物理化学学报 >> 2005, Vol. 21 >> Issue (10): 1102-1107.doi: 10.3866/PKU.WHXB20051008

研究论文 上一篇    下一篇

气相中Sc+和Ti+与CS2反应的计算研究

高立国; 王永成; 耿志远; 陈晓霞; 吕玲玲; 戴国梁; 王冬梅   

  1. 西北师范大学化学化工学院, 甘肃省高分子材料重点实验室, 兰州 730070
  • 收稿日期:2005-01-25 修回日期:2005-04-20 发布日期:2005-10-15
  • 通讯作者: 王永成 E-mail:wangyc@nwnu.edu.cn

Theoretical Study of the Reaction of Sc+ and Ti+ with CS2 in Gas Phase

GAO Li-guo; WANG Yong-cheng; GENG Zhi-yuan; CHEN Xiao-xia; LÜ Lingling; DAI Guo-liang; WANG Dongmei   

  1. College of Chemistry and Chemical Engineering, Northwest Normal University, Gansu Key Laboratory of Polymer Materials, Lanzhou 730070
  • Received:2005-01-25 Revised:2005-04-20 Published:2005-10-15
  • Contact: WANG Yong-cheng E-mail:wangyc@nwnu.edu.cn

摘要: 以Sc+和Ti+与CS2反应作为第一前过渡金属离子与CS2反应的范例体系. 采用密度泛函(UB3LYP/6-311+G*)方法计算研究了Sc+和Ti+在基态和激发态与CS2反应的反应机理. 全参数优化了反应势能面上各驻点的几何构型, 用频率分析方法和内禀反应坐标(IRC)方法对过渡态进行了验证. 计算了不同多重度下的反应交叉势能面. 确定了Sc+和Ti+与CS2的反应为插入-消去反应, 找到了基态和激发态金属离子与CS2反应的主要通道.

关键词: 过渡金属离子, 二硫化碳, 反应机理, 密度泛函理论

Abstract: The reaction of Sc+ or Ti+ with CS2, which was selected as a representative system of reactions of first early transition-metal ions with CS2. The reaction mechanism of Sc+ or Ti+ in ground state and excitated state with CS2 has been studied using the density functional theory (DFT) at B3LYP/6-311+G* level. The geometries for reactants, the transition states and the products were completely optimized. All the transition states were verified by the vibrational analysis and the intrinsic reaction coordinate (IRC) calculations. A potential energies curve-crossing diagram was investigated for state correlation between early intermediate IM1 and reactants in the reaction of Sc+,Ti+ with CS2. The result showed that the reaction mechanism between first early transition-metal ions and CS2 was an insertion-elimination mechanism. The main reaction path channel was detected in the reaction of Sc+ or Ti+ ground state and excitated state with CS2.

Key words: Transition-metal ion, Carbon bisulfide, Reaction mechanism, Density functional theory