引用本文:
【打印本页】   【HTML】   【下载PDF全文】   View/Add Comment  【EndNote】   【RefMan】   【BibTex】
←前一篇|后一篇→ 过刊浏览    高级检索
本文已被:浏览 1604次   下载 1488 本文二维码信息
码上扫一扫!
分享到: 微信 更多
C-S Activation of CS2 by Nb+ in Gas Phase
Xiao-li Song,Li-guo Gao*
Author NameAffiliation
Xiao-li Song College of Chemistry and Chemical Engineering, Yulin College, Yulin 719000, China 
Li-guo Gao* College of Chemistry and Chemical Engineering, Yulin College, Yulin 719000, China 
Abstract:
The reaction of Nb+ with CS2, producing cationic transition-metal sulfide and CS, was taken as a representative example to elucidate the overall mechanism of reactions of second-row early transition metal ions with CS2. The reactions in both triplet and quintet state were studied by using the UB3LYP density functional method with the Stuttgart pseudo potentials and corresponding basis sets for Nb+ and the standard 6-311+G(2d) basis sets for C and S. The geometries for reactants, the transition states, and the products were completely optimized. All the transition states were verified by vibrational analysis and intrinsic reaction coordinate calculations. The results show that the reaction mechanism between niobium ion and CS2 is an insertion-elimination mechanism. Intersystem crossing may occur in the reaction Nb+ with CS2 and a minimum energy crossing point was found.
Key words:  Second-row early transition metal ion, Reaction mechanism, Intersystem crossing, Minimum energy crossing point
FundProject:
C-S Activation of CS2 by Nb+ in Gas Phase
宋小利,高立国*
摘要:
以Nb+与CS2反应作为第二前过渡金属离子与CS2反应生成金属硫化物离子和CS的范例体系. 采用密度泛函UB3LYP方法,对于Nb+采用Stuttgart赝势基组,对于C和S采用6-311+G(2d)基组,计算研究了Nb+在基态和激发态时与CS2气相反应的机理. 全参数优化了反应势能面上各驻点的几何构型,并且用频率分析方法和内禀反应坐标方法对过渡态进行了验证. 结果表明Nb+与CS2的反应是插入-消去反应,在反应过程中会发生系间窜越,并且找到了两个势能面的能量最低交叉点.
关键词:  第二前过渡金属离子,反应机理,系间窜越
DOI:10.1088/1674-0068/22/03/297-302
分类号: