Computational Study of the Reactions of Methanol with the Hydroperoxyl and Methyl Radicals. 2. Accurate Thermal Rate Constants

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 115; no. 51; pp. 14599 - 14611
• Main Authors: Alecu, I. M, Truhlar, Donald G
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 29.12.2011
• Subjects: A: Kinetics, Spectroscopy; Combustion; Construction; Kinetics; Mathematical analysis; Mathematical models; Methane - analogs & derivatives; Methane - chemistry; Methanol - chemistry; Methyl alcohol; Methyl radicals; Peroxides - chemistry; Quantum Theory; Rate constants; Temperature; Tunneling
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp209029p

Multistructural canonical variational-transition-state theory with multidimensional tunneling (MS-CVT/MT) is employed to calculate thermal rate constants for the abstraction of hydrogen atoms from both positions of methanol by the hydroperoxyl and methyl radicals over the temperature range 100–3000 K. The M08-HX hybrid meta-generalized gradient approximation density functional and M08-HX with specific reaction parameters, both with the maug-cc-pVTZ basis set, were validated in part 1 of this study (Alecu, I. M.; Truhlar, D. G. J. Phys. Chem. A 2011, 115, 2811) against highly accurate CCSDT(2)Q/CBS calculations for the energetics of these reactions, and they are used here to compute the properties of all stationary points and the energies, gradients, and Hessians of nonstationary points along each considered reaction path. The internal rotations in some of the transition states are found to be highly anharmonic and strongly coupled to each other, and they generate multiple structures (conformations) whose contributions are included in the partition function. It is shown that the previous estimates for these rate constants used to build kinetic models for the combustion of methanol, some of which were based on transition state theory calculations with one-dimensional tunneling corrections and harmonic-oscillator approximations or separable one-dimensional hindered rotor treatments of torsions, are appreciably different than the ones presently calculated using MS-CVT/MT. The rate constants obtained from the best MS-CVT/MT calculations carried out in this study, in which the important effects of corner cutting due to small and large reaction path curvature are captured via a microcanonical optimized multidimensional tunneling (μOMT) treatment, are recommended for future refinement of the kinetic model for methanol combustion.