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Lecture notes PHY3113Quantum mechanics I

Hubert de Guise Department of Physics, Lakehead University, Thunder Bay, Ontario, P7B 5E1

Winter 2010

A typeset using L TEX

by Laura Toppozini, Ben Lavoie, Diane Landry and Hubert de Guise

Contents
1 Introduction: Where we start, where we are going 1.1 Shut up and compute! . . . . . . . . . . . . . . . . . . . . . 1.2 Where did it all go wrong: a naive history of QM . . . . . . . 1.3 How the topics were chosen . . . . . . . . . . . . . . . . . . . 2 Heuristic approach to Schrdingers equation o 2.1 Waves, wave equations and dispersions relations 2.2 Schrdinger equation and dispersion relations . o 2.3 Historical comments . . . . . . . . . . . . . . . 2.4 Statistical interpretation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1 3 4

6 . 6 . 9 . 11 . 12 15

3 Expectation values: another look at some known rules

Quantization and boundary conditions


. . . . . . . . . step . . . . . . . . . . . . . . . .

19
20 20 23 23 24

4 Basic solution to the Schrdinger equation o 4.1 Separation of variables and stationary solutions . 4.2 Two simple examples . . . . . . . . . . . . . . . . 4.2.1 V (x) = constant = V0 . . . . . . . . . . . . 4.2.2 Innite discontinuity: the innite potential

5 General properties of one-dimensional wave functions 26 5.1 The no-degeneracy and oscillatory theorems . . . . . . . . . . 26 5.2 Qualitative features of wave functions. . . . . . . . . . . . . . 29 6 Simple bound state problems in one dimension 6.1 The innite well . . . . . . . . . . . . . . . . . . . 6.2 Detour: Symmetric potentials and their solutions 6.3 The nite well . . . . . . . . . . . . . . . . . . . . 6.3.1 Obtaining a transcendental equation . . . 6.3.2 Example: depth of the deuteron well . . . 6.3.3 Example: The ammonia molecule . . . . . 6.4 The harmonic oscillator . . . . . . . . . . . . . . 6.4.1 Solution . . . . . . . . . . . . . . . . . . . 6.4.2 The harmonic oscillator wavefunctions . . 6.5 (x)-well potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 31 32 34 34 37 40 43 44 48 48

2 7 Multidimensional independent-mode problems 8 Equivalent onedimensional problems: the radial equation 8.1 Separation of variables in three dimensions . . . . . . . . . . . 8.2 The case of hydrogen: V (r) = e2 /4 o r. . . . . . . . . . . . . 8.2.1 Solving the dierential equation . . . . . . . . . . . . . 8.2.2 Hydrogenoid Wave Functions . . . . . . . . . . . . . . 8.3 Isotropic oscillator in three dimensions . . . . . . . . . . . . . 8.4 Constant potentials in three dimensions . . . . . . . . . . . . . 8.4.1 Spherical Bessel functions . . . . . . . . . . . . . . . . 8.4.2 The Innite Spherical Well . . . . . . . . . . . . . . . . 8.4.3 The Finite Spherical Well . . . . . . . . . . . . . . . . 8.5 The Morse potential . . . . . . . . . . . . . . . . . . . . . . . 9 The 9.1 9.2 9.3 9.4 9.5 angular equation Separation of the azimuthal and polar variables. The equation . . . . . . . . . . . . . . . . . . Associated Legendre polynomials . . . . . . . . Spherical harmonics . . . . . . . . . . . . . . . . Angular momentum operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51 54 54 58 58 62 64 68 68 75 76 79 83 83 84 86 87 88

II

Bras and kets


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92
93 93 96 96 97 98 99 99 102 102 105 107 108 108

10 Bras, kets and abstract state vectors 10.1 Introducing the ket vector . . . . . . 10.2 Wavefunctions in the braket notation 10.3 The bra vector . . . . . . . . . . . . 10.4 Projection and closure . . . . . . . . 10.5 |x and (x) . . . . . . . . . . . . . . 10.6 Properties of . . . . . . . . . . . . . 10.6.1 (x) in one dimension . . . . . 10.6.2 (r) in three dimensions . . . 10.7 |p and the Fourier transform . . . . 10.8 The x and p representations . . . . . 10.9 On the use of |k . . . . . . . . . . . 10.10Wave packets and Dirac notation . . 10.10.1 General formulation . . . . .

3 10.10.2 Example: the Gaussian wave packet . . . . . . . . . . . 109 10.10.3 Qualitative feature of the Gaussian wave packet . . . . 112 11 Scattering states 11.1 The potential step . . . . . . . . 11.2 The potential barrier with E > V0 11.3 The potential hole . . . . . . . . 11.4 The potential step with E < V0 . 11.5 The S-matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 . 115 . 116 . 119 . 120 . 122

III

Formalism and calculation tools


. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

126
. . . . . . . . . . . 127 127 129 133 135 136 141 145 146 146 147 149 149 151 . . . . . . . . . . . . us. . . 162 154 . 154 . 154 . 155 . 155 . 156 . 160

12 Linear stu 12.1 Linear spaces . . . . . . . . . . . . . . . 12.2 Inner products and norms . . . . . . . . 12.3 Linear operators . . . . . . . . . . . . . . 12.4 Eigenvectors are special . . . . . . . . . 12.5 The mechanics of matrix diagonalization 12.6 Application: neutrino mixing . . . . . . 12.7 The ammonia molecule revisited . . . . .

13 Hermitian matrices and their properties 13.1 Some denitions . . . . . . . . . . . . . . . . . . . . . . . . . 13.2 Hermitian operators . . . . . . . . . . . . . . . . . . . . . . 13.3 Properties of pairs of hermitian operators . . . . . . . . . . . 13.4 Simultaneous eigenvectors of commuting hermitian operators 14 The postulates of Quantum Mechanics 15 Algebraic approach to some matrix elements 15.1 Some properties of commutators . . . . . . . . . . . . . . 15.1.1 Linear combination of operators in a commutator 15.1.2 [, p] . . . . . . . . . . . . . . . . . . . . . . . . . x 15.2 Harmonic oscillator and the operators a and a . . . . . 15.2.1 a and a . . . . . . . . . . . . . . . . . . . . . . . 15.2.2 Matrix elements of x, p and their powers . . . . . 15.2.3 Application: constructing the eigenfunctions of H ing a . . . . . . . . . . . . . . . . . . . . . . . .

4 15.2.4 Application: the harmonic oscillator coherent state . . 163 15.3 Angular momentum theory and the operators L+ and L . . . 167 15.3.1 Commutation relations for angular momentum operators168 15.3.2 L+ and L . . . . . . . . . . . . . . . . . . . . . . . . 170 15.3.3 Matrix elements of Lx and Ly . . . . . . . . . . . . . . 173 15.3.4 Constructing the simultaneous eigenfunctions of L2 and z . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174 L 16 Uncertainty relations 182 1 B] | . . . . . . . . . . . . . . . . . . . . 182 16.1 A B 2 | [A, 16.2 Understanding the assumptions . . . . . . . . . . . . . . . . . 184 A Complex numbers 186 A.1 A bit of history . . . . . . . . . . . . . . . . . . . . . . . . . . 186 A.2 Adding complex numbers . . . . . . . . . . . . . . . . . . . . . 188 A.3 The complex conjugate . . . . . . . . . . . . . . . . . . . . . . 189 A.4 Multiplication and division . . . . . . . . . . . . . . . . . . . . 190 A.4.1 Multiplying and dividing in the Cartesian representation190 A.4.2 The polar representation . . . . . . . . . . . . . . . . . 191 A.4.3 Eulers theorem . . . . . . . . . . . . . . . . . . . . . . 193 A.4.4 Taking powers and roots . . . . . . . . . . . . . . . . . 196 B Numerical integration and Simpsons rule B.1 Preliminaries . . . . . . . . . . . . . . . . . . . . . . . . . . B.2 Simpsons rule . . . . . . . . . . . . . . . . . . . . . . . . . . B.3 Application: quantum particle outside a harmonic well . . . 199 . 199 . 204 . 205

C Finding zeroes of an equation 209 C.1 Bracketing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209 C.2 Newtons method . . . . . . . . . . . . . . . . . . . . . . . . . 209 D Remarks on some second order dierential equations 211 D.1 The Gauss hypergeometric 2 F1 (a, b, c; z) . . . . . . . . . . . . 211 D.2 The conuent hypergeometric function 1 F1 (a, c; z) . . . . . . . 214 E Hermite polynomials 216 E.1 Series solution . . . . . . . . . . . . . . . . . . . . . . . . . . . 216 E.2 Generating function . . . . . . . . . . . . . . . . . . . . . . . . 219 E.3 Rodrigues formula and orthogonality . . . . . . . . . . . . . . 219

5 F Eigenvectors: On the importance of being proper F.1 General eigenvalue problem . . . . . . . . . . . . . F.2 Diagonalizable matrices . . . . . . . . . . . . . . . . F.3 Tricks of the trade . . . . . . . . . . . . . . . . . . F.3.1 Powers of a matrix . . . . . . . . . . . . . . F.3.2 The determinant and trace conditions . . . . G Collected Problems 2001-2006 222 . 223 . 227 . 228 . 228 . 229 230

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Introduction

1
1.1

Introduction: Where we start, where we are going


Shut up and compute!

Quantum mechanics is an exciting topic: it works and we dont know why. Physicists dont solve problems using Newtons law anymore (they use the more sophisticated HamiltonJacobi formulation), but research journals are full of problems in and problems with quantum mechanics. Quantum mechanics remains a dynamic topic, rejuvenated by the recent advances in the emerging eld of quantum information. What is quantum? The dierence between quantum and, say, classical mechanics is the inherently probabilistic nature of the latter. In quantum mechanics, two identical experiments on two systems prepared in exactly the same manner, can produce dierent results. What quantum mechanics does is provide a prescription to enumerate the possible outcome of the experiment and to calculate the relative probabilities of these outcomes. Before we embark on this course, I must come out clean and dispel some illusions: quantum mechanics is not physics. Quantum mechanics a set of mathematical rules that allow us to understand the physics of microscopic objects and to make calculations veried by experiments. To emphasize the mathematical nature of quantum mechanics, simply note that, if you walk into a lab where experiments on electricity are done, you will nd wires, resistors, capacitors and other such devices. The theory of electrical circuits has a denite materiality: you can take a resistor in your hand and (sometimes) feel its heat when a current ows through it. If, on the other hand, you walk into a quantum optics lab, you will never nd a Hilbert space, an eigenvector or a wave function: the objects that populate a course on quantum mechanics are at least once removed from reality. They are abstract concepts, mathematical devices and rules that we construct so that we can extract information and compare with experiments. In times of despair or confusion (and these times will come), it is always good to remember that quantum mechanics is, ultimately, a mathematical game. What is unusual is that unreal and abstract mathematical constructs actually work in real practical life. The rules of quantum mechanics have been road tested for about 75 years now; they are applicable to a large number of disciplines, from solid state to nuclear physics. The whole set of

Introduction

rules, however abstract and poorly justied, correctly predicts the behavior of microscopic objects, and from this, very non-abstract applications have sprung. Semi-conductor devices, which can be explained using quantum mechanics, work. NMR works. The central objective of this course can be summarized by the famous dictum Shut up and compute! (attributed to R.P. Feynman). You can blame Schrdinger and Heisenberg for that. They were rather o desperate to reproduce some experimental results (spectrum of the hydrogen and other atoms, in fact): they did not care about shortcuts, fuzzy assumptions or whatever else. They found (independently) two methods that worked, without knowing why they worked. If you expect to understand why the rules are the way they are, you have enrolled in the wrong course. This does not imply that the why is unimportant (it is, in fact, absolutely fascinating!); the emphasis on practicality is something that my colleague and I chose to focus on, given the limited amount of time available in the (often crowded) physics curriculum. Furthermore, it is easier to understand the why if one has had some exposure to the mechanics of the calculations. To quote Jean Le Rond dAlembert, french mathematician of the 18th century: Just go on...and faith will soon return. DAlembert was thus reassuring a friend, who had diculty understanding why the rules of calculus were the way they were, this 150 years after the invention of calculus. The textbooks that we have chosen reects our choice. Like all textbooks, they will be liked by some, disliked by others. The best textbook on quantum mechanics (or any other subject) is a matter of personal preference; if you do not like our choice, your are strongly encouraged to head for the library: most quantum mechanics texts have a call number starting with QC 174. The university has over 150 books on the topic. Most of these deal with the how; few deal with the why. If you want to understand the how better, I do not doubt that one of these 150 books will be ideally suited for you. If you want to understand the why better, I suggest that you buy Where does the weirdness go?, by David Lindley, or consult, for instance, Quantum theory: concepts and methods, by Asher Peres (QC 174.12 P417 1995)

Introduction

1.2

Where did it all go wrong: a naive history of QM

The rules of quantum mechanics are not completely arbitrary. Schrdinger, in o particular, was inspired by classical mechanics (what else could have inspired him? That was the only game in town at the time!). Central to classical mechanics is the Hamiltonian function, which, in its simplest conception, represents the total energy of the system. To integrate Hamiltons equations of motion, one normally uses a method developed by Jacobi. Schrdinger (he was trying to solve the hydrogen atom) o knew that blunt application of the HamiltonJacobi method would not work. He decided on a whim to make some (very inspired) transformation and, by magic, stumbled on the famous dierential equation that now bears his name. (If you want to see the path from HamiltonJacobi to Schrdingers equation, o take the graduate quantum mechanics course.) The next task was to actually solve the dierential equation. (There is no physics up to that point, just a really sneaky transformation that could have lead nowhere.) The dierential equation is of a type known as an eigenvalue equation of the SturmLiouville type. Well, Schrdinger knew how to solve o this, so he plowed forward and found that some solutions produced the correct energy for the hydrogen atom while others did not. The nal trick of his paper (rst of a series of three) was to invoke some boundary condition to remove all the unwanted solutions. Voila! We now have found the spectrum of the hydrogen atom without really knowing what we are doing. This is apparently not a serious advance. After all, Bohr had already computed that spectrum. However, Bohrs theory was known to be false because it did not correctly predict the angular momentum of each energy level nor did it correctly count the number of states having a given energy. (This can be determined by Zeeman splitting, something easily done at the time.) Schrdingers solution did agree with all the experimental data from o the hydrogen atom, and also was reasonably good at predicting the spectrum of the helium atom, something at which the Bohr model failed completely. Schrdinger had indeed found something new. o The solutions to the dierential equation Schrdinger called wave funco tions. The name apparently comes because Schrdinger once overheard an o innocent remark at the end of a talk on Compton scattering. The remark was to the eect that, if particles really behaved like waves, there should be a wave equation associated with this behavior. Schrdinger did not really know what to make of those beastly wave funco

Introduction

tions. They are, in general, complex (in the mathematical sense), which precludes directly associating a physical meaning to them. Schrdinger thought o the wave functions were somehow waves that guided the particles along some kind of classical trajectories. That idea rapidly fell apart: under Shut up and compute, others had taken up his prescription and found that the wave function for two electrons (in a helium atom) was actually a function of six variables (three for each electrons). Maybe the wave was guided in sixdimensional space?? It was up to Born, a few years later, to make some sense of it all. He proposed that the meaningful quantity was not the wave function itself but its magnitude squared (which is always a positive number). Born then afrmed that this magnitude squared was a probability density, meaning that it provided information about the probability distribution of a particle (or particles) in space. This is just another example of Shut up and compute: we dont know what the wave function is (in fact, according to Born, the wave function itself has no meaning) but we know how to use it in calculations. I tell this story because it contains two essential elements for this course. First, quantum mechanics tells us about the possible outcome of an experiment designed to measure some physical quantity (here, the possible energy levels). By solving the Schrdinger equation, we answer the question What o are possible levels that can be measured experimentally?. Second, quantum mechanics tells us how to calculate the probability of each outcome. These are two central objectives of the course. To nish this brief history we must allow Dirac to enter. He realized that Schrdinger and Heisenberg were really going the same thing. He aco tually generalized the concept of wave function to that of state vector, and introduced the bra and ket notation that is now commonly used in the eld. Dirac also realized that, most of the time, we only really need properties of wave functions rather than the wave functions themselves: he pioneered the calculation of matrix elements (particularly for the harmonic oscillator) The second half of the course is implicitly devoted to quantum mechanics ` la a Heisenberg and Dirac, but we have some work to do before we get there.

1.3

How the topics were chosen

We cannot cover everything in one term: there is just too much material for that. The course will focus on simple quantum systems: square wells and harmonic oscillators in one and three dimensions, and hydrogenoid atoms.

Introduction

Pretty much any type of problem can be approximated by one of these problems. These problems can all be understood by solving the Schrdinger difo ferential equation. We will mostly be interested in enumerating and counting energy levels. Next, we will deal with the generalization to state vectors. This is much more useful and much more quantum than the wave function approach. The question of what is a state vector in real life is clearly moot in this formalism. The state vector formulation relies on properties of the solutions to the Schrdinger equation much more than on the solution themselves. It o leads to the calculation of matrix elements of operators and the recasting of Schrdingers equation from a dierential eigenvalue problem into a matrix o eigenvalue problem. We will only cover the simplest of examples, which will allow us to understand, for instance, the ammonia molecule, and the probability of nding the molecule in one of its two forms.

Heuristic Schrdinger equation o

Heuristic approach to Schrdingers equao tion

Schrdingers equation is a wave equation, describing wavelike properties of o particles. Schrdingers equation describes how the derivative w/r to time o of a function (called in the jargon a wavefunction) is connected to the value of this function and of its spatial derivatives.

2.1

Waves, wave equations and dispersions relations

A wave is a disturbance in space and time. Normally, a physical wave (like a sound wave or an electromagnetic wave) will carry energy. Mathematically, a wave (in one dimension, to simplify the analysis for the moment) moving in the +x direction is any function of the combination x vt, where x is a position, t is time and v is the velocity of the wave. The combination x vt has units of length, and it mathematically more convenient to consider the dimensionless quantity k (x vt) = kx t, (2.1)

where k, a quantity called the wave vector, has units of inverse length. Clearly, we have kv = (2.2) where is the angular frequency. An example is given in Fig., where we have four plots of (x, t) = 1 , 1 + (2x t)2 (2.3)

for t = 2, 1, 0 and 1. It is clear that the wave travels to the right. A wave traveling to the left would be a function of the combination kx + t. Note that it is not the overall sign of kxt that determines the direction of motion but rather the relative sign of kx and t. Thus, a function of tkx still describes a wave traveling to the right. Note also that the function (x, t) that mathematically describes the wave need not be periodic. One very common type of wave is the socalled harmonic, or free, wave. Mathematically, it is described by the general form (x, t) = a cos (kx t + ) , (2.4)

Heuristic Schrdinger equation o

where is an angle called the initial phase of the wave. This type of wave is obviously periodic. Its amplitude is a. For a variety of reason, it is often more covenient to use complex numbers and represent (x, t) as (x, t) = Aei(kxt) , (2.5)

where A is now a complex number. The mathematical function (x, t) describing the disturbance is usually the solution to a wave equation. For instance, the function (x, t) of Eqn.(2.5) is a solution of the dierential equation 2 1 2 (x, t) 2 2 (x, t) = 0. x2 v t (2.6)

Eqn.(2.6) is so common that it is sometimes referred to as the wave equation. However, this is by no means unique. For instance, the much more complicated partial dierential equation 3 (x, t) + 3 (x, t) + 6(x, t) (x, t) = 0 t x x (2.7)

is known as the Korteweg-de Vries wave equation. It has as a solution the function 1 v , (2.8) (x, t) = v 2 2 cosh (x vt) 2 and it describes shallow water waves. This is still a wave, owing to the xvt combination, but it is not harmonic. There are fundamental dierences between Eqns.(??) and (2.7). First, the form of the dierential equation is completely dierent: Eqn.(??) it contains only second order derivatives whereas Eqn.(2.7) contains derivatives of various order. An extremely important property for quantum mechanics is that Eqn.(??) is linear. This means that, if 1 (x, t) and 2 (x, t) are solutions to Eqn.(??), then (x, t) = 1 (x, t) + 2 (x, t) (2.9)

is also solution for constant and constant . You can verify this directly by substituting Eqn.(2.9) into Eqn.(2.6). However, this does not hold for the solutions to Eqn.(2.7), i.e. (x, t) is not, in general, solution to Eqn.(2.7).

Heuristic Schrdinger equation o

The linearity property of solutions is crucial because it is closely and intimately related to the possibility of producing interference between waves, something that was experimentally veried for particles. In other words, experiment suggests that, in order to describe the known wave properties of particles, we should primarily consider linear wave equations. (Nota: this does not exclude the possibility of nonlinear wave equations; it simply means that such nonlinear equations would not be good at describing some of the known wavelike properties of particles.) When a dierential equation is linear, like Eqn.(??), it usually follows from the dierential equation that some kind of subsidiary condition must be met. This condition usually takes the form of a relation between and k and is known as the dispersion relation for the wave. For instance, the dispersion relation for a real physical piano string is of the form To 2 = + k 2 , (2.10) 2 k o where To is the tension in the string, o is the mass density of the string, and is a small positive constant that would be zero if the string were perfectly exible. Normally, it is possible to recover the dispersion relation from the wave equation. Consider, for instance, the modication of Eqn.(??) 2 1 2 m2 c2 (2.11) (x, t) 2 2 (x, t) = 2 (x, t), x2 c t where an extra term has been added and the velocity is taken to be the speed 2 2 of light c. (Remember that has units of [energy][time], which means m 2c has the correct units of [length]2 ). Inserting the ansatz (x, t) = Aei(kxt) , we nd that we have a solution provided that the dispersion relation k 2 + m2 c2 2 = 2 c2 (2.12)

is satised. This is easily rearranged into ( )2 = ( k)2 c2 + m2 c4 . If one remembers from quantum physics the basic rules E = h = , p = k, (2.14) (2.15) (2.13)

Heuristic Schrdinger equation o

then Eqn.(2.13) is an expression for the relativistic energy of a particle with momentum p and rest mass m. Eqn.(2.11) is candidate for a wave equation appropriate for the description of a quantum relativistic particle. (Whether or not the wave properties of a relativistic particle is actually described by the solutions of Eqn.(2.11) is another matter.) Notice how Eqns.(2.10) and (2.13) contains the physical parameters that the mathematical description of the wave is suppose to embody. Another example of the physics contained in a dispersion relation is provided by the equation 2 = 4N e2 + c2 k 2 , me 2 = p + c2 k 2 (2.16) (2.17)

found to describe the propagation of waves in a plasma. Here, e is the electronic charge, me is the electronic mass and N is the electronic density of 2 the plasma. Eqn.(2.16) shows that, if p > 2 , it is possible for k to become imaginary, in which case the form of Eqn.(2.5) becomes (x, t) = Aex eit , where = (2.18)

1 2 p 2 . (2.19) c In such a case, the wave attenuates with x and there is no oscillation. Again, the dispersion relation describes the physics of the plasma through the ad2 ditional term 4Nee , which itself depends on various physical constants and m the electronic density appropriate to the particular situation at hand.

2.2

Schrdinger equation and dispersion relations o

The phenomenological starting points of Schrdinger equation are the reo lations giving wavelike properties to particles. More specically, to a free particle of momentum p we assign a free wave with wave vector k related to p by the de Broglie relation p = k. (2.20) The energy of a free particle is completely kinetic, so E=
2 2 k p2 = . 2m 2m

(2.21)

Heuristic Schrdinger equation o

10

To transform this into a dispersion relation, we observe that, for photon, the relation E = h = (2.22) holds. Combining these last two equations yields = k 2m
2 2

(2.23)

As a free wave is described by Eqn.(2.5): (x, t) = Aei(kxt) , we need to nd a dierential equation (i.e. a wave equation) that will reproduce the dispersion relation of Eqn.(2.23) when we input Eqn.(2.5) as a solution. We also want our dierential equation to be linear so that we can reproduce interference eects. The simplest thing around is i
2 2 (x, t) = (x, t). t 2m x2

(2.24)

If the particle is not free but evolves in a potential V (x), then the dispersion relation becomes 2 2 k + V (x), (2.25) = 2m and the wave equation is postulated to change to
2 2 (x, t) = (x, t) + V (x)(x, t). (2.26) t 2m x2 This is the timedependent Schrdinger equation. Formally, it amount to a o transformation of the equation E = p2 /2m+V (x) into a dierential equation for (x, t) obtained by replacing the physical quantities E, p and x by the operators

, E H=i t p p = i , x x x = x.

(2.27) (2.28) (2.29)

The simple harmonic wave of Eqn.(2.5) is no longer a solution of Eqn.(2.26), but the harmonic wave is suppose to describe something oscillating freely, not something subject to a potential.

Heuristic Schrdinger equation o

11

2.3

Historical comments

If the derivation of Eqn.(2.26) looks very fake, it is because it is fake and very handwavy. One cannot derive the Schrodinger equation from rst principles. More interestingly, this is NOT how Schrodinger ever approached the problem. His argument was based on classical mechanics. Modern classical mechanics has nothing to do with Newton and is based instead on a the Hamiltonian function H, which is essentially the total energy of the system. In our case, the classical Hamiltonian looks like H= p2 + V (x). 2m (2.30)

The motion of a particle can be obtained from the Hamiltonian using Hamiltons equations of motions. These equations are not always easy to solve, so there is a renement called Hamilton-Jacobi theory, especially powerful when the motion is periodic. In the HamiltonJacobi equation, momentum gets replaced by a partial derivative of the action integral S: S = S . x p2 V (x) dt 2m (2.31) (2.32)

The HamiltonJacobi equation then looks like S S , t) + = 0, x t 2 S S + V (x) + = 0. x t H(x, (2.33) (2.34)

1 2m

If H does not depend on this explicitly (as we are assuming in this discussion), then H is the total energy E of the system so that all of this can be simplied to 2 S 1 (2.35) + V (x) E = 0. 2m x Schrdinger then postulated the form o S = ln (x, t), (2.36)

Heuristic Schrdinger equation o

12

where is some constant. Inserting Eqn.(2.36) into Eqn.(??) yields (after minor tinkering) : (x, t) x
2

1 S (x, t) = (x, t) x x

(2.37) (2.38)

2m (E V (x))2 (x, t) = 0. 2

This is not linear, so a further massaging must be done. Suce it to say that he eventually got what he wanted, i.e. a dierential equation. Schro dinger was gunning for the energy levels of the hydrogen atom; as we will see, it is not the easiest problem to start with. After (again quite articially) imposing boundary conditions on his solution, he found that the got precisely the energy levels of the hydrogen atom if was set to .

2.4

Statistical interpretation

What now of the socalled wave function (x, t)? Let us assume V = 0, so we already know (x, t) = Aei(kxt) . Let P (x, t) = (x, t)(x, t) 0, and consider P (x, t) = t (x, t) (x, t) + (x, t) (x, t) t t (2.39)

Using the Schrdinger equation to change the time derivative into spatial o derivatives: 2 2 i (x, t) = (x, t) , t 2m x2 2 2 i (x, t) = (x, t) , t 2m x2 we obtain P (x, t) = (x, t) t i 2 i 2 (x, t) + (x, t) (x, t) 2m x2 2m x2

. (2.40)

We can clean up the expressions to get 2 i 2 (x, t) 2 (x, t) (x, t) 2 (x, t) P (x, t) = (2.41) t 2m x x i (x, t) (x, t) (x, t) (x, t) (2.42) = x 2m x x

Heuristic Schrdinger equation o This is a continuity equation: (density of stu) + (current of stu) = 0 . t x

13

(2.43)

The stu has density P (x, t) = (x, t)(x, t), which is always 0. This is interpreted in Quantum Mechanics as a probability density, meaning that P (x0 , t0 )dx = (x0 , t0 )(x0 , t0 )dx (2.44) is the probability of nding a system described by (x, t) is a small region b between x0 and x0 + dx at time t0 , and Pab = a P (x, t)dx is the probability of nding the system described by (x, t) in the interval a x b. Note that the probability of nding the system exactly at x0 is
x0

Px0 x0 =

P (x, t)dx = 0 ,
x0

(2.45)

contrary to one of the numerous incorrect examples found in Beiser. Obviously, a requirement is that the total probability of nd the particle somewhere in space, i.e. in the interval < x < , be 1, i.e.

1=

P (x, t)dx =

(x, t)(x, t)dx .

(2.46)

This is known as the normalization condition. Let us come back to (x, t) = Aei(kxEt/ ) . Note that (x, t)(x, t) = AA 0 so

1 = |A|

dx = !

(2.47)

This is a conict between the physical interpretation and the mathematical apparatus: well resolve (but not completely solve) that bug later. The conict is similar to calculating the total energy of a plane wave in electromagnetic theory: since this is proportional to the integral of |E|2 , which is constant for a plane wave propagating in vacuum, integrating over the entire space gives an innite value for the total energy, an obvious nonsense. Like in electromagnetic theory, a plane wave is really just an idealization, and we shouldnt be too surprised if, in such cases, things take a left turn.

Heuristic Schrdinger equation o

14

Anyways, with P (x0 , t) identied as a probability density, we now note that the probability current is J(x, t) = i 2m (x, t) (x, t) (x, t) x (x, t x (2.48)

What about problems with potential energies? There, we simply extend the procedure by directly adding V (x) +i
2 2 (x, t) + V (x0 , t)(x, t) (x, t) = t 2m 2x2

(2.49)

Provided that V (x) is real and does not depend on t , the interpretation of P (x, t) as a probability density and J(x, t) as a probability current still holds. Note that, since P (x, t)dx = 1 , the probability of nding the particle somewhere is independent of t, as expected. Finally, observe that, if

P (x, t)dx = 1 , we necessarily have, for continuous (x, t) (which is rea

sonable),
x

lim (x, t) = 0 .

(2.50)

Solutions for which Eq.(2.50) is applicable are known as bound states. As the name implies, such wave functions describe bound particles which cannot escape to innity. Solutions for which Eq.(2.50) does not apply are known as free states (or scattering states).

Expectation values

15

Expectation values: another look at some known rules

Suppose that we want to calculate the average weight of the students in the class. If Nwi students have weight wi , then the average weight is w =
i

w i Nw i

(3.1)

Now suppose that we want to compute the average w as a function of time. Then, w(t) = wi Nwi (t) (3.2)
i

What we mean by this is that the average weight may change in time because the number of student with a given weight will change in time. The weight wi that occurs on the R.H.S. does not change in time. For instance, if today there are 5 students weighing 60kg, 3 students weighing 65kg and 7 students weight 70kg, then the average weight is w(today) = 60.5 + 65.3 + 70.7 5+3+7 (3.3)

If tomorrow there are 4 students weighing 60kg, 5 weighing 65kg and 6 weighing 70, then the average weight is w(tomorrow) = 60.4 + 65.5 + 70.6 4+5+6 (3.4)

Even if the average weight w(t) varies with t , the individual values of weights, 60kg, 65kg, 70kg, do not. Going now to the continuous case, the summation becomes an integral and the discrete distribution becomes the distribution P (w, t) P (w, t)w dw w(t) = (3.5) P (w, t)dw and w(t) = O(w, t)w dw P (w, t)dw (3.6)

Expectation values

16

The variation in time of the average weight is due to the variation in time in the distribution of these weights: the weight w = 65kg is the same at all t. Let us apply this to

x(t) =

P (x, t) x dx ,

(3.7)

where P (x, t) = (x, t)(x, t) , Then,

P (x, t)dx = 1 .

(3.8)

x(t) =

P (x, t)xdx , J(x, t) xdx = xJ(x, t) x


J(x, t)dx

(3.9)

i =x 2m i 2m

(x, t) (x, t) (x, t) (x, t) x x (x, t) (x, t) (x, t) x

(x, t) x

dx. (3.10)

The boundary term is zero if we assume limx (x, t) = 0 . In the last term, integrate by parts

(x, t) (x, t)dx = (x, t) (x, t) x

(x, t)

(x, t) x (3.11)

(x, t)

(x, t) dx x

so that i x(t) = m

(x, t)

(x, t) dx x

(3.12)

Expectation values The momentun p = mx , thus p = m x is therefore given by

17

p(t)

= i

(x, t)

(x, t)dx x

(3.13)

(x, t) (x, t)dx p

(3.14)

. (3.15) x Thus, the rule of Eq.(3.15), which had initially been guessed at using plane waves, is now shown to be consistent with our previous assumptions about the nature of (x, t) and of (x, t) (x, t) even in cases where the solution is not a plane wave. Now, in the Schrdinger equation, o p = i i the term
2 2 (x, t) = (x, t) + V (x)(x, t) t 2m x2 2

with

(3.16)

2 p2 , (3.17) 2 2m x 2m i.e. the kinetic energy. The remains to see if we can interpret V (x) as a potential energy. Consider a hypothetical case where there is no kenetic energy. Then all the energy is potential, and P (x, t) is constant (the particle 2 (x, t) = 0 in the Schrdinger equation, we does not move). Setting o x2 have i and P (x, t) = (x, t)(xt) eiV (x)t/ (x, 0)eiV (x)t/ (x, 0) (3.19) = (x, 0)(x, 0) = P (x, 0) (3.20) independent of time. Thus, V (x) can be properly thought of as a potential energy. (x, t) = V (x)(x, t) = (x, t) = eiV (x)t/ (x, 0) t (3.18)

Expectation values The Schrdinger equation o i


2 2 (x, t) = (x, t) + V (x)(x, t) t 2m x2

18

(3.21)

is therefore an operation transcription of a statement about energy: E i , t (3.22) (3.23) (3.24)

2 2 p2 , 2m 2m x2 V (x) V (x) .

19

Part I

Quantization and boundary conditions


In this part of the course, we will look rst at energy quantization. It is an experimentally veriable fact that energy quantization occurs only when the motion of a particle or group of particles is spatially conned or bounded. If the motion is not conned, as is the motion of a free charged particle, there is no energy quantization. Mathematically, the connement appears by imposing appropriate boundary solutions of the Schrdinger equation. Energy quantization in bound o states and boundary conditions are closely linked. The properties of the resulting solutions will also be examined. In Chapter 8, we will extend the analysis to the quantization of angular momentum.

Basic solutions

20

4
4.1

o Basic solution to the Schrdinger equation


Separation of variables and stationary solutions
2 2 (x, t) = (x, t) + V (x)(x, t) t 2m t2

The (full, timedependent) Schrdinger equation reads o i (4.1)

We look for solutions of this partial dierential equation using the technique of separation of variables, i.e. we assume (x, t) = (t)(x) Plugging this ansatz into Schrdingers equation, we nd i d 2 d2 (t) (x) = (t) (x) + V (x)(x) dt 2m dx2 (4.3) (4.2)

This is a functional identity valid t, x so dividing by (t)(x), we get i 1 (t) d (t) dt =


2 1 d2 (x) + V (x)(x) (x) 2m dx2

(4.4)

The l.h.s. depends on t only, and is always equal to the right h.s., which depends on x only. Thus, both sides must be equal to the same constant which we call E. Hence, i 1 d(t) = E dt = (t) = AeiEt/ (t) 2 d2 (x) + V (x)(x) = E(x) 2m dx2 (x, t) = eiEt/ (x) (4.5) (4.6)

with (4.7) Eqn.(4.6) is known as the timeindependent, or stationary Schrdinger o equation. It depends explicitly on the potential V (x) and so the solutions to Eqn.(4.6) vary from one problem to the next. The entire time dependence of (x, t) is contained in the complex exponential eiEt/ ; provided that we nd E (via the solution Eqn.(4.6), we do not really need to worry about the

Basic solutions

21

time dependence: this is why a good deal of this section is devoted to solving Eqn.(4.6). Let us look more closely at one of the essential properties of this type of separable solution: the probability density (x, t) (x, t) = (x)(x) , (4.8)

does not depend on time. Thus, solutions of the form of Eqn.(4.7) are known as stationary solutions. This does not mean that the probability density is always timeindependent. For instance, if 1 (x, t) and 2 (x, t) are two solutions of the timedependent Schrdinger equation having dierent time dependence: o 1 (x, t) = eiE1 t/ 1 (x) , then the linear combination (x, t) = 1 (x, t) + 2 (x, t) (4.10) 2 (x, t) = eiE2 t/ 2 (x) , E1 = E2 , (4.9)

is also a solution of Eqn(4.1) but (x, t) (x, t) will depend on t. We have explicitly restricted our wave functions to separable functions. Is this a serious restriction? The answer is no, but must be interpreted carefully. Not every solution to the Schrdinger equation is separable; for o instance, the solution (x, t) of Eqn.(4.10) is not separable: it is not possible to write (x, t) as a function of x only multiplied by a function of t only. However, it can be shown that every solution of the Schdinger equation can o be written as a sum of separable solutions. This can be compared to the following statement for ordinary functions of one variable: not every function is a polynomial function, but (barring pathological cases) every function can be expanded as a sum of polynomial (think Taylor series). In this statement, polynomial plays the role of separable solution in the previous paragraph. It is also important to realize that not all solutions of the Schdinger o equation are acceptable as wavefunctions: Eqn.(2.50) is an example of a restriction on the possible solutions to the Schrdinger equation if a solution o is to describe a bound system. More generally, the legal solutions must satisfy a certain number of conditions. We impose on the wave functions the extra conditions that (x) be everywhere continuous, nite and single valued.

Basic solutions There are also conditions on the derivative d(x)/dx. Consider

22

d2 (x) + V (x)(x) = E(x) (4.11) 2m dx2 Push V (x)(x) to the right hand side and integrate from to :
2

where

2m

( () ()) =

(E V (x))(x)dx ,

(4.12)

d(x) . (4.13) dx Now recall some geometrical properties of integrals of general functions f (). Let m and M denote, respectively, the min and max of a function f () over the interval [a, b] . Then (x)
b

m(b a)
a

f ()d M (b a)

(4.14)

Use this with a = , b = , = x and f = V E, and take the limit 0:


0

lim 2m lim

(V (x) E)(x)dx lim 2M .


0

(4.15)

Thus, unless m or M , we have, by the sandwich theorem of calculus lim( () ()) 0 , (4.16)
0

i.e. is continuous at x = 0. A similar argument can be used to prove the result for any value x = x0 . The proof fails if m or M , meaning that the product (V (x) E)(x) blows up somewhere. This can happen if (x) blows up (which will only happen in some very specic and very rare circumstances), if E becomes innite (also rather pathological) or if V (x) has an innite discontinuity somewhere. Otherwise, (x) will be continuous. Curiously enough, innite discontinuities in V (x) are rather frequent: the prime example is the innitely deep well, where V suddenly goes from 0 to + at the ends of the well. We will see other examples of useful innite discontinuity later. Having dealt with the continuity of (x), we now impose that (x) be nite everywhere: indeed, the calculation of p involves (x), and it doesnt make much sense to have innite momentum, as this would imply innite kinetic energy. Finally, (x) should also be singlevalued.

Basic solutions

23

4.2

Two simple examples

Before we consider problems with complicated potentials, let us gain some experiences with two very simple but illustrative examples. 4.2.1 V (x) = constant = V0 .

By separation of variables, we have (x, t) = eiEt/ (x) d (x) + V0 (x) = E(x) 2m dx2 2 d2 (x) = (E V0 )(x) = 2m dx2
2 2

(4.17) (4.18) (4.19)

Assume E V0 0. Then the general solution is expressed in terms of two constants A, B, with (x) = Aeikx + Beikx k 2m Therefore, (x, t) = Aei(kxt) + Bei(kx+t) . The term is kx t describes a (free) particle moving to the right p dxAei(kxt) i Aei(kxt) x (4.22) (4.23) (4.21)
2 2

= E V0

k=

2m(E V0 )
2

(4.20)

+ k

Furthermore, if t increases, then x must also increase to keep kx t constant. Similarly, Bei(kx+t) describes a particle moving to the left. Assume now E V0 < 0. Then, the solution is of the form (x) = Aex + Bex 2m In this case, (x, t) = Ae(xit) + Be(x+it) . (4.25)
2 2

= V0 E

2m(V0 E)
2

(4.24)

Basic solutions 4.2.2 Innite discontinuity: the innite potential step

24

Consider another simple example: V (x) = 0 if x < 0 if x > 0 (4.26)

Suppose some source is placed at x = . Then we have, for x < 0 (x) = Aeikx + Beikx , k = 2mE : (4.27) On the right hand side, we have E V (x) < 0 and thus = 2m(E V ) = . Oops! Well, on the right of the barrier, let us write (x) = Ceikx + Deikx , (4.29) (4.28)

and try to determine the two constants C and D. Substituting k = i, we get (x) = Ce+x + Dex . (4.30) Since C and D are constants, they can be determined by choosing any point x > 0. Choose any nite x, say x = x0 . Then, as (x) must be nite everywhere and, in particular, at x0 , (since (x)(x) must itself be nite everywhere), the term e+x must be removed from the solution since it is at x0 : loosely, this amount to setting C = 0 in the expression for (x). One can imagine being nasty and choosing C = ex0 , so that the product Cex is nite at x0 . That doesnt do a lot of mileage, as this product is innite for any point to the right of x0 : there is no way around it: we have to remove the term in ex . Let us now look at the term Dex . For any nite D, this is zero everywhere on the right of the barrier: this term disappears by itself. Again, one can play games and choose D to be, say, D = ex0 so that the produce Dex0 is nite at x0 . The problem is as before: if x < x0 , then Dex would blow up. Hence, we conclude that we must also remove the term containing D from the solution: we have eectively argued that, on the right of the barrier, (x) 0.

Basic solutions By continuity at x = 0, we therefore have (0) = A + B = 0 A = B This gives, for x < 0, the solution (x) = A(eikx eikx ) = A sin kx .

25

(4.31)

(4.32)

Note that, if the barrier is at x = L rather than x = 0, we can simply translate the solution so that it becomes (x) = A sin k(x L) . There is so particular restriction on k, so all energies are permitted. (4.33)

General properties of (x)

26

General properties of one-dimensional wave functions

In this section, we will discuss some general properties of wave functions. Some of these properties are formal, others are less formal, but all are useful to have a better qualitative understanding of wavefunctions.

5.1

The no-degeneracy and oscillatory theorems

Suppose () is solution to the Schrdinger equation describing the nth o bound state of a system, having energy En , i.e. () is solution to the Schrdinger equation o 2m d2 () + 2 [En V ()] () = 0. 2 d (5.1)

Then, there is no other function, other than multiple of () , that has this energy. This is a proof by contradiction. Indeed assume () and () are both solutions, with () = c () for an arbitrary complex constant c. Then: 2m 1 d2 1 d2 () = 2 [En V ()] = () , () d 2 () d 2 which can be rearranged into 0 = () = so that () d d d2 d2 () () 2 () , d 2 d d d () () () () d d d () () d d () d (5.2)

(5.3)

= ,

(5.4)

where is a constant. However, for the wave functions to be normalizable, we need

lim () = lim () = 0.

(5.5)

General properties of (x) Therefore, evaluating Eqn.(5.4) at innity gives = 0 and thus () d d () = () () , d d 1 d 1 d () = () . () d () d

27

(5.6) (5.7)

Integrating gives () = c () , with c a constant, in contraction with the assumption that () and () have the same energy but () = c () . This result is obviously applicable to one-dimensional problems where, for instance, = x, but it is also applicable to a much larger class of problems. For instance, the radial part of the Schrdinger equation can be written in o the form of a one-dimensional equation: ( + 1) 2m 1 d2 (r) + 2 [En V (r)] , 2 (r) dr r2 (5.8)

where the radial wave function R(r) is related to the auxiliary wave function (r) by R(r) = (r) /r. Thus, Eqn.(5.8) is the Schrdinger equation deo scribing a one-dimensional particle restricted to r 0 subject to an eective potential 2 ( + 1) , (5.9) Vef f (r) = V (r) + 2m r2 with the extra term known as the centrifugal term, which depends on the angular quantum number . Because the eective potential depends on , we have added this extra subscript to En . Our result applies to (r) and thus to R(r), meaning that, for specied , only one solution (r) will have energy En . Note that, since Vef f depends on , there may be more than one wave function that will have energy E = En , but these wave functions will be labeled by dierent values of , i.e. these wave functions will be solutions for dierent eective potentials. (This is precisely the situation of the hydrogen atom.) Next, we will prove what is called the oscillatory theorem. For convenience of notation, recall H= d2 + V (). 2m d 2
2

(5.10)

V () may or may not be an eective potential: this is irrelevant to our argument.

General properties of (x) The oscillatory theorem states that, if H1 () = E1 1 () , H2 () = E2 2 () , E 1 < E2 ,

28

(5.11)

then 2 () has more zeroes (nodes) than 1 (). To show this, manipulate the Schrdinger equation so that o
2 2 d2 d2 1 1 1 () + E1 = V () = 2 () + E2 , 1 () 2m d 2 2 () 2m d 2

(5.12)

which one then reorganizes as 2 () d2 d2 d 1 () 1 () 2 2 () = 2 d d d


2

2 ()

d d 1 () 1 () 2 () d d (5.13)

2m

(E2 E1 ) 1 ()2 ().

Integrating from = a to = b, we nd
2 b

2m

(E2 E1 )
a

d1 ()2 ()

2 (b)

d d 1 (b) 1 (b) 2 (b) d d d d 2 (a) 1 (a) 1 (a) 2 (a) d d

(5.14)

If one chooses the points a, b to be consecutive zeroes of 1 , and if 1 is continuous, then 1 does not change sign over the interval [a, b] . We can assume, without loss of generality, that 1 is positive on this interval, so that 1 (a) 0 and 1 (b) 0. Then, using these with 1 (a) = 1 (b) = 0 in Eqn.(5.14), we obtain
2 b

2m

(E2 E1 )
a

d1 ()2 () = 2 (b)

d d 1 (b) 2 (a) 1 (a). d d

(5.15)

Assume now that 2 () is always positive on [a, b] . Then the integrand is positive, so the integral will be positive (the area under a positive curve is necessarily positive!) On the right hand side, however, the rst term is negative by virtue of 1 (b) 0 while the second is positive. Overall, the

General properties of (x)

29

right hand side is therefore negative, while the left side is negative, a contradiction : 2 () cannot be always positive on [a, b] , meaning that between two consecutives zeroes of 1 (), the function 2 () must itself go through zero. In other words, 2 () has more zeroes than 1 (). This proves the theorem. The theorem is beautifully illustrated with the harmonic oscillator wave function. By inspection, the wave function for the lowest energy has no zeroes, the wave functions for the next lowest energies have one, two, three, etc. nodes, the number of nodes increasing with the energy. It is also easily veried that, between two nodes of a solution, another solution of higher energy will go through zero at least once. The theorem can also be veried for hydrogen wave functions, although it must be done a little more carefully: for xed (since the eective onedimensional potential depends on and we must compare solutions in the same potential), solutions with higher energies have a larger number of zeroes.

5.2

Qualitative features of wave functions.

Is there a way to understand physically the contents of the oscillatory theorem? Consider the geometrical interpretation of d2 2m () = 2 [En V ()] () . 2 d (5.16)

at a point where En V () 0. This is the classical region where the total energy is greater than the potential energy. Obviously, this must hold in classical physics, as the kinetic energy if always positive and the total energy is the sum of kinetic and potential energy. The left hand side of Eqn.(5.16) is the curvature of the function () . Evaluated at a point 0 where (0 ) is positive, we see that the curvature must be negative, i.e. the function () must curve downwards when it is positive. Likewise, if (0 ) is negative, then the curvative is positive, so that () must curve upwards when it is negative. This is typical of oscillatory functions, and can be veried using the solutions of the innite well or the harmonic oscillator. Note that, for points where En V () < 0, the curvature of () is positive for positive () and negative for negative () , a behaviour typical of the exponential function. Next, the magnitude of the curvature at 0 is, basically, given by En V (0 ). If En V (0 ) is large, then the function has a large curvature at

General properties of (x)

30

Figure 1: Left: In the classically allowed region, a positive wave function must have a negative curvature. Right: in the same region, a negative wave function must have a positive curvature.

that point; if En V (0 ) is small, () will be atter than elsewhere at 0 . In a harmonic oscillator, for instance, the curvature of the solution is always maximal at the center of the well 0 = 0, and this is the point where En V (0 ) is largest. Finally, since 2 d2 p2 (5.17) 2m d 2 2m is interpreted as the kinetic energy, we expect that intervals where p2 /2m is large correspond to intervals where the particles moves fast, whereas intervals where p2 /2m is small correspond to intervals where the particles moves slowly. Hence, the probability of nding the particle in an interval where it is moving fast should be less than the probability of nding the particle in an interval where it moves slowly. Where therefore expect that () () and thus () itself will have a smaller amplitude in the fast region than in the slow region. Again, this can be veried for the known wave functions.

Simple bound states

31

6
6.1

Simple bound state problems in one dimension


The innite well

Suppose next that we place two innite steps at x = 0 and x = L, so that , if x 0, 0 , if 0 < x < L, (6.1) V (x) = , if x L . Inside this innite well, we have (x) = Aeikx + Beikx At x = 0, we have (0) = 0 since the potenial step is innite there: (0) = 0 = A + B A = B (x) = A sin kx (6.3) (6.2)

Next, at x = L , we also need to have (L) = 0 : (L) = A sin kL = 0 (6.4)

Clearly if A = 0 , then we have accomplished nothing because (x) = 0 everywhere: (x)(x) = 0 everywhere and we are describing nothing. Thus, the only way to satisfy simultaneously (0) = (L) = 0 is to choose those values of k for which n (6.5) sin kL = 0 kn = L The subscript n on kn has been introduced to distinguish between the various discrete values kn that will make kn satisfy sin kn L = 0. There are two things to note. First, because the potential steps are , we did not use any conditions on the continuity of d ; in fact d is dx dx discontinuous at x = 0 or x = L since V (x) has an innite discontinuity at x = 0 and x = L. The second and most crucial observation is that only a discrete (or quantized) set of values of k can make this work. Since k = p, we have (6.6) kn = pn = 2mEn .

