CBr+O_2反应在二重态势能面上的机理研究(英文)

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。

Theoretical mechanistic study of the CBr+O2 reaction on the doublet potential energy surface

A computational study of the CBr+O2 reaction has been carried out by employing the UB3LYP/6-311+ +G(d,p)and QCISD (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+O2 and CH+O2 reactions are discussed in order to clarify the Br atom substitution effect on 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 form a chain-like peroxide XCOO.The bromo atom substitution has an effect on the reactivity,the number of product channels and the formation processes of products.