The Chemical Bond E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 871

Veröffentlichungsjahr: 2014

Beschreibung

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.

Leseprobe

Table of Contents

Cover

Related Titles

Title Page

Copyright

Preface

References

List of Contributors

Chapter 1: The Physical Origin of Covalent Bonding

1.1 The Quest for a Physical Model of Covalent Bonding

1.2 Rigorous Basis for Conceptual Reasoning

1.3 Atoms in Molecules

1.4 The One-Electron Basis of Covalent Binding: H

2

+

1.5 The Effect of Electronic Interaction in the Covalent Electron Pair Bond: H

2

1.6 Covalent Bonding in Molecules with More than Two Electrons: B

2,

C

2,

N

2

, O

2

, and F

2

1.7 Conclusions

Acknowledgments

References

Chapter 2: Bridging Cultures

2.1 Introduction

2.2 A Short History of the MO/VB Rivalry

2.3 Mapping MO-Based Wave Functions to VB Wave Functions

2.4 Localized Bond Orbitals – A Pictorial Bridge between MO and VB Wave Functions

2.5 Block-Localized Wave Function Method

2.6 Generalized Valence Bond Theory: a Simple Bridge from VB to MOs

2.7 VB Reading of CASSCF Wave Functions

2.8 Natural Bonding Orbitals and Natural Resonance Theory – a Direct Bridge between MO and VB

2.9 The Mythical Conflict of Hybrid Orbitals with Photoelectron Spectroscopy

2.10 Conclusion

Appendix

References

Chapter 3: The NBO View of Chemical Bonding

3.1 Introduction

3.2 Natural Bond Orbital Methods

3.3 Beyond Lewis-Like Bonding: The Donor–Acceptor Paradigm

3.4 Conclusion

References

Chapter 4: The EDA Perspective of Chemical Bonding

4.1 Introduction

4.2 Basic Principles of the EDA Method

4.3 The EDA-NOCV Method

4.4 Chemical Bonding in H

2

and N

2

4.5 Comparison of Bonding in Isoelectronic N

2

, CO and BF

4.6 Bonding in the Diatomic Molecules E

2

of the First Octal Row E = Li–F

4.7 Bonding in the Dihalogens F

2

– I

2

4.8 Carbon–Element Bonding in CH

3

-X

4.9 EDA-NOCV Analysis of Chemical Bonding in the Transition State

4.10 Summary and Conclusion

Acknowledgements

References

Chapter 5: The Valence Bond Perspective of the Chemical Bond

5.1 Introduction

5.2 A Brief Historical Recounting of the Development of the Chemical Bond Notion

5.3 The Pauling–Lewis VB Perspective of the Electron-Pair Bond

5.4 A Preamble to the Modern VB Perspective of the Electron-Pair Bond

5.5 Theoretical Characterization of Bond Types by VB and Other Methods

5.6 Trends of Bond Types Revealed by VB, AIM and ELF

5.7 Physical Origins of CS Bonding

5.8 Global Behavior of Electron-Pair Bonds

5.9 Additional Factors of CS Bonding

5.10 Can a Covalent Bond Become CS Bonds by Substitution?

5.11 Experimental Manifestations of CS Bonding

5.12 Scope and Territory of CS Bonding

Appendix

5.A Modern VB Methods

5.B The Virial Theorem

5.C Resonance Interaction and Kinetic Energy

References

Chapter 6: The Block-Localized Wavefunction (BLW) Perspective of Chemical Bonding

