INTRODUCTION TO

Quantum
Mechanics
SECOND EDITION

DAVID J. GRIFFITHS
 Fundamental Equations

Schrodinger equation:
9*
ih\342\200\224 = //*
dt

Time-independent Schrodinger equation:

Hty = Ef, *= fe~iEt/h

Hamiltonian operator:

2m

Momentum operator:
p = -ihV

Time dependence of an expectation value:

^->\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, [Lv, Lz) = ihLx, [L-, Lx]

Pauli matrices:
'0 P '0 -i'
a, = =
I
a~
A 0 ^=/ 0 0
 Fundamental Constants

Planck's constant: h = 1.05457x 1(T34J s

Speed of light: c = 2.99792 x 108 m/s

Mass of electron: me = 9.10938 x 10-31 kg

Massof proton: mp = 1.67262x 10\"27

kg

Charge
of proton: e = 1.60218 x 10\"I9C

Charge of electron: -e = -1.60218 x 10-19 C

Permittivity of space: eo = 8.85419x 10-'2 C2/Jm

Boltzmann constant: kg = 1.38065 x 10~23 J/K

Hydrogen Atom

Fine structureconstant: or =
1/137.036
47t\302\243ohc

a =
fl2
4jT\342\202\254o h
Bohr radius: 5.29177 x 10-11 m
mee2 amec

m ee4
Bohr energies: En
=
-4 (n= 1,2,3,...)
2(47te 0)\302\2762

9 9
h2 a~mec~
Binding energy: -EX = = 13.6057 eV
2m ea2 2

1
Ground state: e -rja
y/jta^

l
Rydbergformula: X
~
ny nj

Rydberg constant: R = = 1.09737 x 107/m

2nhc
Introduction to

Quantum Mechanics

Second Edition

David J. Griffiths
Reed College

^^^KiiH PearsonEducation
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CONTENTS

PREFACE vii

PARTI THEORY

1 THE WAVE FUNCTION 1

1.1 The Schrbdinger Equation 1
1.2 The Statistical Interpretation 2

1.3 Probability 5
1.4 Normalization 12
1.5 Momentum 15
1.6 The Uncertainty Principle 18

2 TIME-INDEPENDENT SCHRODINGER EQUATION 24

2.1 Stationary States 24
2.2 The Infinite Square Well 30
2.3 The Harmonic Oscillator 40
2.4 The Free Particle 59

2.5 The Delta-Function Potential 68

2.6 The Finite Square
Well 78

3 FORMALISM 93
3.1 Hilbert Space 93
3.2 Observables96
3.3 Eigenfunctions of a Hermiiian Operator 100

iii
 3.4 Generalized Statistical Interpretation106
3.5 The
Uncertainty Principle 110
3.6 Dirac Notation 118

4 QUANTUMMECHANICS IN THREE DIMENSIONS 131

4.1 Schrodinger Equation in Spherical Coordinates131
4.2 The
Hydrogen Atom 145
4.3 Angular Momentum 160
4.4 Spin 171
5 IDENTICAL PARTICLES 201
5.1 Two-Particle Systems 201
5.2 Atoms 210
5.3 Solids218
5.4 Quantum Statistical Mechanics 230

PART II APPLICATIONS

6 TIME-INDEPENDENT PERTURBATION THEORY 249

6.1 Nondegenerate
Perturbation Theory 249

6.2 Degenerate Perturbation Theory 257

6.3 The Fine Structure of Hydrogen 266
6.4 The Zeeman Effect 277
6.5 HyperfineSplitting283
7 THE VARIATIONAL PRINCIPLE 293
7.1 Theory 293
7.2 The GroundStateof Helium299
7.3 The
Hydrogen Molecule Ion 304

8 THE WKB APPROXIMATION 315

8.1 The \"Classical\" Region
316

8.2 Tunneling 320

8.3 The Connection Formulas 325

9 TIME-DEPENDENT PERTURBATION THEORY 340

9.1 Two-Level Systems 341
9.2 Emission and
Absorption of Radiation 348
9.3 Spontaneous Emission 355

10 THE ADIABATIC APPROXIMATION 368

10.1 The Adiabatic Theorem 368

10.2 Berry's Phase 376
 Contents v

11 SCATTERING 394
11.1 Introduction 394
11.2 Partial Wave Analysis 399
11.3 Phase Shifts 405
408
11.4 The Born Approximation

12 AFTERWORD 420

12.1 The EPR Paradox 421

12.2 Bell's Theorem423
12.3 The No-Clone Theorem 428
12.4 Schrodinger's Cat 430
12.5 The Quantum Zeno Paradox 431

APPENDIX LINEAR ALGEBRA 435

A.l Vectors435
A.2 Inner Products 438

A.3 Matrices 441

A.4 Changing Bases 446
A.5 Eigenvectorsand Eigenvalues 449

A. 6 Hermitian Transformations 455

INDEX 459
PREFACE

UnlikeNewton'smechanics, Maxwell's or
electrodynamics, or Einstein's relativity,
quantum theory was not even created\342\200\224or definitively packaged\342\200\224by one
individual, and it retains to this day some of the scars of its exhilarating
but traumatic

youth. There is no general consensus as to what its fundamental principles are, how
it should be taught, or what it really \"means.\" Every competent physicist can \"do\"
quantum mechanics,but the stories tell ourselves about what we are doing are
we

as variousasthe tales Scheherazade, and almost

of as implausible. Niels Bohr said,
\"If you are not confused quantum physics then you haven't really understood
by

it\"; Richard remarked, \"I think

Feynman I can safely say that nobody understands
quantum
mechanics.\"

The purpose of this teach you

book is to to do quantum mechanics.
how
Apart
from some essential in
background Chapter 1, the deeper quasi-philosophical

questions are saved for the end. I do not believe one can intelligently discuss what

quantum mechanics means until one has a firm sense of quantum what

mechanics does. But if you absolutely cannot wait, by

all means read the Afterword
immediately following Chapter 1.
Not only is quantum theory conceptually rich, it is also technicallydifficult,
and exact solutions to all but the most artificial textbook examplesare few and far
between. It is therefore essential to develop specialtechniques for
attacking more

realistic problems. Accordingly, this book is divided into two parts;' Part I covers
the basic theory, and Part II assembles arsenal of approximation schemes, withan

illustrative applications. Although it is important to keepthe parts logically two

separate, it is not necessary to study the material in the order presented h ere. Some

'This structure was inspired by David Park's classic text, Introduction to the Quantum Theory,
3rd ed.. McGraw-Hill, New York (1992).

vii
instructors, for example, may wish to treat
time-independent perturbation theory

immediately after Chapter 2.

This book is intended for a one-semester or one-year course at the junior or
senior level. A course will have to concentrate mainly on Part
one-semester I;

a full-year course have room for supplementary

should material beyond Part II.

The reader must be familiar with the rudiments of linearalgebra(assummarized

in the Appendix), complex numbers, and calculus up through partial derivatives;
someacquaintance with Fourier analysis and the Dirac delta function would help.

Elementary classical mechanics is essential, of course, and a little electrodynamics

would be useful in places. As always, the more physics and math you know the
easier it will be, and the more you get your study. But I would like
will out of
to emphasize that
quantum mechanics is not, in my view, something that flows

smoothly and naturally from earlier theories. On the it

contrary, representsan
abrupt and revolutionary departure from classical ideas, calling forth a wholly new

and radically counterintuitive way of thinking about the world. That, indeed, is

what makes it such a fascinating subject.

At first glance, this book may strike you as forbiddingly mathematical.We
encounter Legendre, Hermite, and Laguerre polynomials, spherical harmonics,
Bessel, Neumann, and Hankel functions, Airy functions, and even the Riemann
zeta function\342\200\224not to mention Fourier transforms, Hilbert spaces, hermitian
operators, Clebsch-Gordan coefficients, and Lagrange multipliers. Is all this baggage
really necessary?Perhapsnot, but
physics is like carpentry: Using the right tool
makes the job easier,notmore difficult, and teaching quantum mechanics without
the appropriate mathematical equipment is like asking
the student to dig a
foundation with a screwdriver. tediousand divertingif
(On the other hand, it can be
the instructor give feels
obliged to use of each elaborate lessons on the proper
tool. own instinct is to hand the students shovels and tell
My
start them to

They
digging. may develop blisters at first, but I still is the most efficient think this

and exciting way to learn.) any rate, I can assure you that there is no deep
At

mathematics in this book, and if you run into something unfamiliar, and you don't

find my explanation adequate, by all means ask someone about it, or look it up.
There are many good booksonmathematical methods\342\200\224I
particularly recommend

Mary Boas, Mathematical Methods in the Physical Sciences, 2nd ed., Wiley, New

York (1983), or George Arfken and Hans-Jurgen Weber,Mathematical Methods for

Physicists, 5th ed., Academic Press, Orlando (2000). But whatever you do, don't
let the mathematics\342\200\224which, for us, is only a tool\342\200\224interfere with the physics.
Several readers have noted that there are fewer worked examplesin this book
than is customary, and that some important material is relegatedto the problems.
This is no accident. I don't believe you can learn quantum mechanics without doing
many exercises for yourself. Instructorsshouldof course go
over as many problems
in class as time allows, but studentsshouldbe warned that this is not a subject
about which anyone has natural intuitions\342\200\224you're developing a whole new set
of muscles here, and there is simplyno substitute for calisthenics. Mark Semon
 Preface ix

suggested a \"MichelinGuide\"to the problems, varying

that I offer with numbers
of stars to indicate the level of and importance. This seemed difficulty like a good
idea (though, like the qualityofa restaurant, thesignificancea problem of is partly
a matter of taste); I adopted the following rating
have scheme:

* an essential problem that every reader should study;

* * a somewhat more difficultor moreperipheral problem;

* * * an unusually challenging problem, that may take over an hour.

(No stars at all means fast food: OK if you're hungry, but not very nourishing.)
Most of the one-star problems appear at the end of the relevant section; most of
the three-starproblemsare at the end of the chapter. A solution manual is available
(to instructors only)
from the publisher.
In preparing the second edition I have tried to retain as much as possible the
spirit of the first.The only wholesale change is Chapter 3, which was much too
long and
completely
diverting; rewritten, with the background material
it has been
vectorspaces
on finite-dimensional with which most students at this level (a subject

are already comfortable)relegatedto the Appendix. have added some examples I

in Chapter 2 (and fixed the awkward definition of raising and lowering operators
for the harmonic oscillator).In laterchapters I have made as few changes as I
could, even preservingthe numberingof problems equations, where possible. and

The treatment is streamlined in places (a better introduction to momentum angular

in Chapter 4, for instance, a simpler proof of the adiabatictheoremin Chapter

10, and a new section on partial wave phase shiftsin 11). Inevitably, the Chapter

second edition is a bit longer the first, which I regret, but I hope it is cleaner
than

and moreaccessible.
I have benefited and advice of
from the comments
colleagues, who many

read the originalmanuscript, pointed out weaknesses (or errors) the first edition, in

suggested improvements in the presentation, and suppliedinterestingproblems. I

would like to thank in particular P. K. (Worcester Polytech), Greg BeneshAravind

(Baylor), David Boness (Seattle), Burt Brody (Bard), Carter (Drew), Edward Ash

Chang (Massachusetts), Peter Collings (Swarthmore), Richard Crandall (Reed),

Jeff Dunham (Middlebury), Greg Elliott (Puget Sound), John Essick (Reed),Gregg
Franklin
(Carnegie Mellon), Henry Greenside (Duke), Paul Haines (Dartmouth),
J. R. Huddle (Navy), Larry Hunter (Amherst), David Kaplan (Washington), Alex
Kuzmich (GeorgiaTech),Peter Leung (Portland State), Tony Liss (Illinois), Jeffry
Mallow (Chicago Loyola), James McTavish (Liverpool), James Nearing (Miami),
Johnny Powell (Reed), Krishna Rajagopal(MIT),Brian Raue (Florida

International), Robert Reynolds (Reed), Keith Riles (Michigan), Mark Semon (Bates),
HerschelSnodgrass Clark), John Taylor (Lewis and (Colorado), Stavros Theodor-
akis (Cyprus), A. S. Tremsin (Berkeley), Dan Velleman (Amherst), Nicholas
Wheeler (Reed), Scott Willenbrock (Illinois), William Wootters (Williams),Sam
Wurzel (Brown), and Jens Zorn (Michigan).
Introduction to

Quantum Mechanics
 PARTI THEORY

CHAPTER 1

THE WAVE FUNCTION

1.1 THE SCHRODINGER

EQUATION

Imagine a particle w, constrained to move alongthe x-axis,

of mass to subject

some specified force (Figure 1.1).

F(x.t) The program of classical mechanics
is determine
to the position of the particle at any given time: x(t). Once we

know that, we can figure out the velocity =

dx/dt), the momentum (p = (v

mv), the kinetic (T

= (l/2)mv2),
energy
or any other dynamical variable of
interest. how do we go about determining x(/)?
And
apply Newton's We

second law: F = ma. (For conservative systems\342\200\224the only kind we shall

consider, and, fortunately, the only kind that occur at the microscopic level\342\200\224the
force can be expressed as the derivative of a potentialenergy function,1F =

\342\200\2243V/3.V,
and Newton's law reads mdrxjdt1 = \342\200\224dV/dx.) This, together with

appropriate initial conditions (typically the positionand velocity at t = 0),

determines x{t).

Quantum mechanics quite differently.In this

approaches this same problem
case what we're looking particle's wave function,
for is the f), and we get W(x,

it by solving the Schrodinger equation:

9vj/ fi1 dH ,, ,
axil A]
at 2m

1
Magnetic forces are an exception, but let's not worry about ihem just yet. By the way. we shall
assume throughout this book that the motion is nonrelalivislic (,i\302\273
<SC c).

1
2 Chapter 1 The Wave Function

m
* r{X,t)
o n
X

x(t)

FIGURE 1.1: A \"particle\" constrained to move in one dimensionunderthe influence

of a specified force.

Here i is the square root of and

\342\200\2241, h is Planck's constant\342\200\224or rather, his original
constant (/?) divided by 2tt:

h = =
\342\200\224
1.054572 x 10~34J s. [1.2]
2tt

The Schrodingerequation a role plays logically analogous to Newton's second

law: Given suitableinitialconditions (typically, ty{x, 0)), the Schrodinger equation
determines ty(x,t) for all time, future just as, in classical mechanics, Newton's
law determines x(t) for all time.2 future

1.2 THE STATISTICAL INTERPRETATION

But what exactly is this \"wave function,\" and what does it do for you once you've
got it? After all, a particle, by its nature, is localized at a point, whereas the wave

function (as its name suggests) is spread out in space(it'sa function of x, for any

given time /). How can such an

object represent the state of a particle'? The answer
is providedby Bom's statistical interpretation of the wave function, which says
that \\^(x, t)\\2 gives the probability of finding the particleat point x, at time t\342\200\224or,
more precisely,3

probability of finding the particle

=
[1.3]
/J.a
\\V(x\\t)\\2dx
between a and /?, at time t.

Probability is the area under the graph of \\ty |2. For the wave function in Figure 1.2,
you
would be quite likely to find the particle in the vicinity of point A, where |4>|2
is large, and relatively mh likely to find it near point B.

^For first-hand
a delightful account of the origins of the Schrodinger equation see the article by

Felix Bloch Today. December 1976.

in Physics
wave
\342\200\242'The function itself is complex, but |*|2 = *** (where ** is the complex conjugate of
*) is real and nonnegalivc\342\200\224as a probability, of course, must be.
 Section 1.2: The Statistical Interpretation 3

*M2

B C x

FIGURE 1.2: A typical wave function. The shaded area represents the probability of

rinding
the particle between a and b. The particlewouldbe relatively likely to be found
near A, and unlikely to befoundnear B.

The statistical interpretation indeterminacy into

introduces a kind of
quantum mechanics, for even if you know everything the theory has to tell about you

the particle (to wit: its wave function), still cannot predict with certainty
you
the
outcome of a simple experimentto measure its
position\342\200\224all quantum
mechanics has to offer is statistical information about the possible results. This
indeterminacy has been profoundly disturbing to physicists and philosophers alike,
and it is natural to wonder whether it is a fact of nature, or a defectin the

theory.

Suppose
I do measure the position of the particle, and I find it to be at point
C.4 Question: Where was the particlejust before I made the measurement? There
are three plausible answers to thisquestion,
and they serve to characterize the main
schools of thought regardingquantum indeterminacy:

1. The realist position: The particle was at C. Thiscertainly seems like a

sensible
response, and it is the one Einstein advocated. Note, however,that if this is

true then quantummechanics is an incomplete theory,sincetheparticle really was

at C, and
yet quantum mechanics was unable to tellus so. To the realist,

indeterminacy
is not a fact of nature, but a reflection of our ignorance. As
d'Espagnat put
it, \"the position of the particle was never indeterminate, but was merely unknown
to the experimenter.\"5Evidently 4> is not the whole story\342\200\224some additional

information (known as a hidden variable) is needed to a

provide completedescription
of the
particle.
2. The orthodox position: The particle wasn 7 really anywhere. It was the act
of measurement that forced the particleto \"take a stand\" (though how and why it
decided on the point C we dare not ask). Jordan said it most starkly: \"Observations
not only disturb what is to be measured, they produce it ... We compel (the

4Of course, no measuring instrument is perfectly precise: what I mean is that the particle was
found in the vicinity of C. to within the tolerance of the equipment.
\342\200\242'Bernardd'Espagnat, \"The Quantum Theory and Reality\" (Scientific American. November 1979.
p. 165).
4 Chapter 1 The Wave Function

particle) to assume a definite position.\"6 This view (the so-called Copenhagen

interpretation), is associated with Bohr and his followers. Among physicists it

has always been the most widely accepted position.Note,however, that if it is

correct there is something very peculiar about the act of measurement\342\200\224something

that over half a century of debate has done preciouslittleto illuminate.

3. The
agnostic position: Refuse to answer. This is not quite as silly as it

sounds\342\200\224after all, what sense can there be in making assertionsaboutthe status

of a particle a measurement,
before when the only way of knowing whether you
were right is precisely to conducta measurement, in which case what you get is no
longer \"before the measurement?\"It is metaphysics (in the pejorative sense of the

word) to worry about something that cannot, by its nature, be tested. Pauli said:
\"Oneshouldno more rack one's brain about the problem of whether somethingone
cannotknow anything about exists all the same, than about the ancientquestion of
how
many angels are able to sit on the pointofa needle.\"7 For decades this was the

\"fall-back\" position of most physicists: They'd try to sell you the orthodox answer,
but if you were persistent they'd retreatto theagnostic response,
and terminate the

conversation.

fairly recently, all three positions(realist,orthodox,

Until and agnostic) had
their partisans. But in 1964 John Bellastonished thephysics community by showing
that it makes an observable difference whether the particlehad a precise(though
unknown) position prior to the measurement, or not. Bell's discovery effectively

eliminated agnosticism as a viable option, and made it an experimental question

whether 1 or 2 is the correct choice. I'll return to thisstory at the end of the book,
when you will be in a betterpositionto appreciate Bell'sargument; for now, suffice
it to say that the experiments have decisivelyconfirmed the orthodox
interpretation:8 A
particle simply does not have a precise position priorto measurement, any

more than the ripples on a pond do; it is the measurementprocessthat insists on

one particular number, and thereby in a sense createsthe specific result, limited

only by the statistical weighting imposed by

the wave function.
What if I made a second measurement, immediately
after the first? Would I
get C again, or doesthe act of measurement coughup some completely new
number each time? On this question everyone is in agreement: A repeated measurement
(on the same particle) must return the same value. Indeed, it would be tough to
prove that the particle was really found at C in the first instance,if this couldnot
be confirmed by immediate repetition of the measurement. How doesthe orthodox

\"Quoted in a lovely article by N. David Mennin. \"Is the moon there when nobody looks?\"
(Physics Today. April 1985. p. 38).

7Quolcd by Mermin (footnote 6). p. 40.

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 variable
hidden 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 pedagogical point of
view, to adopt a clear and coherent platform at this stage, and worry about the alternatives later.
 Section 1.3: Probability

tM2

C x

FIGURE 1.3: Collapse of the wave function: graph of |>P|2 immediately after a
measurement has found the particle at point C.

account
interpretation for the fact that the second measurement is bound to yield
the value C? Evidently the first measurement radically alters the wave function,

so that it is now sharply peaked about C (Figure1.3). We say that the wave
function
collapses, upon spike at the point C (it soonspreads
measurement, to a
out

again, in accordance with the Schrodinger equation, so the secondmeasurement

mustbemadequickly).Thereare,then, two entirely distinct kinds of physical
processes:
\"ordinary\" ones, in which the wave function evolves in a leisurelyfashion
under the Schrodinger equation, and \"measurements,\" in which ^ suddenly and
discontinuouslycollapses.9

1.3 PROBABILITY

1.3.1 Discrete Variables

Because of the statistical interpretation,probabilityplaysa central role in

quantum

mechanics, so I digress now for a briefdiscussion

of probability theory. It is mainly

a questionof introducing some notationand terminology, and I shall do it in the

a
context of simpleexample.
Imagine
a room containing fourteen people, whose ages are as follows:

oneperson aged 14,

one person aged 15,

three people aged 16,

JThe role of measurement in quantum mechanics is so critical and so bizarre that you may
well be wondering what precisely constitutes a measurement. Does it have to do with the interaction
between a microscopic(quanlum) system and a macroscopic (classical) measuring apparatus (as Bohr

insisted), or is it characterized by the leaving of a permanent \"record\" (as Heisenberg claimed), or does
it involve the intervention of a conscious \"observer\" (as Wigner proposed)? I'll return to this thorny
issue in the Afterword: for the moment let's lake the naive view: A measurement is the kind of thing
that a scientist does in the laboratory, with rulers, stopwatches, Geiger counters, and so on.
6 Chapter 1 The Wave Function

two people aged 22,

two people aged 24.
five
people aged 25.

If we let N(j) represent the number of peopleof age j, then

N(U)
= 1,

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

N(25) = 5,

while N(17), for instance,is zero. The total number of people in the room is
00
tf = X>c/). [1.4]
7=0

(In the example, of course, N = 14.) Figure 1.4 is a histogram of the data. The

following are some questions one might ask aboutthisdistribution.

Question 1. If you selected one individual at randomfrom this group, what

is the probability that this person's age would be 15?Answer: One chance in
14, since there are 14 possiblechoices,all equally likely, of whom only one has
that particular age. If P(j) is the probability of getting age j, then P(14) =
1/14, P(15) = 1/14,P(16)= 3/14, and so on. In general,

=
N(j)
P(j) [1.5]
N

N(J) I

j i i J I L
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 j

FIGURE 1.4: Histogram showing the number of people, NO), with age ;, for the
distributionin Section1.3.1.
 Section1.3: Probability 7

Notice that the probability of getting either 14 or 15is the sum of the individual
probabilities (in this case, 1/7). In particular, the sum of all the probabilities is
1\342\200\224you're
certain to get some age:
oo
= i. [1.6]
En/)
7=0

Question 2. most probable age? Answer: 25, obviously;five

What is the
people share this age, whereas at most three have any other age. In general, the
most probable j is the j for which P(j) is a maximum.
Question 3. What is the median age? Answer: 23, for 7 people are younger
than 23, and 7 are older. (In general, the medianis that value of j such that the

probability of getting a largerresultis the same as the probability of getting a

smaller result.)
Question4. What is the average (or mean) age? Answer:

(14) + (15) + 3(16)+ 2(22) + 2(24) + 5(25) 294

= 21.
14 14
In general, the average value of j (which we shall write thus: (/')) is

0\ = \342\200\224jv\342\200\224
=
1^, j nj). [1.7]
7=0
Notice that there with the average age or the medianage\342\200\224in
need not be anyone
this example nobody happens 21 or 23. In quantum mechanics to be
the average

is usually the quantity of interest; in that context it has come to be called the
expectation value. It'sa misleading term, since it suggests that this is the outcome
you would be most likely
to get if you made a single measurement {that would
be the most probable value, not the average value)\342\200\224but I'm afraid we're stuck
with it.
Question 5. What is the average of the squares of the ages? Answer: You

could get 142 = 196, with probability 1/14, or 152= 225, with
probability 1/14,

or 16~ = 256, with probability 3/14, and so on. The

average, then, is

00

U2) = ^J2PU)- [1.8]

7=0
In general,the average value of some function of j is given by

[1.9]
8 Chapter 1 The Wave Function

N(j) A Nil) i

i i i i i i i i i i i i i i i i i i i i i
> >
123456789 10/ 123456789 10/
FIGURE 1.5: Two histograms with the same median, same average, and same most
probable value, but different standard deviations.

(Equations1.6,1.7, and 1.8 are, if you Beware:

like, special cases of this formula.)
The
average of the squares, (j2), is not equal, in general, to the squareof the
average, (./)2. For instance, if the room contains just two babies, aged 1 and 3,

then (x1) = 5, but (x)2 = 4.

Now,thereisa conspicuous difference between the two histograms in Figure 1.5,
even though they
have the same median, the same average, the samemostprobable
value, and the same number of elements: The first is sharplypeakedabouttheaverage
value, whereas the second is broad and flat. (The first might represent the age profile
for students in a big-cityclassroom, the second,perhaps, a rural one-room school-
house.) We need a numerical measureof the amount of \"spread\" in a distribution,
with respect to the average.The mostobvious way
to do this would be to find out
how far each individual deviates from the average,

Aj = j-{j), [l.io]
and
compute the average of Aj. Trouble is, of course, that
you get zero, since, by
the nature of the average,Aj is as often
negative as positive:

(aj) =
J2u
- u))pu) = J2 Jpw - u) \302\243
p(j)

= U)
- (j) = o.

(Note that (j) is constant\342\200\224it does not change as you go from one member of
the sampleto another\342\200\224so it can be taken outside the summation.) To avoid this
irritating problem you might decide to average the absolute value of Aj. But
absolutevaluesare nasty to work with; instead, we get around the sign problem
by squaring before averaging:

a2 = ((Aj)2). [1.11]
 Section1.3: Probability 9

This quantity is known of the distribution;a

as the variance square itself (the

root of the average of the square of the deviation average\342\200\224gulp!) is from the

called the standard deviation. The latter the customarymeasureof the spread
is
about (j).
There is a useful little theorem on variances:

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

= -
\302\243
j2P(j) 2U)^jP(j) + U)2 J2 P{j)
= U2)-2U)(j) + U)2
=
U2)-U)2.

Taking the square root, the standarddeviationitself can be written as

= ~
\302\260
y/(J2) U)2- [1.12]

In practice, this is a much faster way to a: Simply calculate (/2) and (j)2,
get
subtract, and take the square root. Incidentally, I warned you a moment ago that
{j~) is not, in general, equal to (j)~. Since a~ is plainly nonnegative
(from its

definition in Equation 1.11), Equation 1.12 implies that

(r)>0*)2, [i.i3]

and the two are only

equalwhen a = 0, which is to say, for distributions
with no

spread at all (every member having the same value).

1.3.2 Continuous Variables

So far, assumed that we are dealingwith

I have a discrete variable\342\200\224that is, one

that can on only certain isolated values (in the example,j had
take to be an

integer, since I gave ages only in years). But it is simple enough

to generalize to

continuous distributions. If I select a randompersonoff the street, the probability

that her age is precisely 16 years,4 hours,27 minutes, and 3.333 ... seconds is
zero. The only sensible thing to speak about is the probabilitythat her age lies in
some interyal\342\200\224say,
between 16 and If the interval is sufficiently short, this
17.

probability is proportional to the length of the interyal. For example,the chancethat

her age is 16 plus two days is presumablytwicethe probability
between 16 and
that it is between 16 and 16 plus one day. (Unless,I suppose, there was some

extraordinary baby boom 16 years ago, on exactly that

day\342\200\224in
which case we
have simply chosen an interval too longfor the rule to apply. If the baby boom
 The Wave Function

lasted six hours, we'll take intervals of a secondor less,to be on the safe side.
Technically, Thus
we're talking about infinitesimalintervals.)

that an individual (chosen 1 ,., r, , ...

probability
.. \\ L
lies between x
,\342\200\242
and j/ , j x \\=p{x)dx. [1.14]
I at random) (a* + ax) J

The proportionality factor, p(x), is often looselycalled \"the

probability
of getting
A',\" but this is sloppy language; a betterterm is probability density. The probability
that x lies between a and b (a. finite interval) is given by the integral of p(x):

= /I P(x)dx,
Pah= P(x [1.15]
Ja

and the rules we deduced for discrete distributionstranslatein the obvious way:

p(x)dx, [1.16]
/+oo-oc

xp(x)dx, [1.17]
-oo
/+oo

f(x)p(x)dx, [1.18]
/+0C -oo

a2 ee <(Aa-)2) = (x2) - (a)2. [1.19]

Example1.1 Suppose
I
drop a rock off a cliff of height h. As it falls. I snap a
million photographs, at random intervals. On each pictureI measure the dssUince

the rock has fallen. Question: What is the average of all these distances' That rs

to say, what is the time average of the distancetraveled?10

Solution: The rock starts out at rest, and picks up speed as it falls; it spends more
time near the top, so the average distancemust be less than h/2. Ignoring air
resistance, the distance x at time t is

=
1 9
*(') \342\200\242
J*'

The velocity is dx/dt = gt, and the totalflighttimeis T =

y/2h/g. The probability
that the camera flashes in the interval dt is dt/T, so the probability that a given

l0A statistician will complain that I am confusing the average of a finite sample (a million, in

this case) with the \"true\" average the whole continuum). This can
(over be an awkward problem for
the experimentalist, especially when the sample size is small, but here I am only concerned, of course,
with the true average, lo which the sample average is presumably a good approximation.
 Section 1.3: Probability 11

P(x)\"

FIGURE 1.6: The probabilitydensityin Example 1.1: p(x) = l/(2</hx).

photograph shows a distance in the correspondingrange dx is

dt _ dx
_
1
jg dx.
T~~giy2h~27n=x

Evidently the probabilitydensity (Equation 1.14) is

1
p(x) = , (0 < x < h)
2Vhx

(outside this range, of course, the probability density is zero).

We can check this result, using Equation 1.16:

1 =
1
= l.
dx
I 0 ly/hx 2Vh M

The
average distance (Equation 1.17) is

1 /2 h
r3/2

Jo iVte 2Vh \\ 3'

which is somewhat less than /?/2, as anticipated.

Figure
1.6 shows the graph of p(x). Notice that a probability density can
be infinite, though probability itself (the integral of p) must of course be finite
(indeed, less than or equal to 1).
12 Chapter
1 The Wave Function

*Problem 1.1 For the distributionof agesin Section 1.3.1:

(a) Compute (./2) and (j)2.

(b) Determine Ay for each j, and use Equation 1.11 to computethe standard
deviation.
(c) Use your results in (a) and (b) to check Equation 1.12.

Problem 1.2
(a) Find the standard deviation of the distribution in Example 1.1.
(b) What is the probability that a photograph, selected at random, would showa
distancex more than one standard deviation away from the average?

*Problem 1.3 Considerthe gaussian distribution

p(x)
= Ae-k{x~a)\\

where A, a, and k are

positive real constants. (Look up any integrals you need.)

(a) Use Equation1.16 to determine A.

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

(c) Sketch the graph of p(x).

1.4 NORMALIZATION

We return now to the statistical interpretation of the wave function (Equation 1.3),
which says that \\ty(x, t)\\2 is the probabilitydensity for
finding the particle at point
x, at time t. It follows (Equation1.16) that the integral of |^|2 must be 1 (the
particle's got to be somewhere):

= l. [1.20]
/+oo
-co
\\V(x,t)\\2dx

Without this, the statistical interpretationwouldbe nonsense.

However, this requirement should disturb you: After all, the wave functionis
supposed to be determined by the Schrodinger equation\342\200\224we
can't go imposing
an extraneous condition on ^ without
checking that the two are consistent. Well, a
 Section1.4: Normalization 13

glance at Equation if ^(jc, f) isa solution, too is A^U, /), where

1.1 reveals that so

A is any (complex) constant. What we must do, then, is pickthis undetermined

multiplicative factor so as to ensure that Equation 1.20 is satisfied.This process

is called normalizing the wave function. For some solutions to the Schrodinger

equation integral the is infinite; in that case no multiplicative factor is goingto

make it 1. The same goes for the trivial solution = 0. Such non-normalizable
vj/

solutions cannot represent particles, and be rejected. must

Physically realizable
states correspond to the square-integrable solutionsto Schrodinger's equation.11

But wait a minute! Suppose I have normalizedthe function at time t = 0. wave

How do I knowthat it will stay normalized, as time goes on, and ^ evolves? (You

can't keep ^normalizing the wave function, for then becomes a function of t, A

and you no longer a solution

have to the Schrodinger equation.) Fortunately, the
Schrodingerequationhasthe remarkable
property that it automatically preserves the
normalization of the function\342\200\224without
wave this crucial feature the Schrodinger
equation would be incompatible the statistical with
interpretation, and the whole

theory would crumble.

This is so
important,
we'd better pause for a careful proof. To begin with,

+0O +oc a
l*(*, t)\\2d \\V(x,t)\\2dx. [1.21]
dt;_ oo -oo dt

(Note that the integral is a function only of t, so I usea total derivative (d/dt)
in the first expression, but the integrand is a functionof x as well as r, so it's a
partial derivative (d/dt) in the secondone.)By the product rule,

9 9 9* 8V*
\342\200\224
|vl/|2
= \342\200\224
(vi/*vi/)
= ijr + vl/. [1.22]
dt dt dt dt
Now the Schrodinger equationsays that

9^ iti d2V i
[1.23]
dt 2m dx- n

and hence also (taking the complexconjugateof Equation 1.23)

9** ih d2V* / *
[1-24]
dt 2m dx1 ft

so

9,-, i 92vl>* \\ 9 9* 8V*

\342\200\2241*1
=
\342\200\236
* [1.25]
dt Im
2m. \\ dx2 9x2 1 dx 2m \\
dx dx

t) must go to zero faster

1
'Evidently *(.v. than \\/y/[x], as |.v| \342\200\224*\342\226\240
oo. Incidentally, normalization
only fixes the modulus of A: the phase remains undetermined. However, as we shall see, the latter
carries no physical significance anyway.
 The Wave Function

The integral in Equation 1.21can now be evaluated explicitly:

d f+00 w
\342\226\240 m\"> J
^ /\"t*9^ 9Vr / +00
\342\200\224
|vl/(.r,r)|~</.r
= \342\200\224 \342\200\224
* [1.26]
af / 2m (**- 3jc 3x \342\200\22400
J.qo \\

But *!>(*. f) must go to zero asx goesto (i) infinity\342\200\224otherwise

the wave function

would not be normalizable.12 It follows that

d f+\302\260\302\260
\342\200\224
\\V(x,t)\\2dx
= 0, [1.27]
dt J_oo

and hence that the integral is constant (independent of time); if ^ is normalized

at t = 0, it stays normalized for all future time. QED

Problem1.4 At time t = 0 a particle is represented by

the wave function

A-, if 0 < x < a,

a
V(x, 0) = \342\200\242 (b - x)
if a < x < b,
(b-a)
0. otherwise,
where A, a, and b are constants.

(a) Normalize vj> (that is, find A, in terms of a and /?).

(b) Sketch 0), as a function W(x, of x.

(c) Where is the particlemost likely

to be found, at t = 0?

(d) What is the probability of finding the particle to the left of al Check your

result in the limiting cases b = a and b = 2a.

(e) What is the expectation value of x?

^Problem 1.5 Consider the wave function

where A, k, positive real constants.(We'llsee

and co are in
Chapter 2 what potential
(V) actually produces such a function.) wave

(a) Normalize vj>.

(b) Determine the expectation values of x and x2.

,2A good mathematician can supply you with pathological counterexamples, but they do not arise
in physics; for us the wave function always goes to zero at infinity.
 Section 1.5: Momentum 15

(c) Find the standard deviation of x. Sketchthe graph of \\W\\2, as a function

of a\", and mark ((x) -f- er) and {(x) er), the sense in
\342\200\224
the points to illustrate

in x. What
which er represents the \"spread\" is the probability that the particle
would be found outsidethisrange?

1.5 MOMENTUM
For a particle in state vj>, the expectation value of x is

x\\V(x,t)\\2dx [1.28]
-00
/+oo

What exactly does this mean? It emphatically does not mean that if you measure
the position of one particle over and over again,j x\\^\\2dx
is the average of the
results you'll get. On the contrary:The first measurement (whose outcome is
indeterminate) collapse will the the value
wave functionobtained, to a spike at actually

and the subsequent measurements (if they're performed quickly) will simplyrepeat
that same result. Rather, (x) is the average of measurements performedon particles
all the state ^, which means that either you must some way of returning the
in find

particle to its originalstate each measurement, or else you have to prepare a

after

wholeensembleof particles, in the same state ^, and measure the positionsof each

allof them: is the average of these results. (I like to picturea

(x) of bottles on row

a shelf, each containing a particle in the state ^ (relative tothecenter the bottle). of

A graduate student with a ruler is assignedto each and at a signal they all bottle,

measure the positions of their respective particles. then construct a histogram We

of the results, which should |vl>|2, and compute the average,

match which should
agree with
(x). (Of course, since we're only using a finite sample, can't expect we

perfect agreement, but the more bottles use, the closer we ought to come.)) In we

short,the expectation value is the average of repeated measurements on an

ensemble
of identically prepared systems, not the average of repeated measurementson
one and the same system.
Now, as time goes on, (x) will change (becauseof the time dependence
of ^), and we might be interested in knowing how fast it moves. Referringto
Equations1.25 and 1.28, we see that13

d{X) \342\200\242-\" --- - '--\" '--- - -dx.

[1.29]
dt J dt 2m J dx \\ dx dx ,

To keep things from gelling too cluttered. I'll suppress the limits of integration.
 The Wave Function

This expression can be simplified

usingintegration-by-parts:14
d(x) ih C /.,3^ 9^*
\342\226\240*dx. [1.30]
dt 2m /(*\342\200\242?
dx

(I used the fact that dx/dx = 1, and threw away the boundary term, on the ground
that vj>
goes to zero at ( + ) infinity.) Performing another integration by parts, on
the second term, we conclude:

d(x)
=
/ V* \342\200\224dx [1.31]
dt m J cix

What are we to make of this result? Note that we're talking about the
\"velocity\" of the expectation value of A', which is not the same thing as the velocityof
theparticle. Nothing
we have seen so far would enable us to calculatethe velocity
It's
of a particle. not even clear what velocity means in quantum mechanics: If the
particledoesn't have a determinate position (prior to measurement), neither does it
have a well-definedvelocity. All we could reasonably probability of
ask for is the

gettinga particularvalue.We'll see in Chapter 3 how to construct the probability

density for velocity, ^; for given our present purposes it will suffice to
postulate that the expectation value of the velocity is equal to the time derivative of the

expectation value of position:

,(v) \\ =
d{x)
[1-32]
dt

Equation 1.31 tells us, then, how to calculate (v) directly from ^.
Actually, it is customary to work with momentum (p = mv), rather than

velocity:

[1.33]

14
The product rule says that

d.f, ,.dg df
ax ax dx

from which it follows that

Under the integral sign. then, you can peel a derivative off one factor in a product, and slap it onto the
other one\342\200\224it'll cost you a minus sign, and you'll pick up a boundary term.
 Section 1.5: Momentum 17

Let me write the

expressions for (.v) and (p) in a more suggestive way:

= [1.34]
(a-)
J ty*(x)Vd.x,

(p)= [1.35]
Jv*(j^)vdx.
We say that the operator15 x \"represents\" position, and the operator(/?//)(3/3.v)
\"represents\" momentum, in quantum mechanics; to calculate expectation values we
\"sandwich\"the appropriateoperator between ^* and ^, and integrate.
That's cute, but about other quantities? what The fact is, all classical
dynamicalvariables can be expressed in terms of position and momentum.Kineticenergy,
for example, is

l
rT = -mv 2 = P2 \342\200\224,
2 2m

and angular momentum is

L = r x m\\ = r x p

course, does not occur motion

(the latter, of for in one dimension). To calculate
the expectation of any such quantity, Q{x,
value
p), we simply replace every p

by (fi/i)(d/dx), insert the resulting operator between ^* and ^, and integrate:

(Qix.p)) = [1.36]
J**Q(x,~^Vdx.

For example,the expectation value of the kinetic energy is

a2*
(T) = I1371
W*a^
Equation
1.36 is a recipe for computing the expectationvalue of any dynamical

quantity, for a it subsumesEquations1.34

particle in state ^; and 1.35 as special
cases. I have tried in this section to Equation 1.36 seem make
plausible, given
Bom's statistical interpretation,but the that this represents truth is such a radically
new way
of doing business (as compared with classical mechanics) that it's a good
ideato get some practice using it before we come back (in Chapter 3) and put it
on a firmer theoretical foundation. In the meantime, if you prefer to think of it as

an axiom, that's fine with me.

'-''An \"operator\" is an instruction lo do something lo the function that follows it. The position
operator lells you lo multiply by .v: Ihe momentum operator tells you to differentiate with respect lo
.v (and multiply the result by
\342\200\224
ih). In this book all operators will be derivatives
(d/clt, ch/clt~.
a-/i)xciy. etc.) or multipliers (2. i. x~. etc.). or combinations of these.
18 Chapter 1 The Wave Function

Problem 1.6 Why can't you directlyonthemiddle

do integration-by-parts
expression in
Equation 1.29\342\200\224pull
the time derivative over onto x, note that dx/dt = 0,
and conclude that
d(x)/dt
= 0?

^Problem 1.7 Calculate d{p)/dt. Answer:

Equations1.32 (or the first part of 1.33) and 1.38 are instances of Ehrenfest's
theorem, which tells us that expectation values obey classical laws.

Problem 1.8 Suppose you

add a constant Vo to the potential energy (by
\"constant\"

I mean independent of x as well as /). In classical

mechanics this doesn't change

anything, but what about quantum mechanics? Show that the wave function picks
up a time-dependent phase factor: exp(\342\200\224iV^t/h).
What effect does this have on
the expectation of a dynamical value variable?

1.6 THE UNCERTAINTY PRINCIPLE

Imagine that
you're holding rope, and you generatea
one end of a very long
wave
by shaking it up and down rhythmically (Figure 1.7). If someone asked you

\"Precisely where is that wave?\" you'd probably think he a little bit nutty: The was

wave isn't precisely where\342\200\224it's spread

any
out over 50 feet or so. On the other
hand,if he asked what its wavelength
you is, you could give him a reasonable
answer:It looks about 6 feet. By contrast, if you gave the rope a suddenjerk
like

(Figure 1.8), you'd get a relatively narrow bump traveling down the line. Thistime
the first
question (Where precisely is the wave?) is a sensibleone, the second and

(What is its wavelength?) seems nutty\342\200\224it isn't even vaguely periodic, so how
can you assign a wavelength to it? Of course, you can draw intermediate cases, in

which the wave is fairly well localizedand the wavelength is fairly well defined,
but there is an inescapable trade-offhere:The more precise a wave's position is,
the less preciseis its wavelength,
and vice versa.16 A theorem in Fourier analysis
makes all thisrigorous, but for the moment I am only concerned with the qualitative
argument.

That's why a piccolo player must be right on pitch, whereas a double-bass player can afford to
wear garden gloves. For the piccolo, a sixty-fourth note contains many full cycles, and the frequency
(we're working in the time domain now, instead of space) is well defined, whereas for the bass, at a
much lower register, the sixty-fourth note contains only a few cycles, and all you hear is a general sort
of \"oomph,\" with no very clear pitch.
 Section 1.6: The Uncertainty Principle 19

50 x (feet)

FIGURE 1.7: A wave with a (fairly) well-defined wavelength,

but an ill-defined

position.

AH
* 10 20 30 40 50 x (feet)

FIGURE 1.8: A wave with a (fairly) well-defined position, but an ill-defined

wavelength.

This applies, of course, to any wave phenomenon, and hencein particularto

the quantum
mechanical wave function. Now the wavelength of ^ is relatedto the
momentum of the particle by the de Broglie formula:17

h lit ft
P = = [1.39]
l
Thusa spreadin wavelength corresponds to a spread in momentum, and our general
observation now
says that the more precisely determined a particle's position is,
is
the lessprecisely its momentum. Quantitatively,

[1-40]

where ax is the standard deviationin x, ap

is the and standard deviation in /?.
This is Heisenberg'sfamousuncertaintyprinciple. (We'll prove it in Chapter 3,
but I wanted to mentionit right so you can test away,
it out on the examples in
Chapter 2.)
Please understand what the uncertainty principle means: Like position
measurements, momentum measurements yield precise answers\342\200\224the
\"spread\" here

refers fact that measurements on identicallypreparedsystems

to the do not yield
identical results. You can, if you want, construct a state such that repeated
position measurements will be very close together (by making ^ a localized\"spike\,
but you will pay a price: Momentum measurements on this state will be widely
scattered. Or you can prepare a slate with a
reproducible momentum (by making

l7I\"ll prove this in due course. Many authors lake the de Broglie formula as an axiom, from
which they then deduce the association of momentum with the operator (h/i)(B/dx). Although this is
a conceplually cleaner approach, il involves diverting mathematical complications lhal I would rather

save for later.

