Jean-Louis Basdevant Jean Dalibard The Quantum Mechanics Solver How to Apply Quantum Theory to Modern Physics With 56 Figures, Numerous Problems and Solutions G }) SpringerProfessor Jean-Louis Basdevant Professor Jean Dalibard Ecole Polytechnique Ecole Normale Supérieure Département de Physique Département de Physique 91128 Palaiseau Cedex, France Laboratoire Kastler Brossel 24, rue Lhomond Email; [email protected] poly -polyvecisa 75231 Paris Cedex 05, France Email: [email protected] Library of Congress Cataloging-in-Publication Data Basdevant, J. L. (Jean-Louis) The quantum mechanics solver : how to apply quantum theory to modern physics / Jean-Louis Basdevant, Jean Dalibard. p. cm. — (Advanced texts in physics, ISSN 1439-2674) Includes bibliographical references and index. ISBN 3540634096 (alk, paper) 1. Quantum theory--Problems, exercises, etc. I. Dalibard, J. Il. Title. Il. Series. QC174.15 .B37 2000 530.12'076—-de21 99-058086 ISSN 1439-2674 ISBN 3-540-63409-6 Springer-Verlag Berlin Heidelberg New York This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broad- casting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from ‘Springer-Verlag. Violations are liable for prosecution under the German Copyright Law. Springer-Verlag is a company in the BertelsmannSpringer publishing group © Springer-Verlag Berlin Heidelberg 2000 Printed in Germany ‘The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant pro- tective laws and regulations and therefore free for general use. ‘Typesetting: Data conversion by EDV-Beratung F. Herweg, Hirschberg Cover design: design ¢ production GmbH, Heidelberg Printed on acid-free paper SPIN 10569975 s6/s14a/di_ 543210Preface Quantum mechanics is an endless source of new questions and fascinating observations. Examples can be found in fundamental physics and in applied physics, in mathematical questions as well as in the currently popular debates on the interpretation of quantum mechanics and its philosophical implica- tions. Teaching quantum mechanics relies mostly on theoretical courses, which are illustrated by simple exercises often of a mathematical character. Reduc- ing quantum physics to this type of problem is somewhat frustrating since very few, if any, experimental quantities are available to compare the results with, For a long time, however, from the 1950s to the 1970s, the only alterna- tive to these basic exercises seemed to be r d to questions originating from atomic and nuclear physics, which were transformed into exactly soluble problems and related to known higher transcendental functions. In the past ten or twenty years, things have changed radically. The devel- opment of high technologies is a good example. The one-dimensional square- well potential used to be a rather academic exercise for beginners. The emer- gence of quantum dots and quantum wells in semiconductor technologies has changed things radically. Optronics and the associated developments in infra- red semiconductor and laser technologies have considerably elevated the social rank of the square-well model. As a consequence, more and more emphasis is given to the physical aspects of the phenomena rather than to analytical or computational considerations. Many fundamental questions raised since the very beginnings of quantum theory have received experimental answers in recent years. A celebrated ex- ample is the verification of Bell’s inequalities, which has been confirmed in decisive experiments since the late 1970s. Another is the neutron interfer- ence experiments of the 1980s, which gave experimental answers to 50 year old questions related to the measurability of the phase of the wave function. More recently, the experiments carried out to quantitatively verify decoher- ence effects and “Schrédinger-cat” situations have raised considerable interest with respect to the foundations and the interpretation of quantum mechanics. This book consists of a series of problems concerning present-day experi- mental or theoretical questions on quantum mechanics. All of these problems are based on actual physical examples, even if sometimes the mathemati-VI Preface cal structure of the models under consideration is simplified intentionally in order to get hold of the physics more rapidly. The problems have all been given to our students in the Ecole Polytechnique and in the Ecole Normale Supérieure in the past 15 years or so. A special feature of the Ecole Polytechnique comes from a tradition which has been kept for more than two centuries, and which explains why it is neces- sary to devise original problems each year. The exams have a double purpose. On one hand, they are a means to test the knowledge and ability of the stu- dents. On the other hand, however, they are also taken into account as part of the entrance examinations to public office jobs in engineering, administrative and military careers. Therefore, the traditional character of stiff competitive examinations and strict meritocracy forbids us to make use of problems which can be found in the existing literature. We must therefore seek them among. the forefront of present research. Most of these problems have been set after a ‘er course on quantum mechanics at the senior undergraduate level, which gives you an idea of the type of problems involved. They were given in written examinations which lasted for four hours. Statistically, most students would cover 75% of the content of each problem, and between 5 and 10% of the students gave a more or less complete and correct answer. The three last problems of this book have been designed for the graduate studies program at the Ecole normale supérieure and Université Pierre et Marie Curie. Their solution requires a somewhat deeper knowledge of quantum mechanics, such as second quantization. We are indebted to many colleagues who either gave us driving ideas, or wrote first drafts of some of the problems presented here. We are par- ticularly grateful to Yves Quéré for “Colored centers in ionic crystals”, Gilbert Grynberg for “Unstable diatomic molecule”, “The hydrogen atom in crossed fields”, “Hidden variables and Bell’s inequalities”, “Spectroscopic measurement on a neutron beam” and “Molecular lasers”, Frangois Jacquet for “Neutrino oscillations”, Philippe Grangier for “Schrédinger’s cat”, Jean- Noél Chazalviel for “Hyperfine structure in electron spin resonance”, Thierry Jolicoeur for “Magnetic excitons”, Bernard Equer for “Probing matter with positive muons”, Vincent Gillet for “Energy loss of ions in matter”, and Yvan Castin, Jean-Michel Courty and Dominique Delande for “Quantum reflection of atoms on a surface” and “Quantum motion in a periodic potential”. one-semes Palaiseau, January 2000 Jean-Louis Basdevant Jean DalibardContents 1, Colored Centers in Ionic Crystals. 