物理化学学报 >> 2005, Vol. 21 >> Issue (08): 829-833.doi: 10.3866/PKU.WHXB20050802

研究论文 上一篇    下一篇

电子转移溶剂重组能计算的自洽反应场新方法

马建毅; 李娟琴; 何荣幸; 傅克祥; 李象远   

  1. 四川大学化工学院, 成都 610065; 四川大学物理学院, 成都 610065
  • 收稿日期:2004-12-20 修回日期:2005-03-07 发布日期:2005-08-15
  • 通讯作者: 李象远 E-mail:xyli@scu.edu.cn

New SCRF Method for Solvent Reorganization Calculation in Electron Transfer

MA Jian-yi; LI Juan-qin; HE Rong-xing; FU Ke-xiang; LI Xiang-yuan   

  1. College of Chemical Engineering, Sichuan University, Chengdu 610065;College of Physics, Sichuan University, Chengdu 610065
  • Received:2004-12-20 Revised:2005-03-07 Published:2005-08-15
  • Contact: LI Xiang-yuan E-mail:xyli@scu.edu.cn

摘要: 基于非平衡溶剂化理论, 推导了用于非平衡溶剂化能数值计算的类导体屏蔽模型(COSMO)的相关公式. 在此基础上, 修改了HONDO99中COSMO模块, 并用以估算了[(CH2)2C]+—(CH2)n—C(CH2)2(n=1~13)体系中的电子转移溶剂重组能. 结果表明, 溶剂重组能值与电子转移距离的倒数有很好的线性关系. 根据溶剂重组能数值解结果, 用新的双球模型给出了合理的给受体球半径.

关键词: 非平衡溶剂化, 电子转移, 数值计算, 溶剂重组能, 双球模型

Abstract: Base on the nonequilibrium solvation theory, the numerical calculation formulas for the conductor-like-screening-model (COSMO) have been established. Some new routines have been coded and added into the COSMO module in HONDO99 package, and accordingly the solvent reorganization energy has been evaluated for electron transfer in the radical cations [(CH2)2C]+—(CH2)n—C(CH2)2(n=1~13).The numerical results indicate a good linear relationship between the reorganization energy and the reciprocal of the electron transfer distance. According to the numerical results, the sphere radius of the donor (or acceptor) has been fitted with the novel two-sphere model. The value is consistent with that by other methods.

Key words: Nonequilibrium solvation, Electron transfer, Numerical calculation, Solvent reorganization energy, Two-sphere model