342\226\240=
(d)
5\"
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 threedimensional
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
electronelectron
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
semiconductors,
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'
\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
\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]
...,
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(oneparticle)
stationary state(Figure5.3).Eachblockin thisgrid,and
hencealsoeachstate,occupies
a volume
a
71
7t
[5.40]
Ixlyk
of \"Aspace,\"where
practice,
number\342\200\2241
electrons
(Equation5,40):
Thus
kF
\342\226\240=
[5.41]
(3p7T2)1/3,
where
P=
Nq
~
[5.42]
h2
EF = \342\200\224(3pir2)2/3>
2m
[5.43]
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
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
~\"m^
(7t3/V)
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
=2
3
y_5Pdv = _2
\302\243tot
=2
3
JVV
^\302\276
1071\302\275
= (3jt2)2/3^2
P5/3
5m
[5.46]
Section5.3:Solids 223
dP
V\342\200\224.
dV
Show that B =
224
I'articles
Chapter5 Identical
all electronnucleus
forces!Actually, it is rather
and\" electronelectron
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 onedimensional
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]
f(x + a) =eiKa\\ff(x),
[5.49]
2a
2a
3a
4a
5a
6a
FIGURE5.5iThe Diraccomb,Equation5.57.
so
'\"It would bemorenatural to let the delta functions go;down, as to representthe attractive force
of the nuclei.But then there would be negative energy solutions as well as positive energy solutions,
Sinceall we'retrying to do here
and that makes the calculations more cumbersome(seeProblem
to
t
he
of
it
is
this
lessplausibleshape;if it .comforts
is explore consequences periodicity,
simpler adopt
as
think
of
the
nuclei
at
you,
residing
5.20).
+#/2,+3a/2,+5a/2,
Section53:Solids
225
[5.50]
For a periodicpotential
D commutes
with the Hamiltonian:
(Equation5.47)*.
W, H] = 0,
[5.51]
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
x\342\200\224we
then\342\200\224since
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
[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 xaxisaroundin 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,
[556]
Nl
7=0
\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
< a),
[5.59]
to the
Accordingto Bloch'stheorem,the wave functionin the cellimmediately
left of theoriginis
[5.60]
499 (1930).
l8R.de L. Kronig and W. G.Penney, Proc.R. Soc.Land.,ser.A, 130,
McGrawHilljNew
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 KronigPenney
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,
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
Ei
band
\342\226\240
gap
band
\342\226\240
\342\226\240gap
band
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)
(b)
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.
y/\342\200\2242mE/h
\342\200\224tea,
4,...,
230
Particles
Chapter5 Identical
5.4 QUANTUMSTATISTICAL
MECHANICS
At
configuration.
\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]
Section5.4:Quantum Statistical
Mechanics 231
(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 (oneparticle)
of all
occupationnumber, for the state\\//n. The collection
numbers for a given 3particle
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
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]
\\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]
only
one.
I'drather
not worry
about\342\200\224maybe
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 Ej 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
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^/{xaxb,xc)
(b)
Constructthe completely
for three
symmetric wave function^{xaxb^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.
\\}/\\
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 oneparticle
are E\\, E2,
Now consider
energies
d\\, di,
(i.e.,thereare distinctoneparticle
\302\2433...., with degeneracies
stateswith energy
Supposewe put N particles(allwith the samemass)into
we are interested
in the configuration
thispotential;
for which
(N\\.N2,
there are N\\ particleswith energy E\\, N2 particleswith energy Ej, and so on.
Question:How many different ways can this be achieved(or, moreprecisely,
to thisparticularconfiguration)?
The answer,
how many distinctstatescorrespond
identical
Q(N\\, Afa. Afy.
dependson whether the particlesare distinguishable,
or identical
fermions,
bosons,sowe'lltreat the three casesseparately.22
How many ways are there to
First,assumethe particlesare distinguishable.
the N\\ to be placedin the first \"bin\"?
select(from the N availablecandidates)
dj,....
d\342\200\236
E\342\200\236).
N^....),
\342\200\242
\342\200\242.),
An
234
Chapter5 IdenticalParticles
chooseN\\,\"
'W
Answer: the binomialcoefficient,
/N\\
,AV
AH
N\\\\(N
[5.73]
Ni)\\
soon:
N(N
 2)...(N
N{+
\\)(N
\\)
\342\200\224
AH
(NNi)l
Nil(N N\\)\\
The samegoesfor bin 2, of course,exceptthat there are now only (N
\342\200\224
N\\)
N.
(NN{)ldp
N2\\(N
N\\
N2)\\
Q(N{.N2.N3
,...)
N{\\(N
N\\
(NNi)ld* (NNXN2Yd^
N2\\(N N{ N2YN3\\(N Ni N2N3Y
N\\Y
,Ni
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 Nparticlestatein which a
statesare occupied.
Moreover,only oneparticlecan
specificset of oneparticle
occupyany given state.There are
states\342\200\224the
Section5.4:Quantum Statistical
Mechanics
ways
to choosethe
N\342\200\236
235
,,
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 Nparticlestatein which a
statesare occupied,
but thistime there is no restriction
specificsetof oneparticle
on the number of particlesthat can sharethe sameoneparticle
state.For the nth
\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
(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
oneparticle
'11
tf,....)
' = TT {Nn+?\"~l)[
[5.77]
N\342\200\236\\(d\342\200\236l)\\
\302\253=l
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
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
of severalvariables,
x$,...)
=
G(.Y..T2.A3
= F + Xif\\ +X2f2+
A.i.A.2....)
[5.80]
dG =
0;
dG =
0.
[5.81]
dx\342\200\236
we let
00
G = \\n(Q)+a
\"\302\243w\302\273
00
+ P EYjNnEn
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
 MAT*!)]
oo
G = ln(AH) + J2
[N\302\253
lnW\342\200\236)
[5.83]
oo
+ ot
+P
*\302\243>\342\200\236
EJ^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)aPE\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]
 WW,!)
CO
G = J2 0nM>0
\\n[(d\342\200\236
N\342\200\236)!]}
\302\253=i
00
+ a NJ^Nn + fi
H
=I
[5.88]
00
\302\243\302\243>\342\200\236\302\243\342\200\236
H=l
the
first
two
will
large\342\200\224as
5.4.1\342\200\224then
all:
238
Particles
Chapter5 Identical
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\236N\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)
[5.90]
0E\342\200\236.
N\342\200\236)
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]
a0E\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
I5'95!
e^tlLy
(b) What
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,
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
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 = yea
\\
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]
temperature:
= T^fkBT
[5101]
5th
Section205.
ed..Wiley. New York (1997).
28See.
Yariv
for example.
(footnote 22).Section15.4.
Section5.4:Quantum Statistical
Mechanics
241
fi(T)= akBT,
[5.102]
state):
MAXWELLBOLTZMANN
e(\342\202\254H)/kBT
\302\253(0
1
\342\200\242
e(\342\202\254H)/k/]T
_j_
_
e{eH)/kBT
FERMIDIRAC
[5.103]
BOSEEINSTEIN
\\
The MaxwellBoltzmann
distributionis the classical
result,for distinguishable
and the Bosethe FermiDirac
distributionappliesto identical
particles;
fermions,
Einsteindistributionis for identicalbosons.
The FermiDirac
distribution
has a particularly simplebehavioras T > 0:
0, if 6 < (1(0),
oo, if e > fi(0).
AeH)/kBT
so
[5.104]
n(e)
All
Fermi energy:
At(0)
= EF.
[5.105]
\"softens\"
the cutoff,as
As the temperaturerises,the FermiDirac
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)
fx(T) = kBT
\\Vj
[5.107]
\\mkBT
constraint
(Equation5.78)becomes
N
k2
2^Jo
0
e\\(h'ki/2m)n\\lkBT+
dk.
[5.108]
(Equation5.79)reads
tr
r\302\260\302\260
In1 2m Jo
kA
+
e\\.(hlk/2m)n\\lkBT
dk.
[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]
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:
\342\200\2241,
SeeF. Mandl.StatisticalPhysics.Wiley.
11.5.
Section
London (1971).
244
Particles
ChapterS Identical
everything
=\342\200\224\342\200\224L
= 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)'
(b)
2.90xlO\"3mK
Vu =
j.
rcilill
[5.114]
\342\200\242
significantdigits.
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.
T4 =
(7.57x 1016Jm_3K4)
/ 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 distinctoneparticle
How many different threeparticle
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:
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
\342\200\224
=\302\276
(a)
hck,
Replaceh k/2min Equation5.44by the ultrarelativistic
expression,
and calculate
\302\243tot
(b)
in
thisregime.
electron
gas.
Repeatparts(a) and (b) ofProblem5.35forthe ultrarelativistic
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
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
J:
d_
H=l
[5116]
248
Particles
Chapter5 Identical
and similarresultsfor higherderivatives.
Answer:
3
+
E = Nfico(\\ ehulkBT\\.
(b)
(c)
\\iehw/kBTJ
\342\200\224\342\200\224j\342\200\224j^r
[5.117]
J
/ia\302\273,
PART II APPLICATIONS
CHAPTER6
TIMEINDEPENDENT
PERTURBATIONTHEORY
6.1NONDEGENERATEPERTURBATIONTHEORY
6.1.1
GeneralFormulation
Schrodinger
equationfor some
Supposewe have solvedthe (timeindependent)
infinite squarewell):
potential(say, the onedimensional
H\302\260*!
= E,W
[61]
setof orthonormal
obtaininga complete
eigenfunctions,
i/r^,
{fnWl)=^,n
[6.2]
Hilrn
E\342\200\236yjr\342\200\236,
[6.3]
249
250
Perturbation
Chapter6 TimeIndependent
Theory
V(x)k
^\\
H=
H\302\260
+ XH',
[6.4]
seriesin X:
En
= En + XEn + X~E~ +
[6.5]
[6.6]
(H\302\260
(E\302\260
\342\226\240\342\226\240\342\226\240].
or (collecting
likepowersof X):
\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),
[6.8]
6.1.2FirstOrderTheory
Takingthe inner productof Equation6.7with
\\J/\302\256
(that
is, multiplying by
(if/\302\256)*
and integrating),
//\302\260
is hermitian,
so
(^1^)= 1,so2
\302\243i
(^HU\302\260).
[6.9]
*!m= JIHtx)2.
252
Perturbation
Theory
Chapter6 TimeIndependent
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 firstorder
Solution:In thiscaseH' = Vq, and the firstordercorrection
to the energy of the
/?th stateis
= <V0? W,?>= VoWflV\302\260> = V0.
E\\
Vfo
\302\243\342\200\236
allthe higher
theory yieldsthe exactanswer.Evidently for a constantperturbation
corrections
extendsonly halfway
vanish.3On the otherhand,if the perturbation
acrossthe well (Figure6.3),then
\342\200\242
\"
a Jo
E\342\200\236
\342\200\224x
^0
\342\200\224.
\302\243j)^
 EM.
= {W
infinite
[6.10]
square
well\342\200\224the
same
Section6.1:Nondegenerate
Perturbation
Theory
253
V(x)\342\200\236
Vo
>
ri = Ec\"V\302\260.
[6.11]
\302\243(\302\243\302\260
\\jrfj
in
first term
6.5reveals thai
a glance at Equation
Alternatively,
is 1 and
[if/,]
Equation
*
\342\226\240
*\342\226\240\"('
\\\\[/\302\256)
first
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?)+
but
(^1^,))
\\j/}t
254
Perturbation
Chapter6 TimeIndependent
Theory
If / = n, the left sideis zero,and we recoverEquation6.9;if I ^ n, we get
(\302\2430_\302\243J)cW=_^0WU0>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
firstorderperturbationtheory:The firstordercorrection
to
the energy,EJ}, is given by Equation6.9,and the firstordercorrection
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),
H' = oc8(xa/2),
where a
is a constant.
Findthe firstorder
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
are
E\342\200\236
= (n + \\/2)h(o,
(n
= 0. 1.2,
...),
\342\200\224\302\273
Section6.1:Nondegenerate
Perturbation
Theory
255
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)
width
of
(b)
6.1.3SecondOrder
Energies
as before,we take the inner productof the secondorder equation
Proceeding
(Equation6.8)with
if/\302\256:
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 TimeIndependent
so
the sum excludes
m = n, and allthe othersare orthogonal),
(because
E\302\260
E\302\260
or, finally.
3 E
=
0r//u/,0\\i2
/rO _ c0
[6.15J
mfin
*Problem6.4
Find the secondorder
correctionto the energies(E2.)for the potential
in Problem6.1.Comment:You can sum the seriesexplicitly,
obtaining
for oddn.
the secondorder
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 onedimensional
harmonic
so that the potential
potential.
Supposewe turn on a weak electricfield
energy is shiftedby an amount H' =
oscillator
(\302\243),
\342\200\224qEx.
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:
NonRelativistic
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,
HigherOrder
SpectralPerturbation (unpublished Reed Collegereport. 2000).
Illuminating
formulations of timeindependent perturbation theory include the DelgarnoLewismethod 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
\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 thefirstordercorrection
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.
6.2.1TwoFoldDegeneracy
Supposethat
H\302\260tf
= 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]
E\302\260:
H\302\260x}/0
= E0x}/0.
