Physics - Quantum Mechanics For Undergraduates

QUANTUM MECHANICS
Professor John W. Norbury

Physics Department
University of Wisconsin-Milwaukee
P.O. Box 413
Milwaukee, WI 53201
November 20, 2000

Contents
1 WAVE FUNCTION 7
1.1 Probability Theory . . . . . . . . . . . . . . . . . . . . . . . . 8
1.1.1 Mean, Average, Expectation Value . . . . . . . . . . . 8
1.1.2 Average of a Function . . . . . . . . . . . . . . . . . . 10
1.1.3 Mean, Median, Mode . . . . . . . . . . . . . . . . . . 10
1.1.4 Standard Deviation and Uncertainty . . . . . . . . . . 11
1.1.5 Probability Density . . . . . . . . . . . . . . . . . . . 14
1.2 Postulates of Quantum Mechanics . . . . . . . . . . . . . . . 14
1.3 Conservation of Probability (Continuity Equation) . . . . . . 19
1.3.1 Conservation of Charge . . . . . . . . . . . . . . . . . 19
1.3.2 Conservation of Probability . . . . . . . . . . . . . . . 22
1.4 Interpretation of the Wave Function . . . . . . . . . . . . . . 23
1.5 Expectation Value in Quantum Mechanics . . . . . . . . . . . 24
1.6 Operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1.7 Commutation Relations . . . . . . . . . . . . . . . . . . . . . 27
1.8 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
1.9 Answers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2 DIFFERENTIAL EQUATIONS 35
2.1 Ordinary Differential Equations . . . . . . . . . . . . . . . . . 35
2.1.1 Second Order, Homogeneous, Linear, Ordinary Differ-
ential Equations with Constant Coefficients . . . . . . 36
2.1.2 Inhomogeneous Equation . . . . . . . . . . . . . . . . 39
2.2 Partial Differential Equations . . . . . . . . . . . . . . . . . . 42
2.3 Properties of Separable Solutions . . . . . . . . . . . . . . . . 44
2.3.1 General Solutions . . . . . . . . . . . . . . . . . . . . . 44
2.3.2 Stationary States . . . . . . . . . . . . . . . . . . . . . 44
2.3.3 Definite Total Energy . . . . . . . . . . . . . . . . . . 45
1
2 CONTENTS
2.3.4 Alternating Parity . . . . . . . . . . . . . . . . . . . . 46

2.3.5 Nodes . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.3.6 Complete Orthonormal Sets of Functions . . . . . . . 46
2.3.7 Time-dependent Coefficients . . . . . . . . . . . . . . 49
2.4 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.5 Answers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3 INFINITE 1-DIMENSIONAL BOX 53

3.1 Energy Levels . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
3.2 Wave Function . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.3 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3.4 Answers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
4 POSTULATES OF QUANTUM MECHANICS 65

4.1 Mathematical Preliminaries . . . . . . . . . . . . . . . . . . . 65
4.1.1 Hermitian Operators . . . . . . . . . . . . . . . . . . . 65
4.1.2 Eigenvalue Equations . . . . . . . . . . . . . . . . . . 66
4.2 Postulate 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
4.3 Expansion Postulate . . . . . . . . . . . . . . . . . . . . . . . 68
4.4 Measurement Postulate . . . . . . . . . . . . . . . . . . . . . 69
4.5 Reduction Postulate . . . . . . . . . . . . . . . . . . . . . . . 70
4.6 Summary of Postulates of Quantum Mechanics (Simple Version) 71
4.7 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
4.8 Answers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
I 1-DIMENSIONAL PROBLEMS 77
5 Bound States 79
5.1 Boundary Conditions . . . . . . . . . . . . . . . . . . . . . . . 80
5.2 Finite 1-dimensional Well . . . . . . . . . . . . . . . . . . . . 81
5.2.1 Regions I and III With Real Wave Number . . . . . . 82
5.2.2 Region II . . . . . . . . . . . . . . . . . . . . . . . . . 83
5.2.3 Matching Boundary Conditions . . . . . . . . . . . . . 84
5.2.4 Energy Levels . . . . . . . . . . . . . . . . . . . . . . . 87
5.2.5 Strong and Weak Potentials . . . . . . . . . . . . . . . 88
5.3 Power Series Solution of ODEs . . . . . . . . . . . . . . . . . 89
5.3.1 Use of Recurrence Relation . . . . . . . . . . . . . . . 91
5.4 Harmonic Oscillator . . . . . . . . . . . . . . . . . . . . . . . 92
CONTENTS 3
5.5 Algebraic Solution for Harmonic Oscillator . . . . . . . . . . 100

5.5.1 Further Algebraic Results for Harmonic Oscillator . . 108
6 SCATTERING STATES 113

6.1 Free Particle . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
6.1.1 Group Velocity and Phase Velocity . . . . . . . . . . . 117
6.2 Transmission and Reflection . . . . . . . . . . . . . . . . . . . 119
6.2.1 Alternative Approach . . . . . . . . . . . . . . . . . . 120
6.3 Step Potential . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
6.4 Finite Potential Barrier . . . . . . . . . . . . . . . . . . . . . 124
6.5 Quantum Description of a Colliding Particle . . . . . . . . . . 126
6.5.1 Expansion Coefficients . . . . . . . . . . . . . . . . . . 128
6.5.2 Time Dependence . . . . . . . . . . . . . . . . . . . . 129
6.5.3 Moving Particle . . . . . . . . . . . . . . . . . . . . . . 130
6.5.4 Wave Packet Uncertainty . . . . . . . . . . . . . . . . 131
7 FEW-BODY BOUND STATE PROBLEM 133

7.1 2-Body Problem . . . . . . . . . . . . . . . . . . . . . . . . . 133
7.1.1 Classical 2-Body Problem . . . . . . . . . . . . . . . . 134
7.1.2 Quantum 2-Body Problem . . . . . . . . . . . . . . . . 137
7.2 3-Body Problem . . . . . . . . . . . . . . . . . . . . . . . . . 139
II 3-DIMENSIONAL PROBLEMS 141
8 3-DIMENSIONAL SCHRÖDINGER EQUATION 143

8.1 Angular Equations . . . . . . . . . . . . . . . . . . . . . . . . 144
8.2 Radial Equation . . . . . . . . . . . . . . . . . . . . . . . . . 147
8.3 Bessel’s Differential Equation . . . . . . . . . . . . . . . . . . 148
8.3.1 Hankel Functions . . . . . . . . . . . . . . . . . . . . . 150
9 HYDROGEN-LIKE ATOMS 153

9.1 Laguerre Associated Differential Equation . . . . . . . . . . . 153
9.2 Degeneracy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
10 ANGULAR MOMENTUM 159

10.1 Orbital Angular Momentum . . . . . . . . . . . . . . . . . . . 159
10.1.1 Uncertainty Principle . . . . . . . . . . . . . . . . . . 162
10.2 Zeeman Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
10.3 Algebraic Method . . . . . . . . . . . . . . . . . . . . . . . . . 164
4 CONTENTS
10.4 Spin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165

10.4.1 Spin 12 . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
10.4.2 Spin-Orbit Coupling . . . . . . . . . . . . . . . . . . . 167
10.5 Addition of Angular Momentum . . . . . . . . . . . . . . . . 169
10.5.1 Wave Functions for Singlet and Triplet Spin States . . 171
10.5.2 Clebsch-Gordon Coefficients . . . . . . . . . . . . . . . 172
10.6 Total Angular Momentum . . . . . . . . . . . . . . . . . . . . 172
10.6.1 LS and jj Coupling . . . . . . . . . . . . . . . . . . . 173
11 SHELL MODELS 177

11.1 Atomic Shell Model . . . . . . . . . . . . . . . . . . . . . . . 177
11.1.1 Degenerate Shell Model . . . . . . . . . . . . . . . . . 177
11.1.2 Non-Degenerate Shell Model . . . . . . . . . . . . . . 178
11.1.3 Non-Degenerate Model with Surface Effects . . . . . . 178
11.1.4 Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . 179
11.2 Hartree-Fock Self Consistent Field Method . . . . . . . . . . 180
11.3 Nuclear Shell Model . . . . . . . . . . . . . . . . . . . . . . . 181
11.3.1 Nuclear Spin . . . . . . . . . . . . . . . . . . . . . . . 181
11.4 Quark Shell Model . . . . . . . . . . . . . . . . . . . . . . . . 182
12 DIRAC NOTATION 183

12.1 Finite Vector Spaces . . . . . . . . . . . . . . . . . . . . . . . 183
12.1.1 Real Vector Space . . . . . . . . . . . . . . . . . . . . 183
12.1.2 Complex Vector Space . . . . . . . . . . . . . . . . . . 185
12.1.3 Matrix Representation of Vectors . . . . . . . . . . . . 188
12.1.4 One-Forms . . . . . . . . . . . . . . . . . . . . . . . . 188
12.2 Infinite Vector Spaces . . . . . . . . . . . . . . . . . . . . . . 189
12.3 Operators and Matrices . . . . . . . . . . . . . . . . . . . . . 191
12.3.1 Matrix Elements . . . . . . . . . . . . . . . . . . . . . 191
12.3.2 Hermitian Conjugate . . . . . . . . . . . . . . . . . . . 194
12.3.3 Hermitian Operators . . . . . . . . . . . . . . . . . . . 195
12.3.4 Expectation Values and Transition Amplitudes . . . . 197
12.4 Postulates of Quantum Mechanics (Fancy Version) . . . . . . 198
12.5 Uncertainty Principle . . . . . . . . . . . . . . . . . . . . . . . 198
13 TIME-INDEPENDENT PERTURBATION THEORY, HY-

DROGEN ATOM, POSITRONIUM, STRUCTURE OF HADRONS201
13.1 Non-degenerate Perturbation Theory . . . . . . . . . . . . . . 204
13.2 Degenerate Perturbation Theory . . . . . . . . . . . . . . . . 208
CONTENTS 5
13.2.1 Two-fold Degeneracy . . . . . . . . . . . . . . . . . . . 209

13.2.2 Another Approach . . . . . . . . . . . . . . . . . . . . 211
13.2.3 Higher Order Degeneracies . . . . . . . . . . . . . . . 212
13.3 Fine Structure of Hydrogen . . . . . . . . . . . . . . . . . . . 212
13.3.1 1-Body Relativistic Correction . . . . . . . . . . . . . 212
13.3.2 Two-Body Relativistic Correction . . . . . . . . . . . 216
13.3.3 Spin-Orbit Coupling . . . . . . . . . . . . . . . . . . . 217
13.4 Zeeman effect . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
13.5 Stark effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
13.6 Hyperfine splitting . . . . . . . . . . . . . . . . . . . . . . . . 221
13.7 Lamb shift . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
13.8 Positronium and Muonium . . . . . . . . . . . . . . . . . . . 221
13.9 Quark Model of Hadrons . . . . . . . . . . . . . . . . . . . . . 221
14 VARIATIONAL PRINCIPLE, HELIUM ATOM, MOLECULES223

14.1 Variational Principle . . . . . . . . . . . . . . . . . . . . . . . 223
14.2 Helium Atom . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
14.3 Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
15 WKB APPROXIMATION, NUCLEAR ALPHA DECAY 225

15.1 Generalized Wave Functions . . . . . . . . . . . . . . . . . . . 225
15.2 Finite Potential Barrier . . . . . . . . . . . . . . . . . . . . . 230
15.3 Gamow’s Theory of Alpha Decay . . . . . . . . . . . . . . . . 231
16 TIME-DEPENDENT PERTURBATION THEORY, LASERS235

16.1 Equivalent Schrödinger Equation . . . . . . . . . . . . . . . . 236
16.2 Dyson Equation . . . . . . . . . . . . . . . . . . . . . . . . . . 240
16.3 Constant Perturbation . . . . . . . . . . . . . . . . . . . . . . 241
16.4 Harmonic Perturbation . . . . . . . . . . . . . . . . . . . . . . 244
16.5 Photon Absorption . . . . . . . . . . . . . . . . . . . . . . . . 247
16.5.1 Radiation Bath . . . . . . . . . . . . . . . . . . . . . . 247
16.6 Photon Emission . . . . . . . . . . . . . . . . . . . . . . . . . 249
16.7 Selection Rules . . . . . . . . . . . . . . . . . . . . . . . . . . 249
16.8 Lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
17 SCATTERING, NUCLEAR REACTIONS 251

17.1 Cross Section . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
17.2 Scattering Amplitude . . . . . . . . . . . . . . . . . . . . . . . 252
17.2.1 Calculation of cl . . . . . . . . . . . . . . . . . . . . . 255
6 CONTENTS
17.3 Phase Shift . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257

17.4 Integral Scattering Theory . . . . . . . . . . . . . . . . . . . . 259
17.4.1 Lippman-Schwinger Equation . . . . . . . . . . . . . . 259
17.4.2 Scattering Amplitude . . . . . . . . . . . . . . . . . . 261
17.4.3 Born Approximation . . . . . . . . . . . . . . . . . . . 262
17.5 Nuclear Reactions . . . . . . . . . . . . . . . . . . . . . . . . 264
18 SOLIDS AND QUANTUM STATISTICS 265

18.1 Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
18.2 Quantum Statistics . . . . . . . . . . . . . . . . . . . . . . . . 265
19 SUPERCONDUCTIVITY 267
20 ELEMENTARY PARTICLES 269
21 chapter 1 problems 271

21.1 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
21.2 Answers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
21.3 Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273

22.1 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
22.2 Answers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
22.3 Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283

23.1 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
23.2 Answers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
23.3 Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289

24.1 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
24.2 Answers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
24.3 Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
Chapter 1
WAVE FUNCTION
Quantum Mechanics is such a radical and revolutionary physical theory that

nowadays physics is divided into two main parts, namely Classical Physics
versus Quantum Physics. Classical physics consists of any theory which
does not incorporate quantum mechanics. Examples of classical theories are
Newtonian mechanics (F = ma), classical electrodynamics (Maxwell’s equa-
tions), fluid dynamics (Navier-Stokes equation), Special Relativity, General
Relativity, etc. Yes, that’s right; Einstein’s theories of special and general
relativity are regarded as classical theories because they don’t incorporate
quantum mechanics. Classical physics is still an active area of research today
and incorporates such topics as chaos [Gleick 1987] and turbulence in fluids.
Physicists have succeeded in incorporating quantum mechanics into many
classical theories and so we now have Quantum Electrodynamics (combi-
nation of classical electrodynamics and quantum mechanics) and Quantum
Field Theory (combination of special relativity and quantum mechanics)
which are both quantum theories. (Unfortunately no one has yet succeeded
in combining general relativity with quantum mechanics.)
I am assuming that everyone has already taken a course in Modern
Physics. (Some excellent textbooks are [Tipler 1992, Beiser 1987].) In
such a course you will have studied such phenomena as black-body radi-
ation, atomic spectroscopy, the photoelectric effect, the Compton effect, the
Davisson-Germer experiment, and tunnelling phenomena all of which cannot
be explained in the framework of classical physics. (For a review of these
topics see references [Tipler 1992, Beiser 1987] and chapter 40 of Serway
[Serway 1990] and chapter 1 of Gasiorowicz [Gasiorowicz 1996] and chapter
2 of Liboff [Liboff 1992].)
7
8 CHAPTER 1. WAVE FUNCTION
The most dramatic feature of quantum mechanics is that it is a proba-

bilistic theory. We shall explore this in much more detail later, however to
get started we should review some of the basics of probability theory.
1.1 Probability Theory

(This section follows the discussion of Griffiths [Griffiths 1995].)
College instructors always have to turn in student grades at the end of
each semester. In order to compare the class of the Fall semester to the class
of the Spring semester one could stare at dozens of grades for awhile. It’s
much better though to average all the grades and compare the averages.
Suppose we have a class of 15 students who receive grades from 0 to 10.
Suppose 3 students get 10, 2 students get 9, 4 students get 8, 5 students get
7, and 1 student gets 5. Let’s write this as
N (15) = 0 N (10) = 3 N (4) = 0

N (14) = 0 N (9) = 2 N (3) = 0
N (13) = 0 N (8) = 4 N (2) = 0
N (12) = 0 N (7) = 5 N (1) = 0
N (11) = 0 N (6) = 0 N (0) = 0
N (5) = 1
where N (j) is the number of students receiving a grade of j. The histogram
of this distribution is drawn in Figure 1.1.
The total number of students, by the way, is given by
∞
X
N= N (j) (1.1)
j=0
1.1.1 Mean, Average, Expectation Value

We want to calculate the average grade which we denote by the symbol j̄ or
hji. The mean or average is given by the formula
1 X
j̄ ≡ hji = j (1.2)
N all
P
where j means add them all up separately as
all
1
hji = (10 + 10 + 10 + 9 + 9 + 8 + 8 + 8 + 8 + 7 + 7 + 7 + 7 + 7 + 7 + 5)
15
= 8.0 (1.3)
1.1. PROBABILITY THEORY 9
Thus the mean or average grade is 8.0.

Instead of writing many numbers over again in (1.3) we could write
1
j̄ = [(10 × 3) + (9 × 2) + (8 × 4) + (7 × 5) + (5 × 1)] (1.4)
15
This suggests re-writing the formula for average as
∞
1 X
hji ≡ j̄ = jN (j) (1.5)
N j=0
where N (j) = number of times the value j occurs. The reason we go from
0 to ∞ is because many of the N (j) are zero. Example N (3) = 0. No one
scored 3.
We can also write (1.4) as
µ ¶ µ ¶ µ ¶ µ ¶ µ ¶
3 2 4 5 1
j̄ = 10 × + 9× + 8× + 7× + 5× (1.6)
15 15 15 15 15
3
where for example 15 is the probability that a random student gets a grade
of 10. Defining the probability as
N (j)
P (j) ≡ (1.7)
N
we have ∞
X
hji ≡ j̄ = jP (j) (1.8)
j=0
Any of the formulas (1.2), (1.5) or (1.8) will serve equally well for calculating
the mean or average. However in quantum mechanics we will prefer using
the last one (1.8) in terms of probability.
³ Note that when talking ábout probabilities, they must all add up to 1
3 2 4 5 1
15 + 15 + 15 + 15 + 15 = 1 . That is
∞
X
P (j) = 1 (1.9)
j=0
Student grades are somewhat different to a series of actual measurements

which is what we are more concerned with in quantum mechanics. If a
bunch of students each go out and measure the length of a fence, then the
j in (1.1) will represent each measurement. Or if one person measures the
energy of an electron several times then the j in (1.1) represents each energy
measurement. (do Problem 1.1)
In quantum mechanics we use the word expectation value. It means
nothing more than the word average or mean. That is you have to make
a series of measurements to get it. Unfortunately, as Griffiths points out
[p.7, 15, Griffiths 1995] the name expectation value makes you think that
it is the value you expect after making only one measurement (i.e. most
probable value). This is not correct. Expectation value is the average of
single measurements made on a set of identically prepared systems. This is
how it is used in quantum mechanics.
1.1.2 Average of a Function

Suppose that instead of the average of the student grades, you wanted the
average of the square of the grades. That’s easy. It’s just
∞ ∞
1 X 2 1 X X
j̄ ≡ hj i =
2 2
j = 2
j N (j) = j 2 P (j) (1.10)
N all N j=0 j=0
Note that in general the average of the square is not the square of the average.
hj 2 i =
6 hji2 (1.11)
In general for any function f of j we have

∞
X
hf (j)i = f (j)P (j) (1.12)
j=0
1.1.3 Mean, Median, Mode

You can skip this section if you want to. Given that we have discussed the
mean, I just want to mention median and mode in case you happen to come
across them.
The median is simply the mid-point of the data. 50% of the data points
lie above the median and 50% lie below. The grades in our previous example
were 10, 10, 10, 9, 9, 8, 8, 8, 8, 7, 7, 7, 7, 7, 5. There are 15 data points,
so point number 8 is the mid-point which is a grade of 8. (If there are an
even number of data points, the median is obtained by averaging the middle
two data points.) The median is well suited to student grades. It tells you
exactly where the middle point lies.
The mode is simply the most frequently occurring data point. In our
grade example the mode is 7 because this occurs 5 times. (Sometimes data
will have points occurring with the same frequency. If this happens with 2
data points and they are widely separated we have what we call a bi-nodal
distribution.)
For a normal distribution the mean, median and mode will occur at the
same point, whereas for a skewed distribution they will occur at different
points.
(see Figure 1.2)
1.1.4 Standard Deviation and Uncertainty

Some distributions are more spread out than others. (See Fig. 1.5 of [Grif-
fiths 1995].) By “spread out” we mean that if one distribution is more spread
out than another then most of its points are further away from the average
than the other distribution. The “distance” of a particular point from the
average can be written
∆j ≡ j − hji (1.13)
But for points with a value less than the average this distance will be nega-
tive. Let’s get rid of the sign by talking about the squared distance
(∆j)2 ≡ (j − hji)2 (1.14)
Then it doesn’t matter if a point is larger or smaller than the average.

Points an equal distance away (whether larger or smaller) will have the
same squared distance.
Now let’s turn the notion of “spread out” into a concise mathematical
statement. If one distribution is more spread out than another then the
average distances of all points will be bigger than the other. But we don’t
want the average to be negative so let’s use squared distance. Thus if one
distribution is more spread out than another then the average squared dis-
tance of all the points will be bigger than the other. This average squared
distance will be our mathematical statement for how spread out a particular
distribution is.
The average squared distance is called the variance and is given the sym-
bol σ 2 . The square root of the variance, σ, is called the standard deviation.
The quantum mechanical word for standard deviation is uncertainty, and we
usually use the symbol ∆ to denote it. As with the word expectation value,
the word uncertainty is misleading, although these are the words found in
the literature of quantum mechanics. It’s much better (more precise) to use
the words average and standard deviation instead of expectation value
and uncertainty. Also it’s much better (more precise) to use the symbol σ
rather than ∆, otherwise we get confused with (1.13). (Nevertheless many
quantum mechanics books use expectation value, uncertainty and ∆.)
The average squared distance or variance is simple to define. It is
1 X
σ 2 ≡ h(∆j)2 i = (∆j)2
N all
1 X
= (j − hji)2
N all
∞
X
= (j − hji)2 P (j) (1.15)
j=0
Note: Some books use N 1−1 instead of N1 in (1.15). But if N 1−1 is used
then equation (1.16) won’t work out unless N 1−1 is used in the mean as
well. For large samples N 1−1 ≈ N1 . The use of N 1−1 comes from a data
set where only N − 1 data points are independent. (E.g. percentages of
people walking through 4 colored doors.) Suppose there are 10 people and
4 doors colored red, green, blue and white. If 2 people walk through the red
door and 3 people through green and 1 person through blue then we deduce
that 4 people must have walked through the white door. If we are making
measurements of people then this last data set is not a valid independent
measurement. However in quantum mechanics all of our measurements are
independent and so we use N1 .
Example 1.1.1 Using equation (1.15), calculate the variance for

the student grades discussed above.
Solution We find that the average grade was 8.0. Thus the
“distance” of each ∆j ≡ j − hji is ∆10 = 10 − 8 = +2, ∆9 = 1,
∆8 = 0, ∆7 = −1, ∆6 = −2, ∆5 = −3 and the squared distances
are (∆10)2 = 4, (∆9)2 = 1, (∆8)2 = 0, (∆7)2 = 1, (∆6)2 = 4,
(∆5)2 = 9. The average of these are
µ ¶ µ ¶ µ ¶
3 2 4
σ 2
= 4× + 1× + 0×
15 15 15
µ ¶ µ ¶
5 1
+ 1× + 9×
15 15
= 1.87
However this way of calculating the variance can be a pain in the neck
especially for large samples. Let’s find a simpler formula which will give us
the answer more quickly. Expand (1.15) as
X³ ´
σ2 = j 2 − 2jhji + hji2 P (j)
X X X
= j 2 P (j) − 2hji jP (j) + hji2 P (j)
where we take hji and hji2 outside the sum because they are just numbers
(hji = 8.0 and hji2 = 64.0 in above example) which have already been
P P
summed over. Now jP (j) = hji and P (j) = 1. Thus
σ 2 = hj 2 i − 2hji2 + hji2
giving
σ 2 = hj 2 i − hji2 (1.16)
Example 1.1.2 Repeat example 1.1.1 using equation (1.16).

Solution
1
hj 2 i = [(100 × 3) + (81 × 2) + (64 × 4) + (49 × 5) + (25 × 1)]
15
= 65.87
hji2 = 82 = 64
σ 2 = hj 2 i − hji2 = 65.87 − 64 = 1.87
in agreement with example 1.1.1. (do Problem 1.2)

1.1.5 Probability Density

In problems 1.1 and 1.2 we encountered an example where a continuous vari-
able (the length of a fence) rather than a discrete variable (integer values of
student grades) is used. A better method for dealing with continuous vari-
ables is to use probability densities rather than probabilities. The probability
that the value x lies between the values a and b is given by
Z b
Pab ≡ ρ(x)dx (1.17)
a
This equation defines the probability density ρ(x) The quantity ρ(x)dx is
thus the probability that a given value lies between x and x + dx. This Ris just
like the ordinary density ρ of water. The total mass of water is M = ρdV
where ρdV is the mass of water between volumes V and V + dV .
Our old discrete formulas get replaced with new continuous formulas, as
follows: Z
∞
X ∞
P (j) = 1 → ρ(x)dx = 1 (1.18)
j=0 −∞
∞
X Z ∞
hji = jP (j) → hxi = xρ(x)dx (1.19)
j=0 −∞
∞
X Z ∞
hf (j)i = f (j)P (j) → hf (x)i = f (x)ρ(x)dx (1.20)
j=0 −∞
∞
X Z ∞
σ 2 ≡ h(∆j)2 i = (j − hji)2 P (j) → σ 2 ≡ (∆x)2 = (x − hxi)2 ρ(x)dx
j=0 −∞
= hj 2 i − hji2 = hx2 i − hxi2
(1.21)
In discrete notation j is the measurement, but in continuous notation the
measured variable is x. (do Problem 1.3)
1.2 Postulates of Quantum Mechanics

Most physical theories are based on just a couple of fundamental equations.
For instance, Newtonian mechanics is based on F = ma, classical electrody-
namics is based on Maxwell’s equations and general relativity is based on the
Einstein equations Gµν = −8πG Tµν . When you take a course on Newtonian
1.2. POSTULATES OF QUANTUM MECHANICS 15
mechanics, all you ever do is solve F = ma. In a course on electromag-

netism you spend all your time just solving Maxwell’s equations. Thus these
fundamental equations are the theory. All the rest is just learning how to
solve these fundamental equations in a wide variety of circumstances. The
fundamental equation of quantum mechanics is the Schrödinger equation
h̄2 ∂ 2 Ψ ∂Ψ
− 2
+ U Ψ = ih̄
2m ∂x ∂t
which I have written for a single particle (of mass m) moving in a potential
U in one dimension x. (We will consider more particles and more dimensions
later.) The symbol Ψ, called the wave function, is a function of space and
time Ψ(x, t) which is why partial derivatives appear.
It’s important to understand that these fundamental equations cannot be
derived from anywhere else. They are physicists’ guesses (or to be fancy, pos-
tulates) as to how nature works. We check that the guesses (postulates) are
correct by comparing their predictions to experiment. Nevertheless, you will
often find “derivations” of the fundamental equations scattered throughout
physics books. This is OK. The authors are simply trying to provide deeper
understanding, but it is good to remember that these are not fundamental
derivations. Our good old equations like F = ma, Maxwell’s equations and
the Schrödinger equation are postulates and that’s that. Nothing more. They
are sort of like the definitions that mathematicians state at the beginning of
the proof of a theorem. They cannot be derived from anything else.
Quantum Mechanics is sufficiently complicated that the Schrödinger equa-
tion is not the only postulate. There are others (see inside cover of this book).
The wave function needs some postulates of its own simply to understand
it. The wave function Ψ is the fundamental quantity that we always wish to
calculate in quantum mechanics.
Actually all of the fundamental equations of physical theories usually
have a fundamental quantity that we wish to calculate given a fundamental
input. In Newtonian physics, F = ma is the fundamental equation and the
acceleration a is the fundamental quantity that we always want to know
given an input force F . The acceleration a is different for different forces
F . Once we have obtained the acceleration we can calculate lots of other
interesting goodies such as the velocity and the displacement as a function
of time. In classical electromagnetism the Maxwell equations are the funda-
mental equations and the fundamental quantities that we always want are
the electric (E) and magnetic (B) fields. These always depend on the funda-
mental input which is the charge (ρ) and current (j) distribution. Different
ρ and j produce different E and B. In general relativity, the fundamental

equations are the Einstein equations (Gµν = −8πGTµν ) and the fundamen-
tal quantity that we always want is the metric tensor gµν , which tells us how
spacetime is curved. (gµν is buried inside Gµν ). The fundamental input is
the energy-momentum tensor Tµν which describes the distribution of matter.
Different Tµν produces different gµν .
Similarly the fundamental equation of quantum mechanics is the Schro-
dinger equation and the fundamental input is the potential U . (This is
related to force via F = −∇U or F = − ∂U ∂x in one dimension. See any book
on classical mechanics. [Chow 1995, Fowles 1986, Marion 1988, Goldstein
1980].) Different input potentials U give different values of the fundamental
quantity which is the wave function Ψ. Once we have the wave function we
can calculate all sorts of other interesting goodies such as energies, lifetimes,
tunnelling probabilities, cross sections, etc.
In Newtonian mechanics and electromagnetism the fundamental quanti-
ties are the acceleration and the electric and magnetic fields. Now we all can
agree on what the meaning of acceleration and electric field is and so that’s
the end of the story. However with the wave function it’s entirely a different
matter. We have to agree on what we mean it to be at the very outset. The
meaning of the wave function has occupied some of the greatest minds in
physics (Heisenberg, Einstein, Dirac, Feynman, Born and others).
In this book we will not write down all of the postulates of quantum
mechanics in one go (but if you want this look at the inside cover). Instead
we will develop the postulates as we go along, because they are more under-
standable if you already know some quantum theory. Let’s look at a simple
version of the first postulate.
Postulate 1: To each state of a physical system there cor-

responds a wave function Ψ(x, t).
That’s simple enough. In classical mechanics each state of a physical system

is specified by two variables, namely position x(t) and momentum p(t) which
are both functions of the one variable time t. (And we all “know” what
position and momentum mean, so we don’t need fancy postulates to say
what they are.) In quantum mechanics each state of a physical system is
specified by only one variable, namely the wave function Ψ(x, t) which is a
function of the two variables position x and time t.
Footnote: In classical mechanics the state of a system is specified by x(t)
1.2. POSTULATES OF QUANTUM MECHANICS 17
and p(t) or Γ(x, p). In 3-dimensions this is ~x(t) and p~(t) or Γ(x, y, px , py )
or Γ(r, θ, pr , pθ ). In quantum mechanics we shall see that the uncertainty
principle does not allow us to specify x and p simultaneously. Thus in
quantum mechanics our good coordinates will be things like E, L2 , Lz , etc.
rather than x, p. Thus Ψ will be written as Ψ(E, L2 , Lz · · ·) rather than
Ψ(x, p). (E is the energy and L is the angular momentum.) Furthermore
all information regarding the system resides in Ψ. We Rwill see later that the
expectation value of any physical observable is hQi = Ψ∗ Q̂Ψdx. Thus the
wave function will always give the values of any other physical observable
that we require.
At this stage we don’t know what Ψ means but we will specify its meaning
in a later postulate.
Postulate 2: The time development of the wave function is

determined by the Schrödinger equation
Ã !
h̄2 ∂ 2 ∂
− 2
+ U Ψ(x, t) = ih̄ Ψ(x, t)
2m ∂x ∂t
(1.22)
where U ≡ U (x). Again this is simple enough. The equation governing the
behavior of the wave function is the Schrödinger equation. (Here we have
written it for a single particle of mass m in 1–dimension.)
Contrast this to classical mechanics where the time development of the
momentum is given by F = dp dt and the time development of position is given
by F = mẍ. Or in the Lagrangian formulation the time development of the
generalized coordinates is given by the second order differential equations
known as the Euler-Lagrange equations. In the Hamiltonian formulation
the time development of the generalized coordinates qi (t) and generalized
momenta pi (t) are given by the first order differential Hamilton’s equations,
ṗi = −∂H/∂qi and q̇i = ∂H/∂pi .
Let’s move on to the next postulate.
Postulate 3: (Born hypothesis): |Ψ|2 is the probability

density.
This postulate states that the wave function is actually related to a proba-
bility density
Footnote: Recall that every complex number can be written z = x + iy

and that
z ∗ z = (x − iy)(x + iy) = x2 + y 2 ≡ |z|2 .
ρ ≡ |Ψ|2 = Ψ∗ Ψ (1.23)
where Ψ∗ is the complex conjugate of Ψ. Postulate 3 is where we find
out what the wave function really means. The basic postulate in quantum
mechanics is that the wave function Ψ(x, t) is related to the probability for
finding a particle at position x. The actual probability for this is, in 1-
dimension,
Z A
P = |Ψ|2 dx (1.24)
−A
P is the probability for finding the particle somewhere between A and −A.
This means that
|Ψ(x, t)|2 dx = probability of finding a particle between posi-

tion x and x + dx at time t.
In 3-dimensions we would write

Z
P = |Ψ|2 d3 x (1.25)
which is why |Ψ|2 is called the probability density and not simply the proba-
bility. All of the above discussion is part of Postulate 3. The “discovery” that
the symbol Ψ in the Schrödinger equation represents a probability density
took many years and arose only after much work by many physicists.
Usually Ψ will be normalized so that the total probability for finding the
particle somewhere in the universe will be 1, i.e. in 1-dimension
Z ∞
|Ψ|2 dx = 1 (1.26)
−∞
or in 3-dimensions Z ∞
|Ψ|2 d3 x = 1 (1.27)
−∞
The probabilistic interpretation of the wave function is what sets quan-

tum mechanics apart from all other classical theories. It is totally unlike
anything you will have studied in your other physics courses. The accelera-
tion or position of a particle, represented by the symbols ẍ and x, are well
1.3. CONSERVATION OF PROBABILITY (CONTINUITY EQUATION)19
defined quantities in classical mechanics. However with the interpretation

of the wave function as a probability density we shall see that the concept
of the definite position of a particle no longer applies.
A major reason for this probabilistic interpretation is due to the fact that
the Schrödinger equation is really a type of wave equation (which is why Ψ is
called the wave function). Recall the classical homogeneous wave equation
(in 1-dimension) that is familiar from classical mechanics
∂2y 1 ∂2y
= (1.28)
∂x2 v 2 ∂t2
Here y = y(x, t) represents the height of the wave at position x and time t
and v is the speed of the wave [Chow 1995, Fowles 1986, Feynman 1964 I].
From (1.22) the free particle (i.e. U = 0) Schrödinger equation is
∂2Ψ 2m ∂Ψ
= −i (1.29)
∂x2 h̄ ∂t
which sort of looks a bit like the wave equation. Thus particles will be rep-
resented by wave functions and we already know that a wave is not localized
in space but spread out. So too is a particle’s wave property spread out over
some distance and so we cannot say exactly where the particle is, but only
the probability of finding it somewhere.
Footnote: The wave properties of particles are discussed in all books on
modern physics [Tipler 1992, Beiser 1987, Serway 1990].
1.3 Conservation of Probability (Continuity Equa-

tion)
Before discussing conservation of probability it will be very helpful to review
our knowledge of the conservation of charge in classical electromagnetism.
1.3.1 Conservation of Charge

In MKS (SI) units, Maxwell’s equations [Griffiths 1989] are Gauss’ electric
law
∇ · E = ρ/²0 (1.30)
and Gauss’ magnetic law
∇·B=0 (1.31)
and Faraday s law

∂B
∇×E+ =0 (1.32)
∂t
and Ampère’s law
1 ∂E
∇×B− = µ0 j (1.33)
c2 ∂t
Conservation of charge is implied by Maxwell’s equations. Taking the diver-
gence of Ampère’s law gives
1 ∂
∇ · (∇ × B) − ∇ · E = µ0 ∇ · j
c2 ∂t
However ∇ · (∇ × B) = 0 and using Gauss’ electric law we have
1 1 ∂ρ
− = µ0 ∇ · j
c2 ²0 ∂t
Now using c2 = µ01²0 we get
Footnote:The form of the continuity equation is the same in all systems
of units.
∂ρ
∇·j+ =0
∂t
(1.34)
which is the continuity equation. In 1-dimension this is
∂j ∂ρ
+ =0 (1.35)
∂x ∂t
The continuity equation is a local conservation law. The conservation law in
integral form is obtained by integrating over volume.
Thus Z I
∇ · j dτ = j · da (1.36)
by Gauss theorem and

Z Z
∂ρ d dQ
dτ = ρ dτ = (1.37)
∂t dt dt
where Z
Q≡ ρ dτ (1.38)
1.3. CONSERVATION OF PROBABILITY (CONTINUITY EQUATION)21
R R
The step dtd
ρ dτ = ∂ρ ∂t dτ in (1.37) requires some explanation. In general
ρ can be a function
R
of position
R
r and time t, i.e. ρ = ρ(r, t). However
the integral ρ(r, t)dτ ≡ ρ(r, t)d3 r will depend only on time as the r
coordinates will be integrated over. Because the whole integral depends
d
only on time then dt is appropriate outside the integral. However because
ρ = ρ(r, t) we should have ∂ρ ∂t inside the integral.
Thus the integral form of the local conservation law is
I
dQ
j · da + =0
dt
(1.39)
Thus a change in the charge Q within a volume is accompanied Hby a flow of
i
current across a boundary surface da. Actually j = area so that j · da truly
is a current I
i ≡ j · da (1.40)
so that (1.39) can be written

dQ
i+ =0 (1.41)
dt
or
dQ
i=− (1.42)
dt
truly showing the conservation of the charge locally. If we take our boundary
surface to be the whole universe then all currents will have died out at the
universe boundary leaving
dQ
=0 (1.43)
dt
where
Q ≡ Quniverse
which is the charge Renclosed in

R
the whole universe. Integrating (1.43) over
dQ
time we either have dt dt = O dt+ constant = constant which gives Q =
RQ
constant or we can write Qif dQ
dt dt = 0 which gives Qf − Qi = 0 or Qf = Qi .
Thus the global (universal) conservation law is
Q ≡ Quniverse = constant. (1.44)

or
Qf = Qi (1.45)
Our above discussion is meant to be general. The conservation laws can
apply to electromagnetism, fluid dynamics, quantum mechanics or any other
physical theory. One simply has to make the appropriate identification of j,
ρ and Q.
Finally, we refer the reader to the beautiful discussion by Feynman [Feyn-
man 1964 I] (pg. 27-1) where he discusses the fact that it is relativity, and
the requirement that signals cannot be transmitted faster than light, that
forces us to consider local conservation laws.
Our discussion of charge conservation should make our discussion of prob-
ability conservation much clearer. Just as conservation of charge is implied
by the Maxwell equations, so too does the Schrödinger equation imply con-
servation of probability in the form of a local conservation law (the continuity
equation).
1.3.2 Conservation of Probability

In electromagnetism the charge density is ρ. In quantum mechanics we
use the same symbol to represent the probability density ρ = |Ψ|2 = Ψ∗ Ψ.
Calculate ∂ρ
∂t .
∂ρ ∂
= (Ψ∗ Ψ)
∂t ∂t
∂Ψ ∂Ψ∗
= Ψ∗ + Ψ
∂t ∂t
and according to the Schrödinger equation in 1-dimension
" #
∂Ψ 1 h̄2 ∂ 2 Ψ ih̄ ∂ 2 Ψ i
= − 2
+ U Ψ = 2
− UΨ
∂t ih̄ 2m ∂x 2m ∂x h̄
∂Ψ∗ ih̄ ∂ 2 Ψ∗ i
=− + U Ψ∗
∂t 2m ∂x2 h̄
(assuming U ∗ = U ) we can write
Ã !
∂ρ ih̄ ∂ 2 Ψ ∂ 2 Ψ∗
= Ψ∗ 2 − Ψ
∂t 2m ∂x ∂x2
· µ ¶¸
∂ ih̄ ∂Ψ ∂Ψ∗
= Ψ∗ − Ψ
∂x 2m ∂x ∂x
1.4. INTERPRETATION OF THE WAVE FUNCTION 23
Well that doesn’t look much like the continuity equation. But it does if we
define a probability current
µ ¶
ih̄ ∂Ψ∗ ∂Ψ
j≡ Ψ − Ψ∗ (1.46)
2m ∂x ∂x
for then we have
∂ρ ∂j
+ =0 (1.47)
∂t ∂x
which is the continuity equation in 1-dimension and represents our local law
for conservation of probability.
Now let’s get the global law for conservation ofRprobability. In 1-dimension
∞
we integrate the continuity equation (1.47) over −∞ dx to get
Z ∞ Z ∞
∂ρ ∂j
dx = − dx
−∞ ∂t −∞ ∂x
Z · ¸∞
d ∞ ih̄ ∂Ψ∗ ∗ ∂Ψ
= ρ dx = − Ψ −Ψ
dt −∞ 2m ∂x ∂x −∞
In analogy with our discussion about the current located at the boundary
of the universe, here we are concerned about the value of the wave function
Ψ(∞) at the boundary of a 1-dimensional universe (e.g. the straight line).
Ψ must go to zero at the boundary, i.e.
Ψ(∞) = 0
Thus Z
d ∞
|Ψ|2 dx = 0 (1.48)
dt −∞
which is our global conservation law for probability. It is entirely consistent
with ourRnormalization condition (1.26). Writing the total probability P =
R
ρdx = |Ψ|2 dx we have
dP
=0 (1.49)
dt
analogous to global conservation of charge. The global conservation of prob-
ability law, (1.48) or (1.49), says that once the wave function is normalized,
say according to (1.26) then it always stays normalized. This is good. We
don’t want the normalization to change with time.
1.4 Interpretation of the Wave Function

A beautifully clear description of how to interpret the wave function is found
in Sec. 1.2 of [Griffiths 1995]. Read this carefully.
1.5 Expectation Value in Quantum Mechanics

(See pages 14, 15 of [Griffiths 1995]).
For a particle in state Ψ, the expectation value of y is
Z ∞
hxi = x|Ψ|2 dx (1.50)
−∞
The meaning of expectation value will be written in some more postulates

later on. Let’s just briefly mention what is to come. “The expectation
value is the average of repeated measurements on an ensemble of identically
prepared systems, not the average of repeated measurements on one and the
same systems” (Pg. 15, Griffiths [1995]).
1.6 Operators
In quantum mechanics, physical quantities are no longer represented by ordi-
nary functions but instead are represented by operators. Recall the definition
of total energy E
T +U =E (1.51)
where U is the potential energy, and T is the kinetic energy
1 p2
T = mv 2 = (1.52)
2 2m
where p is the momentum, v is the speed and m is the mass. If we multiply
(16.1) by a wave function
(T + U )Ψ = EΨ (1.53)
then this is the Schrödinger equation (1.1) if we make the replacements
h̄2 ∂ 2
T →− (1.54)
2m ∂x2
and
∂
E → ih̄ (1.55)
∂t
The replacement (16.4) is the same as the replacement
∂
p → −ih̄ (1.56)
∂x
1.6. OPERATORS 25
(Actually p → +ih̄ ∂x
∂
would have worked too. We will see in Problem 1.4
why we use the minus sign.) Let’s use a little hat (∧) to denote operators
and write the energy operator
∂
Ê = ih̄
∂t
(1.57)
and the momentum operator
∂
p̂ = −ih̄
∂x
(1.58)
What would the position operator or potential energy operator be? Well in
the Schrödinger equation (1.1) U just sits there by itself with no differential
operator. For a harmonic oscillator for example U = 12 kx2 we just plug 12 kx2
into the Schrödinger equation as
Ã !
h̄2 ∂ 2 1 ∂
− 2
+ kx2 ψ(x, t) = ih̄ ψ(x, t) (1.59)
2m ∂x 2 ∂t
which is the Schrödinger equation for a harmonic oscillaor potential. Evi-

dently these potentials don’t get replaced with differential operators. They
just remain as functions. We could write the harmonic oscillator operator as
1
Û = U (x) = kx2 (1.60)
2
Now most potentials are just functions of position U (x) so if Û = U (x) it

must follow that
x̂ = x
(1.61)
That is, the position opeator is just the position itself.
OK, we know how to write the expectation value of position. It’s given
in (1.50), but how about the expectation value of momentum? I can’t just
R
∞ R∞
write hpi = −∞ p|Ψ|2 dx = −∞ pΨ∗ Ψdx because I don’t know what to put in
for p under the integral. But wait! We just saw that in quantum mechanics
p is an operator given in (1.58). The proper way to write the expectation
value is
Z ∞ µ ¶
∂ ∗
hp̂i = Ψ −ih̄ Ψdx (1.62)
−∞ ∂x
Z ∞
∂Ψ
= −ih̄ Ψ∗ dx (1.63)
−∞ ∂x
In fact the expectation value of any operator Q̂ in quantum mechanics is
Z
hQ̂i ≡ Ψ∗ Q̂Ψdx
(1.64)
which is a generalization of (1.19) or (1.50).
This would give
Z
hxi = Ψ∗ xΨdx
which gives the same result as (1.50).

But given an arbitrary quantity Q, how do we know how to write it in
operator form? All we have so far are the operators for T , U , p and x. Well,
it turns out that any arbitrary operator Q̂ can always be written in terms of
p̂ and x̂.
Example 1.6.1 Write down the velocity operator v̂, and its
expectation value.
Solution We have p̂ = −ih̄ ∂x
∂
and p = mv. Thus we define the
velocity operator
p̂
v̂ ≡
m
Thus
ih̄ ∂
v̂ = −
m ∂x
1.7. COMMUTATION RELATIONS 27
The expectation value would be

Z µ ¶
ih̄ ∂
hvi = Ψ∗ − Ψ dx
m ∂x
Z
ih̄ ∂Ψ
= − Ψ∗ dx
m ∂x
1.7 Commutation Relations

We are perhaps used to mathematical objects that commute. For example
the integers commute under addition, such as 3+2 = 2+3 = 5. The integers
also commute under multiplication, such as 3 × 2 = 2 × 3 = 6. Also matrices
commute under matrix addition, such as
µ ¶ µ ¶ µ ¶ µ ¶ µ ¶
2 1 1 3 1 3 2 1 3 4
⊕ = ⊕ = (1.65)
1 2 1 1 1 1 1 2 2 3
(Notice that I have used a special symbol ⊕ for matrix addition because it
is very different from ordinary addition + of real numbers.)
Matrices do not however commute under multiplication. For example
µ ¶ µ ¶ µ ¶
2 1 1 3 3 6
⊗ = (1.66)
1 2 1 1 3 5
but µ ¶ µ ¶ µ ¶
1 3 2 1 5 7
⊗ = (1.67)
1 1 1 2 3 3
so that matrix multiplication is non-commutative.
Note also that our operators x̂ and p̂ do not commute. Now with oper-
ators they must always operate on something, and for quantum mechanics
that something is the wave function Ψ. We already know that p̂Ψ = −ih̄ ∂Ψ
∂x
and x̂Ψ = xΨ, so now let’s combine them. Thus
∂
p̂x̂Ψ = p̂xΨ = −ih̄ (xΨ)
µ ∂x ¶
∂Ψ
= −ih̄ Ψ + x (1.68)
∂x
and
∂Ψ ∂Ψ
x̂p̂Ψ = −ih̄ x̂ = −ih̄ x (1.69)
∂x ∂x
Thus x̂ and p̂ do not commute! That is x̂p̂ 6= p̂x̂.

