硝酰阳离子和二氧化氮分子的弯曲变形研究  

Theoretical Studies of the Bending Transformation of Nitronium and Nitrogen Dioxide

作　　者：曹阳[1] 吕春绪[1] 蔡春[1] 魏运洋[1] 李斌栋[1] 吕早生[2] 

机构地区：[1]南京理工大学化学系,南京210094 [2]武汉科技大学化学与环境工程学院,武汉430081

出　　处：《物理化学学报》2002年第6期527-537,共11页Acta Physico-Chimica Sinica

基　　金：教育部博士点基金(BJ9701);江苏省自然科学基金(BK99071)资助项目

摘　　要：采用密度泛函理论的B3LYP方法（6-311+G＊基组）计算了NO2+、NO2以及其它与硝化反应机理研究相关的分子、离子和激发态的结构与性质.进而研究了当键角在90°-180°之间变化时,这些相关物质能量的变化规律,由此探讨了不同硝化机理发生的可能性,为以后进一步研究不同结构与活性的芳香化合物的硝化反应机理提供依据.Density functional theory (DFT) with the B3LYP method and 6-311+G* basis set has been employed to investigate the geometries and other properties of NO2+, NO2 and some other molecules, ions and their transitional or excited states that concern the mechanism of aromatic nitration. Furthermore, the relative energies and other properties of these substances have been studied with the bond angle ranging from 90degrees to 180degrees at fixed bond length at the same level. From the results obtained, the occurrence possibilities of various nitration mechanisms, including electrophilic reaction mechanism and electron transfer mechanism, have been discussed. Each possibility depends on the first ionization potential and electron richness of aromatic substrates. Polar solvents are considered to be favorable for nitration reactions. The works reported here are ready for the further theoretical and experimental studies of the mechanism of nitration.

关 键 词：二氧化氮分子 硝化反应 硝酰阳离子 弯曲变形 电子转移 密度泛函理论 量子化学 

分 类 号：O621[理学—有机化学]