[6.18]
As we
Typically,the perturbation(//') will \"break\"(or \"lift\") the degeneracy:
6.9)\342\200\224we
258
Perturbation
Theory
Chapter6 TimeIndependent
E
Eo
H=
H\302\260+XH'
E=E\302\260
and
+ \\E1+\\2E2+ >,
yjr
ifr\302\260
+ Xifr1 + X2x}/2+
[6.20]
#V\302\260
+ M#
But /f0!//0=
\302\243\302\260i/f0
V\302\260
+ #V) +
E\302\260\\lr\302\260
+ X(E
V\302\260
+ ^V) +
tfV
+#>\302\260
\302\243V
\302\243
V\302\260.
[621]
(Equation6.16),we obtain
=aEl.
*{^a\\H'\\fQa)+0{tf\\H'\\1,$)
or, morecompactly,
aWaa+0Wab=aEl,
where
W,j
[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]
WahWba)
= 0.
[6.26]
Wba
that
we conclude
E\\=
Waa
+ Wbb
\302\261
J{Waa
Whh)2
+ 4\\Wab\\*
W*b,
[6.27]
4=
Waa
W\302\260ff'Wr\302\260),
El = Wbb = Wjlff'l^).
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)
260
Perturbation
Theory
Chapter6 TimeIndependent
then
Wab
i/r\302\243
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
statesones
with
and H'\\ pickas your unperturbed
operatorA that commutes
that are simultaneously
of and A. Then useordinaryfirstorder
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
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\243ff'Wr\302\243)=0;
(e)
{\\j/\\\\H'\\fQ\302\261)
= 0);
\302\253i/rji/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
onedimensional
Section6.2:Degenerate
Perturbation
Theory
where n
= 0, +1,+2,
...,
261
= 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' = V0ex2/a\\
L. (Thisputsa little\"dimple\"in the potential
at x = 0,as though
where a
to
we bentthe wire slightlyto make a \"trap.\")Findthe firstorder
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
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
6.2.2HigherOrderDegeneracy
In the previoussectionI assumedthe degeneracywas twofold,but it is easy to
seehow the methodgeneralizes.
Rewrite Equations6.22and 6.24in matrix form:
ff:
\302\243)6)=^6)
of the Wmatrix;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 nfolddegeneracy,
of the n x n
matrix
Wij
= W?\\H'\\rf).
[6.29]
262
Perturbation
Theory
Chapter6 TimeIndependent
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 2fold
(If you'renervous aboutmy casualgeneralization
equation.6
to /?folddegeneracy,
work Problem6.10.)
degeneracy
H\302\260,
characteristic
the threedimensional
infinite cubicalwell (Problem4.2):
Example6.2 Consider
.
V(\\\\y.z) = oo
otherwise.
[6.30]
<\342\200\236,\342\200\236(V,
z)
(^z)
(^J
[6.31]
+ nh.
<nvn: = ^(\302\273l+nl
[6.32]
 3^.
a1
2m
[6.33]
E?
 3^:.
ma1
[6.34]
[6.35]
Now let'sintroduce
the perturbation
H' =
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 firstorder
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]
= wcc = ]v0.
4
The offdiagonal
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 TimeIndependent
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;
iy2
= 1+
\302\253
\302\253
1705; iw3 =
*
*\302\253
0.2795.
+ 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 firstorder
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
ft,
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
t\302\260
fa
[6.41]
(^  1M/a/2.
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 TimeIndependent
where Vq
'(16)0
0
0
V0 I
0^
e 2,
and eigenvalues
of theunperturbedHamiltonian
(a) Write down the eigenvectors
(e = 0).
(b)
to an /?fold
Problem6.10In the text I assertedthat the firstordercorrections
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
=^^
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 socalled
fine structure,which is actually dueto two distinctmechanisms:
a
relativisticcorrection,and spinorbit
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
Problem6.11
(a)
(b)
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 TimeIndependent
and the canonical
substitution
p
{h/i)Vyieldsthe operator
\342\200\224>
r = \302\243v2.
2m
But Equation6.44is the
formula is
[6.45]
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,
4m 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+m2c4mc2.
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 lowestorder8
correction
to the Hamiltonian
is evidently
relativistic
P4
8m
[6.50]
10
(511.000
\342\200\224
6.50.
6.49.
expectation
In firstorderperturbation
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]
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
where
E\342\200\236
\\[r\342\200\236im
[6.55]
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
somesleightofhand in
\342\200\224
p. 17.
this
270
Perturbation
Theory
Chapter6 TimeIndependent
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
5=0
\342\200\2242
\342\200\224
\342\200\2243
\342\200\2247.
* *Problem6.14Findthe (lowestorder)
to the energy levelsof
relativistic
correction
in Example2.5.
the onedimensional
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
= 4nh2
+ <P2/I*>L2ffrr2gd\302\243
o
i/0i00\302\273
which goeslike
1
VOiOO
=\342\200\224^expir/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/
6.3.2SpinOrbit
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 = fiB.
[6.58]
To beginwith, we needto figure out the magneticfieldof the proton(B) and the
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.
272
Perturbation
Chapter6 TimeIndependent
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
;\342\200\242
2m
H\302\243)\302\273
fie =
jit,
S.
[6.60]
Sii
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/we~rJ
I did the analysisin the restframe
But there is a seriousfraud in thiscalculation:
so
(\342\200\224)
\\
\342\200\224
8;reo/m2c2r3
angular
J = L + S,
[6.62]
...
274
Perturbation
Chapter6 TimeIndependent
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
LS=(J2L2S2),
[6.63]
r
/(/ +1/2)(/+l)nV
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 (
ls
.
=^(3+^)
1/2/
2mc2\\
[6.66)
J
L
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)
[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/
numbers\342\200\224the
276
Perturbation
Theory
Chapter6 TimeIndependent
\342\200\242
\342\226\240
\342\200\242
\342\200\242
\342\200\242
(\302\2433
\302\2432)
A\302\243,
A\302\243
A\302\243
Hz)\342\200\224not
....
...
Problem6.19The exactfinestructure
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)20,2/
Section6.4:TheZeemanEffect
277
S
fis = m
[6.69]
fi, = ^L
2m
[6.70]
+ 2S).Bexl.
/^ = ^(L
2m
[6.71]
external fieldin
\302\243cxl
/\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 TimeIndependent
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
But L = J
\342\200\242
[6.73]
and
[6.74]
2S)=/(\\+
^)j\\
+ 1)+3/4+ ./(./+1)/(/
(J). [6.75]
2./(7+ 1)
_ fJ.BgjBcx[mj.
Ez =
l
\342\200\242
where
eh
[6.76]
^5 eV/T
liB= 2m = 5.788x 100
[6.77]
Bohrmagneton.The totalenergy is the sum of the finestructure
is the socalled
part (Equation6.67)and the Zeemancontribution
(Equation6.76).For example,
\342\200\224
Section6.4:TheZeemanEffect
the groundstate
(\302\273
levels:
279
13.6
eV(l+ a2/4)
\302\261
[6.78]
(XBB^
\342\200\2241/2.
Theseenergiesare
ZeemanEffect
6.4.2StrongField
If #ext ^>
B'mi, the
\"good\"
quantum numbersare now n, I, mi,and ms (but not j and mj
because\342\200\224in
\342\200\224Bexl(Lz
+ 2Sz),
eV
13.6(1+e^/4)
/77/
= 1/2
FIGURE
upperline(ntj
In this
\342\200\2241/2)
has slope
PaschenBack
effect.
\342\200\2241.
280
Perturbation
Theory
Chapter6 TimeIndependent
and the \"unperturbed\"energies
are
Enm,ms =
13.6eV
n7
HBBexdmi+ 2m,).
[6.79]
4=
[6.80]
The relativistic
is the sameasbefore(Equation6.57);forthe spinorbit
contribution
term (Equation6.61)we need
[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]
(Equation6.82).
(Equation6.79)and the fine structure contribution
* *Problem6.23 Consider
the (eight)n = 2 states,2/m/m.v).Findthe energy of
eachstate,under strongfield
Zeemansplitting.
Expresseachanswer as the sum of
three terms:the Bohrenergy,the finestructure
to or),and the Zeeman
(proportional
how
contribution
to /j.bBcx1).
If you ignorefine structure altogether,
(proportional
many
Section6.4:TheZeemanEffect
281
ZeemanEffect
6.4.3IntermediateField
In the intermediate
and we must treat the
regimeneitherH'z nor H'{% dominates,
two on an equalfooting,as perturbations
to the BohrHamiltonian
(Equation6.42):
[6.83]
=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^)= 11l)i=^),
l!i> =V27310)ii)+VT731l)i^),
+ V273l1)11^i),
*6 = lH> =vT7310)H)
Tfc
^7^11^)= 71/3111)1^)
+v^73io>ii^>,
^ = li =^) = 72/311
i> + Vl7310)i
^).
In this basisthe nonzeromatrix elementsof H{s are all on the diagonal,
and given by Equation6.66;H'zhas four offdiagonal
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
282
Perturbation
Theory
Chapter6 TimeIndependent
where
y
= (a/8)213.6
eV and
\302\243
= nBBexl.
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]
/\"8eext
Section6.5:HyperfineSplitting 283
TABLE6.2: Energy levelsfor the n =2 statesof
hydrogen,with fine structureand Zeemansplitting.
= \302\24325y+jS
= E~25yp
= E2y+2/3
=
e4
E2y2p
= E2 3y+f}/2
+ V4y2 + (2/3)yff + fi2/4
H = E2 3y+p/2 V4y2 + (2/3)yff + ff2/4
= E2 3y p/2+ V4y2 (2/3)yfi+ fi2/4
+
*8 = E2 3y ^/2 V4y2
\342\202\254l
\342\202\2542
\342\202\2543
\342\202\2545
\342\202\2547
(2/3)y\302\243
\302\2432/4
an^
#iv
anc*
constructthe
cases.
6.5 HYPERFINESPLITTING
a magnetic
The protonitselfconstitutes
dipole,thoughits dipolemoment is much
[6.85]
made up of three quarks,and itsgyromagnetic
structure,
(Theprotonis a composite
the
dipole as a spinning
goesto
infinity
(with
ft
, +. 2/zo
~.~
r,,,
r)r
[3(^
fi]
4tt/
with
Mo
\342\200\242
^, .
\342\200\224fi8\\r).
term in Equation
[6.86]
treating
charged sphericalshell, in the limit as the radius goesto zero and the charge
held constant). SeeD. J. Griffiths. Am. J. Phys.. 50.698(1982).
284
Perturbation
Theory
Chapter6 TimeIndependent
Sothe Hamiltonian
of the electron,
in the magneticfielddueto the proton's
dipolemoment,is (Equation6.58)
magnetic
\342\226\240
\342\200\236,
\342\200\242
\342\200\242
r
5>td
,(r).
[6.87]
3mpme
Accordingto perturbationtheory, the firstordercorrectionto the energy
value of the perturbingHamiltonian:
(Equation6.9)is the expectation
67tmpme
MQgpg2
/3(Sj, r)(Se r) Sp Se
\342\200\242
\342\200\242
\342\226\240
r3
M~S7tmpme\\
\\
[6.88]
f*Q8Pe2lo v..rm2
3mpme
In the groundstate(orany otherstatefor which / = 0) the wave functionis
and the first expectation
value vanishes(seeProblem6.27).
symmetrical,
= l/ina3),so
from Equation4.80we find that 1^100(0)12
Meanwhile,
,
\302\253
spherically
JMpf_{S sy
37rmpmea*
E,
[6g9]
involvesthe dot
which involvesS L).
productof two spins(contrast
spinorbit
coupling,
In the presenceof spinspin
coupling,the individualspinangular momenta
of the totalspin,
are no longerconserved;
the \"good\"
statesare eigenvectors
\342\200\242
S = St> + SP.
As
[6.90]
i(S2S2S2).
[6.91]
Eur
M
\342\200\224
Wj4
+ 1/4. (triplet):
breaksthe spindegeneracy
of the groundstate,liftingthe
Spinspin
coupling
and depressing
the singlet(seeFigure6.13).The energy gap
tripletconfiguration
is evidently
AE
3m\342\200\236mccr
[6.93]
Section6.5:HyperfineSplitting 285
Triplet
i
Unperturbed
AE
\\
\\
\\
\\
\\
\\
Singlet
'
stateis
A\302\243
\342\200\224
= 1420MHz.
[6.94]
(a r)(b  r) sm0d0d<$> =
\342\200\242
to demonstrate
that
for stateswith /
(a
\342\200\242
b)
[6.95]
'3(S\342\200\236.r)(Ser)S\342\200\236Sc
,3
4tt
\342\200\224
= 0.
286
Perturbation
Chapter6 TimeIndependent
Theory
FURTHERPROBLEMSFORCHAPTER6
to the groundstateenergy of hydrogendue
Problem6.29 Estimatethe correction
to the finite sizeof the nucleus.
Treat the protonas a uniformly chargedspherical
insidethe shellisconstant:
shellof radiusb, sothe potential
energy of an electron
is
this isn'tvery realistic,but it the simplestmodel,and it will
give us the right orderof magnitude.
Expandyour resultin powersof the small
parameter(b/a),where a is the Bohrradius,and keeponly the leadingterm, so
\342\200\224e1/{Aneob)\\
AE
\342\200\224~
= A(b/a)\".
Your business
is to determinethe constantA and the powern. Finally,put in
b % 1015
m (roughly the radiusof the proton)and work out the actual number.
with fine structure and hyperfine structure?
How doesit compare
Problem6.30Considerthe isotropicthreedimensional
harmonic oscillator
(Problem4.38).Discussthe effect(in first order)of the perturbation
H' = Xx2yz
(forsomeconstant
X) on
(a) the groundstate;
(b) the (triply
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
atoms(Problem6.31).
