22251 PRESTON POLYTECHNIC LIBRARY & LEARNING RESOURCES SERVICE This book must be returned on or before the date last stamped 5 530.12 MES cl ho A/C 022319 1 | Lan t eo TIMINLMNMNNAI NY Se BY® “so107 000 573 334 TT = [| PLEASE PETHON To rAMDIIC TNRTCATENFROM THE SERIES IN PHYSICS University of Amsterdam University of Groni ips’ Research Laboratories, Eindhoven Monographs : Bax, Elementary Introduction to Molecular §) Po Boncu Buorvien and'S."V. ‘beasuimov, The Green Function Method in Statistical Mechanics L. Grezpuno, R, pe Groor and P. Mazvz, Non-Equilibrium Thermodynamics . Hosemaxw and S. N. Baoowt, Direct Analysis of Diffraction by Matter H. J, Lexis, Beta for Pedestrians PH. E. Mever and E. Baver, Group Theory. The Application to Quantum ‘Mechanies 8. Ranmes, The Wave Mechanics of Electrons in Metals D, Tr Haar, Elements of Hamiltonian Mechanics 8. Tomowaca, Quantum Mechanics ition of Electror tie Waves in Plasma B. v. v. 8. R. Edited Volumes: J. pa Bors end G. E, Usumrmsox (editore) Studies in Statistical Mechanics, ol FUNDAMENTAL PROBLEMS IN STATISTICAL MEOHANICS. Proceedings of the ‘NUFFIC International Summer Course in Science (Nijenrode, 1961 G._M. Grawane and A. C. Hort1s Hauusrr (editors), Proceedings of the 7th International Conference on Low srature Physics (Toronto, 1960) H.C, van pz Hoxsz, C. ps Jaczr and A. F. Moore (editors), Space Research II. cosedings of the Becond International Space Selance Symposium (Florence, 1961) H. Katuaraxn-Bust, (editor), Space Research, Proceedings of the Ist Inter- ‘national Space Science Symposium (Nice, 1960) H Macken (editor), Proceedings of the ‘6th International Conference on ‘Tonization Phenomena in Gases (Munich, 1961) S. F. Smcee (editor), Progress in the Astronsutical Soiences, Vol. I E, Wour (editor), Progress in Optics, Vol. I QUANTUM MECHANICS VOLUME II ALBERT MESSIAH ‘Saclay, France TRANSLATED FROM THE FRENCH BY J. POTTER Oreay (S.-et-0.), France 1965 NORTH-HOLLAND PUBLISHING COMPANY AMSTERDAMNo part of this book may be reproduced in any form by print, photoprint, microfilm or any other meane without written permission from the publisher ORIGINAT TITLE: MECANIQUE QUANTIQUE, VOL. 11 aokCANIQUE QUANTIQUE I AND It WERE PUBLISHED BY DUNOD, PARIS PUBLISHER: NORTH-HOLLAND PUBLISHING COMPANY, AMSTERDAM SOLE DISTRIBUTORS FOR U.S.A.t INTERSCIENCE PUBLISHERS, 8 division of JOHN WILEY & SONS, INC. - NEW YORK ©1961 North-Holland Publishing Company, Amsterdam Second Printing 1964 Third Printing 1965 ve? HARRIS COLLEGE & PRESTON Fluctuat nec mergiturOUTLINE VOLUME I ‘THE FORMALISM AND ITS INTERPRETATION I. Tum Omioms or Quanrom Taxory TL. Marrer Waves axp tae Scardprvamn Equariox TIL. Ove-Dneewstowat Quanrizep SysTems TV. Sraristi0a, INTERPRETATION AND TRE UNCERTAINTY RELATIONS V. Dsvuzormenz or THe Formanism op Wave MECHANICS AND 17S INTERPRETATION VI. Crassicar Arrroxnmation aNp THE WKB Merson VII. Gunzrax Formacism: (A) Mataemavicar Framework VIL. Gewsrat Formarism: (B) Pxysican Cowrexr SIMPLE SYSTEMS IX, Separation oy Vartanues. CawrnaL POTENTIAL X. Scarrsema Prosrems. Prase Surrrs XI. Tae Covroms Ivreraction XI. Tas Harmonre Oscritaror Avpenprx A. Disrrpurions, d-rONCTION, AND FouRmmn TRANSFORMATION Avrenprx B. SPEcrAL FuNevions aNp AssociaTep FoRMuLAr Ispex vo Vouume I VOLUME II SYMMETRIES AND INVARIANCE XII. Axourar Momewrem in Quantum Mnomantos XIV. Ipexmica: Parricues. Tas Pavur Excuusio Prixcrere XV. Ixvanraxce anp Conservation Laws. Tam REversa METHODS OF APPROXIMATION XVI. Sramonany Perrusations XVI, Avrroxntare Soxvrioxs or THs Equation or Motion XVII. Vartarionan Merrop aNp Reuarep Promuems XIX. Coxusiox THzory ELEMENTS OF RELATIVISTIC QUANTUM MECHANICS XX. Retarvistio Tuzory or ras Execraox XXI. Quansmarion or THE Execrnomacxetic Freup Avpexprx ©, Vector Apprrion Corrricrents ap RozatioN MATRICES Arrnxpix D. Exzmzxrs or Grour Tazory Genwran INpExi mr. Iv. CONTENTS oF vouumE 11 PART THREE SYMMETRIES AND INVARIANCE CHAPTER XIII ANGULAR MOMENTUM IN QUANTUM MECHANICS 1, Introduction . EIGENVALUES AND EIGENFUNCTIONS OF ANGULAR MOMENTUM 2. Definition of angular momentum. 