TY - JOUR
T1 - Rate constants for the hydrogen abstractions in the OH-initiated oxidation of glycolaldehyde. A variational transition-state theory calculation
AU - Ochando-Pardo, Montserrat
AU - Nebot-Gil, Ignacio
AU - González-Lafont, Angels
AU - Lluch, José M.
PY - 2004/6/10
Y1 - 2004/6/10
N2 - 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.
AB - 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.
U2 - 10.1021/jp031363z
DO - 10.1021/jp031363z
M3 - Article
VL - 108
SP - 5117
EP - 5125
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 23
ER -