Chemical Bond

Gernot Frenking studied chemistry at the Technical University Aachen (Germany). He then became a research atudent in the group of Prof. Kenichi Fukui in Kyoto (Japan) and completed his PhD and his habilitation at Technical University Berlin (Germany). He was then a visiting scientist at the University of California, Berkeley (USA) and a staff scientist at SRI International in Menlo Park, California (USA). Since 1990 he is Professor for Computational Chemistry at the Philipps-Universitat Marburg. Sason Shaik is a graduate of the University of Washington (USA), where he also obtained his PhD. After a postdoctoral year at Cornell University, he became Lecturer at Ben-Gurion University of the Negev (Israel), where he became Professor in 1988. In 1992 he moved to The Hebrew University where he is Professor and the Director of the Lise Meitner-Minerva Center for Computational Quantum Chemistry.

• Preface xiiiList of Contributors xxiii1 The Physical Origin of Covalent Bonding 1Michael W. Schmidt, Joseph Ivanic, and Klaus Ruedenberg1.1 The Quest for a Physical Model of Covalent Bonding 11.2 Rigorous Basis for Conceptual Reasoning 31.3 Atoms in Molecules 101.4 The One-Electron Basis of Covalent Binding: H2+ 131.5 The Effect of Electronic Interaction in the Covalent Electron Pair Bond: H2 341.6 Covalent Bonding in Molecules with More than Two Electrons: B2 ,C2 , N2 ,O2 ,and F2 511.7 Conclusions 62Acknowledgments 65References 652 Bridging Cultures 69Philippe C. Hiberty and Sason Shaik2.1 Introduction 692.2 A Short History of the MO/VB Rivalry 692.3 Mapping MO-Based Wave Functions to VB Wave Functions 742.4 Localized Bond Orbitals – A Pictorial Bridge between MO and VB Wave Functions 782.5 Block-Localized Wave Function Method 792.6 Generalized Valence Bond Theory: a Simple Bridge from VB to MOs 802.7 VB Reading of CASSCF Wave Functions 822.8 Natural Bonding Orbitals and Natural Resonance Theory – a Direct Bridge between MO and VB 832.9 The Mythical Conflict of Hybrid Orbitals with Photoelectron Spectroscopy 852.10 Conclusion 87Appendix 88References 883 The NBO View of Chemical Bonding 91Clark R. Landis and Frank Weinhold3.1 Introduction 913.2 Natural Bond Orbital Methods 923.3 Beyond Lewis-Like Bonding: The Donor–Acceptor Paradigm 1063.4 Conclusion 117References 1184 The EDA Perspective of Chemical Bonding 121Gernot Frenking and F. Matthias Bickelhaupt4.1 Introduction 1214.2 Basic Principles of the EDA Method 1254.3 The EDA-NOCV Method 1264.4 Chemical Bonding in H2 and N2 1274.5 Comparison of Bonding in Isoelectronic N2 ,CO and BF 1334.6 Bonding in the Diatomic Molecules E 2 of the First Octal Row E = Li–F 1354.7 Bonding in the Dihalogens F2 –I2 1444.8 Carbon–Element Bonding in CH3 -X 1464.9 EDA-NOCV Analysis of Chemical Bonding in the Transition State 1484.10 Summary and Conclusion 155Acknowledgements 156References 1565 The Valence Bond Perspective of the Chemical Bond 159Sason Shaik, David Danovich, Wei Wu, and Philippe C. Hiberty5.1 Introduction 1595.2 A Brief Historical Recounting of the Development of the Chemical Bond Notion 1605.3 The Pauling–Lewis VB Perspective of the Electron-Pair Bond 1625.4 A Preamble to the Modern VB Perspective of the Electron-Pair Bond 1655.5 Theoretical Characterization of Bond Types by VB and Other Methods 1685.6 Trends of Bond Types Revealed by VB, AIM and ELF 1705.7 Physical Origins of CS Bonding 1785.8 Global Behavior of Electron-Pair Bonds 1815.9 Additional Factors of CS Bonding 1835.10 Can a Covalent Bond Become CS Bonds by Substitution? 1845.11 Experimental Manifestations of CS Bonding 1875.12 Scope and Territory of CS Bonding 190Appendix 1925.A Modern VB Methods 1925.B The Virial Theorem 1935.C Resonance Interaction and Kinetic Energy 195References 1956 The Block-Localized Wavefunction (BLW) Perspective of Chemical Bonding 199Yirong Mo6.1 Introduction 1996.2 Methodology Evolutions 2026.3 Exemplary Applications 2096.4 Conclusion 2236.5 Outlook 225Acknowledgements 225References 2257 The Conceptual Density Functional Theory Perspective of Bonding 233Frank De Proft, Paul W. Ayers, and Paul Geerlings7.1 Introduction 2337.2 Basics of DFT: The Density as a Fundamental Carrier of Information and How to Obtain It 2357.3 Conceptual DFT: A Perturbative Approach to Chemical Reactivity and the Process of Bond Formation 2387.4 Conclusions 264Acknowledgments 264References 2658 The QTAIM Perspective of Chemical Bonding 271Paul Lode Albert Popelier8.1 Introduction 2718.2 Birth of QTAIM: the Quantum Atom 2748.3 The Topological Atom: is it also a Quantum Atom? 2788.4 The Bond Critical Point and the Bond Path 2848.5 Energy Partitioning Revisited 2958.6 Conclusion 302Acknowledgment 303References 3039 The Experimental Density Perspective of Chemical Bonding 309Wolfgang Scherer, Andreas Fischer, and Georg Eickerling9.1 Introduction 3099.2 Asphericity Shifts and the Breakdown of the Standard X-ray Model 3119.3 Precision of Charge Density Distributions in Experimental and Theoretical Studies 3139.4 Core Density Deformations Induced by Chemical Bonding 3229.5 How Strongly Is the Static Electron Density Distribution Biased by Thermal Motion? 3259.6 Relativistic Effects on the Topology of Electron Density 3269.7 The Topology of the Laplacian and the MO Picture – Two Sides of the Same Coin? 3309.8 Elusive Charge Density Phenomena: Nonnuclear Attractors 333References 33910 The ELF Perspective of chemical bonding 345Yuri Grin, Andreas Savin, and Bernard Silvi10.1 Introduction 34510.2 Definitions 34710.3 Simple examples 35810.4 Solids 36910.5 Perspectives 375Appendix 37610.A Mathematical expressions of calculated basin properties 37611 Relativity and Chemical Bonding 383Peter Schwerdtfeger11.1 Introduction 38311.2 Direct and Indirect Relativistic Effects and Spin–Orbit Coupling 38711.3 Chemical Bonding and Relativistic Effects 39311.4 Conclusions 400Acknowledgments 400References 400Index 405

“The two volumes would serve upper-level undergraduates who are well versed in mathematics and chemistry, but they are most suitable for graduate students, faculty, and researchers in chemistry.  The exhaustive chapter references make each book a useful go-to reference source.  Highly recommended. Upper-division undergraduates, graduate students, and researchers/faculty.”  (Choice, 1 May 2015)