3. Characteristic algebraic relations. 4. Spectrum of J? and Jz, 6. Eigenvectors of J? and Je. Construction of the invariant subspaces #W). 6. Standard representation {J?J:}. 7. Conclusion. ORDITAL ANGULAR MOMENTUM AND THE SPHERICAL HARMONICS 8. The spectrum of [# and 9, Definition and construction of the spherical harmonies. ANGULAR MOMENTUM AND ROTATIONS ©. 0. . 1. 10, Definition of rotation, Euler angles. 11, Rotation of a physi- cal system. Rotation operator. 12, Rotation of observables. 13. Angular momentum and infinitesimal rotations. 14. Con- struction of tho operator R (« 6 y). 15. Rotation through an ‘angle 2a and half-integral angular momenta. 16. Irreducible invariant subspaces. Rotation matrices RW. 17. Rotational invarianee and conservation of angular momentum. Rotational degeneracy. 18. The hypothesis of electron spin. 19. Spin } and the Pauli matrices. 20, Observables and wave functions of spin } particle. Spinor fields. 21. Vector fields and particles of spin 1. 2% Spin- dependent interactions in atoms. 23. Spin-dependent nucleon- nucleon interactions. ADDITION OF ANGULAR MOMENTA 24. Tho addition problem. 25. Addition theorem for two angular momenta. 26, Applications and examples. 27. Eigenvectors of the total angular momentum. Clebsch-Gordon coefficients. 28. Application: two-nucleon system. 29. Addition of three or more angular momenta, Racah coefficients. ‘3sj’ 507 508 519 523 555QUANTUM MECHANTOS InmeDUCIBLE TENSOR OFERATORS «© 2 | | ww... 30. Representation of scalar operators. 31. Irreducible tensor operators. Definition. 32. Representation of irreducible tensor operators. Wigner-Eckhart theorem. 33. Applications. CHAPTER xIV SYSTEMS OF IDENTICAL PARTICLES. PAULI EXCLUSION PRINCIPLE 1, Identical particles in quantum theory Swsnmrnmation rostuaTe ©... 2, Similar particles and the symmetrical representation. 3. Por- mutation operators. 4. Algebra of permutation operators. Sym- metrizers and antisymmetrizers. 6. Identical particles and the symmetrization postulate. 6. Bosons and Bose-Kinstein statis- tics. 7. Fermions and Fermi-Dirao statistics. Exclusion prin- ciple. 8. It is always necessary to symmotrize the wave-function. 9%. Collision of two spinless identical particles. 10. Collision of two protons. 11. Statistics of atomic nuclei. 12. Complex one patel field approximation. 19. The Thomas-Fermi model of the atom. 14, Nucloon systems and isotopic spin. 16. Utility of isotopic spin. Charge independence. CHAPTER xv INVARIANCE AND CONSERVATION THEOREMS. TIME REVERSAL 1. Introduction . ‘MATREMATICAL COMPLEMENTS, ANTILINEAR OPERATORS . . 2. Threo useful theorems. 3, Antilinear operators in Hilbert space. 4. Antilinear transformations. 5. Antilinear operators ‘and representations. ‘TRANSFORMATIONS AND GROUPS OF TRANSFORMATIONS... 6. Transformations of the dynamical variables and dynamical states of a system. 7, Groups of transformations, 8 Groups of transformation operators 9. Continuous groups and infinitesi- mal transformations. Translations. Rotations. 10. Finite groups. Reflections. INVARIANOE OF THE EQUATIONS OF MOTION AND CONSERVATION 11, Invariant observables, 12. Symmetry of the Hamiltonian and conservation laws. 13. Invariance properties and the evolution 569 582 586 32 633 643 655 CONTENTS: of dynamical states. 