FIGURE6.14: Two nearbypolarizable
[6961
FurtherProblems
forChapter6
287
The Coulombinteraction
between the atomsis
H', =
e
RX\\
(e~
47T\342\202\2540\\R
(a)
e~
R+X2
e~
\\
RX\\+X2/
[6.97]
H' ^ 
'
[6.98]
\342\200\236V
intotwo harmonicoscillator
Hamiltonians:
H=
2.1(,
_\302\2431_\\
.)*?
'
+ r^P+ ^U+
2 \\ 2^c0/?3
2m
[6.99]
\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
[6.101]
(d)
\302\243
\302\2430
1^
\\7T\342\200\224)
n
[6102]
* *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 TimeIndependent
of H(k).The FeynmanHellmann
theorem22
statesthat
eigenfunctions
iH*\"1?1*1)
[61031
are
eitherthat En is nondegenerate, degenerate\342\200\224that the
(assuming
the \"good\"
linearcombinations
of the degenerate
eigenfunctions).
Hint:UseEquation6.9.
theorem.
(a) Provethe FeynmanHellmann
harmonicoscillator,
(i) usingk = co (this
(b) Apply it to the onedimensional
value of V), (ii)usingk = h (thisyields
yieldsa formula for the expectation
(T)),and (iii)usingk = m (thisyieldsa relationbetween {T) and
Compareyour answers to Problem2.12,and the virial theorempredictions
or\342\200\224if
i//\342\200\236's
(V'\302\273.
(Problem3.31).
* *Problem
6.33 The FeynmanHellmann
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
* * *Problem
6.34 ProveKramers'relation:25
6.103while
working
on his undergraduate
[6.104]
thesis at MIT
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 FeynmanHellmanntheorem (Problem 6.32).
seeS.Balasubramanian,
(1997).
Am.
J. Phys. 68.959(2000).
Further Problems
forChapter6
289
\342\200\224
11
= 7(/ + 1)
r
ar
na 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 (r1),(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(r2) and (r3).
(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.
H's= eEexlz =
<?\302\243\"cxt>*cos0.
in
groundstateenergy is not affectedby thisperturbation,
order.
The first excitedstateis 4folddegenerate:
tJ/iqq, ^21i> ^210.
^211Using
firstorder
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 TimeIndependent
Theory
Noticethat the resultsare independent
of the appliedfield\342\200\224evidently
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,<310z320)
=
answer:<300z310)
(31\302\261lz32\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 deuterongfactoris 1.71.
<\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 lowestorder
correction
to the groundstateenergy.
the firstordercorrections
to the energy of the first excitedstates
(c) Calculate
=
(/?
2).Into how many levelsdoesthisfourfolddegenerate
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)
(A
+ Br + Cr2)e~r/acos9;
constantsA, B,
and
that
solve
Equation6.10.
correctionto the
the secondorder
(ii) Use Equation6.14to determine
is zero,as you found in
groundstateenergy (the firstordercorrection
Problem6.36(a)).
Answer: ~m(3a~eEeKl/2h)~.
(b) If the protonhad an electricdipolemoment p, the potential
energy of the
electronin hydrogenwouldbe perturbedin the amount
= epcos6
H'
(i)
Ajreor
function.
292
Perturbation
Theory
Chapter6 TimeIndependent
(ii) Showthat the totalelectric
dipolemoment of the atom is (surprisingly)
zero,to thisorder,
(iii)
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 (timeindependent)
The variationalprinciple
will get you an upperboundfor
Schrodinger
equation.
which is sometimes
allyou need,and often,if you'recleveraboutit, very
closeto the exactvalue.Here'show it works:Pick any normalized
function\\j/
whatsoever;I claimthat
\302\243\"gs,
\302\243gs,
\302\243gs
[7.1]
\\ff
'ifthe Hamiltonian
= ^2 ^\"'
c\302\273
with
//
\\j/\342\200\236
E\342\200\236
argument
\\j/\342\200\236.
is unchanged.
293
294
Since\\j/ is normalized,
1=
(ifr\\ilr)
HI
Meanwhile,
5.,,,,,).
hi
\302\2731
(//)>\302\243gs\302\243>n2
<
\302\243gs
E\342\200\236,
\302\243gs.
tr
d~
2m dx2
\342\226\240=
77
H\342\200\224mco~x'
xj/(x) = Aehx\\
where b
[7.2]
is a constant,and A is determined
by normalization:
lIAPjT.^^IAP/J^Ad)\"4.[7.3,
Now
where, in
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>
[77]
lho>.
d1
2mh1ax\342\200\224
\342\200\224^a8(x).
\302\2432S
{V) = a\\A\\2
~bx
JOG
8{x)dx=
aj
\342\200\224
Tt
Evidently
d ;m = ^2
db (H) 2m
\342\200\224
'
\302\253
J2icb
= n0 => b, =
2//7\302\2752
nti4
;\342\200\224.
296
So
(#)min =
which is indeedsomewhathigherthan
\302\243\342\200\236s,
ry<
jttr
[7
sincen > 2.
Ax,
A(a.v).
0.
where A
1
if
if
[7.1i
otherwise,
is determined
by normalization:
=A2
./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).
\342\200\242^Therc
N.
Section7.1:Theory
dvj//dx
297
a/2
thiscase
df
A,
\342\200\224A.
~dx
0,
[7.12]
hence
(H) =
h2A
2m
h2A
2m
{a/D+ (a)]=
[if; (0)2xff
Theexactgroundstateenergy is
works (12> 7T2).
2m
I2h2
2ma
[7.13]
= Titr1/2ma2
(Equation2.27),sothe theorem
\">
\302\243gs
h2A2a
\302\273.2
is extraordinarilypowerful,and embarrassingly
The variational principle
easy
oscillator
where A
and b is an adjustable
is determinedby normalization
parameter.
\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 onedimensional
(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
the
and
E. Bright
Section26.
(1935.
paperbackedition 1985).
299
Problem7.5
to provethat firstordernondegenerate
(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 secondorder
groundstateis always negative.Confirmthat this is indeedthe case,by
perturbation
examiningEquation6.15.
two protons(alsosomeneutrons,
which are irrelevant to our purpose).
containing
The Hamiltonian
forthissystem(ignoringfine structureand smallercorrections)
is:
H=
_\302\273l(vf
2w
ir!;.
i)
+
V?)^(l
\\n
+ 
47T6Q
t\"2
l*l
\342\200\224
T2
[7.14]
represents
\302\243gs
it
electron\342\200\224see
Egs =
eV (experimental).
78.975
[7.15]
+2e*
helium,
= e2
a\342\200\224;
r
[716]
300
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^01+^
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
[719]
(ff)=8\302\243,+(Vee).
where8
e2
8 \\2
f_4(''i+')/u,
[7.21]
and hence
h= J/
d3n= /
lri~r2l
rfsinfo/W/fr./ty,.[7.22]
\"
y/rj + rlZnncosOi
fn
/
'

sin07
,
=clQ1
Jr2 + r2
2r\\n cos#2
//2
Jrj + tj 2rincos02
\342\200\224
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
301
Z2n
Kr
f\\
^1
M A
/^
,^
y2
<t>2
x2
ofcoordinates
for the r2integral
FIGURE7.4: Choice
(Equation7.20).
>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 \\
reAnJar2dn\\
^4r2/i7/22^r2+
/.
2n\\
[7.24]
,4r,/\302\253l
<r4riAVisin0i
dr\\dQ\\d<$>\\,
The angular integrals
are easy (4tt),and the r\\ integralbecomes
/;[*'(\302\245)
Finally,then,
(y> =
and
therefore
(H) =
( e1
\\
128
4^(4^)=2\302\243l=34eV'
109eV + 34 eV = 75eV.
\342\200\22479
[725]
[7.26]
302
1/\302\276
Z3
iMri.r?)= \342\200\224eZ{n+ri)/a.
na5
[7.27]
(neglecting
H=
2mh1(Vf1+ vf) 9
L
\342\200\224
 n.J
e1 /Z Z\\
+
An
e0 \\n
/'1
_j_y
rir2/
The expectation
value of H is evidently
2) (
jfM/1
1)+ (VM).
^\\
k47T60
[7.29]
.
[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,
2)(5/4)Z
E\\
= [2Z2+ (27/4)Z]\302\243i.
[7.32]
303
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
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
\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);
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
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
H=
\342\200\224
Vz
_ +_
[7.35]
Mr) = ^=e'/(>,
[7.36]
e
+e
+e FIGURE7.5: Thehydrogenmolecule
ion,H+
Section73:The HydrogenMolecule
lorn
JOS
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
=
I ee (ifo(ri)litota))
e^W\"dh.
A
na* J[
[7.39J
=r
[7.40]
and therefore
I=
L
(
no* J
e>laeJr2+R21>R\342\204\2420l\302\253r2sin6d
rd6d<t>.
<.
2<
rz=Jrz+R22rRcosQ
..0y A\\
=r
\\
1
y
FIGURE7.6:
Coordinates
oil(Equation7.39).
for the calculation
[7.41]
306
let
The 0 integralis trivial (2;r).To do the 6 integral,
v
Then
_l'R
1 f+R
/Cn ey/r+R22rRcoSe/as[nedg
/
=
r~>
JO
g.v/\302\253v</v
J\\r'\\rR\\
+ R + a) e^rR^a(\\rR\\+a)].
\\e{r+R)/a(r
\342\200\224
2 r
CR
/ = ^ e~R,a/ (r + R + a)elrlar
dr + e~Rla / (rt
a*Rl
C\302\260\302\260
Jo
Jo
+ eR/a f
 r + a)rdr
{rR+a)elrlardi^.
I = eRla
'\342\231\246(JH(S)\"
[7.42]
A'=2(1'+ /)
[7.43]
that
r2m
(where E\\
samewith rn
4tt\342\202\254o
t'i
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)
+ ^002)
\\4^6o/
\342\200\242
_>\"2
>I
Section7.3:The HydrogenMolecule
Ion
307
It followsthat
(H)= Ei2\\A\\'
47T60,
^o(ri))
[7.44]
n lfo(ri)>.
[7.45]
= a(i/fo(ri) 1 foO'i)).
[7.46]
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
[749]
vpp
= ^  = ^1.
2aF
l
47T60 R
\342\200\224E\\,
of x = R/a, is lessthan
F{x)=
1+
[7.50]
and expressed
as a function
+ (l+x)e2n
i(\\(2/3)x2)e*
I
l+(l+:c+ (l/3)jrV*
j\"
(\342\200\22413.6
308
0.5
1
1.2
of a bound
FIGURE7.7: Plotof the functionF(x),Equation
7.51,showingexistence
state(x isthe distance
betweenthe protons,
in units of the Bohrradius).
value is 2.8eV (the
calculated
bindingenergy is 1.8eV, whereas the experimental
as always, overestimates
the groundstate
hence
variational principle,
never mind:The essential
underestimates
the strength of the
pointwas
to seewhether bindingoccursat all;a bettervariational functioncanonly make
the potential
well even deeper.
energy\342\200\224and
bond\342\200\224but
\342\231\246Problem
answers
f = AWo(n) toin)].
[7.52]
Without
ir^A[ir0(ri)+ ei4,ifoOl)]'Bondingoccurswhen
But the
[7.53]
Further Problems
for Chapter7
309
\342\200\2241;
FURTHERPROBLEMSFORCHAPTER7
Problem7.11
(a)
*rU) ~
harmonic
toobtaina boundon the groundstateenergy of the onedimensional
oscillator.
What is the \"best\"value of a? Compare{H)m[nwith the exact
derivative)
energy.Note:Thistrial functionhas a \"kink\" in it (a discontinuous
at +fl/2;do you needto take account
of this,as I did in Example7.3?
(b) Use \\f/(x) = Bsm(jrx/a)on the interval (~a,a)to obtaina boundon the
first excited
state.Comparethe exactanswer.
**Problem7.12
(a)
310
\"n(4\302\253
2(2//+ 1)
ma)
(b)
~l1/2
1)(4/73)
'
tf (JO
(A'2
+ b2)\"
mco
/7(4\302\253
5)(4/73)117
2(2//+ 1)
'
lim (l + ~)
ez= >!>oo
z\\\302\273
\\
is determined
and b is an adjustable
Answer:
by normalization
parameter.
11.5eV.
V(T) =
4tt\342\202\254q
/ 0),
the Coulombpotential
_ fir
[7.54]
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 usingsecondorder
perturbation
where /?
(a)
(b)
theory.
(c) Estimatethe groundstateenergy of the perturbed
system usingthe variational
a
trial
with
functionof the form
principle,
\\jf
= (cos0)^,+ (sin
\302\242)1(/1,.
[7.56]
where 0 is an
(d)
in
adjustable
parameter.Note:Writing the linearcombination
thisway isjusta neat way to guarantee that i/r is normalized.
Compareyour answers to (a),(b),and (c).Why is the variational principle
so accurate,
in thiscase?
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]
312
is \"rubberband
helium,\"in which the Coulombforcesare
simpleexample15
replacedby Hooke'slaw forces:
A
n2
H=
 ma>2\\ri Ti]2.
[7.59]
n, T2, to
=(ri+r2).
v=\342\200\224(nn),
V2
V2
[7.60]
harmonic
turns the Hamiltonian
threedimensional
intotwo independent
oscillators:
H=
\"
2m
\342\200\242\342\200\224V\342\200\236
V72
2 2
u
+
+, ma)
2
(1X)marv2
V2 +
2
2m
\"
[7.61]
(b) What
(c)
\342\200\224
+ ^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\236Z>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
438(1984).
