Direct ab initio dynamics study of rate constants and kinetic isotope effects for C2(A3Π u ) + CH3OH reaction

Abstract

The hydrogen abstraction of CH3OH by C2 (A3Π u ) has been investigated by direct ab initio dynamics over a wide temperature range 200–3000 K. The potential energy surfaces (PESs) have been constructed at the UCCSD(T)/aug-cc-pVTZ//UMP2/6-311++G(d,p) levels of theory. Two different hydrogen abstractions on the methyl and hydroxyl sites of methanol are considered. For the methyl H-abstraction, it is essentially a hydrogen atom transfer (HAT), whereas the hydroxyl site H-abstraction is better described as a proton coupled electron transfer (PCET) according to the Natural Bond Orbital (NBO) analysis. The results suggest that the methyl site reaction is dominant, and the calculated rate constants are roughly consistent with available experimental values. On the other hand, the temperature dependence of deuterium kinetic isotope effects (KIEs) analysis reveals a substantial normal isotope effect in the methyl H-abstraction process, while normal and inverse KIEs coexist in the hydroxyl H-abstraction channel. Furthermore, the three and four–parameter expressions of Arrhenius rate constants are also provided within 200–3000 K.