Simple bound states

32

Thus we nd that the possible values of E are also quantized, i.e. they form a discrete set indexed by the quantum number n : kn = n = L 2mEn En = n , 2mL2
2 2 2

kn =

n , L

n Z+

(6.7)

We can distinguish the various acceptable solutions by their energies, or by the label n. Thus, the full timedependent solution with energy En is n (x, t) = A eiEn t/ sin(kn x) (6.8)

The last job to do is to normalize n (x) and, by the same token, normalize n (x, t). This is easily done

1=

dx n (x)n (x)

=
0

dx n (x)n (x) ,

(6.9)

since n (x) = 0 for x < 0 and x > L Thus: 1 = AA


0 L

dx sin2 (kn x)
L

(6.10) (6.11)
0

1 1 sin 2kn x = A A + x 2 4kn

Now recall that kn L = n, sin 2n = 0 Thus, we end up with 1 = A A Choosing A =


2 L

L . 2

(6.12)

will normalized the wave functions, so that we have n (x) = n (x, t) = 2 sin kn x L 2 i n2 2 t/2mL2 e sin kn x L (6.13) (6.14)

6.2

Detour: Symmetric potentials and their solutions

Some potentials have the property that V (x) = V (x). These are known as symmetric potentials. Furthermore, although some potential are not explicitly symmetric, it is often possible to trick the problem into believing that

Simple bound states

33

the potential is symmetric. For instance, the innite well of section 6.1 can be transformed into a symmetric well under the change of variables = xL/2, so that the potential well now extends from to +. Other examples of 1 symmetric potentials include the harmonic oscillator V (x) = 2 kx2 of section 6.4 and the square well of nite depth of section 6.3. We now prove the following important claim. Suppose the potential is symmetric: V (x) = V (x). Then it is always possible to choose the solutions (x) of the corresponding timeindependent Schrdinger equation to o be either even functions, (x) = (x), or odd functions, (x) = (x). To prove this, suppose (x) is solution to d2 (x) + V (x)(x) = E(x) , 2m dx2
2

(6.15)

and make the change x x to get d2 (x) + V (x)(x) = E(x) . 2m dx2


2

(6.16)

Note that, under this change, d2 /d(x)2 = d2 /dx2 . As the potential is symmetric, V (x) = V (x), we see that (x) is also solution to the timeindependent Schrdinger equation with the same o energy. Now, recall that any linear combination of two solutions of the time independent Schrdinger equation with the same energy is also a solution of o the timeindependent Schrdinger equation. Thus, we can combine (x) and o (x) into two new linear combinations 1 + (x) = ((x) + (x)) , 2 1 (x) = ((x) (x)) . 2 (6.17)

which are also solutions to the Schrdinger equation for this potential. The o solutions (x) also have energy E. The functions + (x) and (x) are, respectively, even and odd. This proves the claim. What this doesnt mean is that, if there is an even solution for a given energy E, there is also an odd solution with that energy. In fact, we will show that this is never the case in general. What it does say is that, if you set up your problem so that V (x) = V (x), then you can nd solutions that are even or odd. This will be claried by examples below.

Simple bound states

34

6.3
6.3.1

The nite well


Obtaining a transcendental equation

Consider a well of nite depth, described by a symmetric potential of the form if x < L , 0 V0 if L x L , V (x) = (6.18) 0 if x > L . where V0 > 0. This is a symmetric potential, so we expect that, inside the well at least, solutions will be of the form (x) = Aeikx + Beikx . The even and odd combinations of these are, in fact, (x) = A cos(kx) and (x) = B sin(kx), respectively. The bound states will have energies < 0, so we write E = , with E < 0 and > 0. Let us look for even solutions. Once again, we have three regions, so we have three regions for the solutions: if x < L , Cex A cos(kx) if L x L , (x) = (6.19) Cex if x > L . As always, k = = 2m(E V )
2

= =

2m(V0 )
2

, (6.20)

2m(V E)
2

2m
2

In writing the form of (x), we have explicitly used the symmetry of V (x) to instantly reduce the number of unknown amplitudes: the amplitude of the decreasing exponentials must be identical by symmetry. We now proceed along the familiar lines. By continuity of (x) at x = L, and by continuity of d/dx at x = L, we nd A cos(kL) = CeL , kA sin(kL) = CeL .

(6.21)

Taking now the ratio of these equation to eliminate A and B, we nd, after multiplication by L, kL tan(kL) = L . (6.22)

Simple bound states

35

It is not possible to solve the equation algebraically: it must be solved numerically. To do this, we need to write explictly Eqn.(6.22) in the form 2mL2 V0
2

V0

tan

2mL2 V0
2

V0

2mL2 V0
2

V0

, (6.23)

and use the variables = 2mL2 V0


2

z=

V0

1.

(6.24)

so that Eqn.(6.22) becomes 1 z tan 1 z tan 1 z

= z, = z . 1z (6.25)

Before we actually solve this, it is worth observing that the parameter has no units and is completely determined by the properties of the potential (its depth V0 , its half-width L) and by the mass of the particle trapped in this potential. For instance, in problems where the particle is an electron, typical energies are in eV and typical lenghts are measured in units of the Bohr radius a0 . Thus, writing L = a0 , we have typical values of given in the table below (using the mass of the electron): V0 (in eV) 1 (no units) 1 2 3 1 1 1 (no units) 0.2708 0.5417 0.8125 0.4691 0.6056 0.8565

3 5 10

For nucleartype problems, with masses of the other of proton or neutron masses, V0 is most often measured in M eV and L in F = 1015 m. Typical values of are comparable if somewhat a little lower. Returning now to Eqn.(6.25), we solve using a graphical method. Let us assume, for the sake of argument, that = 4. On the same graph, plot of

Simple bound states

36

the left hand side and the right hand side of Eqn.(6.25). You get something like Fig. 2. The intersections of the two curves are the points where tan(4 1 z) = z/(1 z) and therefore represent the values of z that are solutions to Eqn.(6.25). Note that, for plotting purposes, 0 < z 1.
5 4 3 2 1

0.2

0.4

0.6

0.8

Figure 2: The graphical solutions to Eqn.(6.25) with = 4.

First, we see that there are two intersection points and thus two solutions. They can be located precisely by numerically solving Eqn.(6.25). This gives: z2 = 0.192 , z1 = 0.902. Thus, assuming that we know the depth V0 of the potential, we can recover 1 = z1 V0 = 0.902 V0 and so forth. Given the energies, we can recover k1 , k2 , 1 and 2 . Using Eqn.(6.21), we can obtain the ratios C1 /A1 and C2 /A2 in our two solutions 1 (x) and 2 (x). Finally, using the normalization condition, we can determine, say, A1 and A2 . This closes the problem of solving for even wave functions. Now, the same tactics must be applied to odd wave functions. This time, however, our solution looks like if x < L , Cex A sin(kx) if L x L , (x) = (6.26) Cex if x > L .

Simple bound states

37

Note the way in which the sign of C changes with the region, so as to make the wave function odd. It is quite easy to work out that, after the same manipulations as before, we eventually get (1 z) . (6.27) tan 1 z = z
z 0.2 0 0.4 0.6 0.8 1

Figure 3: The graphical solutions to Eqn.(6.27) with = 4.

Clearly, there is only one bound state, with energy obtained from z3 = 0.617. It is worth observing that the lowest energy for the even solution is lower than the lowest energy of the odd solution. 6.3.2 Example: depth of the deuteron well

As a rst approximation, the force between a neutron and a proton can be described by an attractive square-well potential, given in Eqn.(G.132) and illustrated in Fig. 33. for r 0 , V0 for r R0 , V (r) = (6.28) 0 for r > R0 . Here, r is the relative radius between the two nucleons, and V0 > 0.

Simple bound states

38

V=0

V=Vo MeV r=R o

Figure 4: An approximation to the nuclear well.

The range R0 of the nuclear force is known to be of the order of the Compton wavelength of the pion: R0 = m c , (6.29)

where m = 139MeV/c2 is the mass of the pion Knowing that the protonneutron has a only one bound state with energy 2.22MeV, and knowing this state has angular momentum = 0, we can nd the depth of the potential V0 as follows. Because the region r 0 is inaccessible, the wave function for a bound state in this potential must be 0 at r 0. Thus, we have 0 if r 0 , A sin kr , if 0 < r R0 , (6.30) (r) = r Be if r > R0 . This form in each region is the only one that will satisfy the boundary conditions: (0) = 0 and () 0. The energy of the bound state is 2.22M eV , which we write , with = 2.22M eV . Inside the well, the timeindependent Schrdinger equation o is 2 2 d (r) V0 (r) = (r) , (6.31) 2m dr2 which can be written more simply as d2 (r) = (V0 ) (r) . 2m dr2
2

(6.32)

Simple bound states

39

Clearly, V0 > , i.e. the well must be deeper than 2.22M eV to accommodate a bound state of that energy, so the r.h.s. of Eq.(6.32) is negative, justifying the oscillatory form of (r) inside the well, with k 2 = 2(V0 )/ 2 and the reduced mass of the system. The cosine term cannot appear as it does not satisfy the boundary condition (0) = 0. For r > R0 , outside the well in the classically forbidden region, we have d2 (r) = (r) , 2m dr2
2

(6.33)

which must be again of the form suggested for the wavefunction to be normalizable. Here, 2 = 2/ 2 . The continuity of the wavefunction at r = 0 is guaranteed by the choice of the sine term for the wavefunction inside the well. Because there is an innite jump the potential at r = 0, there is no condition on the derivative of at that point. The continuity of the wavefunction and of its derivative at r = R0 yields A sin(kR0 ) = BeR0 , kA cos(kR0 ) = BeR0 . (6.34) (6.35)

We can divide the rst equation by the second to eliminate the factors A and B and obtain k tan(kR0 ) = , tan
2 2(V0 )R0 2 2(V0 )

(6.36)
2

= =

2/ V0

(6.37) (6.38)

We know and we are looking for V0 . So, to solve this equation, we set z = V0 / and rearrange to V0 2 2( 1)R0 = V0 1 , (6.39) tan 2 tan
2 2 R0 2

z1

= z 1.

(6.40)

Simple bound states We now compute the numerical factor


2 2 R0 2

40

2
2

m2 c2

2 = m2 c2

2 c2 . m2 c4

(6.41)

The reduced mass is given by 1/ = 1/mp +1/mn . Taking mass of the proton 1 and the neutron to be equal to 940MeV/c2 , we get c2 = 2 940. Thus, we have 2 2 R0 940 2.22 = = 0.329 (6.42) 2 1392 and thus, we are looking for solutions to (6.43) tan 0.329 z 1 = z 1 ,

10 -2

20

30

40

-4

-6

-8

-10

Figure 5: The graphical intersection of the curves tan(0.329 z 1) and z 1.

A plot of this shows there is a single intersection near z = 30. A rened search yields z = 29.49, and thus V0 = 29.49 = 65.5M eV . This completes the calculation of V0 . 6.3.3 Example: The ammonia molecule

The ammonia molecule, NH3 , is in the form of pyramid, with the nitrogen atom at vertex and three hydrogen atoms at the base. The nitrogen atom

Simple bound states

41

may be at one of two symmetric equilibrium positions: above or below the plane of the hydrogen atoms. The molecule is illustrated in Fig.G. (Both gures taken from Wikipedia at http://en.wikipedia.org/wiki/Ammonia ).

Figure 6: The ammonia molecule, showing the nitrogen atom in relation to the three planar hydrogen atoms.

The potential energy for the motion of the nitrogen atom is illustrated in Fig.7 as the smooth Wshape curve. The gure also illustrates the approximation of this potential by a innite onedimensional square well with a central bump of height V0 = 0.245eV. The innite walls are located at b = 0.5548 1010 m; the central bump extends from a to +a, with a = 0.2298 1010 m.
b

Vo

ba

Figure 7: The potential for the nitrogen atom of the ammonia molecule. The exact potential (wavy line) is approximated by an innite square well with a bump in the middle (heavy line).

We will look for the lowest energy states of this molecule. The energy will

Simple bound states

42

be denoted E. It is measured from the bottom of the well and thus positive. Let x denotes the position of the nitrogen atom. If x > 0, then the nitrogen atom is above the hydrogen plane, while the nitrogen atom is below this plane when x < 0. We expect on general grounds that an even wave function will have less curvature than the odd wavefunction, so we will assume our wavefunction to be even. Our candidate wavefunction is B sin(k(b + x)) if b x a , (x) = (6.44) A (ex + ex ) if a < x < a , B sin(k(b x)) if a x b . It is certainly even under the transformation x x, and it satises the boundary condition that (b) = 0 because the wavefunction outside the well must be 0. Both the increasing and decreasing exponentials appear as both as solution of the Schrdinger equation when one assumes E < V0 . (If o it turns out there are no solutions with E < V0 , this assumption will have to dropped and the form of the wavefunction in the region of the central bump will have to be modied.) As always, we set = 2m(V0 E)
2

k=

2mE
2

(6.45)

The continuity of and d/dx at x = a gives two equations: A ea + ea A ea ea = B sin(k(b a)) , = B k cos(k(b a)) . (6.46) (6.47)

The continuity of and its derivative at x = a gives the same two equations. Dividing these so as to eliminate A and B, we obtain the consistency equation: 1 1 ea + ea = tan(k(b a)) . (6.48) a ea e k To bring this to a solvable form, we set = 2mV0 a2
2

= 3.91 ,

z=

E , V0

(6.49)

Simple bound states where mN H3 : b: 2mV0 a2


2

43

2300 MeV/c2 0.5548 1010 m : 15.3182

c: a: 2mV0 a2
2

197.3 MeV 1015 m 0.2298 1010 m : 3.9138

1 + b/a : 1.4143 and so obtain the transcendental equation tan(5.54 z) ) . = 3.911z z (e e3.91 1z ) 1 z (e3.91
1z 1z

+ e3.91

(6.50)

The solution is obtained graphically by using the graph of Fig.8.


0.2 -0.5 -1 -1.5 -2 -2.5 -3 0.4 0.6 0.8 1

tan(5.54 z) = . Figure 8: Graphical solutions to z (e3.91 1z e3.91 1z ) 1 z (e3.91


1z

+ e3.91

1z )

Visibly, there are two solutions, at z = 0.228 and z = 0.844. Thus, from z = E/V0 , we see that the lowest energy state is located at E = 0.228 V0 = 0.056eV. The second even level is located at E = 0.206eV. There is, of course, an odd level with energy in between those of the two even levels. There are more even levels, but their energy is above the bump, so the form of the wavefunction must be modied before a search for these solutions can occur.

6.4

The harmonic oscillator

The harmonic oscillator is important as many potentials can be approximated by a harmonic potential for suciently small displacements. For a harmonic

Simple bound states oscillator, we have


1 V (x) = 2 kx2 .

44

(6.51)

o The timeindependent Schrdinger equation for (x) is now 6.4.1 Solution d2 1 (x) + 2 kx2 (x) = E(x) . 2m dx2
2

(6.52)

To simplify the notation, let us introduce = k , m = m x, = 2E , (6.53)

so that we can rewrite the dierential equation in x as d2 () + ( 2 )() = 0 . d 2 (6.54)

To proceed, we examine the boundary conditions of the problem. V (x) (or V ()) is continuous everywhere, so we get nothing from that. On the other hand, () must be nite everywhere, and, in particular, (x) must remain nite at = . Thus, for , we can write d2 () 2 () 0 , d 2 () = p e
2 /2

(6.55)

This is an approximate equality, and we can verify that solutions of the form (6.56)

are approximately solutions provided that p is nite. To show this, we concentrate on () and work out d p 2 /2 2 2 e = p p1 e /2 p e /2 d d2 p 2 /2 2 2 e = p(p 1) p2 e /2 p p1 e /2 2 d 2 2 (p + 1) p e /2 + 2 p e /2 p(p 1) (2p + 1) 2 +1 = p+2 e /2 4 2 2 p e
2 /2

(6.57)

(6.58) (6.59) (6.60)

Simple bound states for if p/ 2 0 .


+ 2 /2

45

(6.61)

The same argument holds for p e . However, we can throw out this 2 solution because the wave function must remain nite everywhere, and p e /2 diverges for large . Since we know approximately how () behaves for large , let us write () = e and try to determine H(). Plugging this form for (x) into d2 () + ( 2 )() = 0 d 2 gives: d d 2 () = e /2 H() d d 2 2 = e /2 H() + e /2 H () d d2 2 2 () = e /2 H() + e /2 H () 2 d d 2 2 2 = e /2 H() + 2 e /2 H() e /2 H () e and thus, [ 2 H() 2H () + H () + ( 1)H() 2 H()]e which can be simplied to H () 2H () + ( 1)H() = 0 . Now the equation y 2y + 2ny = 0 (6.69) is known as Hermites dierential equation. By the condition of Eqn.(6.61), we are restricted to solutions of nite degree; these are the socalled Hermite (6.68)
2 /2 2 /2 2 /2

H()

(6.62)

(6.63)

(6.64) (6.65)

H () + e

2 /2

H ()

(6.66)

=0

(6.67)

Simple bound states polynomials Hn (): H0 () = 1 H2 () = 4 2 2 H1 () = 2 H3 () = 8 3 12

46

(6.70)

H4 () = 16 4 48 2 + 12 H5 () = 32 5 160x3 + 120 It is shown in Appendix E how to solve explicitly Eqn.(6.69). It is also shown in Eqs. (E.16) and (E.17) that, unless the factor n in Eq.(6.69) is a 2 positive integer, the solution to Eq.(6.69) eventually grows like e2 and thus makes the whole wavefunction (x) e
2 /2

e2

(6.71)

divergent. Thus, we rediscover the restriction that H() be a polynomial of nite degree in . With the identication 2n = 1 , we have 2n = 2En 1 1 En = (n + 2 ) , (6.72)

with n a positive integer. Going back to the old variables, we obtain the nth allowed solutions n (x) = Nn Hn m
1

x emx

2 /2

(6.73) (6.74)

n (x, t) = n (x)ei(n+ 2 )t

where Nn is a normalization constant: it is tricky to work out but one ultimately nds: 1 m 1/4 . (6.75) Nn = 2n n! The rst few solutions are plotted in Fig. 6.4.1, with the wavefunction on the left and the corresponding probability density on the right.

Simple bound states

47

0.7 0.6 0.5 0.4 0.3 0.2 0.1 -4 -2 0.6 0.4 2 4 -4 -2

0.5 0.4 0.3 0.2 0.1 2 0.4 0.3 4

0.2 -4 -2 -0.2 -0.4 -0.6 0.6 0.4 0.2 -4 -2 -0.2 -0.4 -4 0.6 0.4 0.2 -4 -2 -0.2 -0.4 -0.6 -4 -2 2 4 -2 0.35 0.3 0.25 0.2 0.15 0.1 0.05 2 4 2 4 2 4 -4 -2 0.35 0.3 0.25 0.2 0.15 0.1 0.05 2 4 2 4 0.2 0.1

Figure 9: The harmonic oscillator wave functions for n = 0, 1, 2, 3 and their respective probability densities. Note the eveness of the solutions.

Simple bound states 6.4.2 The harmonic oscillator wavefunctions

48

Heres an explicit list of the rst few harmonic oscillator wavefunctions: n 0 1 2 3 4 m m m m m


1/4

n (x) emx
2 1/4
2 /2

3/4

x emx )
2 1/4

2 /2

(6.76) emx
2 /2

1/4

1+2x2 m

3/4

(3+2x2 m )
3 1/4

emx
2

2 /2

1/4

312x2 m +4x4 ( m ) 2 6 1/4

emx

2 /2

6.5

(x)-well potential

We now introduce one nal type of potential: the socalled well. The Dirac (x) function will be discussed at greater length in Sec.10.6. For the moment, it is useful to think of the well as a innitely deep well that is innitely thin. First, imagine the function f (x, ) 0 if x < , 1 (6.77) f (x, ) = if x , 0 if x > . in the limit 0. Figure 6.5 gives an idea of f (x, ) for = 10, 100 and 1000. One can see that the function becomes a very very thin spike with decreasing .

In the limit where 0, the spike becomes a Dirac , i.e. (x) = lim f (x, ) ,
0

(6.78)

Simple bound states


10 8 6 4 2 100 80 60 40 20 1000 800 600 400 200

49

-0.4

-0.2

0.2

0.4

-0.4

-0.2

0.2

0.4

-0.4

-0.2

0.2

0.4

Figure 10: A sequence of f (x, ) converging to a function. Here, we have f (x, 1/10), f (x, 1/100), f (x, 1/1000).

where f (x, ) is dened in Eqn.(6.77). Thus, we consider a potential of the form V (x) = (x) , where > 0. This is a discontinuous potential well with no width. The Schrdinger equation for this potential takes the form o d2 (x) (x)(x) = E(x) . 2m dx2
2

(6.79)

(6.80)

Because this is an innite step, there is a discontinuity in (x): (0+ ) (0 ) = 2m


2

(0) .

(6.81)

Since V (x) = 0 for x = 0, and V (0) = , the expression for wavefunction on the left and on right of the potential is (x) = Aex + Bex , x < 0 , Cex + Dex , x > 0 , (6.82)

where, as always, = 2m , = E > 0. 2 Now, if (x) is to remain nite at x = , we must have A = 0 and D = 0. The condition of continuity of (x) at x = 0 yields B =C. (6.83)

Using this in Eqn.(6.81) for the discontinuity of (x) provides another equation: when evaluated at the discontinuity, the jump in (x) gives C C = 2m
2

C ,

(6.84)

Simple bound states with solution =

50

m
2

(6.85)

This is the only possible solution for , and thus there is only one bound state with energy 2 = m2 2
4

2mE
2

E=

m2 . 2 2

(6.86)

The well is useful in many approximations where it replaces the exact potential due to atomic nucleus. Examples include the KrnigPenney model o in solid state physics and simple models bonding and antibonding in the H2 molecule.

Independent modes

51

Multidimensional independent-mode problems

We now consider a class of multidimensional problems that can be reduced to a number of independent problems. The results are applicable to some problems describing a single particles in two or three dimensions, to some problems dealing with many particles in one or several dimensions, or to combinations of several particles in more than one dimensions. Suppose that one can nd variables , so that the Schrodinger equation can be written as i (, , t) = t
2 2 2 + V () + U () (, , t). 2m 2 2m 2 2

(7.1)

Under the usual identications i E , i p , t

p ,

(7.2)

Eqn.(7.1) is nothing than a statement about the total energy of the system, which is now equal to the sum of total energies for the variables , . Note that the masses m and m need not be the same. Assuming (, , t) = (t)(, ) leads to the separation of the time component: (, , t) = eiEt/ (, ) , (7.3) with E the separation constant and where the timeindependent wave function (, ) satises
2 2 2 + V () + U () (, ) = E(, ). 2m 2 2m 2 2

(7.4)

To convert this last equation from a partial to a pair of ordinary dierential equations, we look once again for a separable solution: (, ) = X () N () . This yields N () d2 X () + V ()X () 2m d 2 2 d2 N () + U ()N () +X() 2m d 2
2

(7.5)

= E X() N () . (7.6)

Independent modes Dividing through by X() N () and reorganizing, we obtain d2 X () + V ()X () 2m d 2 2 d2 1 N () + U ()N () =E N () 2m d 2 1 X()
2

52

(7.7)

Since both sides must be equal for all values of and all values of , they must be both equal to a common constant E . Denoting E = E E and rearranging yields d2 + V () X () = E X () , 2m d 2 2 d2 + U () N () = E N () , 2m d 2
2

(7.8) (7.9)

with the constraint E + E = E. Each of the previous two equations can then be solved separately, producing solutions of the form (, , t) = eiEt/ X () N () . (7.10)

Note that we have not specied if , refer to a single particle in two dimensions or to two particles in one dimension. In the former case, one could identify = x, = y. In the latter, one would have = x1 for the rst particle and = x2 for the second. This technique is directly applicable to, for instance, the problem of nding the energy levels of a single particle in a two-dimensional innite well having length Lx and Ly in the x and y directions, respectively. Clearly then, Eqn.(7.8), with V = 0 and the boundary condition X (0) = X(Lx ) = 0 will give nx x 2 sin (7.11) X(x) = Lx Lx while Eqn.(7.9), with U = 0 and the boundary conditions N (0) = N (Ly ) = 0, will give ny x 2 sin . (7.12) N (y) = Ly Ly

Independent modes Furthermore, Enx = Eny =


2 2 2 nx / 2 2 2 ny /

53

2mL2 , x 2 2mLy , = 2m
2 2

E = Enx + Eny

n2 n2 y x + 2 2 Lx Ly

(7.13)

Another example is the isotropic two-dimensional harmonic oscillator, with Hamiltonian H= 1 1 p2 + p2 + m 2 (x2 + y 2 ), x y 2m 2 (7.14)

which can be separated in two one-dimensional oscillators, one along x and the other along y. The possible energies are
1 E = nx + 2 + ny + = (N + 1) , 1 2

(7.15)

where N = nx + ny .

The radial equation

54

Equivalent onedimensional problems: the radial equation

We now consider a class of problems for which we can use our results from one dimensions. When the potential depends only on the combinaison r = x2 + y 2 + z 2 of the x, y, z variables in three dimensions, a change of coordinates from Cartesian to spherical allows one to seek solutions of the timeindependent Schdinger equation in the form of a product o (x, y, z) (r, , ) = R(r)f (, ) , (8.1)

where R(r) and f (, ) are solution to the radial and angular Schrdinger o equations, respectively. The radial solutions R(r) can be considered as onedimensional functions provided that the radius r is properly restricted to nonnegative values.

8.1
If

Separation of variables in three dimensions


px px = i (8.2)

d dx in one dimension, we can pretty much guess that px px = i , py py = i , x y pz pz = i , z

(8.3)

and the timeindependent Schrdinger equation in three dimensions becomes o


2

2m

2 2 2 + 2+ 2 x2 y z

+V(

x2 + y 2 + z 2 ) (x, y, z) = E(x, y, z) . x2 + y2 + z2) (8.4) and

We now take advantage of the special form of V : V ( introduce the spherical coordinates z = r cos , where r = (x2 + y 2 + z 2 )1/2 , = arctan x2 + y 2 , z2 y = r sin sin ,

x = r sin cos ,

(8.5)

= arctan

y x

(8.6)

The radial equation Thus, r = + + z r z z z 2z 1 = + 2 x2 + y 2 + z 2 r 1 + x2 +y2 2


z

55

(8.7) x2 + y 2 1 z2 (8.8) (8.9) (8.10)

1 sin r r r = + + y r y y y 2y = 2 x2 + y 2 + z 2 r 1 y 1 1 + + y2 x2 +y 2 z (x2 + y 2 )1/2 1+ 1 + x2 z2 = cos = sin sin

1 x

(8.11)

1 tan sin + 2 r 1 + tan r sin 1 1 (8.12) + 1 + tan2 r sin cos sin sin cos2 = sin sin + cos2 + (8.13) r cos r sin r sin cos cos sin cos = sin sin + + (8.14) r r r sin After manipulations of a similar caliber, one nds = x + 1 1 + 2 +y 2 z x2 + y 2 + z 2 r 1 + x z2 x 1 1+
x2 y2

x2 + y 2 x (8.15)

1 x2

= sin cos

1 tan cos + 2 r 1 + tan r sin r sin sin 1 2 2 1 + tan r2 sin cos2 cos sin cos = sin cos + r r r sin

(8.16) (8.17)

The radial equation

56

We actually need terms like 2 /x2 . More straightforward but tedious manipulations eventually produce 2 2 1 1 2 + 2+ 2 = 2 r2 + 2 2 x y z r r r r sin 2 1 + 2 2 2 r sin sin (8.18)

Note that this form is set up for separation of variables, as derivatives are neatly separated out. Hence, (r, , ) satises 1 2m r2 r
2

1 + 2 sin r r sin +V (r)(r, , ) = E(r, , ) r2

2 1 (r, , ) r2 sin2 2 (8.19) (8.20)

Assume (r, , ) = R(r)Y (, ) . Inserting this into the timeindependent Schrdinger equation, dividing o through by R(r)Y (, ), and multiplying by 2mr2 / 2 gives, after rearrangement: 1 d R(r) dr d 2mr2 R(r) + (E V (r)) 2 dr 1 1 1 2 = sin + Y (, ) sin sin2 2 r2 (8.21) Y (, ) .(8.22)

The left hand side depends only on r, while the right hand side depends only on the angular variables (, ). If this equality is to hold for every (r, , ), both sides must be equal to a common constant, denoted for convenience by ( + 1) with 0. Thus, we now have the two dierential equation d 1 d 2m ( + 1) r2 R(r) + 2 (E V (r))R(r) = R(r) (8.23) 2 dr r dr r2 1 1 2 sin + Y (, ) = ( + 1)Y (, ) (8.24) sin sin2 2 The eigenvalue equation for r depends explicitly on the potential V (r). The solution to Eqn.(G.43) will therefore depend on V (r); nothing further

The radial equation

57

can be said until we know what V (r) is. On the other hand, the eigenvalue equation for the angular part is always the same and does not depend on the details of V (r), provided that V (r) is a function of r only (this was the original assumption that allowed the separation of variables). Thus, the angular equation can be solved once and for all: this will be done later. Eqn.(G.43) can be further simplied, since 1 d r2 dr r2 d dr R(r) = 1 d 2 r R (r) r2 dr 1 = 2 2rR (r) + r2 R (r) r 2 R (r) + R (r) = r

(8.25)

Observing that

1 d2 d2 2 dR rR(r) = 2 R(r) + , 2 r dr dr r dr 1 d 2 r r2 dr d R(r) dr = 1 d2 rR(r) r dr2

(8.26) (8.27)

we obtain

The radial equation now takes the form ( + 1) 1 d2 2m rR(r) + 2 (E V (r)) R(r) R(r) = 0 . 2 r dr r2 Multiplying through by r, we obtain, using (r) = rR(r), ( + 1) d2 2m (r) + 2 (E V (r))(r) (r) = 0 , 2 dr r2 2 2 d2 ( + 1) (r) + V (r) + (r) = E(r) . 2 2m dr 2m r2 (8.28)

(8.29)

Eqn.(8.29) is nothing but the Schrdinger equation for the potential o Ve (r) = V (r) + ( + 1) . 2m r2
2

(8.30)

The extra term is a centrifugal barrier, that imposes conservation of angular momentum on the radial motion of the particle. We see that, in order to solve Eqn.(8.29), it is not sucient to know V (r) but one must also specify . This parameter will be later identied as the

The radial equation

58

angular momentum quantum number; for the moment, it just enters via the separation constant ( + 1). In spite of the similarities between Eqn.(8.29) and the onedimensional Schrdinger equation, we note that the boundary conditions on (r) are cero tainly dierent from those of a 1-d problem. The variable r is, by geometrical considerations, restricted to r > 0, so we must have, by continuity of the wave function, (r) = 0 for r < 0, and thus (r) = 0 at r = 0. [Nota: Typo in Schaum 8.13]

8.2
8.2.1

The case of hydrogen: V (r) = e2 /4 o r.


Solving the dierential equation 4 2 2 o 4 2 o = me2 me2

Let us dene the Bohr radius: ao = (8.31)

and the dimensionless quantity = r/ao . Then we get d d 1 d d = = dr d dr ao d and thus


2 ( + 1) m2 e4 1 2 m2 e4 d2 () + V () + () 2m (4 o )2 4 d2 2m (4 o )2 4 2 me4 d2 me4 ( + 1) () + V () + () = E() = (8.33) 2 2 d2 2 2 2(4 o ) 2(4 o ) 2

(8.32)

The combination

me4 2(4 o )2

13.6eV

(8.34)

is a convenient energy scale, so we dene E me4 2(4 o )2


2

(8.35)

and rearrange to get the much cleaner expression d2 ( + 1) () + V () + () = () 2 d 2 (8.36)

The radial equation with Let V () = e2 me2 4 o r (4 o ) me4 1 = 2 (4 o )2


4

59

V () V () = , E

E = , E

() = R() . 1 2 V () = .

(8.37)

(8.38)

The radial part of Schrdinger for the Coulomb problem now reads like o ( + 1) d2 2 () + + () = () 2 d 2
0 0

(8.39)

In spherical coordinates, the radial probability density is 2 |R()|2 . If 2 |R()|2 d = |()|2 d (8.40)

is to remain nite, we require () 0 as and () 0 as 0. In the limit , the dierential equation becomes d2 () = () . d2 (8.41)

The solution to this depends on the sign of . If > 0, then () e . which is oscillatory. As we want () 0 for If < 0, then () ei , 0. , we choose () e , so that E = E < To nd the solution for nite , we write () = e (). The function () must now satisfy with () 0 0 (so that () 0 as 0). as in the full dierential equation we Taking the ansatz () = ()e obtain,
d () = e () + e () (8.42) d 2 d2 () = e () + 2 e () + e () d2 = e () 2 e () + e () (8.43)

and thus e
() + 2 e () e () ( + 1) 2 e () = e () 2

(8.44)

The radial equation or

60

( + 1) 2 () = 0. (8.45) 2 Next we consider the small behaviour of this equation: as 0 we get ( + 1) () = 0 () 2 () 2

() 2 () +

(8.46)

Since () 0 as 0, and () = e () 0 as 0, we must have () s with s 0 for small . To determine s, take () s to get: () = s(s 1)s2 , () = ss1 . and insert this in Eqn.(8.46) to obtain s(s 1)s2 2 ss1 ( + 1)s2 = 0 s2 s(s 1) 2 s ( + 1) = 0 (8.47) (8.48)

(8.49)

To solve, we observe that, as 0, the most pathological term is of the form s2 (s(s 1) ( + 1)) . (8.50) To eliminate this term, we need s(s 1) = ( + 1) s = + 1, so () behaves like +1 for small . Note that another solution to Eqn.(8.49) is s = , but this violates the condition that s 0. Furthermore, with this choice, we have, as 0, () 1 (2 ( + 1)) , (8.51) which always remains nite as 0: the choice s = + 1 save the wavefunction for small . To interpolate between 0 and nite , we write () = +1 L(). Since () = +1 L()e must remain nite as , the function L() is restricted to functions such that

lim +1 L()e

0.

(8.52)

Using () = +1 L() in Eqn.(8.45), we obtain the derivatives () = ( + 1) L() + +1 L () () = ( + 1) 1 L() + 2( + 1) L () + +1 L () (8.53) (8.54)

The radial equation

61

So our dierential equation Eqn.(8.45) is turned into a dierential equation for L(): +1 L () + 2( + 1) L () + ( + 1) 1 L() 2 ( + 1) L() 2 +1 L () + 2 L() ( + 1) 1 L() = 0 , (8.55) or, after factoring a common nonzero factor of : L () + 2 + 2 2 L () 2 ( + 1) 1 L() = 0 Let = 2 , d d d d = =2 . d d d d

(8.56) (8.57)

Then L () = 4L () = 2 L () 2 L () = 2 L () . (8.58) (8.59)

This transforms the second order dierential equation Eqn.(8.56) into 1 2 L () + (2 + 2 ) L () ( + 1 )L() = 0 (8.60)

The term in bracket is an example of Laguerres dierential equation: xy + (k + 1 x)y + qy = 0 , (8.61)

itself a special case of the conuent hypergeometric dierential equation, Eqn.(G.44): zu (z) + (c z)u (z) au(z) = 0 . Here we have x = , c = 2( + 1), k = 2 + 1, 1 a = ( + 1 ) = q, (8.62)

The solutions to this are generalized Laguerre functions Lk (x). These q functions remain nite as x only if a is a negative integer, in which case these functions are generalized Laguerre polynomials. Hence we need 1 a = ( + 1 ) Z . (8.63)

The radial equation For this to occur, we must have 1 Z, so set = 1/n2 to get 1/ = nr . This, in turn, implies that r E E E = E = 2 En = 2 . nr nr Since a 0, we have the extra condition + 1 nr 0 , or nr + 1, which restricts the possible values of . 8.2.2 Hydrogenoid Wave Functions

62

(8.64)

(8.65)

(8.66)

A solution to the conuent hypergeometric equation xy (x) + (c x)y (x) ay(x) = 0 that remains nite at x = 0 and x is the function y(x) = 1 F1 (a, c; x) = 1 + a(a + 1) x2 a(a + 1)(a + 2) x3 ax + + + ... c 1! c(c + 1) 2! c(c + 1)(c + 2) 3!

with a Z . Comparing with our equation L () + (2(l + 1) ) L () ( + 1 nr )L() = 0 , we see that y() = 1 F1 ( + 1 nr , 2( + 1); ). The associated Laguerre polynomials are related to 1 F1 via Lk () = a (k + a)! 1 F1 (a, k + 1; ). k!a! (8.68) (8.67)

Going back to the original variable 2r , = 2 = nr ao

The radial equation we have thus found nr , (r) = and 2r nr a o


+1

63

er/nr ao 1 F1 ( + 1 nr , 2( + 1);

2r ) ao nr

(8.69)

2r , nr ao (8.70) where the radial wave function Rnr (r) has been properly normalized. +1 The rst few L2+1nr (x) are given below. They follow Batemans convention, and are those produced by Mathematica c . Rnr (r) = 2 nr ao er/nr ao 2r nr ao
+1 L2+1nr

(nr 1)! 2nr (nr + )!

1 2

nr 1 2 3

+1 L2+1nr (x) 0 1

0 2x 1 1 0 1 (6 6x + x2 ) 2 1 4x 2 1 0 1 (24 36x + 12x2 x3 ) 6 1 1 (20 10x + x2 ) 2 2 6x 3 1


1 0 24 (120 240x + 120x2 20x3 + x4 ) 1 1 (120 90x + 18x2 x3 ) 6 2 1 (42 14x + x2 ) 2 3 8x 4 1

The rst few normalized complete hydrogen radial wave functions Rnr (r) are thus

The radial equation

64

nr 1 2

Rnr (r) 0 2er/a0 0 1 1


3/2

0 1 2

a0 (2 r/a0 ) er/2a0 3/2 2 2a0 r er/2a0 5/2 2 6a0 (2r2 18ra0 + 27a2 ) 0 2er/3a0 7/2 81 3a0 2r (4 2r/3a0 ) er/3a0 5/2 27 3a0 2 2r2 r/3a0 e 7/2 81 15a0

These wave functions agree with those in Schaums.

8.3

Isotropic oscillator in three dimensions


1 V (r) = m 2 r2 . 2

We next consider the case of a threedimensional isotropic oscillator, with (8.71)

The radial equation for (r) = rR(r) becomes 2m d2 (r) + 2 2 dr 1 ( + 1) E m 2 r2 (r) (r) = 0 2 r2 (8.72)

For = 0, this is just the ordinary 1-d harmonic oscillator. For = 0, we 1 are working in an eective potential V (r) = 2 m 2 r2 + 2mr2 ( + 1), which drives the particle away from the origin as r 0. Set m k2 E 2mE = k2, = , = = (8.73) 2 2

The radial equation

65

nr =1,L=0 2 0.5 1.5 1 0.5 0.4 0.3 0.2 0.1 1 2 3 4 5 1

nr =1,L=0

nr =2,L=0 0.6 0.4 0.2

0.2 0.175 0.15 0.125 0.1 0.075 0.05 0.025 8 10 2

nr =2,L=0

10

nr =2,L=1 0.14 0.12 0.1 0.08 0.06 0.04 0.02 2 4 6 8 10

0.2 0.175 0.15 0.125 0.1 0.075 0.05 0.025 2

nr =2,L=1

10

nr =3,L=0 0.14 0.3 0.2 0.1 0.12 0.1 0.08 0.06 0.04 0.02 5 10 15 20 25 5

nr =3,L=0

10

15

20

25

Figure 11: The rst few hydrogeno wave functions and their respective probad bility densities.

The radial equation to get

66

d2 ( + 1) (r) + k 2 2 r2 (r) = 0 2 dr r2 For large r, we have

(8.74)

d2 (r) 2 r2 (r) , (8.75) 2 dr which, in a manner similar to the onedimensional oscillator, produces the asymptotic behavior 2 (r) rs er /2 , (8.76) as long as s is nite. For small r, we have ( + 1) d2 (r) (r) , (8.77) 2 dr r2 which produces, as in manner similar to the hydrogen atom solution, (r) r Thus, set (r) = r
+1 +1

(8.78)

f (r)e

r2 /2

nite. Now (8.79) f (r) (8.80)

1 d 2 (r) = ( + 1 r2 )f (r) + rf (r) r er /2 dr 2 2 d 1 1 r2 /2 ( + 1) + r2 3 + r2 2 (r) = r e 2 dr 2 +2r + 1 r2 f (r) + r2 f (r) , so that we get the dierential equation

1 r2 /2 re r f (r) + 2( + 1 r2 )f (r) + r k 2 (2 + 3) f (r) = 0 . 2 (8.81) To proceed, we need to make a change of variables similar to the one dimensional case: set t = r2 and obtain d dt d d d = = 2r = 2 t , (8.82) dr dt dr dt dt d d2 d 2 d d2 = 2 t 2 t = 2 t + 2 t 2 , dr2 dt dt dt 2 t dt = 2 d d2 + 4t 2 . dt dt (8.83)

The radial equation This converts our dierential equation to t t (2f (t) + 4t f (t)) + 2( + 1 t)2 f (t) t 1 k 2 (2 + 3) f (t) = 0 +2 2 Thus: tf (t) + + 3 t f (t) + 2 (2 + 3) k2 4 4 f (t) = 0 .

67

(8.84)

(8.85)

We now compare Eqn.(8.85) with the standard form of the conuent hypergeometric dierential equation: xy + (c x)y ay = 0 and nd
3 f (t) = 1 F1 (nr , + 2 ; t) ,

(8.86) (8.87) n r Z+ . (8.88)

where a=

(2 + 3) k2 4 4

= nr ,

This last requirement must be enforced if the series solution


1 F1 (a, c; x)

=1+

a(a + 1) x2 a(a + 1)(a + 2) x3 a x+ + + ... c c(c + 1) 2! c(c + 1)(c + 2) 3!

is to terminate at some nite degree, thereby guaranteeing that (r) 0 as r . Alternately comparing with the associated Laguerre equation xLk (x) + (k + 1 x)Lk (x) + nLk (x) = 0 n n n we nd f (t) = Lnr (t) Going back to the original variables, we nd 2 +3 E = nr + E= 2 4 2nr + + 3 2 = n+ 3 2 , (8.90)
+1/2

(8.89)

The radial equation

68

with n = 2nr + . Since nr Z+ , i.e. nr = 0, 1, 2, 3, . . . whereas = 0, 1, 2, . . ., we nd n = 0, 1, 2, . . . subject to the restrictions = n, n 2, n 4, . . . , 0 n, n 2, n 4, . . . , 1 if n is even if n is odd (8.91)

The solutions, properly normalized, work out to Rn (r) = ( + 1/2)!nr ! (nr + + 1/2)! + Lnr 1 1
3 2 +1/2

3 2

2 +3/2 er

2 /2

r Ln+1/2 (r2 ) r

(8.92)

nr 0 0 1 0 1 0 2 1 0

(r2 )

Rn (r)
23/4 1/4 25/4 1/4

0 0 1 1 0 2 2 2 1 3 3 3 0 4 2 4 4 4

er
2 3

2 /2

r er
3 2

2 /2

r2

2 3/4 3 1/4

r2 er
2 /2

2 /2

1
5 2

7/4 4 1/4 15

r2 er r
5 2

r2

5/4 4 1/4 15

r2 er
2 /2

2 /2

1
1 (15 8 7 2

4 20r2 + 42 r4 )

2 9/4 105 1/4

r3 er

3/4 1 1/4 (15 30

20r2 + 42 r4 )er r2
7 2

2 /2

r2

2 7/4 105 1/4

r2 er
2 /2

2 /2

11/4 8 3 105 1/4

r4 er

8.4
8.4.1

Constant potentials in three dimensions


Spherical Bessel functions

Suppose V = Vo , some constant. Then, the radial part of the Schrdinger o equation can be written as,
2

2m

d2 ( + 1) 2 dr r2

(r) + Vo (r) = E(r),

(r) = rR(r) (8.93)

The radial equation which we rewrite as


2 d2 ( + 1) (r) + (r) = (E Vo ) (r) 2 2m dr 2m r2 Suppose E > Vo , and dene 2

69

(8.94)

2m (E Vo )
2

(8.95)

The radial equation takes the form ( + 1) d2 (r) + k 2 (r) = 0 2 dr r2 Let = kr, which produces k2 or k2 d2 () ( + 1) 2 () + k 2 () = 0 d2 (8.98) d d d d = =k , dr d dr d d2 d2 = k2 2 , dr2 d (8.96)

(8.97)

( + 1) d2 () () + () = 0 (8.99) 2 d 2 Consider rst the case where = 0. This is equivalent to the one dimensional case: the possible solutions are 0 () = sin or 0 () = cos . Here, we use the sine and cosine functions rather than the exponentials i e because it is easier to enforce the requirement 0 (0) = 0; this means that we must keep only 0 () = sin as a valid solution in a region that includes = 0. For = 0 and small we have as usual () +1 . (Note that, for large values of , () A sin + B cos . Thus we set () = +1 (). Now, d () = ( + 1) l () + +1 () (8.100) d d2 () = ( + 1) 1 () + 2 ( + 1) () + +1 () (8.101) d2 Substituting in Eqn.(8.99), we nd +1 ()+2 ( + 1) ()+ ( + 1) 1 () ( + 1) 1 ()+ +1 () = 0 (8.102)

The radial equation or () +

70

2 ( + 1) () + () = 0 .

(8.103)

Note that, contrary to the harmonic oscillator or to the hydrogen atom, we get no real mileage out of the condition because the solution A sin + B cos . is oscillatory: this is because there is no forbidden region where we expect the character of the solution to be a decreasing exponential. Now consider the derivative of Eqn(8.103): () Setting = , we get Eqn.(8.104) becomes + 2 2 ( + 1) 2 ( + 1) + ( + ) + = 0 2 (8.108) = , = + , = + + = 2 + , (8.105) (8.106) (8.107) 2 ( + 1) 2 ( + 1) () + () + () 2 (8.104)

which can be reorganized to + (2 + 2 ( + 1)) + + 2 (l + 2) + = 0. 2 ( + 1) 2 ( + 1) + = 0, (8.109)

1 Thus, if is a solution for , then = is a solution for + 1. This is a recursion relation for the solutions. We will write this recursion as

1 +1 () = ,

(8.110)

using to dierentiate the various solutions. To start the recursion, we note that we already know the form of the solution for = 0: it is simply 0 () = sin . Since our recursion is for ()

The radial equation rather than (), we have 1 sin , 1 1 0 () = 1 () = 0 () =

71

1 1 cos 2 sin

(8.111) to label (8.112)

and so forth. Now recall that () = +1 (), and R() = ()/. So, using the sequence of solutions that go to 0 as 0, we have () = +1 () , with () = 1 d d 1 () = 1 d d 0 () = 1 d d 1 sin . R () = ,

(8.113)

Now, we dene the spherical Bessel function j () by j () = (1) 1 d d 1 sin , (8.114)

so that R () = j () (the overall sign is immaterial) is a solution that satises the boundary conditions at 0. j () satises the recursion relations j +1 () = 2 +1 j () j 1 () (8.115) (8.116)

d j () = j () j +1 () . d The rst few j () functions are: j () 0


1

sin
1 2 3 3

1 1 cos +

sin
1

2 3 cos + 2 3 4 5
15 3 + 1 10 2

sin
15 4

cos + cos +
1

6 2

sin
45 3

105 + 4 945 + 5

105 5

1 420 4

sin +
15 2

105 3

cos +

945 6

sin

The radial equation

72

L=0 1 0.8 0.6 0.4 0.2 0.2 5 -0.2 L=1 0.4 0.3 0.2 0.1 5 -0.1 5 L=2 0.3 0.2 0.1 5 -0.1 L=2 0.25 0.2 0.15 0.1 0.05 5 -0.05 -0.1 10 15 20 1.2 1 0.8 0.6 0.4 0.2 5 10 15 20 1.2 1 0.8 0.6 0.4 0.2 5 10 15 20 1 0.8 0.6 0.4 0.2 10 15 20 5 1 0.8 0.6 0.4

L=0

10 L=1

15

20

10 L=2

15

20

10 L=2

15

20

10

15

20

Figure 12: The spherical Bessel functions of the rst kind j () (left) and the corresponding probability densities (right) 2 j 2 (). Notice how the probability density goes to 0 near = 0, which makes these functions suitable to describe particles that have access to the region of small .

The radial equation

73

Of course, we have only considered solution that are 0 at = 0. In some problems, there are regions where = 0 is excluded, for instance because a barrier or some other consideration preclude the particle from reaching the origin. In such a problem, we must then also consider the solution 0 () = cos as acceptable. Since the recursion relation simply starts with cos rather than sin , we have another family of solutions, denoted by n () and dened by cos 1 d (8.117) n () = (1) +1 d For these we have: n ()
1 0 cos 1 1 sin 1 2

cos
1

2 3 sin + 33 + 3 4 5
15 3 + 1 10 2 105 3

cos
15 4

sin +

6 2

cos
45 3

105 + 4 945 + 5

sin + 105 + 5
1

1 420 4

cos
15 2

sin + 945 + 6

cos

When functions of an exponential type, such as ei , are required, one use spherical Hankel functions of the rst kind, which are morally the equivalent of eix = cos x + i sin x , and dened by h () iei
ei (i 2 (1)

0 1 2 3 4

+ ) + 3i + 2 )

iei (3 3 4 5

ei (15i 15 + 6i2 + 3 ) ei (105i 105 + 445i2 + 103 i4 )

The radial equation

74

L=0 1 0.75 0.5 0.25 5 -0.25 -0.5 -0.75 -1 L=1 1 0.75 0.5 0.25 5 -0.25 -0.5 -0.75 -1 L=2 1 0.75 0.5 0.25 5 -0.25 -0.5 -0.75 -1 L=3 1 0.75 0.5 0.25 5 -0.25 -0.5 -0.75 -1 10 15 20 4 3.5 3 2.5 2 1.5 1 0.5 5 10 15 20 4 3.5 3 2.5 2 1.5 1 0.5 5 10 15 20 4 3.5 3 2.5 2 1.5 1 0.5 5 10 15 20 1 0.8 0.6 0.4 0.2 5

L=0

10 L=1

15

20

10 L=2

15

20

10 L=3

15

20

10

15

20

Figure 13: The spherical Bessel functions of the second kind, or Neumann functions, n () (left) and the corresponding probability densities (right) 2 n2 (). Notice how the probability density does not go to 0 near = 0: these functions cannot describe particles that have access to the region of small .

The radial equation

75

There are also spherical Hankel functions of the second kind, which are (1) conjugate to h . 8.4.2 The Innite Spherical Well

Consider the spherical well dened by V (r) = 0 if r < a , if r > a .

Dene, as before, k = 2mE/ 2 . By continuity of R(r), R(r) = 0 for all r > a. The only acceptable solution to the radial equation is thus, R (kr) = Aj (kr), where A is some normalization constant. The boundary condition R(r) = 0 at r = 0 precludes the use of the n (kr) function. Since we must have R(r) = 0 at r = a, we see that the energy levels are determined via k through the condition j (ka) = 0. As j0 (ka) = sin(ka) , we have as usual, the condition ka ka = n , n = 1, 2, 3, . . . or kn =
2 2

n . a
2 2 2

(8.118)

kn These states have energies En given by En0 = 2m = n2ma2 . For = 1 we need to solve j1 (ka) = 0. Plotting this function we nd the approximate zeroes as:

ka = 4.4934, 7.725, 10.9041, 14.0662, 17.2208 , so we have E11 = E21 E31 Similarly for (4.49)2 , 2m a2 2 (7.725)2 , = 2m a2 2 (10.9041)2 , etc . = 2m a2
2

( = 1)

(8.119)

= 2, we need the zeroes at j2 (ka), which are found to be ka = 5.76, 9.10, 12.32, 15.51, 18.69 , ( = 2)

The radial equation and so E12 E22 (5.76)2 , = 2m a2 2 (9.10)2 , etc . = 2m a2


2

76

(8.120)

It is therefore convenient to make a table of the zeroes of j (ka) n 1 2 3 4 5 8.4.3 =0 2 3 4 5 =1 4.49 7.73 10.90 14.07 17.22 =2 =3 =4 =5 =6 5.76 6.99 8.18 9.35 10.51 9.10 10.41 11.70 12.97 14.20 12.32 13.70 15.04 16.35 17.65 15.51 16.92 18.30 19.65 20.98 18.69 20.12 21.52 22.90 24.26

The Finite Spherical Well V0 if r < a , 0 if r > a ,

Suppose now V (r) = (8.121)

where V0 > 0. Let = E so that, for bound states with E < 0, we have > 0. Dene, as was done for the onedimensional case in Eqn.(6.20), k= 2m (V0 )
2

2m ( )
2

(8.122)

The wave function inside the well must be of the form R(r) = Aj (kr). Outside the well, only the solution which decreases exponentially with r is admissible. For = 0 this is clearly R(r) er (1) = h0 (ir) , r
(1)

(8.123)

so, for = 0 we nd, by recursion, R(r) = Bh (ir). (Note that, since the problem has spherical symmetry, the angular momentum is conserved so that the same value of must be used on both sides of the discontinuity.

