Sag, (45. b PE Stephen Gasiorowicz University of Minnesota a8 EN. wisTiTuu, BE Pz 38 Betty “ | pi Ste John Wiley and Sons, Inc. new york - london + sydney + torontopreface This book is intended to setve as an introduction co quantum physics. In writing it, I have kept several guidelines in mind 1. First, it is helpful for the development of intuition in any new field of study to start with a base of detailed knowledge about simple systems. I have therefore worked out a number of problems in great detail, so thar the insight thus obrained can be used for more complex systems. 2. Every aspect of quantum mechanics has been helpful in understanding some physical phenomenon. I have therefore laid great stress on applications at every stage of the development of the subject. Although no atea of quantum physics is totally developed, my intention is to bridge the gap. between a modern physics course and the more formal development of quantum mechanics. Thus, many applications are discussed, and I have stressed order-of-magnitude estimates and the importance of numbers. 3. In keeping with the level of the book, the mathematical structure has been kept as simple as possible. New concepts, such as operators, and new mathematical cools necessarily make their appearance. I have dealt with the former mote by analogy than by precise definition, and I have minimized the use of new tools insofar as possible. In approaching quantum theory, I chose to start with wave mechanics and the Schrédinger equation. Although the state-vector approach gets at the essential structure of quantum mechanics more rapidly, experience has shown that the use of more familiar tools, such as differential equations, makes the theory more accessible and the correspondence with classical physics more transparent. The book probably contains a little more material than can comfortably be covered in one year. The basic material can be covered in one academic quarter. vilviii Preface Ik consists of Chapters 1 to G, 8, and 9, in which the motivation for a quantum theory, the Schrédinger equation, and the genetal framework of wave mechanics ate coveted, A number of simple problems ate solved in Chapter 5, and their relevance to physical phenomena is discussed. The generalization to many particles and to three dimensions is developed. The second-quarter material deals, directly with acomic physics problems and uses somewhat more sophisticered tools. Here we discuss operator methods (Chapter 7), angular momentum (Chapter 11), the hydrogen atom (Chapter 12), operators, macrices, and spin (Chapter 14), the addition of angular momenta (Chapter 15), time-independent perturbation theory (Chapter 16), and the real hydrogen atom (Chapter 17). ‘This material prepares the student to cope with a large variety of problems that are discussed duting the third and lust quarter. These problems include the inter- action of chaeged particles with a magnetic field (Chaptet 13), the helium atom (Chapter 18), problems in the radiation of atoms and related topics (Chapters 22 and 23), collision theory (Chaprer 24), and the absorption of radiation in macrer (Chapter 25). This material is supplemented by a’ more qualitative discussion of the struccure of atoms and molecules (Chapters 19 to 21). The last chapter on elementary particles and theit symmetries setves the dual purpose of describing some of the recent advances on that frontier of physics and of showing how the basic ideas of quantum theory have found applicability in the domain of very short distances. Several topics arise naturally as digressions in the development of the subject matter. Instead of lengthening some long chapters, I have placed this material in a seperate “Special Topics” section. There, telativistic kinematics, the equivalence principle, the WKB approximation, a detailed treatment of lifetimes, line widths and scattering resonances, and the Yukawa theory of nuclear forces are discussed. For the same season, a brief introduction to the Fourier integral, the Dirac dela function, and some formal material dealing with operators have been placed in mathematical appendices at the end of the beok. Lam indebted to my colleagues at the University of Minnesota, especially Benjamin Bayman and Donald Geffen, for many discussions on the subject of quantum mechanics. I am grateful to Eugen Merzbacher, who read the manu- script and made many helpful suggestions for improvements. I also thank my students in the introductory quantum mechanics course that I taught for several years. Their evident interest in the subject led me to the writing of the supple- mencal notes that later became this book. Stephen Gasiorowiexcontents Chapter 1 The Limits of Classical Physics 1 Black Body Radiation: the laws of Wien and Rayleigh-Jeans; the Planck formula. 