Ab initio calculations at different levels of theory have been performed for the title H-abstraction reactions. Total energies at stationary points of the potential energy surfaces for the reaction systems were obtained at MP2 and MP4 levels and improved by using Gaussian-2 (G2) methodology. The calculated G2 heats of reaction agree well with the experimental ones for both methoxy (product resulting from hydroxyl-side attack) and hydroxymethyl (product resulting from methyl-side attack) reaction channels. Calculations of the potential energy surfaces for the reaction systems show that H-abstraction from methanol by H, CH3, and OH (for methoxy reaction channel) proceeds by simple metathesis. The mechanism of the hydroxymethyl channel of reaction CH3OH + OH appears to be more complex, and it may consist of two consecutive processes. The reaction rate is determined by the energy barrier of the first process. Differences in the heights of the calculated energy barriers explain the differences in the reactivity of H, CH3, and OH toward methanol. The calculated barriers indicate a significant dominance of the hydroxymethyl formation channel for the CH3OH + H and CH3OH + OH reaction systems. Rationalization of the derived energy barriers has been made in terms of the polar effect. The calculated rate constants are in very good agreement with experiment and allow a description of the kinetics of the reactions under investigation in a wide temperature range with the precision that is required by practical applications such as modeling of the chemistry of methanol combustion.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry