金属-苯配合物的密度泛函理论研究

ELECTRON TRANSFER REACTION MECHANISM BETWEEN M-C _6H_6 AND M^+-C_6H_6 COMPLEXES

用密度泛函理论 (DFT/BLYP)在 6 - 31G基组水平上研究了金属原子 -苯与离子 -苯配合物的气相电子转移过程 ,得到了M(Li,Na,Mg) -C6H6和M+-C6H6络合物以及它们之间电子转移过程中的先驱络合物的最优几何构型和电子结构 .同时利用线性坐标确定了过渡态的结构 .结果表明 :DET方法计算得到的单体即原子 (离子 ) -苯的构型同MP2结果较为一致 .通过分析过渡态及单体的原子上的电荷分布 ,对电子转移的反应机理进行了探讨 ,给出了反应活化能及电子转移反应的耦合矩阵元 。

DFT/BLYP method is used theoretically to investigate the electron transfer(ET) reactions between M(Li,Na,Mg)-C 6H 6 and M +-C 6H 6 complexes in the gas phase. The geometry optimization of the metal-benzene complexes and the encounter state in the process of ET reaction performed at 6-31G basis set level. It shows that there are relatively strong interactions between them. Additionally, the geometry of transition state is also obtained with the linear coordinate method. Also the activation energy, the coupling matrix element and the rate constant of the ET reaction are calculated.