Modern electronic structure theory and applications in organic chemistry / editor, Ernest R. Davidson.

Format:

Book

Contributor:

Davidson, Ernest R.

Language:

English

Subjects (All):

Physical organic chemistry.

Chemistry, Physical and theoretical.

Physical Description:

1 online resource (389 p.)

Place of Publication:

Singapore ; River Edge, N.J. : World Scientific, c1997.

Language Note:

English

Summary:

This volume focuses on the use of quantum theory to understand and explain experiments in organic chemistry. High level ab initio calculations, when properly performed, are useful in making quantitative distinctions between various possible interpretations of structures, reactions and spectra. Chemical reasoning based on simpler quantum models is, however, essential to enumerating the likely possibilities. The simpler models also often suggest the type of wave function likely to be involved in ground and excited states at various points along reaction paths. This preliminary understanding is n

Contents:

Preface; Contents; Some Theoretical Applications to Organic Chemistry; 1 Ground State Examples; 2 Excited State and Open Shell Examples; Conclusion; References; Ab Initio Studies of Elimination Reaction Mechanisms; 1. Introduction; 2. Mechanistic Aspects; 3. Gas-phase Experimental Studies; 4. Computational Studies; 5. Conclusions; References; Computational Analyses of Prototype Carbene Structures and Reactions; 1 Introduction; 2 Electronic Structure Computations; 3 Energies and Structures of Prototype Carbenes; 4 Reactions of Carbenes; 5 Summary and Outlook; References

Violations of Hund's Rule in Organic Diradicals - Where to Look for Violations and How to Identify Them1 Introduction; 2 Where to Look for Violations of Hund's Rule in Molecules; 3 How to Identify Violations of Hund's Rule Experimentally; 4 Where to Look for Violations of the Strictest Version of Hund's Rule; 5 How Can a Violation of Hund's Rule Be Identified in a [4n]Annulene?; References; Ab Initio Methods for the Description of Electronically Excited States: Survey of Methods and Selected Results; 1 Introduction; 2 Spectroscopy of Electronically Excited States

3 Theoretical Methods for the Treatment of Excited States4 Results; 5 Conclusions and Opportunities; References; Long-Range Intramolecular Interactions: Implications for Electron Transfer; 1 Introduction; 2 TT+ TT_ and TT+* TT_* Splittings: Through-space and Through-bond Interactions; 3 Use of NBO's in analyzing TB interactions; 4 Connections with the Electron/hole Transfer Problem; 5 Effective two-level Hamiltonians; 6 The Role of Solvent in Mediating Electronic Coupling; 7 TT -> TT* Excited States of Non-conjugated Dienes; 8 Conclusions; References; The Breathing Orbital Valence Bond Method

1 Introduction2 Historical Background; 3 The Breathing Orbital Valence Bond Method; 4 Application to the Problem of Symmetry-breaking. The H2O2- Potential Surface; 5 The Compared Natures of the C-Cl and Si-CI Bonds; 6 The Lone Pair Bond Weakening Effect in HnX-H Bonds; 7 The Uniform Mean-Field Hartree-Fock Procedure; 8 Summary and Conclusion; References; Index

Notes:

Description based upon print version of record.

Includes bibliographical references and index.

ISBN:

9789812839756

9812839755