Reaction of Atmospherically Relevant Sulfur-Centered Radicals with RO2 and HO2
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Reaction of Atmospherically Relevant Sulfur-Centered Radicals with RO2 and HO2. / Chen, Jing; Lane, Joseph R.; Kjaergaard, Henrik G.
I: Journal of Physical Chemistry A, Bind 127, Nr. 13, 2023, s. 2986-2991.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Reaction of Atmospherically Relevant Sulfur-Centered Radicals with RO2 and HO2
AU - Chen, Jing
AU - Lane, Joseph R.
AU - Kjaergaard, Henrik G.
N1 - Funding Information: We thank Dr. Torsten Berndt for helpful discussions. This project was supported by the Alfred P. Sloan Foundation (G-2019-12281), the Independent Research Fund Denmark (9040-00142B), the High-Performance Computing Center at the University of Copenhagen, and the New Zealand eScience Infrastructure (NeSI). Publisher Copyright: © 2023 American Chemical Society.
PY - 2023
Y1 - 2023
N2 - The atmospheric oxidation of dimethyl sulfide and other emitted sulfur species leads to the formation of the methylthio radical, CH3S, which can be further oxidized to the CH3SO and CH3SO2 radicals. We investigated computationally the reactions of these three sulfur-centered radicals with the peroxy radicals ROO and HOO. Our results demonstrate that CH3S and CH3SO react with these peroxy radicals to form short-lived peroxide intermediates, which then decompose via a concerted O-O bond scission and S═O double bond formation that results in an increased valence of the sulfur atom. In contrast, CH3SO2 reacts to form stable CH3S(O)2OOR and CH3S(O)2OOH peroxide products, as sulfur is already at its highest valence. Multireference methods were used to describe these reactions in which the valence of the sulfur atom changes.
AB - The atmospheric oxidation of dimethyl sulfide and other emitted sulfur species leads to the formation of the methylthio radical, CH3S, which can be further oxidized to the CH3SO and CH3SO2 radicals. We investigated computationally the reactions of these three sulfur-centered radicals with the peroxy radicals ROO and HOO. Our results demonstrate that CH3S and CH3SO react with these peroxy radicals to form short-lived peroxide intermediates, which then decompose via a concerted O-O bond scission and S═O double bond formation that results in an increased valence of the sulfur atom. In contrast, CH3SO2 reacts to form stable CH3S(O)2OOR and CH3S(O)2OOH peroxide products, as sulfur is already at its highest valence. Multireference methods were used to describe these reactions in which the valence of the sulfur atom changes.
U2 - 10.1021/acs.jpca.3c00558
DO - 10.1021/acs.jpca.3c00558
M3 - Journal article
C2 - 36975390
AN - SCOPUS:85151361128
VL - 127
SP - 2986
EP - 2991
JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
SN - 1089-5639
IS - 13
ER -
ID: 345274435