Theoretical estimation of Hammett σ_p constants of organic radical groups  

作　　者：WANG Chen FU Yao LIU Lei 

机构地区：[1]Department of Chemistry, University of Science and Technology of China, Hefei 230026, China [2]Department of Chemistry, Tsinghua University, Beijing 100084, China

出　　处：《Chinese Science Bulletin》2010年第25期2904-2908,共5页

基　　金：supported by the Specialized Research Fund for the Doctoral Program of Higher Education (200800030074);the National Natural Science Foundation of China (20832004)

摘　　要：A quantum chemistry method was developed to calculate the Hammett substituent constants of various organic radicals. These newly obtained constants allow,for the first time,the quantitative analysis of the electron demand of organic radicals. Calcula-tions reveal that the electron demand of organic radicals varies dramatically. It was demonstrated that the Hammett relationship of bond dissociation energies is determined only by the change of electron demand during the homolysis process.A quantum chemistry method was developed to calculate the Hammett substituent constants of various organic radicals. These newly obtained constants allow, for the first time, the quantitative analysis of the electron demand of organic radicals. Calcula- tions reveal that the electron demand of organic radicals varies dramatically. It was demonstrated that the Hammett relationship of bond dissociation energies is determined only by the change of electron demand during the homolysis process.

关 键 词：量子化学计算方法 Hammett常数 有机自由基 估计 组织 量化分析 使用系统 键离解能 

分 类 号：O621[理学—有机化学] TQ533.9[理学—化学]