Rate Constants for the Hydrogen Abstractions in the OH-Initiated Oxidation of Glycolaldehyde. A Variational Transition-state Theory Calculation

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 108; no. 23; pp. 5117 - 5125
• Main Authors: Ochando-Pardo, Montserrat, Nebot-Gil, Ignacio, González-Lafont, Angels, Lluch, José M
• Format: Journal Article
• Language: English
• Published: American Chemical Society 10.06.2004
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp031363z

The reaction between the OH radical and glycolaldehyde has been theoretically studied for the first time. By means of preliminary MP2(FC)/6-31G*, B3LYP/6-31G*, CBS-Q, G2, and G3 electronic structure calculations, two main processes have been determined, CH2OHCHO + OH → CH2OHCO + H2O and CH2OHCHO + OH → CHOHCHO + H2O, in clear agreement with experimental data. Then the variational transition-state theory rate constants with multidimensional tunneling corrections (when necessary) (VTST-MT) have been calculated using dual-level interpolation algorithms. The theoretical rate constant for the global process at 298 K of 3.83 × 10-11 cm3 molecule-1 s-1 is in reasonable agreement with the experimental value. In the temperature range 100−350 K, we predict a clear inverse dependence of the global rate constant on temperature.