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J Am Chem Soc. 2001 Mar 7;123(9):2018-24.

On the importance of prereactive complexes in molecule-radical reactions: hydrogen abstraction from aldehydes by OH.

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  • 1Laboratorio de Química Computacional y Teórica, Facultad de Química, Universidad de La Habana, Havana 10400, Cuba.

Abstract

In this work, the OH + formaldehyde and OH + acetaldehyde reactions have been characterized using accurate ab initio methods with large basis sets. The results clearly indicate that the reaction occurs by hydrogen abstraction, and that the OH addition channel is unfavorable. Close to zero (for formaldehyde) and negative (for acetaldehyde) activation energy values are obtained, which are in excellent agreement with the experimentally observed values. The reaction rate constants, calculated using the classical transition-state theory as applied to a complex mechanism involving the formation of a prereactive complex, reproduce very well the reported experimental results. Consideration of the prereactive complex is shown to be essential for the determination of the height of the energy barrier and thus for the correct calculation of the tunneling factor.

PMID:
11456824
[PubMed]
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