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Theoretical study of deactivation and isomerization pathways of 1,2-dithiete in excited electronic states

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Abstract

The potential energy surface crossings for 1,2-dithiete have been investigated using the complete active space self-consistent field (CASSCF) method and simple group theory. Using the full Pauli-Breit spin-orbit coupling (SOC) operator \( (\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\frown}$}}{H} _{SO} ) \) which consists of the one-electron \( (\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\frown}$}}{H} _{SO1} ) \) and two-electron \( (\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\frown}$}}{H} _{SO2} ) \) terms, we estimate the strengths of the SOC (198.37 cm−1 when symmetry is imposed, and 211.35 cm−1 with no symmetry constraints), which plays an essential role in the spin transitions between different spin states. The calculations show that the photolysis of 1,3-dithiol-2-one leads to the formation of trans-dithioglyoxal (trans-MinS0) as a primary product which subsequently gives a secondary product identified as thiolthioketene. Our calculated results are in close agreement with the experimental observations.

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Authors and Affiliations

  1. College of Life Science and Chemistry, Tianshui Normal University, Tianshui, 741001, China

    LingLing Lv, Sheng Yang, XiaoFang Wang, Kun Yuan & XinWen Liu

  2. College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, 730070, China

    YongCheng Wang

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  1. LingLing Lv
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  2. Sheng Yang
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  3. XiaoFang Wang
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  4. Kun Yuan
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  5. XinWen Liu
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  6. YongCheng Wang
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Correspondence to LingLing Lv.

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Supported by the “QingLan” Talent Engineering Funds by Tianshui Normal University

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Lv, L., Yang, S., Wang, X. et al. Theoretical study of deactivation and isomerization pathways of 1,2-dithiete in excited electronic states. Sci. China Ser. B-Chem. 52, 1176–1185 (2009). https://doi.org/10.1007/s11426-009-0138-4

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  • DOI: https://doi.org/10.1007/s11426-009-0138-4

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