Computational Study of the Mechanism and Product Yields in the Reaction Systems C2H3 + CH3 ⇄ C3H6 ⇄ H + C3H5 and C2H3 + CH3 → CH4 + C2H2

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2002-08, Vol.106 (30), p.6952-6966
• Main Authors: Stoliarov, Stanislav I, Knyazev, Vadim D, Slagle, Irene R
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp014059j

The mechanism of the radical−radical reaction C2H3 + CH3 (1) was studied by quantum chemical methods. The pathways of reaction channels observed in previous experimental studies, as well as those of other potential channels, were investigated. The results of the quantum chemical study and of the earlier experimental work were used to create a model of the chemically activated route (C2H3 + CH3 ⇄ C3H6 → H + C3H5) of reaction 1. In this model, energy- and angular momentum-dependent rate constants are calculated using the RRKM method in combination with the microcanonical variational selection of the transition states. Pressure effects are described by solution of the master equation. Temperature and pressure dependences of the rate constants and product yields were investigated. The model was used to predict the rate constants and branching fractions of reaction 1 at temperatures and pressures outside the experimental ranges. The same model was used to analyze kinetics of two other reactions which occur on the same potential energy surface:  the thermal decomposition of propene (2) and the reaction of H atom with allyl radical, H + C3H5 ⇄ C3H6 → C2H3 + CH3 (3). The results demonstrate the increasing importance of the CH3 + C2H3 channels in both reactions 2 and 3 at high temperatures (above ∼1500 K).