FC(O)O自由基与NO反应机理的理论研究

用密度泛函理论(DFT)的B3LYP方法,在6-311G(d,p)基组水平上研究了FC(O)O自由基与NO反应的微观机理，全参数优化了反应过程中各反应物、中间体、过渡态和产物的几何构型，在CCSD(T)水平上计算了它们的能量，振动分析结果证实了中间体和过渡态的真实性，从对FC(O)O与NO的反应机理的研究结果看，FC(O)O与NO反应为4条反应通道多步反应过程，其反应的主要通道是FC(O)O+NO→M3→TS6→M5→FNO+CO₂，其主要产物是自由基FNO和CO_{2关键词：密度泛函理论反应机理反应通道}

Theoretical study on the reaction mechanism of the reaction of FC(O)O with NO

Density functional theory was used to study the mechanism of the reaction of FC(O)O with NO. The geometric configurations of reactants, intermediates, transition states and products were optimized by B3LYP method at 6-311G(d,p) level. The energies of stationary points along the pathway were calculated at CCSD(T) level. Intermediates and transition states were confirmed by the results of vibrational analysis. From the results of the reaction mechanism of the reaction of FC(O)O with NO, one can see that the reaction of FC(O)O+NO has four pathways and several steps. Comparing the four pathways’activation energies, one can find that the pathway FC(O)O+NO→M3→TS6→M5→FNO+CO₂ is the main reaction pathway and FNO radical and CO₂ are the main products, which is in good agreement with the result reported in the literature.