OXO(X=Cl,Br)自由基与CO和NO自由基反应机理的理论研究  

Theoretical studies of the mechanism on the reaction CO,NO radicals with OXO(X=Cl,Br) radicals

作　　者：黄伣丽[1] 李玥[2] 张辉[2] 

机构地区：[1]黑龙江省科学院石油化学研究院,黑龙江哈尔滨150040 [2]哈尔滨理工大学化学与环境工程学院,黑龙江哈尔滨150080

出　　处：《东北师大学报（自然科学版）》2012年第3期91-94,共4页Journal of Northeast Normal University(Natural Science Edition)

基　　金：国家自然科学基金资助项目(20973049);教育部博士点基金资助项目(20112303110005);哈尔滨市优秀学科带头人基金资助项目(2011RFJGS026)

摘　　要：对CO和NO自由基与OXO(X=Cl,Br)自由基反应机理进行了理论研究.在MP2/6-311+G(d,p)水平下优化了反应物、产物、中间体和过渡态的几何构型,并对所有平衡构型进行了简谐振动频率分析.在相同的计算水平下以过渡态为出发点,利用内禀反应坐标(IRC)理论得到了反应的最小能量路径(MEP),能量信息的进一步校正在较高的MC-QCISD//MP2/6-311+G(d,p)水平下完成.研究结果表明,该反应体系可发生氧抽提反应,其中NO与OClO的反应是最具有动力学优势的.In this paper,theoretical investigations are completed on the reaction mechanism for NO,CO radicals with OXO（X =Cl,Br） radicals.Geometries of the reactants,products,complexes,and transition states are optimized at the MP2/6-311＋G（d,p） level,the harmonic vibration frequencies of the equilibrium geometries are calculated at the same level.The minimum energy path（MEP） is obtained by the intrinsic reaction coordinate（IRC） theory at the same level,and the high level energetic information is further refined by the MC-QCISD method.The result shows that,the oxygen Abstraction reaction can occur in this reaction system,and the reaction of NO and OClO has the most advantage of dynamics.

关 键 词：大气化学 反应机理 过渡态 

分 类 号：O641.1[理学—物理化学]