Mechanistic and Kinetic Approach on the Propargyl Radical (C 3 H 3 ) with the Criegee Intermediate (CH 2 OO).

The detailed reaction mechanism and kinetics of the C 3 H 3 + CH 2 OO system have been thoroughly investigated. The CBS-QB3 method in conjunction with the ME/vRRKM theory has been applied to figure out the potential energy surface and rate constants for the C 3 H 3 + CH 2 OO system. The C 3 H 3 + CH 2 OO reaction leading to the CH 2 -[cyc-CCHCHOO] + H product dominates compared to the others. Rate constants of the reaction are dependent on temperatures (300-2000 K) and pressures (1-76,000 Torr), for which the rate constant of the channel C 3 H 3 + CH 2 OO → CH 2 -[cyc-CCHCHOO] + H decreases at low pressures (1-76 Torr), but it increases with rising temperature if the pressure P ≥ 760 Torr. Rate constants of the three reaction channels C 3 H 3 + CH 2 OO → CHCCH 2 CHO + OH, C 3 H 3 + CH 2 OO → OCHCHCHCHO + H, and C 3 H 3 + CH 2 OO → CHCHCHO + CH 2 O fluctuate with temperatures. The branching ratio of the C 3 H 3 + CH 2 OO → CH 2 -[cyc-CCHCHOO] + H channel is the highest, accounting for 51-98.7% in the temperature range of 300-2000 K and 760 Torr pressure, while those of the channels forming the products PR10 (OCHCHCHCHO + H) and PR11 (CHCHCHO + CH 2 O) are the lowest, less than 0.1%, indicating that the contribution of these two reaction paths to the title reaction is insignificant. The proposed temperature- and pressure-dependent rate constants, together with the thermodynamic data of the species involved, can be confidently used for modeling CH 2 OO-related systems under atmospheric and combustion conditions.