Mechanism and rate constants of the CH₂ + CH₂CO reactions in triplet and singlet states: A theoretical study

Abstract

Ab initio and density functional CCSD(T)‐F12/cc‐pVQZ‐f12//B2PLYPD3/6‐311G** calculations have been performed to unravel the reaction mechanism of triplet and singlet methylene CH 2 with ketene CH 2 CO. The computed potential energy diagrams and molecular properties have been then utilized in Rice–Ramsperger–Kassel–Marcus‐Master Equation (RRKM‐ME) calculations of the reaction rate constants and product branching ratios combined with the use of nonadiabatic transition state theory for spin‐forbidden triplet‐singlet isomerization. The results indicate that the most important channels of the reaction of ketene with triplet methylene lead to the formation of the HCCO + CH 3 and C 2 H 4 + CO products, where the former channel is preferable at higher temperatures from 1000 K and above. In the C 2 H 4 + CO product pair, the ethylene molecule can be formed either adiabatically in the triplet electronic state or via triplet‐singlet intersystem crossing in the singlet electronic state occurring in the vicinity of the CH 2 COCH 2 intermediate or along the pathway of CO elimination from the initial CH 2 CH 2 CO complex. The predominant products of the reaction of ketene with singlet methylene have been shown to be C 2 H 4 + CO. The formation of these products mostly proceeds via a well‐skipping mechanism but at high pressures may to some extent involve collisional stabilization of the CH 3 CHCO and cyclic CH 2 COCH 2 intermediates followed by their thermal unimolecular decomposition. The calculated rate constants at different pressures from 0.01 to 100 atm have been fitted by the modified Arrhenius expressions in the temperature range of 300–3000 K, which are proposed for kinetic modeling of ketene reactions in combustion. © 2018 Wiley Periodicals, Inc.