20 Chapter 1 The Wave Function

^ sinusoidal wave), but in that case, positionmeasurements

a long will be widely
scattered. And, of course, if you're in a really bad moodyou can create a state for
which neither position nor momentum is well defined: Equation 1.40 is an
inequality,and there's no limit on how big ax and ap can be\342\200\224just
make ^ some long
wiggly line with lots of bumpsand potholes and no periodic structure.

* Problem 1.9 A
particle of mass m is in the state

V(x,t) = Ae-al(mx2/ti)+i'\\

where A and a are positive real constants.

(a) Find A.
(b) For what
potential energy function V(x) does ^ satisfy the Schrodinger
equation?
(c) Calculate the
expectation values of x, x~, p, and p .
(d) Find ax and
ap.
Is their product consistent with the uncertainty principle?

FURTHER PROBLEMSFOR CHAPTER 1

Problem 1.10 Consider of tt

the first 25 digits in the decimalexpansion (3, 1, 4,

1,5,9,...).

(a) If you selected one numberat random,fromthisset,what are the probabilities

of getting each of the 10 digits?

(b) What is the most probable digit? What is the median digit? What is the

average value?

(c) Find the standard deviation for this distribution.

Problem 1.11broken car speedometer is

The needle on a free to swing,
and

bounces perfectly off the pins at either end, so that if you give it a flick it is
equally likely to cometo restat any angle between 0 and tt.

(a) What is the probability density, p(0)? Hint: p(6)d6 is the probabilitythat
the needle will come to rest between 9 and (0+d0). Graphp(0) asa function
of 6, from \342\200\224tt/2
to 3tt/2. (Of course, part of this interval is excluded,so p
is zero there.) Make sure that the total probability is 1.
 Further Problems for Chapter 1 21

(b) Compute (6), (0-), and a, for this distribution.

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

Problem 1.12 We consider the same device as the previous problem, but this time
we are interested in the .*-coordinate of the needle point\342\200\224that is, the \"shadow,\"
or \"projection,\" of the needle on the horizontalline.

(a) What is the probability density p(.r)? Graph p(x) as a functionof ,v, from
to
\342\200\2242r +2/-, where r is the length of the needle.Makesurethe total
probability
is 1. Hint: p(x)dx is the probability that the projection lies between
x and (x + dx). know (from You Problem 1.11) the probability that 9 is in
a given range;the questionis, what interval dx corresponds to the
interval dOl

(b) Compute (x), (x2), and a, for this distribution.

Explain
how you could have
obtained these results from part (c) of Problem 1.11.

* * Problem 1.13 Buffon's needle. A needle of length dropped at random onto a

/ is
sheet of paperruled with
parallel lines a distance I apart. What is the probability
that the needle will cross a line? Hint: Refer to Problem1.12.

Problem1.14 Let Pab(t) be the probability of finding a particle in the range

(a < x < h), at time t.

(a) Show that

**J\302\260\302\261
=
j(a.t)-J(b.t),
dt

where

ift ( dV
J(x.t) = \342\200\224
4/
[V^^-V*
\342\200\224

2\302\273r V
2/7/ \\ 3,v
dx dx

What units of J(x. t)l Comment:

are the J is called the probability current,
because it tells you the rate at which probabilityis \"flowing\" past the point
x. If Pc,b(t) is increasing, then more probability is flowing into the region at
one end than flows out at the other.

(b) Find the probability current for the wave function in Problem 1.9. (This is
not a very pithy example, I'm afraid; we'll encounter more substantial ones
in due course.)
 The Wave Function

* Problem 1.15 Suppose you wanted to describe an unstable particle, that

spontaneously disintegrates with a \"lifetime\" t. In that case the total probabilityof

finding
the particle somewhere should not be constant, but should decrease at

(say) an exponential rate:

'+00
Pit) \\V(x,t)\\2dx = e-'tT.
/-t-oo
-00

A crude way of achieving this result is as follows. In

Equation 1.24 we tacitly
assumed that V\" (the potential energy) is real. That is certainly reasonable, but it
leads to the \"conservation of probability\" enshrined in Equation 1.27. What if we
assignto V an
imaginary part:

V = Vo-iT,

where Vq is the true potential energy and r is a positivereal constant?

(a) Show that (in place of Equation 1.27) we now get

dt n
(b) Solve for P(t), and find the lifetime of the particle in terms of F.

Problem1.16 Show that

d f\302\260\302\260
\342\200\224
/ ** vj/, dx = 0
dt y_oo
for any
two (normalizable) solutions to the Schrodinger equation, ty\\ and vi/2.

Problem 1.17 A particle is represented (at time t = 0) by the wave function

f A(a2-x2]

I o. otherwise.

(a) Determine the normalizationconstantA.

(b) What is the expectation value of .v (at time t = 0)?

(c) What is the expectation value of p (at time t = 0)? (Note that you cannot

get it from p = md{x)/dt. Why not?)

(d) Find the expectation value of x2.

(e) Findthe expectation value of p2.

(f) Find the uncertainty in .v (ax).

 Further Problems for Chapter 1 23

(g)
Find the uncertainty in p (crp).

(h) Check that your results are consistentwith the uncertainty principle.

Problem 1.18 mechanicsis

In general, quantum relevant when the de Broglie
wavelength of the particle in question(h/p) is greater than the characteristic size
of the system (d). In at (Kelvin) thermal
equilibrium temperature 7\\ the average
kinetic energy of a particleis

p- =
\342\200\224
3
-kBT
2/77 2

(where ks is Bol'tzmann'sconstant),so the

typical
de Broglie wavelength is

_ h
v/3/77/V/jr

this problemis
The purpose of to
anticipate which systems will have to be treated
quantum mechanically,and which can safely be described classically.

(a) Solids. The lattice spacingin a typicalsolidis around d = 0.3 nm. Find the
temperature below the free18 electrons in which a solid are quantum
mechanical. Below what temperature are the nuclei in a solid quantum mechanical?

(Use sodium as a typical case.) Moral: The free electronsin a solid are

always quantum mechanical; the nuclei are almost never quantum

mechanical.The same goes for liquids (for which the interatomicspacingis roughly
the same), with the exception of helium below 4 K.
(b) Gases. For what temperatures are the atoms in an ideal gas at
pressure P

quantum mechanical? Hint: Use the ideal gas law {PV

= NkgT) to deduce
the interatomic spacing. Answer: T < (I/ ks)(h2 /3m)*/5 P2^5. Obviously
(for the gas to show quantum behavior) we want as possible,
m to be as small
and P as large
as possible. Put in the numbers for helium at atmospheric
pressure.Is hydrogen in outer space (where the interatomic spacing is about
1 cm and the
temperature is 3 K) quantum mechanical?

l8In a solid Ihe inner electrons are attached to a particular nucleus,and for them the relevant
size would be the radius of the atom. But the outermost electrons are not attached, and for them the
relevant distance is the lattice spacing. This problem pertains to the outer electrons.
CHAPTER 2

TIME-INDEPENDENT

SCHRODINGER EQUATION

2.1 STATIONARY STATES

In Chapter 1 we talked a lot about the wave function, and how you use it to
calculate various quantities of interest.Thetimehascome to stop procrastinating,
and confront what is, logically, the prior question:How do you get ^(x, t) in the
first place? We need to solve the Schrodinger equation,

9vl/ h1 92*
/ft\342\200\224=
-
\342\200\224\342\200\224+ V\302\245. [2.1]
dt 2m dx-

for a specified potential1 V(x, t). In this chapter (and most of this book) I shall
assume that V is independent of t. In that case the Schrodinger equationcan be
solved by
the method of separation of variables (the physicist's first line of attack
on any partial differential equation): We look for solutions that are simpleproducts,

V(x.t) = f{x)<p(t). [2.2]

where xj/ (lower-case) is a function of .v alone, and <p
is a function of t alone. On
its face, this is an absurd restriction, and we cannot hope to get more than a tiny

'It is tiresome to keep saying \"potential energy function.\" so most people just call V the
\"potential.\" even though this invites occasional confusion with electric potential, which is actually
potential energy per unit charge.

24
 Section 2.1: Stationary States 25

subsetof all solutions in this way. But hang on, because the solutions we do obtain

turn out to be of great interest. Moreover(as is typically the case with separation
of variables) we will be able at the end to patch together the separable solutions
in such a way
as to construct the most general solution.
For separable solutions we have

9* dtp d2V d2yfr

v 2
dt dt dx =^

equationreads
(ordinary derivatives, now), and the Schrodinger

h2
d2f

2m dx-

Or, dividing through by yfr<p:

h2 1 d2ir
\342\200\224
in + V. [2.3]
<p dt 2m \\f/
dx2

Now, the left side is a functionof t alone, and the right side is a function of
x alone.2 The only way this can possibly be true is if both sides are in fact

constant\342\200\224otherwise, by varying t, I could change the left side without touching

the right side, and the two would no longerbe equal. (That's a subtle but crucial

argument, so if it's new to you,be sure to pause and think it through.) For reasons
that will appearin a moment, we shall call the separation constant E. Then

.\342\200\236ld<p
//2--7-
= \302\243.

<p
dt

or
d<p iE

~dt=~ h
[2.4]

and
h2 1 d2xj/
+ v --= E.
2m \\j/ dx2

or
h2 d2i/
2m dx1
Ef. [2-5]

ofvariableshas
Separation turned a
partial differential equation into two
ordinary differential equations (Equations 2.4 and 2.5). The first of these(Equation
2.4)

-Note that this would not be true if V were a function of t as well as .v.
Time-Independent Schrodinger Equation

is easy to solve(just multiply through by dt and integrate); the general solution is

C exp(\342\200\224i.Et/Ii),
but we might as well absorb the constant C into \\j/ (since the quantity
of interest is the product yjr<p).
Then

(p(t)
= e-[Et^. [2.6]

The second (Equation2.5)is the time-independent called

Schrodinger equation;
we can go no further it until the potentialwith V(x) is specified.
The rest of this chapter be devoted to solving the time-independent
will

Schrodinger equation, for a of simple potentials. But

variety
before I get to
that have every
you right to ask: What's so great about separablesolutions?
After all, most solutions to the (time dependent) Schrodinger equation do not
take the form \\Jf(x)<p(t). I offer three answers\342\200\224two of them physical, and one
mathematical:
1. They are stationary states. Although
the wave function itself,

y(x,t) = xl/(x)e-iE'/n, [2.7]

does (obviously)dependon t, the

probability density,

|vi/(X; t)\\2 = *** = ^e+iEt'hi;e-iE,'h = |i/r(x)|2, [2.8]

does not\342\200\224the time-dependence cancels out.3 The same thing happens in

calculating
the expectation value of any dynamical variable; Equation 1.36 reducesto

(Q(X, p))
=
^*Q L l\302\261\\^djCt [2.9]
j

Evety expectation value is constant in time; we might as well dropthe factor <p(t)

altogether, and simply use \\j/

in place (Indeed, it is common to refer to
of ^. \\Jf as

\"the wave function,\" but this is sloppy language can be dangerous, and that it is
important to remember that the true wave function always carries that exponential
time-dependent factor.) In particular, {x) is constant, and hence (Equation 1.33)
(p) = 0. Nothingever happensin a stationary
state.

2. They are states of definite total energy. In classicalmechanics,

the total

energy (kinetic plus potential) is called the Hamiltonian:

P2
H(x,p) = ^-
2m
+ V(x). [2.10]

3 For normalizable solutions,E must be real (see Problem 2.1(a)).

 Section 2.1: Stationary States 2.7

The corresponding Hamiltonian

operator, obtained by the canonical substitution
p -> (h/i)(d/dx), is therefore4
h2 92
H =
---^+ V(x). [2.11]
2m ox-
Thusthe time-independent Schrodinger equation (Equation 2.5) can be written

Hf = Ejfr, [2.12]

and the expectation value of the total energy is

(H)= f f*Hirdx = E ( \\yj/\\2

dx = E f \\V\\2dx = E. [2.13]

(Notice that the normalization of *I/ entails the normalization of \\j/.)Moreover,

H2ir = H(Hir) = H{Ef) = E(Hf)

=
E2i/,

and hence

(H2) = f yj/*H2yj/dx= E2 = E2.

j \\^\\2dx

So the variance of H is

ajd = (H2)-(H)2 = E2-E2=0. [2.14]

But remember, if a = 0, then every memberof the sample must share the same
value (the distribution has zero spread). Conclusion:A separable solution has the

property that every measurement of the total energyis certainto return the value
E. (That's why I chose that letter for the separation constant.)
3. The
general solution is a linear combination of separable solutions. As
we're about to discover, the time-independent Schrodinger equation (Equation2.5)
yields an infinite collection of solutions (ijfi(x), xj/jix), foix),...), each with

its associated value of the separation constant (E\\, Ei, thus there is a \302\2433,...);

different wave function for each allowedenergy:

*i (x, t) = xl/{(x)e-iEi'/h, vi/2(A% t)

= if2(x)e-iE2^h, ....
Now (as you can easily check for yourself) the (time-dependent) Schrodinger
equation (Equation 2.1) has the property that any linear combination5of solutions

4Whenever confusion might arise. I'll put a \"hat\" C) on the operator, to distinguish it from the
dynamical variable it
represents.

5A linear combination of the functions f\\ (z). /2(2) is an expression of the form

/U) = n/iU) + Q/2(<-) + --- \342\200\242

where q. ct. ... are any (complex) constants.

Time-Independent Schrodinger Equation

is itself a solution. Once we have found the separable solutions, then, we can
immediatelyconstructa much more general solution, of the form

CO

\302\245(*. t)
= [2.15]
J^cMx)e-',E\"'/h-
11=1

It so happens that every solution to the (time-dependent) Schrodinger equation

can be written in this form\342\200\224it is simply a matter of finding the right constants
(cj, ci, ...) so as to fit the initial hand. You'll see
conditions for the problem at
inthe following
sections how all this works out in practice, and in Chapter3 we'll

put
it into more elegant language, but the main point is this:Once solved you've

the ti me- in dependent Schrodinger equation, you're essentiallydone; from getting

there to the general solution of the time-dependent Schrodingerequationis, in

principle, simple and straightforward.

has happened in the last four pages,so let me recapitulate,
A lot from a
somewhat different perspective. Here's the genericproblem:You'regiven a (time-

independent) potential V(x), and the starting wave function^(.v,0); your job is

to find the wave function, ^(x, t), for any subsequent time t. To do this you must
solvethe (time-dependent)
Schrodinger equation (Equation 2.1). The strategy6 is
first to solve the time-in dependent Schrodinger equation (Equation 2.5); this yields,
in general, an infinite set of solutions (\\j/\\ (x), \\j/2(x), 1^3CO,.. each
\342\226\240), with its own
associated energy (\302\2431, Ei, \302\2433,...). To fit ^(a-,0) you write down the general
linearcombination of these solutions:

00

vI/(x,0) = [2-16]
]Tc,,iMa-):

the miracleis that

you can always match the specified initial state by appropriate

choice of the .
constants c\\, ci, C3, ... To construct W(x, t) you simply tack onto
each term its characteristic
timedependence, exp(\342\200\224/\302\243,,///2):

00 CO

-iE\342\200\236t/tt
V(x. 0-- ,if\342\200\236(x)e r%(-V 0.
\302\273=1 \302\273=1

The separable solutions themselves,

%(x,t) = ifn(x)e-iE\"'/r\\ [2.18]

\"Occasionally you can solve the time-dependent Schrodinger equation without recourse to
separation of variables\342\200\224-see. for instance. Problems 2.49 and 2.50. But such cases are extremely rare.
 Section 2.1: Stationary States 29

are stationarystates, sense that in the all probabilities and expectation values are
independentof time, property but this is emphatically not shared by the general
solution(Equation2.17); the energies are different, for different stationary states,
and the exponentialsdo not cancel, when you calculate |^|2.

Example 2.1 Suppose a particle starts out in a linear combination of just two

stationary states:

*(*. 0) = ci fi (x) + cifiix).

(To keep things simple I'll assume that the constants cn and the states \\j/n(x)
are

real.) What is the wave function *I>(a\\ t) at subsequent times? Find the probability
density, and describeits motion.
Solution: The first part is easy:

vl/(A% t)
= c\\f\\{x)e-iE^fh + c2 i/o (*)<?\"'\" \302\2432'//!,

where E\\ and Ei are the energies associated with

\\f/[ and xj/j. It follows that

|y(.v,Ol2 = (cifieiE^^ +c2f2eiE2/h)(ciirie-iEi,/'1 +C2f2e~iE2/l1)

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

(I used Euler's formula, expIB \342\200\224

cos B -f- i sin B, to simplify the result.)Evidently
the
probability density oscillates sinusoidally, at an angular frequency (E2\342\200\224
Ei)/h;
this is certainly not a stationary state. But notice that it took a linear combination
of states (with different energies)to produce motion.7

^Problem 2.1 Prove the following three theorems:

(a) For normalizablesolutions, the
separation constant E must be real. Hint:
Write E (in Equation2.7) as +
\302\243o 'T (with Eq and F real), and show that

if Equation 1.20 is to hold for all t, T must be zero.

(b) The time-independent wave function \\j/(x) can always

be taken to be real
(unlike ty(x. t), which is necessarily complex). This doesn't mean that every
solution to the time-independentSchrodingerequationis real; what it says

is that if you've got one that is not, it can always be expressed as a linear
combination of solutions (with the same energy) that are. So you might as
well stick to i/r's that are real. Hint: If i/(x) satisfies Equation 2.5, for a
given E, so toodoes its complex conjugate, and hence also the real linear
combinations (i/r + \\f/*) and i(if/
\342\200\224
if/*).

'This is nicely illustrated by an applet at the Web site http://lhorin.adnc.com/~topquarky

quantum/deepwellmain.html.
30 Chapter! Time-Independent Schrodinger Equation

(c) If V(x) is even function an (that is, V(\342\200\224x)

= V(x)) then \\j/(x) can always
be taken to be either even or odd. Hint: If yfr(x) satisfies Equation 2.5, for
a given E, so too does \\f/(\342\200\224x),
and hence also the even and odd linear
combinations yfr(x)
+
\\fr(\342\200\224x).

*Problem 2.2 Show that E must exceed the minimum value of V(x), for every
normalizable solution to the time-independent Schrodinger equation.What is the

classical analog to this statement? Hint: Rewrite Equation in the form

2.5

d2i/ 2m

dxl tr

if E < Vmin, then \\j/ and its second derivative always have the same sign\342\200\224argue

that such a function cannot be normalized.

2.2 THE INFINITE SQUARE WELL

Suppose

0. ifO<A'<\302\253,
V(x)
otherwise
[2.19]
oo.

(Figure 2.1). A in this

particle potential is completely free, except at the two ends
(x = 0 and x =a), where an infinite force preventsit from escaping.A classical
model would be a cart on a frictionless horizontalair track, with perfectly
elastic

bumpers\342\200\224it just keeps bouncing back and forth forever. (This potential is
artificial, of course, but I urge you to treat it with respect. Despiteits simplicity\342\200\224or

rather, precisely because of its simplicity\342\200\224it

serves as a wonderfully
accessible test case for all the fancy machinery that comes later. We'll refer back to it

frequently.)

V(x)i

->- FIGURE 2.1: The infinite square well poten-

x tial (Equation 2.19).
 Section 2.2: The InfiniteSquare Well 31

Outside the well, ij/(x) = 0 (the probabilityof finding the particle there is
zero). Inside the well, where V = 0, the time-independent Schrodinger equation
(Equation 2.5) reads
h2 d2ir
=
y Ex//, [2.20]
2m dx

or
d2^ 1^ , u r
=
^2m\302\243
mil
\342\200\224=-= \342\200\224k-d/, where /: \342\200\224-\342\200\224. [2.21]
dx1 h

(By writing it in this way, I have

tacitly assumed that E > 0; we know from
Problem2.2 that E < 0 won't work.) Equation 2.21 is the classicalsimple
harmonic oscillator equation; the general solution is

\\//(x) = A s'mkx + B cos kx, [2.22]

where A and B are arbitrary constants. Typically, these constants are fixed by the

boundary conditions of the problem. What are the appropriateboundary

conditions for i/f(x)? Ordinarily, both yj/
and d\\J//dx are continuous, but where the
potential goes to infinity only the first of these applies. (I'll prove these boundary
conditions, and account for the exception when V = oo, in Section 2.5; for now I
hope you
will trust me.)

Continuity of \\//(x) requires that

^(0) = \\/r(a)
= 0, [2.23]

so as to join onto the solutionoutsidethewell.What does this tell us about A and

5? Well,

t/K0)
= Asin0 + ficos0 = fi,

so B = 0, and hence

i/r(x)
= Asmkx. [2.24]

Then \\j/(a) = Asinka, so either A = 0 (in case we're left with

which the
trivial\342\200\224non-normalizable\342\200\224solution }Jr(x)
= 0), or else sin ka = 0, which means

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
solutions give nothing new, since sin(\342\200\2240)
= \342\200\224
sin(0) and we can absorb the
minus sign into A. Sothe distinct solutions are

mt
=
k\342\200\236 \342\200\224. with n = 1, 2, 3. ... [2.26]
a
 Time-Independent Schrodinger Equation

A
Vi(*)| V|/2(X) \302\2453W-

FIGURE 2.2: The first three stationary states oftheinfinite square well (Equation 2.28).

Curiously, the boundary condition at x = a

doesnot determine the constant

A, but rather the constant k, and hencethe possiblevaluesof E:

[2.27]

In radical contrast to the classical case, a quantum particle in the infinite square
well cannot have
just any old energy\342\200\224it
has to be one of these special allowed
values.8To find A, we normalize \\}/:

|A|2 sm2(kx) dx = | A\\2- = 1, so \\A\\2

= -.
fJo 2 a

This only determinesthe magnitudeof A, but it is simplest to pick the positive real
root: A =
*J2/a (the phase of A carries no physical significance anyway).
Inside

the well, then, the solutions are

(X)
= J~ [2.28]
tyn
v!sin(T*)-

As
promised,
the time-independent Schrodinger equation has delivered an
infinite set of solutions (one for each positive integer n). The first few of theseare
plottedin Figure
2.2. They look just like the standing waves on a stringof lengtha;
\\J/\\, which carries the lowest energy, is called the ground state, the others,whose
energies increase in proportion to n2, are called excited states. As a collection, the
functions ^\342\200\236(x) have some interesting and important properties:
1. They are alternately even and odd, with respect to the center of the well:
t/^i is even, \\j/2 is odd, 1//3 is even, and so on.9

8Nolice lhal the quantization of energy emerged as a rather technical consequence of the
boundaryconditions on solutions to the time-independent Schrodinger equation.
9To make this symmetry more apparent, some authors center the well at the origin (running it
from \342\200\224
a to The even
+\302\253)\342\200\242 functions are then cosines, and the odd ones are sines.SeeProblem 2.36.
 \\

Section 2.2: The Infinite Square Well 33

2. As you go up in energy, each successive statehas one more node (zero-

crossing): \\f/i
has none (the end points don't count), fa has one, fa has two, and
so on.
3. They are mutually orthogonal, in the sense that

[jfm(xrfa(x)dx
= 0, [2.29]

whenever m ^ n. Proof:

I fat(x)*fa(x) dx = - / sin sin dx

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

1 rr \\ fm+n
= -1 cos (m-n Ttx \342\200\224
cos Ttx
\\~|
dx
,

a Jo I V a J \\
a
/J

\342\200\224
. (m n \\ 1 . (m + n \\\\
\342\200\224\342\200\224 \342\200\224
sin Ttx sin Ttx \\
(m
\342\200\224
n)Tt
n)it \\
\\ aa )/ (in +
(in + n)Tt \\ a ) \\

sin[(w \342\200\224
n)rt] sin[(w + n)7t]
= 0.
il (m \342\200\224
n) (m + n)

Note that this argument does not work if m = n. (Can you spot the point at which
it fails?) In that case nonnalization tells us that the integral is 1. In fact, we can
combine orthogonalityand normalization
intoa single statement:10

/ fa,(x)*fa (x)dx = 5,,,,,, [2.30]

where 5,,,,,(the so-calledKronecker delta) is defined in the usual way,

_ J 0, if iw
#\302\253;
[231]
1. \\fm=n.
5\"\"'-j

We say that the \\J/'s

are orthonormal.

4. They are complete, in the sense that

any other function, ./(.*), can be
of them:
expressed as a linearcombination
oo nr oo

fix) = = sin [2.32]

]T c\342\200\236fa(x)
J- ]T c\342\200\236
(\342\200\224.vj
n=\\ /7=1

In this case the Vr's-are real, so the * on rjrm is unnecessary, but for future purposes it's a good
idea to get in the habit of putting it there.
 Time-Independent Schrodinger Equation

I'm not about to prove the completenessofthefunctions sin(tmx/a), if you've but

studied advanced calculus you will recognize Equation 2.32 is nothing but the that

Fourier series for f(x), the fact that \"any\" function can be expanded in this
and

way
is sometimes called Dirichlet's theorem.11
The coefficients can
c\342\200\236 be evaluated\342\200\224for a given f(x)\342\200\224by
a method I call

Fourier's trick, which beautifully exploits the orthonormalityof {\\//n}: Multiply

both sides of Equation 2.32 by \\//m(x)*,and integrate.

oo . oo

,\342\200\236\302\253./(*)*
= = =
cm. [2.33]
\302\243>,\342\200\236\342\200\236
/ E,/\302\253-v\302\273V,W*
/1=1 /1 = 1

(Notice how the Kronecker delta kills every term in the sum except the one for

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

=
\342\226\240n / fnO x)*f(x)dx. [2.34]

These four properties are extremely powerful,and they are not peculiar to the
infinite square well. The first is true whenever the potential itself is a
symmetric
function;the secondis universal, regardless of the shape of the potential.13
Orthogonality
is also quite general\342\200\224I'll
show you the proof in Chapter 3. Completeness
holds for all the
potentials you are likely to encounter, but the proofs tend to be
nasty and laborious; I'm afraid most physicists simply assume completeness, and
hope for the best.
The stationary states (Equation 2.18) of the infinitesquarewell are evidently

*,,(.,.,) = sin e-'V-*/2'-2)'. [2.35]

y| (\342\204\242x)

I claimed (Equation 2.17) that the most generalsolution to the (time-dependent)

Schrodinger equation is a linear combination of stationary states:

\302\245(*. t) = sin e-''(\"~V/?/W)'. [2.36]

Y,c\302\273yJ- (\342\200\224A\")
/7 = 1

''
See, for example, Mary Boas, Mathematical Methods in the Physical Sciences, 2d cd. (New
York: John Wiley, 1983), p. 313; ,/'(.v) can even have a finite number of finite discontinuities.

'-It doesn't matter 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-
Wesley, Reading. MA, 1961), p. 126.
 Section 2.2: The Infinite Square Well 35

(If you doubt that this is a solution, by

all means check it!) It remains only for
me to demonstrate that I can fit any prescribed initial wave function, ^(.v. 0), by
appropriate choice of the coefficients c\342\200\236:

CO

=
^-,0) ^,,^).
/1=1

of the
The completeness \\j/'s (confirmed in this case by Dirichlet's
theorem)
guarantees that I can always express ^(.v,0) in this way, and their orthonormality
licensesthe use of Fourier's trick to determine the actual coefficients:

=
c\342\200\236 J- sin *(-v. 0) dx. [2.37]
(\342\200\224Jc)

Given the initial

That does it: wave function, ^(.v.0), we first compute the
expansion coefficients using Equation c\342\200\236, 2.37, and then plug these intoEquation2.36
toobtain vl>(.\\\\ t). Armed with the wave function, we are in a positionto compute any

dynamical quantities of interest, using the procedures in Chapter 1. And this same

ritual applies to any potential\342\200\224the only things that change are the functional form
of the 1^'s and the equation for the allowed energies.

Example 2.2 A
particle in the infinite square well has the initial wave function

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

a).

for some constant A (see Figure 2.3). Outside the well, of course, ^ = 0. Find

V(x.t).

A ^(x, 0)

FIGURE 2.3: The starting wave functionin Example 2.2.

 Time-Independent Schrodinger Equation

Solution: First we need to determineA, by normalizing vl>(.v, 0):

1= = |A|2
r|\302\245(jr,0)|2</jc fax2(a-x)2dx = \\A\\2^
M
Jo JO

SO

A= /?\302\260.
V a5

The /7th coefficient is (Equation 2.37)

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

\342\226\240

2v/l5 T
fa . nm v
f 2 . //77T \\
= \342\200\224=\342\200\224
<:/ .v sin I \342\200\224x dx \342\200\224
I x sin I \342\200\224x dx
/
a* v I \\ J
L Jo a Jo a
_

2\\/l5( \\/ a \\2 //77T \\ ax /nn \\\\

= \342\200\224\342\200\224
sin
\\a f\342\200\224) f\342\200\224x)
/ cos!\342\200\224a)
ai [ 1_V/77T/ \\ a /J7T V a
/J 0

\342\200\224
\342\200\236/ \\2a . (nit \\ (nitx/a)- 2 /tut \\
\342\200\224
2 I .v sin \342\200\224a*
J
cos
=\342\200\224 \342\200\224x
J
V/77r/ \\ a / {nit ay \\ a /

2v^l5 o3 3(/77T)2 -2
: =
C0S(/77T) + a1 COS(/77T)+ CT =- COS(0)
a- /77T (nity (nity

4</l5 r
-
-=; [COS(0) COS(/77T)]
(mty
if /7 is even.

10,8vT5/(/7tt)3. if /7 is odd.

Thus (Equation 2.36):

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

Loosely speaking, c\342\200\236

tells you the \"amount of that
yjf\342\200\236 is contained in vl/.\"
Some people like to say that is
|c\342\200\236|2 the \"probability of finding the particle in the
/7th
stationary state,\" but this is bad language; the particle is in the state not 4>,

ty,,, and, anyhow, in the laboratory you

don't \"find a particle to be in a particular
state\"\342\200\224you measure some obseivable, and what you get is a number.As we'll
see in
Chapter 3, what tells
|c\342\200\236|2 you is the probability that a measurement of the
 Section2.2: The Infinite Square Well 37

energy would yield the value (a

E\342\200\236 competent measurement will always return one
of the \"allowed\" values\342\200\224hence the name\342\200\224and is
\\c\342\200\236\\2
the probability of getting
the particular value E\342\200\236).

Of course, the sum of these probabilities should be 1,

[2.38]

Indeed, this follows from the normalization of vj/ (the are

c\342\200\236's independent of time,
so I'm going to do the prooffort = 0; if this bothers you, you can easily generalize
the argument to arbitrary t).

\\
^ / CO \\

(CO
oc oc

= fm(x)*fn(x)dx
E EC'\302\273C\302\273
/
m=\\ n=\\

CO CO CO

= =
J21lc\302\273>c\"8\302\273\"' J2\\c\"\\2-
lt=l 111=1 \302\273=1

(Again, the Kronecker delta picks out the term m = n in the summation over m.)
Moreover, the expectationvalue of the energy
must be

CO

[2.39]

n=\\

and this too can be checked directly: The time-independent

Schrodinger
equation

(Equation 2.12) says

Hfn = E\342\200\236Vo,. [2.40]

so

(H) = V*HVdx = H dx
J J (]Tc\342\200\236,Vo\342\200\236)* (][>\"V0,)

= =
E Ec'\302\273c\302\273\302\243\302\273 *\302\243*\302\273dx
/
E ic\302\273i2\302\243\302\273-

Notice that the probability of getting of time,

a particular energy is independent and

so, a fortiori, is the expectation value of H. This isa manifestation

of conservation
of
energy in quantum mechanics.
 Time-Independent Schrodinger Equation

Example 2.3 In Example

2.2 the starting wave function (Figure 2.3) closely
resembles the ground state yfr\\ (Figure 2.2). This suggests that \\c\\ \\2 should dominate,
and in fact

The rest of the coefficientsmake up the difference:14

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

480/?2
_ 5/32
y^ J_
7T4ma2 fr1^ n4 ma2
,,=1.3.5....

As one might expect, it is very close to E\\ = 7T2h~/2ma2\342\200\224slightly larger, because

of the admixture of excited states.

Problem 2.3 Show there is no acceptable that solution to the (time-independent)

= 0 or E < 0. (This is a
Schrodingerequationfor the infinitesquare well with E

special case of the general theorem in Problem 2.2, but this time do it by explicitly

solving the Schrodinger equation, and showing that you cannot meet the boundary
conditions.)

^Problem 2.4 Calculate (x), (x~), {p), (p2), ax, and ap, for the /ith stationary state
of the infinite
square well. Check that the uncertainty principle is satisfied. Which

state comes closest to the uncertainty limit?

*Problem 2.5 A
particle
in the infinite square well has as its initial wave function

an even mixture of the first two stationary states:

*U.0) = A[ylr\\(x) + f2(x)l

1
You can look up the series

1 7T6
J_ + + j_
+\"\"~_
lfl 3^ 56 %()
and

111 1 1 h \342\226\240
\342\226\240
jr4
= \342\200\224
\342\226\240

H 34 54 96
in math tables, under \"Sums of Reciprocal Powers\"or \"Riemann Zela Function.\"
 Section 2.2: The Infinite Square Well 39

(a) Normalize ^(x,0). (That is, find A. This is very easy,if you exploit the
orthonormalityof yfri. Recall that, having
%f/\\ and normalized ^ at t = 0,
you can rest assured stays normalized\342\200\224if
that it you doubt this, check it
explicitly after doingpart (b).)
(b) Find ty(x,t) and \\ty(x,t)\\2. Express the latter as a sinusoidalfunctionof
time,as in
Example 2.1. To simplify the result, let a>
=
jr-ft/2ma-.

(c) Compute (x). Notice that it oscillates in time.What is the angular frequency
of the oscillation? What is the amplitude oftheoscillation? your (If amplitude
is greater than a/2, go directly to jail.)
(d) Compute (p). (As Peter Lorre would say, \"Do it ze kveek
vay, Johnny!\

(e) If you measured the energy of this particle, what values might you get, and
what is the probabilityof gettingeachof them? Find the expectation value
of H. How doesit comparewith E\\ and \302\2432?

Problem 2.6 Although the overall phase constant of the wave function is of no

physical significance (it cancels out whenever you calculate a measurable quantity),
the relative phase of the coefficients in Equation 2.17 does matter. For example,
suppose we change the relative phase of \\f/\\ and \\j/2 in Problem 2.5:

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

where (p is some constant. Find ^(x, t), \\ty(x,t)\\-, and (,r), and compareyour
results with what you got before. Study the special cases <p = tt/2 and $> = tt.
of this
(For a graphicalexploration problem
see the applet in footnote 7.)

*Problem 2.7 A
particle
in the infinite square well has the initial wave function15

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

(a) Sketch W(x, 0), and determine the constant A.

(b) Find V(x.t).

1
is no
\342\200\242'There restriction in principle on the shape of the starting wave function, as long
as il is normalizable. In parlicular, ty(.v.O) need nol have a conlinuous derivative\342\200\224in facl, il
doesn't even have to be a conlinuous function. However,
you iry if 10 calculate (H) using
f ty(.v. 0)*//ty(.v-. 0)dx in such a case,you may encounter technical difficulties, because the second
derivative of #(x. 0) is ill-defined. Il works in Problem 2.9 because the discontinuities occur at Ihe end
points, where ihe wave function is zero anyway. In Problem 2.48 you'll see how to manage cases like
Problem 2.7.
40 Chapter2 Time-Independent Schrodinger Equation

(c) What is the probability that a measurement of the energy would yieldthe
value E\\ ?

(d) Find the expectation value of the energy.

Problem2.8 A
particle of mass m in the infinite square well (of width a) starts

out in the left half of the well, and is (at t =

0) equally likely to be found at
any

point in that region.

(a) What is its initial wave function, vJ/(a',0)? (Assume it is real. Don't forget
to normalizeit.)
(b) What is the probability that a measurement of the energy would yieldthe
value
7T2/72/2ma2l

Problem 2.9 For the wave function in Example 2.2, find the expectation value of
H, at time t = 0, the \"oldfashioned\"way:

(H)
= I V(x. 0)*HV(x, 0) dx.

Comparethe resultobtained in
Example 2.3. Note: Because (H) is independent of
time, there is no loss of
generality in using t = 0.

2.3 THE HARMONIC OSCILLATOR

The a classical
paradigm
for harmonic oscillator is a mass m attached to a spring
k. motion
of forceconstant The is governed by Hooke's law,

d2x
Fv = i =
\342\200\224kx m --^
dt-

(ignoring friction), and the solutionis

x(t) = A sin(atf) + B cos(atf),

where

co = J- m [2.41]
V

is the (angular) frequency of oscillation. The potentialenergyis

V(x)= ^kx2;
[2.42]

its graph is a parabola.

 Section 2.3: The HarmonicOscillator 41

V(X)A

FIGURE 2.4: Parabolic approximation (dashed curve) to an arbitrary potential,in

the neighborhood of a local minimum.

Of course, there's no such thing as a perfect harmonic oscillator\342\200\224if

you
stretch it too far the spring is going to break, and typically Hooke's law fails
long before that point is reached.But practically any potential is approximately

parabolic, in the neighborhood of a local minimum

(Figure 2.4). Formally, if we
expand V(.v) in a Taylor series about the minimum:

V(x) = V(x0) + V'(xo)(x - a-o) + iV\"(jto)(*

-
*o)2 + \342\226\240
\342\200\242
\342\200\242
,

subtract V(xo) (you can add a constant to V(a\") with impunity, since that doesn't

change the force), recognize that V'(xo)

= 0 (since a'o is a minimum), and drop the
terms
higher-order (which are negligible as long as (x \342\200\224
.vo) stays small), we get

V(x) =
^V\"(x0)(x-x0)2,
which describessimple harmonic oscillation the point xo), with an effective
(about

spring constant = ^\"(a-o).16 k That's why the simple harmonic oscillator is so

important: Virtually any oscillatory motion is approximately simple harmonic, as
long as the amplitudeissmall.
The
quantum problem is to solve the Schrodinger equation for the potential
t//
V(x)
\\
*
= -mco 2 x 2 [2.43]

(it is customaryto eliminate spring constant in the favor of the classical frequency,
using Equation2.41). we have seen, it suffices As to solve the time-independent
Schrodingerequation:
tr 1
2
2
= Ef. [2.44]
d2xj/
\342\226\240-
+ -mco x f
2m ax1 pj-
2

l6Note that V\"(.vo) > 0. since by assumption xq is a minimum. Only in the rare case V\"(.vo) = 0
is the oscillation not even approximately simple harmonic.
 Time-Independent Schrodinger Equation

In the literature find two you will entirely different approaches to this problem.
The first is a straightforward \"brute force\" solution to the differential equation,
using the power series method; it has the virtue that the same strategy can be
appliedto many
other potentials (in fact, we'll to use it in Chapter 4 treat the

Coulomb potential). The second is a diabolically clever algebraictechnique,

using
ladder
so-called operators.
I'll show you the algebraic method first, because it is
quicker and
simpler (and a lot more fun);17 if you want to skip the powerseries
method for now, that's fine, but you should certainly plan to study it at some

stage.

2.3.1 Algebraic Method

To begin with, let's rewrite Equation 2.44 in a more suggestive form:

\342\200\224
[p2 + {mcox)2]^
= Ef. [2.45]
2/7/

where p = {h/ i)d/dx is, of course, the momentum operator. The basic idea is to
factor the Hamiltonian,
H= \342\200\224[p2 + {mcox)2]. [2.46]
2m

If these were numbers, it wouldbe easy:

it + v~ =
{in + v){\342\200\224iu + v).

Here, however, it's not quite so simple,becausep x are operators, and and

operators do not, in general, commute {xp is not the same as px). Still, this does

motivate us to examine the quantities

^=^(^+^) [2.47]

(the factorin front is just there to make the final results look nicer).
Well, what is the product a-ci+7

1
a~a+ = {ip + mcox){\342\200\224ip + mcox)
2ft mco

= \342\200\224
[p2 + {mcox)2
- imco{xp - px)].
Inmco

17We'll encounter some of the same strategies in the theory of angular momentum (Chapter 4).
and the technique generalizes to a broad class of potentials in super-symmetric quantum mechanics
(see. for example. Richard W. Robinett. Quantum Mechanics. (Oxford U.P., New York. 1997). Section
14.4).
 Section 2.3: The Harmonic Oscillator 43

there's
As anticipated, an extra term, involving (xp
\342\200\224
px). We call this the
commutator of X and p; it is a measure of how badly they fail to commute. In general,
the commutator of operators A and B (written with square brackets) is

[A, B] = AB
- BA. [2.48]

In this notation,
1 '
CI-CI+ = IP'
-)
+ (ma>x)~]
->
- \342\200\224
[a\\ p]. [2.49]
ol.
2ft m co 2ft

We need to figure
out the commutator of a- and p. Warning: Operators are
notoriouslyslipperyto work with in the abstract, and you are bound to make

mistakes unless you give them a \"test function,\"f(x), to act on. At the end you
can throw away the test function, and you'll beleftwith an equation involving the

operators alone. In the present case we have:

=
ft d
\342\200\236
ft d
=
n df
( X\342\200\224 df \\

[Jr, p]f(x) T -X\342\200\224-f)= Iftf (A\.

i dx i dx i V dx dx J
[2.50]
Dropping the test function, which has served its purpose,

[x, p] = ih. [2.51]

This lovely
and ubiquitous result is known as the canonical commutation
relation.18

With this, Equation 2.49 becomes

1 1
a-a+ = -\342\200\224//
ftCD
+ -.
2
[2.52]

or
H = ftcD I
\342\200\224
[2.53]
a-a+

Evidently the Hamiltonian does not factor perfectly\342\200\224there's that extra \342\200\2241/2
on the

right. Notice that the ordering of a+ and a- is important here; the same argument,
with a+ on the left, yields
1
\342\200\236
1
a+a- = \342\200\224H . [2.54]
ftCD 2

In particular,
[a-,a+] = 1. [2.55]

18In a deep sense all of the mysteries of quantum mechanics can 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.

Time-Independent Schrodinger Equation

So the Hamiltoniancan equally well be written

1
H = hco I
a+a- + [2.56]

In terms of a\302\261, then, the Schrodinger equation19 for the harmonic oscillator takes
the form

= [2.57]
hco
\302\261-)f Ef
(\302\253\302\261*F\302\261i)

(in equations like this you readthe uppersignsall the

way across, or else the lower
signs).
Now, here comesthe crucialstep: claim that if satisfies the Schrodinger I \\j/

equation with energy E, (that is: =

E\\j/), then a+\\j/ satisfies the Schrodinger H\\j/

equation energy (E + hco): H(a+\\f/) = (E + hco){a+\\}/).

with Proof:

H(a+\\j/)
= hco I
a+ci- + - 1
(a+xf/) = hco I a+a-a+ + -a+ J
if/

=
hcoa+ lci-d+ + -) \\f/
=
a+ hco I
a+a- + 1+ -1^

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

(I used Equation
2.55 to replace a~a+ by a+a- + 1, in the secondline. Notice

that whereas the ordering of a+ and a- does matter, the ordering of a\302\261
and

any constants\342\200\224such as h, co, and E\342\200\224does not; an operator commutes with any
constant.)
By the same token,a-\\f/
\342\200\224
is a solution with energy (E hco):

= hco -
\342\200\224 = hcoci- I a+ci- -
\342\200\224
I
] (fl-VO
I
H(ci-\\j/) a-a+ \\f/

= a- hco I a-a+
- 1- - =
a-(H
\342\200\224 = a-(E
\342\200\224

j \\j/ hco)\\j/ hco)\\j/

= (E
- hoj)(a-i/).

Here, then, is a wonderful machine for generating new solutions, with higher and
lower energies\342\200\224if
we could find one solution,
just to get started! We call a\302\261
ladder operators, because they allow us to climb up and down in energy;a+ is
the
raising operator, and a- the lowering operator. The \"ladder\" of states is

illustrated in Fisure 2.5.

19I'm getting tired of writing ''time-independent Schrodinger equation,\" so when it's clear from
the context which one I mean. I'll just call it the \"Schrodinger equation.\"
 Section 2.3: The Harmonic Oscillator 45

FIGURE2.5: The \"ladder\" of states for the harmonic oscillator.

But wait! What if I apply the lowering operator repeatedly? Eventually I'm
going to reacha state with
energy less than zero, which (according to the general
theoremin Problem 2.2) does not exist! At some point the machine must fail.
How can that happen? We know that ci-\\j/ is a new solution to the Schrodinger
equation, but there is no guaranteethatit will be normalizable\342\200\224it might be zero,
or its square-integral might be infinite.In practice it is the former: There occurs a
\"lowest rung\" (call it \\j/o) such that

a-i,0 = 0. [2.58]

We can use this to determine \\j/q(x):

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

or
dxf/Q
mco

Xf0-
dx h

This differential equation is easy to solve:

d\\[/o mco , , mco -,
In y/Q = +
\342\200\224x\" constant.
/ to h /.V\342\200\236.V 2/J

so
_ into
A
2

xj/0(x)
= Ae 2ft .

We might as well normalize it right away:

\\ =
\\A\\2 e-'\"\302\273x2/hdx
(\302\260\302\260 =
\\A\\\\[^-
J-oo V m cc

so A1 = y/mco/jrh, and hence

[2.59]

To determinethe energy
of this state we plug it into the Schrodinger equation (in
the form of Equation 2.57), hco(a+ci- + 1/2)^0 = Eofa, and exploitthe fact that
= 0:
a-xj/o

=
\302\243o [2.60]
\\hco.