1 1.1 The Mollwo-Ivey Law....... 2 1.2 The Jahn~Teller Effect 3 1.3. The Stokes Shift 4 1.4 Solutions : 5 Further Comments on F-Centers . 10 2, Unstable Diatomic Molecule . ist 2.1 Preliminaries u 2.2 A Molecule Which Is Only Stable in Its Excited State....... 12 2.3 Solutions ......... 06.0 eee e cece eee erect e eee 13 3. Neutrino Oscillations .. 17 3.1 Neutrino Mas: 17 3.2. Solutions ... 18 4, Colored Molecular Ions . 21 4.1 Carbohydrate Tons. . 21 4.2 Nitrogenous Ions . .. : . 22 4.3 Solutions 0.0... .00.0eeeceeeccceeeeueeeeetesseeeeees 1 2B 5. Schrddinger’s Cat........... 5.1 The Quasi-Classical States of a Harmonic Oscillator 27 5.2 Construction of a Schrédinger-Cat State. 28 5.3 Quantum Superposition Versus Statistical Mixture. . 29 5.4 The Fragility of a Quantum Superposition . 30 5.5 Solutions ...... 0.00006 cece eee eee eee . . 32 Conclusion 6.0.6... cece eee cece cece teen eect rete terete eee 37 6. Direct Observation of Field Quantization ............... . 39 6.1 Quantization of a Mode of the Electromagnetic Field . 39 6.2 The Coupling of the Field with an Atom .. 41 6.3 Interaction of the Atom and an “Empty” Cavity ........... 42VIL 10. il. 12. Contents 6.4 Interaction of an Atom with a Quasi-Classical State ........ 43, 6.5 Large Numbers of Photons: Damping and Revivals . 44 6.6 Solutions ........ 0... e eee eee eee een een ee 45 FReferenCe sas oie cove reece sere centre nto terres cur seers 52 Decay of a Tritium Atom 53 7.1 The Energy Balance in Tritium Decay . 53 7.2 Solutions ....... 00.0 e eee e eee eee 54 The Hydrogen Atom in Crossed Fields 8.1 The Hydrogen Atom in Crossed Electric and Magnetic Fields 2.2... .... 0 cee eee eee eee eee een eee 57 8.2 Pauli’s Result . 58 8.3 Solutions ... 59 Exact Results for the Three-Body Problem . 9.1 The Two-Body Problem. . 9.2 The Variational Method 9.3. Relating the Three-Body and Two-Body Sectors. 9.4 The Three-Body Harmonic Oscillator 9.5 From Mesons to Baryons in the Quark Model 9.6 Solutio 64 References . 68 Analysis of a Stern-Gerlach Experiment . 69 10.1 Preparation of the Neutron Beam 69 10.2 Spin State of the Neutrons... 71 10.3 The Stern~Gerlach Experiment. 71 10.4 Solutions . 73 Measuring the Electron Magnetic Moment Anomaly...... 79 11.1 Spin and Momentum Precession of an Electron in a Magnetic Field . 11.2 Solutions Neutron Interferometry . 12.1 Neutron Interferences 12.2 The Gravitational Effect . 12.3 Rotating a Spin 1/2 by 360 Degrees. 12.4 Solutions References . 2.06... 6 cece ee cee eee eee een t nee n nents13. 14. 16. 17. 18. Contents IX The Penning Trap 93 13.1 Motion of an Electron in a Penning Trap 93 13.2 The Transverse Motion...........4 94 13.3 Measurement of the Electron Anomalous Magnetic Moment... 95 13.4 Solutions 95 Reference .. 98 Quantum Cryptography 1.02.60. 00000eeeeeeeeeeeeee eee 99 14.1 Preliminaries 99 14.2 Correlated Pairs of Spins 100 14.3 The Quantum Cryptography Procedure - 102 14.4 Solutions 00.04.0600 ee eee eee eee es - 104 Hidden Variables and Bell’s Inequalities . - 109 15.1 The Electron Spin ..........- 15.2 Correlations Between the Two Spins 15.3 Correlations in the Singlet State. 15.4 A Simple Hidden Variable Model 15.5 Bell’s Theorem and Experimental Results 15.6 Solutions References ... . 118 Hyperfine Structure in Electron Spin Resonance . lg 16.1 Hyperfine Interaction with One Nucleus . - 120 16.2 Hyperfine Structure with Several Nuclei . . 120 16.3 Experimental Resul .121 16.4 Solutions . 123 The Spectrum of Positronium . 127 17.1 Positronium Orbital States ... 127 17.2 Hyperfine Splitting ............ 127 17.3 Zeeman Effect in the Ground State - 128 17.4 Decay of Positronium . 129 17.5 Solutions 131 References .. . Magnetic Excitons 135 18.1 The Molecule CsFeBrg ... - 135 18.2 Spin-Spin Interactions in a Chain of Molecules 136 . . 136 18.4 Vibrations of the Chain: Excitons . 138 18.5 Solutions Reference ....19. 20. 21. 22. 23. 24. 25. Contents Probing Matter with Positive Muons ..................005 147 19.1 Muonium in Vacuum . 19.2 Muonium in Silicon . 19.3 Solutions Spectroscopic Measurement on a Neutron Beam . 157 20.1 Ramsey Fringes . 157 20.2 Solutions . 159 Reference .. . 163 The Quantum Eraser . . 165 21.1 Magnetic Resonance «165 21.2 Ramsey Fringes 21.3 Detection of the Neutron Spin State 21.4 A Quantum Eraser .....e. cece ees 21.5 Solutions 0.0.0... .seceeeeeeeeneeeeeeeeeeaeeees . 170 Molecular Lasers 179 22.1 Preliminaries. . 22.2 Molecular Lasers 22.3 Solutions .. Energy Loss by Ions in Matter... 187 23.1 Energy Absorbed by One Atom . 188 23.2 Energy Loss in Matter 188 23.3 Solutions Properties of a Bose-Einstein Condensate . 24.1 Particle in a Harmonic Trap ....... 24.2 Interactions Between Two Confined Particles 24.3 Energy of a Bose-Kinstein Condensate . 24.4 Condensates with Repulsive Interactions 24.5 Condensates with Attractive Interactions 24.6 Solution: Further Comments ........ 0.0.0 ese ee eee eee eee e eee eenneeeeees + 205 205 207 + 208 Quantum Reflection of Atoms from a Surface. . 25.1 ‘The Hydrogen Atom-Liquid Helium Interaction . 25.2 Excitations on the Surface of Liquid Helium . . 25.3 Quantum Interaction Between H and Liquid He . 25.4 The Sticking Probability » 208 25.5 Solutions » 209 References oo. . 0... ceeceeeceveeeeeeeeeeeeeee eset eetaeeeenees 215Contents XI 26. Laser Cooling and Trapping 26.1 Optical Bloch Equations for an Atom at Rest 26.2 The Radiation Pressure Force . 26.3 Doppler Cooling 26.4 The Dipole Force . 26.5 Solutions ...... 27. Quantum Motion in a Periodic Potential 27.1 Band Structure in a Periodic Potential . 27.2 Bloch 27.3 Solutions 6.0... 