Theoretical study on the H-atom abstraction reactions of pentanol + HȮ, part I: five branched pentanol isomers.

The chemical kinetic studies of hydrogen atom (H-atom) abstraction reactions by hydroperoxyl (HȮ) radicals from five branched pentanol isomers, including 3-methyl-1-butanol, 2-methyl-1-butanol, 1,1-dimethyl-1-propanol, 1,2-dimethyl-1-propanol, and 2,2-dimethyl-1-propanol were investigated systematically through high-level calculations. Geometry optimization, frequency analysis, and zero-point energy (ZPE) corrections were performed for six reactants, twenty-three transition states (TSs), and twenty-four products at the M06-2X/6-311++G(d,p) level of theory. The intrinsic reaction coordinate calculation was performed at the same level of theory to confirm the transition state connection.

An kinetics study on 2-methyl-2-butanol oxidation induced by ˙OH radicals.

High-level calculations were performed to investigate the kinetics of the important initial steps of 2-methyl-2-butanol (2M2B) oxidation. Hydrogen-atom abstraction reactions by hydroxyl (˙OH) radicals, dehydration reactions of 2M2B molecules, and unimolecular isomerization and decomposition reactions of 2M2B radicals produced by H-atom abstraction were all included in this work. The potential energy surfaces were characterized at the QCISD(T)/CBS//M06-2X/6-311++G(d,p) level of theory.