6.1 Introduction

6.2 Methodology Evolutions

6.3 Exemplary Applications

6.4 Conclusion

6.5 Outlook

Acknowledgements

References

Chapter 7: The Conceptual Density Functional Theory Perspective of Bonding

7.1 Introduction

7.2 Basics of DFT: The Density as a Fundamental Carrier of Information and How to Obtain It

7.3 Conceptual DFT: A Perturbative Approach to Chemical Reactivity and the Process of Bond Formation

7.4 Conclusions

Acknowledgments

References

Chapter 8: The QTAIM Perspective of Chemical Bonding

8.1 Introduction

8.2 Birth of QTAIM: the Quantum Atom

8.3 The Topological Atom: is it also a Quantum Atom?

8.4 The Bond Critical Point and the Bond Path

8.5 Energy Partitioning Revisited

8.6 Conclusion

Acknowledgment

References

Chapter 9: The Experimental Density Perspective of Chemical Bonding

9.1 Introduction

9.2 Asphericity Shifts and the Breakdown of the Standard X-ray Model

9.3 Precision of Charge Density Distributions in Experimental and Theoretical Studies

9.4 Core Density Deformations Induced by Chemical Bonding

9.5 How Strongly Is the Static Electron Density Distribution Biased by Thermal Motion?

9.6 Relativistic Effects on the Topology of Electron Density

9.7 The Topology of the Laplacian and the MO Picture – Two Sides of the Same Coin?

9.8 Elusive Charge Density Phenomena: Nonnuclear Attractors

References

Chapter 10: The ELF Perspective of chemical bonding

10.1 Introduction

10.2 Definitions

10.3 Simple examples

10.4 Solids

10.5 Perspectives

Appendix

10.A Mathematical expressions of calculated basin properties

References

Chapter 11: Relativity and Chemical Bonding

11.1 Introduction

11.2 Direct and Indirect Relativistic Effects and Spin–Orbit Coupling

11.3 Chemical Bonding and Relativistic Effects

11.4 Conclusions

Acknowledgments

References

Index

End User License Agreement

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Guide

Cover

Table of Contents

Preface

Chapter 1: The Physical Origin of Covalent Bonding

List of Illustrations

Figure 1.1

Figure 1.2

Figure 1.3

Figure 1.4

Figure 1.5

Figure 1.6

Figure 1.9

Figure 1.7

Figure 1.8

Figure 1.10

Figure 1.11

Figure 1.12

Figure 1.13

Figure 1.14

Figure 1.15

Figure 1.16

Figure 1.17

Figure 1.18

Figure 1.19

Scheme 2.1

Scheme 2.2

Scheme 2.3

Scheme 2.4

Figure 2.1

Scheme 2.5

Figure 2.2

Figure 3.1

Figure 3.2

Figure 3.3

Figure 3.4

Figure 3.5

Figure 3.6

Figure 3.7

Figure 3.8

Figure 3.9

Figure 3.10

Figure 3.11

Figure 3.12

Figure 4.1

Scheme 4.1

Figure 4.2

Figure 4.3

Figure 4.4

Figure 4.5

Figure 4.6

Figure 4.7

Figure 4.8a

Figure 4.9

Figure 4.10

Figure 4.11

Figure 4.12

Figure 4.14

Figure 4.13

Figure 5.1

Figure 5.2

Figure 5.3

Figure 5.4

Scheme 5.1

Figure 5.5

Scheme 5.2

Scheme 5.3

Figure 5.6

Figure 5.7

Figure 5.8

Figure 5.9

Scheme 5.4

Figure 5.10

Figure 5.11

Figure 5.12

Scheme 5.5

Scheme 5.6

Figure 5.13

Scheme 5.7

Figure 5.14

Scheme 5.8

Figure 6.1

Figure 6.2

Figure 6.3

Figure 6.4

Figure 6.5

Figure 6.6

Figure 6.7

Figure 6.8

Figure 6.9

Figure 6.10

Figure 7.1

Figure 7.2

Figure 7.3

Figure 7.4

Figure 7.5

Figure 7.6

Figure 7.7

Figure 7.8

Figure 8.1

Figure 8.2

Figure 8.3

Figure 8.4

Figure 8.5

Figure 8.6

Figure 8.7

Figure 8.8

Figure 8.9

Figure 8.10

Figure 8.11

Figure 8.12

Figure 9.1

Figure 9.2

Figure 9.3

Figure 9.4

Figure 9.5

Figure 9.6

Figure 9.7

Figure 9.8

Figure 9.10

Figure 9.10

Figure 9.11

Figure 9.13

Figure 9.13

Figure 10.1

Figure 10.2

Figure 10.3

Figure 10.4

Figure 10.5

Figure 10.6

Figure 10.7

Figure 10.8

Figure 10.9

Figure 10.10

Figure 10.11

Figure 10.12

Figure 10.13

Figure 10.14

Figure 10.15

Figure 10.16

Figure 10.17

Figure 10.18

Figure 10.19

Figure 10.20

Figure 10.21

Figure 10.22

Figure 10.23

Figure 10.24

Figure 10.25

Figure 10.26

Figure 10.27

Figure 10.28

Figure 11.1

Figure 11.2

Figure 11.3

Figure 11.4

List of Tables

Table 1.1

Table 1.2

Table 1.3

Table 1.4

Table 2.1

Table 2.2

Table 3.1

Table 3.2

Table 3.3