6. cece cee eee eee eee eee eer e eee eee e eee 230 Author Index ..... 6.0.6 c eee cc eee n ee neeet nee net e rete 239 Subject Index .......60.ceecceeceeeceeeeeeeesneeneetesenesens 2411. Colored Centers in Ionic Crystals When a vacancy is created in a crystal, an electron may be trapped at this location. This bound electron can absorb light at well defined frequencies, thus changing the color of the crystal. Consider the diatomic crystal NaCl. It is called an ionic crystal because, when the crystal forms, the outer electron of a sodium atom is transferred to a chlorine atom. Hence, in the crystal, the electronic configuration is (Nat, Cl-), and the electrostatic interaction between the Nat and Cl~ ions is responsible for the binding of the structure. The crystal is face centered cubic for both ions. Schematically, the crystal, as seen parallel to one face of the cube can be represented as in Fig. 1.1. Such a structure, called the NaCl structure, is very frequently encountered. It is, in particular, the structure of all alkali halides. t+ - + - + - + = + - a + - + - + - + - + - O:cr @ : Nat Fig. 1.1. Structure of the ionic crystal Nat Cl”. These crystals are transparent if they are sufficiently pure. However, if they are irradiated by energetic photons (X or 7 rays), alkali halides become colored. The reason for this is the following. A photon can eject an anion from its site, creating an unoccupied site called a vacancy. This anion vacancy, surrounded by positively charged ions, can trap an electron and restore the local electrical neutrality of the crystal. The trapped electron has a series of energy levels. It can absorb light and jump from the ground state to an2 1. Colored Centers in Ionic Crystals t+ 7 yor - +1 }+ + |a \ Noe tot 4 ye Fig. 1.2. Structure of an F-center in a NaCl crystal. excited state. This process is responsible for the color of the crystal. The elec- tron trapped in the vacancy is called a colored centre, or F-center (from the German Farbenzentrum). The structure of an F-center is shown on Fig. 1.2. 1.1 The Mollwo-Ivey Law Let a be the lattice spacing, the distance between two neighboring Na+ ions. Measurements of the wavelengths \ or energies ¢ of absorption lines on various alkali halides have been performed by Mollwo and Ivey. The results are displayed in Fig. 1.3. They show that the variations of the absorption energy with the lattice spacing a follow a simple law. 1.1.1. Express the empirical law that emerges from these measurements as e=Ka", (1.1) where € is in eV and a is in A. This is called the Mollwo-Ivey law. Since, in good approximation, the absorption energy ¢ depends only on the lattice spacing a and not on its particular nature, one may assume that the shapes of F-centers are the same for all of these crystals and that they only differ by their sizes. The simplest model one can build consists in assuming that the Z positive t neighbors to the F-center form a cubic square well potential inside which the electron is trapped. In first approximation, we shall assume that it is an infinitely deep potential well: v=0 for 0 < ayz as a function of 7 . 1.3 The Stokes Shift We can now give a simple account of the absorption and emission of light by an F-center. In Sect. 1.1, we have described the absorption of light by an F-center. After a time of the order of 10~® s, the electron makes a transition to the ground state and emits radiation, called “luminescence”. Experiment shows that the emission lines are systematically shifted to- wards longer wavelengths — or equivalently smaller energies ~ than the corre- sponding absorption lines. This shift, an example of which is shown in Fig. 1.5 is called the Stokes shift. 1.3.1. Let us first assume that most lines are shifted to the infrared part of the spectrum, which is not visible. Under this assumption, by what simple mechanism do the F-centers color a crystal when the crystal is placed in visible light?1.4 Solutions 5 emission || absorption KBr (20K) Absorption coefficient (arb. un.) 00 05 10 15 20 25 30 Energy (eV) Fig. 1.5. Absorption and emission spectra of an F-center in KBr at low tempera- ture. The maxima of the two lines are respectively at 2.06 and 0.92 eV, Data are taken from W. Gebbart and A. Kuhnert, Physica Status Solidi, 14, p.157 (1966). 1.3.2. What are the respective colors of the crystals KI, KCI, and NaCl after they have been exposed to X-rays? We recall that the colors of the spectrum of visible light are, for increasing values of the energy, red (from 1.65 to 2.0 eV), orange (from 2.0 to 2.1 eV), yellow (from 2.1 to 2.3 eV), green (from 2.3 to 2.55 eV), blue (from 2.55 to 2.65 eV) and violet (from 2.65 to 3.1 eV). We also recall that “complementary colors” are colors which, when associ- ated, give back white light. The main couples of complementary colors are yellow-violet, red-green and blue-orange. Hence when blue is absorbed by a substance in natural white light, the substance appears to be yellow. 1.3.3. We shall now attempt to give a simple description of the Stokes shift. We shall assume that the elecronic excitation or de-excitation times are neg- ligible compared to typical times for local distortions of the crystal, these being, in turn, much shorter than the lifetimes of the excited states (of the order of 10~® s) Under these assumptions, give a simple description of the absorption and emission of light by an F-center, using the results of Sect. 1.2. 1.3.4, More quantitatively, show that the results of Sect. 1.2 give a good account of the experimental result shown in Fig. 1.5. 1.3.5. Justify the assumption made in question 1.3.1 by showing that for most crystals of Fig. 1.3, the emission line is in the infrared part of the spectrum. Specify for which crystals this occurs. 1.4 Solutions Section 1.1 1.1.1. The experimental points lie on a straight line in a log-log plot. The experimental law is of the form ¢ = Ka” with K & 68 and n = —1.85.6 1. Colored Centers in lonic Crystals 1.1.2, There are Z = 6 positive ions at a distance a/2 of the F-center. 1.1.3. Choosing the origin at a vertex of the cube, (a) the ground state, with energy FE, = 3A°n?