采用密度泛函理论UB3LYP方法对Co+在三重态及五重态势能面上催化N2O与C2H6进行循环反应的两态反应机理进行了研究.运用Harvery方法优化了两自旋态势能面5个最低能量交叉点(MECP)，计算了MECP处自旋-轨道耦合作用.采用Landau-Zener公式计算了自旋翻转处的系间窜越几率，各MECP处均可发生有效系间窜越.通过应用Kozuch提出的能量跨度模型， Co+催化N2O与C2H6在298K下反应生成CH3CHO时有最大的TOF值3.35×10-21 s-1.
The spin-forbidden mechanism of the reaction between N2O and C2H6 catalyzed by Co+ has been investigated using UB3LYP density functional theory. The Harvey method has been applied to opti-mize five minimum energy crossing points (MECP) on both triplet and quintet potential energy surfaces. Possible spin inversion processes are discussed by means of spin-orbit coupling calcula-tions. According to the calculation of probability of electron hopping using the Landau-Zener for-mula, effective intersystem crossing may occur at each MECP. The energetic span model proposed by Kozuch has been applied to the catalytic cycles, and shows the turnover frequency reaches 3.35 × 10-21 s-1 when Co+ catalyzes the reaction to produce CH3CHO at 298K.
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