The radial equation

77

Now, in any region the wave function R (r) is a linear combination of spherical Bessel functions, which, in particular, satisfy (see Eqn.(8.115)): d d j (kr) = k j () , dr d = k = r kr j (kr) j +1 (kr) , (8.124) (8.125)

j (kr) k j +1 (kr)

d (1) h (ir) = h (ir) i h +1 (ir) dr r and j +1 (kr) = h +1 (ir) = for 2 +1 kr 2 +1 ir j (kr) j 1 (kr) n (ir) n 1 (ir)

(8.126) (8.127)

1. We can use this to our advantage. From continuity at r = a, we have Aj (ka) = Bh (ia) .
(1)

(8.128)

From continuity of the derivatives at r = a, we have A d d j (kr)|r=a = B h (kr)|r=a . dr dr j (ka) h (ia) . = j (ka) h (ia) Using Eqns.(8.124) and (8.125), we obtain a k j +1 (ka) h +1 (ia) . = i j (ka) a h (ia) (8.131) (8.129)

Their ratio eliminates A and B to yield (8.130)

Using now Eqns.(8.126) and (8.127), this further simplies to j 1 (ka) h 1 (ia) 2 +1 2 +1 k i , = a j (ka) a h (ia) (8.132)

The radial equation or, nally, h 1 (ia) j 1 (ka) = i (1) k j (ka) h (ia)
(1)

78

(8.133)

which is generally simpler since the spherical Bessel functions of lower degree have less complicated denominators. Let us apply this general analysis to = 0, just to see that we really recover what we know from the analysis of odd functions (since R(r) = 0 at the origin) of the onedimensional case of section 6.3. We cannot apply directly Eqn.(8.133) directly, because we have not dened j1 . First, we need explicitly the following four functions sin(ka) , ka 1 i i(ia) (1) e = ea , h0 (ia) = (ia) a sin(ka) cos(ka) j1 (ka) = + , ka (ka)2 1 i (1) ei(ia) (i + ia) = 2 2 ea (1 + a) . (8.134) h1 = 2 (ia) a j0 (ka) = The two parts of Eqn.(8.131) then read k cos(ka) k sin(ka) + j1 (ka) 1 ka (ka)2 k = k cot(ka) + , (8.135) = sin(ka) j0 (ka) a ka i a (1) i 2 2 e (1 + a) h1 (ia) a = 2 2 (a)(1 + a) , = i (1) 1 a a h0 (ia) e a 1 + (8.136) = a so that Eqn.(8.131) itself reads k cot(ka) + as before. 1 1 = + , a a cot(ka) = , k (8.137)

The radial equation

79

Of course, the solutions are not necessarily restricted to spherical Bessel functions of the rst kind if the particle cannot reach the origin: in such cases, there is no grounds to dismiss the second solution, of the type n .

8.5

The Morse potential

Consider nally an example of a potential solvable exactly for l = 0, and which is useful for the analysis of many molecules. V (r) = D e2(rr0 )/r0 2e(rr0 )/r0 For = 0, the radial part of the Schrdinger equation becomes; o d2 () + 2 + 2 2 e 2 e2 () = 0 2 d where = (r r0 ) /r0 , 2 = 2mD
2 2 r0 ,

(8.138)

(8.139)

2 =

2mE
2

2 r0 > 0 .

(8.140)

since E < 0 for bound state (as a consequence of V 0 as r ). The parameters and D depend on the molecule. Let 2 e . (8.141) y= With this somewhat inspired change of variables, d dy d d = = 2e , d dy d dy d = y , dy 2 d d d = y y = 2 y d 2 dy dy 2 d 2 d + 2 y = y 2 dy dy

(8.142) d d2 +y 2 dy dy , (8.143)

The dierential equation, written in terms of y, is then 2 y 2 (y) + 2 y (y) + 2 + y 2 2 y (y) = 0 4 (8.144)

The radial equation

80

This is, in fact, closely related to the dierential equations that weve seen before. For large y (which corresponds physically to large e(rr0 )/r0 , i.e. to values of r near 0, we need the function to go to zero so that it can be square-integrable. In this regime we have 1 (y) + y (y) (y) 0 4 with solution (y) y s ey/2 , where s is nite. This works since 1 (y) = sy s1 ey/2 y s ey/2 2 (8.146) (8.147) (8.145)

1 (y) = s (s 1) y s2 ey/2 sy s1 ey/2 + y s y s ey/2 4 so that 1 1 (y) + (y) + (y) y 4

y s1 1 s 1 y = ey/2 s (s 1) y s2 sy s1 + y s + sy s2 4 2 4 1 1 1 + s2 y 2 sy 1 y 1 , = ey/2 4 2 4 s 1 s2 0. (8.148) ey/2 2 y y 2y On the other hand, for small values of y, 2 (y) 2 2 (y) 0 . (y) + y y Thus, if y s , we have = s (s 1) y s2 , which gives, for small y: s(s 1)y s2 + sy s2 y s2 2 s2 y = 0, 2 2 = 0, s2 s + s 2 = sy s1 , (8.150) (8.149)

(8.151)

The radial equation

81

with solution s = . Since > 0 and is also > 0 on physical grounds, we choose s = so 0 as y 0. Thus we write:

(y) = y / e 2 y f (y) where f (y) is a function which interpolates between y 0 and y . With this ansatz, the dierential equation 1 (y) + (y) + y becomes, using 1 y/2 1+/ e y [(2 y) f (y) + 2yf (y)] 2 1 y/2 2+/2 e (y) = e 2 y 2 4y + 4 ( ) f (y) 2 4 +4y (2 y) f (y) + 42 y 2 f (y) . (8.152) (y) = After straightforward but tedious manipulations, we eventually obtain ey/2 e1+/ (2yf (y) + (2 2y + 4) f (y) ( + 2 2) f (y)) = 0 2 (8.153) We now need to reorganize so that we can compare with the magic formula. yf (y) + (c y) f (y) af (y) = 0 f (y) = 1 F1 (a, c; y) Dividing our dierential equation by 2 : yf (y) + 1 y + from which we extract c=1+ 2 , a= 1 + . 2 (8.155) 2 f (y) 1 + 2 f (y) = 0 , (8.154) 1 1 2 1 + 2 y2 y 4 (y) = 0

The hypergeometric function 1 F1 (a, c; y) is a nite polynomial if a = n, with n Z+ . The series is required to terminate by asymptotic condition

The radial equation y s ey/2 with s nite. Hence 1 2 1 1 = + n+ 2 2 1 = n+ 2 = n n+ =


2 2

82

1 n+ 2

2 n +

1 2

+ 2

(8.156)

2 Going back to the original variables, with 2 = 2mEr0 / 2 , we nd 2

E =

2 2mr0

1 n+ 2 n+ 1 2

1 2 n + 2 2 2 2mr0
2

1 2
2

2mD
2

2 2mr0

2 r0

= D +

2 2 2 2mr0

n+

(8.157)

Finally, since the classical frequency of small oscillation in this problem is 2 = 2D , we note that mr2
0

2 = 2 mr0 and thus

2 2mDr0 1 = 2 2 r0

2 22 mDr0 = 4 m2 r0

22 D = 2 mr0 2

(8.158)

2 2 ( ) 2 = mr2 = 2 2 2mr0 2mr0 2 0 2

(8.159) 2

so that

1 E = D + n + 2 =

1 n+ 2
2 2mDr0 2

(8.160)

with . (8.161)

The angular equation

83

The angular equation

Recall that, in spherical coordinates, the Schrdinger equation for the wave o function (r, , ) reads 1 2m r2 r
2

1 + 2 sin r r sin +V (r)(r, , ) = E(r, , ) r2

2 1 (r, , ) r2 sin2 2 (9.1)

Separation of the angular and radial variables (r, , ) = R(r)Y (, ) . leads to 1 d R(r) dr d 2mr2 R(r) + (E V (r)) 2 dr 1 1 1 2 = sin + Y (, ) sin sin2 2 r2 (9.2)

Y (, ) . (9.3)

Denoting the separation constant by ( + 1) for convenience, we are lead to the angular equation 1 sin sin + 1 2 sin2 2 Y (, ) = ( + 1)Y (, ) (9.4)

The solutions to Eqn.(9.4) are the topic of this section.

9.1

Separation of the azimuthal and polar variables.

Eqn.(9.4) is still a partial dierential equation. To solve, we need further separation between the polar and azimuthal angles. Let us write Y (, ) = () (). Inserting this in the angular equation, dividing through by ()(), multiplying by sin2 and rearranging gives 1 sin () sin 1 d2 () (9.5) () + ( + 1) sin = () d2
2

The left hand side depends only on , and the right hand side only on . Thus, for the equality to hold always, both sides must be equal to a constant, denoted by m2 .

The angular equation From this, we can solve immediately for (): d2 eim () = m2 () = () = d2 2

84

(9.6)

Finally, if the function () is to be 2periodic, we must restrict m to integer values. In other words, since a rotation about z by 2 should physically bring us back to where we started, we must impose the boundary condition ( + 2) = (), which leads to the restriction on m.

9.2

The equation
1 d sin d d d m2 () sin2

Coming back to the -equation, we now get sin () + ( + 1)() = (9.7)

The same equation in the variable occurs for +m or m. Let = cos . Then d d 1 d d = = d d d sin d d d = 1 2 d d d 1 d d sin = (1 2 ) 1 2 2 )1/2 d (1 d d (9.8) (9.9) (9.10)

1 d sin d

with the two minus signs from Eqn.(9.9) cancelling, so that, in terms of , we now have d d m2 (1 2 ) () + ( + 1) () d d 1 2 d m2 d2 () = 0 (9.11) = (1 2 ) 2 () 2 () + ( + 1) d d 1 2 This is not quite the standard form. We rst set () = (1 2 )|m|/2 u() () = (sin )|m| u() (9.12)

The angular equation and rewrite Eqn.(9.11) using:

85

d (1 2 )|m|/2 u() = |m| (1 2 )1+|m|/2 u() + (1 2 )|m|/2 u () , d d2 (1 2 )|m|/2 u() d 2 = (1 2 )1+|m|/2 (1 + (|m| + 1) 2 ) |m| u() +2|m|(1 2 ) u () + (1 2 )2 u () . (9.13) to obtain (1 2 )u ()2 (|m| + 1) u ()+( ( + 1) |m|(|m| + 1)) u() = 0 . (9.14) To bring this to the standard form, we make a nal change of variable: = 1 2z , Changing d/d to d/dz produces z(1 z)u (z) + (|m| + 1 2(|m| + 1)z) u (z) + ( ( + 1) |m|(|m| + 1)) u(z) = 0 , which is of the 2 F1 form with c = |m| + 1 , a = |m| , b = |m| + + 1 . (9.17)
1 z = 2 (1 ) .

(9.15)

(9.16)

We now need to look at the boundary conditions. In terms of , our solution is


1 u() = 2 F1 (|m| , |m| + + 1 , |m| + 1; 2 (1 ))

(9.18)

with = cos . Hence, using Eqn.(9.12), we have () of the form


1 ,m () = (sin )|m| 2 F1 (|m| , |m| + + 1 , |m| + 1; 2 (1 cos )) (9.19)

where the indices and m have been introduces to uniquely identify each solution. The variable cos can range between 1 and 1, so that can cover that range as well, and z can also cover the same range. The diculty with the boundary condition is that, at z = 1, the 2 F1 function diverges unless it is a polynomial containing nitely many terms. This will occur when a or b

The angular equation

86

is a negative integer, which in turn implies that |m| must be a negative integer. Since we know that m is already an integer, we are left with no other option than imposing to be a positive integer greater than |m|. We could, in principle, require that be a negative integer so that |m| + + 1 is a negative integer. We will see, however, that this solution must be rejected on physical grounds. Thus we have almost completely justied the assumption that is a positive integer, an assumption used to solve the radial equation.

9.3

Associated Legendre polynomials

Because of the numerous changes of variables involved in going from Eqn.(9.7) to Eqn.(9.19), it is more practical to study ,m () directly rather than its solution in terms of hypergeometric function. The functions ,m () are the so-called associated Legendre polynomials |m| P () . They are given as follows: for m = 0 , P 0 () = P () is the usual |m| Legendre polynomial. If |m| > , P () = 0 . For other values, one uses lookup tables. m 0 0 1 0 1 2 0 1 2 2 0 1 1 2 2 2 3 3 3 3
3 (1 2 1 2

|m|

()

|m|

()

1 (1 2 )1/2
1 (3 2 2

1 cos sin
1 (3 cos2 2

1)

1)

3(1 )1/2 3(1 2 ) (5 2 3)


1 2

3 sin cos 3 sin2 cos (5 cos2 3)


3 2 (5 cos2 3)

5 2 )(1 2 )1/2 15(1 2 )

15 cos sin2 15 sin3

15(1 2 )3/2

The angular equation They are normalized using


1 1

87

dP m ()P m () =

0
2 ( +m)! 2 +1 ( m)!

if if

= = .

(9.20)

The associated Legendre polynomials are related to the Legendre polynomials P () by dm (9.21) P m () = (1 2 )m/2 m P () . d The Legendre polynomials are themselves obtained by numerous methods, one of which is the socalled Rodriguess formula: P () = d ( 2 1) . 2 ! d 1 (9.22)

or by formal expansion of the generating function G(, h) = (1 2h + h2 )1/2 = P0 () + hP1 () + h2 P2 () + . . .

=
=0

h P () .

(9.23)

9.4

Spherical harmonics

The full solutions to the angular equation are of the form ,m ()m (). It is normal usage to denote the properly normalized combination ,m ()m () by Y m (, ) Y
m (, )

= (1)|m|

( m)!(2 + 1) |m| P (cos )eim 4 ( + m)!

(9.24)

These are known as the spherical harmonics. They satisfy the orthonormalization condition d (Y 1 m1 (, )) Y 2 m2 (, ) = 1 2 m1 m2 = 1 if m1 = m2 and 0 otherwise.
1

(9.25) Note that d = d sin d. The spherical harmonics are ubiquitous in threedimensional problems with spherical symmetry, because separation of variables always leads to

The angular equation

88

the same angular equations regardless of the problem. In other words, the angular part of this kind of problem is always the same, so that the solutions need to be found only once. Because of their usefulness, spherical harmonics have been extensively studied and their properties have been tabulated by many sources. Before we study some of their properties, we establish some basic facts particularly pertinent to quantum mechanics. First, Y m (, ) is complex unless m = 0, owing to the presence of a factor im e . Next, the quantity |Y
2 m (o , o )|

d =

( m)!(2 + 1) 2 ( + m)!

|m|

(cos o )

(9.26)

where d = sin o dd, is the probability of nding a system with angular wavefunction given by Y m (, )in a solid angle of opening d centered around (o , o ). This does not depend on the azimuthal angle . This does not mean that the probability density of a general system will not depend on , just that, if the angular part of the wavefunction can be separated from the radial part and expressed by a single Y m (, ), the probability density will not depend on . This situation is analogous to the separation of time and spatial variables in the timedependent wavefunction (r, , , t). If the wavefunction is separable in t and r, the probability density does not depend on t; the probability can depend on t if the wavefunction is not separable. The best way to plot the probability densities is to use polar plots. In such plots, the magnitude of |Y m (, )|2 is given by the length of the line extending from the origin to the point on the curve. The rst few polar graphs for |Y m (, )|2 are given in Figure 9.4.

9.5

Angular momentum operators

In this section, we would like to understand some the physics associated to the spherical harmonics. Consider the classical angular momentum vector L = r p. In terms of components, and using px px = i , x etc. (9.27)

The angular equation

89

l=0,m=0

l=1,m=0 l=1,m=1

l=2,m=0

l=2,m=1 l=2,m=2

Figure 14: The polar graphs of the rst few |Y |Y ,m (, )|2 .

2 m (, )| .

Note that |Y

2 m (, )|

The angular equation we nd Lx = y pz z py = i Ly = z px xpz = i Lz = xpy y px = i y z z y z x x z y x y x

90

(9.28) (9.29) (9.30)

Converting to polar coordinates to bring out the , variables, we have x = r sin cos y = r sin sin z = r cos and cos cos sin + Lz = i r sin cos sin sin + r r r sin cos sin cos + (9.32) +i r sin sin sin cos r r sin which, after some rapid simplication, can be written cleanly as Lz = i Similarly: Lx = i Ly = i sin cot cos cos cot sin (9.34) (9.35) (9.33) (9.31)

x y z Next, consider L2 L2 + L2 + L2 . This can eventually be brought to the form 1 2 1 2 = 2 L + sin (9.36) 2 2 sin sin This form is important because, up to factors of 2 , this is just the angular equation. In other words, the angular equation can be rewritten L2 Y
m (, )

( + 1)Y

m (, )

(9.37)

The angular equation

91

The physics of Eqn.(9.37) is simple: spherical harmonics are eigenstates of the operator L2 . Thus, we can associate with them a welldened value of the classical quantity L L, in the sense that the uctuation of L2 is zero when the angular wavefunction is of the form Y m (, ). In other words, spherical harmonics describe states that have welldened value for the magnitude of the total angular momentum. Since the square of the magnitude is 2 ( +1), ( + 1). the magnitude itself is usually dened as Furthermore, note that Y m (, ) is also an eigenstate of Lz : Lz Y
m (, )

= i

(1)|m|

( m)!(2 + 1) |m| P (cos ) eim , 4( + m)! (9.38)

= m (1)|m| = m Y
m (, )

( m)!(2 + 1) |m| P (cos ) eim , 4( + m)!

since the dependence of Y m (, ) is of the form eim . Hence, when the angular portion of a wavefunction is of the form Y m (, ), the system described by this wavefunction has a welldened value of the projection Lz of the angular momentum vector L, i.e. Lz = 0 for such states. We are now in a position to justify physically the choice of > 0 in Eqn.(9.19). Clearly, the projection Lz of L on the z axis cannot be greater ( + 1). In other words, |m| must always be than the length L L = smaller than , which is the last piece required to show that must be a positive integer.

92

Part II

Bras and kets


In this part, we will introduce a powerful notation: bras and kets. This allows us to introduce the position and momentum representations, the notion of state vector, and to illustrate further properties of wavefunctions.

Bras and kets

93

10
10.1

Bras, kets and abstract state vectors


Introducing the ket vector

The bound state solutions {i ()} of the timeindependent Schrdinger equao tion all have the following properties: i) They are normalized, i.e.
d i ()i () = 1 ,

where the integral covers the whole range of and d is the appropriate integration element. (If you care to know, d is called an invariant measure.) ii) Two functions with dierent eigenvalues are orthogonal:
d i ()j () = 0 ,

(i = j) .

This is neatly summarized in the single statement


d i ()j () = ij ,

(10.1)

where the Kronecker symbol is dened as ij = 1 if i = j 0 if i = j . (10.2)

Compare these properties with those of the basis vectors 1 = x, 2 = e e y , 3 = z . The former satisfy e i j = ij , e e Thus we see that
d i ()j ()

(10.3)

(10.4)

functions as some sort of inner product. In fact, the denition of Eqn.(10.4) satises all the properties of an inner product.

Bras and kets

94

What else do we know about the properties of basis vectors in ordinary space? Any vector in that space can be written as a linear combination of three linearly independent, preferably orthonormal vector, like 1 , 2 , 3 . e e e Although we will not prove it just now, the solutions of the timeindependent Schrdinger equation also form a basis of orthonormal vectors, in the sense o that any wavefunction can be written as a linear combination of these functions. Now suppose you are given two arbitrary vectors in space, say r and s, and want to compute the inner product r s. One way to do this is to rst write a vector in terms of its components: r = 1 r1 + 2 r2 + z r3 . e e e The component r1 , r2 and r3 are obtained as r1 = 1 r , e r2 = 2 r , e r3 = 3 r . e (10.5)

so that Eqn.(10.5) can be written as r = 1 (1 r) + 2 (2 r) + z (3 r) , e e e e e e = (1 1 +2 2 +3 3 ) r , e e e e e e =


i

(10.6)

i (i r) . e e

In an expression like 1 1 , the dot denotes the operation of taking the inner e e product, so 1 means take the inner product of 1 with whatever is on the e e right. The same kind of expansion can be used for s, and the inner product obtained by the use of r s = r1 s1 + r2 s2 + r3 s3 =
i

ri si .

(10.7)

If the vectors are complex, then we need to use a slightly dierent form:
r s = r1 s1 + r2 s2 + r3 s3 = i ri si .

(10.8)

The complex conjugation is required if the inner product of a vector with itself is to be understood as the length of this vector, something that is necessarily positive. Clearly, with this denition, r s = (s r) . (10.9)

Bras and kets

95

Let us compare all this, and Eqn.(10.7) in particular, with the expression of the inner product of two arbitrary functions f () and g(). For notational purposes, we use f | g to denote this inner product, rather than something like f g. Using Eqn.(10.4), we have f |g f |g

= = =

d f () g() , d g ()f () , g|f

(10.10)

(10.11)

If we remember that an integral is just a continuous sum, we can see that the summation over the components in Eqn.(10.7) is replaced by integral over . This suggests very strongly that, for some specied o , we may think of the number f (o ) as some sort of component of the vector f in the direction of the unit vector o , something which we denote by f (o ) = o | f . In other words, think of f as some abstract vector which we denote by |f . Just like r can be expressed as a column vector explicitly displaying its three components in the basis spanned by i , i = 1, 2, 3, e rx r = ry , rz we can thing of |f as a column vector explicitly displaying its components in the basis spanned by the unit vectors |i , i = , . . . , : . . . . . . f (i1 ) i1 | f rx e1 r ry = e2 r |f = f (i ) = i | f . r= rz e2 r f (i+1 ) i+1 | f . . . . . . (10.12) Note that, for display purposes, one is forced to use discrete indices on the coordinate but it should really be continuous. Thus, the ket vector | is the abstract version of the wavefunction () in the basis spanned by {|i , i = , . . . , } in the same sense that the

Bras and kets

96

vector r is the abstract version of the triple (r1 , r2 , r3 ) of components of r expressed in the basis spanned by 1 , 2 , 3 . e e e

10.2

Wavefunctions in the braket notation

What are the advantages of using | rather than ()? The | does not depend on the choice of basis, just like writing r denotes the vector quite abstractly, without reference to any basis. This is important because, as you know from experience, choosing the right basis often increases the insight into a problem and can lead more rapidly to the correct result. Please note carefully that the basis vectors i have been left quite une specied: they could be basis vectors in spherical, cartesian, or any other coordinate convenient for the problem at hand. Thus, for instance, there are some problems where an abstract ket | m with specied and m is conveniently expressed in spherical coordinates, in which case its explicit expression becomes a Y m (, ): Y
m (, )

, | m

(10.13)

In other problems, the socalled polynomial basis simplies the calculation, and we have z1+m z2m z1 , z2 | m . (10.14) ( + m)!( m)! Likewise, a wavefunction n m (r, , ) solution to the timeindependent Schrdinger equation for the threedimensional harmonic oscillator can be o written as r | n m . In Cartesian coordinates, one would have nx ny nz (x, y, z) = xyz | nx ny nz . (10.15)

The wavefunctions solutions to the onedimensional harmonic oscillator problem are often denoted by the kets |n , so that, using x as the coordinate, we have n (x) = x | n . (10.16)

10.3

The bra vector

Before continuing, it is good to explore the properties of the socalled bra vector f |. This is the continuous analog of the discrete version of symbol

Bras and kets (r) for the vector r, in the sense that the expression rs=
i ri si

97

(10.17)

for ordinary vectors becomes the expression f |g = if we use the continuous sum f| d f () . (10.19) d f ()g() , (10.18)

Note that, just like Eqn.(10.17) has an implicit choice of basis in it (the basis where the components of s and r are si and ri , respectively), Eqn.(10.19) is also basis dependent. This illustrates that, although the inner product r s does not depend on the basis, one must choose a basis in order to actually compute the value of the inner product. Formally, the bra vectors have all the properties of vectors, meaning they can be added together, multiplied by scalars etc. They are called linear functionals in the mathematical literature.

10.4

Projection and closure


Pi = i i e e (10.20)

Consider the combination It is quite clear that, if r is any vector Pi r = i ri , e ri = i r . e (10.21)

In other words, Pi projects from r the component of r that is along the unit vector i . Pi is called a projection operator. e The sum Pi = 1 , l (10.22)
i

the unit operation since, when you feed it an arbitrary vector r, you get r back: Pi
i

r=
i

i ri = r , e

(10.23)

Bras and kets

98

i.e.nothing happens to r. Eqn.(10.22) is called the closure relation, and it expresses the fact that the basis vectors {i } span the space in which r lives. e When expressed in terms of bras and kets, Eqn.(10.22) looks like a continuous sum: 1 = d | | l (10.24) Since 1 does nothing, we have l 1 | l | = | , = | 1 | , l = = d | | , d ()() , (10.25) (10.26)

where | = | , Eqn.(10.11), has been used. Hence, we recover from all these formal properties all the denitions that we started with.

10.5

|x and (x)

We now specialize the discussion to one dimension only, with = x, and dene the ket vector |xo as this vector that satises x|xo = xo |xo , (10.27)

i.e. |xo is an eigenvector of x with eigenvalue xo . We will use the set {|x } as basis vectors and assume Eqn.(10.24) holds and takes the form

1= l

d | x| . x x

(10.28)

Then: |xo =

d | x | xo , x x

(10.29) (10.30)

which implies x | xo = ( xo ) . x In Eqn.(10.30), ( xo ) is the Dirac function, a generalization to conx tinuous variable of the Kronecker delta of Eqn.(10.2). Properties of the function are studied in Sec.10.6.

Bras and kets

99

For the moment, observe that, in accordance with Eqn.(10.12), we have (xo ) = xo | . (10.31)

In accordance with the statistical interpretation of Born, the quantity (xo ) (xo ) dx is the probability of nding the system in a bin of size dx centered around xo . This can be expressed in terms of bras and kets as (xo ) (xo ) dx = | xo xo | dx = | xo | |2 dx , (10.32)

showing how inner products are related to probability densities. We will come back to this later.

10.6
10.6.1

Properties of
(x) in one dimension

Basically, a -function is a generalization to continuous variables of the discrete : 1 if i = j (10.33) ij = 0 if i = j The Dirac -function is dened informally as (x) = with

if x = 0 if x = 0

(10.34)

f (x)(x)dx = f (0) .

(10.35)

As a mathematical object, is really a limit of functions. For instance,


0

lim

(x

2 1 b)2 + 4

= (x b)

(10.36)

is a -function because, if we integrate


0

lim

(x

2 1 b)2 + 4 2

f (x) dx f (x) dx , 1 (x b)2 + 4 2 (10.37) (10.38)

= lim

1 0 2 = f (b) .

Bras and kets Indeed, let


1 (x b) = 2 y , 1 dx = 2 dy .

100

(10.39)

Then, the indenite integral becomes


0

lim

4 1 f ( 2 y + b) dy 2 2) +y 1 y y 1 f () dy , +b = lim b<< f (b) + 2) 0 (1 + y 2 2 y 1 f () = f (b) arctan y + lim dy , (10.40) 0 2 1 + y2 1 2 2 (1 (10.41)

1 f (b) arctan y + 0 ,

and thus Eqn.(10.37) boils down to 1 0 2 lim


1 f (x) dx = f (b) arctan y 2 + 1 2 (x b) 4 (x2 a2 ) =

= f (b) .

(10.42)

To show that

1 ((x a) + (x + a)) , |2a|

(10.43)

letf (x) be any function with f () 0. Then


dx(x2 a2 )f (x) = +

dx(x2 a2 )f (x)
0

dx(x2 a2 )f (x) .

(10.44)

Let y = x2 a2 , x2 = y + a2 x =

y + a2 dx = 1
2|

y+a2 |

dy. Making

Bras and kets these substitutions, we nd


a2

101

dx(x2 a2 )f (x) dy 2 + 2 y + a2 dy

(y) f (

y + a2 ) +

dy y + a2 dy

a2 2

(y) f (

y + a2 )

(y) f ( y + a2 ) + (y) f ( y + a2 ) 2 2 y + a2 y + a2 a 2) f ( a) 1 f ( a + = (f (a) + f (a)) = 2|a| 2|a| |a| 1 f (x)((x a) + (x + a))dx , (10.45) = 2|a| =
a2

which proves the result. Eqn.(10.36) is not the only function that behaves like in some limit. The following is a nonexhaustive list of equally valid choices: (x b) = lim e(xb) / , 0 e|xb|/ = lim , 0 2 sin2 xb . = lim 0 ( xb )2
2 2

(10.46) (10.47) (10.48)

The function satises the formal identities: i) (x) = (x), ii) x(x) = 0, iii) (ax) = |a|1 (x), iv) (x2 a2 ) = |2a|1 [(x a) + (x + a)], v) (a x)(x b) dx = (a b),

vi) f (x)(x a) = f (a)(x a), vii) [f (x)] = (x xo )/|f (xo )|, where xo is such that f (xo ) = 0. To prove any of these statements, one must supply to an identity an arbitrary continuous function f (x) which vanishes at innity, and integrate over x.

Bras and kets 10.6.2 (r) in three dimensions

102

In three dimensions, the threedimensional function is dened to have properties similar to its onedimensional cousin. The basic property d3 r (r ro )f (r) = f (ro ) (10.49)

remains. If a cartesian system of coordinate is chosen, then Eqn.(10.49) can be factored in the obvious way: (r r0 ) = (x xo )(y yo )(z zo ) , with d3 r = dx dy dz. In spherical coordinates, we have (r r0 ) = = r2 1 (r ro )( o )( o ) , sin (10.51) (10.52) (10.50)

1 (r ro )(cos cos o )( o ) . r2

Please note that (r ro ) has a vectorial argument, whereas (r ro ) has a scalar argument: the former is dened in three dimensions whereas the latter is a onedimensional .

10.7

|p and the Fourier transform

N.B.: This is covered in section 10.3 of Haberman. How to go from our notation to his will be claried below. We now introduce the ket |p . This is an eigenstate of the operator p in the sense that p|po = po |po . (10.53) Since |po is an eigenstate of p, |po has a welldened value of momentum. Using the basis vectors {|x }, we can easily obtain the wavefunction describing a particle with a welldened momentum: this is just a free particle with wavefunction x | p = p (x) = Aeipx/ , (10.54) where k = p and where the constant A will be determined below. Hence, we have obtained (almost) an expression for x | p .

Bras and kets Consider now the general ket | and the expression

103

(p) = p |

dx p | x x | , dx A eipx/ (x) , (10.55)

where the complex conjugate of Eqn.(10.54) has been used. Thus, (p) is the Fourier transform of (x). Now, if Eqn.(10.32) gives the probability of nding the system in a bin of size dx around xo , then we will say that (po ) (po ) dp = | po | |2 dp (10.56)

is the probability of nding the system with momentum p between po and po + dp. The probability distribution in momentum space is the Fourier transform of the probability distribution in position space! We now pin down the multiplicative factor A in x | p = Aeipx/ . In the denition of Fourier transform pairs, there is an extra factor 1/2 that must be accounted for. The choice x|p = leads to the expressions 1= l

1 eipx/ 2

(10.57)

dx |x x|

(10.58)

and 1= l

dp |p p| .

(10.59)

for the closure relations in position and momentum space, and to the correct factor of 1/2 in the expression of Fourier transform pairs. We will adopt these denitions. (This is not quite the denition of Haberman. See below.). We can use this to show a useful equality between the function and

Bras and kets Fourier transform. Start from Eqn.(10.30) and insert Eqn.(10.59): (x xo ) = =

104

x | xo ,

(10.60) (10.61) (10.62) (10.63)

dp x | p p | xo ,

1 2 1 = 2 =

dp eipx/ eipxo / , dp eip(xxo )/ ,

showing that (x) is the Fourier transform of constant momentum space function (p) = 1. In other words, a sharp value of x corresponds to a perfectly undetermined momentum distribution, since the momentum distribution is constant (every value of p is as probable as every other value of p). Inversely, we have (p po ) = =

p | po ,

(10.64) (10.65) (10.66) (10.67)

dx p | x x | po ,

1 2 1 = 2 =

dx eipx/ eipo x/ , dx ei(ppo )x/ ,

Note that Haberman, in the tradition of mathematicians, uses the convention dierent from the convention in physics.

Haberman x

(p) = (x) =
1 2 1 2

us p/

f (x) =

F ()eix d

(x)eipx/ dx (p)eipx/ dp

F () =

1 2

x f ()ei d x x

Bras and kets

105

10.8

The x and p representations


x||p = p x | p = peipx/ . p (10.68)

Let us now consider x | p = eipx/ . By denition p|p = p|p so we have

Hence we deduce x||p p i ipx/ e , x i x|p , x

(10.69) (10.70)

Now, using closure on p, we have 1 x|| = p 2 Using Eqn.(10.70), this becomes x|| = p 1 2

dp x||p p | . p

(10.71)

dp

x|p x

p| .

(10.72)

But we are dierentiating w/r to x and integrating w/r to p : we can pull the derivative out of the integral sign: x|| p = i = i = i = i = i
1 dp x | p p | , x 2 1 dp|p p| | , x| x 2 x| 1 | , l x x| , x (x) . x

(10.73) (10.74) (10.75) (10.76) (10.77)

With the previous equation, we have just justied the use of rule p i when p acts on any function of x. x (10.78)

Bras and kets Likewise, since x|xo by denition, we have

106

x|| x

d x|| x | , x xx d x x | x x x | , x

(10.79) (10.80) (10.81) (10.82)

= =

d x (x x)(x) , x x

= x(x) , where Eqn.(10.30) has been used. This justies the use of xx

(10.83)

when x acts on functions of x. Eqns.(10.78) and (10.82) are referred to as the xrepresentation of the operators p and x. Likewise, (x) is called the xrepresentation (or position representation) of the wavefunction or the state vector. Besides functions of x, like (x), we now know that it is possible to express the contents of a state vector | not as a function of the position but as a function of the momentum p. What are the expressions of p and x when they act on functions of p? Start with

p|| x

d p|| x | , x xx d x p | x x | , x

(10.84) (10.85) (10.86) x| , (10.87) (10.88) (10.89) (10.90)

= =

d xeipx/ x | , x d x i ip/ e x p

d p | x x | , x p p| d | x | , , x x = i p p| = i (p) . = i p p = i

Bras and kets Hence, when x acts on functions of p, we have the rule xi . p

107

(10.91)

Note the sign dierence with Eqn.(10.78). Lastly, we have, using p|po = po |po , we have

p|| p

d p|| p | p pp d p p | p p | p

(10.92) (10.93) (10.94) (10.95) (10.96)

= =

d p (p p) p | p

= p p| = p(p) , which shows that, acting on momentum wavefunctions, we have p p.

(10.97)

Using Eqns.(10.91) and (10.96), we can write the Schrdinger equation o in momentum space: 1 p|2 | + p|V (x)| = E p | , p 2m 1 2 p (p) + V (i )(p) = E(p) . 2m p (10.98)

(10.99)

This formulation is useful in some selected problem where V is constant, periodic (like in a crystal) or momentum dependent (as in some nuclear models).

10.9

On the use of |k

In many problems, it is simpler to use the plane wave expression eikx , with k = p. This has the advantage of not having any annoying factors of in

Bras and kets numerous formulae. The adjustments as simple to make: simply set in any formula involving p and replace every p by k. Thus: x|k (x xo ) (k ko ) (k) (x) 1 = eikx , 2 1 dk eik(xxo ) , = 2 1 dx ei(kko )x , = 2 1 (x)eikx dk , = 2 1 (k)eikx dx , = 2

108 =1

(10.100) (10.101) (10.102) (10.103) (10.104)

10.10

Wave packets and Dirac notation

The objective of this section is to illustrate the versatility and power of Dirac notation by solving problems related to the propagation in time of wave packets. 10.10.1 General formulation

Suppose that, at t = 0, we are given an arbitrary state vector |(0) for the system. What is |(t) ? For the free particle, the p representation is particularly useful. We have p2 V = 0 and E = 2m . The solutions to the timeindependent Schrdinger o equation form a continuous set |p . In the xrepresentation, we have x | p = eipx/ , with E =
p2 . 2m

(10.105)

Each |p evolves in time according to |p(t) = |p eiEt/ , (10.106)

where E = p2 /2m. It is worth mentioning that, for every value of E, there is +p and p such that E = p2 /2m. At any time t, we have

1= l

dp |p(t) p(t)| =

dp |p p| .

(10.107)

Bras and kets As we know |p(t) , we can write

109

|(0)

dp |p(0) p(0) | (0) , dp |p(0) p | (0) .

(10.108)

Now, p | (0) is an inner product, i.e. a number, depending on p, possibly complex, but still a number. In other words, it is a complex function of p but not of t. Thus, it is timeindependent, in the sense that once evaluated at t = 0, this inner product remains the same. Let us call this number (p). It is worth mentioning that, for every value of E, there is +p and p such that E = p2 /2m. The time evolution of |(t) is then obtained by using the known evolution of |p(0) in time:

|(t) =

dp |p(t) (p) , dp eip


2 t/2m

(10.109) (10.110)

|(t) =

|p (p) .

As a wave function in position space, we have (x, t) = =

x | (t)

(10.111)
2 t/2m

dp eip

x | p (p) ,
2 t/2m

(10.112) (10.113)

1 2

dp eip

eipx/ (p) .

Alternatively, using the {|k } basis, one obtains in a similar way: 1 (x, t) = 2 where (k) = k | (0) . 10.10.2 Example: the Gaussian wave packet ko (x, 0) = 1 (2)
1 4

dk ei

k2 t/2m ikx

(k) ,

(10.114)

(10.115)

Suppose that

ex

2 /4 2

eiko x ,

(10.116)

Bras and kets

110

where ko is real and measured in [m]1 and is real positive, with units of [m]1 also. The parameter is related to the width of the wave packet. Please note carefully the presence of the eiko x factor. Although the spatial probability density does not depend on ko : 1 2 2 |ko (x, 0)|2 = ex /2 , 2 (10.117)

the wavefunction ko (x, 0) does and this will lead to dierent physical predictions. What is (x, t)? The rst step is to compute (k, 0). This is just the Fourier transform of (x, 0). By denition, 1 (k, 0) = 2

dx

1 (2)
1 4

eikx ex

2 /4 2

eiko x

(10.118)

There are several steps to evaluating this integral, the rst of which is to complete the square:
e( 4 (x/) +i(kko )x+(i(kko )) 1 dx (k, 0) = 1 2 (2) 4 x 1 2 2 dx e+(i(kko )) e( 2 +i(kko )) = 3 (2) 4 x 1 2 2 2 e (kko ) dx e( 2 +i(kko ) ) = 3 (2) 4
1 2 2 (i(kk ))2 ) o

(10.119)

(10.120)

x 1 To compute the integral, let y = 2 +iko so that dy = 2 dx, or dx = 2dy. Then x 2 2 (10.121) dyey = 2 dxe( 2 +iko ) = 2

(This integration is not strictly correct because the limits of integration should be adjusted to reect the changes in variables, but the nal result is correct.) Therefore, we have found: (k) = 2
1/4

2 (kk

2 o)

(10.122)

Notice how the factor of eiko x has crept up in the momentum space wave function, which is now a Gaussian with center shifted to ko .

Bras and kets Now, we need to plug this in 1 (x, t) = 2 1 = 2


111

dk ei
1/4

k2 t/2m ikx

(k)
k2 t/2m ikx 2 (kko )2

(10.123) e e (10.124)

dk ei

It is interesting to verify that this is still a solution of the Schrdinger o equation: i p2 (x, t) (x, t) = t 2m 1/4 2 (x, t) = i t 2 = 2 = 2 Note that i 2 2
1/4

(remember that V=0)!

dk

ei

k2 t/2m ikx 2 (kko )2

dk i
1/4

i k 2 2m k i e 2m
2 2

ei e

k2 t/2m ikx 2 (kko )2

dk

k2 t/2m ikx 2 (kko )2

. 10.125) (

(x, t) = constant (x, t) , t so this is certainly not a solution with welldened energy. Next, we need to compute p2 (x, t) . 2m Since (x, t) is expressed in the x-representation, we have , x 2 2 p2 = , 2m 2m x2 p = i

(10.126)

(10.127)

(10.128) (10.129)

Bras and kets so that 1 p2 (x, t) = 2 = 2 2 2


1/4

112

1/4

dk ei

k2 t/2m

2 ikx 2 (kko )2 e e 2m x2 (ik)2 2m eikx e


2 (kk )2 o

dk ei dk ei

k2 t/2m

2 = 2 (x, t)! = i t It works! 10.10.3

1/4

k2 t/2m

k 2m

2 2

eikx e

2 (kk )2 o

(10.130)

Qualitative feature of the Gaussian wave packet

We now need to evaluate 2 2


1/4

dk ei

k2 t/2m ikx 2 (kko )2

(10.131)

This particular integral can be obtained in closed form. However, to avoid inessential clutter, we will set m = 1 kg and = 1 meter. Using tables, we nd

dk e So

i k2 t/2 ikx (kko )2

2 2 e(x 2i ko 4iko x)/(2i = 2 2+i t

t+4 2 )

(10.132)

(x, t) =

1/4

e(ix

2 2

2 ko t+4ko x)/(2 t4i)

2+i t

(10.133)

Note that, for t = 0, we recover (x, 0) = = as required. 2 1 2


1/4

e(ix

2 +4k x)/(4i) o

2 ,

,, (10.134)

1/4

eiko xx

2 /4

Bras and kets The probability density (x, t)(x, t) is given by P (x, t) = = 2 e(ix
2 2

113

2 ko t+4ko x)/(2 t+4i)

e(ix

2 2

2i t
2 /(4+ 2 t2 )

2 ko t+4ko x)/(2 t4i)

2+i t

2 e2(x ko t) 4+

2 t2

(10.135)

This is a real function (ouf!) At t = 0, we have P (x, 0) = 1 2 1 2 2x2 /4 2 e = ex /2 2 (10.136)

so that checks out. We can easily calculate x(t) . However, before we launch into the mathematics, let us analyze the problem from a physical perspective. For xed t = to , the maximum of P (x, to ) is to be found at x = ko t. If we recall that k = p, we see that, for successive values of time ti+1 > ti , the maximum of the probability density is displaced in the positive x at velocity ko . Thus, the factor of eiko x in the initial ko (x, 0) makes a huge dierence in the physics of the problem, this despite the fact that ko (x, 0)ko (x, 0) does not depend on ko . 2 t2 + 4, Next, the width of the wave packet is proportional to the which occurs in the argument of the exponential. For large negative t, the width is large, decreasing as t approaches zero, and increasing again for increasing positive t. Broadly speaking, for t < 0, the wave packet collect itself until it reaches its thinnest value at t = 0 and then broadens again for t > 0. Let us now see this in more details. The average value of x(t) is given by

x(t)

dx x P (x, t) ko t . (10.137)

Thus, the average position of the wave packet, i.e. the center of gravity, follows the maximum. This is not unexpected. The average momentum is obtained by rst computing the average k and

Bras and kets multiplying by . Thus,

114

p(t)

dk |(k)|2 k ,

(10.138)
2

= =

2 ko ,

dk e(kko ) k ,

(10.139) (10.140)

again expected since the momentum distribution is symmetrical about k = ko . Alternatively, we have d ( x(t) ) = ko , dt Next, consider p

(recall m = 1.)

(10.141)

x2 (t)

dx x2 P (x, t)
2 2 (1 + 4ko )t2

(10.142) (10.143)

1 4+ 4

(If youre worried about the units looking funny, it is because we have set m = 1 and = 1.) Thus x(t) = = x2 x 2 , 1+
2 t2

(10.144) (10.145)

In particular, at t = 0, we have x = 1. Now, p2 : k2

dk k 2 |(k)|2 , (10.146) .
2 t2

1 2 + ko , = 4 and thus p = The product px =


1 2 1 2

(10.147) (10.148)

1+

in accordance with the Heisenberg uncertainty principle.

Scattering states

115

11

Scattering states

We now consider the problem of solving the timeindependent Schrdinger o equation for states with E > V (). From our previous discussion of the qualitative features of the solutions of the timeindependent Schrodinger equation, we have d2 () = (E V ())(), 2m d 2
2

(11.1)

with a positive right hand side: the solution will be of an oscillatory type, with () not necessarily zero. This kind of solution, known as scattering states, describe free (rather than bound) particles. For convenience, we will limit our discussion to onedimensional problems, where = x. Also for convenience, we will consider only cases where V (x) is a rectangular barrier or rectangular well.

11.1

The potential step


0 if x 0, V0 if x > 0.

Recall rst the case where V (x) = We assume E > V0 .


E>V

(11.2)

V0

x=0

Figure 15: The potential step.

Scattering states In such problems, it is convenient to dene k1 = 2mE


2

116

k2 =

2m(E V0 )
2

(11.3)

We assume a particle incoming from , so that, in the region on the left of the barrier, region 1, we have (x) = Aeik1 x + A eik1 x , (x) = A eik2 x , (11.4) (11.5) where A and R are complex. On the right of the barrier, region 2, we have with T complex. As the discontinuity in the potential is nite, the wave function and its derivative must be continuous at the point of discontinuity. This immediately produces the two equations A + A = A, ik1 A ik1 A = ik2 . (11.6) (11.7)

It is obvious that the amplitude A factors out of the problem. The solution for and is easily found to be 2k1 k1 k2 , . (11.8) =1+= k1 + k2 k1 + k2 This is the best we can do: we have exhausted all the conditions available to us. We cannot determine A. There is no restriction on k1 or k2 , and thus no restriction on the possible energy E of the particle, other than the initial condition that E > V0 . =

11.2

The potential barrier with E > V0

Consider now the problem of a particle, incident from x = , hitting a barrier of heigth V0 and having width L : 0 if x 0, V0 if 0 < x < L, V (x) = (11.9) 0 if L x. It is now natural to divide the problem in three regions: region 1, on the left of the barrier, region 2, inside the barrier, and region 3 on the right of the barrier.

Scattering states
E>V

117

x=0

x=L

Figure 16: The potential barrier with E > V0 .

We consider rst the case where E > V0 . The wavefunction for the system is conveniently written as if x 0, Aeik1 x + A eik1 x ik2 x ik2 x ACe + ADe if 0 < x < L, (11.10) (x) = A eik1 (xL) if L x, where k1 = k3 = 2mE
2

k2 =

2m (E V0 )
2

(11.11)

Continuity of wave function and its derivative at x = 0 and x = L gives four equations: 1+ k1 (1 ) ik2 L Ce + Deik2 L Ceik2 L Deik2 L = = = = C +D, k2 (C D) , , k1 . (11.12) (11.13) (11.14) (11.15)

k2

This is a system of four equations with four unknowns. The two coecients C and D are given by 2k1 (k1 + k2 ) , e2ik2 L (k1 k2 )2 (k1 + k2 )2 2eik2 L k1 (k1 k2 ) . D = e2ik2 L (k1 k2 )2 (k1 + k2 )2 C = (11.16) (11.17)

Scattering states We are primarily interested in and , which are found to be =


2 2 (k1 k2 ) sin k2 L , 2 2 (k1 + k2 ) sin k2 L + 2ik1 k2 cos k2 L 2ik1 k2 = , 2 2 (k1 + k2 ) sin k2 L + 2ik1 k2 cos k2 L

118

(11.18) (11.19)

One notices an interesting feature of these quantities: if the socalled resonance condition is met: k2 L = n, (11.20) then is 0 and = 1 : the wave is completely transmitted through the barrier. For this to happen, we must have
2 k2 L2 =

2m (E V0 )
2

= n2 2 = En = V0 +

n2 2 2 . 2m

(11.21)

The label n has been attached to the nth value of the energy for which there is resonance. For other values of E, some of the wave is transmitted and some is reected. The probability amplitudes for transmission and reections are just

2 2 (k1 k2 ) sin2 k2 L 2 2 2 2 (k1 + k2 ) sin2 k2 L + 4k1 k2 cos2 k2 L 2 2 4k1 k2 2 2 2 2 (k1 + k2 ) sin2 k2 L + 4k1 k2 cos2 k2 L 2 2

, .

(11.22) (11.23)

The behaviour of these quantities is best illustrated graphically. For this purpose, we introduce, as before, the dimensionless quantities = 2mV0 L2
2

z=

E , V0

k1 L = z ,

k2 L = z 1.

(11.24)

The range of z is, by construction, limited to 1 z. With this notation, is written, for instance, as = 4z (z 1) , (2z 1) sin z 1 + 4z (z 1) cos2 z 1 4z (z 1) = 4z(z 1) + sin2 z 1
2 2

(11.25) (11.26)

Scattering states

119

The physical parameters of the system are all contained in . For small values of z 1 (either small or z 1) the term sin2 1 z is small, so that is close to 1. For large values of z, the sine term saturates at 1: the z(z 1) term dominates in the denominator and the ratio once again goes to one. For illustration purposes, it is therefore convenient to choose, say, = 2 and = 5.
1 0.8 0.6 0.4 0.2

2 1 0.8 0.6 0.4 0.2

10

10

Figure 17: The (relative) probability amplitude of the transmitted wave T T for = 2 (top) and = 5 (bottom) for the case where E > V0 > 0.

11.3

The potential hole

The case of V0 is treated much in the same way. If 0 if x 0, V0 if 0 < x < L, V (x) = 0 if L x,

(11.27)

Scattering states we now need k1 = k3 = 2mE


2

120

k2 =

2m (E + V0 )
2

(11.28)

Equations (11.12) , (11.13) , (11.14) and (11.15) remain identical, so that the solutions for and , when expressed in terms of k1 and k2 , remain unchanged. The only dierence is that k2 L = z + 1 , so that = z= E V0 (11.29)

4z (z + 1) . 4z(z + 1) + sin2 z + 1

(11.30)

The same general conclusions regarding the behavior of the transmitted wave remain. In particular, there are transmission resonances at En = V0 + n2 2 2 , 2m (11.31)

and the range of z = E/V0 now extends from 0 to .

11.4

The potential step with E < V0

The last case to consider if a barrier of height V0 but a particle incident from x = having energy E < V0 . Explicitly, 0 if x 0, V0 if 0 < x < L, V (x) = (11.32) 0 if L x. Again we have three regions, with wavefunction written as Aeik1 x + A eik1 x if x 0, ACe2 x + ADe2 x if 0 < x < L, (x) = A eik1 (xL) if L x, with k1 = k3 = 2mE
2

(11.33)

2 =

2m (V0 E)
2

(11.34)

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121

The solution can be obtained by comparaison with the E > V0 case, where k2 = which implies 2 = 2m (V0 E)
2

2m (E V0 )
2

(11.35)

2m (E V0 )
2

1 k2 = ik2 .