/(2ma?), is not degenerate; its wave function vay, 2) = (2/a)* (b) the first excited state has a three-fold degeneracy Wor, Vy, 22 with for instance: sin(wa/a) sin(ny/a)sin(nz/a) ; whee(a,y, 2) = (2/a)*/? sin(war/a) sin(my/a) sin(2nz/a) corresponding to an energy Ey = 6h?x?/(2ma?) 1.1.4. The transition Ey -+ E2 corresponds to the absorption of an energy € = By — E; = 3f'x?/(2ma*) where a is the lattice spacing. This expression is of the type (1.1) with K = 112 and n = —2. The value of n is close to what is experimentally observed (—1.85). The constant K is significantly overestimated. 1.1.5. If the effective extension of the potential is aa = aa, the theoretical formula becomes ¢ = 3h?2?/(2ma?a?), Using the value a = 1.13 correspond- ing to K = 87 (and n = ~2), one obtains a good fit to the data as shown in Fig. 1.6. The effective size of the cube is 13% greater than the lattice size. This is not surprising since each of the six neighboring positive ions attracts the a (Angstréms) « (eV) Fig. 1.6. Absorption lines of F-centers in various alkali halides; comparison of the data and the model developed in question 1.1.5.1.4 Solutions 7 electron of the F-center. In a more realistic potential model of the F-center, the probability for the electron to be outside the vacancy should be non-zero. Section 1.2 1.2.1. Consider the state die (a,y, 2) = (2/ag)*”? sin(wa/ag) sin(my/ap) sin(2t2z/a9) . Under the distortion, it becomes: ale, yz) = (2/c)(2/b)"? sin(ma/c) sin(ny/c) sin(2nz/b) , and the corresponding energy E2 = 61h? /(2ma3) becomes Wn (2 4 y Aine (2 4 Bx 2m (= ?) . Setting 7 = b/c, and imposing that the distortion occurs at constant volume, a3 = cb, one has ¢ = ar" and b= agn?/3, hence 22 he (29?! + an-¥9) Pe oma Similarly, one finds that Wr _ oma (603 47 4/3) ‘0 E , Eby = Clearly, B4,, = E4, on one hand, and E}, on the other are different from E2, and different from one another. The distortion partially lifts the degeneracy. If we study the variation of £3, and E}, with respect to 7, we find that both energies have minimum values: © £%, is minimum for 7 = 2, where it reaches the value nn? B4,(2) = 4.76, ; maz ¢ Eh, is minimum for 7 = \/2/5 ~ 0.63, where it reaches the value 4 (\/2/5) = 5.52 Wnt 22(V 2/5) = 5. Imad Both values are smaller than E>. The first is the absolute minimum. Hence the energy of the first excited state has the minimum value EB = 4.76 h?x?/(2ma3), for a value 7 of the distortion parameter. Since 7 > 1 this corresponds to an F-center stretched along the 2 axis.8 1. Colored Centers in Ionic Crystals 1.2.2. When the F-center is distorted, the ground state energy is _ Aa? = mad 2maz Rn? 2 1 /: B= = 2; 2/3 4/3) . 1= om (at % (an? +7") This function is minimum for 7 = 1, ie. an undistorted center. Any dis- tortion will increase the energy of the ground state. We have, in particular at 7 = 2 where the excited state energy is minimum, E{(qo) = E,(2) = 3.57 hn? /(2ma3) . 1.2.3. The variations of the energy levels with the distortion are shown in Fig. 1.7. Fig. 1.7. Variation of the energy levels, in units h?2?/(2maj), with the distortion parameter 7. Section 1.3 1.3.1. If the emission of light is in the infrared part of the spectrum, it will not produce a coloring of the crystal. The color is only due to absorption. The observed color is the complementary color to that of the absorbed radiation (of energy €). 1.3.2. Among the crystals mentioned, NaCl absorbs violet light (¢ ~ 2.75 eV), its color is therefore yellow. Similarly, KI is green, and KCI is violet. ‘The first time this problem was given to students, it was actually accompanied with three plastic bags containing respectively yellow, green and light violet crystals. The question was to determine what type of alkali halide was contained in each of them, ‘The crystals had been irradiated overnight in a Van de Graaf accelerator. 1.3.3. If an F-center is distorted after absorbing energy (i. after entering its excited state), its energy decreases down to E8. When decaying to the ground state, it will then emit a photon of smaller energy than the energy of the absorbed photon, hence the Stokes shift. Using the Franck-Condon principle, we can represent the successive steps of the absorption-emission process as follows (Fig. 1.8)1.4 Solutions 9 time Fig. 1.8. Schematic time description of the absorption-emission process by an F-center. (0) F-center in its ground state; (1) Absorption of a photon of energy ¢ = Ey — E), instantaneous transition to the degenerate state v2; (2) Distortion of the F-center. The electronic energy decreases down to E9. The corresponding energy difference E)—E3 is transferred to the thermal vibrations (phonons) of the crystal. (3) De-excitation. This process is instantaneous, and occurs on a distorted center. The emitted photon has energy E8 — E%(n). (4) The F-center recovers its original symmetry. The corresponding energy E'(no) — Ei, is again released in the crystal thermal vibrations. 1.3.4. From the previous considerations, the energy of the emission line is, within our model, nn? Ren? e! = BS — Ei (10) = =—9 (4.76 — 3.57) = 1.19 . 2 — Bilao) = aig (476 8.81) = 1199 This emission energy is smaller than the absorption energy; the ratio ise" /e ~ 0.4. The experimental result for KBr is ~ 0.44 (see Fig. 1.5). The agreement of the model with experiment is quite acceptable. 1.3.5. The ratio e’/e calculated above does not depend on ag, and therefore should not depend on the nature of the crystal. For an absorption energy near the upper part of the visible spectrum, i.e. ~ 3.1 eV, the calculated emission energy is of the order of 3.1 x 0.4 = 1.14 eV which lies in the infrared region. We therefore conclude that if the absorbed light is in the visible part of the spectrum, (crystals ranging from RbI to KF in Fig. 1.3) then the emission lines lie outside of the visible spectrum. This is the assumption of Sect. 1.3.1.10 1. Colored Centers in Tonic Crystals Further Comments on F-Centers 1. The mechanism by which the F-centers form js still unclear. There are several proposals (the most plausible being due to Pooley) which are based on the assumption that the X-ray photons can ionize the anions once (A> -» A) or twice (A + A+). The resulting species, either electrically neutral or positively charged, is then in a very unstable situation in the middle of all the positive ions. It is then ejected from its site, leaving behind a vacancy (F-center) and reaching an interstitial position. The color can also be obtained by adding impurities (such as a few Ca** ions in NaCl) to the crystal. This the reason why many minerals with a marked ionic character are found colored in nature, while they are transparent if they are pure (like quartz) . They were contaminated by other ions when they crystallized. 