OBrO+NO反应机理的量子化学研究  

Quantum Chemical Investigation on the Reaction Mechanism of OBrO with NO

作　　者：赵岷[1] 潘秀梅[1] 刘朋军[1] 孙昊[1] 苏忠民[1] 王荣顺[1] 

机构地区：[1]东北师范大学化学学院功能材料化学研究所

出　　处：《高等学校化学学报》2003年第9期1648-1651,共4页Chemical Journal of Chinese Universities

基　　金：教育部"跨世纪优秀人才培养计划"基金(批准号:教技函[2001]3);东北师范大学青年教师基金(批准号:111382)

摘　　要：用密度泛函B3LYP/6-311+G^(##)和高级电子相关偶合簇CCSD(T)/6-311+G^(##)方法研究了 OBrO与NO反应的微观机理。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,通过频率振动分析对过渡态和中间体进行了确认。结果表明;该反应是多通道多步骤的放热反应,分别可以在单重态和三重态势能面上进行,OBrO与NO通过加成及加成-消除机理分别形成产物BrONO_2和BrO+NO_2,从能量上看,形成离解产物的通道更容易进行。The reaction mechanism between OBrO and NO was studied by using the B3LYP/6-311+G* * and the high-level electron-correlation CCSD(T)/6-311+G* * single-point levels. The geometries of reac-tants, transition states, intermediates and products were optimized and verified by frequency analysis. The results show that the reaction is multi-channel and multi-step exothermic. It may proceed on singlet and triplet potential energy surface(PES). OBrO and NO may react via addition or addition-elimination mechanism to form the products BrONO2 and BrO+NO2. In view of energy, the channel of forming the products BrO+NO2 is more favorable.

关 键 词：OBrO NO 反应机理 量子化学 密度泛函方法 大气 臭氧平衡 动力学 自由基反应 

分 类 号：X515[环境科学与工程—环境工程] O641.3[理学—物理化学]