Mechanistic and Kinetic Approach on the Propargyl Radical (C3H3) with the Criegee Intermediate (CH2OO)

Tien V Pham; Hoang T T Trang

doi:10.1021/acsomega.3c00491

Mechanistic and Kinetic Approach on the Propargyl Radical (C₃H₃) with the Criegee Intermediate (CH₂OO)

ACS Omega. 2023 May 3;8(19):16859-16868. doi: 10.1021/acsomega.3c00491. eCollection 2023 May 16.

Authors

Tien V Pham¹, Hoang T T Trang²

Affiliations

¹ School of Chemical Engineering, Hanoi University of Science and Technology, Hanoi 100000, Vietnam.
² Department of Chemistry, Hanoi Architectural University, Hanoi 100000, Vietnam.

Abstract

The detailed reaction mechanism and kinetics of the C₃H₃ + CH₂OO 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 C₃H₃ + CH₂OO system. The C₃H₃ + CH₂OO reaction leading to the CH₂-[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 C₃H₃ + CH₂OO → CH₂-[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 C₃H₃ + CH₂OO → CHCCH₂CHO + OH, C₃H₃ + CH₂OO → OCHCHCHCHO + H, and C₃H₃ + CH₂OO → CHCHCHO + CH₂O fluctuate with temperatures. The branching ratio of the C₃H₃ + CH₂OO → CH₂-[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 + CH₂O) 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 CH₂OO-related systems under atmospheric and combustion conditions.