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

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Multiconformer transition state theory rate constants for the reaction between OH and α,ω-dimethoxyfluoropolyethers. / Viegas, Luís P.

In: International Journal of Chemical Kinetics, Vol. 51, No. 5, 05.2019, p. 358-366.

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Viegas, Luís P. / Multiconformer transition state theory rate constants for the reaction between OH and α,ω-dimethoxyfluoropolyethers. In: International Journal of Chemical Kinetics. 2019 ; Vol. 51, No. 5. pp. 358-366.

Bibtex

@article{a6cd6b0b4c6f47d3ac705d9c842026ff,
title = "Multiconformer transition state theory rate constants for the reaction between OH and α,ω-dimethoxyfluoropolyethers",
abstract = "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.",
keywords = "atmospheric chemistry, dimethoxyfluoropolyethers, multiconformer transition state theory",
author = "Viegas, {Lu{\'i}s P.}",
year = "2019",
month = "5",
doi = "10.1002/kin.21259",
language = "English",
volume = "51",
pages = "358--366",
journal = "International Journal of Chemical Kinetics",
issn = "0538-8066",
publisher = "JohnWiley & Sons, Inc.",
number = "5",

}

RIS

TY - JOUR

T1 - Multiconformer transition state theory rate constants for the reaction between OH and α,ω-dimethoxyfluoropolyethers

AU - Viegas, Luís P.

PY - 2019/5

Y1 - 2019/5

N2 - 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.

AB - 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.

KW - atmospheric chemistry

KW - dimethoxyfluoropolyethers

KW - multiconformer transition state theory

UR - http://www.scopus.com/inward/record.url?scp=85062338717&partnerID=8YFLogxK

U2 - 10.1002/kin.21259

DO - 10.1002/kin.21259

M3 - Journal article

AN - SCOPUS:85062338717

VL - 51

SP - 358

EP - 366

JO - International Journal of Chemical Kinetics

JF - International Journal of Chemical Kinetics

SN - 0538-8066

IS - 5

ER -