DFT研究大气环境中HCNO与Cl反应的产物通道  

DFT investigation on the production channels for the reaction of atomic radical Cl with HCNO 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山东省高校无机化学重点实验室,曲阜273155

出　　处：《四川大学学报（自然科学版）》2013年第4期791-796,共6页Journal of Sichuan University(Natural Science Edition)

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

摘　　要：用密度泛函理论研究了大气环境中Cl与雷酸(HCNO)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B3LYP/6-311++G**优化的构型基础上,利用CCSD(T)/6-311++G**方法对各驻点的单点能量进行校正;通过振动分析对过渡态和中间体构型进行了确认.计算结果表明:Cl与HCNO分子的反应通过Cl对HCNO分子中O或C原子进攻的多步反应得到了三种产物.其中,Cl加成到HCNO分子中O原子上消去OCl基团的反应是主反应通道,P1(HCN+OCl)为主要产物.The reaction mechanisms of atomic radical C1 with HCNO in the atmosphere were investigated with the DFT. The geometrical parameters of the reactants, transition states, intermediates and the products were optimized at the 6-311＋＋G^＊＊ and 6-311G^＊＊ basis sets, respectively. Based on the opti- mized geometries in the B3LYP/6-311＋＋G^＊＊ , The single point energies of the species were corrected at the CCSD（T）/6-311＋＋G^＊＊ level of theory, and the intermediates and transition states were detec- ted by the frequency analysis. The calculation results show that the CI＋ HCNO reaction involves the multi-channel mechanism of atomic radical C1 kissing the O or C of HCNO for three kinds of products. The dominant reaction channel is atomic radical C1 addition to the terminal O-atom of HCNO, followed by the elimination of OC1. And consequently the major product is P1 HCN＋OC1.

关 键 词：DFT HCNO 反应机理 

分 类 号：O641[理学—物理化学]