2. The model of Sect. 1.1 accounts for the Mollwo-Ivey law quite reasonably. It is, of course, very simplistic. The actual potential is by no means in- finitely deep. By electron spin resonance experiments, one can show that the wave function extends up to the eighth ionic shell surrounding the F-center, ie. much further than ao/2. 3. The F-centers can move around. A nearby anion can jump into the F- center, which therefore moves in the reverse direction. This process in- volves the crossing of a potential barrier, and is favored by an increase in temperature. The mobility of an F-center increases with the temperature. Owing to this mobility, the F-centers tend to disappear, for instance when they reach the surface of the crystal. One can see the color disappear if the crystals are heated. The color can also disappear progressively if the als are exposed to natural light. In fact, the F-centers can then be ionized by ultraviolet photons, which can eject the electron from its vacancy.2. Unstable Diatomic Molecule In a diatomic molecule, the interaction between the atoms depends on their electronic configuration. It is conceivable that a molecule is stable if one of the atoms is electronically excited, and unstable if both atoms are in their ground state. We study here such a s and we focus in particular on the dissociation of the molecule when the initially excited atom decays to its ground state. 2.1 Preliminaries 2.1.1. Consider a particle of mass M moving along the x axis and placed in the potential Vj (2): V(x) = +00 for x < x0 =0 for x > a. Let. g(x) be a stationary solution of the Schrédinger equation with energy £. It can be written, for z > zo, as eu (w) = elM@-20) 4 Bee-20) , (a) Express k in terms of E (b) What is the value of gx (c) What is the value of B? (d) Write the general solution of the Schrédinger equation in terms of the functions yy,(x) - 2.1.2. We now consider a. par placed in the potential Va(:r): Va(a cle of mass M moving along the « axis and +00 for x < 29 =Vo+Mufx?/2 for > ao. where Vo is a constant . (a) What is the wave function for x < xo? (b) Express the eigenfunctions y,,(x) of the Hamiltonian in terms of the normalized Hermite functions ;(y) = cre”? foe ols? (c) What are the corresponding energy lev12 2. Unstable Diatomic Molecule 2.2 A Molecule Which Is Only Stable in Its Excited States Consider a diatomic molecule XY. Let x be the distance between the nuclei (or between the centers of gravity) of the two atoms X and Y. The potential energy between the two atoms depends on the excitation state of the electrons. Let V(x) be this potential energy (for a given electronic state). Then the (lowest) energy levels of the relative motion of the two atoms are obtained by solving the one-dimensional Schrédinger equation vie Vv _ Oar ag? 207) + V(e) ox) = Egle), (2.1) where M is the reduced mass M = Mx My /(Mx + My). Let V = V,(x) be the potential energy when the electrons are in the ground state and V = V,(x) the potential energy when one electron is in its first excited state. The molecule is assumed to be such that Ve(«) has a minimum at 2 = zo whereas Vg(zr) is a decreasing function of x, such as shown in Fig. 2.1. Potential energy xo x Fig. 2.1. Variations of the two potentials V,, and V. as a function of the interatomic distance x. 2.2.1. Indicate without calculation whether the stationary states of equation (2.1) are bound states or scattering states (in which case the molecule does not have a stable configuration) in the two cases V = Ve(«r) and V = Vg(z) . What conclusion may be drawn concerning the stability, or the existence, of the molecule XY when the electrons are in the ground state or in the excited state? In your opinion, of the three molecules N2, Hep, HCl, which one could be described by this type of model?2.3 Solutions 13 2.2.2. One can build a simple model for this problem by using Ve(at) = Vi(x) (question 2.1.1) and Ve(a) = Vo(.r) (question 2.1.2). Let the stationary solutions be y(z) in the first case and Ya(z) in the second case. Show that the wave function xi (a) = C (x — 29) e~@*-40)"/2 fora > a9 = for 2 <0, where a = Mwo/h, and C is a normalization constant, is a stationary solution in the second case V = Vy. What is the corresponding energy E? Do solutions with energies less than EF’ exist?) Explain why. 2.2.3. In the initial state, the molecule is assumed to be in the excited elec- tronic state, and its wave function is x; (a). It can fall back into the electronic ground state by radiating the excitation energy E. One can show that the probability of finding the atoms in the final state yq() is proportional to 2 tae= | [ rao) ex) a Calculate this quantity. We recall that eo 2eikY dy = Va 2.2.4, The molecule is assumed to be initially at rest. One measures the velocity v of the atom X, of mass Mx, in the final state of the de-excitation process. Let P(v) be the probability distribution for finding the velocity v. How does P(v) vary with » (one can set v3 = Mfwo/M%). For which value Um of v is P(v) maximum? Calculate v,, for My = My = 6 x 107?” kg, and wy = 3x 10! st? 2.3 Solutions Section 2.1 2.1.1, One has the usual relations nk? k v2ME14 2. Unstable Diatomic Molecule For x < x0, ~x(x) = 0; hence, by writing the continuity equations at x = 20, 1+B=0, ie. B=-1, and gx(2) = isin k(x — x0) for x > xr. The general solution is a wave packet formed with these stationary solutions, w(x, t) = 0 for x < xo, and, for x > x9, we, t) -[ a(k) sin k(x — ao) e# /2M) ag, 0 where a(k) is arbitrary (provided that the expression is square integrable). 