Elucidation of the oxidation mechanism of naturally emitted reduced sulfur compounds, especially dimethyl sulfide, plays a central role in understanding background acid precipitation in the natural environment. Most frequently, theoretical studies of the addition and H-elimination reactions of dimethyl sulfide with hydroxyl radicals are studied considering the presence of oxygen that further reacts with the radicals formed in the initial steps. Although the reaction of intermediate species with additional hydroxyl radicals has been considered as part of the global mechanism of oxidation, little if any attention has been dedicated to the possibility of reactions of the initial radicals with a second OH molecule. In this work, we performed a computational study using quantum-chemical methods, of the mechanism of H-abstraction from dimethyl sulfide under normal atmospheric conditions and in reaction chambers at different O2 partial pressure, including complete absence of oxygen. Additionally, important rate coefficients were computed using canonical and variational transition state theory. The rate coefficient for abstraction affords a 4.72 × 10-12 cm3 molecule-1 s-1 value, very close to the most recent experimental one (4.13 × 10-12 cm3 molecule-1 s-1). According to our best results, the initial methyl thiomethyl radical was obtained at-25.2 kcal/mol (experimentally-22.4 kcal/mol), and four important paths were identified on the potential energy surface. From the interplay of thermochemical and kinetic arguments, it was possible to demonstrate that the preferred product of the reaction of dimethyl sulfide with two hydroxyl radicals is actually dimethyl sulfoxide.

H-Abstraction from Dimethyl Sulfide in the Presence of an Excess of Hydroxyl Radicals. A Quantum Chemical Evaluation of Thermochemical and Kinetic Parameters Unveils an Alternative Pathway to Dimethyl Sulfoxide

Salta Z.
;
Lupi J.;Barone V.;
2020

Abstract

Elucidation of the oxidation mechanism of naturally emitted reduced sulfur compounds, especially dimethyl sulfide, plays a central role in understanding background acid precipitation in the natural environment. Most frequently, theoretical studies of the addition and H-elimination reactions of dimethyl sulfide with hydroxyl radicals are studied considering the presence of oxygen that further reacts with the radicals formed in the initial steps. Although the reaction of intermediate species with additional hydroxyl radicals has been considered as part of the global mechanism of oxidation, little if any attention has been dedicated to the possibility of reactions of the initial radicals with a second OH molecule. In this work, we performed a computational study using quantum-chemical methods, of the mechanism of H-abstraction from dimethyl sulfide under normal atmospheric conditions and in reaction chambers at different O2 partial pressure, including complete absence of oxygen. Additionally, important rate coefficients were computed using canonical and variational transition state theory. The rate coefficient for abstraction affords a 4.72 × 10-12 cm3 molecule-1 s-1 value, very close to the most recent experimental one (4.13 × 10-12 cm3 molecule-1 s-1). According to our best results, the initial methyl thiomethyl radical was obtained at-25.2 kcal/mol (experimentally-22.4 kcal/mol), and four important paths were identified on the potential energy surface. From the interplay of thermochemical and kinetic arguments, it was possible to demonstrate that the preferred product of the reaction of dimethyl sulfide with two hydroxyl radicals is actually dimethyl sulfoxide.
atmospheric chemistry; computational study; DMS; DMSO; H-Abstraction; multigeneration OH oxidation
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11384/83360
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