Definition of some units Angstrém 1A = 107m (order of magnitude of the atomic dimensions) Fermi IF =107'm (order of magnitude of the nuclear dimensions) Barn 1b = 10°78 m? — (10-* AP ~ (10 FP Electron Volt 1 eV = 1,602 189(5) x 107"? joule Useful orders of magnitude Electron rest energy : m,c? = 0.5 MeV [0.511 003(1) x 10% ev] Proton rest energy : M,c? = [000 MeV [938.280(3) x 10° eV] Neutron rest energy : Myc? = | 000 MeV [939.573(3) x 10° ev) One electron volt corresponds to : a frequency vy = 2.4 x 10" Hz through the relation E = hv [2.417 970(7) x 10% Hz] awavelength 4 = 12000A ‘through the relation A = c/v [12 398.52(4) A] i 8.000 cm=! [8 065.48(2) cm-*] a temperature T~12000K through the relation £ = ky7 [11 604.5(4) K] a wave number Ina | gauss magnetic field (10 * Tesla) : the electron cyclotron frequency v, = w,/2x = ~ gB/2nm, is v, = 2.8 MHz [2.799 225(8) x 106 Hz] the orbital Larmor frequency vy, = «w,/2n = — ipBfh = vil2 4 MHz [1.399 612(4) x 10 Hz] (this corresponds by definition to a g = | Landé factor) sv, itSome general physical constants h= 6626 18(4) x 10-** joule second Planck's constant he & = 1.054 89(6) x 10° joule second Speed of light (in vacuum) = ¢ = 2.997 924 58(1) x 10° m/s Electron charge 4 = — 1,602 189(5) x 107" coulomb Electron mass my = 9.109 53(5) x 107* ky 1.672 65(1) x 10727 kg, {1} x 19-27 Proton mass M, ape = 1 836.1515(7) Ae = Wings = 2426 9098) x 107? A Elect Co jel uaa {i = fifmgc = 3861 591(7) x 10-2 A Fine structure constant ages ee aaa (dimensionless) Groghe he 137.0360) Bohr radius ay = & = 0.529177 1(5)A Hydrogen atom ionization energy (without proton recoil — E,, = a*m,c?/2 = 13.605 80(5) eV fect) Rydberg’s constant Ra, = — Ey, (he = 1.097 373 18(8) x 105 em? “Ciasical” electron ragius 7, = ro Spo EH 9pm Bohr magneton Hy = Gh/2m, = — 9.274 08(4) x 10-* joule/tesla Electron spin g factor 9, = 2 x 1.001 159 657(4) ‘Nuclear magneton My = — gh/2M, = 5.05082(2) x 107?7joule/testa Boltzmann's constant ky = 1.380.66(4) x 107? joule/K Avogadro's number N, = 6.022.05(3) x 1074Useful Identities U : scalar field; A,B ... : vector fields. Vx (VU) =0 v.(VU) = AU V.(Vx A)=0 Vx (Vx A)=V(V.A)— AA rope A x (B x C) = (A. C)B— (A. BIC Ax (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 B). DJC — [(A = B).C]D = [(C x D).A]B — [(C x D). BJA vy) =uwaew A (UV) UAV + (VU). (WH) + VAU Vv. (UA) UV.A+A.VU Vv x (UA) U VxA+ (WU) A V.(Ax B) =B.(VxA)— A. (VxB) v(A RY Ax (Vx R)ERx (Ve A)4 RV ALAVR Vx (A x B)=A (V.B)—B(V.A)+B.V A-A.V B NB. : BVA vector field whose components are : (BV A= BPA, = DB A Vax, (i= Je2fo2"r2— QUA) = Weal dfb2"¥e ~ ere] = “Ov xa ore — 2H + 2 (cus si Lint vane us ~ 02'¥2) = AW xa eo" — 242 = WW xa) fxp"¥o — 22°F + g (ous 4/Logtre — 02h" own] = Wa) soitre — oe"re) = ‘WW xa) ae 'Fe- ORI =V . a2 aun wouss ag A trom + 4 ge ae Venu ibe ob +tnete gk yee a 25 le ie 4 aaa aa 2 (9 us 4[42:02] = “0a sana = “(nal 2 sfeine) = aa) 5 deine = “a Zz bs00'y taun"y— = "P| ~ 2 gusty ~ 9s00"y = ty bs00'y + Ous'y ~ = *y 3 9109" + pus‘y = *y us 'y + 6:00" = z frre e 5 ratty + eye ty et ey 3 (ov00= a «es (Caen 5 = fe a es — ee e Oo uersense9 swiaysAs e}eUIps0o0D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 band, the chapters are based on the lectures given in the two courses, On the other hand, the “complement 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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 (Gee “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 wi 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 thei 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 f1) 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 a: bys ples 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intropucTion 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 cal 4 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. wee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 mast 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 (separation 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 ost important chapters with their simplest complements, For a more advanced course, one could add the remaining chapters and use more av FIGURE 5 Variations with respect to k of the fonction to be Integrated over k in order to obtain (x. 0). In ‘figure (a), x is fixed at a value such that |x — x,| > 1/4k, and the function to be integrated oscillates several tots within the interval AK. In figure (b,x is fixed such that [v — xo] <= I/Ak, and the function tobe Integrated hardly onellats, eo that ite integral over fakes ona relatively large vale. Consequently, the center of the wave packet [point where |y(x, 0)| is maximum] is situated at When x moves away from the value xo, |y(x, 0)| decreases. This decrease becomes appreciable if ¢!