Definition of some units Angstrom 1A =10-'°m (order of magnitude of the atomic dimensions) Fermi 1F =10-'5m (order of magnitude of the nuclear dimensions) Barn 1b = 10-7 m? = (10~* AP = (10 FP Electron Volt L eV = 1.602 189(5) x 10-19 joule Useful orders of magnitude Electron rest energy : m,c? = 0.5 MeV [0.511 003(1) x 108 eV] Proton rest energy : M,c? = 1 000 MeV [938.280(3) x 10° eV] Neutron rest energy : M,c? ~ 1000 MeV [939.573(3) x 108 eV] One electron volt corresponds to: afrequency ~ 2.4 x 10'* Hz through the relation E = hv [2.417 970(7) x 10" Hz) awavelength 2 ~12000A through the relation 4 = c/v [12 398.52(4) A] a wave number } = 8000cm-! [8 065.48 (2) em-*] a temperature T = 12000 K through the relation E = kaT [11 604.5(4) K] Ina I gauss magnetic field (10 * Tesla): the electron cyclotron frequency v, = «,/2n = — gB/2nm, is y= 2.8 MHz [2.799 228(8) x 10° Hz] the orbital Larmor frequency», = «1/2n = — pBjh = v,/2 isv, = 14 MHz [1.399 612(4) x 10° Hz] (this corresponds by definition to a g = 1 Landé factor) etSome genoral physical constants Planck's constant Speed of light (in vacuum) Electron charge Electron mass Proton mass Neutron mass Electron Compton wavelength Fine structure constant (dimensionless) Bohr radius Hydrogen atom ionization energy (without proton recoil effec) Rydberg’s constant ” Classical” electron radius Bohr magneton Electron spin g factor Nuclear magneton Boltzmann's constant Avogadro's number he { he 6.626 18(4) x 10-** joule second Jy = 1.054 589(6) x 107% joule second 2.997 924 58(1) x 10° m/s q = — 1.602 189(5) x 107! coulomb im, = 9.109 53(5) x 107?! kg M, = 1.672 65(1) x 107?” kg M, = 1.674 95(1) x 107?7 kg ae = 1836.1515(7) A, = hime = 2.426 309(4) x 10-7 A 4, = him = 3861 591(7) x 107? A ieee * Graghe he 137.036 011) ay = 4& = 0.529.177 1(5) A — By, = a2mgc2/2 = 13,605 80(5) eV co = — E,, /he = 1.097 373 18(8) x 105 om=* ry = 2 = 2817 938(7) fermi «arene Hy = gh/2m, = — 9.274 08(4) x 10-* joule/tesla 9. = 2 x 1.001159 657(4) My = — gh/2M, = 5.050822) x 10?” joulejtesia ky = 1.380 66(4) x 10°? joule/K. N4 = 6:022.05(3) x 10?Useful Identities U : scalar field; A, B, . : vector fields. Vx (VU) =0 v. (VU) = V.(Vx A)=0 Vx (Wx A) =V(V. A) — Letrxy 7 voto ite xL rar eer te rae Pe A x (Bx C)= (A. C)B — (A. BIC A x (Bx C)+Bx (Cx A)+C x (A x B)=0 {A x B).(C x D) = (A.C)(B.D) — (A. D)(B.C) (A x B)x (C x D) = [(A x B). DJC — [(A x B).C]D = [(C x D). AJB — [(C x D). BJA v (UV) uw+vw A (UV) = UAV + 2(VU). (VF) + VAU v.(UA) UVA+A.VU Vx (UA) =U VKA+(WU)x A V.(A x B) =B.(VxA)—A.(VxB) V (A.B) Ax (Vx B)+Bx (Vx A)+B.V A+A.V B Vx (Ax B)=A(V.B)—B(V.A)+B.V A-A.V B NB: BVA vector field whose components are : (BV A= BPA = 5B A, as, W=xn2)sfao"¥2 — 2Uyaal = “Ww xa) a102%¥2 ~ dol*¥de] = Iv xa) QFE — 32h) + 2 (a ws 2) L2K4vN2 9 ws - O2"¥2] = AW xa) 4272 ~ 22°¥2 = “WW xa) Ss (o ws AiLoei*¥e ~ a2t*y ousig) = tv xa) seth = 4hoe vel = “WW xa) e 22 O88 yay) BOO oy 2H O29 copay 24 ge vere gee oman suid te tects 33 220 etl ws BOE a yet #2 @ et . of ae ous) tad ae a0) F778 Be x — 3 (ous »:[92I09) = “low seine = (aa) azgine) + 3 ine) = na) seein) = “nad ‘Ine + 6 vine = tna) deine = “nad *a(xging) = 08 2 0500 + ous 'y — (S0aFy = ¥ 9 gus 'y ~ 9 509° = *y| 6 s00'y + Ous*y - = *y (eeaty = 7 g 900" + ous ’y = ‘Y! sup 'y + o100'y =v Geary = y z pec reerans VEN ty ey ety eae 3 (@ea= 9 oda a (eva =a a ae 7 Now fa SG ‘ — vt a Nn oe reoueyds eoupunAd uersos1e9 swiayshs a}eUulps00gIntroduction Structure and level of this text It is hardly necessary to emphasize the importance of quantum mechanics in modern physics and chemistry. Current university programs naturally reflect this importance. In French universities, for example, an essentially qualitative introduction to fundamental quantum mechanical ideas is given in the second year. In the final year of the undergraduate physics program, basic quantum mechanics, and its most important applications are studied in detail. This book is the direct result of several years of teaching quantum mechanics in the final year of the undergraduate program, first in two parallel courses at the Faculté des Sciences in Paris and then at the Universités Paris VI and Paris VII. We felt it to be important to mark a clear separation, in the structure of this book, between the two different but complementary aspects (lectures and recitations) of the courses given during this time. This is why we have divided this text into two distinct parts (see the “Directions for Use” at the beginning of the book), On the one hand, the chapters are based on the lectures given in the two courses, which we compared, discussed and expanded before writing the final version. On the other hand, the “complements” grew out of the recitations, exercises and problems given to the students, and reports that some of them prepared. Ideas also came from other courses given under other circumstances or at other levels (Particularly in the graduate programs). As