Computational Study of the Reaction of Atomic Oxygen with Acetone in the Gas Phase

Abstract

Mechanisms and kinetics of the reaction of atomic oxygen with acetone have been investigated using ab initio quantum chemistry methods and transition state theory. The structures of the stationary points along the possible reaction pathways were obtained using the second-order Møller-Plesset theory and the coupled-cluster theory with single and double excitations with the triple-zeta quality basis sets. The energetics of the reaction pathways were calculated at the reduced second-order Gaussian-3 level and the extrapolated full coupled-cluster/complete basis set limit. The rate coefficients were calculated in the temperature range 200-3000 K, with the detailed consideration of the hindered internal rotation and the tunneling effect using Eckart and the semiclassical WKB approximations. It is shown that the predominant mechanism is the direct hydrogen abstraction producing hydroxyl and acetonyl radicals. Although the nucleophilic OC addition/elimination channel leading to CH3 and CO2 involves comparable barrier with the direct hydrogen abstraction channel, kinetically it cannot play any role in the overall reaction. It is predicted that the rate coefficients show positive temperature dependence in the range 200-3000 K and strong non-Arrhenius behavior. The tunneling effect plays a significant role. Moreover, the reaction has strong kinetic isotope effect. The calculated results are in good agreement with the available experimental data. The present rigorous theoretical work is helpful for the understanding of the characteristics of the reaction of atomic oxygen with acetone.

Intramolecular hydroxycarbene C–H-insertion: The curious case of (o-methoxyphenyl)hydroxycarbene

“…For the elucidation of solvent effects, M06-2X/cc-pVDZ-computations with the Polarization Continuum Model [35] (PCM) were performed, containing radii based on the United Atom Topological Model as implemented in Gaussian09. Tunneling half-lives τ 1/2 of carbenes 5 and 12 were estimated employing a) a simple Eckart barrier methodology [36–37], and b) the one-dimensional Wentzel–Kramers–Brillouin approximation [13–14 37–38]. …”

Computational Study of the Reaction of CH2(X3B1) with CH3OH

“…25,26 The details of this methodology have been discussed elsewhere and we have used it successfully in the reaction of atomic oxygen with acetone. 27 Basically, the MEP was first calculated at a low level of theory such as B3LYP/6-311G(d,p), and then the individual energy along the MEP was extrapolated to the high level such as G4 or W1U. For TS1 and TS2, a total of 68 and 132 points along the MEP can be obtained at the B3LYP/6-311G(d,p) level of theory (see the Supporting Information).…”