(11.36)

In other words, we can simply take the solutions for E > V0 and replace k2 i2 to obtain the solution for E < V0 . To convert sin(k2 L), for instance: sin(k2 L) = 1 2 L 1 ik2 L e eik2 L e e2 L , 2i 2i = i sinh (2 L) .
1 2

(11.37)

Likewise, cos(k2 L)

e2 L + e2 L = cosh (2 L) so that
2 (k1

E>V0 E<V0 = =

2ik1 (i2 ) 2 2 )(i sinh(2 L)) + 2ik1 (i2 ) cosh(2 L)


2 k1 ) sinh(2 L)

(2 2

2ik1 2 . 2ik1 2 cosh(2 L)

(11.38)

It is once again possible to illustrate the behaviour of these coecients in terms of the dimensionless variables and z. This is done on gure 11.4.
0.5 0.4 0.1 0.3 0.2 0.1 0.02 0.2 0.4 0.6 0.8 1 0.2 0.4 0.6 0.8 1 0.08 0.06 0.04 0.14 0.12

Figure 18: The (relative) probability amplitude of the transmitted wave for = 2 (left) and = 5 (right) for the case where V0 > E > 0.

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122

11.5

The S-matrix

Thus far, we have restricted ourselves to problems where particles are incident from x = . Our objective is to extend our results to the case where particles are incoming from both x = and x = : we can always recover the case of particle incident from only one direction by setting the appropriate amplitude equal to zero at the end of the problem. In generalizing, we are able to setup a more realistic problem, which can be pictured as below. Two particles, initially far apart, interact in a small region and emerge, usually with their energies and momenta changed, from the interaction region. This is illustrated in gure 11.5

Figure 19: The schematic representation of scattering: two particles enter an interaction region and emerge with dierent energies and (in general) wave vectors.

In the onedimensional case, this picture is somewhat naive but one can nevertheless easily imagine the situation. As always, it will be convenient to divide the problem in three regions: the interaction region is taken to extend between x = 0 and x = L. On the left of the interaction region, we have a wavefunction of the type (x, t) = AL ei(tk1 x) + BL ei(t+k1 x) , whereas, on the right of the interaction region, we have (x, t) = BR ei(tk1 x) + AR ei(t+k1 x) . (11.40) (11.39)

Notice how the amplitudes of the waves traveling towards the interaction regions need not have identical amplitudes. The wavefunctions have also been written so that the reected wave on the left and right have, respectively,

Scattering states

123

amplitude BL and BR rather than AL L and AR R . Thus, we can set, for instance, R = 0 to deal with particles incident from x = only. The reason for using (x, t) rather than the timeindependent (x) in to emphasize the traveling wave nature of these solutions. In general, the wavefunction inside the interaction region will have some complicated form, but it will be a superposition of a wave traveling to the right and a wave traveling to the left: (x, t) = Cg(t k2 x) + Df (t + k2 x). (11.41)

In general, the wave number k2 is a (possibly terribly complicated) function of x through the energy E of the particle and the potential V (x) present in the interaction region: k2 = k2 (x). It is usually assumed that these incident amplitudes are known, so that the problem is one of nding BL and BR in terms of the given amplitudes AR and AL . Clearly, the special case of a particle incident from x = only can be recovered by setting AR = 0. In general, we thus have six unknown amplitudes AL , BL , C, D, AR and BR but only four conditions: continuity of the wavefunction and its derivative at x = 0, and the continuity of the wavefunction and its derivative at x = L. Thus we can solve for any four in terms of two. We choose to solve in terms of the known amplitudes AR and AL . In particular, the reected waves in each sector will be some linear combination AR and AL , something of the type BL = S11 AL + S12 AR , BR = S21 AL + S22 AR . This is most conveniently expressed in matrix form as BL BR The matrix S= = S11 S12 S21 S22 S11 S12 S21 S22 AL AR . (11.44) (11.42) (11.43)

(11.45)

is known as the scattering matrix, or S matrix. Its coecients are determined by the continuity conditions on the wave functions and its derivative, and depend on the potential through these boundary conditions.

Scattering states

124

To recover what we already know from the case of a particle incident from x = only, we need to set AR = 0, in which case the transmission and reections coecients become |BL |2 |BR |2 2 2 (11.46) = = 2 = |S11 | , 2 = |S21 | . |AL | |AL | A similar interpretation of the coecients |S22 |2 and |S12 |2 can be made in terms of particles incident from x = + only, when AR = 0. We can squeeze more information from the S matrix. Suppose we have a bound state rather than a scattering state. Then, the energy E of the particle is negative rather than positive. The expression for k1 , which is k1 = 2mE/ 2 for scattering states (assuming V = 0 outside the interaction region), becomes k1 2m |E| / 2 = i1 , with 1 = 2m |E| / 2 . Furthermore, the coecients AR and AL must be zero, as these represent waves incident from the left and the right, respectively. Thus, for instance, if the particle is incident from the left, the coecients and in Eqn.(11.46) will become innite. In other words, if you want to locate bound states, substitute k1 i1 in the S matrix and nd the values of E (via k2 ) where these coecients become innite. A good example of this procedure is aorded by the square hole. There, V = V0 is constant, and we already have S11 and S12 through Eqns.(11.18) and (11.19): both have the same denominator
2 2 k1 + k2 sin k2 L + 2ik1 k2 cos k2 L,

(11.47)

which will make the expressions blow up when 0. Thus, remembering that, for the hole k2 = 2m( |E| + V0 )/ 2 and substituting k1 i1 = i 2m |E| / 2 , we have
2 k2 2 1 2 0 = 2 + k2 sin k2 L + 21 k2 cos k2 L (11.48) 1 sin k2 L = 21 k2 cos k2 L. (11.49)

This doesnt look particularly familiar because we worked out the bound states for a nite well of width 2L centered at x = 0 rather than a well having the dimensions appropriate for this problem. This is not a serious issue, though: we can easily work out the bound states of the hole of depth V0 and width L. The wave function must have the form if x < 0, Ae1 x , B sin k2 x + C cos k2 x , if 0 x L, (x) = (11.50) 1 (xL) De , if x > L.

Scattering states

125

Matching the wave function and its derivative at x = 0 and x = L gives A 1 A D 1 D = = = = C, Bk2 , B sin k2 L + C cos k2 L, k2 cos k2 L Ck2 sin k2 L. (11.51) (11.52) (11.53) (11.54)

Put together, these eventually produce 1 k2 + k2 1 sin k2 L = 2 cos k2 L, (11.55)

with is just another form of Eqn.(11.48): everything is ne.

126

Part III

Formalism and calculation tools


In this part, we introduce the tools and the formalism required to go beyond simple quantization of energy. The formalism of quantum mechanics borrows heavily from the theory of linear vector spaces. The major dierence between the quantum mechanical vector spaces and ordinary, threedimensional vector space that we are all familiar is that the quantum version is innitedimensional. Many of the notions familiar to ordinary threespace, such as orthogonality, linear dependence, completeness, carry over to the innitedimensional case, with the caveat that one must take care to make sure that the sums or integral that arise are meaningful, i.e. they converge in the mathematical sense.

Linear stu

127

12
12.1

Linear stu
Linear spaces

Schrdinger equation (the full timedependent version) is a linear dierential o equation: the sum of any two solutions is also a solution. Further, one can multiply any solution by a complex scalar, and add it to another so multiplied solution and still get a solution. These two properties are typical of vectors in a linear space. Linear spaces (or vector spaces) are populated by vectors, and the adjective linear means that vectors which inhabit the space i) can be added together to form other vectors, and ii) can be multiplied by (real or complex) numbers to make new vectors. The dimension of the vector space need not be nite. Example 12.1 The following sets are all vector spaces: 1. The set of all ntuples of real numbers. If x = (x1 , x2 , . . . , xn ) and y = (y1 , y2 , . . . , yn ) are vectors in this space, then addition is dened by x + y = (x1 + y1 , x2 + y2 , . . . , xn + yn ). Multiplication of a vector by a scalar is dened as x = (x1 , x2 , . . . , xn ). This is an n dimensional space; 2. The set of all innite sequences of numbers (x1 , x2 , . . . , xk , . . .) such

that
k=1

|xk |2 < . Addition of two vectors is dened as in 1.; this


2

innitedimensional space is called an

space;

3. The set of all those functions of a real variable x which can be differentiated innitely many times. Addition of two vectors f and g dened pointwise, i.e. (f + g)(x) = f (x) + g(x), and scalar multiplication dened by (af )(x) = a(f (x)). This is an innitedimensional space; a basis for this space is given by the set of basis vectors {1, x, x2 , x3 , . . .}. Note that the dimension of the vector space (here, innitedimensional) is independent of the number of variables in the problem (here, one). The component of the vector f (x) on the basis vector xn is just the coecient cn of xn in the Taylor series expansion

Linear stu

128

of xn . The set {1, x, x2 , x3 , . . .} is not the only possible set of basis vectors: there are many (in fact, innitely many) possible choices of basis functions. 4. The set of all functions of a real variable x for which the integral |(x)|2 dx makes sense and is < . The range of integration can be nite or innite. Addition and multiplication by a scalar are dened as in 3.; this is an innitedimensional space known as an L2 space. 5. The set of all functions x of one real variable t which are solutions to the equation d2 x(t)/dt2 = 2 x(t), with addition and scalar multiplication dened as in 3.; this is either a twodimensional real space or a one dimensional complex space, depending on whether or not we allow the scalars to be real or complex. (Note again that the dimension of the vector space does not depend on the number of variables in the problem. In particular, we have a twodimensional real vector space even if we have a single independent variable, t.) A basis for the real space is given 1 0 by the two basis vectors = cos(t) and = sin(t). A 0 1 basis for the complex space is given by the basis vector eit . Clearly, this space is a subspace of the space described in 4.

From now on, we will denote a generic vecto space by V. An element in V, i.e. a vector, will be written as | . The symbol is just a symbol, with no more signicance than any other symbol; one could have written , but its just more practical for future use to use | . Thus, |a , | , |1 are all example of abstract vectors. Technically speaking, | is called the ket . Two vectors |1 and |2 are said to be linearly independent is one is not a multiple of the other, i.e. if there is no complex number such that |1 = |2 . A vector | is said to be linearly independent of a set {|1 , |2 , . . . , |n } if is it impossible to write | as a linear combinations of the vectors in the set, i.e. if the equation | =
i

i |i ,

(12.1)

has no solution.

Linear stu

129

The largest number of linearly independent vector in V is the dimension of V. It is also possible to choose a basis in V, which is a set of linearly independent vector having the same dimension as V. (One must be careful when V is innitedimensional to make sure that we have enough vectors.) If things are done right, any vector | in V can then be written as a unique linear combinations of the basis vectors {|i } in V: | =
i

i |i .

(12.2)

The complex coecients i are called the components of | in the basis {|i }.

12.2

Inner products and norms

We need now to generalize the notion of length (or norm) and angles between vectors in three dimensions to an arbitrary complex vector space. An inner product is a rule that assigns to a pair of vectors a (generally complex) number. Oftentimes, this operator is denoted by a dot, , so that the inner product of a with b is written a b. We want to generalize this. Suppose that V is an ndimensional vector space, and that vectors in V can be represented by an ordered n-tuple: | | = (1 , . . . , n ) , = (1 , . . . , n ) .

(12.3)

Their inner product will be denoted by | and is dened as


n

|
i=1

i , i

(12.4)

where is the complex conjugate of the component i . i If V is an innitedimensional vector space, then the above denition of inner products holds provided that the sum converges, i.e.

|
i=1

i i < .

(12.5)

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130

The complex conjugation in the denition of the inner product is important. The length of a vector (also known as the norm of this vector), a quantity that should always be positive, is given by = | , (12.6)

a denition possible only because | is necessarily nonnegative under the denition of the inner product. This denition of lenght implies that =0 0. Using this, it is possible to construct, starting from any basis in V, an orthonormal basis for V. An orthonormal basis is one where all basis vectors are of unit length and any two distinct vectors are orthogonal to one another. In symbols, if |ei denotes an normalized basis state ei | ej = ij , where the symbol ij 1 if i = j , 0 if i = j . (12.9) (12.8) | = 0 . (12.7)

Two vectors are said to be orthogonal if their inner product is 0: | =

Example 12.2 Gram-Schmidt orthonormalization. Suppose we are given three vectors |1 , |2 and |3 . These vector are not necessarily orthonormal, i.e. they dont necessarily satisfy i |j = ij . (12.10)

How do we construct from these an orthonormal basis?. First, pick any one vector, say |1 . Which one is inessential. To obtain a normalized vector from |1 , divide it by its norm. Thus, we dene the rst normalized vector to be |1 . (12.11) |e1 = 1 |1 Select now a second vector, say |2 , and consider the combination |2 = |2 + |e1 . (12.12)

Linear stu Orthogonality to |e1 implies e1 |2 = 0 = e1 |2 + e1 |e1 = e1 |2 + ,

131

(12.13) (12.14)

which implies = e1 |2 = |2 2 |2 1 |2 1 |1 , (12.15) (12.16) (12.17) (12.18) (12.19)

1 |2 , 1 |1 = [ 2| 2 |e1 e1 |] [|2 2 |e1 |e1 ] = 2 |2 2 e1 |2 2 |e1 + e1 |e1 2 |e1 2 |e1 | 1 |2 |2 = 2 |2 | e1 |2 |2 = 2 |2 1 |1 = |2 |e1 e1 |2 = |2 |1

We can then normalize |2 to obtain |e2 = = , 2 |2 |2 |e1 e1 |2 2 |2 | e1 |2 |


2

|2

(12.20) . (12.21)

To nd a third orthogonal vector, pick a vector other than the rst two, say |3 , and write |3 = |3 + |e1 + |e2 (12.22) and impose e1 |3 e2 |3 = 0 = e1 |3 + + e1 |e2 = e1 |3 + , = 0 = e2 |3 + e2 |e1 + = e2 |3 + . (12.23) (12.24)

This determines , , from which |3 can be normalized to obtain |e3 . As an example, consider the problem of nding an orthonormal basis two dimensions given two vectors |a = 2 1i , |b = 1 i . (12.25)

Linear stu To nd |e1 , start from |b to get |e1 = |b 1 = 2 b |b 1 i 1 , e1 | = (1, i) 2

132

(12.26)

To obtain |e2 , we start from |a and write |a = |a |e1 e1 |a 1 1 2 2 (1, i) = i 1i 1i 2 1 1 2 (3 i) = i 1i 2 1 1 1i 43i = = . 2 2 2i + 3i 1 2 1+i

(12.27)

It happens, by luck, that |a is already normalized, so that |e2 = One can verify that 1 e1 |e2 = (1, i) 2 2 1i 1+i 1 = (1 + i i + 1) = 0. 2 2 (12.29) 1 2 1i 1+i . (12.28)

Everything generalizes to the higher dimensions in an obvious way. The general abstract denition of an inner product is obtained by requiring that the operation | satisfy the following properties: i. | = | . Note that | is a number, so that it makes sense to take its complex conjugate.
ii. 1 1 + 2 2 | = 1 1 | + 2 2 | for any two arbitrary complex numbers 1 and 2 ,

iii. | 0.

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133

For the space of squareintegrable functions (this is an innitedimensional space), we obtain an inner product as the continuous version of Eq.(12.4): provided that
b

dx |(x)|2 < ,
b

(12.30)

then |
a

dx (x)(x) .

(12.31)

Note that = 0 implies that f (x) = 0 almost everywhere, i.e. except on a set of measure zero. There also exists a useful inequality between the norms and inner product of two vectors, known as the Schwartz inequality: | | | . (12.32)

12.3

Linear operators

An operator (or an operation) is a rule that transforms any input (a vector) into an output (another vector) according to some prescribed instructions. For instance, an n n matrix acting on an ndimensional vector space is an operator, as it transforms any vector to another vector according to the rules of matrix multiplications. An important family of operators are the linear operators: if you feed a sum of vectors + to a linear operator O, the output will the sum of the outputs obtained by applying the operator on each member of the sum individually: O( + ) = (O) + (O) , and O(k) = k(O) , k C . (12.33)

Matrices are examples of linear operators. Taking the square root is an example of an operator that is not linear: acting on numbers (which one can think of as vectors in a onedimensional space), we have x + y = x + y. In the space of functions, the derivative operator d/dx is a linear operator: d (f (x) + g(x)) = dx d f (x) + dx d g(x) dx . (12.34)

For the kinds of operators that we will be dealing with, and for the kinds of functions that well be looking at, it is possible, in principle, to construct

Linear stu

134

a matrix for the operator d/dx, although this matrix could turn out to be innitedimensional (because the space of functions is innitedimensional). Linear operators can usually be represented by matrices. Given a basis and an inner product, the matrix element of the operator O between two vectors |i and |j is dened by Oij = i |O|j . Example 12.3 The operator x. Let us compute the matrix representation of the operator x, with matrix elements computed between the rst three solutions 0 (x) , 1 (x) and |2 (x) of the Schrdinger equation for the harmonic oscillator. For simplicity, we o will write these vectors as |0 , |1 and |2 , respectively. We now compute n||r . To simplify the calculation, we will switch to x the variable dened by m Then n||r x 1 2n n!2r r! 1 = 2n n!2r r! =

2

= x.

(12.35)

d e Hn ()

Hr () (12.36)

de Hn ()Hr ()

Use the recursion relation for Hermite polynomials: Hr+1 () 2Hr () 2rHr1 () , 1 Hr () = (Hr+1 () + 2rHr1 ()) , 2 = (12.37) (12.38)

to get n||r x = 1 2n n!2r r!

1 m 2 de Hn () (Hr+1 () + 2rHr1 ())


2

(12.39)

1 1 n+r n!r! m 2 2

2r+1 (r + 1)! for n = r + 1 , 2r2r1 (r 1)! for n = r 1 . (12.40)

Linear stu Thus, we have two nonzero matrix elements: r + 1||r x = = = r 1||r x = = = Thus, we have the 1 1 2r+1 (r + 1)! 1/2 m 2 [22r+1 (r + 1)!r!r]

135

1 1 2r+1 (r + 1)r! m 2 2r 2r! r + 1 r+1 (12.41) 2m 1 1 2r 2r1 (r 1)! m 2 [22r+1 (r 1)!r!r]1/2 1 2 1 r1 r2 (r 1)!2r r (r 1)! m 2 2 1 r= r (12.42) m 2 2m following matrix for the operator x 0 1 0 1 0 2 , (12.43) 2m 2 0 0

where the basis states are ordered so that the rst line, for instance, contains the matrix elements x00 , x01 and x02 , in this order.

12.4

Eigenvectors are special

Suppose we have some linear operator T , and a normalized eigenvector | such that T | = | , (12.44) Then, by denition, T T2

= |T | , = , = |(T )2 | , = |T T | , = |T | , = 2 .

(12.45) (12.46) (12.47) (12.48) (12.49) (12.50)

Linear stu

136

T 2 T 2 = 0. Thus, we can associate to | a well so that T = dened value of T . The simplest example of this situation is when T is represented by a diagonal matrix in some basis. Suppose {|i , i = 1, ..., n} is a basis for our problem, and that, in this basis, T has the form 1 0 0 . . . 0 0 2 0 . . . 0 T = . (12.51) ... . . 0 0 0 ... 0 n In this basis, we have, for instance, 1 0 0 1 0 |1 , |2 0 , . . . . . . 0 0 Then, clearly, using simple matrix multiplication, T |i = |i . (12.53)

etc .

(12.52)

In other words, T is diagonal in the basis spanned by the eigenvectors of T .

12.5

The mechanics of matrix diagonalization

Recall again the motivation for our problem. Suppose we have an operator T and a normalized state | such that T | = | . Then |T | |T 2 | = , = |T T | = 2 (12.55) (12.56) (12.54)

and the uncertainty on the quantity T represented by the operator T is |T 2 | |T | T = = 0.


2

2 ()2

(12.57) (12.58)

Linear stu

137

Thus, if there is no uncertainty on the value of T (it is certainly ), we can use the eigenvalue to distinguish various eigenvectors of T , i.e. we can use as a label so that T | = | . (12.59) How do we nd eigenvectors and eigenvalues of an operator? First, we need a basis, i.e. a set {|i , i = 1, ..., n} of orthonormal vectors which will be used to calculate matrix elements of T via Tij = i |T |j . There is no reason to suspect that |j is an eigenvector of T . Once we have the matrix representation of T , we nd the eigenvalues of T , and from the eigenvalues we recover the eigenvectors. To illustrate the procedure, suppose we are given a basis in which some operator T is represented by the 3 3 matrix 1 0 1 T = 1 2 i , 1 0 i 2
1 2

(12.60)

which has been computed using 0 0 1 |1 = 0 , |2 = 1 , |3 = 0 . 1 0 0 The eigenvalues are those solutions to the equation det T 1 l = 0,

(12.61)

(12.62)

where 1 is the (here, 3 3) unit matrix l 1 0 0 1= 0 1 0 . l 0 0 1 Constructing T 1 and obtaining the determinant yields l 1 1 0 2 1 i 2 0 = det 1 1 0 i 2
9 9 = 3 + 1 2 + 4 8 . 2

(12.63)

(12.64) (12.65)

Linear stu

138

Unless you have a lot of experience with cubic, it is not clear that this can be rewritten as 0=
3 2

3 2

1 2

(12.66)

One practical way to nd the solutions is to recall that the eigenvalues of a hermitian matrix must be real, plot 9 9 1 f () = 3 + 2 + 2 4 8 (12.67)

and looks for values of where f () crosses the axis. This is illustrated in Fig. 20.
4 3 2 1 -2 -1 -1 -2 1 2

9 9 1 Figure 20: The polynomial f () = 3 + 2 2 + 4 8 .

3 1 3 In any event, the eigenvalues are 2 , 2 and 2 . Let us nd the corresponding eigenvectors. Assume 3 2 (12.68) | 3 = 3 |1 + 3 |2 + 3 |3 = 3 , 2 2 2 2 2 3
2

Linear stu and insert this in 3 | 3 T | 3 = 2 2 2 3 3 2 3 2 3 = 3 , 2 2 2 3 3 2 2 3 2 3 = 0. 2 3


2

139

(12.69) (12.70)

1 0 1 1 i 2 1 0 i 2 1 1 0 1 2 i 0 i 1 This leads to the system

1 2

(12.71)

3 + 3 = 0,
2 2 2 2

(12.72) (12.73) (12.74)

3 2 3 + i 3 = 0,
2 2

i 3 3 = 0.
2

Notice how the sum of Eqn.(12.72) and Eqn.(12.73) add up to a multiple of Eqn.(12.74), indicating that we really have two equations for three unknowns. We will solve everything in terms of 3 , so
2

3 = 3 ,
2 2 2

(12.75)
2 2

3 = i 3 = i 3 . Hence, the rst eigenvector is 3 (|1 + |2 i|3 ) ,


2

(12.76)

(12.77)

which can be normalized to 1 1 i | 3 = |1 + |2 |3 2 3 3 3 In a similar manner, one nds | 3


2

1 1 = 1 . 3 i

(12.78)

| 1

1 2 i = |1 |2 |3 , 6 6 6 i 1 = |1 + |3 . 2 2

(12.79) (12.80)

Linear stu

140

One can verify explicitly, for instance, that 1 3 1 1 2 1 0 2 2 2 1 1 i 2 = 1 + 1 + 1 = 3 , (12.81) 2 1 i i 0 i 2 3i 2i 2 2 1 3 (12.82) = 2 . 2 i Notice how the eigenvectors are orthogonal, and, because they are normal ized, in fact orthonormal. In the | 3 , | 3 , | 1 , the operator T is now 2 2 2 diagonal since, for instance, 3 , (12.83) 3 |T | 3 = 2 2 2 3 |T | 3 = 0, (12.84)
2 2

1 |T | 3
2 2

= 0.

(12.85)

Indeed, in this basis, we have the matrix representation of T as 3 0 0 2 3 T = 0 2 0 1 0 0 2 The change from the {|1 , |2 , |3 } basis to the basis can be written in matrix form by noting that |1 |2 |3
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2

(12.86)

| 3 , | 3 , | 1
2

= | 3 3 |1 + | 3 3 |1 + | 1 1 |1 ,
2 2 2

(12.87) (12.88) (12.89) (12.90)

= | 3 3 |2 + | 3 3 |2 + | 1 1 |2 , = | 3 3 |3 + | 3 3 |3 + | 1 1 |3 , Mab = a |b .

and constructing the matrix In this way, quite clearly,


3

|b

=
a=1 3

|a Mab ,
Mba a | a=1

(12.91) (12.92)

b | =

Linear stu Obviously, we have, for instance, from | 3 =


2

141
1 |1 3

1 |2 3

i |3 3

1 = , 3 1 3 |2 = , 2 3 i 3 |3 = , 2 3 and so forth, which leads directly to the matrix 1 1 1 3 |1


2

(12.93) (12.94) (12.95)

M =

3 1 3 i 3

6 2 6 i 6

2 i 2

0 .

(12.96)

Notice how M = (M t ) = M 1 , i.e. M is unitary and how each column is made from the normalized eigenvectors of T Thus, 1 1 1 3 0 0 3 6 2 2 1 2 3 T M = 3 6 0 0 2 0 1 i i i 0 0 2 3 6 2 3 0 0 2 3 (12.97) = M 0 2 0 , 1 0 0 2 3 0 0 2 3 (12.98) M 1 T M = M 1 M 0 2 0 , 1 0 0 2 3 0 0 2 3 (12.99) = 0 2 0 . 1 0 0 2 Thus, the change of basis obtained from M , which transform the |i to the |a basis as it expresses the |i as linear combination of the new basis vectors |a , makes the operator T diagonal, with the eigenvalues on the diagonal.

12.6

Application: neutrino mixing

The neutrino is a particle that is found to participate in reactions driven by the weak interaction. It has long been thought that its mass is very small

Linear stu

142

or zero and thus that it travels at the speed of light. In this section, we give a practical application of diagonalization of a Hamiltonian by looking at mixing 1 between two types of neutrinos, the socalled electron and muon neutrinos, e and , respectively, which occur in the reactions e + n p + e , + n p + . (12.100) (12.101)

The states |e and | are eigenstates of the weak interaction Hamiltonian Hweak , but they are not eigenstates of the freeparticle Hamiltonian Hf ree (basically, the mass of the particle), i.e. Hf ree |e Hf ree | = me |e , = m | . (12.102) (12.103)

In other words, once the particles are no longer subject to Hweak , they will become free particles but not eigenstates Hf ree . This gives rise to a phenomenon known as neutrino oscillation. Let the eigenstates of Hf ree be |1 and |2 , respectively, so that Hf ree |1 Hf ree |2 = m1 c2 |1 , = m2 c |2 .
2

(12.104) (12.105)

Because these are eigenstates of the free Hf ree , their time evolution, once they have escaped the interaction region, is just |1 eiE1 t/ , |2 eiE2 t/ . We can write |1 |2 = cos |e + sin | , = sin |e + cos | (12.108) (12.109) (12.106) (12.107)

for the normalized mass eigenstates, where is the socalled mixing angle.
1

see: W.C. Haxton and B.R. Holstein, arXiv:hep-ph/9905257 for details

Linear stu

143

(This is not the most general linear combination, but it is enough to illustrate the situation). These can be turned around to yield |e | = cos |1 sin |2 , = sin |1 + cos |2 . (12.110) (12.111)

In the basis spanned by |e and | , we identify |e and write e | Hf ree |e = (cos 1 | sin 2 |) Hf ree (cos |1 sin |2 ) , 12.113) ( 2 = cos 1 | Hf ree |1 sin cos 2 | Hf ree |1 sin cos 1 | Hf ree |2 + sin2 2 | Hf ree |2 (12.114) 2 2 2 2 = m1 c cos + m2 c sin , (12.115) f ree | e | H = (cos 1 | sin 2 |) Hf ree (sin |1 + cos |2 ) (12.116) = (m1 m2 )c2 cos sin , (12.117) | Hf ree |e = e | Hf ree | , (12.118) | Hf ree | = (sin 1 | + cos 2 |) Hf ree (sin |1 + cos |2 ) (12.119) = m1 c2 sin2 + m2 c2 cos2 . (12.120) Hence, we have the matrix Hf ree in the {|e , | } basis, given by Hf ree = m1 c2 cos2 + m2 c2 sin2 (m1 m2 )c2 cos sin (m1 m2 )c2 cos sin m1 c2 sin2 + m2 c2 cos2 , (12.121) 1 0 , | 0 1 (12.112)

showing explicitly that neither |e nor | have a simple time evolution. Let us nd the eigenstates of Hf ree (we know these are |1 , |2 but lets do it anyways to show the diagonalization procedure.)

Linear stu The eigenvalues obtained from det

144

m1 c2 cos2 + m2 c2 sin2 (m1 m2 )c2 cos sin (m1 m2 )c2 cos sin m1 c2 sin2 + m2 c2 cos2 =0 (12.122) 2 2 2 2 2 2 2 2 = m1 c cos + m2 c sin m1 c sin + m2 c cos (m1 m2 )2 c4 cos2 sin2 (12.123) 2 = m1 c2 cos2 + m2 c2 sin2 + m1 c2 sin2 + m2 c2 cos2 + m1 c2 cos2 + m2 c2 sin2 m1 c2 sin2 + m2 c2 cos2 m2 2m1 m2 + m2 c4 cos2 sin2 (12.124) 1 2 2 2 = (m1 + m2 ) c +m1 m2 c4 cos4 + sin4 + 2 cos2 sin2 (12.125) 2 2 4 = (m1 + m2 ) c + m1 m2 c , (12.126)

which can be solved to yield = = (m1 + m2 ) c2 (m1 + m2 ) c2 (m1 + m2 )2 c4 4m1 m2 c4 2 (m1 + m2 )2 c4 , (12.127) (12.128) (12.129)

2 2 (m1 + m2 ) c (m1 + m2 ) c2 = 2

so that 1 = m1 c2 , 2 = m2 c2 , (12.130) (12.131)

as expected. One easily veries that the eigenstates are correctly given by Eqns. (12.108) and (12.109). Suppose now some weak process yields, say, |e as a nal product. The time evolution of this vector, once it has escaped the interaction region, is |e |e (t) = cos |1 eiE1 t/ sin |2 eiE2 t/ . (12.132)

Linear stu

145

The probability that it will have oscillated to | after a time t is given as a postulate by Pe (t) = | | e (t) |2 = = = = |1 cos eiE1 t/ |2 sin eiE2 t/ sin cos eiE1 t/ cos sin eiE2 t/ 2 sin cos sin sin 2 sin (E1 E2 ) t 2
2 2 2 2

(12.133) (12.134) (12.135) (12.136) (12.137) ,

(E1 E2 ) t 2

Thus, the oscillation frequency is half of the energy (or mass) dierence between the mass eigenstates. This phenomenon is a sensitive test of neutrino masses, given m1 = m2 and a non-zero mixing angle. If neutrinos (which are produced at fantastic rates in the core of stars) were found to have non-zero mass, the cosmological consequences would be non-trivial. In 1998, unambiguous evidence that some were missing from atmospheric cosmic ray decay experiments. The rate of coming directly from above agreed with predictions, but the rate of passing straight through the earth was about half of what was predicted. It is suggested that the dierence be the result of the extra time-of-ight across the Earth. As a result, one nd that the mass dierence between the neutrinos is in the range 101 eV E 102 eV with a mixing angle consistent with = /4. (12.138)

12.7

The ammonia molecule revisited

Linear stu

146

13
13.1

Hermitian matrices and their properties


Some denitions
M (M T ) = M , (13.1)

Let M be an n n square matrix. If M satises the basic property that

then M is called hermitian. Closely related is the denition of an antihermitian matrix: M = M . Note that, if M is antihermitian, then iM is hermitian. A real hermitian matrix is symmetric (M T = M ) and a real antihermitian matrix is antisymmetric. Finally, a matrix M is unitary if, by denition, M 1 = M . These denitions are summarized as follows: type hermitian antihermitian symmetric antisymmetric unitary denition M = M M = M MT = M M T = M M 1 = M all real hermitian matrices all real antihermitian matrices can be written as eiH , with H hermitian orthogonal M 1 = M T can be written as eiL , with L antisymmetric A square matrix is invertible if its determinant is nonzero. The trace of a square matrix is the sum of its diagonal elements. The determinant and trace of products of matrices have the following properties. Let A and B be two n n matrices. Then, Det(AB) = Det(BA) , Tr(AB) = Tr(BA) . (13.2) remark

Two matrices A and B are similar if there is a socalled intertwining matrix T so that A = T B T 1 . (13.3)

Linear stu Similar matrices have identical traces and determinants, since Det(A) = = = Tr(A) = = = Det(T B T 1 ) = Det (T B) T 1 Det T 1 (T B) = Det T 1 T ) B) , Det (B) , Tr(T B T 1 ) = Tr (T B) T 1 Tr T 1 (T B) = Tr (T 1 T ) B) , Tr (B) .

147

(13.4)

(13.5)

13.2

Hermitian operators

Let O be an operator acting on some vector space V, and let |i be a basis for this space. The matrix elements of O are dened, as usual, by Oij = i | Oj i |O|j . (13.6)

The hermitian adjoint of O is denoted by O . Given any two vectors | is this operator with matrix elements dened by and | , O | O = = O | , | O , O | . (13.7) (13.8)

Note that the adjoint of an operator is dened via matrix elements, which implies that some inner product is specied. An operator O is hermitian if O = O, i.e. if, for any two vectors, O | = | O . (13.9)

Theorem 13.1 Every diagonal matrix element of a hermitian operator T is real. Proof: Consider | T = T | = T | = | T . Theorem 13.2 Every hermitian operator T is unitarily similar to a diagonal operator, i.e. every hermitian operator can be written as T = U 1 D U , where 1 is diagonal. U is unitary (U = U ) and D Proof: This is a proof by recursion. It starts by assuming that the theorem holds for 2 2 matrices; one then assumes that it holds for n n and shows that the results holds for (n + 1) (n + 1). The details will not be given here.

Linear stu

148

Theorem 13.3 The eigenvalues of a hermitian operator are real. Proof: Let | be an eigenvector corresponding to eigenvalue , i.e. T | = | . Then: |T = | , (13.10) | = | T , = T = | . (13.11) Thus, we nd = , which proves the result. Theorem 13.4 Let T be hermitian, and let |1 and |2 be two eigenvectors corresponding to respective eigenvalues 1 and 2 . Then, 1 | 2 = 0 unless 1 = 2 . Proof: Start with 1 | T 2 = 2 1 | 2 , (13.12) = T 1 | 2 = 1 | 2 ,
1

= 1 1 | 2 ,

(13.13)

where hermiticity of T and reality of 1 has been used. Combining Eqn.(13.12) and Eqn.(13.13), we have 0 = (1 2 ) 1 | 2 , (13.14) from which the claim follows. Thus, two eigenvectors of corresponding to distinct eigenvalues of a hermitian operator are necessarily orthogonal. Theorem 13.5 If T is hermitian, then one can nd a set {|i } of orthogonal that completely span the space V on which T acts. In other eigenvectors of T words, any vector in V can be written as a linear combination of eigenvectors of T . For practical applications, this theorem is usually written in the form of a completeness relation, i.e. 1= l
i

|i i | .

(13.15)

The combination |k k | (xed k) is called a projector. Finally, we observe that, if A is arbitrary, then A + A is hermitian. This is clear since | (A + A ) = | A + | A by linearity. Then, | (A + A ) = | A + | A = A | + A | , = (A + A ) | , (13.16) which proves the claim.

Linear stu

149

13.3

Properties of pairs of hermitian operators

We start by noting that, if A and B are arbitrary, then simple matrix ma nipulations show that AB = B A . Dene the commutator [A, B] of two arbitrary operators A and B by [A, B] AB B A . (13.17)

Theorem 13.6 If A and B are hermitian, and if [A, B] = 0, then AB is hermitian. Proof: We will show that Eqn.(13.9) holds for the product AB under the condition stated in the theorem. Start with | AB = | AB . (13.18)

Next, denote by the state B| = |B , so that we can rewrite the right hand side of Eqn.(13.18) as |(AB) (AB)| = A| = |A . Combining this with the fact that A is hermitian, we have | AB = A | B . (13.20) (13.19)

Denote now by | the state A| , so that A| = |. Then, using now the fact that B is hermitian | AB = = | B = B | = B A | , AB | ,

(13.21)

where the last step is allowed by the assumption that [A, B] = 0, so that AB = B A. Eqn.(13.21) is identical to Eqn.(13.9), which proves the theorem.

13.4

Simultaneous eigenvectors of commuting hermitian operators

We now show the last but most important result, which deals with pairs of commuting hermitian operators.

Linear stu

150

Let A and B be hermitian, and assume they commute. Let | be an eigenvector of B, B| = B | . (13.22) Then, | is also an eigenvector of A if B occurs once in the set of eigenvalues of B. Proof: If B occurs only once, any other eigenvector of B having an eigen value dierent from B is orthogonal to | , and any other eigenvector of B having B as eigenvalue must be a multiple of | . We now examine A| . For clarity, write A| = | . Then, B| = B A| = AB| , = B A| = B | .

(13.23)

Thus, | is also an eigenvector of B, with the same eigenvalue B as | . Thus, | is a multiple of | , or, in other words, | = A| = A | , which proves the claim. (13.24)

Postulates

151

14

The postulates of Quantum Mechanics

The postulates of quantum mechanics provide a physical interpretation and a physical background to the mathematical machinery of the previous sections. Postulate I: A physical system is completely dened by specifying a ket vector |(t) belonging to the space H of all possible states of the system. The dimension of H is the number of possible distinct outcomes of all measurements that can be one on the system. Note that specifying a ket dispenses with having to choose a particular representation (x or p) and allows for the inclusion of states which have no space or momentum wave functions. Postulate II: To every measurable physical quantity O (called an observable), there corresponds a hermitian operation O acting on H. Postulate III: The possible results of a measurement of O are the eigenvalues of O . Postulate IV: Let be a physical quantity with corresponding hermitian operator . i We denote by |n the kets such that
i i |n = n |n .

(14.1)

Suppose the eigenvalue n occurs gn times. The label i is required to differentiate eigenvectors of with the same eigenvalue n ; there are of course precisely gn such eigenvectors. Suppose a physical system is described by the ket normalized | . When is measured on this system, the probability P (n ) of obtaining the value n for is given by
gn

Pn =
i=1

i | n | | 2 ,

(14.2)

with the sum running over all eigenstates having eigenvalue n . Postulate V:

Postulates

152

If the measurement of in the state | gives n , then immediately after the measurement, the state is given by
gn i |n i=n i n | i 2 i | n | | 1/2

(14.3)

This is known as the measurement postulate. It is quite controversial, and is the source of numerous paradoxes. Consider the simplest case where n occurs once. Then, if is found to have value n . Then | instantly becomes | |n n | | n | | (14.4)

If we measure with result n , it must be that, immediately after the measurement, the value of is certainly n :| must be changed to |n , which is the state for which will certainly give n as eigenvalue. Since n occurs with probability n | , measuring to be n amounts to the (linear) projection |n n | = n (14.5) Note that n n = |n n | = n (14.6) Why is a measurement represented by |n n | ? Suppose we ask: is the outcome of measuring equal to n ? The only two answers are either 0 (i.e.no) or 1 (i.e.yes). This is the same as nding the two solutions to ( 1) = 0 2 = 0 2 = which is precisely the property n n = n . Postulate VI: The time evolution of a state |(t) is governed by the Schrdinger equao tion: |(t) = H|(t) i (14.8) t Note that, since the Schrdinger equation is a rst order dierential equao tion, one needs only to specify |(0) to completely determine |(t) . (14.7)

Postulates We claim that |(t) =


n

153

eiEn t/ |n n |(0) ,

(14.9)

where

H|n = En |n .

(14.10)

If the eigenvalue En occurs more than once, then the sum in Eq.(14.9) must extend to every eigenvector with this eigenvalue. To show this, observe that, at t = 0 , we have |(0) =
n

|n n |(0) = |(0)

(14.11)

since |n n | = 1 . l
n

(14.12)

Next, i =
n

|(t) = t

i
n

iEn

eiEn t/ |n n |(0)

(14.13) (14.14) (14.15) (14.16)

En eiEn t/ |n n |(0) HeiEn t/ |n n |(0)


n

= H|(t)

So |(t) is solution to Schrdinger which satises the correct boundary o condition at t = 0 . By the uniqueness theorem on solutions to rst order dierential equation, this is the only solution. Finally, we mention Ehrenfest theorem: i d = dt , H + . t (14.17)

In particular, if ddt = 0 , i.e. is a constant of motion, which implies , H = 0 (provided that does not depend explicitly on t).

Matrix elements

154

15

Algebraic approach to some matrix elements

The calculation of matrix elements in some basis is essential if we want to nd eigenvectors and eigenvalues of some operators. This type of calculation is simplied in some problems using algebraic properties of operators. The whole setup does not require much in the way of integral and derivatives, but displaces the problem to one where heavy use of commutators is required.

15.1
15.1.1

Some properties of commutators


Linear combination of operators in a commutator

We start by noting that the commutator [A, B] of any two linear operators satises [A, B] AB B A , = B A AB , = [B, A] , i.e. the commutator is antisymmetric in its arguments. In particular, [A, A] = [A, A] = 0 . Any operator commutes with itself. Now, consider [A, B] = = AB B A AB

(15.1) (15.2) (15.3)

(15.4)

(15.5) , (15.6) (15.7) (15.8)

BA

= B A A B , = [A , B ] .

Next, for A, B and C linear, and , , arbitrary complex numbers, [A, B + C] = A B + C B + C A , = AB + AC B A C A , (15.9) (15.10)

Matrix elements since the operators are linear. We can rearrange the last line as [A, B + C] = AB B A + AC C A , = [A, B] + [A, C] .

155

(15.11) (15.12)

Thus, a commutator containing a sum can be expanded as a sum of commutators, with multiplicative constants factored in front. 15.1.2 [, p] x

We end by showing that [, p] is just i 1 by considering an arbitrary ket | x l using the xrepresentation. Thus x| [, p] | x d d )(x) (i )(x(x)) , dx dx d(x) d(x) + i (x) + x , = ix dx dx = x(i (15.13) (15.14)

where the rule for the derivative of a product has been used. Since | is arbitrary, the right hand side simplies to i (x) so that we have [, p] = i 1 , x l valid for any function. Alternatively, using the prepresentation, we have p| [, p] | x = = i +i d dp (p(p)) p i d(p) dp d(p) , dp d(p) p i , dp (15.16) (15.17) (15.18) (15.15)

(p) + p

= i (p) , which again implies Eq.(15.15).

15.2

Harmonic oscillator and the operators a and a


1 2 1 p + 2 m 2 x2 . H= 2m

The Hamiltonian for the onedimensional simple harmonic operator is (15.19)

Matrix elements 15.2.1 a and a

156

Dene two (nonhermitian) operators a = = a = 1 m xi p, 2 2m i m x p , 2 m i m x+ p . 2 m

(15.20) (15.21)

This choice is motivated by classical mechanics: the (complex) variables = m 2 x+ i p m , = m 2 x i p m (15.22)

have simple time evolution. Consider now [, a ]. We have a a, a = = = = = i i m x+ p, x p , 2 m m i i i m i [, x] + x, p + p, x + p, p x 2 m m m m i m i [, p] + [, x] , x p 2 m m i m i i 1+ (i 1 l l) , 2 m m 1 1+21=1 . l 1 l l 2 (15.23) , (15.24) (15.25) (15.26) (15.27)

Matrix elements Furthermore, a a = = = = = i i m x p p , x+ 2 m m i i 1 m x2 px + xp + 2 2 p2 2 m m m i m 1 x2 + [, p] + 2 2 p2 , x 2 m m 1 2 1 1 1 p + 2 m 2 x2 2 1 , l 2m 1 1 H21 , l

157

(15.28) , (15.29) (15.30) (15.31) (15.32)

where H is the harmonic oscillator hamiltonian. Thus, H = a a + 2 1 . 1 l Note that the combination a a is hermitian. Let N = a a . Note that N , a = a a, a , (15.35) (15.36) (15.37) (15.38) (15.39) (15.34) (15.33)

= a aa a a a , = a aa a a + a a a a a , = a = a , a, a + a a a a a ,

where [, a ] = 1 has been used. Likewise, one can show [N , a] = by a l a expanding everything, but it is easier to use Eq.(15.8) and see that N , a

= ( ) = a , a a = N , ( ) , = N, a ,

(15.40) (15.41) (15.42)

Matrix elements

158

a where N = N (hermiticity of N ) and ( ) = a (transpose of a transpose is unit, conjugate of conjugate is unit) have been used. Since N is hermitian, it has a complete set of orthonormal eigenstates. Let |n be such an eigenstate with eigenvalue n, i.e. N |n = n|n . |n is also assumed to be normalized. Since 1 H = (N + 2 ) , (15.44) (15.43)

1 it is clear than |n is also an eigenstate of H, with eigenvalue (n+ 2 ) . From Sec.(5.1), we know that no two eigenstates of H have the same eigenvalue, unless they are multiple one of the other. Thus, |n is also the unique (up to a choice of phase in the normalization) eigenstate of N with eigenvalue n. Observe rst that (|n ) = n| . Let a|n = | . | may not be a a normalized, as we dont know what is the result of operating on |n with a. Consider now

0 |

= n| a|n a = n|N |n = n n | n , = n.

(15.45) (15.46) (15.47)

Thus, n 0. Next, let us look more closely at a|n . We can nd more about this state by using N a|n = = = N a aN + aN |n , N , a + aN |n , + aN |n , a (15.48) (15.49) (15.50) (15.51)

= |n + n a|n = (n 1)|n . a a

This show that a|n is an eigenstate of N with eigenvalue n 1, and must therefore be proportional to the unique (up to a choice of phase in the nor malization) eigenstate of N with eigenvalue n 1, i.e. a|n = dn |n 1 . (15.52)

Matrix elements

159

But n 1 must be nonnegative (simply repeat Eq.(15.47) starting with | = a|n 1 ). Thus, there is a lowest value of n, call it nmin such that a|nmin = 0 . To discover what this value is, note that, from Eq.(15.52), n| a|n = d dn n 1 | n 1 = n n | n , a n which justies the choice dn = Thus, a|nmin = implies n. (15.54) (15.55) (15.56) (15.57) (15.53)

nmin |nmin 1 = 0

nmin = 0 nmin = 0 .

Hence, the lowest eigenvalue of N is n = 0. For this state, a|0 = 0. The kest is also the lowestenergy eigenket of the onedimensional harmonic oscillator, 1 with energy 2 . Next, we investigate a |n . Once more, we have N a |n = = = N a a N + a N |n , N , a + a N |n , a + n |n , a (15.58) (15.59) (15.60) (15.61)

= (n + 1) |n , a

where [N , a ] = + has been used. Thus, a |n is an eigenstate of N with a eigenvalue n + 1, and is therefore proprotional to |n + 1 . Let a |n = cn |n + 1 . (15.62) We then have c cn = n = = n|a |n , a n| aa a a + a a |n , n| a, a + N |n , (15.63) (15.64) (15.65) (15.66)

= (n + 1) .

Matrix elements The choice cn = n + 1 is convenient, so we obtain a |n = n + 1|n . n + 1|n + 1 .

160

(15.67)

Summarizing, we have a|n = n|n 1 , 15.2.2

a |n =

(15.68)

Matrix elements of x, p and their powers

Let us illustrate the virtues of using a and a in computing matrix elements of x and p. We will use quite a bit the results aa = aa a a + a a = [, a ] + a a = N + 1 , a l (15.69) aN = aN N a + N a = [, N ] + N a = a + N a , a (15.70) a N = a N N a + N a = [ , N ] + N a = + N a . (15.71) a a Consider specically the matrix elements of x3 . Expressing x in terms of a and a , and taking powers, we obtain
3 3/2

= = =

2m
3/2

a +a a + a

2m

a + a

(15.72) (15.73) (15.74)

2m
3/2

a + a

a + a ,

2m

a + a

a a + aa + a a + aa .

We now use Eqn.(15.69) to simplify to


3/2

x =

2m

a + a

a a + 1 + 2N + aa , l

(15.75)

and distribute further to obtain


3/2

2m

a a a + a + 2 N + a aa a +a a + a + 2N + aaa . (15.76) a a

Matrix elements Application of Eqns.(15.71) and (15.70) yields


3/2

161

2m
3/2

( )3 + a + 2 N + N a a a + N + 1 a + a + 2N + a3 , l a (15.77)

2m
3/2

( )3 + a + 2 N + N a a a +N a + a + a + 2N + a3 , a (15.78)

2m

( )3 + 2 + 2 N + N a + N + a + 2N + a3 (15.79) a a a a . a

Using now Eqns.(15.69)(15.71), we nd 2 + 2 N + N a = 3N a , a a N a + a + 2N = 3N , a a so that x = Thus,


3/2 3 3/2

(15.80) (15.81)

2m

( )3 + 3N + 3N + a3 . a a a

(15.82)

x3 |n

+3(n + 1) n + 1 |n + 1 +3n n |n 1 + So, we have, in tabular form: 3/2 3 m| x |n = 2m

2m

(n + 1) (n + 2) (n + 3) |n + 3

n (n 1) (n 2) |n 3(15.83) .

(n + 1) (n + 2) (n + 3) if m = n + 3 3(n + 1) n + 1 if m = n + 1 . if m = n 1 3n n n (n 1) (n 2) if m = n 3 (15.84)

Matrix elements 15.2.3

162

Application: constructing the eigenfunctions of H using a

We know that a|0 = 0. Using the xrepresentation, we have 0 = x||0 , a i d m x i = 2 m dx d0 (x) . = x0 (x) + m dx (15.85) x|0 , (15.86) (15.87)

This rstorder dierential equation is easily solved: m d0 (x) = x dx , dx m 2 x , ln 0 (x) ln N0 = 2 2 0 (x) = N0 emx /2 , (15.88) (15.89) (15.90)

where the integration constant N0 must be determined from the normalization condition:

1 =

dx 0 (x) 0 (x) = |N0 |2 , m m m


1/4

dx emx

2/

(15.91) (15.92)

= |N0 |2 from which we nd

N0 = 0 (x) =

, emx
2 /2

(15.93) , (15.94)

1/4

in accordance with Eqns.(6.73) and (6.70). From x| |0 = 1 x | 1 = 1 (x) , a and the expression for a , we nd i m x| x p |0 2 m = = m 2 m 2 x d m dx x|0 ,

(15.95)

(15.96) (15.97) .

x0 (x)

d0 (x) m dx

Matrix elements Using the explicit expression of Eq.(15.94), we have m mx2 /2 d mx2 /2 e xe = dx and so 1 (x) = From x| |1 = a and Eq.(15.99), we nd 2 2 (x) = = 2 (x) = m 2 m m x
1/4

163

(15.98)

1/4

m 2 x emx /2 .

