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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical Studies of the Gas-Phase Reactions of S-Methyl Methanesulfinothioate (Dimethyl Thiosulfinate) with OH and Cl Radicals: Reaction Mechanisms, Energetics, and Kinetics
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Theoretical Studies of the Gas-Phase Reactions of S-Methyl Methanesulfinothioate (Dimethyl Thiosulfinate) with OH and Cl Radicals: Reaction Mechanisms, Energetics, and Kinetics

机译：S-甲基甲磺酸甲磺酸甲酯（二甲基硫酸二硫酸盐）气相反应的理论研究，用OH和CL自由基：反应机制，能量和动力学

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摘要

The mechanisms, energetics, and kinetics of the gas-phase reactions of terrestrial plant-derived dimethyl thiosulfinate (DMTS) with the atmospheric oxidants OH and Cl radicals were investigated using high-level ab initio calculations. The results show that the addition of OH and Cl radicals to the sulfinyl [-S(=O)] of DMTS, followed by S(=O)-S single bond cleavage to form methanesulfinic acid + CH3S center dot and methanesulfinyl chloride + CH3S center dot, respectively, are the more dominant reactions. The barrier heights for the reactions with OH and Cl radicals were found to be -5.6 and -12.7 kcal/mol relative to the energies of the starting reactants, respectively, when computed at the CCSD(T)/aug-cc-pVTZ//M06-2X/6-311++G(3df,3pd) level of theory. The rate constants for all possible pathways of DMTS + (OH)-O-center dot/Cl-center dot reactions were investigated using the MESMER kinetics code over the temperature range between 200 and 300 K. The calculated global rate constants for the DMTS + (OH)-O-center dot and DMTS + Cl-center dot reactions at 300 K were found to be 1.42 x 10(-11) and 3.72 x 10(-11) cm(3) molecule(-1) s(-1), respectively. In addition, the thermochemistry of all possible paths and branching ratios was determined. The atmospheric chemistry implications of the DMTS + (OH)-O-center dot/Cl-center dot reactions are discussed.
机译：使用高水平AB初始计算研究了陆地植物衍生的二甲基硫代硫酸酯（DMT）与大气氧化剂OH和Cl自由基的机制，能量学和动力学。结果表明，向DMT的磺酰基[-S（= O）]中加入OH和Cl自由基，其次是S（= O）单键切割，形成甲磺酸+ CH3S中心点和甲磺酰氯+ CH3s分别是中心点，是更大的反应。当在CCSD（T）/ Aug-CC-PVTZ //在CCSD（T）/ AUG-CC-PVTZ //时，发现与OH和Cl自由基的反应的反应的阻隔高分为-5.6和-12.7kcal / mol。 M06-2X / 6-311 ++ G（3DF，3PD）理论水平。使用MESMER动力学代码在200和300K之间的温度范围内研究了DMT +（OH）-O-中心点/ CL中心点反应的所有可能途径的速率常数。计算的全球速率常数为DMTS + （OH）-O-中心点和DMTS + CL中心点反应在300 k下发现为1.42×10（-11）和3.72×10（-11）cm（3）分子（-1）S（ - 1）分别。此外，确定了所有可能的路径和支化比的热化学。讨论了DMTS +（OH）-O中心点/ CL中心点反应的大气化学意义。

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