I6S.Chandrasekhar.Astrophys. J. 100.176(1944).
and R.
Bcttcga,Am.
J.Pins.52,
FurtherProblems
for Chapter7
313
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\"
shortrange)
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 crossshaped
regionshown in Figure7.8.The \"arms\"of the
iszerowithin the cross,and infinite in
outto infinity. The potential
crosscontinue
this configuration
the shadedareasoutside.
admitsa positiveenergy
Surprisingly,
boundstate.18
(a) Showthat the lowestenergy that can propagateoffto infinity
\302\243
threshold
\342\200\224
is
8ma2'
l7The classic
330(1957):for a
paperon muoncatalyzed fusion is J.D.Jackson.Phys.Rev. 106,
more recent popular review, seeJ. Rafelski and S.Jones,ScientificAmerican, November 1987,
page 84.
l8This model is taken from R. L. Schult el
In the presence
Phys. Rev. B 39.5476 (1989).
a
bound
state
becomes
this
the
of quantum tunneling
is
reverse:A classically
unbound;
classically
state is quantum mechanically bound.
al\342\200\236
i;\302\273bound
314
a
a
l/r
(*,>>)=
value of H.
Normalizeit to determineA, and calculatethe expectation
Answer:
i 7.3. i
Example
CHAPTER 8
to the timeindependent
solutions
in one
approximate
Schrodinger
equation
idea
can be appliedto many otherdifferential
and
(the samebasic
equations,
in
to the radialpart of the Schrodinger
It is
equation three dimensions).
i
n
boundstateenergies
and tunnelingratesthrough potential
useful calculating
dimension
particularly
barriers.
ideaisasfollows:Imaginea particleof energy E movingthrough
The essential
a regionwhere the potentialV(x) is constant.
If E > V, the wave functionis of
the form
f(x) =
Ae\302\261ikx,
with
= y/2m(E V)/h.
in
315
316
ir(x) =
And
solution
\\j/
is exponential:
with* = ^2m(VE)/h.
Ae\302\261KX.
remainspracticallyexponential,
exceptthat
functionsof x.
implement.
8.1THE \"CLASSICAL\"
REGION
The Schrodinger
equation,
h1 d2xl/
Y
2m dx2
+ V(x)\\f/ = Exf/,
p2
dxl
hl
where
[8.2]
is the classical
formula for the momentum of a particlewith totalenergy E and
potentialenergy V(x).For the moment,I'll assumethat E > V(x),so that p(x)
is real;we callthisthe \"classical\"
region,for obviousreasons\342\200\224classically the
particleis confinedto this range of x (seeFigure8.1).In general, is some
\\j/
f(x) = A{x)ei(f>(x).
[8.3]
dx
and
=
d\"%
dx
[A\"
= (A'+ /A0V0.
[84]
Section8.1:The \"Classical\"
Region
317
V(x)k
E
Classical
region
the particleis confinedto the regionwhere
FIGURE8.1:Classically,
\302\243
> V(x).
Putting thisintoEquation8.1:
A\"
[8.5]
A{<t>'Y=
^A,
or
A\"
=A
(0)
 TT
h~
[8.6]
and
2A'4>'+ A4>\"
= 0. or
(a20')'= 0.
[8.7]
A20'= C2. or
[8.8]
where C
general\342\200\224so
318
*{/p(x)dx.
[8.9]
constants
can be absorbed
(I'llwrite thisas an indefiniteintegral,for
intoC, which may thereby becomecomplex.)
It followsthat
now\342\200\224any
[8.10]
solutionwill be a linearcombination
of two such
general(approximate)
terms,onewith eachsign.
and the
Noticethat
W(x)\\2 =
[8.11]
p(x)
physicalrationale.
somespecified
function, if 0 < x < a,
otherwise.
oo.
V(x)i
a
FIGURE8.2: Infinite squarewellwith a bumpy bottom.
[8.12]
Section8.1:The \"Classical\"
Region
319
1
==
\\c+emx)+ CeW**
or, moreconveniently,
M*) =
TpU)
[8131
where (exploiting
the freedomnotedearlierto imposea convenient
lowerlimiton
the integral)
1 fx
0U) =
 Jo/ p{x')dx>.
[8.141
\302\242(0)=1171 (/7
1,2.3,...)
[8.15]
Conclusion:
x)dx = rnih.
Jo
[8.16]
Thisquantization
condition
determines
the (approximate)
allowedenergies.
For instance,
if the well has aflatbottom(V(x)= 0),then p(x) = y/2mE (a
and Equation8.16sayspa = nnti,or
constant),
E\342\200\236
= nTTrr
2ma
>
is the old formula for the energy levelsof the infinite square well
yieldsthe exactanswer (the
(Equation2.27).In thiscasethe WKB approximation
so droppingA\" costus nothing).
amplitudeof the true wave functionis constant,
which
(\302\243\"\342\200\236)
an infinite
of
(Figure6.3):
V(x) =
V0.
\342\200\242
0,
oo, otherwise.
320
Vo
and
E\342\200\236
E\302\256
classical\342\200\224regime).
where f(x)
here\342\200\224any
eif{x)/tl,
is somecomplexfunction.(Notethat
intoSchrodinger's
(in the form of Equation8.1),and show
equation
that
ihf\"(f')2+ p2 = 0.
(b) Write
that\342\200\224to
first
orderin
h\342\200\224you
recover
= ln(z)f inn,
both
exponentiating
ln(\342\200\224z)
try
8.2TUNNELING
Sofar, I have assumed
that E > V, so p{x)isreal.But we can easilywrite down
the sameas
the corresponding
resultin the new classical
region(E <
V)\342\200\224it's
Section8.2:Tunneling
321
f(.x)=
[8.17]
,\302\261};f\\p<x)\\dx
VlpOOl
for example,
the problemof scattering
from a rectangularbarrier
Consider,
with a bumpy top(Figure8.3).To the leftof the barrier(x < 0),
[8.18]
is the incidentamplitude,
B is the reflected
and k = ^JlinE/h
amplitude,
(seeSection2.5).To the right of the barrier{x > a),
where A
\\}/(x)=
[8.19]
Feikx;
r = IFI2
o'
[8.20]
is(x)=
IhtiMx'Kdx'
/\342\200\242\342\226\240>
UalPix'Hdx'
V\\pixT\\
V\\P(xT\\
[8.21]
V(x),i
E
*\342\226\240
c1
Inthis casethe
necessarilyfrom
Equation
wave function
8.5,although
study
the alternative
322
1 ^^^^^^^^^^
/l\\
'
1'
A\\
/
I1
^^
\342\226\240
\342\200\224
1
1
\\
\302\260
JL **:
/ \\ / \\
\342\200\224
\342\200\224
from a high,
FIGURE8.4: Qualitativestructure of the wave function,for scattering
broadbarrier.
If the barrieris very high and/orvery wide (which is to say,if the probability
is small),then the coefficient
of tunneling
of the exponentially
term (C)
increasing
must be small(in fact, it would be zero if the barrier were infinitely broad),and
the wave functionlookssomething
of the
like3Figure8.4.The relativeamplitudes
incidentand transmittedwaves are determined
of
essentially
by the totaldecrease
the exponential
overthe nonclassical
region:
so that
_]
T=e~2y. withy =
^h
rJo
[8.22]
\\p(x)\\dx.
neutrons\342\200\224by
(1996).
Am.J.Phys.64, 1061
Tunneling,\"
8.10.
see Barry
R. Holstein.
Section8.2:Tunneling
323
/(0.,
x.
Coulombrepulsion
E\302\273
/i
r2
Nuclearbinding
\342\200\224
V0
nucleus.
radioactive
to a repulsivecoulombic
tail(Figure8.5),and identifiedthe escapemechanism
as
quantum tunneling(thiswas, by the way, the first timethat quantum mechanics
had beenappliedto nuclearphysics).
If E is the energy of the emittedalphaparticle,the outerturning point(/2) is
determined
by
2Ze~ =
,,
[8.23]
r
\342\200\236
\302\243.
The exponent
8.22)is evidently6
y (Equation
n
Y
ft
1 2Ze2
'2m
J,
\342\200\236\\
Cff
>'
k47ren
 E \\dr = y/2mE
h
\302\253),
Typically,/i
approximation
<\302\243
Vm
\"
\342\200\224
\342\200\224
V2
sin
'
\342\200\224
\\dr.
\\/ri(r2ri)
[8.24]
(sine= e):
y
= y/lmE [TT
\342\200\224\342\200\224
yn 2VnnJ =
K\\\342\200\224
Kiy/Zn
[8.25]
6In this casethe potential does not drop to zero on the left side of the barrier (moreover. Liu's is
is all \\vc really
really a threedimensional problem),but the essentialidea, contained in Equation 8.22.
need.
324
^
(^)
= 1.980MeV'/2,
[8.26]
and
Kl=(jL\\'2^= j.485fin\"1/2.
[8.27]
[8.28]
\342\200\224ely.
it hardly matters,
for the exponential
factor
Unfortunately,we don'tknow
as we go from
varies over a fantasticrange (twentyfive ordersof magnitude),
one radioactivenucleusto another:relative to this the variation in v is pretty
if you plotthe logarithmof the experimentally
In particular,
measured
insignificant.
lifetimeagainst1/n/E,the resultis a beautifulstraight line(Figure8.6),7just as
8.25and 8.28.
you wouldexpectfrom Equations
v\342\200\224but
the lifetimes
of U238and Po212,
**Problem8.4 Calculate
usingEquations8.25and
8.28.Hint:The densityof nuclearmatter is relatively constant(i.e.,thesamefor
all nuclei),so (ri)3 is proportional
to A (the number of neutronsplus protons).
Empirically,
n =(1.07fm)A1/3.
[8.29]
cd.,
(1992);
McGrawHill
it was
7Ffom David Park. Introduction to the Quantum Theory, 3rd
O.
Vol.
and
Rasmussen,\"Alpha Radioactivity,\" Encyclopedia Physics.
42,
adapted from Pcrlman
This material is reproducedwith permissionof The McGrawHillCompanies.
Springer(1957).
I.
J.
of
Section8.3:The Connection
Formulas
'
'
'
'
'
l_l
1_1
325
1_L
[MeV]
(E = me1).
\342\200\224
[8.30]
8.3 THECONNECTIONFORMULAS
In the discussion
so far I have assumedthat the \"walls\"of the potentialwell (or
326
 jt^
Linearized
potential
/^~
Turning
point nJ
>
Patching
region
X
Classical
Nonclassical
region
region
Mx) =
+ Ce^uw]t ifx<Qt
Vpm [2teUV*w
[8.31]
if .v > 0.
DeUu\\P^')\\dx\\
J\\p(xj\\
the positive
(AssumingV(x) remainsgreaterthan E for all x > 0, we can exclude
oo.)Our task is to jointhe
exponentin this region,becauseit blowsup as x
two solutions
at the boundary.
But there is a seriousdifficulty here:In the WKB
0).The true
\\j/ goesto infinity at the turning point(where p(x)
approximation,
the WKB
wave function,of course,has no suchwild
anticipated,
methodsimply failsin the vicinity of a turning point.And yet, it is precisely
the
at the turning points
that determine
the allowedenergies.
What
boundaryconditions
i
s
WKB
we needto do,then, splicethe two
solutions
together,
usinga \"patching\"
\342\200\224>
\342\200\224\302\273
behavior\342\200\224as
reading.
E+V'(0)x,
[8.32]
you
may wish to
skip it on a
first
Section8.3:The Connection
Formulas
for this
and solvethe Schrodinger
ft2
2m
327
linearized
V:
d2^P
=
ax1 + [E + V{0)xwP Etp,
\342\200\224rr
or
d2ifrp
[8.33]
tf.v
where
a=
1/3
[8.34]
ft
= ax.
[8.35]
so that
(Ftp =
~aW
[8.36]
**'\342\226\240
TABLE8.1:Someproperties
ofthe Airy functions.
Differential Equation:
\342\200\224'
= zv.
dissolutions:
IntegralRepresentation: Ai{z) =
\342\200\224
cos
(t+\302\253)*
Asymptotic Forms:
Ate)7\302\275^
 M2
z\302\2730:
\302\253
0.
yjn;
1/4
Classically,a linear potential means a constant force, and hence a constant acceleration\342\200\224the
It is ironic that
simplestnontrivial motion possible,and the starting point for elementary mechanics.
the same potential in quantum mechanics gives rise to unfamiliar transcendental functions, and plays
only
328
B/(z)
1.8
1.6
1.4
rV
A
0.5
0.4
0.3 A
0.2
0.1
1.2 /
1.0
a!
0.2tM /
0.3V
.8
'
/\\8/\\
r6 V3
/
/
^^
'
0.4
\\l
\\
/l
/~7 \\5/
y
\\l
\\
4
0.5
i
'
.6
.4
/ .2
/
2/1 12
.2
.4
.6
.8
I
3\302\275
1.0
aAi{ax)+ bBiiptx).
