气相中Cu+和Zn+与CS2反应的计算研究

以Cu⁺和Zn⁺与CS₂反应作为第一过渡金属离子与CS₂反应的范例体系. 采用密度泛函UB3LYP/6-311+G^*方法计算研究了第一过渡金属离子在基态和激发态与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. 并用UCCSD(T)/6-311G^*方法对各驻点作了单点能量校正. 在Cu⁺与CS₂反应中, 计算了单重态初始中间体¹IM1到三重态插入型中间体³IM2的反应交叉势能面. 确定了第一过渡金属离子与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 Cu+ and Zn+ with CS2 in Gas Phase

The reaction of Cu+ and Zn+ with CS2, was selected as a representative system of reactions of first-row transition metal ions with CS2. The reaction mechanism between first-row transition metal ions in ground state and excited state and CS2 has been studied using the density functional theory (DFT) at UB3LYP/6-311+G level. The geometries for reactants, the transition states and the products were com- pletely optimized. All the transition states were verified by the vibrational analysis and the intrinsic reaction coordinate calculations. For each stationary point, single-point UCCSD(T) energy calculations were carried out. A potential energy curve-crossing diagram was investigated for state correlation between singlet 1IM1 and triplet 3IM2 in the reactin of Cu+ with CS2. The result showed that the reaction mechanism between first-row transition metal ions and CS2 was an insertion-elimination mechanism. The main reaction path channel was detected in the reaction of metal ions in ground state and excited state with CS2.