气相电子转移过程中AH2＋AH＋（－）2电子自交换反应内氛重组能的从头算研究

Studies on the Inner sphere Reorganization Energies for AH 2/AH +(-) 2 Electron Self exchange Reactions in Electron transfer Processes from Ab Initio Calculation

提出了一种适用于精确计算ＡＨ２（Ａ＝Ａｌ，Ｓｉ，Ｐ，Ｓ）型分子内氛重组能的最新方案，并对其进行了合理推广。在ＨＦＳＣＦ水平上利用不同基组（６—３１Ｇ＊＊，６－３１＋Ｇ＊＊，ＤＺ，ＤＺＰ）计算了自交换反应的内氛重组能，并确定了其参数值。通过优化分子的几何结构参数和对应的能量性质与实验观测值和理论值的比较可以证明是一种有效的方法。在忽略了键长－键角耦合对势能面贡献的情况下，采用函数模型建立了几种计算公式，并对其进行了讨论，同时还分析了不同计算方案中的共同点。

This article presents an application of the accurate calculation scheme proposed recently for the inner sphere reorganization energies of molecules of the type AH 2(A=Al,Si,P and S). A reasonable extension has been made. The inner sphere reorganization energies for the title thermal electron self exchange reactions are calculated in terms of ab initio MO self consistent field method(HFSCF) at different basis set levels(6 31G ** ,6 31+G ** ,DZ,and DZP)and the involved parameters are also determined. These calculated results have been calibrated by comparing optimized molecular geometrical parameters and corresponding energy properties with the experimental findings or other theoretical values. An approximation, in which the contribution from the bond length bond angle to the potential energy surface is neglected, is adopted in constructing the calculation formulas via the function model. Its adequacy is discussed. Agreement among different calculation schemes is analyzed.