Computational Study of the Reactions of Methanol with the Hydroperoxyl and Methyl Radicals. 1. Accurate Thermochemistry and Barrier Heights

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2011-04, Vol.115 (13), p.2811-2829
• Main Authors: Alecu, I. M, Truhlar, Donald G
• Format: Article
• Language: English
• Subjects: A: Molecular Structure, Quantum Chemistry, General Theory; biofuels (including algae and biomass), hydrogen and fuel cells, combustion, carbon capture
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp110024e

The reactions of CH3OH with the HO2 and CH3 radicals are important in the combustion of methanol and are prototypes for reactions of heavier alcohols in biofuels. The reaction energies and barrier heights for these reaction systems are computed with CCSD(T) theory extrapolated to the complete basis set limit using correlation-consistent basis sets, both augmented and unaugmented, and further refined by including a fully coupled treatment of the connected triple excitations, a second-order perturbative treatment of quadruple excitations (by CCSDT(2)Q), core−valence corrections, and scalar relativistic effects. It is shown that the M08-HX and M08-SO hybrid meta-GGA density functionals can achieve sub-kcal mol−1 agreement with the high-level ab initio results, identifying these functionals as important potential candidates for direct dynamics studies on the rates of these and homologous reaction systems.