~*"*-**) oscillates approximately once when & traverses the domain Ak, that is, when: Ak. (x = x9) = 1 (C17) If Ax is the approximate width of the wave packet, we therefore have : Ak. Ax 21 (c-18) We are thus brought back to a classical relation between the widths of two functions which are Fourier transforms of each other. The important fact is that the product 4x . 4k has a lower bound; the exact value of this bound clearly depends an the precise definition of the widths Ax and Ak A wave packet such as (C-7) thus represents the state of a particle whose probability of presence, at the time ¢ = 0, is practically zero outside an interval of approximate width Ax centered at the value xy. COMMENT: The preceding argument could lead one to believe that the product Ax. Ak is always of the order of I [¢f. (C-17)]. Let us stress the fact that this is a lower limit. Although it is impossible to construct wave packets for which the product Ax . Ak is negligible compared to I, it is perfectly possible to construct packets for which this product is as large as desired [see, for example, complement G,, especially comment (ii) of §3-c]. This is why (C-18) is written in the form of an inequality.C._WAVE PacKETs 3. Heisenberg uncertainty relation In quantum mechanics, inequality (C-18) has extremely important physical consequences. We intend to discuss these now (we shall stay, for simplicity, within the framework of a one-dimensional model) We have seen that a plane wave e'**—°%" corresponds to a constant proba- bility density tor the particle's presence along the Ux axis, for all values of This result can be roughly expressed by saying that the corresponding value of 4x is infinite. On the other hand, only one angular frequency w, and one wave vector k, ate involved. According to the de Broglie relations, this means that the energy and momentum of the particle are well-defined : E = ha and p = hiky Such a plane wave can, moreover, be considered to be a special case of (C-7), for which g(k) is a « delta function » (appendix 11): ak) = 5(k — ko) (c-19) The corresponding value of Ak is then zero. But this property can also be interpreted in the following manner, using the principle of spectral decomposition (¢f. § A-3 and B-2). To say that a particle, described at = 0 by the wave function y(x,0) = 4c, has a well-determined momentum, is to say that a measurement of the momentum at this time will definitely yield p = hk. From this we deduce that e" characterizes the eigenstate corresponding to p = hk. Since there exists a plane wave for every real value of k, the eigenvalues which one can expect to find in a measurement of the momentum on an arbitrary state include all real values. In this case, there is no quantization of the possible results : as in classical mechanics, all values of the momentum are allowed. Now consider formula (C-8). In this formula, y (x, 0) appears as a linear superposition of the momentum eigenfunctions in which the coefficient of e!* is a(k). We are thus led to interpret |a(X)|? (to within a constant factor) as the proba~ bility of finding p = hk if one measures, at = 0, the momentum of a particle whose state is described by (x, £). In reality, the possible values of p, like those of x, form a continuous set, and |g(k)|? is proportional to a probability density: the probability d(x) of obtaining a value between hk and h(k + dk) is, to within a constant factor. la(k)|? dk. More precisely. if we rewrite formula (C-8) in the form: Wx, 0) fro re oP. (C-20) Vinh we know that ¥(p) and y(x, 0) satisfy the Bessel-Parseval relation (appendix I): Jes oF a [mor o» (can If the common value of these integrals is C, d%(x) 4 |W(x, 0)}? dx is the probability of the particle being found, at ¢ = 0, between x and x + dx. In the same way : (C-22) 7