With our foot now securely plantedonthe bottom

rung (the ground state of the
quantum oscillator), we
simply apply the raising operator (repeatedly) to generate
the excitedstates,20
increasing the
energy by hco with each step:

[2.61]

where is
A\342\200\236 the normalization constant. the raising operator
By applying
(repeatedly) to t/tq, then, we can (in principle) construct all21 the stationary states of

20In the case of the harmonic oscillator it is customary, for some reason, to depart from the usual

practice, and number the states starting with n 0, instead

\342\200\224 of n = 1. Obviously, the lower limit on the
sum in a formula such as Equation 2.17 should be altered accordingly.

-lNote that we obtain all the (normalizable) solutions by this procedure. For it\" there were some
other solution, we could generatefrom it a second ladder, by repeated application of the raising and
lowering operators.But the bottom rung of this new ladder would have to satisfy Equation 2.58, and

since that leads inexorably to Equation 2.59, the bottom rungs would be the same, and hence the two
ladders would in fact be identical.
 Section 2.3: The Harmonic Oscillator 47

the hamionicoscillator. Meanwhile, without ever doing that explicitly, we have

determinedthe allowedenergies.

Example2.4 Find the first excited state of the harmonic oscillator.

Solution: UsingEquation2.61,

'
_>mo i
1/4
( d
i/i (x) =
A\\ \\ (mo)\\
= e u'
A\\a+\\j/0 -^3-+m(i)X )\\\342\200\224T

[2.62]
/ma>\\' lima) _w<jdl.2

=AiU v\342\200\224~

We can normalize it \"by

hand\":

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

I wouldn't want to calculate xf/so this way (applying the raising operator fifty

times!), but never mind: In principle Equation 2.61 does the job\342\200\224except
for the

normalization.

You can even get the normalization algebraically,but it takes some fancy

footwork, so watch closely. We know that a\302\261\\f/n

is proportional to \\j/n\302\261\\,

a+\\lfn
=
fn+\\,
c\342\200\236 a- fn = dn VOi\342\200\224i [2-63]

but what are the proportionality factors, and

c\342\200\236 First
d\342\200\236'l note that for \"any\"22
functions f(x) and g(x),
/\302\2730O

= [2.64]
f*(a\302\261g)dx (aTf)*gdx.
/00
-co \302\253/\342\200\224CO

(In the language of linear algebra, a^ is the hermitian conjugateof a \302\261.)

Proof:

= max
/ f*(ct\302\261g)dx / f*(Th\342\200\224+ )gdx..
J-cc y/lhmo) J-oo V
dx J

-~0f course, the integrals must exist, and this means that /(.v) and g(x) must go to zero at
\302\261oo.
Time-Independent Scbrodinger Equation

and integration by parts takes

f f*(dg/dx)dx to \342\200\224
J(df/dx)*gdx (the boundary
terms vanish, for the reason indicatedin footnote22),so
-I*
1
= + mcox) f =
gdx (a^fTgdx,
<

/00 -co
\302\261g)dx
y/2hm(D J-oQ l_\\
dx /OO
-oc

QED
In particular,
/\302\273CO
* = *
(fl ^/i) (A ^/i)
\302\261
^A\"
(flTfl VOi) VOi ^A' \342\200\242

/OO
\302\261
/ \302\261
-co J-oc

But (invoking Equations 2.57 and 2.61)

a+a-fn = mjr\342\200\236, a-a+f\342\200\236

=
(n+l)f\342\200\236. [2.65]

so

/\302\2730C

=
|T/r\342\200\236+I|2c/A\" (/1 +
1)/ ./-co l^nl2^-
J-oc /OO -co
\302\273oo /\302\273CO /\302\273CO

= = n
(\302\253_^,)*(\302\253-^)^ K|2 / |^,-i|2\302\253/jr llM2*/*.
/OO
-OO \302\253/\342\200\224oo
/
\302\253/\342\200\224OO

But since and

\\j/\342\200\236 +_ \\
^r\342\200\236
are normalized, it follows that \\c\342\200\236
\\~
= n +1 and |2
=
|J\342\200\236 \302\273,

and hence

a+f\342\200\236
= Jn + 11/0,+1, fl-^n = Vnfn-i- [2.66]

Thus

1 1 ,

1 1 1 1
* = =
(fl+)Vo*
71\302\260^1 VJT2 V4 V4\342\200\2423
\342\200\242
2

and so on. Clearly

= [2.67]
^/1 -j== (0+^^0-

which is to say that the normalization factor in Equation 2.61 is An

=
1/VhT (in
particular, A\\
= 1, confirming our result in Example 2.4).
 Section2.3: The Harmonic Oscillator 49

As in the case of the infinite squarewell,the stationary states of the harmonic

oscillator are orthogonal:

f*fndx = 5, inn- [2.68]

/co-oc
This can be proved using Equation 2.65, and Equation2.64 twice\342\200\224first
moving

a+ and then moving a_:

/\302\273oo
*
(a+fl-)
ir*\342\200\236
dx
ir\342\200\236 =n I tfr dx
f\342\200\236
/oo-oo J -oo
/\302\2730O

{a-\\jrm)*{a-ifn)dx= / (a+a-f,\342\200\236)*$\342\200\236
dx
/OO
-oo J\342\200\224oc

CO

fmfndx.
='\"/ oo

Unless w = /7, then, f\\l/*\\f/\342\200\236dx

must be zero. Orthonomiality means that we
can again use Fourier's trick (Equation 2.34) to evaluate the coefficients, when we
expand ty(x,0) as a linear combination of stationary states (Equation 2.16), and
is
|c\342\200\236|2 again the probability that a measurement of the energy would yield the
value En.

Example 2.5 Find the expectation value of the potential energy in the /7 th state
of the harmonic oscillator.
Solution:
1 tt\\ 1 o/ 1
(V) = { -mco~x~) = -ma>~ I \\js*x-\\j/n
d: x.
2\"

There's a beautiful device for evaluating integralsof thiskind (involving powers

of .,v or p): Use the definition (Equation 2.47) to express .v and p in terms of the
raising and lowering operators:

h lima)
=
(C1++CI-): p /./ \342\200\224-\342\200\224(\302\253+\342\200\224fl_). [2.69]
2m (o

In this example we are interestedin .v2:

n r
A'\" =
(a+)2 + (a+a-) + (fl_fl+) + (a-)2
2ni(o

So
ft\302\256
f I*
(V) *: (a+)~ + (a+a-) + (fl-fl+) + (ci-Y \\j/n
dx.
-T
 Time-Independent Schrodinger Equation

But (a+)2Voi is (apart from normalization)1^,,+2, is orthogonal to which \\j/n,

and

the same goes for (a-)2\\f/n, which is proportional to i/n-2- So those terms drop

out, and we can use Equation 2.65 to evaluate the remainingtwo:

(V)
=
ha)
\342\200\224
(n + n + 1) =
1
-ha> In +
(
- .
\\\\

J
As it
happens, the expectation value of the potential energy is exactly half the
total (the other half, of course, is kinetic). This is a peculiarity of the harmonic
oscillator,as we'll see later on.

\342\231\246Problem 2.10

(a) Construct 1/^2 (-0-

(b) Sketch \\J/o, \\j/\\, and 1/0.

(c) Check the orthogonality of t/tq, \\j/\\, and 1/0, by explicit integration. Hint: If
you exploit the even-ness and odd-ness of the functions, there is really only
one integral left to do.

\342\231\246Problem 2.11

(a) Compute (x), (/?). (.v2), and (p2), for the states\\f/o (Equation 2.59) and \\f/\\

(Equation 2.62), by explicit integration. Comment: In this and other problems

involving
the harmonic oscillator it simplifies matters if you introduce the
variable =
\302\243 s/mco/h x and the constant a = (mco/nh)x^.

(b) Checkthe uncertainty principle for these states.

(c) Compute (T) (the average kinetic energy) and {V) (the average potential
energy) for these stales. (No new integrationallowed!)Is theirsumwhat you
would expect?

*Problem 2.12 Find (a*),(p), (x2), (p2), and (T), for the /7th stationary state of the
harmonic oscillator,usingthemethodof Example
2.5. Check that the uncertainty
principle is satisfied.

Problem 2.13 A
particle in the harmonic oscillator potential starts out in the state

*(.r.O) = A[3^o(*)+4TM.v)].
(a) Find A.

(b) Construct *(.v.r) and |vI/(a\\f)|2.

 Section2.3: The Harmonic Oscillator 51

(c) Find (x) and (p). Don't get too excited if they oscillate at the classical

frequency; what would it have been had I specified faix), instead of \\j/\\ (x)?
Check that Ehrenfest's theorem (Equation 1.38) holds for this wave function.

(d) If you measured the energy of this particle, what values might you get, and
with what probabilities?

Problem 2.14 A
particle is in the harmonic oscillator
ground state of the with

classical frequency a>, when suddenly the spring constant quadruples, so to' = 2a>,

without initially changing the wave function (of course, will now evolve vj/

differently,
because the Hamillonian has changed). What is the probability a that

measurement of the energy would still return the value ftco/21 is the probability What

of getting ftcol [Answer: 0.943.]

2.3.2 AnalyticMethod
We return now to the Schrodinger equation for the harmonic oscillator,

ft1 d2xj/ V 1 , ,
+ -m(D2x2xj/
= Ef. [2.70]
2m dx2 2
and solveit directly, by the series method. Things look a little cleaner if we

introduce the dimensionless variable

I mm
Imco
III [2.71]
Vfiv;
in terms of the
\302\243 Schrodinger equation reads

d2yj/
i^-K [2.72]

where K is the energy,in units of (l/2)/?a>:

_ 2E
K [2.73]
ftco
Our problemis to solve Equation 2.72, and in the process obtain the \"allowed\"
values of K (and henceof E).
To begin with, note that at very large \302\243
(which is to say, at very large x), \302\2432

completely dominates over the constant K, so in this regime

-Jr * *V< [2.74]

d$~

which has the approximate solution (check it!)

1r(%)
% Ae~t2/2 + Be+*1/2. [2.75]
 Time-Independent Schrodinger Equation

The B term is clearly not normalizable (it blows up as |jc| -> oo);the physically

acceptable solutions, then, have the asymptotic form

^(S) -\342\226\272
( )^2/2< at large \302\243. [2.76]

This suggests that we \"peel off\" the exponentialpart,

W$) = /i($)\302\253~|2/2, [2.77]

in hopes that what remains, /?(\302\243), has a simpler functional form than i/r(\302\243)
itself.23

Differentiating Equation 2.77,

df (dh \\ _ti/2

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

so the Schrodinger equation (Equation 2.72) becomes

d2h
\342\200\224
dh
-2l;\342\200\224 + (K-\\)h=0. [2.78]
#f- d%

I propose to look for solutions to Equation 2.78 in the form of power series
in \302\243.

h<&)
= fl0 + fl|? +02^2 + =
\342\200\242
\342\226\240-
J2ajtJ- [2J9]
/=0

Differentiating the series term by term,

-=0,+ 2a2\302\243 + 3a^2 + =

\342\200\242
\342\200\242 V
\342\200\242
JaiSJ~
j=Q
and
\302\260\302\260
d2h
=
\342\200\224j 2c,2 + 2 \342\200\242
3fl3\302\243 + 3 \342\200\242
+
4\302\2534\302\2432
--- =
T]U + 1)0' + 2)aj+2^.

that
-\342\200\242'Note some approximations to motivate
although we invoked Equation 2.77. what
follows is exact. of stripping off the asymptotic
The device behavior is the standard first step in
the power series method for solving differential equations-\342\200\224see, for example. Boas (footnote 11).
Chapter 12.
-4This is known as the Frobenius method for solving a differential equation. According to
Taylor's iheorem. any reasonably well-behaved function can be expressed as a power scries, so

Equation 2.79 ordinarily involves no loss of generality. For conditions on the applicability of the
method, see Boas (footnote 11) or George B. Arfken and Hans-Jurgen Weber, Mathematical Methods

for Physicists. 5th cd.. Academic Press.Orlando (2000). Section 8.5.

 Section 2.3: The Harmonic Oscillator 53

Putting these into Equation 2.78, we find

oo

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

= 0.
\302\243\342\200\242'' [2.80]
7=0

It follows (from the uniquenessof power series expansions25) that the coefficient
of each power of \302\243
must vanish,

(j + 1)(7 + 2)aj+2 - 2jaj + (K

-
l)aj
= 0,

and hence that

(2j + 1-K)
a;+->
J
= a;.J [2.81]
(./ + 1)0+2)

This recursion formula is entirely equivalentto the Schrodinger equation.

Starting with ao, it generates all the even-numbered coefficients:

(1-/0 (5-K) (5-/0(1-/0

a2 = a4
= = a0t
\342\200\224^-\302\253>.
\342\200\224^-a{), \342\200\224[j-a2

and starting with a\\, it generates the odd coefficients

=
\302\2533
(3-K)
^ =
(7-/0 = (7-/0(3-/0 \"\342\200\242\342\200\242\342\200\242
\342\200\224g\342\200\224-.. -^-^ 120 fl,<

We write the complete solution as

/*(\302\243)=/*even(S) + /*odd(\302\243). [2.82]

where

hcvcn(Z) = +
\302\2530 aii1 + \302\2534?4 H

is an even function of built

\302\243, on ao, and

= +
---
/*odd(\302\243) fli\302\243+fl3\302\2433+tf5\302\2435

is an odd function, built on a\\. Thus Equation 2.81determines /z(\302\243) in terms of

two arbitrary constants (ao and a\\)\342\200\224which is just what we would expect, for a
second-orderdifferentialequation.
However, not all the solutions so obtained are normalizable. For at very large

j, the recursion formula becomes (approximately)

2
c'j+2 \302\253
-aj,

^Sce. for example. Arfkcn (footnote 24). Section 5.7.

 Time-Independent Schrodinger Equation

with the (approximate)solution

%
C
a,- .
7
072)!

for some constant C, and this yields(at large where

\302\243, the higher powers dominate)

'?; ^ 072)! ^j\\q

Now, if /7 goes like exp(\302\2432),
then \\(/ (remember \\f/l\342\200\224that's
what we're trying to
calculate) goes like exp(\302\2432/2) (Equation 2.77), which is precisely the asymptotic
behavior we didn't want.26 There is only one way to wiggle out of this: For

normalizable solutions the power series must terminate. There must occur some
\"highest\" j (call it /?), such that the recursion formula spitsout an+2
= 0 (this will
truncate either the series /zCvcn or the series /7 odd; the one must be zero from
other
the start: ci\\
= 0 if n is even, and ciq
= 0 if n is odd). For physically acceptable
solutions,then, Equation
2.81 requires that

K = 2h + 1.

for some non-negative

integer /7, which is to say (referring to Equation 2.73) that
the energy must be

=
E\342\200\236 (n + -)h(o. for n =0.1,2 [2.83]
Thus we recover, by a completely different method, the fundamental quantization
condition we found algebraically in Equation 2.61.
It seems at first rather surprising that the quantization of energy should
emerge from a technical detail in the powerseriessolution to the Schrodinger
equation, but let's look at it from a different perspective.Equation2.70 has
solutions, of course, for any value of E (in fact, it has two linearly independent
solutions for every E). But almost all of thesesolutions blow
up exponentially at

large x, and hence are not normalizable.Imagine,for example, using an E that

is slightly less than one of the allowed values (say, 0.49/?a>), and plotting the
solution(Figure 2.6(a)); the \"tails\" fly off to infinity. Now try an E slightly larger
(say, 0.51/\"7a>); the \"tails\"now blow up in the other direction (Figure2.6(b)).As
you tweak the parameter in tiny increments from 0.49 to 0.51,the tailsflip over

when you pass through 0.5\342\200\224only

at precisely 0.5 do the tails go to zero, leaving
a normalizable
solution.27

-\"It's no surprise lhal the ill-behaved solutions are still contained in Equation 2.81: this recursion
relation is equivalent to the Schrodinger equation, so it's got to include both the asymptotic forms we
found in Equation 2.75.
27
It is possible to set this up on a computer, and discover the allowed energies\"experimentally.\"
You might call it the wag the dog method: When the tail wags, you know you've just passed over an
allowed value. See Problems2.54-2.56.
 Section2.3: The Harmonic Oscillator 55

2 :
1.5 '-

>v
X 0.5
1 i 1

-4 -2 2
4$
-0.5
-1
\\
-1.5
-2
(a)

ji

1.5

/o.5 \"

1 1 >
-4 ./^1 -2 2 ^
-0.5 n
\\
-1 ':

-1.5
-2
(b)

FIGURE 2.6: Solutionsto the Schrodinger equation for (a) E = 0.49 fico, and

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

For the allowed values of K, the recursion formula reads

-
-20? j)
\302\253y+2 fly- [2.84]
(7 + 1)(7+2)

If n = 0, there is only one term in the series (we must pick a \\ 0 to kill /20Cid,

and 7=0 in Equation 2.84 yields \302\2532

= 0):

/?()(\302\243) =flo.

and hence

= $~12
V'o(\302\243) a0e
Time-Independent Schrodmger Equation

(which, apart from the normalization,reproduces Equation 2.59). For n = 1 we

take = 0,28 and Equation 2.84 with j = 1 yields
\302\253o \302\2533
= 0, so

M$) = <M$.

and hence

= a^e-^~'2
tfr,($)

Equation 2.62). For n =

= \342\200\224 \342\200\224
(confirming 2, 7 0 yields \302\2532 2\302\253o> and 7=2 gives
= 0, so
\302\2534

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

M$) = \302\253od -2$2)\302\253\"*2/2.

and so on. (Compare Problem 2.10, where this last resultwas obtained by algebraic
means.)
In general, will
//\342\200\236(\302\243)
be a polynomial of degree 11in involving
\302\243, even powers
only, if n is an even integer, and odd powers only, if n is an odd integer. Apart
from the overall factor (\302\253o or a\\) they are the so-called Hermite polynomials,
The
#\342\200\236(\302\243).29 first few of them are listed in Table 2.1. By tradition, the arbitrary

multiplicative factor is chosen so that the coefficient of the highest power of \302\243

is 2\". With this convention, the normalized30 stationary states for the harmonic
oscillatorare
1/4

fn(x) =
mco 1
-f-/2
:#\342\200\236($)<? [2.85]

They are identical (of course) to the oneswe obtained algebraically in Equation 2.67.

TABLE 2.1: The first few Hermite

polynomials, H\342\200\236(%).

= 1,
H0-
=
Hy- \302\276.

== 2,
H2 4^2_
== -
#3 8\302\2763 1\302\276

= -
HA-- 16\302\2764 48\302\2762+ 12,
=
H5- 32\302\2765-160^- 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 2.17.

30I shall not work out the normalization constant here: if you are interested in knowing how it is

done, see for example Leonard Schiff, Quantum Mechanics, 3rd ed., McGraw-Hill, New York (1968).
Section 13.
 Section 2.3: The Harmonic Oscillator 57

In Figure2.7(a) I have plotted \\j/n(x) for the first few /?'s. The quantum

oscillator is strikingly different from its classical counterpart\342\200\224not only are the

energies but the position distributionshave

quantized, some bizarre features. For
instance, the probability of findingthe particleoutside the
classically allowed range
(that is, with x greater than the classical amplitude for the energy in question) is
not zero (seeProblem 2.15), and in all odd states the probability of findingthe

particleat the center is zero. Only at large n do we beginto seesome resemblance

to the classical case. In Figure 2.7(b) I have
superimposed the classical position
distribution on the quantum one (for n = 100); if you smoothed out the bumps,
the two would fit
pretty well (however, in the classical case we are talking about
the distributionof positions for one over time oscillator, whereas in the quantum
case we are talkingaboutthe distribution over an ensemble of identically prepared
systems).31

Problem 2.15 In the groundstateoftheharmonic

oscillator,
what is the probability
(correct to three significant digits) of finding the particle outsidethe classically
allowed
region? Hint: Classically, the energy of an oscillator is E = (l/2)ka2=
{\\/2)marar,
where a is the amplitude. So the \"classically allowed region\"for an
oscillator of energy E extends from \342\200\224y/2E/mco2 to +y/2E/mco2. Look in a math
or \"Error
table under \"NormalDistribution\" Function\" for the numerical value of
the integral.

Problem 2.16 Usethe recursion formula

(Equation 2.84) to work out //5(^) and
//g(\302\243). Invoke the convention that the coefficient of the highestpowerof is
\302\243 2\"

to fix the overall constant.

* *Problem 2.17 In this problem we explore some of the more useful theorems(stated
without
proof) involving Hermite polynomials.

(a) The Rodrigues formula says that

Hn^)
= e-*\\ [2.86]
(-\\)\"e^(J^j
Use it to derive H$ and //4.

(b) The following recursion relation gives you Hn+\\ in terms of the two
preceding
Hermite polynomials:

= -
//\342\200\236+,(\302\243) 2\302\243//\342\200\236(\302\243)
2/7#\342\200\236_,(\302\243). [2.87]

Use it, together with your answer in (a), to obtain//5 and H^.

-
'The parallel is perhaps more direct if you interpret the classical distribution as an ensemble of
oscillators all with the same energy, but with random starting times.
2 Time-Independent Schrodinger Equation

/7 = 3

/7 = 2

/7=1

/7 = 0

(a)

|Vl00(x)i20.24r

0.20-

0.16-

0.12

0.06
-

0.04 -

(b)

FIGURE 2.7: (a) The first four stationary states of the harmonic oscillator. This
material is used by permission of John Wiley 8c Sons, Inc.; Stephen Gasiorowicz,
Quantum Physics, John Wiley
8c Sons, Inc., 1974. (b) Graph of |^iool2> w^h l^e

classical distribution (dashed curve) superimposed.

 Section 2.4: TheFree Particle 59

(c) If
you differentiate an nth-order polynomial, you get a polynomialof order
(n
\342\200\224
1). For the Hermite polynomials, in fact,

^=2,7//,,,^). [2.88]

Checkthis, by differentiating H$ and H(>.

(d) Hn (\302\243)is the \302\273thz-derivative, at z = 0, of the generating function exp(\342\200\224z2 +

2z%)\\ or, to put it another way, it is the coefficientof z\"/n\\ in the Taylor
series expansion for this function:

=
\302\253-=2+2*
5^/^). [2.89]
/7=0

Use this to rederiveHq, H\\, and Hi.

2.4 THE FREE PARTICLE

We turn next to what should have been the simplest case of all: the free particle

(V(x) = 0 everywhere). Classically this wouldjust mean motion at constant

velocity,
but in quantum mechanics the problem is surprisingly subtle and tricky. The
Schrodinger
time-independent equation reads

h2 d2i/
= Ef. [2.90]
2m dx\\
or
d~\\l/ i y/2mE
\342\200\224L=
-k2f, vj\\ierek=- . [2.91]
dx- h

So far, it's the same as inside the infinite square well

(Equation 2.21), where the
potential is also zero; this time,however, I prefer to write the general solution in
exponential form (instead of sines and cosines), for reasons that will appear in due
course:
yjr (x)
= Aeikx + Be-ikx. [2.92]
Unlike the infinite square well, there are no boundary
conditions to restrict the
possible values of k (and hence of E); free particle the can carry any (positive)
energy. Tacking on the standard time dependence, exp{\342\200\224iEt/h),

vl/(x, t)
= Aeik{x-^n + Be-iHx+^n. [2.93]
Now, any function of x and t that depends on these variables in the special
combination(x + vt) (for some constant v) represents a wave of fixed profile,
travelingin the :pf-direction, at
speed v. A fixed point on the waveform (for
 Schrodinger
Time-Independent Equation

example, a maximum or a minimum) corresponds to a fixed value of the argument,

and hence to x and t such that

x + vt = constant, or x= =fvt + constant.

Since every point on the waveform is moving along the same velocity, its with

shape doesn't change as it propagates. Thusthe term in Equation 2.93 first

represents a wave traveling to the right, and the second represents a (of the same wave

energy) going to the left. By the since they only differ by the sign in front of
way,

k, we
might as well write

Vk{.\\\\t) = Aei{kx-!^t\\ [2.94]

and let k run negative to cover the case of waves traveling to the left:

=
, y/lmE f
k > 0 => traveling to the right, \342\200\236
__.,
k \302\261 . with .. , ,
traveling to the left.
{ , r\302\253. [2.951 J
/j [
k < 0 =>

Evidently the \"stationary states\" particle are propagating

of the free waves; their

wavelength
= 2n/\\k\\, and,
is k accordingto the de Broglie (Equation formula 1.39),

they carry momentum

p = hk. [2.96]
The speedof these waves (the coefficient of t over the coefficient of x) is

^quantum
-*'*' _
\342\200\224
~
\342\200\224
w
E

\302\253 \342\226\240
nan
l~-\"'J

On the other hand, the classical speed of a free particle with energy E is given by
E = (l/2)mir (pure kinetic,since V = 0), so

_=
2E _
= [2.98J
^classical \\/
m ^'quantum-

Apparently the quantum

mechanical wave function travels at half the speed of the
particleit is supposed to represent! We'll return to this paradox in a moment\342\200\224there

is an even more serious problem we need to confrontfirst: This wave function is

not normalizable. For

r+oo
V];Vkdx = \\A\\2 / dx = |A|2(oo). [2.99]
/-t-oo
-co J\342\200\224oo

In the case of the free particle, then, the separablesolutionsdo not represent
physically realizable states. A free particle cannot exist in a stationary state; or,
to put
it another way, there is no such thing as a free particle a definite with

energy.
 Section 2.4: The Free Particle 61

But that doesn't meanthe separable solutions are of no use to us, for they
play a mathematical role that is entirely independent of their physical
interpretation. The general solution to the time-dependent Schrodinger equation is stilla
linear combination of separable solutions (only this time it's an integral over the
continuous variable k, instead of a sum over the discrete index n):

[2.100]

(The quantity l/y/ln is factored out for convenience; what plays the role of the
coefficient in
c\342\200\236 Equation 2.17 is the combination
(\\/y/2n)<p(k)dk.) Now this
wave function can be normalized (for appropriate 0(fc)). But it necessarily carries
a range of fc's, and hence a range of energies and speeds. call it a wave We

packet.32
In the generic quantum problem, we are given ty(x, 0), and we are asked to
find y(x,t). For a free
particle the solution takes the form of Equation 2.100;
the only question is how to determine 0(fc) so as to match the initial wave
function:

0) =
ikx
* (jr. 0 (*)<?'\" dk. [2.101]
-co

This is a classic problemin Fourieranalysis;

the answer is provided by Plancherel's
theorem (see Problem 2.20):

[2.102]

F(k)is called the of f(x)\\

Fourier f(x) is the inverse Fourier
transform

transform of
F(k) only (theis in the sign of the exponent).Thereis, of
difference
course, some restriction on the allowable functions: The integrals have to exist}*

For our purposes this is guaranteed by the physical requirement that ^(.v. 0) itself

-^Sinusoidal waves extend out to infinity, and they are not normalizable. But superpositions of
such waves lead to interference, which allows for localization and normalizability.
\342\226\240,3The
necessary and sufficient condition on f(x) is that
/^, \\f(x)\\2dx be finite. (In that

case f^ -3C \\F(k)\\-dk is also finite, and in fact the two integrals are equal.) SecArfken (footnote 24).
Section 15.5.
Time-Independent Scbrodinger Equation

be normalized.Sothesolution to the generic quantum problem, for the free particle,

is Equation2.100, with

[2.103]

Example 2.6 A free particle, inthe

which is initiallylocalized range
<
\342\200\224a x < a,
is released at time t = 0:

_
_
f A, if \342\200\224
a < x < a,

[ 0, otherwise,

where A and a are positive real constants. Find ty (x, t).

Solution: First we need to normalize 4>(a\\ 0):

pa
|vI/(a\\0)|2c/a- = \\A\\2 / dx = 2a\\A\\2 => A =
/oo-oo J\342\200\224a

Next we calculate \302\242(1(), using Equation 2.103:

11 1
1 Ca 1 ,-ikx

V27T V2fl J-a IJllCl -ik

Jka _ p\342\200\224ika 1 sin (ka)

kJWa 2i \342\226\240s/tFci
k

Finally, we plug this back into Equation 2.100:

=
If00 sin(fctf) ;a... m2m \342\200\236
*(jc.r) \342\200\224=
/
\342\200\224^-\342\200\224e'^-^0 dk. [2.104]
Tty/la J-oo k

Unfortunately, this integral cannot be solvedin tenns of

elementary functions,

though it can of course be evaluated numerically (Figure2.8).(Thereare,in fact,

precious few cases in which the integral for vJ/(a\\ t) (Equation 2.100) can be
calculated
explicitly; see Problem 2.22 for a particularly beautiful example.)
It is illuminating to explore the limiting cases. If a is very small, the starting
wave function is a nicely localized spike (Figure 2.9(a)). In this case we can use

the small angle approximation to write sm(ka) %

ka, and hence

<t>{k)
 Section 2.4: The FreeParticle 63

u|\302\245(x,0l2

FIGURE 2.8: Graph of |*(x, t)\\2 (Equation 2.104) at t = 0 (the rectangle)and at

t = ma2/h (the curve).

V(X, 0) m

V2a

/a/n

(a) (b)

FIGURE 2.9: Example2.6, forsmalla. (a) Graph of W(x, 0). (b) Graph of 4>{k).

it's yfotf, since the fc's cancelled out (Figure 2.9(b)). This is an example of the

uncertainty principle: If the spread in position is small,the spreadin momentum

(and hence in k\342\200\224see
Equation 2.96) must be large. At the other extreme {large
a) the spreadin positionis broad (Figure 2.10(a)) and

=
'TTsinffcfl)
*(*)
ka

Now, sinz/z has its at z = 0, and drops to zero

maximum at z = i tt (which, in
this context,means = +
n/a). So for large a, 0(/:) is a
k
sharp spike about k = 0

(Figure 2.10(b)). This time it's got a momentum well-defined but an ill-defined
position.
Time-Independent Scbrodinger Equation

V(x. 0)

V2a

(a) (b)

FIGURE 2.10: Example 2.6, for large a. (a) Graph of *(x, 0). (b) Graph of $(&).

I return now to the paradox noted earlier: the fact that the separable solution

*I>it(..Y, f) in Equation 2.94 travels at the \"wrong\" speed for the particle it
ostensibly represents. Strictly when we discovered
speaking, the problem evaporated
that Wk is not state.
a physically Nevertheless, it is of interestto
realizable
discover how velocity is contained in the free particle
information about wave function

(Equation 2.100). The essential idea is this: A wave packet is a superposition of

sinusoidal functions whoseamplitude ismodulated by 0 (Figure 2.11); it consists of
\"ripples\"contained within an \"envelope.\" What corresponds to the particle velocity
is not the speedof the ripples so-called
individual
(the phase velocity), but rather
the speed of the envelope(thegroup depending on the nature
velocity)\342\200\224which,

of the waves, can be greater less than, or equal to, the velocity of the ripples
than,

that
go to make it up. For waves on a string,the group is the same as the velocity

phase velocity. For water it is one-half the

waves phase velocity, as you may have

noticed when you toss a rock into a pond (if you concentrate ona particularripple,
you
will see it build up from the rear, move through the group, and fade
forward

away at the front, while the groupasa propagates out at half the speed). What
whole

I need to is that
show for the wave function of a free particlein mechanics quantum

FIGURE2.il: A wave packet. The

\"envelope\" travels at the group velocity; the
\"ripples\"
travel at the phase velocity.
 Section 2.4: The Free Particle 65

the group velocity is twice the phase velocity\342\200\224just right to represent the classical
particle speed.
The problem, then, is to determine the
group velocity of a wave packet with
the general form
1 P+OO

t) = -== dk.
*(*,
s/2tt
/
J-oo
0(Jt)e'(*jr_fttf)

(In our case co = (hk2/2m), but what I have to say now applies to any kind
of wave packet, regardlessof its dispersion formula for a> as a relation\342\200\224the

function of k.) Let us assume 0(fc) is narrowly peaked about some particular
that

value ko. (Thereis illegal about a broad spread

nothing
in k, but such packets wave

change shape rapidly\342\200\224since

different components travel at different speeds\342\200\224so

the whole notion of a \"group,\" with a well-defined velocity,losesits meaning.)

Since the integrand is negligible except in the vicinity of ko, may we as well

Taylor-expand the function co(k) about that point, and keep only the leading terms:

coik) = coo + co'Q(k -ko),

where co'0
is the derivative of co with respect to k, at the point ko.

Changing variables from k to s = k

\342\200\224
ko (to center the integral at ko), we
have

t) = -== + 5)<?'K*o+J)*-(\"o+4,J>r] ds.

vl>(.v,
/ <j)(ko

V 2TX J-oo

At t = 0,

1 f+oa
*(x, 0) = -= / 0(\302\243o + s)e'(kQ+s)x ds,
\\I2ti -co
J\342\200\224oo

and at later times

1 r+oo
vl/(.v. t) = -\342\200\224e'\"<-a>n'+M\302\273'> /
0(^o + synko+sKx-^n ds
\\j2ti J\342\200\224oo

Except for the shift from x to (a- \342\200\224

co0t),
the integral is the same as the one in
vi>(x,0). Thus

- [2.105]
vJ/(a\\ t) = g-'^-^o)^^ co'0t.0).
Apart
from the phase factor in front (which won't affect |vj/|2in any event) the
wave packet evidently moves along at a speed (o'Q:

dco
= [2.106]
\"group -77-

(evaluated at k = ko). This is to be contrasted

with the ordinary phase velocity
co
\342\200\224\342\200\242
\"phase , [2.1071
 Time-Independent Scbrodinger Equation

In our case, a> =

(hk2/2m), so co/k = (hk/2m), whereas dco/dk = (ftk/m),which
is twice as great. This confirms that it is the group velocityof the wave packet,

not the phase velocity of the stationary states, that matches the classical particle
Velocity:
^classical\342\200\224 = [2.10oJ
ugroup 2l)phase-

Problem 2.18 Show that [Aelkx+ Be~lkx]and [C coskx + D sin kx] are equivalent
ways of writing
the same function of x, and determine the constants C and D in
termsof A and B, and vice versa. Comment: In quantum mechanics, when V = 0,
the exponentials represent traveling waves, and are most convenient in discussing
the free particle, whereas sines and cosines correspond to standing waves, which

arise naturally in the case of the infinite squarewell.

Problem2.19 Find the probability current, J (Problem 1.14) for the free particle
wave function Equation 2.94. Which direction does the probability current flow?

*Problem2.20 This problem is designed to guide you through a \"proof\"of Plan-

cherel'stheorem, by starting with the theory of ordinary Fourier series on a finite
interval,and allowing that interval to expand to infinity.

(a) Dirichlet's theorem says \"any\" function that

f{x) on the interval +a]
[\342\200\224a,

can be expanded as a Fourier series:

CO

f(x)
= sin(n-7rx/a) + bn cosijmx/a)}.
2^[\302\253/i

Show that this can be written

equivalently as

00

n=\342\200\224OG

What is in
c\342\200\236, terms of and
a\342\200\236 bnl

(b) Show (by appropriate modification of Fourier's trick) that

C\" = f{x)e-'mnx'a dx.

TaL a

(c) Eliminate n and in

c\342\200\236 favor of the new variables k = (nn/a) and F(k) =
Show
\342\200\242v/2/ttac\342\200\236.
that (a) and (b) now become
\302\260\302\260
1 1 f+a
f(x)
= -== V F(k)eikxAk: F{k) =-= f(x)e-''kxdx,
V^,,^ V2^J-\342\200\236-

where Afc is the increment in k from one n to the next.

 Section 2.4: TheFree Particle 67

(d) Take the limit a oo

\342\200\224> to obtain Plancherel's theorem. Comment: In view
of their quite differentorigins,it is surprising (and delightful) that the two
formulas\342\200\224one for F(k) in terms of f(x), the other for f(x) in terms of

F(k)\342\200\224have such a similar structure in the limit a oo.

-*\342\200\242

Problem 2.21 A free particle has the initial wave function

vl>(.T.0)
= Ae~alxl,

where A and a are positivereal constants.

(a) Normalize ^(jt, 0).

(b) Find <f)(k).

(c) Construct ty(x,t), in the form of an integral.

(d) Discuss the limiting cases {a very large, and a very small).

*Problem 2.22 The gaussian wave packet. A free particle has the initial wave
function

vl>(.v,0)= Ae-\"x\\
where A and a are constants (a is real and positive).
(a) NormalizeV(x,0).
(b) Find W(x,t). Hint: Integrals of the form

e-\302\253,x-+bx) dx
/+OC
-oo

can be handled by \"completing the square\":Let y

=
s/a[x + (b/2a)], and
note that (ax2 + hx) = y2
\342\200\224
(b2/4a). Answer:

/2a\\i/4 e-ax2/[l+ainal/m)\\
\342\200\224
vl>(.v.D= =\342\226\240

\\7r / y/\\ +(2ihat/m)

(c) Find 1^(.1-, t)\\^. Express your answer in terms of the quantity
I a
w =
Y
1 +(2hat/m)2'

Sketch |^|2 (as a function of x) at t = 0, and again for some very large t.

Qualitatively, what happens to |^|2, as time goes on?

(d) Find (.v), (/?), (.v2), (p2), ax, answer: (p2) =

and ap. Partial ah2, but it

may take some algebra to reduce it to this simple form.

(e) Doesthe uncertainty principle hold? At what time t does the system come
closestto the uncertainty
limit?
68 Chapter 2 Time-Independent Schrodinger Equation

2.5 THE DELTA-FUNCTION POTENTIAL

2.5.1 Bound States and Scattering States

We have encountered two very

different kinds of solutions to the time-independent
Schrodinger equation: For the infinitesquare well and the harmonic oscillator they
are normalizahle, and labeled a discrete index by n; for the free particle they
are

non-normalizable, and labeled variable k. The formerrepresent

by a continuous
physically
realizable states in theirlatter do not; butin bothcases
own right, the the

general solution to the time-dependent Schrodinger equation is a linearcombination

of stationary states\342\200\224for the first type this combination takes the form of a sum

(over whereas
\302\253.), for the second it is an integral (over k). is the physical What

significance of this distinction?

In classical mechanicsa one-dimensional time-independent can give potential

rise to tworather different kinds of motion.If V{x)rises than the particle's higher

total energy (E) on either side (Figure2.12(a)), the particle is \"stuck\" in the
then

potential rocks back

well\342\200\224it and forth between the turning points, but it cannot
escape (unless, o f course, provide
it with a source
you of extra energy, such as
a motor, we're not talking about that). We call this a bound state. on the
but If,

other hand, E exceeds V(x) on one side(or both), the particle comes in from then

\"infinity,\" slows down or speedsup underthe influence ofthepotential, returns and

to infinity (Figure 2.12(b)). (It can't get trapped in the potentialunlessthereis some

mechanism, such as friction, to dissipate energy, but again, we're not about talking

that.) We call this a scattering state. Some potentials admit only bound states (for

instance, the harmonic oscillator); some allow only scattering states (a potential
hill no
with
dips in it, for example); some permit both kinds,depending on the
energy
of the particle.
The solutions to the Schrodingerequationcorrespond
two kinds of to
precisely

bound and scattering states. The distinction is even cleanerin the domain, quantum

because the phenomenon of tunneling (which we'll come to allows the shortly)

particle to \"leak\" through any finite potential barrier,so the thing that matters only

is the potential at infinity (Figure 2.12(c)):

< [V(-oo) and V(+oo)] =$> bound state, ,,. \342\200\236Q1

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

In \"real life\" most potentials go to zero at infinity, in which case the criterion
simplifies even further:

< 0 => bound state, ._ . \342\200\236,

IE
E > 0 => scattering state.

Because the infinite square well and harmonic oscillator potentials go to infinity as
x \342\200\224>
+oo, they admit bound states only; because the free particlepotentialis zero
 Section 2.5: The Delta-Function Potential 69

Classical turning points

(a)

Classical turning point

V(x)k

(c)

FIGURE 2.12: (a) A bound state, (b) Scattering states, (c) A classical bound state, but
a quantum scattering state.

everywhere, it only allows scatteringstates.34 this In section (and the following

one) we shall explore potentials give rise to both that kinds of states.

34
If you are irritatingly observant, you may have noticed that the general theorem requiring
E > Vmjn (Problem 2.2) does not really apply to scattering states, since they are not normalizable
anyway. If this bothers you, try solving the Schrodinger equation with E < 0. for the free particle, and
 Time-Independent Schrodinger Equation

8(x)

_^ FIGURE 2.13: The Dirac delta function

x (Equation 2.111).

2.5.2 The Delta-Function Well

The Dirac delta function is an infinitely high, infinitesimally

narrow
spike at the

origin, whose area is 1 (Figure 2.13):

with = 1. [2.111]
^H\302\260oo.lltl]- \302\243%*)\302\253**

Technically, it isn't a functionat all, since it is not finite at x = 0 (mathematicians

callit a generalized function, or distribution).35 Nevertheless, it is an extremely
useful construct in theoreticalphysics.(Forexample, electrodynamics in the charge
density of a point charge is a deltafunction.) be a spike
\342\200\224
that 8(x a) Notice would

of area 1 at the point a. you multiply 8(x a) by an ordinary If

\342\200\224
function f(x),
it's the sameas multiplying f(a), by

f(x)8(x -a) = f{a)8{x - a), [2.112]

because the
product is zero anyway except at the point a. In particular,
r+oo

f(x)8(x
- a) dx = f(a) / 8(x - a) dx =
f(a). [2.113]
/+0O
-oo J\342\200\224oo

That's the most important property of the delta function:Underthe integralsign it

serves to \"pick out\" the value of /(.*) at the point a. course, the integral need (Of

not go from to
\342\200\224oo -f-oo: all that matters is that the domain of integrationinclude
the
point a, so a e to a + e would
\342\200\224
do, for e > 0.) any

Let's consider a potential of the form

V(x) = -a8(x), [2.114]

note thai even linear combinations of these solutions cannot be normalized. The positive energy solutions
by themselves constitute a complete set.
-^The delta function can be thought of as the limit of a .sequence of functions, such as rectangles
(or triangles) of ever-increasing height and ever-decreasing width.
 Section 2.5: The Delta-Function Potential 71

where a is somepositiveconstant.36
This is an artificial potential, to be sure (so was
the infinite squarewell), it's but
delightfully simple to work with, and illuminates
the basic theory a minimum with of analytical clutter. The Schrodinger equation
for the delta-function reads well

h2 d2i/ Y
-
a8(x)1r = Ejr; [2.115]
2m dx2
it yieldsboth bound states (E < 0) and scattering states (E > 0).
We'lllook first at the bound states. In the region x < 0, V(x) = 0, so

2m E 2
d2f
= ron*!
zt$=k$, [2.116]
dx1
\342\200\224T
ft1

where
K = ^\342\200\224r \342\200\242 [2.117]
n

{E is negative, by assumption, so k is real and positive.)The general solution to

Equation 2.116 is
i/(x) = Ae-KX+BeK\\ [2.118]

but the first term blows up as x -\302\273

\342\200\224oo,so we must choose A = 0:

\\l/{x)= BeK\\ (x<0). [2.119]

In the region x > 0, V(x) is again zero, and the generalsolutionis of the form

F exp(-Kx) + Gexp(/c.r); this time it's the secondterm that blows up (as x ->
+00), so
yj/{x)
= Fe-KX. (x > 0). [2.120]

It remains only to stitch thesetwo functions together, using the appropriate

boundary conditions at jc = 0. I quotedearlierthe standard boundary conditions
for \\j/:

\\. if/ is always continuous;

2. dty/dx is at where the potential is infinite. [2.121]
continuous except points

In this case the first boundary condition tells us that F = B, so

f BeKX. (x < 0).

:%Thedelta function itself carries units of Mkngth (see Equation 2.111). so a has the dimensions

energy x length.
Time-Independent Schrodinger Equation

FIGURE 2.14: Bound state wave function for the delta-function potential
(Equation 2.122).