Let’s now define the commutator of two arbitrary mathematical objects
A and B as
[A, B] ≡ AB − BA
(1.70)
Where AB ≡ A ◦ B which reads A “operation” B. Thus for integers under
addition we would have [3, 2] ≡ (3 + 2) − (2 + 3) = 5 − 5 = 0 or for integers
under multiplication we would have [3, 2] = (3 × 2) − (2 × 3) = 6 − 6 = 0.
Thus if two mathematical objects, A and B, commute then their commutator
[A, B] = 0. The reason why we introduce the commutator is if two objects
do not commute then the commutator tells us what is “left over”. Note a
property of the commutator is
[A, B] = −[B, A] (1.71)

µ ¶ µ ¶
2 1 1 3
For our matrices A ≡ and B ≡ that we had before, then
1 2 1 1
the commutator is
µ ¶ µ ¶ µ ¶
3 6 5 7 2 1
[A, B] = AB − BA = − = (1.72)
3 5 3 3 0 −2
where we have used (1.66) and (1.67).

We are interested in the commutator [x̂, p̂]. In classical mechanics
[x, p]classical = 0 (1.73)
because x and p are just algebraic quantities, not operators. To work out
quantum mechanical commutators we need to operate on Ψ. Thus
[x̂, p̂]Ψ = (x̂p̂ − p̂x̂)Ψ

µ ¶
∂Ψ ∂Ψ
= −ih̄ x + ih̄ Ψ + x
∂x ∂x
= ih̄Ψ (1.74)
Now “cancel” the Ψ and we have
[x̂, p̂] = ih̄ .

(1.75)
The commutator is a very fundamental quantity in quantum mechanics. In
section 1.6 we “derived” the Schrödinger equation by saying (T̂ + Û )Ψ = ÊΨ
p̂2
where T̂ ≡ 2m and then introducing p̂ ≡ −ih̄ ∂x∂
and Ê ≡ ih̄ ∂t ∂
and x̂ ≡ x.
The essence of quantum mechanics are these operators. Because they are
operators they satisfy (1.75).
An alternative way of introducing quantum mechanics is to change the
classical commutation relation [x, p]classical = 0 to [x̂, p̂] = ih̄ which can only
be satisfied by x̂ = x and p̂ = −ih̄ ∂x
∂
.
Thus to “derive” quantum mechanics we either postulate operator defi-
nitions (from which commutation relations follow) or postulate commutation
relations (from which operator definitions follow). Many advanced formula-
tions of quantum mechanics start with the commutation relations and then
later derive the operator definitions.
Figure 1.1: Histogram showing number of students N (i) receiving a grade

of i.
Figure 1.2: Location of Mean, Median, Mode

1.8 Problems
1.1 Suppose 10 students go out and measure the length of a fence and the
following values (in meters) are obtained: 3.6, 3.7, 3.5, 3.7, 3.6, 3.7, 3.4, 3.5,
3.7, 3.3. A) Pick a random student. What is the probability that she made
a measurement of 3.6 m? B) Calculate the expectation value (i.e. average
or mean) using each formula of (1.2), (1.5), (1.8).
1.2 Using the example of problem 1.1, calculate the variance using both
equations (1.15) and (1.16).
1.3 Griffiths Problem 1.6.

Hints: Some useful
q integrals are [Spiegel, 1968, pg.98]
R ∞ −ax2
0 e
1
dx = 2 πa
R∞
xm e−ax dx =
2 Γ[(m+1)/2]
0 2a(m+1)/2
√
Also note Γ(3/2) = 2π
Properties of the Γ function are listed in [Spiegel, 1968, pg.101]
1.4 Calculate dhxi

dt and show that it is the same as the velocity expectation
value hvi calculated in Example 1.6.1.

1.9. ANSWERS 33
1.9 Answers
1.1 A) 0.2 B) 3.57
1.2 0.0181
q
1.3 Griffiths Problem 1.6. A) A = λ
π B) hxi = a, hx2 i = a2 + 1
2λ ,
σ = √12λ
Chapter 2
DIFFERENTIAL
EQUATIONS
Hopefully every student studying quantum mechanics will have already taken
a course in differential equations. However if you have not, don’t worry. The
present chapter presents the very bare bones of knowledge that you will need
for your introduction to quantum mechanics.
2.1 Ordinary Differential Equations

A differential equation is simply any equation that contains differentials or
derivatives. For instance Newton’s law
d2 s
F =m (2.1)
dt2
is a differential equation because of the second derivative contained in the
2
acceleration a ≡ ddt2s and s is distance.
In what follows below, let’s write the first derivative of the function y(x)
d2 y
with respect to x as y 0 (x) ≡ dx
dy
and the second derivative as y 00 (x) ≡ dx 2 . We
will not be considering higher order derivatives. The order of the differential
equation is simply the degree of the highest derivative. For example
y 00 + a1 (x)y 0 + a2 (x)y = k(x) (2.2)
is called a second order differential equation because the highest derivative y 00

is second order. If y 00 wasn’t there it would be called a first order differential
equation.
35
36 CHAPTER 2. DIFFERENTIAL EQUATIONS
Equation (2.2) is also called an ordinary differential equation because y

is a function of only one variable x, i.e. y = y(x). A partial differential
equation occurs if y is a function of more than one variable, say y = y(x, t)
∂y
and we have derivatives in both x and t, such as the partial derivatives ∂x
and ∂y
∂t . We shall discuss partial differential equations later.
Equation (2.2) is also called an inhomogeneous differential equation be-
cause the right hand side containing k(x) is not zero. k(x) is a function of
x only. It does not contain any y, y 0 or y 00 terms and we usually stick it on
the right hand side. If we had
y 00 + a1 (x)y 0 + a2 (x)y = 0 (2.3)
it would be a second order, ordinary, homogeneous differential equation. By
the way, the reason I don’t write say a0 (x)y 00 in (2.2) or (2.3) is because the
a0 (x) can always be absorbed into the other coefficients.
Equation (2.2) is also called a differential equation with non-constant
coefficients, because the a1 (x) and a2 (x) are functions of x. If they were
not functions but just constants or ordinary numbers, it would be called a
differential equation with constant coefficients.
Equation (2.2) is also called a linear differential equation because it is
linear in y, y 0 and y 00 . If it contained terms like yy 00 , y 2 , y 0 y 00 , y 02 , etc., it
would be called a non-linear equation. Non-linear differential equations sure
are fun because they contain neat stuff like chaos [Gleick 1987] but we will
not study them here.
Thus equation (2.2) is called a second order, inhomogeneous, linear, or-
dinary differential equation with non-constant coefficients. The aim of differ-
ential equation theory is to solve the differential equation for the unknown
function y(x).
2.1.1 Second Order, Homogeneous, Linear, Ordinary Differ-

ential Equations with Constant Coefficients
First order equations are pretty easy to solve [Thomas 1996, Purcell 1987]
and anyone who has taken a calculus course can work them out. Second order
equations are the ones most commonly encountered in physics. Newton’s law
(2.1) and the Schrödinger equation are second order.
Let’s start by solving the simplest second order equation we can imagine.
That would be one which is homogeneous and has constant coefficients and
is linear as in
y 00 + a1 y 0 + a2 y = 0 (2.4)
2.1. ORDINARY DIFFERENTIAL EQUATIONS 37
where now a1 and a2 are ordinary constants. The general solution to equa-
tion (2.2) is impossible to write down. You have to tell me what a1 (x), a2 (x)
and k(x) are before I can solve it. But for (2.4) I can write down the general
solution without having to be told the value of a1 and a2 . I can write the
general solution in terms of a1 and a2 and you just stick them in when you
decide what they should be.
Now I am going to just tell you the answer for the solution to (2.4).
Theorists and mathematicians hate that! They would prefer to derive the
general solution and that’s what you do in a differential equations course.
But it’s not all spoon-feeding. You can always (and always should) check you
answer by substituting back into the differential equation to see if it works.
That is, I will tell you the general answer y(x). You work out y 0 and y 00 and
substitute into y 00 + a1 y 0 + a2 y. If it equals 0 then you know your answer is
right. (It may not be unique but let’s forget that for the moment.)
First of all try the solution
y(x) = r erx (2.5)
Well y 0 (x) = r2 erx and y 00 (x) = r3 erx and upon substitution into (2.4) we
get
r2 + a1 r + a2 = 0 (2.6)
This is called the Auxilliary Equation. Now this shows that y(x) = r erx
will not be a solution for any old value of r. But if we pick r carefully, so
that it satisfies the Auxilliary equation then y(x) = r erx is a solution. Now
the auxilliary equation is just a quadratic equation for r whose solution is
q
−a1 ± a21 − 4a2
r= (2.7)
2
√
−a + a2 −4a
Now if a21 −4a2 > 0 then r will have 2 distinct real solutions r1 = 1 2 1 2
√
−a1 + a21 −4a2
and r2 = 2 . If a21 − 4a2 = 0, then r will have 1 real solution
r1 = r2 = r = − a21 . If a21 − 4a2 < 0 then r will have 2 complex solutions
√ 2
a1 −4a2
r1 ≡ α + iβ and r2 = α − iβ where α = − 2 and iβ =
a1
2 . We often
just write this as r = α ± iβ. We are now in a position to write down the
general solution to (2.4). Let’s fancy it up and call it a theorem.
Theorem 1. The general solution of y 00 + a1 y 0 + a2 y = 0 is

y(x) = Aer1 x + Ber2 x if r1 and r2 are distinct roots
y(x) = Aerx + Bxerx if r1 = r2 = r is a single root
Notes to Theorem 1
i) If r1 = r2 = r is a single root then r must be real (see discussion above).
ii) If r1 and r2 are distinct and complex then they must be of the form
r1 = α + iβ and r2 = α − iβ (see discussion above). In this case the
solution is
y(x) = A e(α+iβ)x + B e(α−iβ)x

= eαx (A eiβx + B e−iβx )
= eαx (C cos βx + D sin βx)
= eαx E cos(βx + δ)
= eαx F sin(βx + γ)
which are alternative ways of writing the solution. (do Problem 2.1)
Generally speaking the exponentials are convenient for travelling waves
(free particle) and the sines and cosines are good for standing waves
(bound particle).
Example 2.1.1 Solve Newton’s law (F = ma) for a spring force

(−kx).
2
Solution In 1-dimension F = ma becomes −kx = mẍ (ẍ ≡ ddt2x ).
Re-write as ẍ + ω 2 x = 0 where ω 2 ≡ m
k
. This is a second order
differential equation with constant coefficients (and it’s homoge-
neous and linear). The Auxilliary equation is
r2 + ω 2 = 0
(obtained by substituting x(t) = r ert into the differential equa-

tion). The solution to the Auxilliary equation is
r = ±iω
which gives α = 0 and β = ω in Theorem 2.1.1. Thus the solution

is
x(t) = B eiωt + C e−iωt

= D cos ωt + E sin ωt
= F cos(ωt + δ)
= G sin(ωt + γ)
which is our familiar oscillatory solution for a spring.

Now let’s determine the unknown constant. This is obtained from
the boundary condition. Let’s assume that at t = 0 the spring is
at position x = 0 and at t = T4 (T = period, ω = 2π
T ) the spring
attains its maximum elongation x = A (A = Amplitude). Let’s
use the solution x(t) = D cos ωt + E sin ωt.
Then x(0) = 0 = D. Thus D = 0. And x( T4 ) = A = E sin 2π T
T 4 =
π
E sin 2 = E. Thus E = A. Therefore the solution consistent
with boundary conditions is x(t) = A sin ωt where A is the am-
plitude. Thus we see that in the classical case the boundary
condition determines the amplitude.
(do Problem 2.2)
2.1.2 Inhomogeneous Equation

The next simplest differential equation to solve puts a function on the right
hand side of (2.4) as
y 00 + a1 y 0 + a2 y = f (x) (2.8)
where f (x) is called the inhomogeneous term.
We now have to distinguish between a particular solution and a general
solution. A general solution to an equation contains everything, whereas a
particular solution is just a little piece of a general solution. (A very crude
example is the equation x2 = 9. General solution is x = ±3. Particular
solution is x = −3. Another particular solution is x = +3). Theorem 1
contains the general solution to the homogeneous differential equation (2.4).
Theorem 2 The general solution of y 00 + a1 y 0 + a2 y = f (x) is
y = yP + y H
where yH is the general solution to the homogeneous equation and yP is a

particular solution to the inhomogeneous equation.
This is a really great theorem. We already have half of our solution to

(2.8). It’s yH which is given in Theorem 2. If we can get yP we have the
complete solution. And yP is easy to get!
Remember yP is a particular solution so any old solution that you can
find is a legitimate answer to yP . There are 3 methods for find yP . These
are called i) Guessing, ii) method of Variation of Parameters and iii) method
of Undetermined Coefficients.
Guessing is the best method. If you can guess the answer (for yP ) just add
it to yH (from Theorem 1) and you have the complete answer! (y = yP +yH ).
The method of Variation of Parameters is also useful [Purcell 1987], but
we will not use it.
We will use the method of Undetermined Coefficients, which I prefer to
call the method of Copying the Inhomogeneous Term. Take a look at Table
2.1.
Table 2.1
if f (x) = try yP =
bm xm + bm−1 xm−1 + · · · b1 x + b0 Bm xm + Bm−1 xm−1 + · · · B1 x + B0
beαx Beαx
b cos βx + c sin βx B cos βx + C sin βx ≡ A cos(βx + δ)

= F sin(βx + γ) etc.
Modification: if a term of f (x) is a solution to the homogeneous

equation then multiply it by x (or a higher power of x)
This Table gives you a summary of how to find yP . For example if the
differential equation is
y 00 + 3y 0 + 2y = 3 sin 2x
then the particular solution will be yP = B sin 2x. In other words just change
the constant in the inhomogeneous term and you have the particular solution.
That’s why I like to call it the method of Copying the Inhomogeneous Term.
There is one caveat however. If a function the same as the inhomogeneous
term appears in the homogeneous solution then the method won’t work. Try
multiplying by x (or some higher power) to get yP .
Example 2.1.2 Newton’s law for a spring with a forcing function

is ẍ + ω 2 x = A cos αt.
A) Find a particular solution and show that it satisfies the dif-

ferential equation.
B) What is the general solution?
Solution
A) Copy the Inhomogeneous Term. Try xP = B cos αt. Let’s

check that it works.
ẋP = −Bα sin αt

ẍP = −Bα2 cos αt
Substituting we get for the left hand side
ẍP + ω 2 xP = −Bα2 cos αt + ω 2 B cos αt

= B(ω 2 − α2 ) cos αt
which equals the right hand side if A = B(ω 2 − α2 ). Thus

the Undetermined Coefficient is
A
B=
ω2 − α2
and the particular solution is
A
xP (t) = cos αt
ω2 − α2
B) The general solution is just x = xH + xP and we found xH

in Example 2.1.1. Thus the general solution is
A
x(t) = E cos(ωt + δ) + cos αt
ω2 − α2
(do Problem 2.3)
In a differential equations course you would prove Theorems 1 and 2

and then you would be happy and satisfied that the solutions I claimed are
correct. If you have not taken a differential equations course you can still
be happy and satisfied that the solutions are correct because you can always
check your answers by substituting back into the differential equation! You
should always do this anyway, just to make sure you haven’t made a mistake.
(See Problem 2.2) Thus if you have not yet studied differential equations then
simply use Theorems 1 and 2 as a recipe for getting the answer. Then check
your answer always to satisfy yourself that it is correct.
We have now finished our discussion of ordinary differential equations.
We are not going to consider equations with non-constant coefficients.
If you are interested in higher order equations with constant coefficients
then these are easy to solve once you know how to solve second order equa-
tions. See Purcell and Varberg [Purcell 1987].
2.2 Partial Differential Equations

Partial differential equations involve more than one variable such as y(x, t)
∂y ∂2y
and involve partial derivatives such as ∂x and ∂y
∂t or ∂x∂t etc. The typical
method of solution of a partial differential equation (PDE) involves the tech-
nique of Separation of Variables. For a function of two variables y(x, t) this
technique splits the single P DE into two ordinary differential equations! We
solve these with our previous techniques. We call these the separable solu-
tions because they are obtained with the technique of separation of variables.
However separable solutions are not general solutions of the P DE. The
general solution of a P DE is a linear combination of separable solutions.
The technique of separation of variables is fairly easy to apply and we will
study it using the Schrödinger equation as our example. But remember this
technique will work on the wide variety of P DE’s encountered in physics.
(However the technique won’t work on all P DE’s such as the Wheeler-
DeWitt equation for a scalar field.)
We wish now to show how the partial differential Schrödinger equation
(1.1) gets reduced to two ordinary differential equations (ODE’s). Notice
that Ψ(x, t) is a function of the two variables x and t. The fundamental
technique in Separation of Variables is to write Ψ as a product of two separate
2.2. PARTIAL DIFFERENTIAL EQUATIONS 43
functions ψ(x) and f (t) which are functions of a single variable. That is
Ψ(x, t) = ψ(x)f (t) (2.9)
Now all you have to do is substitute this ansatz back into the original P DE
dψ ∂2Ψ d2 ψ
and everything will fall out. We calculate ∂Ψ
∂x = dx f (t) and ∂x2 = dx2 f (t)
df
and ∂Ψ
∂t = ψ(x) dt to give
h̄2 d2 ψ df
− 2
f (t) + U (x)ψ(x)f (t) = ih̄ψ(x)
2m dx dt
Divide the whole thing through by ψ(x)f (t) and
h̄2 1 d2 ψ 1 df
− 2
+ U (x) = ih̄
2m ψ dx f dt
But now notice that the left hand side is a function of x only and the right
hand side is a function of t only. The only way two different functions of two
different variables can always be equal is if they are both constant. Let’s call
the constant E and make both sides equal to it. Thus
Ã !
h̄2 d2
− + U ψ = Eψ
2m dx2
(2.10)
and
1 df E −i
= = E (2.11)
f dt ih̄ h̄
and these are just two ordinary differential equations, which we know how
to solve! Equation (2.10) is only a function of x and is called the time-
independent Schroödinger equation (for 1 particle in 1 dimension). We shall
spend a whole chapter on solving it for different potential energy functions
U (x). That is we will get different solutions ψ(x) depending on what function
U (x) we put in. The second equation (2.11) can be solved right away because
it doesn’t have any unknown functions in it. It’s just an easy first order ODE
which has the solution
f (t) = Ce− h̄ Et
i
(2.12)
(do Problem 2.4)
Thus the separable solution to the time dependent Schrödinger equation
(1.1) is
Ψ(x, t) = ψ(x)e− h̄ Et
i
(2.13)
(We will absorb normalization constants into ψ(x).)
What is the constant E? Obviously it’s the total energy because the
h̄2 d2
kinetic energy operator is T = − 2m dx2
and (2.10) is just
(T + U )ψ = Eψ
Compare to (16.3).
2.3 Properties of Separable Solutions

The separable solutions Ψ(x) have many important properties which we shall
now discuss.
2.3.1 General Solutions

When we actually solve (2.10) for a specific potential U (x) in the next chap-
ter we will see that a whole set of solutions ψ(x) is generated, and each
solution will correspond to a different value for the total energy. Let’s use
the subscript n to denote the different solutions ψn (x) corresponding to the
different energies En , where n = 1, 2, 3 . . ..
The general solution to the time-dependent Schrödinger equation is a
linear combination of separable solutions
X
cn ψn (x)e− h̄ En t
i
Ψ(x, t) = (2.14)
n
where cn are the expansion coefficients. We will see specifically what these
are below.
2.3.2 Stationary States

A stationary state is one which never changes with time. Both the proba-
bility density and the expectation value of any variable are constant. The
probability density
|Ψ(x, t)|2 = Ψ∗ Ψ = ψ ∗ (x)e h̄ Et ψ(x)e− h̄ Et = ψ ∗ (x)ψ(x)

i i
(2.15)
2.3. PROPERTIES OF SEPARABLE SOLUTIONS 45
is constant in time because the time dependence of the wave function cancels
out. This also happens for any expectation value
Z Z
∗
hQi = Ψ (x, t)QΨ(x, t)dx = ψ ∗ (x)Qψ(x)dx (2.16)
because Q does not contain any time dependence. Remember all dynam-
ical variables can be written as functions of x or p only Q = Q(x̂, p̂) =
Q(x, −ih̄ dx
d
).
With equation (2.13) our normalization condition (1.26) can alternatively
be written Z ∞
ψ ∗ (x)ψ(x)dx = 1 (2.17)
−∞
2.3.3 Definite Total Energy

By the term definite total energy we mean that the total energy uncertainty
is zero. Defining the Hamiltonian operator
h̄2 d2
Ĥ ≡ −
+ U (x) (2.18)
2m dx2
the time independent Schrödinger equation (2.10) is
ĤΨ = EΨ (2.19)
Thus from (2.16)
Z Z
hHi = ψ ∗ Ĥψdx = E ψ ∗ ψdx = E (2.20)
which is as we expect. Using (1.16) the uncertainty in the total energy

operator Ĥ is
2
σH = hH 2 i − hHi2 (2.21)
Now
Z Z Z
∗ ∗
hH i =
2 2
ψ Ĥ ψdx = ψ Ĥ Ĥψdx = E ψ ∗ Ĥψdx
= E2 (2.22)
so that
2
σH =0 (2.23)
The uncertainty in the total energy is zero! Remember that the expectation
value is the average of a set of measurements on an ensemble of identically
prepared system. However if the uncertainty is zero then every measurement
will be identical. Every measurement will give the same value E.
2.3.4 Alternating Parity

Recall that an even function obeys f (x) = f (−x) and an odd function obeys
f (x) = −f (−x). We say that an even function possesses even or positive
parity whereas an odd function possesses odd or negative parity.
For even potentials U (x) [N N N only for even ???] the n = 1 solution
has even parity, the n = 2 solution has odd parity, n = 3 even, n = 4 odd,
etc. That is the parity alternates for each successive solution.
2.3.5 Nodes
A node is a point where the function ψ(x) becomes zero (we are not including
the end points here). As n increases the number of nodes in the wave function
increases. In general the wave function ψn (x), corresponding to En , will have
n − 1 nodes.
Thus ψ1 has 0 nodes, ψ2 has 1 node, ψ2 has 2 nodes. Thus the number
of nodes in the wave function tells us which energy level En corresponds to
it.
2.3.6 Complete Orthonormal Sets of Functions

Orthonormality
Let’s first review a little bit about vectors. The scalar product, often
called inner product, of two vectors is defined as
A · B ≡ AB cos θ (2.24)
where A ≡ |A| is the magnitude of A and θ is the angle between A and B.
We can write vectors in terms of basis vectors êi as
X
A= Ai êi (2.25)
i
where the expansion coefficients Ai are called the components of A, with
respect to the basis set {êi }. If the basis vectors are orthogonal to each
other (êi · êj = 0 for i 6= j) and are of unit length, i.e. normalized (êi · êj = 1
for i = j) then we can write
êi · êj = δij (2.26)
for our orthonormal (orthogonal and normalized) basis. The Kronecker delta
symbol is defined as (
1 if i = j
δij = (2.27)
0 if i 6= j
The Kronecker delta is an object which has the effect of killing sums. Thus
X
Cj δij = Ci (2.28)
j
(Prove this.)
The inner product of two arbitrary vectors (2.24) can be alternatively written
XX XX X
A·B= Ai Bj êi · êj = Ai Bj δij = Ai Bi
i j i j i
Thus X
A·B= Ai Bi (2.29)
i
which could have served equally well as our definition of inner product.
The components or expansion coefficients Ai can now be calculated by
taking the inner product between the vector A and the basis vector êi . Thus
X X X
êi · A = êi · Aj êj = Aj êi · êj = Aj δij = Ai
j j j
giving
Ai = êi · A (2.30)
Now let’s look at functions. It turns out that the separable solutions
form a function space which is a complex infinite-dimensional vector space,
often called a Hilbert space [Byron 1969]. For an ordinary vector A the
components Ai are labelled by the discrete index i. For a function f the
components f (x) are labelled by the continuous index x. The discrete index
i tells you the number of dimensions, but x is a continuous variable and so
the function space is infinite dimensional.
The inner product of two functions g and f is defined by [Byron 1969,
Pg. 214]
Z b
hg | f i ≡ g ∗ (x)f (x)dx (2.31)
a
where we now use the symbol hg | f i instead of A·B to denote inner product.
This definition of inner product is exactly analogous to (2.29), except that
we have the complex component g ∗ (x).
The word orthonormal means orthogonal and normalized. An orthonor-
mal (ON) set of functions obeys
Z
∗
ψm (x)ψn (x)dx = δmn (2.32)
analogous to (2.26), where instead of distinguishing functions by different

letters (f versus g) we distinguish them with different subscripts (ψm versus
ψn ). An orthogonal (m 6= n) set of functions obeys
Z
∗
ψm (x)ψn (x)dx = 0 (2.33)
and a normalized (m = n) set of functions obeys

Z
ψn∗ (x)ψn (x)dx = 1 (2.34)
which we had in (2.17).
Completeness
All separable solutions ψn (x) form an orthonormal set and the vast ma-
jority are also complete. A set of functions {ψn (x)} is complete if any other
function be expanded in terms of them via
X
f (x) = cn ψn (x) (2.35)
n
Now this looks exactly like the way we expand vectors in terms of basis
vectors in (2.25), where the components Ai correspond to the expansion
coefficients cn . For this reason the functions ψn (x) are called basis functions
and they are exactly analogous to basis vectors.
Equation (2.30) tells us how to find components Ai and similarly we
would like to know how to calculate expansion coefficients cn . Looking at
(2.30) you can guess the answer to be
Z
cn = hψn | f i = ψn∗ (x)f (x)dx (2.36)
which is just the inner product of the basis functions with the function.
(do Problem 2.5)
One last thing I want to mention is the so-called completeness relation or
closure relation (Pg. 69 [Ohanian 1990]). But first I need to briefly introduce
the Dirac delta function defined via
Z ∞
f (x)δ(x − a)dx ≡ f (a) (2.37)
−∞
which is nothing more than a generalization of the Kronecker delta symbol

in equation (2.28). Whereas the Kronecker delta kills sums, the Dirac delta
function is defined to kill integrals. (We shall discuss the Dirac delta in
more detail later on.) Now recall that a complete set of basis functions
allows us to expand any other function in terms of them as in (2.35), where
the coefficients cn are given in (2.36). Thus
X
f (x) = cn ψn (x)
n
XZ
= ψn∗ (x0 )f (x0 )dx0 ψn (x)
n
Z " #
X
0
= f (x ) ψn∗ (x0 )ψn (x) dx0 (2.38)
n
and for the left hand side to equal the right hand side we must have
X
ψn∗ (x0 )ψn (x) = δ(x0 − x)
n
(2.39)
which is called the completeness relation or the closure relation. One can
see that if a set of basis functions {ψn (x)} satisfies the completeness relation
then any arbitrary function f (x) can be expanded in terms of them.
2.3.7 Time-dependent Coefficients

By the way, what if our arbitrary function f (x) is instead a function of time
also, like f (x, t) or Ψ(x, t) in (2.14)? This is easy to handle. Let’s absorb
the time dependence into the coefficient and write
cn (t) ≡ cn (0)e− h̄ En t
i
(2.40)
where cn ≡ cn (0). Then (2.14) is simply

X
Ψ(x, t) = cn (t)ψn (x) (2.41)
n
or X X
Ψ(x, 0) = cn (0)ψn (x) = cn ψn (x) (2.42)
n n
and therefore we still expand our function Ψ in terms of the complete set of
basis functions ψn (x).
2.4 Problems
2.1 Griffiths, Problem 2.19.
2.2 Refer to Example 2.1.1. Determine the constants for the other 3 forms
of the solution using the boundary condition (i.e. determine B, C, F , δ, G,
γ from boundary conditions). Show that all solutions give x(t) = A sin ωt.
2.3 Check that the solution given in Example 2.1.2 really does satisfy the
A
differential equation. That is substitute x(t) = E cos(ωt + δ) + ω2 −α 2 cos αt
2
and check that ẍ + ω x = A cos αt is satisfied.
2.4 Solve equation (2.11).
2.5 Prove that cn = hψn | f i (Equation (2.36)).

2.5. ANSWERS 51
2.5 Answers
2.1
C = A + B, D = i(A − B) for C cos kx + D sin kx
A = F2 eiα , B = F2 e−iα for F cos(kx + α)
G −iβ
G iβ
A = 2i e , B = − 2i e for G sin(kx + β)
2.2
B = 2iA
C = − 2i
A
δ = π2 F = −A
γ=π G=A
2.3 f (t) = Ae− h̄ Et (equation (2.12)

i
Chapter 3
INFINITE
1-DIMENSIONAL BOX
One of the main things we are interested in calculating with quantum me-
chanics is the spectrum of the Hydrogen atom. This atom consists of two
particles (proton and electron) and it moves about in three dimensions. The
Schrödinger equation (2.10) is a one particle equations in one dimension.
The mass of the particle is m moving in the x direction. We will eventually
write down and solve the two body, three dimensional Schrödinger equation
but it’s much more complicated to deal with than the one particle, one di-
mensional equation. Even though the one particle, one dimensional equation
is not very realistic, nevertheless it is very worthwhile to study for the fol-
lowing reasons. i) It is easier to solve and therefore we can get some practice
with solutions before attacking more difficult problems. ii) It contains many
physical phenomena (such as energy levels and tunnelling) that are found
in the two particle, three dimensional problem and in the real world. It
is much better to learn about these phenomena from a simple equation to
begin with.
In this chapter we are going to study the single particle in an infinite
1-dimensional box. This is one of the simplest examples to study in quantum
mechanics and it lets us illustrate many of the unusual features of quantum
theory via a simple example.
Another important reason for studying the infinite box at this stage is
that we will then be able to understand the postulates of quantum mechanics
much more clearly.
Imagine putting a marble in an old shoe box and then wobbling the box
53
54 CHAPTER 3. INFINITE 1-DIMENSIONAL BOX
around so that the marble moves faster and faster. Keep the box on the
floor and wobble it around. Then the marble will have zero potential energy
U and its kinetic energy T will increase depending on how fast the marble
moves. The total energy E = T + U will just be E = T because U = 0. In
principle the marble can have any value of E. It just depends on the speed
of the marble.
We are going to study this problem quantum mechanically. We will use
an idealized box and let its walls be infinitely high. We will also restrict it
to one dimension. (Even though this is an idealization, you could build such
a box. Just make your box very high and very thin.) There is a picture of
our infinite 1-dimensional (1-d) box in Figure 3.1.
What we want to do is to calculate the energy of a marble placed in the
box and see how it compares to our classical answer (which was that E can
be anything).
Even though Figure 3.1 looks like a simple drawing of a 1-d box it can also
be interpreted as a potential energy diagram with a vertical axis representing
U (x) and the horizontal axis being x. Now inside the box U = 0 because
the marble is just rattling around on the floor of the box. Because the box
is infinitely high then the marble can never get out. An equivalent way of
saying this is to say that U (x ≤ 0) = ∞ and U (x ≥ a) = ∞ for a box of
width a.
3.1 Energy Levels

Let’s now solve the Schrödinger equation inside the box where U = 0. (This
is why the infinite box is a very easy example to start with. There’s no
simpler potential than U = 0, except for a completely free particle. More on
this later.) Substitute U = 0 into (2.10) and we have
−h̄2 00
ψ = Eψ
2m
d2 ψ
where ψ 00 ≡ dx2
. Let’s condense all of these annoying constants into one via
√
2mE
k≡ (3.1)
h̄
giving
ψ 00 + k 2 ψ = 0 (3.2)
3.1. ENERGY LEVELS 55
which is just a second order, homogeneous differential equation with constant

coefficients. The Auxilliary equation is
r2 + k2 = 0 (3.3)
which has solutions

r = ±ik (3.4)
According to Theorem 1 the solution is (α = 0, β = k)
ψ(x) = C cos kx + D sin kx (3.5)
(We could have picked any of the other solutions, e.g. ψ(x) = E cos(kx + δ).
These other solutions are explored in problem 3.2.) Thus ψ(x) is a sinusoidal
function! Let’s try to figure out the unknown constants. We would assume
it works just like the classical case (see Example 2.1.1) where the constants
are determined from the boundary conditions.
What are the boundary conditions? Now we have to think quantum
mechanically, not classically. In Figure 3.1 I have written ψ = 0 in the
regions outside the infinite box. This is because if the walls are truly infinite
the marble can never get out of the box. (It can’t even tunnel out. See later.)
Thus the probability of finding the marble outside the box is zero. This is our
quantum mechanical boundary condition. Mathematically we write
ψ(x < 0) = ψ(x > a) = 0 (3.6)
Now the marble is inside the box and so the probability of finding the marble
inside the box is not zero.
ψ(0 < x < a) 6= 0 (3.7)
OK, so we know the marble won’t be outside the box, but it will be inside.
But what happens right at the edge of the wall? Is the marble allowed to be
there or not? ψ(x) is supposed to be a well behaved mathematical function.
That is, it is not allowed to have infinities, spikes and jumps (discontinuities).
In fancy language we say that the wave function and its derivatives must be
continuous. Thus the wave function outside the box must equal the wave
function inside the box at the boundary. Therefore the wave function inside
the box must be zero at the wall.
ψ(x = 0) = ψ(x = a) = 0 (3.8)

This is the mathematical statement of our quantum mechanical boundary

condition. Notice it says nothing about the amplitude of the wave function.
Therefore, unlike the classical case of Example 2.1.1, the boundary condition
will not tell us the amplitude. (We will see in a minute that we get the
amplitude from the normalization condition (2.34).)
Combining (3.5) and (3.8) we have
ψ(x = 0) = 0 = C (3.9)
Thus C = 0 and therefore (3.5) becomes
ψ(x) = D sin kx (3.10)
Combining this with (3.8) gives
ψ(x = a) = 0 = D sin ka (3.11)
which means
sin ka = 0 (3.12)
(We don’t pick D = 0, otherwise we end up with nothing. Actually nothing
is a solution, but it’s not very interesting.) This implies that ka = 0, ±π,
±2π · · ·. The ka = 0 solution doesn’t interest us because again we get
nothing (ψ = 0). Also the negative solutions for ka are no different from
the positive solutions because sin(−ka) = − sin ka and the minus sign can
be absorbed into the normalization. The distinct solution are
nπ
k= n = 1, 2, 3 · · · . (3.13)
a
Now from (3.1) this gives
h̄2 k 2 π 2 h̄2
En = = n2 (3.14)
2m 2ma2
Thus the boundary condition tells us the energy! (not the amplitude). And
see how interesting this energy is. It depends on the integer n. Thus the
energy cannot be anything (as in the domial case) but comes in discrete steps
according to the value of n. We say that the energy is quantized. Because
there are only certain values of E allowed, depending on the value of n, I have
π 2 h̄2 π 2 h̄2
added a subscript to E in (3.14) as En . Thus E1 = 2ma 2 , E2 = 4 2ma2 = 4E1 ,
E3 = 9E1 , E4 = 16E1 etc. Thus
En = n2 E 1 (3.15)
3.2. WAVE FUNCTION 57
This energy quantization is one of the most important features of quantum

mechanics. That’s why it’s called quantum mechanics. A picture of the
allowed energy levels for the infinite box is shown in Figure 3.2. Another
very important feature is the lack of a zero energy solution. E = 0 is not
allowed in quantum mechanics. The quantum marble simply can never sit
still.
What about the classical limit? Notice that if the box is very wide (a
is large) then the infinite tower of energy levels will get very close together
and E1 ≈ 0. If the levels are close together it will appear that the marble
can have any value of energy because the closely spaced levels will look like
a continuous distribution. (Do Problem 3.1)
3.2 Wave Function

Let’s return to the wave function. From (3.10) and (3.13) we have
nπ
ψ(x) = D sin x (3.16)
a
but we still don’t have D. This is determined not from the boundary con-
ditions but from the normalization conditions (2.34), which for our example
is written Z Z Z
0 a ∞
|ψ|2 dx + |ψ|2 dx + |ψ|2 dx = 1 (3.17)
−∞ 0 a
However ψ = 0 outside the box, so that the first and third integrals are zero,
leaving Z a
nπ
D2 sin2 x dx = 1 (3.18)
0 a
which gives
Footnote:The integral is easily evaluated using cos 2θ = 1−2 sin2 θ where
θ ≡ nπx
a . q
D2 a2 = 1 giving D = 2
a. Thus our solution (3.16) is
r
2 nπ
ψn (x) = sin x (3.19)
a a
which we see is different for each value of n (which is why I add a subscript
to ψn .) Several of these wave functions are plotted in Figure 3.3. Recall that
the value of n characterizes the energy level En . Thus for every En there is
a separate ψn . These are combined in Figure 3.4.
q
2
Example 3.1 Check that ψ2 (x) = a sin 2π
a x is normalized.
Ra
Solution We need to check that 0 ψ2∗ ψ2 dx = 1
Z a Z
2 a 2 2π
ψ2∗ (x)ψ2 (x)dx = sin x dx
0 a 0 a
2a
= =1
a2
Example 3.2 Check that ψ2 (x) and ψ1 (x) are mutually orthog-
onal.
Ra
Solution We need to check that 0 ψ2∗ (x)ψ1 dx = 0
Z a Z a
2 2π π
Define I ≡ ψ2∗ (x)ψ1 (x)dx = sin x sin x dx
0 a 0 a a
Z a
4 π π
= sin2
x cos x dx using sin 2θ = 2 sin θ cos θ
a0 a a
π π π
Let u = sin x ⇒ du = cos x dx.
a a a
Z 0
4a
Thus I= u2 du = 0
aπ 0
because u = 0 for x = 0 and u = 0 for x = a.
In these exercises we checked orthonormality for some specific functions.

We have already proved normality for any function via (3.19) and Griffiths
(Pg. 27) proves orthogonality for any functions where m 6= n.
Figure 3.1: Infinite 1-dimensional Box with Width a.

Figure 3.2: Energy levels for Infinite 1-dimensional Box

Figure 3.3: Wave Functions for Infinite 1-dimensional Box

Figure 3.4: Energy Levels and Wave Functions for Infinite 1-dimensional
Box
3.3. PROBLEMS 63
3.3 Problems
3.1 Consider the infinite 1-dimensional box. If the particle is an electron,

how wide would the box have to be to approximate classical behavior?
(Hint: Classical behavior will pertain if the energy levels are “closely
spaced” or if E1 is close to zero. The latter condition is easier to quantify,
but close to zero compared to what? The only “natural” energy side is the
rest mass of the electron. Thus let’s just say that classical behavior pertains
2
if E1 = m100
ec
.)
3.2 For the infinite 1-dimensional box, show that the same energy levels
and wave functions as obtained in (3.14) and (3.19) also arise if the other
solution y(x) = Ae(α+iβ)x + Be(α−iβ)x is used from Theorem 1.
3.4 Answers
3.1 a ≈ 10, 000 fm = 10−11 m (approximately)

Chapter 4
POSTULATES OF
QUANTUM MECHANICS
We have already studied some of the postulates of quantum mechanics in

Section 1.2. In this chapter we are going to develop the rest of the postulates
and we shall also discuss the fascinating topic of measurement in quantum
theory. Before getting to the other postulates however, we shall need a little
bit more mathematical background.
4.1 Mathematical Preliminaries

4.1.1 Hermitian Operators
With all those i’s floating around in the definitions of operators like p̂ ≡
−ih̄ ∂x
∂
or Ê ≡ ih̄ ∂t
∂
, we might wonder whether the expectation values of these
operators are real. We want them to be real or otherwise the expectation
values of p̂ or Ê won’t correspond to the momentum or energy that we
actually measure in the real world.
Let’s check that the expectation values of p̂ and Ê are real.
Example 4.1.1 Show that the expectation value of the momen-

tum operator is real (i.e. show that hp̂i = hp̂i∗ ).
Solution
Z ∞ ∂Ψ
hp̂i = −ih̄ Ψ∗ dx
−∞ ∂x
65
66 CHAPTER 4. POSTULATES OF QUANTUM MECHANICS
Z ∞ ∂Ψ∗
therefore hp̂i∗ = ih̄ Ψ dx
−∞ ∂x
Z ∞
= ih̄ ΨdΨ∗
−∞
½ Z ∞ ¾
= ih̄ [ΨΨ∗ ]∞
−∞ − Ψ∗ dΨ
−∞
where we have used integration by parts. The first boundary

term is zero, giving
Z ∞ ∂Ψ
hp̂i∗ = −ih̄ Ψ∗ dx
−∞ ∂x
= hp̂i
(do Problem 4.1)

Now an operator which has a real expectation value is called an
Hermitian operator.
The operators that we have encountered so far, such as the momentum
h̄2 ∂ 2
operator p̂ ≡ −ih̄ ∂x∂
, the kinetic energy operator T̂ ≡ − 2m ∂x2
, the energy
operator Ê ≡ ih̄ ∂t all have real expectation values and are therefore all Her-
∂
mitian operators. In fact it seems eminently reasonable that all observables

in quantum mechanics should be real.
4.1.2 Eigenvalue Equations

We have already seen what happens when operators act on functions. For the
infinite 1-dimensional box the Hamiltonian operator inside the box (U = 0)
h̄2 d2
was Ĥ = − 2m dx2
acting on the wave function
√
2mE
ψ(x) = D sin kx where k≡
h̄
(see equation (3.1)). With Ĥ acting on ψ as in Ĥψ we have
h̄2 h̄2 k 2
Ĥψ = − (−Dk 2 sin kx) = D sin kx
2m 2m
h̄2 2mE
= D sin kx
2m h̄2
= E D sin kx
= Eψ
4.2. POSTULATE 4 67
This is kind of interesting if you think about it. A complicated operator

Ĥ acts on a function ψ and gives back the function ψ multiplied by a number
E!
Think about what might have happened instead. A general operator B̂
might do all sorts of weird things to functions, φ. We might have
B̂φ = φ2
or
B̂φ = φ + 7
or µ ¶2
dφ
B̂φ =
dx
or
B̂φ = bφ
(4.1)
where b is a number. It’s this last operator equation which is the special one
and it’s just like Ĥψ = Eψ. In fact this last operator equation is so special
that it’s given a name. It’s called an eigenvalue equation. An eigenvalue
equation is one in which an operator B̂ acts on a function φ and gives back
simply the original function multiplied by a number b. In such a case the
function φ is called an eigenfunction and the number b is called an eigenvalue.
The eigenvalue and eigenfunctions need not be unique. There might be lots
of them in which case we would write
B̂φi = bi φi (4.2)
4.2 Postulate 4
Having discussed Hermitian operators and eigenvalue equations, we are ready
to formulate our next postulate.
Postulate 4: To every physical observable b there corre-

sponds a Hermitian operator B̂ such that
B̂φi = bi φi .
This makes a lot of sense. In classical mechanics we have observbles like

energy and momentum, but in quantum mechanics we don’t have these any
more. They get replaced by operators. But we still want to observe things
so we say in the postulate that our observables are represented by operators.
And they are special Hermitian operators to ensure that the observables are
ordinary real numbers. The observables that we talked about in classical
mechanics will now be expectation values of Hermitian operators which will
be real. Furthermore these operators satisfy eigenvalue equations with the
eigenvalue being the expectation value of the operator. Recall how this works
for energy where the eigenvalue equation is ĤΨ = EΨ and the expectation
value is (at fixed time)
Z ∞
hHi = Ψ∗ ĤΨ dx
−∞
Z X X XX Z
= c∗n ψn∗ Ĥ cm ψm dx = c∗n cm ψn∗ Ĥψm dx
n m n m
XX Z XX Z
= c∗n cm ψn∗ Em ψm dx = c∗n cm Em ψn∗ ψm dx
n m n m
XX X
= c∗n cm Em δmn = |cn | En
2
n m n
for normalized eigenfunctions ψn . Thus Postulate 4 is hopefully eminently
reasonable.
Finally notice that the converse of Postulate 4 is not necessarily true.
Just because we can dream up a Hermitian operator, it doesn’t mean that
it corresponds to a new physical observable.
In summary, Postulate 4 is saying that the only possible results of mea-
surement are the eigenvalues of the corresponding operator.
We have already seen that the energy observable has eigenvalue E, cor-
responding to the Hermitian operator Ĥ. In that case we had Ĥψn = En ψn
where the eigenvectors are ψn .
4.3 Expansion Postulate

Postulate 5: (Expansion Postulate) Any wave function can
P
be expanded in terms of φi , i.e. ψ = ci φi .
i
In other words, the eigenfunctions of an observable (see Postulate 4) form

basis functions for any wave function.
4.4. MEASUREMENT POSTULATE 69
Postulate 5 can be stated differently:
Postulate 50 : {φi } form a CON set, where the φi are eigen-

functions of observables.
We have also seen that this postulate makes sense. With the energy
eigenfunctions ψn (x) we are able to expand the general eigenfunctions as
X X
i
Ψ(x, t) = cn Ψn (x, t) = (4.3)
n n
(see Section 2.3.7). At t equal to some fixed time to we have
X
Ψ(x, to ) = c0n ψn (x)
n
(4.4)
where
c0n ≡ cn e− h̄ En to
i
with the time dependence absorbed into the constant. Equation (4.4) is
very important. Let us think specifically about the infinite 1-dimensional
box. The wave function for the whole box is Ψ(x, to ), which is a linear
combination of all individual solutions ψn (x). Equation (4.4) could easily
be verified. Take each solution ψn (x), and add them all up and you will still
have a solution! Thus the most general state of the infinite 1-dimensional
box is Ψ(x).
4.4 Measurement Postulate

Postulate 6: (Measurement Postulate) If the state of a sys-
tem is ψ, then the probability that a measure-
ment finds the system in state φj is |cj |2 .
Again let us illustrate this with the 1-dimensional box. The box is in
P
the general state Ψ = cn ψn (x). If you make a measurement then the
n
probability of finding the system in state ψn (x) is |cn |2 .
Recall the probability density is |Ψ|2 so that

X X
|Ψ|2 = Ψ∗ Ψ = c∗n ψn∗ cm ψm e h̄ (Em −En )t
i
n m
The probability is the integral of the probability density. Thus the normal-
ization is
Z ∞ XX Z
c∗n cm ψn∗ (x)ψm (x)dx e h̄ (Em −En )t
i
1= |Ψ|2 dx =
−∞ n m
XX
c∗n cm δnm e h̄ (Em −En )t
i
=
n m
X X
= c∗n cn = |cn |2
n n
showing that Postulate 6 is consistent with the probabilities adding up to 1

and indeed that it is reasonable to interpret each |cn |2 as a probability.
4.5 Reduction Postulate

Now we come to the most famous postulate in quantum mechanics.
Postulate 7: (Reduction Postulate) A coherent superposi-

tion ψ collapses to an eigenfunction φj upon
measurement.
Before we make a measurement on the particle in the box, the state is

P
a coherent superposition ψ = cn ψn . When we make the measurement we
n
find the energy of the particle to be one of En , or the state to be one of ψn .
(Recall, from postulate 6, that the probability to get a particular ψn or En
is |cn |2 .)
What happened when we made the measurement? The act of making
the measurement forced the general state ψ to collapse to a particular state
ψn . This collapse must occur because otherwise an immediate second mea-
surement might not yield the same En .
This collapse of the wave function has mind-boggling philosophical im-
plications. A nice quick discussion is given on Pages 2-4 of Griffiths [1994].
If we have two identically prepared 1-dimensional boxes then when a
measurement is made the first box might collapse to ψ3 and the second
box might collapse to ψ10 . Because the wave function has collapsed then
4.6. SUMMARY OF POSTULATES OF QUANTUM MECHANICS (SIMPLE VERSION)71
immediate subsequent measurements will still give ψ3 and ψ10 . If the wave
functions had not collapsed then we might have got ψ5 and ψ13 on subsequent
measurements. That is we would keep measuring a different energy for the
system which is crazy.
4.6 Summary of Postulates of Quantum Mechan-

ics (Simple Version)
We summarize our postulates for the 1-particle, 1-dimensional case.
1. To each state of a physical system there corresponds a wave function

Ψ(x, t).
2. The time development of the wave function is determined by the Schrö-

dinger equation
Ã !
h̄2 ∂ 2 ∂
− +V Ψ(x, t) = ih̄ Ψ(x, t)
2m ∂x2 ∂t
3. (Born hypothesis) |Ψ|2 is the probability density.
4. To every physical observable b there corresponds a Hermitian operator

B̂ such that B̂φi = bi φi .
5. (Expansion Postulate) {φi } from a CON set, such that any wave func-
P
tion can be written ψ = ci φi .
i
6. (Measurement Postulate) If the state of a system is ψ then the proba-

bility that a measurement finds the system in state φi is |ci |2 .
7. (Reduction Postulate) A coherent superposition ψ collapses to an eigen-

function φi upon measurement.
We shall write a more fancy version later on in terms of quantities called

bras and kets.
Example 4.6.1 This problem concerns the relationship between

expectation values and eigenvalues. Assuming that B̂φi = bi φi ,
calculate the expectation value hB̂i.
Solution
Z
hB̂i ≡ Ψ∗ (x)B̂Ψ(x)dx (at fixed time)
Z X X
= c∗i φ∗i B̂ cj φj dx using the Expansion postulate
i j
XX Z
= c∗i cj φ∗i B̂φj dx
i j
XX Z
= c∗i cj φ∗i bj φj dx
i j
XX Z
= c∗i cj bj φ∗i φj dx
i j
XX X
= c∗i cj bj δij = c∗i ci bi
i j i
X
= |ci | bi 2
(4.5)
i
We previously found that |ci |2 is the probability of finding the

system in state φi if the state of a system is ψ (see Postulate 6).
Writing P (i) ≡ |ci |2 we see that
X
hB̂i = P (i)bi = hbi
i
using our average formula from (1.8). Thus the expectation value
is the average of the eigenvalues.
The interpretation of (4.5) is that if the state of a system is ψ then
|ci |2 is the probability of a measurement yielding the eigenvalue
bi .
Thus in a measurement it is the eigenvalues that are actually
measured (with a certain probability).
Example 4.6.2 If the state of a system ψ is already one of the

eigenfunctions φi , then what is the expectation value hB̂i?
4.6. SUMMARY OF POSTULATES OF QUANTUM MECHANICS (SIMPLE VERSION)73
Solution ψ = φi
Z
hB̂i = ψ ∗ B̂ψ dx
Z
= φ∗i bi φi dx
Z
= bi φ∗i φi dx
= bi
Thus if the system is already in state φi with eigenvalue bi , then

a further subsequent measurement is certain to return the value
bi (unit probability).
The postulates of quantum mechanics tell us why we need to perform

measurements on a set of identically prepared systems, rather than a series
of measurements on a single system. When we make a measurement on
a single system in state ψ, it collapses to state φi with eigenvalue bi upon
measurement. We just saw in the above examples that if we measure it again
it will still be in state φi because it has already collapsed. Thus repeated
measurements will keep giving us the measured eigenvalue bi .
A different identically prepared system will also be in state ψ but on
measurement it might collapse to state φj with eigenvalue bj . Another sys-
tem might collapse to φk with eigenvalue bk . Thus the only way we are going
to get a distribution of different eigenvalues, which we can subsequently av-
erage, is by using a set of identically prepared systems.
4.7 Problems
4.1 Show that the expectation value of the Hamiltonian or Energy operator
is real (i.e. show that hÊi is real where Ê = ih̄ ∂t
∂
).
4.2 Find the eigenfunctions of the momentum operator assuming that P̂ φ =

pφ where p is the momentum.

