硝基烃光异构化反应密度泛函理论计算.pdfVIP

理化学学报(Wuli Huaxue Xuebao) December Acta Phys. Chim. Sin., 2006, 22(12) ：1489 1494 1489 [Article] 硝基烃光异构化反应的密度泛函理论计算 张树强 王雅琼 郑旭明* (浙江理工大学理学院应用化学系, 教育部先进纺织材料重点实验室, 杭州 310018) 摘要 采用DFT(B3LYP)计算方法, 在6鄄31G* 水平上获得了反式鄄 鄄硝基苯乙烯、硝基乙烯和硝基甲烷基态异构 化反应时的过渡态分子结构, 并计算了异构化能垒及激发态电子跃迁能. 结果显示, 反式鄄 鄄硝基苯乙烯和硝基苯 与硝基甲烷相比具有较短的过渡态C—N 键长, 较低的异构化能垒, 并且随着不饱和度的增加, 硝基苯和反式鄄 鄄 硝基苯乙烯电子垂直跃迁能与基态异构化反应过渡态之间能量的差值 E 迅速减小. 从能量的角度分析, 取代 基的不饱和度越大, 越有利于激发态势能面与异构化反应势能面发生锥型或漏斗交叉, 因而越有利于光化学反 应沿光异构化通道进行. 激发态分子的初始电子运动的定域或离域特征的差别可能是导致硝基苯等硝基芳烃与 硝基甲烷等硝基烷烃光解通道不同的一个重要原因. ： 关键词 光异构化, 电子跃迁能, 密度泛函理论, 硝基烃 ： 中图分类号 O643 Density Functional Theory Investigation of the Photoisomerization Reaction of Nitroalkanes and Nirroaromatic Compounds ZHANG, Shu鄄Qiang WANG, Ya鄄Qiong ZHENG, Xu鄄Ming* (Key Laboratory of Advanced Texile Materials of Ministry of Educations, Department of App lied Chemistry, College of Science, Zheji ang Sci Tech University, Hangzhou 310018, P. R. China) Abstract The geometry structures and the energy barriers for the ground鄄state isomerization reactions of nitromethane, nitroethylene, nitrobenzene, and trans鄄 鄄nitrostyrene were computed using B3LYP/6鄄31G* level of theory. Their electronic transition energies were obtained using B3LYP鄄TD/6鄄31G* calculations. The results indicated that the C—N bond lengths of trans鄄 鄄nitrostyrene and nitrobenzen were significantly shorter than that of