The mechanism research on the reaction HCNO + HO2: a theoretical investigation

摘要

The mechanism of reaction HCNO + HO2 is investigated by means of CCSD(T)/6-311 + G(d,p)// B3LYP/6-311 + G(d,p) method, in which Pi with the i = 1, 2, 3, …, 7 are involved, to determine a more reasonable pathway. Among four possible entrance patterns, the attack of oxygen to carbon is the most energetically feasible leading to complex al. Starting from the al, the rupture of O2-O3 bond to form P3 (HC(O)NO + OH) is the most favorable pathway. Alternatively, the a1 undergoes N-O1 bond rotation to form the isomer a2. A concerted O2-O3 bond and C-N bond cleavage leading to P4 (OH + HCO + NO) is the secondary feasible pathway. Other products are not energetically accessible because of higher barrier-consumed and/or complicated processes. We hope that the present work would be helpful to experimentally identify the product distributions and deeply understand the mechanism of the title reaction.