Unified Valence Bond Theory of Electronic Structure

1. Front Matter

   Pages N2-VIII

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2. The Conceptual Power of Molecular Orbital - Valence Bond (MOVB) Theory

   1. Front Matter

      Pages 1-11

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   2. The Induced Deexcitation Model

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      Pages 12-59

   3. Why do Organolithium Monomers have Strange Structures?

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      Pages 60-103

   4. The Molecular Orbital-Valence Bond Theory of Excited States

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      Pages 104-150

   5. The “Forbidden” World of Chemistry

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      Pages 151-185

   6. The Concept of Natural Ligand Nonbonded Repulsion. The Ethane Paradigm

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      Pages 186-206

   7. Conformational Isomerism of N2H4 and Derivatives. The Stereochemical Consequences of “Forbiddenness” Removal

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      Pages 207-230

   8. Geometric Isomerism: The Simplest Illustrator of Orbital Symmetry Control of Molecular Stereochemistry

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      Pages 231-249

   9. Structural Isomerism and the Electronic Basis for Ligand Segregation on C2 Cores

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      Pages 250-264

   10. The Saga of “Hypervalent” Molecules

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       Pages 265-298

   11. The Molecular Orbital-Valence Bond Theory of Inorganic Chemistry

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       Pages 299-340

   12. How to build Bridges by Molecular Orbital-Valence Bond Theory: The Structures of A2X4 Molecules

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       Pages 341-357

   13. Why Benzene prefers to substitute and an Olefin likes to add?

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       Pages 358-371

   14. Why “Effective” Bonds exist when “Real” Bonds are Absent: The Electronic Structure of the (1.1.1.) Propellane

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       Pages 372-380

   15. The Detailed Electronic Structure of Carbocyclic Molecules and the Concept of Superaromaticity

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       Pages 381-390

   16. The Explicit Theory of “Real” Electrocyclizations of Closed and Open Shell Molecules

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       Pages 391-417

3. Beyond Monodeterminantal MO Theory

   1. Front Matter

      Pages 418-419

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   2. Frontier Configurations and a New Classification of Annulenes

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      Pages 420-431

   3. Frontier Configuration Theory of Spin Selection

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      Pages 432-456

The bond diagrammatic representation of molecules is the foundation of MOVB theory. To a certain extent, this kind of representation is analogous to the one on which "resonance theory" is based and this fact can be projected by a comparison of the various ways in which MOVB theory depicts a species made up of three core and two ligand MO's which define two subsystems containing a total of six electrons and the ways in which "resonance theory" (i. e. , qualitative VB theory) depicts a six-electron-six-AO species such as the pi system of CH =CH-CH=CH-CH=O. The 2 different pictorial representations are shown in Scheme 1 so that the analogies are made evident. First of all, the total MOVB diagrammatic representation of the 6/5 species is obtained by a linear combination of three complete bond diagrams, as in Al, which describe the optimal linear combination of!l! MOVB Configuration Wavefunctions (CW's). By the same token, a total VB diagrammatic representation of the 6/6 species can be obtained by writing a "dot structure", as in Bl, and taking this to mean the optimal linear combination of all VB CW's. Next, we can approxi­ mate the MOVB wavefunction of the 6/5 species by one complete (or detailed) bond dia­ gram" (A2). No simple VB representation analogy can be given in this case. Alterna­ tively, we can approximate the MOVB wavefunction by a linear combination of compact bond diagrams, as in A3, in the way described before.

• Applications
• Isomer
• Structure
• aromatic
• classification
• electron
• hybridization
• inorganic chemistry
• lithium
• molecule
• organic chemistry
• polarization
• spin
• stereochemistry
• system

• Department of Chemistry, University of Washington, Seattle, USA

  Nicolaos Demetrios Epiotis

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