Theoretical studies on the kinetics of hydrogen abstraction reactions of H and CH3 radicals from CH3OCH3 and some of their H/D isotopologues.

Abstract

The hydrogen abstraction reactions by H and CH3 radicals from CH3OCH3 and some of their H/D isotopologues are studied by semiclassical transition state theory. Many high-level density functional, ab initio, and combinatory quantum chemical methods, including B3LYP, BB1K, MP2, MP4, CCSD(T), CBS-Q, and G4 methods, are employed to compute the energies and rovibrational properties of the stationary points for the title reactions. Xij vibrational anharmonicity coefficients, used in semiclassical transition state theory, are computed at the B3LYP, BB1K, and MP2 levels of theory. Thermal rate coefficients and kinetic isotope effects are computed over the temperature range from 200 to 2500 K and compared with available experimental data. The computed rate constants for the title reactions are represented as the equation k(T) = ATn exp[−E(T + T0)/(T2 + T02)].