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

P. Szalay, A. Karpfen, H. Lischka

Research output: Contribution to journalArticle

47 Citations (Scopus)

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
Publication statusPublished - Feb 15 1989

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butadiene
Excited states
Geometry
geometry
excitation
Excitation energy
planar structures
twisting
constrictions
Scanning
optimization
scanning
energy
1,3-butadiene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Geometry relaxation effects in the 1 1Bu and 2 1Ag states of trans-1,3-butadiene. / Szalay, P.; Karpfen, A.; Lischka, H.

In: Chemical Physics, Vol. 130, No. 1-3, 15.02.1989, p. 219-228.

Research output: Contribution to journalArticle

Szalay, P. ; Karpfen, A. ; Lischka, H. / Geometry relaxation effects in the 1 1Bu and 2 1Ag states of trans-1,3-butadiene. In: Chemical Physics. 1989 ; Vol. 130, No. 1-3. pp. 219-228.
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