金属原子（离子）-苯配合物的电子转移反应

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滤态的结构，结果表明：ＤＦＴ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。先驱络合物具有Ｃ６ν对称性，给体与受体间距离

Electron Transfer Reaction Mechanism between M-C6H6 and M+ -C6H6 Complexes

DFT/BLYP method is used to investigate theoretically the electron transfer (ET) reactions between M(Li, Na, Mg)-C6H6 and M+-C6H6 complexes in the gas phase. The geometry optimization of the metal-benzene complexes and the encounter state in the process of ET reaction was performed at 6-31G basis set level. The precursor complex has C6 symmetry, the distance between acceptor and donor is about 0.30～0.36 nm, which yields the bonding energy approximately 0.9～1.5 eV. It shows that there are relatively strong interactions between them. The geometry of transition state is also obtained by the linear coordinate method. The activation energy, the coupling matrix element and the rate constant of the ET reaction are calculated. According to the reorganization energy of the ET reaction, the values obtained from George-Griffith-Marcus (GGM) method (the contribution only comes from the diagonal elements of the force constant matrix) are larger than those obtained from Hessian matrix method (including the contribution from both diagonal and off -diagonal elements),which suggests that the coupling interactions between different vibrational modes are important to the inner-sphere reorganization energy for the ET reactions in gaseous phase.