Cl对气态亚硝酸(HONO)直接提氢反应机理的研究  

Study on the direct hydrogen abstraction reaction mechanism of nitrous acid(HONO) with Cl

作　　者：刘晓静[1] 黄菊[2] 何伟平[1] 王德堂[1] 

机构地区：[1]徐州工业职业技术学院化学工程学院,徐州221140 [2]徐州工程学院化学化工学院,徐州221111

出　　处：《原子与分子物理学报》2016年第6期973-977,共5页Journal of Atomic and Molecular Physics

基　　金：徐州工业职业技术学院科技基金资助(XGY201409)

摘　　要：采用密度泛函理论研究了Cl对气态亚硝酸(HONO)直接提取氢的反应机理.在B3LYP/6-311G(d,p)水平上,优化得到了反应途径上的反应物、中间体、过渡态和产物的几何构型;通过频率分析对各分子构型进行了确认;并利用QCISD(T)方法计算了各分子单点能量.计算结果表明,HONO分子具有顺式和反式两种构型;常温条件下,Cl对顺式构型直接提取氢的反应竞争性具有明显优势,其主要反应途径为:cis-HONO+Cl→cis-M1→cis-TS→cis-M2→HCl+NO_2.The mechanism of atomic radical Cl with nitrous acid（HONO） was investigated with the density functional theory（DFT）. The geometrical parameters of the reactants,transition states,intermediates and the products were optimized at the level of 6-311G（d,p）. Based on the optimized geometries,the intermediates and transition states were detected by the frequency analysis; and the reliable single point energies of the species were computed by employing the QCISD（T） methods. The calculation results show that there are two conformers（cis and trans） of the molecule HONO. The reactions of atomic radical Cl with cis-HONO are the competitive dominant reaction paths,and the paths are cis-HONO ＋ Cl→cis-M1→cis-TS→cis-M2→HCl ＋ NO_2.

关 键 词：气态亚硝酸(HONO) CL 密度泛函理论 抽氢反应 反应机理 

分 类 号：O643[理学—物理化学]