大气中F与ClNO_2/ClONO反应机理的理论研究

Theoretical Study on the Reaction Mechanism of Atomic Radical F with Nitryl Chloride and Chlorine Nitrite in the Atmosphere

用B3LYP理论研究了大气中F与硝酰氯(ClNO2)及顺/反亚硝酸氯(ClONO)分子反应的机理.在6-311++G**的基组水平上,优化得到了反应物、过渡态、中间体和产物的几何构型,通过振动分析对过渡态和中间体构型进行确认.计算结果表明:F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F与cis-ClONO发生的直接Cl提取反应是主反应通道,产物P1(NO2+ClF)为主要产物.

The reaction mechanisms of atomic radical F with nitryl chloride and cis- and trans-chlorine nitrite in the atmosphere were investigated with the B3LYP theory. The geometrical parameters and energy of the reactants, transition states, intermediates and the products were optimized at the 6-311＋＋G＊＊basis set. And the intermediates and transition states were detected by the frequency analysis. The calculation results show that the F＋ ClONO reaction has three different mechanisms, but atomic radical F attacks on ClNO2 molecular in two different ways. The Cl-abstraction reactions between F and cis-ClONO are main reaction, and consequently the major product is P1 （NO2＋ClF）.