4.8. ANSWERS 75
4.8 Answers
A) r
30
A=
a5
B)
a
hxi =
2
hpi = 0
5h̄2
hHi =
ma2
ci = 0.99928
c2 = 0
c3 = 0.03701
Part I
1-DIMENSIONAL
PROBLEMS
77
Chapter 5
Bound States
In physics most problems can either be considered as a bound state problem

or a scattering problem. For example the orbits of planets constitute a bound
state problem in gravity, whereas the paths of comets (those with hyberbolic
trajectories, not periodic comets) constitute the scattering problem. Another
example is that of electrons in orbit around a nucleus constituting the atomic
bound state problem, whereas firing electrons at a nucleus in an accelerator
is a scattering problem.
Quantum mechanical bound states are quite different to classical bound
states. The table illustrates some of the differences.
Table 5.1 Properties of Bound States
Classical Bound State Quantum Mechanical Bound State

Particle can have any Particle can only take on certain
energy, E discrete values of energy, En
Particle can have zero energy Particle cannot have zero energy
E1 = 0 E1 6= 0
Particle is trapped in the Particle can escape (or tunnel)
potential well if E < U from the potential well
where U is the potential energy even if E < U
The reason as to why we study such idealized simple problems as 1-

dimensional potential wells (with only 1 particle) is that they exhibit the
general properties listed in Table 5.1.
A very nice summary of the properties of potential wells and barriers can
be found in Table 6-2 on Page 243 of Eisberg and Resnick (1974).
79
80 CHAPTER 5. BOUND STATES
The infinite 1-dimensional well that we studied in Chapter 3 only admits

bound state solutions. A particle could never scatter from the well because
it is infinitely deep. It’s a bit like a black hole. Once you fall in you can
never get out.
The infinite 1-dimensional well was introduced in Chapter 3 so that we
could better understand the postulates of quantum mechanics. In this chap-
ter we shall study two more 1-dimensional bound state problems, namely
the finite well and the harmonic oscillator. We will write the Schrödinger
equation as
2m
ψ 00 + (E − U )ψ = 0
h̄2
(5.1)
5.1 Boundary Conditions

Suppose we have a boundary located at position as shown in Fig. 5.1.
The left region of the boundary is designated as region I and the right side
is region II. When we studied the infinite square well we assumed that the
wave function was continuous across the boundary. That is
ψI (a) = ψII (a) (5.2)
In this section we wish to discuss a second boundary condition that must
be satisfied, namely that the first derivative of the wave function must be
continuous at the boundary of a finite potential. That is
ψI0 (a) = ψII
0
(a) (5.3)
To see this again consider Fig. 5.1. The wave function drawn at the
top of the figure certainly satisfies (5.2), yet it does not satisfy (5.3) and
therefore is not allowed. Why not? The middle figure in Fig. 5.1 shows the
first derivative ψ 0 on both sides of the boundary. Obviously then the second
derivative ψ 00 (shown at the bottom of Fig. 5.1) has an infinite spike at the
boundary. The Schrödinger equation forbids this because U , E and ψ in the
Schrödinger equation are all finite and therefore ψ 00 must be finite as well.
This means that (5.3) must hold at the boundary.
The only exception is when U = ∞, as in the case of the infinite square
well. If U = ∞ then ψ 00 can also be infinite and thus (5.3) was not used for
the infinite square well.
5.2. FINITE 1-DIMENSIONAL WELL 81
5.2 Finite 1-dimensional Well

The finite 1-dimensional well admits both bound state and scattering solu-
tions. If the well is say 20 MeV deep and you scatter in with 80 MeV then
you might scatter out with 60 MeV. In this chapter however we will examine
only the bound state solutions. The scattering solutions will be studied in
the next chapter.
The finite 1-dimensional well is sketched in Fig. 5.1. For convenience we
imagine the well to have a depth of −U0 in the center of the well and U = 0
beyond both edges of the well located at x = −a and x = +a. (We could
have chosen U = U0 beyond both edges and U = 0 in the center and x = 0 to
x = +a. These other combinations are explored in the problems. Of course
the energies and wave functions will always be equivalent.)
Because of the way we have drawn the finite square well potential in Fig.
5.2 the bound states will correspond to
Bound States: E < 0 (5.4)
whereas scattering states are
Scattering: E>0 (5.5)
In this chapter we will only consider bound states, E < 0. In Regions I and
III (x < −a and x > a), we have U = 0 so that the Schrödinger equation
(5.1) is
2mE
ψ 00 + 2 ψ = 0 (5.6)
h̄
but despite the similarity to (3.1) and (3.2) it is not the same equation
because here E is negative. Define
2mE
κ̄2 ≡ (5.7)
h̄2
and thus √
2mE
κ̄ ≡ (5.8)
h̄
but remember now κ̄ is complex because E is negative, whereas in (3.1) k
was real. Proceeding write
ψ 00 + κ̄2 ψ = 0 (5.9)
with Auxilliary equation

r2 + κ̄2 = 0 (5.10)
with solutions
r = ±iκ̄ (5.11)
yielding
ψI (x) = A eiκ̄x + B e−iκ̄x

= C cos κ̄x + D sin κ̄x (5.12)
However the C cos κ̄x + D sin κ̄x solution doesn’t make any sense because κ̄
is complex. Actually (5.8) can alternately be written
s
2m|E|
κ̄ = i ≡ iκ0 (5.13)
h̄
where κ0 is real, and (5.11) becomes
r = ±κ0 (5.14)
yielding
0 0
ψI (x) = A eκ x + B e−κ x (5.15)
which is equivalent to (5.12) because r = ±iκ̄ is actually real. We can avoid
the confusion above if we just agree to always choose κ or k or whatever to
be real at the outset.
5.2.1 Regions I and III With Real Wave Number

Thus let’s start again and write the Schrödinger equation as
(−2mE)
ψ 00 − ψ=0 (5.16)
h̄2
Because E is negative, −E will be positive. Define
2mE
κ2 ≡ − (5.17)
h̄2
or s
2mE
κ≡ − (5.18)
h̄2
which is real because E is negative. Thus
ψ 00 − κ2 ψ = 0 (5.19)
with Auxilliary equation

r 2 − κ2 = 0 (5.20)
with real solutions
r = ±κ. (5.21)
Thus for Regions I and III
ψ(x) = A eκx + B e−κx (5.22)
However, as it stands this wave function blows up for x → ∞ and x → −∞.

Thus in Region I we must have B = 0 and Region II must have A = 0.
These are our boundary conditions. Thus
ψI (x) = A eκx (5.23)

−κx
ψIII (x) = B e (5.24)
which are now both finite for x → ±∞.

We will need to impose further boundary conditions on ψ 0 , so we note
them now.
ψI0 (x) = A κeκx (5.25)

0 −κx
ψIII = −B κe (5.26)
5.2.2 Region II
In the region −a < x < a we have U = −U0 so that (5.1) becomes
2m
ψ 00 + (E + U0 )ψ = 0 (5.27)
h̄2
Now even though E < 0 we will never have E < U0 so that E + U0 will
remain positive. Thus we can define
2m
k2 ≡ (E + U0 ) (5.28)
h̄2
safe in the knowledge that
s
2m(E + U0 )
k≡ (5.29)
h̄2
is real. We use the same symbol for k here as in (3.1) because the Auxilliary
equation and solutions are the same as before in Section 3.1. Equations
(3.3)–(3.5) will be the same as here except with k defined as in (5.29). Thus
ψII (x) = C cos kx + D sin kx. (5.30)
and the derivative is

0
ψII (x) = −Ck sin kx + Dk cos kx (5.31)
5.2.3 Matching Boundary Conditions

We have previously imposed the boundary conditions at infinity for ψI and
ψII . Now we will match the wave functions and their derivatives at the
boundaries between each of the three regions.
The requirement
ψI (−a) = ψII (−a) (5.32)
yields
A e−κa = C cos(−ka) + D sin(−ka)

= C cos ka − D sin ka (5.33)
and
ψI0 (−a) = ψII
0
(−a) (5.34)
yields
Aκ e−κa = −Ck sin(−ka) + Dk cos(−ka)

= Ck sin ka + Dk cos ka (5.35)
We have two equations (5.33) and (5.35) and three unknowns, A, C, D.

Nevertheless let us solve for the two unknowns C and D in terms of A and
let A be later determined from the normalization requirement. Equation
(5.33) gives
A e−κa + D sin ka
C= (5.36)
cos ka
which is substituted into (5.35), which is then solved for D to give
µ ¶
−κa κ
D = Ae cos ka − sin ka (5.37)
k
and substituting back into (5.36) gives

µ ¶
κ
C = A e−κa cos ka + sin ka (5.38)
k
Thus we now have
A −κa
ψII (x) = e [(κ cos ka − k sin ka) sin kx
k
+(k cos ka + κ sin ka) cos kx] (5.39)
0 −κa
ψII = Ae [(κ cos ka − k sin ka) cos kx
−(k cos ka + κ sin ka) sin kx] (5.40)
with ψI (x) still given in (5.23) and (5.25).

Let us now match wave functions at the second boundary. For region II
we now use (5.39) and (5.40) instead of (5.30) and (5.31).
The requirement
ψII (a) = ψIII (a) (5.41)
yields
A −κa
e [(κ cos ka − k sin ka) sin ka + (k cos ka + κ sin ka) cos ka]
k
= B e−κa (5.42)
and
0 0
ψII (a) = ψIII (a) (5.43)
yields
A e−κa [(κ cos ka − k sin ka) cos ka − (k cos ka + κ sin ka) sin ka]
= −Bκ e−ka (5.44)
We have two equations (5.42) and (5.44) and four unknowns A, B, κ, k.

Nevertheless let us solve for B from both equations and then combine the
results. Equation (5.42) gives
A
B= [2κ cos ka sin ka + k(cos2 ka − sin2 ka)] (5.45)
k
and (5.44) gives
A
B= [2k cos ka sin ka − κ(cos2 ka − sin2 ka)] (5.46)
κ
Combining (5.45) and (5.46) yields
κk(1 − tan2 ka) = (k 2 − κ2 ) tan ka (5.47)
which is a quadratic equation for either unknown k or κ. Let us solve for κ

in terms of k. Thus re-arranging (5.47) gives
κ2 tan ka + κk(1 − tan2 ka) − k 2 tan ka = 0 (5.48)
which has the quadratic solution

q
−k(1 − tan2 ka) ± k 2 (1 − tan2 ka)2 + 4k 2 tan2 ka
κ= (5.49)
2 tan ka
which reduces to
κ = k tan ka (5.50)
or
κ = −k cot ka (5.51)
These are the same results as given in Griffiths (1995), equation (2.136), pg.
62 and in Gasiorowicz (1996), equation (5.63), pg. 90.
Recall the two equations (5.42) and (5.44) and four unknowns A, B, κ,
k. The best we can do is eliminate two unknowns and solve for the other
two. Equation (5.45) or (5.46) gives B in terms of A, κ and k. Equations
(5.50) and (5.51) give κ in terms of k. Thus we have solved for B and κ in
terms of the remaining two unknowns A and k. We expect to determine A
separately from normalization, just as we did for the infinite square well.
Let us then summarize our solutions for the finite square well, inserting
the constants we have solved for. We have
ψI (x) = A eκx (5.52)

A
ψII (x) = e−κa [(κ cos ka − k sin ka) sin kx
k
+(k cos ka + κ sin ka) cos kx] (5.53)
A
ψIII (x) = [2κ cos ka sin ka + k(cos2 ka − sin2 ka)] (5.54)
k
with κ given by (5.50) or (5.51).
In writing ψIII (x) we used (5.45) but we could equally well have used
(5.46). It does not matter.
Let us further simplify these wave functions by explicitly substituting

(5.50) and (5.51). Upon substituting κ = k tan ka into (5.53) and (5.54) we
obtain the following simplifications
ψI (x) = A eκx (5.55)

A
ψII (x) = e−κa (k cos ka − κ sin ka) cos kx (5.56)
k
ψIII (x) = A e−κx (5.57)
where we note that ψII (x) is an even function. The other substitution κ =
−k cot ka gives
ψI (x) = A eκx
A
ψII (x) = e−κa (κ cos ka − k sin ka) sin kx (5.58)
k
ψIII (x) = −A e−κx (5.59)
where now ψII (x) is an odd function. Also note that ψIII (x) in (5.59) is
simply the negative of ψIII (x) given in (5.57).
5.2.4 Energy Levels

In the expressions for the wave function, equations (5.55)–(5.59) we have the
one unknown constant A that will later be determined from normalization,
just like the case of the infinite square well. (do Problems 5.1 and 5.2)
There are the two other constants κ and k. Actually only one of these
are unknown because equations (5.17) and (5.28) imply that
2mU0
κ2 + k 2 = (5.60)
h̄2
Thus κ and k were related from the very beginning! There was really only
one undetermined constant, either κ or k.
In the case of the infinite square well the value of k was determined to
be k = nπa from the boundary conditions. This gave us energy quantization
2 h̄2
via En = k2m .
For the finite well the boundary conditions gave us (5.50) and (5.51).
Thus k (or κ) is determined! Thus the energy is already determined!
Look at it this way. Consider the even parity solution (5.50) and (5.60).
They are two equations in two unknowns κ and k. Therefore both κ and k
are determined and consequently the energy E is calculated from (5.17) and
(5.28).
The trouble is though that the two simultaneous equations (5.50) and
(5.60) for κ and k cannot be solved analytically. We have to solve them
numerically or graphically. This is done as follows. Equation (5.60) is the
equation for a circle as shown in Fig. 5.3. The other equation (5.50) (for
even parity) relating κ and k is shown in Fig. 5.4. The solutions of the
two simultaneous equations (5.50) and (5.60) are the points where the two
Figures 5.3 and 5.4 overlap. This is shown in Figure 5.5 where there are
4 points of intersection which therefore corresponds to 4 quantized energy
levels, which are drawn on the potential energy
√ diagram in Fig. 5.6. Notice
2mU0
that the radius of the circle in Fig. 5.3 is h̄ . Thus the radius depends
on the strength of the potential U0 . Looking at Fig. 5.5 then if the potential
U0 is very weak (small radius) then there might be zero bound states (zero
intersections), whereas if the potential well is very deep (large U0 , thus large
radius) then there may be many bound states (many points of intersection).
Thus the number of bound states depends on the depth of the potential well,
or equivalently, on the strength of the potential.
Similar considerations also hold for the odd parity solution (5.51).
5.2.5 Strong and Weak Potentials

Consider what happens if the potential
√ is very strong, or equivalently if the
√
2m(E+U0 )
well is very deep. From k = h̄ we will have k ≈ 2mU h̄
0
so that
the solution of (5.60) will be κ = 0. Then solving the even parity equations
(5.50) yields
tan ka = 0 (5.61)
or
nπ
k= (5.62)
a
√
2m(E+U0 )
Putting this back into k = h̄ gives
n2 π 2 h̄2
En = − U0 (5.63)
2ma2
which is identical to the solution for the infinite square well. (For the infinite
well we had U = 0 inside the well, whereas for the finite well we had U = −U0
inside the well.)
5.3. POWER SERIES SOLUTION OF ODES 89
Notice too that the wave functions become the same as for the infinite
well.
Let us now consider the case of weak potentials or shallow wells.
Given that the number of energy levels depends on the number of in-
tersection points, as shown in Fig. 5.5, which depends on the radius of the
circle or the strength of the potential, we might expect that for a very weak
potential there might be zero bound states. This is not the case however.
For a weak potential, there is always at least one bound state. Again refer to
Fig. 5.5. No matter how small the circle is, there will always be at least one
intersection point or one bound state.
(do Problem 5.3)
5.3 Power Series Solution of ODEs

In the next section we consider the solution of the Schrödinger equation for
the 1-dimensional harmonic oscillator potential U = 12 kx2 . Unfortunately
the time-independent Schrödinger equation can no longer be solved with our
standard methods. We will instead use the power series technique (Kreyszig,
1993).
In this section we shall review this technique and show how it can be
used to obtain an answer that we already know, namely the solution to the
infinite square well potential. The time-independent Schrödinger equation
was
ψ 00 + k 2 ψ = 0 (5.64)
and the solution was
ψ(x) = A sin kx + B cos kx (5.65)
which is obtained before imposing boundary conditions and before specifying
the coordinates of the well (which were subsequently specified as x = 0 and
x = a).
Recall the Taylor series expansion [Spiegel, 1968, pg. 110] written as
(x − x0 )2 00 (x − x0 )2 000
f (x) = f (x0 ) + (x − x0 )f 0 (x0 ) + f (x0 ) + f (x0 ) + · · ·
2! 3!
(5.66)
which specifies the expansion of the function f (x) about the point x = x0 .
Thus the wave function (5.65) is expanded about x = x0 = 0 as
" #
(kx)2 (kx)5 (kx)7
ψ(x) = A kx − + − + ···
3! 5! 7!
" #
(kx)2 (kx)4 (kx)6
+B 1− + − + ··· (5.67)
2! 4! 6!
which is nothing more than an alternative version of (5.65).

Let us now introduce the power series method of solution [Kreyszig 1993].
We expand ψ(x) as a power series
∞
X
ψ(x) = am xm (5.68)
m=0
and calculate the derivatives

∞
X
ψ 0 (x) = mam xm−1 (5.69)
m=1
∞
X
ψ 00 (x) = m(m − 1)am xm−2 (5.70)
m=2
which are substituted back into the differential equation (5.64) to give
∞
X
am [m(m − 1)xm−2 + k 2 xm ] + k 2 (a0 + a1 x) = 0 (5.71)
m=2
We now simply write out all the terms in the sum explicitly and then
equate like coefficients of xm to 0. This yields
2.1a2 + k 2 a0 = 0
3.2a3 + k 2 a1 = 0
4.3a4 + k 2 a2 = 0
5.4a5 + k 2 a3 = 0
6.5a6 + k 2 a4 = 0 etc. (5.72)
where x · y ≡ x × y. These equations can be solved in terms of only two

unknown constants a0 and a1 . Thus
k2 k2
a2 = − a0 = − a0
2.1 2!
k2 k2
a3 = − a1 = − a1
3.2 3!
k2 k4
a4 = − a2 = + a0
4.3 4!
5.3. POWER SERIES SOLUTION OF ODES 91
k2 k4
a5 = − a3 = + a1
5.4 5!
k2 k6
a6 = − a4 = − a0
6.5 6!
k2 k6
a7 = − a5 = − a1 etc. (5.73)
7.6 7!
These are substituted back into the solution (5.68) to yield
ψ(x) = a0 + a1 x + a2 x2 + a3 x3 + a4 x4 + · · ·
k2 k2
= a0 + a1 x − a0 x2 − a1 x3
2! 3!
k4 k 4
+ a0 x4 + a1 x5 + · · ·
"4! 5! #
(kx) 2 (kx)4 (kx)4
= a0 1 − + − + ···
2! 4! 6!
" #
a1 (kx)3 (kx)5 (kx)7
+ kx − + − + ··· (5.74)
k 3! 5! 7!
a1
= a0 cos kx + sin kx (5.75)
k
which we recognize as our familiar solution (5.65) with A ≡ ak1 and B ≡ a0 !
5.3.1 Use of Recurrence Relation

The power series solution can be streamlined by using a recurrence relation,
or recursion formula for the expansion coefficients.
In equation (5.70) note that m is simply a dummy variable which is
summed over. Let’s use a different dummy variable called m + 2. Thus in
(5.70) we make the replacement m → m + 2 to give
∞
X
00
ψ (x) = (m + 2)(m + 2 − 1)am+2 xm+2−2
m+2=2
X∞
= (m + 2)(m + 1)am+2 xm (5.76)
m=0
which is exactly the same as (5.70). Substituting both this and (5.68) back
into the Schrödinger equation (5.64) gives
∞
X
[(m + 2)(m + 1)am+2 + k 2 am ]xm = 0 (5.77)
m=0
instead of (5.71). The advantage of using the new sum in (5.76) is that it is
very straightforward to equate like coefficients of xm to 0 in equation (5.77).
This yields
−k 2
am+2 = am (5.78)
(m + 2)(m + 1)
which is called a recurrence relation, which is a compact formula for each of
the expressions in equations (5.73).
5.4 Harmonic Oscillator

The harmonic oscillator potential is
1
U (x) = mω 2 x2 (5.79)
2
The Schrödinger equation ψ 00 + 2m

h̄2
(E − U )ψ = 0 gets quite messy with this
potential so let’s change variables. Define
r
mω
y≡ x (5.80)
h̄
and
2E
²≡ (5.81)
h̄ω
then the Schrödinger equation is
d2 ψ
+ (² − y 2 )ψ = 0 (5.82)
dy 2
We could use the power series method directly on this equation, but it will get
very complicated. It’s easier to write the wave function as another function
multiplied by an asymptotic function.
By asymptotic we mean the region where x or y goes to infinity. For y
very large the Schrödinger equation becomes
d2 ψ
− y2ψ = 0 (5.83)
dy 2
which has the solution ψ(y) = A e−y

2 /2
where A is a constant. This can be
checked by substitution.
5.4. HARMONIC OSCILLATOR 93
Let’s then write the solution to (5.82) as
ψ(y) ≡ h(y)e−y
2 /2
(5.84)
(NNN See Griffith footnote (14), pg. 38 and see Boas). Substituting this
into the Schrödinger equation (5.82) we obtain a differential equation for
the function h(y) as
h00 − 2yh0 + (² − 1)h = 0 (5.85)
where h0 ≡ dh 00 2
dy and h ≡ dy 2 . We will solve this differential equation with
d h
the power series method. Writing

∞
X
h(y) = am y m (5.86)
m=0
X∞ ∞
X
h0 (y) = = mam y m−1 = mam y m−1 (5.87)
m=1 m=0
∞
X ∞
X
h00 (y) = m(m − 1)am y m−2 = (m + 2)(m + 2 − 1)am+2 y m+2−2
m=2 m+2=2
X∞
= (m + 2)(m + 1)am+2 y m (5.88)
m=0
In (5.87) we have not made the replacement m → m + 1 because of the

yh0 term in (5.85) which will give yh0 ∼ yy m−1 = y m , without having to
make the m → m + 1 replacement. Substituting the above three equations
into (5.85) we obtain
∞
X
[(m + 2)(m + 1)am+2 − (2m + 1 − ²)am ]y m = 0 (5.89)
m=0
and equating like powers of y m gives the recurrence relation

2m + 1 − ²
am+2 = am (5.90)
(m + 2)(m + 1)
Just as our power series solution for the infinite square well gave us two
separate series for aodd and aeven so too does the harmonic oscillator via
(5.90). Obviously all of the aeven coefficients are written in terms of a0 and
the aodd coefficients are written in terms of a1 .
But now we run into a problem. For very large m the recurrence relation
is
2
am+2 ≈ am (5.91)
m
P∞
Thus the ratio of successive terms for the power series h(y) = m=0 am y m
for large m will be
am+2 y m+2 (2m + 1 − ²) 2 2y 2
= y ≈ (5.92)
am y m (m + 2)(m + 1) m
Now recall the series
∞
X xm x2 x3
x
e = =1+x+ + + ··· (5.93)
m=0
m! 2! 3!
gives
∞
X
x2 x2m
e =
m=0
m!
x4 x6 x8
= 1 + x2 + + + + ···
2! 3! 4!
∞
X xm
= (5.94)
m=0,2,4...
(m/2)!
which gives for the ratio of successive terms

xm+2 2x2
= (5.95)
(m/2)xm m
the same as (5.92). Thus for large m we must have
∞
X 2
h(y) = am y m ≈ ey (5.96)
m=0
Therefore the wave function

Ã ∞
!
X
−y 2 /2
e−y
m 2 /2
ψ(y) = h(y)e = am y
m=0
y 2 −y 2 /2 y2
≈ e e =e (5.97)
which blows up for y → ∞. That’s out problem. The wave function is not
normalizable.
This problem can only be solved if the series terminates. That is, at some
value of m, the coefficient am and all the ones above it are zero. Then the
2
series will not behave like ey at large y (i.e. large x). Thus for some value
m ≡ n, we must have
am+2 ≡ an+2 = 0 (5.98)
If this is the case then the recurrence relation (5.90) tells us that all higher
coefficients (eg. an+4 , an+6 etc.) will also be zero.
Now we have no idea as to the value of n. All we know is that it must be
an integer like m. Our argument above will work for n = 0, n = 1, n = 2,
n = 3 etc. That is, we will get finite normalizable wave functions for any
integer value of n, and all of these wave functions will be different for each
value of n because the series will terminate at different n values. (We can
see quantization creeping in!)
There is another piece to this argument. We have noted that there are
actually two independent power series for aeven and aodd . The above argu-
ment only works for one of them. For example, if the even series terminates,
it says nothing about the odd series, and vice versa. Thus if the even series
terminates, then all of the coefficients of the odd series must be zero and
vice versa. (We also expect this physically. For the infinite square well, aeven
corresponded to cos kx and aodd corresponded to sin kx. See equation (5.64).
We know from the properties of separable solutions that the eigenfunctions
will alternate in parity. Thus it makes sense that for a particular value of n
will correspond to either aeven or aodd but not both.)
The requirement (5.98) together with (5.90) gives
2m + 1 − ² ≡ 2n + 1 − ² = 0 (5.99)
yielding
2E
²≡ = 2n + 1 (5.100)
h̄ω
or
µ ¶
1
En = n + h̄ω n = 0, 1, 2, . . .
2
(5.101)
which is our quantization of energy formula for the harmonic oscillator. Just
as with the infinite and finite square wells, the energy quantization is a result
of imposing boundary conditions. In the case of the harmonic oscillator, the

boundary condition is that the wave function should be finite as x → ∞.
An important feature of the harmonic oscillator energy levels is that
they are equally spaced, as shown in Fig. 5.8. Contrast this to the infinite
square well energy levels (En = n2 E1 ) in which the spacing gets bigger as
n increases. See Fig. 3.2. (Note for the infinite well we had n = 1, 2, 3, . . .,
whereas for the harmonic oscillator we have n = 0, 1, 2, 3 . . .).
Let us now turn our attention to the wave function. Recall h(y) ≡
P∞ m which will be a different series for each value of n. Let us
m=0 am y
therefore distinguish each series using the notation
X
n
hn (y) = am y m (5.102)
m=0
and Ã !
X
n
−y 2 /2
e−y
m 2 /2
ψn (y) = hn (y)e = am y (5.103)
m=0
Also the recurrence relation (5.90) now becomes
(n) 2(m − n)
am+2 = am (5.104)
(m + 2)(m + 1)
where we have substituted (5.100) into (5.90). Thus the recurrence relation
is different for different values of n. For n = 0, we have
h0 (y) = a0 (5.105)
and
ψ0 (y) = a0 e−y
2 /2
. (5.106)
For n = 1 we have a0 = 0 (even series is all zero) and
h1 (y) = a1 y (5.107)
and
ψ1 (y) = a1 y e−y
2 /2
. (5.108)
For n = 2, we have all aodd = 0 (odd series is all zero) and
h2 (y) = a0 + a2 y 2 (5.109)
For n = 2 the recurrence relation (5.104) is

(2) 2(m − 2)
am+2 = am (5.110)
(m + 2)(m + 1)
giving
(2)
a2 = −2a0 (5.111)
Thus
h2 (y) = a0 (1 − 2y 2 ) (5.112)
and
ψ2 (y) = a0 (1 − 2y 2 )e−y
2 /2
. (5.113)
For n = 3 we have aeven = 0 (even series all zero) and
h3 (y) = a1 y + a3 y 3 (5.114)
with
(3) 2(m − 3)
am+2 = am (5.115)
(m + 2)(m + 1)
giving
(3) 2
a3 = − a1 (5.116)
3
Thus µ ¶
2
h3 (y) = a1 y − y 3 (5.117)
3
For n = 4 we have aodd = 0 (odd series all zero) and
h4 (y) = a0 + a2 y 2 + a4 y 4 (5.118)
with
(4) 2(m − 4)
am+2 = am (5.119)
(m + 2)(m + 1)
giving
(4)
a2 = −4a0 (5.120)
(4) 1 4
a4 = − a2 = + a0 (5.121)
3 3
Notice that for n = 4 we have a2 = −4a0 , whereas for n = 2 we had
a2 = −2a0 . Thus you must be very careful to work out the recurrence
relation separately for each value of n. Thus
µ ¶
4
h4 (y) = a0 1 − 4y + y 4
2
(5.122)
3
and µ ¶
4
ψ4 (y) = a0 1 − 4y 2 + y 4 e−y /2 .
2
(5.123)
3
The functions hn (y) are related to the famous Hermite polynomials
Hn (y), [Spiegel, 1968, pg. 151] the first few which are defined as
H0 (y) = 1
H1 (y) = 2y
H2 (y) = 4y 2 − 2
H3 (y) = 8y 3 − 12y
H4 (y) = 16y 4 − 48y 2 + 12 (5.124)
We can relate our hn (y) more directly to Hn (y) by re-writing
h0 (y) = a0 (1) = a0 H0 (y)

a1 a1
h1 (y) = (2y) = H1 (y)
2 2
a0 a0
h2 (y) = − (4y − 2) = − H2 (y)
2
2 2
a1 a1
h3 (y) = − (8y − 12y) = − H3 (y)
3
12 12
a0 a0
h4 (y) = (16y − 48y + 12) = H4 (y)
4 2
(5.125)
12 12
The Hermite polynomials satisfy Hermite’s differential equation [Spiegel,
1968, pg. 151]
z 00 − 2yz 0 + 2nz = 0 (5.126)
where n = 0, 1, 2 . . . and z 0 ≡ dz(y)

dy with solutions
z(y) ≡ Hn (y) (5.127)
Recall we had h00 − 2yh0 + (² − 1)h = 0 but with ² = 2n + 1. Thus this

becomes h00 − 2yh0 + 2nh = 0 which is Hermite’s ODE. That is the Hermite
polynomials satisfy
Hn00 − 2yHn0 + 2nHn = 0 (5.128)
You can check simply by substituting each of (5.124) into (5.128). The
Hermite polynomials also satisfy the following recurrence relations [Spiegel,
1968, pg. 151]
Hn+1 = 2yHn − 2nHn−1 (5.129)
Hn0 = 2nHn−1 (5.130)

which again you can check by explicit substitution.
The Hermite polynomials can be obtained from Rodrigue’s formula [Spiegel,
1968, pg. 151]
n
2 d
(e−y )
2
Hn (y) = (−1)n ey n
(5.131)
dy
∞
X
2 1
e2ty−t = Hn (y)tn (5.132)
n=0
n!
The function on the left is called a generating function of the Hermite poly-
nomials. (This can be checked by expanding the generating function in terms
of its Taylor series expansion.)
One of the most important properties of the Hermite polynomials is that
they form an ON set. This is seen from the following integrals [Spiegel, 1968,
pg.152]
Z ∞
e−y Hm (y)Hn (y)dy = 0 for m 6= n
2
(5.133)
−∞
Z ∞
√
e−y Hn (y)2 dy = 2n n! π
2
(5.134)
−∞
(Hn (y) can be Normalized simply by multiplying them by √ 1

√ .) Again
2n n! π
these two equations can be checked explicitly by substituting some of the
Hn (y) from (5.124).
Let us now return to our wave functions, which we wrote as ψ(y) =
h(y)e−y /2 . We have found different h(y) depending on n, and we should
2
also put in a normalization factor. Thus the wave functions should be written
as
ψn (y) = Cn hn (y)e−y /2
2
(5.135)
where Cn is a normalization. Using a different normalization An we can
write ψ in terms of the Hermite polynomials
ψn (y) = An Hn (y)e−y
2 /2
(5.136)
Normalization requires
s
Z ∞ Z ∞
h̄
1 = ψn∗ (x)ψn (x)dx = ψn∗ (y)ψn (y)dy
−∞ mω −∞
s
Z ∞
h̄ 2
e−y Hn (y)2 dy
2
= A
mω n −∞
s
h̄ 2 n √
= A 2 n! π (5.137)
mω n
q q
where we have used y ≡ mω
h̄ x and dx = h̄
mω dy and (5.134). This gives
¡ mω ¢1/4
An = πh̄ √1 so that the normalized Harmonic Oscillator wave func-
2n n!
tions are finally
µ ¶1/4
mω 1
Hn (y)e−y /2
2
ψn (x) = √ (5.138)
πh̄ n
2 n!
q
where y ≡ mω
h̄ x. This result together with the energy formula En =
1
(n + 2 )h̄ωcompletes our solution to the 1-dimensional harmonic oscillator
problem. The first few eigenfunctions and probabilities are plotted in Fig.
5.9. Note that for the odd solutions, the probability of the particle in the
center of the well is zero. The particle prefers to be on either side. (See also
Fig. 2.5, pg. 42 of [Griffiths, 1995].)
(do Problems 5.4–5.9)
5.5 Algebraic Solution for Harmonic Oscillator

In this section we shall solve the Schrödinger differential equation for the har-
monic oscillator with an alternative method. This illustrates a very unique
and novel approach to solving ODEs, and relies on algebra rather than cal-
culus. The ideas presented here are used extensively in quantum field theory.
Recall the Schrödinger equation for the oscillator
h̄2 d2 ψ 1
− + mω 2 x2 ψ = Eψ (5.139)
2m dx2 2
Defining the Schrödinger equation in terms of the Hamiltonian operator
Ĥψ = Eψ (5.140)
5.5. ALGEBRAIC SOLUTION FOR HARMONIC OSCILLATOR 101
then
p2 1
+ mω 2 x2
Ĥ = (5.141)
2m 2
for the harmonic oscillator Hamiltonian. (We are going to be lazy and just
write p instead of p̂ and x instead of x̂.) Let us define two new operators
1
â ≡ √ (mωx̂ + ip̂) (5.142)
2mh̄ω
and
1
â† ≡ √ (mωx̂ − ip̂) (5.143)
2mh̄ω
or in our lazy rotation
)
a 1
≡√ (mωx ± ip)
a† 2mh̄ω
(5.144)
(Read a† as “a dagger”.) Everyone [Goswami, 19xx, pg. 143; Liboff, 1992, pg.
191; Ohanian, 1990, pg. 151; Gasiorowicz, 1996, pg 131] uses this definition
except Griffiths [1995, pg. 33]. Also everyone uses the symbols a and a† , but
Griffiths uses a+ and a− . Notice that
a† = a∗ (5.145)
which is called the Hermitian conjugate of a. In general the Hermitian

conjugate of a matrix is the complex conjugate of the transpose matrix.
A† ≡ Ã∗ (5.146)
Ã !
A11 A12
where Ã is the transpose of A. Thus if A ≡ then Ã =
A21 A22
Ã ! Ã !
A21 A22 A∗21 A∗22
and A† = . A matrix is Hermitian if
A11 A12 A∗11 A∗12
A† = A (5.147)
and it can be shown (see later) that Hermitian matrices have real eigenvalues.
Our operator a is a 1-dimensional matrix so obviously we just have a† = a∗ .
We shall pursue all of these topics in much more detail later. Let’s return
to our operators in (5.144).
The operators in (5.144) can be inverted to give
s
h̄
x= (a + a† ) (5.148)
2mω
and s
mh̄ω †
p=i (a − a) (5.149)
2
(do Problem 5.10) Now the operators a and a† do not commute. In fact
using [x, p] = ih̄, it follows that
[a, a† ] = 1 (5.150)
(do Problem 5.11) The Hamiltonian can now be written in three different
ways as
1
H = (aa† + a† a)h̄ω
2
= (aa† − 12 )h̄ω
= (a† a + 12 )h̄ω (5.151)
Thus an alternative way to write the Schrödinger equation for the harmonic
oscillator is
(aa† − 12 )h̄ωψ = Eψ
(5.152)
or
(a† a + 12 )h̄ωψ = Eψ
(5.153)
which are entirely equivalent ways of writing the Schrödinger equation com-
pared to (5.139). A word of caution!
(aa† − 12 )h̄ωa† ψ 6= Ea† ψ (5.154)

and similarly for (5.153). The reason is because a and a† do not commute.
The correct statement is
a† (aa† − 12 )h̄ωψ = Ea† ψ

= (a† aa† − 12 a† )h̄ωψ
= (a† a − 12 )h̄ωa† ψ (5.155)
which is quite different to (5.153). Note that (5.155) is not the Schrödinger
equation. The Schrödinger equation is (5.152) or (5.153). To turn (5.155)
into a Schrödinger equation we add h̄ωa† ψ to give
(a† a − 12 )h̄ωa† ψ + h̄ωa† ψ = Ea† ψ + h̄ωa† ψ
which is
(a† a + 12 )h̄ωa† ψ = (E + h̄ω)a† ψ (5.156)
Define ψ 0 ≡ a† ψ and E 0 ≡ E + h̄ω and we have
(a† a + 12 )h̄ωψ 0 = E 0 ψ 0 . (5.157)
Thus we have the following “theorem”.
Theorem 5.1 If ψ satisfies the Schrödinger equation with

energy E, then a† ψ and aψ satisfy the
Schrödinger equation with energy E + h̄ω and
E − h̄ω respectively.
The proof of the a† ψ piece of this theorem is simply the collection of equa-
tions from (5.155) to (5.157). The aψ piece is done in the problems. (do
Problem 5.13) The second Schrödinger equation corresponding to (5.156) is
(aa† − 12 )h̄ωaψ = (E − h̄ω)aψ (5.158)
Corollary If ψ satisfies the Schrödinger equation with

energy E, then a†n ψ and an ψ, where n is in-
teger, satisfy the Schrödinger equation with
energy E + nh̄ω and E − nh̄ω respectively.
I will leave you to prove this by induction. (do Problem 5.14) This means
for example, that
(aa† − 12 )h̄ω aaa ψ = (E − 3h̄ω)aaaψ (5.159)

or
(a† a + 12 )h̄ω a† a† ψ = (E + 2h̄ω)a† a† ψ (5.160)
Thus the operators a† and a when applied to the wave function ψ either
raise or lower the energy by an amount h̄ω. For this reason a† is called the
raising operator or creation operator and a is called the lowering operator
or destruction operator or annihilation operator.
So by repeatedly applying the destruction operator a to ψ we keep low-
ering the energy. But this cannot go on forever! For the harmonic oscillator
with the minimum of potential U = 0 at x = 0 we can never have E < 0.
The harmonic oscillator must have a minimum energy E0 , with correspond-
ing wave function ψ0 such that
aψ0 = 0 (5.161)
Now substitute this into the Schrödinger equation (5.153) to give
(a† a + 12 )h̄ωψ0 = E0 ψ0 (5.162)
giving
E0 = 12 h̄ω (5.163)
because a† a h̄ω ψ0 = 0 according to (5.161).
Corollary restated If ψ0 satisfies the Schrödinger equation

with energy E0 = 12 h̄ω (which we have
just found that it does), then a†n ψ0 satis-
fies the Schrödinger equation with energy
E0 + nh̄ω = (n + 12 )h̄ω.
Thus the Schrödinger equation (5.153) can be written
(a† a + 12 )h̄ωψn = En ψn (5.164)
where
An †n
ψn = a ψ0 (5.165)
A0
with An and A0 being normalization constants. (We have written ψn =
An †n †n
A0 a ψ0 instead of ψn = An a ψ0 because the latter expression gives ψ0 =
A0 ψ0 for n = 0 which is no good.) Also
En = (n + 12 )h̄ω (5.166)
which is the same result for the energy that we obtained with the power
series method.
Let’s now obtain the wave functions ψn which can be obtained from
n †n
ψn = A A0 a ψ0 once we know ψ0 . Using (5.161)
1
aψ0 = √ (mωx + ip)ψ0 = 0 (5.167)
2mh̄ω
we have (with p = −ih̄ dx

d
)
dψ0 mω
=− xψ0 (5.168)
dx h̄
which is a first order ODE with solution
ψ0 = A0 e− 2h̄ x
mω 2
= A0 e−y = A0 H0 (y)e−y
2 /2 2 /2
(5.169)
q
with y ≡ mω h̄ x which is the same solution that we found for the power
series method. (Recall H0 (y) = 1). To obtain ψn is now straightforward.
We have
· µ ¶¸n
An †n 1 d
e− 2h̄ x
mω 2
ψn = a ψ0 = An √ mωx − h̄ (5.170)
A0 2mh̄ω dx
q
However let’s first write a† a little more simply. Using y ≡ mω
h̄ x we have
) µ ¶
a 1 d
= √ y±
a† 2 dy
(5.171)
(Exercise: Prove this.) Thus (5.170) is
µ ¶n
An †n 1 d
e−y
2 /2
ψn = a ψ0 = An √ n y − (5.172)
A0 2 dy
Example 5.5.1 Calculate ψ1 , without normalization.

Solution
µ ¶
A1 † 1 d
e−y /2
2
ψ1 = a ψ 0 = A1 √ y −
A0 2 dy
1 1
= A1 √ 2ye−y /2 = A1 √ H1 (y)e−y /2
2 2
2 2
A very useful formula to use in calculating ψn is
Hn+1 = 2yHn − Hn0 (5.173)
obtained by combining (5.129) and (5.130).
Example 5.5.2 Calculate ψ2 , without normalization.

Solution
A1 † † A2 †
ψ2 (y) = a a ψ0 = a ψ1
A0 A1
µ ¶
A2 1 1 d
H1 (y)e−y /2
2
= A1 √ √ y −
A1 2 2 dy
1
= A2 H2 (y)e−y /2
2
(do Problem 5.15)

From the above examples and from Problem 5.15 we have
ψ0 = A0 H0 (y)e−y /2
2
(5.174)
1
ψ1 = A1 √ H1 (y)e−y /2
2
(5.175)
2
1
ψ2 = A2 H2 (y)e−y /2
2
(5.176)
2
1
ψ3 = A3 √ H3 (y)e−y /2
2
(5.177)
2 2
1
ψ4 = A4 H4 (y)e−y /2
2
(5.178)
4
Obviously the generalization is

1
ψn = An √ n Hn (y)e−y /2
2
(5.179)
2
Let us now obtain the normalization constants.
Example 5.5.3 Calculate A0 .

Solution
Z ∞
ψ0∗ (x)ψ0 (x)dx = 1
−∞
s
Z ∞
h̄
= ψ0∗ (y)ψ0 (y)dy
mω −∞
s
Z ∞
h̄ 2
H0 (y)2 e−y dy
2
= A
mω 0 −∞
s
πh̄ 2
= A using equation (5.123)
mω 0
Thus µ ¶1/4
mω
A0 = (5.180)
πh̄
Example 5.5.4 Calculate An for arbitrary n.

