OE isiaeies Gi ntoeatsany ae | fy | Pe Zan DS ie ESSAYS PSEQuantum Chemistry Fifth Edition IRA N. LEVINE Chemistry Department Brooklyn College City University of New York Brooklyn, New York sg 3 w e 2 PRENTICE HALL, Upper Saddle River, New Jersey 07458To my quantum chemistry students: Vincent Adams, Ricardo Alkins, Byongjae An, Salvatore Atzeni, Abe Auerbach, Andrew Auerbach, Joseph Barbuto, David Baron, Christie Basseth, Sene Bauman, Howard Becker, Michael Beitchman, Anna Berne, Kamal Bharucha, Susan Bienenfeld, Mark Blackman, Toby Block, Allen Bloom, Demetrios Boyce, Diza Braksmayer, Steve Braunstein, Paul Brumer, Jean Brun, Lynn Caporale, Richard Carter, Shih-ching Chang, Ching-hong Chen, Hongbin Chen, Huifen Chen, Kangmin Chen, Kangping Chen, Guang-Yu Cheng, Yu-Chi Cheng, El-hadi Cherchar, Jeonghwan Cho, Ting-¥i Chu, Kyu Suk Chung, Joseph Cincotta, Robert Curran, Joseph D’Amore, Ronald Davy, Aly Dominique, Xiao-Hong Dong, Barry DuRon, Azaria Eisenberg, Myron Elgart, Musa Elmagadam, Anna Eng, Stephen Engel, Quianping Fang, Larry Filler, Seymour Fishman, Donald Franceschetti, Mark Freilich, Michael Freshwater, Tobi Eisenstein Fried, Joel Friedman, Kenneth Friedman, Aryeh Frimer, Mark Froimowitz, Paul Gallant, Hong Gan, Mark Gold, Stephen Goldman, Neil Goodman, Roy Goodman, Isaac Gorbaty, Steven Greenberg, Michael Gross, Zhijie Gu, Judy Guiseppi-Henry, Lin Guo, Runyu Han, Sheila Handler, Warren Hirsch, Richard Hom, Kuo-zong Hong, Mohammed Hossain, Fu-juan Hsu, Bo Hu, Jong-chin Hwan, Leonard Itzkowitz, Mark Johnson, Kirby Juengst, Abraham Karkowsky, Spiros Kassomenakis, Michael Kittay, Colette Knight, Barry Kohn, Yasemin Kopkalli, David Kurnit, Athanasios Ladas, Alan Lambowitz, Bentley Lane, Yedidyah Langsam, Surin Laosooksathit, Chi-Yin Lee, Stephen Lemont, Elliot Lerner, Jiang Li, Zheng Li, Israel Liebersohn, Joel Liebman, Steven Lipp, Letian Liu, James Liubicich, John Lobo, Rachel Loftoa, Wei Luo, Dennis Lynch, Mohammad Malik, Pietro Mangiaracina, Louis Maresca, Allen Marks, Tom McDonough, Antonio Mennito, Ira Michaels, Bin Mo, Paul Mogolesko, Safrudin Mustopa, Irving Nadler, Stuart Nagourney, Kwazi Ndlovu, Harold Nelson, Wen-Hui Pan, Padmanabhan Parakat, Frank Pecci, Albert Pierre-Louis, Paloma Pimenta, Eli Pines, Jerry Polesuk, Arlene Gallanter Pollin, James Pollin, Lahanda Punyasena, Cynthia Racer, Munira Rampersaud, Caleen Ramsook, Robert Richman, Richard Rigg, Bruce Rosenberg, Martin Rosenberg, Robert Rundberg, Edward Sachs, Mahendra Sawh, David Schaeffer, Gary Schneier, Neil Schweid, Judith Rosenkranz Selwyn, Gunnar Senum, Steven Shaya, Ailen Sheffron, Wu-mian Shen, Yuan Shi, Lawrence Shore, Alvin Silverstein, Barry Siskind, Jerome Solomon, De Zai Song, Henry Sperling, Joseph Springer, Charles Stimler, Helen Sussman, David Trauber, Choi Han Tsang, King-hung Tse, Michele Tujague, Irina Vasilkin, Natalya Voluschuk, Sammy Wainhaus, Alan Waldman, Huai Zhen Wang, Zheng Wang, Robert Washington, Janet Weaver, William Wihlborg, Peter