Multiconformer transition state theory rate constants for the reaction between OH and α,ω-dimethoxyfluoropolyethers

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DOI

  • Luís P. Viegas

In this work, we have calculated rate constants for the tropospheric reaction between the OH radical and 훼,휔 -dimethoxyfluoropolyethers. The latter are a specific class of the hydrofluoropolyethers family with the general formula CH 3 (OCF 2 CF 2 )푝(OCF 2 )푞OCH 3 , from which we have selected three case studies: 푝0푞2, 푝0푞3, and 푝2푞0. The calculations were performed by applying a cost-effective protocol developed for bimolecular hydrogen-abstraction reactions and based on multiconformer transition state theory relying on computationally accessible M08-HX/apcseg-2//M08-HX/pcseg-1 calculations. Within the protocol's uncertainties and approximations, the results show that (1) the calculated rate constants have the same order of magnitude and (2) if observed together with previous experimental and theoretical investigations, the chain length (that varies with q and p) is seen to have a small effect on the rate constant, which is consistent with the “no discernible effect” reported in the experimental work.

Original languageEnglish
JournalInternational Journal of Chemical Kinetics
Volume51
Issue5
Pages (from-to)358-366
Number of pages9
ISSN0538-8066
DOIs
Publication statusPublished - May 2019

    Research areas

  • atmospheric chemistry, dimethoxyfluoropolyethers, multiconformer transition state theory

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