This is the perfect complement to ‘Chemical Bonding – Across the Periodic Table’ by the same editors, who are two of the top scientists working on this topic, each with extensive experience and important connections within the community.
The resulting book is a unique overview of the different approaches used for describing a chemical bond, including molecular-orbital based, valence-bond based, ELF, AIM and density-functional based methods. It takes into account the many developments that have taken place in the field over the past few decades due to the rapid advances in quantum chemical models and faster computers.
Inhoudsopgave
Preface xiii
List of Contributors xxiii
1 The Physical Origin of Covalent Bonding 1
Michael W. Schmidt, Joseph Ivanic, and Klaus Ruedenberg
1.1 The Quest for a Physical Model of Covalent Bonding 1
1.2 Rigorous Basis for Conceptual Reasoning 3
1.3 Atoms in Molecules 10
1.4 The One-Electron Basis of Covalent Binding: H2+ 13
1.5 The Effect of Electronic Interaction in the Covalent Electron Pair Bond: H2 34
1.6 Covalent Bonding in Molecules with More than Two Electrons: B2 , C2 , N2 , O2 , and F2 51
1.7 Conclusions 62
Acknowledgments 65
References 65
2 Bridging Cultures 69
Philippe C. Hiberty and Sason Shaik
2.1 Introduction 69
2.2 A Short History of the MO/VB Rivalry 69
2.3 Mapping MO-Based Wave Functions to VB Wave Functions 74
2.4 Localized Bond Orbitals – A Pictorial Bridge between MO and VB Wave Functions 78
2.5 Block-Localized Wave Function Method 79
2.6 Generalized Valence Bond Theory: a Simple Bridge from VB to MOs 80
2.7 VB Reading of CASSCF Wave Functions 82
2.8 Natural Bonding Orbitals and Natural Resonance Theory – a Direct Bridge between MO and VB 83
2.9 The Mythical Conflict of Hybrid Orbitals with Photoelectron Spectroscopy 85
2.10 Conclusion 87
Appendix 88
References 88
3 The NBO View of Chemical Bonding 91
Clark R. Landis and Frank Weinhold
3.1 Introduction 91
3.2 Natural Bond Orbital Methods 92
3.3 Beyond Lewis-Like Bonding: The Donor–Acceptor Paradigm 106
3.4 Conclusion 117
References 118
4 The EDA Perspective of Chemical Bonding 121
Gernot Frenking and F. Matthias Bickelhaupt
4.1 Introduction 121
4.2 Basic Principles of the EDA Method 125
4.3 The EDA-NOCV Method 126
4.4 Chemical Bonding in H2 and N2 127
4.5 Comparison of Bonding in Isoelectronic N2 , CO and BF 133
4.6 Bonding in the Diatomic Molecules E 2 of the First Octal Row E = Li–F 135
4.7 Bonding in the Dihalogens F2 –I2 144
4.8 Carbon–Element Bonding in CH3 -X 146
4.9 EDA-NOCV Analysis of Chemical Bonding in the Transition State 148
4.10 Summary and Conclusion 155
Acknowledgements 156
References 156
5 The Valence Bond Perspective of the Chemical Bond 159
Sason Shaik, David Danovich, Wei Wu, and Philippe C. Hiberty
5.1 Introduction 159
5.2 A Brief Historical Recounting of the Development of the Chemical Bond Notion 160
5.3 The Pauling–Lewis VB Perspective of the Electron-Pair Bond 162
5.4 A Preamble to the Modern VB Perspective of the Electron-Pair Bond 165
5.5 Theoretical Characterization of Bond Types by VB and Other Methods 168
5.6 Trends of Bond Types Revealed by VB, AIM and ELF 170
5.7 Physical Origins of CS Bonding 178
5.8 Global Behavior of Electron-Pair Bonds 181
5.9 Additional Factors of CS Bonding 183
5.10 Can a Covalent Bond Become CS Bonds by Substitution? 184
5.11 Experimental Manifestations of CS Bonding 187
5.12 Scope and Territory of CS Bonding 190
Appendix 192
5.A Modern VB Methods 192
5.B The Virial Theorem 193
5.C Resonance Interaction and Kinetic Energy 195
References 195
6 The Block-Localized Wavefunction (BLW) Perspective of Chemical Bonding 199
Yirong Mo
6.1 Introduction 199
6.2 Methodology Evolutions 202
6.3 Exemplary Applications 209
6.4 Conclusion 223
6.5 Outlook 225
Acknowledgements 225
References 225
7 The Conceptual Density Functional Theory Perspective of Bonding 233
Frank De Proft, Paul W. Ayers, and Paul Geerlings
7.1 Introduction 233
7.2 Basics of DFT: The Density as a Fundamental Carrier of Information and How to Obtain It 235
7.3 Conceptual DFT: A Perturbative Approach to Chemical Reactivity and the Process of Bond Formation 238
7.4 Conclusions 264
Acknowledgments 264
References 265
8 The QTAIM Perspective of Chemical Bonding 271
Paul Lode Albert Popelier
8.1 Introduction 271
8.2 Birth of QTAIM: the Quantum Atom 274
8.3 The Topological Atom: is it also a Quantum Atom? 278
8.4 The Bond Critical Point and the Bond Path 284
8.5 Energy Partitioning Revisited 295
8.6 Conclusion 302
Acknowledgment 303
References 303
9 The Experimental Density Perspective of Chemical Bonding 309
Wolfgang Scherer, Andreas Fischer, and Georg Eickerling
9.1 Introduction 309
9.2 Asphericity Shifts and the Breakdown of the Standard X-ray Model 311
9.3 Precision of Charge Density Distributions in Experimental and Theoretical Studies 313
9.4 Core Density Deformations Induced by Chemical Bonding 322
9.5 How Strongly Is the Static Electron Density Distribution Biased by Thermal Motion? 325
9.6 Relativistic Effects on the Topology of Electron Density 326
9.7 The Topology of the Laplacian and the MO Picture – Two Sides of the Same Coin? 330
9.8 Elusive Charge Density Phenomena: Nonnuclear Attractors 333
References 339
10 The ELF Perspective of chemical bonding 345
Yuri Grin, Andreas Savin, and Bernard Silvi
10.1 Introduction 345
10.2 Definitions 347
10.3 Simple examples 358
10.4 Solids 369
10.5 Perspectives 375
Appendix 376
10.A Mathematical expressions of calculated basin properties 376
11 Relativity and Chemical Bonding 383
Peter Schwerdtfeger
11.1 Introduction 383
11.2 Direct and Indirect Relativistic Effects and Spin–Orbit Coupling 387
11.3 Chemical Bonding and Relativistic Effects 393
11.4 Conclusions 400
Acknowledgments 400
References 400
Index 405
Over de auteur
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 Ph D 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 Ph D. 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.
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