\\}/{x) is plotted in Figure 2.14. The second boundary condition tells us nothing;
this is (like the infinite squarewell) the exceptional casewhere V is infinite at the
join, and it's clear from the graph that this function has a kink at x = 0. Moreover,
up to this point the delta function has not come intothe story at all. Evidently the
delta function must determine the discontinuityin the derivativeof \\j/, at x = 0.
I'll show you now how this works, and as a by-product we'll see why d\\f//dx is

ordinarily continuous.
The idea is to integrate the Schrodingerequation, from
\342\200\224
e to +e, and then
take the limit as e \342\200\224>
0:

-\342\200\224
I V(x)xj,(x)dx = E I f{x)dx. [2.123]
-^jdx+l

The first integral is nothing but d\\[//dx, evaluated at the two end points;the last
integralis zero, in the limit e -\302\2730, since it's the area of a sliver with
vanishing
width and finite height. Thus

dir
A
'djj_ = lim =
-^- lim / V(x)xj/(x)dx. [2.124]
dx ~dx +\342\202\254
dx
-J
)
/r 6->o
J-\342\202\254

Typically, the on the right is again zero, and that's why

limit dif/fdx is ordinarily
continuous. when V(.\\') is infinite at the boundary,this argument
But fails. In

particular, if V(.v) = \342\200\224

a8(x), Equation 2.113 yields

d\\J/ 2ma
A \342\226\240^(0). [2.125]
.dx J h2

For the case at hand (Equation 2.122),

df/dx
= -BKe~K\\ for >
(\342\200\236y 0). so d\\j//dx\\, = \342\200\224
Bk,

df/dx = +BKe+K-\\ for (jc < 0), so d\\j//dx\\_ = +Bk.

and hence A(d\\f//dx)
= \342\200\2242Bk. And i/r(0)
= B. So Equation 2.125 says
ma
k= [2.126]
h2
 Section 2.5: The Delta-Function Potential 73

and the allowedenergy(Equation2.117)is

h-K- ma~
E = [2.127]
2m

Finally, we normalize \\f/:

>+00 /\302\273oo
\\E\\-

\\i/(x)\\2 dx = 2\\B\\2
e~lKX clx = \342\200\224 = 1,
/
/+oo-oo ./0 \302\253

so (choosing, for convenience, the positive real root):

B = Jk = y/ma
[2.128]

Evidently the delta-function well, regardless of its \"strength\" a, has exactly one
bound state:

ma~
nx)=\"/mae-'na^t'2; E = \" [2.129]
h 2/72

What about scattering states, with E > 0? For .v < 0 the Schrodinger equation
reads

d2f 2mE
, /2 ,
~dx~5 n-
where

=
\\j2mE
k [2.130]
h

is real and positive. The general solution is

if(x) = Aeikx + Be~ikx. [2.131]

and this time we cannot rule out either term, since neither of them blows up.
Similarly, for .v > 0,

yj/ (x)
= Feikx + Ge~ikx. [2.132]

The continuityof \\j/(x)

at x = 0
requires that

F + G= A + B. [2.133]

The derivatives are

dxjf/dx = ik [Feikx- Ge-'kx). for (.v > 0), so

dxj//dx\\+
= i.k(F - G),
dif/dx = ik (Aeikx
-
Be-''kx), for (x < 0), so dxj//dx\\_
= ik(A
- B).
 Time-Independent ScbrodingerEquation

and henceA{df/dx)= ik(F-G-A + B). Meanwhile, xf/(0) = (A + B), so the

second boundary
condition (Equation 2.125) says

2ma
ik(F -G- A + B) = (A + fl), [2.134]

or, morecompactly,
met
F- G =
A(l + 2ij8)
- 5(1 - 2/\302\243). where 0 = [2.135]

Having imposed both boundary conditions,we are left with two equations
(Equations 2.133 and 2.135) in four unknowns (A, B, F, and G)\342\200\224five, if you
count k. Normalization won't help\342\200\224this
isn't a normalizable state. Perhaps we'd
better pause, then, and examinethe physicalsignificance these various of

constants. Recall that exp(ikx) gives rise (when coupled with the time-dependent
factor to
exp(\342\200\224i.Et/ft))
a wave function propagating to the right, and exp(\342\200\224ikx)

leads to a wave propagating to the left. It follows A (in Equation 2.131) is the that

amplitude of a wave
coming in from the left, B is the amplitude of a wave

to
returning
the left, F (Equation 2.132) is the amplitude of a traveling off to the wave

right, and G is the amplitude ofa coming in from the

wave
right (see Figure 2.15).
In a typicalscattering experiment particles are fired in from one direction\342\200\224let's

say, from the left. In that case the amplitude of the wave coming in from the right
will be zero:
G = 0, (for scattering from the left); [2.136]

A is the amplitude of the incident B is the wave, amplitude of the reflected wave,
and F is the amplitudeof the transmitted wave.
Solving Equations 2.133 and
2.135 for B and F, find we

ifi 1
B = A, F = [2.137]
l-ifi \\-ifi
(If you want to study scattering from the right, set A = 0; then G is the incident
amplitude, F is thereflectedamplitude, and B is the transmitted amplitude.)

Ae ikx Fe ikx

\342\226\240ikx -ikx
B& Ge

FIGURE 2.15: Scattering from a delta

! function well.
 Section 2.5: The Delta-Function Potential 75

Now, the probabilityof finding

the particle at a specified location is given by

|vl> |2, so the relative27 probability that an incident particle will be reflected back is

\\B\\2 P2
& =
= 7TTT = t2-138]
T-T-^T-
\\A\\2 1+^2

R is called the reflection coefficient. (If you have a beam of particles,it tells
you
the fraction of the incoming number that will bounce back.) Meanwhile,the
is
probabilityof transmission given by the transmission coefficient

IFI2 1
T = = [2'1391
W TW
Of course, the sum of these probabilities should be 1\342\200\224and it is:

R + T=\\. [2.140]

Notice that R and T are functions of /3, and hence (Equations 2.130and 2.135)
of E:
1 1
R = = -. T = [2.141]
1 + (2h2E/ma2)' 1+ (ma2/2h2E)

The higher the energy, the greater the probabilityof transmission

(which certainly

seems reasonable).
This very tidy, but there is a stickymatter of principle
is all that we cannot

altogether ignore: These scattering wave functions are not normalizable, so they
don't actually represent possible particle states. But we know what the resolution to
this problem is: We must form normalizable linear combinations of the stationary
states,just as we did for the free particle\342\200\224true physical particles are represented
by the resulting wave packets. Though straightforward
in messy
principle, this is a
business in practice, and this point at it is best to turn the problem over to a
computer.38 Meanwhile, since it is impossible to create a normalizable free-particle
wave function without involving a range of energies, R and T shouldbe interpreted
as the
approximate reflection and transmission probabilities for particles in the
vicinity
of E.

Incidentally, it might strike you as peculiar that we were able to analyze a

quintessentially time-dependent problem (particlecomesin, scatters off a potential,

-7This is 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 probabilities for the incident and
reflected waves is meaningful. More on this in the next paragraph.
38Numerical studies of wave packets scattering off wells and barriers reveal extraordinarily rich

su'ucture. The classic analysis is A. Goldberg,H.M. Schey. and J. L. Schwartz, Am. J. Pliys.35, 177
(1967); more recent work can be found on the Web.
 Time-Independent Schrodinger Equation

= a5(x)

_._iV(x)
x FIGURE 2.16: The delta-function barrier.

and flies off to infinity) using stationcuy states. After all, \\j/ (in Equations 2.131
and 2.132) is simply a sinusoidalfunction,
complex, time-independent, extending

(with constant amplitude) to infinity in both directions. And yet, by imposing

appropriate boundary conditions on this function we were able to determine the

probabilitythat a particle (represented a localized wave packet) by
would bounce
off, or pass through, the T
potential. he mathematical miracle behind this is, I

suppose, the fact that by taking linear combinations of statesspread over all space,
and with
essentially trivial time dependence, we can construct wave functions that
are concentrated about a (moving) point, with quite elaborate behaviorin time (see
Problem2.43).
As
long relevant equations on the table, let's lookbriefly
as we've got the at

the case of a delta-function barrier (Figure 2.16). Formally,all we have to do is

change the sign of a. Thiskills the bound state, of course (Problem 2.2). On the
other hand, the reflectionand transmission coefficients, which depend only on a\",
are unchanged.Strangeto say, the particle is just as likely to pass through the barrier

as to cross over the well! Classically, of course, a particle cannot make it over an

infinitely high barrier, regardless of its energy. In fact, classicalscattering problems

are
pretty dull: If E > Vmax> then T = 1 and R = particle 0\342\200\224the
certainly
makes it over; if E < V^ax then T = 0 and R = rides up the hill
1\342\200\224it until
it runs out of steam, and then returns the same way it came. Quantum scattering
problems are richer: The much
particle has some nonzero probability of passing
through the potentialevenif E < Vmilx. We call this phenomenon tunneling; it is
the mechanism that makes possible much of modern electronics\342\200\224not to mention

spectacular advances in microscopy. Conversely, even if E > Vmax there is a

possibility that the particle will bounce back\342\200\224though I wouldn't advise driving
off a cliff in the hope that quantum mechanics will save you (see Problem 2.35).

*Problem2.23 Evaluate the following integrals:

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

- tt) dx.
(b) /0\302\260\302\260[cos(3x)
+ 2]8(x

(c) /+1exp(|.t|+3)5(A--2)dT.
 Section2.5: The Delta-Function Potential 77

Problem 2.24 Delta functions live under integralsigns,and two expressions (D\\ (x)
and Di{x)) involving delta functionsare saidto be equalif
\342\200\242
+ 00 C+OQ
/(.t)D, (x) dx = / f(x)D2(x) dx,
-CO J\342\200\224OQ

for every (ordinary) function f(x).

(a) Show that

8(cx) = ^-8(x). [2.142]
where c is a real constant. (Be sure to check the case where c is negative.)

(b) Let 6(x) be the step function:

\302\243<\302\243
^
\342\200\242Hi

(In the rare case where it actually matters, we define 0(0) to be 1/2.) Show

that
d9/dx
= 8(x).

* ^Problem 2.25 Check the for the wave function

uncertainty principle in
Equation 2.129. Hint: Calculating(p1) is the derivative of tricky, because \\(/
has

a step discontinuity at x = 0. Use the resultin Problem2.24(b). Partial answer:

(P1)
= Ona/h)2.

^Problem 2.26 What is the Fouriertransformof 8(x)lUsing Plancherel's theorem,

show that
1 f+oc
8(x) = \342\200\224
/
eikx dk. [2.144]
lit ./-oc

Comment: This formula gives any respectable mathematician apoplexy. Although

the integral is clearly infinite when x = 0, it doesn't converge (to zero or
anything else) when x ^ 0, since the integrand oscillatesforever.Thereare ways
to patch it up (for instance, you can integrate from \342\200\224Lto +L, and interpret

Equation 2.144 to mean the average value of the finite integral, as L \342\200\224>\342\200\242
oo).

The source of the problem is that the delta function doesn't meet the requirement
(square-integrability) for Plancherel'stheorem(see footnote 33). In spite of this,
Equation 2.144 can be extremelyuseful,if handled with care.

^Problem 2.27 Consider the double delta-function potential

V(x) = -<x[8(x+ a) + 8(x

-
a)],

where a and a are positiveconstants.

78 Chapter 2 Time-Independent Scbrodinger Equation

(a) Sketch this potential.

(b) How many bound states does it possess? Find the allowed energies, for a =
h~/ma
and for a = n-/4ma, and sketch the wave functions.

* ^Problem 2.28 Find the transmission coefficientfor the potentialin Problem2.27.

2.6 THE FINITE SQUARE WELL

As a last example, consider the finite squarewell potential

\342\200\224 \342\200\224
Vq, for a<x<a,
V(x)
=
0. for |.v| > a,
[2.145]

where Vo is a (positive) constant (Figure 2.17). Like the delta-functionwell, this

potential admits both bound states (with E < 0) and scattering states(with E > 0).

We'll look first at the bound states.

In the region x < the
\342\200\224a
potential is zero, so the Schrodinger equation reads

h1 d1* d2ir 9
=
E$.
\342\200\224\342\200\224\342\200\224T
or -\342\200\224=K-1r,
2m ax- dx-

where

k =
y/\342\200\2242mE
[2.146]

is real and positive. The general solution is \\j/(x) = A exp(\342\200\224kx) + B exp(/CA'), but
the first term blows up (as a\" \342\200\224>
\342\200\224oo), so the physically admissible solution (as
before\342\200\224see
Equation 2.119) is

f(x) = BeKX, for a\" < -a. [2.147]

FIGURE 2.17: The finite

square well

(Equation 2.145).
 Section 2.6: The FiniteSquare Well 79

In the region
\342\200\224
a < x < a, V(x) = and
\342\200\224Vo, the Schrodinger equation reads

2m dx1
- - Vof = E\\j/, or
dx
\342\200\2243-
=
-1-f,

where
I. MH. li
[2..48]

Although E is negative, for bound states, it must be greater Vq, by the than
\342\200\224

old theorem E > Vm\\n (Problem 2.2); so / is also real and positive. The general
solution is39

\\f/(x)
= C sin(/.r) -f D cos(/x), for \342\200\224
a < x < a, [2.149]

where C and D are constants. arbitrary Finally, in the region .v > a the potential
is again zero; the generalsolutionis \\jr{x)
=
Fexp(-Kx) + Gexp(/c.t), but the
second term blows up (as x 00), so \342\200\224> we are left with

ir(x) = Fe~K\\ forx > a. [2.150]

The next step is to impose boundary conditions: \\J/ and difr/dx continuous at
and
\342\200\224a +a. But we can save a little time by noting that this potential is an even
function, so we can assume with no loss of generality that the solutionsare either
even or odd (Problem 2.1(c)). The advantage of this is that we need only impose
the boundary conditions on one side (say,at +a); the other side is then automatic,
since \\j/(\342\200\224x) = +\\j/(x). I'll work out the even solutions; you get to do the odd

ones in Problem 2.29. The cosineis even (and the sine is odd), so I'm looking for
solutionsof the form

Fe KX. for .Y > a.

Mx)
= D cos(/.v). for 0 < x < a. [2.151]
\\j/(\342\200\224x).
for a < 0.

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

=
Fe~Ka Dcos(/tf). [2.152]

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

-KFe~Ka= -ID sin(/fl). [2.153]

Dividing Equation 2.153 by Equation 2.152, we find that

/r=/tan(/fl). [2.154]

can.
\342\200\242^You if you like, write the general solution in exponential form (C'e'lx + D'e~'x). This

leads to the same final result, but since the potential is symmetric we know the solutions will be either
even or odd. and the sine/cosine notation allows us to exploit this directly.
 Time-Independent Schrodinger Equation

FIGURE 2.18: Graphical solution to Equation2.156,for Zo

= 8 (even states).

This is a formula for the allowedenergies,sincek and I are both functions

of E. To solve for E, we first adopt some nicer notation: Let

z = la. and zo = \342\200\224

yJlmVo. [2.155]
n

According to Equations 2.146 and 2.148,(k2+12) = 2m

Vo/li2, so xa =
Jzq
\342\200\224
z1,

and Equation 2.154 reads

tan z = - 1. [2.156]
yjizu/z)2
This is a transcendental equation for z (and hence for E) as a function of zo

(which is a measure of the \"size\"of the well).It can be solved numerically, using
a computer, or graphically, by plotting tanz and yJ(zo/z)2
\342\200\224
1 on the same grid,
and looking for points of intersection (seeFigure 2.18). Two limiting cases are of
special interest:
1. Wide, deep well. If zo is very large, the intersections occur just slightly
below zn
=
hjt/2, with n odd; it follows that

rrn-n-
En + V0
=
9 \342\200\242 [2.157]
2m(2a)

But E + Vb is the energy above the bottomof the well, and on the right side
we have precisely the infinite square well energies, for a well of width 2a (see

Equation 2.27)\342\200\224or rather, half of them, since this n is odd. (The other ones,of
course, come from the odd wave functions, as you'll discover in Problem 2.29.)So
the finite
square well goes over to the infinite square well, as Vq
\342\200\224>
oo; however,
for any finite Vq there are only a finite number of bound states.
2. Shallow,narrow well. As zo decreases, there are fewer and fewer bound
states, until finally (for zo < the lowest odd state disappears)only one
tt/2, where
remains. It is
interesting to
note, however, that there is always one boundstate,no
matter how \"weak\" the well becomes.
 Section 2.6: TheFiniteSquare Well 81

You're welcome to normalize f (Equation 2.151), if you're interested

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

f(x) = Aeik* + Be~ikx, for (x < -a). [2.158]

where (as usual)

k=?-\342\200\224. [2.159]
n

Inside the well, where V(x) = \342\200\224

Vo>

f(x)
= C sin(Zx) + D cos(/a), for (-a < x < a), [2.160]

where, as before,

, = 2^\302\261W. [2.m
n

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

f{x) = Feikx. [2.162]

Here A is the incident amplitude, B is the reflected amplitude, and F is the

transmitted
amplitude.40

There are four boundary conditions: Continuity of f(x) at

\342\200\224
a says

Ae~ika + Beika = -C sin(/\302\253) + D cos(/a), [2.163]

continuity of dfjdx at \342\200\224

a gives

ik[Ae~ika
- Beika] =
l[C cos(/a) + D sin(/a)] [2.164]
continuity
of f(x) at +a yields

C sin(/\302\253) + D cos(/\302\253)
= Feika. [2.165]

and continuity of dfjdx at +a requires

/[Ccos(/fl)
- Dsin(/fl)] = ikFeika. [2.166]

40We could look for even and odd functions, as we did in the case of bound states, but the

scaltering problem is inherenlly asymmetric, since the waves come in from one side only, and ihc
exponential notation (representing traveling waves) is more natural in this context.
 Time-Independent Schrodinger Equation

FIGURE 2.19: Transmissioncoefficientasa functionofenergy (Equation 2.169).

We can use two of these to eliminateC and D, and solve the remaining two for
B and F (seeProblem2.32):
= i
.sin(2/a) 2 2
\342\200\224
B (/
\342\200\224tt-.\342\200\224 k )F. [2.167]
2kl
-2ika
F = [2.168]
cos(2/a)-/^psin(2/fl)
coefficient
The transmission (T
=
|F|2/|A|2), expressed in terms of the
original variables, is given by

V2
T~x = 1+ [2.169]
4^^0)^(1^^^)-
Notice that T = 1 (the well becomes \"transparent'\")whenever the sine is zero,
which is to say, when

-H-y/2m(En + V0)=njr, [2.170]

n

where n is any integer. The energies for perfect transmission,then, are given by

n~7T~n~
E\302\273+ Vo = [2.171]
2m(2fl)2'
which happento be precisely the allowed energies for the infinite square well. T
is plottedin Figure2.19,asa function of energy.41

*Problem 2.29 Analyze the odd bound state wave functions for the finite square
well. Derive the transcendental equation for the allowedenergies, and solve it

graphically. Examine the two limiting cases. Is there always an odd bound state?

41 This remarkable has been observed in the laboratory, in the form of the Ramsauer-
phenomenon
Townsend effect. For an illuminating discussion see Richard W. Robineii, Quantum Mechanics. Oxford
U.P.. 1997. Section 12.4.1.
 Section 2.6: TheFiniteSquare Well 83

Problem 2.30 Normalize \\f/(x) in Equation 2.151, to determine

the constants D
and F.

Problem 2.31 The Dirac delta functioncanbe thought of as the limiting case of a
rectangle of area 1, as theheightgoes infinity and the width goes to zero. Show
to

that the delta-functionwell (Equation 2.114)is \"weak\" potential (even though it a

is infinitely deep), in the sense zq 0. Determine the bound

that state energy for
\342\200\224>

the delta-functionpotential, treating it as the limit of a finite square well. Check

by

that your answer is consistent with Equation 2.129. Also show Equation 2.169 that

reduces to Equation 2.141 in the appropriatelimit.

Problem2.32 Derive Equations 2.167 and 2.168. Hint: Use Equations 2.165 and
2.166 to solve for C and D in terms of F:
k
C= sin(la) + i- cos(la) eikaF\\ D = cos(la) \342\200\224
i- sin(/tf) eikaF.

Plug these back into Equations 2.163and 2.164. Obtain the transmission coefficient,
and confirm Equation 2.169.

* ^Problem 2.33 Determinethe transmission coefficient for a rectangular barrier

(same as Equation 2.145, only with V(x) = +Vb > 0 in the region \342\200\224
a < x < a).
Treat separately the three cases E < Vq, E Vq, and E > Vq (note = that the
wave function inside the barrier is differentin the threecases).Partialanswer: For

E < V0,42

^Problem 2.34 Consider the \"step\" potential:

... . ( 0, if jc <0.
V(X)=\\ V0. ifx>0.

(a) Calculate the reflection coefficient, for the case E < Vq, and comment on
the answer.

(b) Calculate the reflection coefficientforthe caseE > Vq.

(c) For a potential such as this, which does not go back to zero to the right of
the barrier,the transmission coefficient is not simply |F|2/|A|2 (with A the

4-This is a goodexampleof tunneling\342\200\224classically the particle would bounce back.

Chapter 2 Time-Independent SchrodingerEquation

nV(X)

-V0

FIGURE 2.20: Scattering from a \"cliff\" (Problem 2.35).

incident amplitude and F the transmitted amplitude), becausethe transmitted

wave travels at a different speed. Show that

for E > Vq. Hint: You can figure it out using Equation 2.98, or\342\200\224more
elegantly,
but less informatively\342\200\224from the probability current (Problem 2.19).
What is T, for E < V01

(d) For E > Vb, calculate the transmission coefficient for the step potential, and
check that T + R = 1.

Problem 2.35 A
particle of mass m and kinetic energy E > 0 approaches an

abrupt potential drop Vo (Figure 2.20).

(a) What is the probability that it will \"reflect\" back, if E = V0/3? Hint: This
is just like Problem 2.34, except that the step now goes down, insteadof up.

(b) I drew the figure so as to make you think of a car approaching a cliff, but
obviously the probabilityof \"bouncing
back\" from the edge of a cliff is far
smaller than what you got in (a)\342\200\224unless you're Bugs Bunny. Explain why
a cliff. Hint:
this potential does not correctlyrepresent In Figure 2.20 the
potential energy of the car dropsdiscontinuously .t = 0;
\342\200\224
to Vo, as it passes

would this be true for a falling car?

(c) When a free neutron entersa nucleus,it experiences a drop in sudden

potential
energy, V = 0 outside to
from around 12 MeV (million electron volts) \342\200\224

inside. Suppose a neutron,emitted kinetic energy 4 MeV by a fission with

event, strikes such a nucleus. is the probability it will be absorbed,

What

thereby initiating another fission?Hint: calculated the probability of You

reflection in part (a); use T = R to get the probability of transmission

1
\342\200\224

through the surface.

 Further Problems for Chapter 2 85

FURTHER PROBLEMS FOR CHAPTER 2

Problem2.36 Solve the time-independent Schrodinger equation with

appropriateboundary conditions for the \"centered\" infinite square well: V(x) = 0 (for

<
\342\200\224a x < +a), V(x) = oo (otherwise). Check that your allowed energies are
consistent with mine (Equation 2.27), and confirmthat your \\f/'$ can be obtained
from mine (Equation 2.28) by the substitution x \342\200\224>\342\226\240
(x + a)/2 (and appropriate
renormalization). Sketch your first three solutions,and compareFigure 2.2. Note
that the width of the well is now 2a.

Problem 2.37 A particle in the infinite squarewell (Equation 2.19) has the initial
wave function

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

Determine A, find W(x. t), and calculate (x), as a function of time. What is the

expectation value of the energy?Hint: sin\" 6 and cos\" 6 can be reduced, by repeated
application of the trigonometric sum formulas, to linear combinationsof sin(w#)
and cos(w0), with m = 0. 1. 2, ... . /?.

* Problem 2.38 A particle of mass m is in the groundstateoftheinfinite square well

(Equation 2.19). Suddenly the well expands to twice its original size\342\200\224the right

wall moving from a to 2a\342\200\224leaving

the wave function (momentarily) undisturbed.
The energy of the particleis now measured.

(a) What is the most probable result? What is the probability of getting that
result?

(b) What is the next most probable result, and what is its probability?
(c) What is the expectation value of the energy? Hint: If you
find yourself
confronted with an infinite series, try
another method.

Problem 2.39

(a) Show that the wave functionof a particle in the infinite square well returns
to its original form after a quantum revival time T = Anur/nti. That is:
vl/(jr. T) = W(x. 0) for any state (not just a stationarystate).

(b) What is the classical revival time, for a particle of energy E bouncing back

and forth between the walls?

(c) For what energy are the two revival times equal'?43

4- The fact that the classical and quantum revival times bear no obvious relation to one another
(and the quantum one doesn't even depend on the energy) is a curious paradox: see Daniel Slyer.
Am.J.Phys.69,56(2001).
86 Chapter
2 Time-Independent Schrodinger Equation

Problem 2.40 A particle of mass m is in the potential

oo (a- < 0),

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

(a) How many bound states are there?

(b) In the highest-energy bound state, what is the probability that the particle
wouldbe found outside the well (x > a)? Answer: 0.542, so even though it
is \"bound\"
by the well, it is more likely to be found outside than inside!

Problem 2.41 A particle of mass m in the harmonic oscillator potential

(Equation 2.43) starts out in the state

unco \\ _wm1.2
vI/(a,0)
= AI I -2 /\342\200\224a-I <T^A ,

for some constant A.

(a) What is the expectation value of the energy?

(b) At some later time T the wave function is

\\ \"no ,.2
1 +2 / e~^x ,
(unco a)

for some constantB. What is the smallest possible value of Tl

Problem 2.42 Findthe allowedenergies of the half harmonic oscillator

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

vr U)~ \342\200\224
I

J oo. for a <0.

(Thisrepresents, for
example, a spring that can be stretched, but not compressed.)
Hint:Thisrequires some careful thought, but very little actual computation.

* ^Problem 2.43 InProblem2.22 analyzed you the stationary gaussian free particle
wave packet. Now solvethe sameproblem for the traveling gaussian wave packet,
starting with the initial function wave

vl/(A-,Q) = A<rflA'V/v

where / is a real constant.

 Further Problems for Chapter 2 87

* *Problem 2.44 Solve the time-independentSchrodinger equation for a centered

infinite square well with a delta-function barrier in the middle:

... , f a8(x), for \342\200\224
a < x < +\302\253,

[
oo, for |jc| > a.

Treat the even and odd wave functions separately. Don't bother to normalize them.
Find the allowedenergies if necessary). How (graphically,
do they compare with
the corresponding energiesin the absenceof the delta function?
Explain why the

odd solutions are not affected the delta function. Comment by on the limiting cases
a 0
\342\200\224> and a oo.
\342\200\224>

Problem 2.45 If two (or more) distinct44solutionsto the (time-independent)

Schrodinger equation have thesame energy E, these states are said to be
degenerate. For example, the states are doubly
free particle solution degenerate\342\200\224one

representing motion to the right, and the othermotiontotheleft. we have never But

encountered normalizable degenerate solutions, and this is no accident. the Prove

following theorem: In one dimension45 there are no degeneratehoundstates. Hint:

Suppose there are two solutions, and \\j/2, with the same energy E. Multiply the
\\j/\\

Schrodingerequation for
\\f/\\ by i/^, and the Schrodinger equation for \\f/2 by \\f/\\,
and subtract, to show that {^/id^\\/dx \342\200\224
\\f/\\d\\//2/dx) is a constant. Use the fact
that for normalizablesolutions\\j/ 0 at
\342\200\224> + oo to demonstrate that this constantis
in fact zero. Conclude that xj/i is a multiple of \\j/\\,
and hence that the two solutions
are not distinct.

Problem 2.46 Imagine

a bead of mass m that slides frictionlessly arounda circular
wire
ring of circumference L. (This is just like a free particle,exceptthat \\j/(x +

L) = t^(a')-) Find the stationary states (with appropriate normalization) and the

corresponding allowed energies. Note that there are two independent solutions for

each energy En\342\200\224corresponding

to clockwise and counter-clockwise circulation;
call them tJ/*(x) and \\J/~(x).
How do you account for this degeneracy, in view of
the theoremin Problem2.45 (why
does the theorem fail, in this case)?

**Problem 2.47 Attention:This is a strictly qualitative problem\342\200\224no

calculations

allowed! Consider the \"double square well\" potential (Figure 2.21). Supposethe

44If two solutions differ only by a multiplicative constant (so that, once normalized, they differ
only by a phase factor e\"^). they represent the same physical slate, and in this sense they are not distinct
solutions. Technically, by \"distinct\" I mean \"linearly independent.\"

45Indimensions such degeneracy is very common,

higher as we shall see in Chapter 4. Assume
that the not consist of isolated piecesseparated
potential does by regions where V = co\342\200\224two isolated
infinite square wells, for instance, would give rise to degenerate bound stales, for which the particle is
either in the one or in the other.
88 Chapter 2 Equation
Time-IndependentSchrodinger

kV(x)

-vn

FIGURE 2.21: The double square well (Problem

2.47).
depth Vq and the width a are fixed, and large enoughso that several bound states
occur.

(a) Sketch the ground state wave function \\j/i and the first excited state t/t2,
(i) for the case b = 0, (ii) for b % a, and (iii) for b ^> a.
(b) Qualitatively,how do the correspondingenergies and Ei) (E\\ vary, as b goes
from 0 to oo? Sketch and Ejib) on the same graph. E\\(b)

(c) The double well is a very primitive one-dimensional model for the potential
experienced by an electron in a diatomic(the two wells represent molecule
the attractive force of the nuclei). are free to move,
If the nuclei will they

adopt the configuration of minimum energy. In view of conclusions in your

(b), does the electron tend to draw the nuclei together, or push them apart?
(Of course, there is alsothe internuclear repulsion
to consider, but that's a
separate problem.)

Problem 2.48 In Problem2.7(d) got the expectation

you value of the energy by

summing the series in Equation 2.39, but 1 you (in footnote 15) not to
warned try
it

the \"old fashioned way,\" (H) = f V(x.0)*HV(x.0)dx, becausethe

first
discontinuous derivative of ty(x. 0) renders the second derivative problematic. Actually,

you could have done it using integration by parts, but the Dirac delta function
affords a much cleanerway to handle such anomalies.

(a) Calculate the first derivative of ^(.v.O) (in Problem2.7),and express the

answer in terms of the step function, 9(x \342\200\224

a/2), defined in Equation 2.143.
(Don't worry about the end points\342\200\224just
the interior region 0 < .v < a.)
(b) Exploit the resultofProblem2.24(b) to write the second derivative of W (x, 0)
in terms of the delta function.

(c) Evaluate the integral f W(x.0)*HV(x,0)dx, and check that you get the
same answer as before.
 Further Problems for Chapter 2 89

* * ^Problem2.49
(a) Show that

/ mco\\ 1/4 mco

+ \302\243* - 2axe-il0t}
exp
in fa+\302\243(,+,-*-)
\\ 2 m

satisfies the time-dependentSchrodingerequation for the harmonic oscillator

potential (Equation 2.43). Here a is real constant any

with the dimensions of
length.46

(b) Find \\^(x, t)\\2, and describe the motion of the wave packet.

(c) Compute (x) and (p), and check that Ehrenfest's theorem (Equation 1.38) is
satisfied.

**Problem 2.50 Considerthe moving delta-function well:

V(x,t) = -aS(x-vt),

where v is the (constant) velocity of the well.

(a) Show that the time-dependent Schrodinger equation admits the exact solution

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

where E = \342\200\224ma~/2tr
is the bound-state energy of the stationary delta
function. Hint: Plugit in and check it! Use the result of Problem 2.24(b).

(b) Find the expectationvalueof the Hamiltonian in this state, and comment on
the result.

* * ^Problem2.51 Consider the potential

V(x) = secrr(fl.Y),
m
where a is a positiveconstant, and \"sech\" stands for the hyperbolic secant.

(a) Graph this potential.

(b) Check that this potential has the ground state

\\j/q(x) = A sech(rtA').

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

46This rare exampleof an exact closed-form solution to the time-dependent Schrodinger equation
was discovered by Schrodinger himself, in 1926.
 Time-Independent Schrodinger Equation

(c) Show that the function

\342\200\224
/ik atenh(ax)\\
fkti) = A I
,-;\342\200\242\"
I eikx,
V ik+a J
= as usual) solvesthe
(where k y/2niE/ti, Schrodingerequation for any

(positive) energy E. Since tanhz as

-\302\273\342\200\2241 z -\302\273\342\200\224oo,

fk(x)
% Ae,kx. for large negative x.
This represents,then,a wave
coming in from the left with no
reflected
accompanying
wave (i.e., no term exp(\342\200\224/Aw)).
What is the asymptotic form
of fkix) at large positivex? What are R and T, for this potential?
Comment: This is a famous example of a reflectionless potential\342\200\224every incident

particle, regardless of its energy, passes right through.47<

Problem 2.52 The scattering matrix. The theory of scatteringgeneralizes in

a pretty obvious way to arbitrary localized potentials (Figure 2.22). To the left
(Region I), V(x) = 0, so

/2mF
fix) = Ae,kx + Be~iL\\ where k = -\342\200\224-.
n
[2.173]

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

f (a)
= Feikx + Ge~ikx. [2.174]
In between (Region II), of course, I can't tell you what f is until you specify
the

potential, but because the Schrodinger equation is a linear,second-order

differential

equation, the general solution has got to be of the form

f(x)
= Cfix) + Dgix).

where /*(a') and g(x) are linearly two

independent particular solutions.48 There
will be four boundary conditions (two joining Regions I and II, and two joining

Vix) A
Aeikx peikx

Be-'kx ^/ \\ Ge~ikx

Region I Region II Region III

FIGURE 2.22: Scattering from an arbitrary localized potential (Vix) = 0 exceptin

Region II); Problem 2.52.

47R. E, Crandall and B. R. Lill. Annals of Physics. 146.458 (1983).

48Sce any book on differential equations\342\200\224for example, J. L. Van Iwaarden. Ordinary Differential
Equationswith Numerical Techniques. Harcourl Brace Jovanovich, San Diego, 1985,Chapter 3.
 Further Problems for Chapter 2 91

Regions II and III). Two of these can be used to eliminate C and D, and the other
two can be \"solved\" for B and F in terms of A and G:

B =SUA + S\\2G. F = S2\\A + S22G.

The four coefficients S{j, which depend on k (and hence on E), constitute a 2 x 2
matrix S, called the scattering matrix (or S-matrix, for short).The S-matrixtells
you
the outgoing amplitudes (B and F) in terms of the incomingamplitudes (A

and G):
B\\ fSu Sl2\\(A\\
[2A75]
C So
In the typicalcaseof scattering from the left, G = 0, so the reflectionand
transmission coefficients are

2 |F|2
\\B\\2 I/\"!2
= |52i I2 [2.176]
G=0
For scattering from the right, A =0, and

\\F\\2 -> \\B\\2

Rr
~ = \\Sn\\2 [2.177]
lap 4=0 Id' A=0

(a) Construct the S-matrix for scattering from a delta-function well

(Equation 2.114)'.

(b) Construct the S-matrix for the finite square well (Equation2.145).Hint:This
requires no new work, if you carefully exploit the symmetry of the problem.

* * ^Problem 2.53 The transfer matrix. The S-matrix (Problem 2.52) tells you the
outgoing amplitudes (B and F) in terms of the incomingamplitudes and (A

G)\342\200\224Equation 2.175. For some purposes it is more convenient to with the work

transfer matrix, M, which gives you the amplitudes the right of the potential
to
(F and
G) in terms of those to the left and B): (A

\\Gj \\M2l

(a) Find the four elements of the Af-matrix, in terms of the elements of the
S-matrix, and vice versa.Express /?/, 7/, /?,-, and 7)- (Equations 2.176 and
2.177) in terms of elementsof the M-matrix.

(b) Suppose you have a potential consisting of two isolated pieces(Figure2.23).

Show that the M-matrix for the combination is the product of the two
M-matrices for each section separately:
M = M2Mi. [2.179]
(This obviously generalizes to any number of pieces, and accounts for the
usefulnessof the M-matrix.)
92 Chapter
2
Time-Independent Schrodinger Equation

^
Mh /W.

1/=0 1/=0 1/=0

FIGURE 2.23: A
potential consisting of two isolated pieces (Problem 2.53).

(c) Construct the M-matrix for scattering from a single delta-function potential
at point a:
V (.t)
= -a8(x-a).

(d) By the method of part (b), find the M-matrix for scattering from the double
deltafunction
V(x) = -a[8(x + a) + 8(x
-
a)].
What is the transmissioncoefficient for this potential?

Problem 2.54 Find the ground state energy of the harmonicoscillator, five to

significant digits, by the \"wag-the-dog\" method. That is, solve Equation 2.72
numerically, varying K until you get a wave function goes to zero at large that In
\302\243.

Mathematica, appropriate input code would be

PIot[EvaIuate[u[x]/.NDSoIve[{u\"[x]-(x2 - K)*u[x] 0, u[0] == 1, ==

u'[0] == 0), u[x], {x, 10\"8,10), -> 10000]], {x, a, b), MaxSteps

PlotRange -> {c, d}];

(Here(a, is the horizontal
b) range of the graph, and (c, d) is the vertical
range\342\200\224

start with a = 0, b = 10, c = d = 10.) We know that the correct solution is

\342\200\22410,

K = 1,so might start with a \"guess\" of K = 0.9. Notice

you
the \"tail\" of the what

wave function does. Now K = 1.1, and note that the tail flipsover.
try
Somewhere

in between those values lies the correct solution. Zero in on it bracketing K by

tighter and tighter. As you do so, you want to adjust a, b, c, and d, to zero may

in on the cross-over point.

Problem 2.55 Find the three excited first state energies (to five significant digits)
for the harmonicoscillator, wagging by
the dog (Problem 2.54). For the first (and
third) excitedstate will need to set you u[0] == 0. \302\253'[0]
== 1.

Problem 2.56 Find the first four allowed energies(to five

significant digits) for

the infinite square well, by wagging the dog. Hint: Refer to Problem 2.54, making
appropriatechangesto the differential equation. This time the condition you are
looking for is u{\\)
= 0.
CHAPTER 3

FORMALISM

3.1 HILBERT SPACE

In the last two chapters we have stumbled on a numberof interesting properties

of

simple quantum systems. featuresof specific

Some of these are \"accidental\"
potentials (the even spacing of energy levels for the harmonic oscillator,for example),
but others seem to be more general, and it would be nice to prove them once and
for all (the uncertainty principle, for instance,and the orthogonality of stationary

states). The purpose of this chapter is to recast the in a more powerful theory form,
with that in mind. There is not much here that is genuinely new; the idea, rather,
is to make coherentsense of what we have already discovered in particular cases.
Quantumtheory is basedon two constructs: wave functions and operators. The
state of a system is represented by
its wave function, observables are represented
by operators. Mathematically, wave functions satisfy the defining conditions for
abstract vectors, and operatorsact on them as linear transformations. So the
natural language of quantum mechanicsis linearalgebra.1
But a form of linear algebra
it is not, I suspect,which you are immediately with

familiar. In an N-dimensional spaceit is simplest represent a vector, \\a), by the to

AMuple of its components,{a,,}, respect to a specified orthonormal basis:

with

ai
|or> a =
-\302\273\342\200\242
[3.1]

W/

If you have never studied linear algebra, you should read the Appendix before continuing.

93
Formalism

The inner product, (a\\f$),

of two vectors (generalizing the dot product in three
dimensions)is the complex number,

= + 4- -
\342\200\242
\342\226\240
+ [3.2]
(ct\\P) a\\b\\ a$b2 a*NbN.

Linear transformations, T, are represented by matrices (with

respect to the specified
basis), whichact on vectors(toproduce new vectors) by the ordinary rules of matrix
multiplication:
\342\200\242\342\226\240\342\226\240
(t\\\\ t\\2 t\\N\\ /fli\\
ti i /22 hN cn
ljB>
= T\\a) b = Ta = [3.3]

But the \"vectors\" we encounter in quantum (for the most part)

mechanics are

functions, and they

live in infinite -dimensional spaces. For them the //-tuple/matrix
notationis awkward, at best, and manipulations that are well-behaved in the finite-
dimensional case problematic. can be (The underlying reason is that whereas the
finite sumin Equation3.2 always exists, an infinite sum\342\200\224or an integral\342\200\224may not

converge, in which case the inner productdoesnotexist, any argument involving and

inner products is immediately suspect.) Soeventhoughmostofthe and terminology

notation should be familiar, it pays to approach this subject caution. with

The collection of all functions of constitutes a vector space, but for our .v

purposes it is too
much
large. To represent a possible physical state, the wave

function ^ must be normalized:

= 1.
\\V\\2dx
I
The set of all square-integrable functions, on a specified interval,2

f(x) such that \\f(x)\\~dx < oo. [3.4]

f
a
constitutes (much smaller) vector space (see Problem 3.1(a)). Mathematicians
call it Li(a. b)\\ physicists call it Hilbert space.3 In quantum mechanics, then,

Wave functions live in Hilbert space. [3.5]

2For us.the limits (a and b) will almost always be \302\261oo. but we might as well keep things more

general for the moment.

-^Technically,a Hilberlspaceis a complete inner product space, and the collection of square-

integrable functions is only one example of a Hilberl space\342\200\224indeed, every finite-dimensional vector
space is trivially a Hilberl space. But since Lj is Ihe arena of quantum mechanics, it's what physicists
generally mean when they say \"Hilbert space.\" By Ihe way. ihe word complete here means lhal any
Cauchy sequence of functions in Hilberl space converges lo a function that is also in the space: it has no
\"holes\" in il. jusl as the set of all real numbers has no holes (by contrast, ihe space of all polynomials,
for example, like ihe set of all rational numbers, certainly does have holes in it). The completeness
of a space has nothing lo do wilh ihe completeness (same word, unfortunately) of a set of functions,
which is the properly lhal any oilier function can be expressed as a linear combination of them.
 Section 3.1: Hilbert Space 95

We define the inner product of two functions, f(x) and g(x), as follows:

(f\\g)= / f(x)*g(x)dx. [3.6]

If / and g are both square-integrable (that is, if they are both in Hilbert space),
their inner productis to exist guaranteed (the integral in Equation 3.6 converges to
a finite number).4This from the follows integral Schwarz inequality:5

\\g{x)\\2dx. [3.7]
\\j f{xTg{x)dx\\<JJ,\\f{x)\\2dxj
You can check for yourself that Equation 3.6 satisfiesall the conditions
for an inner

product (Problem 3.1(b)). Notice in particular that

= [3-8]
<*l/> (f\\8)*-

Moreover, the inner product of f(x) with itself,

(/1/)= / \\ftx)\\2dx. [3.9]

is real and non-negative;it's zeroonly6 when f(x)

= 0.
A function is said to be normalized if its inner product with itself is 1; two
functions are orthogonal if theirinner product
is 0; and a set of functions, {/\342\200\236},
is orthonormal if they are normalized and mutually orthogonal:

(fm\\f,,)=Sm\342\200\236. [3.10]

Finally,a set of functions is complete if any other function (in Hilbert space) can
be expressed as a linearcombination them: of

CO

f(x) = [3.11]
^2cnf\342\200\236{x).

/7=1

4ln Chapter 2 we were obligedon occasion to work with functions that were not nqrmalizable.
Such functions lie outside Hilbert space,and wc are going to have to handle them with special care, as
you will see shorlly. For the moment. 1 shall assumethat all Ihe functions we encounter are in Hilbert
space.
a proof,
\342\200\242'For see F. Riesz and B. Sz.-Nagy.Functional Analysis (Unger, New York, 1955),
Section 21. In -a finite dimensional vector space the Schwarz inequality, |(a|y3)|- < (a|a)(/0|/3), is
easy to prove (see Problem A.5). But that proof assumes the existence of the inner products, which is
precisely what we are trying to estabiisli here.
6What about a function that is zero
everywhere except at a few isolated points? The integral
(Equation 3.9) would vanish,
though the function
still evenitself does not. If this bothers you, you
should have been a math major. In physics such pathological functions do not occur, but in any case, in
Hilbert space two functions that have the same square integral are considered equivalent. Technically,
vectors in Hilbert space represent equivalence classes of functions.
96 Chapter 3 Formalism

If the functions (.v)}

{f\342\200\236
are orthonormal, the coefficients are given by Fourier's trick:

ctt = (f\342\200\236\\f). [3.12]

as you for yourself. I anticipatedthis terminology,

can check of course,back
in Chapter 2. (The stationary states for the infinite square well (Equation 2.28)
constitute a complete orthonormal set on the interval (0. a); the stationary states
for the harmonic oscillator(Equation 2.67or 2.85) are a complete orthonormal set
on the interval (\342\200\224oo. oo).)

Problem 3.1

(a) Show that the set of all square-integrable

functions is a vector space (refer
to Section A.l for the definition).Hint:The main problem is to show that
the sum of two square-integrable functionsis itselfsquare-integrable. Use

Equation 3.7. Is the set of all nonnalized functionsa vectorspace?

(b) Show that the integral in Equation 3.6 satisfies the conditionsfor an inner
A.2).
product(Section

* Problem 3.2

(a) For what range of v is the function f(x) = xv in Hilbert space, on the
interval (0. 1)? Assume v is real, but not necessarilypositive.
(b) For the specific case v =
1/2, is f(x) in this Hilbert space? What about

x/(.v)? How about (d/dx)f(x)1

3.2 OBSERVABLES

3.2.1 Hermitian Operators

The expectation value of an observable <2(.\\\\ p) can be expressed very neatly in

inner-product notation:7

((2)= fv*QVdx = mQV). [3.13]

Remember ihal Q is the operator constructed from Q by the replacement p s (ft/i)d/dx.

-\302\273\342\226\240
/3
These operators arc linear, in the sense that

Q\\af{x) + bg{x)] = aQf(x) + bQg(x).

for any functions f and g and any complex numbers a and b. They constitute linear transformations
(Scclion A.3) on the space of all functions. However, they sometimes carry a function inside Hilbert
 Section 3.2: Observables 97

Now, the outcomeof a measurement has

got to be real, and so, a fortiori, is the
averageof many
measurements:

(Q) = {Q)*. [3.14]

of
But the complexconjugate an inner product reverses the order (Equation 3.8), so

<*|6*> = <G*I*>. [3-15]

and this must hold true for any wave function vj/. Thus operators representing
obsetvables have the very special property that

(f\\Qf)
= (Qf\\f) for all/(.v). [3.16]

We call such operators hermitian.

