Computational Chemistry of Cyclopentane Low Temperature Oxidation

Cycloalkanes are significant constituents of conventional fossil fuels, but little is known concerning their combustion chemistry and kinetics, particularly at low temperatures. This study investigates the pressure dependent kinetics of several reactions occurring during low-temperature cyclopentane combustion using theoretical chemical kinetics. The reaction pathways of the cyclopentyl + O2 adduct is traced to alkylhydroperoxide, cyclic ether, β-scission and HO2 elimination products. The calculations are carried out at the UCCSD(T)-F12b/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory. The barrierless entrance channel is treated using variable-reaction-coordinate transition state theory (VRC-TST) at the CASPT2(7e,6o) level of theory, including basis set, geometry relaxation and ZPE corrections. 1-D time-dependent multiwell master equation analysis is used to determine pressure-and temperature-dependent rate parameters of all investigated reactions. Tunneling corrections are included using Eckart barriers. Comparison with cyclohexane is used to elucidate the effect of ring size on the low temperature reactivity of naphthenes. The rate coefficients reported herein are suitable for use in cyclopentane and methylcyclopentane combustion models, even below ~900 K, where ignition is particularly sensitive to these pressure-dependent values.