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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 :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C6v对称性 ,给体与受体间距离在0.30～0.36nm ,络合物的稳定化能在0.9～1.5eV之间 ,表明两者间存在较强的相互作用.另外 ,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 ,并进一步计算出反应的速率常数.对于电子转移反应的重组能 ,通过George Griffith Marcus(GGM)公式(只包含力常数矩阵中的对角元素的贡献)和Hessian矩阵法(包括对角元素和非对角元素的贡献)进行了计算.结果表明,不同振动模式间的耦合作用对气相电子转移反应的内氛重组能有重要影响
The gas-phase electron transfer of benzene and ionic benzene complexes was investigated by density functional theory (DFT / BLYP) at the 631G basis set. The complex of M (Li, Na, Mg) C6H6 and M + C6H6 As well as the optimal geometry and electronic structure of the precursor complexes during the electron transfer between them were also investigated. The structure of the transition state was also determined by linear coordinates. The results showed that the calculated monomer of the DFT method, ) Benzene, which is in good agreement with that of MP2.The precursor complex has C6v symmetry with a distance between donor and acceptor ranging from 0.30 to 0.36 nm, and the stability of the complex can be between 0.9 and 1.5 eV, indicating In addition, the reaction mechanism of electron transfer was discussed by analyzing the transition states and the charge distributions on the atoms of the monomers, and the coupling matrix elements of activation energy and electron transfer reaction , And further calculated the rate constants of the reaction.For the recombination energy of the electron transfer reaction, through the George Griffith Marcus (GGM) formula (only contains the contribution of diagonal elements in the force constant matrix) and Hessian matrix method (including diagonal elements and non- The contribution of the diagonal elements) were calculated. The results indicate that the atmosphere coupling between different vibration modes in gaseous phase reaction to have an important impact recombinant