Sason S Shaik: A Chemist's Guide to Valence Bond Theory, Gebunden

Kurzbeschreibung

Intended for chemists who are not necessarily experts on theory, but have some background in quantum chemistry, The Chemist s Guide to Valence Bond Theory is designed to teach chemists how to use VB theory to think concisely and rigorously and how to use VB computations.

Inhaltsangabe

PREFACE xiii 1 A Brief Story of Valence Bond Theory, Its Rivalry with Molecular Orbital Theory, Its Demise, and Resurgence 1 1.1 Roots of VB Theory 2 1.2 Origins of MO Theory and the Roots of VB–MO Rivalry 5 1.3 One Theory is Up the Other is Down 7 1.4 Mythical Failures of VB Theory: More Ground is Gained by MO Theory 8 1.5 Are the Failures of VB Theory Real? 12 1.5.1 The O2 Failure 12 1.5.2 The C4H4 Failure 13 1.5.3 The C5H5þ Failure 13 1.5.4 The Failure Associated with the Photoelectron Spectroscopy of CH4 13 1.6 Valence Bond is a Legitimate Theory Alongside Molecular Orbital Theory 14 1.7 Modern VB Theory: Valence Bond Theory is Coming of Age 14 2 A Brief Tour Through Some Valence Bond Outputs and Terminology 26 2.1 Valence Bond Output for the H2 Molecule 26 2.2 Valence Bond Mixing Diagrams 32 2.3 Valence Bond Output for the HF Molecule 33 3 Basic Valence Bond Theory 40 3.1 Writing and Representing Valence Bond Wave Functions 40 3.1.1 VB Wave Functions with Localized Atomic Orbitals 40 3.1.2 Valence Bond Wave Functions with Semilocalized AOs 41 3.1.3 Valence Bond Wave Functions with Fragment Orbitals 42 3.1.4 Writing Valence Bond Wave Functions Beyond the 2e / 2c Case 43 3.1.5 Pictorial Representation of Valence Bond Wave Functions by Bond Diagrams 45 3.2 Overlaps between Determinants 45 3.3 Valence Bond Formalism Using the Exact Hamiltonian 46 3.3.1 Purely Covalent Singlet and Triplet Repulsive States 47 3.3.2 Configuration Interaction Involving Ionic Terms 49 3.4 Valence Bond Formalism Using an Effective Hamiltonian 49 3.5 Some Simple Formulas for Elementary Interactions 51 3.5.1 The Two Electron Bond 51 3.5.2 Repulsive Interactions in Valence Bond Theory 52 3.5.3 Mixing of Degenerate Valence Bond Structures 53 3.5.4 Nonbonding Interactions in Valence Bond Theory 54 3.6 Structural Coefficients and Weights of Valence Bond Wave Functions 56 3.7 Bridges between Molecular Orbital and Valence Bond Theories 56 3.7.1 Comparison of Qualitative Valence Bond and Molecular Orbital Theories 57 3.7.2 The Relationship between Molecular Orbital and Valence Bond Wave Functions 58 3.7.3 Localized Bond Orbitals: A Pictorial Bridge between Molecular Orbital and Valence Bond Wave Functions 60 Appendix 65 3.A. 1 Normalization Constants, Energies, Overlaps, and Matrix Elements of Valence Bond Wave Functions 65 3.A. 1.1 Energy and Self Overlap of an Atomic Orbital Based Determinant 66 3.A. 1.2 Hamiltonian Matrix Elements and Overlaps between Atomic Orbital Based Determinants 68 3.A. 2 Simple Guidelines for Valence Bond Mixing 68 Exercises 70 Answers 74 4 Mapping Molecular Orbital - Configuration Interaction to Valence Bond Wave Functions 81 4.1 Generating a Set of Valence Bond Structures 81 4.2 Mapping a Molecular Orbital–Configuration Interaction Wave Function into a Valence Bond Wave Function 83 4.2.1 Expansion of Molecular Orbital Determinants in Terms of Atomic Orbital Determinants 83 4.2.2 Projecting the Molecular Orbital–Configuration Interaction Wave Function Onto the Rumer Basis of Valence Bond Structures 85 4.2.3 An Example: The Hartree–Fock Wave Function of Butadiene 86 4.3 Using Half Determinants to Calculate Overlaps between Valence Bond Structures 88 Exercises 89 Answers 90 5 Are the ''Failures'' of Valence Bond Theory Real? 94 5.1 Introduction 94 5.2 The Triplet Ground State of Dioxygen 94 5.3 Aromaticity–Antiaromaticity in Ionic Rings CnHnþ/ 97 5.4 Aromaticity / Antiaromaticity in Neutral Rings 100 5.5 The Valence Ionization Spectrum of CH4 104 5.6 The Valence Ionization Spectrum of H2O and the ''Rabbit Ear'' Lone Pairs 106 5.7 A Summary 109 Exercises 111 Answers 112 6 Valence Bond Diagrams for Chemical Reactivity 116 6.1 Introduction 116 6.2 Two Archetypal Valence Bond Diagrams 116 6.3 The Valence Bond State Correlation Diagram Model and Its General Outlook on Reactivity 117 6.4 Construction of Valence Bond State Correlation Diagrams for Elementary Processes 119 6.4.1 Valence Bond State Correla

Rezension

"The textbook provides a qualitative overview of the possibilities within the VB approach. As such, we strongly recommend it, both to interested chemists and to university libraries." ( Angewandte Chemie International Edition , December 8, 2008)

Klappentext

Modern valence bond theory and state-of-the-art methodologies

Since the 1980s, valence bond (VB) theory has enjoyed a renaissance characterized both in the qualitative application of the theory and in the development of new methods for its computer implementation. Written by leading authorities, this is the premier reference on current VB theory and applications in a pedagogical context, perhaps the first such attempt since Pauling's The Nature of the Chemical Bond. After an introduction, A Chemist's Guide to Valence Bond Theory pre-sents a practical system that can be applied to a variety of chemical problems in a uniform manner. Concise yet comprehensive, it includes:
*

A tour of some VB outputs and terminology
*

An explanation of basic VB theory
*

A discussion of various applications of the VB method to chemical problems, encompassing bonding problems, aromaticity and antiaromaticity, the dioxygen molecule, polyradicals, excited states, organic reactions, inorganic / organometallic reactions, photochemical reactions, and catalytic reactions
*

Samples of inputs / outputs and instructions for interpreting results
*

A short programmable outline for converting molecular orbital wave functions to VB structures
*

A guide for performing VB calculations

Complete with exercises and answers at the end of chapters, numerous solved problems, and a glossary of terms and symbols, this is the authoritative guide for computational chemists, chemical physicists, and research chemists in organic and organometallic / inorganic chemistry concerned with reactivity and molecular structure. It is also an excellent text for advanced undergraduate and graduate students.

Sonstiges

Lieferung vom Verlag mit leichten Qualitätsmängeln möglich