Cl对气态亚硝酸（HONO）直接提氢反应机理的研究

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+NO2．%The mechanism of atomic radical Cl with nitrous acid ( HONO) was investigated with the density func-tional theory ( DFT). The geometrical parameters of the reactants, transition states, intermediates and the prod-ucts 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 domi-nant reaction paths, and the paths are cis-HONO+Cl→cis-M1→cis-TS→cis-M2→HCl+ NO2.