2.1.2. We set z = ¢~:r9. For z > 0 the potential is harmonic. The condition V =e for z < 0 implies that the wave functions should vanish at the origin. The stationary solutions are therefore, for z > 0, the eigenfunctions of a harmonic oscillator in z which vanish at z = 0, ie. the Hermite functions of odd indices, the variable being za, with a = Mwo/h: Xa(z) x Dans ((x — 20) Va) for x > xo =0 forr< zo , and E, = Vo + (2n — 4)hwo, n= 1 The ground state is E, = Vo+(3/2)hwo and the corresponding wave function is a(x) x (a — ape #0)? Section 2.2 2.2.1. In case 1 (V = Vg), the system is unbound; one has only scattering states. In case 2 (V = V,), there are some eigenstates of the Hamiltonian corre- sponding to bound states, at least if the well depth in rp is deep enough. The potentials of Fig. 2.1 describe a molecule which is unstable when the elec- trons are in the ground state (the potential V,(r) is repulsive and the molecule dissociates spontaneously into two atoms). Among the three molecules under consideration, only He could be described by this model, since both Nz and HCl are known to be very stable in their ground electronic state. Actually the molecule He2 can also be formed in its electronic ground state since the potential V, has in reality a very shallow minimum. There is a single bound state in this potential well, with a binding energy ¢ ~ —10~7 eV (average in- ternuclear distance of 50 A), which was observed only recently. In contrast, it is quite easy to form and detect Hez molecules in an excited electronic state, for instance in discharges in a cell filled with atomic helium. ' See, e.g., W. Schéllkopf and J. P. Toennies, Science 266, 1345 (1994).2.3 Solutions 15 2.2.2. The first antisymmetric Hermite function (in x — 29) is x4(x), which satisfies all criteria. The corresponding eigenvalue is Ey = Vo + (3/2)hwo which is the lowest energy value for which the wave function vanishes at. the origin. There are no states with energies lower than Ey for the potential Vela) « 2.2.3. Using the results of question 2.1.1 one obtains, setting y = x — x9 20 2 =41C? yen? sin ky dy hee | | © ule )ee(a) de 0 = Vr/Qa) e“*/2). If we take the derivative Kft e/a) 2a ° We have f° e-@¥"/? cos ky dy with respect to k, we obtain: [ yee? sin ky dy = 0 and therefore I= 2nC? ke oF 2.2.4. The above formula gives, up to a normalisation factor, the probability density of the relative momentum of the two atoms in the final state p hk = Mv,, where v, is the relative velocity of the two particles P(p)~ pe? Han?) Since the molecule is at rest in the initial state, the total momentum is zero and the atoms have momenta p and —p. The probability P(v) is, up to a multiplicative factor, P(v) ~ ve vue with o2 = ah? /M3. = Mhwo/M3. The probability density P(v) peaks at the value v = vo. Using the numerical values given in the text, and taking into account that M = Mx/2 for Mx = My, one finds vp © 1600 ms~?.. Neutrino Oscillations At present, most experimental limits on the neutrino masses with zero.! Nevertheless several theoretical and cosmological arguments indi- cate that these masses should be finite. The purpose of the following chapter is to give an example of how one can measure the neutrino mass differences using a quantum oscillation effect. The underlying theory is based on the idea that the two neutrinos v, and v,, are actually two different states of the same physical entity which we will call a “neutrino”. 3.1 Neutrino Masses and the Associated Oscillations In normal dé and more generally in weak interactions, the electron is associated with a neutral particle, the neutrino y.. There exists in Nature a particle, called the pz lepton, whose physical properties appear to be com- pletely similar to those of the electron except for its mass: m,, ~ 200 me. The p lepton, or muon, has weak interactions identical to those of the electron, but it is associated with a different type of neutrino, the muon neutrino v,.. For instance, a neutrino beam produced in an accelerator can interact with a neutron n inside a nucleus to produce a proton via the reactions: wtn—opte Myth pt py (31) whereas the reactions vy, +n — p+ por vy, +n — p+e are never observed. This is how neutrinos can be detected and identified. Similarly, the decay of a 7~ meson can proceed via the two modes: x7 4 +y, (dominant mode), and 7 > ¢ + Ve, (3.2) whereas ™ > +Ve or m~ +e +1, are never observed. The reactions (3.2) are used to produce neutrinos abundantly in accelerator: In these accelerators, one produces neutrinos with a well defined momen- tum p. In all of the following, we shall assume that if m is the mass of the neutrino under consideration, and E its energy, the mass is so small that T See ho the recent experimental results reported by Fukuda et al., Phys. Rev. Lett, 81, 1562 (1998).18 3. Neutrino Oscillations in the experimental conditions one has E >> mc?. Therefore the energy, the momentum and the mass are related by: 204 ; mc B= Vpe + mic ~ pet 2pe and, in very good approximation, the neutrinos travel at the speed of light c. Let ff be the Hamiltonian of a free neutrino of momentum p, and |v;) and |v) the eigenstates of H: Hl) = Esti), lve) = El») where mc! 2pe Ey = pet : Ey = pe+ Here my and mg are the masses of the two states |v;) and |v), and we assume that m; Am», my > m2. Suppose the physical states, corresponding to the particles produced in reaction (3.2), or to the particles detected via reaction (3.1), are not |1) and |v) but rather linear combinations of these states: |ve) = |v1) cos + |v2) sin 14) sin + |v») cos, (3.3) where @ is some mixing angle. 3.1.1. At time f = 0, one produces a neutrino of momentum p in the state |v,,). Calculate |y(t)) in terms of |v1) and |v) . 3.1.2. What is the probability of detecting this neutrino in the state |v.) at a later time ¢? Express the result in terms of 8, ¢, p, t, and Am? = m? — mi. 3.1.3. The detection is done in a target located at a distance | from the production point. Express the above probability in terms of I. 3.1.4, Assume that the mixing in (3.3) is maximum, i.e. @ = 7/4. What is the distance | where the number of detected y. is maximum, assuming that Am?c! = 1 (eV)? and that pe = 10 GeV = 10!