气相中Mo^+与CS_2反应的理论研究  

Theoretical Study of the Reaction of Mo^+(~6S,~4G) with CS_2

作　　者：余仕问[1] 陈广[1] 侯能邦[1] 姚立峰[1] 

机构地区：[1]曲靖师范学院化学化工学院,云南曲靖655011

出　　处：《曲靖师范学院学报》2011年第6期8-12,32,共6页Journal of Qujing Normal University

基　　金：国家自然科学基金项目(30730003);曲靖师范学院项目(2009QN033)阶段性研究成果

摘　　要：用密度泛函理论中B3LYP方法详细研究了Mo+(6S,4d5,4G,4d5)与CS2的反应机理.为了得到更为准确的活化能和反应的能量,在B3LYP优化好的结构的基础上,用耦合族理论(CCSD(T))计算了各个驻点的单点能.计算结果显示,活化C-S键的反应机理为是插入-消出机理.反应Mo+(6S)+CS2(1Σ)→MoS+(4Σ-)+CS(1Σ)在反应过程中经过六重态-四重态势能面交叉,我们确定势能面交叉点(CP).所有的计算结果都和已有的理论和实验值进行了比较.The quartet and doublet potential energy surfaces（PESs） for reactions of Mo＋（6S,4G） with CS2 in the gas phase have been investigated in detail by means of density functional method（B3LYP） to elucidate the mechanisms of Mo＋ reacting with CS2.The coupled cluster single-point calculations（CCSD（T）） using B3LYP optimized geometries were performed to obtain more accurate results.The sextet and quartet reactions have an insertion-elimination mechanism.It is found that the reaction of the 6S gound state of Mo＋ to yield MoS＋ is spin-forbidden Mo＋（6S） ＋CS2（1Σ）→MoS＋（4Σ-） ＋ CS（1Σ）and the crossing points were approximately determined.All of the results have been compared with the existing experimental and theoretical data.

关 键 词：钼离子 二硫化碳 自旋禁阻反应 密度泛函理论 

分 类 号：O614.61[理学—无机化学]