Solution
s
Z ∞
h̄
ψn∗ (y)ψn (y)dy = 1
mω −∞
s
Z ∞
h̄ 2 1
Hn (y)2 e−y dy using (5.181)
2
= A
mω n 2n −∞
s
πh̄ 2
= A n! using (5.134)
mω n
Thus µ ¶1/4
mω 1
An = √
πh̄ n!
giving
An 1
=√ (5.181)
A0 n!
An †n
Thus we finally have from ψn = A0 a ψ0 ,
1
ψn = √ a†n ψ0
n!
(5.182)
and
µ ¶1/4
mω 1
Hn (y)e−y /2
2
ψn = √
πh̄ n
2 n!
(5.183)
which is identical to the result we obtained with the power series method.
5.5.1 Further Algebraic Results for Harmonic Oscillator

We have obtained the energy and wave functions for the harmonic oscillator
and thus we have completely solved the harmonic oscillator problem. In this
section I just want to show you some other useful results that arise when
one uses the creation and annihilation operators.
We previously found En = (n + 22 )h̄ω. The Schrödinger equation is
Hψn = En ψn (5.184)
with H given by any of the three expressions in (5.151). Choosing the third
expression we have
(a† a + 12 )h̄ωψn = (n + 12 )h̄ωψn
or
a† aψn = nψn (5.185)
Also the second expression gives (aa† − 12 )h̄ωψn = (n + 12 )h̄ωψn to give
aa† ψn = (n + 1)ψn (5.186)

Defining the number operator

N̂ ≡ a† a (5.187)
gives
N ψn = nψn
(5.188)
which is the Schrödinger equation! Thus
H = (n + 12 )h̄ω (5.189)
Now some useful results are (do Problem 5.16 and 5.17)
Z ∞ Z
(aψn )∗ aψn dx = ψn∗ a† aψn dx (5.190)
−∞
and Z Z
(a† ψn )∗ a† ψn dx = ψn∗ aa† ψn dx (5.191)
n †n
Before we had ψn = AA0 a ψ0 and we had to go to a lot of trouble to find
that A √1
A0 = n! . We can get this result here more quickly.
n
√
Example 5.5.5 Show that a† ψn = n + 1ψn+1 .
Solution Writing
An †n
ψn = a ψ0
A0
and
An+1 † †n An+1 †
ψn+1 = a a ψ0 = a ψn
A0 An
we have
Z
∗
ψn+1 ψn+1 dx = 1
µ ¶ Z
An+1 2
= (a† ψn )∗ (a† ψn )dx
An
µ ¶ Z
An+1 2
= ψn∗ aa† ψn dx
An
µ ¶ Z
An+1 2
= ψn∗ (n + 1)ψn dx
An
which follows from (5.186), giving

An+1 1
=√
An n+1
Thus
√
a† ψn = n + 1ψn+1
(5.192)
An+1 †
Actually instead of ψn+1 = An a ψn
we would just have written
ψn+1 = Ca† ψn because we know from Theorem 5.1 that this ψn+1
satisfies the Schrödinger equation. As above we would then find
1
C = √n+1 .
Similarly it can be shown (do Problem 5.18) that
√
aψn = nψn−1
(5.193)
which is consistent with aψ0 = 0.
Example 5.5.6 Show that ψn = √1 a†n ψn .

n!
Solution We have
An †n
ψn = a ψ0
A0
An ³ † ń−1 † An ³ † ń−1
= a a ψ0 = a ψ1
A0 A0
√
where we have used a† ψ0 = 0 + 1ψ0+1 = ψ1 .
Continuing
An ³ ń−2 An ³ † ń−2 √
ψn = a† a† ψ1 =
a 2ψ2
A0 A0
An ³ ń−3 √ An ³ † ń−3 √ √
= a† 2a† ψ2 = a 2 3ψ3
A0 A0
An ³ ń−4 √ √ An ³ † ń−4 √ √ √
= a† 2 3a† ψ3 = a 2 3 4ψ4
A0 A0
Thus we have
An √
ψn = n!ψn
A0
√
and we must therefore have A
A0 n! = 1 or
n An
A0 = √1
n!
giving
1
ψn = √ a†n ψ0
n!
Later we are going to introduce “Dirac notation.” This involves, among

other things, writing
ψn ≡ |ni (5.194)
Let us summarize our results in both notations. Thus
H = (N + 12 )h̄ω and N ≡ a† a (5.195)
We have the Schrödinger equation
N ψn = nψn or N |ni = n|ni (5.196)
and the creation and annihilation operators

√ √
a† ψn = n + 1ψn+1 or a† |ni = n + 1|n + 1i (5.197)
√ √
aψn = nψn−1 or a|ni = n|n − 1i (5.198)
and
1 1
ψn = √ a†n ψ0 or |ni = √ a†n |0i (5.199)
n! n!
Finally, recall that En = (n + 12 )h̄ω resulted from
aψ0 ≡ 0 or a|0i ≡ 0 (5.200)
which is consistent with (5.198).

Chapter 6
SCATTERING STATES
In the previous chapter we studied bound state problems and in this chapter
we shall study un-bound or scattering problems. For bound state problems,
the most important things to know were the wave functions and discrete en-
ergy levels En . However for scattering problems the energy E is not discrete
and can be anything. We are particularly interested in the wave functions
which we shall use to determine the transmission and reflection coefficients
T and R.
6.1 Free Particle

Conceptually, the simplest scattering state is the free particle where U = 0
everywhere. However, we will see that some care is required in specifying
the wave functions.
If U = 0 everywhere and E > 0 then the solutions to the Schrödinger
equation are the same as inside the infinite square well, namely
ψ(x) = C cos kx + D sin kx

= A eikx + B e−ikx (6.1)
where
h̄2 k 2
E ≡ h̄ω ≡ (6.2)
2m
In the case of the infinite well we imposed boundary conditions and found
that ψ(x) = D sin nπ a x and also that the energy was quantized. However for
the free particle we have no such boundary conditions and thus the energy
of the free particle can be anything.
113
114 CHAPTER 6. SCATTERING STATES
Something we do need to specify for a free particle is whether it is trav-

elling to the Left or Right. We need this because later we will consider scat-
tering a free particle from a potential barrier and we want to know whether
the incident particle is coming in from the Left or Right (in 1-dimension).
The outgoing wave will typically be in both directions. Suppose the incident
wave comes in from the Left. Then the reflection coefficient will be the Left
outoing amplitude divided by the Left incoming amplitude and the trans-
mission coefficient will be the Right outgoing amplitude divided by the Left
incoming amplitude.
With the solution in (6.1) the notion of Left and Right is most easily
expressed with the exponential solutions. Also the notion of a wave travelling
to the Left or Right means we must bring in time dependence, thus
Ψ(x, t) = ψ(x)e−iωt
= A ei(kx−ωt) + B e−i(kx+ωt) (6.3)
There are no boundary conditions and no quantization and so (6.3) is our
solution. Recall the wave equation in 1-dimension from ordinary mechanics,
∂2y 1 ∂2y
− =0
∂x2 v 2 ∂t2
where y = y(x, t) is the height of the wave at position x and time t and v is
the speed of the wave [Feynman, 1964]. Solutions of the wave equation are
(obviously) called waves. Ψ(x, t) in (6.3) is a solution to the wave equation
with wave speed
s
ω E
vp ≡ ± =
k 2m
(6.4)
which we shall call the phase velocity. (This also just comes from v = f λ
with ω ≡ 2πf and k ≡ 2π ω 2π ω
λ to give v = 2π k = k .) Exponential solutions of
the type (6.3) are called plane waves. Another way to see where the phase
velocity comes from, and how Left and Right moving waves enter the picture
is to consider waves of constant phase. This means that
kx ± ωt = constant. (6.5)
Thus
ω
x=C∓ t (6.6)
k
6.1. FREE PARTICLE 115
and the wave speed

dx ω
=∓ (6.7)
dt k
in agreement with (6.4).
For x = C − ωk t, then as t increases, x decreases which is a wave travelling
to the Left and vp ≡ dx dt = − k . For x = C + k t, then as t increases, x
ω ω
increases and the wave travels to the Right or vp ≡ dx ω

dt = + k . Thus in (6.3)
eikx travels to Right

−ikx
e travels to Left
We have seen that the free particle wave A eikx + B e−ikx travels to the
Left or Right. To specify a wave travelling to the Left, we set A = 0, giving
ψL = B e−ikx (6.8)
and similarly for a wave travelling to the Right, B = 0 and
ψR = A eikx (6.9)
Alternatively we can write k as negative or positive and write only
ψ = C eikx (6.10)
and just identify
k>0 wave travelling to Right

k<0 wave travelling to Left
What are we to make of our infinite square well bound³ state solution ´
ψ = D sin kn x? Well write it as ψ = D sin kn x = D eikn x − e−ikn x
2i
and we see that the bound state solution is a superposition of Left and Right
travelling waves that constructively interfere to produce a standing wave. It’s
just like the way we get standing waves on a string. The travelling waves
reflect from the boundaries to produce the standing wave.
Let’s return to our discussion of the free particle. There are two diffi-
culties with the above analysis. First consider a classical free particle where
U = 0 so that E = 12 mv 2 + 0 giving
s
2E
vclassical = = 2vp (6.11)
m
which is double the quantum speed vp ! This seems very strange.

Secondly consider, for example, the Left wave.
Z ∞
ψL∗ ψL dx = B 2 × ∞ (6.12)
−∞
Thus the Left and Right waves are not normalizable! But actually this is
not really a problem because it’s Ψ(x, t) not ψ(x) which is supposed to be
normalizable.
Recall that for the bound discrete states En we had
∞
X
i
Ψ(x, t) = (6.13)
n=1
and each ψn (x) corresponded to a definite energy, and it turned out that
each ψn (x) was normalizable. Ψ(x, t) does not contain a definite energy
but a whole bunch of them. For the free particle, the fact that ψ(x) is not
normalizable means that “there is no such thing as a free particle with a
definite energy.” [Griffiths, 1995, pg. 45].
For the free particle ψ(x) cannot be normalized but Ψ(x, t) can be. Thus
the normalized free particle wave function contains a whole bunch of energies,
not just a single energy. Also these energies are continuous, so instead of
2 π 2 h̄2
E = En = n2ma 2 for the infinite well, let’s write
h̄2 k 2
E = Ek = (6.14)
2m
where k now represents a continuous index (rather than En ). Thus instead
of (6.13) we now have
∞Z
1
dk φ(k)ψk (x)e− h̄ Ek t
i
Ψ(x, t) = √
2π −∞
Z ∞
1
= √ dk φ(k)ei(kx−ωt) (6.15)
2π −∞
R∞ P
where dk replaces and k is allowed to be both positive and negative
−∞ n
to include Left and Right waves. φ(k) replaces Cn . The factor √12π is an
arbitrary factor included for convenience. The definition (6.15) could be
made without it.
Ψ(x, t) in equation (6.15) is called a wave packet because it is a collection
of waves all with different energies and speeds. Each of the separate waves
6.1. FREE PARTICLE 117
travels at its own particular speed given by the phase velocity. A good
picture of a wave packet is Figure 2.6 of Griffiths [1995, pg. 47].
Recall how we obtained the coefficients cn in (6.13). We wrote
X
Ψ(x, 0) = cn ψn (x) (6.16)
n
and from the ON property of the basis set {ψn (x)} we obtained
Z ∞
cn = hψn | Ψ(x, 0)i ≡ ψn∗ (x)Ψ(x, 0)dx (6.17)
−∞
Plancherel’s theorem in Fourier analysis says that if

Z ∞
1
f (x) ≡ √ F (k)eikx dk (6.18)
2π −∞
then Z ∞
1
F (k) ≡ √ f (x)e−ikx dk (6.19)
2π −∞
f (x) and F (k) are called a Fourier transform pair. (If (6.18) did not have
√1 in front then F (k) would have to have 1 in front.) Thus we can get
2π 2π
the “expansion coefficient” φ(k). Write
∞ Z
1
ψ(x) ≡ Ψ(x, 0) = √ dk φ(k)ψk (x)
2π −∞
Z ∞
1
= √ dk φ(k)eikx (6.20)
2π −∞
and Plancherel’s theorem tells us that the “expansion coefficients” or Fourier
transform is
Z ∞ Z ∞
1 −ikx 1
φ(k) = √ dxΨ(x, 0)e =√ dxψ(x)e−ikx (6.21)
2π −∞ 2π −∞
which we could have guessed anyway by looking at (6.17) and identifying

ψk∗ (x) = e−ikx .
6.1.1 Group Velocity and Phase Velocity

We have seen that the wave packet (6.15) consists of a collection of waves
2 2
each with energy Ek = h̄2m
k
moving with phase velocity vp = ωk . What then
is the speed with which the whole wave packet moves? It turns out (see
below) that the speed of the whole wave packet, called the group velocity, is
given by
dω
vgroup = (6.22)
dk
The dispersion relation is the formula that relates ω and k. From
2 2
E = h̄ω = h̄2m k
, we see that the dispersion relation for the plane wave
is
h̄k 2
ω(k) = (6.23)
2m
giving
dω h̄k
vgroup = =
dk m s
√
h̄ 2mE 2E
= = = vclassical (6.24)
m h̄ m
Evidently then it is the group velocity of the wave packet that corresponds
to the classical particle velocity.
Example 6.1 Two waves differ by dω in frequency and by dk

in wave number. Superpose the waves and show that the phase
speed is ωk but the superposed wave speed (group speed) is dω
dk .
(See [Beiser, 1987, pg. 96])
Solution
Let ψ1 = A cos(ωt − kx)

and ψ2 = A cos[(ω + dω)t − (k + dk)x]
Using cos A + cos B = 2 cos 12 (A + B) cos 12 (A − B) we obtain
ψ = ψ1 + ψ 2
1 1
= 2A cos [(2ω + dω)t − (2k + dk)x] cos (dωt − dkx)
2 µ ¶ 2
dω dk
≈ 2A cos(ωt − kx) cos t− x
2 2
³ ´
Now cos dω
2 t − dk
2 x has a tiny wavelength compared to
³ ´
cos(ωt − kx) and thus cos dω
2 t − dk
2 x represents a plane wave
6.2. TRANSMISSION AND REFLECTION 119
³ − kx)´ with amplitude modulated by the factor

cos(ωt
2 t − 2 x . Thus the modulating factor is the wave packet
cos dω dk
speed given by dω
dk , whereas the phase speed is
ω
k. See Figure 3.4
of Beiser [1987, pg. 95].
6.2 Transmission and Reflection

We shall now consider scattering from some simple 1-dimensional potentials.
In studying these problems students are strongly encouraged to refer to Table
6-2 from Eisberg and Resnick [1974, pg. 243]. Students should learn this
Table because it summarizes so well many of the features of bound state and
scattering problems.
In both bound and scattering problems we are interested in obtaining
the wave functions. For bound states we are also interested in the discrete
energy levels. For scattering we are also interested in the transmission and
reflection coefficients, just as in classical electrodynamics. In fact it is very
worthwhile at this stage to go back over the course you took in classical
electrodynamics and review the discussion of transmission and reflection
coefficients [Griffiths, 1989].
In quantum mechanics we define the reflection coefficient as
¯ ¯
¯ jR ¯
R ≡ ¯¯ ¯ (6.25)
j ¯
i
where jR is the reflected probability current density and ji is the incident

probability current density. The transmission coefficient is defined as
¯ ¯
¯ jT ¯
T ≡ ¯¯ ¯¯ (6.26)
j i
where jT is the transmitted probability current density. R and T are related

always via
R+T =1 (6.27)
due to probability conservation. Recall the definition of probability current
density from Chapter 1 as
µ ¶
ih̄ ∂ψ ∗ ∂ψ
j≡ ψ − ψ∗ (6.28)
2m ∂x ∂x
for 1-dimension. When actually calculating j it saves time to use the alter-
native expression µ ¶
h̄ ∂ψ
j= Im ψ ∗ (6.29)
m ∂x
where Im stands for “Imaginary Part”. For example Im(a + ib) = b. (do
Problem 6.1)
6.2.1 Alternative Approach

There is an alternative way to calculating transmission and reflection co-
efficients based on amplitude and speed. Recall the local conservation of
probability from Chapter 1 as
∂ρ
+∇·j=0 (6.30)
∂t
or
∂ρ ∂j
+ =0 (6.31)
∂t ∂x
for 1-dimension,
R
where ρ is the probability density
R
and the probability
P = ρ dx for 1-dimension. Integrating (6.31) over dx gives
∂P
j=− (6.32)
∂t
Now in scattering the incident, reflected and transmitted waves will always
be of the form
ψ = Aeikx (6.33)
(where k can be either negative or positive.) This is because the incident,
reflected and transmitted waves will always be outside the range of the
potential where U = 0,√ so that the Schrödinger equation will always be
ψ 00 + k 2 ψ = 0 with k = 2mE
h̄ for incident, reflected and transmitted waves.
This Schrödinger equation always has solution Aeikx + Be−ikx . However the
incident piece, the reflected piece and the transmitted piece will always ei-
ther be travelling to the Left or Right and so will either be Aeikx or Be−ikx
but not both. This is accomplished in (6.33) by letting k be negative or
positive. Using (6.33), the plane wave probability for incident, reflected and
transmitted waves will be
Z Z
∗
P = ψ ψdx = |A| 2
dx = |A|2 x (6.34)
6.3. STEP POTENTIAL 121
Note that, unlike Chapter 1, we are not integrating over the whole universe
and so j will not vanish. Thus from (6.32) we have
|j| = |A|2 v (6.35)
where v = dx dt is the speed of the wave. Thus the reflection and transmission
coefficients become ¯ ¯ ¯ ¯
¯ AR ¯2 vR ¯ AR ¯ 2
R = ¯¯ ¯ = ¯ ¯ (6.36)
Ai ¯ vi ¯A ¯
i
and
¯ ¯ ¯ ¯ s
¯ AT ¯2 vT ¯ AT ¯2 ET
T = ¯¯ ¯ = ¯¯ ¯ (6.37)
Ai ¯ vi Ai ¯ Ei
using (6.11). Note that the reflected and incident wave will always be in
the same region (or same medium) and so vR = vi always. The above
formulas are exactly analogous to those used in classical electrodynamics
[Griffiths, 1989] and obviously (6.37) with the factor vvTi is just the refractive
index.
¯ ¯
If the transmitted wave has the same speed as the incident wave then
¯ ¯2
T = ¯ AATi ¯ .
6.3 Step Potential

The finite step potential is shown in Fig. 6.1. In region I (x < 0) there is
no potential, U = 0, but in region II (x > 0) the potential is U = U0 all the
way out to infinity. (U = U0 for 0 < x < ∞).
The scattering problem we wish to consider is an incident particle coming
in from the Left (to the Right) with energy E < U0 . Classically the particle
would just bounce off the wall and return to x = −∞. We shall see however
that a quantum wave will slightly penetrate the barrier. (See Table 6-2 of
Eisberg and Resnick [1974, pg. 243].)
In region I we have
ψ 00 + k 2 ψ = 0 (6.38)
with √
2mE
k= (6.39)
h̄2
and solution
ψI (x) = Aeikx + Be−ikx

≡ ψi + ψR (6.40)
or we can write ψ(x) = C cos kx+D sin kx, however as mentioned before, the
complex exponential solution enables us to specify the boundary condition
(Left or Right) much more easily. The incident wave travels to the Right and
the reflected wave to the Left. Thus in (6.40) we have made the identification
ψi = Aeikx (6.41)
and
ψR = Be−ikx (6.42)
In region II we have
2m(E − U0 )
ψ 00 + ψ=0 (6.43)
h̄2
or
2m(U0 − E)
ψ 00 − ψ=0 (6.44)
h̄2
Now for our first problem we are considering E < U0 and thus 2m(E − U0 )
is negative, but 2m(U0 − E) is positive and thus we use the second equation
(6.44) which is
ψ 00 − κ2 ψ = 0 (6.45)
with p
2m(U0 − E)
κ≡ (6.46)
h̄
which is real because E < U0 . The solution is
ψ(x) = Ceκx + De−κx (6.47)
but for x → +∞ then Ceκx blows up, so we must have C = 0. Thus
ψII (x) = De−κx ≡ ψT (6.48)
which is the transmitted wave ψT . Let us now impose boundary conditions.
ψI (x = 0) = ψII (x = 0)
gives
A+B =D
and
ψI0 (x = 0) = ψII
0
(x = 0)
6.3. STEP POTENTIAL 123
gives
Aik − Bik = −κD
Thus the wave functions become
µ ¶ µ ¶
D κ ikx D κ −ikx
ψI (x) = 1+i e + 1−i e
2 k 2 k
≡ ψi + ψR (6.49)
and ψII (x) remains as given in (6.48).

Let us now calculate the reflection coefficient from (6.25) and (6.29). We
have
µ ¶
h̄ ∗ ∂ψR
jR = Im ψR
m ∂x
2 ·µ ¶ µ ¶ ¸
h̄ D κ ikx κ −ikx
= Im 1+i e (−ik) 1 − i e
m 4 k k
Ã !
h̄ D κ2
= − k 1+ 2
m2 k
and µ ¶ Ã !
h̄ ∂ψi h̄ D κ2
ji = Im ψi∗ = k 1+ 2
m ∂x m2 k
giving ¯ ¯
¯ jR ¯
R = ¯¯ ¯¯ = 1
j i
which tells us that the wave is totally reflected. From equation (6.27) we
expect T = 0, that is no transmitted wave. (Exercise: Show that you get
¯ ¯2
¯ ¯
the same result by evaluating ¯ B
A ¯ directly.)
Example 6.2 Prove that T = 0 using (6.25).
Solution
µ ¶
h̄ ∂ψT
jT = Im ψT∗
m ∂x
h̄ 2
= D Im [e−κx (−κ)e−κx ]
m
= 0
because ψT is purely real and has no imaginary part. Thus

¯ ¯
¯ jT ¯
T = ¯¯ ¯¯ = 0
j
i
as expected.
Example 6.3 Prove T = 0 using (6.37).
Solution
ET E − U0
=
Ei E
q
but E < U0 thus EET0 is complex, which would give complex T
which can’t happen.
Thus T = 0 (see Griffith’s Problem 2.33)
Even though the transmission coefficient is zero, the wave function still
penetrates into the barrier a short distance. This is seen by plotting the
wave function. (See Table 6-2 of Eisberg and Resnick [1976, pg. 243].)
(do Problem 6.2)
6.4 Finite Potential Barrier

The finite potential barrier is shown in Fig. 6.2. We shall analyze the
problem for an incident particle with energy E < U0 .
In regions I and III, we have U = 0 and E > 0 so that the Schrödinger
equation is
2mE
ψ 00 + 2 ψ = 0. (6.50)
h̄
The solution is
ψ = Aeikx + Be−ikx (6.51)
where √
2mE
k≡ (6.52)
h̄2
6.4. FINITE POTENTIAL BARRIER 125
We assume that the incident particle comes in from the Left. Thus in region
III the wave will only be travelling to the right. Thus
ψI (x) = Aeikx + Be−ikx

≡ ψi + ψR (6.53)
and
ψIII (x) = Ceikx (6.54)
In region III we can write
2m(E − U0 )
ψ 00 + ψ=0 (6.55)
h̄2
or
2m(U0 − E)
ψ 00 − ψ=0 (6.56)
h̄2
but we will use the second equation because U0 > E. Thus
ψ 00 − κ2 ψ = 0 (6.57)
with p
2m(U0 − E)
κ≡ (6.58)
h̄
which is real. Thus
ψII (x) = Deκx + Ee−κx (6.59)
The boundary conditions are
ψI (−a) = ψII (−a) (6.60)
giving
Ae−ika + Beika = De−κa + Eeκa (6.61)
and
ψI0 (−a) = ψII
0
(−a) (6.62)
giving
ikAe−ika − ikBeika = κDe−κa − κEeκa (6.63)
and
ψII (a) = ψIII (a) (6.64)
giving
Deκa + Ee−κa = Ceika (6.65)
and
0 0
ψII (a) = ψIII (a) (6.66)
giving
κDeκa − κEe−κa = ikCeika (6.67)
Equations (6.61), (6.63), (6.65) and (6.67) are the coupled equations we
need to solve for the constants A, B, C, D, E. Let’s plan a little strategy
before jumping in. We want to calculate the transmission coefficient, which
is ¯ ¯2
¯C ¯
T = ¯¯ ¯¯ (6.68)
A
Thus we only need C in terms of A (or vice versa) and hopefully the other
constant will cancel. After all this algebra is done we get
· ¸
U02 2a q
T −1 = 1 + sinh2 2m(U0 − E) (6.69)
4E(U0 − E) h̄
(do Problem 6.3). The important point here is that even with E < U0 we
have T 6= 0. Classically the particle would bounce off the barrier and never
undergo transmission. Yet quantum mechanically transmission occurs! This
phenomenon is called tunnelling. It is again instructive to plot the wave
functions from equations (6.53) and (6.54). This is done in Table 6-2 of
Eisberg and Resnick [1974, pg. 243]. We can see that the wave function
penetrates all the way through the barrier.
6.5 Quantum Description of a Colliding Particle

The Schrödinger equation does not automatically give us the concept of a
particle. We saw that the Schrödinger equation gave us non-normalizable
plane waves eikx as separable solutions with the complete solution being
given in (6.20) as a wave packet. But we don’t know the “expansion coeffi-
cients” φ(k) and so we don’t know ψ(x) ≡ Ψ(x, 0). Actually any φ(k) will do
and Ψ(x, 0) will be a solution to the Schrödinger equation. If we knew φ(k)
we would have Ψ(x, 0) and vice versa, if we knew Ψ(x, 0) we could deduce
φ(k) from (6.21). Both Ψ(x, 0) and φ(k) are not specified by the Schrödinger
equation. We have to make them up.
We want to describe a localized particle and that’s pretty hard to do
when all you have are wave solutions. But wait! Think about classical
solitons. Suppose somehow we had a wave packet as shown in Fig. 6.3. If
6.5. QUANTUM DESCRIPTION OF A COLLIDING PARTICLE 127
such a localized wave packet moved to the left or right, it would be a pretty
good wave packet description of the concept of a classical particle. Such a
wave packet is represented by
ψ(x) ≡ Ψ(x, 0) = Ae−a(x−x0 )

2
Z ∞
1
≡ √ dk φ(k)ψk (x)
2π −∞
Z ∞
1
= √ dk φ(k)eikx (6.70)
2π −∞
and is called a Gaussian wave packet. Such a Gaussian wave packet is widely
used in quantum mechanics as a way to think about localized particles.
You can think of (6.70) as specifying some sort of initial conditions. Since
Ψ(x, 0) and φ(k) are arbitrary we are free to choose them to correspond to a
particular physical system that we want to study. That’s what we are doing
with our Gaussian wave packet. We are choosing to study a localized wave.
After all, there aren’t any other boundary conditions we can use on the free
particle solutions to the Schrödinger equation.
By the wave, in (6.70), the height of the wave packet is specified by A
and the width of the packet is proportional to 1/a. (Exercise: check this by
plotting various Gaussian wave packets with different A and a.)
Now previously we found that the plane wave solutions ψk (x) = eikx are
not normalizable, but we claimed this didn’t matter as long as Ψ(x, t) is
normalizable. Let’s check this for our Gaussian wave packet. To do this you
can use the famous Gaussian integral
Z ∞
r
−ax2 +bx π b2 /4a
dx e = e
−∞ a
(6.71)
Of course we don’t need the whole quadratic ax2 +bx+c because it’s obvious,
from (6.71), that
Z ∞ r
−ax2 +bx+c π b2 +c
dx e = e 4a
−∞ a
Example 6.4 Normalize the Gaussian wave packet.
Solution
ψ(x) ≡ Ψ(x, 0) = A e−(x−x0 )
2
Z ∞
1 = ψ ∗ (x)ψ(x)dx
−∞
Z ∞
e−2a(x−x0 ) dx
2
= A2
−∞
Z ∞
= A2 e−2ax0 e−2ax
2 2 +4ax
0x
dx
−∞
r
π 16a2 x0
= A2 e−2ax0
2
e 8a
2a
r
2 π
= A
2a
Thus
µ ¶1/4
2a
A=
π
and
µ ¶1/4
2a
e−a(x−x0 )
2
ψ(x) ≡ Ψ(x, 0) = (6.72)
π
is the normalized Gaussian wave packet centered at x = x0 .
This example shows that even though plane waves are not normalizable,
the superposed wave packet is normalizable.
6.5.1 Expansion Coefficients

The expansion coefficients φ(k) tell us the relative weightings of the sines
and cosines, or plane waves eikx , that are added up to make the Gaussian
wave packet. We get them using (6.21).
Example 6.5 Find φ(k) for the Gaussian wave packet.

Solution From (6.21) and (6.72) we have the Fourier transform

Z∞
1
φ(k) = √ dx ψ(x)e−ikx
2π −∞
µ ¶1/4 Z ∞
1 2a
dx e−a(x−x0 ) e−ikx
2
= √
2π π −∞
µ ¶1/4 Z ∞
1 2a −ax20
dx e−ax +(2ax0 −ik)x
2
= √ e
2π π −∞
µ ¶1/4 r
1 2a π (2ax0 −ik)2 /4a
e−ax0
2
= √ e
2π π a
Thus
1 k2
φ(k) = 1/4
e− 4a −ikx0 (6.73)
(2πa)
Thus our Gaussian wave packet is

µ ¶
2a 1/4 −a(x−x0 )2
ψ(x) ≡ Ψ(x, 0) = e
π
µ ¶ Z
a 1/4 ∞ 2
− k4a ik(x−x0 )
= dk e e (6.74)
2π 3 −∞
Note that (6.73) is also a Gaussian (ignore x0 or set it to zero). Thus the
Fourier transform of a Gaussian is a Gaussian.
6.5.2 Time Dependence

Our time dependent wave function is
Z ∞
1
Ψ(x, t) = √ dk φ(k)ei(kx−ωt) (6.75)
2π −∞
h̄2 k2
with Ek ≡ h̄ω = 2m . This should tell us how our Gaussian wave packet
behaves in time.
Example 6.6 Calculate Ψ(x, t) and |Ψ(x, t)|2 for the Gaussian
wave packet.
Solution Using (6.75) and (6.73) we have

Z ∞
1 1 k2 h̄k 2
Ψ(x, t) = √ dk exp (− − ikx0 ) exp [i(kx − t)]
2π (2πa)1/4 −∞ 4a 2m
h̄k2
where we had to substitute the dispersion
R
relation ω(k) = 2m
because we are doing an integral dk. Thus
Z µ ¶
1 1 1 h̄
Ψ(x, t) = √ 1/4
dk exp [− +i t k 2 + (ix − ix0 )k]
2π (2πa) 4a 2m
s
1 1 π 1 h̄
= √ 1/4 1 h̄
exp [(ix − ix0 )2 /4( + i t)]
2π (2πa) 4a + i 2m t
4a 2m
finally giving
µ ¶1/4 r
2a m −ma(x − x0 )2
Ψ(x, t) = exp [ ] (6.76)
π m + i2ah̄t m + i2ah̄t
This yields
r s
2 m2 a m2 a
|Ψ(x, t)|2 = exp [−2 (x − x0 )2 ]
m2 + 4a2 h̄2 t2
π m2 + 4a2 h̄2 t2
(6.77)
for the probability density.
These are wonderful results! They tell us how the Gaussian wave packet
changes with time. We can now Rreally see the utility of calculating φ(k),
plugging it into (6.75), doing the dk integral and finally getting out some
real answers!
The probability density (6.77) is very interesting. As time increases,
the amplitude decreases and the width of the wave packet increases. The
Gaussian wave packet “spreads out” over time. This is illustrated in Fig.
6.4. The wave packet dissipates. Initially the packet is well localized, and we
“know” where the particle is, but after a long time the packet is so spread
out that we don’t know where the particle is anymore.
6.5.3 Moving Particle

The wave packet Ψ(x, 0) = Ae−a(x−x0 ) in (6.70) describes a wave stationary
2
at x = x0 . However we want a moving particle, say a wave packet initially

propagating to the Right. We might have hoped that tacking on the time
dependence e−iωt in (6.75) would have given us a moving particle, but no
luck! What the time dependence did tell us was that the wave packet dissi-
pates, but our solutions (6.76) and (6.77) still won’t budge. They are still
clamped down at x = x0 .
We are back to our original problem discussed at the beginning of Section
6.5. The Schrödinger equation does not give us a particle and it also does
not give us a moving particle. We have to put both things in by hand, or
“specify initial conditions.”
Actually this is easy to do. The particle is fixed at x = x0 , so let’s just
make x0 move! A good way to do this is with
p0
x0 = t (6.78)
m
Thus our moving Gaussian wave is
p0
e−a(x− m t)
2
and now we have a moving wave. Just make the substitution (6.78) in all of
the above formulas.
6.5.4 Wave Packet Uncertainty

(do Problems 6.4 and 6.5)
In Problem 6.4, the uncertainty in position and momentum for the Gaus-
sian wave packet is calculated. The results are
s
m2 + 4a2 h̄2 t2
σx =
4am2
and
√
σp = h̄ a
For t = 0 we see that
1
σx (t = 0) = √
2 a
but σx gets larger as t increases. This corresponds to the spreading of the
wave packet as time increases and we are more and more uncertain of the
position of the wave packet as time goes by (even thogh hxi = x0 ).
For t = 0 the product is

h̄
σx σp (t = 0) = (6.79)
2
but for t 6= 0 we have
q
h̄
σx σp (t 6= 0) = 1 + 4a2 h̄2 t2 /m2 (6.80)
2
which indicates that
h̄
σx σp (t 6= 0) > (6.81)
2
We can combine the above results into
h̄
σx σp ≥
2
which is the famous Uncertainty Principle. Here we have shown how it comes
about for the Gaussian wave packet. Later we shall prove it is general.
Chapter 7
FEW-BODY BOUND
STATE PROBLEM
In previous chapters we have only considered the 1-body problem represented

by a particle of mass m. However most problems in nature involve few or
many bodies.
In this chapter we shall see that the two body problem can be solved
for any potential U (x). The few-body problem (i.e. more than 2 bodies)
cannot be solved in general, but we shall see how the few-body problem can
be solved for the harmonic oscillator potential. As we shall see, all of these
statements apply to both classical mechanics and quantum mechanics.
It is very interesting to note that the 2-body problem cannot be solved in
relativistic quantum mechanics. While the 2-body scattering problem can be
solved with perturbative techniques (Feynman diagrams) if the interaction
potential is weak, the strong interaction scattering problem and the bound
state problems are described by the Bethe-Salpeter equation which cannot
be solved in general.
[General Relativity]
7.1 2-Body Problem

One of the most important classical 2-body bound state problems is the
Earth-Sun system. One of the important quantum 2-body bound states is
the Hydrogen atom.
Before proceeding, we shall define some 2-body coordinates to be used
below. Let x1 be the coordinate of the first body and x2 the coordinate of
133
134 CHAPTER 7. FEW-BODY BOUND STATE PROBLEM
the second body. Define the relative coordinate
x ≡ x1 − x2 (7.1)
and the Center of Mass (CM) coordinate
m1 x1 + m2 x2
X≡ (7.2)
m1 + m2
These of course can be inverted to give

m2
x1 = X + x (7.3)
M
and
m1
x2 = X − x (7.4)
M
where we have defined the total mass
M ≡ m1 + m2 (7.5)
Also in what follows we assume that particles 1 and 2 interact via a

potential U of the form
U = U (x1 − x2 ) = U (x) (7.6)
This is a crucial assumption and it is the reason as to why we will be able

to solve the 2-body problem for any potential of the form U (x). Notice only
the coordinate x enters the potential. That is the force only depends on the
relative distance x = x1 − x2 between the particles. If U also depended on
X then we would not be able to solve the 2-body problem.
7.1.1 Classical 2-Body Problem

Newton’s Laws
Newton’s second law of motion for bodies labelled 1 and 2 is
ΣF1 = m1 ẍ1 (7.7)
and
ΣF2 = m2 ẍ2 (7.8)
7.1. 2-BODY PROBLEM 135
Assuming that the particles interact through the potential U then these
equations become
∂U
− = m1 ẍ1 (7.9)
∂x1
and
∂U
− = m2 ẍ2 (7.10)
∂x2
Now with U ≡ U (x1 − x2 ) = U (x) we have
∂U ∂U ∂x ∂U
= = (7.11)
∂x1 ∂x ∂x1 ∂x
and
∂U ∂U ∂x ∂U
= =− (7.12)
∂x2 ∂x ∂x2 ∂x
giving
dU
− = m1 ẍ1 (7.13)
dx
and
dU
+ = m2 ẍ2 (7.14)
dx
Equations (7.9) and (7.10) or (7.13) and (7.14) are a set of coupled equations.
They must be solved simultaneously to obtain a solution. But notice the
following. With our new coordinates X and x we get
µ ¶
1 1 dU dU
Ẍ = (m1 ẍ1 + m2 ẍ2 ) = − + =0 (7.15)
M M dx dx
giving
M Ẍ = 0
(7.16)
and
1 dU 1 dU
ẍ = ẍ1 − ẍ2 = − −
m1 dx m2 dx
m1 + m2 dU
= − (7.17)
m1 m2 dx
Defining the reduced mass
m1 m 2
µ≡ (7.18)
m1 + m2
we get
dU
− = µẍ
dx
(7.19)
Thus equations (7.16) and (7.19) are uncoupled equations which we can solve
separately. Thus we say that we have solved the 2-body problem! Notice
also that these equations are equivalent 1-body equations for a “particle” of
mass M and acceleration Ẍ and another separate “particle” of mass µ and
acceleration ẍ moving in the potential U (x). We have also shown that the
“particle” of mass M is the center of mass “particle” and it moves with zero
acceleration.
Lagrangian Method
For a Lagrangian L(qi , q̇i ) where qi are the generalized coordinates, the equa-
tions of motion are µ ¶
d ∂L ∂L
− =0 (7.20)
dt ∂ q̇i ∂qi
for each coordinate qi . For our 2-body problem in 1-dimension we identify
q1 ≡ x1 and q2 ≡ x2 . The 2-body Lagrangian is
1 1
L(x1 , x2 , ẋ1 , ẋ2 ) = m1 ẋ1 2 + m2 ẋ2 2 − U (x1 − x2 ) (7.21)
2 2
Lagrange’s equations are
µ ¶
d ∂L ∂L
− =0 (7.22)
dt ∂ ẋ1 ∂x1
and µ ¶
d ∂L ∂L
− =0 (7.23)
dt ∂ ẋ2 ∂x2
which yield the coupled equations (7.9) and (7.10). (Exercise: Prove this.)
The trick with Lagrange’s equations is to pick different generalized coor-
dinates. Instead of choosing q1 = x1 and q2 = x2 we instead make the choice
q1 ≡ X and q2 ≡ x. Using equations (7.1) and (7.2) in (7.21) we obtain
1 1
L(x, X, ẋ, Ẋ) = M Ẋ 2 + µẋ2 − U (x) (7.24)
2 2
(Exercise: Show this.) Lagrange’s equations are
µ ¶
d ∂L ∂L
− =0
dt ∂ Ẋ ∂X
and µ ¶
d ∂L ∂L
− =0
dt ∂ ẋ ∂x
which yield (7.16) and (7.19) directly. (Exercise: Show this.)
To summarize, the trick with the Lagrangian method is to choose X and
x as the generalized coordinates instead of x1 and x2 .
7.1.2 Quantum 2-Body Problem

The time-independent Schrödinger equation is
Hψ = Eψ (7.25)
and the 1-body Hamiltonian is
p21
H= + U (x1 ) (7.26)
2m1
Making the replacement p1 → −ih̄ dxd1 gives

" #
h̄2 d2
− + U (x1 ) ψ(x1 ) = Eψ(x1 ) (7.27)
2m1 dx21
which is an ordinary differential equation that we have already studied ex-

tensively.
The 2-body Hamiltonian is
p21 p2
H= + 2 + U (x1 − x2 ) (7.28)
2m1 2m2
Obviously E is the total energy of the system E = E1 + E2 . Thus we have

" #
h̄2 ∂ 2 h̄2 ∂ 2
− − + U (x1 − x2 ) ψ(x1 , x2 ) = Eψ(x1 , x2 ) (7.29)
2m1 ∂x21 2m2 ∂x22
which is our 2-body Schrödinger equation. The problem now is not that
we have 2 coupled equations, as in the classical case, but rather instead
of the ordinary differential equation (for the variable x1 ) that we had for
the 1-body Schrödinger equation (7.27), we are now stuck with a partial
differential equation (7.29) for the variables x1 and x2 .
Fortunately it’s easy to take care of. Consider an arbitrary function

f (x1 , x2 ). Thus for example
∂f ∂f ∂x ∂f ∂X
= + (7.30)
∂x2 ∂x ∂x2 ∂X ∂x2
giving
∂ ∂x ∂ ∂X ∂ ∂ m2 ∂
= + =− + (7.31)
∂x2 ∂x2 ∂x ∂x2 ∂X ∂x M ∂X
Similarly
∂ ∂ m1 ∂
=+ + (7.32)
∂x1 ∂x M ∂X
Thus we obtain
µ ¶2
∂2 ∂2 m2 ∂ 2 m2 ∂2
= − 2 + (7.33)
∂x22 ∂x2 M ∂x∂X M ∂X 2
and µ ¶2
∂2 ∂2 m1 ∂ 2 m1 ∂2
2 = + 2 + (7.34)
∂x1 ∂x2 M ∂x∂X M ∂X 2
Finally we have, upon substitution of (7.33) and (7.34),
1 ∂2 1 ∂2 1 ∂2 1 ∂2
2 + 2 = + (7.35)
m1 ∂x1 m2 ∂x2 µ ∂x2 M ∂X 2
∂2
where the “cross terms” ∂x∂X have cancelled out. Thus the Schrödinger
equation (7.29) becomes
" #
h̄2 ∂ 2 h̄2 ∂ 2
− − + U (x) ψ(X, x) = Eψ(X, x) (7.36)
2M ∂X 2 2µ ∂x2
which is still a partial differential equation but now U depends on only one
variable and we are now able to successfully apply the technique of separation
of variables. Thus we define
ψ(X, x) ≡ W (X)w(x) (7.37)
and
E = E1 + E2 ≡ EX + Ex (7.38)
which is a sum of center-of-mass and relative energy. Upon substitution of
(7.37) and (7.38) into (7.36) we obtain
h̄2 d2 W (X)
− = EX W (X)
2M dX 2
(7.39)
and
h̄2 d2 w(x)
− + U (x)w(x) = Ex w(x)
2µ dx2
(7.40)
which are now two uncoupled ordinary differential equations.
Just as in the classical case, where we found two equivalent 1-body equa-
tions (7.16) and (7.19), so too have we found in quantum mechanics two
equivalent 1-body Schrödinger equations.
One is for the center of mass “particle” of mass M and one is for the
reduced mass “particle” of mass µ. In the classical case, the center of mass
equation was identical to a free particle equation (7.16) for mass M , so too
in the quantum case we have found the center of mass Schrödinger equation
is for a free particle of mass M . In the classical case the solution to (7.16)
was
Ẍ = 0 (7.41)
and in the quantum case the solution to (7.39) is
W (X) = Aeikx + Be−ikx (7.42)
which is the free particle plane wave solution where
√
2M Ex
K≡ (7.43)
h̄
In the classical case, to get the relative acceleration equation we just make
the replacement x1 → x and m1 → µ to get the 2-body relative equation
(7.19). We see that this identical replacement is also made for the quantum
equation (7.40).
We can now go ahead and solve the 2-body quantum equation (7.40)
using exactly the same techniques that we have used previously. In fact we
just copy all our previous answers but making the replacement m → µ and
treating the variable x as x ≡ x1 − x2 .
7.2 3-Body Problem

Part II
3-DIMENSIONAL
PROBLEMS
141
Chapter 8
3-DIMENSIONAL
SCHRÖDINGER
EQUATION
The 2-body, 3-dimensional Schrödinger equation is

h̄2 2 ∂Ψ
− ∇ Ψ + U Ψ = ih̄ (8.1)
2µ ∂t
with Ψ ≡ Ψ(r, t) where r is a 3-dimensional relative position vector and the
Laplacian operator in Cartesian coordinates is
∂2 ∂2 ∂2
∇2 ≡ + + (8.2)
∂x2 ∂y 2 ∂z 2
or in Spherical polar coordinates
µ ¶ µ ¶
1 ∂ ∂ 1 ∂ ∂ 1 ∂2
∇2 = r2 + sin θ + (8.3)
2
r ∂r ∂r 2
r sin θ ∂θ ∂θ r2 sin2 θ ∂φ2
Using separation of variables Ψ(r, t) ≡ ψ(r)χ(t) we obtain the 2-body, 3-
dimensional time-independent Schrödinger equation
h̄2 2
− ∇ ψ + U ψ = Eψ (8.4)
2µ
and with χ(t) = e−i/h̄Et . The general solution is
X
Ψ(r, t) = ψ(r)χ(t) = cn ψn (r)e−i/h̄En t (8.5)
n
143
144 CHAPTER 8. 3-DIMENSIONAL SCHRÖDINGER EQUATION
In general the 2-body potential will be a function U = U (r) and therefore

it is preferable to use ∇2 in spherical polar coordinates rather than Cartesian
coordinates. Also U = U (r) hints that we solve (8.4) using separation of
variables according to
ψ(r) ≡ ψ(r, θ, φ) ≡ R(r)Y (θ, φ)) (8.6)
where we have separated out the radial and angular pieces. Substituting
into (8.4) and dividing by RY gives
µ ¶
1 d dR 2µr2 1 L2 Y
r2 + (E − U ) = (8.7)
R dr dr h̄2 Y h̄2
where the angular momentum operator is defined as
" µ ¶ #
1 ∂ ∂ 1 ∂2
L̂ ≡ −h̄
2 2
sin θ + (8.8)
sin θ ∂θ ∂θ sin2 θ ∂φ2
In equation (8.7) the left hand side is a function of r only and the right
hand side is a function of θ, φ only. Thus both sides must equal a constant
defined as l(l + 1), giving
µ ¶
1 d dR 2µr2 1 L2 Y
r2 + (E − U ) = ≡ l(l + 1) (8.9)
R dr dr h̄2 Y h̄2
8.1 Angular Equations

Equation (8.9) gives the angular equation
L2 Y = l(l + 1)h̄2 Y (8.10)
which is an eigenvalue equation. We separate variables again with
Y (θ, φ) ≡ Θ(θ)Φ(φ) (8.11)
and dividing by ΘΦ gives
µ ¶
1 d dΘ 1 d2 Φ
sin θ sin θ + l(l + 1) sin2 θ = − (8.12)
Θ dθ dθ Φ dφ2
Again the left side is a function of θ and the right side is a function of φ and
so they must both be equal to a constant defined as m2 , giving
µ ¶
1 d dΘ 1 d2 Φ
sin θ sin θ + l(l + 1) sin2 θ = − ≡ m2 (8.13)
Θ dθ dθ Φ dφ2
8.1. ANGULAR EQUATIONS 145
The equation easy to solve is
−1 d2 Φ
= m2 (8.14)
Φ dφ2
which has solution
Φ(φ) = Aeimφ + Be−imφ

≡ A0 eimφ
= eimφ (8.15)
In the first line m is a fixed value, but in the second line we allow m to
take on both positive and negative values. The third line arises because we
will put all of the normalization into the Θ(θ) solution.
The periodic boundary condition is
Φ(φ + 2π) = Φ(φ) (8.16)
giving
eim(φ+2π) = eimφ (8.17)
and thus
ei2πm = 1 (8.18)
implying
m = 0, ±1, ±2 . . . (8.19)
m is called the azimuthal quantum number. Equation (8.19) effectively means
0
that the azimuthal angle is quantized! (Write Φ = eimφ ≡ eiφ and thus φ0 is
quantized.)
The other angular equation becomes
µ ¶ h i
d dΘ
sin θ sin θ + l(l + 1) sin2 θ − m2 Θ = 0 (8.20)
dθ dθ
Making the substitution

x ≡ cos θ (8.21)
this reduces to
" #
00 0 m2
(1 − x )Θ − 2xΘ + l(l + 1) −
2
Θ=0 (8.22)
1 − x2
with Θ ≡ Θ(cos θ) and Θ0 ≡ d cos 00 2

