NH_2与ClO自由基反应机理  

Reaction mechanism of NH_2 with ClO

作　　者：赵岷[1] 信雅楠[1] 李新华[1] 李冰[1] 刘晓东[1] 

机构地区：[1]渤海大学化学化工学院,辽宁锦州121000

出　　处：《辽宁工程技术大学学报（自然科学版）》2006年第6期958-960,共3页Journal of Liaoning Technical University (Natural Science)

基　　金：辽宁省自然科学基金资助项目(20061073)

摘　　要：利用量子化学理论方法,研究了与大气臭氧层损耗密切相关的自由基反应NH2+ClO的微观机理。在密度泛函B3LYP/6-311+G(d,p)水平上优化得到反应路径上的反应物,过渡态,中间体和产物的几何构型,并通过振动频率分析对过渡态和中间体进行了确认。在高级电子相关组态相互作用QCISD(T)/6-311+G(d,p)水平上进行了单点能计算,得到了反应体系的势能面信息。结果表明,该反应经过缔合、H-转移和离解等过程,最终可以得到五种产物,分别为H2NO+Cl,H2NClO,HCl+HNO,H2+NO+Cl和NH+HClO。由于形成产物H2NO+Cl的活化势垒较低,因而是主要反应通道,而形成产物NH+HClO的通道从动力学上看是最不利的。The mechanism for the radical reaction of NH2＋ClO crucial to stratospheric ozone depletion has been investigated theoretically. The geometries of reactions, transition states, intermediates and products have been optimized by B3LYP/6-311＋G（d,p） level and verified by frequency analysis. Single point energies have been calculated and the potential energy surface information has been obtained at the high-level electron-correlation QCISD（T）/6-311＋G（d,p） level. The results show that five products of H2NO＋Cl, H2NClO, HCl＋HNO, H2＋NO＋Cl and NH＋HClO can be obtained by association, H-shift and dissociation. The channel to yield H2NO＋Cl is the dominant one with lower energy barrier. The route to NH＋HClO is difficult kinetically.

关 键 词：NH2 CLO 反应机理 过渡态 

分 类 号：O641[理学—物理化学]