we pointed out in the “Directions for Use”, the chapters as a whole constitute, more or less, a course we would envisage teaching to fourth-year college students or those whose level is equivalent. However, the complements are not intended to be treated in a single year. The reader, teacher or student, must choose between them in accordance with his interests, tastes and goals. Throughout the writing of this book, our constant concern has been to address ourselves to students majoring in physics, like those we have taught over the past several years. Except in a few complements, we have not overstepped those limits. In addition, we have endeavored to take into account what we have seen of students’ difficulties in understanding and assimilating quantum 3INTRODUCTION mechanics, as well as their questions. We hope, of course, that this book will also be of use to other readers such as graduate students, beginning research workers and secondary schoo! teachers. The reader is not required to be familiar with quantum physics : few of our students were. However, we do think that the quantum mechanics course we propose (see “General approach”, below) should be supplemented by a more descriptive and more experimentally oriented course, in atomic physics for example. General approach We feel that familiarity with quantum mechanics can best be acquired by using it to solve specific problems, We therefore introduce the postulates of quantum mechanics very early (in chapter III), so as to be able to apply them in the rest of the book. Our teaching experience has shown it to be preferable to introduce all the postulates together in the beginning rather than presenting them in several stages, Similarly, we have chosen to use state spaces and Dirac notation from the very beginning. This avoids the useless repetition which results from presenting the more general bra-ket formalism only after having developed wave mechanics uniquely in terms of wave functions. In addition, a belated change in the notation runs the risk of confusing the student, and casting doubts on concepts which he has only just acquired and not yet completely assimilated. After a chapter of qualitative introduction to quantum mechanical ideas, which uses simple optical analogies to familiarize the reader with these new concepts, we present, in a systematic fashion, the mathematical tools (chapter Il) and postulates of quantum mechanics as well as a discussion of their physical content (chapter III), This enables the reader, from the beginning, to have an overall view of the physical consequences of the new postulates. Starting with the complements of chapter III we take up applications, beginning with the simplest ones (two-level systems, the harmonic oscillator, etc.) and becoming gradually more complicated (the hydrogen atom, approximation methods, etc.). Our intention is to provide illustrations of quantum mechanics by taking many examples from different fields such as atomic physics, molecular physics and solid state physics. In these examples we concentrate on the quantum mechanical aspect of the phenomena, often neglecting specific details which are treated in more specialized texts. Whenever possible, the quantum mechanical results are compared with the classical ones in order to help the reader develop his intuition concerning quantum mechanical effects, This essentially deductive viewpoint has led us to avoid stressing the historical introduction of quantum mechanical ideas, that is, the presentation and discussion of experimental facts which force us to reject the classical ideas. We have thus had to forego the inductive approach, which is nevertheless needed if physics is to be faithfully portrayed as a science in continual evolution, provoked by constant confrontation with experimental facts. Such an approach seems to us to be better suited to an atomic physics text or an introductory quantum physics course on a more elementary level. Similarly, we have deliberately avoided any discussion of the philisophicalINTRODUCTION implications of quantum mechanics and of alternative interpretations that have been proposed. Such discussions, while very interesting (see section 5 of the biblio- graphy), seem to us to belong on another level. We feel that these questions can be fruitfully considered only after one has mastered the “orthodox” quantum theory whose impressive successes in all fields of physics and chemistry compelled its acceptance Acknowledgements The teaching experiences out of which this text grew were group efforts, pursued over several years. We want to thank all the members of the various groups and particularly, Jacques Dupont-Roc and Serge Haroche, for their friendly collaboration, for the fruitful discussions we have had in our weekly meetings and for the ideas for problems and exercises which they have suggested. Without their enthusiasm and their valuable help, we would