HCNO与F反应机理的理论研究

Theoretical study on reaction mechanism of HCNO with F

利用量子化学计算方法,采用密度泛函理论(DFT)研究了大气环境中F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:F与HCNO分子的反应有两种不同的反应机制.其中,F加成到HCNO分子中O原子上消去OF基团的反应是主要反应通道,P1(HCN+OF)为主要产物.

According to the calculation method of quantum, the reaction mechanisms of atomic radical F with HCNO in the atmosphere were investigated with the DFT. The geometrical parameters of the re actants, transition states, intermediates and the products were optimized at the 6-311＋ ＋G＇＂ and 6- 311G＇＂ basis sets, respectively. Based on the optimized 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 detected by the frequency analysis. The calculation results show that the F＋ HCNO reaction has two different mechanisms. The dominant reaction channel is a- tomic radical F addition to the terminal O-atom of HCNO, followed by the elimination of OF And conse- quently the major product is PI（HCN＋OF）.