A theoretical study of cyclic ether formation reactions

Abstract

Cyclisation reactions of hydroperoxyl–alkyl radicals forming cyclic ethers and hydroxyl radicals play an important role in low temperature oxidation chemistry. These reactions contribute to the competition between radical chain propagation and chain branching reaction pathways which dominate the reactivity of alkanes at temperatures where negative temperature coefficient (NTC) behaviour is often observed. This work is motivated by previous experimental and modelling evidences that current literature rate coefficients for these reactions are in need of refinement and/or re-determination. In light of this, the current study presents quantum-chemically-derived high-pressure limit rate coefficients for all cyclisation reactions leading to cyclic ether formation in alkanes ranging in size from C2 to C5. Ro-vibrational properties of each stationary point were determined at the M06-2X/6-311++G(d,p) level of theory. Coupled cluster (CCSD(T)) and Møller–Plesset perturbation theory (MP2) methods were employed with various basis sets and complete basis set extrapolation techniques to compute the energies of the resulting geometries. These methods, combined with canonical transition state theory, have been used to determine 43 rate coefficients, with enough structural diversity within the reactions to allow for their application to larger species for which the use of the levels of theory employed herein would be computationally prohibitive. The validity of an alternative, and computationally less expensive, technique to approximate the complete basis set limit energies is also discussed, together with implications of this work for combustion modelling.