'The Phoroelecttic Effect. The Compvon Eifect. Electron Diffraction, The Bohr Atom: the postulates; experimental consequences; the Correspondence Principle. The Wave-Particle Problem. Chapter 2 Wave Packets and the Uncertainty Relations 27 The gaussian wave packer; che propagation of packets; group velocity; the De Broglie relation. The Uncertainty Relations: measurement of position of an clectron; the two-slit experiment; the “reality” of orbits ia the Bohr atom; the energy-time uncertainty relation; the uses of the relations for numerical estimates. Chapter 3. The Schrédinger Wave Equation 45 so ‘The fee particle equation. The probability interpretation. Flux conservation, Expectation values. The momentum opetator. The reality of expectation values. The equation for a particle in 2 , porential.x Contents Chapter 4 Eigenfunctions and Eigenvalues ‘The energy eigenvalue equation. The particle in a box: eigenfunctions and eigenvalues; orthogonality of eigenfunctions; the expansion postulace and the interpretation of the expansion coefficients, Parity. Momentum eigenfunctions; unnormalizable states; degeneracy and simultaneous cigenfunctions. Chapter 5 One-Dimensional Potentials The potential step; reflection and transmission coefficients, The potential well and bound states. The potential bartier: tunnelling; cold emission; tunnelling chrough thin films; alpha decay. One- dimensional models of molecules and the delta-function potential. The Kronig-Penney model. The harnonic oscillator. Chaprer 6 ~The General Structure of Wave Mechanics Eigenfunctions and the expansion theorem; analogy with vector spaces. Linear operators; hermitian operators; completeness; degenetacy; complete sets of commuting observables. The uncertainty relations. The classical limit of quantum theory. Chapter 7 Operator Methods in Quantum Mechanics The harmonic oscillator problem: raising and lowering operators; eigenstates and eigenvalues. The interpretation of the wave fanction as probability amplitude. The time-development of a system in terms of operators; the Schrédinger and the Heisenbetg pictures. Chapter 8 N-Particle Systems The Schrédinger equation for N-particle systems. Momentum conservation; separation of center of mass motion; reduced mass, Identical particles; symmetry under their interchange, The Panli Principle. Fermions and bosons in a box; the Fermi energy. Chapter 9 ‘The Schrédinger Equation in Three Dimensions Separation of center-of-mass motion; invariance under rotations; the separation of angular momentum. The redial equation. Fermi effergy for three-dimensional box. Chaprer 10 Angular Momentum ‘The expression for L?; algebraic method for solving the L, and L* ' eigenvalue problem; raising and lowering operarors; Legendre fanctions. $7 75 111 127 141Contents Chapter 11 The Radial Equation Behavior at the origin; behavior for large r. The free particle; spherical Bessel functions; incoming and outgoing spherical waves; phase shifts. The squate well: bound states; deep wells; shell stracture; continuum solutions. Chapter 12. The Hydrogen Atom Simplification of the radial equation. Quantum numbers; degeneracy. Wave functions and relations to “orbits.” Chapter 13 Interaction of Electeons with Electromagnetic Field Maxwell equations. Coupling of electrons to vecror potential. Equation for electron in a uniform magnetic feld, The normal Zeeman effect. Electron motion in a uniform magnetic field; illustration of correspondence principle. Flux quantization; the Bohm-Aharanoy Effect. Chapter 14 Operators, Matrices, and Spin Matrix representation of harmonic oscillator operators. Matrix representation of angular momentum 1 operators. Spin matrices; spinors, The precession of spin in a magnetic field; paramagnetic resonance. Chapter 15 The Addition of Angular Momenta The addition of two spins }4; singlet and wiplet cigeafunctions. Spin-orbital angular momentum addition. The Exclusion Principle and angular momencum staces. Chapter 16 Time Independent Perturbation Theory First-order energy shift. Second-order perturbation theory. Degenerate perturbation theory. The Stark Effect: absence of linear shift for ground state; electric dipole moments; second-order shift, Linear Stark effect for 2 = 2 