About the Book
Molecular Structure and Energetics Volume 1 Edited by Joel F. Liebman Arthur Greenberg This series has as its theme two of the most widespread, fundamental and important concepts in chemistry: molecular structure and energetics. The scope of the series ranges from species as elegantly simple as elemental boron and carbon to those as ill-defined, yet important, as atmospheric particulates; from rearrangements in clusters to the strain and aromaticity of organic molecules; from the energies of protonation of atoms and diatomic molecules to the binding of substrates to natural and synthetic enzymes. Each volume consists of chapters by leading specialists, and is focused on a common theme. Each essay provides a tutorial review which is generally in a form that blends theory and experiment as well as rigor and intuition. Volume 1, Chemical Bonding Molecules, examines nine topics in the fundamental, conceptual and theoretical framework of molecular structure and energetics. All the essays explicitly compare and interweave findings from experiment and from both calculational and qualitative theory.
Table of Contents:
Foreword; Preface; 1. The Nature of the Chemical Bond Fifty Years Later: The Relative Electronegativity of Atoms Seen in Perspective; Linus Pauling and Zelek S. Herman, Linus Pauling Institute of Science and Medicine, Palo Alto, California; 1. Introduction; 2. The Relative Electronegativity of Atoms; 3. Correlation of Double--Bond Character in One Bond with Ionic Character in Another; 4. The Nitrogen Trifluoride Molecule; 5. The Phosphorus Trifluoride Molecule; 6. The Oxygen Difluoride Molecule; 7. Electronegativity Equalization; 8. Conclusions; 2. Isoelectronic Molecules; Henry A. Bent, North Carolina State University, Raleigh, North Carolina; 1. Introduction; 2. Isoelectronic Atomic Systems; 3. Isoelectronic Radicals; 4. The Importance and Unimportance of Protons; 5. The United Atom Theorem; 6. The Methane--Neon Family: N = 1, V = 8; 7. The Ethane--Fluorine Family: N = 2, V = 14; 8. The Ethylene--Oxygen Family: N = 2, V = 12; 9. Multicenter Bonding; 10. The Acetylene--Nitrogen Family: N = 2, V = 10; 11. The Allene--Carbon Dioxide Family: N = 3, V = 16; 12. Isoelectronic Intramolecular Interactions; 13. The Propylene--Ozone Family: N = 3, V = 8; 14. Isoelectronic Intermolecular Interactions; 15. The Isobutane to Diacetylene Families: N = 4, V = 26, 24, 22, 20, 18; 16. The Tetramethylmethane--Tetrafluoroborate Family: N = 5, V = 32; 17. Nonexistent Isoelectronic Systems; 18. Anticoincident Isoelectronic Spin Sets; 19. Comparison of H 2 O and Li 2 O (g) Molecules; 20. Position of Hydrogen in the Periodic Table; 21. Anticoincident, Nonisolectronic Spin Sets: Dioxygen; 22. Anticoincident, Nonisolectronic Spin Sets: NO, NO 2 , CH 3 , CH 2 ; 23. Systems with Expanded Octets; 24. Systems with Transition Metal Atoms; 25. Systems Containing Protonated Bonds to Boron; 26. The Borane--Atomic Oxygen Family: N = 1, V = 6; 27. Highly Coordinatively Unsaturated Systems (N = 1, V = 4, 2); 28. Boron Heteroatom Analogues of C 5 H 5 -- and the B n H n 2-- Family; 29. The C - H Bond Methylene "Insertion Reaction"; 30. Crystalline Inorganic Compounds; 31. Metals; 32. Oxide Ion--Electride Ion Structural Isomorphism; 33. Electride Ion--Hydride Ion Isomorphism; 34. Oxide Ion--Electride Ion Chemical Isomorphism; 35. Organic--Inorganic Linguistic