Oxidation of pentan-2-ol – Part I: Theoretical investigation on the decomposition and isomerization reactions of pentan-2-ol radicals

Theoretical investigations on the kinetics of pentan-2-ol radical decomposition and isomerization reactions have been carried out in this work, together with the thermochemistry data calculations for important species involved in the reaction process. The B2PLYPD3/6-311++G(d,p) level of theory was used to optimize the geometries of all of the reactants, transition states, products and also the hindered rotor treatment for lower frequency modes. Single-point energies of all species are determined at the ROCCSD(T) level using the cc-PVQZ and cc-pVTZ which were extrapolated to the complete basis set limit (CBS). RRKM/Master Equation has been solved to calculate the pressure- and temperature-dependent rate coefficients for all channels in the pressure range of 0.01–100 atm over 300–2000 K. Pressure and temperature dependent branching fractions of key species produced from different pentan-2-ol radicals shows that 1- and 2-pentene are important bimolecular products. The kinetics and thermochemistry data for the title reactions has been used in the part II of this work for model development for pentan-2-ol oxidation.