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利用MP2/6-311++G(d,p)//B3LYP/6-311++G(d,p)对CH3SS与XO(X=F,Cl,Br)的反应机理进行了研究.着重从电子密度拓扑分析角度讨论了化学键的生成和断裂.计算结果表明单线态反应为主要反应通道,且由于该通道的反应能垒低、放热明显,说明CH3SS与XO在大气中比较容易进行.电子密度拓扑分析表明,在单线态抽氢反应通道中存在着四元环状过渡结构,随着反应进行,此四元环状过渡结构通过一个T-型结构变为三元环状过渡结构,最后环状结构消失得到产物.
The reaction mechanism of CH3SS with XO (X = F, Cl, Br) was studied by using MP2 / 6-311 ++ G (d, p) // B3LYP / 6-311 ++ G (d, p) The formation and cleavage of chemical bonds are discussed from the topological analysis of electron density. The calculated results show that the singlet reaction is the main reaction channel, and the CH3SS and XO are easier to be carried out in the atmosphere due to the low energy barrier and the exothermic heat. The topological analysis of electron density shows that there exists a quaternary cyclic transition structure in the singlet hydrogen abstraction channel. With the reaction proceeding, the quaternary cyclic transition structure becomes a three-membered cyclic transition structure through a T- The final ring structure disappears to give the product.