states. Chapter 17. The Real Hydrogen Atom Relativistic mass corrections. Spin-orbit coupling. Anomalous Zeeman Effect; Hyperfine interaction. & Chapter 18 The Helium Atom 4 First approximation. First-order shift due to ¢-¢ cepulsion, The first excited states. Exchange energy. The Ritz vatiational principle. Autoionization. xi 179 195 209 227 245 255 271 283xii Contents Chapter 19 The Structure of Atoms “The variational principle and the Hartree equations. The periodic table. Qualitative discussion of consequences of shel] structure in ators, Chapter 20 Molecules Approximate Schrodinger equation; electronic, vibrational, and rotational motion, The H+ molecule; vatiational trial wave function; spins of nuclei and spectra; specific heats of molecules Chapter 21 Molecular Structure ‘The H; molecule. Molecular orbitals. Bonds. Qualitative description of some simple molecules; hybrid orbitals. Chapter 22 The Radiation of Atoms Time dependent perturbation theory. The electromagnetic interactions; semiclassical description; phase space; the Golden Rule, Matrix element calculation; selection rules; the 2P ~— 18 transition rate. The effects of spin. Chapter 23 Selected Topics in Radiative Transitions Lifetime and line width; collision broadening; Doppler shift. ‘Méssbauer Effect, Induced absorption and emission, The lasct. ‘Chapter 24 Collision Theory Collision cross section; optical theorem; inelastic cross sections. Black disc scattering, Scattering ar low energies; resonant scattering for square well; effective range formula. Spin dependence in neucroa-proton scatrering. The Born approximation. Scattering of identical particles. Coherent scattering and the Bragg conditions. Chapter 25 The Absorption of Radiation in Matter The photoelectric effect; angular dependence; energy dependence. Compion scattering. Antiparticles, and pair production Chapter 26° Elementary Particles and Their Symmetries Blectrons and positrons; positronium and its decay modes; charge conjugation. Baryons, antibaryons, and mesons. Isotopic spin conservation, The ptoblem of A° decay and production; associated production; the scrangeness quantum number; selection rules, Unitary symmeuy; the discovery of the a-, the quark model. Parity nanconservation in K decay; general tests. The K° — K° system. 299 341 365 379 42sContents Special Topics ‘I. Relativistic Kinematics Il, The Equivalence Principle If. The Wentzel-Kramers-Brillouin Approximation IV. Lifetimes, Line Widths, and Resonances Vv. The Yukawa Theory Appendices A, The Fourier Integral and Dela Functions B. Operators References Physical Constants Index xiii 459 461 469 473 481 487 489 495 501 507 509ie chapter 1 The Limits of Classical Physics The end of the nineteenth century and the beginning of the twentieth witnessed a crisis in physics. A setics of experimental results required concepts totally incompatible with classical physics. The development of these concepts, in a fascinating interplay of radical conjectures and brilliant experiments, led finally to the qaamtum sheory.' Out objective in this chapter is to describe the background of this crisis and, armed with hindsight, to expose the new concepts in a manner chat, while not historically correct, will make the transition to quantum theory less mysterious for the reader. The new concepts, the particle properties of radiation, the wave properties of matter, and the quantization of physical quantities will emerge in the phenomena discussed below. A. Black Body Radiation When a body is heated, it is scen to radiate, In equilibrium the light emitted ranges over the whole spectrum of frequencies v, with a spectral distri- bution thar depends boch on the frequency or, equivalently, on the wavelength of the light ); and on the temperature, One may define a quantity E(A, T), the emissive power, as the energy emitted ac wavelength ) per unit area, per unit time. Theoretical research in the field of thermal radiation began in 1859 with the work of Kirchhoff, who showed that for a given X, the ratio of the emissive power E to the absorptivity 4, defined as the fraction of incident radiation of wavelength d that is absorbed by the body, is the same for all bodies, Kirchhoff considered two emitting and absorbing parallel plates and showed from the equilibrium condition that the energy emitted was equal to the energy absorbed (for cach 4), that the ratios E/A must be the same for the two plates. Soon An interesting account of the development of quantum theory may be found in M. Jammer, The Conceptual