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