14. Symmetries of the Stark and Zeeman effects. IV. Time REVERSAL AND THE PRINCIPLE OF MICROREVERSISILITY 15, Time translation and conservation of energy. 16. Time reversal in classical mechanics and in quantum mechanics. 17. ‘The time-reversal operation. Spinless particle. 18, General defi- nition of time reversal. 19, Time reversal and complex conjuga- tion. 20. Principle of microroversibility. 21. Consequence: ‘Kramers degeneracy. 22, Real rotation-invariant Hamiltonian. PART FOUR METHODS OF APPROXIMATION CHAPTER XVI STATIONARY PERTURBATIONS 1, General introduction to Part Four . I. PERTURBATION OF A NON-DEGENERATE LEVEL. 2... 2. Expansion in powers of the perturbation, 3. First-order per- turbations. 4. Ground state of the helium atom. 5. Coulomb energy of atomic nuclei. 6. Higher-order corrections. 7. Stark effect for a rigid rotator. TL, PERTURBATION OF A DEGENERATE LEVEL, sesso 8 Elementary theory. 9. Atomic levels in the absence of spin- orbit forees. 10. Spin-orbit forces. LS and jj coupling. 11. The atom in LS coupling. Splitting due to spin-orbital coupling. 12. ‘The Zeeman and Paschen-Back effects. 13, Symmetry of H and removal of degeneracy. 14. Quasi-degeneracy. IIL Expiicrr Forss FOR THE PERTURBATION EXPANSION IN ALL cactaiiatitale cyrainey mecaiye 8, Nota, Yeriet oe 15. The Hamiltonian H and its resolvent G(2). 16. Expansion of G(e), P and HP into power series in V. 17. Calculation of eigenvalues and eigenstates. CHAPTER xvIr APPROXIMATE SOLUTIONS OF THE TIME-DEPENDENT SCHRODINGER EQUATION 1. Change of “representation” and perturbation treatment of a part of the Hamiltonian 722 724QUANTUM MECHANICS 4. Case when V is independent of time. Conservation of unpor- turhed energy. 5. Application to the calculation of rose suction inthe Born approximation. 6, Periodic perturbation. Resonances. SUDDEN OR ADIABATIO CHANGE OF THE HAMILTONIAN . 7. The problem and the results. 8. Rapid passage and the sudden ‘pproximation, 9. Sudden reversal of a Sap field. 10. Adiabatic passage. Generalities. Trivial case. 11. “Rotating axis ropreeentation”. "12. Proof of the adiabatic theorem, 13. Adia- batie approximation. 14. Adiabatic reversal of a magnetic field. OmAPTER XviIr 739 THE VARIATIONAL METHOD AND ASSOCIATED PROBLEMS a. a. a. 1. The Ritz variational method . VARIATIONAL METHOD FOR BOUND STATES... e 2. Variational form of the eigenvalue problem. 3. Variational calculation of discrete levels. 4. A simple example: the hydrogen atom. 5. Discussion. Application to the calculation of excited levels. 6. Ground state of the helium atom. ‘Tue Hartree ap Fock-Dirac aroms. 7. Theself-consistent field method. 8, Calculation of [0]. 9. The Fock-Dirac equations. 10. Discussion. 11. The Hartree equa- tions. ‘Tw eravorune oF wouecunes |. 12. Generalities. Separation of the electronic and nuclear motions. 13. Motion of the electrons in the presence of fixed nuclei. 14. ‘The adiabatic approximation. 15. Hamiltonian for the nuclei in the adiabatie approximation. 16. The Born-Oppenheimer method. 17, Notions on diatomic molecules. CHAPTER XIx COLLISION THEORY 1. Introduction. FREE WAVE GREEN'S FUNCTION AND THE Bony APPROXIMATION 2, Integral representations of the seattoring amplitude. 3. Cross sections and the 7 matrix. Microreversibility. 4. The Born approximation. 5. Integral equation for scattering. 6. The ‘Born expansion. 7. Validity criterion for the Born approxima- tion, 8. Elastic scattering of electrons by an atom. 9. Central Potential. Calculation of phase shifts. 10. Groen’s function as fan operator. Relation to the resolvent of Ho GENERALIZATION TO DISTORTED WAVES 11, Generalized Born approximation. 