首页 | 本学科首页   官方微博 | 高级检索  
     检索      

Nonequilibrium solvation theory: Comparison,modification and application
作者姓名:FUKexiang  LIXiangyuan  ZHUQuan
作者单位:CollegeofChemicalEngineering,SichuanUniversity,Chengdu610065,China
基金项目:国家自然科学基金,教育部跨世纪优秀人才培养计划 
摘    要:Faults existing in the current theories of nonequilibrium solvation have been clarified in this report.Based on a novel expression of solvation free energy for nonequilibrium, generalized formulations of solvent reorganization energy for electron transfer and of solvation shift for spectrum have been established. Furthermore, a new form of solvent reorganization energy for electron transfer in two-sphere case, which greatly differs from the one by Marcus, has been deduced. A single-sphere model for solvation shift of spectrum has been put forward both by deducing the generalized formulations and by showing the correct forms of self-energy of reaction field. It has been concluded that the current theories overestimate the solvent reorganization energy and the solvation shift by a factor of about 2. By applying the models established, the discrepancies between the theory and experiments before have been perfectly explained.

关 键 词:非平衡溶剂理论  修正  应用  电子转移  溶剂重构能量  反应场  溶剂交换
收稿时间:2003-01-24
修稿时间:2003-04-14

Nonequilibrium solvation theory: Comparison,modification and application
FUKexiang LIXiangyuan ZHUQuan.Nonequilibrium solvation theory: Comparison,modification and application[J].Chinese Science Bulletin,2003,48(10):965-970.
Authors:Kexiang Fu  Xiangyuan Li  Quan Zhu
Institution:FU Kexiang1,2, LI Xiangyuan1 & ZHU Quan1 1. College of Chemical Engineering, Sichuan University, Chengdu 610065, China; 2. College of Physics, Sichuan University, Chengdu 610065, China
Abstract:Faults existing in the current theories of non- equilibrium solvation have been clarified in this report. Based on a novel expression of solvation free energy for nonequilibrium, generalized formulations of solvent reor- ganization energy for electron transfer and of solvation shift for spectrum have been established. Furthermore, a new form of solvent reorganization energy for electron transfer in two-sphere case, which greatly differs from the one by Mar- cus, has been deduced. A single-sphere model for solvation shift of spectrum has been put forward both by deducing the generalized formulations and by showing the correct forms of self-energy of reaction field. It has been concluded that the current theories overestimate the solvent reorganization energy and the solvation shift by a factor of about 2. By apply- ing the models established, the discrepancies between the theory and experiments before have been perfectly explained.
Keywords:electron transfer  solvent reorganization energy  reaction field  solvation shift  
本文献已被 CNKI 维普 万方数据 SpringerLink 等数据库收录!
点击此处可从《中国科学通报(英文版)》浏览原始摘要信息
点击此处可从《中国科学通报(英文版)》下载免费的PDF全文
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号