Theoretical Studies of the Reaction of Hydroxyl Radical with Methyl Acetate

Abstract

The mechanisms and the kinetics of the OH (OD) radicals with methyl acetate CH3C(O)OCH3 are investigated theoretically. The dual-level direct dynamics method is employed in the calculation of the rate constants. The optimized geometries and frequencies and the gradients of the stationary points are calculated at the MP2/6-311G(d,p) level. The energetic information of potential energy surfaces is further refined by the multicoefficient correlation method based on QCISD (MC-QCISD) using the MP2/6-311G(d,p) geometries. Four channels are found for the title reaction. The calculated results reveal that there exists an attractive well (reactant complex) in each entrance H-abstraction channel, that is, the H-abstraction reaction makes a stepwise mechanism. The rate constants are calculated by the canonical variational transition-state theory (CVT) with the interpolated single-point energies (ISPE) approach in the temperature range of 200-1200 K. The small-curvature tunneling effect (SCT) approximation is used to evaluate the transmission coefficient. The calculated rate constants are in good agreement with the experimental ones in the measured temperature range. It is shown that the "out-of-plane hydrogen abstraction" from the methoxy end is the dominant channel at the lower temperatures, and the other two H-abstraction channels should be taken into account with the temperatures increasing. The kinetic isotope effects (KIEs) for the three H-abstraction channels and the total reaction are "inverse", and these theoretically calculated KIEs as a function of temperature are expected to be useful for the future laboratory investigation.