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分离处理π σ π体系中的给体 ,受体和σ桥体 ,在HF/4 31G和HF/DZP水平上优化了联苯 ,联苯负离子自由基 ,萘和萘负离子自由基的几何构型 ,计算了分子间电子转移的内重组能 .取线性反应坐标R =0 .5 ,在STO 3G水平上用变分原理和分子轨道跃迁能方法 ,计算了π σ π体系自交换反应的电子转移矩阵元 .对交叉反应体系 ,沿线性反应坐标搜寻最小轨道能级分裂Δmin,确定了电子转移矩阵元和过渡态构型 .用Marcus双球模型计算液相电子转移的溶剂重组能 ,结合半经典模型计算了几种以联苯负离子自由基为给体 ,联苯和萘为受体的π σ π体系分子内电子转移速率常数 .
The geometries of donor, acceptor and σ-bridge in π σ π system were optimized and the geometric configurations of biphenyl, biphenyl anion, naphthalene and naphthalene anion were optimized at HF / 4 31G and HF / DZP levels , The intramolecular recombination energy of electron transfer between molecules was calculated. Taking the linear reaction coordinate R = 0.5, the electron transfer of the self-exchange reaction of π σ π system was calculated by the method of variational principle and molecular orbital transition energy at the level of STO 3G Matrix element.For the cross-reaction system, searching for the minimum orbital energy level split Δmin along the linear reaction coordinate, the electron transfer matrix elements and the transition state configurations were determined.The solvent recombination energy of liquid electron transfer was calculated by Marcus double sphere model, In the model, the intramolecular electron transfer rate constants of π σ π system using biphenyl anion as donor, biphenyl and naphthalene as acceptor have been calculated.