Development of Quantum Mechanics, McGraw-Hill, New York, 1966,2 Quantum Physics thereafter, he observed that for a black body, defined as a surface that totally absorbs all radiation that falls on it, so that A = 1, the function E(A, T) is a universal function. In order to study this function it is necessary co obtain the best possible source of black body radiation. A practical sofution to this problem is to con- sider the radiation emerging from a small hole in an enclosure heated to a tem- perature T. Given the imperfections in the surface of the inside of the cavity, ic is clear that any radiation falling on the hole will have no chance of emerging again. Thus the surface presented by the hole is very nearly “totally absorbing,” and consequently the radiation coming from it is indeed “black body radiation.” Provided the hole is small enough, this radiation will be the same as that which falls on the walls of the cavity. It is therefore necessary to understand the distti- bution of radiation inside a cavity whose walls are at a temperature T. Kirchhoff showed chat the second law of chermodynamics requires that the radiation in the cavity be isotropic, that is, that the flux be independent of direction; that it be homogeneous, that is, the same at all points; and that it be the same in al] cavities at the same temperatute—all of this for each wavelength* ‘The emissive power may, by simple geomectic arguments, be shown to be connected with the energy density «(s, T) inside the cavity. The relation is wo, = SRD a) ‘The energy density is the quantity of theoretical interest, and further under- standing of it came in 1894 from the work of Wien, who, again using very general arguments, showed that the energy density had to be of the form uA, T) =X? fat) (4-2) with f still an unknown function of a single vatiable. If, as is convenient, one deals instead with the energy density as a function of frequency, x(», T), then it follows from the fact that alo, T) = ah, n|o = 5p HT) (1-3) 2 These matters are discussed in many textbooks on modern physics and statisticel physics. References can he found at the end of this chapter. 4 Wien considered a perfectly selecting spherical cavity contracting adiabatically. The redistribution of the energy as a function of A has to be caused by the Doppler shift on reflection. See Chap:er V in F. K, Richunyer, B. H. Kennard, and J. N. Cooper Intro. duction to Modern Physics, McGraw-Hill, New York, 1969.The Limits of Classical Physics 3 ee T= 1409°K nS T= 1646"K of T= 1259°K Ya Fig. 1-1, Experimental verification of Eq. 1-2 in the form u(,7)/TS = a universal function of x7. that the Wien law reads aly, T) = v¥g (2) (1-4) The implications of this law, which was confirmed experimentally (Fig. 1.1), are twofold: 1. Given the spectral distribution of black body radiation at one tem- peracure, the distribution at any other temperature can be found with the help of the expressions given above. 2. If the function f(x)—or, equivalently, the function g(x)—has a maxi- mum for some value of x > 0, then the waveleagth Ayes at which the energy density, and hence the emissive power, has its maximum value, has the form A Drax = Tr Ga-s) where 4 is a universal constant. Wien used a model (of no interest, except to the historian) to predict a foun for g(v/T). The form was s0/T) = cree ao. and, remarkably enough, this form, containing two adjustable parameters, fit the high frequency (low wavelength) data very well. ‘The formula is not, how:4 Quantum Physics a) Planck \ \ se Paviich— sears 477 1 10,000 20,000 30,003 40,000 50,000 20,000 40,000 60,000 Waveloagth in A ~——> Wavelength in 8 ——> @ ) Fig. 1-2. (4) Distribution of power radiated by a black body at various tempera- tures, (8) Comparison of daca ar 1600°K with Planck formula and Rayleigh-Jeans formula, exer, in accord with some very general notions of classical physics. Rayleigh, in 1900, derived the result uy, T) = we aT (1-7) where & is Boltzmann's constant, & = 1.38 X 107" erg/deg and cis the velocity of light, ¢ = 3.00 X 10" cm/sec. The ingredients that went into the derivation were (1) the classical law of equipartition of energy, according to which the average energy per degree of freedom for a dynamical system in equilibrium is, in this context,' AT, and (2) the calculation of the number of modes (i.c., degrees of freedom) for electromagnetic radiation with frequency in che interval (», » + dy), confined in a cavity.