气相中Y^+活化CS_2中的C—S键(英文)

C—S Activation of CS_2 by Y^+ in Gas Phase

以Y+与CS2反应作为第二行前过渡金属离子与CS2反应的范例体系.采用密度泛函UB3LYP方法,对于Y+采用Stuttgart赝势基组,对于CS2采用6-311+G(2d)基组,计算研究了Y+离子在基态和激发态时与CS2气相反应的机理.并用UCCSD(T)方法在相同的基组水平上对各驻点作了单点能量校正.结果表明Y+离子与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.

The reaction of Y＋ with CS2, which was selected as the representative system of the reactions of second-row transition metal ions with CS2, was investigated using density functional theory （DFT） with the Stuttgart pseudo potentials and corresponding basis sets for Y＋ and the standard 6-311＋G（2d） basis sets for C and S atoms. Single-point UCCSD（T） energy calculations were carried out for each stationary point. The object of this investigation was the elucidation of the reaction mechanism. The result shows that the reaction mechanism between yttrium ion and CS2 is an insertion-elimination mechanism. Intersystem crossing may occur in the reaction of Y＋ with CS2 and a minimum energy crossing point has been found. All theoretical results are in line with early experiments.