12, Generalization of tho 762 763 778 731 801 802 822 am. Iv. m. Born expansion. 13. Green’s functions for distorted waves. 14. Applications. Definition and formal properties of T. 15. Note on the I/r potentials. ComPLEX COLLISIONS AND THE BORN APPROXIMATION... 16. Generalities. Cross sections. 17. Channels. 18, Calculation of eross sections. 7’ matrices. 19. Integral representations of the transition amplitude. 20 The Born approximation and its generalizations. 21. Scattering of fast electrons by an atom. 22. Coulomb excitation of nuclei. 23. Green's functions and integral equations for stationary scattering waves. 24. Scattering of @ particle by two scattering centers. 25. Simple scattering. Interference. 26. Multiple scattering. ‘VARIATIONAT, CALCULATIONS OF TRANSITION AMPLITUDES 27. Stationary oxpressionsforthe phase shifts. 28. Thovariational calculation of phase shifts. Discussion. 20. Extension to complex collisions. GENERAL PROPERTIES OF THE TRANSITION MATRIX 20. Conservation of flux. Unitarity of tho S matrix, 81. ‘Tho Bohr-Peierls-Plaozek relation (optical theorem). 32. Miororever- sibility. 33. Invariance properties of the 7” matrix. PART FIVE ELEMENTS OF RELATIVISTIC QUANTUM MECHANICS OmAPTER xx THE DIRAC EQUATION GuweRaL neTRODUOTION, © 6 6 1. Relativistic quantum mechanics. 2. Notation, various con- ventions and definitions. 3. The Lorentz group. 4. Classical relativistic dynamics. ‘Tae Diao AND Kusix-Gonpox squations - oie 5. The Klein-Gordon equation. 6. The Dirac equation. 7. Con- struction of the space 61. Dirac representation. 8, Covariant form of the Dirac equation. 9. Adjoint equation. Definition of the current. INVARIANCE PROPERTIES OF THE DInac EQUATION . . 10, Properties of the Dirac matrices. 11, Invarianes of the form of the Dirac equation in an orthochronous chango of referential. 12. Transformation of the proper group. 13. Spatial reflection and the orthochronous group. 14, Construction of covariant quantities. 15. A second formulation of the invarianes of form: transformation of states. 16. Invariance of the law of motion. 858 815 884 896wi L m1 QUANTUM MECHANICS 17, Transformation operators. Momentum, angular momentum, Parity. 18, Conservation laws and constants of the motion, 19. Time reversal and charge conjugation. 20. Gauge invariance. Dynamical variables of a Dirac particle. 23, The free electron. Plane waves. 24. Construction of the plane waves by a Lorenta ‘transformation. 25. Central potential. 26, Freespherical waves. 27. The hydrogen atom. Now-Retatrvisrio ur or TH Dirac xquarion . .. 28. Large and small components. 29. The Pauli theory as the non-relativistic limit of the Dirac theory. 30. Application: hyperfine structure and dipole-dipole coupling. 31. Higher-order corrections and the Foldy-Wouthuyson transformation. 32. FW transformation for a free particle. 33. FW transformation for @ particle in a field. 34. Electron in a central electrostatic potential, 35. Discussions and conclusions. NEGATIVE ENERGY SOLUTIONS AND POSITRON THEORY. . 36. Properties of charge conjugate solutions. 37. Abnormal behavior of the negative energy solutions. 38. Reinterpretation Of the negative energy states. Theory of “holes” and positrons, 39. Difficulties with the “hole” theory. OWAPTER xx1 FIELD QUANTIZATION. RADIATION THEORY Vass 0 Giese ihre cr marr ahead QuaNTIZATION OF 4 REAL SCALAR FIELD 2... ‘i 2. Classical free field. Normal vibrations. 3. Quantization of the free field. 4. Lagrangian of the field. Momentum conjugate to Mr). 6. Complex basis functions. 6. Plane waves. Definition Of the momentum. 7. Spherieal waves. Definition of the angular momentum, 8. Space and time reflections. Courtine wire ax atomic system. 