HS和HOO抽氢反应机理的研究  

Studies on the hydrogen abstraction reaction mechanism of HS with HOO

作　　者：王智香[1] 曹佳[1] 高楼军[1] 付峰[1] 

机构地区：[1]延安大学化学与化工学院,陕西延安716000

出　　处：《分子科学学报》2015年第1期42-46,共5页Journal of Molecular Science

基　　金：陕西省教育厅专项科研计划项目(2013JK0667);延安大学资助项目(YDQ2013-16)

摘　　要：在B3LYP/6-311+G(3df,2p)水平上对HS和HOO反应中的所有物种进行了几何构型优化和频率计算,采用QCISD(T)/6-311+G(3df,2p)方法获得了各物种的单点能,构建了HS和HOO反应在单、三重态势能剖面.结果表明,HS与HOO反应体系中存在2种不同的抽氢通道,在单、三重态势能面上生成的产物分别为[1P1(H2O2+1S),1P2(H2S+1 O2)]和[3P1(H2O2+3S),3P2(H2S+3O2)].标题反应主要发生在三重态势能面上,优势通道[R→3 TS2→3P2(H2S+3O2)]的活化能为9.99kJ·mol-1.此结果对认识大气硫迁移转变规律具有实际意义.Geometry optimization and frequency calculations of all the species for the reaction of HS with HOO were calculated using B3LYP/6-311＋G（3df,2p） method. Single point energies of all the stationary point were computed at the QCISD（T）/6-311＋G（3df,2p） level. Single potential energy surface and triple potential energy surface were constructed. Four major reaction channels （five paths） and two kinds of hydrogen abstraction were investigated. The corresponding products for the singlet potential energy surface and triplet potential energy surface for the results show that there are four products： [3P1 （H2O2 ＋3S）, 3P2 （H2S＋3O2）] and [1p1 （H2O2＋1S） , P2 （H2S＋1O2）]. Channel R→3TS2→3P2（H2S＋3O2） is dominant happened on the triplet potential energy surface with the ap- parent activation energy of 9.99 kJ· mol-1. This result has practical significance for understanding of the atmospheric sulfur conversion rules.

关 键 词：HOO HS 抽氢反应机理 势能面 

分 类 号：O641[理学—物理化学]