[8.37]
for appropriate
constants
a and h.
wave function in the neighborhood
Now \\J/p is the (approximate)
of the origin;
ourjob i.sto match it to the WKB solutions
in the overlapregionson eitherside
(seeFigure8.9).Theseoverlapzonesare closeenoughto the turning pointthat the
linearized
to
potentialis reasonablyaccurate(sothat \\j/p is a goodapproximation
the true wave function),and yet far enoughaway from the turning pointthat the
WKB approximation
is reliable.10
In the overlapregionsEquation8.32holds,and
therefore(in the notationof Equation8.34)
[8.38]
In particular,
in overlapregion2,
I \\p(x')\\dx'= Hay2Jo
I V?dx' = h(ax)3/1,
3
Jo
This is a delicatedoubleconstraint, and it is possibleto concoctpotentials so pathological that
no such overlap region exists.
SecProblem
However, in practical applications this seldomoccurs.
8.8.
Section8.3:The Connection
Formulas 329
VWKB
\302\245WKB
Vp
Turning
point
Overlap 1
overlap2
Patching
region
eW\\
*>
[8.39]
V7k*3/4vl/4
2, \\V>
2^W(ax)1/4\"
we seethat
Comparingthe two solutions,
iMv)=
a=
Alt
ah
.1\342\200\224D,
b
'
and
J*(ax)1/4
e$lax)\302\273\\
= 0.
[8.40]
[8.41]
j p{x')dx'= ^h{~ax)^
[8.42]
W = ^^71
HI \\Ber^a^'2+ Ce'Vax)y'2'
^aV4(A)i/4
L
[8.43]
'At first glance it seemsabsurd to use a laigezapproximation 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
+4
tp(x) V^(ffA)1/4sin (axy12
3
=5
_ ei:r/4gi'j(ar.t). [8.44]
iTr/A^^ax)'''L
,*.V2'
;2/_\302\273^.V2
yi\"(ff.v)'/42/
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 socalled
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.
= tin.
p(x)dx+4
\342\200\224
(/?
= I.2.
3,...),
or
[8.47]
Formulas
Section8.3:The Connection
331
considerthe \"halfharmonicoscillator,\"
For instance,
, morx~. if x > 0,
V(x) = I 2
[8.48]
otherwise.
0.
In thiscase
= mcoJxj;
p(x) = J2m[E (\\/2)mtox]
\342\200\224
\342\200\224
,v
where
\342\226\240
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 thispaiticularcasethe WKB approximation
the exactallowed
actually delivers
the odd energies
of theJulI harmonicoscillator\342\200\224see
(which are precisely
energies
Problem2.42).
332
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.
2D
sin62(x), where 9i(x) =
Mx) =
.Vt
p{x')dx'+.
4
Mij\302\243
(Equation8.46),or as
2D' sin
9\\
1
C*
7T
p{x')dx' 4
A Jxi
/
modulo
[8.51]
iV(x)
(a)
(b)
(c)
and downwardsloping
8.11:Upwardsloping
turning points.
FIGURE
l~Not
lit\342\200\224an
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 semiclassical
(largen) regime,the distinction
approximation
than in substance.
In any event, the resultis extraordinarily
morein appearance
allowedenergies
without ever
(approximate)
powerful,for it enablesusto calculate
solvingthe Schrodinger
equation,by simplyevaluating one integral.The wave
functionitselfhas droppedoutof sight.
* *Problem8.5Consider
the quantum mechanical
analogto the classical
problemof
a ball (massm) bouncingelastically
on the floor.13
(a) What is the potential
energy, as a function of heightx abovethe floor?(For
ballcan'tget there at all.)
is
negative.v, the potential
(b) SolvetheSchrodinger
equationfor thispotential,
expressing
your answer in
terms of the appropriate
Airy function(notethat Bi(z)blowsup for largez,
and must thereforebe rejected).
Don'tbotherto normalize
\\J/(x).
(c) Usingg = 9.80m/s2 and m = 0.100
kg, find the first four allowedenergies,
in joules,correct
to three significant
digits.Hint:SeeMiltonAbramowitzand
Irene A. Stegun,Handbookof Mathematical
Dover,New York
Functions,
(1970),page478;the notationis definedon page450.
(d) What is the groundstateenergy,in eV, of an electronin thisgravitational
on the average?Hint:Use
field?How high off the groundis thiselectron,
the virial theoremto determine
{x).
infinite\342\200\224the
\342\231\246Problem
approximation.
\302\243\342\200\236,
\342\226\240
Am.
bouncing ball seeJ. GeaBanacloche,
and
J. Phys. 67,776(1999)
334
\342\231\246Problem
harmonicoscillator.
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 largezform of the Airy function is goodto 1%.)
* *Problem8.9 Derive the connectionfonnulasat a downwardsloping
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
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]
barrier.
Further Problems
for Chapter8
^_^
V(x)k
^s^
I
\342\200\242\342\200\224\"\"\"^
__
335
*1
X2
FURTHERPROBLEMSFORCHAPTER8
**Problem8.11
Use the WKB approximation
to find the allowedenergiesof the
generalpowerlawpotential:
V(A)=<*.vf\\
where v
E\342\200\236
=a
(\302\253
3' (&)
\" 1/2)/2,
[8.53]
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]
8.53is not
669(1937).
(\302\253
51,
336
/\302\276
V(r)
= V0\\n(r/a)
between
(for constants
Vb and a).Treat only the caseI = 0.Showthat the spacing
the levelsis independent
of mass.Partialanswer:
\302\243,,+1
E\342\200\236
'n+3/4\"
Vftln
kn
 1/4,
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(xa)(bx)dx (y/h2
J/a x
=
Enl =
\342\200\236
\302\273
and n
\302\273
[8.56]
/2. Answer:
eV
13.6
+ VWTT)]2
[n (1/2)
[8.57]
* * *Problem8.15Consider
the caseof a symmetrical doublewell, suchas the one
We are interested
in boundstateswith E < V(0).
picturedin Figure8.13.
.\302\276
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
Xi
[8.58]
9if/, p(x)dx.
(b)
tan0=
where
[8.59]
\302\2612e0.
0=JrV \\p(x')\\dx'.
l
[8.60]
the (approximate)
allowedenergies(notethat E
Equation8.59determines
comesinto.vi and .\\'2, so 9 and 0 are bothfunctionsof
in a high and/orbroadcentralbarrier,in which
(c) We are particularly interested
case0 is large,and e^ is huge.Equation8.59then tellsus that 9 must be
very closeto a halfinteger
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
_ /
hco
1 \\
[8.63]
\302\243\342\200\236
well\342\200\224or,
0)=^(^++^).
*(x,
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 crudeonedimensional
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.
\342\200\224
<\302\243
(c)
339
Further Problems
for Chapter8
somereasonable
numbers:Vq = 20 eV (typicalbindingenergy for an
=
outerelectron),
a 1010m (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,
1997,p. 74.
CHAPTER 9
TIMEDEPENDENT
PERTURBATIONTHEORY
equation,
HV =
can be solvedby
a*
ih\342\200\224.
dt
of variables:
separation
Hir =
E\\fr.
Section9.1:TwoLevelSystems
341
an
atom.
9.1TWOLEVELSYSTEMS
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
Any
HQ^h
= Ehfh.
[9.1]
= <W.
[9.2]
statecan be expressed
as a linearcombination
of them;in particular,
W) = caylfa+cbtb.
[9.3]
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/faeiE\"t/n+ chirheiEht/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\2532
+ cfc2=l.
[9.5]
9.1.1
ThePerturbedSystem
Now suppose
we turn on a timedependent
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)irbciEh,/r'.
*(0= ca(t)iraeiE\"'/ri
[9.6]
342
Perturbation
Theory
Chapter9 TimeDependent
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)
We solveforca(t)and cb(t)by
Schrodinger
equation,
HV=ih
r) Vl/
where H =
\342\200\224.
dt
H\302\260
+ H'(t).
[9.7]
+ cb[H'fb}eiE*\"h
+cb[H%}]eiE\"\"h
+ca[H'x};fl]eiE\"'/r'
cfl[ffVfl>'\302\243\"'/A
= ih\\cafaeiE\"'lh
+ch1rheiEht/r'
CalH'Me'W+cWMe'W^h
[9.8]
\342\200\242
[tfl^\302\253f'\302\243^+c^tf\"'\"\302\243*,/A]
of
exploitthe orthogonality
\\fra
and
mH'Wj):
=
//'\342\226\240
\\}/a,
h L
\"\"
\\j/b
[9.9]
(A//,)*. Multiplyingthrough by
[9.10]
\"/j
picksout cb:
= ihcbeiEht/n.
+ cb^b\\H'\\ifb)eiEkt'h
cflM,ff'lfci>*~'\302\243','//'
and hence
cft
i[^,,+
caH'baei(E<>E\302\253\302\273l*}
[9.11]
Section9.1:TwoLevel
Systems
343
Ka = Kb=V
[912]
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]
9.1A
electricfieldE =
hydrogenatom is placedin a (timedependent)
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 twostateconfiguration\342\200\224assuming
transitions
to higher
excitedstatescan be ignored.
\342\231\246Problem
\342\231\246Problem
c\342\200\236(DI2
thissystem oscillates
between\"pure\\fra\" and \"somei/f/,.\"
Comment:Ostensibly,
Doesn'tthiscontradict
that no transitions
occurfor timemy generalassertion
No,but the reasonis rather subtle:In thiscase and
independent
perturbations?
of the Hamiltonian\342\200\224a measurement
of the
i/f/; are not,and never were,eigenstates
In timedependent
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 TimeDependent
= 1 and
= 0, and let Uai, = U*Hl = a. If
= 1.What is
and c/,(/),and checkthat \\ca(t)\\2+ c/,(/)2
the net probability(Pa*i>for t
occurs?Hint:You might
oo)that a transition
of rectangles.
want to treat the deltafunctionas the limit of a sequence
Answer:
Pa+h= s\\n2(\\a\\/h).
assumethat Ua(l =
Cb(oo)= 0, find
ca(\342\200\224oo)
\302\242//,/,
c\342\200\236(t)
\302\273
9.1.2TimeDependent
Perturbation
Theory
So far, everything isexact:We have madeno assumption
aboutthe sizeof the
of
perturbation.
But if H' is \"small,\"
we can solveEquation9.13by a process
as follows.Supposethe particlestartsout in the lowerstate:
approximations,
successive
cfl(0)=l. cfr(0) = 0.
[9.15]
ZerothOrder:
l,
[9.16]
40)(O= O.
in parentheses
to indicatethe orderof the approximation.)
(I'llusea superscript
values
To calculate
the firstorderapproximation,
we insertthe zerothorder
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 .secondorder
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 secondorder
wouldbe the integralpart alone.)
correction
'(/))\342\200\242
Section9.1:TivoLevelSystems
345
* *Problem9.4 Suppose
you don7 assumeH'aa =
H'bh
= 0.
=
Findca(t) and ci,(t)in firstorderperturbation
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,,:
[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 firstorder
perturbation
and
to
Comment
on
answer
(a).
compareyour
theory,
any discrepancies.
\342\231\246Problem
generalcaseffl(0)= a, q,(0)= h.
**Problem9.6 Calculate
ca(t) and ct,(t),to secondorder,for a timeindependent
(Problem9.2).Compareyour answer with the exact result.
perturbation
'Noticethat
if the perturbation
the two states.
true
c\342\200\236
is modified in cvciy even order, and q, in every odd order; this would not be
included diagonal terms, or if the system started out in a linear combination of
346
Perturbation
Chapter9 TimeDependent
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]
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\273oo))l
i;y
(w()+w)l' ei(on)(o)t
i
\342\226\240]*\342\200\242
[9.25]
CO
\342\200\224
COQ
+ co
a>o
;\302\273
[9.26]
\342\200\224co\\.
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]
Pa+b(t) =
/ \\.7
\\Cb(T)\\
\\Vab\\2
h2
 co)t/2]'
sin2[(&>o
(coqcoy\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.
TwoLevelSystems
Section9.1:
347
PMI
9.1:
FIGURE
Transition
as a functionof time, for a sinusoidal
probability
(Equation9.28).
perturbation
transition
probabilityoscillatessinusoidally
(Figure9.1).After risingto a
of \\Vab\\2/h{cooco)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 TimeDependent
down beforeit
jji
\"ha
Uol
Hha^~e
\342\200\242
Tit
Hab
_
vab
\342\200\224e
TO ?Q1
\\i0\\
l929J
\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
(a)
[9.30]
+ (Wab\\/h)2.
yJ(oJCO0)2
never exceeds
(b)
the transition
Determine
probability,Pa~*h(0,and show that
= 1.
1.Confirmthat \\ca(t)\\2+ c/,(Y)2
(c)
(d)
At
it
OF RADIATION
9.2 EMISSIONAND ABSORPTION
9.2.1Electromagnetic
Waves
wave (I'll refer to it as \"light,\"though it couldbe infrared,
electromagnetic
consists
ultraviolet,
microwave,Xray, etc.;thesedifferonly in their frequencies)
electricand magneticfields
of transverse (and mutually perpendicular)
oscillating
of a passinglightwave, responds
(Figure9.3).An atom,in the presence
primarily
to the electriccomponent.
If the wavelength is long(comparedto the sizeof the
An
Section9.2:Emission
andAbsorption
of Radiation 349
Electric
field
Magneticfield
FIGURE9.3: An electromagnetic
wave.
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]
[9.33]
to zero(seeProblem9.1for someexamples).
