Theoretical Studies on Isomerization and Decomposition Reactions of 2-Methyl-1-butanol Radicals

Abstract

2-Methyl-1-butanol (2M1B) is a favorable candidate of substitute fuels characterized with high energy density and low hygroscopicity. 2M1B radicals, which are the products of H-abstraction reactions of 2M1B, and their isomerization and decomposition reactions play a cardinal impact on the distribution of combustion products. In this work, the primary isomerization and decomposition reaction channels of 2M1B radicals were investigated by using QCISD(T)/CBS//M062x/cc-pVTZ and CBS-QB3 method, respectively. The accurate phenomenological temperature- and pressure-dependent rate constants covering temperatures of 250–2500 K and pressures from 1 × 10–3 to 1 × 103 bar along with high-pressure limit rate constants for these channels were computed by solving the RRKM/master equation. The calculations revealed that the isomerization reaction of RC2 → RC6 has the highest energy barrier among these reactions, while the decomposition reaction RC6 → CH3CH2CHCH3 + CH2O has the lowest energy barrier. Furthermore, the comp...