From electronic structure to model application of key reactions for gasoline/alcohol combustion: Hydrogen-atom abstractions by CH3Ȯ radical

Abstract

H-atom abstraction by methoxy radical (CH3Ȯ) plays an important role in capturing the kinetics of reactions between gasoline components and alcohols. This study focuses on determining the reaction rates and thermodynamic properties of methoxy radical reactions with five gasoline fuel components: n-heptane, iso-octane, 1-hexene, cyclopentane and toluene. Electronic structure calculations were performed for all the stationary points with M06-2X/6−311++g(d,p) method. G3 composite method with atomization method is used for determining ΔfH0 of all the closed shell and radical species, using which the necessary thermodynamic data of all the species was determined. Coupled cluster theory QCISD(T)/cc-pVXZ (where X = D and T) and Møller–Plesset perturbation theory MP2/cc-pVXZ (where X = D, T and Q) were used to calculate single point energies. Subsequently, rate constants for all hydrogen atom abstraction channels have been performed using conventional transition state theory with unsymmetric tunneling corrections. A systematic comparison of rates for abstraction from different sites within the same species and same site from different species is done in order to get insights into this reaction class. The computed thermodynamic properties and rate constants were incorporated in to a recent gasoline mechanism to investigate the impact of the calculations performed in this work. A shift in predicted NTC (negative temperature coefficient) behavior and significant reduction in model reactivity is observed upon incorporating the rates calculated herein.