CH_2XO(X=Cl,Br)与O_2反应机理的理论研究  

Theoretical Studies on the Mechanism of CH_2XO(X=Cl,Br)with O_2

作　　者：谢鹏涛[1] 李晓艳[2] 曾艳丽[2] 郑世钧[2] 孟令鹏[2] 

机构地区：[1]邯郸学院化学系,河北邯郸056005 [2]河北师范大学化学与材料科学学院,河北石家庄050016

出　　处：《河北师范大学学报（自然科学版）》2011年第2期173-178,共6页Journal of Hebei Normal University：Natural Science

基　　金：国家自然科学基金(20973053;20771033;20801017);河北省自然科学基金(B2008000141;B2008000138;B2010000371);河北省教育厅科研基金(2009137);河北师范大学博士基金(L2008B06);河北师范大学一般基金(L2009Y06);邯郸市科学技术研究与发展计划项目(0823108064-3);邯郸学院博士;硕士科研启动项目(2007009)

摘　　要：采用B3LYP和MP2方法在6-311++G(d,p)水平上研究了CH2XO(X=Cl,Br)自由基与O2反应的微观机理,找到了3个可能的反应通道,其中生成HC(O)X+HO2的通道为主反应通道,验证了动力学实验结果.运用电子密度拓扑分析方法讨论了反应过程中化学键的变化规律及结构过渡态与反应热之间的关系,为大气化学中CH2XO的实验研究提供理论依据.The reaction mechanism of CH2XO（X = Cl, Br）radical with O2 were investigated by using B3LYP and MP2 methods with the 6-311 ＋ ＋ G（d, p） basis sets. Three reaction channels were found. HC（O）X and HO2 were the main product, which are well consistent with the experiential results. From the view of topological analysis of electron density, the changes of chemical bonds in the reactions, the relationship between the structure transition state and the reaction energy were discussed, which would be helpful for the experimental study of the atmospheric chemistry.

关 键 词：甲基卤氧自由基 反应机理 结构过渡态 电子密度拓扑分析 

分 类 号：O641.12[理学—物理化学]