Bonding in singlet and triplet butalene: insights from spin-coupled theory

David L Cooper, Peter B Karadakov, Brian J Duke

Research output: Contribution to journalArticleResearchpeer-review

3 Citations (Scopus)

Abstract

Spin-coupled (SC, equivalent to full generalized valence bond) calculations for the 1Ag ground state of butalene at its optimal D2h planar geometry show that cross-ring Dewar-like modes of spin coupling are of comparable importance to the more usually considered Kekulé-like modes. There are marked similarities to the SC description of one of the isomers of benzo[1,2:4,5]dicyclobutadiene. A complication for both of these systems is the existence of SC solutions in which some of the orbitals resemble in- and out-of-phase combinations of semilocalized atom-centered orbitals. The lowest triplet state, for which a nonplanar C2v geometry is preferred, is somewhat more straightforward to analyze: the SC description of the 3B2 state is dominated by a very simple pattern of two π bonds and two well-localized triplet-coupled orbitals.
Original languageEnglish
Pages (from-to)2169-2175
Number of pages7
JournalThe Journal of Physical Chemistry A
Volume119
Issue number10
DOIs
Publication statusPublished - 2015

Cite this