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 perturbation theory. The geometrical parameters of the reactants, transition states, intermediates and the products were optimized at the 6-311+ +G** and 6-311G** basis set, respectively. Based on the optimized geometries 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 + C10N0 reaction has three different mechanisms, but atomic radical H attacks on C1NO2 molecular in two different ways. The Cl-abstraction reactions between H and CINO2 and trans-ClONO are competitive dominant reaction paths, and the major product is PI NO2 + HC1.%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.
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