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A Theoretical and Computational Analysis of the Methyl-Vinyl + O2 Reaction and Its Effects on Propene Combustion

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journal contribution
posted on 07.11.2017 by Xi Chen, C. Franklin Goldsmith
A detailed analysis of the reaction of CH3CCH2 and CH3CHCH with molecular oxygen is presented. The C3H5O2 potential energy surface was characterized using a combination of electronic structure methods. The majority of the stationary points on the PES was determined at the CCSD­(T)-F12a/cc-pVTZ-F12//B2PLYPD3/cc-pVTZ level of theory, with the remaining transition states computed using multireference methods. Microcanonical rate theory and the master equation are used to determine the temperature- and pressure-dependent rate coefficients for each reaction channel. The main product channels are CH2O + CH3CO for CH3CCH2 and CH3CHO + CHO for CH3CHCH. The rate constants for these two reactions at 1 atm are k = 9.03 × 1022 × T–3.21 × exp–2162/T and 1.50 × 1019 × T–2.10 × exp–1260/T cm–3 mol–1 s–1, respectively. In contrast to C2H3 + O2, the methyl-vinyl + O2 reactions remain chain propagating, even at high temperatures. The new rate coefficients were implemented in a detailed mechanism taken from the literature. These changes have a modest effect on the ignition delay time and laminar flame speeds for propene combustion.