Thislicensesour usual
integrates
that the diagonalmatrix elements
of H' vanish.Thus the interaction
of
assumption
3For visible light
is reasonable:
but
the field.
it
A.
would
~ 5000A.while the
not
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//cformula for a manifestly timedependent 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.
electrodynamics,
9.33
9.21
350
Perturbation
Chapter9 TimeDependent
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
\\
/
(cooco)~
In thisprocess,the atom absorbsenergy
E(l = hcoQ from the electromagnetic
field.We say that it has\"absorbed
a photon\"(Figure9.4(a)).(As I mentioned
the word \"photon\"really belongs
to quantumelectrodynamics
[the quantum
field],whereas we are treating the fielditself
theory of the electromagnetic
But thislanguageis convenient,
as longas you don'treadmoreintoit than
is really there.)
I could,of course,gobackand run the wholederivationfor a system that starts
offin the upperstate(crt(0) = 0, c/,(0)= 1).Doit for yourself,if you like;it comes
outexactly the same\342\200\224except that thistime we'recalculating
Pb*a= \\ca (OI,the
down to the lower level:
probabilityof a transition
,._,<\342\200\236
\342\200\224
\302\243/,
earlier,
classically.
JWO = ({J^)~
h
J
p.36]
\"\342\226\240*(\302\253.\302\253*/2]_
\\
(cooco)~
way\342\200\224'all
\342\200\224coo
\342\200\224coo
iscalledstimulatedemission.
(a) Absorption
(b) Stimulatedemission
predicted
by Einstein,
emission
(c) Spontaneous
atoms:(a) absorption,
and Absorption
Section9.2:Emission
of Radiation
351
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,
5.113),
dates
352
Perturbation
Theory
Chapter9 TimeDependent
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 nonmonochromatic,
electromagnetic
unpolarized,
if it were immersed
for instance,
from all directions\342\200\224such as it wouldencounter,
in thermal radiation.
9.2.3IncoherentPerturbations
wave is10
The energy densityin an electromagnetic
u
where Eq
jEl
[9.37]
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)=
\342\200\224
f\302\260\302\260
\342\200\224rl^l2
P(CO)
using
(coq
tt>)2
quantum
\"scat.ofthepants\"
[9.39]
see
electrodynamics,
I0D.Griffiths.
= (e0/2)E2+(\\/2na)B2.
electricand
n
= (qE~=
\302\2530^5
cos\"(to/).
incoherent.
full
(<?o/2)\302\243^.
and Absorption
Section9.2:Emission
of Radiation 353
(Figure9.2),whereas
as well replacep(a))by p(a>o),and take
a\302\273o
outsidethe integral:
Pb^aiO=
o
;(o>o cor
/
Jo
\342\200\224^P(too)
\342\202\254Qtr
do).
\342\200\224
[9.40]
Loo
dx=n.
[9.41]
^fp(w0)r.
[9.42]
\342\200\224
we find
Pb^aif)=
60\302\253\"
it
 Re(/i)n +
;}'
i\\m(p.)
n\\~
\342\200\242
in
general it
will
be complex.
Since
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:
lA2
l/\302\273.r2
+ l/Iv2+
l/\302\273;2.
354
Perturbation
Chapter9 TimeDependent
Theory
Za
n
^.0
^^
\\
/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/*cos0sin0
cos39
An
(2tt)=
/l2.
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
coq =
\342\200\224
(\302\243/,
Ea)/hP
transition
strength
of
the perturbation
at
the
transition
frequency.
Section9.3:Spontaneous
Emission 355
9.3 SPONTANEOUSEMISSION
p(cdq)\342\200\224call
number
told,then,
^
at
= NhA
NhBhf,p(coQ)+ NtlBllhp(co()).
[9.48]
followsthat
P(coo)=
xp
(Na/Nh)Bah
[9.49]
\342\200\224.
Blm
in thermal equilibrium
at temperature T, is
number of particleswith energy
to the Boltzmann
factor,expiE/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*\"<*'BahBba
of thermal radiation:
p((o)=
^ . ..a?_
h
[9.52]
we conclude
that
Comparingthe two expressions,
Bab = Bba
'\"'Normally
I'd use R
Einstein's notation in
^Assume that
this
for a
transition
context.
rate,
but out
[9.53]
of deferenceto
dcrAlic
everyone follows
N(, and N/, are very large, so we can treat them as continuous functions of time
and ignore statistical fluctuations.
Charles Kittel and Herbert Krocmcr.Thermal Plnsirx.2nd ed. (Freeman.
l6See,for example.
New York. 1980),Chapter
3.
356
Perturbation
Theory
Chapter9 TimeDependent
and
A
[9.54]
^1Bha.
(A)\342\200\224which
for\342\200\224in
3<?o\302\253\"
[9.56]
...
emission
Section9.3:Spontaneous
Emission 357
9.3.2TheLifetimeof anExcitedState
rate for spontaneous
Equation9.56is ourfundamentalresult;it givesthe transition
emission.
now, that you have somehowpumpeda largenumber of atoms
Suppose,
intothe excitedstate.As a resultof spontaneous
thisnumberwill decrease
emission,
as time goeson; specifically,
in a time interval dt you will losea fractionAdt
of them:
dNb =
ANhdt,
[9.57]
there is no mechanism
to replenishthe supply).17
(assuming
Solvingfor Nb(t),
we find:
Nh(t)
= Nh(0)eA';
[9.58]
with
evidently the number remainingin the excitedstatedecreases
exponentially,
a time constant
r =
[9.59]
j.
A
\342\200\224>
...
to
a chargeq is attachedto a springand constrained
Example9.1 Suppose
alongthe .vaxis.
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
+
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 TimeDependent
where co is the natural frequency of the oscillator.
(I no longerneedthisletterfor
the frequency of the stimulating
son'
But we'retalking aboutemission,
radiation.)
must be lower than n\\ forour purposes,
then.
and the
occuronly to statesonesteploweron the \"ladder,\"
Evidently transitions
frequency of the photonemittedis
coq =
E\342\200\236E\342\200\236>
(n +
\\/2)lico(n'+\\/2)hco
= (/7
h
\342\200\224
)co =
co.
L9.62J
the systemradiates
The
oscillator
Not surprisingly,
at the classical
frequency.
transition
rate (Equation9.56)is
A
1
= nq~orv
[9.63]
^^
*=
(9.64]
nq^co
\342\226\240>
q~co07T
C\302\260
\342\202\254()111
P= /JC0\\ \\EhaA.
[9.65]
For comparison,
let'sdeterminethe average powerradiatedby a classical
oscillator
with the sameenergy.According
to classical
the power
electrodynamics,
radiatedby an accelerating
chargeq is given by the Larmorformula:18
p = crcr_
OJTfQC
[966]
Fora harmonicoscillator
with amplitude
and the acceleration
.\\'o. v(/) = xq cos(cot),
is a = \342\200\224xoco2cos(cot).Averagingovera full cycle,then,
~>
p=
.1 4
<r*o\302\253>
\\2rreoc3
isSec,for example.
Griffiths (footnote 10).
Section 11.2.1.
Section9.3:Spontaneous
Emission 359
But the energy of the oscillator
is E =
>
classical
limit (h
\342\200\224>
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 109secondsfor 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
elements
are
(n'l'm'\\r\\nlm).
I9ln fact, if wc
identical.
expressP in
terms of
the
two
formulas arc
360
Perturbation
Chapter9 TimeDependent
Theory
Cleverexploitation
of the angular momentum commutation
relationsand the heron
mitieity of the angular momentum operatorsyieldsa setof powerfulconstraints
thisquantity.
[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]
= {n'l'm'\\{LzxxLz)\\nlm)
(/i7'//?'[L,.v]/i/w>
= ih{n'l'm'\\y\\nlm).
= (in m)h{n'l'm'\\x\\nlm)
\342\200\224
Conclusion:
v\342\200\224you
[9.70]
{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,
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]
of (the z component
;20conservation
of)
momentum
t
hat
the
atom
whateverthe
takes
away.
angular
requires
giveup
photon
\342\200\224
[9.74]
= 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'/Vr/7/m).
= H4[l'(l'
[9.75]
Conclusion:
+1)1(1+ 1)]:
[9.76]
But
+
[I'(l'+l)l(l
\\))
= (l' + l+\\)(l'I)
and
so the first
[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 TimeDependent
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]
0\342\200\224this
selection
\342\200\224
possibility\342\200\224though
to lowerenergy
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 lowerenergy
state
with /= 1.It is calleda metastablestate,and itslifetime
is indeedmuch longer
than that of, for example,
the IP states(1^211,
states
^210^ and 1^21 1)Metastable
do eventually decay,by collisions,
or by what are (misleadingly)
calledforbidden
transitions
transitions
emission.
(Problem9.21),or by multiphoton
\342\231\246Problem
that
 
\342\200\242
Further Problems
for Chapter9
363
then {n'l'm'\\x\\nlm)=0.
(b)
(c)
FURTHERPROBLEMSFORCHAPTER9
**Problem9.15Developtimedependent
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,
Generalize
Equation9.6to read
*(0=
\302\243cII(f)iM~/\302\243,,,/A.
[9.81]
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 firstorder
perturbation
theory)
C'N
(0 =
H'NN(t')dt'.
17/
Jo
n
[9.84]
364
Perturbation
Chapter9 TimeDependent
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)
[986]
\342\200\242
EMy
sinusoidal
functionof time:H' = V cos(cot).
Making
the usual assumptions,
occuronly to stateswith energy
show that transitions
Em = E^ + ftco, and the transition
probabilityis
H' is a
(d) Now suppose
Pn^m =
\\Vmn\\2
/,,J
Em + ftco)t/2ft]
,,
(EN  EM
\342\200\224
sin2[(\302\243w
\302\261
nco)
[9.87]
a multilevel
in incoherent
(e) Suppose
system isimmersed
electromagnetic
Section
9.2.3
that
the
transition
as
a
s
how
rate for
Using
guide,
stimulated emission
is given by the sameformula (Equation9.47)as for a twolevelsystem.
radiation.
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**
your answers.
FurtherProblems
for Chapter9
365
\342\231\246Problem
Vq
<\302\243
ratio
* * *Problem9.20 Magneticresonance.A spin1/2
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
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
= y/(a)a)o)2+ n2
[9.91]
366
Perturbation
Theory
Chapter9 TimeDependent
(d)
If the particlestarts out with spinup (i.e.,ciq = \\, bo = 0), find the
probabilityof a transitionto spindown, as a function of time.Answer:
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 gfactorof 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
[9.93]
\342\226\240
<\302\243
\342\200\242
we considered
The first term givesriseto the allowed(electricdipole)transitions
in the text;the secondleadsto socalled
forbidden(magneticdipoleand electric
quadrupole)transitions
(higherpowersof k r leadto even more \"forbidden\"
associated
with highermultipole
transitions,
moments).21
\342\200\242
(a)
. r)(k
Rb^a = J^\\{a\\(H
1For a systematic treatment
\342\200\242
r)\\b)\\2.
[9.95]
367
Further Problems
for Chapter9
oscillator
the forbiddentransitions
(b) Show that for a onedimensional
go from
level n to level n
and k)
is
\342\200\224
fiqcon(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 twophoton
and the lifetime
emission,
is abouta tenth of a second.22)
4^\342\200\224
+ 1 if /' = /+1,
2/ + 1
{
/
earl x
12/1 if
I' =
[9.97J
11.
where
1=Jo/
[9.98]
r3R\342\200\236i(r)R\342\200\236r(r)dr.
\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 InjLjg; 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
368
secFrank
discussionof classicaladiabatic processes,
S.Crawford. Am. J.
Section10.1:
TheAdiabatic
Theorem
369
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)
BornOppenheimer
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]
*'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)
If
* * *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]
^i(x.t)=
J2c\342\200\236<i>\342\200\236(x.t):
[10.4]
(a)
Checkthat Equation10.3satisfies
the timedependent
Schrodinger
equation,
with the appropriate
boundary conditions.
2S.W. Doescherand M. H.Rice.Am. J. Plm. 37, 1246
(1969).
Section10.1:
TheAdiabaticTheorem
(b)
371
*(,.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]
$(0=
(Ei(t')dt'.
fi
[10.6]
Jo
E\342\200\236(t)
10.1.2
Proofof theAdiabaticTheorem
but
The adiabatic
theoremis simpleto state,and it soundsplausible,
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,JT 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.,AddisonWesley.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
%(t) =
[10.8]
ifr\342\200\236eiEnt/h.
are
If the Hamiltonian
and eigenvalues
changeswith time,then the eigenfunctions
themselves
timedependent:
HMW) = EnWn{t).
but they
[10.9]
stillconstitute
set
(at any particularinstant) an orthonormal
(iMOIlMO)=*!,,,,.
[1010]
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 timemdependent
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]
= 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,.
[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\236i/o,),
it
[10.18]
\302\243,\342\200\236)(i/o\342\200\236i/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^.
C,\342\200\236(l/r,\342\200\236l/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]
955(2000)!
(V/mlV/,\302\273}
not
trivial.
SecA. C.Aguiar
yjfw
entails
Pinto et
((l/tlt)(if\342\200\236i\\',l'm}
Milium)+
374
Chapter10 TheAdiabaticApproximation
(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
Section10.1:
TheAdiabaticTheorem
375
'
sin(a/2)J
/cos(\302\253/2A
[10.30]
The exactsolution
to the timedependent
Schrodinger
equationis (Problem10.2):
i
\\cos(Xt/2)
^ sin(A//2)lcos(a/2)eico,/+ ^ 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
Evidently the
=
<x(/)lx(\302\273)l2
co
\342\200\224
. a sin
. (Xt
sin
\\2
[10.34]
\342\200\224
\\2
/?/(\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
out with
spin
376
Chapter10 TheAdiabaticApproximation
2n/l
4n/k
6k/X
8n/X
* *Problem10.2Checkthat Equation10.31
satisfies
the timedependent
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
northsouth.