never have been able to undertake and carry out the writing of this book. Nor can we forget what we owe to the physicists who introduced us to research, Alfred Kastler and Jean Brossel for two of us and Maurice Lévy for the third. It was in the context of their laboratories that we discovered the beauty and power of quantum mechanics. Neither have we forgotten the importance to us of the modern physics taught at the C.E.A. by Albert Messiah, Claude Bloch and Anatole Abragam, at a time when graduate studies were not yet incorporated into French university programs. We wish to express our gratitude to Ms. Aucher, Baudrit, Boy, Brodschi, Emo, Heyvaerts, Lemirre, Touzeau for preparation of the manuscript.Foreword This book is essentially a translation of the French edition which appeared at the end of 1973, ‘The text has undergone a certain number of modifications. The most important one is an addition of a detailed bibliography, with suggestions concerning its use appearing at the end of each chapter or complements. This book was originally conceived for French students finishing their undergraduate studies or beginning their research work. It seems to us however that the structure of this book (Ceparation into chapters and complements — see the “Directions for use”) should make it suitable for other groups of readers. For example, for an undergraduate elementary Quantum ‘Mechanics course, we would recommend using the inost important chapters with their simplest ‘complements. For a more advanced course, one could add the remaining chapters and use more ifficakt complements. Finally itis hoped that some of the more advanced complements will help students in the transition from a regular Quantum Mechanics course to current research topics in various fields of Physics. We wish to thank Nicole and Dan Ostrowsky, as well as Susan Hemley, for the care and enthusiasm which they brought to this translation. Their remarks often led to an improvement of the original text. In addition, we are grateful to Mrs. Audoin and Mrs. Mathiew for their aid in organizing the bibliography. C. Cohen-Tannoudji B.Diu F, LaloéWaves and particles. Introduction to the fundamental ideas of quantum mechanicsOUTLINE OF CHAPTER 1 A. ELECTROMAGNETIC WAVES AND PHOTONS. Light quanta and the Planck-Einstein relations Wave-particle duality: 4a, Analysis of Young's double-shit experiment , Quantum unification of the two aspects of light, ‘The principle of spectral decomposition 8. MATERIAL PARTICLES. ‘The de Broglie relations AND MATTER WAVES. 2, Wave functions; Schrédinger equation ©. QUANTUM DESCRIPTION 1. Free particle OF A PARTICLE: 2. Form of the wave packet ata given time WAVE PACKETS 3. Heisenberg uncertainty relation 4, Time evotution of a free wave packet D. PARTICLE IN A TIMEINDEPENDENT ‘SCALAR POTENTIAL Separation of variables. Stationary states ‘a, Existence of stationary states >. Superposition of stationary states One-dimensional “square” potentials. Qualitative study 4, Physical meaning of a square potential . Optical analogy ¢. ExamplesCHAPTER 1_WAVES AND PARTICLES In the present state of scientific knowledge, quantum mechanics plays a funda- ‘mental role in the description and understanding of natural phenomena. In fact, phenomena which occur on a very small (atomic or subatomic) scale cannot be explained outside the framework of quantum physics. For example, the existence and the properties of atoms, the chemical bond and the propagation of an electron in a crystal cannot be understood in terms of classical mechanics. Even when we are concerned only with macroscopic physical objects (that is, whose dimensions are comparable to those encountered in everyday life), it is necessary, in principle, to begin by studying the behavior of their various constituent atoms, ions, elec- trons, in order to arrive at a complete scientific description. There are many phenomena which reveal, on a macroscopic scale, the quantum behaviour of nature. It is in this sense that it can be said that quantum mechanics is the basis of our present understanding of all natural phenomena, including those traditionally treated in chemistry, biology, et From a historical point of view, quantum ideas contributed to a remarkable unification of the concepts of fundamental physics by treating material particles and radiation on the same footing, At the end of the nineteenth century, people distinguished between two entities in physical phenomena : matter and radiation. Completely different laws were used for each one. To predict the motion of material bodies, the laws of Newtonian mechanics (cf. appendix III) were utilized. Their success, though of long standing, was none the less impressive. With regard to radiation, the theory of electromagnetism, thanks to the introduction of Maxwell's equations, had produced a unified interpretation of a set of phenomena which had previously been considered as belonging to