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Influence of Water on the Gas-Phase Reaction of Dimethyl Sulfide with BrO in the Marine Boundary Layer
ACS Omega ( IF 3.7 ) Pub Date : 2021-01-13 , DOI: 10.1021/acsomega.0c05945
Junyao Li 1 , Narcisse T. Tsona 1 , Shanshan Tang 1 , Xiuhui Zhang 2 , Lin Du 1
ACS Omega ( IF 3.7 ) Pub Date : 2021-01-13 , DOI: 10.1021/acsomega.0c05945
Junyao Li 1 , Narcisse T. Tsona 1 , Shanshan Tang 1 , Xiuhui Zhang 2 , Lin Du 1
Affiliation
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The effect of a single water molecule on the reaction of dimethyl sulfide (DMS) with BrO reaction has been investigated using quantum chemical calculations at the CCSD(T)/6-311++G**//BH&HLYP/aug-cc-pVTZ level of theory. Two reaction mechanisms have been considered both in the absence and the presence of water, namely, oxygen atom transfer and hydrogen abstraction, among which the oxygen atom transfer was predominant. Five reaction channels were found in the absence of water, in which the channels starting from the cis-configuration of the pre-reaction complexes were more favorable because of the low energy barrier. The inclusion of water slightly decreased the energy barrier height of most oxygen atom transfer channels, while making the hydrogen abstraction channels more complex. While the effective rate coefficients for the oxygen atom transfer paths are found to have decreased by 3–7 orders of magnitude in the presence of water relative to the water-free reactions, the negligible fraction of reactants that are effectively clustered with water does not significantly change the overall rate of the formation of dimethyl sulfoxide and Br. The present results show that the overall mechanism and rate of the DMS + BrO reaction may not be affected by humidity under atmospheric conditions.
中文翻译：
水对海洋边界层中二甲硫与BrO气相反应的影响
在CCSD（T）/ 6-311 ++ G ** // BH＆HLYP / aug-cc-pVTZ处使用量子化学计算研究了单个水分子对二甲基硫（DMS）与BrO反应的影响理论水平。在不存在和存在水的情况下，已经考虑了两种反应机理，即氧原子转移和氢提取，其中氧原子转移是主要的。在没有水的情况下发现了五个反应通道，其中通道从顺式开始由于低能垒，反应前配合物的-构型更有利。包含水会稍微降低大多数氧原子转移通道的能垒高度，同时使夺氢通道更加复杂。尽管发现在水存在下，相对于无水反应，氧原子传递路径的有效速率系数降低了3–7个数量级，但与水有效簇化的可忽略的反应物分数却没有显着降低改变二甲基亚砜和Br的整体形成速率。目前的结果表明，DMS + BrO反应的总体机理和速率可能不受大气条件下的湿度影响。
更新日期：2021-01-26
中文翻译：
水对海洋边界层中二甲硫与BrO气相反应的影响
在CCSD（T）/ 6-311 ++ G ** // BH＆HLYP / aug-cc-pVTZ处使用量子化学计算研究了单个水分子对二甲基硫（DMS）与BrO反应的影响理论水平。在不存在和存在水的情况下，已经考虑了两种反应机理，即氧原子转移和氢提取，其中氧原子转移是主要的。在没有水的情况下发现了五个反应通道，其中通道从顺式开始由于低能垒，反应前配合物的-构型更有利。包含水会稍微降低大多数氧原子转移通道的能垒高度，同时使夺氢通道更加复杂。尽管发现在水存在下，相对于无水反应，氧原子传递路径的有效速率系数降低了3–7个数量级，但与水有效簇化的可忽略的反应物分数却没有显着降低改变二甲基亚砜和Br的整体形成速率。目前的结果表明，DMS + BrO反应的总体机理和速率可能不受大气条件下的湿度影响。
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