摘要
On the basis of the electromagnetic field theory and the spherical cavity approximation, the expressions ofGibbs free energies under equilibrium and non-equilibrium solvation conditions are obtained by solving the electrostatic potential equations with boundary conditions. The surface charges produced by the orientational polarization of equi-librium solvation are taken fixed in the case of non-equilibrium situation, for the slow-response of the orientational polarization to electron transfer of the solvent molecules. Anew expression of solvent reorganization energy has beenobtained and this method is applied to the electron transfer systems, NO+/NO, NO2+/NO2, and NO2+/NO. The solvent reorganization energies have been evaluated.
On the basis of the electromagnetic field theory and the spherical cavity approximation, the expressions ofGibbs free energies under equilibrium and non-equilibrium solvation conditions are obtained by solving the electrostatic potential equations with boundary conditions. The surface charges produced by the orientational polarization of equi-librium solvation are taken fixed in the case of non-equilibrium situation, for the slow-response of the orientational polarization to electron transfer of the solvent molecules. Anew expression of solvent reorganization energy has beenobtained and this method is applied to the electron transfer systems, NO+/NO, NO2+/NO2, and NO2+/NO. The solvent reorganization energies have been evaluated.
基金
This work was supported by the National Natural Science Foundation of China (Grant No. 39970183).
关键词
分子内
电子传递
溶剂重排能
定向极化
自由能
电子极化
计算方法
electron transfer, solvent reorganization energy, orienta-tional polarization, electronic polarization.
