Chemical dynamics study on the gas-phase reaction of the D1-silylidyne radical (SiD; X2Π) with deuterium sulfide (D2S) and hydrogen sulfide (H2S)
| Autor: | Srinivas Doddipatla, Mateus X. Silva, Tom J. Millar, Ralf I. Kaiser, Shane J. Goettl, Breno R. L. Galvão, Zhenghai Yang, Chao He |
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| Rok vydání: | 2021 |
| Předmět: |
chemistry.chemical_classification
Hydrogen Sulfide Hydrogen sulfide General Physics and Astronomy chemistry.chemical_element Reaction intermediate 010402 general chemistry Photochemistry 01 natural sciences Sulfur Transition state 0104 chemical sciences chemistry.chemical_compound chemistry Deuterium 0103 physical sciences Elementary reaction Physical and Theoretical Chemistry 010303 astronomy & astrophysics |
| Zdroj: | Physical Chemistry Chemical Physics. 23:13647-13661 |
| ISSN: | 1463-9084 1463-9076 |
| DOI: | 10.1039/d1cp01629f |
| Popis: | The reactions of the D1-silylidyne radical (SiD; X2Π) with deuterium sulfide (D2S; X1A1) and hydrogen sulfide (H2S; X1A1) were conducted utilizing a crossed molecular beams machine under single collision conditions. The experimental work was carried out in conjunction with electronic structure calculations. The elementary reaction commences with a barrierless addition of the D1-silylidyne radical to one of the non-bonding electron pairs of the sulfur atom of hydrogen (deuterium) sulfide followed by possible bond rotation isomerization and multiple atomic hydrogen (deuterium) migrations. Unimolecular decomposition of the reaction intermediates lead eventually to the D1-thiosilaformyl radical (DSiS) (p1) and D2-silanethione (D2SiS) (p3) via molecular and atomic deuterium loss channels (SiD–D2S system) along with the D1-thiosilaformyl radical (DSiS) (p1) and D1-silanethione (HDSiS) (p3) through molecular and atomic hydrogen ejection (SiD–H2S system) via indirect scattering dynamics in barrierless and overall exoergic reactions. Our study provides a look into the complex dynamics of the silicon and sulfur chemistries involving multiple deuterium/hydrogen shifts and tight exit transition states, as well as insight into silicon- and sulfur-containing molecule formation pathways in deep space. Although neither of the non-deuterated species – the thiosilaformyl radical (HSiS) and silanethione (H2SiS) – have been observed in the interstellar medium (ISM) thus far, astrochemical models presented here predict relative abundances in the Orion Kleinmann-Low nebula to be sufficiently high enough for detection. |
| Databáze: | OpenAIRE |
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