HCNO+OH反应机理的理论研究

Theoretical Study on the Mechanism of the OH+HCNO Reaction

为揭示HCNO与OH自由基反应的微观机理,采用密度泛函理论(DFT)在B3LYP/6-311G(d,p)水平上对该体系可能出现的7个反应通道上各反应物、中间体、过渡态和产物的几何构型进行了搜索、几何全优化和振动分析验证,并在QCISD(T)/6-311G(d,p)水平上进行了能量校正.计算结果表明:各反应通道均为多步过程,反应的主产物为H2NO+CO和HCO+HNO,它们分别经历通道3和通道7而最后生成.

The geometries of reactants, intermediates, transition states and products were fully optimized using the B3LYP/6 - 31 I G（ d, p） level in order to reveal the micromechanism of the reaction between HCNO molecule and OH radical, in which the products Pi with i = 1 - 7 are involved. Intermediates and transition states were confirmed through the vibration analysis. The energies of stationary points along the pathways were also calculated at the QCISD （T）/6-311G（ d, p） level. Our study indicates that there are many reaction pathways for the title reaction and the main reaction pathways should be P3 （H2NO ＋ CO） and P7 （HCO ＋ HN0）.