θ and Θ ≡ d cos2 θ . Equation (8.22) is
dΘ d Θ
recognized as the famous Legendre Associated Differential Equation [Spiegel,

1968] which has as solutions the Associated Legendre Functions of the First
Kind, Plm (x). The properties of these functions, as well as specific values
are given on pg. 149 of [Spiegel, 1968]. Note that l is an integer meaning
effectively that the θ space is quantized. That is
l = 0, 1, 2 · · ·
(8.23)
A few points to note. Firstly, we could have solved (8.20) directly by the
power series method. Using a cut-off would have quantized l for us, just like
the cut-off quantized E for the harmonic oscillator. Secondly, for m = 0, the
Legendre Associated Differential Equation becomes the Legendre Differential
Equation with the Legendre Polynomials Pl (x) as solutions, whereas above
we have the Legendre function of the first kind Plm (x). Thirdly we have
already noted that l is required to be integer as given in (8.23). Fourthly,
the properties of the Legendre function also requires
m = −l, · · · + l
(8.24)
For example, if l = 0 then m = 0. If l = 1, then m = −1, 0, +1. If l = 2,
then m = −2, −1, 0, +1, +2.
Thus we have found that the solutions of the angular equations are char-
acterized by two discrete quantum numbers m and l. Thus we write (8.11)
as
Ylm (θ, φ) = Aeimφ Plm (cos θ) (8.25)
where A is some normalization. If we normalize the angular solutions to
unity then the overall normalization condition will require the spatial part
to be normalized to unity also. Let’s do this. The result is [Griffith, 1995]
s
(2l + 1) (l − |m|)! imφ m
Ylm (θ, φ) = ² e Pl (cos θ)
4π (l + |m|)!
(8.26)
where ² ≡ (−1)m for m ≥ 0 and ² = 1 for m ≤ 0. These are normalized as
in Z Z
2π π
∗
dφ dθ sin θYlm (θ, φ)Yl0 m0 (θ, φ) = δll0 δmm0 (8.27)
0 0
8.2. RADIAL EQUATION 147
8.2 Radial Equation

Using the substitution
u(r) ≡ rR(r) (8.28)
the radial Schrödinger equation (8.9) becomes
" #
h̄2 d2 u l(l + 1)h̄2
− + U (r) + u = Eu
2µ dr2 2µr2
(8.29)
This is often called the reduced Schrödinger equation for the reduced wave
function u(r). (R(r) is the radial wave function.) For l = 0 this is the same
form as the 1-dimensional Schrödinger equation! For l 6= 0 it is still the same
form as the 1-dimensional equation with an effective potential
l(l + 1)h̄2
Ueffective (r) ≡ U (r) + (8.30)
2µr2
Note that precisely the same type of thing occurs in the classical case.
The normalization of the wave function is now the volume integral
Z
dτ |Ψ(r, t)|2 = 1 (8.31)
R
where the volume integral dτ is to be performed over the whole universe.
In spherical coordinates we have
Z ∞ Z π Z 2π
r2 dr sin θdθ dφ |Ψ(r, θ, φ)|2 = 1 (8.32)
0 0 0
However Ψ(r, θ, φ) ≡ R(r)Y (θ, φ) and Y (θ, φ) is already normalized to unity

via (8.27). This means that R(r) must also be normalized to unity via
Z ∞
r2 dr |R(r)|2 = 1 (8.33)
0
This procedure of separately normalizing Y (θ, φ) and R(r) is quite conve-

nient because it follows that the u(r) in (8.28) must be normalized as
Z ∞
dr |u(r)|2 = 1
0
(8.34)
Remember, it is actually the u(r) that we solve for in the radial Schrödinger
equation (8.29). If the reduced wave functions u(r) are normalized according
to (8.34), then everything else is normalized.
8.3 Bessel’s Differential Equation

Many times we will be interested in the solutions for a constant potential
U0 . For example, consider the infinite spherical well defined as
U (r) = 0 for r < a

= ∞ for r > a (8.35)
In both cases the potential is constant. For a free particle U = 0 everywhere

and is another example of a constant potential. Another example is a finite
spherical well defined as
U (r) = 0 for r < a

= U0 for r > a (8.36)
In this section we wish to consider the solutions to a constant potential

U0 in the classical region where E > U0 . The equation we will end up with
is the Bessel differential equation (BDE).
The equation that leads directly to the BDE is the Schrödinger equation
for R(r), and not the equation for u(r). The solutions of the BDE are called
Bessel functions. R(r) is directly proportional to a Bessel function, whereas
u(r) is r times a Bessel function. Thus we shall find it convenient to directly
solve the equation for R(r) which we re-write as
r2 R00 + 2rR0 + [k 2 r2 − l(l + 1)]R = 0 (8.37)
where R = R(r) and R0 ≡ dR/dr and

p
2µ(E − U0 )
k≡ (8.38)
h̄
which is real in the classical region E > U0 . The above equations are valid
for arbitrary U (r), but the following discussion of solutions is only valid for
the potential U = U0 (or, of course, U = 0).
Now the BDE is [Spiegel, 1968, pg. 136]
8.3. BESSEL’S DIFFERENTIAL EQUATION 149
x2 y 00 + xy 0 + (x2 − ν 2 )y = 0
(8.39)
where y = y(x), y0 ≡ dy
dx and ν ≥ 0. The solutions are [Spiegel, 1968, pg.
137, equation 24.14]
y(x) = A Jν (x) + B Nν (x) (8.40)
where Jν (x) are Bessel functions of order ν and Nν (x) are Neumann func-
tions of order ν. (The Neumann functions are often called Weber functions
and given the symbol Yν (x). See footnote [Spiegel, 1968, pg. 136]. However
Yν (x) is lousy notation for us, because we use Y for spherical harmonics.)
If the dependent variable is
η ≡ kr (8.41)
rather than x, then the BDE is [Arfken, 1985, pg. 578]
d2 y dy
r2 +r + (k 2 r2 − ν 2 )y = 0
dr2 dr
(8.42)
where y = y(kr) = y(η). (Exercise: show this)
Now the radial Schrödinger equation (8.37) does not look like the Bessel
equations (8.39) or (8.41). Introduce a new function [Arfken, 1985, pg. 623]
defined as
√
w(η) ≡ η R(r) (8.43)
i.e. √
w(kr) = kr R(r) (8.44)
Then the radial Schrödinger equation (8.37) becomes
" µ ¶2 #
2w
2d dw 1
r +r + k2 r2 − l + w=0
dr2 dr 2
(8.45)
which is the BDE. (Exercise: show this)
Notice that the order of the Bessel and Neumann functions is
1
ν =l+ (8.46)
2
and we found previously that l = 0, 1, 2, 3 · · · giving therefore the half integer

values
1 3 5
ν = , , ··· (8.47)
2 2 2
Comparing (8.45) to (8.42) and using (8.40) gives our solution as
w(η) = A Jl+ 1 (η) + B Nl+ 1 (η) (8.48)

2 2
These Bessel and Neumann functions of half integer order are tabulated in
[Spiegel, 1968, pg. 138]
Now these Bessel and Neumann functions of half integer order are usually
re-defined as Spherical Bessel functions and Spherical Neumann functions of
order l as follows [Arfken, 1985, pg. 623]
r
π
jl (x) ≡ J 1 (x) (8.49)
2x l+ 2
r
π
nl (x) ≡ N 1 (x) (8.50)
2x l+ 2
giving r r
0 2η 2η
w(η) = A jl (η) + B 0 nl (η) (8.51)
π π
w(η)
Thus using R(r) = √
η
R(r) = A jl (η) + B nl (η) (8.52)

q q
where A ≡ A0 2
π and B ≡ B 0 2
π. Introducing u(r) ≡ rR(r) gives
u(r) = Ar jl (kr) + Br nl (kr) (8.53)
in agreement with [Griffiths, 1995, equation 4.45, pg. 130].
8.3.1 Hankel Functions

Explicit formulas for the Spherical Bessel and Neumann functions are [Ar-
fken, 1985, pg. 628; Griffiths, 1995, pg. 130]
µ ¶l
l 1 d sin x
jl (x) = (−x) (8.54)
x dx x
8.3. BESSEL’S DIFFERENTIAL EQUATION 151
and µ ¶l
1 d cos x
nl (x) = −(−x) l
(8.55)
x dx x
giving, for example,
sin x
jo (x) = (8.56)
x
and
cos x
no (x) = − (8.57)
x
Thus jl (x) can be thought of as a “generalized” sine function and nl (x) as a
“generalized” cosine function. Now if the solution of a differential equation
can be written as
y = A0 sin kr + B 0 sin kr (8.58)
which is useful in bound state problems, it can also be written
y = A eikr + B e−ikr (8.59)
which is useful in scattering problems with
eikr = cos kr + i sin kr (8.60)
and
e−ikr = cos kr − i sin kr (8.61)
Similarly the Hankel functions (of first and second kind) are defined as
[Spiegel, 1968, pg. 138]
Hν(1) (x) ≡ Jν (x) + i Nν (x) (8.62)
and
Hν(2) (x) ≡ Jν (x) − i Nν (x) (8.63)
and are also solutions of the BDE, i.e. (8.40) can also be written
y(x) = A Jν (x) + B Nν (x)

(1) (2)
= C Hν (x) + D Hν (x)
(8.64)
In 3-d bound state problems (for arbitrary l) the Bessel and Neumann func-
tions are useful, whereas in scattering the Hankel functions are more useful.
Footnote: Given that J and N (or j and n) are the generalized sine and
cosine, then Hν is actually like ie−ikr = sin kr + i cos kr and Hν is like
(1) (2)
−ieikr = sin kr − i cos kr.

Similarly we can also define Spherical Hankel functions as
(1)
hl (x) ≡ jl (x) + i nl (x) (8.65)
and
(2)
hl (x) ≡ jl (x) − i nl (x) (8.66)
Thus, for example,
eix
o = −i
h(1) (8.67)
x
and
e−ix
h(2)
o (x) = i (8.68)
x
Thus the solutions (8.52) and (8.53) to the Schrödinger equation can also
be written
Rl (r) = A jl (kr) + B nl (kr)

(1) (2)
= C hl (kr) + D hl (kr)
(8.69)
or
ul (r) = Ar jl (kr) + Br nl (kr)

(1) (2)
= Cr hl (kr) + Dr hl (kr)
(8.70)
Chapter 9
HYDROGEN-LIKE ATOMS
The hydrogen atom consists of one electron in orbit around one proton with
the electron being held in place via the electric Coulomb force. Hydrogen-
like atoms are any atom that has one electron. For example, in hydrogen-like
carbon we have one electron in orbit around a nucleus consisting of 6 protons
and 6 neutrons. The Coulomb potential for a hydrogen-like atom is
1 Ze2
U (r) = − (9.1)
4π²0 r
in MKS units. Here Z represents the charge of the central nucleus.
We shall develop the theory below for the 1-body problem of an electron
of mass me interacting via a fixed potential. (We will do this so that we can
pull out well known constants like the Bohr radius which involves me ). If
one wishes to consider the 2-body problem one simply replaces me with µ
in all the formulas below.
9.1 Laguerre Associated Differential Equation

With the harmonic oscillator problem studied in Chapter 8, we solved the
Schrödinger equation with the power series method and found that our solu-
tions were the same as the Hermite polynomials. A different approach would
have been to closely inspect the Schrödinger equation and observe that it
was nothing more than Hermite’s differential equation. We would then have
immediately known that the solutions were the Hermite polynomials without
having to solve anything. (Of course the way you find solutions to Hermite’s
differential equation is with the power series method.)
153
154 CHAPTER 9. HYDROGEN-LIKE ATOMS
Many books [Griffiths, 1995] solve the Hydrogen atom problem with the
power series method just as we did with the harmonic oscillator. They find
that the solutions are the famous Associated Laguerre Polynomials. We shall
instead follow the latter approach described above. We will closely inspect
the Schrödinger equation for the Hydrogen atom problem and observe that it
is nothing more than Laguerre’s Associated Differential Equation (ADE). We
then immediately conclude that the solutions are the Laguerre Associated
Polynomials. (Of course all good students will do an exercise and prove, by
power series method, that the Laguerre associated polynomials are, in fact,
solutions to Laguerre’s ADE.)
Inserting the Coulomb potential (9.1) into the reduced Schrödinger equa-
tion (8.29) gives
" #
d2 u 2me 1 Ze2 l(l + 1)
+ −k 2
+ − u=0 (9.2)
dr2 h̄2 4π²0 r r2
where we have used me instead of µ and me is the mass of the electron. Also
we have defined √
+ −2me E
k≡ (9.3)
h̄
because the bound state energies E of the Coulomb potential are negative
(E < 0). Now define a new variable
ρ ≡ 2kr (9.4)
giving (9.2) as
· ¸
d2 u 1 λ l(l + 1)
2
+ − + − u=0 (9.5)
dρ 4 ρ ρ2
with
me Ze2 1
λ≡ (9.6)
h̄2 4π²0 k
As with the harmonic oscillator we “peel off” the asymptotic solutions.
For ρ → ∞, equation (9.5) is approximately
d2 u 1
− u=0 (9.7)
dρ2 4
with solution
u(ρ) = Ae 2 ρ + Be− 2 ρ
1 1
(9.8)
9.1. LAGUERRE ASSOCIATED DIFFERENTIAL EQUATION 155
but this blows up for ρ → ∞ and thus we must have A = 0. Thus
u(ρ → ∞) = Be− 2 ρ
1
(9.9)
For ρ → 0, equation (9.5) is approximately
d2 u l(l + 1)
− u=0 (9.10)
dρ2 ρ2
with solution
u(ρ) = Cρl+1 + Dρ−l (9.11)
which can be checked by substitution. This blows up for ρ → 0 and thus we
must have D = 0. Thus
u(ρ → 0) = Cρl+1 (9.12)
Thus we now define a new reduced wave function v(ρ) via
u(ρ) ≡ ρl+1 e− 2 ρ v(ρ)

1
(9.13)
with the asymptotic behavior now separated out. Substituting this into
(9.5), and after much algebra, we obtain (do Problem 9.1)
ρv 00 + (2l + 2 − ρ)v 0 + (λ − l − 1)v = 0 (9.14)
with v 0 ≡ dv
dρ and v 00 ≡ d2 v
dρ2
. Laguerre’s ADE is [Spiegel, 1968, pg. 155]
xy 00 + (m + 1 − x)y 0 + (n − m)y = 0 (9.15)
with y 0 ≡ dx
dy
and the solutions are the associated Laguerre polynomials
m
Ln (x), which are listed in [Spiegel, 1968, pg. 155-156] together with many
useful properties, all of which can be verified similar to the homework done
for the Hermite polynomials in Chapter 5. Note that n and m are integers.
We see that the Schrödinger equation (9.14) is actually the Laguerre ADE
and the solutions are
v(ρ) = L2l+1
λ+l (ρ) (9.16)
Thus our complete solution, from (9.13) and (9.14) is
u(r) = Aρl+1 e− 2 ρ L2l+1

1
λ+l (ρ) (9.17)
where we have inserted a normalization factor A. Note that this looks dif-
ferent [Griffiths, 1995] in many other quantum mechanics books because of
different conventions. This is most clearly explained in [Liboff, 1992, pg.

439].
Before proceeding we need to make a very important observation about
quantization. Recall that for the harmonic oscillator the energy quantization
condition followed directly from the series cut-off which was required for finite
solutions. When one solves the Laguerre ADE by power series method one
also needs to cut off the series and that is where the integer n comes from
2l+1
in Lmn (x). Our solution is Lλ+l (ρ) and we already know that l is an integer.
Therefore λ must also be an integer. Thus
λ = n = 1, 2, 3 . . .
(9.18)
which gives our energy quantization condition. Combining (9.18), (9.6) and
(9.3) gives
Ã !2
me Ze2 1 Z2 E1
En = − 2 2
≡ − 2 ER ≡ 2
2h̄ 4π²0 n n n
(9.19)
where the Rydberg energy is defined as
me e4
ER ≡ = 13.6 eV (9.20)
2(4π²0 h̄)2
The energy levels are plotted in Fig. 9.1. Notice that the spacing decreases
as n increases.
We now wish to normalize the reduced wave function (9.17), using (8.34).
This is done in Problem 9.2 with the result that
s
Z (n − l − 1)!
A= (9.21)
an2 [(n + l)!]3
where the Bohr radius is defined as
4π²0 h̄2
a≡ = 0.529 × 10−10 m ≈ 1Å (9.22)
me e2
which is a characteristic size for the hydrogen atom. Thus k becomes
Z
k= (9.23)
na
9.2. DEGENERACY 157
u(r)
Using r = 2k u(ρ)
ρ the final wave function is
ψnlm (r, θ, φ) = Rnl (r)Ylm (θ, φ)

sµ ¶3
2Z (n − l − 1)! l − 1 ρ 2l+1
= ρ e 2 Ln+l (ρ)Ylm (θ, φ)
na 2n[(n + l)!]3
(9.24)
or
sµ ¶3 µ ¶l µ ¶
2Z (n − l − 1)! 2Z 2Z
e− na r L2l+1
Z
ψnlm (r, θ, φ) = r n+l r Ylm (θ, φ)
na 2n[(n + l)!]3 na na
(9.25)
which are the complete wave functions for Hydrogen like atoms.
9.2 Degeneracy
Let us summarize our quantum numbers. For the hydrogen like atom we
have, from (9.19)
E1
En = 2 (9.26)
n
where n is the principal quantum number such that (see (9.18))
n = 1, 2, 3 · · · (9.27)
We already know from (8.23) that the orbital quantum number is
l = 0, 1, 2, · · · (9.28)
and from (8.19) and (8.24) that the magnetic quantum number is
ml = 0, ±1, ±2 · · · ± l (9.29)
However, looking at the wave function in (9.25) we see that in order to avoid
(undefined) negative factorials we must also have, for hydrogen-like atoms,
the condition
l = 0, 1, 2, · · · n − 1 (9.30)
That is l cannot be bigger than n − 1.

Thus the wave function is specified by 3 quantum numbers n, l, m sub-
ject to the conditions (9.27), (9.29) and (9.30) for hydrogen like atoms. (3
dimensions, 3 numbers!) Recall that for the 1 dimensional problem we had
only the principal quantum number n. (1 dimension, 1 number!) The wave
function ψnlm in (9.25) depends on all 3 quantum numbers. Thus the first
few wave functions are
for n = 1, ψ100
for n = 2, ψ200 , ψ210 , ψ21−1 , ψ211
for n = 3, ψ300 , ψ310 , ψ31−1 , ψ311
ψ320 , ψ32−1 , ψ321 , ψ32−2 , ψ322
etc. However the energy En in (9.26) depends only on the principal quantum
number n. Thus the energy level E1 has only 1 wave function, but E2 has
4 wave functions associated with it and E3 has 9 wave functions. E2 is said
to be 4-fold degenerate and E3 is said to be 9-fold degenerate.
We shall see later that this degeneracy can be lifted by such things as
external magnetic fields (Zeeman effect) or external electric fields (Stark
effect). In the Zeeman effect we will see that the formula for energy explicitly
involves both n and ml .
Chapter 10
ANGULAR MOMENTUM
10.1 Orbital Angular Momentum

We define the orbital angular momentum operator as
L̂ ≡ r̂ × p̂ (10.1)
just as in the ordinary vector definition in classical mechanics. This gives
L̂x = ypz − zpy
µ ¶
∂ ∂
≡ −ih̄ y −z (10.2)
∂z ∂y
and similarly
L̂y = zpx − xpz
µ ¶
∂ ∂
≡ −ih̄ z −x (10.3)
∂x ∂z
and
L̂z = xpy − ypx
µ ¶
∂ ∂
≡ −ih̄ x −y (10.4)
∂y ∂x
The above relations lead to the following angular momentum commutators
[Li , Lj ] = ih̄²ijk Lk
(10.5)
and
159
160 CHAPTER 10. ANGULAR MOMENTUM
[L2 , Li ] = 0
(10.6)
where Li is any of Lx , Ly , Lz and L2 ≡ L2x + L2y + L2z . The Levi-Civita
symbol is defined as


 +1 if ijk are an even permutation of 1, 2, 3
²ijk = −1 if ijk are an odd permutation of 1, 2, 3 (10.7)

 0 if ijk are not a permutation of 1, 2, 3
(For example ²123 = +1, ²231 = +1, ²321 = −1, ²221 = 0.) These commu-
tation relations are proved in the problems. (do Problems 10.1 and 10.2)
Notice that in (10.5) a sum over k is implied. In other words
X
[Li , Lj ] = ih̄ ²ijk Lk (10.8)
k
In (10.5) we have made use of the Einstein summation convention in which

P
a sum is implied for repeated indices. (Example: A · B = Ai Bi ≡ Ai Bi =
i
A1 B1 + A2 B2 + A3 B3 .)
In spherical polar coordinates, the relation to Cartesian coordinates is
x = r sin θ cos φ (10.9)

y = r sin θ sin φ (10.10)
z = r cos θ (10.11)
and by change of variables the angular momentum operators become

µ ¶
∂ ∂
Lx = ih̄ sin φ + cot θ cos φ (10.12)
∂θ ∂φ
µ ¶
∂ ∂
Ly = ih̄ − cos φ + cot θ sin φ (10.13)
∂θ ∂φ
∂
Lz = −ih̄ (10.14)
∂φ
and " #
µ ¶
1 ∂ ∂ 1 ∂2
L = −h̄
2 2
sin θ + (10.15)
sin θ ∂θ ∂θ sin2 θ ∂φ2
10.1. ORBITAL ANGULAR MOMENTUM 161
which we previously defined in (8.8). Actually in (8.8) it was just a definition,

whereas above we have shown that
L2 = L2x + L2y + L2z (10.16)
Let us invent two additional operators defined as

µ ¶
±iφ ∂ ∂
L± ≡ Lx ± iLy = ±h̄e ± i cot θ (10.17)
∂θ ∂φ
We shall see the utility of these operators in a moment. It can now be shown
that (do Problem 10.3)
L2 Ylm (θ, φ) = l(l + 1)h̄2 Ylm (θ, φ) (10.18)
and
Lz Ylm (θ, φ) = mh̄Ylm (θ, φ) (10.19)
which are often written in Dirac notation as
L2 | lmi = l(l + 1)h̄2 | lmi
(10.20)
and
Lz | lmi = mh̄ | lmi
(10.21)
Thus we have found that the operators L2 and Lz have simultaneous eigen-
functions |lmi = Ylm such that l = 0, 1, 2, 3 . . . and m = −l . . . + l.
Commutator Theorem Two non-degenerate operators have simultaneous eigen-
function iff the operators commute.
Thus the fact that L2 and Lz have simultaneous eigenfunctions is an
instance of the commutator theorem. The question is, since say L2 and Lx
also commute, then won’t they also have simultaneous eigenfunctions? The
answer is no because Lx , Ly , and Lz do not commute among themselves
and thus will never have simultaneous eigenfunctions. Thus L2 will have
simultaneous eigenfunctions with only one of Lx , Ly and Lz .
Equation (10.20) tells us that the magnitude of the angular momentum
is
q
L= l(l + 1)h̄ l = 0, 1, 2, . . .
(10.22)
√
For example, for l = 2 then L = 2h̄ (which does have the correct units for
angular momentum). Because of the angular momentum quantum number
we see that angular momentum is quantized. But this is fine. We have seen
that energy is quantized and we now find that angular momentum is also
quantized. But here’s the crazy thing. The projection, Lz , of the angular
momentum is also quantized via (10.21) with the magnitude of projection
being
Lz = mh̄ m = −l, . . . + l
(10.23)
You see even if the magnitude L is quantized, we would expect classically
that its projection on the z axis could be anything, whether or not L is
quantized. The fact that Lz is also quantized means that the vector L can
only point in certain directions! This is shown in Fig. 10.1. This is truly
amazing! Thus, quite rightly, the quantization of Lz is referred to as space
quantization.
The angular momentum raising and lowering operators have the property
that q
L± Ylm (θ, φ) = h̄ l(l + 1) − m(m ± 1)Ylm±1 (θ, φ) (10.24)
or
q
L± | lmi = h̄ l(l + 1) − m(m ± 1) | l m ± 1i
(10.25)
which raise or lower the value of n. (do Problem 10.4)
10.1.1 Uncertainty Principle

Recall our Uncertainty theorem from Chapter 6 which stated that if
[A, B] = iC then ∆A∆B ≥ 12 |hCi|. The commutation relation (10.5) there-
fore implies
h̄
∆Li ∆Lj ≥ |h²ijk Lk i| (10.26)
2
10.2. ZEEMAN EFFECT 163
For example [Lx , Ly ] = ih̄Lz implies
h̄
∆Lx ∆Ly ≥ |hLz i| (10.27)
2
10.2 Zeeman Effect

ml is called the magnetic quantum number because its presence is felt when
an atom is placed in a magnetic field. Each of the energy levels splits into
smaller levels determined by m. This phenomenon is called the Zeeman
effect. Let us see how it comes about.
Let’s consider a hydrogen-like atom. The single electron is circulating
around the nucleus and so it acts as a tiny magnetic dipole as shown in Fig.
10.2. If the atom is then placed in an external magnetic field then the dipole
acquires some potential energy. This extra potential energy is acquired by
the circulating electron and results in a shift of the electron energy levels.
Thus we want to calculate this potential energy, which for a magnetic dipole
µ placed in a field B is
U = −µ · B = −µB cos θ (10.28)
where θ is the angle between the dipole moment µ and the external magnetic
field B. Define the z direction to be in the direction of B. Thus µ cos θ = µz
and
U = −µz B (10.29)
Thus we need to calculate µz now. The dipole moment for the current loop
of Fig. 10.2 is
µ = iAn̂ (10.30)
where i is the current, A is the area of the loop and n̂ is the vector normal
to the plane of the loop. The magnitude is
−e 2
µ = iA = πr (10.31)
T
where −e is the electron charge, T is the period and r is the radius of the
loop. The angular momentum is
2πr2
L = mvr = m (10.32)
T
−e
and combining with (10.31) gives µ = 2m L or
µ ¶ µ ¶
e −e
µ=− L ≡ γL ≡ g L (10.33)
2m 2m
where the gyromagnetic ratio γ is defined as the ratio of µ to L and we have
also introduced the so-called g-factor. For the above example we have
−e
γ= (10.34)
2m
and
g=1 (10.35)
(Be careful because some authors call g the gyromagnetic ratio!) Thus
µ ¶ µ ¶
e e
µz = − Lz = − ml h̄ ≡ −µB ml = −g µB ml (10.36)
2m 2m
where the Bohr magneton is defined as
eh̄
µB ≡ . (10.37)
2m
Thus the interaction potential energy is
eh̄
U = ml µB B = ml B
2m
(10.38)
where we don’t need to worry about the − sign because ml takes on both +
and − signs via ml = −l, . . .+l. Now there are 2l+1 possible different values
for ml . Thus a spectral line of given l will be split into 2l + 1 separate lines
when placed in an external magnetic field. (In the absence of a field they
will not be split and will all have the same energy.) The spacing between
each of the split lines will be µB B. See Fig. 10.3.
Notice that the splitting of the spectral lines will be bigger for bigger
magnetic fields. This is great because if we notice the Zeeman effect in
the spectra of stars we can easily figure out the magnetic fields. In fact by
observing the spectra of sunspots, people were able to find the strength of
magnetic fields in the region of sunspots!
10.3 Algebraic Method

See [Griffiths, 1995, Section 4.3]
10.4. SPIN 165
10.4 Spin
The Stern-Gerlach experiment performed in 1925 [Tipler, 1992] showed that
the electron itself also carries angular momentum which has only 2 possible
orientations. As nicely explained in [Griffiths, 1995] this angular momentum
is intrinsic to the electron and does not arise from orbit effects. The half
integral values of spin that we discovered above in the algebraic method are
obviously suitable for the electron. The Stern-Gerlach experiment implies a
spin s = 12 for the electron with 2 projections ms = + 12 and ms = − 12 .
The theory of spin angular momentum is essentially a copy of the theory
of orbital angular momentum. Thus we have (see (10.5) and (10.6)
[Si , Sj ] = ih̄²ijk Sk (10.39)
and
[S 2 , Si ] = 0 = [S 2 , S] (10.40)
Similarly from (10.20) and (10.21) we have
S 2 | smi = s(s + 1)h̄2 | smi (10.41)
and
Sz | smi = mh̄ | smi (10.42)
(Note that before our m meant ml and here our m means ms .) Finally from
(10.23) q
S± | smi = h̄ s(s + 1) − m(m ± 1) | s m ± 1i (10.43)
where
S± ≡ Sx ± iSy (10.44)
Now in the theory of orbital angular momentum with the spherical har-
monics, which were solutions to the Schrödinger equation, we only had
l = 0, 1, 2, . . .. But we saw from the algebraic method that half integer values
can also arise (but there won’t be solutions to the Schrödinger equation). In
the theory of spin we use all values, that is
1 3
s = 0, , 1, , . . . (10.45)
2 2
and we still have
m = −s, . . . + s. (10.46)
1
10.4.1 Spin 2
All of the quarks and leptons (such as the electron and neutrino) as well as
the neutron and proton carry an intrinsic spin of 12 . Thus we shall study
this now in some detail.
Now in our orbital angular momentum theory the eigenfunctions |lmi
were just the spherical harmonic functions and the operators L2 , Lz were just
angular differential operators. It turns out that for spin 12 it is not possible
to find functions and differential operators satisfying the algebra specified in
equations (10.39)–(10.46), but it is possible to find matrix representations.
The eigenfunctions are
¯ Ã !
¯1 1 1
¯
¯ 2 2 i ≡ χ+ ≡ 0
(10.47)
for spin “up” and Ã !

¯
¯ 1 −1 0
¯
¯ 2 2 i ≡ χ− ≡ 1
(10.48)
for spin “down”. Now we can work out the operators. This is done in
[Griffiths, 1995, pg. 156]. I will just write down the answer which you can
check by substituting.
Given the eigenstates (10.47) and (10.48) then the operators in (10.41)
and (10.42) must be
Ã !
h̄ 0 1
Sx = (10.49)
2 1 0
Ã !
h̄ 0 −i
Sy = (10.50)
2 i 0
Ã !
h̄ 1 0
Sz = (10.51)
2 0 −1
from which S 2 and S± can easily be deduced as

Ã !
2 3 2 1 0
S = h̄ (10.52)
4 0 1
Ã !
0 1
S+ = h̄ (10.53)
0 0
Ã !
0 0
S− = h̄ (10.54)
1 0
10.4. SPIN 167
Actually the matrices Si are often written

h̄
S≡ s (10.55)
2
where s are the famous Pauli Spin Matrices
Ã !
0 1
σx ≡
1 0
(10.56)
Ã !
0 −i
σy ≡
i 0
(10.57)
Ã !
1 0
σz ≡
0 −1
(10.58)
In problems 10.5–10.8, it is shown very clearly that the spin 12 operators
Si acting on |smi obey exactly the same algebra as the operators Li acting
on |lmi = Ylm . Similar operators and states can also be found for all of the
half integer values of spin angular momentum. (We only considered spin 12 ,
but arbitrary l).
10.4.2 Spin-Orbit Coupling

There are several classic experiments which demonstrate the reality of spin
1
2 for the electron. These are the Stern-Gerlack experiment, the anomalous
Zeeman effect and hyperfine structure. These are all discussed in most books
on Modern Physics.
In this section we wish to briefly discuss another important piece of
evidence for spin 12 and that is the effect of spin-orbit coupling which is
responsible for a doubling splitting of spectral lines.
Actually in the spectrum of hydrogen one observes fine structure and

hyperfine structure which is the splitting of spectral lines. The fine structure
is due to two effects, namely relativity and spin-orbit coupling. The hyperfine
structure, which is about 1000 times smaller than fine structure, is due to a
spin interaction with the nucleus. (One also observes the so-called Lamb shift
which is a shift of the 22 S1/2 state relative to the 22 P1/2 state). The other
effects such as the Zeeman effect, anomalous Zeeman effect and Stark effect
are due to the presence of external magnetic and relative fields respectively.
Let us now consider the fine structure effect of spin-orbit coupling. From
the point of view of the nucleus, the electron constitutes a current loop
around it, but from the point of view of the electron, it sees a positively
charged nucleus moving around it. Thus the electron feels a magnetic field
due to the orbiting nucleus. The strength of this field is the same as the
magnetic field at the center of a circular current loop, which from Ampere’s
law is
µ0 i µ0 ve
B= = (10.59)
2r 4πr2
¡ ¢
in MKS units where i is the current i = Te = 2πr v
e , v is the speed of the
nucleus and r is the orbital radius.
So now our problem is like the normal Zeeman effect where the orbiting
¡ e ¢
electron, with magnetic moment µz = − 2m Lz interacted with the external
magnetic field with interaction energy U = −µz B. (See equations (10.36)
and (10.29)). Similarly the spin-orbit effect is the spin magnetic moment
µz ∝ Sz (10.60)
interaction with the magnetic field produced by the orbiting nucleus and the
interaction energy again is
U = −µ · B = −µB cos θ = −µz B (10.61)
except that now µz comes from (10.60) and the magnetic field from (10.59).
In the Zeeman effect we used Lz = ml h̄ in (10.31) and so the interaction
energy (10.38) was directly proportional to ml . Thus if l = 1 the splitting
was 3-fold (ml = 0), or if l = 2 the splitting was 5-fold (ml = 0, ±1, ±2),
etc.
Similarly here we have
Sz = ms h̄
but for the electron ms has only two values (ms = ± 12 ) and so there will
only be double splitting of the spectral lines, rather than the 3-fold, 5-fold,
10.5. ADDITION OF ANGULAR MOMENTUM 169
etc. splitting observed in the Zeeman effect. The actual magnitude of the
splitting is calculated in equations (6.65) and (6.66) of [Griffiths, 1995]. The
point of our discussion was simply to show that spin leads to a double split-
ting of spectral lines.
A more physical understanding of this double splitting can be seen from
Fig. 10.4 and 10.5.
The spin-orbit effect occurs for all states except for S states (l = 0). This
can be seen as follows. The magnetic field due to the proton is proportional
to the electron angular momentum L as
B∝L
or, more correctly, the angular momentum of the proton from the electron’s
point of view. The dipole moment of the electron is proportional to its spin
µ∝S
Thus from U = −µ · B in (10.61) we have
U ∝S·L
or
U ∝ S · L = Sz L = ms l(l + 1)h̄
which is zero for l = 0 (S states). As shown in Fig. 10.5, the spin-orbit
interaction splits the P state but not the S state.
10.5 Addition of Angular Momentum

Suppose we have a pion of spin 1 in orbit around a nucleon of spin 12 . The
composite particle is called a delta particle. What will be the spin of the
delta? The spin 1 particle has spin projections of 0, +1, −1 and the spin 12
particle has projections + 12 , − 12 . Obviously the projections of the delta will
be all combinations of these, namely
1
2, − 12
3 3
2, 2
− 12 , − 32
These projections form naturally into the groups M = 12 , + 12 and M =

− 32 , − 12 , + 12 , + 32 because we know that projections jump in integer steps.
Thus, the total spin of the delta must be either J = 12 or J = 32 .
We can always work out total spin combinations like this but it is easier
to just use some simple rules.
For
j ≡ j1 + j 2 (10.62)
then the magnitude of j is obtained from
|j1 − j2 | ≤ j ≤ j1 + j2
(10.63)
with j jumping in integer steps. Here j1 and j2 are the magnitudes of the
individual spins. Also
m = m1 ± m2
(10.64)
because jz = j1z ± j2z . From our previous example with j1 = 1 and j2 = 12
we have |1 − 12 | ≤ j ≤ 1 + 12 giving 12 ≤ j ≤ 32 , implying j = 12 or 32 .
The symbol j can be either orbital angular momentum l or spin angular
momentum s
1
Example 10.1 Two electrons have spin 2. What is the total
spin of the two electron system?
Solution
1 1
S1 = , S 2 =
2 2
¯ ¯
¯1 ¯
¯ − 1¯ ≤ S ≤ 1 + 1
¯2 2¯ 2 2
O≤S≤1
S jumps in integer steps, therefore S = 0 or 1.
10.5. ADDITION OF ANGULAR MOMENTUM 171
Example 10.2 What are the possible spin projections in the

previous example?
Solution
1 1 1 1
m1 = + , − m 2 = + , −
2 2 2 2
1 1
m = m1 + m2 = + =1
2 2
1 1
or m = − =0
2 2
1 1
or m = − + =0
2 2
1 1
or m = − − = −1
2 2
Evidently the m = 0, ±1 belong to S = 1 and the other m = 0
belongs to S = 0. S = 1 is called the triplet combination and
S = 0 is called the singlet combination.
10.5.1 Wave Functions for Singlet and Triplet Spin States

From the previous two examples we have seen that by combining wave func-
tions | 12 12 i and | 12 – 12 i we can end up with singlet and triplet wave functions
|0 0i and |1 1i, |1 0i, |1 –1i. How are these all related to each other? Let’s
use the symbols ¯ À
¯1 1
¯
¯ 2 2 ≡↑ (10.65)
and ¯ À
¯1
¯ − 1 ≡↓ (10.66)
¯2 2
The |1 −1i state can only contain ↑ states. Thus
|1 1i =↑ ↑ (10.67)
and similarly
|1 − 1i =↓↓ (10.68)
Note that both of these states are symmetric under interchange of particles
1 and 2. The |0 0i and |1 0i states must contain an equal admixture of ↑
and ↓ in order to get M = 0. Thus
|0 0i = A(↑↓ ± ↓↑) (10.69)
and
|1 0i = A0 (↑↓ ± ↓↑) (10.70)
Now assuming Ã
each | 1 1 i and | 1 − 12 i are separately normalized, i.e. h 12 21 |
! 2 2
1
2 2 i = (1 0)
1 1
= 1, then we must have A = A0 = √12 . Thus the only
0
difference between |0 0i and |1 0i can be in the ± sign. Now for the + sign
the wave function will be symmetric under interchange of particles 1 and
2, while the − sign gives antisymmetry. Thus the + sign naturally belongs
to the |1 0i state. Therefore our final composite wave functions are for the
S = 1 symmetric triplet
|1 1i = ↑↑ (10.71)
1
|1 0i = √ (↑↓ + ↓↑) (10.72)
2
|1 − 1i = ↓↓ (10.73)
and for the S = 0 antisymmetric singlet
1
|0 0i = √ (↑↓ − ↓↑)
2
(10.74)
10.5.2 Clebsch-Gordon Coefficients
10.6 Total Angular Momentum

We have seen that there are two types of angular momentum, namely orbital
angular momentum L and intrinsic spin angular momentum S. We have seen
that the magnitude of L is
q
L= l(l + 1) h̄ (10.75)
10.6. TOTAL ANGULAR MOMENTUM 173
and
Lz = ml h̄ (10.76)
Also the magnitude of S is
q
S= s(s + 1) h̄ (10.77)
and
Sz = ms h̄ (10.78)
We now define the total angular momentum J to be the sum of orbital and
spin angular momenta as
J≡L+S (10.79)
Before we had L, Lz , S and Sz in terms of the quantum numbers l, ml , s,
ms . Let us define new quantum numbers j and mj such that the magnitude
of J is q
J ≡ j(j + 1) h̄
and
Jz ≡ mj h̄
From (10.63) and (10.64) we obviously have
j =l±s
and
m j = ml ± m s
10.6.1 LS and jj Coupling

Suppose we have a whole collection of electrons orbiting a nucleus as in an
atom. The electrons will each have individual spin Si and individual orbital
angular momenta Li . How do we figure out the total spin J for the whole
collection of electrons? In other words what is the total angular momentum
of the atom? There are at least two ways to do this.
In the LS coupling scheme the Li and Si are added separately as in
X
L ≡ Li (10.80)
i
X
S ≡ Si (10.81)
i
J ≡ L+L (10.82)
In the LS coupling scheme the total angular momentum state is usually

expressed in spectroscopic rotation
2s+1
LJ (10.83)
where the letters S, P , D, F or s, p, d, f etc. are used to denote the states

L = 0, 1, 2, 3, etc.
In the jj coupling scheme we have each individual Li and Si added to
give an individual bf J i , as in
Ji ≡ Li + Si
X
J ≡ Ji
i
LS coupling holds for most atoms and for weak magnetic fields. jj coupling
holds for heavy atoms and strong magnetic fields. jj coupling also holds for
most nuclei. [Beiser, pg. 264-267, 1987; Ziock, pg. 139, 1969]
The physical reasons as to why LS coupling holds versus jj coupling can
be found in these two references. The basic idea is that internal electric forces
are responsible for coupling the individual Li of each electron into a single
vector L. Strong magnetic fields can destroy this cooperative effect and
then all the spins act individually. Normally a single electron “cooperates”
P P
with all other electrons giving L = Li and S = Si . However in a
i i
strong magnetic field (internal or external), all the electrons start marching
to the orders of the strong field and begin to ignore each other. Then we get
Li = Li + Si .
Example 10.3 If one electron is in a P state and another is in

a D state what is the total spin on both LS and jj coupling? In
LS coupling what is 2s+1 LJ ?
Solution
1 1
S1 = , S2 =
2 2
l1 = 1 (P state) l2 = 2 (D state)
LS Coupling:
L = L1 + L2
10.6. TOTAL ANGULAR MOMENTUM 175
|L1 − L2 | ≤ L ≤ L1 + L2
|1 − 2| ≤ L ≤ 1 + 2 ⇒ L = 1, 2, 3
S = S1 + L2
|S1 − S2 | ≤ S ≤ S1 + S2
| 12 − 12 | ≤ S ≤ 1
2
+ 12 ⇒ S = 0, 1
J=L+S
|L − S| ≤ J ≤ L + S
S L J 2s+1 L
J
0 1 1 1P
1
2 2 1D
2
3 3 1F
3
1 1 0, 1, 2 3P 3P 3P
0 1 2
2 1, 2, 3 3D 3D 3D
1 2 3
3 2, 3, 4 3F 3F 3F
2 3 4
jj Coupling:
J = L1 + S1
|L1 − S2 | ≤ J1 ≤ L1 + S1
|1 − 12 | ≤ J1 ≤ 1
2
⇒ J1 = 1 3
,
2 2
|L2 − S2 | ≤ J2 ≤ L2 + S2
|2 − 12 | ≤ J2 ≤ 2 + 1
2
3
2
≤ J2 ≤ 5
2
⇒ J2 = 3 5
,
2 2
J = J 1 + J2
|J1 − J2 | ≤ J ≤ |J1 + J2 |
J1 J2 J
1
2
3
2
1, 2
1
2
5
2
2, 3
3
2
3
2
0, 1, 2, 3
3
2
5
2
1, 2, 3, 4
Note that the notation 2s+1 L is meaningless in jj coupling.