Now I carry it (stillswingingnorthsouth)
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.
0 = A/R2 = Q.
[10.36]
polygon.
378
Chapter10 TheAdiabaticApproximation
2A
in
FIGURE10.7: Path of a Foucaultpendulum,
ofoneday.
the course
Q= sin6
d6d\302\242
= 2n(cos6)$
=2tt(\\cos60).
[10.37]
Relative to the earth (which has meanwhile turned through an angleof 2n), the
of the Foucaultpendulumis In cos
resultthat is ordinarily
daily precession
obtainedby appealto Coriolisforcesin the rotatingreference
frame,9 but is seen
in thiscontext
to admit a purely geometrical
interpretation.
A systemsuchas this,which doesnot return to its original
statewhen
arounda closedloop,is saidto be nonholonomic.
(The \"transport\"in
transported
questionneednot involvephysicalmotion:What we have in mind is that the
parametersof the system are changedin somefashionthat eventually returns them
to theirinitialvalues.)Nonholonomic
systemsare ubiquitous\342\200\224in a sense,every
device:At the end of eachcyclethe car has
cyclicalengineis a nonholonomic
movedforward a bit,or a weight hasbeenliftedslightly,or something.
The idea
has even beenappliedto the locomotion
of microbes
in fluidsat low Reynolds
number.10
My projectfor the next sectionis to study the quantum mechanics
of
nonholonomic
The
is
does
adiabatic
essential
this:
How
the
processes.
question
are
final statedifferfrom the initialstate,if the parametersin the Hamiltonian
carriedadiabatically
around someclosedcycle?
6\302\276\342\200\224a
Section10.2:Berry'sPhase
379
10.2.2GeometricPhase
In Section10.1.2I showedthat a particlewhich startsout in the /?th eigenof H(t),
in the /?th eigenstate
stateof #(0) remains,under adiabatic
conditions,
its wave functionis
phasefactor.Specifically,
pickingup only a timedependent
(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 socalled
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
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 parameterspace,
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
1
vi/0
1 T
+ _vi/0e'r,
[10.46]
In thiscase
M2 =
=
d*ol2(lWr)(l + *'T)
\\m\\2{\\
+cosD= vI>02cos2(r/2).
[10.47]
(footnote
Shapere
Section10.2:Berry'sPhase
381
\302\242=
3>
/ (V x A)
\342\200\242
da
/,\342\226\240
i
\"flux\"
\342\200\242
x A), and
dr.
[10.49]
of a \"magneticfield\"
= /V*x<iMV*iM,
\"B\"
[1050]
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?
\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)
= eimtl2eii^o,a)tiieio,t/ix+{l)
+i
CO
\342\200\224
. I(CO\\t
. a sin
sin
V
co\\
e+'0)t/2x(t).
[10.53]
\342\200\224>
MO =
[1054]
Section10.2:Berry'sPhase
383
so the geometric
(where E+ = hu>\\/2, from Equation10.29),
phaseis
y+(t)
= (cosff1)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]
(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+
\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=2Sr
[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]
\342\200\224sQ.)
10.2.3TheAharonovBohm
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
<p
for
Section10.2:Berry'sPhase
385
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]
H=
I/I\342\200\224
\\
\342\200\224
[10.65]
ijVqA) +cJ<P.
V
condition
\342\200\242
= 0),14
2kr 0.
A=r\342\200\224
(r>a),
[10.66]
H=
[10.67]
W.
Aharonov
and
386
Chapter10 TheAdiabaticApproximation
passes.
\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
\302\243^(0)
[10.68]
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\261V2^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 twofolddegeneracy
Thesolenoid
ofthe beadonaring
(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 timedependent
The (timedependent)
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]
V* = eig{iVgW+
but Vg
= {q/h)A,so
lVq\\
e''\302\253(VvI>');
* = t^VV.
[10.78]
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 (curlfree)
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!
Arfr =
=
7jth /(\302\276M d<t>)
q<$>
[10.81]
\302\261
~2h~
Beam
recombined
Solenoid
10.11:
FIGURE
The AharonovBohmeffect: The electron
beam
passingeither sideof a longsolenoid.
splits,with half
Section10.2:Berry'sPhase
389
(rR)
phasedifference=
[10.82]
interference
which has been
Thisphaseshift leadsto measurable
(Equation10.47),
confirmedexperimentally
and others.16
by Chambers
As Berry pointedout in his first paperon the subject,
the AharonovBohm
effectcan be regardedas an exampleof geometric
phase.Supposethe charged
particleis confinedto a box(which iscenteredat pointR outsidethe solenoid)
by
a
a potentialV(r
moment
we're
to
10.12.
(In
Figure
going transport
the boxaroundthe solenoid,
soR will becomea function of time,but for now it is
of the Hamiltonian
are determined
by
just somefixed vector.)The eigenfunctions
\342\200\224
R)\342\200\224see
1
2m
We
,>
+ V(rR)
VgA(r)
i
ifr\342\200\236
= E,,1//,,.
[10.83]
where17
g
= e,gyjr'n.
l fA(r')
[10.84]
[10.85]
\342\200\242</!\342\200\242'.
390
Chapter10 TheAdiabaticApproximation
and i/r' satisfies
the sameeigenvalue
only with A
equation,
It2
2m
\342\200\224>
0:
, + V(rR)
[10.86]
V2
\342\200\224
\\fr'lt
\\fr\342\200\236)
= V*
[VV/,(r R)]
= i
 R).
A(R)^^(r R) + <r*V*#,(r
we find
=
=
 jw'n{r  R)]*V^(r
\302\273a(R)
R) d3r
d\\
[10.87]
\342\200\224V,
of the Hamiltonian
eigenstate
+ V, which we know from Section2.1is zero.So
an
[10.88]
that
we conclude
Putting thisintoBerry'sformula (Equation10.45),
YniT)
f
A(R)
\342\226\240dR=j
j{VxA)da=
q<$>
[10.89]
'^Incidentally,in
is almost
an identity:
this
\"B\"
(Equation 10.50)
Further Problems
for Chapter10
the enclosed
flux
remainsgaugeinvariant.
measurable\342\200\224only
391
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,slightlyoffcenter:19
V{x) =
f(t)8 (x
  e) .
\302\260
time t. Answer:
(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/)
this
expression
^Julio GeaBanaclochc,
Am. J. Pliys. 70.307 (2002)usesa rectangular barrier:the deltafunction
version was suggestedby M. Lakner and J. Peternelj.
Am. J. Phyx. 71.519
(2003).
1
392
Chapter10 TheAdiabaticApproximation
(f)
** *Problem10.9Supposethe onedimensional
harmonicoscillator(massm,
to a driving forceof the form F(t) = mcofit),where fit)
frequency co) is subjected
is somespecified
function(I have factoredout mar for notationalconvenience;
is
of length).The Hamiltonian
fit) hasthe dimensions
\302\2532
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)itt')]dt'.
[10.91]
to the (timedependent)
(b) Showthat the solution
Schrodinger
equationfor this
it startedout in the /7th stateof the undriven oscillator
oscillator,
assuming
\\ff\342\200\236(x)
as
,1,/^
q>ix,t)= ,t
yrnix
\342\200\224
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
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
/.
(Equation
by
parts.
20GeaBanaclochc
(footnote 19)discussesthe evolution of the wave function
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
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 timedependent
):
geometric
phasefactor (Equation10.21
(a)
(b)
c,\342\200\236(0)
 jf' U,n{t')A^l(r')\\^('')e'(*(r')fl\302\253tf'))
,/,'. po.95]
cHi(t)= J^y/mf
f{t')e^'dt'.
2h
V
Jo
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:Elastichardsphere
scattering.
Example
= 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]
To my ear.the
'Thisis terrible language: D isn't a differential, and it isn't a crosssection.
would attach more naturally to da.But I'm afraid we'restuck with
words \"differential crosssection\"
this terminology. I should also warn you that the notation
D($) is nonstandard: Mostpeoplejust call it
a
11.3
l
ook
makes
like
da/dQ\342\200\224which
tautology. I think it will be less confusing if we give
Equation
the differential crosssection
its own symbol.
396
Chapter11 Scattering
da
*
I
\302\243
'',
FIGURE
da = D(0)dQ.
[11.3]
D{9) sing d$
[11.4]
negative\342\200\224hence
so
(
. /e\\
ficos(0/2)/*sin(g/2)\\= &
2
sing V
) 4
[11.5]
[11.6]
of 6.
Thisexampleis unusual,in that the differentialcrosssection
is independent
The totalcrosssection
is the integralof D(6),overall solidangles:
D(6)dQ;
\342\200\242/
[117]
11.1:
Introduction
Section
397
isscattered
by the target.
a = (R2/4)J
dQ = jiR2,
[11.8]
\"hitormiss.\"
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
.
^) = 1dN
[11.10]
11.1
* * *Problem
Rutherfordscattering.An incident
ofcharge<? and kinetic
particle
offa heavy stationaryparticleof chargeqj.
energy E scatters
(a)
= (qiqi/SjteoE)cot(6/2).
the differential
crosssection.
Determine
Answer:
scattering
Answer: b
(b)
qm
D(0)=
J6tt\342\202\2540E
sin2{9/2).
[11.11]
B.Marion
Fort
Worth,
and
you
might
want
to refer to a
book on classical
mechanics,such as Jerry
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.
= 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 threedimensional
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].
9.
Section11.2:
PartialWave
Analysis
399
vdt
FIGURE
time dt.
differential
crosssection.
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.
solidangledQ:
dP =
^scattered2dV =
\\A\\2\\
f\\2
r*
\\J
(vdt)r2dQ.
da = \\f\\2dQ,and hence
D(9)=
= \\f(9)\\2.
^d\\l
[11.14]
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
R{r)
eikr
,
r
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
functions:
\302\253(/\342\226\240)
= Arjiikr)+ Bm,{kr).
[11.18]
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:
[11.19]
11.1.large
At
(i),(kr)
/i
.(2),
/\\
R{r)~~hl,l){kr).
[11.20]
0), is
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)
<p
402
Chapter11 Scattering
m
/2/+ 1
=
y>.0)
n
y^/>,(cos0).
[11.22]
yjr{r.9)=
\342\200\242
eikz+ k
[11.23]
partialwave amplitude.
Now, for very
so
11.1),
Jkr 1
[11.24]
\\l/{}\\9)*xA\\e'KZ
where
CO
/(0)= 2^(2/+l)tf,P,(cos0).
[11.25]
/=()
D(0)=
+ l)aiai'^/(cos#)P/'(cos0).[11.26]
/(0)2= J2Yl{2l+i){2l'
r
and the totalcrosssection
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)isdistinctlynonzero),
The onlyproblemis
(Equation11.23),
boundary conditions.
usingthe appropriate
All that
\302\253/,
PartialWave
Section11.2:
Analysis
403
\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).
Example11.3Quantumhardspherescattering.Suppose
oo, for < a,
V(r) =
0, for r > a.
/\342\200\242
[11.29]
[11.30]
ir(a,6)=0.
so
[11.31]
oo
\302\243V(2/
/=0
+ 1)\\ji(ka) + ika,/iJ'^Jta)]Pi(cos9)= 0
[11.32]
ji(ka)
01=1=77 .
khy\\ka)
[11.33]
6For a guide to the proof, seeGeorgeArfken and HansJurgen 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 totalcrosssection
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 lowenergyscattering: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
crosssection
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
crosssection
is
for low energy hardsphere
scattering.
Surprisingly,
areaofthe
crosssection\342\200\224in fact, a is the totalsurface
fourtimesthe geometrical
of longwavelength
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 headoncrosssection.
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 lowenergy
delta**Problem11.4Consider
scattering
functionshell:
V(r)
=a8(ra),
the scattering
Calculate
where a and a are constants.
amplitude,
/(0),the
crosssection,
D{6),and the totalcrosssection, Assume ka 1,so that
differential
a.
<\302\243
Section11.3:
PhaseShifts
405
\302\253o
11.3PHASESHIFTS
Consider
first the problemof onedimensional
from a localized
scattering
potential
=
<
on
the
a
jc
halfline
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)
[11.37]
a).
[11.38]
\342\200\224A,
V^o(a')=
(eikx
 e~ikx)
(V(x)= 0).
\342\200\224a)
[11.39]
takesthe form
[11.40]
FIGURE11.7:Onedimensional
froma localized
scattering
potentialboundedonthe
an
infinite
wall.
right by
406
Chapter11 Scattering
the phase
The whole theory of scattering
reducesto the problemof calculating
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 threedimensional
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
(Jf
\302\273
D H142]
Sofor larger
~ (I)'e\"'*rl
=
tf % &{2l^l)
\
\e'kr
J Pi(cos6) (V(r) 0).
I
2ikr
[11.43]
(_!/<,<*>\342\200\242]
[11.44]
wave (dueexclusively
to the /7, component
Thinkof it as a converging
spherical
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\\
is the
talking
\"partial
about
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
we find9
(Equation11.44),
k (^  0 = \\*sinW
[11.46]
It followsin particular(Equation11.25)
that
oo
[11.47]
/=0
and
(Equation11.27)
CO
Art
a = ~J2(2l+ l)sm2(8,).