(15.99) (15.100)

2 x | 2 = 22 (x) ,

1/4

d m 1/4 m mx2 /2 xe ,(15.101) m dx 1 m 2 2 2 x 1 emx /2 , (15.102) 2 1 m 2 2 2 x 1 emx /2 , (15.103) 2 2

and so forth. The whole sequence can thus be constructed without solving the dierential equation resulting from the use of the Schrdinger equation o in the position representation. 15.2.4 Application: the harmonic oscillator coherent state

1 Let C, and let |n be the harmonic oscillator state with energy (n+ 2 ) . At t = 0, the coherent state |(0) is dened by

|(0) = e

||2 /2 n=0

n |n n!

(15.104)

What is |(t) , the coherent state at time t? We start with |(0) = e


||2 /2

n=0

n |n n!

(15.105)

Since |n is an eigenstate of the harmonic oscillator hamiltonian H = 1 1 a a + 2 with eigenvalue n + 2 , the time evolution of |n is simply

Matrix elements |n(t) = ei(n+ 2 )t |n and thus |(t) = e


||2 /2
1 n ei(n+ 2 )t |n n! 1

164

(15.106)

n=0

Note that |(t) is normalized, as (t) |(t) = e = e = e = e


||2

( )m i(m+ 1 )t 2 e m| m! m=0

n=0

1 n ei(n+ 2 )t |n n!

(15.107) , (15.108) (15.109) (15.110)

||2

( )m n i(mn)t e m| n , m! n! m,n=0 ( )m n i(mn)t e mn , m! n! m,n=0

2 2 ||2n = e|| e|| = 1. n!

||2

||2

n=0

Let us show that a|(t) = ei Then, since a is linear, a |(t) = e|| = e|| = e||
2

|(t) . Recall that a |n =

n |n 1 .

/2 n=0 /2 n=0 /2 n=0

1 n ei(n+ 2 )t a |n n!

, , ,

(15.111) (15.112) (15.113) (15.114) .

1 n ei(n+ 2 )t n |n 1 n! n (n 1)!

ei(n+ 2 )t |n 1
1

= eit e||

/2 n=0

n1 (n 1)!

ei(n1+ 2 )t |n 1

The sum properly starts at n = 1 since the n = 0 term does not exist. Thus, setting m = n 1, we can rewrite this sum in terms of m, with m starting at m = 0. Hence, we have a |(t) = eit e||
2

/2

1 m ei(m+ 2 )t |m m! m=0

(15.115) (15.116)

= eit |(t) .

Matrix elements A useful secondary result, which follows immediately from above, is [ |(t) ] = a = (t)| a e
it

165

(15.117)

|(t)

= e

it

(t)|

(15.118)

Let us now nd p(t) and x(t) for |(t) . Starting from the denitions a= we have x= and thus x(t) = = = 2m 2m 2m (t)| a |(t) + (t)| a |(t) eit + eit eit + eit , (t) |(t) , (15.121) (15.122) (15.123) 2m a + a , p=i m 2 a a , (15.120) m 2 x+ i p , m a = m 2 x i p , m (15.119)

which is real, as expected. We can clean this up by writing = || ei to obtain 2 || cos (t ) x(t) = (15.124) m Likewise, p(t) m (t)| a |(t) (t)| a |(t) 2 m eit eit (t) |(t) = i 2 = 2m || sin (t ) = i (15.125) (15.126) (15.127)

which is again real.

Matrix elements

166

Finally, let us compute xp for |(t) and verify the Heisenberg uncertainty principle. We need x2 and p2 . From x and p, we nd x2 = = p2 2m a + a a
2 2

2m m 2

+ a a + aa + ()2 , a

(15.128) (15.129)

2m m = 2 m = 2

+ 2 a + 1 + ()2 , a a
2

a a a
2

a a aa + ()2 (15.130) a , (15.131)

2 a 1 + ()2 , a a

where aa = aa a a + a a = a, a + a a = 1 + a a has been used. Thus, x2 (t) = 2m (t)| a


2

(15.132)

|(t) + 2 (t)| a a |(t) +1 + (t)| a2 |(t) ,(15.133)

= = = p2 (t)

2m 2m

eit

+ 2 + 1 + eit
2

(15.134) (15.135) (15.136)

eit + eit

+1 ,

2m m = 2

4 ||2 cos2 (t ) + 1 . (t)| a


2

|(t) 2 (t)| a a |(t) 1 + (t)| a2 |(t) ,(15.137)

m 2 eit 2 1 + eit 2 m 2 eit eit 1 , = 2 m 4 ||2 sin2 (t ) 1 , = 2 m 4 ||2 sin2 (t ) + 1 . = 2 =

(15.138) (15.139) (15.140) (15.141)

Matrix elements We now need (x(t))2 = = x2 (t) x(t) 2m


2

167

(15.142)

4 ||2 cos2 (t ) + 1 2 ||2 cos2 (t ) m (15.143) (15.144) (15.145)

(p(t))2

. 2m = p2 (t) p(t) 2 , m 4 ||2 sin2 (t ) + 1 = 2 2m ||2 sin2 (t ) m . = 2 =

(15.146) (15.147)

Hence, m = . (15.148) 2m 2 2 The coherent state saturates the uncertainty relation for all times. x(t)p(t) =

15.3

Angular momentum theory and the operators L+ and L


1 2 Y (, ) = ( + 1)Y (, ) , (15.149) sin2 2

We looked already in section 9 at the radial dierential equation 1 sin sin Y (, ) +

and showed that the solutions where the spherical harmonics Y m (, ). In this section, we present an alternative method of analyzing this equation, which emphasizes the operator aspect of angular momentum operators.

Matrix elements 15.3.1

168

Commutation relations for angular momentum operators

Recall the three angular momentum operators Lx = y pz z py = i = i Ly = = Lz = = cos y z z y (15.150) (15.151) (15.152) (15.153) (15.154) (15.155) (15.156) They are all hermitian operators since they are constructed from commuting hermitian operators like x and py . The operator L L L2 + L2 + L2 , (15.157) x y z is likewise hermitian. We now systematically consider commutators of angular momentum operators. We recall rst that [, px ] = i 1 , x l [, py ] = 0 , x (15.158)

cotan sin , z px xpz = i z x , x z , i sin cotan cos xpy y px = i x y , y x i .

etc., which is most easily shown in the position representation, where x x, px i , x (15.159)

and similarly for y , py , z and pz . Thus, if f (x, y, z) is an arbitrary function, [, px ] = xpx f (x, y, z) px x f (x, y, z) x = i x f (x, y, z) + i 1 + x x x = i 1 f (x, y, z) , l (15.160) f (x, y, z) , (15.161) (15.162)

Matrix elements

169

using the product rule for derivative in Eq.(15.161). Eq.(15.159) follows from the observation that f (x, y, z) is arbitrary. Next, one can show, most easily in Cartesian coordinates, that [Lx , Ly ] = i Lz , [Ly , Lz ] = i Lx , [Lz , Ly ] = i Ly . (15.163)

Notice how the indices are cyclically permuted between x, y and z.. Let us summarize this as follows by dening ijk , where i, j, k can take the values x, y, z, as be a symbol dened as follows: ijk = 0 if i = j, j = k or i = k , xyz = yzx = zxy = +1 yxz = xzy = zyx = 1 The commutators are then easily summarized as [Lj , Lk ] = i jkl Ll . (15.167) (15.164) (15.165) (15.166)

It is also easy to show that L2 , Li = 0 for i = x, y, z. To show this, consider, for instance, i = 3. L2 , Lz = = x y L2 + L2 + Lz , Lz x y z L2 , Lz + L2 , Lz + L2 , Lz , (15.168) (15.169) (15.170)

= Lz , L2 Lz , L2 y y = Lz , Ly Lx Lx Lz , Lx Lz , Ly Ly Ly Lz , Ly

(15.171)

= (i Ly )Lx Ly (i Ly ) (i Lx )Ly Ly (i Lx )(15.172) = i Ly Lx + i Ly Lx i Ly Ly + i Ly Ly , (15.173) = 0. (15.174) Thus, L2 and one component of angular momentum can be chosen to be simultaneously diagonal, i.e it is possible to assign to nd angular states with simultaneous denite values of L2 and one of Li . If we choose i = z, then these angular states, expressed in spherical coordinates, are nothing but the Y m (, ) that we found by solving the angular dierential equation.

Matrix elements

170

Let us establish some facts. The operations Li are all hermitian. Let | be any vector (not necessarily normalized), and dene | Li | The corresponding | is then | = = Li | | Li

(15.175)

, = |Li ,

(15.176) (15.177)

where the hermiticity of Li has been used. By the denition of the inner product, we have 0 | = = Hence, for any vector | , |L2 | 0 , since L2 =
i=x,y,z

|Li Li | , | Li
2

(15.178) (15.179)

| .

(15.180) (15.181)

i L2 .

15.3.2

L+ and L L+ = Lx + iLy , L = Lx iLy .

We now introduce two operators: (15.182) (15.183)

Note that L+ and L are not hermitian. In fact, L+ We then have Lz , L+ = Lz , Lx + iLy = Lz , Lx + i Lz , Ly (15.185) (15.186) (15.187) = i Ly i(i Lx ) = (Lx + iLy) = L+

= L .

(15.184)

Matrix elements Similarly Lz , L = L Furthermore, L+ , L = = Lx + iLy , Lx iLy (Lx , iLy + iLy , Lx

171

(15.188)

(15.189) (15.190) (15.191)

= 2i Lx , Ly = 2i Lz = 2 Lz Also: L+ L = (Lx + iLy )(Lx iLy ) x y = L2 + iLy Lx iLx Ly + L2 = L2 + L2 + i Ly , Lx = L2 + L2 + i(i )Lz x y x y x y z z z = L2 + L2 + L2 L2 + Lz = L2 L2 + Lz From this m|L+ L | m = m|L L | m L | m 2 0 z m|(L2 L2 + Lz )| m 2 ( ( + 1) m2 + m) m| m 0 ( + 1) m(m 1)
2

(15.192) (15.193) (15.194) (15.195)

(15.196) (15.197) (15.198) (15.199) (15.200)

= = = ( + 1) m(m 1) or 1 + 2 Similarly, from


2

1 m 2

(15.201)

m|L L+ | m 0, we nd ( ( + 1) m(m + 1)) 0 ( + 1) m(m + 1) 1 + 2


2

(15.202) (15.203)
2

1 m+ 2

(15.204)

Matrix elements

172

From this, we conclude, depending on the relative signs of the square roots, that 1 1 m 2 2 1 1 + m + 2 2 1 1 + m+ 2 2 1 1 + m 2 2 + Putting these together, we have m . (15.209) m + 1, m , m , m 1. (15.205) (15.206) (15.207) (15.208)

To obtain relations between the various | m , consider the state L | m . Then: Lz L | m = = = = Lz L L Lz + L Lz | m Lz , L + L Lz | m L + L Lz | m (15.210) (15.211) (15.212)

L | m + m L | m = (m 1) L | m (15.213)

Thus, L | m is an eigenstate of Lz with eigenvalue m 1. Hence, L | m is proportional to |l, m 1 since Lz | , m 1 = (m 1)| , m 1 . Let L | m = C | , m 1 , (15.214) where C is the proportionality factor to be found. Observe that, for L | m to be normalized m|L L | m = 1 = m|L+ L | m , = |C |2 l, m 1|l, m 1 = |C |2 = 2 [ ( + 1) m(m 1)] ( + m)( m + 1) . So that, ( + m)( m + 1)| , m 1 (15.218) (15.215) (15.216) (15.217)

Thus, we can choose C = L | m =

Matrix elements Similarly, consider L+ | m . Lz L+ | m = (Lz L+ L+ Lz + L+ Lz )| m = ( Lz , L+ + L+ Lz )| m

173

(15.219) (15.220)

= ( L+ + L+ Lz )| m = L+ | m + L+ m| m (15.221) = (m + 1)L+ | m (15.222) Thus, L+ | m = C+ | , m + 1 . To nd C+, start with + m|L L+ | m = 1 = |C+ |2 = m|L L+ | m 2 = m|(L2 Lz Lz ) m = 2 ( + 1) m2 m m| m , ( m)( + m + 1). and ( m)( + m + 1)| , m + 1 ( m)( m + 1)| , m 1 (15.227) (15.228) (15.223) (15.224) (15.225) (15.226)

from which we obtain C+ = L+ | m L | m 15.3.3 Since = =

Matrix elements of Lx and Ly L+ = Lx + iLy , L = Lx iLy ,

we obtain the matrix elements of Lx and Ly through Lx =


1 2

L+ + L ,

Ly =

1 2i

L+ L .

(15.229)

Using Eq.(15.228), we nd m |Lx | m m |L y | m =


1 2

( m)( + m + 1) ( + m)( m + 1) ( m)( + m + 1)

m ,m+1 m ,m1 , m ,m+1 m ,m1 . (15.231) (15.230)

1 +2 1 = 2i 1 2i

( + m)( m + 1)

Matrix elements

174

Thus, for a state with = 1, we have the possible kets | m = |11 , |10 and |1, 1 . The matrix representation of Lx in this basis is obtained by noting that the nonzero matrix elements are 10|Lx |11 10|L |11 = 2 , = 2 =
1 2 1 2

(1 + 1)(1 1 + 1) , (15.232)

11|Lx |10 1, 1|Lx |10

= = =

10|Lx |1, 1

(15.233) 2 x , (15.234) 10|L |11 = 10|Lx |11 = 2 1 1 1, 1|L |10 = 2 (1 + 0)(1 0 + 1) ,(15.235) 2 2 , (15.236) 2 2 . (15.237) 1, 1|L |10 = 1, 1|Lx |10 = x 2

Thus, in the threedimensional space spanned by |11 , |10 and |1, 1 , we have 0 1 0 2 1 0 1 . Lx (15.238) 2 0 1 0 This is a hermitian matrix, as expected since Lx is a hermitian operator. Likewise, one readily nds that, when = 1, 0 1 0 2 1 0 1 . Ly (15.239) 2i 0 1 0 Finally, we have 1 0 0 Lz 0 0 0 . 0 0 1

(15.240)

Note that, as matrices, we have, of course, [Lx , Ly ] = i Lz etc. 15.3.4 Constructing the simultaneous eigenfunctions of L2 and Lz .

Let , | m = Y m (, ). From the condition m , it follows that there must be a lowest m, i.e there must exists mmin such that L |mmin = 0.

Matrix elements

175

If not, then successive application of L on | m would eventually produce a state where m < . Obviously, the smallest value of m is . Let us consider, using spherical coordinates, L = Lx iLy + cos cotan cos sin cotan d + cotan (i2 sin i cos ) = ei d d , = ei + i cotan d = ei + i cotan = i sin We also have, in spherical coordinates, Lz = i . Using this on the ket | , in the , | basis, we nd (15.247) (15.248) (15.246) (15.241)

(15.242) (15.243) (15.244) (15.245)

Y , (, ) = Y , (, ) , Lz Y , (, ) = i Y , (, ) = g()ei Since m = is the smallest possible value of m, we have L Y , (, ) = 0 . This translates into the dierential equation for g(): with solution g() = C (sin ) , d + i(i )cotan g() = 0 d

(15.249)

(15.250)

(15.251)

Matrix elements so that Y , (, ) = C (sin ) ei

176

(15.252)

The integration constant C is determined from the normalization condition. d|Y , (, )|2 = 1 = |C |2 = 2|C |2
0 0 2

d
0

d sin (sin )2 (15.253) (15.254)

d sin (sin )2

To integrate, let = cos and d = sin d. The limits of integration must be adjusted. When = 0, = 1 and when = , = 1 so
0

d sin (sin )2

=
1 1

d(1 2 ) d (1)n
n=0

(15.255) ! 2n n!(n )!
1 1

=
1

(15.256) , (15.257) (15.258) (15.259)

=
n=0

(1)n

2n+1 ! n!(n )! 2n + 1 1 l , n 2n + 1

= 2 = To see this, let


1 1

(1)n
n=0 2 +1

2 ( !)2 (2 + 1)!

= 1. 3
1

d(1 2 ) = = 2:

= 1
1

1 1 1 + 3 3

4 23 8 = = . (15.260) 3 3! 6

Similarly, for
1 1

d(1 2 )2 = 2

2 3 3 + (15.261) , 3 5 0 0 16 (15 10 + 4) 2 1 =2 = , (15.262) = 2 1 + 3 5 15 15 128 16 25 2 2 = = (15.263) = 5! 2345 15 d(1 2 2 + 4 ) = 2

Matrix elements and so forth. Thus, Y , (, ) = (2 + 1)! 1 (sin ) ei 4 !2

177

(15.264)

To obtain the remaining spherical harmonics, consider , |(L+ ) +m | , and recall that L+ | m = Then: (L+ ) +m | , = (L+ ) +m1 | , + 1 2 1 = (L+ ) +m2 | , + 2 (2 ) (2 1) 2 2 = (L+ ) +m3 | , + 3 (2 )(2 1)(2 2) 1 2 3 and generally: , |(L+ ) +m | , Hence, Y ,m (, ) = , | m = Using L+ = i ei i cotan = ei + i cotan Y , (, ) = and +m , |L+ | , =
+m i( +m)

( m)( + m + 1) | , m + 1

(15.265)

(15.266) (15.267)
3

(15.268)

(2 )!( + m)! , | , m ( m)!

+m

(15.269)

( m)! , |(L+ ) +m | , (2 )!( + m)!

1
+m

(15.270)

(15.271) (15.272) (15.273)

(2 + 1)! 1 2 (sin ) ei 4 ! + i cotan


+m

Y , (, ) , (15.274)

Matrix elements we nally arrive at Y ,m (, ) = ( m)! (2 )!( + m)! e


i

178

(2 + 1)! 1 4 !2
+m

+ i cotan

(sin ) ei (15.275) .

For example, consider the case where Y1,1 (, ) = = Y1,0 (, ) =

= 1 . Then, 6 sin ei (15.276) , 16 (15.277)

(2 1 + 1)! 1 1 sin ei = 4 1! 2! 3 sin ei 8 (1 0)!3 1 1 i(1+0) e (1 + 0!4 1! 21 i cos cos + i sin ei

(15.278)

= = Y1,1 (, ) =

3 1 i e 4 2 3 cos , 4

cos (i) sin ei , (15.279) sin (15.280)

(1 1)! 3 1 1 (1 + 1)! 4 1! 2! e
i

+ i cotan

sin ei (15.281)

3 1 i e + i cotan 2 4 2 ei + icotan sin ei 3 1 i e 8 2 + i cotan 2 cos

(15.282) (15.283) (15.284)

= =

3 i e ( sin ) = 8

3 i e sin 8

Matrix elements An alternative is to work directly in Cartesian coordinates. Lx = y pz z py = i Lz = xpy y px Ly = pz + z px = i x The expressions for L+ and L are then L+ = Lx + iLy = L = Lx iLy = Clearly, z z +i x y i x y (x + iy) z (x iy) z x +z z x . y z z y ,

179

(15.285) (15.286) (15.287)

(15.288) (15.289)

(15.290) L (x iy) = z(1 i(i)) = 0 z (x iy) = i (ix y 1) = (x + iy) = (x iy)(15.291) L Thus, (x iy) is proportional to Y1,1 (, ), or x, y, z|1, 1 = 1 Y11 Quite clearly, then: L (x iy) = 0 , so (x iy) = Y , (, ) Using spherical coordinates: x iy = r sin cos ir sin sin = rei (sin ) (x iy) = r ei (sin ) = r 2 ! Let x, y, z| , = (x iy) = r 2 ! 4 , | , . (2 + 1)! (15.298) 4 Y , (, ) (2 + 1)! (15.295) (15.296) (15.297) (15.294) Lz (x iy) = (x iy)l (15.293) (15.292)

Matrix elements Then x, y, z|(L+ ) +m | , = (2 )!( + m)! x, y, z| m ( ) +m , ( m)! 4 , |(L+ ) +m | , , (2 + 1)! 4 (2 + 1)! (2 )!( + m)! Y ,m (, ) ( m)!

180

(15.299) (15.300) (15.301)

=r2 ! =r2 ! On the other hand,

x, y, z|(L+ ) +m | , = (L+ ) +m (x iy) = ( )


+m

(15.302) (15.303) (x + iy) z


+m

+i x y

(x iy) (15.304) (15.305)

= ( ) +m r 2 ! or Y ,m (, ) = 1 1 r 2 !

4 ( + m)! Y ,m (, ) (2l + 1) ( m)!

( m)!(2 + 1) ( + m)!4 + (x + iy) x y z


l+m

(x iy) .(15.306)

Matrix elements For instance: Y1,1 (, ) =

181

2! 3 1 3 1 1 (x iy) = (x iy) (15.307) 1 1! r2 0!4 r 8 13 1 1 Y1,0 (, ) = r 2 1 1 4 z +i (x iy) (x iy)(15.308) x y z 11 3 (2z 0) = r 2 4 0! 3 11 Y1,1 (, ) = r2 2!4 z +i x y = = 1 r 3 8 z +i y y 3 z 4 r (15.309)

(x iy)

(x iy)15.310) ( (15.311) (15.312)

(x + iy)

z z

3 (x + iy) 8 r

Note that Y (, ) = (1)m Y ,m (, ) . ,m

Uncertainty relations

182

16

Uncertainty relations

The purpose of this section is to present a rigorous discussion of the uncertainty relation.

16.1

A B

1 2|

[A, B] |

Let | be any normalized state. If |X| = X , then, by denition, we have, for any observable X: X X X , (X)2 = = = = | X X
2

(16.1) |
2

|X 2 2X X + X 2 | |X 2 | 2 |X| X + X |X 2 | X 2 , X2 X 2 0 .

(16.2)

We now show the uncertainty relation: (A)2 Proof: Let |A A| |B B| = A| | |A| , = B| | |B| (B)2 1 2 | [A, B] | . 4 (16.3)

(16.4)

where |A is any normalized state. (Be mindful of this condition: the proof can break down if |A is non normalizable.) Note, for future reference, that the strict equality holds only if |B is proportional to |A . Then, by Schwarz inequality, A |A B |B | A |B |2 Assuming that A and B are hermitian, we have A |A = |AA| = (A)2 , (16.6) (16.5)

Uncertainty relations

183

and similarly for B |B . Still under the assumption that the operators are hermitian, the inner product on the right-hand side of Eq.(16.5) can be developped into A |B = = |AB| (16.7) 1 1 | 2 (AB BA) + 2 (AB + BA)| . 16.8) (
1 2

Consider now the rst term of this last sum:


1 1 | 2 (AB BA)| = | 2 [A, B]| =

|[A, B]| .

(16.9)

The operator [A, B] = AB B A is clearly anti-hermitian, since [A, B] = = = = (AB B A) , (AB) (B A) , B A A B B A AB = [A, B] ,

(16.10)

using the fact that A and B are hermitian. Now, the expectation value of an anti-hermitian operator C (i.e. such that C = C) is purely imaginary, since it changes sign under complex conjugation: |C|

= |C | = |C| .

(16.11)

Let us therefore denote |[A, B]| ic , with c R. On the other hand, the operator AB + BA is clearly hermitian; its expectation value is purely real and denoted by c+ . Hence A |B = 1 1 2 (c + c2 ) c2 + 4 4 1 2 | [A, B] | . 4 Putting it all together, we get | A |B |2 = (A)2 (B)2 | A |B |2 1 2 | [A, B] | , 4
1 (ic 2

+ c+ ) ,

(16.12)

(16.13)

which proves the claim. In particular, if A = x , B = p so that [, p] = i 1 we then obtain x l, x p


1 2

(16.14)

Uncertainty relations

184

16.2

Understanding the assumptions

Suppose that |x0 is an eigenstate of x, i.e. x|x0 = x0 |x0 . Then, clearly, x = 0 for this state, and x p 0 p = =
1 | 2 1 | 2 1 2

x0 |[, p]|x0 | , x x0 |i 1 |x0 | , l x0 |x0 .

(16.15)

If we go with the assumption that |x0 is normalizable to 1 and that p is 1 hermitian, then we are in trouble: the r.h. side is 2 while the l.h. side is 0 if p is nite. If p , the l.h. side must be considered much more carefully: one must use Fourier analysis arguments to show, using a sequence of normalizable states approaching |x0 , that p when x 0. The state |x0 is itself nonnormalizable. Alternatively, if we insist on x0 |x0 = 1, then it follows that p cannot be hermitian.

Uncertainty relations

185

Figure 21: As soon as they are under observation, the atoms behave dierently.

Complex numbers

186

Complex numbers

The entire eld of classical mechanics can studied using real numbers only. It is possible to use complex numbers (or quaternions, or octonions), but their introduction is incidental and represents merely a (sometimes good) trick to help with the calculations. By contrast, complex numbers are essential to quantum mechanics.

A.1

A bit of history
mz + b = 0 , m, b R , (A.1)

If you are given the linear equation

then the solution z to this equation is also a real number. However, if you are asked to solve the quadratic equation az 2 + bz + c = 0 , (A.2)

where, once again, the coecients a, b, c R, then it may be that the solutions b b2 4ac (A.3) z = 2a do not exists over the reals if the discriminant b2 4ac < 0. In order to solve all quadratic equations, we need to introduce a new kind of number called the complex number. The simplest complex number is i, and its basic property is that i2 = 1 . Suppose b2 4ac < 0. Then, write b2 4ac = (4ac b2 ) = i2 (4ac b2 ) (A.5) (A.4)

where 4ac b2 > 0. Since we know (in principle) how to compute the square root of a positive number like 4ac b2 , the square root of a square like i2 , and the square root of a product, we nd that b i2 (4ac b2 ) b i 4ac b2 = . (A.6) z = 2a 2a

Complex numbers

187

Example A.1 The roots of the quadratic equation 3z 2 2z + 1 = 0 are 1 1 z+ = 3 (1 + i 2) and z = 3 (1 i 2). When b2 4ac < 0, the solutions z to Eq.(A.2) are made of parts: two the real part, b/2a, and another part, called the imaginary part, 4ac b2 , which comes multiplied by the imaginary unit i. Please note that both the real and imaginary parts are real numbers, as a, b and c are real and, by assumption, 4ac b2 > 0. One writes a general arbitrary complex number z = x + iy, where x and y are both real. x is the real part of z, often denoted x = Re(z), and y = Im(z) is the imaginary part of z. Two complex numbers z1 and z2 are equal if their real and imaginary parts are respectively equal, i.e. if z1 = x1 + iy1 and z2 = x2 + iy2 , then z 1 = z 2 x1 = x2 and y1 = y2 . (A.7)

Example A.2 Consider the complex number z = 3 + i. Its real part is 3 and its imaginary part is . A number is real if its imaginary part is 0, otherwise it is complex. If the real part of a complex number is 0, then one often says that this number is purely imaginary. If you are now given a cubic equation: az 3 + bz 2 + cz + d = 0 , a, b, c, d R , (A.8)

then you may think one would require the introduction of yet another type of number, the simplest of which (call it putatively j), would be such that j 3 = 1 (or some similar property related to the third power of j). It turns out, however, that this is not so. The great triumph of algebra, as contained in the Fundamental Theorem of Algebra, is the observation that, for any equation of type
n

an z + an1 z

n1

+ . . . + a0 =
p=0

ap z p = 0 ,

(A.9)

with ap R, one can nd all the solutions using at most complex numbers. You never need to use anything more complicated than complex numbers to solve an algebraic equation of any degree if the coecients are real.

Complex numbers

188

A.2

Adding complex numbers

It is convenient to associate with a complex z = x + iy a point (x, y) on the R2 plane. Usually, the horizontal axis of the plane is chosen as the real axis, while the vertical axis is the imaginary axis. Hence, all real numbers lie on the horizontal axis, and purely imaginary numbers on the vertical axis. This representation is known as the Cartesian representation of the complex numbers. It is illustrated in g.22.
Im(z)

z=(x,y) y

Re(z) x

Figure 22: The Cartesian representation of a complex number z = x + iy.

The Cartesian representation is useful to picture the operation of addition of two (or more) complex numbers. If z1 = x, +iy, and z2 = x2 +iy2 , then the sum z3 = z1 + z2 is this complex number x3 + iy3 such that x3 = x1 + x2 and y3 = y1 + y2 . Adding complex numbers therefore corresponds, graphically, to adding vectors in R2 having, respectively, (x1 , y1 ) and (x2 , y2 ) as components. The general properties of addition of complex numbers are obvious: 1. z1 + z2 = z2 + z1 , i.e. the order in which they are added doesnt matter, 2. z1 + (z2 + z3 ) = (z1 + z2 ) + z3 , 3. 0 = 0 + 0i = 0i is the neutral element: z + 0 = 0 + z = z, 4. if z1 = x, +iy,, then its inverse z1 = x1 iy1 is unique and such that z1 + (z1 ) = 0, 5. if k R, then k(z1 + z2 ) = kz1 + kz2 = k(x1 + x2 ) + ik(y1 + y2 ) = kx1 + kx2 + iky1 + iky2 ,

Complex numbers 6. if k, m R, then (k + m)z = kz + mz, 7. if k, m R, then k(mz) = (km)z, 8. 1z = z.

189

Example A.3 Let z1 = 4 3i, z2 = e2 + i ln(2) be two complex numbers. Then z1 + z2 = (4 + e2 ) + i(3 + ln(2)) , 7z1 = 7(4 3i) = 28 21i , etc.

A.3

The complex conjugate

There is a very important complex number associated to z: it is called the complex conjugate of z and is usually denoted by z (or z ). z is the complex number z = x iy, obtained by changing i i everywhere in z. 1 One sees that the real part x of z can be obtained from x = 2 (z + z ) while the imaginary part is obtained from i z z = 2iy i(z z ) = 2y y = (z z ) . 2 (A.10)

Example A.4 Let z1 = 4 3i, z2 = e2 + i ln(2) be two complex numbers. Their respective complex conjugates are
z1 = 4 + 3i , z2 = e2 i ln(2) .

Next, note that z z = (x + iy) (x iy) = x2 + y 2 0 . (A.11)

Thus, z z is necessarily real and non-negative. In fact, it is zero only if z = 0; thus z z measures the square of the length of the complex number z in the R2 plane. It is customary to denote the length of z, called the modulus of z, by (A.12) |z| + z z .

Complex numbers

190

Example A.5 Let z = 3 + 4i. Then z = 3 4i, z z = 25 |z| = 5 .

A.4
A.4.1

Multiplication and division


Multiplying and dividing in the Cartesian representation

Let z1 = x, +iy, and z2 = x2 + iy2 be two complex numbers. Their product z3 = z1 z2 is dened by simply considering i like any other number and applying the usual distributivity of multiplication: z1 z2 = (x1 + iy1 ) (x2 + iy2 ) , = x1 x2 + iy1 x2 + ix1 y2 + i2 y1 y2 , = (x1 x2 y1 y2 ) + i(x1 y2 + y1 x2 ) , where we have used i2 = 1. Example A.6 Let z1 = 4 3i, z2 = e2 + i ln(2). Then z1 z2 = (4e2 + 3 ln(2)) + i(3e2 + 4 ln(2)).

(A.13)

Division by a complex number requires the use of the complex conjugate. We dene the quotient z3 =
z1 z2 z1 z2 z1 = . z2 z2 z2 z2 z2

(A.14)

The denominator z2 z2 is a real number, so that

x2 y1 x1 y2 2 x2 + y2 2 (A.15) This kind of manipulation can become quite cumbersome, especially if the numerator and denominators contain multiple products of complex numbers. z3 = =

y1 x1 +i z2 z2 z2 z2

y2 x2 i z2 z2 z2 z2

x1 x2 + y 1 y 2 +i 2 x2 + y2 2

Complex numbers

191

Example A.7 Let z1 = 4 3i, z2 = e2 + i ln(2). Then 4e2 3 ln(2) z1 = 4 +i z2 e + ln(2)2 3e2 4 ln(2) e4 + ln(2)2 .

A.4.2

The polar representation


Im(z)

z=(cos( ) , sin( )) sin( ) Re(z) cos( )

Figure 23: The polar representation of a complex number z = (cos + i sin ).

To multiply complex numbers, it is convenient to use the socalled polar representation. Since z z is the square of the length of z = x + iy, we consider the vector z in the plane R2 and note that, by simple trigonometry, we can dene an angle such that x = cos , y = sin , = |z| = zz . (A.16) Thus, when = 0, z is real, whereas, when = /2, z is purely imaginary. It is then a simple matter to write z = x + iy = (cos + i sin ) , with = |z| = z z , tan = y . x (A.17) (A.18)

Complex numbers

192

The combinaison cos + i sin will soon become supremely important. For the moment, let us write it in the shorthand notation cos + i sin cis() . (A.19)

In particular , if z = cis(), then the complex conjuage z = cis(). Example A.8 Let z1 = 1 + i 3, z2 = 3 + 4i. Their polar forms are, respectively, z1 = 2 cis( 2 ) , 3
4 z2 = 5 cis(arctan( / 3)) .

If z1 = x1 + iy1 , z2 = x2 + iy2 , then their product is simply expressed, in the polar representation, as z1 z2 = 1 2 (cos 1 + i sin 1 ) (cos 2 + i sin 2 ) , = 1 2 (cos 1 cos 2 sin 1 sin 2 ) +i1 2 (cos 1 sin 2 + sin 1 cos 2 ) , = 1 2 cos(1 + 2 ) + i1 2 sin(1 + 2 ) , = 1 2 cis(1 + 2 ) . One thus observes the fundamental property that cis(1 ) cis(2 ) = cis(1 + 2 ) . Division is also quite easy:
z1 z2 1 2 1 z1 = = 2 cis(1 2 ) = cis(1 2 ) . z2 z2 z2 2 2

(A.20)

(A.21)

(A.22)

Example A.9 Let z1 = 3i , z2 = 1 + i 3. The polar representation of z1 is z1 = 3 cis( ), and the polar representation of z2 was obtained in the 2 previous example. We have, on the one hand, z1 z2 = 3i(1 + i 3) = 3 3 3i = 6 cis( 7 ) 6 while, on the other hand, z1 z2 = 3 cis( ) 2 cis( 2 ) = 6 cis( 7 ) , 2 3 6

Complex numbers as expected. Example A.10 Let z1 = 3i , z2 = 1 + i 3. Then 3 z1 = cis( ) 6 z2 2 as can be conrmed using the Cartesian representation.

193

A.4.3

Eulers theorem

Eq.(A.21) is quite remarkable. If one thinks of cis as a function, then it is wise to ask what are the known functions that possess this property cis() cis() = cis( + ) . The answer is that (besides the trivial constant function) there is only one: the exponential function. Indeed, if f (x) = ex , then f () f () = f ( + ). What we have observed is that there is (apparently, at least) a connection between cis and the exponential function. There are several ways of nding the link: let us assume that cos + i sin = Aek , A, k C . (A.23)

Recall now the Taylor series for cos , sin and ekx : cos = 1 1 2 1 4 + + ... , 2! 4! 1 3 1 5 sin = + + . . . , 3! 5! 1 2 2 1 3 3 ek = 1 + k + k + k + . . . 2! 3!

(A.24)

Since Eq.(A.23) is a functional relation, it must hold for every , so that we can compare the l.h.s and r.h.s of Eq.(A.23) term by term. Writing the rst few terms of this expansion: 1 + i 1 2 1 + . . . = A + Ak + A k 2 2 + . . . . 2! 2! (A.25)

From the terms in 0 (i.e. the constant terms), we have A = 1. From the terms in , we have i = Ak. Using A = 1, we immediately nd that k = i.

Complex numbers

194

We can verify that this choice holds for all powers in . Hence, we nd a famous formula, called Eulers theorem: cos + i sin = ei . (A.26)

(Euler proved hundreds of theorems in just about every eld of mathematics that existed when Euler was around; these theorems are called Eulers theorem on this or Eulers theorem on that, depending on the particular theorem at hand. Eq.(A.26) is so important that it is does not have a special name: its simply called Eulers theorem.) A rst consequence of Eq.(A.26) is that cos =
1 2

ei + ei ,

sin =

1 i e ei . 2i

(A.27)

Eq.(A.27) is extremely useful in proving trigonometric identities. Example A.11 Using Eq.(A.27), one can prove that cos( + ) = cos() cos() sin() sin() . From the expression for cos() and sin(), we have cos() cos() = = = sin() sin() = = =
1 1 ei + ei 2 ei + ei , 2 1 ei(+) + ei() + ei() + ei(+) , 4 1 1 cos( + ) + 2 cos( ) , 2 1 1 ei ei 2i ei ei , 2i 1 ei(+) ei() ei() + ei(+) 4 1 1 2 cos( + ) + 2 cos( ) .

We can add these to results to obtain the desired trigonometric identity. Example A.12 Let m, n be integers. Show that
2

cos(m) cos(n) d =
0

0, ,

if m = n , if m = n .

To show this, we use, from the previous example, cos(m) cos(n) = 1 i(m+n) e + ei(mn) + ei(mn) + ei(m+n) , 4

Complex numbers

195

so that, by integrating the exponential functions, and assuming that m = n,


2

cos(m) cos(n) d
0

1 1 1 ei(n+m) + ei(mn) 4 i(m + n) i(m n)


2

1 1 ei(mn) + ei(mn) + i(m n) i(m + n) 0 1 1 1 ei2(n+m) 1 ei2(mn) 1 = 4i (m + n) (m n) 1 1 ei2(mn) 1 ei2(mn) 1 + (m n) (m + n) 1 = [1 1 + 1 1 + 1 1 + 1 1] , 4i = 0. If m = n, then cos(m) cos(m) = so that
0 2

1 2im 1 e + 2 + e2im = 2 (cos(2m) + 1) , 4


2

1 sin(2m) + cos(m) cos(m) d = 2 2m

= ,
0

which completes the proof of the result. Another consequence of Eulers theoreom is as follows: set = . Then ei + 1 = 0 . (A.28)

Euler couldnt imagine that these seemingly completely unrelated numbers, e, i, the angle , and the numbers 1 and 0, could come together in this the simplest of all mathematical relations. Indeed, Euler considered this result a proof of the existence of God. Putting all of this together, we nally have the polar form of a complex number z as z = (cos() + i sin()) = ei = cis() . (A.29)

Complex numbers A.4.4 Taking powers and roots

196

The use of Eq.(A.29) makes it particularly easy to take powers of complex numbers. Thus, if p is an integer and z = ei , then z p = p eip = p cisp. (A.30)

Example A.13 Let z = 1 + i 3. To compute z 3 , rst use (a + b)3 = we 3 2 2 3 a + b + 3ab + b and expand explicitly (1 + i 3)3 with a = 1 and 3a b = i 3 to nd z3 = 8 . Using the polar form with z = 2 cis( 2 ), we immediately nd 3 z 3 = 23 cis(2) = 8 . Try computing z 17 with the Cartesian representation! One would think that the extension of Eq.(A.30) to the case where p is 1 fractional (say, / 2) would be easy: z /2 =
1

ei/2 .

(A.31)

However, there is a subtelty involved in taking roots. Even with real numbers, we know that 25 = 5 , (A.32) that is, there are two solutions. Thus, we expect that
1 z / 2 = ei/2 , i/2 i/2 e = e .

(A.33)

How can we generalize this to taking the nth root? One would expect to nd n solutions. For instance, the four (complex) numbers z1 , z2 , z3 and z4 4 such that zk = 1 are simply 1, i since (i)4 = 1. Let us go back to the logic of nding the two numbers z1 and z2 such that 2 2 z1 = z2 = 25. We start by nding one number, say , such that 2 = 25. Let = 5. Next, consider the all the numbers whose square is 1: there are two because were calculating a square root, and they are 1 = 1 and 2 = 1.

Complex numbers

197

One then easily sees that the two solutions to z 2 = 25 are z1 = 1 = +5 and z2 = 2 = 5. This works because zk = k , 2 zk = (k )2 , = (k )2 2 , = 1 25 ,

(A.34)

2 since, by construction, k = 1 and 2 = 25. The procedure to obtain all the nth root of the complex number z is based on this line of thought, along with the observation that k = (e2ik/p )p = e2ik = 1. To nd the nth root of z, start with one complex number such that n = z. Finding is actually quite simple: just express z = ei and then n = 1/n ei/n . Then, multiply by all the numbers k such that k = 1. n The complete list of complex numbers k such that k = z is then simply obtained by multiplying in turn by every k = e2ik/n . Example A.14 Let z = 1/2 + i 3/2. To nd all the numbers z 1/4 , let us 4 rst nd one number z1 such that z1 = z. We use the rst polar form of z, from which we obtain

z1 = z 1/4 = ( cis( 2 ))1/4 = cis( 2 ) = 3 12

3 2

1 + 2 i.

Next, note that 1 = e2i/4 = i , 2 = e22i/4 = 1 , 3 = e23i/4 = i , 4 = 4 e24i/4 = 1 , are the four numbers such that k = 1. Thus, the four roots are 1 z1 = i 2 z1 = 3 z1 = 4 z1 =
3 1 1 + 2 i = 2 + i 23 2 1 1 23 + 2 i = ei/6 ei 1 i 23 + 2 i = ei/3 1 z1 = 23 + 2 i .

= ei/6 ei/2 = e2i/3 = e7i/6

(A.35)

Example A.15 Let be a complex number such that n = 1 (n is a positive integer). Show that, if = 1, then
n

+ + + ... +

n1

+ =
p=1

p = 0 .

Complex numbers Proof: Suppose that


n n p=1

198 = A , A C . Then,
n n

p=1

= A =
p=1

p+1

=
p=1

p , = A ,

(A.36)

since n+1 = n = . Thus, A = A. There are two solutions: = 1, which contrary to the original assumption that = 1 and so must be rejected, or A = 0, which is the only solution compatible with = 1. QED.

Simpsons rule

199

Numerical integration and Simpsons rule

It is always possible to nd the derivative of a function, but it is not always possible to reverse the process and nd an expression for dx g(x) . (B.1)

Two examples will suce to illustrate this: one cannot solve the indenite integrals sin x 2 . (B.2) dx ex , or dx x Quite generally, it may therefore not be possible to evaluate the denite integral
b

dx g(x)
a

(B.3)

by simple means. One must then proceed numerically, keeping in mind that Eq.(B.3) represents the area under the curve.

B.1

Preliminaries

There are many ways of understanding the socalled Simpson s rule , but the following is particularly intuitive. Take the function g(x) in Eq.(B.3) and approximate it over the interval [a, b] by a polynomial: g(x) c0 + c1 x + c2 x2 + ...cn xn ,
b b

(B.4)

with the coecients c0 , ..., cn chosen in some way to be specied. Then, dx g(x)
a a

dx c0 + c1 x + c2 x2 + ...cn xn ,

(B.5)

which can be integrated easily. Consider, as a very simple example, the problem of numerically integrating
2

ex dx.

(B.6)

Of course, this is a made up problem: we can easily get a primitive for the corresponding indenite integral and nd the exact result
2 0

ex dx = ex

2 0

= e2 + 1 0.8647.

(B.7)

Simpsons rule

200

We will use this simply as a guide to see how close various numerical schemes come to the true answer. One could approximate this integral by replacing the ex by a straight line: ex c0 + c1 x. (B.8) To determine the coecients, use x = 0 and x = 2 to get the system e0 = c0 , which immediately yields c0 = 1 ,
2 0

e2 = c0 + 2c1

(B.9)

c1 =

ex dx
0

e2 1 , 2
2 0

(B.10)

1 (c0 + c1 x) dx = c0 x + 2 c1 x2 1 42

= 2c0 +

c1 = 2(c0 + c1 ) = 1.1359 .

(B.11)

We can get a feel for what is going on by considering Fig.24. We see that the linear approximation is always above the function ex , and the area under the straight line is visible larger than the area under ex .
1

Figure 24: The function ex and its linear approximation by c0 + c1 x over the range [0, 2].

Alternatively, we could consider replacing ex by the quadratic ex c0 + c1 x + c2 x2 , (B.12)

5. 1

5. 0

2. 0

8. 0 6. 0

c0+c1x e-x

4. 0

Simpsons rule using the three points x = 0, x = 1 and x = 2 to get: e0 = c0 , e1 = c0 + c1 + c2 , e2 = c0 + 2c1 + 4c2 . Solving for the coecients yields c0 = 1 , so that
2 0

201

(B.13)

c1 =

1 4e + 3e2 , 2e2
2 0

c2 =

1 2e + e2 2e2

(B.14)

e dx

c0 + c1 x + c2 x2 dx

(B.15) (B.16)

8 = 2c0 + 2c1 + 3 c2 = 0.8689.

The situation is now illustrated on Fig.25. The quadratic curve does a much better job of approximating ex than the straight line, with the result that the approximate value of the integral is much closer to the exact value than corresponding result for the straight line.
1

c0+c1x+c2x2
8. 0

e-x

Figure 25: The function ex and its linear approximation by c0 + c1 x + c2 x2 over the range [0, 2].

Intuitively, it is clear that, as we add more and more terms to the polynomial on the right hand side of Eq.(B.4), we are increasing the accuracy of the calculation. However, the improvement in accuracy is done at the cost

5. 1

5. 0

2. 0

6. 0 4. 0

Simpsons rule

202

of increasing the diculty in specifying the coecients ci . If we keep very few terms, the coecients will be easy to evaluate but the calculation will not be so precise. A nice way to balance this is to start dividing the interval of integration, i.e. use the result
b b

dx f (x) =
a a

dx f (x) +

dx f (x).

(B.17)

In our example, we can choose = 1 so that


2 0

ex dx =
0

ex dx +
1

ex dx.

(B.18)

We can then approximate the exponential over each subinterval. Thus, in the interval [0, 1], we can use ex c1 + c1 x + c1 x2 , 0 1 2 and the points x = 0, x = 1/2 and x = 1 to get e0 = c1 , 0 1/2 1 1 e = c1 + 2 c1 + 4 c1 , 1 2 0 e1 = c1 + c1 + c1 , 0 1 2 so that c1 = 1 , 0
1 0

(B.19)

(B.20) (B.21) (B.22)

c1 = 1

1 4e1/2 + 3e , 2e

c1 = 2 2
1 0

1 2e1/2 + e e

, (B.23)

1 ex dx (c1 x + 1 c1 x2 + 3 c1 x3 ) 2 0 2 1

c1 0

1 2

c1 1

1 3

c1 2

= 0.6223.

(B.24)

In the interval [1, 2], we choose x = 1, x = 3/2 and x = 2 so that e1 = c2 + c2 + c2 , 0 1 2 3/2 2 9 3 2 e = c0 + 2 c1 + 4 c2 , 2 e2 = c2 + 2 c2 + 4 c2 , 0 1 2

(B.25)

Simpsons rule and c2 = 0 5 12e1/2 + 7e 3 8e1/2 + 6e , c2 = , 1 e2 2e2 1 2e1/2 + e , c2 = 2 2 e2


2 1

203

(B.26)

2 1

1 ex dx (c2 x + 1 c2 x2 + 3 c2 x3 ) 2 0 2 1

= and thus

c2 0

3 2

c2 1

7 3

c2 2

= 0.2326

(B.27)

2 0

ex dx 0.8649 .

(B.28)

This is illustrated in Fig.26. We see that there is practically no visible dierence between the piecewise approximation by a quadratic and the exact curve. The nal area is close to the true area under the curve ex .
1

Figure 26: The function ex and its linear approximation by c0 + c1 x + c2 x2 over the range [0, 2].

Before we discuss the generalization of this scheme, let us point out some of the features of the previous calculation. First, note that we used the points 3 1 x = 0, 2 , 1, 2 and 2. The point x = 1 was used twice. We will label these points as 3 1 x0 = 0 , x 1 = 2 , x 2 = 1 , x 3 = 2 , x 4 = 2 . (B.29)

5. 1

5. 0

2. 0

8. 0 6. 0 4. 0

Simpsons rule

204

If we dene a segment as a segment of the curve between xn and xn+1 , we see that we used four segments to compute the integral, each segment having the 1 same length xn+1 xn = 2 . You can verify for yourself that, had we written
2 0

ex dx =
0

2/3

ex dx +

4/3 2/3

ex dx +

2 4/3

ex dx ,

(B.30)

we would have used six segments. In fact, it is quite clear that, if we approximate g(x) on each segment by a quadratic, the total number of segments will always be even.

B.2

Simpsons rule

A systematic method to proceed with the numerical integration is as follows. To evaluate Eqn.(B.1), one rst divides the interval [a, b] into an even number n = 2m of equal segments of length h = (b a)/2m. The boundaries of the ith segment will be denoted by xi and xi+1 , i.e. the ith segment runs between [xi , xi+1 ], with x0 = a, x1 = a + h, xn = b and xi+1 xi = h. We start by evaluating the function g(x) at every one of the 2m points, thus obtaining a table of values containing xi and g(xi ). Next, we consider three consecutive values g(xi ), g(xi+1 ), g(xi+2 ) and t through those points the parabola Ax2 + Bx + C, with A, B, C unknowns to be adjusted so that the parabola goes exactly through g(xi ), g(xi+1 ), g(xi+2 ). These are the ci s j of the previous section. In order to nd A, B, C, we therefore need to solve the three equations Ax2 + Bxi + C = g(xi ) i 2 Axi+1 + Bxi+1 + C = g(xi+1 ) Ax2 + Bxi+2 + C = g(xi+2 ) i+2

(B.31)

Suppose now we have found A, B, C. We then have, on the consecutive segments [xi , xi+1 ] and [xi+1 , xi+2 ] as approximation of g(x) as Ax2 + Bx + C. We can then integrate this:
xi+2 xi+2

dx g(x)
xi xi

dx Ax2 + Bx + C ,
xi+2 xi

A 3 B 2 x + x +Cx 3 2

(B.32)

Simpsons rule

205

If we remember that xi+1 = xi + h, xi+2 = xi + 2h, we eventually nd, using the solutions for A, B, C, that
xi+2

dx g(x)
xi

h (g(xi ) + 4g(xi+1 ) + g(xi+2 )) . 3

(B.33)

Eqn.(B.33) is the basis for Simpsons rule. Clearly, we have now


xi+4 xi+2 xi+4

dx g(x)
xi

=
xi

dx g(x) +
xi+2

dx g(x) ,

h (g(xi ) + 4g(xi+1 ) + g(xi+2 ) 3 +g(xi+2 ) + 4g(xi+3 ) + g(xi+4 ))

(B.34)

and so forth, until we nally obtain


b

dx g(x)
a

(b a) [g(x0 ) + g(x2m ) 6m +2 (g(x2 ) + g(x4 ) + . . . + g(x2m2 )) +4 (g(x1 ) + g(x3 ) + g(x5 ) + . . . + g(x2m1 )] B.35) (

Note that the accuracy of this method increases with decreasing h, i.e. with increasing number of intervals n = 2m.

