Kinetic modeling of methyl pentanoate pyrolysis based on ab initio calculations.

Recently, methyl pentanoate (MP) was proposed as a viable biodiesel surrogate to petroleum-based fuels. To better understand the pyrolysis chemistry of MP, the unimolecular decomposition kinetics of MP is theoretically investigated on the basis of ab initio calculations; ten primary channels, including four intramolecular H-shifts and six C-C and C-O bond fissions, are identified. The geometries are optimized at the M06-2X/cc-pVTZ level of theory, and accurate barrier heights are determined using the DLPNO-CCSD(T)/CBS(T-Q) method, which shows a good performance against the CCSD(T)/CBS(T-Q) method with an uncertainty of 0.5 kcal mol-1 for small methyl esters. The atomization enthalpy method is adopted to obtain the thermodynamics of involved species. The Rice-Ramsperger-Kassel-Marcus/master equation theory coupled with one-dimensional hindered rotor approximation is employed to calculate the phenomenological rate constants at 500-2000 K and 0.01-100 atm. The branching ratio analysis indicates that two reactions, MP ↔ CH3OC([double bond, length as m-dash]O)CH3 + CH2CHCH3 and MP ↔ CH3OC([double bond, length as m-dash]O)CH2 + CH2CH2CH3, are the dominant channels at low and high temperatures, respectively. The model from Diévart et al. [Proc. Combust. Inst., 2013, 34(1), 821-829] is updated with our calculations, and the modified model can yield a better prediction in reproducing the ignition delay times of MP at high temperatures. This work provides a comprehensive investigation of MP unimolecular decomposition, and can serve as a prototype for understanding the pyrolysis of larger alkyl esters.