Introduction to Relativistic Quantum Chemistry

Kenneth G. Dyall, Knut Faegri

  • 出版商: Oxford University Press
  • 出版日期: 2007-04-19
  • 售價: $1,150
  • 貴賓價: 9.5$1,093
  • 語言: 英文
  • 頁數: 544
  • 裝訂: Hardcover
  • ISBN: 0195140869
  • ISBN-13: 9780195140866
  • 相關分類: 化學量子

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This book provides an introduction to the essentials of relativistic effects in quantum chemistry, and a reference work that collects all the major developments in this field. It is designed for the graduate student and the computational chemist with a good background in nonrelativistic theory. In addition to explaining the necessary theory in detail, at a level that the non-expert and the student should readily be able to follow, the book discusses the implementation of the theory and practicalities of its use in calculations. After a brief introduction to classical relativity and electromagnetism, the Dirac equation is presented, and its symmetry, atomic solutions, and interpretation are explored. Four-component molecular methods are then developed: self-consistent field theory and the use of basis sets, double-group and time-reversal symmetry, correlation methods, molecular properties, and an overview of relativistic density functional theory. The emphases in this section are on the basics of relativistic theory and how relativistic theory differs from nonrelativistic theory. Approximate methods are treated next, starting with spin separation in the Dirac equation, and proceeding to the Foldy-Wouthuysen, Douglas-Kroll, and related transformations, Breit-Pauli and direct perturbation theory, regular approximations, matrix approximations, and pseudopotential and model potential methods. For each of these approximations, one-electron operators and many-electron methods are developed, spin-free and spin-orbit operators are presented, and the calculation of electric and magnetic properties is discussed. The treatment of spin-orbit effects with correlation rounds off the presentation of approximate methods. The book concludes with a discussion of the qualitative changes in the picture of structure and bonding that arise from the inclusion of relativity.

Table of Contents

PART I: Foundations
1. Introduction 3
2. Basic Special Relativity
3. Relativistic Electromagnetic Interactions 17
PART II: The Dirac Equation: Solutions and Properties
4. The Dirac Equation 33
5. Negative-Energy States and Quantum Electrodynamics 51
6. Relativistic Symmetry 65
PART III: Four-Component Methodology
9. Operators, Matrix Elements and Wave Functions under Time Reversal
10. Matrices and Wave Functions under Double-Group Symmetry 147
11. Basis Set Expansions of Relativistic Electronic Wave Functions 173
12. Correlation Methods 207
13. Molecular properties 233
14. Density Functional Approaches to Relativistic Quantum Mechanics 261
PART IV: Approximations to the Dirac equation
15. Spin Separation and the Modified Dirac Equation 277
16. Unitary Transformations of the Dirac Hamiltonian 295
17. Perturbation Methods 321
18. Regular Approximations 353
19. Matrix Approximations 377
20. Core Approximations 393
21. Spin-orbit Configuration Interaction Methods 423
PART V: The nature of the relativistic chemical bond
22. Relativistic Effects on Molecular Bonding and Structure 449
Appendix A: Four-vector quantities 473
Appendix B: Vector relations 474
Appendix C: Elements of group theory 475
Appendix D: Group tables 477
Appendix E: Change of Metric for Modified Wave Functions 483
Appendix F: Two-Electron Gauge Terms for the Modified Dirac Operator 485
Appendix G: The Second-Order Term of the Douglas-Kroll Expansion 487
Appendix H: Transformed Operators for Electric and Magnetic Properties 489
Appendix I: Gauge Term Contributions from the Breit Interaction to the Breit- Pauli Hamiltonian 492
Appendix J: Approximations in Relativistic Density Functional Theory 494
Appendix K: The Cowan-Griffin and Wood-Boring Equations. 496
Appendix L: Supplementary Reading 497
Bibliography 500