B.3

Application: quantum particle outside a harmonic well

As an example of application, we consider the probability of nding a particle described by the rst excited state of a harmonic oscillator to be outside the classically allowed region. First, we need to nd the classical turning points, i.e. those values of x for which the potential energy is equal to the total energy of a particle; in principle, a particle has no kinetic energy at that point and must therefore turn around its motion. To nd the turning points, we need the energy of a particle described by the wavefunction 1 (x) given in Eq.(6.76): m 3/4 2 2 x emx /2 . 1 (x) = 1/4

Simpsons rule

206

1 The potential for this system is V (x) = 2 m 2 x2 , so 1 (x) is solution of

d2 1 1 (x) + 2 m 2 x2 1 (x) = E1 1 (x) , 2m dx2


2

(B.36)

from which we can infer the energy E1 of the particle. Using d m 3/4 2 mx2 /2 m 2 mx2 /2 1 (x) = e x e , 1/4 dx m 3/4 2 mx2 /2 m 2 e x , = 1 1/4 m m2 2 d2 m m 3/4 2 mx2 /2 1 (x) = e x 2 x+ 2 dx2 1/4 m 3/4 2 3m m2 2 2 2 x emx /2 + x , = 2 1/4 3m m2 2 2 + x 1 (x) , = 2 we rapidly nd

(B.37) x3 ,

(B.38) (B.39)

d2 1 1 (x) + 2 m 2 x2 1 (x) 2m dx2 2 3m m2 2 2 1 + x 1 (x) + 2 m 2 x2 1 (x) , (B.40) = 2 2m 3 m 2 x2 m 2 x2 + 1 (x) , (B.41) = 2 2 2 = 3 1 (x) . (B.42) 2
2

Comparing this with gives E1 =


3 2

d2 1 (x) + 2 m 2 x2 1 (x) = E1 1 (x) 2 1 2m dx


2

(B.43) (B.44)

The turning points are thus located at


1 2

m 2 x2 =

3 2

x =

3 m

(B.45)

Simpsons rule

207

The probability of nd the particle in the classically forbidden region is thus


x 1 (x) 1 (x) dx + x x+ 1 (x) 1 (x) dx

m
x+

+ =2 3
m

2 2 x2 emx / dx 3/2 2 m 2 x2 emx / dx 3/2 2 m 2 x2 emx / dx .


3/2

(B.46) (B.47)

Alternatively, the probability of nding the particle in the forbidden region is just 1(Probability of nding the particle in the classical region), i.e 3 m m 3/2 2 2 mx2 / x e 12 (B.48) dx . 0 Using m m x, dx , = d = (B.49) brings Eq.(B.48) and Eq.(B.47) to the form 4 1
3 0 3
2

d 2 e ,

and

d 2 e .

(B.50)

d 2 e . Choose n = 10 segments so that m = Let us work on 0 2 5, (b a) = 3, h = 3/10 and g() = 2 e . We have the following: n 0 1 2 3 4 5 n 0
3 10 3 5 3 3 10 2 53 3 2

g(n ) 0 0.02911 0.10643 0.20611 0.29702 0.35428

n
3 5 3 7 10 4 53 3 9 10

g(n )

6 7 8 9 10

0.36676 0.33799 0.28149 0.21393 0.149361 (B.51)

Simpsons rule Using Eq.(B.35) gives


3

208

d 2 e

3 (0 + 0.149361 30 +2(0.10643 + 0.29702 + 0.36676 + 0.28149) +4(0.02911 + 0.20611 + 0.35428 + 0.33799 + 0.21393)) , (B.52) = 0.3937 . (B.53)

Thus, the probability is approximately 4 1 0.3937 = 0.112 . (B.54)

Finding zeroes

209

Finding zeroes of an equation

There are many situation where one cannot nd an algebraic solution to the problem at hand. Two examples are the solutions to Eqs.(6.43) and (6.50). Here, we briey review two methods. The rst one is simple bracketing, while the second is known as Newtons method for numerically solving equations.

C.1

Bracketing

Bracketing is easy. Suppose you want to nd the solution to the equation x2 = 2. We rewrite this as y(x) = x2 2 (C.1) and notice that y(1) = 1 but y(2) = 2. Thus (because y(x) is continuous), the correct value lies between x = 1 and x = 2. Split the interval and evaluate for x = 3/2. Then: y(3/2) = 1/4 so the correct value lies between x = 1 and x = 3/2. Split again and evaluate for x = 5/4 to get y(5/4) = 7/16, so the correct value lies between 5/4 and 3/2. Next, try x = 11/8 to get 7/64 and so forth, until the interval is suciently narrow to properly estimate 2.

C.2

Newtons method
f (x + x) = f (x) + x f (x) , (C.2)

Near a point x, a function can always be approximated by a straight line

df . (C.3) dx x Suppose that we have xn so that f (xn ) is approximately (but not exactly) 0. Then, we replace f (x) near xn by a straight line and nd the value xn+1 for which this straight line crosses 0, i.e. set x = xn+1 xn so that f (x) = 0 = f (xn ) + (xn+1 xn )f (xn ) , which immediately gives xn+1 = xn f (xn ) . f (xn ) (C.5) (C.4)

where

If this is done right, then f (xn+1 ) should be closer to 0 than f (xn ).

Finding zeroes

210

We can illustrate the procedure, and the geometrical interpretation of the procedure, by looking for a numerical approximation to 2, i.e. looking for a value of x so that f (x) = x2 2 = 0 . (C.6) df = 2x , dx so that we have the iteration formula xn+1 = xn x2 2 n 1 = 2 xn + 2xn
1 xn

We start with

(C.7)

(C.8)

We use as initial guess x0 = 1. This yields x1 = 3/2. Using now x1 = 3/2, we obtain x2 = 17/12 1.41667 and, in sequence, x3 = 577/408 1.41422 and x4 = 665857/470832 1.41421.
2 2

x2-2

x
1 2 5. 1 1 5. 0

2x-3

Figure 27: Left: The curve x2 2 near x0 = 1. Right: the same curve with its approximation by the straight line 2x 3 near x0 = 1. Note that the straight line crosses the axis at x1 = 3/2; this becomes the new value for the next iteration.

Dierent values of the initial guess x0 aect the rate of convergence. For instance, using x0 = 7/5 (which is justied because x2 = 49/25 is obvi0 ously very close to 2) produces the sequence x0 = 7/5 = 1.2, x1 = 99/70 1.41429, x2 = 19601/13860 1.41421.

5. 1

5. 0

x2-2
1 1 2 -

3 -

2 -

Hypergeometric and conuent solutions

211

Remarks on some second order dierential equations

This section is heavily inuenced by J.B. Seaborn, Hypergeometric Functions and their applications 1991 Springer-Verlag, NY. Regrettably, our library does not have a copy of this excellent text.

D.1

The Gauss hypergeometric 2 F1 (a, b, c; z)


u (z) + P (z)u (z) + Q(z)u(z) = 0 . (D.1)

Any second order dierential equations can be written in the form

The problem consists in nding u as an explicit function of z. When the functions P (z) and Q(z) are rational, it is always possible, usually after many changes of variables, to write Eqn.(D.1) in the standardized form z(1 z)u + [c (a + b + 1)z]u abu = 0 (D.2) where a, b and c are constant. Eqn.(D.2) is known as the Gauss or the hypergeometric dierential equation. To solve, we expand u(z) in series:

u(z) =
n=0

an z n+s ,

(D.3)

where an are expansion coecients (unrelated to the a of Eqn.(D.2)). The lowest power of z in the expansion is taken to be s: there is no a priori reason to suppose s = 0. Inserting Eqn.(D.3) into Eqn.(D.2) we obtain

0 = z(1 z)
n=0

an (n + s)(n + s 1) z n+s2

+[c (a + b + 1)z]
n=0

an (n + s) z

n+s1

ab
n=0

an z n+s . (D.4)

Hypergeometric and conuent solutions Collecting like powers of z yields

212

0 =

an (n + s)(n + s + c 1) z n+s1
n=0

an [(n + s)(n + s + a + b) + ab] z n+s .


n=0

(D.5)

One can isolate the term z s1 and relabel the rst sum so as to obtain 0 = a0 s (s + c 1) z s1

+
n=0

[(n + s + 1)(n + s + c) an+1 (D.6)

[(n + s + a + b)(n + s) + ab] an ] z n+s .

Since this must hold for every z, every coecient of individual powers of z must vanish independently. This produces s (s + c 1) a0 = 0 , (n + s)(n + s + a + b) + a b an+1 = an , (n + s + 1)(n + s + c) (D.7) (D.8)

which is a recursion relation between consecutive coecient in the series. The series is obviously interesting only if a0 = 0, which implies s = 1 c or s = 0. If we set s = 0, we obtain an+1 = so that a1 = a2 a2 an ab a0 , c a (a + 1) b (b + 1) = a0 , 1 2 c(c + 1) a (a + 1) (a + 2) b (b + 1) (b + 2) a0 , = 1 2 3 c(c + 1)(c + 2) a (a + 1) . . . (a + n 1) b (b + 1) . . . (b + n 1) = a0 . n! c (b + 1) . . . (c + n 1) (n + a)(n + b) an , (n + 1)(n + c) (D.9)

(D.10)

(D.11)

Hypergeometric and conuent solutions Let (a)n = a(a + 1)(a + 2)...(a + n 1) = (a + n 1)! , (a 1)! a0 = 1

213

(D.12)

denote the rising factorial. The solution with s = 0 can then be written as

u(z) =
n=0

(a)n (b)n z n , (c)n n!

(D.13) (D.14)

2 F1 (a, b, c; z)

The form 2 F1 indicates that the numerator contains two rising factorials and the denominator only one. If a or b is a negative integer, then 2 F1 is a polynomial. One can show that, if s = 1 c, then u(z) = z 1c 2 F1 (a + 1 c, b + 1 c, 2 c; z), (c = 2, 3, 4 . . .) (D.15)

is also solution. Many functions are expressible as hypergeometric functions. For instance, 1 ln(1 + x) = x
2 F1 (1, 1, 2; x)

/2 0

(1)(2)(1)(2) (x)2 (1)(1) (x) + 2 (2)(3) 2! 3 (2)(3)(2)(3) (x ) ... + (2)(3)(4) 3! x x2 x3 ... = 1 + (D.16) 2 3 4 1 1 1 2 d = (D.17) 2 F1 ( , , 1; k ) 2 sin2 2 2 2 1k = 1+

The hypergeometric function 2 F1 is convenient to denote solutions of differential equations. For instance, the solution to Legendre equation (1 x2 )u 2xu + n(n + 1)u = 0 (D.18)

can be transformed into the standard form of Eqn.(D.2) using z = (1 x)/2, or x = 1 2z : (1 x2 ) = (1 x)(1 + x) = 2z(2 2z) = 4z(1 z) d dz 1 d d = = dx dz dx 2 dz (D.19) (D.20)

Hypergeometric and conuent solutions so that Eqn.(D.18), written in terms of z, becomes 4z(1 z)

214

1 d 1 d2 u(z) 2(1 2z)( ) u(z) + n(n + 1)u(z) = 0 , 2 4 dz 2 dz d2 d z(1 z) 2 u + (1 2z) u + n(n + 1)u = 0 . (D.21) dz dz

The solution is then instantaneous. Comparing with the standard form of Eqn.(D.2), we have immediately a = n, b = (n + 1) and c (a + b + 1)z = c (n + n + 1 + 1)z = c 2z = 1 2z c = 1 . Thus, the solution to Eqn.(D.21) is simply z(1 z) d d2 u + (1 2z) u + n(n + 1)u = 0 u(z) = 2 F1 (n, n + 1, 1; z) . 2 dz dz (D.22) In terms of the original variable x: u(x) = 2 F1 (n, n + 1, 1; 1x ). 2 (D.23)

D.2

The conuent hypergeometric function 1 F1 (a, c; z)


zu (z) + (c z)u (z) au(z) = 0 (D.24)

Another family of dierential equations is of the type

with solution u(z) = 1 F1 (a, c; z) where


1 F1 (a, c; z)

=1+

a(a + 1) z 2 a(a + 1)(a + 2) z 3 az + + + ... c 1! c(c + 1) 2! c(c + 1)(c + 2) 3!

(D.25)

The second solution is u(z) = z 1c 1 F1 (a + 1 c, 2 c; z). (Note that one can show 1 F1 (a, c; z) = ez 1 F1 (c a, c; z)) An alternate form of Eqn.(G.44) is obtained if we make the change z = 2 . Then d d 1 d 1 d d = = = , dz d dz 2 d 2 z d 1 d 1 d 1 1 d 1 d2 d2 = = 2 + dz 2 2 d 2 d 4 d d2 (D.26) . (D.27)

Hypergeometric and conuent solutions so that Eqn.(G.44) becomes 2 1 d 1 d2 u(2 ) 2 u(3 ) 4 d2 4 d 1 d u(2 ) 4au(2 ) = 0 +(c 2 ) 2 d d 2c 1 d2 u(2 ) + 2 u(2 ) 4au(2 ) = 0 . d2 d

215

(D.28)

As an example, consider Hermites dierential equation: Hn 2xHn + 2ny = 0 . It has the solution 1 2 (2n)! 1 F1 (n, ; x ) n! 2 3 (2n + 1)! 2x 1 F1 (n, ; x2 ) H2n+1 (x) = (1)n n! 2 Another useful example is Bessels dierential equation: H2n (x) = (1)n x2 J (x) + xJ (x) + (x2 2 )J = 0 , with solution 1 eix x (D.32) 1 F1 ( + , 2 + 1; 2ix) . ! 2 2 Two other examples are worth mentioning. The solutions to Laguerres dierential equation J (x) = xy (x) + (1 x)y (x) + ny(x) = 0 , can be expressed as Ln (x) = 1 F1 (n, 1; x) . Closely related are associated Laguerre functions Lm (x) = n which are solutions to xy (x) + (m + 1 x)y(x) + ny(x) = 0 . (D.36) (n + m)! 1 F1 (n, m + 1; x) n!m! (D.35) (D.34) (D.33) (D.29) (D.30)

(D.31)

Hermite polynomials

216

E
E.1

Hermite polynomials
Series solution

We need to solve H () 2H () + 2nH() = 0 Write H() in the form of a power series

(E.1)

H() = a0 + a1 + a2 2 + a3 3 + . . . =
r=0

ar r

(E.2)

and place Eqn.(E.2) into Eqn.(E.1) to get: H 2 H = a1 + 2a2 + 3a3 2 + 4a4 3 + . . .

(E.3) r ar r ,
r=0 3

= 2 a1 + 2a2 2 + 3a3 3 + . . . = 2
2

(E.4) (E.5) (E.6)

H () = 2a2 + 2 3a3 + 3 4a4 + 4 5 + . . . ,

=
r=0

r(r 1) ar r2 ,

The rst nonzero term of this last sum is for r = 2, so we can shift the summation index and rewrite it as

H ()) =
r=0

(r + 1)(r + 2)ar+2 r .

(E.7)

Collecting terms, Eq.(E.1) now becomes


0 =
r=0

(r + 2)(r + 1)ar+2 2
r=0

r ar + 2n
r=0

ar r ,

(E.8) (E.9)

=
r=0

[(r + 1)(r + 2)ar+2 + 2(n r)ar ] r .

Since this must hold for every value of , the coecient of each power of must be 0 : i.e. (r + 1)(r + 2)ar+2 + 2ar (n r) = 0 ar+2 = 2ar (r n) (r + 1)(r + 2) (E.10) (E.11)

Hermite polynomials

217

Let us now look at the behavior of the recursion relation of Eq.(E.11). For very large r, we have ar+2 At this point we recall that e2
2

2ar 2ar r = . 2 r r

(E.12)

1 1 = 1 + (2 2 ) + 2 (2 2 )2 + 3! (2 2 )3 + . . . ,

(E.13) (E.14)

=
n=0

2n 2n = n!

c2n 2n ,
n=0

where c2n = and note that we have c2n+2 =

2n , n!

(E.15)

2 2n+1 n! c = c2n . n 2n (n + 1)! 2 n

(E.16)

Comparing Eqs.(E.16) and (E.12), we see that the series solution of Eq.(E.2) will eventually grow like 2 y() e2 , (E.17) unless the series is truncated. To produce a polynomial and thus avoid the behavior of Eq.(E.17), we must select some integer r = n so that all values an+2 , an+4 , . . . obtained via Eq.(E.11) are 0. Thus, choosing for instance n = 0 yields the sequence r=0: r=2: 2a0 (0 0) = 0, 12 2(2 0) 2a2 (2 0) = 0, a4 = 34 34 a2 = (E.18) (E.19)

since a2 = 0. It is clear that all subsequent choices of even values of r will yield ar = 0. We do not have any conditions on the odd values of r because of the form of the recursion relation. However, one trivial solution is to set a1 = 0 so that all ar s are 0. Thus, for this choice of n and with a1 = 0, a0 is the only nonzero coecient. Thus, our rst polynomial solution to Eq.(E.1) is H0 () = a0 . (E.20)

Hermite polynomials

218

Next, choose n = 1. Here, we see that we will not have any condition of the even rs, so we will choose the trivial solution a0 = 0 so that a2n = 0. Thus, we have 2a1 (1 1) = 0, r=1: a3 = (E.21) 23 2a3 (3 1) =0 (E.22) a5 = r=3: 45 since a3 = 0. Hence, the series stops at n = 1 and yields H1 () = a1 . (E.23) Choosing now n = 2 yields the sequence 2a0 (0 2) = 2a0 , (E.24) r=0: a2 = 12 2a2 (2 2) = 0, r=2: a4 = (E.25) 34 2a4 (4 2) = 0, (E.26) a6 = r=4: 56 since now a4 = 0. For this choice of n and with a1 = 0, this polynomial is H2 () = a0 2a0 2 = a0 (1 2 2 ) . The process is easily summarized: r=n 0 ai a2 = a4 = 1 a3 = a5 = 2 a2 = a4 = 3 a3 = a5 = 4 a2 = a4 =
2a0 (00) =0 12 2a2 (20) = 0... 34 2a1 (11) 23 2a3 (31) 45

(E.27)

Hn ()

H0 () = a0

=0 = 0... H1 () = a1 H2 () = a0 (1 2 2 )
2 H3 () = a1 3 3

2a0 (02) = 2a0 12 2a0 (22) = 0... 34 2a1 (13) 23 2a1 (33) 45 2a0 (04) 12 2a2 (24) 34 2 = 3 a1

= 0... = 4a0
1 4 = 3 a2 = 3 a0

4 H4 () = a0 1 4 2 + 3 4

Hermite polynomials

219

The values of a0 , a1 for each polynomial Hn () is determined historically by choosing the coecient of n in Hn () to be +2n . This in turn leads to

2 2 de Hn () = 2n n!

(E.28)

E.2

Generating function

Alternatively, the set of all Hermite polynomials can be obtained from the generating function

(x, h) = e

2xhh2

=
n=0

Hn (x)

hn . n!

(E.29)

Thus, expanding the generating function in powers of h: 1 1 (x, h) = 1 + (2xh h2 ) + (2xh h2 )2 + (2xh h2 )3 + ... 2 3! 1 = 1 + 2xh h2 + (4x2 h2 4xh3 + h4 ) 2 1 + (8x3 h3 3 4x2 h2 h2 + 3 2xhh4h ) + ... 3! h3 = 1 + h2x + h2 (2x 1) + (8x3 + 12x) + ... 3! 1 2 1 (E.30) = H0 (x) + hH1 (x) + h H2 (x) + h3 H3 (x)... 2 3! and so, for instance, H0 (x) = 1 , H1 (x) = 2x , H2 (x) = 4x2 2 , H3 (x) = 8x3 12x (E.31)

E.3

Rodrigues formula and orthogonality

The Hermite polynomials can also be obtained by the socalled Rodrigues formula: n 2 2 d (E.32) Hn () = (1)n e+ n e . d Thus, we have n=0: n=1: H0 () = 1 , H1 () = (1)e
2

(E.33) d d e = e (2)e = 2 , (E.34)


2 2 2

Hermite polynomials etc. Consider now, for any function y(), e


2

220

d 2 e y () d

= e

2e y + e y

(E.35) (E.36)

= y 2 y ,

where y () dy()/d. Substituting Hn () for y(), we can write Eq.(E.1) in the form 2 2 d e Hn () + 2n Hn () = 0 , e (E.37) d 2 2 d e Hm () + 2m Hm () = 0 . e (E.38) d Multiplying the rst by Hm () and the second by Hn () yields d 2 e Hn () + 2n Hm () Hn () = 0 , d 2 2 d e Hm () + 2m Hn () Hm () = 0 . Hn () e d Hm () e
2

(E.39) (E.40)

Subtracting produces e
2

Hm ()

d d 2 2 e Hn () Hn () e Hm () d d +2(n m)Hn () Hm () = 0 ,
2

(E.41)

which can be rearranged, after premultipliation by e , into d 2 e (Hm () Hn () Hm ()Hn ()) d 2 +2(n m)Hn () Hm () e = 0 . Integrating from to + yields

(E.42)

dx

d 2 e (Hm () Hn () Hm ()Hn ()) d

+2(n m)

dx Hn () Hm () e = 0 , (E.43)

2

(Hm () Hn () Hm ()Hn ())

+2(n m)

dx Hn () Hm () e = 0 . (E.44)

Hermite polynomials Using e (Hm () Hn () Hm ()Hn ()) we nally obtain

221

= 0,

(E.45)

2(n m)

dx Hn () Hm () e = 0 .

(E.46)

Eq.(E.46) shows that two dierent Hermite polynomials are orthogonal 2 w/r to the weight function e . In particular, it follows from Eq.(6.73) that any two solutions of the timeindependent Schrdinger equation for the o harmonic oscillator are orthogonal.

Eigenvectors

222

Eigenvectors: On the importance of being proper

In quantum mechanics, things live in a Hilbert space. This is an abstract space, populated by vectors which, in examples that weve seen so far, are functions solutions of the Schrodinger equation. From the Schrdinger equation, we have not only concluded that function o space is relevant, but also that a rather important object is a linear operator H, which, in one dimension, reads H= 2 + V (x). 2m x2
2

(F.1)

There are more general linear operators: we have studied their abstract properties in the previous two sections, focusing in particular on hermitian operators. We want to capitalize on these properties. Up to now, our strategy to solve the (timedependent) Schrdinger equao tion has been to attack the equation Schrdinger, i.e. solve (using kets to o make this as general as possible) i |(t) = H |(t) t (F.2)

by solving the dierential equation. A special subset of solutions are particularly useful: the separable solutions: if |E satises H |E = E |E , (F.3) then |E (t) = eiEt/ |E , (F.4)

In some specic cases, it is possible to solve directly this dierential equation (using either the x or prepresentation.) However, in most cases, it is not possible. Indeed, for more general systems, in more than one dimension or for more than one particle, solving Eqn.(F.3) directly is practically impossible. In conclusion, we need a change in the mechanics of solving Eqn.(F.3) so that this equation can be solved quite generally. We have seen that, under broad assumptions, p and x are hermitian operators, and so is H. Thus, instead of solving Eqn.(F.3) as a dierential

Eigenvectors

223

equation, we will try to solve it as a matrix equation. The dierence between the two approaches is this: in the dierential approach, we try to solve for |E directly in a single step. In the matrix approach, we start by choosing some basis states to obtain the matrix realization of H. If we are lucky in the choice of our basis states, then H will be diagonal; the basis states are then the solutions |E themselves. In general, the choice of basis states is based on experience and educated guesses; H will not be a diagonal matrix. The solutions to Eqn.(F.3) are then expressed as a linear combination of the basis states, and these specic linear combination will have an easy timeevolution. The matrix approach is more versatile because we have complete freedom in choosing the basis states. Of course, a bad choice of basis means that we will have to do a lot of work to solve Eqn.(F.3), but we can still obtain a solution. This is better that directly solving the dierential equation for |E which, as mentioned before, sometimes cant be done. It is important to realize that, in both cases, we are aiming to nd |E , because, if we know |E , we instantly know the time evolution of |E (t) through Eqn.(F.4). Besides their mathematical practicality in computing the timeevolution of the state, |E is also physically important because that E | H 2 H 2 |E = 0, the uctuation in energy for this state, E = i.e. |E has a welldened energy. This is true quite generally, if | satises T | = | , then T = 0, so states with the property T | = | are obviously of great physical importance. To solve T | = | in general, and to solve H |E = E |E in particular, one must solve the associated eigenvalue problem. This is done by an algorithm presented in the next section.

F.1

General eigenvalue problem

Suppose that you are given some n n matrix M . Then, its eigenvalues are, by denition, the roots of the characteristic equation det (M 1 n ) = 0 , l (F.5)

where 1 n is the n n unit matrix. This is a denition. Theres nothing to l understand about it; its just something that one needs to remember.

Eigenvectors Example F.1 The eigenvalues of the matrix K= 2 1 1 2

224

(F.6)

are obtained by solving the characteristic equation det 2 1 1 2 1 0 0 1 = det 2 1 1 2 = 2 +4+3 = 0 .

The solutions are 1 = 3 and 2 = 1. These are the eigenvalues of the matrix. Example F.2 The eigenvalues of 1 1 2 the matrix 27 15 2 3 3 2

are obtained by solving the characteristic equation 1 0 0 1 27 15 det 1 2 3 0 1 0 0 0 1 2 3 2 1 27 15 2 3 = 3 + 2 + 16 16 = 0 . = det 1 2 3 2 It is possible, in principle, to obtain the roots algebraically. A more expedient but approximate method is to plot the polynomial and locate the zeroes graphically. If more accuracy is required, then one can simply use the intersection method, using our approximate location as initial guesses. (The drawback is that this makes it dicult to locate multiple occurences of a given root.) In any event, the solutions for the case at hand are 1 = 4, 2 = 1 and 3 = 4. The eigenvector | associated with an eigenvalue is just this vector | that satises the equation M | = | (F.7) To nd | , one must know . Plugging into Eq.(F.7), one obtains a linear system of n equations with n unknowns. In this system, only n 1

Eigenvectors

225

equations will be linearly independent, which means that it is possible to nd n 1 components of | in terms of the last one. To completely determine the problem, we will always require that | = 1. The unknown phase of the last entry will always be taken as 1. Example F.3 The eigenvectors of the matrix 2 1 1 2 (F.8)

are found as follows. Choose the rst eigenvalue 1 = 1 and let | denote the corresponding eigenvector. Assume a general form for | : | = and consider 1 2 = 1 1 2 , (F.9)

2 1 1 2

1 2

(F.10)

from which we obtain the system of equations 21 + 2 = 1 1 + 2 = 0 , 1 22 = 2 1 2 = 0 . (F.11) (F.12)

Obviously, these equations are not linearly independent. There is a single linearly independent equation for two variables, so we choose to solve 2 in terms of 1 : the immediately gives 2 = 1 and thence | = 1 1 1 (F.13)

After normalization: | = 1, we nally obtain the normalized eigenvector 1 | = 2 1 1 . (F.14)

The (normalized) eigenvector , corresponding to the eigenvalue = 3, is easily shown to be, following the same procedure, 1 | = 2 1 1 . (F.15)

Eigenvectors

226

Example F.4 The eigenvectors 1 1 2

of the matrix 27 15 2 3 . 3 2

are obtained as follows. The rst eigenvector, (lets call it |1 ) is associated with the eigenvalue 1 = 4 and is solution to 1 27 15 11 11 1 2 3 12 = 4 12 . (F.16) 2 3 2 13 13 This gives the linear system 311 2712 1513 = 0 11 612 313 = 0 211 312 213 = 0 (F.17)

with solution 11 = 13 /5 , 12 = 813 /15. From the condition 1 |1 = 1, we obtain


13 13

64 1 + +1 25 225

= 13 13

298 225

15 = 1 13 = 298

(F.18)

from which it follows that the normalized |1 is simply 1/5 15 8/15 . |1 = 298 1

(F.19)

For the second eigenvector, |2 , associated to 2 = 1, we have the system 21 221 2722 1523 = 0 322 323 = 0 , 322 +23 = 0 (F.20)

with solution 21 = 423 /3 , 22 = 523 /9. From the normalization condition 2 |2 = 1, we obtain
1623 23 2523 23 + + 23 23 , 9 81

(F.21)

Eigenvectors from which it follows that 250 9 23 23 = 1, or 23 = . Thus, 81 5 10 4/3 9 |2 = 5/9 . 5 10 1

227

(F.22)

Finally, the last eigenvector, |3 is associated with the eigenvalue 3 = 4. |3 is given by 3 1 0 . (F.23) |3 = 10 1 The universal recipe for nding the eigenvalues and eigenvectors of a matrix M is thus: 1. Find the solution to the characteristic equation Det(M 1 = 0. This l) will give you all the eigenvalues. 2. For each eigenvalue, nd the corresponding eigenvector by solving M |i = i |i . 3. Do not forget to normalize your eigenvectors such that i |i = 1.

F.2

Diagonalizable matrices

An n n matrix M is called diagonalizable if and only if there is a set of n linearly independent vectors, each of which is nonnull and is an eigenvector of M . If M is diagonalizable, then it can be written in the form M = U D U 1 , (F.24)

where D is a diagonal matrix containing as entries the eigenvalues of M . Thus, if {1 , . . . , n } are the eigenvalues of M , then, if M is diagonalizable, we can write 1 1 ... (F.25) M =U U n

Eigenvectors

228

Furthermore, the rst column of the matrix U 1 is the eigenvector associated with 1 , the second column is the eigenvector associated with 2 , etc. Please note that, technically, a multiple of the ith eigenvector can appear in column i, i.e. it is not strictly necessary for the eigenvectors to be normalized to obtain U 1 . Once U 1 is found, then its inverse U can be obtained in the usual way. Example F.5 The matrix K of Eqn.(F.6) is diagonalizable. The matrix U 1 is obtained from the eigenvectors of K, and it is easy to nd that 1 U 1 = 2 1 1 1 1 1 U= 2 1 1 1 1 . (F.26)

(The matrices U and U 1 turn out to be the same in this case; this is not true in general.) It is then easy to verify that 2 1 1 2 1 = 2 1 1 1 1 1 0 0 3 1 2 1 1 1 1 . (F.27)

Example F.6 The matrix + =

0 1 is not diagonalizable. Both of its 0 0 eigenvalues are 0. The rst (unnormalized) eigenvector is (1, 0)t , while the second is the null vector (0, 0)t

F.3
F.3.1

Tricks of the trade


Powers of a matrix

What can one do with diagonalizable matrices. Well, rst observe that, if M = U D U 1 , then M 2 = U D U 1 U D U 1 = U D2 U 1 M p+1 = M p M , = U D U 1 U D U 1 = U Dp+1 U 1 ,

(F.28)

It is easy to compute powers of D since it is just a diagonal matrix: p+1 1 .. (F.29) Dp+1 = . . p+1 n

Eigenvectors

229

This is a very numerically ecient way of computing powers of M since one must calculate the matrices D, U and U 1 only once. It is not only faster but also more accurate than multiplying the matrix M many times by itself. Suppose now that M is a diagonalizable matrix such that, for some integer p > 0, we have M p = 1 Since we can write l. M = U D U 1 , with D the diagonal matrix containing the eigenvalues, we nd M p = 1 = U Dp U 1 . l (F.31) (F.30)

Multiplying this equality from the left by U 1 and from the right by U , we have p 1 ... U 1 U 1 = 1 = Dp = l l (F.32) p n Thus, p = 1 i, i.e. the pth power of every eigenvalue is 1. In other words, i all the eigenvalues are to be found in the set of pth root of unity. Example F.7 Consider the matrix 0 i 0 Q = i 0 0 . 0 0 1

(F.33)

It is easy to verify the Q2 = 1 and that the eigenvalues of Q are {1, 1, 1}. l,

F.3.2

The determinant and trace conditions

We can also make the following statements, valid for any n n matrix. The trace of a matrix is the sum of its diagonal elements. Thus, the trace of a matrix S is given by tr(S) = s11 + s22 + . . . + snn . One can show that the trace of S is equal to the sum of the eigenvalues. For instance, the trace of the matrix Q of the previous example is tr(Q) = 0 + 0 1 = 1 is indeed equal to the sum of the three eigenvalues. The determinant of a matrix S is computed in the usual way, and is equal to the product of the eigenvalues: det(S) = 1 2 . . . n . It is also easy to verify this property with the matrix Q of previous example or, for that matter, for all the matrices of all the examples presented thus far.

Problems

230

Collected Problems 2001-2006


6(1 + i) 2(1 i).

1. Let z =

a) What is the real part of z? b) What is the imaginary part of z? c) What is z ? d) Express z in polar form. e) Compute z 3 using the Cartesian and the polar representations of z. f) Find all the complex numbers solutions to z 1/5 . g) Find all the complex numbers solutions to z 3/5 by - using z 3 and nding these numbers solutions to (z 3 )1/5 , - using the solutions to z 1/5 and raising them to the third power. - Are both calculations identical? 2. Let 3 9 3 14 3 1 M = 9 15 3 14 8 14 3 14 12

(G.1)

a) What is the determinant of M ? b) What is the characteristic polynomial of this matrix? c) Find the eigenvalues of M - by making a plot of the characteristic polynomial, - identifying one or all of the roots of the characteristic equation. If you identify one root, you may factor it out of the cubic equation and solve the resulting quadratic. d) Verify the trace condition on the eigenvalues, e) Verify the determinant condition on the eigenvalues.

Problems

231

3. (15 points) Using our denition of the uctuation of a physical quantity, show that the uctuation O of the physical quantity O associated with the operator O can be written as (O O )2 . O = (G.2) 4. (10 points) Consider the wave function (x, t) = Aeipx/ + Beipx/ eip
2 t/2m

(G.3)

Find the probability current corresponding to this wave function. 5. (25 points) (Easy) Let m () = | m = eim . Let d 1 O = 2 ei 1 + i d
1 + 2 ei 1 i

d d

(G.4)

and dene the inner product of two functions () and () by | = 1 2


2 0

d () () .

(G.5)

1. Given the above denition of the inner product, show that the states |1 , |0 and |1 are normalized and pairwise orthogonal, 2. Construct a 3 3 matrix O with matrix elements Oij given by i |O|j for i, j = 1, 0, 1. Is the matrix O hermitian? 3. What are the eigenvalues of O? Is it true that the sum of eigenvalues of O equals the trace of O? Is it true that the determinant of O equals the product of the eigenvalues of O? 4. What are the eigenvectors of O? Are they orthogonal? 6. (25 points) (Moderately dicult) Getting familiar with commutators The commutator of two matrices A and B is dened by [ A, B ] AB BA. The commutator of two operators A and B is dened as follows. Let | be any vector. Then [ A, B ]| AB B A | . (G.6) i) Show that, for three operators A, B and C, [ A, B C ] = [ A, B ]C + B[ A, C ] . (This is know as the derivative property.)

Problems
ii) What is [ x, p ]?

232

d O = iii) Show that, if | is a solution to Schrdingers equation, then o dt i [ H, O ]. A consequence of this is that, if an operator O commutes with the Hamiltonian, the corresponding physical quantity is conserved in time (i.e. it is a constant of motion). iv) Show that, if X and O are operators, then 1 1 eX OeX = O + [ X, O ] + [ X, [ X, O ] ] + [ X, [ X, [ X, O ] ] ] + . . . (G.7) 2! 3! (Hint: use the denition eX = 1 + X + l

1 2 (X) + . . .) 2!

7. (30 points) (Easy) Application of the square well. Let us suppose that the potential felt by a neutron in the nucleus can be approximated an innite square well of the type V (x) = with L = 1012 meters. 1. What is the minimal kinetic energy of a neutron in this well? 2. Assuming that the potential of Eqn(G.8) is also applicable to an electron in a nucleus: i) What is the minimal kinetic energy of an electron in this well? ii) What is the potential energy of an electron located at a distance L = 1012 m (i.e. just outside the well) if the nucleus has an electric charge of 50e? iii) Is the potential energy calculated in ii) enough to bind an electron having the kinetic energy calculated in i)? 3. Verify that Heisenbergs uncertainly relation x p stationary states of this well.
1 2

if 0 x < L , if x L .

(G.8)

holds for the

8. (30 points) (Fairly dicult) Bound states of Schrdingers equation o

Problems
Let us dene a potential V (x) by + 0 V (x) = V0

233

if x < 0 , if 0 x < L , if x L .

(G.9)

Find the bound states of the Schrdinger equation using brute force (something o which, admittedly, one should only do as a last result): 1. The wave function that is solution to Schrdingers equation for this poteno tial must have amplitude 0 x < 0. Why? 2. The solution must have the form A sin(kx + ) in the region 0 x < L. Why? What must be the value of if the wave function is to have no amplitude at x = 0? 3. The wave function must have the form Ce(xL) for x L. Why? 4. Show that, at x = L, the coecients k and are related by z = n arctan z , 1z (G.10) 2mV0 L/ .

where n is an integer (positive or negative), z = E/V and =

5.) How many bound states will this potential accomodate if = 9? What are the energies of these bound states? 6.) What must be (approximately) the value of V0 for this potential to bind a neutron having a lowest energy of 8 MeV if L = 1012 m? (Note: 1 Mev= 1.602 1013 Joule) 9. (15 points) Consider the following potential if x < L/2 , U (x) if L/2 < x < L/2 , V (x) = if x > L/2 . This potential is illustrated in gure 29 Find the bound states for this potential. 1) For x < 0, write (x) = A cos(kx) + B sin(kx), while, for x > 0, write (x) = C cos(kx) + D sin(kx).

(G.11)

Problems
V

234

x=L /2

x=0

x=L /2

Figure 28: The potential of Eqn.(G.21). 2) Show that the boundary conditions imply: A=C, B = D = mU A
2

(G.12)

3) Show that the energies are given by the solutions to tan mU kL = 2 . 2 (G.13)

10. (20 points) (Looks harder than it is). Double well. + Consider a (very crude) model of a singly ionized hydrogen molecule H2 , where the sole electron sees the sum of the attractive Coulomb potentials of the two separated protons. Our model for the potential is a sum of two functions:
1 1 V (x) = U (x + 2 L) U (x 2 L) ,

(G.14)

such that me U 2 /2 2 = 13.6eV, i.e. U = 0.53 27.2 eV so that the binding A energy of this electron is the same as if there was a single (more complicated) potential well rather than two discrete wells. Show that this potential accomodates two bound states (one even and one odd) with energies given by 2 ), (G.15) eL = (1 with E = 2 2 /2m and = 2me U/ 2 , and nd these energies for the electron with the values of U given above and L = 2 /me U . 11. (20 points) (Straightforward but somewhat tedious) Separation of variables

Problems

235

1. Consider the Hamiltonian for a one-dimensional system of two particles of masses m1 and m2 , each subjected to their own potential V1 (x1 ) and V2 (x2 ) without interacting with one another: H = H1 + H2 , p2 p2 1 + V1 (x1 ) + 2 + V2 (x2 ) . = 2m1 2m2

(G.16)

Assuming that the wave function (t, x1 , x2 ) for the system can be factorized: (t, x1 , x2 ) = (t)(x1 )(x2 ) , (G.17) and that (t, x1 , x2 ) satises the Schrdinger equation: Show that (x1 ) o and (x2 ) respectively satisfy H1 (x1 ) = E1 ( x1 ) , H2 (x2 ) = E2 (x2 ) (G.18)

and that (t) = eiEt/ with E = E1 + E2 . 2. Suppose now that the particles are subjected to a potential which only depends on their relative position x1 x2 : H= p2 p2 1 + 2 + V (x1 x2 ) . 2m1 2m2 (G.19)

i) Write the Schrdinger equation using the new variables x and X, where o x = x1 x2 relative distance m1 x1 + m2 x2 center of mass . X = m1 + m2

(G.20)

ii) Using separation of variables, show that the time dependence is given by eiEt/ . iii) Using separation of variables, nd the equation of motions (i.e. the Schrdinger equation) for the relative and center of mass coordinates. o iv) Show that wave function describing the center of mass coordinates is that of a free particle with mass m1 + m2 with energy Ecm , v) Show that the wave function describing the relative motion of the partim1 + m2 with energy E Ecm . cles is that of a particle of reduced mass m1 m2

Problems

236

12. (Requires a good deal of thoughts) A qualitative picture of what is required for bound states. Consider the following potential if 0 < |x| < L , 0 V0 if L < |x| < L + , V (x) = (G.21) 0 if |x| > L + . This potential is illustrated in gure 29
V

x=L /2

x=0

x=L /2

Figure 29: The potential of Eqn.(G.21). Using your knowledge of the solution for the potential barrier of nite width, show that this potential cannot have stationary states: 1) (5 points) The wave functions (x) for this potential must satisfy either (0) = 0 or else d(0)/dx = 0. Why? 2) Show that there are no solutions to the above two equations, which means that this potential cannot accomodate stationary states. Explain why this is so by comparing the potential with the case where or with the potential of gure 30. Why could this second potential accomodate stationary states? This potential is illustrated in gure 29 13. A particle of mass m is trapped in a harmonic potential such that = k/m. At t = 0, the wave function describing this particle is given by (x, 0) = 1 n (x) , where the sum n goes from N s to N + s with N s 1. 2s n

Problems

237

Vo

Vo

x=L

x=0

x=L

Figure 30: The alternate to the potential of Eqn.(G.21). 1. (5 points) What is the form of the wave function (x, t) at any time t? 2. (15 points) Show that < x > (t) varies (co)sinusoidally in time with amplitude 2 N/m, and compare the frequency of oscillation with the classical result. 14. (30 points) Compute the following matrix elements for the onedimensional harmonic oscillator: n|x2 |m , n|p2 |m , and n|x3 |m . Hint: there are exactly 10 nonzero matrix elements. 15. The simplest molecules of noble gasses, such as Ne, arise from interactions between the two atoms that can be modeled by the LennardJones potential: V (x1 x2 ) = 4Vo x1 x2
12

x1 x2

(G.22)

where and Vo are constants determined for each noble gas ( = 2.7410 m , Vo = 0.0031eV for Ne). 1. (5 points) Use the relative and center of mass coordinate to separate the problem into center of mass and relative coordinates and write down the Schrdinger equation for the relative coordinate. o 2. (5 points) Find the minimum xo of the potential, and evaluate what is this minimum value known as the equilibrium point.

Problems

238

3. (10 points) Expand the potential V around the equilibrium point xo to show that V can be approximately written
1 V (x) = Vmin + 2 k(x xo )2 + (x xo )3 + O[(x xo )4 ] .

(G.23)

Estimate numerically k and using the values of Vo and for Ne. should be signicantly smaller than k. 4. (5 points) Ignoring the cubic term on the ground that it is small, estimate what is the ground state energy of the molecule, assuming that the center ofmass energy is known. 5. (10 points) Using 0 (xxo ) and 1 (xxo ) as basis states and the harmonic oscillator matrix elements from the previous problem, construct the 2 2 matrix for the operator H describing the relative motion of the molecules, 1 using as potential V (x) = Vmin + 2 k(x xo )2 + (x xo )3 . 6. (10 points) Diagonalize this 2 2 matrix and nd the (improved) ground state energy of the molecule (again assuming that the centerofmass energy is known). 16. (A problem that will require numerical integration). The classical turning points for the motion of a particle in one dimension are those values x of x between which a particle is constrained to move by the law of classical mechanics. For a particle in a onedimensional harmonic well, 1. (5 points) Find the classical turning points as a function of the energy En of the nth eigenstates of the harmonic oscillator Hamiltonian. 2. (15 points) Compute the probability of nding the particle in the classically forbidden region, i.e. in the region where x > x+ and where x < x , for the n = 0, 1 and 2 states. 3. (10 points) From the previous result, and using common sense, guess the probability of nding the particle in the classically forbidden region if n . Explain briey your answer. 17. Let us dene, in the usual way, the operators a, a , b and b so that [a, a ] = 1 , l [a, b] = [a , b] = [a, b ] = [a , b ] = 0 , [b, b ] = 1 l (G.24)

Let |na , nb be the common eigenstates of a a and b b.

Problems

239

1. (10 points) Show that the three operators a b, ab , a a b b satisfy the same commutation relations as the operators L+ , L , Lz . 2. (10 points) Compute the operator L L in terms of a, a , b and b . 3. (5 points) Show that |na , nb is an eigenstate of L L (expressed in terms of a , a, b and b). What is the corresponding eigenvalue? 4. (5 points) What is the correspondence between |na , nb and |lm ? (i.e. express j and m in terms of na and nb .) 5. (5 points) Using the previous result, show that lm |L+ |lm = na + 1, nb b|n , n , and that lm |L |lm = n 1, n + 1|ab |n , n . 1|a a b a a b b 18. (20 points) Compute the matrix elements l m |Lx |lm and l m |Ly |lm 1. By expressing Lx and Ly in terms of L+ and L , 2. By expressing Lx and Ly in spherical coordinates and using properties of m (, ). Yl 19. (25 points) Show explicitly that the l = 2 spherical harmonics are given by Y22 (, ) Y21 (, ) Y20 (, ) = 20. (20 points) Let nlm (, , ) = Rn ()Ylm (, ) = , , | nlm , with Rnl () some function of the radial coordinates. 1. Write the matrix element n ,l=2,m=0 |x2 |n,l=0,m=0 as an integral over the radial coordinate multiplied by an integral over the angular coordinates. 2. Evaluate the radial part of this matrix element (i.e. the integral that contains Ylm (, )s.) = =
15 1 32 r 2 (x

iy)2 iy)

= =

15 1 8 r 2 z(x 2 5 1 16 r 2 (2z

x2 y 2 ) =

15 sin2 e2i , 32 15 cos sin ei , 8 5 (3 cos2 1) . 16

(G.25)

Problems

240

21. Consider a particle in a central potential. Given that |lm is an eigenstate of L L and Lz : 1. (20 points) Compute the sum (Lx )2 + (Ly )2 , 2. (5 points) For which values of l and m does the above sum vanish? 22. (30 points) Using the normalized eigenfuctions of the hydrogen atom in the n = 1 states, 1. For all the allowed values of l and m, obtain the probability densities Pnl (r) = 4r2 |Rnl (r)|2 , where Rnl (r) is the radial part of the wave function. 2. Compute r radius,
nl

in all cases, and express your answer in terms of the Bohr

3. Find the maximum of Pnl (r) for each allowed value of l and m. Express your answer in terms of the Bohr radius. 23. (15 points) Let Q0 = (22 y 2 x2 ). Express this operator in terms of a radial z part multiplied by a spherical harmonics. Compute the following matrix elements using the states |nlm of the spherical threedimensional harmonic oscillator: 1. 220|Q0 |000 , 2. 420|Q0 |220 , 3. 440|Q0 |220 .

24. The Kratzer molecular potential (total: 65 points). This is a nice exam problem: it combines many To investigate the rotationvibration spectrum of a diatomic molecule, Kratzer has used the potential a2 a 2 . V (r) = 2D r 2r The solution to the Schrdinger equation can be factorized into o 1 (r, , ) = (r)Ylm (, ) r 1. (5 points) Using the dimensionless abbreviations = r , a 2 = 2 ma2
2

(G.26)

E,

2 = 2

ma2
2

D,

(G.27)

with > 0 and real > 0, show that the radial equation for (r) takes the form d2 () 2 2 + l(l + 1) + 2 + 2 () . (G.28) d 2 2

Problems
2. (5 points) Justify the choice of the form () = e f () . 3. (10 points) Show that f () satises f () + (2 2)f () + (2 + 2 2 )f () = 0 . 4. (5 points) Show that a solution to the above dierential equation is f () = 1 F 1 ( + 2 , 2; 2) ,

241

(G.29)

(G.30)

(G.31)

where is solution to ( 1) = 2 + l(l + 1) . 5. (5 points) Show that the energies are quantized, such that En = 4 . 2ma2 (n + )2
2

(G.32)

6. (5 points) For most molecules, >> 1. Express in terms of and expand your expression for En to order 1/ 2 . We now consider a perturbative approach to this problem 7. (5 points) Find the minimum r0 of the potential and expand V (r) around that minimum, keeping all terms of degree 3 or lower in (r r0 ). 8. (5 points) Write the total Hamiltonian as a sum of H0 + Hpert . Identify clearly the perturbative term. 9. (15 points) Using the states |nlm of the harmonic oscillator, nd the rst and second order correction to the ground state energy. 10. (5 points) Check your answer by comparing with the result of [6.] 25. (20 points) Consider the matrix M =
3 8 1 3 19 72 13 48 5 18 13 48 17 48 7 18 67 144

. (G.33)

Problems
a) Show that = 1 is an eigenvalue of M . b) Find the eigenvectors of M . c) Find the matrix M 1/2 . d) Find the matrix M .

242

26. (100 points) Consider the problem of a particle trapped in a innite potential well of width L. Inside the well, there is an extra potential bump V (x) of width w given by 0 , if x < 1 (L w) 2 1 1 (G.34) V (x) = V , if 2 (L w) < x < 2 (L + w) . 0 0 , if x > 1 (L + w) 2 a) Find the conditions that the wave function must satisfy at x = and x = 1 (L + w). 2
1 2 (L

w)

1 Suppose that V0 is 2 of the energy of the lowest eigenstate for a square well of width L, with w = L/10.

b) (20 points) Find the lowest three energies for this well, and compare them with the lowest three energies of the square well . c) (20 points) Find an expression for the lowest energy eigenstate valid everywhere inside the well. Make sure that your wave function is normalized. d) (5 points) Make a plot of the probability density of this wave function. e) (5 points) What is the overlap between your solution and the lowest wavefunction for the square well problem?
3 f-g-h-i) Repeat the previous calculations assuming now that V0 is 2 times the energy of the lowest eigenstate for a square well of width L with w = L/10.

27. (30 points) Let C, and let |n be the harmonic oscillator state with energy 1 (n + 2 ) . At t = 0, the coherent state |(0) is dened by |(0) = e||
2 /2

n |n n! n=0

(G.35)

Problems
a) (5 points) What is |(t) , the coherent state at time t? b) (5 points) Show that a|(t) = ei
t |(t)

243

c) (5 points) Find p(t) and x(t) for |(t) . d) (10 points) Find p2 (t) and x2 (t) for |(t) . e) (5 points) Compute xp for |(t) . 28. (15 points) A particle of mass m is trapped in a harmonic potential such that = k/m. At t = 0, the wave function describing this particle is given 1 |n , where the sum over n goes from N s to N + s with by |(0) = 2s n N s 1. a) (5 points) What is the form of the wave function |(t) at any time t? b) (10 points) Show that x(t) varies (co)sinusoidally in time with amplitude 2 N/m, and compare the frequency of oscillation with the classical result. 29. (20 points) Compute the matrix elements n|x3 |m and n|x4 |m for the one dimensional harmonic oscillator. 30. (50 points) The Morse potential. To investivate the vibrational spectrum of a diatomic molecule, Morse has introduced the potential V (x) = D e2x 2ex . (G.36)

a) (5 points) Find the point x0 where this potential is minimum. This is the equilibrium point. b) (5 points) By expanding V in series about x0 , write an approximate expression for V up to and including terms in (x x0 )4 :
1 V (x) V0 + 2 m 2 (x x0 )2 + (x x0 )3 + (x x0 )4 .

(G.37)

c) (5 points) Converting to = (x x0 )/x0 , write the timeindependent Schrdinger equation for this problem using the approximate expression for o V found in Eq.(G.55). Identify explicitly the Hamiltonian operator H.

