在两态模型近似下,运用不同的计算方法评估了面心放置苯二聚体分子间电子转移耦合矩阵元.其中,基于孤立轨道依据二聚体自洽计算得到的单电子Hamiltonian(Fock矩阵)直接求解的电子转移积分的计算方法能方便地考虑孤立轨道的非正交性所带来的影响得到准确的有效电子转移积分的数值解.在该孤立轨道方法下,基函数和分子间距对电子耦合积分的影响也被系统研究.结果表明,相对基于过渡态理论寻找“两态能量差最小”计算的精确电子耦合值,基函数D95V计算结果表现出最好距离相关性. In the approximation of the two-state model, different calculation methods were used to evaluate the intermolecular electron-transfer coupling matrix element between two benzene dimers. Among them, the single electron Hamiltonian (Fock matrix) The method of calculating the electron transfer integral directly solves the problem of obtaining an accurate numerical solution of the effective electron transfer integral under the influence of the non-orthogonality of the orbital path.In this orbit method, The influence of the coupling integral is also studied systematically.The results show that the relative distance between the D95V basis and the D95V is the best, because of the search for the exact electron coupling value based on the transition state theory.