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Exploring the Reactivity of Hydrofluoropolyethers toward OH through a Cost-Effective Protocol for Calculating Multiconformer Transition State Theory Rate Constants

Cite this: J. Phys. Chem. A 2018, 122, 50, 9721–9732
Publication Date (Web):November 16, 2018
https://doi.org/10.1021/acs.jpca.8b08970
Copyright © 2018 American Chemical Society

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    Abstract

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    In this work, we propose a cost-effective protocol for the calculation of rate constants within the framework of multiconformer transition state theory. We have developed this methodology while calculating for the first time on a theoretical level rate constants for a series of six reactions between the OH radical and hydrofluoropolyethers: the latter are promising third-generation CFC replacements whose atmospheric impact is still widely unknown. Our investigation, which is based on computationally accessible M08-HX/apcseg-2//M08-HX/pcseg-1 calculations, shows that two of our rate constants are within a factor of 0.6 and 1.4 of experimental data, a good result that probably benefits from some error cancellation. It also exhibits a reactivity trend, for which we provide detailed insights that could be used to shed new light on the general reactivity of ethers toward OH. Finally, because the studied reactions share a ubiquitous mechanism in atmospheric chemistry, we hope that our protocol can be routinely applied to explore the reactivity of computationally challenging reactions and to pave new ways in the development of greener CFC replacements.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpca.8b08970.

    • Cartesian coordinates and electronic energies for the lowest energy conformers (HFPE0 and TS0) of the six studied reactions; imaginary frequencies of all TS0; technical details concerning optimizations, basis set superposition error, and tunneling calculations (PDF)

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    This article is cited by 18 publications.

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