Actually, most books require an ostensibly strongercondition:

(f\\Qg)= (Qf\\z)
for all fix) and all g(x). [3.17]

But it turns out, in spite of appearances, this is perfectly equivalent to my that

definition (Equation 3.16), as you prove in Problem 3.3. So use whichever will

you like. The essentialpointis a hermitian operator can be applied either to that

the member
first of an inner product or to the second, the same result, and with

hermitian operators naturally arise in quantum mechanicsbecausetheirexpectation

values are real:

Observables are represented by hermitian operators. [3.18]

Well, let's checkthis. Is the momentum operator, for example, hermitian?

tide h oo C\302\260\302\260

gdx = (pf\\g).
f\302\260\302\260 /hdf\\*
if\\pg)= r~dX
dx
= -f*g
i -do
+ [\"-f) [3.19]
J_oo i J_00 \\
i dx)

1 used integration by parts, of course,and threw

away the boundary term for the
usual reason: If f(x) and g(x) aresquare integrable, they must go to zero at ioo.8

space into a function outside it (see Problem 3.2(b)). and in this case the domain of the operator may
have to be restricted.
,s
is not quite true. A.s 1 mention in Chapter
Actually, this 1. there exist pathological functions
that are but do not go to zero at infinity.
square-integrablc However, such functions do not arise in

physics, and if you are worried about it we will simply restrict the domain of our operators to exclude
them. On finite intervals, though, you really do have to be more careful with the boundary terms,
and an operator that is hermitian on (\342\200\224oo.
oo) may not be hermitian on (0. co) or (\342\200\224n, n). If you're

wondering about the infinite square well, it's safest to think of those wave functions as residing on the
infinite line\342\200\224they just happen to be zero outside (0. a).
 Formalism

Notice how the complex conjugation of i compensates for the minus sign picked
up
from integration by parts\342\200\224the operator d/dx (without the i) is not hermitian,
a possible
and it does not represent observable.

*Problem 3.3 Show that if {h\\Qh) = (Qh\\h) for all functions h (in Hilbert space),
men (f\\Qg) = (Qf\\g) f\302\260r all
/ and g (i-e-> tne two definitionsof
\"hermitian\"\342\200\224Equations
3.16 and 3.17\342\200\224are equivalent). Hint: First let h = f + g, and
then let h =
f + ig.

Problem 3.4

(a) Show that the sum of two hermitian operators is hermitian.

(b) Suppose Q is hermitian, and or is a complex number. Under what condition

(on a) is a Q hermitian?

(c) When is the product of two hermitian operatorshermitian?

At

(d) Show that the position operator (.v = x) and the hamiltonianoperator(H =
are hermitian.

Problem 3.5 The hermitian conjugate (or adjoint) of an

operator Q is the

operator Qf such that

(f\\Qg) = (Q\\f\\g) (for all / and g). [3.20]

(A hermitian operator, then, is equal to its hermitian conjugate: Q = Q'.)
(a) Find the hermitian conjugates of ,v, i, and d/dx.

(b) Constructthehermitianconjugate of the harmonic oscillator raising operator,

\302\253+(Equation 2.47).

(c) Show that (<2^)f = R*Qf-

3.2.2 DeterminateStates
Ordinarily,
when you measure an observable Q on an ensemble of identically
prepared systems, state ^, you do not get the same
all in the same result each

time\342\200\224this is the indeterminacy of quantum mechanics.9 Question: Would it be

possible to prepare a state such that eveiy measurementof is certain Q to return

the same value (call it q)l This would be, if like, a determinate you state, for
the observable Q. (Actually, already know one example: Stationary we states are
determinate states of the Hamiltonian; a measurement of the total energy,
on a

I'm talking about competent measurements, of course\342\200\224it's always possible to make a mistake.
and simply get the wrong answer, but that's not the fault of quantum mechanics.
 Section 3.2: Observahles 99

particle in the stationary state %, is certain to yield the corresponding \"allowed\"

energy \302\243\342\200\236.)

Well, the standard deviation of Q, in a determinatestate,wouldbe zero,which

is to say,

-
o1 = (\302\2532
-
(<2\302\2732>
=
(*|(G <?)2*>= (\302\2532
~
q)V\\{Q
~
<?)*> = 0. [3.21]
(Of course,if every
measurement gives q, their average is also q: (Q) = q. I also

used the fact that Q, and hence also Q \342\200\224

q, is a hermitian
operator, to move one
factorovertothe first term in the inner product.) But the only function whoseinner
product with itself vanishes is 0, so

QV=qV. [3.22]
This is the eigenvalueequation for the
operator Q; ^ is an eigenfunction of Q,
and q is the
corresponding eigenvalue. Thus

Determinate states are eigenfunctions of Q. [3.23]

Measurement
of Q on such is certain to yield the eigenvalue,q.
a state
Note that the eigenvalue is a number (not an operator or a function). You can

multiply any eigenfunction by a constant, and it is still an

eigenfunction, with the
same eigenvalue. Zero does not count as an eigenfunction (we exclude it by defi-
nition\342\200\224otherwise
At
every number would be an eigenvalue, since Q 0 = q0= 0 for

any operator Q and all q). But there's nothing wrong

with zero as an eigenvalue.
The collection of all the eigenvaluesof an
operator is called its spectrum.
Sometimes two (or more) linearly independent eigenfunctions share the sameeigenvalue;
in that case the spectrum is said to be degenerate.
states
For example,determinate of the total energy are eigenfunctions of the
Hamiltonian:
Hf = Eir. [3.24]
which is precisely the time-independent Schrodinger equation. In this context we
use the letter E for the eigenvalue, and the lowercase \\j/ for the eigenfunction (tack
on the factor exp(\342\200\224iEt/h)
to make it 4>, if you like; it's still an eigenfunction

of//).

Example 3.1 Consider the operator

d
Q= i \342\200\224
< [3.25]
dq>

where 0 is the usual polar coordinatein two dimensions. (This operator might arise
in a physical contextif we were studying the bead-on-a-ring; see Problem 2.46.)
Is Q hermitian?Findits eigenfunctions and eigenvalues.
100 Chapter 3 Formalism

Solution: Here we are working with functions /(0.) on the finite interval 0 < 0 <
2tt, and stipulate that

/(0 + 2tt) = /(0). [3.26]

since0 and 0 + 2tt describe the same physical point. Usingintegration
by parts,

so Q is hermitian (this time the boundaryterm disappears by virtue of Equation 3.26).

The eigenvalue equation,

i-^-fW)=
d<$>
\302\242/(0)- [3-27]

has the general solution

/(0) = Ac-'**. [3.28]

Equation3.26restricts the
possible values of the q:

e-ic,2n = , ^ 9 = 0, +1. \302\2612,... [3.29]

The spectrum of this operator is the set of all integers,

and it is nondegenerate.

Problem 3.6 Consider the operator Q = d2/d02, where (as in Example 3.1)
0 is the azimuthal angle in polar coordinates, and the functions are subject to
Equation 3.26. Is Q hermitian?Findits eigenfunctions
and eigenvalues. What is
the spectrum of <2? Is the spectrumdegenerate?

3.3 EIGENFUNCTIONS OF A HERMITIAN OPERATOR

Our attention is thus directed to the eigenfunctions of hermitianoperators

(physically:
determinate states of observables). These fall into two categories: If the
spectrumis discrete (i.e., the eigenvalues are separated from one another) then the
eigenfunctionslie in and they constitute physically
Hilbert realizable states.
space

If the spectrumis continuous (i.e., eigenvalues fill out an entire range) then the

the eigenfunctionsare not normalizable, they do not represent possible wave and

functions (though linear combinations of a spread them\342\200\224involving necessarily

in eigenvalues\342\200\224may be normalizable). Some operators have a discrete spectrum

only (for example,the Hamiltonian the harmonic oscillator), for some have only a
continuous spectrum (for example,thefree particle Hamiltonian), and some have

both a discrete part and a continuous (for example, the part

Hamiltonian for a
 Section 3.3: Eigenfunctionsof a HermitianOperator 101
finite
square well). The discrete case is easier to handle, becausethe relevantinner
productsare guaranteed
to exist\342\200\224in fact, it is very similar to the finite-dimensional

theory (the eigenvectors of a hermitian matrix). I'll treat the discretecasefirst, and

then the continuous one.

3.3.1 Discrete Spectra

of a hermitianoperator
Mathematically,the normalizableeigenfunctions have two

important properties:

Theorem 1: Their eigenvalues are real.

Proof: Suppose
Qf = qf*

(i.e., fix) is an eigenfunction of Q, with

eigenvalue q), and10

(/1(2/) = ((2/1/)

(<2 is hermitian). Then

ci(f\\f)=cj*(f\\f)
iq is a number, so it comes outside the integral, and becausethe first function
in the inner product is complex conjugated (Equation 3.6), so toois the q on

the right). But (/1/) cannot be zero (/(.y) = 0 is not a legal eigenfunction),
so q = q*, and hence q is real. QED

This is comforting: If you measure an observable on a particlein a determinate

state, you will at least get a real number.

Theorem 2: Eigenfunctions
belonging to distinct eigenvalues are

orthogonal.

Proof: Suppose

Qf = clf and Qg = q'g,

and Q is hermitian. Then (f\\Qg) = (Qf\\g), so

q'{f\\g)=q*{f\\g)
(again, the inner productsexist eigenfunctions are in because the Hilbert
space by assumption). But q is real (from Theorem 1),soif q' ^ q
it must

be that (f\\g) = 0. QED

,()U is here ihai we assume ihe eigenfunctions arc in Hilbert space\342\200\224otherwise the inner product
might not exist at all.
102 Chapter 3 Formalism

That's why
the stationary states of the infinite square well, for example,or the
harmonicoscillator, are
orthogonal\342\200\224they are eigenfunctions of the Hamiltonian
with distinct eigenvalues. But thisproperty is not peculiar to them, or even to the
Hamiltonian\342\200\224the same holds for determinate states of any observable.
Unfortunately, Theorem2 tells us
nothing about degenerate states (q' = q).
However, if more) two
eigenfunctions (or share the same eigenvalue, any
linear combination of them is itself an eigenfunction, with the same eigenvalue
(Problem 3.7(a)), use the Gram-Schmidt orthogonalization
and we can
procedure (Problem A.4) to construct orthogonal eigenfunctions witliin each degenerate
subspace.It is neveralmost
necessary to do this explicitly (thank God!), but it can

always
be done in principle. So even in the presence of degeneracythe
can
eigenfunctions be chosen to be orthogonal, and in setting up the formalismof quantum

mechanics we shall assume that this has already been done. licenses the use That

of Fourier's trick, which depends on the orthonormality of the basis functions.

In a yjm'te-dimensional vector space the eigenvectors of a hermitian matrix

have a third fundamental property: They span the space vector can be (every

expressed as a linear combination of them). the proof does not Unfortunately,

generalize to infinite-dimensional spaces. But the property itself is to the essential

internal consistency of quantum mechanics, so (followingDirac11) will take it we

as an axiom (or, more precisely, as a restriction the class of hermitian operators on

that can represent observables):

Axiom: The eigenfunctions of operator an observable are complete: Any

as a
function (in Hilbert space) can be expressed linear combination of

them.12

Problem 3.7
At

(a) Suppose that f{x) and g(x) are two eigenfunctions of an operator Q, with
the same eigenvalue q. Show that any linear combination of / and g is itself
an
eigenfunction of Q, with eigenvalue q.
(b) Check that f(x)
= exp(.v) and g(x) = exp(\342\200\224a)
are eigenfunctions of the

operator d2/dx2, with the same eigenvalue.Constructtwo linear

combinations of / and g that are o

orthogonal eigenfunctions nthe interval 1).
(\342\200\2241.

P. A. M. Dirac. 77k' Principle!; of Quantum Mechanics. Oxford University Press, New York

(1958).

'-In some specific cases completeness is provable (wc know that the stationary states of the
infinite square well, for example, arc complete,because of Dirichlef s theorem). It is a little
awkward lo call something an \"axiom\" that is provable in some cases, but 1 don't know a better way to
handle it.
 Section 3.3: Eigenfunctions of a Hermitian Operator 103

Problem 3.8

(a) Check that the eigenvalues of the hermitian operator in Example 3.1 are real.
Show that the eigenfunctions (for distinct eigenvalues) are orthogonal.

(b) Do the same forthe operator in Problem 3.6.

3.3.2 Continuous Spectra

If the spectrumof a operator is continuous, the eigenfunctions
hermitian are not
normalizable, and the proofsof Theorems 1 2 fail, because the inner products and

may not exist. Nevertheless,there is a sense which the three essential properties in

(reality, orthogonality, and completeness) s till hold. think it's best to approach I

this subtle case through specificexamples.

Example3.2 Find the eigenfunctions and eigenvalues of the momentum operator.

Solution: Let fp{x) be the eigenfunction and
p the eigenvalue:

= [3.30]
T-^-fP(.x)
i ax pfP(x).

is
The generalsolution
= Ae*x>h.
fp{x)

This is not square-integrable, for any (complex) value of p\342\200\224the momentum

operator has no eigenfunctions in Hilbert space. And yet, if we restrict ourselves to

real eigenvalues, we do recover a kind of ersatz\"oithononnality.\" Referring to

Problems 2.24(a) and 2.26,

/\302\2730O

fp(x)fp(x)dx
= \\A\\2 / eHP-W dx = \\A\\227rh8(p - p'). [3.31]
/OO
-OO J \342\200\224
OO

If we pick A = X/^/lnh, so that

= [3.32]
fp(x) -jL=eipxlK

then
(fp'\\fP)=&(p-p'). [3-33]
which is strikingly reminiscent of true
orthonormality (Equation 3.10)\342\200\224the indices

are now continuous variables, and the Kronecker delta has becomea Dirac delta,
but otherwise it looks just the same. I'll call Equation 3.33 Dirac orthonormality.
 Formalism

Most important, the eigenfunctions are complete, with thesum (in Equation3.11)
replaced by
an integral: Any (square-integrable) function f{x) can be written in
the form

1
poo
c{p) fp{x) dp
= -==
/ dp.
c{p)eiPx'h [3.34]
/OC-oo \\JlMn J-oo

The expansion coefficient (now a function, as

c(p)) is obtained, always, by Fourier's

trick:
/\302\2730O

= c(p)8(p
- p')dp = c(p'). [3.35]
c(p)(fP'\\fp)dp /
/OC-oo J-oc

Alternatively, you can get them from Plancherel's theorem(Equation2.102),for

the expansion (Equation 3.34) is nothing but a Fourier transform.

of
The eigenfunctions momentum (Equation 3.32) are sinusoidal, with
wavelength

X = ^. [3.36]
P
This is the old de
Broglie formula (Equation 1.39), which I promised to prove at

the appropriate It turns out to be a littlemoresubtle

time. than de Broglie imagined,
because know that there is actuallyno suchthing
we now as a particle with
determinate momentum. But we could make a normalizable wave packet with a narrow

range of momenta, and it is to such an

object that the de Broglie relation applies.
What are we to make of Example 3.2? Although none of the eigenfunctions
of p lives in Hilbertspace,a certain family of them (those with real eigenvalues)
reside in the \"suburbs,\" nearby with a kind of quasi-normalizability. They do not
representpossible physical states, but they are still very useful (as we have
already

seen, in our study of one-dimensional scattering).13

Example 3.3 Findthe eigenfunctions and

eigenvalues of the position operator.
Solution: Let gy{x) be the eigenfunction and y the eigenvalue:

= [3.37]
xgy(x) ygy(x).

13What about the eigenfunctions with notire&l eigenvalues? These are not merely non-
normalizable\342\200\224they actually blow up at \302\261oo. Functions in what 1 called the \"suburbs\" of Hilbert space
(the entire area is sometimes called a \"rigged Hilbert space\":see. for example,
metropolitan Leslie
Ballentine's Quantum Mechanics: A Modern Development, World Scientific, 1998) have the property
that although they have no (finite) inner product with themselves, they do admit inner products with all

members of Hilbert space. This is not true for eigenfunctions of p with nonreal eigenvalues. In
I showed
particular. that the momentum operator is hermitian for functions in Hilbert space, but the argument
depended on dropping the boundary term (in Equation 3.19). That term is still zero if g is an
of p with a real eigenvalue (as long
eigenfunction as f is in Hilbert space), but not if the eigenvalue has an
imaginary part. In this sense any complex number is an eigenvalue of the operator p, but only real numbers
are eigenvalues of the hermitian operator /3\342\200\224theothers lie outside the space over which p is hermitian.
 Section 33: Eigenfunctions of a Hermitian Operator 105

Here y is a fixed number (for any given eigenfunction), but x is a continuous

variable. What function of ,v has the property that multiplying it by x is the same
as multiplying it by the constant y? Obviously it's got to be zero, exceptat the one
point x = y; in fact, it is nothing but the Dirac delta function:

= A8(x -y).
gy(x)

This time the eigenvaluehastobe real; eigenfunctions the are not square-integrable,
but again they admit Dirac orthonormality:

/\302\27300

= \\A\\2 8{x
-
y')8(x - y)dx = -
y'). [3.38]
/00
-co
gp(x)gy(x)dx
\" /
J\342\200\224oo
\\A\\28(y

If we pick A = 1, so

gy(x) = 8(x-y). [3.39]

then

= [3-40]
{gy>\\gy) &(y-y')-

These eigenfunctions are also complete:

/\302\273oo
/\302\273oo
/\342\226\240no

/( c(y)g,(x)dy= / c{y)8(x-y)dy, [3.41]

/no-co \302\253/\342\200\224oo

with

c{y)
= /(>') [3.42]

(trivial, in this case, but you can get it from Fourier's trick if you insist).

If the spectrum of a hermitianoperatoris continuous (so the eigenvalues are

labeled by a continuous variable\342\200\224p
or y. in the examples; z, generically, in what
follows), the eigenfunctionsare notnormalizable, are not they in Hilbert space and
they do not representpossiblephysicalstates; the nevertheless, eigenfunctions with
real eigenvalues are Dirac orthonormalizable and complete (with the sum now an

integral). Luckily, this is all really require. we

Problem 3.9

(a) Cite a Hamiltonianfrom Chapter2 (other than the harmonic oscillator) that
has only a discrete spectrum.

(b) Citea Hamiltonian

Chapter from 2 {other than the free particle) that has only
a continuousspectrum.
106 Chapter
3 Formalism

(c) Cite a Hamiltonian (other from Chapter 2 than the finite square well) that
has both a discrete and a continuous part
to its spectrum.

Problem 3.10 Is the ground state of the infinite square well an eigenfunction of
momentum? If so, what is its momentum? If not, why not?

3.4 GENERALIZED STATISTICAL INTERPRETATION

In Chapter 1 I showed you how to calculate the probability that a particle would be
found in a particular location, and how to determine the expectation value of any
observable quantity. In Chapter2 learned how to find the possible
you outcomes
of an energy measurementand their probabilities.I now in a position to state am

the generalized statistical interpretation, subsumes all of this and enables which

you to figure out the possible results any measurement, and their probabilities.
of

Together with the Schrodingerequation tells you how the wave function (which

evolves in time) it is the foundationof mechanics. quantum

Generalized statistical interpretation: If you measure an observable Q(x, p)

on a particle the state W(x, f), you are certain to get one of the eigenvalues
in of

the hermitian operator Q{x. If the spectrum of Q is discrete, the

\342\200\224ihcl/dx).

of
probability getting the particular eigenvalue qn associated with the orthonormalized
eigenfunction f\342\200\236(x) is

where =
|c\342\200\236|2. c\342\200\236 (f\342\200\236\\V). [3.43]

If the spectrum is continuous, with real eigenvaluesq{z) associated Dirac- and

orthonormalized eigenfunctions fz(x), the probability of getting a result in the

rangedz is
\\c(z)\\2dz where c(z) = (/s|*). [3.44]

Upon measurement, the wave function \"collapses\" to the corresponding eigen-

state.14
The statistical interpretationis radically different from anything we encounter
in classical physics. A somewhat different perspective helps to make it plausible:
The eigenfunctionsof an observable operator are complete, so the wave function
can be as a linear
written combination of them:

V{x,t) = [3-45]
J2c'iMx)-
n

In the case of continuous specira ihe collapse is lo a narrow range aboul the measured value,
depending on the precision of the measuring device.
 Section 3.4: Generalized StatisticalInterpretation 107

I'll
(Forsimplicity, assume that the spectrum is discrete; it's easy to generalize this
argument
to the continuous case.) Because the eigenfunctions are orthonormal, the
coefficientsare given by Fourier's trick:15

=
-\302\273 (/i.l*>= f\342\200\2360c)*nx,t)dx. [3.46]
j

Qualitatively, tells
c\342\200\236 you \"how much is
/\342\200\236 contained in vj>,\" and given that a
measurement has to retum one of the eigenvalues of Q, it seems reasonable that

the probability of getting the particular eigenvalue q\342\200\236

would be determined by the
\"amount of in
/\342\200\236\"
^. But because probabilities are determined by the absolute

square of wave function, the

the precise measure is actually |c\342\200\236|2.That's the
essential burden of the generalized statistical interpretation.16
Of course, the total probability (summed over all possible outcomes) has got
to be one:
\302\243k\342\200\236l2
= l. [3.47]

and sure enough, this follows from the normalizationof the wave function:

= =
Jl J2 c*,,c\"8\"'\" J2 c'*c\302\253= Jl ic\302\273|2- [3.48]

n' \"

Similarly, the expectation value of Q should be the sum overall possibleoutcomes

of the eigenvalue times the probability of getting that eigenvalue:

=
<<2)
E>\"U2- [3.49]

Indeed,

(Q) = mQ^) = [3.50]

l\\Tcn'f,A Qj2c\"f\"

l5Notice thai the lime dependence\342\200\224which is not al issue here\342\200\224is carried by ihe coefficients;
to make this explicit, we should really wrile c\342\200\236(.t).

l6Again, I am
scrupulously avoiding the all-loo-common assertion \"\\cn\\2 is ihe probabilily lhal
the
particle the stale f\342\200\236.\"
is in This is nonsense. The particle is in the stale *, period. Rather, \\cn |2 is
the probabilily that a measurement of Q would yield the value qn. It is true that such a measurement
will collapse ihe stale lo the eigenfunclion so one could
/\342\200\236, corrcclly say \"|c-;;l** is ihe probabilily that
a particle which is now in the stale * u'/7/ be in the stale J'\342\200\236 subsequent lo a measurement of Q\" ...
but that's a completely different assertion.
108 Chapter 3 Formalism

but Qf\342\200\236 so
=q\342\200\236f\342\200\236,

(Q) = = =
[3.51]
^2^2c*,cHq\342\200\236(fn'\\f\342\200\236) ^2^2c*,cHq\342\200\2368\342\200\236'\342\200\236 J^<?/i|cw|2.

So far, at least, everything looks consistent.

Can in this we
reproduce, language, the original statistical interpretation for
positionmeasurements? Sure\342\200\224it's real overkill, but worth checking. A
measurement of x on a particle in state ^ must return one of the eigenvalues of the
position operator. Well, in Example 3.3 we found that every (real) number y
is an

eigenvalue of a\\ and the corresponding (Dirac-orthonormalized) eigenfunction is

gy(x) = 5
\342\200\224
(a- y). Evidently

*(jr-y)*(jr.r)djr = \302\245(y.O, [3.52]

/oo-oo

so the probability of getting a result in the range dy is \\W(y, t)\\2dy, which is

precisely the original statistical interpretation.

What about momentum? In Example 3.2 we found that the eigenfunctions of
the momentum
operator are
fp(x)
= (l/*l/27rh~)exp{ipx/fi), so

1 f\302\260\302\260

c(p)
=
(fpm
= -==
/ e-\"}X/h*(x.t)dx. [3.53]

Thisis such an important quantity that we give it a special name and symbol:the
momentumspace wave function, <\302\243(/?, r). It is essentially the Fourier transform
of the (position space) wave function *(x,f)\342\200\224which, by Plancherel's theorem,
is its inverse Fourier transform:

*(p,0 = -i=/ e-^WVix.Odx; [3.54]

v!/(a\\ t)
= \342\200\224==
e'px/n<$>{p, t)dp. [3.55]
/
V2tt/7 7-00

According to the generalizedstatisticalinterpretation, probability the that a

of
measurement momentum would yield a result in the range dp is

Mp,t)\\2dp. [3.56]

Example
3.4 A
particle of mass m is bound in the delta function well V(x) =

\342\200\224cc8(x). What is the probability that a measurement of its would

momentum
yield
a value greater than po = ma,/hi
 Section3.4: Generalized Statistical Interpretation 109

Solution: The (position space) wave function is (Equation2.129)

(where E = \342\200\224ma2/2fi2).
The momentum space wave function is therefore

1 Vma^-iEt/h 'E\"
H ~e
4>0>,r) =
f\302\260\302\260
e-iPx/ne-ma\\x\\/n2 dx = y-
J-z-co * P2 + Pq
(I looked up
the integral). The probability, then, is
oo
2 I*00 i . -
i PPO -l
3
= + tan

p2 + pI
\342\200\224i^dp
(pl + ps> \\P0/
A\302\2730

1 1
\"
_ = 0.0908
4 2Jr

(again, I looked up
the integral).

Problem 3.11 Find the momentum-space wave function, <\302\243(/?, f), for a particle in
the ground stateof the harmonic oscillator. is What the probability (to 2
significant
digits) that a measurement of p on a particle in this state would a value
yield
outside the classical range (for the same energy)?
Hint: Look in a math table
under \"NormalDistribution\" or Function\" \"Error for the numerical part\342\200\224or
use

Mathematica.

Problem 3.12 Show that

n a
(x) = I<S>*(-^iz\\<S>dp. [3.57]
^P,

Hint: Notice that x exp(ipx/h) = \342\200\224ifr(d/dp)exp(ipx/Ii).

In momentum space, then, the position operator is i lid/dp. Moregenerally,

in position space;
/**fiRs)*'x'
(Q(x.p))= \342\200\242

h 9
[3.58]

0(2 \342\200\224-r-, pl^dp, in momentum space.

I/ V
i dp )

In principle you can do in

all calculations momentum
space just as well (though
not always as easily) as in position
space.
110 Chapter
3 Formalism

3.5 THE UNCERTAINTY PRINCIPLE

I stated the uncertainty principle (in the form oxop

> h/2), back in Section 1.6,
and you have checked it several times, in the problems. But we have never actually
proved this section I will prove a moregeneralversion
it. In of the uncertainty
principle, and explore some of its implications.The argument is beautiful, but
rather abstract, so watch closely.

3.5.1 Proof of the Generalized Uncertainty Principle

For any observable A, we have (Equation 3.21):

a\\ = ((A
- (A))*\\(A
-
(A)m = (/|/>,

where / = (A
\342\200\224
(A))^. Likewise, for any other observable, B,

<7B
=
(g\\g)' where 8 = & - WW-
Therefore (invoking
the Schwarz inequality, Equation 3.7),

=
(f\\f)(g\\g)
> \\(f\\g)\\2- [3-59]
\302\26014

Now, for any complex number z,

n2
\\z\\2
=
[Re(z)]2 + [Im(z)]2 > [Im(z)]2 = [3.60]
2i

Therefore, letting z
=
(f\\g),

o\\a\\ >
- . [3.61]

(J;[(f\\g) (g\\f)]j
But

(f\\g)
= ((A - (A))V\\(B
-
(B)m = (vl/|(A - (A))(B - <*))\302\245)

=
{V\\(AB
- A(B) - B(A) + (A)(B)m
= (V\\ABV)
-
(B)(V\\AV)
- (A)(V\\BV) + {A){B)-(V\\V)

= + (A)(B)
(AB)-(B)(A)-(A)(B)

= (AB)-(A)(B).

Similarly,

(g\\f) = (BA)-(A)(B),
 Section 3.5: The Uncertainty Principle 111

so
a a a a a a
</!*)
\"
(g\\f) = (AB) - (BA) = {[A, B])t

where

[A. fl] = Afl - SA

of the
is the commutator two
operators (Equation 2.48). Conclusion:

1
[3.62]
<rlcri>[-([lB])J
(:

This is the (generalized) uncertainty You might think

principle. the i makes it
trivial\342\200\224isn't the right side negative'? No, for the commutator of two hermitian
operatorscarriesits own factor of i, and the two cancel out.17
As an example, suppose the first observable is position (A = x), and the
second is momentum (B = (h/i)d/dx). We worked out their commutator back in
Chapter 2 (Equation 2.51):

[x. p] = ih.
So

> = ,
\302\260l*\\
(\302\261itl) g)
or, since standarddeviationsare by their nature positive,

VxOp
> -. [3.63]

That's the originalHeisenberg uncertainty principle, but we now see that it is just
one applicationof a more general theorem. much

There is, in fact, an \"uncertaintyprinciple\" for every pair ofobservables whose

operators do not commute\342\200\224we call them incompatible observables. Incompatible

observables do not have sharedeigenfunctions\342\200\224at least, they cannot have a

complete set of common eigenfunctions (see Problem 3.15). By contrast, compatible

(commuting)observables
do admit
complete sets of simultaneous eigenfunctions.18

l7More precisely,the commutator of two hermitian operators is itself anti-hermitian (Q* = \342\200\224Q),

and its expectation value is imaginary (Problem 3.26).

l8This corresponds to the fact that noncommuting matrices cannot be simultaneously diagonalized
(that is, they both be brought
cannot to diagonal form by the same similarity transformation), whereas

commuting hermitian matrices can be simultaneously diagonalized. See Section A.5.

Chapter 3 Formalism

For example, in the hydrogenatom (as we shall see in Chapter 4) the Hamilto-
nian, the magnitudeof the momentum, angular
and the z component of angular
momentumare mutually compatible observables, and we will construct
simultaneous
eigenfunctions of all three, labeled by their respective eigenvalues.Butthere is
no eigenfunction of
position that is also an eigcnfunction of momentum, because
these operatorsareincompatible.
Note that the uncertainty principle is not an extra assumption in quantum

theory, but rather a consequence of the statistical interpretation.You might wonder

how it is enforced in the laboratory\342\200\224why
can't you determine (say) both the
position and the momentum of a particle? You can certainly measure the position
of the particle, but the act of measurement the wave function to a
collapses narrow

spike, which necessarily carries a broad range of wavelengths (hencemomenta)

in its Fourierdecomposition.you If now measure the momentum, the state will
collapseto a long sinusoidal wave, with (now) a well-defined wavelength\342\200\224but

the
particle no longer has the position you got in the first measurement.19 The

problem, then, is that the second measurement rendersthe outcomeof the first

measurement obsolete. Only if the wave function were simultaneously eigenstate an

of both observables would it be possible to make the secondmeasurement without

disturbing the state of the particle (the second collapse wouldn'tchange anything,

in that case). But this is only possible, in general, if the observables two are

compatible.

*Problem 3.13

(a) Prove the followingcommutator

identity:
[AB, C]
= A[B. C] + [A. C]B. [3.64]
(b) Show that

[x\".p]
= ihtvcn-1.

(c) Show more generally that

[f(x),p] =01^-, [3.65]

ax
for any function f(x).

IJNiels Bohr was at pains to track down the mechanism by which the measurement of .v (for

instance) destroys the previously existing value of p. The crux of the mailer is lhal in order to determine
the position of a particle you have to poke it with something\342\200\224shine light on it. say. Bui these photons
imparl to the particle a momentum you cannot control. You now know the position, but you no longer
know ihe momentum. His famous debates with Einstein include many delightful examples, showing
in detail how experimental constraints enforce the uncertainly principle. For an inspired account see
Bohr's article in Albert Einstein: Philosopher-Scientist, edited by P. A. Schilpp, Tudor, New York

(1949).
 Section 3.5: The Uncertainty Principle 113

*Problem 3.14 Provethe famous \"(your name) uncertainty principle,\" relating the
uncertainty in position (A
= x) to the uncertainty in energy (B = p2/2m+ V):

h
oxoh >\342\200\224\\(p)l
2/77

For stationary states this doesn't tell you much\342\200\224why not?

Problem 3.15 Show that two noncommutingoperatorscannot a complete

At At
have set

of common eigenfunctions. Hint: Show that if P and Q a complete have set of

At At

common eigenfunctions, then [P. Q]f = 0 for function in Hilbert space.any

3.5.2 The Minimum-Uncertainty Wave Packet

We have twice encountered functions
wave that hit the position-momentum
uncertainty
limit
{axap
= Ii/2): the ground state of the harmonic oscillator
(Problem2.11) and the Gaussian wave packet for the free particle (Problem 2.22).
Thisraises an
interesting question: What is the most general minimum-uncertainty
wave packet?Looking back at the proof of the uncertainty principle, we note that
there were two points at which in equalities came intothe argument:Equation3.59
and
Equation 3.60. Suppose we require that each of thesebe and see an
equality,

what this tells us about *I>.

The Schwarz becomes an equality when one functionis a

inequality
multiple
of the other: g(x) = c/(.v), for some complexnumberc (seeProblem A.5).

Meanwhile, in Equation 3.60 I threw away the real part of z\\ equality results if

Re(s) is to say, if Re(/|g) = Re(c(/|/)) = 0.

= 0, which Now, (/|/) is certainly
real, so this means the constantc mustbe imaginary\342\200\224let's purely
call it ia. The

necessary and sufficient condition for uncertainty, then, minimum is

g(x) = iaf(x), where a is real. [3.66]

For the position-momentum uncertainty principle this criterion becomes:

* = ia{x~ [3-67]
(7 Tx ~{p))
<jr))**

which is a differential equation for * as a function of .v.Its generalsolution

(Problem 3.16) is

V(x) = Ae-\302\260{x-{x))2/2liei{p)x/h. [3.68]

Evidently the minimum-uncertainty wave packet is a gaussian\342\200\224and the two

examples
we encountered earlier were gaussians.20

-^Note thai it is only the dependence of * on .v that is at issue here\342\200\224the \"constants\" -4. a. (x).
and (p) may all be functions of lime, and for thai mailer * may evolve away from ihe minimal form.

All I'm asserting is lhat if, at some instant, the wave function is gaussian in .v. then (al thai instant) the

uncertainly product is minimal.

114 Chapter 3 Formalism

Problem 3.16 Solve Equation

3.67 for W(x). Note that (x) and (p) are constants.

3.5.3 The Energy-Time Uncertainty Principle

The position-momentum uncertainty principle is often written in the form

h
AxAp>-\\ [3.69]

Ajv (the \"uncertainty\" in ,v) notation (and sloppy language)forthestandard

is loose
O 1
deviation of the results of repeated measurements on identicallypreparedsystems.-1
Equation 3.69 is often paired with the energy-time uncertainty principle,

AtAE>-. [3.70]

Indeed, in the context of special relativitythe energy-time form might be thought

of as a consequence of the position-momentum version, because .v and t (or
rather, ct) go togetherin the position-time p and E (or rather, four-vector, while

E/c) go together in the energy-momentum Soin a relativistic

four-vector. theory

Equation 3.70 would be a necessary concomitant to Equation3.69. we're not But

doing relativistic quantum mechanics. The Schrodinger equationis explicitly non-

relativistic: It treats t and .v on a very unequal footing (as a differentialequation

it is first
in t, but second-order
-order in x), and Equation 3.70 is not emphatically

implied by Equation 3.69. My purpose now is to derivethe uncertainty energy-time

principle, and in the course of that derivation to persuade you that it is really an
altogether differentbeast,whosesuperficial resemblance to the position-momentum
uncertainty principle is actually quite misleading.
After all, position, momentum, and energy are all dynamical variables\342\200\224
measurable characteristics of the system, at any given time. But time itself is
not a
dynamical variable (not, at any rate, in a nonrelativistictheory): You don't

go out and measure the \"time\"of a particle,as you might its position or its energy.
Time is the independentvariable,of the dynamical quantities are which

In
functions.
particular, the At in the energy-time uncertainty principle not the
is
standarddeviation of a collection of time measurements; roughly speaking (I'll
make thismoreprecise a moment) it is the time it takes the
in to change system

substantially.

\"'Many casual applications of the uncertainly principle are actually based (often inadvertently) on
a completely different\342\200\224and sometimes quite unjustified\342\200\224measure of \"uncertainty.\" Conversely, some
perfectly rigorous arguments use other definitions of \"uncertainly.'' See Jan Hilgevoord. Am. J. Phxs.
70, 983 (2002).
 Section 3.5: The Uncertainty Principle 115

As a measure of how fast the system is changing,let us

compute the time
derivative of the expectation value of someobservable, Q(.x, p, t):

d
=
d * /9* dQ
IT QV)+[V
V + *
*<G> *<*'\302\253*>= dt
Now, the Schrodinger equation says
9*
ih \342\200\224
= HV
dt

(where H = p2/2m + V is the Hamiltonian). So

d 1-* 1 * \342\200\236 I dQ
-r(Q) = -tt{HV\\QV) + -mQHV) + -f-
dt in in \\ at

a a
But H is hermitian, so (HV\\QV) = {y\\HQV), and hence

[3.71]

This is an interesting and useful result in its own right (see Problems3.17 and

3.31). In the typical case where the operator does not dependexplicitly on time,22

it tells us that the rate of change of the expectation determined

value is by the
commutator of the operator with the Hamiltonian. In particular, if Q commutes
with H, then (Q) is constant, and in this Q is a consented quantity.
sense

Now, suppose we
pick A = H and B = Q, in the generalized uncertainty

principle (Equation 3.62), and assume that Q does not depend explicitlyon t:

n>
\342\200\224
aHaQ
(W-tef^HfH\342\204\242)2-

Or, more simply,

d(Q)
OhOq dt [3.72]

Let's define AE = 07/, and

= aQ --
At [3.73]
\\d(Q)/dt\\

\342\200\224Operators that depend explicitly on t are quite rare, so almost always 'dQ/'dt = 0. As an
example of explicit lime dependence, consider the potcnlial energy of a harmonic oscillator whose
spring constant is changing (perhaps the temperature is rising, so the spring becomes more flexible):
Q = (l/2)w[ft>(/)]V.
 Formalism

Then
~
AEAt>~,
2 [3.74]
and that's the energy-time uncertainty principle. But notice what is meant by Af,

here: Since

d(Q)
OQ = Ar,
dt
Af
represents the amount of time expectation value of Q to change
it takes the by

one standard deviation.23 In particular, Ar depends entirely on observable what

(<2) you care to look at\342\200\224the

change might be rapid for one observable and slow
for another. But if Af is small, then the rate of changeof all must be observables

very gradual; or, to put it the otherway around, if any observable changes rapidly,
the \"uncertainty\"in the energy must be large.

Example 3.5 In the extreme case of a stationary state, for which the energy is
uniquely determined, all expectationvaluesare constant in (AE
= 0 time =>\342\226\240

Ar = in fact we noticed some time ago (see Equation 2.9). To make

oo)\342\200\224as

somethinghappen must take a linear combination of at least two stationary

you

states\342\200\224say:

If a, b, \\fr\\, and fa are real,

E2 -
2ah^ {x)in{x)cos(-
E\\
|*(*, t)\\2
= a2d/r, (.0)2 + b2tyi(x))2 + t

The period of oscillation is r = 2ttH/(E2 \342\200\224

E\\). Roughly speaking, AE = Ei \342\200\224
E\\

and At = t (for the exact calculationseeProblem3.18), so

AE At = 27ih,

which is indeed >h/2.

Example3.6 How
long does it take a free-particle wave packet to passby a
particular
point (Figure 3.1)? Qualitatively (an exact version is exploredin Problem 3.19),
Ar =
Ax/v
= mAx/p, but E = p2/2m, so AE =
pAp/m. Therefore,

pAp mAx
AE At = -\342\200\224 =
AxAp,
m p
which is >ft/2 by
the position-momentum uncertainty principle.

is
\342\200\242^This sometimes called the \"Mandelstam-Tamm\" formulation of the energy-time uncertainty
principle. For a review of alternative approaches see Paul Busch, Found. Phys. 20, 1 (1990).
 Section3.5: The
Uncertainty Principle 117

Ax-

FIGURE 3.1: A free particle wave packet approaches the point A

(Example 3.6).

Example 3.7 about 10~23seconds,beforespontaneously

The A particle lasts
disintegrating. you If of all measurements of its mass,
make a histogram
get you

a kind of bell-shaped curve centered at 1232 MeV/c2, a width of about 120 with

MeV/c2 (Figure 3.2). does the rest energy (mc2) sometimes come out higher
Why

than 1232, and sometimes lower? Is this experimental error? No, for

AE At = (\342\200\224 MeV (10-23 sec) = 6 x 10~22MeV sec,

]

whereas h/2
= 3 x 10-22 MeV sec. So the spreadin m is about as small as the
uncertainty principle allows\342\200\224a particle with so short a lifetime just doesn't have
a very
well-defined mass.24

1100 1200 1300 1400

MASS (MeV/c2)

FIGURE3.2: Histogram of measurements of the A mass (Example 3.7).

24
Actually, Example 3.7 is a bit of a fraud. You can't measure 10-23 secon a stop-watch, and in
practice the lifetime of such a short-lived particle is inferred from the width of the mass plot, usingthe
uncertainty principle as input. However, the point is valid, even if the logic is backwards. Moreover,
if you assume the A is about the same size as a proton (~10-'*5 m), then 10--3 sec is roughly the

time it takes light to cross the particle, and it's hard to imagine that the lifetime could be much less

than that.
118 Chapter 3 Formalism

Notice the variety

of specific meanings attaching to the term At in these
examples:In Example
3.5 it's a period of oscillation; in Example 3.6 it's the time
it takesa particle to
pass a point; in Example 3.7 it's the lifetime of an unstable

particle. In every case, however, At is the time it takes forthe systemto undergo

\"substantial\" change.
It is often said that the uncertainty principle means energy is not strictly

conserved in quantum mechanics\342\200\224that you're allowed to \"borrow\" energy AE,

as long as you \"pay
At % h/(2AE); the greaterthe violation,
it back\" in a time
the brieferthe periodover which it can occur. Now, there are many legitimate
readingsof the energy-time uncertainty principle, but this is not one of them.
Nowhere does quantum mechanics license violation of energy conservation, and
certainly no suchauthorization entered into the derivation of Equation 3.74. But the
uncertainty principle is extraordinarily robust: can be misused It without leading
to seriously incorrect results, and as a consequence physicists are in the habit of

applying it rather carelessly.

*Problem3.17 Apply Equation 3.71 to the following special cases: (a) Q = 1;

(b) Q
= H; (c) Q = x; (d) Q = p. In each case, comment on the result,
with particular reference to Equations1.27,1.33,1.38, and conservation of energy
(comments following Equation 2.39).

Problem 3.18 Testthe energy-time uncertainty principle for the wave function in
Problem 2.5 and the observablex, calculating by 07/, ax, and d{x)/dt exactly.

Problem 3.19 Test the energy-timeuncertainty principle for the free particle wave
packet in Problem 2.43 and the observable
\342\200\236v,
by calculating an, ax, and d(x)/dt
exactly.

Problem 3.20 Show that the energy-time uncertainty principle reduces to the \"your
name\" uncertainty principle (Problem 3.14), when the observable in question is x.

3.6 DIRACNOTATION
Imagine
an ordinary vector A in two dimensions (Figure 3.3(a)). How wouldyou
describethis vector to someone? The most convenient way is to set up
cartesian axes, x and >\\ and specify the components of A: Ax = f
\342\200\242
A, = ./
\342\200\242
A
Ay

(Figure 3.3(b)). Of course, your sister might have drawn a different set of axes,
x' and y\\
and she would report different components: Ax = V
\342\226\240
A. A'y
= j' \342\226\240
A

(Figure 3.3(c)). But it's all the same vector\342\200\224we're simply expressing it with

respect to two different bases ({/\\ j} and {?',./'}). The vector itself lives \"out there

in space,\" independent of anybody's (arbitrary) choice of coordinates.

 Section3.6: Dime Notation 119

(a) (b) (c)

FIGURE 3.3: (a) Vector A. (b) Components of A with respect to xy axes.

(c) Components of A with respect to x'y axes.

The same is true for the state of a in quantum mechanics. It is

system
represented by a vector, \\\302\243{t)),
that lives \"out there in Hilbert space,\" but we can
expressit with
respect to any number of different bases. The wave function W(.v. t)

is actually the coefficient in the expansion of \\S) in the basis of position

eigenfunctions:

V(x,t) = (x\\S(t)). [3.75]

(with \\x) standing for the eigenfunction of .v with eigenvalue .v),25 whereas the
momentum
space wavefunction <t>(p.r) is the expansion of \\S) in the basis of
momentum eigenfunctions:

<5>{p,t)
= (p\\S{t)) [3.76]

(with \\p) standing for the eigenfunction of /5

with eigenvalue /?).26 Or we could
expand \\S) in the basis of energy eigenfunctions (supposing for simplicity that the
spectrum is discrete):
=
c\342\200\236(t) (n\\4(t)) [3.77]

(with \\n) standing for the /7th eigenfunction of H)\342\200\224Equation 3.46. But it's all the
same state; the functionsW and \302\242,and the collection of coefficients {c,,}, contain
exactly the same information\342\200\224they
are simply three different ways of describing
the same vector:
I
9ipx/h
\302\245(*./>
=
t)S(x-y)dy $>(p.t) dp
/#(>'. -I Jhih

= [3.78]
J2^e-iE\"r/h^n(x).

