Geometry relaxation effects in the 1 1B2 and 2 1A1 states of cis-1,3-butadiene

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

doi:10.1016/0301-0104(90)87069-N

Geometry relaxation effects in the 1 ¹B₂ and 2 ¹A₁ states of cis-1,3-butadiene

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

Chemistry and Biochemistry

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Abstract

MCSCF and MRCI calculations on the first three singlet states of cis-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 the terminal CH₂ groups. Geometry relaxations in and excitation energies to the 1 ¹B₂ and 2 ¹A₁ states are discussed in detail. For planar structures the covalent 2 ¹A₁ state is lower in energy than the 1 ¹B₂ state. If non-planar geometry relaxations are allowed we find that among the structures considered the lowest-lying non-planar excited singlet state is ionic with one terminal CH₂ group rotated by 90°. A detailed comparison with the results on trans-butadiene is also given.

Original language	English
Pages (from-to)	355-363
Number of pages	9
Journal	Chemical Physics
Volume	141
Issue number	2-3
DOIs	https://doi.org/10.1016/0301-0104(90)87069-N
State	Published - Mar 1 1990

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title = "Geometry relaxation effects in the 1 1B2 and 2 1A1 states of cis-1,3-butadiene",

abstract = "MCSCF and MRCI calculations on the first three singlet states of cis-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 the terminal CH2 groups. Geometry relaxations in and excitation energies to the 1 1B2 and 2 1A1 states are discussed in detail. For planar structures the covalent 2 1A1 state is lower in energy than the 1 1B2 state. If non-planar geometry relaxations are allowed we find that among the structures considered the lowest-lying non-planar excited singlet state is ionic with one terminal CH2 group rotated by 90°. A detailed comparison with the results on trans-butadiene is also given.",

author = "Szalay, {P. G.} and A. Karpfen and H. Lischka",

note = "Funding Information: This work was supported by the Austrian “Fonds zur Fiirderung der wissenschaftlichen Forschung”, Project No. P65OOC.T he calculations have been performed on the IBM 3090-400 VF of the computer center of the University of Vienna within the European Academic Supercomputing Initiative sponsored by IBM, and on the NAS 9 160 computer of the “Interuniversitlres EDV-Zentrum”, Vienna. The authors are grateful for ample supply with computer time.",

year = "1990",

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doi = "10.1016/0301-0104(90)87069-N",

language = "English",

volume = "141",

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T1 - Geometry relaxation effects in the 1 1B2 and 2 1A1 states of cis-1,3-butadiene

AU - Szalay, P. G.

AU - Karpfen, A.

AU - Lischka, H.

N1 - Funding Information: This work was supported by the Austrian “Fonds zur Fiirderung der wissenschaftlichen Forschung”, Project No. P65OOC.T he calculations have been performed on the IBM 3090-400 VF of the computer center of the University of Vienna within the European Academic Supercomputing Initiative sponsored by IBM, and on the NAS 9 160 computer of the “Interuniversitlres EDV-Zentrum”, Vienna. The authors are grateful for ample supply with computer time.

PY - 1990/3/1

Y1 - 1990/3/1

N2 - MCSCF and MRCI calculations on the first three singlet states of cis-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 the terminal CH2 groups. Geometry relaxations in and excitation energies to the 1 1B2 and 2 1A1 states are discussed in detail. For planar structures the covalent 2 1A1 state is lower in energy than the 1 1B2 state. If non-planar geometry relaxations are allowed we find that among the structures considered the lowest-lying non-planar excited singlet state is ionic with one terminal CH2 group rotated by 90°. A detailed comparison with the results on trans-butadiene is also given.

AB - MCSCF and MRCI calculations on the first three singlet states of cis-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 the terminal CH2 groups. Geometry relaxations in and excitation energies to the 1 1B2 and 2 1A1 states are discussed in detail. For planar structures the covalent 2 1A1 state is lower in energy than the 1 1B2 state. If non-planar geometry relaxations are allowed we find that among the structures considered the lowest-lying non-planar excited singlet state is ionic with one terminal CH2 group rotated by 90°. A detailed comparison with the results on trans-butadiene is also given.

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ER -

Geometry relaxation effects in the 1 ¹B₂ and 2 ¹A₁ states of cis-1,3-butadiene

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