Table 4.1

Table 4.2

Table 4.3

Table 4.4

Table 4.5

Table 4.6

Table 4.7

Table 5.1

Table 5.2

Table 6.1

Table 6.2

Table 6.3

Table 6.4

Table 6.5

Table 6.6

Table 7.1

Table 7.2

Table B4.1

Table 8.1

Table 9.1

Table 9.2

Table 10.1

Table 11.1

Table 11.2

Table 11.3

Table 11.4

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Edited by Gernot Frenking and Sason Shaik

The Chemical Bond

Fundamental Aspects of Chemical Bonding

The Editors

Prof. Dr. Gernot Frenking

Philipps-Universität Marburg

FB Chemie

Hans-Meerwein-Strasse

35032 Marburg

Germany

Prof. Dr. Sason Shaik

Hebrew University

Institute of Chemistry

Givat Ram Campus

91904 Jerusalem

Israel

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Preface

One of the fundamental territories of chemistry is the chemical bond, the glue from which an entire chemical universe is constructed [1]. The bond serves as a bridge between the apparent magic of chemistry (the chemical transformation) and the way this magic is conceived at present in terms of molecules changing into one another by breaking old bonds and making new ones. For a while it seemed that chemists have, by and large, abandoned their territory as if everything about bonding is known and well understood; the frontier has moved to nano and bio, leaving the original territory untended. This, however, was a wrong impression, as the interest in bonding has quickly revived to be accompanied by many interesting theoretical approaches to probe the origins of bonds, many novel bonding motifs, and even experimental studies that describe imaging of bonds being broken and remade using atomic force microscopy [2]. The bond is becoming again a central intellectual arena, and one can even find allusions to the bond as an elementary particle of chemistry, so-called “bondon” [3]. This “return of the bond” has prompted the two editors to edit these two volumes on bonding, and it is only fitting that their publication date is close to the centenary of the Lewis seminal paper on electron-pair bonding.

The idea of “bonding” may even have alchemical origins in the spiritual outlook of matter, where the conjuctio or union of the opposites is the ultimate synthesis necessary to drive the change of lower matter to gold [4]. In chemistry, the roots of the bond concept date way back to the efforts of chemists to grapple with the magic of chemistry, the formation substances and their transmutation [5]; these efforts have led to the formulation of “chemical theories” in which “affinities” between materials were considered to unite “more compounded” substances. Interestingly, the “affinity” was not defined as a static property of substances but as a dynamic one, in conformity with the “chemical magic” that a substance exists one time and then disappears making place for a new one.

In 1675, Lemery published his book Course de Chymie [6, 7] and used “elective affinities” as terminology that describes the selective replacement of one metal by others in the chemistry of salts [7]a. In 1718, Etienne Francois Geoffroy systematized this phenomenon in his table of rapports, namely, affinities. [7]b Historian Ursula Klein [8] credits Geoffroy as the first scientist to generalize the basic concept of modern chemistry – that of the “compound” with “chemical affinity” between the constituents. The tables of affinities became so important to chemists, because they documented the chemical selectivity of the known chemical bodies of the day. We learn of the importance of affinity tables from the story of Swedish chemist Torben Bergman, who assembled thousands of affinity data [9], and presented his table as a gift to the Duke of Parma. Building on Geoffroy's “theory,” another Frenchman, Peirre-Joseph Macquer, published in 1749–1751 his two-volume monographs: “Chimie Theorique” and “Chimie Practique,” [10] in which he gave rules of chemical combination. As cited by the historian Siegfried, these rules sound very modern to our contemporary ear (p. 144 in Ref. [5]).