-5I don't want to call it gx (Equation 3.39). because that is its form in the position basis, and
the whole point here is to free ourselves from any particular basis. Indeed, when I first defined Hilbert
space as the set of squarc-intcgrable functions\342\200\224over x\342\200\224that was already too restrictive, committing
us to a specificrepresentation (the position basis). 1 want now to think of it as an abstract vector space,
whose members can be expressed with respect to any basis you like.
26In it would be
position space /;>(.v) (Equation 3.32).
Chapter 3 Formalism

Operators (representing observables) are linear transformations\342\200\224they

\"transform\" one vector into another:

=
\\fi) Q\\a). [3.79]

Just as vectors are represented, with respect to a particular basis {\\e\342\200\236)},21 by their

components,

|a> = with an = (e\342\200\236\\a): \\0)

= with =
b\342\200\236 (e\342\200\236\\fi), [3.80]
][>\342\200\236k\342\200\236). ][>\342\200\236k\342\200\236),

operators are represented (with respect to a particularbasis) by

their matrix

elements28

{em\\Q\\en)=Q,m. [3.81]

In this notation Equation 3.79 takes the form

J>.ki.) = J>\302\253fik,i).
[3.82]
n n

or, taking the inner product with \\em),

=
\302\243M*\302\273\302\273k\302\253) \302\243fl\302\253<*i\302\253lfiki.).
[3.83]
n n

and hence

\302\273

Thus the tell you how the componentstransform.

matrix elements
Later on we will encounter systems that admit only a finite number (N) of
linearlyindependent states.In that case \\S(t)) lives in an A7-dimensional vector
space; it can be representedas a column of (N) components (with respect to a
given basis), and
operators take the form of ordinary (N x N) matrices.These
arethe simplest quantum systems\342\200\224none
of the subtleties associated with infinite-
dimensional vector spaces arise.Easiest of all is the two-state system, which we
explore in the followingexample.

Example3.8 Imagine
a system in which there are just two linearly independent
states:29
|1>= and |2)
=
Q (\302\260).

Til assume llic basis is discrete: otherwise n becomes a continuous index and the sums arc
replacedby integrals.

-sThis terminology is inspired, obviously, by the linile-dimcnsional case, but the \"matrix\" will
now typically have an infinite (maybe even uncountable) number of elements.
2
Technically, the \"equals\" signs here mean \"is represented by.\" but I don't think any confusion
will arise if we adopt the customary informal notation.
 Section 3.6: Dirac Notation 121

The most generalstateis a normalized linear combination:

\\4) =a\\l)+ b\\2) = , with + \\b\\2 = 1.

(ab\\ \\a\\2

The Hamiltonian can be expressedas a (hermitian) matrix; suppose it has the

specific form

-c o-
where g and h are real constants. If the system starts out (at t = 0) in state |1),
what is its state at time tl

Solution: The (time-dependent) Schrodinger equation says

ih \342\200\224
\\S)
= H\\S). [3.85]
dt
As always, we begin by solving the time-w dependent Schrodinger equation:

H\\t) = \302\243|<t); [3.86]

that is, we look for the eigenvectors and eigenvaluesof H. The characteristic

equation determines the eigenvalues:

a (h-E
det . = (/7 - E)2 - g2
= 0 h
=\302\273
- E = T8 => E\302\261 = h \302\261
g.
\302\243
8 h E\\
\\

Evidently the allowed energies are (h + g) and (h

\342\200\224
g). To determine the
eigenvectors, we write

= {h\302\2618) =* ha +sP =
= {h\302\261g)a^f} a.
\302\261

C 0 CO CO

so the normalized eigenvectors are

1 ( 1 \\
=
l*\302\261>
J2\\\302\261K

Next we expand the initial state as a linearcombination eigenvectors of of the

Hamiltonian:

K(0)) = = + k-)).
Q -^(k+)
Finally,
we tack on the standard time-dependence exp(\342\200\224iE\342\200\236t/h):

=
\\4(t)) -l=[e-i{h+8)t'n\\4.+)+e-i(h-g)t/n\\4-)]
V2
122 Chapter 3 Formalism

2 c-Whl^+c\302\256/*

= le-iht/h fe-.s.,.>+e>-8'/n\\_-
-igt/h
~ e h cos(gtfh)
e-igt/H eigtltt J -i sin(gf//J)

If you doubt this result, by all means check it: Doesit satisfy the
time-dependent

Schrodinger equation? Does it match the initial state when t = 0?

This is a crude model for (amongother things)
neutrino oscillations. In
that case |1) represents the electronneutrino, and |2) the muon neutrino; if the
Hamiltonian has a nonvanishingoff-diagonal term (g) then in the course of time
the electronneutrino will turn into a muon neutrino (and back again).

Dirac proposedto chop the bracket notation for the inner product, (a|/3), into
two pieces, he called bra,
which (a|, and ket, \\/3) (I don't know what happened to
the c). The latter is a vector, but what exactly is the former? It's a linear function
of vectors,in the sense that when its right) it yieldsa (complex)
it hits a vector (to
number\342\200\224the inner product. (When an operator hits a vector, it delivers another
vector; when a bra hits a vector, it delivers a number.) In a functionspace,the bra

can be thought of as an instruction to integrate:

(/1
-/' [\342\200\242\342\200\242\342\200\242]dx,

with the ellipsis

\342\200\242
\342\200\242
] waiting
[\342\200\242 filled by whatever function the bra encountersin
to be

the ket to its right.

In a finite-dimensional vector space, with the vectors expressed
as columns,
Cll
=
\\a) [3.87]

the correspondingbra is a row vector:

(a\\
=
{a*a*_ ... a*) [3.88]
The collection of all bras constitutes another vector space\342\200\224the
so-called dual

space.
The license to treat bras as separateentitiesin their own right allows for
some powerful and pretty notation(though I shall not exploit it in this book). For
example, if |ck)
is a normalized vector, the operator

P = \\a)(ct\\ [3.89]
 Section 3.6: Dirac Notation 123

picks out the portionof any other vector that \"lies along\" |a):

P\\fi) = (ct\\P)\\a);

we call it the projection operator onto the one-dimensionalsubspacespannedby

|a). If is
{\\e\342\200\236)}
a discrete orthonormal basis,

(\302\253\302\253k\302\273)-=8\302\273\302\273. [3.90]

then
= l
\302\243h,)<e\342\200\236l
[3.91]
n

(the identity operator). For if we let this operator act on any vector |a), we recover
the expansion of \\a) in the {\\en)} basis:

= \\a). [3.92]
J2\\en)(e\342\200\236\\a)
n

Similarly, if (|e;)} is a Dirac orthonormalized continuous basis,

(e-\\ez>)=8(z-z'), [3.93]
then

\\ez)(ez\\dz=\\. [3.94]
J

Equations 3.91 and 3.94 are the tidiest ways

to express completeness.

Problem 3.21 Show that projection operatorsare idempotent:P2 = P. Determine

the eigenvalues of P, and characterize its eigenvectors.

Problem 3.22 Considera three-dimensional vector

space spanned by an
orthonormalbasis |1), |2), |3). Kets |a) and \\fi) are given by

|a)=i|l)-2|2)-/|3), |/J)=/|1)+2|3).

(a) 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)*.
(c) Find all nine matrix elements of the operator A = \\a)(fi\\, in this basis, and
construct the matrix A. Is it hermitian?
124 Chapter 3 Formalism

Problem 3.23 The Hamiltonian for a certain two-level system is

# = 6(|1)<1|-|2)(2| + |1)<2|+ |2)(1|),

where |1>, |2> is an orthonormal is a number
basis and e
the dimensions with of

energy. Find its eigenvalues and eigenvectors (as linearcombinations 11) of and

|2)). What is the matrix H representing H respect to this basis? with

Problem 3.24 Let Q be an operator with a complete set of orthonormal

eigenvectors:

(ii
= 1,2.3,...).
Q\\e\342\200\236)=q\342\200\236\\e\342\200\236)

Show that Q can be written in terms of its spectral decomposition:

Hint: An operator is characterized by its action on all possiblevectors,so what

you must show is that

Q\\a) = ]T//Hk\342\200\236
)(<?\342\200\236! I\302\253>,

for any
vector \\a).

FURTHER PROBLEMS FOR CHAPTER 3

Problem 3.25 Legendre polynomials. Usethe Gram-Schmidt

procedure

(Problem A.4) to orthonormalize the functions 1, .v, x2, and x3, on the interval <
\342\200\2241

x < 1. You may recognize the results\342\200\224they are (apart from the normalization)30
Legendre polynomials (Table 4.1).

Problem 3.26 anti-hermitian An (or skew-hermitian) operator is equal to minus

its hermitianconjugate:
=
Qf -Q. [3.95]

(a) Show that the expectation value of an anti-hermitian operator is imaginary.

(b) Show that the commutatorof two hermitian operators is anti-hermitian. How
about the commutator of two fl/m-hermitian operators?

?'Legendre didn'l know what the best convention would be: he pickedthe overall factor so that
all his functions would ao to 1 at x = 1. and we're stuck with his unfortunate choice.
 Further Problems for Chapter 3 125

Problem 3.27 Sequential measurements. An operator A, representing

observable A, has two normalized eigenstates \\j/\\
and i/o, with eigenvalues ci\\ and ct2,

respectively. Operator B, representing observable B, has two normalized

eigenstates 0| and 02, with eigenvalues h\\ and bi. The eigenstates are related by

f\\ = (30, +407)/5, fo = (401

-
302)/5.

(a) Observable A is measured, and the value a\\ is obtained. What is the state of
the system (immediately)after thismeasurement?
(b)
If B is now measured, what are the possible results, and what are their

probabilities?

(c) Right after the measurement of B, A is measured again. What is the

probability
of getting oi? (Note that the answer would be quitedifferent if I had

told you the outcome of B

the measurement.)

**Problem3.28 Find the momentum-space wave function \302\242,,(p. t) for the nth
stationary state of the infinite square well. Graph \\<&\\(p,t)\\2and \\<&2(p< t)\\2, as

functions of p (pay particular attention to points the p

= -tnnh/a). Use \302\242,,(/7. t)

to calculate the expectation value of p2. Compare your answer to Problem 2.4.

Problem 3.29 Consider the wave function

1
_ il7txl'\\
\342\226\240.e -nX < x < nX.
q/(A\\0)= \\/2n~A.

0, otherwise,

where n is some positive integer. This functionis purely sinusoidal (with wavelength
X) on the interval \342\200\224nX< x < nX, but it still carries a range of momenta,because
the oscillations do not continue out to infinity. Find the momentum space wave
function \302\242(/7,0). Sketch the graphs of |^(a-,0)|2 and |\302\253J>(/?, 0)|2, and determine
their widths, wx and wp (the distance between zeros on either side of the main
peak).Note what happens to each width as n oo.
->\342\200\242
Using wx and wp as estimates
of A.t and A/?,
check that the uncertainty principle is satisfied. Warning: If you try

calculating ap, you're in for a rude suiprise. Can you diagnosethe problem?

Problem 3.30 Suppose

0) = (-oo < x < oo)

.v- + a-y.
vl>(.\\\\ \342\200\224^

for constants A and a.

126 Chapter 3 Formalism

(a) Determine A, by normalizing ty(.\\\\0).

(b) Find (x), (x2), and ax (at time t = 0).

(c) Find the momentum space wave function <\302\243>(/?, 0),
and check that it is
normalized.

(d) Use <\302\243(/?, 0) to calculate (/?), {p2), and ap (at time t = 0).
(e) ChecktheHeisenberg uncertainty principle for this state.

* Problem 3.31 Virial theorem. Use Equation3.71 to show that

[3-%i
i<\">=2<r>-(*9'

where T is the kineticenergy (H = T + V). In a stationary state the left side is

zero (why?)
so

2(T)
= [3.97]
Lx^-\\.

This is calledthe virial theorem. Use it to prove that (T) = (V) for stationary
statesof theharmonicoscillator, and check that this is consistent with the results
you got in Problems2.11 2.12. and

Problem 3.32 In an interesting version of the energy-time uncertainty principle31

Ar = t/jt, where r is the time it takes \\j/(.v, r) to evolve into a state
orthogonal to vl/(x,0). Test this out, using a wave function that is an equal admixture
of two (orthonormal) stationary states of some (arbitrary) potential: vj/(jt, 0) =

(lA/2)Wri(jr) + fo(*)].

**Problem 3.33 Findthe elements matrix {n\\x\\n') and {n\\p\\n') in the (orthonormal)
basis of stationarystates the harmonic for oscillator (Equation 2.67). You already
elements
calculated the \"diagonal\" =
(\302\273 ri) in Problem 2.12; use the same
technique for the general case. the corresponding (infinite) matrices, and
Construct X P.

Show that (l/2/n)P2 + (mar/2)X2 = H is diagonal,in thisbasis. its diagonal Are

elements what you would expect? Partial answer:

(\302\2731*1\302\273')
= + \342\200\242 [3-98]
yj^ (Vn7*,,.,,'-! V\302\273~5\342\200\236',\342\200\236-i)

See Lev Vaidman, Am. J. Phys. 60. 182(1992)I'or a proof.

 Further Problems for Chapter 3 127

Problem 3.34 A harmonic oscillator is in a state such that a measurementof the

energy
would yield either (l/2)/?a> or (3/2)/?a>, with equal probability. What is the

largest possible value of (p) in such a state? If it assumes maximal this value at
time t = 0, what is W(x, r)?

* * ^Problem Coherent states of the harmonic oscillator.Among

3.35 the stationary
states of the harmonic oscillator (|/j) = \\j/\342\200\236(x), Equation 2.67) only n = 0 hits the
uncertainty limit (axap = h/2); in
general, axap
= (2h- + l)/i/2, as you
found

in Problem 2.12. combinations

But certain linear (known as coherent states) also
minimize the uncertainty product. They are (as it turns out) eigenfunctions of the
lowering operator}2

a-\\a) = a\\a)
(the eigenvaluea canbe any complex number).

(a) Calculate {x2), (/?), (p2) in the state

(x), Hint: Use the technique \\a). in
Example 2.5, and remember a+ is the hermitian conjugate of Do
that \302\253_. not
assume a is real.

(b) Find ax and

ap;
show that axap
= ///2.

(c) Like any

other wave function, a coherent state can be expandedin terms of
energy eigenstates:

CO

|Qf) = ]Pc\342\200\236|/?).

//=0

Show that the expansion coefficients are

a\"
=
Cn \342\200\224f=c0-

(d) Determine cq by normalizing |a). Answer: exp(\342\200\224|a|2/2).

(e) Now put in the time dependence:

\\n)^e-iE\"'/h\\n),
and show that \\a(t)) remains an eigenstate of a-, but the eigenvalue evolves
in time:
a(t) = e~itota.

So a coherent state stays coherent, and continues to minimize

theuncertainty
product.

-There are no normalizable eigenfunctions of the raising operator.

128 Chapter 3 Formalism

(f) Is the groundstate(|\302\253= 0)) itself a coherent state? If so, what is the

eigenvalue?

Problem 3.36 Extended uncertainty principle.33 The generalized uncertainty

principle (Equation 3.62) states that

aAaB '
^^C)
At At

where C = -i[A. B],

(a) Show that it can to

be strengthened read

^I>~((02+(\302\243>)2), [3-99]

yy At At Al

where D = AB + BA-2(A)(B).Hint: Keep the Re(z) term in Equation 3.60.

(b) Check Equation 3.99 for the case B =At

A (the standard uncertainty principle
is trivial, in this case, since C = 0; unfortunately,
the extended uncertainty
principle doesn't help much either).

Problem 3.37 The Hamiltonian for a certain three-level system is represented by

the matrix

where a, b, and c are real numbers (assumea \342\200\224

c ^
+ b).

(a) If the system starts outin the state

what is |4(/))?

(b) If the system starts out in the state

what is \\S{t))l

For interesting commentary and references, see R. R. Puri, Phys. Rev. A 49, 2178 (1994).
 Further Problems for Chapter 3 129

Problem 3.38 The Hamiltonian for a certain three-level system is represented by

the matrix

/1 0 0N

H = Ao> 0 2 0
\\0 0 2,

Two other observables, A and B, are represented by

the matrices

/0 1 0\\ /2 0 0N

A = X 1 0
0]
, B = /x 0 0 1
\\0 0 2/ V0 1 0,

where a>, A., and /x are positive real numbers.

of H,
(a) Find the eigenvalues and (normalized)eigenvectors A, and B.

(b) Suppose the system starts out in the generic state

with |cj|2 + |C2|2 + |C312= 1. Findthe expectation values (at t = 0) of H,

A, and B.
(c) What is \\<8(t))1 the energy of this state (at
If you measured time t), what

values might you get, and what is the probability of each?Answer the same

questions for A and for B.

* ^Problem 3.39

(a) Fora function

f(x) that can be expanded in a Taylor series,show that

fix+x0)
= ^^/11 f(x)

(where xq is any
constant distance). For this reason, p/h is called the
generator of translations in space. Note: The exponential of an operator is defined
by
the power series expansion: e& = 1 + Q + (1/2)(22+ d/3!)fi3+ ....
(b) If vj/(.v, r) satisfies the (time-dependent) Schrodinger equation, show that

Vix,t + to) = e-i\"H)/hVix,t)

(where to is any constant time); \342\200\224H/h

is called the generator of translations
in time.
130 Chapter3 Formalism

(c) Show that the expectation value of a dynamical variable Q(x, p, t), at time

t + to, can be written34

((2),+,,,= {^{x.t)\\eifl^hQ{x.p,t + tQ)e-ifl'ttln\\^(x,t)).

Use this to recover Equation 3.71. Hint: Let to = dt, and expandto first

order in dt.

* ^Problem 3.40

(a) Write down the time-dependent \"Schrodinger equation\" in momentum space,

for a free particle, and solve it. Answer: exp(\342\200\224ip2t/2mh) 0(p, 0).

(b) Find \302\242(/7,0)

for the traveling gaussian wave packet (Problem 2.43), and
construct <\302\243>(/?, t) for this case. Also construct |0(/?, t)\\2, and note that it is

independent of time.

(c) Calculate (p) and {p2) evaluating the appropriate by integrals involving 0,
and compare your answers to Problem2.43.

(d) Show that {H) = (p)2/2m + {H)q (where the subscript 0 denotes the
stationary gaussian), and comment on this result.

34In particular, if we set, 0. and

\342\200\224
drop the subscript on Iq.

= <*(.*.
{Q(t))= (*(A-.r>|j2l*(.v.0> 0)11/-1 QUmx.0)).

where U = exp{\342\200\224iHr/ti). This says that you can calculate expectation values of Q either by

sandwiching Q between ^(.v, t)* and *(.v.f), as we have always done (letting the wave functions carry
the time dependence), or else by sandwiching U~]QU between *(.v.0)* and *(.v.0). letting the

operator carry the lime dependence. The former is called the Schrodinger picture, and the lallcr ihe
Heisenberg picture.
CHAPTER 4

QUANTUM MECHANICS IN
THREE DIMENSIONS

4.1 SCHRODINGER
EQUATION IN SPHERICAL COORDINATES

The generalization to three dimensionsis straightforward. Schrodinger's equation

says

=
ili\342\200\224 HV; [4.1]
at

the Hamiltonian operator1 H is obtained from the classical energy

{-mv2 + V =
\302\261-{p2.+p1x + p1) + V
2 2m

by the standard prescription (applied now to y and z, as well as .v):

h B fl B Ad
Px -^77-- Pv -^77-. Pc \"* 7 7-. [4.2]
i 3.v i 3v / az

'Where confusion might otherwise occur I have been putting \"hats\" on operators, to distinguish
them from the corresponding classical obscrvables. I don't think there will be much occasion for
ambiguily in this chapter, and the hats gel lo be cumbersome,so I am going lo leave them off from
now on.

131
132 Chapter 4 Quantum Mechanicsin Three Dimensions

or

[4.3]

for short. Thus

9* n2 ,
=
ih\342\200\224 [4.4]
dt 2m

where
a2 a2 92
V2 = [4.5]
9^+9v^+9?
is the
Laplacian, in cartesian coordinates.
The potential energy V and the wave function ^ are now functions of r=
(.v. v, z) and t. The probability of finding the particlein the infinitesimal
volume

d3r = dxdyclz is 1^(1%t)\\2d3r, and the normalization conditionreads

|2 j3
\\V\\-d*r= 1 [4.6]
/
with the integral taken is
over all space.If the potential independent
of time, there

will be a complete set of stationary states.

^\342\200\236(r.t)
=
^,,(^-1 E\"'/fi, [4.7]

where the spatial wave function satisfies

\\fr\342\200\236 the lime-independent Schrodinger
equation:

h1 ,
\342\200\224
V^ + Vf = Eyjt. [4.8]
2m

The generalsolution to the (lime-dependent) Schrodinger equation is

^{T,t) = [4.9]
J2c\"^n(T)e-iE\"'/r\\

with the constants determined

c\342\200\236 by the initial wave function, 4>(r, 0), in the
usual way. (If the potential admits continuum states, then the sum in Equation4.9
becomes an integral.)
 Section 4.1: Schrodinger Equation in Spherical Coordinates 133

*Problem4.1
(a) Work out all of the canonical commutation relations for componentsofthe
r
operators and p: [a-, v], [x, py], [x, px], [pY. pz], and so on. Answer:

in, Pj]
= -lPh
rj] = ihSij, [/7./7] = [ph pj] = 0, [4.10]

where the indices stand for x, y, or z, and = x, = v, and rz = z.

rx ry

(b) Confirm Ehrenfest's theorem for 3-dimensions:

= -(p). and -^-<p)= <-VV>. [4.11]

at
^-(r) in at

(Each of these, of course, stands for three equations\342\200\224one

for each

component.) Hint: First check that Equation 3.71 is valid in three dimensions.

(c) FormulateHeisenberg's uncertainty principle

in three dimensions. Answer:

oxaPx
> h/2, a,alh. > h/2. aza,h> h/2, [4.12]

but there is no restriction on, say, axaPv.

4.1.1 Separationof Variables

Typically,
the is a function
potential only of the distance from the origin. In that
case it is natural to adopt spherical coordinates,(r.9, \302\242) (see Figure 4.1). In

spherical coordinates the Laplacian takes the form\"

, 1 a /?3\\ 1 3 / 9 \\ 1 ( 92 \\

9r
/\342\226\240-
\\ 9/-/ r*sm9d9\\ 99 J r2sin-9 \\30^/
then,
In sphericalcoordinates, the
time-independent Schrodinger equation reads

r
h2 1 3 / 23^\\
\"
1 3 / . 1
/32^
+
<hfr\\
+
2m 7-lu- V ~dr~) ~r~l^9d9 \\*m0~dO ) ~rh*n1~9\\WJ]
+ V$ = E\\lf. [4.14]

We begin by looking for solutions that are separable into products:

i/(r,0.fr = R(r)Y(O^). [4.15]

-In principle, this can be obtained by change of variables from the cartesian expression
(Equation 4.5). However, there-arc much more efficient ways of getting it; see. for instance, M. Boas,
Mathematical Methods in the Physical Sciences. 2nd ed.. (Wiley. New York. 1983), Chapter 10.
Section 9.
134 Chapter4 Quantum Mechanics in Three Dimensions

FIGURE 4.1: Spherical coordinates: radius r, polarangle 9, and azimuthal angle \302\242.

Putting this into Equation 4.14, we have

//2 Y d R 9 R 92y
sin0\342\200\224 +
2/77 P-dr [! dr ) r2 sin 0 90 M J ,-2 sin2 0 902 J
+VRY=ERY.
-> it-T.
Dividing by RY and multiplying by -2////-//7

[1 d ( -ydR\\ 2m/-2 )

+ ^1^(,^ + -^1=0.
Y sin 0 90 39 J sin2 0 902

The term in the first curly bracket depends only on /\\ whereas the remainder

depends only on 0 and 0; accordingly,each must be a constant. For reasons that

will appear in due course,3I will write this \"separation constant\" in the form /(/+1):

1 d / -,dR\\ 2m r2
[4.16]

1 f 1 9 / . JY\\ 1 92y)
\342\200\224
sir\302\2730 ) + -^-- =-/(/ + 1). [4.17]
Y sin 0 90 90/ sin20 90:

that there is no loss of generality

\342\200\242
Note here\342\200\224at this stage I could be any complex number.
Later on we'll discover that / must in fact be an inieger. and il is in anticipation of that result that I
express the separation constant in a way that looks peculiar now.
 Section 4.1: ScbrodingerEquationin Spherical Coordinates 135

*Problem 4.2 Use separation of variablesin cartesiancoordinates to solve the

infinite cubical well (or \"particle in a box\:

[0. ' if are all between 0 and a:

V(x. v. z) = {
.v, 'v. z
\342\226\240
tU
oo, otherwise.
[

(a) Find the stationary states, and the correspondingenergies.

(b) Call the distinct energies in order
\302\243j. \302\2432.\302\2433. \342\200\242\342\200\242\342\200\242
\342\200\242 of increasing energy.
Find E\\. \302\2432.\302\2433, \302\2434.\302\2435, and E&. Determine their degeneracies (that is, the
number of differentstates share the same that
energy). Comment: In one
dimension degenerate bound statesdo not occur (see Problem 2,45), but in
three dimensions they are very common.

(c) What is the degeneracy of \302\24314, and why is this case interesting?

4.1.2 The Angular Equation

Equation4.17 determines the

dependence of yp
on 9 and 0; multiplying by Y sin2 0,

it becomes:
9 ( dY\\ d2Y 9
[418]
sin^r^)+^=-'('+i)sin^
You
might recognize this equation\342\200\224it
occurs in the solution to Laplace's equation
in classical electrodynamics. As always, we try separation of variables:

Y(0, 0) = 0(0)0(0). [4.19]

Plugging
this in, and dividing by 0<\302\243>, we find:

f 1 o ) 1 dr$
sin0\342\200\224 sin0\342\200\224 + /(/+1)51112 0+--^=0.
0 dO \\ d9 J
<$> d<$>-

The first term is a function only of 9, and the secondis a function only of 0, so
each must be a constant.This time4 I'll call the separation constant m2:
'
1
+ 1) sin29 = m2:
\342\200\242 \342\226\240

0
sin
\302\253d
9\342\200\224
d9
(

\\
J\302\256'
sin0\342\200\224\342\200\224
d9
+ /(/ [4.20]

,\302\243/2*=-m'. [4.21]
O dfr

\"'Again, there is no loss of generality here, sinceat this stage in could be any complex number:
in a moment, though, we discover
will that m must in fact be an integer. Beware: The letter 111 is
now doing double duty, as mass and as a separation constant. There is no graceful way to avoid this
confusion, since both uses are standard. Some authors now switch to M or /i for mass, but I hate to

change notation in mid-stream, and I don*t think confusion will arise, as long as you are aware of the

problem.
136 Chapter 4 Quantum Mechanicsin ThreeDimensions

is
The 0 equation easy:

*
d2\302\256
^,,,
= -m-$
...2*
=*.
. _Jm*
= e,m<p.
\302\242(0) [4.22]

[Actually, there are /wo solutions: exp(zw0) and exp(\342\200\224?'m0), but we'll cover the
latter by allowing m to run negative. There could also be a constant factor in
front, but we might as well absorb that into 0. Incidentally,in electrodynamics we

would write the azimuthal function (\302\242) in terms of sines and cosines, instead of
exponentials,becauseelectricpotentials must be real. In quantum mechanics there
is no such constraint,and the exponentials are a lot easier to work with.] Now,
when 0 advances by 2rt, we return to the same point in space (see Figure4.1),so
it is natural to require that5

\302\242(0 + 271-) = 0(0). [4.23]

In other words,exp[/m(0+ 2n)] = exp(/w0),

or exp(27n'//z)
= 1. From this it
follows that m must be an integer:

m =0,+1, \302\2612 [4.24]

The 9 equation,

+ [1(1+ 1) sin2 9
-
m2]0 = 0. [4.25]
sin9^ (sin 0^)

is not so simple. The solution is

0(0) = A
Pj\" (cos 9), [4.26]

where P\"' is the associated Legendre function, defined

by6

I\"1'
/ d \\
= (1 - a-2)I'\"I/2 \342\200\224
P,(x). [4.27]
P/\"(jr) f
J

and Pi(x) is the /th Legendre polynomial,defined by the Rodrigues formula:

[4-28]
M-Mil1*2-1*-

is more
\342\226\240\"'This slippery than it looks. After all. the probability density (|4>|2) is single-valued

regardless of m. In Section 4.3 we'll obtain the condition on in by an entirely different\342\200\224and more

compelling\342\200\224argument.

^Notice that
Pj~'\"
\342\200\224
Pj\".
Some authors adopt a different sign convention for negative values
of in: see Boas (footnote 2), p. 505.
 Section 4.1: Schrodinger Equation in
Spherical Coordinates 137

TABLE 4.1: The first few Legendrepolynomials,

P/(.v):(a) functional form,
(b) graphs.
i
1
= 1
^0
^1 = X
P2 = j(3.v2
- 1) Py//'/I
-
P3 = M5x>
1
/\\j
y^)
3x)
-l / N. N. / / 1 x
-+
P* = 1(35,- - 30.v
3)
P5= 1(6^
- 70.v*+15.v)
\"^ -l
(a) (b)

For example,

Po(-v) = 1. P\\(x) = - \342\200\224

{x1
-
1) =.r.
lax

1 ( d \\ ~, , 1 -,

and so on. The first few Legendre polynomials are listed in Table 4.1. As the name

suggests, P/(.v) is a polynomial (of degree /) in .v, and is even or oddaccording to

the parity of /. But P\"'(x) is not, in general, a m is odd it carries polynomial\342\200\224if

a factor of Vl \342\200\224
x1:

= i(3A-2-l). pUx) = I(3a-2-1) =3.*V7 x-

P,\302\260(A-)
2 ~ (1-x^/2^- dx

9 r-
2
^(.v) = ]f1
-(3a* 1) = 3(1-a-2).
(l-.v2)(\302\243) 2

etc. (On the otherhand, what we need is

Pj\" (cos 9), and Vl - cos2 9 = sin 9, so

Pj\" (cos 9) is always a polynomial in cos 0, multiplied\342\200\224if

m is odd\342\200\224by sin0.

Some associated Legendre functions of cos# are listedin Table4.2.)

Notice that / must be a nonnegative integer, for the Rodriguesformula to
make
any sense; moreover, if \\m\\
> 1, then Equation 4.27 says Pj\" = 0. For any

given /, then, there are (2/ + 1) possiblevaluesof m:

/ = 0, 1. 2. m = -l. -/+1 0.
\342\226\2401. 1, ... , /- 1. /. [4.29]
But wait! Equation 4.25 is a second-order differential equation: It shouldhave two

linearly independent solutions, for any old values of / and m. Where are all the
138 Chapter 4 Quantum Mechanics in ThreeDimensions

TABLE 4.2: Some associated Le'gendre functions, P\"'(cos9): (a) functionalform,

(b) graphs of/* = P\"'(cos9) (in these plots r you tells the magnitude of the function in
the direction 0; each figure should be rotated about the z-axis).
a\"

r0
-
p\302\260- i1 pV =
^(3 cos29-1) p,'(^
-e&

P\\
= sin 9 p!
= 15 sin 9(1- cos2 9)
'i.:

= cos 9 p}
= 15 sin2 $ cos0 ^(^
P\\]

8-** -^
Pl = 3s\\rr9 rh \\sin 9(5cos20-1) ->Z

P\\
= 3 sin B cos e P{h | (5 cos3 0 - 3 cos 0) pV(W) CO ^>

(a) (b)

other solutions? A/z.yiv<?/*:

They e.mf, of course, as mathematical solutions to the
equation,but they
are
physically unacceptable, because they blow up at 0 = 0
and/or 9 = n (see Problem 4.4).
is
Now, the volume elementin sphericalcoordinates7

=
dyT r1^medrdOd(f), [4.30]

so the normalization condition (Equation 4.6) becomes

/\\\\lf\\2r2^\\-\\Bdrd6d(j)= \\R\\2r2 dr \\Y\\2 sin 0 d$ d<j) =

j j

It is convenient to normalize R and Y separately:

nlTt nrt
poo
I \\R\\2r2dr=[ and / / |r|2 sin0</0 d<t>
= 1. [4.31]
Jo Jo Jo

7Sce.lor instance. Boas (footnote 2). Chapter 5. Section 4.

 EquationinSpherical
Section 4.1: Schrodinger Coordinates 139
TABLE 4.3: The first few spherical harmonics, Yju(6.\302\242).

'/2
COS0 ^ \" = ~ 3
(5 9
C\302\260S3 ^
C\302\260S
y?-(i)\"2 (ifc)

= +
'/2
sin 0 (5 cos2 0-
y^1 (^) 1)*\302\261'*

= I ~\342\200\224
I sin- 6> cos Qe x-\"''
^-(4)^(3^-1) Yf-

'/2
Yfl
=+ sin & cos Be**
(\302\247|)

The normalized angular wave functions8 are calledsphericalharmonics:

=
/(2/+l)(/-|m |)!
V\"\"*
,-mfl4 ,\342\200\236

1^(0, 0) g/A/ +
P/\"(cos0). [4.321
47T (/ |w|)!

where e = (\342\200\2241)'\" for m > 0 and e = 1 for /// < 0. As we shall prove later on,
they are automatically orthogonal, so

pin pir
/
' &]*[YI?(0,0)]
/ [Yi\"{0, sin0</0<ty
=
5//'5mm', [4.33]
JO JO
In Table 4.3 I have listedthe first few spherical harmonics. For historical reasons, /
is calledthe azimuthal quantumnumber, and /// the magnetic quantum number.

^Problem 4.3 Use Equations 4.27, 4.28,and 4.32, to construct Fj and 7-,1.Check
that they are normalizedand orthogonal.

Problem4.4 Show that

0(0) = Aln[tan(0/2)]

8Thc normalization factor is derived in Problem 4.54: e (which is always 1 or -1) is chosen
for consistency with the notation we will be using in the theory of angular momentum: it is reasonably

standard, though some older booksuse other conventions. Notice that

i\" lv\302\273'\\*
=
y,-'\" (-\\)\"'{y;\
140 Chapter 4 Quantum Mechanics in Three Dimensions

satisfies the 6 equation (Equation 4.25), for / = m = 0. This is the unacceptable

\"second solution\"\342\200\224what's wrong with it?

^Problem Use Equation 4.32 to constructYJ(6,

4.5 0) and
Y$(6. \302\242).(You can take

P-2 from Table 4.2, but you'll have to work out

PJ from Equations 4.27
and 4.28.)
Check that they satisfy the angular equation (Equation 4.18), for the appropriate
valuesof I and m.

* ^Problem 4.6 Starting from the Rodrigues formula,derivethe orthonormality

condition for Legendre polynomials:

\302\273//'\342\226\240 [4.34]
\302\243\342\204\242w*=(tt

Hint: Use integration by parts.

4.1.3 The Radial Equation

Notice that the angular wave function, Y(9, \302\242),is the same for all
part of the
spherically symmetric potentials; the actual shape of the potential, V{r), affectsonly
the radial part of the wave function, R(r), which is determined by Equation 4.16:

'
odR'
d_ (
-^[V(r)-E]R
= l(l + l)R. [4.35]
dt n~

This equation simplifies if we change variables: Let

u{r) = rR(r), [4.36]

so that R = u/r, dR/dr = [r(du/dr) - u]/r2, (d/dr)[r2(dR/dr)]

= rd2u/dr2\\

and hence

h2 d2u /?2 /(/ + 1)

2ni dr
7 + V +
2m r-
u = Eu. [4.37]

This is called the radial equation;9 it is identical to the one-dimensional inform

Schrodinger equation (Equation 2.5), except that the effectivepotential,

=
h2 1(1 + 1)
Veff V + [4.38]
2/7/ r2

Those w's are masses,of course\342\200\224ihc separation consiant m does not appear in the radial
equation.
 Section 4.1: Schrodinger Equation in SphericalCoordinates 141

contains an extra piece, the so-called centrifugal term, (ti2/2m)[l(l + l)/r2]. It

tendsto throw the
particle outward (away from the origin), just like the
centrifugal(pseudo-)force
in classical mechanics. Meanwhile, the normalization condition
(Equation 4.31) becomes
\\u\\2dr=\\. [4.39]
L
That's as far as we can go until a specific potentialV{r) is provided.

Example4.1 Consider the infinite spherical well,

0, if r < a:
V(r) =
oo, if r > a.
[4.40]

Find the wave functions and the allowed energies.

Solution: Outsidethe well, the wave function is zero; inside the well, the radial
equation says
/-/2,, rid n
~ r/(/ + D ,,i1
d-u _i_

[4.41]
dr2 L
>-2 J

where
s/lmE
k_ [4.42]

as usual. Our problem is to solve this

equation, subject to the boundary condition
u(a) = 0. The case/ = 0 is easy:

d2u
y
= \342\200\224
k^u =$> u(r) = A sin(A-r) + B cos(kr).
dr

But remember, theactual radial wave function is R(r) = w('*)/'\". and [cos(kr)]/r
blows up as r -> 0. So10 must we choose B = 0. The boundary condition then

requires sin(/rfl)
= 0, and hence ka n.
= rm, for someinteger The allowed energies
are evidently
n-n-n-
E\342\200\2360
= (n = 1.2.3, ...), [4.43]
2m a2

is wave function be nornuilizable. it he ~

'^Actually, all wc require that the not that finite: /?(;\342\200\242)

I//- at the origin is normalizable (becauseof the r2 in Equation 4.31). For a more compelling proof
that B = 0. sec R. Shankar. Principles of Quantum Mechanics (Plenum. New York. 1980).p. 351.
142 Chapter4 Quantum Mechanics in Three Dimensions

the same as for the one-dimensional infinitesquare (Equation 2.27). well

Normalizing u(r) yields A = -J2ja\\ tacking on the angular part (trivial, in this instance,
since Yq{0, \302\242)
=
1/V4~7r), we conclude that

1 sin(fljrr/fl)
= \342\200\242
Vr\342\200\236oo -j= [4.44]
V27Ttf r

[Notice that the stationary states are labeled by three quantum numbers, /7,/, and
tn: tynimO'i #> 0). The energy, however, depends only on and /: n \302\243\342\200\236/.]

The general solution to Equation 4.41 (for an arbitrary integer /) is not so

familiar:

u(r) = Arji(kr) + Brni(kr). [4.45]

where ji(x) is thespherical Bessel function of order /, and /?/(a) is the spherical
Neumannfunction /. of order They are defined as follows:

/ /1 d V sin.y , /'1 d cos a r_ ,,,

;,(*) =
V
= _ .
; ,7/(A-) _(_.v)/ [4.46]
\\x ax /
(-*)'(\342\200\224_)
x \\xax/ x

For example,

sin.Y cos A'

./0(-0
= : \302\253oCO
= ;
A* X

1 d /sinx\\ sin a cos.y

Mx) = (-a)- \342\200\224 = \342\200\224
:
a ax \\
X / A\" A

-,/1 */ \\~ sin a 9/l ^/ \\ a cos a \342\200\224

sin a

\\a-<1y/ a \\xdxj a3

3 sin a \342\200\224
3a cos x \342\200\224
x2 sin x

and first few spherical Besseland

so on. The Neumann functions are listed in
Table 4.4. For small a sinA = x a3/3! (where
\342\200\224
+ a5/5!
\342\200\224
\342\200\242\342\200\242\342\200\242
and cosa =

1-a2/2 + a4/4! ),

1 A A2
7o(.v)%l; ./iCO%-: /2(.v)
* -;
/10(.0\302\276\342\200\224:
a 3 15
etc. Notice that Bessel functions are finite at the origin, but Neumann functions
blowup at the origin. Accordingly, we must have Bi = 0, and hence

R(r) = Aji(kr). [4-47]

 Section 4.1: Schrodinger Equation in Spherical Coordinates 143

TABLE 4.4: The first few spherical Bessel and Neumann functions,
7/z (-v) and /i/(.v); asymptotic forms for small .v.

sinx COS
./0=
.V
=
\302\2730
x

sin .v cos -V cos .v sin x

./1
.v x x- x

./3= 1 \\ . 3 (3 1 \\
ji
J~ \342\200\224r sin.v ~ cos,v ~
>h=-\\ \342\200\224$ cos .v y sin .v
V.v3 W x2 Vx3 x) A-

-
Jl
2'n
(2/+ 1)!A
I
' ,^.(2^
i
1, for.v\302\253i.

2'/! x/+1

There remains the boundary condition, R(a) = 0. Evidently

/: must be chosen
such that
j,(ka) = 0: [4.48]
that is, (ka) is a zero of the /th-order spherical Besselfunction. Now, the Bessel

functions are oscillatory (see Figure 4.2); each one has infinite number an of zeros.

V8 / v10 \\ 12 V .14 X

-.31-

FIGURE 4.2: functions.

Graphs of the first four sphericalBessel
144 Chapter
4 Quantum Mechanics in Three Dimensions

But (unfortunately for us) they are not located at nice sensible points (such as n.
or mj, or
something): they have to be computed numerically.11 At any rate, the

boundary condition requires that

k = -/3,,/. [4.49]
a
where /3,,/ is the \302\253thzero of the /th spherical Bessel function. The allowed energies,
then, are given by

=
E,\342\200\236
/^Ai [4.50]
2m ci-

and the wave functions are

9. =
fnlmir. \302\242) A\342\200\236,M[}\342\200\236ir/a)Y;\"{0. \302\242). [4.51]

with the constant to

A\342\200\236i be determined by normalization. Each energy level is
(2/ 4- l)-fold degenerate, since there are (21 + 1) different values of m for each
value of / (see Equation 4.29).

Problem 4.7

(a) Fromthe definition

(Equation 4.46), construct n\\(.x) and /n(-v).

(b) Expand the sines and cosines to obtain approximate formulas for /ii(.v) and
ni(x), valid when .v <$C 1. Confirm that they blow up at the origin.

Problem4.8

(a) Check that Arj\\(kr) satisfies the radial equation with V(r)
= 0 and /=1.

(b) Determine graphicallythe allowedenergies the infinite spherical well, for

when 1=1. Show for large /;., (tl27i2/2mcr)(n + 1/2)2. Hint:

that =\302\276
E\342\200\236\\

First show = tan .v. Plot .v and tan.v on the same

./i(.v)
= 0 => that
graph, .v

and locate the points of intersection.

Abramowiiz and Siegun. eds.. Handbook of Mathematical Functions. (Dover. New York. 1965).
Chapter 10. provides an extensive listing.
 Section 4.2: The Hydrogen Atom 145

* *Problem4.9 A
particle of mass m is placed in a.finite spherical well:

if r < a;
V(r) =
-Vb.
\342\226\240

0, ifr>a.

Find the groundstate, by solving the radial equation with / = 0. Show that there

is no bound state if Vocr <iz~

4.2 THE HYDROGEN ATOM

The
hydrogen atom consists of a heavy, essentially motionless proton(we may as
well put it at the origin), of chargee, together with a much lighter electron (charge
that
\342\200\224e) orbits around it, bound by the mutual attraction of oppositecharges(see
Figure 4.3). From Coulomb's law, the potential energy (in SI units)is

e2 1
V(r)
=
[4.52]

and the radial equation (Equation 4.37) says

!~r cl^u e1 1 //2 /(/+1)~

7 + 1 5
u = En. [4.53]
2m dr2 r
4tz\342\202\254q 2m r-

Our problemisto solve equation for this u and

(/\342\226\240), determine the allowed energies,
E. The hydrogen atom is such important an case that I'm not going to hand you
the

solutions this time\342\200\224we'll work them out in detail, by the method we used in the
analyticalsolutiontotheharmonicoscillator. (If any step in this process is unclear,
you may wish to refer backto Section2.3.2 for a more complete explanation.)

-e
(electron)

FIGURE 4.3: The hydrogen

atom.
146 Chapter 4 Quantum Mechanics in Three Dimensions

Incidentally, the Coulomb potential (Equation 4.52) admits continuum states(with

E > 0), describing electron-proton scattering, as well as discretebound states,
representing
the hydrogen atom, but we shall confine our attention to the latter.

4.2.1 The Radial Wave Function

Our first task is to tidy up the notation. Let

sJ-lmE
K = [4.54]
h

(For bound states, E is negative,so k is real.) Dividing Equation 4.53 by E, we

have
1 d2u
1
we2 1 /(/ + !)'
+ u.
k2 dr2 2n\342\202\254ofi2K b<r) (Kr)2

This suggests that we introduce

me-
p= Kr, and po \342\200\224
[4.55]
27T\342\202\254qITK

so that
d2u po /(/+1)
1 T t [4.56]
dp*

Next we examine the asymptoticform of the solutions. As p \342\200\224>

oo, the

constant term in the brackets dominates, so (approximately)

d2u =
u.
dp7

The general solution is

u(p) = Ae~p + Bep. [4.57]

up (as p
\342\200\224
but ep blows \342\200\224>
oo), so B 0. Evidently,

~ Ae~p. [4.58]
u(p)

for largep. On the other hand, as p -\302\2730 the centrifugal term dominates;12
approximately,
then:

d2u /(/+1)

dp- p-

'-This argument does nol apply when I = 0 (although the conclusion. Equation 4.59, is in fact

valid for that case loo). But never mind: All I am Irving lo do is provide some motivation lor a change
of variables (Equation 4.60).
 Section 4.2: The Hydrogen Atom 147

The general solution(checkit!)is

=
u(p) Cpl+* +Dp~!.

but p,-/ ' blowsup (as p \342\200\224>

0), so D = 0. Thus

~ /+1
\302\253(p) Cp [4.59]

for small p.
The next
step is to peel off the asymptotic behavior, introducing the new

function v(p):

u(p)
= pl+le-pv(p), [4.60]

in the hope v(p) that will turn out to be simpler than u(p). The first indications
are not auspicious:

du dv~
l -pp
\342\200\224
=
p'e (/ + 1- p)v + p \342\200\224

dp dp.

and

d2u /(/+1)1 dv d2v

= p'\302\253~' -2/ - 2+ p + v + 2(/ + 1
dp2 { P . dp dp2
In termsof v(p), then, the radial equation (Equation 4.56) reads

d~v
- dv - 2(/ +
+ 2(/ + 1 p)\342\200\224 + [p0 1 )]v = 0. [4.61]
p\342\200\2247
dp- ap

Finally, we assume the solution, v(p), can be expressed as a power series

in p:
oo

v(p)
= \342\226\240 [4.62]
Ylc.iPi
7=0

Our problem is to determine the coefficients (co.c\\. co....). Differentiating term

by term:
oc 00
dv x\342\200\224v .. , -c-^ .

dp
u u

[In the secondsummation have I renamed the \"dummy index\": j +

\342\200\224>
j 1. If this
troubles you, write out tlie first few terms explicitly, and check it. You may object
148 Chapter 4 Quantum Mechanics in ThreeDimensions

that the sum should now begin at j = \342\200\224

1, but the factor (./ + 1) kills that term
anyway,
so we might as well start at zero.] Differentiating again,

d~V t\342\200\224v ; I
= + ikv+ip'-1.
^ E^./

Insertingthese into
Equation 4.61, we have

OO oc

Y,j(j
+ DoW+2(/ +1) j^u + u<--j+\\pj
./=0 j=0

-2 + [p0 - 2(/ + 1)] = 0.

