Geometry relaxation effects in the 1 1Bu and 2 1Ag states of trans-1,3-butadiene

P. G. Szalay, A. Karpfen, H. Lischka

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Abstract

MCSCF and MRCI calculations on the first three singlet states of trans-1,3-butadiene are presented. Flexible basis sets were applied and full geometry optimization was carried out at the MCSCF level for planar and selected non-planar structures including twisting and pyramidalization of terminal CH2-groups. Geometry relaxations in and excitation energies to 1 1Bu and 2 1Ag states are discussed in detail. For planar structures the covalent 2 1Ag state is lower in energy than the 1 1Bu state. If non-planar geometry relaxations are allowed, the lowest lying non-planar excited singlet state turns out to be ionic with one terminal CH2 group rotated by 90°. Limitations of the current investigations due to restrictions in the MRCI treatment and because of incomplete scanning of excited state surfaces are pointed out.

Original languageEnglish
Pages (from-to)219-228
Number of pages10
JournalChemical Physics
Volume130
Issue number1-3
DOIs
StatePublished - Feb 15 1989

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