® “The equipantition law predicts tha: che energy per degsee of freedom is &T/2, For an oscillator—and the modes of the electromegnetic field ate simple harmonic oscillacors— a contriburion of £1/2 from the kinetic energy is marched by a like contribution from the potential energy, giving £7. 5 We will need this result again, and derive it in Chapter 23. The number of modes is dest/ct, further muliplied by a factor of 2 because transverse electromagnetic waves cor- respond to two-dimensional harmonic oscillators .The Limits of Classical Physics 5 ‘The Rayleigh-Jeans law (1-7) (Jeans made a minor contribution to its derivation) does not agree with experiment at high frequencies, where the Wien formula works, though it does fir the experimental curve at low frequencies (Fig. 1.2). The Rayleigh-Jeans law cannot, on genetal grounds, be correct, since the toral energy density (integrated over all frequencies) is predicted to be infinite! In 1900, Max Planck found a formula by an ingenious interpolation between the high-frequency Wien formula and the low-frequency Rayleigh- Jeans law. The formula is ay, T) = Set ae 7 (1-8) where 4, Planck's constant, is an adjustable parameter whose numerical value was found to be 4 = 6.63 X 10-* erg sec. This law approaches the Rayleigh Jeans form when v > 0, and reduces to at) = hewn emi h = = venir (9) when the frequency is large, or, more accurately, when hy >> &T. If we rewsite the formula as a product of che number of modes [we obtain this from (1-7) by dividing the energy density by #T] and another factor that can be interpreted as the average enetpy per degree of freedom sx? hy eT) = FD eat ant buf AT =a Ter 4 (1-10) ‘we see that the classical equipartition law is altered whenever the frequencies ate not small compared with &T/k. This altetation in che equiparcition law shows that the modes have an avetage energy that depends on their frequency, and that the high frequency modes have a very small average energy. This effective cut-off removes che difficulty of the Rayleigh-Jeans density formula: the total energy in a cavity of unit volume is no longer infinite. We have Bek f° vt ur) = ef. by eat _ Sah (ETNA (ho /kT)* db /KE) “at Nas jg eet = StH f . =e T ° we (Qin)6 — Quantum Physics The integral can be evaluated,* and the result is the Scefan-Bolczmann expression for the total radiation energy per unit volume U(T) = aT! (1-12) with a = 7.56 X 107 erg/cm? deg’, derived much earlier, except for the numerical constant in front, on the basis of thermodynamical reasoning. A departure from the pure equipattition law was not entitely unexpected: one consequence of it was the Dulong-Petit law of specific heats, according to which the product of the atomic (or molecular) weight and che specific heat is a constant for all solids; yet departures from the Dulong-Petit predictions were observed as eatly as 1872.7 These departures indicated that the specific heat decreased at lowet temperatures.* The unqualified success of his formula drove Planck to search for’ its origin, and within two months he found that he could derive it by assuming that the energy associated with each mode of the electcomegnetic field did not vaty continuously (with average value £T) but was an integral multiple of some minimum quantum of energy & Under these circumstances a calculation of the average energy associated with cach mode, using the Boltzmann probability distribution in a system of equilibrium at temperature T, (1-13) led to be u 2 HPe) 7 SS ag cotir =O, > oer as «ore ~ 2 i) det (ee 19 -f de xtere em . > = i. * os “Sete Ore — 8 2 + Aceording co the equipertition law an assembly of N oscillators (and a lattice of atoms with elastic forces between them may be so viewed) will have enevgy 3NET, the factor 3 coming from the fact that the oscillarots in ¢ solid are three-dimensional, rather than two-dimensional as for the radiition eld in an enclosure. The specific heat for a mole is obtained by cifferendating with respece co T and setting N — No, Avogadro's number, so that C, = 3Nok = 3K where K = 8.28 x 10° erg /deg. ® Specific heats will be discussed very briefly in Chaprer 20.