[11.48]
/=0
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)
Answer:
Ae lika
/~\\i
kik'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).
/kr).
408
Chapter11 Scattering
wave has the sameamplitude
asthe incidentwave.
(b) Confirmthat the reflected
(c)
Answer: 8
very
\342\200\224ka.
(Example11.3)?
Problem11.7
Findthe 5wave (/ = 0)partial wave phaseshift 8o(k)forscattering
from a deltafunction
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 timeindependent
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
[1150]
[,,.51]
S3(r).
[11.52]
tf3r0.
^(r) = f G(r 1())0(10)
[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) =
f 83(rr0)Q(r0)d*ro=Q(r).
[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)= 13feisrd\\
[11.56]
and (seeEquation2.144)
so Equation11.52says
It follows1'that
(2jt)V2(*252)'
we find:
Putting thisbackintoEquation11.54,
\302\253(s)
G(r)
10
Warning:
(2;r)3J
skip straight
[11.
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
\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_*>
k2s2ds.
[11.60]
G(r)=
=
seisr
oo
se
\342\200\224isr
ds
ds
+ k)
/oo
oo (sk)(s
^h~h)
[11.61]
f(z) dz =
2jrif(zo),
/  zo)
(z
[11.62]
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
411
lm(s)
= +k
s^7
s=k
Re(s)
.f
sk
\342\200\224k
up a minus sign):
h=
se isr
j Sk
s+k
ds =
se isr
\342\200\224Ini
Sk
= meikr
\342\200\224
s=k
[11.64]
Conclusion:
G(r)=
Jkr
=
ik [(\"\"*) (\"\"\"')] 4JIT
[11.65]
(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 freeparticleSchrodinger
equation,
(V2+fc2)Vo= 0.
[11.68]
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^> rofor all points
i/r(r) at pointsfar away from the scattering
that contribute
to the integralin Equation11.67,
so
r r02= r2 + r2  2r
and hence
\342\200\242
r0 = r2 (l
rr0= rrr0.
 2^).
[11.69]
[11.70]
Section11.4:
The BornApproximation
413
Let
k = kr:
then
^ eikreikro
^/Ar\342\200\224r0
and therefore
[11.71]
,'Arr0 Jkr
rro
e ikro
[11.72]
[11.73]
\\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~ 2ntt
Thisis in the standardform (Equation11.12),
and we can readoff the scattering
amplitude:
[11.76]
f<6<*) = ^7T7 eik'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]
/(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
FIGURE
approximation:pointsin
direction.
the scattered
in
k
incidentdirection,
11.11;
\342\200\224
the process.)
/(0.0)=
,l
2nh
[11.80]
on r, sincethereis no likelihood
of confusion
at thispoint.)
(I droppedthe subscript
scattering.14
Suppose
Example11.4 Lowenergysoftsphere
V0. if /* < a.
V(r) =
0. if r > a.
In thiscasethe lowenergy
amplitudeis
scattering
[11.81]
[11.82]
m2 ~ /2//?%'
dQ
3/r
da
a=4,T
' 2m
Voa
\\
[11.83]
3\\2
[11.84]
.~3fV
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]
(k'k)
= Kr0coseo.
[11.86]
eiKr\302\260c\302\260se^(ro)rtsm60drod6odfo.
[11.87]
\342\226\240r0
Then
^y
f(6) = 27r/r Jf
/(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]
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]
416
Chapter11 Scattering
or (usingEquations11.89and
11.51):
/((9)=
q\\qi
__.
[11.93]
ll\"\"2
sin2(0/2)
167re0E
\342\200\224
q\\qi
,2
[11.94]
16^e0^sin2(^/2)
11.11).
which is precisely
It happensthat for
the Rutherford formula (Equation
the Coulombpotential,
classical
the Bomapproximation,
and quantum
mechanics,
fieldtheory all yieldthe sameresult.As they say in the computer
business,the
Rutherford formula is amazingly \"robust.\"
\342\231\246Problem
in the Bomapproximation,
forsoft11.10
Findthe scattering
amplitude,
reducesto
11.11
to confirmthe expression
Problem
Evaluate the integralin Equation11.91,
on the right.
**Problem11.12
for scatteringfrom a Yukawa
Calculatethe total crosssection
potential,in the Bom approximation.
Expressyour answer as a functionof E.
\342\231\246Problem
in Problem11.4,
11.13
For the potential
(a)
(b)
in the
with the answer toProblem11.4,
(c) showthat your resultsare consistent
appropriate
regime.
11.4.3
TheBornSeries
is similarin spiritto the impulseapproximationin
The Bom approximation
classical
we beginby pretending
theory.In the impulseapproximation
scattering
Section11.4:
The BornApproximation
417
Actual
trajectory
Scatteringcenter
11.12:
FIGURE
Theimpulse
undeassumes
that the particlecontinues
approximation
the transversemomentumdelivered.
flected,and calculates
and computethe
particlekeepsgoingin a straight line (Figure11.12),
transverseimpulsethat wouldbe deliveredto it in that case:
that
the
I
[11.95]
F\302\261dt.
If the deflection
is relatively small,thisshouldbe a goodapproximation
to the
transversemomentum impartedto the particle,and hencethe scattering
angleis
6 = tan1(I/p),
[11.96]
is the incidentmomentum.
Thisis, if you like,the \"firstorder\"
impulse
order
is
what
with:
no
we
started
deflection
at all).
zeroth
(
the
approximation
the incident
Bornapproximation
Likewise,in the zerothorder
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
firstordercorrection
of higherorder
which presumably convergeto the exactanswer.
corrections,
The integralform of the Schrodinger
equationreads
where p
V(r) = Vo(r)+
where \\}/o
J r0)V(r0)f(ro)d3r0,
g{v
[11.97]
is the incidentwave,
m elkr
g{r)= 27th2 r
[11.98]
\342\200\224f
the factorIm/ti1,for
is the Green'sfunction(intowhich I have now incorporated
and V is the scattering
convenience),
Schematically,
potential.
^ = ^()+ f gVf.
for \\j/, and plugit
Supposewe take thisexpression
f = ^+
gV^o +
[11.99]
in under the integralsign:
JJ gVgVf.
[11.100]
418
Chapter11 Scattering
=
\302\245o
11.13:
ofthe Bornseries(Equation11.101).
Diagrammaticinterpretation
FIGURE
= t0 +
gV^o +
J J gVgV^o+ J J J gVgVsVifa+
. [11.101]
11.15
Findthe scattering
forlowenergy
scattering
softsphere
amplitude
* * *Problem
in the secondBornapproximation.
Answer:
\342\200\224
(2mVbrt3/3/T)[l(4mVQa2/5h~)].
\342\200\224
11
FURTHERPROBLEMSFORCHAPTER
** *Problem
 trk Joo
/
irn
\342\200\224
C\302\260\302\260
eik\\xx\302\273W(x0)x!/(xo)dx0.
[11.102]
Further Problems
for Chapter11
419
to developthe Bom
Useyour resultin Problem11.16
11.17
* *Problem
for onedimensional
(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 onedimensional
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
a = ^Im(/(0)).
[11.104]
AT
Hint:UseEquations11.47and 11.48.
to determine
the totalcrosssection
Problem11.20
Usethe Bomapproximation
for scattering
from a gaussian
potential
V(x) =
Ae\"^'1.
CHAPTER
12
AFTERWORD
determine
agnosticresponse)?
to the realist,quantum mechanics
is an incomplete
According
theory,for even
if you know everything quantummechanics
hasto tellyou aboutthe system(towit:
its wave function),
stillyou cannotdetermine
allof itsfeatures.Evidently there is
someotherinformation,
which (together
with ty)
external to quantum mechanics,
is requiredfor a complete
of physicalreality.
description
The orthodoxposition
forif the act of
raiseseven moredisturbingproblems,
measurement forcesthe systemto \"takea stand,\"helpingto createan attribute
that was not there previously,1
aboutthe
then there is something
very peculiar
is not mystical, as somepopularizers would like to suggest.
which Niels Bohr elevated to the status of a cosmicprinciple
(complementarity),makeselectronssound like unpredictable adolescents,who sometimesbehave like
The
it
socalled
waveparticle duality,
420
TheEPR Paradox
Section12.1:
ro
421
FIGURE12.1:Bohm'sversion of the
EPRexperiment:
A
at restdecaysinto
7r\302\260
an electronpositron
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.
electronand a positron:
directions
momentum
4oM+
iU)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
(1935).
Chapter12 Afterword
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
twoparticle
as the productof two oneparticle
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 oneparticle
the system.
Provethe following
stateswoulddisentangle
theorem:
state\342\200\224a
combination
= 8,,.
a twolevelsystem,0H)and 0/,),with (0,0y)
Consider
(Forexample,
state
might represent
spinup and 0/,)spindown.)The twoparticle
0\342\200\236)
+
a0,,(l))0,,(2))
\302\2430/;(1))0\342\200\236(2))
Section12.2:Bell'sTheorem
(with
or
423
as a product
# 0 and ft ^ 0) cannotbe expressed
llMD>hM2)>.
\\\\ffr)
Hint:Write
\\\\j/r)
and
\\iffs).
10/\302\276).
12.2BELL'STHEOREM
is correct,
Einstein,Podolsky,and Rosendid notdoubtthat quantum mechanics
of physical
as far as it goes;they only claimedthat it is an incomplete
description
other quantity, X, is
reality:The wave functionis not the whole
the stateof a system fully.We callX
needed,in additionto ^, to characterize
the \"hiddenvariable\"because,at thisstage,we have no ideahow to calculate
or measureit.3Over the years,a number of hiddenvariable theorieshave been
to supplement
and
they tendto be cumbersome
proposed,
quantum mechanics;\"*
but never
1964the programseemedeminently worth
implausible,
But in that year J. S.Bellprovedthat any localhiddenvariable theory
pursuing.
with quantum mechanics.5
is incompatible
Bellsuggested
a generalization
of the EPR/Bohm
Insteadof
experiment:
and positrondetectors
he allowed
orienting the electron
alongthe samedirection,
the component
The first measures
of the electron
them to berotatedindependently.
of a unit vectora, and the secondmeasures
the spinof the
spinin the direction
b (Figure12.2).For simplicity,
let'srecordthe spins
positronalongthe direction
in unitsof h/2\\ then eachdetector
the value +1 (forspinup) or
registers
(spin
the
direction
i
n
A
f
or
tableof
results, many
down),along
question.
decays,
look
like
this:
might
story\342\200\224some
mind\342\200\224until
\342\200\2241
7r\302\260
+1
+1
1
+1
1
1
1
1
+1
+1
1
1
1
+
beautifully
written.
424
Chapter12 Afterword
7t\302\260
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 antiparallel
\342\200\224a),
[12.2]
then every productis +1,so
P(a,a)= +l.
[12.3]
P(a,b)= a b
[12.4]
with
is that thisresultis incompatible
(seeProblem4.50).What Belldiscovered
any
localhiddenvariabletheory.
X (X varies,in
electron/positron
systemis characterized
by the hiddenvariable(s)
someway that we neitherunderstandnorcontrol,from onepiondecayto the next).
of
is independent
Supposefurther that the outcomeof the electronmeasurement
the orientation
(b) of the positrondetector\342\200\224which may, after all,be chosen
by the
at the positron
endjustbeforethe electron
is made,and
measurement
experimenter
hencefar toolate for any subluminal
messageto get backto the electrondetector.
Then there existssomefunctionA (a,X) which
(This is the localityassumption.)
and someotherfunctionB(b,X) for
givesthe resultof an electronmeasurement,
the positron
measurement.
Thesefunctionscan only take on the values+ 1:6
A(a,A.) = + l; B(b,X)=
[12.5]
\302\261l.
theory\342\200\224even
Section12.2:Bell'sTheorem
425
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]
P(a.b) =
 I p(X)A(a.
X)A(b, X) dX,
[12.8]
 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
[12.11]
or, moresimply:
P(a.b)P(a.c)< 1 + P(b.c).
[12.12]
of Equations12.5and 12.6),
for we have
(subjectonlyto the minimal requirements
whateveras to the nature or number of the hiddenvariable(s),
made no assumptions
ortheirdistribution
(p).
But it is easy to showthat the quantum mechanical
(Equation12.4)
prediction
with Bell'sinequality.
three
Forexample,
a
ll
vectorsliein
is incompatible
suppose
426
Chapter12 Afterword
FIGURE12.3: An orientation
of the detectors
that
violations
of
Bell's
quantum
inequality.
demonstrates
casequantum
0.707
\302\243
With
Bell'sinequality:
1
 0.707= 0.293.
Bell'smodification,
far more
then, the EPR paradoxprovessomething
inequality.8
cameas
the experimental
of quantum mechanics
confirmation
Ironically,
of a shockto the scientific
But notbecause
it spelled
the demise
community.
had longsinceadjustedto this (and for thosewho
of \"realism''\342\200\224most physicists
couldnot, there remainedthe possibility
of nonlocalhiddenvariable theories.
something
experiments
Aspect.P. Grangier.and
seeG.Weihs
al.
81.
Section12.2:Bell'sTheorem
427
'Y
U
r\342\200\224/
Projector
Bug
Screen^
FIGURE12.4: Theshadowofthe bug movesacross
the screenat a velocityt/ greater
than c, provided
the screenisfar enoughaway.
time\342\200\224the
cause\342\200\224and
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 system and the measuring
of the wave function.
apparatus, and for supplying an intelligible mechanism for the collapse
428
Chapter12 Afterword
12.3THE