Theoretical study of reactions in the multiple well H2/S2 system.
作者： Chenlai (Ryan) Zhou , Karina Sendt , Brian S. Haynes
DOI: 10.1021/JP903185K
关键词: Singlet fission 、 Bar (unit) 、 Reaction rate constant 、 Molecular physics 、 Chemistry 、 Potential energy surface 、 Valence (chemistry) 、 Excited state 、 Photochemistry 、 Singlet state 、 Intersystem crossing
摘要: The potential energy surface of the H2/S2 system has been characterized at full valence MRCI+Davidson/aug-cc-pV(Q+d)Z level theory using geometries optimized MRCI/aug-cc-pVTZ level. analysis includes channels occurring entirely on either singlet or triplet as well those involving an intersystem crossing. RRKM-based multiple calculations allow prediction rate constants in temperature range 300−2000 K between 0.1 and 10 bar. Of SH recombined surface, stabilization rovibrationally excited adduct HSSH is low-pressure limit 1 bar, but it a comparable to that forming another major set products H2S + S (via crossing) temperatures below 1000 K; higher temperatures, HSS H becomes dominant product. For reaction S, presence crossing allows formation H2SS, most which rearranges stabilizes under atmospheri...
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