Rate constants for the hydrogen abstractions in the OH-initiated oxidation of glycolaldehyde. A variational transition-state theory calculation

Montserrat Ochando-Pardo; Ignacio Nebot-Gil; Angels González-Lafont; José M. Lluch

doi:10.1021/jp031363z

Rate constants for the hydrogen abstractions in the OH-initiated oxidation of glycolaldehyde. A variational transition-state theory calculation

Montserrat Ochando-Pardo, Ignacio Nebot-Gil, Angels González-Lafont, José M. Lluch

Research output: Contribution to journal › Article › Research › peer-review

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Abstract

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.

Original language	English
Pages (from-to)	5117-5125
Journal	Journal of Physical Chemistry A
Volume	108
Issue number	23
DOIs	https://doi.org/10.1021/jp031363z
Publication status	Published - 10 Jun 2004

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@article{9b0c7c21cb4e415ea211056d018661c1,

title = "Rate constants for the hydrogen abstractions in the OH-initiated oxidation of glycolaldehyde. A variational transition-state theory calculation",

abstract = "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.",

author = "Montserrat Ochando-Pardo and Ignacio Nebot-Gil and Angels Gonz{\'a}lez-Lafont and Lluch, {Jos{\'e} M.}",

year = "2004",

month = jun,

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doi = "10.1021/jp031363z",

language = "English",

volume = "108",

pages = "5117--5125",

journal = "Journal of Physical Chemistry A",

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publisher = "American Chemical Society",

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Rate constants for the hydrogen abstractions in the OH-initiated oxidation of glycolaldehyde. A variational transition-state theory calculation. / Ochando-Pardo, Montserrat; Nebot-Gil, Ignacio; González-Lafont, Angels ; Lluch, José M.

In: Journal of Physical Chemistry A, Vol. 108, No. 23, 10.06.2004, p. 5117-5125.

Research output: Contribution to journal › Article › Research › peer-review

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 -

Rate constants for the hydrogen abstractions in the OH-initiated oxidation of glycolaldehyde. A variational transition-state theory calculation

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