Abstract
H/vinyl conical intersections are proposed to have a potential role in the photochemical hula-twist isomerization of hexatriene. The hula twist is a novel volume-conserving isomerization mechanism for polyenes in rigid media. Conical intersections involving partial migration of a hydrogen and inversion of a carbon are explored as potential pathways for hula-twist isomerization. These structures are geometrically ideal for a volume-conserving process, but are energetically unfavorable. Calculations were carried out using the complete active space self-consistent field (CASSCF) method and the 6-31G(d) basis set. Inclusion of electron correlation using CASPT2 calculations resulted in significant lowering of conical intersection energies. The structures and energetics of H/vinyl structures are compared and contrasted with kinked-diene structures and the conventional one-bond-flip process of cis–trans isomerization of tEt-hexatriene. The results are related to H/vinyl and kinked-diene conical intersections previously studied for butadiene.
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