Computational Study of the HCCO + NO Reaction: ab Initio MO/vRRKM Calculations of the Total Rate Constant and Product Branching Ratios

Accurate thermochemistry for major product channels of the HCCO + NO (R1) reaction was established at the CCSD(T)/6-311+G(3df,2p) and QCISD(T)/6-311+G(3df,2p) levels of theory based on the potential energy surface (PES) calculated by density functional B3LYP/6-311G(d,p) method. Two barrierless entrance pathways forming trans - and cis -nitrosoketene ( 1 and 2 ) have been mapped out following the minimum energy paths. Using isodesmic reaction analysis, the standard enthalpy of formation for 1 is found to be 17.8 ± 1.7 kcal/mol. The recently reported PES of the nitrosoketene decomposition (Vereecken, L.; Sumathy, R.; Carl, S. A.; Peeters, J. Chem. Phys. Lett. 2001, 344, 400) has been appended with two additional pathways to form HCNO + CO (R1a) and HCN + CO 2 (R1b) products. A lower-energetic transition state for the decomposition of 2 to HCNO + CO has been found, and a new stepwise pathway for the decomposition of 1,2-oxazet-4-one ( 3 ) to HCN + CO 2 has been considered in competition with a more favorable concerted pathway. The effective total rate constant and products distribution have been calculated in the framework of multichannel and multiquantum well kinetic model, and the effects of P and T have been evaluated by weak collision master equation/RRKM approach with a variational treatment of the entrance channels. Our predicted total rate constant, k R1 ( T ) = 1.37 × 10 16 T -0.98 exp(−190/ T ) cm 3 mol -1 s -1, exhibits a negative temperature dependence in very good agreement with experiment. The α(R1b) branching fraction can be given by 0.5 exp(− T /67.1) + 0.3 exp(− T /2592) in the 250−2500 K temperature range, which is also well-supported by available experimental data.