OClO+NO→ClO+NO_2反应机理的密度泛函理论研究  

DFT study on the reaction mechanism of OClO+NO→ClO+NO_2

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：《东北师大学报（自然科学版）》2003年第4期33-38,共6页Journal of Northeast Normal University(Natural Science Edition)

基　　金：教育部"跨世经优秀人才培养计划基金资助项目(教技函[2001]3)

摘　　要：　采用密度泛函理论方法研究了OClO+NO→ClO+NO2反应的微观机理.在B3LYP/6-31+G 水平上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.研究结果表明,该反应是多通道的放热反应,分别可以在单重态和三重态势能面上进行,OClO与NO通过加成-消除机理形成离解产物ClO+NO2.从能量上看,单重态通道比三重态通道更容易进行,整个反应放出热量为149 000kJ/mol.The reaction mechanism of OClO+NO→ClO+NO_2 has been studied using density functional theory.The geometries of reactants,transition states,intermediates and products have been optimized by the B3LYP/6-31+G~* basis set and verified by frequency analysis.The results show that the reaction is multi-channel and exothermic.It may proceed on singlet and triplet potential energy surface.OClO and NO can react by an addition-elimination mechanism to form product ClO+NO_2.In view of energy,the singlet channel is more favorable than the triplet one.The reaction heat is 149.130 kJ/mol.

关 键 词：密度泛函理论(DFT) OClO 反应机理 过渡态 

分 类 号：O641[理学—物理化学]