非平衡溶剂效应的约束平衡理论及在电子转移中的应用

摘要

基于经典热力学约束平衡方法，采用新非平衡溶剂化理论研究了NpO+2-NpO2+2体系电子转移反应的溶剂重组能，采用限制密度泛函理论实现电荷定域，用积分方程可极化连续介质模型获得水溶液中极化电荷。计算结果表明，新双球模型和数值解都给出了一致的溶剂重组能理论计算值。%A novel nonequilibrium solvation theory established recently by the authors was introduced. Differing from the traditional ones, the present theory was based on the constrained equilibrium principle of classical thermodynamics. The calculations of solvent reorganization energy were performed with the electron transfer system of NpO+2-NpO2+2 as an example. The constrained density functional theory was adopted for the charge localization of the system and IEF-PCM was used for the gain of polarization charges in water. Both two-sphere model and numerical solution give consistent and reasonable solvent reorganization energies.