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Fluctuating Double-Bond Localization and Charge Migration in π Systems

✍ Scribed by Edgar Heilbronner; Sason Shaik

Book ID
102860335
Publisher
John Wiley and Sons
Year
1992
Tongue
German
Weight
981 KB
Volume
75
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

In π systems with localized double bonds, the switch from one localization pattern to another symmetry‐equivalent one, and the corresponding changes in electron distribution are often considered to proceed via a delocalized transition state of higher symmetry. We present a different mechanism, according to which the double‐bond localization and the concomitant charge distributions can fluctuate without change in energy and without passing through a delocalized, higher‐symmetry transition state. This result is obtained within a simple, independent‐electron (HMO‐type) treatment.

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