J
(do Problem 10.10)

Chapter 11
SHELL MODELS
Clearly atoms and nuclei are very complicated many body problems. The
basic idea of any shell model is to replace this difficult many body problem
by an effective 1-body problem.
In the case of atoms, instead of focusing on the very complicated behav-
iors of all the electrons we instead follow the behavior of 1 electron only.
The shell model approximation is to regard this single electron as moving
in an overall effective potential which results from all of the other electrons
and the nucleus. This is often called the mean field approximation, an it is
often a surprisingly good method. The same idea holds in the nuclear shell
model where a single nucleon’s behavior is determined from the mean field
of all the other nucleons.
11.1 Atomic Shell Model

11.1.1 Degenerate Shell Model
For the moment, let us imagine that the mean field is just the Coulomb
potential. We have found that n = 1, 2, 3 · · · and l = 0, 1, 2 · · · n − 1 and
ml = −l · · · + l. Thus for n = 1 we have l = 0(s) and ml = 0. For n = 2
we have l = 0(s) or 1(p) and ml = 0 or 0, ±1, etc. Thus for the Coulomb
potential, the n = 1, 2, 3 · · · shells consist of the following subshells:
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
177
178 CHAPTER 11. SHELL MODELS
Now the s subshells have l = 0 and ml = 0. Electrons have ms = ± 12 and

recall that the Pauli principle states that no two fermions (electrons) can
have the same quantum numbers. Thus it is possible for two electrons to
have quantum numbers n and l = 0 but not three. Similarly 6 electrons can
have quantum numbers n, l = 1 but not 7 or 8. This is symbolized with
(s)2 , (p)6 , (d)10 , (f )14 . Notice that the numbers keep increasing by 4.
Thus if we keep putting electrons into the Coulomb mean field we might
get a configuration as shown in Fig. 11.1 for 60 electrons.
11.1.2 Non-Degenerate Shell Model

Actually the atomic shell model doesn’t work quite like that discussed above.
The reason is that the mean field is not exactly a Coulomb potential. As
pointed out by [Shankar, pg. 379, 1980], if all the electron orbitals were
circular, we might expect a mean Coulomb potential, with the inner electrons
merely shielding the inner nuclear charge to produce a net reduced charge.
However only s(l = 0) orbitals are circular and the potential is no longer a
purely 1r potential. The effect of this is to lift the degeneracy in l.
From plots of the spherical harmonics we see that an electron in a low l
orbit spends more time near the nucleus than an electron with high l. Thus
an electron with large l will have the nuclear charge more screened out and
therefore will feel a reduced nuclear charge resulting in a larger energy. Thus
for a given n, states with higher l have higher energy. [Shankar, pg. 379-380,
1980].
This lifting of degeneracy is shown in Fig. 11.2.
11.1.3 Non-Degenerate Model with Surface Effects

It might seem very peculiar that, for example, the 3p electrons in Fig. 11.2
can really be considered to move in a Coulomb mean field. That this is
really so is beautifully illustrated in Fig. 11.3 which shows that for a typical
electron not near the edge of the atom, the effects of all the electrons cancel
out. Thus for intermediate distance electrons the non-degenerate shell model
of Fig. 11.2 is basically correct. Fig. 11.3 clearly shows that the reason the
many-body problem reduces to a 1-body problem is because the effects of
the many bodies cancel out.
However for electrons near the edge of the atom, surface effects come
into play and the Coulomb mean field picture breaks down. The reason for
11.1. ATOMIC SHELL MODEL 179
this is shown in Fig. 11.3. Thus the shell model picture of Fig. 11.2 is not
correct for the outermost electrons.
The way that the outer shells are filled is shown in Fig. 11.5. Thus for
2 6 10 14 but rather (4s)2 (4p)6
60 N d the outer shell is not (4s) (4p) (4d) (4f )
10 2 6 2
(4d) (5s) (5p) (6s) (4f ) . 4
Fig. 11.5 neatly explains the Periodic Table. All students should fill all
the shells in Fig. 11.5 and watch how the periodic table arises. (Exercise: do
this). Fig. 11.5 is often represented in tabular form as shown in Table 11.1.
Fig. 11.5 and Table 11.1 are very misleading. They show you correctly
how the outer shells fill, but Fig. 11.5 does not represent the energy level
diagram of any atom. The outer electrons are arranged according to Table
11.1 and Fig. 11.5 but the inner electrons of a particular atom are arranged
according to Fig. 11.2. The clearest representation of this is shown in Fig.
11.6 which correctly shows the outer electrons and the inner electrons.
Why then do people use misleading figures like Fig. 11.5 and Table 11.1?
The chemical properties of atoms only depend on the outer electrons. The
inner electrons are essentially irrelevant, and so who cares how they are
arranged? It doesn’t really matter.
In order to avoid confusion it is highly recommended that Fig. 11.6 be
studied carefully.
11.1.4 Spectra
We have seen that the outer shells are filled according to Fig. 11.5, but
that the inner shells are more properly represented in Fig. 11.2. (And both
figures are combined in Fig. 11.6). What figure are we to use for explaining
the spectrum of an atom? Well the spectrum is always due to excitations of
the outer electrons and so obviously we use Fig. 11.5. (This supports what
we said earlier. Neither the chemical properties or the spectra care about
the inner electrons. It’s the outer electrons, hence Fig. 11.5, that determine
all the interesting behavior.) We summarize this in Table 11.2.
The ground state configuration of Hydrogen is (1s)1 . For Sodium it is
(1s)2 (2s)2 (2p)6 (3s)1 . The spectrum of Hydrogen is determined by transitions
of the (1s)1 electron to the higher states such as (2s)1 or (2p)1 or (3s)1 or
(3p)1 or (3d)1 , etc. The spectrum of Sodium is determined by transitions
of the (3s)1 electron to states like (3p)1 or (4s)1 etc. (Actually energetic
transitions also occur by promoting say one of the (2p)6 electrons to say
(3s)1 or higher).
When electronic transitions occur, a photon carries off the excess energy
and angular momentum according to certain selection rules. Thus we need

to know the angular momenta of the atomic states undergoing transitions.
Let us look at Hydrogen and determine the angular momenta of the ground
and excited states.
Example 11.1 Determine the angular momentum for the n =

1, 2 levels of Hydrogen.
Solution
The ground state of H is (1s)1

Thus l = 0 s = 1/2 ⇒ j = 1/2
⇒ n2S+1 LJ = 12 S1/2
The first excited states are (2s)1 or (2p)1
(2s)1 : l = 0 s = 1/2 ⇒ j = 1/2
⇒ n2S+1 LJ = 22 S1/2
1
(2p)1 : l = 1 s = ⇒ j = 1/2, 3/2
2
⇒n 2S+1
LJ = 2 P1/2 , 22 P3/2
2
(do Problem 11.1)

These excited states and possible transitions are shown in Fig. 11.7. The
figure shows how the 22 P1/2 and 22 P3/2 states are split by the spin-orbit
interaction (which does not affect the S state). Also the higher states are
also split by the spin-orbit interaction. The figure also shows how the 2 S1/2
and 2 P1/2 states are split. This is called the Lamb Shift and is a result of
quantum fluctuations of the vacuum. (See [Beiser, pg. 268, 1987; Ziock, pg.
139-140, 1969]).
11.2 Hartree-Fock Self Consistent Field Method

See [Matthews, pg. 44, 1986].
11.3. NUCLEAR SHELL MODEL 181
11.3 Nuclear Shell Model

The effect of spin-orbit coupling in atoms is rather small and has no effect
on the ground state configurations in the periodic table. However in nuclei,
Mayer and Jensen showed in 1949 that the nuclear spectra would only be
explained by assuming a rather large spin-orbit interaction. [Beiser, pg. 430,
1987].
The nuclear shell model is shown in Fig. 11.8 which represents the filling
of the outer shells and does not represent the energy level diagram of any
particular nucleus [Eisberg and Resnick, pg. 585, 1974]. Thus the Fig. 11.8
is “analogous to the diagram that could be constructed for atoms using only
the left side” of Fig. 11.6 [Eisberg and Resnick, pg. 585, 1974].
The left side of Fig. 11.8 is analogous to the right side of Fig. 11.5, both
of which contain no spin-orbit coupling. If spin orbit coupling was large
in atoms, then the right side of Fig. 11.5 would be further split as in the
right side of Fig. 11.8. In atoms we have only one type of particle, namely
electrons. However in nuclei we have two types of particle, namely protons
and neutrons. Thus we have a double copy of Fig. 11.8; one for protons and
one for neutrons.
11.3.1 Nuclear Spin

For most atoms and weak magnetic fields the LS coupling scheme is used
to figure out the total spin of the atomic ground states and excited states.
However for the majority of nuclei it is the jj coupling scheme which holds
[Beiser, pg. 430, 1987]. Actually LS coupling holds only for the lightest
nuclei.
Much of nuclear physics research is devoted to a study of nuclear excited
states. In atoms these are generally due to single or multiparticle excitations
of atomic shell orbitals. The same is true for nuclear physics, but many nuclei
are not spherical in shape and so one has to work out the shell model scheme
without the assumption of spherical symmetry. Such a shell model scheme
as a function of nuclear deformation is shown in Fig. 11.9.
Consider the nuclear energy level diagram for the excited states of 41 Ca
shown in Fig. 11.10. From Fig. 11.8 we see that 41 Ca has the major core
40 Ca with 1 nucleon in the 4f
7/2 state. This is confirmed in the energy level
diagram of Fig. 11.10 where the ground state is 7/2. The next level in Fig.
11.8 is the 3p3/2 state and we would expect the first excited state of 41 Ca
to have the nucleon promoted to this state. This is indeed true. The first
excited state in Fig. 11.10 is indeed 3/2.

However the excited states of nuclei involve much more than simple ex-
citation to shell model states. Nuclei vibrate and rotate and so have excited
states corresponding to these modes, some of which appear in the energy
level diagram of Fig. 11.10. Vibrational and rotational modes are not that
important in atoms, but they are quite important in the spectra of molecular
as well as nuclei.
11.4 Quark Shell Model

Chapter 12
DIRAC NOTATION
12.1 Finite Vector Spaces

12.1.1 Real Vector Space
A vector space consists of a set of vectors which can be added to each other
or multiplied by scalars to produce other vectors. (See pg. 76 of [Griffiths,
1995] for a formal definition.) The scalars are real numbers and thus we
have a real vector space.
A vector A can be written in terms of components Ai and unit vectors
êi as
X
A= Ai êi (12.1)
i
Here is an example of a scalar Ai multiplying a vector êi to produce another

vector A. The components Ai are real numbers.
We can also write this in Dirac notation as
X X
|Ai = Ai | êi i ≡ Ai | ii (12.2)
i i
where |Ai ≡ A and |êi i ≡ |ii ≡ êi . We are just using different symbols.
Another way to write this is
X
hA| ≡ Ai hi| (12.3)
i
and for real vector spaces there is no distinction between | i or h |.
183
184 CHAPTER 12. DIRAC NOTATION
The inner product (often called the scalar product) of two vectors is
XX
A·B = Ai Bj êi · êj
i j
XX
≡ Ai Bj gij (12.4)
i j
where the metric tensor is defined as
gij ≡ êi · êj (12.5)
For orthonormal unit vectors, gij = δij and

X
A·B= Ai Bi (12.6)
i
which gives Pythagoras’ theorem as

X
A2 ≡ A · A = A2i = A2x + A2y (12.7)
i
in two dimensions. In Dirac notation we write
A · B ≡ hA | Bi (12.8)
In ordinary notation components Ai are found according to

X
êi · A = Aj êi · êj = Ai (12.9)
j
where we have used êi · êj = δij . In Dirac notation this is
gij ≡ êi · êj = hi | ji = δij
(12.10)
giving X
hi | Ai = Aj hi | ji = Ai (12.11)
j
Finally in ordinary notation we can write

X X X
A= Ai êi = êi · Aêi = êi êi · A (12.12)
i i i
12.1. FINITE VECTOR SPACES 185
and because we must have left hand side = right hand side we have the
identity X
êi êi · = 1 (12.13)
i
Similarly X X X
|Ai = Ai | ii = hi | Ai |ii = |iihi | Ai
i i
yielding
X
|ii hi| = 1
i
(12.14)
which is called the completeness or closure relation because of its similarity to
(??). The usefulness of (12.14) is that it can always be sandwiched between
things because it is unity. For example
X X
hA | Bi = hA | iihi | Bi = Ai Bi (12.15)
i i
In old notation this would be

X X
A·B= A · êi êi · B = Ai Bi (12.16)
i i
Similarly writing a vector in terms of components,

X X
|Ai = |ii hi | Ai = Ai | ii (12.17)
i i
or X X
A= êi êi · A = Ai êi (12.18)
i i
12.1.2 Complex Vector Space

In a complex vector space the scalars can be complex numbers. That is, com-
ponents can be complex. Recall that complex numbers can be represented
as
z = x + iy (12.19)
Now zz = x2 + i2xy − y 2 whereas
|z|2 ≡ z ∗ z = x2 + y 2 (12.20)
which looks like Pythagoras’ theorem. This will help us define an inner
product for complex vectors.
Let’s consider a two-dimensional complex vector
z ≡ z1 ê1 + z2 ê2 (12.21)
where z1 and z2 are complex components. That is z1 = x1 + iy, and z2 =

x2 + iy2 . The inner product of z with itself should give Pythagoras’ theorem
P
as in (12.7). But if we use the formula (12.7) as z 2 = z · z = zi2 we get
i
X
z2 = z · z = zi2 = z12 + z22 = x2 − y 2 (12.22)
i
which is the wrong sign. Thus instead of (12.6) as the scalar product, we
define the scalar product for a complex vector space as
X
A · B ≡ hA | Bi ≡ A∗i Bi
i
(12.23)
In 2-dimensions this gives A · B = hA | Bi = A∗1 B1 + A∗2 B2 which results in
X
z 2 = z · z = hz | zi = zi∗ zi = x2 + y 2 (12.24)
i
which does give Pythagoras theorem.

Now we see the advantage of Dirac notation. For complex vectors (in
2-dimensions) define
|Ai ≡ A1 ê1 + A2 ê2 (12.25)
but define
hA| ≡ A∗1 ê1 + A∗2 ê2 (12.26)
which automatically gives hA | Bi = A∗1 B1 + A∗2 B2 . The distinction between
(12.25) and (12.26) cannot be made with ordinary vector notation A. More
generally
X
|Ai ≡ Ai | ii
i
(12.27)
and
12.1. FINITE VECTOR SPACES 187
X
hA| ≡ A∗i hi|
i
(12.28)
from which follows

XX XX
hA | Bi = A∗i Bj hi | ji = A∗i Bj δij
i j i j
X
= A∗i Bi (12.29)
i
With ordinary vector notation we have to define the scalar product in (12.23).
But with Dirac notation (12.27) and (12.28) imply the scalar product
P
hA | Bi = A∗i Bi . Thus in defining a complex vector space from scratch one
i P P
can either start with hA | Bi ≡ A∗i Bi or one can start with |Ai ≡ Ai | ii
P i i
and hA| ≡ Ai hi|. We prefer the latter.
i
Notice that
hA | Bi = hB | Ai∗
(12.30)
(do Problem 12.1) Actually we could start with this as a definition of our
complex vector space. (do Problem 12.2). Also note that
hA | xBi = x hA | Bi
(12.31)
and
hxA | Bi = x∗ hA | Bi
(12.32)
where x is a (complex) scalar. (Exercise: prove these relations)

12.1.3 Matrix Representation of Vectors

For real vector spaces we can also represent the vectors as matrices. For
example, in 2-dimensions
Ã !
B1
B ≡ |Bi ≡ (12.33)
B2
For the inner product A · B we want our answer to be A · B ≡ hA | Bi =

A1 B1 + A2 B2 . This will work if
hA| ≡ (A1 A2 ) (12.34)
because then
Ã !
B1
A · B = hA | Bi = (A1 A2 ) = A1 B1 + A2 B2 (12.35)
B2
Thus again we see the advantage of Dirac notation. Ordinary vector notation
A provides us with no way to distinguish (12.33)
Ã and!(12.34). Notice above
A1
that (A1 A2 ) = hA| is the transpose of |Ai = .
A2
For complex vector spaces we keep (12.33). For the inner product A · B
we want our answer to be A · B ≡ hA | Bi = A∗1 B1 + A∗2 B2 . This will work
if
hA| ≡ (A∗1 A∗2 ) ≡ |Ai† (12.36)
Ã !
A1
which is the transpose conjugate of |Ai = , often called the Hermitian
A2
conjugate. For a general matrix C the Hermitian conjugate C † is defined as
C † ≡ Cji
∗
(12.37)
(interchange rows and columns and take the complex conjugate of every-
thing.) A matrix H is called Hermitian if
H† = H (12.38)
12.1.4 One-Forms
Note
Ã ! in our matrix representation of real vectors we found that |Ai =
that
A1
and hA| = (A1 A2 ) are rather different objects. For complex vectors
A2
12.2. INFINITE VECTOR SPACES 189
P P
|Ai = Ai | ii and hA| = Ai hi| are also different objects. We seem to
i i
have come across two different types of vector.
In general |Ai is called a vector and hA| is called a covector. Other names
are |Ai is a contravariant vector and hA| is a covariant vector or one-form.
This dual nature of vector spaces is a very general mathematical property.
|Ai is a space and hA| is the dual space.
By the way, in Dirac notation hA| is called a bra and |Ai a ket. Thus
hA | Bi is a braket.
12.2 Infinite Vector Spaces

P
In the previous section the index i occurring in A = |Ai = Ai | ii counted
i
the dimensions. For a 2-dimensional space i has values i = 1, 2 and for 3-
dimensions values i = 1, 2, 3 and so on. We can imagine an infinite number of
dimensions, but it is more convenient to use a continuous index x rather than
a discrete index i, and integrals rather than sums. Thus (using a different
symbol ψ instead of A)
X Z ∞
ψ= ψi êi = dx ψ(x)ê(x) (12.39)
i −∞
is the appropriate generalization. ψ(x) are the infinite number of components

of ψ and ê(x) are the infinite number of basis vectors. In Dirac notation this
is
X Z ∞
|ψi = ψi | ii = dx ψ(x) | xi
i −∞
(12.40)
We have written the infinite number of components as ψ(x) to purposely

suggest the connection with functions. Thus the infinite components of the
abstract vector |ψi are nothing more than ordinary functions! This is where
vector space theory and analysis meet!
Also as all students know, the components of a vector depend on the basis
chosen. |ψi is the abstract vector but ψi change depending on whether the
basis vectors |ii are say Cartesian (î, ĵ, k̂) or Spherical (êr , êθ , êφ ). Similarly
for infinite vectors the components depend on the basis. Equation (12.40)
can be written
Z ∞ Z ∞
|ψi = dx ψ(x) | xi = dp ψ(p) | pi (12.41)
−∞ −∞
ψ(x) is the functional representation of |ψi in coordinate space (|xi) whereas

ψ(p) is the representation in momentum space (|pi). ψ(x) and ψ(p) are
related via a Fourier transform. We shall have more to say about this later.
Let’s not bother with real infinite vectors but instead consider complex
infinite vector space often called Hilbert space. This is the space where quan-
tum mechanics belongs because the wave functions ψ(x) can be real or com-
plex ψ ∗ (x). Thus generalize (12.28) and (12.40) to
X Z ∞
hψ| = ψi∗ hi| = dx ψ ∗ (x)hx|
i −∞
(12.42)
The generalization of hi | ji = δij is
hx | x0 i = δ(x − x0 )
(12.43)
where δ(x − x0 ) is the Dirac delta function, defined as
Z ∞
f (x0 )δ(x − x0 )dx0 ≡ f (x) (12.44)
−∞
The inner product follows as

Z Z ∞
hφ | ψi = dx φ∗ (x) hx| dx0 ψ(x0 ) | x0 i
−∞
Z Z
= dx dx0 φ∗ (x)ψ(x0 ) hx | x0 i
Z
= dx φ∗ (x)ψ(x) (12.45)
Thus the “length” or norm of the vector |ψi is

12.3. OPERATORS AND MATRICES 191
Z
|ψ| ≡ hψ | ψi =
2
dx ψ ∗ (x)ψ(x)
(12.46)
The components are obtained in the usual way. Using (12.40) gives
Z ∞
hx | ψi = hx| dx0 ψ(x0 ) | x0 i
−∞
Z
= dx0 ψ(x0 ) hx | x0 i
= ψ(x)
Thus the components are
hx | ψi = ψ(x)
(12.47)
and
hψ | xi = ψ ∗ (x)
(12.48)
Therefore the completeness or closure relation is
Z
dx |xi hx| = 1
(12.49)
analogous to (12.14). (do Problem 12.3 and 12.4)
Everyone should now go back and review Section 2.3.6.
12.3 Operators and Matrices

12.3.1 Matrix Elements
Suppose we have an operator Â turning an old vector x into a new vector
x0 as in
x0 = Âx (12.50)
We would like to know how the components transform. We already know

that hei | xi ≡ hi | xi = xi . Thus
hei | x0 i ≡ hi | x0 i ≡ x0i = hei | Axi

X
= hei | A xj | ej i
j
X
= hei | A | ej ixj (12.51)
j
X
≡ hi | A | jixj
j
Defining
hei | Â | ej i ≡ hi | A | ji = Aij
(12.52)
gives X
x0i = Aij xj (12.53)
j
for the transformation of components. We have had to introduce matrix

elements Aij in (12.52). Notice that the matrix elements Aij of the operator
A depend on what basis |êi i is chosen. This is exactly analogous to our
previous result where we found that vector components xi depend on the
chosen basis. Equation (12.52) is a matrix representation of the operator.
Just as a vector x can be represented by components xi so too is an
operator Â represented by components Aij .
We can work out similar results for our Hilbert space. The analog of
(12.50)
|ψ 0 i = Â | ψi ≡ |Âψi (12.54)
To work out how the components ψ(x) ≡ hx | ψi transform we write
hx | ψ 0 i ≡ ψ 0 (x) = hx | Âψi
Z
= hx | Â dx0 ψ(x0 ) | x0 i
Z
= dx0 hx | Â | x0 i ψ(x0 ) (12.55)
which is our formula for how the components transform and hx | Â | x0 i is

an infinite-dimensional matrix element.
Example 12.1 Work out the formulae for transformation of

components using the closure relations.
Solution A) Let’s first do the finite-dimensional case.

x0 = Â x
x0i = hi | x0 i = hi | Âxi
X
= hi | Â | ji hj | xi
j
X
= Aij xj
j
B) Now the Hilbert space.

|ψ 0 i = Â | ψi
ψ 0 (x) = hx | ψ 0 i = hx | Â | ψi
Z
= dx0 hx | Â | x0 i hx0 | ψi
Z
= dx0 hx | Â | x0 i ψ(x0 )
We see that this method is a little easier and clearer.
Finally we examine matrix multiplication. Suppose we have operators

A = BC. We can get matrix elements as follows.
Aij ≡ hi | A | ji = hi | BC | ji
X
= hi | B | ki hk | C | ji
k
X
= Bik Ckj (12.56)
k
which is the usual matrix multiplication formula which we have obtained
with the closure relation. Similarly for Hilbert space
hx | A | x0 i = hx | BC | x0 i
Z
= dx00 hx | B | x00 i hx00 | C | x0 i (12.57)
which is our matrix multiplication formula in Hilbert space.

12.3.2 Hermitian Conjugate

The Hermitian conjugate A† of a matrix A is defined as the complex trans-
pose
A† ≡ Ã∗ (12.58)
where Ã is the transpose. In component form this is
A†ij = A∗ji (12.59)
or
hi | A | ji† = hj | A | ii∗ (12.60)
This implies that
(AB)† = B † A† (12.61)
(do Problem 12.5) In equation (12.36) we have the general result for a vector
hψ| = |ψi†
(12.62)
and
hψ|† = |ψi
(12.63)
Defining
A | ψi ≡ |Aψi (12.64)
we also have
hA† φ | ψi = hφ | A | ψi = hφ | Aψi
(12.65)
and
hAφ | ψi = hφ | A† | ψi = hφ | A† ψi
(12.66)
Example 12.2 Show that hA† φ | ψi = hφ | A | ψi
Solution
hφ | A | ψi = |φi† A | ψi
= |φi† A†† | ψi
= (A† | φi)† | ψi
using (AB)† = B † A†
thus
hφ | A | ψi = |A† φi† |ψi

= hA† φ | ψi
(do Problem 12.6)
12.3.3 Hermitian Operators

An operator H is Hermitian if
H = H†
We shall now discuss several important properties of Hermitian operators.
Example 12.3 Prove that eigenvalues of Hermitian operators

are real.
Solution Let H be a Hermitian operator and let λ be its eigen-

value. Thus
H | ψi = λ | ψi
hψ | H | ψi = λhψ | ψi
= hψ | H † | ψi
= hHψ | ψi
= λ∗ hψ | ψi
Thus
λ = λ∗
Example 12.4 Prove that eigenvalues of Hermitian operators

belonging to distinct eigenvalues are orthogonal.
Solution Suppose we have two distinct eigenvalues λ 6= µ such

that
H | ψi = λ | ψi
and H | φi = µ | φi
Thus
hφ | H | ψi = λ hφ | ψi
= hφ | H † | ψi
= hHφ | ψi
= µ∗ hφ | ψi
but λ = λ∗ and µ = µ∗ . Thus if λ 6= µ we must have
hφ | ψi = 0
which means |φi and |ψi are orthogonal.
Thus we have the following important properties of Hermitian operators.
1. Eigenvalues of Hermitian operators are real.

2. Eigenvectors of Hermitian operators belonging to distinct eigen-
values are orthogonal.
3. Eigenvectors of Hermitian operators span the space (i.e. form a
complete set).
Items 2) and 3) can be combined into:
4. Eigenvectors of Hermitian operators form a CON set.
(Note: A set of vectors is said to span the space if every other vector
can be written as a linear combination of this set. For infinite vectors
this means they form a complete set.)
1) implies that Hermitian operators correspond to Observables.
3) implies that the eigenvectors of Hermitian operators (our observ-
ables) form basis vectors.
12.3.4 Expectation Values and Transition Amplitudes

We previously defined the expectation value of an operator as
Z
hAi ≡ dx ψ ∗ (x)Aψ(x) (12.67)
In Dirac notation we write

hAi = hψ | A | ψi (12.68)
Example 12.5 Show that these are equivalent.
Solution
hAi ≡ hψ | A | ψi
Z
= dx dx0 hψ | xi hx | A | x0 i hx0 | ψi
Z
= dx dx0 ψ ∗ (x) hx | A | x0 i ψ(x0 )
we now assume A is a local operator

i.e. hx | A | x0 i ≡ A δ(x − x0 )
Z
⇒ hAi = dx ψ ∗ (x)A ψ(x)
We can also define a transition amplitude

Z
hψ | A | φi = dx ψ ∗ (x) Aφ(x)
where A takes the wave function |φi to |ψi. This hψ | A | φi is nothing more
than a matrix element. Thus we see that the expectation value hAi = hψ |
A | ψi is just a diagonal matrix element.
12.4 Postulates of Quantum Mechanics (Fancy Ver-

sion)
In Chapter 4 we discussed the postulates of quantum mechanics in terms
of the wave function Ψ(x, t). However, now we see that this is only the
component of an abstract vector |Ψ(t)i. We shall now re-state the postulates
of quantum mechanics using Dirac notation.
1. To each state of a physical system there corresponds a state vector

|Ψ(t)i.
2. The time development of the state vector is determined by the Schrö-
dinger equation
∂
Ĥ | Ψi = ih̄ | Ψi
∂t
3. (Born Hypothesis) |ψ|2 ≡ hψ | ψi is the probability density.
4. To every physical observable b there corresponds a Hermitian operator
B̂ such that B̂ | ii = bi | ii.
5. (Expansion Postulate) |ii form a CON set such that any state vector
P
can be written |ψi = ci | ii (i.e. eigenkets of an observable form base
i
kets).
6. (Measurement Postulate) If the state of a system is |ψi then the prob-
ability that a measurement finds the system in state |βi is |hβ | ψi|2 .
7. (Reduction Postulate) A coherent superposition |ψi collapses to an
eigenstate |ii upon measurement.
12.5 Uncertainty Principle

The proof of the Uncertainty Principle is given in [Griffith, Pg. 109, 1995].
It is better stated as a theorem.
Uncertainty Principle If [A, B] = iC
1
then σA σB ≥ |hCi|
2
where σA and σB are the uncertainty in A and B (sometimes written ∆A
and ∆B) and hCi is the expectation value of C.
12.5. UNCERTAINTY PRINCIPLE 199
Example 12.6 Prove the momentum uncertainty principle, namely

σx σp ≥ h̄2 .
Solution
[x, p] = ih̄
... C = h̄
1 h̄
⇒ σ x σp ≥ |hh̄i =
2 2
h̄
... σx σp ≥
2
At this point all students should read Section 3.4.3 of [Griffiths, 1995] dealing
with the energy-time uncertainty principle. Note especially the physical
interpretation on Pg. 115.
Chapter 13
TIME-INDEPENDENT
PERTURBATION
THEORY, HYDROGEN
ATOM, POSITRONIUM,
STRUCTURE OF
HADRONS
We have been able to solve the Schrödinger equation exactly for a variety
of potentials such as the infinite square well, the finite square well, the
harmonic oscillator and the Coulomb potentials. However there are many
cases in nature where it is not possible to solve the Schrödinger equation
exactly such as the Hydrogen atom in an external magnetic field.
We are going to develop some approximation techniques for solving the
Schrödinger equation in special situations. A very important case occurs
when the total potential is a sum of an exactly solvable potential plus a
weak, or small, potential. In technical language this weak potential is called
a perturbation. The mathematical techniques of perturbation theory are
among the most widely used in physics. The great successes of the quantum
field theory of electromagnetism, called Quantum Electrodynamics, hinged
in great part upon the perturbation analysis involved in the so-called Feyn-
man diagrams. Such a perturbative framework was possible due to the weak-
201
202CHAPTER 13. TIME-INDEPENDENT PERTURBATION THEORY, HYDROGEN ATOM
ness of the electromagnetic interactions. The same can be said of the weak
interactions known as Quantum Flavordynamics. In general however the
strong interactions between quarks (Quantum Chromodynamics) cannot be
analyzed within a perturbative framework (except at very large momentum
transfers) and this has held up progress in the theory of strong interac-
tions. For example, it is known that quarks are permanently confined within
hadrons, yet the confinement mechanism is still not understood theoretically.
Consider the time-independent Schrödinger equation
H | ni = En | ni (13.1)
which we wish to solve for the energies En and eigenkets |ni. Suppose the
Hamiltonian H consists of a piece H0 which is exactly solvable and a small
perturbation λV . (We write λV instead of V because we are going to use λ
as an expansion parameter.) That is
H = H0 + λV (13.2)
where we assume that we know the solution of
H0 | n0 i = En0 | n0 i (13.3)
Note that the subscript ‘0’ denotes the unperturbed solution. It has nothing
to do with the ground state when n = 0.
So we know the solution to (13.3) but we want the solution to (13.1).
Let’s expand the state ket and energy in a power series
∞
X
|ni = λi | ni i = |n0 i + λ | n1 i + λ2 | n2 i + · · · (13.4)
i=0
and ∞
X
En = λi Eni = En0 + λEn1 + λ2 En2 + · · · (13.5)
i=0
where, for example, λ | n1 i and λEn1 are the first order corrections to the
exact unperturbed solutions for the state ket |n0 i and energy En0 .
Now simply substitute the expansions (13.4) and (13.5) into the Schrödinger
equation (13.1) giving
∞
X ∞
X ∞
X
(H0 + λV ) λ i | ni i = λj Enj λi | ni i (13.6)
i=0 j=0 i=0
203
or X X X
λ i H0 | ni i + λi+1 V | ni i = λi+j Enj | ni i (13.7)
i i ij
and now we equate like powers of λ.

Let’s first equate coefficients of λ0 . In the first term of (13.7) this gives
i = 0. This does not mean that i = 0 in the second or third terms because the
i is just a separate dummy variable in each of the three terms. The second
term would require i + 1 = 0 which is impossible for any value of positive–
definite i and thus the second term must be absent. The third term i + j = 0
can only work for i = 0 and j = 0. Thus
coefficients of λ0 : H0 | n0 i = En0 | n0 i (13.8)
or
(H0 − En0 | n0 i = 0 (13.9)
which is just the unperturbed Schrödinger equation (13.3).
Now equate coefficients of λ1 . This gives i = 1 in the first term of (13.7).
The second term is i + 1 = 1 giving i = 0 and the third term is i + j = 1
which can happen in two ways. Either i = 0 and j = 1 or i = 1 and j = 0.
Thus
coefficients of λ1 : H0 | n1 i + V | n0 i = En1 | n0 i + En0 | n1 i (13.10)
or
(H0 − En0 | n1 i = (En1 − V ) | n0 i (13.11)
Equating coefficients of λ2 gives i = 2 in the first term of (13.7) and
i + 1 = 2 giving i = 1 in the second term. The third term i + j = 2 can
happen in three ways. Either i = 0 and j = 2 or i = 1 and j = 1 or i = 2
and j = 0. Thus
coefficients of λ2 : H0 | n2 i + V | n1 i = En2 | n0 i + En1 | n1 i + En0 | n2 i

(13.12)
or
(H0 − En0 ) | n2 i = (En1 − V ) | n1 i + En2 | n0 i (13.13)
Similarly the coefficients of λ3 give
(H0 − En0 ) | n3 i = (En1 − V ) | n2 i + En2 | n1 i + En3 | n0 i (13.14)
The general pattern is

(H0 − En0 | nk i = (En1 − V ) | nk−1 i + En2 | nk−2 i

+En3 | nk−3 i + · · ·
+ · · · Enk−1 | n1 i + Enk | n0 i
(13.15)
This result is true for both degenerate and non-degenerate perturbation
theory.
13.1 Non-degenerate Perturbation Theory

Let’s now calculate the energies in perturbation theory.
Look at the zeroth order equation. Multiplying from the left with a bra
hn0 | gives
hn0 | H0 − En0 | n0 i = 0 (13.16)
or
hn0 | H0 | n0 i
En0 = (13.17)
hn0 | n0 i
and assuming |n0 i is normalized via hn0 | n0 i = 1 gives
En0 = hn0 | H0 | n0 i (13.18)
as expected, and is the result that we already would have calculated from
our exact unperturbed Schrödinger equation. That is En0 is already known.
What interests us is the first order correction En1 to the unperturbed energy
En0 . To extract En1 we multiply the first order equation (13.11) on the left
again with the bra hn0 | giving
hn0 | H0 | n1 i − En0 hn0 | n1 i = En1 − hn0 | V | n0 i (13.19)
Now
hn0 | H0 = hn0 | H0† = En0 hn0 | (13.20)
because H0 is Hermitian. Thus the left side of (13.19) is 0. (Note that |n0 i
and |n1 i need not be orthogonal and thus hn0 | n1 i is not 0 in general.) Thus
(13.19) gives
En1 = hn0 | V | n0 i ≡ Vnn

13.1. NON-DEGENERATE PERTURBATION THEORY 205
(13.21)
which Griffiths [Griffiths, 1995] calls the most important result in quantum
mechanics! It gives the first order correction to the energy in terms of the
unperturbed state kets |n0 i which we already know.
Recall the complete expression for the energy in (13.5), which to first
order becomes
En = En0 + λEn1
= hn0 | H0 | n0 i + hn0 | λV | n0 i (13.22)
where λV is the complete perturbation. If you like you can now drop the
expansion parameter λ and just write the perturbation as V in which case
we have
En1 = hn0 | V | n0 i (13.23)
or
En = En0 + En1
= hn0 | H0 | n0 i + hn0 | V | n0 i (13.24)
Example Griffiths example pg. 223
Example 14.1 Evaluate the second order expression for the en-
ergy.
Solution The second order expression is given in (13.13) and we

wish to extract En2 . As before multiply from the left with hn0 |
giving (with the left hand side vanishing as before)
0 = En1 hn0 | n1 i − hn0 | V | n1 i + En2 (13.25)
Now |n0 i and |n1 i are not necessarily orthogonal (OG) and we
are stuck with the term hn0 | n1 i. Can we construct |n1 i OG to
|n0 i? Yes. Define
|n01 i ≡ |n1 i + a1 | n0 i (13.26)
and evaluate (H0 − En0 ) | n01 i giving
(H0 − En0 ) | n01 i = (H0 − En0 ) | n1 i + a1 (H0 − En0 ) | n0 i
The last term is 0 giving (H0 − En0 ) | n01 i = (H0 − En0 ) | n1 i.

Thus |n01 i and |n1 i obey the same equation. Let’s pick
hn0 | n1 i
a1 ≡ − (13.27)
hn0 | n0 i
Now let’s test the orthogonality of |n01 i and |n0 i.

hn0 | n1 i
hn0 | n01 i = hn0 | n1 i − hn0 | n0 i = 0
hn0 | n0 i
showing that |n01 i is OG to |n0 i. Thus from now on let’s always

take |n1 i as having been constructed OG to |n0 i. Thus (13.25)
becomes
En2 = hn0 | V | n1 i (13.28)
The generalization of (13.21) and (13.28) is
Enk = hn0 | V | nk−1 i
(13.29)
Wave Functions
We are assuming that we already know the unperturbed kets |n0 i allowing
us to evaluate En1 = hn0 | V | n0 i but to get the higher corrections Enk we
need |nk−1 i. We shall now discuss how to evaluate these.
Recall the first order equation (13.11). The |n0 i form a CON set and
therefore |n1 i can be expanded in terms of them as
X
|n1 i = cm | m0 i + cn | n0 i (13.30)
m6=n
which is substituted into (13.11) giving

X
cm (H0 − En0 ) | m0 i + cn (H0 − En0 ) | n0 i = (En1 − V ) | n0 i (13.31)
m6=n
13.1. NON-DEGENERATE PERTURBATION THEORY 207
where the term (H0 − En0 ) | n0 i = 0 which is why we wrote the expansion
(13.30) with m 6= n. Operate on (13.31) with hk0 | to give
X
cm (hk0 | H0 | m0 i − En0 hk0 | m0 i) = En1 hk0 | n0 i − hk0 | V | n0 i
m6=n
(13.32)
For k 6= n we have hk0 | n0 i = 0 and hk0 | m0 i = δkm and hk0 | H0 | m0 i =
Em0 hk0 | m0 i = Em0 δkm giving
ck (Ek0 − En0 ) = −hk0 | V | n0 i (13.33)
or
hk0 | V | n0 i
ck = (k 6= n) (13.34)
En0 − Ek0
which are our expansion coefficients for k 6= n.
Example 14.2 Show that cn = 0.
Solution To extract cn multiply (13.30) by hn0 | to give

X
hn0 | n1 i = cm hn0 | m0 i + cn
m6=n
Now hn0 | m0 i = 0 if m 6= n we were able (and did) construct

|n0 i OG to |n1 i giving hn0 | n1 i = 0.
Thus cn = 0.
Thus we could have left off the second term in (13.30) which
would not have appeared in (13.31). (However we got zero there
anyway.)
Upon substitution of (13.34) and cn = 0 into (13.30) finally gives
X hm0 | V | n0 i
|n1 i = | m0 i
m6=n
En0 − Em0
(13.35)
for the first order wave function. Therefore the complete expression for the
second order energy in (13.28) is
X |hm0 | V | n0 i|2
En2 =
m6=n
En0 − Em0
(13.36)
where we used hm0 | V | n0 i = hn0 | V | m0 i∗ . Equations (13.35) and (13.36)
are our final expressions for the corrections to the wave function and energy
given completely in terms of unperturbed quantities.
As a practical matter, perturbation theory usually gives very accurate
answers for energies, but poor answers for wave functions [Griffiths, 1996].
In equations (13.35) and (13.36) we see that the answers will blow up if
En0 = Em0 . That is if there is a degeneracy. Thus we now consider how to
work out perturbation theory for the degenerate case.
13.2 Degenerate Perturbation Theory

In equations (13.35) and (13.36) we see that the expressions diverge if En0 =
Em0 , i.e. for degenerate states. (Perhaps even our first order expression
En1 = hn0 | V | n0 i is not correct.) Let us therefore re-consider perturbation
theory for degenerate states.
However, even though there does not appear to be a problem for the
first order energy En1 = hn0 | V | n0 i, in fact for degenerate states we really
don’t know how to evaluate this. For example, suppose we have two-fold
degeneracy
H 0 | m 0 i = E | m0 i (13.37)
and
H0 | k0 i = E | k0 i (13.38)
then which states are we supposed to use in evaluating En1 ? Do we use
En1 = hm0 | V | m0 i or hk0 | V | k0 i ?
Actually linear combinations are equally valid eigenstates (see below),
i.e.
H0 (α | m0 i + β | k0 i) = E(α | m0 i + β | k0 i) (13.39)
13.2. DEGENERATE PERTURBATION THEORY 209
with the same energy E. Thus should we use the linear combination
|n0 i ≡ α | m0 i + β | k0 i (13.40)
as the state in En1 ? If the answer is yes, then what values do we pick for
α and β ? Thus even for the first order energy En1 we must re-consider
perturbation theory for degenerate states.
Degenerate perturbation theory is not just some exoteric technique. De-
generate perturbations are among the dramatic features of spectral lines. If
a single line represents a degenerate state, then the imposition of an external
field can cause the degenerate level to split into two or more levels. Thus
the subject of degenerate perturbation theory is very important. Actually
non-degenerate theory is almost useless because very few states are actually
non-degenerate.
13.2.1 Two-fold Degeneracy

Let’s consider the case of two-fold degeneracy with
H0 | m0 i = Em0 | m0 i (13.41)
and
H0 | k0 i = Ek0 | k0 i (13.42)
with
hk0 | m0 i = 0 (13.43)
and where the degeneracy is specified via
Em0 = Ek0 ≡ E0 (13.44)
which previously gave a singularity in (13.35) and (13.36).

Now our previous equation (13.15) is valid in both degenerate and non-
degenerate perturbation theory. A linear combination of the state |m0 i and
|k0 i is also a solution to H0 , i.e.
H0 (α | m0 i + β | k0 i) = E0 (α | m0 i + β | k0 i) (13.45)
because Em0 = Ek0 = E0 . This can be rewritten as
(H0 − En0 ) | n0 i = 0 (13.46)

with
|n0 i ≡ α | m0 i + β | k0 i (13.47)
where (13.46) is just the zero order equation (13.15).
We want to calculate the first order correction to the energy. We use
(13.11). In non-degenerate theory we multiplied (13.11) by hn0 |. Here we
shall multiply separately by hm0 | and hk0 |. Thus
hm0 | H0 − En0 | n1 i = hm0 | En1 − V | n0 i (13.48)
Again we can arrange for hm0 | n1 i = 0. Thus we have
0 = αhm0 | En1 − V | m0 i + βhm0 | En1 − V | k0 i

= α(En1 − Vmm ) − βVmk (13.49)
where
Vmk ≡ hm0 | V | k0 i (13.50)
Multiplying (13.11) by hk0 | gives
0 = −αVkm + β(En1 − Vkk ) (13.51)
Equations (13.49) and (13.51) can be written in matrix form as

Ã !Ã !
En1 − Vmm −Vmk α
=0 (13.52)
−Vkm En1 − Vkk β
or Ã !Ã ! Ã !
Vmm Vmk α α
= En1 (13.53)
Vkm Vkk β β
which can be solved for En1 and α and β. Equation (13.52) has solutions if
the determinant of the 2 × 2 matrix is zero. Thus
(En1 − Vmm )(En1 − Vkk ) − Vkm Vmk = 0 (13.54)
(The Hamiltonian H = H0 + V is Hermitian and thus V is also Hermitian

† ∗ . Thus V
km Vmk = |Vkm | ).
implying Vmk = Vmk = Vkm 2
(13.54) is a quadratic equation in En1 , namely
En21 − (Vmm + Vkk )En1 + Vmm Vkk − |Vkm |2 = 0 (13.55)
which has two solutions

13.2. DEGENERATE PERTURBATION THEORY 211
· q ¸
1
En±1 = (Vmm + Vkk ) ± (Vmm − Vkk )2 + 4 | Vkm |2
2
(13.56)
which shows that a two-fold degeneracy is “lifted” by a perturbation. Note
that all of the matrix elements Vkm are known in principle because we know
|m0 and |k0 i and Vkm ≡ hk0 | V | m0 i.
13.2.2 Another Approach

Equation (13.56) is the energy equation for the perturbed eigenvalues. The
terms Vmm and Vkk are just like the result (13.21) from non-degenerate
theory. In fact suppose Vkm = 0, then (13.56) becomes
En+1 = Vmm (13.57)
and
En−1 = Vkk (13.58)
which are identical to the non-degenerate formula (13.21). Thus if somehow
Vkm = 0 then we can just use our results from non-degenerate theory.
What is the difference between Vmm and Vkk ? Recall that we are only
considering doubly degenerate theory. |mi and |ki are the two degenerate
eigenstates that have the same energy, but |mi and |ki are different. See
(13.41) and (13.42). Thus Vmm and Vkk are evaluated by using the two
different degenerate states |mi and |ki respectively.
Now how can we get Vkm = 0? There happens to be a handy little
theorem to use [Griffiths, 1995, pg. 229].
Theorem Let A be a Hermitian operator that commutes with V . If |m0 i
and |k0 i are eigenkets of A with distinct eigenvalues, i.e.
A | m0 i = µ | m0 i, A | k0 i = ν | k0 i, and µ 6= ν
then Vkm = 0.
Proof By assumption [A, V ] = 0. Thus
hm0 | [A, V ] | k0 i = 0
= hm0 | AV − V A | k0 i
= (µ − ν)hm0 | V | k0 i
= (µ − ν)Vmk
But µ 6= ν, thus Vmk = 0.
Thus the following procedure for degenerate states is recommended. Look

for an Hermitian operator A that commutes with V . Find simultaneous
eigenkets of H0 and A, and call them |m0 i and |k0 i and then use formulas
(13.57) and (13.58) to calculate the energies. (If you can’t find such an A,
you will have to use (13.56). [Griffiths, 1995, pg. 230])
13.2.3 Higher Order Degeneracies

See Section 6.2.2 of [Griffiths, 1995, pg. 231].
We do not have time to cover higher order degeneracies. However note
that the procedure for degenerate states remains the same as in the case of
2-fold degeneracy, and we can use the formula for non-degenerate states for
En1 .
13.3 Fine Structure of Hydrogen

We would now like to explore the spectrum of the Hydrogen atom in greater
detail as an application of perturbation theory. Students are referred to the
excellent article by Hänsch, Schawlow and Series [“The Spectrum of Atomic
Hydrogen” by T. W. Hänsch, A. L. Schawlow and G. W. Series, Scientific
American, March 1979, pg. 94]. See also Table 6.1 of Griffiths. [Griffiths,
1996, pg. 237]
The fine structure of Hydrogen consists of two pieces namely the rela-
tivistic correction and spin-orbit coupling.
13.3.1 1-Body Relativistic Correction

In wishing to describe the electron relativistically we should really develop
the theory of Relativistic Quantum Mechanics or Relativistic Quantum Field
Theory which results when Special Relativity and Quantum Mechanics are
combined [Weinberg, 1996]. (No one has yet succeeded in combining Gen-
eral Relativity with Quantum Mechanics). In quantum field theory the
relativistic generalization of the 1-body Schrödinger equation is called the
Klein-Gordon equation for spin-0 particles, or the Dirac equation for spin- 12
particles, or the Rarita-Schwinger equation for spin- 32 particles. (No one
has yet solved the 2-body (special) relativistic bound state problem. The
equation, called the Bethe-Salpeter equation, can be written down in a very
general form but no one can solve it.)
13.3. FINE STRUCTURE OF HYDROGEN 213
We don’t have time to develop the full relativistic theory and instead we
shall just use the simplest possible generalization of the Schrödinger equation
that we can think of.
Recall the kinetic energy for the (non-relativistic) Schrödinger equation
is
p2
T = (13.59)
2m
where p = −ih̄ dx d
for 1-dimension and p = −ih̄5 in 3-dimensions. In the
relativistic case recall that
E =T +m (13.60)
and
E 2 = p2 + m2 (13.61)
giving q
T = p2 + m2 − m (13.62)
where we have left off the factors of c (or equivalently used units where c ≡ 1).
Thus the simplest relativistic generalization of the Schrödinger equation that
we can think of is simply to use (13.62), instead of (13.59), as the kinetic
energy. The resulting equation is called the Relativistic Schrödinger equa-
tion or Thompson equation. (The reason this is the simplest generalization
is because more complicated relativistic equations also include relativistic
effects in the potential energy V . We shall not study these here.)
The trouble with (13.62) is that as an operator it’s very weird. Consider
the Taylor expansion
s µ ¶2
p
T = m 1+ −m
m
p2 p4
≈ − + ··· (13.63)
2m 8m3
The first term is just the non-relativistic result and the higher terms are
relativistic corrections, but it is an infinite series in the operator p = −ih̄ dx
d
.
How are we ever going to solve the differential equation?! Well that’s for
me to worry about. [J. W. Norbury, K. Maung Maung and D. E. Kahana,
Physical Review A, vol. 50, pg. 2075, 3609 (1994)]. In our work now we
p2
will only consider the non-relativistic term 2m and the first order relativistic
correction defined as
p4
V ≡− 3 (13.64)
8m
so that the first order correction to the energy, using equation (13.21) or
(13.23), is
−1 1
En1 = 3
hn0 | p4 | n0 i ≡ − 3 hp4 i (13.65)
8m 8m
In position space this becomes
Z
hn0 | p | n0 i =
4
dr dr0 hn0 | rihr | p4 | r0 ihr0 | n0 i (13.66)
where
Ã !2
h̄2 2
hn0 | ri ≡ ψn∗ (r) 0
and hr | p | r i =
4
− ∇ δ(r − r0 )
2m
giving
Z Ã !2
1 h̄2 2 1
En1 =− 2 drψn∗ (r) − ∇ ψn (r) ≡ − hp4 i (13.67)
8m 2m 8m3
The unperturbed states |n0 i projected into coordinate space are

hr | n0 i ≡ ψn (r) which we found to be
s
(n − l − 1)!
ψnlm (r, θ, φ) = (2k)3 (2kr)l e−kr L2l+1
n+l (2kr)Ylm (θ, φ) (13.68)
2n[(n + 1)!]3
from equation (??) where k ≡ na Z

where a is the Bohr radius.
Thus we could obtain En1 by substituting (13.68) into (13.67), evaluating
∇4 ψnlm (r, θ, φ) and then performing the resulting integral. There is also an
easier way.
We can write
hp4 i = hn0 | p4 | n0 i = hn0 | p2 p2 | n0 i (13.69)
Now
p2 | n0 i = 2m(E − U ) | n0 i (13.70)
implying
†
hn0 | p2 = hn0 | 2m(E − U )† (13.71)
and p2 = p 2† and U = U † giving
hn0 | p2 = hn0 | 2m(E − U ) (13.72)

so that
hp4 i = 4m2 hn0 | (E − U )2 | n0 i (13.73)
or
−1
En1 = h(E − U )2 i
2m
−1 2
= (E − 2EhU i + hU 2 i) (13.74)
2m
2
Thus to get En1 , we only have to calculate hU i and hU 2 i. Now U = − 4π²
1 Ze
0 r
(from equation (9.1) and so what we need are h 1r i and h r12 i. The results are
1 Z
h i= 2 (13.75)
r n a
where n is the principal quantum number and a is the Bohr radius and
[Griffiths, 1995, pg. 238]
1 1
h 2i = 1 (13.76)
r (l + 2 )n3 a2
for Z = 1.
(do Problem 14.1). Thus we obtain
Ã !
E2 4n
En1 =− n −3 (13.77)
2m l + 12
(do Problems 14.2 and 14.3)
But wait a minute ! We used hr|n0 i = ψnlm (r, θ, φ). According to the
procedure for degenrate states weren’t we supposed to find an operator A
p4
that commutes with V = − 8m 3 and then find simultaneous eigenstates of A
p4
and H0 and use the eiegnstates in hn0 |V |n0 i ? Yes ! An we did ! V = − 8m 3
commutes with L2 and Lz . The states Ylm are simultaneous eigenstates of
L2 , Lz and H0 . Thus the states ψnlm = Rnl (r)Ylm (θ, φ) already are the
correct eigenstates to use.
But for example, a two-fold degeneracy, aren’t we supposed to have two
different expressions hm0 |V |m0 i and hk0 |V |k0 i and similarly for higher-fold
degeneracies ? Yes ! And we did ! The states Ylm (θ, φ) are all different for
differnet values of m. Suppose n = 1 then we can have l = 0 and l = 1
which are two degenerate states |l = 0i and |l = 1i. Our answer 13.77 is
different for different values of l. In other words for two-fold degeneracy
(n = 1, l = 0, 1) we had |m0 i = |l = 0i and |k0 i = |l = 1i. We just wrote the
general state as |li or Ylm , but it’s really a collection of states |m0 i and |k0 i.
[NNN work out h r12 i for Z 6= 1. Is (13.77) also valid for Z 6= 1?]
13.3.2 Two-Body Relativistic Correction