J2 jcjpi \302\243cjpj

i=0 7=0

Equating the coefficients of like powersyields

./(./'+ l)c;+i + 1)(7 +

- 2jcj + [po- = 0.
+ 2(/ l)c7+, 2(/ + l)]c/

or:
= [ 2(,/+/+1)-/00 ]
W
{(; +1)0- +*+ 2)}^
[4.63]

This recursion formula determines the coefficients, and hence the functionu(p):
We start with co (this becomes an overall constant, to be fixed eventually by

normalization), and Equation 4.63 gives us c\\\\ putting this back in, we obtain ci,
and so on.13
Now let's see what the coefficients look like for large j (this corresponds to

large p, where the higher powers dominate). In this regimethe recursion formula

says14

2' -~ 2
Cj+[ ~
~

JuTT)Cj JTiCj-
'-'You might wonder why ] didn't use the series method directly on u(p)\342\200\224why factor out the
asymptotic behavior before applying this procedure? Well, the reason for peeling off p'+l is largely
aeslhelic: Wilhoul ihis. the sequence would begin wilh a long siring of zeros(the firsl nonzero coefficient
being r/+|): by factoring out p/+l we obtain a scries thai starts out wilh The
p\302\260. e~p factor is more
critical\342\200\224if you don't pull lhal out. you gel a three-term recursion formula, involving fy+2* <*/+i>
and
Cj (try ii!) and lhal is enormously more difficult to work wilh.

14You might ask why 1 don't drop ihe 1 in j + 1\342\200\224-afterall, I am ignoring 2(/+ 1)- po in ihe
numerator, and 2/ +2 in the denominator. In ihis approximation il would be fine to drop ihe 1 as well,
but keeping il makes the argument a lillle cleaner.Try doing il without the 1. and you'll see what I
mean.
 Section 4.2: The Hydrogen Atom 149

Supposefor a moment that this were exact. Then

V
Cj = \342\200\224cq. [4.64]

so
00
2J
=
V(p) =C0y \342\200\224pi CQ(TP,
7
7=0

and hence
u(p) = cQpl+[ep, [4.65]

which blows up at large p. The positive exponential is preciselythe asymptotic

behavior we didn't want, in Equation 4.57. (It's no accident that it reappears here;
after all, it does represent the asymptotic form of some solutions to the radial

equation\342\200\224they just don't happen to be the ones we're interested in,because they

aren't normalizable.) There is only one way out of this dilemma: The series must
terminate. Theremust occursome maximal
integer, ./max, such that

cOm,v+D=0. [4.66]

(and beyond which all coefficients

vanish
automatically). Evidently (Equation 4.63)

20\"max+/+0-/00 = 0.

Defining
n = ymax +/ + 1 [4.67]

(the so-calledprincipalquantum number), we have

P0
= In. [4.68]

But po determinesE (Equations4.54 and 4.55):

?
n ^
k me4
E = -^- = ,,,-,- [4.69
2m
S7t2\342\202\254^h2pl

so the allowed energies are

150 Chapter 4 Quantum Mechanicsin ThreeDimensions

This is the famous Bohr formula\342\200\224by any measure the most important result in
all of quantum mechanics. Bohr obtained it in 1913 by
a serendipitous mixture
of inapplicable physics and premature
classical quantum theory (the Sehrodinger
equation did not come until 1924).
CombiningEquations4.55 and 4.68, we find that

me' 1 1
K=( [4.71]
\\47teo^'2 / n an'

where

a =
47re0^ = 0.529x 10\"10 m [4.72]
me\"

is the so-called Bohr radius.15 It follows (again,from Equation4.55) that

P
= [4.73]
an

The spatial wave functionsfor hydrogen are labeled by three quantum numbers (n,
I, and m):
fnlm(r,0, \302\242)
= Rnl(r) lf(0, 0), [4.74]

where (referring back to Equations4.36 and 4.60)

Rnl(r) = -pJ+le-pv{p), [4.75]

and v(p) is a polynomial of degree = n 7max

\342\200\224
I \342\200\224
1 in p, whose coefficients are
determined (up to an overallnormalization factor) by the recursion formula

2(j+l + l-n)
Cj+1
(./ + 1)04-2/ +
,7' [4.76]
2)6

The ground state (that is, the state of lowest energy)

is the case n = 1; putting
in the acceptedvaluesforthe physicalconstants, we
get:

2~l
m
E\\ =- = -13.6 eV. [4.77]
2ft2 \\47T\342\202\2540i

is traditional
\342\226\2405It to write the Bohr radius with a subscript: oq. But this: is cumbersome and
unnecessary, so 1 prefer to leave the subscript off.
 Section 4.2: The Hydrogen Atom 151

Evidentlythe bindingenergyof hydrogen (the amount of energy you would have

to impart to the electronin ground the state in order to ionize the atom) is 13.6eV.
Equation 4.67 forces I =-0, whence also m. \342\200\224
0 (see Equation 4.29), so

^ioo(n#,</O = #io(r)^(0,<a [4.78]

The recursion formula truncates after the first term (Equation 4.76 with j = 0
yields C{
=
0), so v(p) is a constant (cq), and

[4.79]
a
it,
Normalizing in accordance with Equation 4.31:

i2
f
/
id i2
\\Rw\\~rdr
2 j lC0l
= -^=- If e \342\200\224Irla
~r/a
r~dr
2 7
= 11^
c0
- - 11,
k a2 Jo 4

so co \342\200\224
%1-sfa. Meanwhile,
=
Y\302\256
ljy/4n, and hence the ground state of hydrogen
is
1
= -r/a
^1()0 (r, 0, \302\242) [4.80]
VjTtf,3

If n = 2 the energyis

=
-13.6 eV
\342\200\224\342\200\224 =
E2 -3.4 eV; [4.81]

this is the first excitedstate\342\200\224or rather, states, since we can have either I \342\200\224
0 (in

which case m = 0) or I = 1 (with m = 0,

\342\200\2241, or +1); evidently four different
states share this same energy.
If I = 0> the recursion relation (Equation4.76)gives

ci \342\200\224
(using
\342\200\224Co j = 0),.. and =
\302\2422 0 (using ;' = 1).,

so v(p) \342\200\224
cq(1
\342\200\224
p), and therefore

[Notice that the expansion coefficients {cj} are completelydifferent for different

quantum numbers n and /.] If I = 1 the recursionformula terminates the series

after a single term; v(p) is a constant,and we find

[4.83]
4a2

(In each case the constant cq is to be determined by

normalization\342\200\224see

Problem 4.11.)
152 Chapter 4 Quantum Mechanics in ThreeDimensions

For arbitrary n, the possible, values of I (consistent with Equation 4.67) are

/= 0,1,2,...,^-1, [4.84]

and for each I there are (21 + 1) possiblevaluesof m

(Equation 4.29), so the total
degeneracy of the energy level E]t is

/j-i

d(n)
=
J] (21 + 1) = a2; [4.85]

The
polynomial v.(p) (defined by the recursion formula, Equation 4.76)isa function
well known to applied mathematicians; apart from normalization, it can be written
as

- [4-86]
v(p) ^SLi(2a)>

where

tf-p (*>= (\"i)p(JA 'H<*> [4.87]

is an associated Laguerre polynomial, and

Lq(x) = (*\"***) [4.88]

e*(J^\\
is the
#m Laguerre polynomial,16 (The polynomials are listed
first few Laguerre
in Table4.5; some associated Laguerre polynomials given in Table 4.6. The
are
first few radial wave functions are listed in Table 4.7, and plotted in Figure4.4.)
The normalized hydrogen wave functions are17

=
*\342\226\240*
IWi^\302\247^'m O' [*->(2rH *\342\204\242 \302\253\342\226\240 [4.89]

They are not pretty, but don't complain\342\200\224this

is one of the very few realistic
systems that can be solved at all, in exact closed form. Notice that whereas the
wave functions depend on all three quantum numbers, the energies (Equation4.70)
are determined by
n alone. This is a peculiarity of the Coulombpotential;in the

16As usual, there, are rival normalization conventions in the literature; 1 have adopted the most
nearly standard one.

17If you want to see how the normalization factor is calculated, study (for example), L. Schiff,
Quantum Mechanics, 2nd ed., (McGraw-Hill, New York, 1968), page 93.
 Section 4.2: The Hydrogen Atom 153

TABLE 4.5: The first few Laguerre polynomials, Lq (x).

Lp-= 1
Lr-= -x- +- 1

= --x2- - Ax + 2
L2

h= =-.\302\2763 + 9x2- 18*+ 6

L4
=--xA- -16^ + 72^-96^ + 24

h~- --x5 + 25X4-- 200X3 + 600x2-

- 600x + 120

L6 = --X\302\253--36^ + 450x4
- 2400x3+ 5400.\302\2762 -4320x + 720

TABLE 4.6: Some associated Laguerre

polynomials,
Lp (x).

j 0 _ 11 L2 = 2
L,0-

Lf=-jc+l
L2 = -6x+18

=
\302\243.0 .^-4^+2 L|=12x2-96x+144

L]-l L3 = 6

Z.J
= -2x + 4 Lj= -24x + 96
- 18
1^ = 3x2 18x + L|=60x2-600x+1200

case of the spherical well, you may recall, the energies dependalsoonI
(Equation 4.50). The wave functions are mutually orthogonal:

/ ^nim ifti'i'm*
>'2 sin # dr d$ # = 8ntI>8n>&mri
\342\226\240 [4,90]

This follows from the orthogonality of the sphericalharmonics(Equation 4.33)

and (for n, ^ nr) from the fact that they are eigenfunctionsof H with distinct

eigenvalues.

Visualizing the hydrogen wave functions is not easy.Chemists liketo draw

\"density plots,\"
in which the brightness of the cloud is proportionalto \\ty\\2 (Figure 4.5).
More quantitative (but perhaps harder to read) are surfaces of constant probability

density (Figure 4.6).

^Problem 4.10 Work out the radialwave functions ./\302\275> ^31, and R32, using the
recursion formula (Equation 4.76). Don'tbotherto normalize them.
154 Chapter 4 Quantum Mechanics in Three Dimensions

TABLE 4.7: The first few radial wave functions for hydrogen,

RiQ=2a~3/2 exp{-r/d)

\342\200\224
#2i =-f=a-312 exp (-r/2a)
V24 a

n _ 2 a,,-3/2
/tan
^30
\342\200\224\342\226\240
-r\342\200\224\342\226\240
V27 3 a 27
i'-h^i&h^-^ \\a

R3i -\302\273_a-M(l -li)(^) exp (-r/3a)

i?32= 4_a-3/2 ^a'

81V30

^4^0474(^1\302\276\302\276^^
- *
-
^4]
ltiV3 -3/204f4&)2)i-p^)
^--ih^i^uw^^
W= \342\200\224l\342\200\224crm(\342\200\224) exp (-r/4a)
768^35

^Problem 4.11

(a) Normalize R20 (Equation 4,82), and constructthe function ^200.

(b) Normalize R21 (Equation 4.83), and construct .^2-11,

i'DO,and yfrji-i-

^Problem 4.12

(a) Using Equation 4.88, work out the first four Laguerre polynomials.

(b) Using Equations 4.86, 4.87, and 4.88, find v(p), for the case n = 5, I = 2,

(c) Find v{p)again (for the case n

\342\200\224
5,. I = 2), but this time get it from the
recursion formula
(Equation 4.76).
 Section 4.2: The Hydrogen Atom 155

FIGURE4.4: Graphs
of the first few hydrogen radial wave functions, HM/(r).

*Problem4.13

(a) Find and (r2) for

(r) an electronin the ground
state of hydrogen. Express
your answers in terms of the Bohr radius.
(b) Find(x) and (x2J for an electron in the ground state of hydrogen. Hint: This
requires no new integration\342\200\224note that r2 \342\200\224
x2 + y2 + z2, and exploit the
symmetry
of the ground state,

(c) Fmd (x2) in the state n \342\200\224

2, =
/\342\226\240 i, m = 1. Warning: This state is not
symmetrical
in jc, y, z. Use x r sitiO
\342\200\224
cos0.
156 Chapter 4 Quantum Mechanicsin ThreeDimensions

(2,0,0) (3,1,0) (4,0,0)

(4,1,0) (4,2,0) (4,3,0)

FIGURE 4.5: Density plots for the hydrogen wave functions I,

(\302\253, m). Imagine each
plot to be rotated about the (vertical) z axis. Printed by permission using '\"Atom in a
Box,\"vl.OiS, by Danger Research. Yon can make your own plots by going to the Web
site http://danger.com.

Problem 4.14 What is the

probable value of r, in the groundstateof
most

hydrogen? (The answer is not zero!) Hint: First you must figure out theprobability that

the electron would be found between r and r + dr.

Problem4.15 A
hydrogen atom starts out in the following linear combinationof
the stationary states n \342\200\224
2,1
\342\200\224
1, m..= 1 and n \342\200\224 /
2,
= 1, m \342\200\224
\342\200\2241:

1
W(r,0)
= \342\200\224Ofon+^21-1).
:x/2

(a) Construct ty(r, t). Simplifyit as much as

you can.

(b) Find the expectation value of the potentialenergy,(V),(Does it depend on

t?) Give both the formula and the actualnumber,in electronvolts.

 Section 4.2: The;Hydrogen Atom 157

FIGURE 4.6: Surfaces of constant|^|2 for the first few hydrogen wave functions.
Reprinted by permissipn from Siegmund Brandt and Hans Dieter Dahmen, ThePicture
Bookof Quantum Mechanics, 3rd ed.. Springer, New York (2001).

4.2.2 The Spectrumof Hydrogen

In
principle,
if you put a hydrogen atom into some stationary state ^nim, it should

stay there forever. However, if you tickle it slightly collision with another
(by atom,
say, or by shining light on it), the electron may undergo a transition to some other

stationary state\342\200\224either by absorbing energy, and moving up to a higher-energy

state,or by giving off energy (typically in the form of electromagnetic radiation),
158 Chapter
4 Quantum Mechanics in Three Dimensions

and moving down.18In practice such

perturbations are always present; transitions
(or, as they are sometimescalled, \"quantum jumps\") are constantly occurring, and
the result is that a containerof hydrogen gives off light (photons), whose energy
corresponds to the difference in energy between the initial and final states:

- ~
Ey = Ei -Ef = -13.6 eV
[ \\
n.
)
. [4.91]

n;f

Now, according to the Planck formula,19the energyof a photonis

proportional to its frequency:

EY
= hv. [4.92]

Meanwhile, the wavelength

is given by K = c/v, so

[4.93]

where 2
R= -^- (
-^
] = 1.097 x 107m\"1 [4.94]

is the
known
Rydberg as constant. Equation 4.93 is the Rydberg formula forthe
spectrum hydrogen; of it was discovered empirically in the nineteenth century, and

the greatest triumph of Bohr's theory was its ability to account for this result\342\200\224and

to calculate R in terms of the fundamental constantsof nature.Transitions to the

ground state (rif

= 1\") he in the ultraviolet; they are known to spectroseopistsas
the Lyman series. Transitions to the first excited state (\302\253/ = 2) fall in the visible

region; they
constitute the Balmer series. Transitions to rif = 3 (the Paschen
series)are in the
infrared; atid so on (see. Figure 4.7), (At room temperature,most
hydrogen atoms are in the obtain the emissionspectrum
ground state; to you
must

first populate the various excited states; typically this is done passing an by
electric

spark through the gas.)

^Problem 4.16 A
hydrogenic atom consists of a single electron orbiting a nucleus
with Z protons (Z = 1 would be hydrogenitself,Z \342\200\224
2 is ionized helium, Z = 3..

By its nature, this involves a unie-ifependent interaction, and the details will have to wait for
Chapter 9; for our present purposes the actual mechanism involved is immaterial.

19The photon is- a quantum of electromagnetic radiation; it's a relativistic objectif thereever was
one, and therefore outside the scope of rionrelalivistic quantum mechanics. It will be useful in a lew

places to speak of photons, and to invoke the Planck formula for their energy, but please bear in mind
that this is external to the theory we are developing..
 Section 4.2: The HydrogenAtom 159

n
\342\226\240
OQ
0
6
5
-1.0 4
Y I Y 'v
3
-2.0 Paschen
series
-3.0 u u u u u

-4.0 Balmer
series
-5.0
-6.0
>
-7.0h
S3
CD
-8.0
C
LU
-9.0h
-10.0
-11.0
-12.0

-13.0
v u u u ,r u
1
\342\200\242\342\200\224
\342\200\22414.0 Lyman series

FIGURE 4.7: Energy levels and transitions in the spectrumof hydrogen.

is doubly ionized lithium, and so on). Determine the Bohr energies En(Z), the
binding energy E\\(Z), the Bohr the Rydberg constantR(Z)
radius a(Z), and for a

hydrogenic atom. (Express your answers as appropriate multiples of the hydrogen

values.) Where in the electromagnetic spectrum would the series fall, Lyman
for

Z = 2 and Z = 3? Hint: There's

nothing much to calculate here\342\200\224in the potential

(Equation 4.52) e2 \342\200\224*

Ze2, so all you have to do in
is make the same substitution
all the final results.

Problem 4.17 Consider the earth-sun analogto the

system as a gravitational
hydrogen atom.

(a) What potential energy function (replacingEquation4.52)?(Let

is the m be

the mass of the earth, and M the massof the sun.)

(b) What is the \"Bohr radius,\" ag, for this system?Work out the actual number.

(c) Write down the gravitational\"Bohr formula,\" and, by equating En to the

classical energy of a planet in a circular orbit of radius r(j, show that n =
\342\226\240yJ'Toja^.
From this, estimate the quantum number n of the earth.
160 Chapter
4 Quantum Mechanics in Three Dimensions

(d) Suppose the to the next lowfer level (n \342\200\224

earth made a transition .1.). How

much energy (in Joules) would be released? What would the wavelength of
the emitted photon (or, more likely, graviton)
be? (Express your answer in
light years\342\200\224is the remarkable answer20 a coincidence?)

4.3 ANGULAR MOMENTUM

As we have seen, the stationary states of the hydrogen atom are labeledby three
quantum numbers: n, I, and m. The principal quantum number determines
(\302\253.)
the

energy state (Equation 4.70); as it

of the turns out, I and m are related to the orbital
angular momentum. In the classical theory
of central forces, energy and angular
momentum are the fundamental conserved quantities, and it is not surprising that
angular momentum
plays a significant (in fact, even more important) role in the
quantum theory.

Classically, the angular momentum of a particle (with respect to the origin)is

given by the formula
L = r x p, [4.95]
which is to say,

Lx = =
ypz-zpy, Ly zpx\342\200\224 xpz, Lz=xj?y-ypx. [4.96]

The corresponding quantum operators are obtained 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 following section we'll
obtain the eigenvalues of the angularmomentum operators by a purely algebraic
technique reminiscent of the one we used in Chapter get the allowed energies 2 to
of the harmonicoscillator; all it is based on the clever exploitation of commutation
relations. we will turn
After that to the more difficult problem of determining the
eigerifunctions.

4.3.1 Eigenvalues

The operators L.x and Ly do not commute; in fact2-

[Lx, Ly]
=
[ypz
-
zpy, zpx
- xpj
= [yPz, ZPx]
~
[yPz> *Pz\\
-
kpy, zpx\\ +[ZPy, *Pzl [4.-97]

20Thariks Lo John Meyer for pqinling this out.

2'Note thai <ili the operators we encounter in quantum mechanics (footnote 15, Chapter 1) are
distributive with respect to addition: A(B + C) ~ AB + AC. In particular, [A, B + C] = [A, B~\\ +
[A, C].
 Section 4,3: Angular Momentum 161

From the eanonieal commutation relations (Equation 4.10) we know that the only
operators here thatfail to commute are x with px, y with py, and z with
pz. So

the two middle terms drop Out, leaving

[LXi Ly]
= ypxipz, z] + xpylzi pz] = ih{xpy- ypx)
=
ihL-z. [4.98]

Of course, we could have startedoutwith [Ly, Lz] or [Lz, Lx], but there is no need
to calculate these separately\342\200\224-we can get them immediately by cyclic permutation
of the indices(x -> v, y
-> z, z-> x):

[LXr Ly] = ihLz; [Ly, Lz]= ihLx; [Lz, Lx] =

ihLy. [4,99]

relations
These are the fundamentalcommutation for angular momentum;

everything else follows from them.

Notice that LXi Ly, and Accordingto
Lz are incompatibleobservables. the

generalized uncertainty principle (Equation 3.62),

~ '
vLsOLy >~\\(LZ)\\. [4.100]

It would therefore be futile to lookfor states that are simultaneously eigenfunctions

of Lx and Ly. On theotherhand,the square of the total angular momentum,

L2 = Lxl + L2 + L2, [4.101]

does commute with 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.

(I used Equation 3.64 to the commutators; simplify note also that any operator
commutes with itself) It follows,of course, that L2 also commutes with Ly and
Lz-
[L2,Z^] = 0, [L2,Ly]=0, [L^LJ^O, [4.102]
162 Chapter 4 Quantum Mechanics in Three Dimensions

or, morecompactly,
[L2,L]= 0. [4.103]

So L2 is Compatible with each component of L, and we can hope to find

simultaneous
eigeristates of L2 and (say) Lz;

.L2f=kf and LJ = iif. [4.104]

We'll use a \"ladder operator\" technique, very similar to the one we appliedto
the harmonic oscillator back in Section 2.3.1. Let

L+ = Lr \302\261iL.y [4.105]

The commutator with L7 is

[Lz, L +] = [Lz, Lx] \302\261

i[Lz, Lyl
=
ihLy \302\261 =
?\342\226\240(-\302\273\302\243*)\302\261
h{Lx \302\261
iLy) yj,

SO
= + .
[LZ,L\302\261]
\302\261HL [4.1Q6]

And, of course,
= o.
[LM\302\261] [4.107]

I claim that if f is an
eigenfunction of L2 and Lz, so also is L\302\261/': Equation 4.107

says
L2(L\302\261/)
=
L\302\261(L2/)
= L\302\261(Xf)
=
HL\302\261f), [4.108]

so L +/ is an eigenfunction of L2, with the same eigenvalue X, and Equation 4.106

says:

= + = \302\261hL + L^{iif)
Lz{L\302\261f) {LzL\302\261-L\302\261Lz)f L\302\261LJ + f

= ({j,\302\261K](L+f% [4.109]

so L + f is an
eigenfunction of Lz with the new eigenvalue fi \342\226\240+
/z. We call L+
the \"raising\" of
operator, because it increasesthe eigenvalue Lz by h, and L_ the
\"lowering*' operator, because it lowersthe eigenvalue h. by

For a given value of -A., then, we obtain of states, with each

a \"ladder\"
\"rung\" separated from its neighbors by one unit of h in the eigenvalueof (see Lz

Figure 4.8). To ascend the ladder we apply the raisingoperator, and to descend, the

lowering operator. But this process cannotgo on forever: Eventually we're going
 Section 4.3: Angular Momentum 163

FIGURE4.8: The \"ladder\" of angular momentum states.

to reach a state for which the

z-eorriporient exceeds the total, and that cannot be.22
Theremust exista \"top rang,\" ft, such that23

L+ft = 0. [4.110]

22Formally, (I1) = (L2) + <L2)+<Lj), but

(*%)
=
iffclf)
= {Lxf\\Lxf)>$ (and likewise
for so.
L,,)\342\200\236
A - (L2) + {i\302\243)+ ^2 > ft.

^Actually, all we can conclude is Ihat

L+ft- is not normalizable\342\200\224its norm could be infinite,
instead of zero.Problem 4.18 explores this alternative.
164 Chapter 4 Quantum Mechanicsin ThreeDimensions

Let hi be the eigenvalue of Lz at this top rung (the appropriatenessof the letter
\"/'\" will appear in a moment):

Lzft=hlft; L2ft=kft. [4.111]

Now,

L+LT = (Lx
+
iLy)(Lx ^iLy)
= L2 + L2^ i(LxLy - LyLx)

I?
\342\200\224 -
l}z^i(ihLz),

or, putting it the other way around,

L2 = + hLz. [4.112]
L\302\261LT L2Z^

It follows that

L2ft = (L-.L++ ut+hLjfi - (0 + h2i2 + nH)fi- = n2w +1)/\342\200\236

and henee

X=h2l(l + 1). [4.113]

This tells us the eigenvalueof L2 in terms of the maximum eigenvalue of Lz.

Meanwhile,thereis also (for the same reason) a bottom rung, j%, such that

L-fh = 0. [4.114]
Let hi be the eigenvalue of Lz at this bottomrung:

Lzfb
=
Hlfbi L2fh = kfh. [4.115]

Using Equation4.112, we have

I>fp
\342\200\242=
(L+L- + L2- hLz)fb = (0 + h2t - h2l)fb
=
h2J(l -\\)h,

and therefore
=
X /z27(7-l). [4.116]

Comparing Equations 4.113 and 4.1-16,we see that 1(1 -f 1) =

7(7 \342\200\224
1), so either
7 = / + 1 (which is absurd\342\200\224the bottom rang would be higher than the top rung!)
of else
7--/. [4.117]
 Section 4.3: Angular Momentum 165

Evidently the eigenvalues of Lz

are mh, where m (the appropriateness of this
letter will alsobe clear iri a moment) goes from \342\200\224/
to +1 in N integer steps. In
particular, it fpllows that I' = +
\342\200\224l N, and hence I = N/2, so I must be an integer
or a half-integer. The eigenfunctions are characterized by
the numbers I and m;

= HH(l + rin
iS-f? 1)jf; LJ\342\204\242
=
hmfi [4.118]

where

- 1, /,
1 = 0, 1/2, 1,-3/2, . m = \342\200\224
I, +
\342\200\2241 1, I [4.119]
Fora given value of /, there are 2/ -f 1 different values of m (i.e., 11 + 1 \"rungs\"
on the \"ladder\.
Some peoplelike to illustrate this result with the diagram in Figure 4.9
(drawn for the arrows are supposedto represent
case I = 2). The
possible angular

momenta\342\200\224in they units same length *Jl(l+ 1)

of h this all have the (in case

Vfr and
\342\200\224
2.45), their z components are the allowed values of 1, m
\342\200\224
(\342\200\2242, 0, 1,

2). Notice that the magnitude of the vectors(theraditisof the sphere) is greater

than the maximum z component! (In general, -^/1(1 1) except + >\342\226\240

I, for the
\"trivial\" case I \342\200\224
0.) Evidently you can't get the angular momentum to pointperfectly
along the z direction. At first, this sounds absurd. \"Why can't Ijust pick my axes
so that z. points alongthe direction of the angular momentum vector?\" Well, to
do this you wouldhave to know all three components simultaneously, and the

FIGURE 43: Aiigular momentumstates(for1= 2).

Chapter
4 Quantum Mechanics in Three Dimensions

uncertainty principle (Equation 4.100)says that's impossible. \"Well, all right, but

surely once in a while, by good fortune, I will

just happen to aim my \302\243-axis along
the direction of L.\" No, no I You have missed the point. It's not merely that you
don't know all three components of L; there simply aren't three components\342\200\224a
particle just cannot have a determinate angular momentum vector, any more than it
can simultaneously have a determinate positionand momentum. If
Lz has a well-

defined value, then Lx and Ly do not. It is misleading even to draw the vectors
in Figure4.9\342\200\224-at best they should be smeared out around the latitude lines, to
indicate that Lx and Ly are indeterminate.
I hope you're impressed: By purely algebraic means, starting with the
fundamental commutation relations for angular momentum (Equation 4.99), we have
determinedthe eigenvalues L2 and of
seeing the eigenfunctions Lz\342\200\224without ever

themselves! We turn now to the problemof constructing eigenfunctions, but the

I should warn you that this is a much messierbusiness. lust you know where so

we're headed, I'll begin with the punch line: =

eigenfunctions of f\342\204\242 Yf1\342\200\224-the

L2 and Lz are nothing but the old spherical harmonics, came upon by which we

a quite different route in Section 4.1.2 (that's chose the letters I and m, why
I

of course). I can now tell you why the spherical harmonicsare orthogonal:
And

They
are
eigenfunctions of hermitian operators (L2 and Lz) belonging to distinct
eigenvalues (Theorem 2, Section 3.3.1),

*Problem 4.1\302\276 The raising and lowering operators change the value of m by one

unit:

L\302\261f{n={Af)f^\302\261\\ [4.120]

where Af is some constant.Question: is What

Af,
if the eigenfunctions are to
be normalized1?Hint: First that
LT is the show hermitian conjugate of L\302\261 (since

Lx and
Ly are observahles, you may assume they
are herimtian . but
\342\226\240..
prove it
if you like); then use Equation 4.112.Answer:

Af = hy/lQ
+ l)-m(m\302\261\\) =
h^(l Tm)(I \302\261m + 1). [4,121]

Note what happens at the top and bottomof the ladder (i.e., when you apply L_|_
to fj or L_ to /\"').

4.19
^Problem
(a) Starting with the canonical commutation relations for position and momentum
(Equation4.10), work out the following commutators:

[Lz, x] = ihy, [Lz, v]

= -ihx, [Lz, z) = 0,
4
,
[Lz,px]= ihpy, [Lz, py]
=
-ihpx, [Lz, pz] = 0,
 Section 4.3; Angular Momentum 167

(b) Use these results to obtain [Lz, L*]

\342\200\224
iHLy directly from Equation 4.96,

(c) Evaluate the commutators[Lz,r2] and {LA, p2] (where, of course, r2 \342\200\224

x2 + +
y\302\260- z2 and p2 = p2x+ p$ + /\302\276).

(d) Show that the Hamiltonian H = (p2/2m) + V commutes with all three
components of L, provided that V\" depends only on r. (Thus H, L2, and Lz

are mutually compatible observables.)

* ^Problem 4.20

(a) Prove that for a particlein a potential V(r) the rate of change of the
expectation value of the orbital angular momentum L is equal to the expectation
value of the torque:

= (N),
|(L)

where
N = rx(-VV).

(Thisis the rotational analog to Ehrenfesfs theorem.)

(b) Show that d(L)/dt \342\200\224

0 for any spherically symmetric potential. (This is one
form of the quantum statement of conservation of angular momentum.)

4.3.2 Eigenfunctions

First of all we need to rewrite Ly, and Lz in spherical coordinates,Now,

Lx,
L \342\200\224
(h/i)(r x V), and the gradient, in spherical coordinates,is;24

V = +0
r\342\200\224 + 0\342\200\224 ; [4.123]
dr r dO r sin0 90

meanwhile, r = rr, so

h ~ 9 \342\226\240 * \342\226\240
\342\200\236 -9 ~ * 1 9
L = r(r x r) f- y
(r x 61)\342\200\224+ (r
K
x 0)
v
_
JBr ;W sine 90.

\"^GeorgeArfken and
Hans-Jurgen Weber, Mathematical Methods for Physicists,5th ed.,
Academic Press, Orlando (2000), Section 2,5.
168 Chapter 4 Quantum Mechanicsin Three Dimensions

But (f x r) = 0, (r x 9) = 0, and (r X 0) = \342\200\2240

(see Figure 4.1), and hence

\302\273
/ --a -: i a
L=-
i 0--0- [4.124]
'

\\
3<9 sin 0 30 /

The unit vectors 9 and 0 canbe resolved into their cartesian components:

9 = (cos 9 cos\302\242)1+ (cos 9 sin 0)j

\342\200\224
(sin#)\302\243; [4.125]

\342\200\224
0 \342\200\224(sin0)f-f- (cos0)J, [4.126]

Thus

. 3
(.-sin0i +cos0;) \342\200\224

1 3
-(eos# cos 0i + cos9 sin0 J \342\200\224
sin 9k)
\342\200\224

sin# 30 _

Evidently
/
-\302\276 3 3 \\
= - - -
cos0eot#
\342\200\224-
Lx I sin0-\342\200\224 , [4.127]
z
\\ 69 \302\242\302\242/

h 3
\342\200\224
Ly
\342\200\224 I +CDS0- sin0:eot0 [4.128]
z' V 3n 30,

and

[4-129]

We shall also need the raising and lowering operators:

h 3 , 3
L+ \342\200\224
Lx + iLi, = (\342\200\224sin0
i eos0)\342\200\224-
\302\261
\342\200\224
(cos0 i
\302\261 sm0)cot#\342\200\224
i d$ 30 _

But eos 0 i
\302\261 sin0
= e*+ i.
'*,, so
' A
3 3
L+ =
,
+
\342\200\224: \342\200\224
\302\261he\302\261ix> J: COt\302\243 [4.130]
.36\302\273 30 ,

111 particular (Problem 4.21(a))

/ 32 32
X+L_ - -^
3 , 3

-^- + cot 9 -\342\200\224h cor 0\342\200\224 [4.131]

d$2 36\302\273
^\302\2422+l^\302\242),
 Section 4,3: Angular Momentum 169

and hence (Problem4.21(b)):

1 3/.9
\342\200\224 \342\200\224 _L 3*_'
L2 = -h' sin (9 + [4.132]
sin e de \\ m sin2 0 d(j>2

We are now in a position to determine//\"(#, \302\242).It's an eigenfunction of L2,

with eigenvalue h2l(l + 1):

1 3/..3sin.0
2 i-KfJ.
= -A\" \342\200\224
+ _1 3^ = fc2/(/ + l)//!
Z//f jf
sin 9(9
6\302\273 V 96 sin2 302
6\302\273 _

But this is preciselythe \"angular equation\" (Equation 4.18). And it's also an
eigenfunction of Lz, with the eigenvalue mh:

=
*<zf?
j^fr=*mfr,

but this is to the azimuthal

equivalent equation (Equation 4.21). We have already
solved this of
system equations: The result (appropriately normalized) is the
spherical harmonic, Fjm(#> \302\242)- Conclusion: Spherical harmonics ait eigenfunctions of
L2 and Lz. When we solved the SchrOdinger equation by separation of variables,
in Seetion4.1, we were inadvertently constructing simultaneous eigenfunctions of
the three commuting operatorsH, L2, and
L?:

Hlfr = Ef, L2iff =h2l{l + 1)^, Lzf = hmifr: [4.133]

Incidentally, we can use Equation 4.132 to rewrite the Sehrodinger

equation
(Equation 4,14) more compactly:

1 -2 9
+V -f Vifr
= Exfr.
2mr2 dr \\j/

is a curious final twist to this story,

There for the algebraic theory of
angular momentum permits I (and hencealsom) to take on ^//-integer values
(Equation 4.119), whereas separation of variablesyieldedeigenfunctions only
for

integer values (Equation 4.29). You might suppose that the half-integersolutions
are spurious, but it turns out that they are of profound importance, as we shall see

in the following sections.

170 Chapter 4 Quantum Mechanicsin ThreeDimensions

^Problem4.21
(a) Derive Equation 4.131 from Equation 4A30,Hint: Use a test function;
otherwise you're likely to drop some terms.

(b) Derive Equation4.132 from

Equations 4.129 and 4.131. Hint: Use
Equation4.112.

^Problem 4.22

(a) What is \302\243+7/? (No calculation allowed!)

(b) Use the result of (a), togetherwith Equation 4.130 and the fact that LzYf
=

MYJ, to determine 7/(0,0), up to a normalizationconstant.

(e) Determine the normalization constant by direct integration. Compare your
final answer to what
you got in Problem 4.5.

Problem 4.23 In Problem4.3 you

showed that

Y}@, 0) = -V15/87T sine cos \342\226\240$<?*.

Apply the raising operator to find Y%.(8,0). Use Equation4.121to getthe

normalization.

Problem 4.24 Two particles of mass m are attachedto theends of a massless rigid
rod of length a. The systemis freeto rotatein three dimensions about the center
(but the center point itself is fixed).

(a) Show that the allowed energies of this rigid rotor are

= = 1, 2,.,.
En \342\200\224-\342\200\224Y\342\200\224,for
\302\253 0,

Hint: First express the (classical)energyin termsof the total angular

momentum.

(b) What are the normalized eigenfunctions for this system? What is the

degeneracy of the nth, energy level?

 Section 4.4: Spin 171

4*4 SPIN

In classical mechanics, a
rigid object admits two kinds of angular momentum:
orbital (L = r x p), associated with the motion of the center of mass, and spin
(S = 1(d),. with associated motion about the center of mass. For example,theearth
has orbital angular momentum attributable to its annual revolution around the sun,
and
spin angular momentum coming from its daily rotation about the north-south
axis. In the classical context this distinction is largely a matter of convenience, for

when you come right down to it, S is nothingbut the sumtotal the \"orbitaT' of

angular momenta of all the rocks and dirt clods go to make up the earth, asthat

they circle aroundthe axis. an analogous But

thing happens in quantum mechanics,
and here the distinction is absolutely In addition to orbital
fundamental. angular
momentum, associated (in the case of with the motion of the electron
hydrogen)

around the nucleus (anddescribed the spherical harmonics),

by the electron also
carries another form of angularmomentum, has nothing to do with motion
which

in space (and which is not, therefore, by any function, of the position

described

variables r, 6, but which is somewhat

\302\242) analogous to classical spin (and for which,

therefore, we use the same word). It doesn't pay to press this too far: The analogy

electron (as far as we know) is a structureless point and its spin angular particle,

momentum cannot be decomposed into orbital angular momentaof constituent

parts (see Problem 4.25).25 Suffice it to say that elementaryparticles intrinsic carry

angular momentum (S) in addition to their ''extrinsic\" angularmomentum(L),

Thealgebraic of spin is
theory
a carbon copy of the theory of orbital angular

momentum, beginning with the fundamental commutation relations:26

[5x, Syl = ihSz, [Sy, Sz]

= ihSx, [Sz:, Sx] = ihSy. [4.134]

It follows(as before)
that the eigenvectors of 52 and satisfy27
51\302\276

S2\\sm)
= h2s(s + l)\\sm); Sz\\sm} = hm\\s m); [4.135]

a contrary
\342\226\240For interpretation, see Hans C. Ohanian, \"What is Spin?\", Am. J. Phys. 54, 500
(1986).
26
We as postulates for the theory of spin; the analogous formulas for orbital
shall take these
angularmomentum were derived from the known
(Equation 4.99) form of the operators (Equation 4.96). In
a more sophisticatedtreatment they can both be obtained from rotational invariance in three dimensions
(see, for example, LeslieE. Ballentihe, Quantum Mechanics: A Modern Development, World Scientific,

Singapore (1998), Section 3.3). Indeed, thesefundamental commutation relations apply \\a all forms of
angular mpmentum, whether spin, orbital, or the combined angular momentum of a compositesystem.
Which Could include some spin and some orbital.
Because the eigenstates of spin are use the \"ket\"
uqL notation
functwnstfor them. (I I will
could have done the same in Section 4.3, of Yfl, but in that context the function
writing \\lm) in place
notation seems more natural.) By the way, I'm running out of letters, so I'll use m for the eigenvalue
of SV, just as I did for Lv: (some authors write M\\ and ms at this stage, just to be absolutely clear).
172 in
Chapter 4 Quantum Mechanics Three Dimensions

and *

= + V-miml 1) (m \302\261
1)), [4.136]
S\302\261\\sm) \\s
hy/sis

= Sx i are not spherical harmonics

where S+ iSy. But this time the eigenvectors
(they're not functionsof $ and <p at all), and there is no a priori reasonto exclude
the
half-integer values of 5 and m:

1 3
= 05
.*\342\226\240 -, lr -,-..; m = -s, -5+1, ... , s - 1, s. [4.137]

It so happens that every elementary particle has a specificarid immutable

value ofwe call the spin of

s, which particular species: pi mesons have spin
that

0; electrons have spih 1/2;photons spin 1; deltas.have spin 3/2; gravitons have
have

spin 2; and so oh. contrast, the orbitalBy angular momentum quantum number
I (for electron an in a hydrogen atom, say) Can take on (integer) value you any

please, and will change from one to another the system is perturbed. But s when

is fixed, for given particle, and this makes the theory of spin comparatively
any

simple.28

Problem 4.25 If the electron were a classical solid sphere, with radius

e2
re = \342\200\224
[4.138]
y
4jr6o7wcz

(the so-called electron radius, obtainedby assumingthe electron's

classical mass is

attributable to energy stored in its electric field, via the Einstein formula E = mc2),
and its angular momentum i$ (l/2)h, thenhow fast (in m/s) would a point on the
\"equator\"be moving?Doesthis model make sense? (Actually, the radius of the
electronis known experimentally to be much less than rc, but this only makes
mattersworse.)

28Indeed, in a mathematical sense, spin 1/2 is the simplest possible nontrivial quantum system, for
it admits just two basis states. In place of an infinite-dimensional Hilbcrt space, with all its subtleties
and complications,we find ourselves working in an ordinary 2-dimensional vector space; in place
of unfamiliar differential equations and fancy we are confronted
functions, with 2x2 matrices and
2-component vectors. For this reason, some authors begin-quantum mechanics with the study of spin.
(An outstanding example is John S. Townsend, A Modern Approach to Quantum Mechanics, University
Books, Sausalito, C.A, 2000.) But the price of mathematical simplicity is conceptual absti'action, and I

prefer not to do it that way.

 Section 4,4: Spin 173

4.4.1 Spin 1/2

By is 5 spin of the particles
\342\200\224
far the most important case 1/2, for this is the that

make up (protons, neutrons, and electrons), as well as all quarks

ordinary matter
and all
leptons. once you understand spin 1/2, it is a simplematterto
Moreover,
work out the formalism for any higher spin. There are just two eigenstates; |^ |},
1 1
which we call spin up (informally, |), and |j (\342\200\2245)), which we call spin down

(4,). Using these as basis the

vectors, general state of a spin-1/2 particle can be
expressed as a two-elementcolumn matrix (or spinor):

X = = aX+ + bx- [4-139]

(b)
with

X+=L [4-140]

representing spin up, and

X-= V [4-141]

for spin down.

the spin operators become2x2
Meanwhile, matrices, which we can work out
by noting their effect on x+ X-. Equation A. and 135 says

S2x+ = and [4-142]

^2X+ SV-^V.
If we write S as a matrix with (as yet) undeterminedelements,

S2 =

then the first equation says

-
:: flffl-H).
\342\200\224
= a The second
so c (3/4)/\302\2762 and 0. equation says

' \302\260
'c d\\ /0\\ 3\342\200\2362/0\\
/<T

so d = 0 and / \342\200\224
(3/4)\302\276 . Conclusion:

* = ^14\302\276
l*Co ?)\342\226\240
174 Chapter 4 Quantum Mechanics in ThreeDimensions

Similarly,
h o - --x-
*
PzX+
=
s?x- [4.144]
^x+,

from which it follows that

h /l o
Sz = [4.145]
2V\302\260 -V

Meanwhile, Equation 4.. 136 says

s+x- = frx+, S-X+= hx-y S+x+

= S-x^ -o,

so
'0 1\" '0 0^
S-U=fi S_ = A..
1
[4.146]
,0 0, o,

+ S_) and -
Now S\302\261
=
Sx \302\261
iSy,
so Sx = (1/2)(5+
Sy
=
(1/2/)(5+ 5_), and
hence
^ - 2 or
11 bar\"2U. o
[4.147]

Since Sjt,. Sy.,, and Sz all carry a factor of hj'1,it is tidier to write S = (hj2)a,
where

'Q -f 1 0
'^s(l o)> \302\260>
j 0 7' ^^ 10 -1 [4.148]

These are the famous Pauli spin matrices. Notice that Sx, Sy, S2, and S are all
hermitian (as they should be, since they represent observables). On the otherhand,
S+ and S- are not hermitian\342\200\224evidently they are not observable.
The eigenspinors of Sz are (of course):
H'
X+
=
eigenvalue + X- eigenvalue J. [4.149]

If you measure Sz
on a particle in the general state x (Equation4.139), you could

get +/1/2, with probability |a|2, or \342\200\224ft/2, with probability \\b\\2.