Problems

244

d) (10 points) Using the reduced mass formula: 1/m = 1/mCl + 1/mH and the parameters given below, evaluate , and for an electron in potential specied by the parameters describing the HCl molecule if: D = 37244 cm1 , 2 /2mx2 = 10.5930 cm1 , = 2.380. What is the equilibrium separation 0 distance x0 between the two atoms in the molecule? e) (5 points) Using the previous values for the paramaters of your potential, construct a 3 3 matrix with matrix elements Hmn = m|H|n using the states |0 , |1 and |2 . (This should be a matrix of number.) f) (10 points) Determine the characteristic polynomial of this matrix, and nd the roots by plotting the polynomial and identifying the zeroes. (Aside: Your energy eigenvalues will have units of cm1 : to convert to eV, use E(eV ) = 3 5 E(cm1 ) 1.2398 104 . The eigenvalues should be near , 2 , 2 . Why?)
1 g) (5 points) Compare the lowest eigenvalue with the energy 2 of the ground 1 state of the oscillator. (The dierence between the eigenvalue and 2 is due to the cubic and quartic terms in Eq.(G.55).)

h) (5 points) What is the wavelength of the photon emitted when a state is deexcited from the rst excited state to the ground state? Is this in the visible, infrared or ultraviolet? 31. (40 points) Consider the three angular momentum states |1, 1 z , |1, 0 |1, 1 z , with Lz |1, m z = m|1, m z . and

a) Construct the 3 3 matrix for the operator Lx . Is this matrix hermitian? Show that the eigenvalues of this matrix are 1, 0, i.e. they are identical to the eigenvalues of the operator Lz . b) Repeat this calculation for the operator Ly . c) Find the linear combinations of |1, m
z

state that are eigenstates of Ly .

d) State the Heisenberg uncertainty relation for Lx Ly , and verify that the relation holds for each of the states |1, m z . 32. (30 points) Suppose that an electron is in a state dened by the wave function 1 ei sin + cos g(r) , (r, , ) = 4 (G.38)

Problems
where
0

245

|g(r)|2 r2 dr = 1 .

(G.39)

a) What are the possible results of a measurement of the z-component of the angular momentum of the electron in this state? b) What is the probability of obtaining each of the possible results found in a)? c) What is the expectation value of Lz ? 33. (20 points) The quadrupole moment operator is dened as Q0 = 2z 2 x2 y 2 . a) Using spherical coordinates, show that this operator is proportional to r2 Y20 (, ). b) Let r, , | = R(r)Y m (, ). Assuming = 1, which magnetic substate (or substates) has the largest average quadrupole moment Q0 . 34. (40 points) Consider a particle represented by the wave function = K(x + y + 2z)er , where r = x2 + y 2 + z 2 , with K, R constants. a) What is the total angular momentum of this particle? b) What is the expectation value of the z-component of angular momentum? c) If the z-component of angular momentum, Lz , were measured, what would be the probability that the result would be + ? d) What is the probability of nding the particle at , and in the solid angle d? ( and are the usual angles in spherical coordinates.) 35. Design a hydrogenoid state | which satises the following requirements: i)Repeated measurements of the energy of a particle described by | produce 5 only the values E = 13.6 eV or E = (13.6/4) eV, ii) E = 8 (13.6) eV, iii) 1 1 Lz = 8 , iv) Lx = 0 , v) Ly = 4 . 36. Find the lowest possible energy of a nucleon having angular momentum = 2 , trapped in the spherical well of depth 8MeV in a nucleus containing 65 nucleons, given that the nuclear radius is r = 1.5 1015 A1/3 , with A the nucleon number, and compare with the energy of such a nucleon in an innite spherical well having the same radius. 37. Let A and B be any operators.

Problems
a) Let eA = 1 + l

246

1 1 1 2 A + A + A3 + . . . 1! 2! 3!
1 3! [A, [A, [A, B]]]

(G.40) + ... (G.41)

Show that 1 eA B eA = B + [A, B] + 2 [A, [A, B]] + b) Use Eq.(G.41) to show that

eiLy Lz eiLy = Lz cos Lx sin .

38. (A review problem on angular momentum) Let = tan()ei . Dene the angular momentum coherent state at t = 0 by 1 | = (G.42) e L+ | , , 2 )j (1 + || where the exponential of an operator is dened in Eq.(G.40), and where | , m is the state such that L2 | , m = 2 ( + 1)| , m , Lz | , m = m | , m . a) Write an explicit expression in terms of and for | if b) For the special case of = 1. = 1, show that | is properly normalized.

1 c) Let H = 2 AL2 + Lz , where is the rotational frequency. Show, on dimensional grounds, that 1/A is proportional to the moment of internia of the system having this Hamiltonian.

d) Find |(t) when

= 1.

e) Compute E and E. f) Compute Lz , Lz , Ly and Ly when tainty relation is satised. = 1, and verify that the uncer-

39. (A review problem on harmonic oscillators and radial wave functions) Consider 1 the twodimensional isotropic harmonic oscillator, with potential V = 2 m 2 (x2 + y 2 ). Let ax = ay = where [ai , a ] j 2m 2m x+ i px m i y+ py 2 a = x a = y 2m 2m i px m i y py , m x

= ij , i, j = x, y.

Problems

247

a) Let | = N a a |0 . Find a constant N that will normalize correctly | . x y b) Find |(t) , where |(0) = | . The coordinate approach. c) Using the known wave functions for the 1-d harmonic oscillator and the expression of x and y in polar coordinates, express | in polar coordinates r, | = (r, ) d) Let Lz = i /. Compute Lz and Lz for the state | . e) What is the probability of measuring Lz = 0 for a particle prepared in the state | ? f) Given the Laplacian in 2-d:
2

1 r r

1 2 , r2 2

use separation of variables to show that eigenstates of H are of the form im . Find the dierential equation that must be satised by the funcf (r)e tion f (r). g) Using the boundary conditions at r = and r = 0, show that f (r) is of the form 2 f (r) = r|m| er /2 F (r) , where F (r) satises d2 F (r) + dr2 2|m| + 1 2r r
2 k 2 /2m.

d F (r) 2(|m| + 1) k 2 F (r) = 0 , dr (G.43)

where = m/ , E =

h) Show that the substitution t = r2 transforms Eq.(G.43) into t d d2 F (t) + (|m| + 1 t) F (t) 2 dt dt
1 2

|m| + 1

k2 4

F (t) = 0 ,

(G.44)

i) Compare Eq.(G.44) with the standard generalized Laguerre functions, and nd the condition for which F (t) will become a polynomial of nite degree. Deduce the possible values of E from that condition.

Problems

248

j) Write all the possible wave functions having energy E1 = 2 , and normalize them properly. (Hint: these are functions of r and .) The Hilbert space approach k) Express H, the Hamiltonian for this system, in terms of ax , a , ay and a . x y l) Is | an eigenstate of H? If yes, what is the energy associated with this state? If no, what is E for this state? m) Show that the operators i a ay , x
1 2i

a ax a ay x y

i ax a y

have commutation relations identical to L+ , L , Lz , and that H commutes 1 with 2 i a ax a ay . x y


1 n) Using 2 i

a ax a ay , compute Lz and Lz . x y

o) Using the polar coordinates, nd an explicit expression for the operator 1 a ax a ay . x y 2i 40. (20 points) (see Griths p.13 prob. 1.8) Consider the wave function (x, t) = Ae|x| eit , where A, , are real constants. a) Normalize , b) Determine the expectation values of x and x2 , c) Find the standard deviation of x. Sketch the graph of |(x, t)|2 as a function of x, and mark the points ( x + ) and ( x ) to illustrate the sense in which represents the spread in x. What is the probability that the particle would be found outside this range? 41. (20 points) (Griths p.13 prob. 1.9) Let Pab (t) be the probability of nding the particle in the range a < x < b at time t. (G.45)

Problems
a) Show that dPab (t) = J(a, t) J(b, t) , dt where J(x, t) i 2m (x, t) (x, t) (x, t) (x, t) x x .

249

(G.46)

What are the units of J(x, t)? b) Find the probability current for the wave function of Eq.(G.45). 42. (20 points) (Griths p. 14 prob. 1.10) Suppose you wanted to describe an unstable particle that spontaneously disintegrates with a lifetime . In that case, the total probability of nding the particle somewhere should not be constant, but should decrease with time at (say) some exponential rate:

P (t)

|(x, t)|2 dx = et/ .

A crude way of achieving this is to assign to the potential of the Schrdinger o equation an imaginary part: V = V0 i , (G.47) where V0 is the true potential energy and is a real positive constant. a) Show that d dt

|(x, t)|2 dx =

P.

(G.48)

b) Solve for P (t) and nd the lifetime of the particle in terms of . 43. (40 points) (Griths p.19 prob. 1.14) A particle of mass m is described by the wave function 2 (x, t) = Aea[(mx / )+it] , (G.49) where A and a are positive real constants. a) Find A. b) For what potential energy function V (x) does (x, t) satisfy the Schrdinger o equation? c) Calculate the expectation values of x, x2 , p and p2 .

Problems

250

d) Find x and p . Is their product consistent with the uncertainty principle? 44. 30 (see Griths p.29 prob. 2.6&2.7) A particle in the innite square well has as its initial wave function an even mixture of the rst two stationary states: (x, 0) = A (1 (x) + 2 (x)) . a) (5 points) Normalize (x, 0). b) (5 points) Find (x, t) and |(x, t)|2 , and express the result in terms of sine and cosine functions of time, using = 2 /2ma2 . c) (5 points) Compute x . What is the frequency of oscillation of x ? What is the amplitude of oscillation? d) (5 points) Compute p e) (5 points) Find the expectation value of H. How does it compare with E1 and E2 ? Although the overall phase constant of the wave function is of no physical signicance, the relative phase of the coecients in Eqn. (G.50) does matter. For example, suppose we change the relative phase of 1 (x) and 2 (x) to (x, 0) = A 1 (x) + ei 2 (x) , where is a constant. f) (5 points) Find (x, t), |(x, t)|2 and x , and compare your results with the results obtained using Eqn.(G.50), where was set to 0. 45. 35 The radial part of Schrdingers equation in three dimensions is given by o (see. Eqn.(4.16)) 1 d R(r) dr r2 dR dr 2mr2
2

(G.50)

(G.51)

(V (r) E) = ( + 1),

(G.52)

where R(r) is the radial wave function and r 0 is the radius. a) (5 points) Show that the change of variable (r) = rR(r) will tranform the radial equation into an equivalent onedimensional problem subject to the condition r 0. What is the equivalent onedimensional potential for this problem?

Problems

251

The nuclear potential can be modeled as a well having a nite depth of 57MeV and radius r0 1.25 A1/3 with A the total number of nucleons. b) (15 points) How many states with angular momentum for 56 F e? What are the energies of these states? 26 = 0 can you nd

c) (10 points) Write down explicitly the normalized wave function for the lowest energy state of 56 F e. Find r for this state if the radial probability density 26 is given by P (r) = r2 |R(r)|2 . (G.53) d) (5 points) What is the probability of nding a nucleon outside the nucleus if it is described by an = 0 wavefunction having the lowest possible energy in the above well? 46. 35 The Morse potential. To investigate the vibrational spectrum of a diatomic molecule, Morse has introduced the potential V (x) = D e2x 2ex , x= r r0 . r0 (G.54)

a) (5 points) Sketch this potential, and show that it has a minimum at r = r0 . This is the equilibrium point. b) (5 points) By expanding V in series about r0 , write an approximate expression for V up to and including terms in (r r0 )2 :
1 V (x) V0 + 2 m 2 (r r0 )2 .

(G.55)

c) (10 points) Using the reduced mass formula: 1/m = 1/mCl + 1/mH and the parameters given below, evaluate for an electron in potential specied by the parameters describing the HCl molecule if: D = 37244 cm1 , 2 /2mr 2 = 10.5930 cm1 , = 2.380. To convert from cm1 to eV, use 0 E(eV ) = E(cm1 ) 1.2398 104 ). What is the equilibrium separation distance r0 between the two atoms in the molecule? d) (5 points) By comparing with the harmonic oscillator, obtain the (approximate) values for the lowest two energy levels of HCl. e) (10 points) By comparing with the wave functions of the harmonic oscillator, write the (approximate) radial wave function R(r) for the state of lowest energy. Compute r using Eqn.(G.53)

Problems

252

47. 40 points (see Flgge prob. 42). Consider the twodimensional isotropic u 1 harmonic oscillator, with potential V = 2 m 2 (x2 + y 2 ). Given H=
2 2

2m

1 + 2 m 2 r2 ,

1 r r

1 2 , r2 2

in polar coordinates, a) Using separation of variables, show that the eigenstates of H are of the form im . f (r)e b) Show that f (r) satises the dierential equation m2 1 f (r) + f (r) 2 f (r) +(k 2 2 r2 )f (r) = 0 , r r k2 = 2mE
2

= (G.56)

c) Show that, for large values of r, the solution must be of the form f (r) 2 rs er /2 with nite s, and that, for small values of r, the solution must be of the form f (r) r|m| . d) Use the ansatz f (r) = r|m| er tion F (r) satises F + 2|m| + 1 2r r
2 /2

F (r) to show that the interpolating func-

F 2(|m| + 1) k 2 F = 0 .

(G.57)

e) Make the change of variable t = r2 and show that F (t) now satises t d2 F dF + [(|m| + 1) t] 2 dt dt
1 2

(|m| + 1)

k2 F = 0. 4

(G.58)

f) Show that the polynomial solutions to the previous dierential equation are F (t) =1 F1 (a, |m| + 1; t), where a= with nr a positive integer. g) Show that this last condition leads to Enr ,m = (|m| + 1 + 2nr )
1 2

(|m| + 1)

k2 nr , 4

(G.59)

Problems

253

48. (15 points) The nuclear potential can be modeled as a well having a nite depth of 57MeV and radius r0 1.25 A1/3 with A the total number of nucleons. How many nuclear states with angular momentum = 1 can you nd for 56 F e? 26 What are the energies of these states? 49. (20 points) A particle of mass m is constrained to move between two concentric impermeables spheres of radii r = a and r = b. There is no other potential. a) (10 points) Show that the lowest E= = 0 state has energy
22

2m(b a)2

(G.60)

b) (10 points) Find the radial wave function R(r) for this lowest state, and obtain the normalized wave function (r) if the normalization condition reads d r2 |(r)|2 dr = 1 . (G.61)

50. (25 points) For a particle of mass m = 1/2, a Schrdinger equation in one o dimension, in units where = 1, reads d2 2sech2 x (x) = (x) . dx2 (G.62)

a) (5 points) Determine the constant in eikx (tanh x + ) that will make this function a solution of this Schrdinger equation. o b) (10 points) Calculate the Smatrix for this problem. c) (10 points) The wave function (x) = sechx happens to satisfy the Schrdinger o equation. Calculate the energy of the corresponding bound state and give a simple argument that it must be the lowest energy state of this potential. (Hint: number of nodes). 51. (30 points) Conserved quantities. a) (10 points) prob. 3.54 page 118 from Griths.

Problems

254

(Particle in a magnetic eld) The Hamiltonian for a spinless charged particle in a magnetic eld B = A is H= e 1 p A , 2m c (G.63)

where e is the charge of the particle, p = (px , py , pz ) is the momentum and A is the potential vector. Let A = B0 y, so that the magnetic eld B = B0 z x is constant along z . b) Prove that px and pz are constants of motions by showing that they commute with the Hamiltonian operator H of the system. c) Show that (x, y, z) = ei(xpx +zpz ) (y) is an eigenstate of px and pz with respective eigenvalues px and pz . d) Write the timeindependent Schrdinger equation for the y coordinates in o terms of px and pz , and 52. (30 points) (based on Griths page 120 prob. 3.58) Imagine a system in which there are just two linearly independent states: |1 = 1 0 , |2 = 0 1 . (G.65) (G.64)

The most general state is a normalized linear combination | = a|1 + b|2 = a b , (G.66)

with aa + bb = 1. Suppose the matrix representing the Hamiltonian is H= where


0 0 g

g
0

(G.67)

R and g C. The timedependent Schrdinger equation is o i | = H| . t (G.68)

a) Find the eigenvalues and normalized eigenvectors of H.

Problems

255

b) Suppose the system starts out (at t = 0) in state |1 . What is the state of the system at time t? The ammonia molecule, N H3 , has a pyramidal shape, with the nitrogen atom at vertex and three hydrogen atoms at the base. Classically, the nitrogen atom may be at one of two symmetric equilibrium positions: to the left or right the plane of the hydrogen atoms. These states are denoted, respectively, by |N H3 and |H3 N . c) Given the energy separation E = 9.84 105 eV , can you reconstruct all the matrix elements (magnitude and phase) of the Hamiltonian matrix? d) Which of the two eigenstates has the lowest energy? (Hint: even/oddness of corresponding wave functions and number of nodes.) e) Find the frequency of oscillation between the |N H3 and |H3 N states. 53. (30 points) Let C, and let |n be the harmonic oscillator state with energy 1 (n + 2 ) . At t = 0, the coherent state |(0) is dened by |(0) = e||
2 /2

n |n n! n=0

(G.69)

a) (5 points) What is |(t) , the coherent state at time t? b) (5 points) Show that a|(t) = ei
t |(t)

c) (5 points) Find p(t) and x(t) for |(t) . d) (10 points) Find p2 (t) and x2 (t) for |(t) . e) (5 points) Compute xp for |(t) . 54. (40 points) Morse revisited. a) (5 points) Compute the matrix elements n|x3 |m for the onedimensional harmonic oscillator. b) (5 points) Expand the Morse potential: V (x) = D e2x 2ex , x= r r0 . r0 (G.70)

near its equilibrium point, including terms in (r r0 )3 .

Problems

256

c) (5 points) Using this expansion for V (x), write the (approximate) Hamilto nian operator H in terms of the operators a and a . d) (10 points)Using |0 , |1 and |2 , obtain the 3 3 matrix representing H in this subspace. e) (5 points)Using the reduced mass formula: 1/m = 1/mCl + 1/mH and the 2 parameters given below for the HCl molecule: D = 37244 cm1 , 2 /2mr0 = 10.5930 cm1 , = 2.380, write the numerical form of the matrix for H. (To 1 to eV, use E(eV ) = E(cm1 ) 1.2398 104 ). convert from cm f) (5 points)Obtain the characteristic equation Det(H 1 = 0 and nd the l) lowest eigenvalue. This will have to be done numerically by plotting the polynomial in and looking for the points where it goes through zero. g) (5 points)Compare this lowest eigenvalue with the one obtained in Problem Set 2. Is this new eigenvalue an improvement when compared with the exam energy (which you can nd from the section in the notes on the Morse potential)? 55. (20 points) Let | m = Y
m (, ).

a) Obtain the matrix representation Mx of the operators Lx between states of angular momentum = 1. b) Find the eigenvalues and normalized eigenvectors |m
x

of Lx .

c) Construct the matrix U , having as its rst column the rst eigenvector of Lx , as its second column the second eigenvector of Lx etc. Show the U is =1 unitary by verifying that U U l. d) Verify that U Mx U is diagonal. 56. (20 points) Let C, and consider 1 | = 1 + ||2 where | , m is the state L L| , m =
2 2 k=0

k L k!

|1, 1 ,

(G.71)

( + 1)ket , m ,

Lz | , m = m | , m .

(G.72)

Problems

257

a) (5 points) Construct explicitly | as a linear combination of the |1, m s. b) (5 points) Show that | is normalized. c) (10 points) Compute Lx Ly for this state, and verify that this product satises the uncertainty relation. 57. (20 points) Let n m (r, , ) = r, , | n, , m be a wave function for a three dimensional harmonic oscillator. a) (5 points) Write explicitly the two wave functions having total energy and magnetic quantum number m = 0.
7 2

b) (5 points) The quadrupole moment operator Q0 is dened as 32 x2 y 2 . z Find an expression for the operator in terms of = 2 spherical harmonics. c) (10 points) Compute the matrix element 000|Q0 |220 using the explicit expression of the appropriate wave functions. 58. (25 points) Let |n m denote the state of a hydrogen atom with energy 13.6/n2 eV, angular momentum and magnetic quantum number m. If, at time t = 0, the state of a hydrogen atome is 1 |100 + |210 + 2|211 + 3|21, 1 |(0) = 10 a) Find the average energy of this state, b) What is |(t) ? c) What is the probability of nding the system with m = 0 as a function of time? d) At time t = 0, what is the probability of nding the electron within 1012 m of the proton? (It is valid to use expansions for small r if need be.) e) Suppose a measurement is made which shows that = 1 and m = 1. Describe the (normalized) state immediately after this measurement. These problems are designed to review some of the material of Modern Physics I & II. 59. (10 points) Basic properties of the Schrdinger equation. o , (G.73)

Problems
a) The timedependent Schrdinger equation in one dimension reads o i
2 2 (x, t) = (x, t) + V (x)(x, t) . t 2m x2

258

(G.74)

Show that, if 1 (x, t) and 2 (x, t) are separately solutions of Eqn.(G.127), then the arbitrary linear combination (x, t) = 1 1 (x, t) + 2 2 (x, t) is also solution for arbitrary complex constants 1 and 2 . b) The timeindependent Schrdinger equation in one dimension reads o d2 (x) + V (x)(x) = E(x) , 2m dx2
2

(G.75)

where E is the eigenvalue of associated to (x). Show that, if 1 (x) and 2 (x) are separately solutions of Eqn.(G.128) with eigenvalues E1 and E2 respectively, then the arbitrary linear combination (x) = 1 1 (x)+2 2 (x) , with 1 and 2 arbitrary complex constants, is not a solution of Eqn.(G.128) unless E1 = E2 . 60. (50 points) Playing with wave functions. Let 0 (x) = where = a
1 2

a2 x2 /2

,
1 2

1 (x) = .

a 2

1 2

2ax ea

2 x2 /2

(G.76)

k/m , a =

a) (5 points) Show 0 (x) and 1 (x) are separately solutions of Eqn.(G.128) 1 with V (x) = 2 kx2 , and nd the corresponding eigenvalues E0 and E1 , b) (15 points) Show 0 (x) and 1 (x) are normalized and orthogonal w/r to the standard 2 inner product:

i | j =

dx i (x)j (x) = ij

0 if i = j , 1 if i = j .

(Suggestion: Find .)

d n e as a function of n knowing

d e =

c) (10 points) Write an expression for 0 (x, t) and 1 (x, t), and use the previous results to show that 0 (x, t) and 1 (x, t) also satisfy i (t) | j (t) = ij .

Problems

259

d) (5 points) Let (x, t) = (cos )0 (x, t) + ei (sin )1 (x, t), where and are real parameters. Show that (x, t) is normalized. e) (5 points) Using (x, t) above, nd the average value of x as a function of time, i.e. compute

x(t) =

dx (x, t) x (x, t) .

(G.77)

61. (15 points) A problem on quantum weirdness. A classical turning point X is a value of x for which the potential energy is equal to the total energy of a particle; in principle, a particle has no kinetic energy at that point and must therefore turn around its motion. a) Use the wave function 0 (x) of Eqn.(G.76) and its energy found in 2.1 to nd the turning points of a classical particle in a harmonic oscillator well. (Hint: there are two turning points...) b) The region between the classical turning points will be referred to as the classically allowed region. The regions not classically allowed are called classically forbidden. Find a denite integral expressing the probability of nding the particle in the classically forbidden region. c) Evaluate the previous integral. You will need to do some numerical integration to obtain the nal result 62. (30 points) Consider the motion of a quantum particle trapped in an innite well with a step. The total width of potential is a, the height of the step is V0 , and the width of the step is a/2. The potential is illustrated in gure G.

Let (x) = A sin(x/a) . (G.78)

a) (2 points) Is the wavefunction of Eqn.(G.78) an eigenstate of the Hamiltonian of this system? b) (3 points) Discuss why the wavefunction of Eqn.(G.78) is a valid wavefunction for this system. c) (2 points) Normalize (x, t).

Problems

260

Figure 31: The potential for this problem. d) (3 points) Find x for a particle described by (x). e) (5 points) Find p for a particle described by (x), and explain why the results is expected on physical grounds. f) (5 points) Find E for a particle described by (x). g) (10 points) What is the maximum height of the potential step V0 that will result in no bound state with energy E < V0 ? 63. (30 points) Consider a particle trapped in an innitely deep well with wavefunction (at t = 0) (x, 0) = A (1 (x) 3i3 (x)) where n (x) is the n solution to the timeindependent Schrdinger for this poteno tial. a) (5 points) Find (x, t). b) (5 points) Find a value for the constant A that will normalize (x, t). c) (5 points) Compute the probability current J(x, t) for this particle. d) (10 points) Using (x, 0), nd x , x, p , p and verify the uncertainty relation. e) (5 points) Using (x, 0), nd E and E. 64. (20 points) The deuteron is a composite particle made from one proton and one neutron. The relative motion of the constituents can be rewritten as the motion of a single particle, having reduced mass given by 1 1 1 = + , mn mp

Problems

261

and evolving in a spherical well of nite depth V0 (V0 > 0). The deuteron has only one bound state with angular momentum = 0. In such circumstances, the solutions of the Schrdinger equation in three dimension reduces to the solutions o of the onedimensional problem provided that the motion is restricted to positive coordinates. Knowing the binding energy E0 = 2.22 M eV , obtain an estimate of V0 if the width r0 of the spherical potential is r0 ( c/140)M eV 1 1015 m , mn c2 mp c2 940M eV , c = 197M eV 1015 m . 65. (30 points) (This is an augmentation of a midterm problem from last year.) The ammonia molecule, N H3 , is in the form of pyramid, with the nitrogen atom at vertex and three hydrogen atoms at the base. The nitrogen atom may be at one of two symmetric equilibrium positions: above or below the plane of the hydrogen atoms. The potential energy for the motion of nitrogen is illustrated in gure 1 as the Wshape curve. The gure also illustrates the approximation of this potential by a innite onedimensional square well with a central bump of height V0 = 0.245eV. The innite walls are located at b = 0.55481010 m; the central bump extends from a to +a, with a = 0.2298 1010 m.

Vo

ba

Figure 32: The potential for the nitrogen atom of the ammonia molecule. The exact potential (wavy line) is approximated by an innite square well with a bump in the middle (heavy line).

a) (2 points) Let x denote the position of the nitrogen atom. Explain why this potential is even under transformation of x x.

Problems
b) (5 points) Show the wave function B sin(k(b + x)) if b x a , (x) = A (ex + ex ) if a < x < a , B sin(k(b x)) if a x b .

262

(G.79)

is even under the transformation x x, and nd a general expression for a wavefunction odd under the transformation x x. c) (3 points) Justify the use of these wave function in searching for solutions of a problem with even potential. In particular, justify the assumptions behind the use of the exponentials to describe the wavefunction in the central region. d) (10 points) Let = 2m(V0 E)
2

k=

2mE
2

(G.80)

Show the energies of the even wave functions can be found from the consistency equation: 1 ea + ea ea ea 1 = tan(k(b a)) , k (G.81)

and nd the corresponding transcendental equation valid for the odd wavefunction. e) (5 points) Using the graphical method described in class, nd the energy of all the even wavefunctions with E < V0 knowing that mN H3 = 2300MeV/c2 and c = 197.5MeV 1015 m. f) (5 points) Determine if there are odd wavefunctions with energy smaller than the height of the central barrier. If there are such a functions, nd their energy; if there is not such function, nd the smallest value of V0 that will allow for one odd state. Part I: Harmonic vibrations of molecules and solids You may want to read prob. 5.11 of Schaum and Beiser before starting these two problems. 66. The interaction between ions in a simple molecular solid can be modeled by the Lennard-Jones potential: V (r) = 4V0 r0 r
12

r0 r

(G.82)

(This parametrization diers from that of the Schaum.)

Problems
a) Show that this potential has a minimum at rmin = 21/6 r0 .

263

b) This potential represents the interaction of a single molecule with the rest of the crystal. For a crystal of N2 , the parameters of the potential are V0 = 0.00791eV and r0 = 3.92 1010 m. Make a plot of V (r) applicable to N2 . Choose a range of r that clearly illustrates the depth of the potential and the position of the minimum. c) (5 points) Expand V (r) in a power series around r = rmin , and show the potential has the approximate form
1 V (r) V0 + 2 m 2 (r rmin )2 .

(G.83)

1 The expression V0 + 2 m 2 (r rmin )2 is the osculating parabola for this potential and transforms V (r) into an approximately harmonic oscillator potential for r rmin , shifted in energy by V0 .

d) (10 points) Use the series expansion to estimate the energies of the lowest three vibration levels of the molecule in the crystal. Express your energies in eV . Be careful about your choice of mass parameter! e) (7 points) What is the approximate energy of a photon emitted in a transition from the n = 1 to the n = 0 vibrational state? Is this in the infrared, visible or ultraviolet light? 67. (30 points) The potential between the two atoms of a diatomic molecule can be modeled by the Morse potential: V (r) = D(e2a(rr0 ) 2ea(rr0 ) ) , (G.84)

where D is the dissociation energy, r0 is the equilibrium position and a is a parameter. The variable r represents the relative distance between the atoms. It is possible to solve the Schrdinger equation exactly for the Morse potential, but o many important features can be understood by looking at the harmonic approximation to this potential. Start by recovering the original article by Morse. The complete reference of the paper is: P.M. Morse, Physical Review vol. 34 page 57 (1929). You will need to do this from a LU computer or from home using rst the Connect from Home feature available from the Library webpage. Once you have logged in, nd the website for Physical Review (any section) and go to PROLA to access older papers. In the small dialog box where you choose the journal, select Phys. Rev (no section; next to last choice) and enter the correct volume and page numbers. Note that Morse denotes his potential by E(r) rather than V (r).

Problems

264

a) (3 points) From the data provided on page 62 of the paper, make a plot of V (r) for 12 conguration of the N2 molecule. Note that r0 is given in 1010 m and that a is measured in 1/(1010 m). The units of D are cm1 , which can be converted to Joules by multiplying by hc, where h is the Planck constant and c is the velocity of light (in cm/sec). Choose a range 0 r rmax that clearly shows the position of the minimum and the depth of the potential. b) (5 points) Show that the minimum of V (r) is located at r = r0 . This is the classical equilibrium position. c) (5 points) Expand the Morse potential in a power series in r r0 around r = r0 , and show the potential has the approximate form V (r) D + Da2 (r r0 )2 . (G.85)

d) (10 points) Use the series expansion to estimate the energies of the lowest three vibration levels of the molecule. Express your energies in eV . (Here, what vibrates are the atoms one relative to the other. The eect of this vibration on the electrons is ignored.) e) (7 points) What is the approximate energy of a photon emitted in a transition from the n = 1 to the n = 0 vibrational state? Is this in the infrared, visible or ultraviolet light? f) (5 points) If we use the exact potential rather than its approximate expression, will the exact energies be higher or lower than the corresponding approximate ones? You need to think about qualitative features of the wavefunction, such as curvature, in order to get a sense of that. Note that the analysis of Prob. 1 is valid for solids, whereas Prob. 2 is applicable to gases... Part II: The Schrdinger equation o 68. (10 points) (see Schaum prob. 3.29 page 49) Consider a particle of mass m held in the potential
1 1 V (x) = V0 (x 2 r0 ) + (x + 2 r0 ) .

(G.86)

(Note that this potential is symmetric, whereas Schaums isnt.) Show there are two bound states and nd a transcendental equation for their energy.

Problems

265

69. (55 points) Find the bound state solutions E < 0 to the Schrdinger equation o for the potential V0 . (G.87) V (x) = cosh2 ( x ) a a) (5 points) Make a plot of this potential for = x/a and V0 = 1 from 5 5. b) (10 points) Make the substitutions (x) = cosh x a
2

u(x) ,

1 4

8mV0 a2

+11 ,

(G.88)

o to convert Schrdinger equation to 4 x d2 u tanh( ) 2 dx a a du 4 2 2 + ( )u = 0 , dx a2 = m a2 , 2 2 = E > 0 . (G.89) x c) (10 points) Introduce the new independent variable z = sinh2 a show this leads the hypergeometric equation z(1 z) d2 u + dz 2
1 2

and

(1 2)z

du + (2 2 )u = 0 . dz

(G.90)

d) (5 points) Show that the two solutions that give even and odd wavefunctions are, respectively, u1 = u2
1 2 F1 ( + , , 2 ; z) , 1 3 1 z 2 F1 ( + + 2 , + 2 , 2 ; z) . =

(G.91)

To show the statement, use the series solution expression for 2 F1 (a, b, c; z). e) (5 points) Show that the solutions of Eqn.(G.91) remain nite at z = 0. f) (5 points) Show that the choice k = transforms the hypergometric function u1 into a polynomial, thereby guaranteeing that the wavefunction (x) = (cosh x )2 u1 (x) goes to 0 at . Find the energies of the even a functions as a function of k = 0, 1, 2, .... This deals with the even solutions.
1 g) (5 points) Show that the choice k = 2 transforms the hypergeometric function u2 into a polynomial so that the odd (x)s go to 0 at . Find the energies of the odd wavefunctions as a function of k = 0, 1, ....

Problems
h) (5 points) Combine these results to show
2

266

En =

2ma2

1 2

8mV0 a2
2

+ 1 (n +

1 2)

n = 0, 1, ... .

(G.92)

i) (5 points) Show the number of discrete levels is equal to the largest integer N satisfying the inequality N<
1 2

8mV0 a2
2

+1

1 2

(G.93)

Independent multiparticle systems 70. Consider a system with two noninteracting identical particles subject to the same potential, so that the total Hamiltonian H of the system can be written as H =
2

2m

2 2 + 2 2 1 2

+ (V (1 ) + V (2 )) (G.94)

= H1 + H2 ,

where 1 , 2 denote the coordinates of particles 1 and 2, respectively. Let n (1 ) be the nth eigenstate of H1 , and m (2 ) the mth eigenstate of H2 , i.e. assume H1 n (1 ) = En n (1 ) , H2 m (2 ) = Em m (2 ) . (G.95)

a) (5 points) Show explicitly that (1 , 2 )n,m = n (1 )m (2 ) is an eigenstate of H and show that the eigenvalue is E = En + Em . b) (10 points) Show that, if (j ) satises
dj n (j )s (j ) = ns ,

(G.96)

then n (1 )m (2 ) satises d1 d2 (n (1 )m (2 )) r (1 )s (2 ) = nr ms . Use this to show that (1 , 2 )n,m is properly normalized. (G.97)

Problems
c) (5 points) Show that the combination A ((1 , 2 )n,m + (1 , 2 )m,n ) ,

267

(G.98)

where A is an arbitrary constant, is an eigenstate of H with eigenvalue E = En + Em . d) (10 points) Find the constant A that will normalize the eigenfunction of Eqn.(G.98). Explain why you need to treat the cases m = n and m = n separately. e) (5 points) Suppose m = n. Compare your result with Eqn.(9.23) of Beiser and discuss how this author doesnt know what hes doing (once more). In the Fermi-gas model of the nucleus, the nuclear constituents move independently one from the other in an average potential, much in the way that electrons move independently from each other in a crystal. The nuclear potential has a form given by (r R0 ) 1 . (G.99) V (r) = V0 1 + exp a (This is called the WoodsSaxon potential, or the inverted Fermi potential.) The parameters are: R0 = r0 A1/3 ; V0 50 M eV ; a 0.5 1015 m ; r0 1.2 1015 m .

Here, A is the total number of nucleons (protons plus neutrons).

Problems

268

The potential actually has a nite but negligible slope at r = 0. Thus, for calculation purposes, one often uses one of three possible approximations: a) The 3dimensional harmonic oscillator: V (r) = V0 1 b) The innite spherical well: V (r) = c) The nite spherical well: V (r) = V0 for r R0 , 0 for r > R0 . V0 for r R0 , for r > R0 . r 1 2 2 = 2 m0 (r2 R0 ) , R0

Consider the case of 56 F e, containing 26 protons and 30 neutrons (A = 56). 26 For the parameter m, use the mass of a nucleon mp mn (protons and neutrons are assumed to have identical mass). 71. (35 points) Lets approximate the WoodsSaxon potential by a harmonic oscillator, as indicated above. a) (5 points) Make a plot of the WoodsSaxon potential appropriate for
56 F e. 26

b) (10 points) List the rst 20 energy levels (accounting for multiplicities) in increasing order of energy by giving the cartesian quantum numbers (nx , ny , nz ) of these levels. In this notation, the lowest energy level is (0, 0, 0). c) (10 points) List the rst 20 energy levels (accounting for multiplicities) in increasing order of energy by giving the quantum numbers (n, ) and the corresponding energies. (Hint: In this notation, the lowest energy level is (0, 0).) You may assume that each (n, ) state contains 2 + 1 substates. d) (10 points) In its simplest form, the Pauli exclusion principle states that no more than two fermion can have the same set of quantum numbers. What is the lowest possible energy of 56 F e, containing (Neutrons and protons 26 are fermions, but they are not identical.) You may assume that, for each separate value of , there are 2 + 1 states. 72. Repeat items iii) and iv) previous problem

Problems

269

a) (10 points) Using the innite spherical well approximation. (No need to replot the potential.) b) (20 points) Using the nite spherical well approximation. 73. Suppose some system is described by the Hamiltonian 1 2 1 p + m 2 2 + , H= 2m 2 where is a constant. a) By completing the square, and making change of variable , show that it is possible to write H in the form 1 2 1 p + m 2 2 + , H= 2m 2 where is a constant. b) Using the solutions to Eqn.(G.101), nd the energy levels of the system in terms of the initial variable . c) Write an explicit expression for the lowest energy wavefunction if is the variable x, which can range from to +. d) Write an explicit expression for the lowest energy wavefunction if is the variable r, which can range from 0 to . 74. Most probable = average. The objective of this problem set is to make sure that you become familiar with some important properties of the wavefunctions that weve obtained thus far. (See Schaum, in particular Eqn.(8.42) and prob. 8.12) Using the denition of the conuent hypergeometric function 1 F1 and the relation between n (r) and 1 F1 : a) Show that the most probable value of r in any hydrogen radial state Rn,n1 with = n 1 is exactly identical to the prediction Bohrs theory. b) Find a closed form expression for the average value of r when the system is in such a state. (G.101) (G.100)

Problems

270

You need to recall that the probability density for the radial coordinate is related to the radial wavefunction R(r) by r2 R (r)R(r). 75. Muonic atoms. (See Schaum prob. 8.8) One way to investigate wavefunctions of hydrogenlike systems is by way of the muonic atom, which is formed when a negative muon is captured by a proton. Because the mass of is much 207me , the reduced mass of the protonmuon system is much smaller than the reduced mass of the protonelectron system. This change aects energy levels and wavefunctions in a very protable way. a) Start by going back to the hydrogen solution. Calculate the binding energy E of the hydrogen atom using the reduced mass of the protonelectron system. Find the dierence (expressed in percentage) between the exact calculation using the reduced mass and the approximate calculation (done in class) using the only the mass of the electron. b) Repeat the previous calculation for the muonic atom, and nd the Bohr radius of this new system. c) The radius of a proton is about 1015 m. Using the hydrogen wavefunctions adjusted for the muonic system, calculate the probability of nd the inside the proton for the following states: n = 3, = 0; n = 3, = 1; n = 3, = 2. To simplify calculations, you might want to justify using an approximation of the form e 1 if is suciently small. d) Discuss the trend with of your previous calculation in the context of the centrifugal term ( + 1)/r2 appearing in the eective potential that occurs in the Schrdinger equation. 76. (10 points) Let |n m be any ket. Show r|n m must satisfy the selection rule n m ||n m = n ||n mm , r r where n ||n r is the radial integral
0 drr3 Rn (r)Rn (r) .

(G.102)

(G.103)

(Note: you cannot evaluate this integral unless you are given supplementary information about the wavefunction.) You may assume r r in spherical coordinates. (Hint: use orthonormality of Y m (, ), i.e. m | m = mm . 77. (20 points) Converting from cartesian to spherical.

Problems

271

a) (2 points) Using Cartesian coordinates, write down explicitly the wave function nx ny nz (x, y, z) for the threedimensional harmonic oscillator state with nx = 0, ny = 0, nz = 2. b) (2 points) What is the energy E of this state. c) (6 points) Convert z 2 to spherical coordinates, and express the result as a sum of Y ,m (, ), i.e. write z 2 = r2
,m

m Y m (, )

(G.104)

(Hint: only

= 2 and

= 0 should appear.)

d) (5 points) Using this, convert your Cartesian wavefunction to a linear combination of spherical wavefunctions n m (r, , ). Verify that the result is properly normalized. e) (5 points) Show that all the spherical wavefunctions n m (r, , ) entering in the expression of nx ny nz (x, y, z) have energy E identical to the energy of the system described by nx ny nz (x, y, z). 78. (20 points) At time t = 0, a hydrogen system is described by the ket |(0) = A 2|100 + |210 + 2|211 + 3|2, 1, 1 (G.105)

where |n m is an eigenket of the hydrogenatom Hamiltonian. a) (3 points) Use orthonormality of ket vectors n m | n m = n n m m to nd a constant A that will normalize |(0) . b) (3 points) Find E . c) (10 points) What is the probability of nding the electron within 1012 meters of the proton (at t = 0)? You may simplify calculations by justifying the use, in the appropriate context, of the approximation ex 1x. (Hint: the probability works out to 3.6 106 .) d) (4 points) Find |(t) . 79. (10 points) The prepresentation.

Problems

272

a) (3 points) Write the Schrdinger equation for the onedimensional harmonic o oscillator using the prepresentation of operators. b) (7 points) By comparing with the solutions in the xrepresentation, nd an explicit expression for the two lowest energy wavefunctions 0 (p) and 1 (p) in pspace. 80. (10 points) [Griths # 2.35 .] A particle of mass m and kinetic energy E > 0 approaches an abrupt potential drop V0 . The potential for this problem is thus: V (x) = 0 if x < 0 V0 if x 0. (G.106)

a) What is the probability that it will reect back if E = V0 /3? b) Do not do part b) c) When a free neutron enters a nucleus, it experiences a sudden drop in potential from V = 0 to V = 12 MeV inside. Suppose a neutron, emitted with kinetic energy 4MeV by a ssion event, strikes such a nucleus. What is the probability that it will be absorbed, thereby initiating another ssion? (Hint: you calculated the probability of reection in part i). Use T = 1 R to get the probability of transmission through the surface.) For this problem, Griths B is what we call whereas his F is our . You are encouraged to read the comment in Prob. 2.34c), which, for us, translates as the following: for a potential step of height V0 , the probability of transmission is not simply but rather (E V0 )/V0 . 81. (15 points) [Griths # 2.38 .] A particle of mass m is in the ground state of the innite square well. Suddenly, the well expands to twice its original size, the right wall moving from a to 2a leaving the wavefunction momentarily undisturbed. The energy of the particle is now measured. a) What is the most probable result for E? What is the probability of getting this result? b) What is the next most probable result, and what is its probability? c) What is the expectation value E of the energy? (Hint: If you nd yourself confronted with an innite series, try another method.) 82. (10 points) [Griths # 3.2 .]

Problems

273

a) For what range of is the function f (x) in the Hilbert space of square integrable function on the interval (0, 1), i.e. for what range of is
1 0 1 b) For the specic case = 2 , is f (x) in the Hilbert space? What about xf (x)? What about (d/dx)f (x)?

dx |f (x)|2 < ?

(G.107)

83. (15 points) [Griths # 3.22 .] Consider a threedimensional vector space spanned by an orthonormal basis |1 , |2 , |3 . Kets | and | are given by | = i|1 2|2 i|3 , a) Find | and | in terms of 1|, 2|, 3|. b) Find | and | conrm that one is the complex conjugate of the other. c) Find all nine matrix elements of the operator A = | | in the basis spanned by |1 , |2 , |3 , i.e. nd the nine quantities i|A|j , where |i , |j are elements of the basis. Construct the matrix A representing the operator A. Is A hermitian? 84. (20 points) [Griths # 3.37 .] The Hamiltonian operator H for a certain threelevel system is represented by the matrix a 0 b HH= 0 c 0 , (G.109) b 0 a where a, b and c are real. a) If the system is initially in the state 0 |(0) = 1 , 0 (G.110) | = i|1 + 2|3 . (G.108)

what is |(t) ? (Hint: only the eigenvectors of H have a simple time evolution, and these eigenvectors form a complete set.)

Problems
b) If the system is initially in the state 0 |(0) = 0 , 1 what is |(t) ?

274

(G.111)

85. (15 points) Creation and destruction operator. A particle of mass m is trapped k/m. At t = 0, the wave function in a harmonic potential such that = describing this particle is given by 1 |(0) = 2s |n ,
n

(G.112) s 1.

where the sum over n goes from N s to N + s with N

a) (5 points) What is the form of the wave function |(t) at any time t? b) (10 points) Show that x(t) varies (co)sinusoidally in time with amplitude 2 N/m, and compare the frequency of oscillation with the classical result. 86. (20 points) Commutators of product operators. a) (5 points) (The derivative rule). Show that, if A, B and C are any three operators, then [A, B C] = [A, B]C + B[A, C] . (G.113) This is known as the derivative rule since it resembles the rule for derivation of a product of functions. Consider two sets of harmonic oscillator creation and destruction operators, a, a and b, b such that [a, a ] = [b, b ] = 1 , l b) (5 points) Let X=
1 2

[a, b] = [a, b ] = [a , b] = [a , b ] = 0 .

(G.114)

a b + a , b

Y =

1 2i

a b a , b

Z=

1 2

a a + b b .

Verify that [X, Y ] = i Z , [Y , Z] = i X , [Z, X] = i Y , (G.115)

i.e. these operators have commutation relations identical to the angular momentum operators Lx , Ly , Lz . (Hint: use the derivative rule.)

Problems

275

c) (5 points) Find the operators J+ and J that play the role of L+ and L in the theory of angular momentum. d) (5 points) Consider the twodimensional normalized oscillator state |na , nb , 1 such that a|na , nb = na |na 1, nb etc.. Show that, if na = 2 (j + m) and 1 nb = 2 (j m), then J+ |na , nb = (j + m + 1)(j m)|na + 1, nb 1 , (G.116)

like the angular momentum result L+ |jm . 87. (15 points) The virial theorem. When a force can be derived from a potential, 1 the virial theorem of classical mechanics states that T = 2 r V . For the special case of a potential of the form V = k rn , we then obtain
1 T = 2n V .

(G.117)

This problem examines the quantum version of this result. a) Let A be any welldened hermitian operator, and let | be any normalized eigenstate of H: H| = E| . (G.118) Find [A, H] = |[A, H]| .
1 p b) Let H = 2m ( )2 + V (r) be the Hamiltonian for a threedimensional particle in a sphericallysymmetric potential. Show that

r [H, ] =

i p, m

[H, p] = i ( V (r)) .

(G.119)

r c) Use the result of part i) with A = p to show that 2 |T | = | r where T is the kinetic energy. d) If V (r) is of the form rn , show that the energy of an eigenstate with energy E is given by n |V | . (G.121) E = 1+ 2 V r | , (G.120)

Problems

276

88. (25 points) The Pauli matrices [see Griths sec. 4.4]. Consider the three 2 2 matrices x = Let Sx =
1 2

0 1 1 0 x etc.

y =

0 i i 0

z =

1 0 0 1

(G.122)

a) (5 points) Using matrix multiplication, show explicitly that the matrices Sx , Sy , Sz satisfy the commutation relation Sx , Sy = i Sz , Sy , Sz = i Sx , Sz , Sx = i Sy . (G.123)

(Note that these are identical to the commutation relations for Lx , Ly and z .) L b) (5 points) What are the possible outcomes of measuring Sz , Sy and Sx , respectively? c) (5 points) Suppose the system is a state with welldened value of Sz . What 1 is the probability of obtaining 2 when measuring Sy ?
1 d) (10 points) The states | that satisfy Sy Sz = 2 | |Sz | |2 are called intelligent. Show that, if a state | is an eigenstate of Sx iSy , where is real, then | is intelligent.

89. (10 points) Let A be any hermitian operator. Let | be any state, and let | be such that A| | with real and nonnegative. Show = A , = A = A2 + A 2 . (G.126) = | + | , = 0, (G.124) (G.125)

90. (10 points) Basic properties of the Schrdinger equation. (see Beiser Exercise o 5.8)

Problems
a) The timedependent Schrdinger equation in one dimension reads o i
2 2 (x, t) = (x, t) + V (x)(x, t) . t 2m x2

277

(G.127)

Show that, if 1 (x, t) and 2 (x, t) are separately solutions of Eqn.(G.127), then the linear combination (x, t) = 1 1 (x, t)+2 2 (x, t) is also solution for arbitrary complex constants 1 and 2 . b) The timeindependent Schrdinger equation in one dimension reads o d2 (x) + V (x)(x) = E(x) , 2m dx2
2

(G.128)

where E is the eigenvalue of associated to (x). Show that, if 1 (x) and 2 (x) are separately solutions of Eqn.(G.128) with eigenvalues E1 and E2 respectively, then the arbitrary linear combination (x) = 1 1 (x)+2 2 (x) , with 1 and 2 arbitrary complex constants, is not a solution of Eqn.(G.128) unless E1 = E2 . 91. (40 points) Playing with wave functions. (You will need material from Griths sections 1.3 to 1.6, and you may want to review Beiser sections 5.5 to 5.8 and Griths section 2.2, in particular Eqn.[2.28].) A particle of mass m is conned to a onedimensional region 0 x a. This is modeled by the potential V (x) = 0 , if 0 x a , , otherwise. (G.129)

At t = 0, the wavefunction is given by (x) = N 1 + cos x a sin x a . (G.130)

a) (5 points) Find the constant N that will normalize the wavefunction. b) (5 points) Show that the normalized wavefunction (x) can be written as a sum of two normalized solutions to the timeindependent Schrdinger o equation for this problem. Give the energy of these two solutions. c) (5 points) Find (x, t). (Hint: Griths Eqn.[2.17], Example 2.1) d) (20 points) Compute x and p as a function of time using (x, t).

Problems

278

e) (5 points) Verify that Heisenbergs uncertainty relation is satised for all times. 92. (10 points) Consider the onedimensional wavefunction (x) = N x x0
n

ex/x0 ,

(G.131)

where N , n and x0 are constants. Using Schrdingers equation, nd the potential V (x) and energy E for which o this wavefunction is an eigenfunction. You may assume V (x) 0 as x . (Hint: obtain an expression for E V (x) independent of any solution (x) and use the condition at to deduce E, then V (x) for any x.) 93. (20 points) A problem on quantum weirdness. (see caption of Fig.5.12 of Beiser) A classical turning point A is a value of x for which the potential energy is equal to the total energy of a particle; in principle, a particle has no kinetic energy at that point and must therefore turn around its motion. a) Start with the harmonic oscillator wave function 1 (x) of Eqn.(6.67) of the course notes, or Eqn.[2.85] of Griths (together with Eqn.[2.71]). Find its energy by inserting this wavefunction into the timeindependent Schrdinger o equation. Note: the (miserable) discussion of Beiser around Eqn.(5.34) of his book is incomplete; the condition that a certain dynamical variable G be restricted to discrete values Gn is that the wavefunction satisfy Eqn.(5.34) and be normalizable.) b) Find the turning points of a classical particle in a harmonic oscillator well. c) The region between the classical turning points will be referred to as the classically allowed region. The regions not classically allowed are called classically forbidden. Find a denite integral expressing the probability of nding the particle in the classically forbidden region. d) Evaluate the previous integral. You will need to do some numerical integration to obtain the nal result In the Fermi-gas model of the nucleus, the nuclear constituents move independently one from the other in an average potential, much in the way that electrons

Problems

279

move independently from each other in a crystal. The nuclear potential has a form given by (r R0 ) 1 . (G.132) V (r) = V0 1 + exp a (This is called the WoodsSaxon potential, or the inverted Fermi potential.) The parameters are: R0 = r0 A1/3 ; V0 50 M eV ; a 0.5 1015 m ; r0 1.2 1015 m .