The 2-body (bound state) problem in relativistic quantum mechanics is un-
solved! The Schrödinger equation can be solved for 1 and 2 bodies but the
relativistic equations, such as Dirac and Klein-Gordon, are 1-body equa-
tions. The problem is always how to make U relativistic. Here we shall just
consider T .
The non-relativistic kinetic energy is
p21 p2
T = T1 + T2 = + 2 (13.78)
2m1 2m2
where p1 = −ih̄ ∂x∂ 1 and p2 = −ih̄ ∂x∂ 2 in 1-dimension.
Introducing the reduced mass µ ≡ mm11+m m2
2
and total mass M ≡ m1 + m2
we found in Chapter 7 that
1 ∂2 1 ∂2 1 ∂2 1 ∂2
+ = + (13.79)
m1 ∂x21 m2 ∂x22 µ ∂x2 M ∂X 2
where x ≡ x1 − x2 and X ≡ m1mx11 +m 2 x2

+m2 . It was this separation (13.79)
that allowed us to solve the 2-body Schrödinger equation in general for all
potentials of the form U (x1 , x2 ) ≡ U (x1 − x2 ) ≡ U (x). By the way, notice
that if we use the center of momentum frame defined by
M Ẋ = 0 = m1 ẋ1 + m2 ẋ2 = p1 + p2 (13.80)
then
p1 = −p2 ≡ p (13.81)
and then
p21 p2 p2
+ 2 = (13.82)
2m1 2m2 2µ
Now the obvious generalization of (13.78) is
T = T1 + T2
q q
= p21 + m21 − m1 + p22 + m22 − m2 (13.83)
or Ã ! Ã !
p21 p2 p41 p42
T ≈ + 2 − + + ··· (13.84)
2m1 2m2 8m31 8m32
which again reduces to the correct non-relativistic expressions (13.78) or
(13.79) or (13.82). When (13.83) is used as the kinetic energy operator, the
resulting equation is called the Relativistic Schrödinger equation or Spin-

less Salpeter equation. (The Thompson equation is nothing more than the
Spinless Salpeter equation with the masses set equal.)
(NNN Can (13.84) be solved analytically in coordinate space?????)
13.3.3 Spin-Orbit Coupling

In Section 10.4.1 we have already briefly studied the effect of spin-orbit
coupling as an example of the physical effect of spin.
Recall that the spin-orbit effect results because from the point of view
of an orbital electron, it sees a positively charged nucleus in orbit around it.
(We want the electron point of view because we want to calculate its energy.)
Thus the electron feels a magnetic field because it is at the center of a current
loop. Now the electron has a dipole moment µ due to its inrinsic spin. The
interaction energy between a magnetic field B and a dipole moment was
given in (10.61) as
U = −µ · B (13.85)
This will cause a change in the energy levels. The way we calculated this
change was simply to add U to the Bohr energy levels. This was a good
guess, and gave us a qualitative understanding, but we didn’t justify this
from the point of view of quantum mechanics. The proper way to do the
calculation is to add (13.85) to the Coulomb potential and solve the new
Schrödinger differential equation for the new energy levels. Unfortunately
we don’t know how to analytically solve this differential equation. Thus we
use perturbation theory, with U = −µ · B treated as the perturbation (which
we called V ).
Equation (10.59) can be written
1 e
B= L (13.86)
4π²0 mc2 r3
where L = mvr and c = √µ10 ²0 . This gives the magnetic field of the orbiting
proton.
We now want the magnetic moment of the spinning electron. Translating
equation (??) we get
e
µ=− S (13.87)
2m
for the classical answer. Actually the correct result, from Dirac’s relativistic
theory is
e
µ=− S (13.88)
m
Thus the interaction energy becomes
e2 1
V = −µ · B = S·L (13.89)
4π²0 m c2 r3
2
However there is also a relativistic kinematic correction, known as Thomas

precession [Jackson, 1975] which throws in a factor of 12 giving
e2 1
V = S·L
8π²0 m c2 r3
2
(13.90)
which is our final expression for the spin-orbit interaction. (Actually if you
had been naive and left out the Dirac correction for µ and the Thomas
precession, you would still have got the right answer, because they cancel
out!)
Now we want to put this expression into our quantum mechanical ¯ formula ¯
¯ ¯
(13.21) for the energy shift. But how are we going to calculate hn0 ¯ r13 S · L¯ n0 i?
Let’s first review a few things about angular momentum.
The full wave function was written in equation (8.6) as ψ(r) ≡ ψ(r, θ, φ) ≡
R(r)Y (θ, φ) or ψnlm (r, θ, φ) = Rnl (r)Ylm (θ, φ). However we also need to in-
clude spin which does not arise naturally in the Schrödinger equation (it is
a relativistic effect). The spin wave function χ(s) must be tacked on as
hr | n0 i ≡ ψ(r) = Rnl (r)Ylm (θ, φ)χ(s) (13.91)
Recall that the spherical harmonics satisfy
L2 Ylm = l(l + 1)h̄2 Ylm (13.92)

Lz Ylm = mh̄ Ylm (13.93)
or
L2 | lmi = l(l + 1)h̄2 | lmi (13.94)

Lz | lmi = mh̄ | lmi (13.95)
where the abstract kets |lmi are usually represented as functions
hθφ | lmi = Ylm (θ, φ) (13.96)

The spin angular momentum kets also satisfy
S 2 | sms i = s(s + 1)h̄2 | sms i (13.97)

Sz | sms i = ms h̄ | sms i (13.98)
where S 2 , Sz and |sms i are usually represented as matrices.

Now in perturbation theory we want to calculate En1 = hn0 | V | n0 i
with V given in (13.90). Thus
·Z ¸
e2 1 ∗ 1
En1 = r 2
dr Rnl (r) 3 Rnl (r) hlm|hsms | S · L | sms i|lmi
8π²0 m2 c2 r
(13.99)
Now Z
∗ 1 1
r2 dr Rnl (r) 3
Rnl (r) = 1 (13.100)
r (l + 2 )(l + 1)n3 a3
(see Griffiths, equation 6.63), but the tricky piece is hL · Si. Recall our
procedure for degenerate states. In this case we have V ∝ L · S and we are to
look for a Hermitian operator A that commutes with V , i.e. find an A that
commutes with L · S. Let’s try a few, say L and S . Well
[L · S, L] 6= 0
and
[L · S, S] 6= 0
However
[L · S, J] = [L · S, L2 ] = [L · S, S 2 ] = [L · S, J 2 ] = 0
(do Problem 14.4)

and so any of J, L2 , S 2 or J 2 will do for the operator A. Now the procedure
for degenerate states is to find simultaneous eigenkets of H0 and A and use
them to calculate the expectation value of V . Such eigenkets are |jmi, |lmi
or |smi. Which to choose? hlm | L·S | lmi or hsm | L·S | smi is complicated.
It’s easier to write
1
L · S = (J 2 − L2 − S 2 ) (13.101)
2
which comes from
J 2 = (L + S) · (L + S) = L2 + S 2 + 2L · S (13.102)
To calculate hL · Si we choose what is convenient, namely

1
hL · Si = [hjm | J 2 | jmi − hlm|hsms | L2 | sms i|lmi
2
−hlm|isms | S 2 | sms i|lmi]
1
= [hjm | J 2 | jmi − hlm | L2 | lmi − hsm | S 2 | smi]
2
h̄2
= [j(j + 1) − l(l + 1) − s(s + 1)] (13.103)
2
giving
e2 1 12 h̄2 [j(j + 1) − l(l + 1) − s(s + 1)]

En1 = (13.104)
8π²0 m2 c2 l(l + 12 )(l + 1)n3 a3
or " #
nEn20 j(j + 1) − l(l + 1) − 3
4
En1 = (13.105)
mc2 l(1 + 12 )(l + 1)
(do Problem 14.5)
The fine-structure correction consists of both the relativistic correction
(13.77) and the spin-orbit correction (13.105). Adding them gives
Ã !
En2 4n
En1 = 3− (13.106)
2mc2 j + 12
to give the grand result for the energy levels of hydrogen including fine
structure as
" Ã !#
13.6eV α2 n 3
Enj =− 1 + 1 −
n2 n2 j+ 2
4
(13.107)
This is known as the fine-structure formula. (do Problem 14.6) Note the
presence of the famous fine structure constant
e2 1
α≡ ≈ (13.108)
4π²0 h̄c 137
13.4 Zeeman effect

reference: D.J. Griffiths, “Quantum Mechanics”, section 6.4
13.5. STARK EFFECT 221
13.5 Stark effect

reference: D.J. Griffiths, “Quantum Mechanics”
13.6 Hyperfine splitting

reference: D.J. Griffiths, “Quantum Mechanics”, section 6.5
reference: D.J. Griffiths, “Introduction to Elementary Particles”, section
5.5
13.7 Lamb shift

reference: D.J. Griffiths, “Introduction to Elementary Particles”, section 5.4
13.8 Positronium and Muonium

reference: D.J. Griffiths, “Introduction to Elementary Particles”, section 5.6
13.9 Quark Model of Hadrons

reference: D.J. Griffiths, “Introduction to Elementary Particles”, sections
5.7 - 5.10
Chapter 14
VARIATIONAL
PRINCIPLE, HELIUM
ATOM, MOLECULES
14.1 Variational Principle
14.2 Helium Atom
14.3 Molecules
223
224CHAPTER 14. VARIATIONAL PRINCIPLE, HELIUM ATOM, MOLECULES
Chapter 15
WKB APPROXIMATION,
NUCLEAR ALPHA DECAY
(Note: these notes closely follow [Griffiths, 1995])

For most of the arbitrary potentials that we can think up, the Schrödinger
equation cannot be solved analytically. However for certain types of poten-
tial, there are certain approximation methods that work well. We have
already explored perturbation theory which is good if we know the answer
to a certain potential which is perturbed.
The Wentzel, Kramers, Brillouin (WKB) approximation is good for cal-
culating energies and tunnelling probabilities through potentials which vary
slowly. If a potential varies slowly then for small changes in position it can
be considered as a finite square well or finite square barrier, and we can thus
use our previous solutions. The difference will be however, that the potential
is not truly flat but varies. Thus we expect that our previous solutions are
valid except that the amplitude and wavelength will change as the potential
changes.
15.1 Generalized Wave Functions

Recall the time-independent Schrödinger equation for 1-body in 1-dimension
for a constant potential U = U0
h̄2 d2 ψ
− + U0 ψ = Eψ (15.1)
2m dx2
225
226CHAPTER 15. WKB APPROXIMATION, NUCLEAR ALPHA DECAY
Recall our discussion in Section 6.3, where we write this as
2m(E − U0 )
ψ 00 + ψ = 0 for E > U0 (15.2)
h̄2
or
2m(U0 − E)
ψ 00 − ψ = 0 for E < U0 (15.3)
h̄2
The region E > U is sometimes called the “classical” region [Griffiths, 1995,
pg. 275] because E < U is not allowed classically. Defining
p
2m(E − U0 )
k≡ (15.4)
h̄
and p
2m(U0 − E)
κ≡ (15.5)
h̄
which are both real for E > U0 and E < U0 respectively. Thus the
Schrödinger equation is
ψ 00 + k 2 ψ = 0 (15.6)
or
ψ 00 − κ2 ψ = 0 (15.7)
with solutions
ψ(x) = A eikx + B e−ikx (15.8)
or
ψ(x) = C eκx + C e−κx (15.9)
(Of course (15.8) can also be written E cos kx + F sin kx, etc.) These wave
functions (15.8) and (15.9) are only the correct solutions for a constant po-
tential U = U0 . If U = U (x) they are not correct! However if U is slowly
varying then over small distances it does approximate a constant potential.
The answers for a slowly varying potential are
A R B R
ψ(x) ≈ √ ei k dx
+ √ e−i k dx
k k
(15.10)
and
15.1. GENERALIZED WAVE FUNCTIONS 227
C R D R
ψ(x) ≈ √ e κ dx
+√ e κ dx
k κ
(15.11)
where now k ≡ k(x) and κ = κ(x) are both functions of x because U =
U (x). I call these the generalized wave functions because they are obviously
generalizations of (15.8) and (15.9) which we had for the constant potential
U = U0 . The generalized wave functions have variable amplitude and variable
wavelength whereas these are constant for (15.8) and (15.9). The variable
wavelength are the k(x) and κ(x) terms in the exponential. Recall p = h̄k =
h
λ.
Let’s now see how to derive the generalized wave functions. In general
any (complex) wave function can be expressed in terms of an amplitude and
phase via
ψ(x) ≡ A(x)eiφ(x) (15.12)
This assumption is not an approximation, but rather, is exact. Let’s find
A(x) and φ(x) by substituting into the Schrödinger equation. For definite-
ness, use the first of the two Schrödinger equations, namely (15.6). Substi-
tution yields
A00 + 2iA0 φ0 + iAφ00 − Aφ02 + Ak 2 = 0 (15.13)
and equating the Real and Imaginery parts gives
A00 + A(k 2 − φ02 ) = 0 (15.14)
and
Aφ00 + 2A0 φ0 = 0 (15.15)
which are exact equations relating the amplitude and phase of the general
wave function (15.12). The second equation can be solved in general by
writing it as
(A2 φ0 )0 = 0 (15.16)
yielding
C
A2 φ0 = C 2 , or A = √ 0 (15.17)
φ
where C is a constant. We don’t use A = ± √C 0 , because A being an
φ
amplitude, will give the same results for all observables whether we use +
or −. The first equation (15.14) cannot be solved in general. (If it could
we would have a general solution of the Schrödinger equation!) The WKB

approximation consists of setting A00 to zero
WKB approximation: A00 ≈ 0 (15.18)
This makes good sense. If the potential is slowly varying over x then the
strength or amplitude of the wave function will only vary slowly.
Thus we can solve (15.14) in general as
φ0 = ±k (15.19)
giving
C
A= √ (15.20)
k
and the general solution of the first order ODE is
Z
φ(x) = ± k(x)dx (15.21)
Thus the generalized wave function (15.12) is written, in the WKB approx-
imation, as
C R
ψ(x) ≈ √ e±i k(x)dx (15.22)
k
The general solution is a linear combination
A R B R
ψ(x) = √ ei k(x)dx
+ √ e−i k(x)dx
k k
in agreement with (15.10). Equation (15.11) can be solved in a similar
manner. (do Problem 15.1)
Example 15.1 Derive the quantization condition

Z a
φ(a) = k(x)dx = nπ (15.23)
0
for a potential well with infinite vertical walls.
Solution (All students should first go back and review the infi-
nite square well potential.)
15.1. GENERALIZED WAVE FUNCTIONS 229
The well is shown in Fig. 8.2 of Griffiths [1995]. It is specified as
U (x) = an arbitrary function if 0 < x < a

= ∞ at x = 0 and x = a.
Clearly we only consider the classical region E > U with the

solution (15.10), which we write as
1
ψ(x) = √ (A sin φ + B cos φ) (15.24)
k
Rx
with φ(x) ≡ k(x0 )dx0 which implies φ(0) = 0.
0
The boundary conditions, as usual, are
ψ(0) = ψ(a) = 0
ψ(0) = 0 implies B = 0 or ψ(x) = √Ak sin φ(x). Then ψ(a) = 0

gives sin φ(a) = 0 implying φ(a) = ±nπ where n = 1, 2, 3 · · ·. As
with the infinite square well we drop the − sign to give
Z a
φ(a) = k(x)dx = nπ
0
Example 15.2 Show how the above quantization condition gives

the exact result for the square well potential. Why is the result
exact?
Solution We have
p
2m[E − U (x)]
k(x) ≡
h̄
For U (x) = 0 = constant we have
√
2mE
k(x) = constant =
h̄
which upon substitution into (15.23) gives
π 2 h̄2
En = n 2
2ma2
in agreement with our previous result for the infinite square well
in (3.14).
The reason why we get the exact result is because A(x) does
not change as a function of x, and so the WKB approximation
A00 ≈ 0 is actually exact.
15.2 Finite Potential Barrier

Before reading this section, please go back and review Section 6.4 where the
finite potential barrier was first introduced.
In Section 6.4 we studied the finite potential barrier with a flat top.
Now we will consider a bumpy top or a top represented by some arbitrary
function. (Compare to the infinite well with a bumpy bottom in Example
15.1.) The potential barrier with a flat top is shown in Fig. 6.2. A bumpy
top is shown in Fig. 15.1. Regions I and III are identical in Figs. 6.2 and
15.1 and thus the solutions in those regions are the same, regardless of the
shape of the top of the potential. Thus from Section 6.4 we still have
ψI (x) = A eikx + B e−ikx
≡ ψi + ψR (15.25)
where √
2mE
k≡ (15.26)
h̄
and ψi and ψR are the incident and reflected waves respectively. Also we
still have
ψIII (x) = C eikx (15.27)
for the transmitted wave.
We would like to study tunnelling and so we consider the case E < U (x)
where the energy of the incident particle is smaller than the potential barrier
(non-classical region). For the
√ flat top barrier we previously had ψII (x) =
2m(U −E)
D eκx + F e−κx where κ ≡ h̄
0
. However we now consider a bumpy
top described by the potential U (x) and so in region II let’s use the WKB
approximately, namely,
D R F −R
ψII (x) ≈ √ e κ dx
+ √ e κ dx
(15.28)
κ κ
15.3. GAMOW’S THEORY OF ALPHA DECAY 231
with p
2m[U (x) − E]
κ(x) ≡ (15.29)
h̄
From our previous experience we know that F is always bigger than D, so
that the dominant effect inside the well is one of exponential decay. Thus
let’s set
D≈0 (15.30)
which will be accurate for high or wide barriers, which is equivalent to the
tunnelling probability being small. Thus
F R
ψII (x) ≈ √ e− κ dx
(15.31)
κ
¯ ¯2
¯ ¯
Now the tunnelling probability is T ≡ ¯ C D
A ¯ but instead of getting A from
(15.27) and (15.25) let’s use the WKB wave function (15.31). Because we
must have ψI (−a) = ψII (−a) and ψII (a) = ψIII (a) then
¯ ¯ Ra
¯C ¯
¯ ¯ = e− −a κ dx (15.32)
¯A¯
giving Z a
T ≈ e−2γ with γ ≡ κ dx (15.33)
−a
with κ(x) given in (15.29) where U (x) > E.
15.3 Gamow’s Theory of Alpha Decay

As an application of the WKB approximation let us consider Gamow’s the-
ory of alpha decay. (Gamow is pronounced Gamof.) Alpha decay is the
phenomenon whereby nuclei spontaneously emit alpha particles (i.e. Helium
nuclei).
The force between two nucleons is very attractive and very short range.
A good model of the force is shown in Fig. 15.2C representing an attractive
finite potential well. The radius of the well is about 1 fm, corresponding to
the range of the nuclear force. Realistic nuclei are made of both neutrons
and protons and therefore the protons experience a repulsive Coulomb force
in addition to the attractive nuclear force. The combination of these two is
shown in Fig. 15.2D.
Consider the nucleus 238 U, which is known to undergo alpha decay. Prior
to alpha decay, Gamow considered the alpha particle to be rattling around
inside the 238 U nucleus, or to be rattling around inside the potential well
of Fig. 15.2D. In this picture notice that the Coulomb potential represents
a barrier that the alpha particle must climb over, or tunnel through, in
order to escape. This is perhaps a little counter-intuitive as one would
think that the charge on the alpha particle would help rather than hinder
its escape, but such is not the case. (It’s perhaps easier to think of Fig.
15.2D in terms of scattering, whereby an incident alpha particle encounters
a repulsive barrier, but if it has sufficient energy it overcomes the barrier and
gets captured by the nuclear force.) Also we will be considering zero orbital
angular momentum l = 0. For l 6= 0 there is also an angular momentum
barrier in addition to the Coulomb barrier.
We are going to use the theory we developed in the previous section for
the finite potential barrier. You may object that Fig. 15.1 looks nothing
like Fig. 15.2D, but in fact they are similar if one considers that we want to
calculate the tunnelling probability for the alpha particle to go from being
trapped at r = r1 to escaping to r = r2 where r2 can be as large as you like.
(Also we developed our previous theory for 1-dimension and here we are
applying it to 3-dimensions, but that’s OK because the radial Schrödinger
equation is an effective 1-dimension equation in the variable r.)
The Coulomb potential between an alpha particle of charge +2e and a
nucleus of charge +Ze is
1 2Ze2 c
U (r) = + ≡ (15.34)
4π²0 r r
where
2Ze2
C≡ (15.35)
4π²0
√
2m[U (r)−E]
Thus (15.33) with κ = h̄ , (15.33) becomes
Z s µ ¶
1 r2 c
γ= 2m −E (15.36)
h̄ r1 r
what is E? It is the energy of the particle at position r2 , i.e. the energy of

the escaped particle. Note if we had set r2 = ∞ we would get γ = ∞, which
is a common disease of the Coulomb potential. Gamow’s model is that the
15.3. GAMOW’S THEORY OF ALPHA DECAY 233
particle has the energy E before it escapes. See Fig. 15.2D. Thus
1 2Ze2
E= (15.37)
4π²0 r2
We obtain
Z p
γ ≈ K1 √ − K2 Zr1 (15.38)
E
with Ã ! √
e2 π 2m
K1 = = 1.980 MeV1/2 (15.39)
4π²0 h̄
and Ã !1/2 √
e2 4 m
K2 = = 1.485 f m−1/2 (15.40)
4π²0 h̄
The above 3 equations are derived in [Griffiths, 1995]. Make certain you can
do the derivation yourself.
We want to know the lifetime τ or half-life τ1/2 of the decaying nucleus.
They are related via
τ1/2 τ1/2
τ= = (15.41)
ln 2 0.693
In the Gamow model of the alpha particle rattling around before emission
then the time between collisions with the wall, or potential barrier would be
2r1
v where v is the speed of the particle. Thus the lifetime would be
τ = time between collisions × probability of escape
or
2r1 −2γ
τ=
e (15.42)
v
where v can be estimated from the energy.
(do Problems 15.2–15.5)
Chapter 16
TIME-DEPENDENT
PERTURBATION
THEORY, LASERS
In 1-dimension the time-dependent Schrödinger equation (1.22) is

Ã !
h̄2 ∂ 2 ∂
− + U Ψ(x, t) = ih̄ Ψ(x, t) (16.1)
2µ ∂x2 ∂t
and in 3-dimensions the equation (8.1) is

Ã !
h̄2 ∂
− ∇2 + U Ψ(r, t) = ih̄ Ψ(r, t) (16.2)
2µ ∂t
In general we have
U = U (r, t) (16.3)
That is the potential energy can be a function of both position and time.
If the potential is not a function of time U 6= U (t) then we were able to
use separation of variable to solve the Schrödinger equation (16.1) or (16.2).
This was discussed extensively in Chapter 2. We found
−i
Ψ(x, t) = ψ(x)e h̄ Et
for U 6= U (t) (16.4)
This very simple time dependence meant that |Ψ|2 ≡ Ψ∗ Ψ was constant
in time. That is Ψ was a stationary state. All expectation values were
235
236CHAPTER 16. TIME-DEPENDENT PERTURBATION THEORY, LASERS
also stationary. All of our studies up to now have been concerned with time-
independent potentials U 6= U (t). Thus we spent a lot of time calculating the
energy levels of square wells, the harmonic oscillator, the Coulomb potential
and even perturbed states, but there was never the possibility that a system
could jump from one energy level to another because of time-independence.
If an atom was in a certain energy level it was stuck there forever.
The spectra of atoms is due to time-dependent transitions between states.
If we are to understand how light is emitted and absorbed by atoms we bet-
ter start thinking about non-stationary states or time-dependent Hamilto-
nians. Thus we are back to the very difficult problem of solving the partial
differential Schrödinger equation, (16.1) or (16.2), for a general potential
U = U (r, t). This time separation of variables won’t work, and the partial
differential Schrödinger equation cannot be solved for general U (r, t).
Thus we can either specialize to certain forms of U (r, t) or we can develop
an approximation scheme known as time-dependent perturbation theory.
16.1 Equivalent Schrödinger Equation

As with time-independent perturbation theory we write the Hamiltonian H
in terms of an unperturbed piece H0 and a perturbation V (t) as in
H = H0 + V (t) (16.5)
analogous to (13.2), (except we are not going to use an expansion parameter

λ here). H0 is the time-independent Hamiltonian (with V (t) = 0),
p2
H0 = + U (r) (16.6)
2m
for which we assume we know the full solution to the time-independent
Schrödinger equation
H0 | ni = En | ni (16.7)
analogous to (13.3). The problem we want to solve is
∂
H | Ψ(t)i = ih̄ | Ψ(t)i (16.8)
∂t
where
hr | Ψ(t)i ≡ Ψ(r, t) (16.9)
16.1. EQUIVALENT SCHRÖDINGER EQUATION 237
Recall the following results from Section 2.3. We can always write the
general solution Ψ(r, t) in terms of a complete set
X
Ψ(r, t) = cn Ψn (r, t) (16.10)
n
For the case U 6= U (t) this was a linear combination of separable solutions
X X
Ψ(r, t) = cn Ψn (r, t) = cn ψn (r)e−iωn t (16.11)
n n
or X X
|Ψ(t)i = cn | n(t)i = cn | nie−iωn t (16.12)
n n
where
|n(t)i ≡ |nie−iωn t (16.13)
and
En
ωn ≡ (16.14)
h̄
We also wrote (16.11) using
c0n (t) ≡ cn e−iωn t (16.15)
as X X
Ψ(r, t) = cn Ψn (r, t) = c0n (t)ψn (r) (16.16)
n n
or X X
|Ψ(t)i = cn | n(t)i = c0n (t) | ni (16.17)
n n
both of which look more like an expansion in terms of the complete set
{ψn (r)} or {|ni}.
For the time-dependent case U = U (t) we write our complete set expan-
sion as X
Ψ(r, t) ≡ cn (t)ψn (r)e−iωn t (16.18)
n
or
X
|Ψ(t)i = cn (t) | nie−iωn t (16.19)
n
= ca (t) | aie−iωa t + cb (t) | bie−iωn t (16.20)
(for 2–level system)
which contains both cn (t) and e−iωn t whereas above for U 6= U (t)we only had
one or the other. Here cn (t) contains an arbitrary time dependence whereas
c0n (t) above only had the oscillatory time dependence c0n (t) ≡ cn e−iωn t .
Equations (16.18) or (16.19) are general expansions for any wave func-
tions valid for arbitrary U (r, t). If we know cn (t) we know Ψ(t). Thus let’s
substitute (16.18) or (16.19) into the Schrödinger equation and get an equiv-
alent equation for cn (t), which we will solve for cn (t), put back into (16.18)
and then have Ψ(t).
Subsituting (16.19) into (16.8) gives
X X
H0 cn (t)e−iωn t | ni + V (t) cn (t)e−iωn t | ni (16.21)
n n
X X
= ih̄ ċn (t)e−iωn t | ni + cn (t)En e−iωn t | ni (16.22)
n n
where ċn ≡ dcdtn .

To extract cn we do the usual thing of multiplying by hm| to give
X X
cn (t)e−iωn t hm | H0 | ni + cn (t)e−iωn t hm | V | ni
n n
= ih̄ ċm e−iωm t + cm Em e−iωm t (16.23)
where hm | ni = δmn has killed the sums on the right hand side. Now
hm | H0 | ni = Em δmn . Thus the first term on the left cancels the second
term on the right to give
−i X
ċm (t) = Vmn (t)eiωmn t cn (t) (16.24)
h̄ n
where
Vmn (t) ≡ hm | V (t) | ni (16.25)
and
ωmn ≡ ωm − ωn . (16.26)
Let’s condense things a bit. Define
vmn (t) ≡ Vmn (t)eiωmn t (16.27)
and because ωmm ≡ 0 this implies
vmm (t) = Vmm (t) (16.28)
Thus
16.1. EQUIVALENT SCHRÖDINGER EQUATION 239
−i
ċm (t) = vmn (t)cn (t)
h̄
(16.29)
where we have used the Einstein summation convention for the repeated
P
index n, i.e. vmn (t)cn (t) ≡ vmn (t)cn (t).
n
Equation (16.29) is the fundamental equation of time-dependent pertur-
bation theory, and it is completely equivalent to the Schrödinger equation.
All we have to do is solve (16.29) for cm (t) and then we have the complete
wave function Ψ(r, t). Thus I call equation (16.29) the equivalent Schrödinger
equation.
So far we have made no approximations!
Actually (16.29) consists of a whole collection of simultaneous or cou-
pled equations. For example, for a 2-level system [Griffiths, 1995], equation
(16.29) becomes
−i
ċa (t) = (vaa ca + vab cb )
h̄
−i
ċb (t) = (vba ca + vbb cb ) (16.30)
h̄
or in matrix form
Ã ! Ã !Ã !
ċb −i vaa vab ca
= (16.31)
ċb h̄ vba vbb cb
The general equivalent Schrödinger equation in matrix form is then
    
ċ1 v11 v12 v13 · · · c1
  
   v21 v22 v23 · · · 
 
 = −i
ċ2  c2 
  
 ċ3  h̄  v31 v32 v33 · · ·  
 c3


   
.. .. .. .. . .
. . . . .
(16.32)
again recalling that, for example v11 = V11 (t) and v21 = V21 (t)eiω21 t . Equa-
tion (16.32) is entirely the same as (16.29) and involves no approximations.
Thus (16.32) is also entirely equivalent to the Schrödinger equation.
16.2 Dyson Equation

If V (t) is small then the equivalent Schrödinger equation (16.29) can be
iterated. Integrating both sides gives
Z Z
t dcm (t1 ) −i t
dt1 = cm (t) − cm (t0 ) = dt1 vmn (t1 )cn (t1 ) (16.33)
t0 dt1 h̄ t0
At t = t0 , the system is in state |ii and cm (t0 ) = δmi . Thus

µ ¶Z
−i t
cm (t) = δmi + dt1 vmn (t1 )cn (t1 ) (16.34)
h̄ t0
The idea of iteration is as follows. For the cn (t1 ) appearing on the right
hand side just write it as a replica of (16.34), namely
µ ¶Z
−i t1
cn (t1 ) = δni + dt2 vnk (t2 )ck (t2 ) (16.35)
h̄ t0
P
where is implied for the repeated index k. Substitute the replica back
k
into (16.34) to give
µ ¶Z ·
−i t
cm (t) = δmi + dt1 vmn (t1 ) δni
h̄ t0
µ ¶ Z t1 ¸
−i
+ dt2 vnk (t2 )ck (t2 )
h̄ t0
µ ¶Z t
−i
= δmi + dt1 vmi (t1 )
h̄ t0
µ ¶2 Z t Z t1
−i
+ dt1 dt2 vmn (t1 )vnk (t2 )ck (t2 ) (16.36)
h̄ t0 t0
P
where we have used vmn (t1 )δni ≡ vnm (t1 )δni = vmi (t1 ). Do the same
n
again. Make a replica of (16.34) but now for ck (t2 ) and substitute. Contin-
uing this procedure the final result is
µ ¶Z
−i t
cm (t) = 1 + dt1 vmi (t1 )
h̄ t0
µ ¶2 Z t Z t1
−i
+ dt1 dt2 vmn (t1 )vni (t2 )
h̄ t0 t0
µ ¶3 Z t Z t1 Z t2
−i
+ dt1 dt2 dt3 vmn (t1 )vnk (t2 )vki (t3 )
h̄ t0 t0 t0
+··· (16.37)
16.3. CONSTANT PERTURBATION 241
or
∞ µ
X ¶ Z Z Z
−i j t t1 tj−1
cm (t) = 1 + dt1 dt2 · · · dtj vmn (t1 )vnk (t2 ) · · · vki (tj )
j=1
h̄ t0 t0 t0
(16.38)
This is called the Dyson equation for cm (t). (Actually what is usually called
the Dyson equation is for a thing called the time evolution operator, but it
looks the same as our equations.) We shall often only use the result to first
order which is
µ ¶Z
−i t
cm (t) = δmi + dt1 vmi (t1 )
h̄ t0
(16.39)
called the Strong Incompletely Coupled Approximation (SICA).
16.3 Constant Perturbation

[NNN constant perturbation was assumed in all my NASA papers and also
is discussed in Merzbacher and Schiff (Pg. 197)].
The simplest perturbation to treat is a constant perturbation. Yikes! you
say. Isn’t that supposed to be the subject of time-independent perturbation
theory that we already discussed? Nope. When we talk about a constant
perturbation in time-dependent perturbation theory what we mean is a po-
tential turned on at time t0 remaining constant, and then being turned off
at time t. Thus our time integral looks like
Z ∞ Z t0 Z t Z ∞
Vki (t0 )dt0 = O dt0 + Vkn dt0 + O dt0
−∞ −∞ t0 t
Z t
= Vkn dt0 (16.40)
t0
(Of course there are other things inside the integrals, but I have left them
out for now.) Vkn can be taken outside of the second integral because it is
constant over the time interval t0 → t, whereas it’s obviously not constant
over the entire time interval −∞ → +∞. Thus overall we still do have a
time dependent interaction. See [Schiff, 1955, 2nd ed., pg. 197; Griffiths,
1995, problems 9.28 9.14, see part c, pg. 320].
Let’s analyze the first order equation (16.39) which is

µ ¶Z
−i t
cm (t) = δmi + dt1 Vmi eiωmi t1
h̄ t0
µ ¶ Z t
−i
= δmi + Vmi dt1 eiωmi t1
h̄ t0
Vmi ³ iωmi t ´
= δmi − e − eiωmi t0 (16.41)
h̄ωmi
Now let’s take t0 = 0 and m 6= i, giving δmi = 0. Thus
1 − eiωmi t
cm (t) = Vmi (16.42)
h̄ωmi
giving
2 1 − cos ωmi t
Pi→m (t) ≡ |cm (t)|2 = |Vmi |2 (16.43)
h̄2 2
ωmi
which is the transition probability for a constant perturbation. Now Pi→m (t)
represents the transition probability between the two states |ii and |mi. For
a two-state system the total probability P (t) is just
P (t) = Pi→m (t) (16.44)
The transition rate is defined as

dP (t)
w≡ (16.45)
dt
which has units of second−1 and is therefore a rate. From (16.43) we get
2 2 sin ωmi t
w= 2 |Vmi | ωmi
h̄
(16.46)
which is the transition rate for a two-level system under a constant pertur-
bation. The amazing thing is that it is a function of time which oscillates
sinusoidally. (See discussion in Griffiths, Pg. 304 of “flopping” frequency.
His discussion is for a harmonic perturbation, which we discuss next, but
the discussion is also relevant here.)
(do Problem 16.4)
16.3. CONSTANT PERTURBATION 243
Now Pi→m (t) represents the transition probability between two states |ii
and |mi. But |ii can undergo a transition to a whole set of possible final
states |ki. Thus the total probability P (t) is the sum of these,
X
P (t) = Pk (t) (16.47)
k
where
Pk (t) ≡ Pi→k (t) ≡ |ck (t)|2 (16.48)
P
If the energies are closely spaced or continuous, we replaced by an integral
k
Z ∞
P (t) = ρ(Ek )dEk Pk (t) (16.49)
0
where ρ(Ek ) is called the density of states. It’s just the number of energy
levels per energy interval dEk . Thus ρ(Ek )dEk is just the number of levels
in interval dEk . Often we will assume a constant density of states ρ which
just then comes outside the integral.
Note that formulas (16.47) and (16.49) involved addition of probabilities.
See Griffiths, Pg. 310 footnote. From (16.43) we get, assuming constant ρ,
and with dEk = h̄dωk
Z ∞
2 1 − cos ωki t
P (t) = |Vki |2 ρ dωk 2 (16.50)
h̄ 0 ωki
We want to change variables using dωk = dωki . However it is important to
realize that Z ∞ Z ∞
dωk = dωki (16.51)
0 −∞
because ωk varies from 0 to ∞ but so also does ωi . Thus when ωk = 0 and
ωi = ∞ then ωki = −∞ and when ωk = ∞ and ωi = 0 then ωki = +∞.
Thus Z ∞
2 1 − cos ωki t
P (t) = |Vki |2 ρ dωki 2 (16.52)
h̄ −∞ ωki
because the integrand is an even function. Using [Spiegel, 1968, Pg. 96]
Z ∞ 1 − cos px πp
2
dx = (16.53)
0 x 2
R∞ 1−cos px
which, due to the integrand being even implies x2
dx = πp, giving
−∞
2π
P (t) = |Vki |2 ρt (16.54)
h̄
from which we use w ≡ dP

dt to obtain
2π
w= |Vki |2 ρ(Ek )
h̄
(16.55)
which is the transition rate for a multi-level system under a constant per-
turbation. This is the famous Fermi Golden Rule Number 2 for a constant
perturbation.
Footnote: Sometimes you might see an alternative derivation as follows.
[NASA TP-2363, Pg. 4]
dP (t)
w ≡ lim
dt
t→∞
Z ∞
2 sin ωki t
= lim |Vki |2 ρ dωk
t→∞ h̄ 0 ωki
Using the representation of the delta function [Merzbacher, 2nd ed., 1970,
pg. 84]
1 sin xθ
δ(x) = lim
π θ→∞ x
giving Z
2 ∞ 2π
w= |Vki |2 ρ dωki πδ(ωki ) = |Vki |2 ρ
h̄ −∞ h̄
It represents a constant rate of transition [Merzbacher, 2nd ed., 1970, pg.
479, equation (18.107)].
16.4 Harmonic Perturbation

Plane electromagnetic (EM) waves consist of harmonically varying (i.e. si-
nusoidally varying) electric and magnetic fields. We can learn a great deal
about the structure of atoms, nuclei and particles by exciting them with EM
radiation (photons) and studying the decay products. This is the reason as
to why we are interested in perturbations.
Let’s write the perturbation as
V (t) = V cos ωt (16.56)

16.4. HARMONIC PERTURBATION 245
which, upon substitution into the first order amplitude (16.39), yields
µ ¶ Z
−i t eiωt1 + e−iωt1 iωmi t1
cm (t) = δmi + Vmi dt1 e
h̄ t 2
µ ¶ "0
−i ei(ωmi +ω)t − ei(ωmi +ω)t0
= δmi + Vmi
h̄ 2i(ωmi + ω)
#
ei(ωmi −ω)t − ei(ωmi −ω)t0
+ (16.57)
2i(ωmi − ω)
which is identical to (16.41) if ω ≡ 0, because (16.56) just becomes V (t) = V .

Again let’s take t0 = 0 and m 6= i, giving δmi = 0. Thus
" #
1 − ei(ωmi +ω)t 1 − ei(ωmi −ω)t
cm (t) = Vmi + (16.58)
2h̄(ωmi + ω) 2h̄(ωmi − ω)
which is identical to (16.42) if ω ≡ 0. When we work out |cm (t)|2 it’s a big
mess. When ω ≈ ωmi the second term dominates so let’s just consider
1 − ei(ωmi −ω)t
cm (t) ≈ Vmi (16.59)
2h̄(ωmi − ω)
giving ¡ω ¢
mi −ω
sin2 t
Pi→m (t) ≡ |cm (t)| ≈ 2
|Vmi |2 2 2
(16.60)
h̄ (ωmi − ω)2
(do Problem 16.1)
This is the transition probability for a two-state system under a harmonic
perturbation. Again using (16.44) and (16.45) gives
1 2 sin(ωmi − ω)t
w= 2 |Vmi | ωmi − ω
2h̄
(16.61)
which is the transition rate for a two-level system under a harmonic pertur-
bation, which like (16.46) also oscillates in time.
For a multi-level system, using the same constant density ρ as before, we
have from (16.60)
³ ´
Z ∞ sin2 ωki −ω
t
1 2
P (t) = |Vki |2 ρ dωk (16.62)
h̄ 0 (ωki − ω)2
ωki −ω
and changing the variable to x ≡ 2 the integral becomes
Z ∞ Z ∞
dωk = dx (16.63)
0 −∞
as before giving
Z ∞
1 1 sin2 xt
P (t) = |Vki |2 ρ dx (16.64)
h̄ 2 −∞ x2
Using [Spiegel, 1968, pg. 96]
Z ∞ sin2 px πp
2
dx = (16.65)
0 x 2
R∞ sin2 px
which, due to the integrand being even implies x2
dx = πp, giving
−∞
π
P (t) = |Vki |2 ρt (16.66)
2h̄
from which we use w ≡ dP
dt to obtain
π
w= |Vki |2 ρ(Ek )
2h̄
(16.67)
which is the transition rate for a multi-level system under a harmonic per-
turbation, or the Fermi Golden Rule Number 2 for a harmonic perturbation,
Footnote: Sometimes you might again see an alternative derivation as
follows [NASA TP-2363, pg. 4]
dP (t)
w ≡ lim
t→∞dt
Z ∞
1 sin(ωki − ω)t
= lim |Vki |2 ρ dωk
t→∞ 2h̄ 0 ωki − ω
and using
sin(ωki − ω)t
lim = πδ(ωki − ω) = πδ(ωk − ωi − ω)
t→∞ ωki − ω
giving Z
1 ∞ π
w= |Vki |2 ρ d(ωki − ω)πδ(ωki − ω) = |Vki |2 ρ
2h̄ −∞ 2h̄
and which again represents a constant rate of transition. (If you want
(16.56) to look the same as (16.55) just rewrite (16.56) as V (t) = 2V cos ωt.)
16.5. PHOTON ABSORPTION 247
16.5 Photon Absorption

Electromagnetic (EM) waves, or photons, consist of mutually orthogonal
electric and magnetic oscillating fields. The electrons in atoms respond pri-
marily to the electric field because of their charge. If we ignore the spatial
variation of the EM fields then [Griffiths, 1995, pg. 306]
E = E0 cos tωt k̂ (16.68)
where we have assumed the field E points in the k̂ direction, and [Griffiths,
equation 9.32]
V (t) = −eE0 z cos ωt (16.69)
Compare this to (16.56). Thus
Vmi = −PE0 (16.70)
where the z component of the electric dipole moment is
P ≡ ehm | z | ii (16.71)
giving from (16.61)
1 2 2 sin(ωmi − ω)t
w= 2 |P| E0 ωmi − ω
(16.72)
2h̄
Here we have in mind that an atomic electron is excited by a single incident
photon polarized in the k̂ direction.
All students should read pages 307-309 of [Griffiths, 1995] for an excellent
discussion of absorption and stimulated emission and spontaneous emission.
These topics are very important in the study of lasers. Note especially that
the rate of absorption is the same as the rate of stimulated emission (just
swap indices).
16.5.1 Radiation Bath

Suppose that instead of excitation by a single photon, the atom is placed
in a radiation bath. Even though we are still considering only a two-level
system (see Fig. 9.4, Griffiths, pg. 307), there will be a large distribution of
incident photon energies entirely analogous to our previous distribution of
continuous final states. Thus we use a density of states formalism to describe
the distribution of incident photons.
We introduce a density of initial states ρ(E) analogous to (16.49) as

Z ∞
P (t) = ρ(E)dE Pk (t) (16.73)
0
Again assuming a harmonic perturbation V (t) ≡ V cos ωt one obtains
π
w= |Vki |2 ρ(E)
2h̄
(16.74)
which is the transition rate for a radiation bath initial state under a harmonic
perturbation and is again the Fermi Golden Rule Number 2, with the density
of initial states in the radiation bath described by ρ(E). (do Problem 16.2)
In the above expression for photons we again have Vki = −PE0 as in
(16.70). However the initial radiation bath is not really characterized by an
electric field E0 but rather by the energy density (this time energy per unit
volume)
1
u = ²0 E02 (16.75)
2
to give
2u
|Vki |2 = |P|2 (16.76)
²0
giving
π
w= |P|2 uρ(E) (16.77)
²0 h̄
(Note: in comparing this with equation (9.43) of Griffiths, realize that ρ(ω0 )
used by Griffiths is actually the energy per unit frequency per unit volume.
This is related to my ρ(E) via ρ(ωh̄0 ) = uρ(E).)
Using the electric dipole moment, analogous to (16.71) as
P ≡ ehm | r | ii (16.78)
and averaging over all polarizations [Griffiths, pg. 311] gives a factor of 1/3,
i.e.
π
w= |P|2 uρ(E)
3²0 h̄
(16.79)
(The averaging works like this; consider r2 = x2 + y 2 + z 2 but now suppose
x2 = y 2 = z 2 giving r2 = 3z 2 and thus z 2 = 13 r2 .)
16.6. PHOTON EMISSION 249
16.6 Photon Emission

Energy levels can decay by either stimulated emission or spontaneous emis-
sion. This is discussed nicely by [Griffiths, 1995]. The transition rates for
these processes are called the Einstein A and B coefficients. [Eisberg and
Resnick, pg. 428].
The stimulated emission rate is Bρ [Griffiths, 1995, pg. 312] where
π
B= |P|2
3²0 h̄2
(16.80)
and the spontaneous emission rate is
ω3
A= |P|2
3π²0 h̄c3
(16.81)
Students should study the derivation of these formulas in [Griffiths, 1995,
pg. 311-312].
The lifetime of an excited state is just [Griffiths, 1995, pg. 313]
1
τ=
A
(16.82)
16.7 Selection Rules

To get the lifetime of a state we always need to calculate P ≡ qh]ψb | r | ψa i.
Specifically for Hydrogen atom wave functions this is
P = −ehn0 l0 m0 | r | nlmi (16.83)
Such a calculation is done in Problem 16.6. There we found that a lot of

these matrix elements are zero. It would be very helpful if we had a quick
way of knowing this rather than always having to grind through integrals.
There are two famous selection rules for photon emission. These are
∆m = ±1, 0
(16.84)
and
∆l = ±1
(16.85)
Transitions will not occur unless these are satisfied. They are very clearly
derived on pages 315-318 of [Griffiths, 1995]. All students should fully un-
derstand these derivations and include them in their booklet write-ups.
16.8 Lasers
Chapter 17
SCATTERING, NUCLEAR
REACTIONS
17.1 Cross Section

Experiments carried out at particle accelerators have had a dramatic effect
on our understanding of the ultimate structure of matter. In principle the
experiment is simple. Fire a beam of particles at a target and watch what
comes out! In reality the phrase “watch what comes out” means count
particles of a certain type at a variety of energies and at a variety of angles.
Usually an experimentalist converts this “count” into a quantity called a
cross section.
The actual count rate N (in units of sec−1 is just the luminosity of the
beam L (cm−2 sec−1 ) times the reaction cross section σ (cm2 ),
N = Lσ (17.1)
Thus to measure a cross section the experimentalist just divides the count
rate by the beam luminosity.
When measuring a total cross section σ, the experimentalist doesn’t mea-
sure either the energy or the angle of the outgoing particle. She just mea-
suress the total number of counts. However one might be interested in how
many particles are emitted as a function of angle. This is the angular dis-
dσ
tribution or angular differential cross section dΩ . Or one instead might be
interested in the number of particles as a function of energy. This is called
dσ
the spectral distribution or energy differential cross section dE . One might
d2 σ
be interested in both variables or the doubly differential cross section dEdΩ .
251
252 CHAPTER 17. SCATTERING, NUCLEAR REACTIONS
These are all related to the total cross section via

Z Z Z
dσ dσ d2 σ
σ= dE = dΩ = dEdΩ (17.2)
dE dΩ dEdΩ
dσ
For example dE is actually a function that one would measure and perhaps
plot. The integral of that function is the total cross section.
17.2 Scattering Amplitude

Quantum mechanics is a theory of waves. The incident beam in our particle
accelerator can be considered as a collection of plane waves Aeikz moving
in the z direction (the beam direction), as shown in Fig. 17.1. When the
ikr
plane wave scatters it turns into an outgoing spherical wave e r modified
by a distortion factor called a scattering amplitude f (θ).
Example 17.1 Justify the use of ψ = Aeikz for an incident beam

of particles.
Solution The asymptotic region is that region where U = 0.