Williamsen, Shiming Wo, Guohua Wu, Jinan Wu, Xiaowen Wu, Ming Min Xia, Wei-Guo Xia, Xiaoming Ye, Ching-Chun Yiu, Wen Young, Xue-yi Yuan, Ken Zaner, Juin-tao Zhang, Hannian Zhao, Li Li Zhou, Shan Zhou, Yun Zhou.Contents PREFACE ix 1 THE SCHRODINGER EQUATION 1 1.1 Quantum Chemistry, 1 1.2 Historical Background of Quantum Mechanics, 2 1.3 The Uncertainty Principle, 5 1.4 The Time-Dependent Schrodinger Equation, 7 1.5 The Time-Independent Schrédinger Equation, 12 1.6 Probability, 14 1.7 Complex Numbers, 16 1.8 Units, 18 1.9 Summary, 18 THE PARTICLE INA BOX 21 2.1 Differential Equations, 21 2.2 Particle in a One-Dimensional Box, 22 2.3. The Free Particle in One Dimension, 28 2.4 Particle in a Rectangular Well, 29 2.5 Tunneling, 31 2.6 Summary, 32 OPERATORS 35 3.1 Operators, 35 3.2 Eigenfunctions and Eigenvalues, 39 3.3 Operators and Quantum Mechanics, 40 3.4 The Three-Dimensional Many-Particle Schrédinger Equation, 46 3.5 The Particle in a Three-Dimensional Box, 49 3.6 Degeneracy, 52 3.7 Average Values, 53 3.8 Requirements for an Acceptable Wave Function, 57 3.9 Summary, 58 THE HARMONIC OSCILLATOR 62 4.1 Power-Series Solution of Differential Equations, 62 4.2 The One-Dimensional Harmonic Oscillator, 65 4.3 Vibration of Molecules,74 4.4 Numerical Solution of the One-Dimensional Time-Independent Schrédinger Equation, 78 4.5 Summary, 89Contents ANGULAR MOMENTUM 94 5.1 Simultaneous Specification of Several Properties, 94 5.2. Vectors, 97 5.3 Angular Momentum of a One-Particle System, 102 5.4 The Ladder-Operator Method for Angular Momentum, 115 5.5 Summary, 120 THE HYDROGEN ATOM 123 6.1 The One-Particle Central-Force Problem, 123 6.2 Noninteracting Particles and Separation of Variables, 125 6.3. Reduction of the Two-Particle Problem to Two One-Particle Problems, 127 6.4 The Two-Particle Rigid Rotor, 130 6.5 The Hydrogen Atom, 134 6.6 The Bound-State Hydrogen-Atom Wave Functions, 142 6.7 Hydrogenlike Orbitals, 150 68 The Zeeman Effect, 154 6.9 Numerical Solution of the Radial Schrédinger Equation, 157 6.10 Summary, 158 THEOREMS OF QUANTUM MECHANICS 163 7.1 Introduction, 163 7.2 Hermitian Operators, 164 7.3 Expansion in Terms of Eigenfunctions, 170 7.4 Eigenfunctions of Commuting Operators, 175 75. Parity, 178 7.6 Measurement and the Superposition of States, 182 7.7 Position Eigenfunctions, 187 78 The Postulates of Quantum Mechanics, 190 7.9 Measurement and the Interpretation of Quantum Mechanics, 194 7.10 Matrices, 198 7.41 Summary, 201 THE VARIATION METHOD 208 8.1 The Variation Theorem, 208 8.2 Extension of the Variation Method, 212 8.3 Determinants, 213 8.4 Simultaneous Linear Equations, 217 8.5 Linear Variation Functions, 220 8.6 Matrices, Eigenvalues, and Eigenvectors,228 8.7 Summary, 235 vvi Contents 9 10 11 12 PERTURBATION THEORY 245 9.1 Introduction, 245 9.2. Nondegenerate Perturbation Theory, 246 9.3 Perturbation Treatment of the Helium-Atom Ground State, 252 9.4 Variation Treatments of the Ground State of Helium, 256 9.5 Perturbation Theory for a Degenerate