Excited-state potential energy surfaces of silaethylene: A MRCI investigation

M. Pitonak; H. Lischka

doi:10.1080/00268970412331333573

Excited-state potential energy surfaces of silaethylene: A MRCI investigation

M. Pitonak, H. Lischka

Chemistry and Biochemistry

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7 Scopus citations

Abstract

Extended MR-CISD calculations have been performed for vertical electronic excitations and for excited-state energy surfaces of silaethylene. Stationary points and conical intersections have been determined using recently developed analytic MR-CI gradients and non-adiabatic coupling terms. The calculations show that in vertical excitations the ππ* (V) state is the lowest excited singlet state. The torsion around the CSi bond is the dominant stabilizing factor, as in the case of ethylene. However, in marked contrast to ethylene this torsion leads directly to a conical intersection with the ground state. CH₂ and SiH₂ pyramidalization and hydrogen migration pathways also have been investigated. Both modes are not expected to play a significant role concerning the excited-state lifetime of silaethylene.

Original language	English
Pages (from-to)	855-862
Number of pages	8
Journal	Molecular Physics
Volume	103
Issue number	6-8
DOIs	https://doi.org/10.1080/00268970412331333573
State	Published - Mar 20 2005

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title = "Excited-state potential energy surfaces of silaethylene: A MRCI investigation",

abstract = "Extended MR-CISD calculations have been performed for vertical electronic excitations and for excited-state energy surfaces of silaethylene. Stationary points and conical intersections have been determined using recently developed analytic MR-CI gradients and non-adiabatic coupling terms. The calculations show that in vertical excitations the ππ* (V) state is the lowest excited singlet state. The torsion around the CSi bond is the dominant stabilizing factor, as in the case of ethylene. However, in marked contrast to ethylene this torsion leads directly to a conical intersection with the ground state. CH2 and SiH2 pyramidalization and hydrogen migration pathways also have been investigated. Both modes are not expected to play a significant role concerning the excited-state lifetime of silaethylene.",

author = "M. Pitonak and H. Lischka",

note = "Funding Information: This work was supported by the Austrian Science Fund within the framework of the Special Research Program F16 and by the Project No. P14442-NO3. The authors also gratefully acknowledge a travel grant by the University of Vienna for one of us (M.P.). The calculations were performed in part on the Schroedinger II Linux cluster of the Vienna University Computer Center.",

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T1 - Excited-state potential energy surfaces of silaethylene

T2 - A MRCI investigation

AU - Pitonak, M.

AU - Lischka, H.

N1 - Funding Information: This work was supported by the Austrian Science Fund within the framework of the Special Research Program F16 and by the Project No. P14442-NO3. The authors also gratefully acknowledge a travel grant by the University of Vienna for one of us (M.P.). The calculations were performed in part on the Schroedinger II Linux cluster of the Vienna University Computer Center.

PY - 2005/3/20

Y1 - 2005/3/20

N2 - Extended MR-CISD calculations have been performed for vertical electronic excitations and for excited-state energy surfaces of silaethylene. Stationary points and conical intersections have been determined using recently developed analytic MR-CI gradients and non-adiabatic coupling terms. The calculations show that in vertical excitations the ππ* (V) state is the lowest excited singlet state. The torsion around the CSi bond is the dominant stabilizing factor, as in the case of ethylene. However, in marked contrast to ethylene this torsion leads directly to a conical intersection with the ground state. CH2 and SiH2 pyramidalization and hydrogen migration pathways also have been investigated. Both modes are not expected to play a significant role concerning the excited-state lifetime of silaethylene.

AB - Extended MR-CISD calculations have been performed for vertical electronic excitations and for excited-state energy surfaces of silaethylene. Stationary points and conical intersections have been determined using recently developed analytic MR-CI gradients and non-adiabatic coupling terms. The calculations show that in vertical excitations the ππ* (V) state is the lowest excited singlet state. The torsion around the CSi bond is the dominant stabilizing factor, as in the case of ethylene. However, in marked contrast to ethylene this torsion leads directly to a conical intersection with the ground state. CH2 and SiH2 pyramidalization and hydrogen migration pathways also have been investigated. Both modes are not expected to play a significant role concerning the excited-state lifetime of silaethylene.

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DO - 10.1080/00268970412331333573

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JO - Molecular Physics

JF - Molecular Physics

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ER -

Excited-state potential energy surfaces of silaethylene: A MRCI investigation

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