Thus the Schrödinger equation, for l = 0, is
∇2 ψ + k 2 ψ = 0
where √
2mE
k≡
h̄
In 1-dimension (the z direction) the Schrödinger equation is
d2 ψ
+ k2 ψ = 0
dz 2
which has solution
ψ = Aeikx
for an incident beam in the z direction.
Let’s discuss the outgoing spherical wave in more detail. When the ex-
perimentalist detects an outgoing scattered particle, the detector is in what
17.2. SCATTERING AMPLITUDE 253
we call the asymptotic region where U = 0 and r → ∞. We found previously

that for a constant potential U = U0 the general solution to the Schrödinger
equation for arbitrary l was given in (8.70) as

(1) (2)
= Cr hl (kr) + Dr hl (kr) (17.3)
√
2m(E−U0 )
where k ≡ h̄ . (For our detector in the asymptotic region we have
U0 = 0.) In problem 17.1 it is shown that
eikr
Rl (r → ∞) = C(−i)l+1 (17.4)
kr
with R(r) ≡ u(r)
r . By the way we shall often need the asymptotic expressions
for these functions, namely
sin(x − lπ/2)
jl (x → ∞) → (17.5)
x
and
cos(x − lπ/2)
nl (x → ∞) → − (17.6)
x
(do Problem 17.1)
(2)
In problem 17.1 we see that hl (kr) corresponds to an incoming spherical
wave and therefore we must have D = 0 because the scattered wave will be
outgoing. Thus the incident plus scattered wave, from (17.3), is
" #
X (1)
ikz
ψ(r, θ, φ) = A e + clm hl (kr)Ylm (θ, φ) (17.7)
lm
u(r)
where we have used R(r) ≡ r . In the asymptotic region this is
" #
X ikr
ikz l+1 e
ψ(r∞ , θ, φ) = A e + clm (−i) Ylm (θ, φ) (17.8)
lm
kr
or " #
eikr
ψ(r∞ , θ, φ) ≡ A eikz + f (θ, φ) (17.9)
r
where we have defined the scattering amplitude as
1X
f (θ, φ) ≡ clm (−i)l+1 Ylm (θ, φ) (17.10)
k lm
Equation (17.9) is very intuitive. It says that the scattering process consists
ikr
of an incident plane wave eikz and an outgoing scattered spherical wave e r .
The advantage of writing it in terms of the scattering amplitude is because
it is directly related to the angular differential cross section [Griffiths, 1995]
dσ
= |f (θ, φ)|2 (17.11)
dΩ
Thus our formula for the angular distribution is
dσ 1 X X l−l0 ∗ ∗
= 2 i clm cl0 m0 Ylm Yl0 m0 (17.12)
dΩ k lm l0 m0
We integrate this to get the total cross section

Z
1 X X l−l0 ∗ ∗
σ= 2 i clm cl m
0 0 Ylm Yl0 m0 dΩ (17.13)
k lm l0 m0
but Z
∗
Ylm Yl0 m0 dΩ = δll0 δmm0 (17.14)
giving
1 X
σ= |clm |2 (17.15)
k 2 lm
But all these equations are overkill! I don’t know of any potential which is
not azimuthally symmetric. If azimuthal symmetry holds then our answers
won’t depend on φ or m. We could leave our equations as they stand and
simply grind out our answers and always discover independence of φ and m
in our answers. But it’s better to simply things and build in the symmetry
from the start. Azimuthal symmetry is simply achieved by setting m = 0.
From equation (??) we had
s
2l + 1 (l − |m|)! imφ
Ylm (θ, φ) = ² e Plm (cos θ) (17.16)
4π (l + |m|)!
where Plm (cos θ) are the Associated Legendre functions, which are related to
the Legendre polynomials Pl (cos θ) by
Pl (cos θ) ≡ Plo (cos θ) (17.17)
Thus s
2l + 1
Ylo (θ, φ) = Pl (cos θ) (17.18)
4π
17.2. SCATTERING AMPLITUDE 255
where ² = 1 for m = 0. The wave functions (17.7) and (17.8) become

 s 
X 2l + 1 (1)
ψ(r, θ) = A eikz + cl hl (kr)Pl (cos θ) (17.19)
l
4π
and
 s 
X 2l + 1 eikr
ψ(r∞ , θ) = A eikz + cl (−i)l+1 Pl (cos θ) (17.20)
l
4π kr
and the scattering amplitude (17.10) is

s
1X 2l + 1
f (θ) = (−i)l+1 cl Pl (cos θ)
k l 4π
(17.21)
which is called the partial wave expansion of the scattering amplitude. Ob-
viously the angular distribution is now written as
dσ
= |f (θ)|2
dΩ
(17.22)
and
1 X 2
σ= |cl |
k2 l
(17.23)
17.2.1 Calculation of cl
(This section closely follows [Griffiths, 1995])
How then do we calculate cl ? Answer: by matching boundary conditions
(as usual). We match the wave function in the exterior, asymptotic region
to the wave function in the interior region near the potential.
It is often useful to write the incident plane wave in spherical coordinates,

just as we did for the outgoing spherical wave. We use Rayleigh’s formula
∞
X
eikz = il (2l + 1)jl (kr)Pl (cos θ) (17.24)
l=0
and put it into (17.3)

 s 
∞
X
il (2l + 1)jl (kr) +
2l + 1 (1)
ψ(r, θ) = A cl hl (kr) Pl (cos θ) (17.25)
l=0
4π
Example 17.2 Calculate the total cross section for scattering

from a hard sphere. (This is the example in [Griffiths, 1995, pg.
361]).
Solution A hard sphere is defined as
U (r) = ∞ for r ≤ a (interior region I)

= 0 for r > a (exterior region II)
The wave function in the interior region is
ψI (r, θ) = 0
because the incident beam cannot penetrate. The exterior wave

function is given (always) by (17.25) as
 s 
X 2l + 1 (1)
ψII (r, θ) = A il (2l + 1)jl (kr) + cl hl (kr) Pl (cos θ)
l
4π
We match these wave functions at the boundary
ψI (a, θ) = ψII (a, θ)
to give
 s 
X 2l + 1 (1)
il (2l + 1)jl (ka) + cl hl (ka) Pl (cos θ) = 0
l
4π
17.3. PHASE SHIFT 257
from which we obtain

q jl (ka)
cl = −il 4π(2l + 1) (1)
hl (ka)
(do Problem 17.2) giving

¯ ¯
4π X ¯ j (ka) ¯2
¯ l ¯
σ= 2 (2l + 1) ¯ (1) ¯
k l ¯ h (ka) ¯
l
which is our final answer. In the low energy limit, ka ¿ 1, this

reduces to [Griffiths, 1995, pg. 362]
σ ≈ 4πa2
17.3 Phase Shift

Rather than calculating the coefficients cl , the theory of scattering is often
formulated in terms of a more physically intuitive quantity called the phase
shift δl . The idea is that the scattering potential causes a change in phase of
the incident wave. Remarkably, the scattering amplitude and cross section
can be expressed entirely in terms of the phase shift.
Some good references for this section are
“Quantum Mechanics” by D. B. Beard and G. B. Beard

(QC174.1.B37) (1970)
“Quantum Mechanics” by G. L. Trigg (QC174.1.T7) (1964)
“Quantum Mechanics” by L. I. Schiff (QC174.1.S34) (1955)
“Principles of Quantum Mechanics” by H. C. Ohanion (1990)
Recall the solution to the Schrödinger equation for constant U (r) = U0

when l = 0 is written in several ways
u(r) = A cos kr + B sin kr

= A sin(kr + δ)
= A[cosδ sin kr + sin δ cos kr]
= A eikr + B e−ikr (17.26)
where in the third line we used sin(A + B) = sin A cos B + cos A sin B. Here
δ is the phase shift and simply serves as an arbitrary constant instead of B.
Now for arbitrary l we wrote equation (8.70) as

(1) (2)
= Cr hl (kr) + Dr hl (kr) (17.27)
Now jl is a “generalized” sine and nl is a “generalized” cosine, so in analogy

with (17.26) we write
ul (r) ≡ Ar [cos δl jl (kr) − sin δl nl (kr)] (17.28)
where we pute a minus sign in front of sin δl because nl (kr) → − cos kr.
[Schiff, 1955, pg. 86 (3rd ed.); Arfken, 1985, pg. 627 (3rd ed.)]. Using the
asymptotic expressions (17.5) and (17.6) we get
· µ ¶ µ ¶¸
Ar lπ lπ
ul (r → ∞) → cos δl sin kr − + sin δl cos kr −
kr 2 2
µ ¶
A lπ
= sin kr − + δl (17.29)
k 2
The relation between the scattering amplitude and phase shift is
∞
1 P
f (θ) = 2ik (2l + 1)(e2iδl − 1)Pl (cos θ)
l=0
∞
1 P
= k (2l + 1)eiδl sin δl Pl (cos θ)
l=0
(17.30)
(do Problem 17.3) and the cross section is easily calculated as
4π X
σ= (2l + 1) sin2 δl
k2 l
(17.31)
(do Problem 17.4) From this result one can prove the famous Optical The-
orem
4π
σ= Im f (0)
k
17.4. INTEGRAL SCATTERING THEORY 259
(17.32)
where Im f (0) denotes the imaginary part of the forward scattering ampli-
tude f (θ = 0). (do Problem 17.5)
(The example of hard sphere scattering is worked out, using phase shift,
in [“An Introduction to Quantum Physics” by G. Sposito, 1970, QC174.1.S68])
(do Problem 17.6)
17.4 Integral Scattering Theory

17.4.1 Lippman-Schwinger Equation
Defining
h̄2 2
H0 ≡ − ∇ (17.33)
2m
the abstract Schrödinger equation is
(E − H0 ) | ψi = U | ψi (17.34)
or
2m
(∇2 + k 2 )ψ = Uψ (17.35)
h̄2
with √
2mE
k≡
h̄
The Schrödinger equation can be solved with Green function techniques.
Writing
(∇2 + k 2 )G(r) ≡ δ 3 (r) (17.36)
the general solution of the Schrödinger equation is
Z
2m
ψ(r) = φ(r) + 2 d3 r0 G(r − r0 )U (r0 )ψ(r0 ) (17.37)
h̄
where G(r − r0 ) is called a Green’s function, and φ(r) is the solution to the
free Schrödinger equation (with U = 0).
In abstract notation this may be written
|ψi = |φi + U G | ψi (17.38)
or just
ψ = φ + U Gψ
(17.39)
Equations (17.37) or (17.39) are just the integral form of the Schrödinger
equation and is often called the Lippman-Schwinger equation. It may be
iterated as
ψ = φ + U Gφ + U GU Gφ + U GU GU Gφ + · · · (17.40)
which is called the Born series. The first Born approximation is just
ψ ≈ φ + U Gφ (17.41)
Equation (17.40) is reminiscent of the series representing Feynman diagrams
and G is often called the propagator. (Read [Griffiths, 1995, pg. 372])
Example 17.4 Show that (17.37) satisfies the Schrödinger equa-

tion.
Solution φ(r) satisfies the free Schrödinger equation,

(∇2 + k 2 )φ = 0
⇒ (∇2 + k 2 )φ(r) = (∇2 + k 2 )φ(r)

Z
2m
+ 2 d3 r0 [(∇2 + k 2 )G(r − r0 )]U (r0 )ψ(r0 )
h̄ Z
2m
= O+ 2 d3 r0 δ 3 (r − r0 )U (r0 )ψ(r0 )
h̄
2m
= U (r)ψ(r)
h̄2
We solve (17.36) for G, plug into (17.37), and we have a general (itera-
tive!) solution for the Schrödinger equation. Problem 17.7 verifies that
eikr
G(r) = − (17.42)
4πr
(do Problem 17.7). Thus
Z ik|r−r0 |
m 3 0e
ψ(r) = φ(r) − d r U (r0 )ψ(r0 )
2πh̄2 |r − r0 |
(17.43)
17.4.2 Scattering Amplitude

The Lippman-Schwinger equation (17.43) is a general equation. Let’s now
apply it to scattering. Obviously
φ(r) = Aeikz (17.44)
represents the incident beam of particles and the second term in (17.43) must
ikr
be f (θ) e r , allowing us to extract the scattering amplitude and calculate the
cross section.
The coordinate system is shown in Fig. 17.2. The coordinate r0 gives the
location of the potential U (r0 ) or scatttering region. The coordinate r is the
location of the detector, and r − r0 is the displacement between the “target”
and detector. In a typical scattering experiment we have r À r0 . To see this
put the origin inside the scattering region. Then r0 just gives the region of
the scattering center, and we put our detector far away so that r À r0 . In
that case
q p
0
|r − r | = |r − r0 |2 = r2 − 2r · r0 + r02
s s
µ ¶2
2r · r0 r0 2r · r0
= r 1− + ≈r 1−
r2 r r2
≈ r − êr · r0 (17.45)
Choose
k ≡ kêr (17.46)
giving
|r − r0 | ≈ r − k · r0 (17.47)
Thus [Griffiths, 1994, pg. 367]
0
eik|r−r | eikr −ik·r0
≈ e (17.48)
|r − r0 | r
giving
Z
m eikr 0
ψ(r) = Aeikz − d3 r0 e−ik·r U (r0 )ψ(r0 ) (17.49)
2πh̄2 r
and thus Z
m 0
f (θ, φ) = − d3 r0 e−ik·r U (r0 )ψ(r0 ) (17.50)
2πh̄2 A
which is an exact expression for the scattering amplitude.
17.4.3 Born Approximation

The (first) Born approximation simply replaces ψ with φ to give
Z
m 0 0
f (θ, φ) ≈ − d3 r0 ei(k −k)·r U (r0 ) (17.51)
2πh̄2
where k points in the incident direction and k0 in the scattered direction.
See Figure 11.10 of [Griffiths, 1995, pg. 368]. The momentum transfer is
defined as
q ≡ k0 − k (17.52)
At low energy q ≈ 0 and
Z
m
f (θ, φ) ≈ − d3 r U (r) (17.53)
2πh̄2
Now assume a spherically symmetric potential U (r) ≡ U (r), then
(k0 − k) · r0 = q · r0 ≡ qr0 cos θ0 (17.54)
giving (17.51) as
Z
m 0 cos θ0
f (θ) ≈ − 2π r02 dr0 sin θ0 dθ0 eiqr U (r0 ) (17.55)
2πh̄2
Using [Griffiths, 1995, equation 11.49, pg. 364]
Z π 2 sin sr
sin θ dθ eisr cos θ = (17.56)
0 sr
gives Z
2m ∞
f (θ) ≈ − r dr sin(qr)U (r) (17.57)
h̄2 q 0
and
θ
q = 2k sin (17.58)
2
Example 17.4 Calculate the scattering amplitude and differen-

tial cross section for scattering from the Yukawa potential
e−µr
U (r) = C (17.59)
r
Solution Z ∞
2m
f (θ) ≈ − C dr sin(qr) e−µr
h̄2 q 0
Z ∞ q
and dr sin(qr) e−µr =
0 µ2 + q2
giving
2mC 1
f (θ) = − 2 µ2 + q 2 (17.60)
h̄
and
dσ 4m2 C 2 1
= 4 (17.61)
dΩ h̄ (µ + q 2 )2
2
(do Problem 17.8)
Example 17.5 Derive the Rutherford scattering cross section

from quantum mechanics.
Solution The Coulomb potential energy is

1 q1 q2
U (r) = (17.62)
4π²0 r
1
Thus in the previous example C = 4π²0 q1 q2 and µ = 0 giving
µ ¶
2m 1 1
f (θ) ≈ − 2 q1 q2
h̄ q 4π²0 q
mq1 q2 1
=
2π²0 h̄2 q 2
√
2mE
Using q = 2k sin θ/2 = 2 h̄ sin θ/2 gives
q1 q 2 1
f (θ) ≈ (17.63)
16π²0 E sin2 θ/2
or
µ ¶2
dσ q1 q2 1
=
dΩ 16π²0 E 2 sin4 θ/2
(17.64)
which is the famous Rutherford scattering formula with the char-
acteristic sin41θ/2 dependence. The same result occurs in classical
mechanics. All students should know how to derive this result
classically.
17.5 Nuclear Reactions

Chapter 18
SOLIDS AND QUANTUM

STATISTICS
18.1 Solids
18.2 Quantum Statistics
265
266 CHAPTER 18. SOLIDS AND QUANTUM STATISTICS
Chapter 19
SUPERCONDUCTIVITY
267
268 CHAPTER 19. SUPERCONDUCTIVITY
Chapter 20
ELEMENTARY
PARTICLES
269
270 CHAPTER 20. ELEMENTARY PARTICLES
Chapter 21
chapter 1 problems
21.1 Problems
1.1 Suppose 10 students go out and measure the length of a fence and the
following values (in meters) are obtained: 3.6, 3.7, 3.5, 3.7, 3.6, 3.7, 3.4, 3.5,
3.7, 3.3. A) Pick a random student. What is the probability that she made
a measurement of 3.6 m? B) Calculate the expectation value (i.e. average
or mean) using each formula of (1.2), (1.5), (1.8).
1.2 Using the example of problem 1.1, calculate the variance using both
equations (1.15) and (1.16).

Hints: Some useful
q integrals are [Spiegel, 1968, pg.98]
R ∞ −ax2
0 e
1
dx = 2 πa
R∞
xm e−ax dx =
2 Γ[(m+1)/2]
0 2a(m+1)/2
√
Also note Γ(3/2) = 2π
Properties of the Γ function are listed in [Spiegel, 1968, pg.101]
1.4 Calculate dhxi

dt and show that it is the same as the velocity expectation
value hvi calculated in Example 1.6.1.
271
272 CHAPTER 21. CHAPTER 1 PROBLEMS
21.2 Answers
1.1 A) 0.2 B) 3.57
1.2 0.0181
q
1.3 Griffiths Problem 1.6. A) A = λ
π B) hxi = a, hx2 i = a2 + 1
2λ ,
σ = √12λ
21.3. SOLUTIONS 273
21.3 Solutions
1.1
Let N (x) be the number of times a measurement of x is made.
Thus
N (3.7) = 4
N (3.6) = 2
N (3.5) = 2
N (3.4) = 1
N (3.3) = 1
total number of measurements N = 10
2
A) Probability of 3.6 is 10 = 15 = 0.2
B)
1 X
x = x
N
1
= (3.7 + 3.7 + 3.7 + 3.7 + 3.6 + 3.6
10
+ 3.5 + 3.5 + 3.4 + 3.3)
= 3.57
1 X
hxi ≡ x = xN (x)
N x
1
= [(3.7 × 4) + (3.6 × 2) + (3.5 × 2)
10
+ (3.4 × 1) + (3.3 × 1)]
= 3
finally
X
hxi = x = xP (x)
x
µ ¶ µ ¶ µ ¶
4 2 2
= 3.7 × + 3.6 × + 3.5 ×
10 10 10
µ ¶ µ ¶
1 1
+ 3.4 × + 3.3 ×
10 10
= 3
1.2
We found the average hji = 3.57. (I will round it off later.) The
squared distances are
(∆3.7)2 = (3.7 − 3.57)2 = 0.0169, (∆3.6)2 = 0.0009,

(∆3.5)2 = 0.0049, (∆3.4)2 = 0.0289, (∆3.3)2 = 0.0729
The average squared distance, using (1.15) is

µ ¶ µ ¶ µ ¶
4 22
σ 2
= 0.0169 × + 0.009 ×
+ 0.0049 ×
10 10
10
µ ¶ µ ¶
1 1
+ 0.0289 × + 0.0729 ×
10 10
= 0.0181
Using the second equation (1.16) we have
hji2 = 3.572 = 12.7449 and

X
hj i = 2 2
j P (j)
µ ¶ µ ¶ µ ¶
4 2 2
= 3.72 × + 3.62 × + 3.52 ×
10 10 10
µ ¶ µ ¶
1 1
+ 3.42 × + 3.32 ×
10 10
µ ¶ µ ¶ µ ¶
4 2 2
= 13.69 × + 12.96 × + 12.25 ×
10 10 10
µ ¶ µ ¶
1 1
+ 11.56 × + 10.89 ×
10 10
= 12.763
Thus σ 2 = hj 2 i − hji2 = 12.763 − 12.7449 = 0.0181 in agreement

with above.
21.3. SOLUTIONS 275
1.3 Griffith’s Problem 1.6
A)
Z ∞
ρ(x) = Ae−λ(x−a)
2
ρ(x)dx = 1
−∞
Z ∞
du
e−λ(x−a) dx
2
= A let u = x − a, = 1, du = dx
−∞ dx
Z ∞
e−λu du e−λu is an even function
2 2
= A
−∞
Z∞
e−λu du
2
= 2A
0
r
1 π
= 2A integral found Pg. 98 of [Spiegel 1968]
2 λ
r
π
= A
λ
s
λ
therefore A =
π
B)
Z ∞ Z ∞
xe−λ(x−a) dx
2
hxi = xρ(x)dx = A
−∞ −∞
Z ∞
−λu2
= A (u + a)e du
−∞
 
Z Z ∞ 
 ∞ 
 −λu2 −λu2 
= A ue du + a e du 
 −∞ | {z } −∞ 
 odd function | {z }
√π
= λ
from above
· r ¸
π
= A 0+a =a
λ
Z ∞ Z ∞
x2 e−λ(x−a) dx
2
hx i =
2 2
x ρ(x)dx = A
−∞ −∞
Z ∞
−λu2
= A (u + a)2 e du
−∞
·Z ∞ Z ∞ Z ∞ ¸
2 −λu2 −λu2 2 −λu2
= A u e du + 2a ue du + a e du
−∞ −∞ −∞
≡ A[I + J + K]
now J = 0 because integrand is an odd function,

r
2 π
and K=a
λ
to evaluate I use Pg. 98 of [Spiegel 1968]
Z ∞ Γ[(m + 1)/2]
xm e−ax dx =
2
0 2a(m+1)/2
Z ∞
√ √
Γ(3/2) π/2 π
x2 e−ax dx =
2
therefore 3/2
= 3/2
= 3/2
0 2a 2a 4a
(See Pg. 101 of [Spiegel 1968])
Now the integrand of I is an even function
Z ∞ Z ∞
√ √
2 −λu2 2 −λu2 π π
therefore I = u e du = 2 u e du = 2 =
−∞ 0 4λ3/2 2λ3/2
" √ r #
π π
Thus hx2 i = A + O + a2
2λ3/2 λ
s r r ¸
·
λ 1 π π 1
= + a2 = + a2
π 2λ λ λ 2λ
21.3. SOLUTIONS 277
C)
Thus
it makes sense
that hxi = a!
1.4 (See Griffiths Pg. 15)
Z
dhxi d
= Ψ∗ xΨdx
dt dt
Z
∂
= (Ψ∗ xΨ)dx
∂t
Z µ ¶
∂Ψ∗ ∗ ∂Ψ
= xΨ + Ψ x dx
∂t ∂t
and according to the Schrödinger equation
" #
∂Ψ 1 h̄2 ∂ 2 Ψ ih̄ ∂ 2 Ψ i
= − 2
+ U Ψ = 2
− UΨ
∂t ih̄ 2m ∂x 2m ∂x h̄
∂Ψ∗ ih̄ ∂ 2 Ψ∗ i
= − 2
+ U Ψ∗ (assuming U = U∗ )
∂t 2m ∂x h̄
Z Ã !
dhxi ih̄ ∂ Ψ∗
2 2
∗ ∂ Ψ
therefore = − xΨ + Ψ x 2 dx
dt 2m ∂x2 ∂x
Z µ ¶
ih̄ ∂ ∂Ψ∗ ∂Ψ
= − x Ψ − Ψ∗ dx
2m ∂x ∂x ∂x
(· µ ¶¸∞ Z µ ¶ )
ih̄ ∂Ψ∗ ∗ ∂Ψ ∂Ψ∗ ∗ ∂Ψ
= − x Ψ−Ψ − Ψ−Ψ dx
2m ∂x ∂x −∞ ∂x ∂x
from integration by parts
but Ψ(∞) = 0 therefore boundary term → 0

Z µ ¶
dhxi ih̄ ∂Ψ ∂Ψ∗
= − Ψ∗ − Ψ dx
dt 2m ∂x ∂x
integrate by parts again on the first term
Z
ih̄ ∂Ψ
= − Ψ∗ dx
m ∂x
hpi
≡
m
= hvi in Example 1.6.1
therefore must have p̂ = −ih̄ ∂x
∂ ∂
(and not p̂ = +ih̄ ∂x ).
1.5 ( Griffiths 1.12)
Z ∞ ∂Ψ
hpi = −ih̄ Ψ∗ dx Ψ ≡ Ψ(x, t)
−∞ ∂x
·Z
∞ ∂Ψ∗ ∂Ψ ¸
d ∂ ∂Ψ
hpi = −ih̄ dx + Ψ∗ dx
dt −∞ ∂t ∂x ∂x ∂t
use the Schrödinger equation
h̄2 ∂ 2 Ψ ∂
− + U (x)Ψ = ih̄ Ψ
2m ∂x2 ∂t
h̄2 ∂ 2 Ψ∗ ∂
− + U (x)Ψ∗ = −ih̄ Ψ∗
2m ∂x2 ∂t
assuming U = U ∗ (real)
Z Ã !
dhpi ∞ h̄2 ∂ 2 Ψ∗ ∂Ψ
⇒ = − + U Ψ∗ dx
dt −∞ 2m ∂x2 ∂x
Z Ã !
∂∞ h̄2 ∂ 2 Ψ
∗
− Ψ − + U Ψ dx
−∞ ∂x 2m ∂x2
"Z Z #
h̄2 ∂ 2 Ψ∗ ∂Ψ
∞ ∞ 3
∗∂ Ψ
= − 2
dx − Ψ dx
2m −∞ ∂x ∂x −∞ ∂x3
Z ∞ µ ¶
∗ ∂Ψ ∗ ∂U ∗ ∂Ψ
+ UΨ −Ψ Ψ−Ψ U dx
−∞ ∂x ∂x ∂x
Z ∞
h̄2 ∂U
= − (I1 − I2 ) − Ψ∗ Ψ dx
2m −∞ ∂x
h̄2 ∂U
= − (I1 − I2 ) − h i
2m ∂x
21.3. SOLUTIONS 279
Z Z
∞ ∂ 2 Ψ∗ ∂Ψ ∂3Ψ ∞
where I1 ≡ dx I2 ≡
dx Ψ∗
−∞ ∂x2 ∂x −∞ ∂x2
dhpi ∂U
... need to show I1 = I2 then will have = −h i
dt ∂x
Z b Z b
recall integration by parts formula f dg = [f g]ba − g df
a a
Z Z Ã !
∞ 3Ψ ∞ ∂2Ψ
∗∂ ∂ ∗
I2 ≡ Ψ 3
dx = Ψ dx
−∞ ∂x −∞ ∂x ∂x2
Z Ã !
∞ ∂2Ψ
∗
= Ψ ∂
−∞ ∂x2
" # Z
2Ψ ∞ ∞ ∂2Ψ ∗
∗∂
= Ψ − ∂Ψ using integration by parts
∂x2 −∞ −∞ ∂x2
| {z }
= 0 because Ψ∗ (∞) = Ψ∗ (−∞) = 0
Z ∞ 2
∂ Ψ ∂Ψ∗
= − 2
dx
−∞ ∂x ∂x
Z ∞ 2 ∗ Z ∞ µ ¶
∂ Ψ ∂Ψ ∂Ψ ∂ ∂Ψ∗
I1 ≡ 2
dx = dx
−∞ ∂x ∂x −∞ ∂x ∂x ∂x
Z ∞ µ ¶
∂Ψ ∂Ψ∗
= ∂
−∞ ∂x ∂x
· ¸ Z ∞ µ ¶
∂Ψ ∂Ψ∗ ∞ ∂Ψ∗ ∂Ψ
= − ∂
∂x ∂x −∞ −∞ ∂x ∂x
| {z }
∂Ψ ∂Ψ
= 0 because must also have (∞) = (−∞) = 0
∂x ∂x
∂Ψ
if slope 6= 0 when Ψ(∞) = 0 would have
∂x
Z µ ¶
∂Ψ∗ ∂ ∂Ψ
∞
= − dx
−∞ ∂x ∂x ∂x
Z ∞
∂Ψ∗ ∂ 2 Ψ
= − 2
dx
−∞ ∂x ∂x
... I1 = I2 QED
Chapter 22
chapter 2 problems
22.1 Problems
2.1 Griffiths, Problem 2.19.
2.2 Refer to Example 2.1.1. Determine the constants for the other 3 forms
of the solution using the boundary condition (i.e. determine B, C, F , δ, G,
γ from boundary conditions). Show that all solutions give x(t) = A sin ωt.
2.3 Check that the solution given in Example 2.1.2 really does satisfy the
A
differential equation. That is substitute x(t) = E cos(ωt + δ) + ω2 −α 2 cos αt
and check that ẍ + ω 2 x = A cos αt is satisfied.
2.4 Solve equation (2.11).
2.5 Prove that cn = hψn | f i (Equation (2.36)).
281
22.2 Answers
2.1
C = A + B, D = i(A − B) for C cos kx + D sin kx
A = F2 eiα , B = F2 e−iα for F cos(kx + α)
G −iβ
G iβ
A = 2i e , B = − 2i e for G sin(kx + β)
2.2
B = 2iA
C = − 2i
A
δ = π2 F = −A
γ=π G=A
2.3 f (t) = Ae− h̄ Et (equation (2.12)

i
22.3. SOLUTIONS 283
22.3 Solutions
2.1 Griffiths Problem 2.19
eiθ = cos θ + i sin θ
Aeikx + Be−ikx = A(cos kx + i sin kx) + B(cos kx − i sin kx)

= (A + B) cos kx + i(A − B) sin kx
≡ C cos kx + D sin kx ⇒ C = A + B D = i(A − B)
Note if D is real then D∗ = D i.e.

−i(A∗ − B ∗ ) = i(A − B)
−A∗ + B ∗ = A − B
satisfied if A = B ∗ (⇒ A∗ = B)
Thus even though D looks complex, it actually can be real.
ei(kx+α) + e−i(kx+α) eiθ + e−iθ

F cos(kx + α) = F using cos θ =
µ ¶ 2 µ ¶ 2
F iα ikx F −iα −ikx
= e e + e e
2 2
F F
≡ Aeikx + Be−ikx ⇒ A = eiα B = e−iα
2 2
ei(kx+β) − e−i(kx+β) eiθ − e−iθ

G sin(kx + β) = G using sin θ =
µ ¶ 2i µ ¶ 2i
G iβ ikx G iβ −ikx
= e e + − e e
2i 2i
G −G −iβ
≡ Aeikx + Be−ikx ⇒ A = eiβ B = e
2i 2i
2.2 Boundary conditions x(0) = 0, x(T /4) = A
i) x(t) = Beiωt + Ce−iωt

x(0) = 0 = B + C therefore C = −B
therefore x(t) = B(eiωt − e−iωt )

= 2iB sin ωt
2π T π
x(T /4) = A = 2iB sin = 2iB sin = 2iB
T 4 2
A A
therefore B = C=−
2i 2i
A iωt
therefore x(t) = (e − e−iωt ) = A sin ωt
2i
ii) x(t) = F cos(ωt + δ)
x(0) = 0 = F cos δ
Therefore either F = 0 or cos δ = 0 ⇒ δ = π
2
(F = 0 means x = 0 always and we don’t have anything. Thus
we take the second solution δ = π2 )
µ ¶
π
therefore x(t) = F cos ωt + = −F sin ωt
2
2π T π
x(T /4) = A = −F sin = −F sin = −F
T 4 2
π
therefore δ = F = −A
2 µ ¶
π
therefore x(t) = −A cos ωt + = −A(− sin ωt) = A sin ωt
2
iii)
x(t) = G sin(ωt + γ)
x(0) = 0 = G sin γ ⇒ γ = π
therefore x(t) = G sin(ωt + π) = G sin ωt
π
x(T /4) = A = G sin = G
2
therefore γ=π G=A
therefore x(t) = A sin(ωt + π) = A sin ωt
22.3. SOLUTIONS 285
2.3
A
x(t) = E cos(ωt + δ) + cos αt
− α2
ω2
Aα
ẋ = −Eω sin(ωt + δ) − 2 sin αt
ω − α2
Aα2
ẍ = −Eω 2 cos(ωt + δ) − 2 cos αt
ω − α2
left hand side:
Aα2
ẍ + ω 2 x = −Eω 2 cos(ωt + δ) − cos αt
ω 2 − α2
Aω 2
+ Eω 2 cos(ωt + δ) + 2 cos αt
ω − α2
A
= (−α2 + ω 2 ) 2 cos αt
ω − α2
= A cos αt
= right hand side
QED
2.4
1 df i
= − E
f dt h̄
Z Z
1 df i
dt = − E dt + C 0 C 0 = constant
f dt h̄
i
ln f = − Et + C 0
h̄
0 0
f (t) = e− h̄ Et+C = eC e− h̄ Et ≡ Ce− h̄ Et
i i i
2.5
Z
hψn | f i ≡ ψn∗ (x)f (x)dx
Z X
= ψn∗ (x) cm ψm (x)dx
m
X Z
= cm ψn∗ (x)ψm (x)dx
m
X
= cm δmn from (2.32)
m
= cn
QED
Chapter 23
chapter 3 problems
23.1 Problems
3.1 Consider the infinite 1-dimensional box. If the particle is an electron,

how wide would the box have to be to approximate classical behavior?
(Hint: Classical behavior will pertain if the energy levels are “closely
spaced” or if E1 is close to zero. The latter condition is easier to quantify,
but close to zero compared to what? The only “natural” energy side is the
rest mass of the electron. Thus let’s just say that classical behavior pertains
2
if E1 = m100
ec
.)
3.2 For the infinite 1-dimensional box, show that the same energy levels
and wave functions as obtained in (3.14) and (3.19) also arise if the other
solution y(x) = Ae(α+iβ)x + Be(α−iβ)x is used from Theorem 1.
287
23.2 Answers
3.1 a ≈ 10, 000 fm = 10−11 m (approximately)

23.3. SOLUTIONS 289
23.3 Solutions
3.1
π 2 h̄2 me c2
E1 = =
2ma2 100
Now rest mass of electron is me c2 = 0.511 MeV and h̄c = 197 MeV fm where
a fermi is fm ≡ 10−15 m. (1 fm ≈ size of proton)
π 2 (h̄c)2 me c2
=
2me c2 a2 100
Therefore
π 2 (h̄c)2
a2 = 100
2(me c2 )2
n2 × 1972 MeV2 fm2
= 100
2 × 0.5112 MeV2
= 73, 343, 292 fm2
a = 8, 564 fm
a ≈ 10, 000 fm = 10−11 m (approximately)
3.2 Boundary conditions ψ(x = 0) = ψ(x = a) = 0. The solution to the

auxilliary equation is given in the text (3.4) as r = ±ik. Thus α = 0 and
β = k where r ≡ α ± iβ. Thus r1 = +ik and r2 = −ik which are distinct
roots. The solution is ψ(x) = Aer1 x + Ber2 x . The other solution from
Theorem 1 is
ψ(x) = Ae(α+iβ) + Be(α−iβ)x

= Aeikx + Be−ikx
ψ(x = 0) = 0 = A + B therefore B = −A
therefore ψ(x) = A(e ikx
− e−ikx ) = 2iA sin kx
ψ(x = a) = 0 = 2iA sin ka
therefore ka = 0, ±π, ±2π
and using same reasoning as in text we get

nπ
k = n = 1, 2, 3 · · ·
a
h̄2 k 2 π 2 h̄2
giving En2 = = n2
2m 2ma2
nπh̄
or En = √
2ma
The wave function normalization follows (3.17) and (3.18). From the above
we have
ψ(x) = A(eikx − e−ikx ) (see Solution to Problem 2.2)

nπ
= 2iA sin kx = 2iA sin x
a
Now Z a nπ
−4A 2
sin2 x dx = 1
0 a
The integral is done in the text (see equation (3.19)) giving −4A2 a2 = 1.
q
Thus A = i 12 2
a
Thus
nπ
ψ(x) = 2iA sin x
r a
1 2 nπ
= 2i i sin x
r2 a a
2 nπ
= − sin x
a a
which is the same as (3.19) except for an irrelevant minus sign.
Chapter 24
chapter 4 problems
24.1 Problems
4.1 Show that the expectation value of the Hamiltonian or Energy operator
is real (i.e. show that hÊi is real where Ê = ih̄ ∂t
∂
).
4.2 Find the eigenfunctions of the momentum operator assuming that P̂ φ =

pφ where p is the momentum.
291
24.2 Answers
A) r
30
A=
a5
B)
a
hxi =
2
hpi = 0
5h̄2
hHi =
ma2
ci = 0.99928
c2 = 0
c3 = 0.03701
24.3. SOLUTIONS 293
24.3 Solutions
4.1 In Section 2.3.3 we saw that the expectation value of the Hamiltonian
was just the total energy, i.e. hHi = E.
h̄2 d2
Instead of using Ĥ = − 2m dx2
∂
+ U let’s instead note that ĤΨ = ih̄ ∂t Ψ
∂
and use Ĥ = ih̄ ∂t . Thus
Z ∞
∂
hĤi = ih̄ Ψ dxΨ∗
−∞ ∂t
Z ∞
∂
hĤi∗ = −ih̄ Ψ Ψ∗ dx
−∞ ∂t
From the Schrödinger equation
h̄2 ∂ 2 Ψ ∂Ψ
− 2
+ U Ψ = ih̄
2m ∂x ∂t
we have Z Z
h̄2 ∞ ∂2Ψ ∞
hĤi = − Ψ∗ dx + Ψ∗ U Ψ dx
2m −∞ ∂x2 −∞
and
h̄2 ∂ 2 Ψ∗ ∗ ∂Ψ∗
− + U Ψ = −ih̄
2m ∂x2 ∂t
assuming
U = U∗
we have
Z Z
h̄2 ∞ ∂ 2 Ψ∗ ∞
hĤi∗ = − Ψ dx + ΨU Ψ∗ dx
2m −∞ ∂x2 −∞
(Z Z ∞ )
h̄ 2 ∞ ∂2Ψ ∂ 2 Ψ∗
⇒ hĤi − hĤi∗ = − Ψ∗ 2 dx − Ψ dx
2m −∞ ∂x −∞ ∂x2
The second integral is evaluated using integration by parts. Define

Z
∂ 2 Ψ∗
∞
I ≡ Ψdx
−∞ ∂x2
Z ∞ µ ¶
∂ ∂Ψ∗
= Ψ dx
−∞ ∂x ∂x
Z ∞ µ ¶
∂Ψ∗
= Ψd
−∞ ∂x
· ¸∞ Z
∂Ψ∗ ∞ ∂Ψ∗
= Ψ − dΨ
∂x −∞ −∞ ∂x
Z
∂Ψ∗ ∂Ψ
∞
= 0− dx
−∞ ∂x ∂x
Z ∞ Z ∞
∂Ψ ∂Ψ∗ ∂Ψ ∗
= − dx = − dΨ
−∞ ∂x ∂x −∞ ∂x
· ¸ Z ∞ µ ¶
∂Ψ ∗ ∞ ∂Ψ
= − Ψ + Ψ∗ d
∂x −∞ −∞ ∂x
Z ∞ µ ¶
∂ ∂Ψ
= 0+ Ψ∗ dx
−∞ ∂x ∂x
Z ∞
d2 Ψ
= Ψ∗ 2 dx
−∞ dx
Thus
hĤi − hĤi∗ = 0
hĤi = hĤi∗
Thus the expectation value of the Hamiltonian operator is real.
4.2
P̂ φ = pφ
∂
P̂ ≡ −ih̄
∂x
∂φ
−ih̄ = pφ
Z
∂x Z
1 ∂φ p
dx = dx
φ ∂x −ih̄
i
ln φ = px
h̄
i
φ = φ0 e h̄ px
which are the momentum eigenfunctions.

Bibliography
[1] J. Gleick, Chaos (Penguin Books, New York, 1987).

[2] P. Tipler, Elementary Modern Physics (Worth Publishers, New York,
1992).
[3] A. Beiser, Concepts of Modern Physics (McGraw-Hill, New York, 1987).
[4] R. Serway, Physics for Scientists and Engineers with Modern Physics,
3rd ed. (Saunders College Publishing, Philadelphia, 1990).
[5] S. Gasiosowicz, Quantum Physics, 2nd ed. (Wiley, New York, 1996).
[6] T.L. Chow, Classical Mechanics (Wiley, New York, 1995).
[7] G.R. Fowles and G.L. Cassiday, Analytical Mechanics, 5th ed. (Saunders
College Publishing, Philadelphia, 1986).
[8] J.B. Marion, Classical Dynamics of Particles and Systems, 3rd ed. (Har-
court Brace Jovanovich College Publishers, New York, 1988).
[9] H. Goldstein, Classical Mechanics, 2nd ed. (Addison-Wesley, Reading,
Massachusetts, 1980).
[10] R.P. Feynman, R.B. Leighton and M. Sands, The Feynman Lectures in
Physics, Volume I (Addison-Wesley, Reading, Massachusetts, 1964).
[11] D.J. Griffiths, Introduction to Quantum Mechanics (Prentice-Hall, En-
glewood Cliffs, New Jersey, 1995).
[12] R.L. Liboff, Introductory Quantum Mechanics (Addison-Wesley, Read-
ing, Massachusetts, 1992).
[13] D.J. Griffiths, Introduction to Electrodynamics (Prentice-Hall, Engle-
wood Cliffs, New Jersey, 1989).
295
296 BIBLIOGRAPHY
[14] M.R. Spiegel, Mathematical Handbook (Schaum’s Outline Series)

(McGraw-Hill, New York, 1968).
[15] E.J. Purcell and D. Varberg, Calculus and Analytic Geometry, 5th ed.
(Prentice-Hall, Englewood Cliffs, New Jersey, 1987).
[16] G.B. Thomas and R.L. Finney, Calculus and Analytic Geometry, 7th
ed. (Addison-Wesley, Reading, Massachusetts, 1988).
[17] F.W. Byron and R.W. Fuller, Mathematics of Classical and Quantum
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[18] H.C. Ohanian, Principles of Quantum Mechanics (Prentice-Hall, En-

glewood Cliffs, New Jersey, 1990).

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What are the postulates of quantum mechanics?

QUANTUM MECHANICS

Professor John W. Norbury

November 20, 2000

2.3.4 Alternating Parity . . . . . . . . . . . . . . . . . . . . 46

3 INFINITE 1-DIMENSIONAL BOX 53

4 POSTULATES OF QUANTUM MECHANICS 65

5.5 Algebraic Solution for Harmonic Oscillator . . . . . . . . . . 100

6 SCATTERING STATES 113

7 FEW-BODY BOUND STATE PROBLEM 133

II 3-DIMENSIONAL PROBLEMS 141

8 3-DIMENSIONAL SCHRÖDINGER EQUATION 143

9 HYDROGEN-LIKE ATOMS 153

10 ANGULAR MOMENTUM 159

10.4 Spin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165

11 SHELL MODELS 177

12 DIRAC NOTATION 183

13 TIME-INDEPENDENT PERTURBATION THEORY, HY-

13.2.1 Two-fold Degeneracy . . . . . . . . . . . . . . . . . . . 209

14 VARIATIONAL PRINCIPLE, HELIUM ATOM, MOLECULES223

15 WKB APPROXIMATION, NUCLEAR ALPHA DECAY 225

16 TIME-DEPENDENT PERTURBATION THEORY, LASERS235

17 SCATTERING, NUCLEAR REACTIONS 251

17.3 Phase Shift . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257

18 SOLIDS AND QUANTUM STATISTICS 265

20 ELEMENTARY PARTICLES 269

21 chapter 1 problems 271

22 chapter 2 problems 281

23 chapter 3 problems 287

24 chapter 4 problems 291

Quantum Mechanics is such a radical and revolutionary physical theory that

The most dramatic feature of quantum mechanics is that it is a proba-

1.1 Probability Theory

N (15) = 0 N (10) = 3 N (4) = 0

1.1.1 Mean, Average, Expectation Value

Thus the mean or average grade is 8.0.

Student grades are somewhat different to a series of actual measurements

1.1.2 Average of a Function

In general for any function f of j we have

1.1.3 Mean, Median, Mode

1.1.4 Standard Deviation and Uncertainty

(∆j)2 ≡ (j − hji)2 (1.14)

Then it doesn’t matter if a point is larger or smaller than the average.

Example 1.1.1 Using equation (1.15), calculate the variance for

Example 1.1.2 Repeat example 1.1.1 using equation (1.16).

in agreement with example 1.1.1. (do Problem 1.2)

1.1.5 Probability Density

1.2 Postulates of Quantum Mechanics

mechanics, all you ever do is solve F = ma. In a course on electromag-

ρ and j produce different E and B. In general relativity, the fundamental

Postulate 1: To each state of a physical system there cor-

That’s simple enough. In classical mechanics each state of a physical system

Postulate 2: The time development of the wave function is

Postulate 3: (Born hypothesis): |Ψ|2 is the probability

Footnote: Recall that every complex number can be written z = x + iy

|Ψ(x, t)|2 dx = probability of finding a particle between posi-