Energy Level, 259 9.6 Simplification of the Secular Equation, 263 9.7 Perturbation Treatment of the First Excited States of Helium, 265 9.8 Comparison of the Variation and Perturbation Methods, 272 9.9 Time-Dependent Perturbation Theory, 272 9.10 Interaction of Radiation and Matter, 275 9.11 Summary, 277 ELECTRON SPIN AND THE PAULI PRINCIPLE 282 10.1 Electron Spin, 282 10.2 Spin and the Hydrogen Atom, 285 10.3 The Pauli Principle, 285 10.4 The Helium Atom, 288 10.5 The Pauli Exclusion Principle, 290 10.6 Slater Determinants,295 10.7 Perturbation Treatment of the Lithium Ground State, 297 10.8 Variation Treatments of the Lithium Ground State, 298 10.9 Spin Magnetic Moment, 299 10.10 Ladder Operators for Electron Spin, 300 10.11 Summary, 302 MANY-ELECTRON ATOMS 305 11.1 The Hartree-Fock Self-Consistent-Field Method, 305 11.2 Orbitals and the Periodic Table, 312 11.3 Electron Correlation, 315 11.4 Addition of Angular Momenta, 318 11.5 Angular Momentum in Many-Electron Atoms, 323 11.6 Spin—Orbit Interaction, 335 11.7 The Atomic Hamiltonian, 337 11.8 The Condon-Slater Rules, 339 11.9 Summary, 342 MOLECULAR SYMMETRY 347 12.1 Symmetry Elements and Operations, 347 12.2 Symmetry Point Groups, 355 12.3 Summary, 362Contents vii 13 ELECTRONIC STRUCTURE OF DIATOMIC MOLECULES 366 13.1 The Born-Oppenheimer Approximation, 366 13.2 Nuclear Motion in Diatomic Molecules, 370 13.3 Atomic Units,375 13.4 The Hydrogen Molecule Ion, 376 13.5 Approximate Treatments of the H3 Ground Electronic State, 381 13.6 Molecular Orbitals for H} Excited States, 390 13.7 MO Configurations of Homonuclear Diatomic Molecules, 396 13.8 Electronic Terms of Diatomic Molecules, 402 13.9 The Hydrogen Molecule, 407 13.10 The Valence-Bond Treatment of H,, 410 13.11 Comparison of the MO and VB Theories, 414 13.12 MO and VB Wave Functions for Homonuclear Diatomic Molecules, 416 13.13 Excited States of Hy, 419 13.14 Electron Probability Density, 421 13.15 Dipole Moments, 423 13.16 The Hartree-Fock Method for Molecules, 426 13.17 SCF Wave Functions for Diatomic Molecules, 436 13.18 MO Treatment of Heteronuclear Diatomic Molecules, 439 13.19 VB Treatment of Heteronuclear Diatomic Molecules, 442 13.20 The Valence-Electron Approximation, 443 13.21 CI Wave Functions, 444 13.22 Summary, 451 14 THE VIRIAL THEOREM AND THE HELLMANN-FEYNMAN THEOREM 459 14.1 The Virial Theorem, 459 14.2 The Virial Theorem and Chemical Bonding, 466 14.3 The Hellmann—Feynman Theorem, 469 14.4 The Electrostatic Theorem, 472 14.5 Summary, 478 15 AB INITIO AND DENSITY-FUNCTIONAL TREATMENTS OF MOLECULES 480 15.1 Ab Initio, Density-Functional, Semiempirical, and Molecular-Mechanics Methods, 480 15.2 Electronic Terms of Polyatomic Molecules, 481 15.3 The SCF MO Treatment of Polyatomic Molecules, 485 15.4 Basis Functions, 486 15.5 Speeding Up Hartree-Fock Calculations, 494 15.6 The SCF MO Treatment of H,0, 498 15.7 Population Analysis, 505 15.8 The Molecular Electrostatic Potential and Atomic Charges, 508 15.9 Localized MOs, 511