° eV? Check that the numerical results make sense considering that present day accelerators are several kilometers long. 3.1.5. In practice, the neutrinos are detected at 1 km from the production point. Knowing that the detector is sensitive to a decrease of 10% in the number of v,,, what limit on Am?c! can one reach by this method? 3.2 Solutions 3.1.1. Initially, the neutrino state is |»(0)) = |v,,) Therefore we have at time t: —|v1) sin 8 + |v») cos 6. |v(t)) = =jr1) sind e4/" + |p) cos. oH,3.2 Solutions 19 3.1.2. The probability amplitude for finding this neutrino in the state |ve) at time ¢ is a = (v|v(t)) =—sin® cos e'*"/* + sing cos@ et?2/f, Hence the probability of detecting a v, at time P= al in? 20 sin? (AE t/(2h)], where AB = By — By = MEamBe _ Amite! 2pe pe 3.1.3. The time delay is t = I/c and the probability is therefore which yields numerically ~~ 12 km. 3.1.5. For a probability P = 0.1, we must have Am®c!/(4hpe2) ~ 0.32, and therefore Amc! ~ 2.6 (eV). In 1998, the first evidence for a neutrino oscillation v,, <> v, was re ported (F, Fukuda et al., Phys, Rev. Lett. 81, 1562 (1998)). The analysis of atmospheric neutrino data resulting from a 535-day exposure of the Super- Kamiokande detector leads to: 5x 10-4 eV? < Amc! < 6x 10-7 eV?.4. Colored Molecular Ions Some pigments are made of linear molecular ions, along which electrons move freely. We derive here the energy levels of such an electronic system and we show how this energy scheme explains the observed color of the pigments. Consider molecular ions of the chemical formula (C,H 42)7, which ean be considered as deriving from polyethylene molecules, such as hexatriene CH 2=CH-CH=CH-CH=CHg, with an even number of carbon atoms, by re- moving a CH* group. In an ion of this type, the bonds rearrange themselves and lead to a linear structure of the following type: (CHp ++» CH-+»CH:+»CH-+-CHy)~ , (4.1) with an odd number n of equally spaced carbon atoms separated by d = 1.4 A. In this structure, one can consider that the +1 electrons of the double bonds of the original polyethylene molecule move independently of one another in a one-dimensional infinite potential well of length L,, = nd: V(x) = +00 for z<0 or t>L, =0 for O0 15 colored? 4,2 Nitrogenous Ions One can replace the central CH group by a nitrogen atom, in order to form ions of the type: (CH ++ CH-+-N-++CH-++ CH)”. (4.3) The presence of the nitrogen atom does not change the distances between atoms but it changes the above square well potential. The modification con- sists in adding a small perturbation dV(x), attractive and localized around the nitrogen atom: V(x) 0 for |r — 42] > 0/2 Vo for where a/d <1 and Vo > 0. 4.2.1. Using first order perturbation theory, give the variations de, of the energy level eg of an electron in the well. For convenience, give the result to leading order in a/d. 4.2.2. Experimentally, one observes that, for the same value of n, the spec- trum of the nitrogenous ions (4.3) is similar to that of the ions (4.1) but that the wavelengths AN are systematically shorter (blue-shifted) if n = 4p + 1, and systematically longer (red-shifted) if n = 4p + 3, than those AY) of the corresponding carbohydrates (4.1). Explain this phenomenon and show that AW and A® are related by: ng wi veal-cy 4 n+2° where 7 is a parameter to be determined. 4.2.3. The nitrogenous ion n = 11 absorbs red light (AS, ~ 6700 A). Check that the ion n = 9 absorbs violet light (AX ~ 4300 A). What is the color of the nitrogenous ion n = 13? 4.2.4, For sufficiently large n, if the nitrogen atom is placed not in the central site but on either of the two sites adjacent to the center of the chain, one observes the reverse effect, as compared to question 4.2.2 . There is a red shift for n = 4p +1 and a blue shift for n = 4p +3. Can you give a simple explanation for this effect?4,3 Solutions 23 4.3 Solutions Section 4.1 4.1.1. The energy levels are ane k? QL? Ek = =1,2, 4.1.2. The ground state energy of the n + 1 electrons is wane Oh R= (n+ 2V(n +3 OF TnL »F ~ bamE2 in Mn+ Nn +3). ‘The energy of the first excited state is wh? ; an? Py= 0+ a lim 1+3)2- (+0) = Bo + re (n +2). 4.1.3. One has hy = Ey — Ey = 7?h?(n + 2)/(2mL2). Since \ = ¢/v, we obtain an absorption wavelength a 8a? m Xe (n+ 2) 4.1.4. From the general form Ay, = 646.33 n?/(n+2), we obtain Ag = 4760 A, Au = 6020 A, Ay3 = 7280 A, in good agreement with experiment. For smaller n, the wavelengths Ay = 3520 A and 5 = 2310 A are in the ultraviolet part of the spectrum. The ions n <7 do not absorb visible light and are thus not colored. For n > 15, the wavelengths Ais = 8550 A and Ayz = 9830 A are in the infrared region. These ions do not absorb visible light in transitions from the ground state to the first excited state. They are nevertheless colored because of transitions to higher excited states. Section 4.2 4.2.1. The normalized wave functions are y(r) = \/2/L, sin(ktz/L,) . One has Ln ta/2 , ben [av(e) vel) |? dx = ~Vo [ Ive(e)|? dx f nna/2 Setting y = oy, (2. heb ba = -74 I. oun? (5 4 St) dy. There are two cases: — L,,/2, one obtains24 4, Colored Molecular Ions © Keven: - 2Vo { . (=) . 5. 3 dex sin? (“7% ) dy, ie. dey = O((a/d)*) Ln Jas? nd The perturbation is negligible. © kodd: Wu re 2 (ery ben = cos} iy. ee Tf 8 Ge dy To first order in a/d, we have dé_ = —2Vya/nd < 0. The exact formulas are: be, - -2 fo-cyte (ka “Ee f-eirtese( 2) The (single particle) energy levels corresponding to even values of k are prac- tically unaffected by the perturbation; only those with k odd are shifted. This is simple to understand. For k even, the center of the chain is a node of the wave function, and the integral defining dex is negligible. For k odd, on the contrary, the center is an antinode, we integrate over a maximum of the wave function, and the perturbation is maximum. 4.2.2. The perturbation to the excitation energy Ey — Ey of question 4.1.2 is OE = be (n+s)/2 — 8€(n41)/2 « © (n+1)/2 even, ie. n = 4p +3, den 41/2 = 0, Wow nd bE = be(nyayp2 = — <0. © (n+1)/2 odd, ie. n= 4p $1, de¢n4sy/2 = 0, 2Voa nd bE = 6 (npyy/2 = >o. We can summarize these results in the compact form awh? (n + 2) apn er aL By Bo + 8B = oT ee ( Cd 13) with y = 4Vgamd/(h)? . We therefore obtain the desired relation 2 = on = 1-(-1)? : aN 1—(-1) Ty For n = 4p+1, the perturbation increases the excitation energy, and decreases An. For n = 4p + 3, it decreases the excitation energy, and increases A,,.4.3 Solutions 25 4.2.3. For the ion n = 11 one obtains the relation (1 — 114/13) = 6000/6700, therefore y ~ 0.12 and AN = 4330 A, in good agreement with experiment. One also obtains A}, = 6600 A, which absorbs red light and gives a green color to the corresponding pigment. Note that the presence of the nitrogen atom yields A} < MY, whereas APs > 9). 