different domains: electricity, magnetism and optics. In particular, the electromagnetic theory of radiation had been spectacularly confirmed experimentally by the discovery of Hertzian waves. Finally, interactions between radiation and matter were well explained by the Lorentz force. This set of laws had brought physics to a point which could be considered satisfactory, in view of the experimental data at the time. However, at the beginning of the twentieth century, physics was to be marked by the profound upheaval that led to the introduction of relativistic mechanics and quantum mechanics. The relativistic " revolution” and the quantum “ revolution” were, to a large extent, independent, since they challenged classical physics on different points. Classical laws cease to be valid for material bodies travelling at very high speeds, comparable to that of light (relativistic domain). In addition, they are also found to be wanting on an atomic or subatomic scale (quantum domain). However, it is important to note that classical physics, in both cases, can be seen as an approximation of the new theories, an approximation which is valid for most phenomena on an everyday scale. For example, Newtonian mechanics enables us to predict correctly the motion of a solid body, providing it is non-relativistic (speeds much smaller than that of light) and macroscopic (dimensions much greater than atomic ones). Nevertheless, from a fundamental point of view, quantum theory remains indispensable. It is the only theory which enables us to understand the very existence of a solid body and the values of the macroscopic parameters (density, specific heat, elasticity, etc...) associated with it. ‘At the present time, we do not yet have at our disposal a fully satisfactory theory unifying quantum and relativistic mechanics since difficulties have arisen in this 9CHAPTER |_ WAVES AND PARTICLES domain. However, most atomic and molecular phenomena are well explained by the non-relativistic quantum mechanics that we intend to examine here. This chapter is an introduction to quantum ideas and “vocabulary”. No attempt is made here to be rigorous or complete. The essential goal is to awaken the curiosity of the reader. Phenomena will be described which unsettle ideas as firmly anchored in our intuition as the concept of a trajectory. We want to render the quantum theory " plausible” for the reader by showing simply and qualitatively how it enables us to solve the problems which are encountered on an atomic scale. We shall later return to the various ideas introduced in this chapter and go into further detail, either from the point of view of the mathematical formalism (chap. 11) or from the physical point of view (chap. 111). In the first section (§A), we introduce the basic quantum ideas (wave- particle duality, the measurement process), relying on well-known optical experi- ments. Then we show (§ B) how these ideas can be extended to material particles (wave function, Schrddinger equation). We next study in more detail the characte- ristics of the “wave packet” associated with a particle, and we introduce the Heisenberg uncertainty relations (§ C). Finally, we discuss some simple cases of typical quantum effects (§ D). ELECTROMAGNETIC WAVES AND PHOTONS 1. Light quanta and the Planck-Einstein relations Newton considered light to be a beam of particles, able, for example, to bounce back upon reflection from a mirror. During the first half of the nineteenth century, the wavelike nature of light was demonstrated (interference, diffraction). This later enabled optics to be integrated into electromagnetic theory. In this framework, the speed of light, c, is related to electric and magnetic constants and light polarization phenomena can be interpreted as manifestations of the vectori character of the electric field. However, the study of blackbody radiation, which electromagnetic theory could not explain, led Planck to suggest the hypothesis of the quantization of energy (1900): for an electromagnetic wave of frequency v, the only possible energies are integral multiples of the quantum fv, where / is a new fundamental constant. Generalizing this hypothesis, Einstein proposed a return to the particle theory (1905): light consists of a beam of photons, each possessing an energy hv. Einstein showed how the introduction of photons made it possible to understand, in a very simple way, certain as yet unexplained characteristics of the photoelectric effect. Twenty years had to elapse before the photon was actually shown to exist, as a distinct entity, by the Compton effect (1924). These results lead to the following conclusion : the interaction of an electro- magnetic wave with matter occurs by means of elementary indivisible processes, in which the radiation appears to be composed of particles, the photons. Particle parameters (the energy £ and the momentum p of a photon) and wave parameters 10