CBr+O_2反应在二重态势能面上的机理研究(英文)  

Theoretical mechanistic study of the CBr+O_2 reaction on the doublet potential energy surface

作　　者：石从云[1] 鲁云洲[1] 何正泉[1] 赵宇飞[1] 吕早生[1] 柯昌美[1] 

机构地区：[1]武汉科技大学化学工程与技术学院,湖北武汉430081

出　　处：《化学研究与应用》2010年第10期1260-1266,共7页Chemical Research and Application

基　　金：武汉科技大学绿色制造与节能减排科技研究中心开放基金(C0903)资助项目

摘　　要：用UB3LYP/6-311++G(d,p)和QCISD(单点能)的方法考察了CBr+O2反应在二重态势能面上的反应机理。研究发现该反应在高温过程中重要,且有两个产物通道,它们分别是BrCO+O和Br+CO2,其中前者为优势通道。为了弄清溴原子取代对次甲基与氧气反应的机理的影响,我们对CBr+O2反应与CH+O2反应的相似性和差异也作了讨论。结果表明:两反应的第一步都是CX(X=H,Br)自由基与氧气反应生成链状过氧化物XCOO,且溴原子取代对反应的活性、产物通道的数量和产物的形成过程等都有影响。A computational study of the CBr ＋ O2 reaction has been carried out by employing the UB3LYP/6-311＋＋G（d,p） andQCISD（single-point energy） methods on the doublet potential energy surface.It is found that the reaction is important in high temperature processes and possesses two product channels,BrCO ＋ O and Br ＋ CO2,and the former channel is preferable.The similarities and discrepancies between the CBr ＋ O2and CH ＋ O2 reactions are discussed in order to clarify the Br atom substitution effecton the reaction mechanism.The first steps of the two reactions are the attack of the CX（X = H,Br） radical on an atom of O2 to forma chain-like peroxide XCOO.The bromo atom substitution has an effect on the reactivity,the number of product channels and theformation processes of products.

关 键 词：理论计算 反应机理 势能面 CBR 氧气 

分 类 号：O641.121[理学—物理化学]