Here, A is the total number of nucleons (protons plus neutrons), and R0 is the nuclear radius. This is the net potential felt by individual nucleons (protons and neutrons). We assume both nucleons to have identical masses: m = mn = mp = 938.919MeV/c2 . You will also need the conversion factor c = 197.326MeV 1015 m. 94. (20 points) = 2 states of 132 Sn 50 The WoodsSaxon potential of Eqn.(G.132) is often approximated by a nite spherical well: V0 for r R0 , V (r) = 0 for r > R0 . (G.133)

V=0

V=Vo MeV r=R o

Figure 33: An approximation to the nuclear well. a) Find the energy of all the = 2 states of
132 Sn 50

using this potential.

b) What is the largest possible energy of a bound state in this potential, i.e. what is the largest E so that E < 0? What is the angular quantum number of this state?

Problems

280

95. The WoodsSaxon potential of Eqn.(G.132) is often approximated by the threedimensional harmonic potential V (r)
1 2 1 2 2 2 m0 r2 2 m0 R0 .

(G.134)

a) (5 points) What is the largest possible energy of a bound state in this potential, i.e. what is the largest E so that E < 0? b) (10 points) What is the probability of nding a nucleon outside the nucleus if the nucleon is in the lowest possible energy state? c) (5 points) What is the average r for a nucleon in the lowest possible state with = 1? 96. (20 points) Hydrogen atom. a) Show that the most probable value of r for an electron in the lowest energy state of a hydrogen atom is a0 . b) Show that the most probable value of r for an electron in the nr = 2, = 1 state of the hydrogen atom is 4a0 . c) Find r for an electron in the nr = 3, = 0 state of a hydrogen atom. d) Find r for an electron in the nr = 3, = 1 state of a hydrogen atom. Compare this with the previous result. Is this compatible with the classical picture of increasing centripetal force with increasing value of ? 97. (10 points) Muonic atoms. Hydrogenlike atoms can be formed in which a muon is bound to a nucleus of charge Ze; such states are called muonic atoms. Muons are heavy electrons in that they have the same electric charge (e) as electrons but are much heavier: m c2 = 105.6MeV whereas me c2 = 0.511MeV. Use the appropriatelymodied hydrogenoid wavefunctions to calculate the probability of nding a muon inside the 209 Bi nucleus assuming the muon is in the 83 lowest energy state of this system. Use the parameters given at the start of the assignment to obtain the radius of 209 Bi. (Hint: reduced mass). 83 98. (10 points) Orthogonality of the angular functions. The angular part of the wavefunction is of the form Y (, ) = ()eim , where () satises 1 d sin d sin d d + ( + 1) m2 sin2 () = 0 . (G.135)

Problems

281

a) (1 points) Make the change of variable x = cos to obtain the socalled associated Legendre equation: (1 x2 )(x) 2x (x) + ( + 1) m2 1 x2 (x) = 0 . (G.136)

Let m (x) denote a solution to Eqn.(G.136). b) (2 point) Show this can be written as d (1 x2 ) (m (x)) + dx ( + 1) m2 1 x2 m (x) = 0 , (G.137)

where denote dierentiation w/r to the argument. c) (5 points) Multiply Eqn.(G.137) by m (x). Write Eqn.(G.137) for L and L multiply it by m (x), then subtract the two to recover d (1 x2 ) m (x)(m (x)) (m (x)) m (x) +( L(L + 1) ( + 1)) m (x)m (x) = 0 . L L L dx (G.138) d) (2 points) Integrate from 1 to 1 to show orthogonality over that interval. 99. (15 points) Orthonormality of wavefunctions. Let |nr m denote a hydrogen ket, so that r, , | nr m = nr
m (r, , )

= Rnr (r)Y m (, ) ,

(G.139)

is a hydrogen wave function. Consider now the state vector at t = 0 1 |100 + |210 + 2 |211 + 3 |21, 1 |(0) = 10 a) (2 points) Show that, at least, nr m | nr m = r| basis and orthonormality of Y m (, ) .)
,

(G.140)

m,m . (Hint: use the

b) (2 points) Show that |(0) is properly normalized, i.e. | = 1. c) (2 points) Find |(t) as a linear combination of kets. For a system described by the state vector |(0) , d) (3 points) What is the average value of energy ?

Problems
e) (3 points) What is the average value of L L? f) (3 points) What is the average value of Lz ? 100. (15 points) p-representation of the harmonic oscillator.

282

a) (5 points) Write the wavefunction 0 (p) for the lowest energy state of a one dimensional harmonic oscillator in the p-representation. (Hint: you may either write the Schrdinger equation in p-space and repeat the solution of o the dierential equation, or compute the Fourier transform of 0 (x).) b) (10 points) Find the probability that p2 /(2m) > E0 . 101. (20 points) The Wigner distribution in one dimension. Consider the function W (x, p) = 1

dy (x + y) (x y) e2ipy/ ,

(G.141)

known in the literature as a Wigner function or Wigner distribution. Using properties of the -function, show a) the probability density in position space |(x)|2 =

dp W (x, p) ,

(G.142)

b) the probability density in momentum space |(p)|2 =

dx W (x, p) .

(G.143)

102. (Bonus: 10 points) The radial wavefunction R(r) near r = 0. In solving the radial equation, we have introduced the auxiliary function (r) = r R(r) and showed that the solution to the radial equation for (r) is similar to a one dimensional problem where a particle is restricted to r 0 in a potential Vef f . The condition that the wavefunction be integrable is then
0

| R(r) |2 r2 dr =
0

| (r) |2 dr .

(G.144)

In this problem, we want to justify the condition


r0

lim (r) 0 .

(G.145)

For small values of r and V not worse than 1/r at the origin, the wavefunction (r) must behave like r +1 or r since the ( + 1)/r2 term dominates. If we select (r) r +1 , Eqn.(G.145) is automatically satised as 0.

Problems
a) (2 points) Suppose we choose instead (r) r , with is impossible to satisfy Eqn.(G.144) by showing that
0

283
= 0. Show that it

| (r) |2 dr =
0

r0

| (r) |2 dr +

r0

| (r) |2 dr

(G.146)

is not normalizable even if r0 is chosen to be so small that (r) r holds for the rst integral. There remains (r) r with = 0, i.e. (r) c, where c is some constant. This implies R(r) c/r for small r, and thus (r, , ) c/r. b) (5 points) Show that 2 (1/r) = 4 3 (r), where 2 = is the Laplacian in spherical coordinate. (Hint: First show that 2 (1/r) = 0 if r = 0. To see what happens at r = 0, consider a small sphere centered at the origin and use Gauss theorem (the divergence theorem) and the identity 2 = . c) (3 points) Thus, argue that unless Vef f contains a function at the origin (which we assume it does not), the choice c = 0 is untenable. 103. (30 points) Imagine a system in which there are just two linearly independent states: 1 0 |1 = , |2 = . (G.147) 0 1 The most general state is a normalized linear combination | = a|1 + b|2 = a b , (G.148)

with aa + bb = 1. Suppose the matrix representing the Hamiltonian is H=


0 g

g
0

(G.149)

where 0 R and g C. The timedependent Schrdinger equation is given in o Eqn.(??). a) (5 points) Find the eigenvalues and normalized eigenvectors of H. b) (10 points) Suppose the system starts out (at t = 0) in state |1 . What is the state of the system at time t?

Problems

284

The ammonia molecule, N H3 , has a pyramidal shape, with the nitrogen atom at vertex and three hydrogen atoms at the base. Classically, the nitrogen atom may be at one of two symmetric equilibrium positions: to the left or right the plane of the hydrogen atoms. These states are denoted, respectively, by |N H3 and |H3 N . c) (5 points) Given the energy separation E = 9.84 105 eV , can you reconstruct all the matrix elements (magnitude and phase) of the Hamiltonian matrix? d) (5 points) Which of the two eigenstates has the lowest energy? (Hint: even/oddness of corresponding wave functions and number of nodes.) e) (5 points) Find the frequency of oscillation between the |N H3 and |H3 N states. 104. (20 points) Given the matrix 0 0 X = 0 0 2 , 1 0 0 where = e2i/3 , a) Find the determinant of this matrix, b) Given that X can be written as X = U 1 D U , where D is diagonal, nd the eigenvalues of X and the corresponding eigenvectors. c) Verify that the sum of the eigenvalues is the trace of the matrix. d) Verify that the product of the eigenvalues is the determinant of the matrix 105. (15 points) A particle of mass m is trapped in a harmonic potential such that = k/m. At t = 0, the wave function describing this particle is given 1 |n , where the sum over n goes from N s to N + s with by |(0) = 2s n N s 1. a) (5 points) What is the form of the wave function |(t) at any time t? (G.150)

Problems

285

b) (10 points) Show that x(t) varies (co)sinusoidally in time with amplitude 2 N/m, and compare the frequency of oscillation with the classical result. 106. (60 points) (A review problem on harmonic oscillators and radial wave functions) Consider the twodimensional isotropic harmonic oscillator, with potential 1 V = 2 m 2 (x2 + y 2 ). Let ax = ay = 2m 2m x+ i px m i y+ py 2 a = x a = y 2m 2m i px m i y py , m x

where [ai , a ] = ij , i, j = x, y. j a) Let | = N a a |0 , with ax |0 = ay |0 = 0. Find a constant N that will x y normalize correctly | . b) Express H, the Hamiltonian for this system, in terms of ax , a , ay and a . x y c) Is | an eigenstate of H? If yes, what is the energy associated with this state? If no, what is E for this state? d) Find |(t) , where |(0) = | . e) Using the known wave functions for the 1-d harmonic oscillator and the expression of x and y in polar coordinates, express | in polar coordinates r, | = (r, ) f) Let Lz = i /. Show that Lz commutes with H. g) What are the possible outcomes of measuring Lz for a system prepared in the state | ? h) What is the probability of measuring Lz = 0 for a particle prepared in the state | ? i) Compute Lz and Lz for the state | . j) Show that the operators i a ay , x
1 2i

a ax a ay x y

i ax a y

have commutation relations identical to L+ , L , Lz , and that H commutes 1 with 2 i ax ax ay ay .

Problems
1 k) Using 2 i

286
a ax a ay , compute Lz and Lz . x y

l) Using the polar coordinates, nd an explicit expression for the operator 1 a ax a ay . x y 2i 107. (30 points) Let |n m be denote the usual hydrogen atom ket and consider the state |(0) = A |311 2 |21, 1 , (G.151) at t = 0, where is real. a) Find a constant A that will normalize this state. b) Find |(t) . c) Find L L . d) Find Lx , Ly and show the uncertainty relation is veried. e) What is the probability of measuring the value Ly = 0 for a system described by |(t) ? f) What is the most probable value of Ly at t = 0? 108. (25 points) Radial momentum operator. We know that px i with [, p ] = i . x Let pr i and f (r) be any function of r. a) Compute pr r f (r) r pr f (r) and compare with Eqn.(G.152). b) We have seen the radial part of the Schrdinger equation can be written as o d 2mr2 dr
2 x

,x x, (G.152) (G.153)

1 + r r

r r,

r2

d dr

R(r) + (V (r) E)R(r)


2

2m

( + 1) R(r) = 0 . r2

Show that the term is nothing but (r )2 R(r). p

2mr2

d dr

r2

d dr

R(r)

Problems

287

c) To establish the conditions under which pr is hermitian, show that the condi tion 0 = | pr | pr , where (r, , ) is a square integrable function, leads to the restriction lim r (r, ) = 0 , (G.154)
r0

showing that (r) = r R(r) must go to zero at the origin, as shown our study of the radial solutions. d) From the previous calculations, one denes the radial momentum operator to be the operator of Eqn.(G.153). Find pr and p2 for a hydrogen atom r system with n = 1 and = 0. Compute pr (Remember to properly introduce an extra r2 factor in your calculation of the average value.) e) Use the results for r and r2 found at Eqn.(8.42) and (8.43) of the Schaum to compute r, and compute the uncertainty product pr r. Is this compatible with the uncertainty principle? Nota: although pr is hermitian, no observable is associated with this operator. To show this, note that, for any , the solution to pr f (r) = f (r) is, to within a constant, eir/ , (G.155) f (r) r which never satises the condition of Eqn.(G.154). The eigenvalue problem for pr has no physically valid solution.

PHY3113: Quantum mechanics I Mid-Term examination If need be, you may refer to the following results: for m, n Z: 1
2

October 27, 2002

dx sin(mx) sin(nx) =
0

dx cos(mx) cos(nx) = mn
0 0

dx sin(mx) cos(nx) = 0 .

1. (total: 40 points) Let R() = cos sin sin cos . (1)

a) (10 points) Knowing that 1 = ei is an eigenvalue of R(), Find all the other eigenvalues of R(). b) (10 points) Is R() a hermitian matrix? Justify your answer. c) (20 points) Find the eigenvectors of R() as a function of the angle . 2. (total: 50 points) Consider a particle with E > 0 trapped in the potential for x < 0, 0 for 0 < x < L/2, V (x) = V0 for L/2 < x < L, for x > L a) (5 points) What is the timeindependent Schrdinger equation for this system? o b) (5 points) In the regions x < 0 and x > L, (x) must be 0. Explain briey why. c) (10 points) In the region 0 < x < L/2, (x) can be written as (x) = A sin(kx). Explain briey why. d) (10 points) In the region L/2 < x < L, (x) can be written as (x) = F sin(k (x L)). Explain briey why? e) (10 points) Find an equation that will determine the possible energies of a particle in this well. f) (10 points) Using the graphs that are supplied, nd the number of states having energy E > 0 but less than 25V0 assuming V0 = 9 2 /2mL2 . Estimate the energies of the lowest three states satisfying the above conditions. 3. (total: 25 points) Given the eigenstates for the innite square-well potential between 0 and L: x | n = n (x) = a) (10 points) Show that p
n

(2)

2 sin(nx/L) , L

(3)

n | p |n = 0 .

b) (5 points) Explain briey how you would prove the more general result p = 0 for any wave function (x) describing a particle in an innite well ((x) is not necessarily an eigenstate of H). b) (10 points) Explain briey how p any state for which () = 0.

= 0 can be expected if | describes any bound state (i.e.

PHY3113: Quantum Mechanics I


MidTerm examination 2004

March 2, 2004

This is an open book exam. There are three questions on two pages. The last page contains graphs relevant to one question. You are allowed 90 minutes. The maximum mark of this exam is 40. If you accumulate more than 40 point, you nal mark will be 40/40. 1. (20 points) Under some circumstances, the motion of an electron in a solid is restricted to two dimensions, with the electron evolving in a harmonic potential of the form
1 1 V0 (x, y) = 2 m 2 x2 + 2 m 2 y 2

(1)

When subjected to a uniform electric eld E = y E directed along the y axis, the potential is modied to
1 1 V (x, y) = 2 m 2 x2 + 2 m 2 y 2 eEy .

(2)

1. (5 points) Write the timeindependent Schrdinger equation for the particle in the potential V0 , and give the o two lowest energies of the electron in the potential V0 (Just state what these energies are.) 2. (5 points) Show the lowest two energies of the electron in the potential V (x, y) are + D and 2 + D, where 1 2 2 1 1 D is a constant. (Hint: 2 m 2 y 2 eEy = 2 m 2 (y eE )2 2 e 2E . 2m m 3. (5 points) Give an explict expression in terms of x, y and t for the timedependent wave function 0 (x, y, t), solution of the Schrdinger equation with potential V (x, y) and having the lowest energy. o 4. (5 points) Estimate the average values x and y for an electron described by (x, y, t). 2. (10 points) Consider the wave function at t = 0 (x, 0) = Ax(x L) , A C. (3)

1. Why can this wave function describe a particle trapped in a onedimensional well having innitely high walls at x = 0 and x = L? Explain your answer carefully. 2. Is this an eigenstate of the Hamiltonian operator for this system? 3. Why can this wave function describe a particle trapped in this well? Explain your answer carefully. 4. Is it possible to normalize the wave function? If yes, do so. If not, explain why it is not possible. 5. For this wave function, is it true that (x, t) = Ax(x L)eiEt/ ? If yes, nd E; if no, explain why this is not true.

Please turn over

2 3. (20 points) The ammonia molecule. The ammonia molecule, N H3 , is in the form of pyramid, with the nitrogen atom at vertex and three hydrogen atoms at the base. The nitrogen atom may be at one of two symmetric equilibrium positions: above or below the plane of the hydrogen atoms. The potential energy for the motion of nitrogen is illustrated in gure 1 as the Wshape curve. The gure also illustrates the approximation of this potential by a innite onedimensional square well with a central bump of height V0 = 0.245eV. The innite walls are located at b = 0.5548 1010 m; the central bump extends from a to +a, with a = 0.2298 1010 m.
b

Vo

ba

FIG. 1: The potential for the nitrogen atom of the ammonia molecule. The exact potential (wavy line) is approximated by an innite square well with a bump in the middle (heavy line).

1. (2 points) Let x denote the position of the nitrogen atom. Show the wave function B sin(k(b + x)) if b x a , (x) = A (ex + ex ) if a < x < a , B sin(k(b x)) if a x b . is even under the transformation x x.

(4)

2. (6 points) Justify the use of this wave function in searching for even solutions with E < V0 : i) discuss why one need a combination of exponentials in the central region and an oscillatory outside the bump, and ii) identify the boundary conditions at x = b and show (x) satises these conditions. 3. (6 points) Let = 2m(V0 E)
2

k=

2mE
2

(5)

Show the energies of the even wave functions can be found from the consistency equation 1 4. (6 points) Let E . (7) V0 Using the correct graph from the ones supplied on the next page, identify the number of states with E < V0 and estimate their respective energy. You will need the following data: =
2

ea + ea ea ea

1 = tan(k(b a)) . k

(6)

2mV0 a2

z=

mN H3 : b: 2mV0 a2
2

2300 MeV/c2 0.5548 1010 m : 15.3182

c: a: 2mV0 a2
2

197.3 MeV 1015 m 0.2298 1010 m : 3.9138 (8)

1 + b/a : 1.4143 In case of emergency, use graph 1.

3
0.2 0 0.4 z 0.6 0.8 1

Graph 1: Solutions to

(e3.91 (e3.91

1z

1z

tan(5.54 z) ) = . z e3.91 1z ) 1 z + e3.91


1z

0.2 0

0.4

0.6

0.8

Graph 2: Solutions to

(e3.91 1z

(e3.91

1z

e3.91 1z ) 1

+ e3.91

1z

) z

tan(3.91 z) . z

0.2 0

0.4

0.6

0.8

4
tan(5.54 1 z) (e3.91 z + e3.91 z ) = (e3.91 z e3.91 z ) z 1z

Graph 3: Solutions to

PHY3113: Intermediate electricity and Magnetism


MidTerm examination Time allocated: 80 minutes

March 7th, 2006

This exam contains 3 questions. Only pen or pencil, eraser and calculator allowed. Everything else is supplied with the exam. Remember to obtain a cheat sheet. If you use any equation from the cheat sheet, please indicate so at the appropriate place on your copy. This maximum score for this exam is 25. If you accumulate more than 25 marks, your score will be 25.

1. (10 points) As a rst approximation, the force between a neutron and a proton can be described by an attractive square-well potential, given in Eqn.(1) and illustrated in Fig. 1. V0 for r R0 , 0 for r > R0 .

V (r) =

(1)

Here, r is the relative radius between the two nucleons.

V=0

V=Vo MeV r=R o

FIG. 1: An approximation to the nuclear well.

The range R0 of the nuclear force is known to be of the order of the Compton wavelength of the pion: R0 = m c , (2)

where m = 139MeV/c2 is the mass of the pion Knowing that the protonneutron has a only one bound state with energy 2.22MeV, and knowing this state has angular momentum = 0, nd the depth of the potential V0 as follows: a) Show that V0 can be found from the solution to the consistency equation k tan(kR0 ) = , where k = 2(V0 )
2

(3)

, =

2
2

and the reduced mass of the protonneutron system. Here = 2.22 is

the negative of the bound state energy. V0 . Reduce the transcendental equation to an equation in terms of z and use one of the graphs supplied b) Let z = at the end of the test to estimate the value of V0 . The mass of the proton can be taken to be the mass of the neutron, with both equal to 940MeV/c2 . You may also need c = 197MeV1015 m.

2. Let n () = 2 sin L n L , (4)

denote a solution to the timeindependent Schrdinger equation for a innitely deep well. Consider the time o dependent wavefunction (x, y, 0) = i1 (x x0 )2 (y) , at t = 0, where x0 is a real constant. a) (2 points) Find E at t = 0. b) (6 points) Find (x, y, t) and the corresponding probability density. c) (2 points) Given the relations d sin2 (n ) = cos (2n) sin (2n) 2 , 4 8n2 2 4n sin (2n) , d sin2 (n ) = 2 4n (6) (7) (5)

nd x . (In case of doubt, use the wavefunction at t = 0.) 3. (10 points) A positronium atom is formed when a positron (e+ ) and an electron (e ) orbit around one another. 1 Given that the reduced mass of the system if 2 me , where me is the electron mass, nd a) the most probable distance between the positron and the electron if the system is in its lowest energy state, b) the average distance between e+ and e if the system is in its lowest energy state. You might need to know that the Bohr radius for the hydrogen problem is a0 = and the following integral: d n e = n n e + d n1 e . (9) 4 0 2 . m e e2 (8)

Please turn over for graphs

Examinations are formidable even to the best prepared, for the greatest fool may ask more than the wisest can answer. - Charles Caleb Colton 2

Some possibly useful graphs

10 -2

20

30

40 -2

10

20

30

40

-4

-4

-6

-6

-8

-8

-10

-10

FIG. 2: z z Left: The graphical intersection of the curves tan(0.4648 1) and 1. Right: The graphical intersection of the curves tan(0.3289 z 1) and z 1.

10 -0.25 -0.5 -0.75 -1 -1.25 -1.5 -1.75 -2

20

30

40

50

60 -0.25 -0.5 -0.75 -1 -1.25 -1.5 -1.75 -2

10

20

30

40

FIG. 3: p (z Left: The graphical intersection of the curves tan(0.3289 z 1) and p 1)/z. Right: The graphical intersection of the curves tan(0.4648 z 1) and (z 1)/z.

PHY3113: Quantum Mechanics I


MidTerm examination

Feb. 25th, 2007

Time allocated: 80 minutes. This exam contains 3 questions. Only pen or pencil, eraser and calculator allowed. Everything else is supplied with the exam. Remember to obtain a cheat sheet. If you use any equation from the cheat sheet, please indicate so at the appropriate place on your copy. This maximum score for this exam is 25. If you accumulate more than 25 marks, your score will be 25. You may (or you may not) need the following: d d2 sechx = sechx tanh x , sechx = sech3 x + sech x 1 sech2 x , dx dx2 d3 sechx = 5 sech3 x tanh x sech x tanh x 1 sech2 x . dx3

(1)

1. (17 points) The wavefunction at t = 0 for a particle of mass m evolving in a onedimensional harmonic potential is (x, 0) = A 0 (x) + where n (x) is the nth excited state of the system. a) (3 points) What is (x, t)? b) (3 points) Is this an eigenstate of the Hamiltonian for the system? c) (2 points) Find a value for the constant A that will normalize (x, 0). Assume d) (5 points) What is E ? What is E? e) (2 points) Is the wavefunction even, odd or neither even nor odd under the transformation x x? f) (2 points) Find x at t = 0. 2. (6 points) A particle of mass m = 1/2 evolves in the potential V (x) = 2 sech2 x ( = 1), where sech x = 1/ cosh x. a) (4 points) Show that the wavefunction (x) = A sech x with A a constant satises the timeindependent Schrdinger equation and nd the energy corresponding to this solution. o b) (2 points) Given the graph of Fig. 1, explain if this wavefunction is or is not the solution with lowest energy.
1 0.8 0.6 0.4 0.2

5 i 2 (x) ,

A C,

(2)

dx n (x)m (x) = mn .

-4

-2

FIG. 1: The graph for the function sech x.

1 3. (7 points) A particle evolves in a plane under the inuence of the potential V (x, y) = 2 m 2 (x2 + y 2 ).

a) (3 points) Write the wavefunction for the lowest energy solution for this problem. Express you answer in terms of , where 2 = x2 + y 2 . What is the energy of this state? 2 b) (2 points) Knowing 0 e d = /2, nd for this state or at least obtain an integral expression for . (Hint: d d) c) (2 points) Find the most probable value of for this state.

PHY3113: Quantum mechanics I Final examination


Nota: If you accumulate more than 100 points, you total mark will be 100%. Section 1. Basics. Maximum: 25 points

Dec.13th, 2001

1.1. (5 points) True or false: a complex number necessarily has a nonzero complex part. Explain your answer. 1.2. (15 points) Let M = 3 2 2 0 . Find M 2 .
1

1.3. (10 points) Using Eulers theorem, prove the equality


1 1 sin + sin = 2 sin 2 ( + ) cos 2 ( ) .

(1)

1.4. (10 points) Compute [, p]. x 1.5. (5 points) Evaluate all the solutions to i1/3 . Section 2. Onedimensional problems. Maximum: 30 points 2.1. (5 points) True or false: all solutions of the (onedimensional) timedependent Schrdinger equation are of the o form (x, t) = eiEt (x). Explain your answer. 1 2.2. (20 points) Let C, and let |n be the harmonic oscillator state with energy (n + 2 ) . At t = 0, the coherent state |(0) is dened by |(0) = e|| a) What is |(t) , the coherent state at time t? b) Show that a|(t) = ei
t
2

/2

n |n n! n=0

(2)

|(t) .

c) Find p (t) and x (t) for |(t) . d) Find p2 (t) and x2 (t) for |(t) . e) Compute xp for |(t) . 2.3. (15 points) Let us dene a potential V (x) by + 0 V (x) = V 0

if x < 0 , if 0 x < L , if x L .

(3)

1. The wave function that is solution to Schrdingers equation for this potential must have amplitude 0 x < 0. o Why? 2. The solution must have the form A sin(kx + ) in the region 0 x < L. Why? What must be the value of if the wave function is to have no amplitude at x = 0? 3. The wave function must have the form Ce(xL) for x L. Why? 4. Show that, at x = L, the coecients k and are related by z , 1z where n is an integer (positive or negative), z = E/V0 and = 2mV0 L/ . z = n arctan (4)

2 2.4. (15 points) Let 0 (x) = 1 a


1 2

x2 /2a2

1 (x) =

1 2a

1 2

x a

ex

/2a2

(5)

1 where = k/m , a = ( / mk) 2 , be two wave functions describing a particle of mass m in a harmonic potential 1 V = 2 kx2 at t = 0. a) What are the energies of 0 (x) and 1 (x)? b) Let (x, t) = (i0 (x, t) 1 (x, t))/ 2. What is the probability of nding the particle described by (x, t) in the state 0 (x, t)? Does this probability depend on t? Section 3. 3dimensional problems. Maximum: 45 points 3.1. (5 points) True or false: In angular momentum theory, the choice of diagonalizing Lz rather than, say, Ly or Lx , is arbitrary. Explain your answer. 3.2. (20 points) Consider a particle in a central potential. Given that |lm is an eigenstate of L L and Lz : 1. (15 points) Compute the sum (Lx )2 + (Ly )2 , 2. (5 points) For which values of l and m does the above sum vanish? 3.3. (20 points) In some problems, it is more convenient to diagonalize Lx rather than Lz . a) If |l, mz
z

is an eigenstate of L L and Lz such that Lz |l, mz |1


x

= mz |l, mz z , show that


z

1 = (|1, 1 6

+ 2|1, 0

+ |1, 1 z )

(6)

is an eigenstate of Lx . b) What are the quantum numbers l and mx specifying |1 x ? c) Find two operators L+ and L such that [Lx , L ] = L . d) Find all the other states having the same value of l but dierent values of mx . 3.4. (20 points) The (unnormalized) wave function (r, , ) = 6 r a0 r r/3a0 e sin sin a0 (7)

is an eigenstate of the Hamiltonian for the hydrogen atom. a) What is the energy of this state? b) Is this an eigenstate of L L? c) Construct explicitly another state, having the same energy as (r, , ), but orthogonal to (r, , ). 3.5. (20 points) To investivate the rotationvibration spectrum of a diatomic molecule, Kratzer proposed the potential V (r) = 2D a2 a 2 r 2r .

For this potential, the solution to the Schrdinger equation can be factorized into a product (r, , ) = o 1 (r)Ylm (, ). Using the dimensionless abbreviations r = r , a 2 = 2 ma2
2

E,

2 = 2

ma2
2

D,

(8)

with > 0 and real > 0, the radial equation for (r) takes the form 2 + l(l + 1) d2 () 2 + 2 + 2 () . d 2 2 (9)

3 a) (5 points) To solve, one sets () = e f () . Explain why this form is justied. b) (5 points) If we substitute Eqn.(10) in the radial equation, one nds that f () must satisfy f () + (2 2)f () + (2 + 2 2 )f () = 0 . with solution f () = 1 F 1 ( where is solution to ( 1) = 2 + l(l + 1) . Explain how this leads to the quantization of energy, i.e. discrete energy levels En , and write En in terms of the mass of the particle and the parameters of the potential. c) (5 points) Are there restrictions on the possible values of l and m for a given n? d) (5 points) Write the complete spatial eigenfunction (r, , ) for the lowest energy level of a particle in this potential. Section 4. Perturbation. Maximum: 10 points 4.1. (5 points) Is it possible to use perturbation theory to diagonalize the matrix 2 4 4 1 ? Explain why? 2 , 2; 2) , (12) (11) (10)

4.2. (10 points) Suppose that a onedimensional harmonic oscillator is perturbed by a potential of the type Vpert = F x. Find the rst nonvanishing correction to the energy of the ground state, and the rst nonvanishing correction to the wave function of the ground state.

PHY3113: Quantum mechanics I Final Examination


Part 1 You must complete the following three problems. 1. (15 points) Let
1 V (x) = 2 m 2 x2 3 16

December 2002

m x . 2

(1)

1) If a particle trapped in the potential V (x) of Eq.(1) is restricted to the harmonic oscillator states |0 and |1 , nd the 2 2 matrix representation of the operator H = p2 /2m + V () x 2) Find the eigenvalues and eigenvectors of H, expressed as linear combinations of |0 and |1 . 3) State the Heisenberg uncertainty principle for x and p, and verify that it holds for a particle described by the with the lowest energy. state | , which is the eigenstate of the H

2. (15 points) A particle of mass m is subject to the threedimensional potential V (r) = 0 if r < r0 . V0 if r > r0 (2)

1) Show that the minimum value of V0 needed to achieve two bound states (E V0 ) with zero angular momentum 2 is V0 = 9 2 2 /8mr0 . You may refer to the graphs below for guidance. 2) With a potential of this depth, nd the energy of the other bound state with = 0. You may refer to the graphs below.

2 1.5 1 0.5 0.2 -0.5 -1 -1.5 -2 0.4 0.6 0.8 1

2 1.5 1 0.5 0.2 -0.5 -1 -1.5 -2 0.4 0.6 0.8 1

3 2 1

0.2 -1 -2 -3

0.4

0.6

0.8

a)

b)

c)

The graphs for a) cot( z/2) and (1 z)/z, b) cot(3 z/2) and (1 z)/z, c) cot(5 z/2) and (1 z)/z, as a function of z. 3. (10 points) Let | , m denote angular momentum states with L L| , m = Compute the product Lx Ly for the state | = relation.
2 3 |2, 1 2

( + 1)| , m and Lz | , m = m | , m .

1 3 |2, 0

, and verify the Heisenberg uncertainty

Part 2 Complete any two of the following three problems. If you attempt more three problems, only the result of the best two will be kept. 4. (30 points) Consider the threedimensional harmonic oscillator state | = N (1 + a )2 |0 , l x where |0 is the ground state with ax |0 = ay |0 = az |0 = 0. 1) What are the possible outcomes of a measurement of the energy E of this state? 2) What is E ? 3) If, at t = 0, a system is described by |(t = 0) = | , what is |(t) ? 4) What are the possible outcomes of a measurement of the angular momentum of a particle described by the state | ? 5) What is Lx for this state? 6) What is the probability of measuring Lz = 0 for this state? 5. (30 points) Let = tan()ei . Dene the angular momentum coherent state at t = 0 by | = 1 e L+ / | , , (1 + ||2 ) (4) (3)

where the exponential of an operator is dened by


eA = 1 + A + 2 A2 + l 1 1 3 3! A

1 4 4! A

+ ... ,

and where | , m is the state such that L2 | , m =


2

( + 1)| , m ,

Lz | , m = m | , m . = 1 and use this to

1 1) (10 points) Let H = 2 AL2 + Lz , where is the rotational frequency. Find |(t) when compute Lz (t) .

2) (10 points) Compute E and E. 3) (10 points) At t = 0, compute Lz , Lz , Ly and Ly when satised. = 1, and verify that the uncertainty relation is

6. (30 points) At time t = 0, the wave function for the hydrogen atom is 1 2i|1, 0, 0 i|2, 1, 0 + 2|2, 1, 1 + 3|2, 1, 1 |(0) = 10 where n, , m are quantum numbers for hydrogen states. 1) (10 points) Calculate E for this state. What is the most probable value of E that one would measure in an experiment? 2) (5 points) What is the probability of nding the particle described by this wave function with = 1 at t = 0? , (5)

3) (10 points) What is the probability of nding the electron withing 1010 meter of the origin (at t = 0). You may use er/a0 1 r/a0 and give your nal answer in terms of the Bohr radius a0 . 4) (5 points) Suppose that a measurement is made which shows that immediately after this measurement. = 1 and Lz = +1 . Describe the state

PHY3113: Quantum mechanics I Final Examination

April 20th, 2004

This exam contains four questions on two pages. You are allowed 3 hours to complete all questions. An equation sheet is supplied. You can use your calculator. The maximum for this exam is 100. If you accumulate more than 100 points, your mark will be 100. 1. (30 points) Let |n denote an eigenket of the operator 1 H= ()2 + p 2m and consider the state vector at t = 0 |(0) = A (4|0 3i|1 ) . 1.1) (5 points) Find a constant A that will normalize |(0) . 1.2) (5 points) Find |(t) . 1.3) (5 points) Find x(t) , and show it is real. 1.4) (5 points) Find p(t) , and show it is real. 1.5) (10 points) For |(0) , obtain xp and show this product satises the Heisenberg uncertainty relation. 2. (30 points) Let |n m denote the eigenket describing an electron trapped in the potential of a hydrogen nucleus. The quantum numbers n, and m are the principal, angular momentum and azimutal quantum numbers, respectively. Let 1 | = 2 3|210 |211 . (3) 2.1) (10 points) Find E. 2.2) (5 points) What is the probability of measuring the value E2 = 13.6/4 eV for the energy of this system? 2.3) (5 points) What is the probability of measuring Lz = +1 for the projection of L along z ? 2.4) (10 points) Find Lx Ly and verify that this product satises the Heisenberg inequality. 3. (25 points) Let |nx , ny be a twodimensional harmonic oscillator ket in Cartesian coordinates, such that ax |nx , ny = nx |nx 1, ny , a |nx , ny = nx + 1|nx + 1, ny , x and similarly for ay and a . y Let the Hamiltonian operator be H = a ax + a ay + 1 + a ay + ax a . x y x y 3.1) (5 points) Show the matrix representing H in the space spanned by the two states |1x , 0y and |0x , 1y is H= 2 1 1 2 . (5) (2)
1 2

m 2 ()2 , x

(1)

(4)

3.2) (5 points) What are the possible outcomes of measuring the energy of this system? 3.3) (5 points) Find the eigenvectors of H. 3.4) (10 points) If the system is in the state |(0) = |1x , 0y at t = 0, what is the probability of nding the system in this state at later times t?

2 4. (20 points) Let us model the potential felt by single nucleon inside a 234 U nucleus as an innite spherical well of radius r0 1.25 A1/3 1015 m, where A is the total number of nucleons. 4.1) (10 points) If |12m is the ket describing the lowest energy state with angular momentum projection m , and |100 the ket describing the lowest energy state with angular momentum which |12m ket will have a nonzero matrix element 100|Q|12m if Q= (Hint: use orthogonality of the Y m (, ).) 4.2) (5 points) Write an explicit expression for the (unnormalized) wave function r, , | 12m for which Eqn.(6) is nonzero. 4.3) (5 points) What is the energy of the transition |12m |100 ? 16 2 0 r Y2 (, ) , 5 = 2 having = 0, identify

(6)

PHY3113: Quantum Mechanics I


Final examination Time allocated: 180 minutes

April 11th, 2006

This exam contains 4 compulsory questions. There is a choice of one between two bonus questions at the end. Only pen or pencil, eraser, calculator and cheat sheet are allowed. Remember to get a cheat sheet. The maximum for this exam is 55. If you accumulate more than 55 points, your nal mark will be 55. Problem 1. (10 points) Consider a particle of mass m trapped in a one-dimensional harmonic well. Let |n denote a time-independent 1-dimensional harmonic oscillator ket. a) (1 point) Write the Hamiltonian for this system in terms of the operators p and x. Consider the system described by |(0) = |0 + |1 , where and are real, and such that + = 1. b) (2 points) What is |(t) ? c) (4 points) Find the values of t for which x(t) is 0. d) (2 points) For = = 1/ 2, nd E as a function of time. e) (1 point) Show that the maximum possible value of x(t) occurs when = = 1/ 2. Problem 2. (14 points) A particle trapped in an innitely deep onedimensional square well with walls at x = 0 and x = L is described at t = 0 by the ket | , such that, inside the well, (x) x | = 30 x (x L) . L5 (2)
2 2

(1)

a) (1 point) Write H in the xrepresentation inside the well. b) (1 point) What is x | outside the well? Justify briey your answer. c) (2 points) Is (x) an eigenstate of the Hamiltonian? d) (2 points) Find p for a system described by (x). Let x | n be an eigenstate of H for this problem. Given
L

dx x(x L)
0

5/2 1 nx 4 2L 2 n3 sin = 0 L L 3

n odd, n even ,

(3)

e) (3 points) What are the possible outcomes of measuring the energy of this system? f) (2 points) What is the probability of measuring E = E1 =
2 2 2mL2 ?

g) (3 points) If a -barrier is added at x = L/2, i.e. in the middle of the well, so that the potential inside the well is now x < 0, 0 x L, V (x) = (x L/2) (4) , x > L, with > 0, show that the new energies of the system are determined by solving the transcendental equation 2mEL 2E = . (5) tan 2 m

Problem 3. (18 points) Let |nr mz be a familiar hydrogen atom eigenket. A particular hydrogen atom is described at t = 0 by one of the following kets: 1 i) |(0) = (|211 |21, 1 ) , 2 1 ii) |(0) = (|333 i|11, 1 ) , 2 i iii) |(0) = (|200 + |102 ) . 2

a) (2 points) Identify the only ket that can represent the state of a hydrogen atom. Explain carefully your answer. b) (2 points) What is |(t) for your ket? c) (5 points) What is r(t) for a system described by your ket? d) (4 points) Show that the correct |(0) is an eigenstate of Lx . e) (2 points) What is the possible outcome, or what are the possible outcomes, of measuring the observable Lx for a system described by the correct |(0) ? f) (3 points) Find Lx Ly and show the uncertainty relation is satised. Problem 4. (13 points) An idealized atom contains only two levels, denoted by |1 and |2 . |1 and |2 are orthonormal. The Hamiltonian describing this idealized atom is plunged in an electric eld of frequency f is given, in matrix form, by g eif t 2 (6) H , g eif t 2 where = E1 E2 f and g is real. a) (3 points) What are the eigenvalues of H? b) (3 points) Suppose = 0. What are the eigenstates of H? c) (2 points) Show the eigenstates are orthogonal. d) (5 points) If = 0 and the system starts at t = 0 in the state |1 , what is the probability that the system will be found in the state |2 as a function of time?

Problem 5. Bonus You may attempt one (1) of the following two questions for bonus. 1) (5 points) A particle of mass m is constrained to move in 3d between two concentric spherical wall of radii r = a and r = b. In other words, the potential for this problem is 0 < r a, , a < r < b, V (r) = 0 , (7) , b r. Find an expression for the energy of the lowest energy wavefunction with = 0.

2) (5 points) Let Lx , Ly and Lz be the usual angular momentum hermitian operators Show that, if |x is an x , then x |Ly |x = x |Lz |x = 0, irrespective of the value of or any other quantum eigenvector of L number.

PHY3113: Quantum Mechanics I


Final examination

April 18th, 2007

Time allocated: 180 minutes. This exam contains 4 compulsory questions plus one choice of bonus question. Only pen or pencil, eraser and calculator allowed. Everything else is supplied with the exam. Remember to obtain a cheat sheet. If you use any equation from the cheat sheet, please indicate so at the appropriate place on your copy. This maximum score for this exam is 55. If you accumulate more than 55 marks, your score will be 25. You may (or you may not) need the following: dx sin2 (x) = x 1 sin(2x) , 2 4 dx x sin2 (x) = 1 1 x2 cos(2x) x sin(2x) . 4 8 4

1. (10 points) A particle of mass m evolves in the potential if x < 0 0 if 0 x < L/2 , V (x) = V0 if L/2 x < L , if x > L , where V0 = 4
2

(1)

2 /2mL2 . This potential is illustrated on the left of Fig.1.

L/2

L/2

z tanh 1 z

FIG. 1: Left: The potential of Eqn.(1). Right: The intersection of the curves tanh(x) = (ex ex )/(ex + ex ).

a) (2 points) Is the wavefunction (x) = 0 0 if x < 0 (2) if x > L,

2/L sin(3x/L) if 0 x L ,

an eigenstate of the Hamiltonian for this system? b) (2 points) What is the average energy E for a particle described by (x) of Eqn.(2)? c) (6 points) How many eigenstates of H have energy less than V0 ? (Hint: e(xL) e(xL) ) If there is one or more bound state, what is (or what are) the energy of these states? You may or may not need the graph on the right of Fig.1 to answer this. Justify your answer carefully. 1

2 -

51 .-

Vo

1 z tan( z) and z tanh( 1 z), where

8. 0

6. 0

4. 0

2. 0

1 -

1 5. 0 50 .-

5. 1

1 z tan z

2. (15 points) Suppose a particle of mass m trapped in a harmonic well is found in the state |n , where H|n = En |n . You may assume 1 2 p + H= 2m
1 2

m 2 x2 = a a +

1 2

1 . l

(3)

a) (5 points) Show that [ x, H ] = i p/m and [ p, H ] = i m 2 x. b) (5 points) Show that n|[H, x p ]|n = 0 . (4)

1 x c) (5 points) Show that n|2 |n /2m = 2 m 2 n|2 |n . One way (but not necessarily the only way) to do this is to p use the result of part a) to evaluate the commutator in Eqn.(4).

3. (15 points) Consider the linear combination of hydrogenatom kets


1 | = 2 |211 i 2 2 |210 1 + 2 |21, 1 .

(5)

a) (5 points) Show this is an eigenstate of Ly . What is the outcome of measuring Ly for a system described by | ? b) (2 points) What are the possible outcomes of measuring Lz for a state described by | ? c) (3 points) What is the most probable value of Lz ? d) (5 points) What the most probable value of r for a system described by | ? 4. (15 points) An idealized twolevel system is described by the Hamiltonian matrix 3 1 = o . H 3 1 a) (2 points) What are the possible value of the energy of this system? b) (3 points) What are the eigenvectors of the system? c) (10 points) If the system starts initially in a state |(0) = in the state 1 0 as a function of time? 0 1 , what is the probability that it will be found

(6)

(Hint: the eigenvectors have a relatively simple form.)

Please turn over for bonus questions

Bonus questions You may attempt one of the following two questions for 5 additional marks. 5. (10 points) Let A be any hermitian operator. Let | be any normalized state, and let | be another normalized state such that A| | with real and nonnegative. Show = A , = A = A2 + A
2

= | + | , = 0,

(7) (8)

(9)

6. (10 points) Show that Heisenbergs uncertainty relation holds for x and p when a quantum state is described by a harmonic oscillator ket |n .

PHY3113: Quantum Mechanics I


MidTerm examination

Feb. 27th, 2009

Time allocated: 55 minutes. This exam contains 3 questions plus one bonus. This exam is out of 20, with a maximum mark of 20. Only pen or pencil, eraser and calculator allowed. Everything else is supplied with the exam. Remember to obtain a cheat sheet. If you use any equation from the cheat sheet, please indicate so at the appropriate place on your copy. 1. (9 points) A particle of mass m is trapped in a harmonic potential V = describing this system is (x, 0) = a) (1 point) What is (x, t)? b) (1 point) Is (x, 0) correctly normalized? If no, normalize it. You may nd it convenient to assume orthogonality of the harmonic oscillator wavefunction: i | j = ij . c) (3 points) What is the average value of energy for a system described by (x, 0)? d) (4 points) What is x for a system described by (x, 0)? You may nd it useful to know that 2n+1 x2 x2 2 x2 dx x e = 0, dx e = , dx x e = 3/2 2 1+i 2 1 0 (x) + 1 (x) . 2
1 2 2 2 m x .

At t = 0, the wavefunction (1)

(2)

2. (9 points) Consider the problem of a particle trapped of mass m in a nite well, extending from a to +a, having depth V0 , where V0 > 0. The particle is bound so E = < 0, i.e. > 0. a) (5 points) Given that the lowest energy solution is even, show that, if a= 4 mV0 the lowest energy state has energy E = V0 /2. (Hint: Assume (3) = V0 /2, recall tan(/4) = 1 and solve for a.)

b) (4 points) Using the value of a given in Eq.(3) and one of the graphs provided on the next page, determine if there is an odd bound state solution. Indicate which one of the graphs is appropriate, and explain your answer carefully. 3. (4 points) A particle of mass m is trapped in a potential of the form V (x) = V0 e+x
2

/2

(4)

a) (2 points) Determine approximately the energies of the lowest two states of the particle. b) (2 points) Do you expect your estimates to be greater or smaller than the rst two true energies of the system? (Hint: expand near the minimum, or alternatively ez 1 + z for small z.) 4. (5 points) Bonus. A particle of mass m is trapped in a potential given by V (x) = (x). The particle is bound, so that E = < 0, so that > 0. Given that the wavefunction describing this system can be written in the form (x) = Aex for x < 0, , Aex for x > 0. (5)

a) (1 point) Show that the choice A = i normalizes (x). b) (4 points) Show that, if
2

ln(2) (6) 2m 1 then the probability of nding the particle in the range x0 to +x0 is 2 . (Hint: to complete the calculation, you will need to relate to the parameter of the potential by nd the energy of the bound state.) x0 =

3.5 3.0 2.5 2.0

3.0 2.5 2.0 1.5

1.5 1.0 1.0 0.5 0.5

0.2

(a)tan(
4

2 1 4

0.4

0.6

z) and

p z/(1 z)

0.8

1.0

0.2

(b)tan(
2 1

1 4 2

0.4

0.6

z) and

p z/(1 z)

0.8

1.0

2 0.2 0.2 2 3 4 4 5 6 0.4 0.6 0.8 1.0 1 2 0.4 0.6 0.8 1.0

p (c)tan( 2 1 z) and (1 z)/z

(d)tan(

2 4

p 1 z) and (1 z)/z

FIG. 1: Intersections of some functions.

PHY3113: Quantum Mechanics I


Final examination

April 8th, 2009

Time allocated: 180 minutes. This exam contains 6 questions plus one bonus. This exam is out of 55, with a maximum mark of 55. Only pen or pencil, eraser and calculator allowed. Everything else is supplied with the exam. Remember to obtain a cheat sheet. If you use any equation from the cheat sheet, please indicate so at the appropriate place on your copy. You may (or you may not) need the following: d d2 sechx = sech3 x + sech x 1 sech2 x , sechx = sechx tanh x , dx dx2 d3 sechx = 5 sech3 x tanh x sech x tanh x 1 sech2 x . dx3

(1)

1. (6 points) A particle of mass m =

1 2

evolves in the potential V (x) = 2 sech2 x ( = 1), where sech x = 1/ cosh x. = 1 and remember m = 1 ). 2

a) (2 points) Write the timeindependent Schrdinger equation for this problem (take o

b) (4 points) Show that the wavefunction (x) = A sech x with A a constant satises the timeindependent Schrdinger equation and nd the energy corresponding to this solution. o c) (2 points) Given the graph of Fig. 1, explain if this wavefunction is or is not the solution with lowest energy.

FIG. 1: The graph for the function sech x.

2. Let |n denote a solution to the Schrdinger equation for the 1dimensional innite potential. A particle of mass o m is described by | = N |1 + i 2|3 a) Find a value of N that will normalize this ket and write x | . b) Is | an eigenstate of the Hamiltonian? If yes, what is E? If no, what is E? c) What is the most probable value of E, and what is the probability of obtaining this value? d) What is x ? (Hint:
1 0

(2)

dx x sin2 (nx) =

1 4

for integer n.)

e) What is |(t) if |(0) = | ? 3. Show that, for a system described by the harmonic oscillator ket |n ,
1 px = (n + 2 )

(3)

4. The Pauli matrices have the form x = Consider the matrix S = x iy where is a real number. a) Is S hermitian? b) What are the eigenvalues of S ? c) Suppose = 2. Show that |1 =
1 2 1 2

0 1 1 0

y =

1 2

0 i i 0

z =

1 2

1 0 0 1

(4)

(5)

i 3

is an eigenvector of S2 .

d) What is the other eigenvector? Is it orthogonal to |1 ? e) Find (x ) (y ) for |1 and show that this product is in agreement with Heisenbergs uncertainty relation. 5. Let |nr mz be a familiar hydrogen atom eigenket. A particular hydrogen atom is described by
1 i i 1 | = 2 |311 2 |31, 1 + 2 |211 2 |21, 1

(6)

a) Show that | is an eigenstate of Lx . b) What are Lz , Ly and Lx for the valid ket? c) What are the possible outcomes of measuring Lz , and what are the probabilities of these outcomes? d) What is the probability of measuring the value Lx = + for a system described by | ? e) Given x= nd || using | . (Hints: x 2 r Y11 (, ) Y11 (, ) 3
3 sin 4

(7)
3 4

d cos3 () =

sin 3 12 ,

d sin4 () =

sin 2 4

sin 4 32 .)

6. For a hydrogen atom described by 200 (r, , ): a) Show that a minimum in the radial probability density occurs at r = 2a0 . b) What is the probability of nding an electron within a distance 2a0 of the nucleus? (Hints: dxx2 ex = x 2 3 x x 3 2 4 x x 4 3 2 e (x + 2x + 2), dxx e = e (x + 3x + 6x + 6), dxx e = e (x + 4x + 12x + 24x + 24).) 7. Bonus You may attempt one (1) of the following two questions for bonus. 1) (5 points) A particle of mass m is constrained to move in 3d between two concentric spherical walls of radii r = a and r = b. In other words, the potential for this problem is 0 < r a, , a < r < b, V (r) = 0 , (8) , b r. Find an expression for the energy of the lowest energy wavefunction with = 0.

2) (5 points) Let A be any hermitian operator. Let | be any normalized state, and let | be another normalized state such that A| | with real and nonnegative. Show = A , = A = A2 + A
2

= | + | , = 0,

(9) (10)

(11)