多肽体系电子转移溶剂重组能计算的自洽反应场方法

With the method of the self-consistent reaction field, the solvent effect on the electron transfer reactions in peptide systems have been investigated. Based on the geometry optimization of peptide in solution, the bond reorganization energy and the reaction heat of the electron transfer reactions in solution have been estimated. The transition state have been determined by using the method of searching the minimum of the splitting energy of the electron transfer system, and the rate constant and the mechanics of electron transfer in peptide system have been investigated in the frame of semi-classical model. The experimental phenomenon of electron transfer in peptide system has been explained theoretically. A new theory of non-equilibrium solvation have been established, amending the error in Marcus' theory that was put forward in 1950s' and Lippert-Mataga equation as well as some other different faults and questions existing in the developing non-equilibrium solvation theories by many international famous scientists. Furthermore, we have obtained the new theory and model fitted for the non-equilibrium solvation in the ultra-fast processes and illustrated some experimental results unable to be explained by Marcus' theory. Our research work has brought some influence in and out the country, and about seventeen articles have been indexed in SCI and cited by different authors.

根据偶极体系与极性溶剂的静电作用原理和计算化学方法，在冻结溶剂反应场条件下建立非平衡溶剂化能的偶极－反应场相互作用模型及电子转移溶剂重组能的计算方法，并应用于多肽体系。用分裂能极小方法确定电子转移过渡态和电子转移矩阵元，结合反应热计算和半经典模型，研究多肽分子内电子转移动力学问题，探讨电子传递机理和解释实验现象。