Since these are the

only possibilities,
\\af + \\b\\2
= l [4.150]

(i.e., the spinor must be normalized)P

29People often say that |a.|2 is the \"probability that the particle is in the spin-up state,\" but this
is sloppy language; what they mean is that if you measured Sz, la]2 is the probability you'd get h/2.
See footnote 16 in Chapter \"3.
 Section 4,4: Spin 175

But what if, instead, you chose to measureSx1What are the possible results,
and what are their respective probabilities?According to the generalized
statistical
interpretation, we heed to know the eigenvalues and eigenspinors of Sx. The
characteristic equation is

-k /J/2 'W ft
= o r
=>\342\226\240 = =*3t=\302\261
ft/2 -X

Not surprisingly, the possible values for Sx are the same as those for Sz. The

eigenspiriors are obtained in thte usual way:

= + 'a'
;(?.oca-* tew.'

so ^ +
\342\200\224 a. Evidently the (normalized) eigenspinors of Sx are

1
/J_\\
ft\" 72 ft'
yW
eigenvalue + *\302\253 eigenvalue [4.151]
1

\342\226\240
72'

As the eigenvectors of a hermitian matrix, they span the space; the generic spinor
X (Equation 4.139) can be expressed as a linear combinationof them:

x = (^)tf + (<L^)xn [4.152]

72 72

If you measure Sx, the +

probabilityof getting+ft/2 is .(1/2.)[a h]1, and the

probability of getting \342\200\224ft/2 is (1/2)\\a,

\342\200\224
b\\2. (You should cheek for yourself that
these probabilities add up to 1:)

Example
4.2 Suppose a spin-1/2 particle is in the state

Wl+T
=
X
'2
76 V ,

What are the probabilities of getting +ft/2 and \342\200\224ft/2,

if you measure Sz and SA?

Solution: Here a = (1+ 0/76 and b

\342\200\224
2/76, so for .S-z the probability of getting
+ft/2 is |(1+0/76|2 = 1/3, and the probability of getting -ft/2 is |2/76|2 =
2/3. For Sx the probability of getting +ft/2 is (1/2)1(3 + 0/76|2 - 5/6, and
176 Chapter 4 Quantum Mechanics in Three Dimensions

the probabilityof getting-h/2 is1(1/2)1(-1 + 0/V6|2

= 1/6. Incidentally, the
expectation value of is Sx

5( h\\ l{ h\\ ft

+ =
6 (+2J 6 N ?
which we could also have obtained more directly:

I'd like now to walk you through an imaginary measurement scenario

involving spin 1/2, because it serves to illustrate in very concrete terms some of the
abstract ideas we discussed back in Chapter 1. Let's say we start out with a

particle in the state x+- asks, \"What is the z-componentof that particle's
If someone
spin angular momentum?\", answer unambiguously: +H/2. For a
we could
measurement of SV is certain asksinstead,
to return that value. But if our interrogator \"What

is the x-componerit of that particle's spin angular momentum?\" we are obliged to

equivocate: If you measure Sx, the chancesare fifty-fifty of getting either h/2 or
the
\342\200\224h/2.
If
questioner is a classical physicist, or a ''realist\"(inthe sense of Section

1.2), he will regard this as an inadequate\342\200\224-hot to say impertinent\342\200\224-response: \"Are

you telling me that you don't know the true state of that particle?'' On the contrary;
I know precisely what the state of the particle is: x+. \"Well, then, how come you
can't tell me what the ^-componentof its spin is?\" Because it simply does not
have a particular x -componentof spin.Indeed, it cannot, for if both Sx and Sz

were well-defined,the principle

uncertainty
would be violated.
At this point our challenger grabsthe test-tube measures the x-component
and

of its spin; let's say he gets the +/I/2. \"Aha!\" (he shouts in triumph), \"You
value

lied! This particlehas a well-defined perfectly value of Sx: h/2,\" Well, sure\342\200\224it

does now, but that doesn't prove it had that value,priorto measurement. your
\"You

have obviously been reduced to splitting hairs. anyway, what happened

And to your
uncertainty principle? I now know both and Sz.\" I'm sorry, but you do not: In
Sx

the courseof measurement,

your you altered the particle's state; it is now in the
statex+ and whereas > you know the value of Sx, you no longer the value pf know

\"But
5\302\276.. I was extremely careful not to disturb the particle I measured Sx\"
when

Very well, if you don't believe me, check it out: Sz, and see
Measurewhat you
get. (Of course, he get +/i/2,
may which will be embarfassihg to my if ease\342\200\224but

we repeat this whole scenario over and over, half the time he get will
\342\200\224h/2.)

To the layman, the philosopher, or the classical physicist,a statementof the

form \"this particle doesn't have a well-defined position\" (or momentum, or x-
component of
spin angular momentum, or whatever) sounds vague, incompetent,
or (worstof all) profound.
It is none of these. But its precise meaning is, I think,
 Section 4.4; Spin 177

almost impossible to convey to anyone who has not studied quantum mechanics

in some depth. If you find your own comprehensionslipping,from time to time

(if you don't, you probably haven't understood the problem), cqme back to the

spin-1/2 system: It is the simplest and cleanestcontext thinking for

through the

conceptual paradoxes of quantum mechanics.

Problem 4.26

(a) Checkthat the spin matrices

(Equations 4.145 and 4.147) obey the
fundamental commutation relations for angular momentum, Equation 4.134.

(b) Show that the Pauli spin matrices (Equation 4.148) satisfy the productrule

ffj<rk
=
8jk + i
2^ ejkim* [4-!53]
l
where the indices stand for x, y, or z, and is
\342\202\254jm
the Levi-Civita symbol:
+ 1 if jkl = 123, 231,.or 312;-1 if jkl
= 132, 213, or 321; 0 otherwise.

*Problem4.27 An electron is in the spin state

-\"CO-

constantA.
(a) Determinethe normalization
(b) Find the expectation values of Sx., Sy, and Sz,
(c) Findthe\"uncertainties\"
crsr, a$v,
and
0\302\276. (Note:
These sigmas are standard
deviations, not Pauli matrices!)

(d) Confirm that your results are consistent with all three uncertainty principles
(Equation4.100 and its cyclic permutations-\342\200\224only with S in place of L, of
course).

^Problem4.28 For the most general normalized spinor x (Equation 4.139),

compute (Sx), (Sy), (Sz), (Sj), (S2), and (S2). Check that (S2) + (S2)+ (S2Z)

=
(S2).

*Problem 4.29

(a) Find the eigenvalues and eigerispinorsof S

Chapter
4 Quantum Mechanics in Three Dimensions

(b) If you measured Sy

on a particle in the general state-,jjf (Equation 4.139),
what values might you get, arid what is the probability of each? Check that
the probabilities add up to 1. Note: a and b need not be real!

(c) If you measuredSy,. what values might you get, arid with what probabilities?

* ^Problem4.30 Construct the matrix Sr representing the component of spin angular

momentum along an arbitrary
direction f. Use spherical coordinates, for which

r = sin6 cos (f>.i + sin 6 sin <p j + cos B k. [4.154]

Find the eigenvaluesand (normalized)

eigenspinors Sr, of Answer:

/ cos(^/2) \\. '

X+
-
(,) _
X~
(/.) _ fe-vmem} ' r415S1
L J
[j* m(0/2)j ^{- cos(6/2) )

Note: You're always free to multiply by an arbitrary phase factor\342\200\224say, el^~so

your answer may not look exactly the same as mine.

Problem 4,31 Construct the spin matrices (S*, Sy, and Sz) for a particle of

spin 1. Hint: How many eigenstates the

of Sz are there? Determine action of
Sz:,.

5+,. and SL on each of these states. Followthe procedure in used the text for
spin 1/2.

4.4.2 Electron in a MagneticField

A
spinning charged particle constitutes a magnetic dipole. Its magnetic dipole
moment,ji, is proportional
to its spin angular momentum, S:

\\i = yS; [4.156]

the proportionalityconstant,y, is called the

gyromagnetic ratio.30 When a
magnetic dipole is placed in a magnetic field B, it experiences a torque,u, x B, which

\"See. for example,D. Griffiths, Introduction to Electrodynamics, 3rd ed. (Prentice Hall, Upper
SaddleRiver, NJ, 1999), page 252. Classically, the gyromagnetic ratio of an object whose charge--and
mass are identically distributed is q/1m, where q is the charge and m is the mass. For reasonsthai are

fully explained only in relatiyistic quantum theory, the gyromagnetic ratio of the electron is (almost)

exactly twice
\342\200\224
\"the classical value: y \342\200\224
e/m.
 Section 4.4: Spin 179

tends to line it up parallelto the field

(just like a compass needle). The energy
associated with this torqueis31

H = -\\lB, [4.157]

so the Hamlltonian of a spinning charged particle, at rest32 in a magnetic field B,

is
# = -yB-S. [4.158]

Example4.3 Larmor precession: Imagine a particle of spin 1/2 at rest in a

uniform
magnetic field, which points in the z-direction:

B = Bok. [4.159]
The Hamiltonian (Equation 4.158), in matrix form, is

H =-yfcS, [4.1601
=-*\302\247\302\243 _0,).
\302\243

The eigenstates of H are the sameas those of Sz:

X+, with energy E+ = -(yBQk)/2,

E- = +(yBq<ft)/2.
[4.161]
X-, with
energy

Evidently the energy is lowest when the dipole moment is parallel to the field\342\200\224just
as it would be classically.
Since the Hamiltonian the generalsolution
is time-independent, to the time-

dependent Schrodiriger equation,

ih%\302\243-=Hx, [4T62]
at
can be expressedin terms of the stationary states:

n
iyBot/2
iyB{)t/2

31
Griffiths (footnote 30), page 281.
32If the particle is allowed to move, there will also be kinetic energy to consider; moreover, it
will be subject to the Lorentz force (q\\ x B), which is not derivable from a potential energy function,
arid hence does,not fit the Schrodinger equation as: we have formulated it so far. I'll show you later

on how to handle this (Problem 4.59), but for the moment let's just assume that the particle is free to
rotate, but otherwise stationary.
180 Chapter 4 Quantum Mechanics in ThreeDimensions

The constantsa and b are determined by the initial conditions:

X-(0) = (f) ,

(of course, \\a\\2 + |&|2 = 1). With no essential loss of generality33 I'll write a \342\200\224

:Cos'(a/2) and b = sin (a/2), where a is a fixed angle physical significance whose

will appear in a moment. Thus

,, /cos(ar/2)ez>B\302\260'/2\\ rA..\342\200\236,

To get a feel for what is happening here* let's calculate the expectation value of S,
as a functionof time:

(\302\276)
=
X (OfS^X (?) = (cos(a/2)^*<\"/2 sin^)^^/2)
ft /0 l\\ /cos(a/2)e'>B^/2\\
X [4.164]
2
(l oj ^/2),-^^/2)
\342\200\224
-sina cos[yB[)t).

Similarly,

(Sy)
= X(.()%X(!) = --sinasin()/5oO, [4.165]

and

($z)= Xlrf&rt (t)

=
^
cos a. [4.166]

Evidently (S) is tiltedat a constantangle ql to the z-axis, and precesses about the
field at the Larmor frequency
=
co yB0, [4.167]

just as it would classically34(see Figure4.10). No surprise here\342\200\224Ehrenfest's

theorem (in the form derived in Problem 4.20) guarantees that (S) evolves

according to
the classical laws. But it's nice to see how this works out in a specific
context.

does
\342\226\240^This assume that a and b are refill you Can work out 'the general case if you like, but all

it does is add a constant to t.

34See, for instance, Tfve Feynman Lectures on Physics (Addison-Wesley, Reading, 1964),Volume
II, Section 34-3; Of course, in the classical case it is the; angular momentum vector itself, not just its
expectation value, that precesses around the magnetic field.
 Section 4.4: Spin 181

z\302\273

FIGURE 4.10: Precession of {3} in a

uniform magnetic field.

Example 4.4 The Stern-Gerlach experiment: In an

inhomogeneous magnetic
field, there is not only a torque,but also &
force, on a magnetic dipole:35

F = VQi-.B). [4.168]

This forcecan be used to separate out particles with a particular spin

orientation, as follows. Imagine a beam of relatively heavy neutral atoms,36travelingin
the y direction, which passes through a region of inhomogeneous magnetic field
(Figure 4,11)\342\200\224say,

h(x, y,z)
= -axi + (Bo + az)k, [4.169]
where Bo is a strong uniform field and the constanta describes a small deviation

from homogeneity. (Actually, what we'd like is just the z component^ but

unfortunately
that's impossible\342\200\224it would violate the electromagnetic law V B = 0; like
it or not, an x component comes along for the ride.) The forceon these atoms is

^Griffiths, (footnote 30), page 258. Note that F is the negative gradient, of the energy
(Equation 4.157).

36We make them neutral so as to avoid the

large-scale deflection that would otherwise result
from the force, and
Lorentz heavy so we can construct localized wave packets and treat the motion
in terms of classical particle ti'ajeclofies. In practice, the Stern-Gerlach experiment doesn't work, for
example,with a beam of free electrons.
 \\

182 Chapter 4 Quantum Mechanics in Three Dimensions

Zn Spin up

Spin down

Magnet

FIGURE 4.11: The Stern-Gerlach apparatus.

But because of the Larmor precession about Bq, & oscillates rapidly,
and

averages to zero; the net force is in the z direction:

=
Fz y<xSz, [4.170]

and the beam is deflected up or down, in proportionto the z component of the

spin angular momentum. Classically we'd expecta smear (because Sz

would not
be quantized), but in fact the beam splits into 2s + 1 separate streams,

beautifully demonstrating the quantization of angular momentum. (If you use silver
atoms,for example, all the inner electrons: are paired, in such a. way that their

spin and orbital angular momenta cancel. The net is

spin simply that of the

outermost\342\200\224unpaired\342\200\224electron, so in this case s = 1/2, and the beam splits

in two.)
Now, that argument was purely classical, to the very final step; \"force\" up

has no place in a proper calculatiori, and

quantumyou might therefore prefer
the following approach to the same We exarriirie the process
problem.37 from the
perspective of a reference that moves along with the beam. In this
frame the frame

Hamiltohian starts out zero, turns on for a time (as the particle passes through T

the magnet), arid then off

again: turns

0, for t < 0,
\342\226\240H
(*)
=
-y(Bo + aZ)Sz, forO<f <T, [4.171]
0, for t > T.

(I ignore the of B,
pesky x cornporient which\342\200\224-lot reasons indicated above\342\200\224is

irrelevant to the problem,) Suppose the atom has spin 1/2, and startsout in the
state
X ft)
=
ax+ + H-, for t < 0.

This argument follows L. Ballentine.-(footnote'26) Section 9.1,

 Section-4.4: Spin 183

While the Hamiltonian

acts,x(0 evolves in the usual way:

X(t) = ax+e~iE+!/n + bX-e~iE-t/h, for0 < t <

T,

where (from Equation 4.158)

E\302\261 ==py(B0 + az)-i [4.172]

and hence it emergesin the state

(for i > T), The two terms now carry momentum in the z direction (see
Equation 3.32); the spin-up component has momentum

ayTh
Pz = -^-s [4.174]
and it moves in the plus-z direction; the spin-down component has the
opposite momentum, and it moves in the minus-z direction. Thus the beam splits
in two, as before. (Note that Equation 4.174 is consistent with the earlier result

(Equation 4.170), for in this ease Sz

=
ft/2, and pZ/
\342\200\224
FZT.)
The Stern-Gerlach experiment has played an important role in thephilosophy
of quantum mechanics, where it serves both as the prototype:for the preparation
of a quantum state arid as an illuminating model for a certain kind of quantum
measurement. We tend casually to assume that the initial stateofa systemis known
(the Schrodinger equation tells us how it subsequently evolves)\342\200\224but it is natural

to wonder how you get systemintoa particular

a state in the first place. Well, if

you Want to
prepare a beam of atoms in a given spin configuration, you pass an

unpolarized beam through a Stern-Gerlach magnet, and select the outgoingstream

you are interested in (closing off the others with suitable bafflesand shutters).
Conversely,
if you want to measure the z component of an atom's spin* you send
it through a Stern-Gerlach apparatus,and recordwhich bin it lands in, I do not
claim that this is always the most practical way to do the job, but it is conceptually
very clean, and hence a useful context in which to explorethe problems of state

preparation arid measurement.

Problem 4.32 In Example 4.3:

(a) If you measuredthe component spin of

angular momentum along the x
direction, at time t, is the probability what that you would get +ft/2?
184 Chapter4 Quantum Mechanics in Three Dimensions

(b) Same question, but for the _y\302\273comp6nent.

(c) Same, for the z component.

* ^Problem 4.33 An electron is at rest in an oscillating magnetic field

B \342\200\224
BQCOs(a)t)k,

where Bq and xo are constants.

(a) Construct the Hamiltonian matrix for this system.

(b) The electron starts out (at t \342\200\224

0) in the spin-up state with respect to the
x-axis % (0) Determine
(that
x+
is: \342\200\224
)\342\200\242 x (?) at any subsequent time. Beware:
This is a time-dependent Hamiltonian, so
you cannot get /(f) in the usual
way from stationary states. Fortunately, in this case you can solvethe time-
dependent Schrodinger equation (Equation 4.162) directly.

(c) Find the probabilityof getting \342\200\224h(2,

if you measure Sx. Answer:

sur srn(a)f) .
\\2cd J

(d) What is the minimum field (Bq) required to force a completeflipin Sx?

4.4.3 Addition of Angular Momenta

Suppose that we have two spin-1/2 particles\342\200\224for

now example, the electron and
the proton in the ground state38of hydrogen. Each can have spin lip or spin down,
so thereare four
possibilities in all:39

tt. U, It, 44, [4.175]

where the first arrow refers to the electron arid the second to the proton.Question:
What is the total angular momentum of the atom? Let

S= S<?) + S(2), [4.176]

3^l put them in the ground stale so there won't be any orbital angular momentum to worry about.

39More precisely, each particle is in a linear combination of spin up; and spin down, and the

composite system is in a linear combinixtion of the four states listed.

 Section 4.4: Spin 185

Eachof these four composite states is an eigenstate of Sz\342\200\224the z components

simply add:

szxiX2 =
(si{) + sf )xiX2= (sPxi)xi + xiisfhi)
=
(hmiXx)X2 + X] (AOT2X2) = ft(m.i + wii)xtxa,

(note that S^ acts only on xi? and S(2^ acts only on xi\\ this notation may not be
elegant, but it. does the job). So m (the quantum number for the composite system)
is just mi + mi;
ff: m l;
f|: m 0;
If: m 0;
44,^ m -1.
At first glance, this doesn't look right: m is supposed to advancein integer

steps,
from \342\200\224
$ to +s, so it appears that s \342\200\224
1 \342\200\224but there is an \"extra\" state
with m = 0. One way
to untangle this problem is to apply the lowering operator,
S_ = s!P + 5l2) to the state ft,- usin\302\247 Equation 4.146:

s_(tt) = (S- t) t +1 (s\302\256 t)

=.(* ^) t + r i)
(\302\276
- mt + u>.

Evidentlythe threestates with s \342\200\224

1 are (in the notation \\sm)):

r in) -tt 1
<
110) =\302\261tu + m. 5 = 1 (triplet). [4-177]
..11-1) = 44

(Asa check, try applying the lowering operator to |1 0); what should you get? See

Problem 4.34(a).) This is called the triplet combination,for the obviousreason.

Meanwhile, the orthogonal state with m = 0 carries s \342\200\224
0:

= i(U
- 5 = 0 (singlet). [4.178]
{|00) W}

(If you apply the raising or lowering operator to this state,you'll get zero. See

Problem 4.34(b).)
186 Chapter 4 Quantum Mechanicsin ThreeDimensions

I claim, then, that the combination of two spin-1/2 particles- can carry a total

spin of 1 or 0, depending on whether they occupy the triplet or the singlet

configuration. To confirm this, I need to prove that the triplet statesare eigenvectors of

S2 with eigenvalue 2h2, and the singlet is an eigenvector of S2 with eigenvalue

0. Now,

S2- = _ . s(2)_
(S(1) + S(2))
.
(S(1) + SC2>) (S(l)f + (vS(2))2 + 2S(1) [4>179fj

Using Equations 4,145 and 4.147,we have

s(1) \342\200\242
smm)
= (sp t)(sf $.+ ism txsf ^) + $n t)(^2) i).

h2
=
-(24t-H)-

Similarly,
= it)-
sP .s^(w
^-(2 n-
It follows that
,2 i fc2

S<\" .S(#|i o) = ^--^,(2

4 If \" t4- +2 f4-
-
W =
4 0),
^-IJ [4.180]
V2
and

fe2 i
. S^IOO) = - -
3^2
[4.181]
-j jj=C24rt
S^ -2 n + ;t)
t4-
-^100).
Returning
to Equation 4.179 (and using Equation 4.142), we conclude that

0 - (
/sn2 3h2 H2\\
= 2/72|10),
9
S2\\\\ 0}
\342\200\224
+
\342\200\224
+2\342\200\224 ] |10) [4.182]

so 110) is indeed an eigenstate of S~ with eigenvalue 2k, and

, ,3k1 3h2 - 3h: , ... -

S2\\Q0) =[ + -r z-r- |0.Q> 0, [4.183]

so |00) is an eigenstate of S2 with eigenvalue 0. (I will leave it for you to confirm

that |1 1) and 1)
|.l\342\200\224 are eigenstates of S2, with the appropriate eigenvalue\342\200\224see

Problem 4,34(6)*)
 Section 4.4: Spin, 187

What we have just done (combining spin 1/2 with spin 1/2 to get spin1 and
spin 0) is the simplest example of a larger problem:If you combine spin s\\ with

spin s.2.,. what total spins s can you get?4\"The answer41 is that you get every spin
from (s-i + 52) down to (s\\ \342\200\224
.\302\276)\342\200\224of
(\302\276
\342\200\224
i'l), if >
\302\2532 integer
\302\2431\342\200\224in steps:

[4.184]

(Roughly speaking, the highest total spin occurswhen the individual spins are

aligned parallel to one another, and the lowest occurs when

they are antiparallel.)
For example, if you package togethera particleof spin3/2 with a particle of spin
2, you could get a total spin 7/2, 5/2, 3/2, 1/2, depending
of or on the configuration.
Anotherexample:If a hydrogen atom is in the state ijfnim, the net angular
(spin plus orbital) is I + 1/2 or I if you now throw in
\342\200\224
momentum of the electron 1/2;

spin of the proton, the atom'stotalangular momentum quantum number is / + 1,

I, or I \342\200\224
1 (and I can be achieved in two distinct ways, depending
on whether the
electron alone is in the / + 1/2 configuration or the I \342\200\224
1/2 configuration).
The combined state \\s m) with total spin s arid z-Component m will be some
linear combination of the composite states |^i mi) 1\302\276
\302\25322):

\\s m)
= 1*1 \302\2731 \302\253a>
> 1\302\276 [4.185]
\302\243 C%%n
m.\\ -\\-m2=m

(because the z components add, the only composite states that contribute are those
for which mi + m.2 \342\200\224
in): Equations 4.177 and 4,178 are special cases of this
general form, 1/2 (I usedthe informalnotationt =
with si = s% =
\\)-> It ^
\342\200\224

1\302\276(-5)).)-
The constants Cs,n^m2m ar? called Clebsch-Gotdan coefficients. A few

of the simplest cases are listed in Table 4.8.42For example, shaded column the of
the 2x1 table tells us that

|30}
= -L|2 1)|1 -1) + |20)|10}
y\302\247
+
-^|2- 1)|11).

In particular,if two
particles (of spin 2 and spin 1) are at rest in a box, and the total

spin is 3, and its z component of

is 0, then a measurement S%
could return the
value h (with probability 1/5), or 0 (with probability 3/5), or \342\200\224h
(with probability

I say spins, for simplicity, but either one (or both) could just as Well be orbital angular
momentum (for which, however, we would use the letter I).
41For a must look in a more advanced instance, ClaudeCohen-Tannoudji,
text; see, for
proof you
Bernard Diu, and Franck Laloe,: Quantum Mechanics, (Wiley, York, 1977), Vol. 2, Chapter X.
New

The generalformula is derived in Arno Bohm, Quantum Mechanics: Foundations and

Applications, 2nd ed., (Springer, 1986), p. 172.
18:8 Chapter 4 Quantum Mechanics,in ThreeDimensions

TABLE 4.8: Clebsch-Gordan coefficients. (A square root sign is understoodfor

every entry; the minus sign, if present, goes outside the radical.)

1/5).Notice that the probabilities add up to 1 (the sum of the squaresof any column

on \"the Clebsch-Gordan table is 1).

These tables also work the other way around:

\\si Ml)\\s2m1)
= V C%$ \\sm)^ [4.186]

For example,the shaded row in the 3/2 x I table tells us that

itlUirv,- ft\\il\\+ /X|3I\\ /I|1I\\

If you put particles of spin 3/2 and

spin
1 in the box, and you know that the
first has mi = 1/2 and the second has mi
\342\200\224
Q (so m is necessarily 1/2), and
you measure the total spin,5, you
could get 5/2 (with probability 3/5), or 3/2
(with probability 1/15), or 1/2 (with probability 1/3). Again, the sum of the
probabilities is 1 (the sum of the squares of each row on the Clebsch-Gordan table
is 1).
If you think this is startingto like sound mystical numerology, I don't blame
you. We will not be the Clebsch-Gordan Using tables much in the rest of the
book, but I wanted you to know where they fit into the scheme of things, in case
sense
you encounter them later oil.In a mathematical this is all applied group
theory\342\200\224what
we are talking about is the decomposition of the direct productof
 Section 4.4: Spin 189

two irreducible representations of the rotationgroupintoa direct sum of irreducible

representations (you can quote that, to impressyour friends).

^Problem 4.34

(a) Apply S_ to 110) (Equation4-177), and confirm that you get V2h\\l -1).
(b) Apply S\302\261 to )00} (Equation 4.178), and confirm that you get zero,

(c) Show that

|11) and 11 -1) (Equation 4.177) are eigenstatesof S2,.with the

appropriate eigenvalue.

Problem Quarks carry spin 1/2.Three

4.35 quarks
bind together to make a baryon
(such as the proton or neutron); quarks (or two more precisely a quark and an
antiquark) bind t
together o a meson (such make
pion or the kaoh). Assume
as the
the quarksare in the ground state (so the orbital angular momentum is zero).

(a) What spins are possible for baryons?

(b) What spins are possiblefor mesons?

Problem 4.36

(a) A particle of spin 1 and a particle of spin 2 are at rest in a configuration

such that the total spinis 3, its z and
component is h. If you measured the
z componentof the momentum angular
of the spin-2 particle, what values
might you get, and is the probability what of each one?

(b) An electron with down

spin
is in the state ^510 of the hydrogenatom.If you

could measure the total angular momentum squared of the electronalone

{not including the proton spin), what values might you get, and what is: the

probability of each?

Problem 4.37 Determine the commutatorof S2 with s|1} (where S = S<1}+ S(2)).
Generalize your result to show that

[S2, S{1)] = 2ifc(S(1)x S(2)). [4.187]

Comment; Because S% does not commute cannothopeto
with S2,, we find states

that are simultaneous eigenvectors of of 52

both. In order to form eigenstates we
190 Chapter 4 Quantum Mechanics in Three Dimensions

need linearcombinations of of eigenstates 5\302\276

. This is precisely Clebsch-
what the
Gordan coefficients(in Equation4..185)do for us. On the other hand, it follows by

obvious inference from Equation4.187 that the sum S^ +SC9- does commute with
S2, which is a specialcase something we of already knew (see Equation 4.103).

FURTHER PROBLEMS FOR CHAPTER4

*Problem 4.38 Consider the three-dimensional harmonic oscillator, for which

the potentialis
Vir) = -mco2r2. [4.188]

(a) Show that separation of variables in cartesiancoordinatesturns this into

three one-dimensional Oscillators, and exploit your knowledge of the latter

to determine the allowed energies. Answer:

EA = (n+3/2)h(D. [4.189]

(b) Determine the degeneracyd(n) of En-

* * ^Problem 4.39 Because the three-dimensional harmonic oscillatorpotential

(Equation 4.188) is spherically symmetric, the Schrodinger equation can be handledby
separation of variables in spherical coordinates, as well as cartesiancoordinates.
Use the
power series method to solve the radial equation. Find the recursionformula
forthe coefficients, and determine the allowed energies. Check your answer against
Equation 4.189.

**Problem4.40
(a) Prove the three-dimensional vi'rial theorem:

2{T) = (t*VV) [4.190]

(for stationary states). Hint: Refer to Problem 3.31,

(b) Apply the virial theoremto thecaseof hydrogen, and show that

(T) = -En; (F)=2EW. [4.191]

 Further Problems for Chapter 4 191

(e) Apply the virial theoremto the three-dimensional harmonic oscillator

(Problem 4.38), and show that in this ease

(T) = (V)
=
En/2. [4.192]

* ^Problem
\342\226\240*\342\226\240\342\226\2404.41 [Attempt this problem only if you are familiar with vector

calculus.] Define the (three-dimensional) probability current by generalization of

Problem 1.14:
J=~
2m
(vl/
vm* - W*
W) . [4.193]

(a) Show that J satisfies the continuityequation

V-J = -|-|*|2, at
[4.194]

which expresses local conservation of probability. It follows (from the

theorem)
divergence that

f J~d* = ~ [ |*f d3r, [4.1.95]

Js (it Jy

where V is a (fixed) volume and S is itsboundary surface. In words: The flow

of probability out through the surfaceis equalto the decrease in probability
of finding the particle in the volume.

(b) FindJ for hydrogen in the state n-:= 2, I \342\200\224 m

1,
\342\200\224
1..Answer:

h
:re-r/asm0$.

(c) If we interpret mj as the flow of mass, the angular momentum is

L = m / (r x J) d?r.

Use this to calculate Lz for the state #2.11, and commentonthe result.

* *. ^Problem 4.42 The (time independent) momentum space wave function in three

dimensions is defined by the natural generalization of Equation 3.54:

^(P) \" [4.196]

Tldm Ie\"i<Pf)/S*W<?*\342\226\240
192 Chapter 4 Quantum Mechanics in ThreeDimensions

(a) Findthe momentum space wave function for the ground state of hydrogen
(Equation4.80).Hint: Use spherical coordinates, setting the polar axis along
the direction of p. Do the 0
integral first. Answer:

1 / o \\ 3/2 1

**) = [4197]
;f(t) [i + iaP,nn-

(b) Check that

0(p) is normalized.

(c) Use 0(p) to calculate (p2), in the ground state of hydrogen.

(d) What is the expectation value of the kineticenergy in this state? Express
your answer as a multiple of Ei, and check that it is consistent with the
virial theorem (Equation4.191).

Problem4.43
(VO for hydrogen in the state n
\342\200\224
(a) Construct the spatial wave function 3,

I = 2, m \342\200\224
1. Express your answer as a function of r, 0, </>, and a (the
Bohr radius) only\342\200\224no
other variables (p, z, etc.) or functions (Y, v, etc.), or

constants (A, cq, etc.), or derivatives, allowed {n is okay, and e, and 2, etc.).

(b) Check that this wave function is properly normalized, by carrying out the
appropriateintegrals over r, 0, and \302\242.

(c)
Find the expectation value of rs in this state. For what range of s (positive
and negative) is the result finite?

Problem4.44
for hydrogen in the state = 3, m = 3.
\342\200\224
(a) Construct the wave function n 4,-. /

Express your answer as a functionof the spherical coordinates r, 6.., and <fi.

(b) Find the expectation value of r in this state.(As always, look up any nontrivial
integrals.)

(c) If you could somehow measure the observableL2 + L2, on an atom in this
state, what value (or values) could you get, and what is the probabilityof
each?

Problem 4.45 What is the probability that an electron in the groundstateof

hydrogen
will be found inside the nucleus?

(a) First calculatethe exact answer, assuming the wave function (Equation 4,80)
is correct all the way
down to r = 0. Let b be the radiusof the nucleus.
 Further Problems for Chapter 4 193

(b) Expand your result as a powerseries in the small number e = 2b/d, and
show that the lowest-order term is the cubic: P \302\253*
(4/3)(fr/a)3. This should
be a suitable approximation, provided that h <^a (which it is).

(c) Alternatively, we might assume that ^.(r) is essentially constant over the
(tiny) volume of the nucleus,so that P -\302\276
(4/3)nb3\\f(0)\\^. Check that you
get the same answer this way.

(d) Use b ^ 10-15 m and a ~ 0.5x 10_10m to

get a numerical estimate for P.
Roughly speaking, this representsthe \"fraction of its time that the electron
spends inside the nucleus.\"

Problem4.46
(a) Use the recursion formula (Equation 4.76) to confirm that when I n \342\200\224
\342\200\224 1

the radial wave function takes the form

p ,
^n(f?-i)
, _ a!
\342\200\224 vn\342\200\224^0\342\200\224rjna
Nnr e ,

and determine the normalization constant Nn by

direct integration.

'(b) Calculate (r) and (r2) for states of the form

ifn{n-\\)m-

(c) Show that the \"uncertainty\" in r (oy) is (r)l\\/2n + 1 for such states. Note
that the fractional spread in r decreases, with increasing n (in this sensethe
system\"begins to; look classical,\" with identifiable circular \"orbits,\" for large
n). Sketchtheradial wave functions for several values of n, to illustrate this
point.

Problem4.47 Coincident spectral lines.43 According to the Rydberg formula

(Equation 4.93) the wavelength
of a line in the hydrogen spectrum is determined
by
the
principal quantum numbers of the initial and final states.Find distinct two

pairs {n,,n/} that yield the same X. For example, {6851, 6409} and {15283, 11687}
will do it, but you're not allowed to use those!

Problem 4.48 Consider the observables A = x2 and B = Lz.

(a) Construct the uncertainty principle for <jaGb-

'(b) Evaluate <jb in the hydrogen state \\//nim.

(c) What can you conclude about (xy) in this state?

4^ISfichplas Wheeler, \"Coincident Spectral Lines\" (unpublished Reed Collegereport, 20Q1).

Chapter 4 Quantum Mechanics in Three Dimensions

Problem 4.49 An electron is in the spin state

(a) Determine the constantA by normalizing x-

(b) If you measured Sz on this electron, values what could you get, and what is
the probabilityof each? is the expectation What value of S^?

(c) If you measured S'x: on this; electron, what values could you get, and what is

the probability of each? expectation value of

What is the Sx-?

(d) If you measured Sy on this electron, what values could you get, and what is
the probability of each? What is the expectationvalue of Sy?

* * ^Problem 4.50 Suppose two spin-1/2 particles areknown to be inthe singlet

configuration (Equation 4.178). Let .\302\276 be the component of the spin angular momentum
of particlenumber 1 in the direction defined by the unit vector a. Similarly, let
angular momentum in the directionb. Show
\342\226\240
$1 be the component of 2's that

= [4.198]
(S^sf)
-jcosB,

where 8 is the angle

between a and b.

* * ^Problem 4.51
coefficients
(a) Work out the Clebsch-Gofdari for the case s\\ = 1/2, \342\200\224
.\302\276

anything. Hint; You're looking for the coefficients A and B in

Is m) - A\\\\ 1)1\302\276 (m
-
i)> + B\\\302\261 (-^))1\302\276 (m + |)),

such that \\sm)

is an eigenstate of S2. Use the method; of Equations4.179
(2)
through 4.182. If you can't figure out what 5\302\243 (for instance) does to ma),
1\302\276

refer back to Equation 4.136 and the line before Equation 4.147. Answer:

2*2 + l V
2^2+1

where the signs are determined by =

S2
s\342\226\240 i 1/2.
(b) Check this generalresult against three or four entries in Table 4.8.
 Further Problemsfor Chapter4 195

Problem 4.52 Find the matrix representing Sx for a particleof spin3/2 (using, as

always, the basis of eigenstates of S^),

Solve the characteristic equation to determine
the eigenvalues of S*.

* * ^Problem 4.53 Work out the spin matrices for arbitrary spin s, generalizing spin 1/2
(Equations 4.145 and 4.147), spin 1 (Problem
4,31), and
spin 3/2 (Problem 4.52).
Answer:

*s 0 0 0\\
0 s --1 0 0
S,= h 0 0 s-2 0

^ 0 0 ~s)
/0 hs 0 0 0 0 \\

h 0 ^-1 0 0 0
0 bS-\\ 0 bs-2 o 0
h 0
,or \342\200\224
\342\200\224
0 ^-2 0 0 0
2 ; fc .
\342\226\240I T '. '. I I
0 0 0 0 0
b~s+i
\\o
0 0 0 b-s+i o )
/0 -ihs 0 0 w . .
0 0 \\

ibs 0 -ih -1 0 0 0
0 ibs~] 0 -th -2 0
\342\200\242\342\200\242\342\200\242
0

S, =
H
0 0 ibs~ 2 0 0 0
2 \342\200\242 \342\226\240 \342\200\242 \342\200\242\342\226\240
;\342\226\240 ;

0 0 0 0 . . . 0 -ik-s+i
0 0 0 i-fe-j+1 0
W

where
= + ,/)Cy+l-7)
bj V^

*. * ^Problem 4.54 Work out the normalization factor for the spherical harmonics, as
follows. From Section 4.1.2 we know that

=
Yff B?t?m*PFiGQs6y,

the problem is to determine the factor (which B\\n

I quoted^ but did not derive,
in Equation 4.32). Use Equations4.120,4.121, and 4.130 to obtain a recursion
196 Chapter 4 Quantum Mechanicsin ThreeDimensions

relation giving B^
in terms of
*Z?zm.
Solve it by induction on m to get B\342\204\242
up to

an overall constant,CQ). Finally, use the resultof Problem4.22 fix the constant. to

You may find the following formula for the derivativeof an associated Legendre

function useful:

dPm
- x1) \342\200\224l- = - [4.199]
(1
dx Vl-x2^1 l mxP'r.

Problem 4.55 The electron in a hydrogen atom occupiesthe combined

spin
and

position state

R2l
(7i/3 3fx+ + VV3YU-) \342\226\240

(a) If you measured the orbital angular momentum squared (L2), what values

might you get, and what is the probabilityof each?

(b) Same for the z component of orbital angular momentum (Lz).

(c) Same for the spin angular momentum squared (S2).

(d) Same for the z componentof spin angular momentum (\302\276).

Let J L
\342\226\240= + S be the total angular momentum.
(e) If you
measured J2, what values might you get, and what is the probability
of each?

(f) Same for Jz.

(g) If you
measured the position of the particle, what is the probabilitydensity
for
finding
it at r, &, (p?

(h) If you measured boththe z component of thespin and the distance from the
origin (note that these are compatibleobservables), what is the probability
density for finding the particle with spin up and at radius r?

* ^Problem
*\342\226\240 4.56

(a) For a function that

/\342\226\240(#') can be expanded in a Taylor series, show that

(where tp is an arbitrary angle). For this reason, Lz/h is calledthe

generator of rotations about the 2-axis, Hint: Use Equation 4.129, and refer to
Problem3.39.
 Further Problems for Chapter 4 197

More generally, L \342\226\240

h/h is the generator of rotations about the directionn, in
\342\200\242
the sense that exp(zL n<p/h) effects a rotation through angle <p (in the right-
hand sense) about the axis ft. In the caseof spin, the generator of rotations
is S \342\200\242
h/h. In particular, for spin 1/2

X, = ei\302\253x^2x [4-200]

tells us how spinors rotate.

(b) Construct the (2 x 2) representing matrix rotation by 180\302\260 about the jc-axis,
and show that it converts \"spin up\" (x+) into \"spin down\" ^s
(x\342\200\224)\302\273 y\302\260u

would expect.

(c) Construct the matrix representing rotation by 90Qaboutthe y-axis, and check

what it does to x+.

(d) Construct the matrix representing rotation by ,360\302\260 about the z-axis. If the
answer is not quite what you expected, discuss its implications.

(e) Show that

ei(a-h)<p/2 =. + i(b \342\200\242
[4.201]
Gos^/2) ff) sin(<p/2).

**Problem4.57 The fundamental commutation relations for angular momentum

(Equation4.99) allow
half-integer for (as well as integer) eigenvalues. But for
orbital angular momentumonly the integervaluesoccur. must There he some
extra constraint in the specific form L - f x p half-integer that excludes values.44

Let a be some convenient constant with the dimensions of length (the Bohr radius,
say, if we're talking about hydrogen), and define the operators

Pi = -
-L
=\342\226\240
q\\ + ;
-\302\276[px (fi/a^y] ;
[* (a2/H)py]

12 s 7!
~ =
[px. + (hia2)y\\ \342\226\240
[x (a2(hyPy\\
r P2
7i

(a) Verify that [qi,qz\\ = [pi, Pi\\ = 0; [q\\}p\\\\

=
[qo, P2~] = ih. Thus the
q's andthe p's satisfy
the canonical commutation relations for position and
momentum, and those of index1 are compatible with those of index 2.

(b) Show that

h \342\226\240
2 -2.,
fl2
=
L* ^t-\342\202\254)+ ^(/>i-H)-

This problem is based on an argument in Ballenline (footnote 26), page 127.

198 Chapter 4 Quantum Mechanics in ThreeDimensions

(c) Check that Lz

= Hi
\342\200\224
H2, where each H is the Hamiltonian for a harmonic
oscillator with mass m \342\200\224
h/a2 and frequency ,co \342\200\224
1.

(d) We know that of the harmonicoscillatorHamiltonian

the eigenvalues are
(n + where
\\/2)hcd,
n 0, 1, 2,... (In the algebraictheory of Section2.3.1
\342\200\224

thisfollows from the. form of the Hamiltonian anci the canonicalcommutation

relations). this to conclude that the eigenvalues of Lz must be integers.
Use

Problem4.58 Deduce the condition for minimum uncertainty in Sx and Sy (that

is, equality in the expression osr(7sy ~>

(h/2)\\{Sz)\\), for a particle of spin 1/2 in
the genericstate (Equation 4.139). Answer: With nO loss of generality we can pick
a to be real; then the condition for minimum uncertainty is that b is either pure
real orelse pure imaginary.

* * ^Problem 4.59 In elassical electrodynamics the force on a particle of

charge q

moving with velocity v through electric and magneticfieldsE and B is given by

the Lorentz force law:
F= <7(E + vxBj. [4.202]

This force cannot be expressedasthe gradientofa scalar potential energy function,

and therefore the Schrodinger equation in its originalform (Equation 1.1)cannot
accommodate it. But in the more sophisticated form

[4.203]
dt
thereis no
problem; the classical Hamiltonian45 is

1
H = --(p
- qAY + 9
q<pt [4.204]
2m

where A is the vector potential (B \342\200\224

V x A.) and <p is the scalar potential (E =
\342\200\224
\342\200\224V<p dA/ftt), so the Schrodinger equation (making the canonical substitution
p -> (h/i) V) becomes

[4.205]

45.
See, for example,H. Goldstein, C. P. Poole, and J. L. Safko, ClassicalMechanics, 3rd ed.,
(Prentice Hall, Upper Saddle River, Nj, 2002), page 342.
 Further Problems for Chapter 4 199

(a) Showthat
~^ = -<(p-?A)}. [4,206]
at m

(b) As always (see Equation 1.32) we identify d(r)fdt with

(v). Show that

m^P- at
= q(E) +
^- {(p xB-Bxp))-%x
2m- m
B)). [4.207]

(c) In particular, if the fields E and B are uniform over the volume of the wave
packet, show that

= q (E + (v) x B), [4.208]

at
m\342\200\224p-

sothe expectation value of (v) moves according to the Lorentz force law, as
we would expect from Ehrenfesf s theorem.

* * ^Problem 4.60 [Refer to Problem 4.59 for background.] Suppose

A: = - A and = Kz2,
-y(xJ cp

where Bq and K are constants.

(a) Find the fieldsE and B.

(b) Find the allowed energies^ for a particleof mass m and charge q, in these
fields. Answer:

E(nu n2) = (\302\253i+ j)hm + (/\302\276+ j)hm, (m, n2 = 0, 1, 2, ...), [4.209]

\342\200\224
where ca\\ = and = Comment: If K' 0 this is the
qBo/m <\302\2732 \342\226\240s/lgKjm..

quantum analog to cyclotron motion; xd\\ is the classical cyclotron frequency,

and it's a free particlein the z direction.The allowed energies, +
(\302\2531 \\)hco\\,
are called Landau Levels.46

^Problem
.\342\226\240* 4.61 [Refer to Problem 4.59 for background.]In classical
the
electrodynamics
potentials A and p are hot uniquely determined;47the physicalquantities
are the fields, E and B.

46For further discussion see Ballentine (footnote 26) Section 11.3.

47See, for example, Griffiths (footnole 30) Section 10.1.2,
200 Chapter 4 Quantum Mechanicsin ThreeDimensions

(a) Show that the potentials

9A
=
\302\242/ 0-.-, A' = A + VA [4.210]
at

(where A is an arbitrary real functionof position and time) yield the same
fields as tp and A. Equation 4.210 is called a. gauge transformation, and the
theory is saidto be gauge invariant..

(b) In quantum mechanics the potentials play a more directrole, and it is of

interest to know whether the theory remains gaugeinvariant Show that

W'=e'>A/% [4.211]

satisfies the Schrodinger equation (4.205) the gauge-transformed with

potentials cp' and A'. Since from ^

M*' differs
only a phase factor, by
it represents
the same physical state,48 and the theory is gauge invariant (see Section

10.2.3 for further discussion).

48That is to say, (r)* d(r)/dt, etc. are unchanged. BecauseA depends on position, (p) (with p

represented by the operator (ft/i)V) does change, but as we found in Equation 4.206, p does not
represent the mechanical momentum (mv) in this context (in lagrangian mechanics it is so-called
canonical momentum).