大气中ClNO_2/ClONO与H多通道反应机理的理论研究  

Theoreticalstudy on the reaction mechanism of atomic radical H with nitryl chloride and chlorine nitrite in the atmosphere

作　　者：武卫荣[1] 岳呈阳[1] 

机构地区：[1]济宁学院化学与化工系,曲阜273155

出　　处：《四川大学学报（自然科学版）》2013年第1期141-147,共7页Journal of Sichuan University(Natural Science Edition)

基　　金：国家自然科学基金(21101075);山东省优秀中青年科学家科研奖励基金(BS2012CL008)

摘　　要：用UMP2理论研究了大气环境中H与硝酰氯(ClNO2)及顺/反亚硝酸氯(ClONO)分子反应的机理.在6-311++G**和6-311G**基组水平上,优化得到了反应物、过渡态、中间体和产物的几何构型;在UMP2/6-311++G**优化的构型基础上,利用CCSD(T)/aug-cc-pVTZ方法得到各驻点的高级单点能量;通过振动分析对过渡态和中间体构型进行了确认.并应用热力学函数讨论了温度对反应机理的影响.计算结果表明:H与ClONO分子的反应有三种不同的反应机制,而对ClNO2分子的进攻有两种不同的反应方式.其中H与ClNO2和trans-ClONO发生的Cl抽提反应是相互竞争的主反应通道,P1(NO2+HCl)为主要产物.The reaction mechanisms of atomic radical H with nitryl chloride and cis- and trans-chlorine nitrite in the atmosphere were investigated with the unrestricted second-order Moller-Plesset perturba- tion theory. The geometrical parameters of the reactants, transition states, intermediates and the prod- ucts were optimized at the 6-311＋＋-G＊＊ and 6-311G＊＊ basis set, respectively. Based on the optimized ge- ometries in the UMP2/6-311＋＋G＊＊ , the senior single point energy of theirs were obtained at the CCSD （T）/aug-cc- pVTZ level, and the intermediates and transition states were detected by the frequency a- nalysis. The effect of temperature on the reaction mechanisms were discussed with application of ther- modynamic function. The calculation results show that the H＋C1ONO reaction has three different mechanisms, but atomic radical H attacks on C1NO2 molecular in two different ways. The Cl-abstraction reactions between H and C1NO2 and trans-C1ONO are competitive dominant reaction paths, and the ma- jor product is P1 NO2 ＋HCl.

关 键 词：硝酰氯 顺 反亚硝酸氯 H自由基 二阶微扰理论 反应机理 

分 类 号：O641[理学—物理化学]