Natural Bond–Bond Polarizability: A Hückel-Like Electronic Delocalization Index
| Autor: | Frank Weinhold, Howard E. Zimmerman |
|---|---|
| Rok vydání: | 2012 |
| Předmět: |
Quantitative Biology::Biomolecules
Chemistry Organic Chemistry Intermolecular force Ab initio Context (language use) Delocalized electron Computational chemistry Polarizability Chemical physics Physics::Atomic and Molecular Clusters Molecular orbital Density functional theory Physics::Chemical Physics Natural bond orbital |
| Zdroj: | The Journal of Organic Chemistry. 78:1844-1850 |
| ISSN: | 1520-6904 0022-3263 |
| Popis: | We show how the bond-bond polarizability index, as originally introduced by Coulson and Longuet-Higgins in the Hückel-theoretic context, can be generalized in the natural bond orbital (NBO) framework to ab initio molecular orbital and density functional theory levels. We demonstrate that such a "natural bond-bond polarizability" (NBBP) index provides a flexible and quantitative descriptor for a broad spectrum of delocalization effects ranging from strong π aromaticity to weak intra- and intermolecular hyperconjugative phenomena. Illustrative applications are presented for representative delocalization effects in saturated and unsaturated species, chemical reactions, and hydrogen-bonding interactions. |
| Databáze: | OpenAIRE |
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