Natural bond-bond polarizability: a Hückel-like electronic delocalization index

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 &quo...

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Veröffentlicht in:Journal of organic chemistry 2013-03, Vol.78 (5), p.1844-1850
Hauptverfasser: Zimmerman, H E, Weinhold, F
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
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Zusammenfassung: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.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo301620k