2. . 1. 9. Coupling to @ system of particles. 10. Weak coupling and Perturbation treatment. 11. Level shifts, 12. Emission of a corpuscle. 13, Quantum theory of decaying states. Line widen. 14, Elastic scattering. Dispersion formula. 15. Resonance scat tering. Formation of a metastable state. 16. Absorption of a corpusele (photo-clectric effect). Radiative capture. CUASSICAL THEORY OF ELECTROMAGNETIC RADIATION. . 17. The equations of the classical Maxwell-Lorentz theory. 18, Symmetries and conservation laws of the classical theory. 19. 919 949 959 960 979 1009 20. Blectro- Self-energy and classicai radius of the electron. magnetic potential. Choice of the gauge. 21. Longitudinal and ‘transverse parts of a vector field. 22. Elimination of the longi- tudinal field. 23. Energy, momentum, angular momentum. 24. ‘Hamiltonian for free radiation. 25, Hamiltonian for radiation coupled to a set of particles. IV. QUANTUM THEORY OF RADIATION «6 ee es es 26. Quantization of free radiation. Photons. 27. Plane waves. Radiation momentum. 28. Polarization. 20. Multipole ex- pansion. Photons of determined angular momentum and parity. 30. Coupling with an atomic system. 31. Emission of a photon by an atom. Dipole emission. 32. Low energy Compton scattering. ‘Tho Thomson formula. Appenprx C. VECTOR ADDITION COEFFICIENTS AND ROTATION MATRICES Appenprx D. ELEMENTS OP GROUP THEORY . . | Genera: INDEX... 1029 1053 1079 1125‘Mon Dieu! ma chére, que ton pére @ la forme enfonede dans la matiére! (Les Précieuses Ridicules, V1). PART THREE SYMMETRIES AND INVARIANCE j 'CHAPTER X1I1 ANGULAR MOMENTUM IN QUANTUM MECHANICS 1. Introduction Symmetry properties of the equations of motion play a large role in Quantum Mechanics as in Classical Mechanics. A systematic and general examination of symmetries and of their consequences will be made in Chapter XV. The present chapter is devoted to symmetries with respect to rotations—one of the most important types. In Quantum Mechanics, as in Classical Mechanics, the rotation of a system brings in its angular momentum, and the rotational invariance of the equations of motion is reflected in the angular momentum being a constant of the motion. Differences with Classical Mechanics arise because the angular momentum is not an ordinary vector but ‘a veetor operator, whose three components do not commute. In section I, we define the angular momentum by the commutation rules for its components J, J, Je (relations (XIII.3)] and solve the eigenvalue problem for JP and J using only these rules and the fact that these three components are observables. The method, due to Dirac, is analogous in many ways to the treatment of the harmonic oscillator in Chapter XII. Section II is devoted to a special ease, the orbital angular momentum of a particle and the construction of the corresponding eigenfunctions (the spherical harmonics). In section III we establish the connection between rotations and angular momentum. The rotation of a physical system is effected by @ certain operator which depends on the components of the total angular momentum, and whose form is given by equation (XIII.60). We show that invariance of the equations of motion under rotation is equivalent to the condition that the Hamiltonian commute with the three angular momentum components, whence the law of con- servation of angular momentum. Experiment shows that most particles possess an intrinsic angular momentum, the spin. The notion of spin is examined in section TV. Section V is devoted to the important problem of the addition of angular momenta. ‘The different operators of Quantum Mechanics may be characterized 507