Isomorphism; 36. Numerical Estimates of Physical Properties Based on the Isoelectronic Principle; 3. Carbenes: A Study in Quantitative and Qualitative Theory; Joel F. Liebman, University of Maryland Baltimore County, Catonsville, Maryland and Jack Simons, University of Utah, Salt Lake City, Utah; 1. Introduction: Why We Study Carbenes; 2. Why Is Carbon Normally Tetravalent?; 3. The XCY Carbene Angle and the Singlet--Triplet Gap: Models, Mnemonics, and Correlatives; 4. Introduction to the Quantitative Aspects; 5. Carbene Orbitals; 6. Carbene Electronic Configurations; 7. Configuration Interaction in Carbenes: Fundamentals; 8. Configuration Interaction in Carbenes: Illustrative Examples; 9. Dichlorocarbene: Admission, Additivity, and Affirmation; 10. Specific Fluorine Substituent Effects; 11. Isoelectronic Reasoning and Carbenes; 12. An Epilogue: Hidden Carbenes and the Dichotomy of Dicoordinate Versus Divalent Carbon; 4. Theoretical Studies of Multiple Bonding to Silicon; Mark S. Gordon, North Dakota State University, Fargo, North Dakota; 1. Introduction; 2. Methodologies; 3. Silylene; 4. Silaethylenes; 5. Silaethynes; 6. Disilene; 7. Disilyne; 8. Aromatic and Delocalized Species; 9. Silanones; 10. Silicon--Phosphorus Bonding; 11. Conclusions; 5. Topological Relationships in Molecular Structures and Energetics; Robert Bruce King, University of Georgia, Athens, Georgia; 1. Introduction; 2. Energetics, Huckel Theory, and the Adjacency Matrix; 3. Vertex Atoms; 4. Localized Polyhedral Systems; 5. Polygonal Systems; 6. Delocalized Deltahedral Systems; 7. Electron--Rich Polyhedral Systems; 8. Electron--Poor Polyhedral Systems; 9. Late Transition Metal Vertices; 10. Summary; 6. Boranes and Heteroboranes; Thomas P. Fehlner and Catherine E. Housecroft, University of Notre Dame, Notre Dame, Indiana; 1. Introduction; 2. Structure: Basic Principles Derived from Geometry; 3. Structure: Approaches to Detailed Bonding Models; 4. Energetics; 5. Reactivity; 6. Perturbation of the Borane Cage by Heteroatoms; 7. Summary; 7. Structural--Electronic Relationships in the Solid State; Jeremy K. Burdett, The University of Chicago, Chicago, Illinois; 1. Introduction; 2. Orbitals in Molecules and Solids via the Conventional Route; 3. Orbitals in Molecules and Solids via the Method of Moments; 4. Variation of Structural Stability with Electron Count; 5. The Instability of Edge--Sharing Tetrahedra; 6. The Structure of Niobium (II) Oxide; 7. Some Qualitative Aspects; 8. Conclusions; 8. A Detailed Derivation of the Schrodinger Equation; Lawrence J. Schaad and B. Andes Hess, Jr., Vanderbilt University, Nashville, Tennessee; 1. Introduction; 2. Fourier Series; 3. The Fourier Integral Theorem; 4. Dirac's O Function; 5. Inclusion of Time Dependence in the Fourier Integral Theorem; 6. The De Broglie Relation; 7. The One--Dimensional, Time--Dependent Schrodinger Equation for a Free Particle; 8. The Time--Dependent Schrodinger Equation for a One--Dimensional Particle in a Potential Field; 9. Time--Independent Potentials; 10. The Schrodinger Equation for N Particles in Three Dimensions; 11. The Schrodinger Equation in Generalized Coordinates; 9. Quantum Chemical Reaction Enthalpies; Janet E. Del Bene, Youngstown State University, Youngstown, Ohio; 1. Introduction; 2. Considerations of Methodology; 3. Applications; 4. Concluding Remarks; Appendix: Basis Set and Method Notation; General Index
