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Ab initio study of the OH + CH2O reaction: The effect of the OH··OCH2 complex on the H-abstraction kinetics

✍ Scribed by Shucheng Xu; R. S. Zhu; M. C. Lin

Publisher
John Wiley and Sons
Year
2006
Tongue
English
Weight
177 KB
Volume
38
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

Kinetics for the reaction of OH radical with CH~2~O has been studied by single‐point calculations at the CCSD(T)/6‐311+G(3__df__, 2__p__) level based on the geometries optimized at the B3LYP/6‐311+G(3__df__, 2__p__) and CCSD/6‐311++G(d,p) levels. The rate constant for the reaction has been computed in the temperature range 200–3000 K by variational transition state theory including the significant effect of the multiple reflections above the OH··OCH~2~ complex. The predicted results can be represented by the expressions k~1~ = 2.45 × 10^‐21^ T^2.98^ exp (1750/T) cm^3^ mol^−1^ s^−1^ (200–400 K) and 3.22 × 10^‐18^ T^2.11^ exp(849/T) cm^3^ mol^−1^ s^−1^ (400–3000 K) for the H‐abstraction process and k~2~ = 1.05 × 10^‐17^ T^1.63^ exp(−2156/T) cm^3^ mol^−1^ s^−1^ in the temperature range of 200–3000 K for the HO‐addition process producing the OCH~2~OH radical. The predicted total rate constants (k~1~ + k~2~) can reproduce closely the recommended kinetic data for OH + CH~2~O over the entire range of temperature studied. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 322–326, 2006

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