Fundamental aspects of chemical bonding

Author(s)

• Frenking, G. (Gernot)
• Shaik, Sason S.

Bibliographic Information

Fundamental aspects of chemical bonding

edited by Gernot Frenking and Sason Shaik

（The chemical bond / edited by Gernot Frenking and Sason Shaik, 1）

Wiley-VCH, c2014

Note

Includes bibliographical references and index

Description and Table of Contents

Description

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.

Table of Contents

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

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Details

• NCID: BB16354488
• ISBN:
  • 9783527333141
• Country Code: gw
• Title Language Code: eng
• Text Language Code: eng
• Place of Publication: Weinheim
• Pages/Volumes: xxv, 411 p.
• Size: 25 cm
• Classification:
  • DC23 : 541.224
• Subject Headings:
  • LCSH : Chemical bonds
• Parent Bibliography ID:
  • BB16354080