Theoretical investigation on low-temperature decomposition kinetics of hdroperoxymethyl formate with multistructural torsional anharmonicity

Abstract

Hydroperoxymethyl formate (HPMF) is an important oxidation intermediate produced during the low-temperature oxidation of dimethyl ether (DME), as its destruction pathways influence not only the low-temperature reactivity but also the formation of acid species. We theoretically studied both the Korcek and conventional decomposition reactions of HPMF via high-level quantum chemical calculation methods. The temperature-dependent rate coefficients were calculated using multistructural transition state theory with small curvature tunneling correction. Kinetic modeling results show that the Korcek decomposition mechanism plays a negligible role on the formation of formic acid but contributes to the formation of carbonic acid.