4.2.4. The distance between a node and an antinode of wx(x) is da = nd/ (2k). For k = (n+ 1)/2 and k = (n + 3)/2 which are the states of interest, we will have respectively dx = nd/(n +1) and 6x = nd/(n+ 3), ie. dz ~ d if n is large. Consequently, if a wave function has a node at the center, it has an antinode in the vicinity of the two adjacent sites, and vice versa. The reasoning is therefore similar to the answer to questions 4.2.1 and 4.2.2, with the reverse effect. The lines are red-shifted if n = 4p + 1 and they are blue-shifted if n = 4p + 3.5. Schrédinger’s Cat The superposition principle states that if |.) and |)) are two possible states of a quantum system, the quantum superposition (|.) + |¢s))/V2 is also an allowed state for this system. This principle is essential in explaining interference phenomena. However, when it is applied to “large” objects, it leads to paradoxical situations where a system can be in a superposition of states which is classically self-contradictory (antinomic). ‘The most famous example is Schrddinger’s “cat paradox” where the cat is in a superposition of the “dead” and “alive” states. The purpose of this chapter is to show that such superpositions of macroscopic states are not detectable in practice. They are extremely fragile, and a very weak coupling to the environment suffices to destroy the quantum superposition of the two states |a) and |»). 5.1 The Quasi-Classical States of a Harmonic Oscillator In this problem, we shall consider high energy excitations of a one-dimensional harmonic oscillator, of mass m and frequency w. The Hamiltonian is written oe yy Pol one H= P+ mute. mm * 3 We denote the eigenstates of H by {|n)}. The energy of the state |n) is By = (n+ 1/2)hw. 5.1.1, Preliminaries. We introduce the operators b/Vmhw and the annihilation and creation operators 4 5 (4-1) v2 We recall the commutato .a!] = 1, and the relations: H = hue(N + 1/2) and N|n) (a) Check that if one works with functions of the dimensionless variables X and P, one has a a= (x + iP)28 5. Schrédinger’s Cat (b) Evaluate the commutator [Nd], and prove that a|n) = Ynjn ~ 1) (5.1) to within a phase factor which we set equal to 1 in what follows. Using (5.1) for n = 0 and expressing 4 in terms of X and P, calculate the wave function of the ground state W(X) and its Fourier transform yo(P). It is not necessary to normalize the result. ( 5.1.2. The quasi-classical states. The eigenstates of the operator @ are called quasi-classical states, for reasons which we now examine. Consider an arbitrary complex number a . Show that the following state ja) =e PO sin) (6.2) la) = ala). 5.1.3. Calculate the expectation value of the energy in a quasi-classical state la). Calculate also the expectation values (x) and (p) and the root mean square deviations Ax and Ap for this state. Show that one has Ax Ap = h/2. is a normalized eigenstate of @ with eigenvalue a: 5.1.4. Following a similar procedure as in question 5.1.1(¢) above, determine the wave function .(X) of the quasi-classical state |a), and its Fourier transform ya(P). Again, it is not necessary to normalize the result. 5.1.5. Suppose that at time ¢ Jao) with a9 = pe’? where p scillator is in a quasi-cla (a) Show that at any later time ¢ the oscillator is also in a quasi-classical state which can be written as e~*/2|a(t)). Determine the value of a(¢) in terms of p,@,w and t. (b) Evaluate (x), and (p);. Taking into account the result of question 5.1.3, and assuming that |a| >> 1, justify briefly why these states are called sical”. 5.1.6. Numerical example. Consider a simple pendulum of length 1 meter and of mass | gram. Assume the state of this pendulum can be described by a quasi-classical state. At time tf = 0 the pendulum is at (2) = | micrometer from its classical equilibrium position, with zero mean velocity. (a) What is the corresponding value of a(0)? (b) What is the relative uncertainty on its position Ax/xo? (c). What is the value of a(t) after 1/4 period of oscillation? 5.2 Construction of a Schrédinger-Cat State During the time interval [0,7], one adds to the harmonic potential, the cou- pling W = hg (ata)? .5.3 Quantum Superposition Versus Statistical Mixture. 29 We assume that g is much larger than w and that wT « 1. Hence, we can make the approximation that, during the interval [0,7], the Hamiltonian of the system is simply W. At time f = 0. the system is in a quasi-classical state |u(0)) = Ja). 5.2.1. Show that the states |r) are eigenstates of W’, and write the expansion of the state |y(7)) at time T on the basis {|n)} 5.2.2. How does |y)(T)) simplify in the particular cases T = 2x/g and T = alg? 5.2.3, One now chooses T = 7/2g. Show that this gives lW(T)) = a (ela) +e" -a)) « (5.3) 5.2.4. Suppose a. is pure imaginary: a = ip. (a) Discuss qualitatively the physical properties of the state (5.3). (b) Consider a value of |a| of the same order of magnitude as in question 5.1.6. In what sense can this te be considered a concrete realization of the “Schrédinger cat” type of state mentioned in the introduction? 5.3 Quantum Superposition Versus Statistical Mixture We now study the properties of the state (5.3) in a “macroscopic” situation al > 1. We choose a pure imaginary, @ = ip, and we set po = pV2mhw. 5.3.1. Consider a quantum system in the state (5.3). Write the (non-normal- ized) probability distributions for the position vs for the momentum of the tem. These probability distributions are represented in Fig. 5.1 for a = Interpret these distributions physically. | Xx P -3-2-10123 -10-5 0 5 10 Fig. 5.1. Probability distributions for the position and for the momentum of a system in the state (5.3) for a = 5i. The quantities X and P are the dimensionless variables introduced in the first part of the problem. The vertical scale is arbitrary.