卤素氮氧化物的结构和光谱性质的理论研究  

Theoretical Studies on Structures and Spectroscopic Properties of Nitryl Halogenides

作　　者：朱军[1] 曹泽星[1] 张乾二[1] 

机构地区：[1]厦门大学化学系,固体表面物理化学国家重点实验室,厦门361005

出　　处：《化学学报》2002年第6期1040-1044,共5页Acta Chimica Sinica

基　　金：国家自然科学基金 (No.2 0 1730 42 );科技部 (No .0 0 1CB10 89)资助项目

摘　　要：通过DFT B3LYP计算 ,优化了卤素氮氧化物XNO2 及其异构体XONO (X =F ,Cl,Br,I)的平衡几何构型 ,预测了异构体的相对稳定性及其相互转化的活化能垒 .在B3LYP和QCISD(T)计算水平上 ,确定了X—NO2 键的解离能 .应用与时间有关的密度泛函理论 (TD B3LYP)计算了XNO2 低激发态的跃迁能 。Density functional theory with the B3LYP functional is used to calculate the equilibrium geometries and harmonic vibrational frequencies of nitryl halogenides XNO2 and XONO (X = F, Cl, Br, I). Stabilities and isomerizations of these isomers are investigated. Dissociation energies of the X-N bond in XNO2 are predicted at the B3LYP/6-311G* and QCISD(T)/ce-pvTZ levels. The electronic transition energies of the most stable XNO2 species have been estimated by time-dependent B3LYP calculations. The electron promotion of a nonbonding electron of the halogen atom X in XNO2 into a pi* orbital on the NO2 moiety, i.e., the n-->sigma* electron excitation, is responsible for the photodissociation of the X-N bond.

关 键 词：结构 卤素氮氧化物 DFT ab initio计算 光谱性质 光解离 臭氧层 大气污染 

分 类 号：O613[理学—无机化学]