‘The Limits of Classical Physics 7 t de -e 2 Ree ard eet 1 | eaeser & = om Tj (1-14) This agrees with (I-10) provided we make che identification b&=h (1-15) and do not change the number of modes. Planck argued that for some unknown teason the atoms in the walls of the cavity emitted radiation in “quanta” with energy rév (x = 1,2,3,. . .), but consistency demanded, as established by Einstein a few years later, that electro. magnetic radiation bebaved as if it consisted of a collecivn of energy quanta with energy bv2 The energy cattied per quantum is extremely small. For light in the optical range, with, say, 4 = 6000 A, 3.3 X 10 erg so that the number of light quanta of this wavelength, emitted by a 100-wart soutce, say, is 100 X 107 10 , = 33x 19 = 3X 10° quanta/sec ‘With so many quanta present, it is perhaps not surprising that we do not ex- perience the particle nature of light directly; we shall see that on a macroscopic scale no deviations from classical optics are expected, Nevertheless, Planck's interpretation of his formula radically changes our picture of radiation. ‘ 'B, The Photoelectric Effect As successful as the Planck formula was, the conclusion from it of the quantum, nature of radiation is hardly compelling, An important contribution to its acceptance came from the work of Albert Einstein, who in 1905 used the °Fot e given frequency » there snay be any integral number of quanta present, and hence the energy can take on the values mb, with 2 = 0,1,2,3,....8 Quantum Physics concept of the quantum nature of light to explain some peculiat properties of metals, when these ate irradiated with visible and ultraviolec lighc. ~ In 1887, the photoelectric effect was discovered by Hertz, who, while engaged in his famous experiments on electromagnetic waves, found that the length of the spark induced in the secondary circuit was reduced when the terminals of the spark gap were shielded from the ultraviolet light coming from the spark in the primary circuit. His observations attracted much interest and the following facts were established by fusther experiments: 1. When polished metal plates are irradiated, they may emit electrons;!* they do not emit positive ions. 2, Whether the plates emit electrons depends on the wavelengch of the light. In general there will be a threshold that varies from metal co metal: only light with a frequency greater than a given threshold frequency will produce a photoelectric current. 3. The magnitude of the current, when it exists, is proportional to the intensity of the light source. 4, The energy of the photoelectrons is independent of the intensity of the light source but varies linearly with the frequency of the incident light. Although the existence of the photoelectric effect can be understood. within the framework of classical electromagnetic theory, since it was known tha there were electrons in metals, and one could imagine them to be accelerated by absorption of radiation, the frequency-dependence of the effect is not compre- hensible within that framework. The energy cartied by an electromagnetic wave is proportional to the-intensity of the source, and frequency has nothing to do with ic, Furthermore, a classical explanation of the effect, which would have co involve the concentration of the energy deposited on single photoelectrons, would catty with it an implied time delay between the arrival of the radiation and the departure of the electron, the delay being longer when the intensity is decreased. In fact, no such time delays were ever observed, at least none longer than 10-® sec, even with incident tadiation of very low intensity. Einstein considered the radiation to consist of a collection of quanta of energy 4v, where » is the frequency of the light. ‘The absorption of a single quantum by an electron—a process chat may take less time than the upper limit quoted above—increases the electron energy by an amount by. Some of the energy must be expended to separate the clectton from the metal. This amount, W (called the work function), might be expected to vary from metal to metal, but should not depend on the electton energy. The rest is available for the electron kinetic energy, so that on the basis of this picture one expects that 1.9 This was established by an ¢/m measurement.‘The Limits of Classical Physics s y= 87 X10" seem? 4080 ~60.~«70 += B0 «80 100~«110~—~*t20 ¥ x0 sac Fig. 1-3. Photoelectric effect data showing a plot of retarding porential necessary to stop electron flow from a meral (lithium), or equivalently, electron kinetic energy, as a function of frequency of the incident light. ‘The slope of the line is h/e. the following relation between electron velocity » and light frequency » hav? = hy — (1-26) should hold. The threshold effect and the linear telation between electron kinetic energy and the frequency ate contained in this formula, The propor- tionality of the cusrent and the source intensity can also be understood in terms