Spectroscopic behaviour, bond properties and charge distribution in methoxy groups in hydrofluoroethers: the effect of neighbouring CF2 group

Radice, Stefano; Toniolo, P.; Avataneo, M.; Patto, U. De; Marchionni, G.; Castiglioni, Chiara; Tommasini, Matteo; Zerbi, G.

doi:10.1016/j.theochem.2004.07.040

Cited by 14 publications

(14 citation statements)

References 13 publications

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“…One of the difficulties in studying reaction is the fact that DM‐FPEs (and, in general, HFPEs) have a rich conformational variety . Such complexity should be included in the rate constant formula, and if one chooses transition state theory as the method of calculation, then it will assume the form of MC‐TST .…”

Section: Methodsmentioning

confidence: 99%

Multiconformer transition state theory rate constants for the reaction between OH and ‐dimethoxyfluoropolyethers

Viegas

2019

Int J of Chemical Kinetics

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In this work, we have calculated rate constants for the tropospheric reaction between the OH radical and α,ω‐dimethoxyfluoropolyethers. The latter are a specific class of the hydrofluoropolyethers family with the general formula CH 3( OCF 2 CF 2)italicp( OCF 2)italicq OCH 3, from which we have selected three case studies: p0q2, p0q3, and p2q0. 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.

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Section: Methodsmentioning

confidence: 99%

Multiconformer transition state theory rate constants for the reaction between OH and ‐dimethoxyfluoropolyethers

Viegas

2019

Int J of Chemical Kinetics

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“…To the best of our knowledge there are very few theoretical investigations that tackle conformational manifold issues in the chemistry of

{HG}^{'}

‐ qp and

HG

‐ qp for

q + p \geq 1

. In fact, only two papers were found, both mainly focusing on the vibrational spectra of such compounds: the first one with BLYP/6‐31G(d,p) calculations on

HG

‐10,

HG

‐01 and

HG

‐11 and the second one with BLYP/6‐311G(d,p) calculations on

{HG}^{'}

‐01,

{HG}^{'}

‐02 and

{HG}^{'}

‐03. In these papers two conformers are found for

HG

‐10 and four are obtained for

{HG}^{'}

‐01.…”

Section: Resultsmentioning

confidence: 99%

“…In fact, only two papers were found, both mainly focusing on the vibrational spectra of such compounds: the first one with BLYP/6‐31G(d,p) calculations on

HG

‐10,

HG

‐01 and

HG

‐11 and the second one with BLYP/6‐311G(d,p) calculations on

{HG}^{'}

‐01,

{HG}^{'}

‐02 and

{HG}^{'}

‐03. In these papers two conformers are found for

HG

‐10 and four are obtained for

{HG}^{'}

‐01. However, it should be stressed that these two articles are considered far from being “a systematic investigation of the conformational space.” Since this work is, as far as we know, the first detailed theoretical comparative conformational study between DH‐FPEs and DM‐FPEs, we will now present some data originating from the optimization process that may be useful for the present and future investigations.…”

Section: Resultsmentioning

confidence: 99%

“…In these papers two conformers are found for

HG

‐10 and four are obtained for

{HG}^{'}

\overset{Δ E_{opt}}{true}, \overset{{grad}_{rms, 0}}{true}

and the total wall clock time for all optimizations in each group of conformers,

{HG}^{'}

‐10 and

HG

‐10.…”

Section: Resultsmentioning

confidence: 99%

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Assessment of model chemistries for hydrofluoropolyethers: A DFT/M08‐HX benchmark study

Viegas

2017

Int J of Quantum Chemistry

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In this work, we report the first detailed theoretical comparative conformational investigation between two different classes of hydrofluoropolyethers: dihydro-and dimethoxyfluoropolyethers.The main objective was to determine a cost-effective computational methodology that could accurately reproduce the energetic rankings and thermal weight factors of the simplest examples of those two classes calculated with M08-HX/triple-f//M08-HX/double-f benchmark model chemistries. Between the tested methodologies, M08-HX/aug-pcseg-2//M08-HX/pcseg-1 was found to be the most appropriate, exhibiting a good accuracy and considerable reduction in computational cost with respect to the benchmark, being more than three times faster than M08-HX/aug-pcseg-2//M08-HX/aug-pcseg-1. This cost-effective approach will be essential in future work when studying larger hydrofluoropolyethers, where the computational complexity associated with increasing number of conformers will require such approximations. K E Y W O R D S atmospheric chemistry, conformational sampling, density functional theory, hydrofluoropolyethers, model chemistry Int J Quantum Chem. 2017;117:e25381.

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“…back-donation of electronic charge or charge injection into p systems). Moreover, once CH bonds are nearby a fluorinated system, stretching frequency and vibrational intensities are strongly affected [3][4][5].…”

Section: Introductionmentioning

confidence: 99%

Two dimensional correlation Raman spectroscopy of perfluoropolyethers: Effect of peroxide groups

Radice¹,

Tommasini²,

Castiglioni³

2010

Journal of Molecular Structure

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Spectroscopic behaviour, bond properties and charge distribution in methoxy groups in hydrofluoroethers: the effect of neighbouring CF2 group

Cited by 14 publications

References 13 publications

Multiconformer transition state theory rate constants for the reaction between OH and ‐dimethoxyfluoropolyethers

Multiconformer transition state theory rate constants for the reaction between OH and ‐dimethoxyfluoropolyethers

Assessment of model chemistries for hydrofluoropolyethers: A DFT/M08‐HX benchmark study

Two dimensional correlation Raman spectroscopy of perfluoropolyethers: Effect of peroxide groups

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