HSS和OH反应机理的理论研究  

Theoretical studies on the reaction mechanism of HSS with OH

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：《计算机与应用化学》2014年第12期1565-1568,共4页Computers and Applied Chemistry

基　　金：陕西省教育厅专项科研计划项目资助(2013JK0667);延安大学青年项目资助(YDQ2013-16);延安大学化学与化工学院自然科学专项基金资助(YDHG2014-12)

摘　　要：应用量子化学计算方法研究HSS和OH的反应机理。在B3LYP/6-311+G(2df,p)水平上对HSS和OH反应过程中所有物种进行了构型优化和频率计算。采用QCISD(T)/6-311+G(3df,2p)方法的能量数据,构建了标题反应的势能剖面。结果表明,HSS和OH反应体系中存在4条通道,主通道为OH中O原子夺取HSS中H原子形成产物P1(H_2O+S_2),该通道包含3条路径其表观活化能分别为-72.15,-33.07和-31.41 kJ·mol^(-1),优势路径经过环状过渡态TS1。基于统计热力学原理,预测了稳定物种的热力学性质。The equilibrium geometries and vibrational frequencies of all stationary points involved in the reaction of HSS and OH are calculated at the B3LYP/6-311＋G（2df,p） level.The single-point energies including zero point energy correction are calculated at the QCISD（T）/6-311＋G（3df,2p） level,as well as the potential energy surface is constructed.The results show that there are four reaction channels for the HSS＋OH reaction system.The formation of P1（H2O＋S2） is main channel including three pathways,Apparent activation energies of the three pathways are-72.15,-33.07 and-31.41 kJ·mol^-1,respectively.The main path take place by the ring transition stare TS1.Thermodynamic properties including formation enthalpies（△fH^θ298K）,entropies（S^θ298K）,and heat capacities（CP） of all the stabilized species are predicted.

关 键 词：HSS OH 反应机理 热力学性质 

分 类 号：O641[理学—物理化学]