气相中Sc+和Ti+与CS2反应的计算研究

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.

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

The reaction of Sc or Ti with CS2, which was selected as a represent ative system of reactions of first early transition-metal ions with CS2. The rea ction mechanism of Sc or Ti in ground state and excitated state with CS2 h as been studied using the density functional theory (DFT) at B3LYP/6-311 G* leve l. The geometries for reactants, the transition states and the products were com pletely optimized. All the transition states were verified by the vibrational an alysis and the intrinsic reaction coordinate (IRC) calculations. A potential ene rgies curve- crossing diagram was investigated for state correlation between early intermedia te IM1 and reactants in the reaction of Sc , Ti with CS2. The result showed tha t the reaction mechanism between first early transition-metal ions and CS2 was a n insertion-elimination mechanism. The main reaction path channel was detected i n the reaction of Sc or Ti in ground state and excitated state with CS2.