Chemical dynamics study on the gas-phase reaction of the D1-silylidyne radical (SiD; XΠ) with deuterium sulfide (DS) and hydrogen sulfide (HS)
The reactions of the D1-silylidyne radical (SiD; X 2 Π) with deuterium sulfide (D 2 S; X 1 A 1 ) and hydrogen sulfide (H 2 S; X 1 A 1 ) were conducted utilizing a crossed molecular beams machine under single collision conditions. The experimental work was carried out in conjunction with electronic s...
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Published in | Physical chemistry chemical physics : PCCP Vol. 23; no. 24; pp. 13647 - 13661 |
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Main Authors | , , , , , , , |
Format | Journal Article |
Language | English |
Published |
Cambridge
Royal Society of Chemistry
23.06.2021
|
Subjects | |
Online Access | Get full text |
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Summary: | The reactions of the D1-silylidyne radical (SiD; X
2
Π) with deuterium sulfide (D
2
S; X
1
A
1
) and hydrogen sulfide (H
2
S; X
1
A
1
) 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 (D
2
SiS) (p3)
via
molecular and atomic deuterium loss channels (SiD-D
2
S system) along with the D1-thiosilaformyl radical (DSiS) (p1) and D1-silanethione (HDSiS) (p3) through molecular and atomic hydrogen ejection (SiD-H
2
S 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 (H
2
SiS) - 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.
Center-of-mass velocity flux contour map for the reaction of the D1-silylidyne radical (SiD) with deuterium sulfide (D
2
S) leading to the gas-phase formation of D2-silanethione (D
2
SiS). |
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Bibliography: | Electronic supplementary information (ESI) available. See DOI 10.1039/d1cp01629f ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1463-9076 1463-9084 |
DOI: | 10.1039/d1cp01629f |