The first experimental observation of the higher-energy trans conformer of trifluoroacetic acid

R. F G Apóstolo, Gábor Bazsó, R. R F Bento, G. Tarczay, R. Fausto

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

We report here the first experimental observation of the higher-energy conformer of trifluoroacetic acid (trans-TFA). The new conformer was generated by selective narrowband near-infrared vibrational excitation of the lower-energy cis-TFA conformer isolated in cryogenic matrices (Ar, Kr, N2) and shown to spontaneously decay to this latter form in the various matrix media, by tunneling. The decay rates in the different matrices were measured and compared with those of the trans conformers of other carboxylic acids in similar experimental conditions. The experimental studies received support from quantum chemistry calculations undertaken at various levels of approximation, which allowed a detailed characterization of the relevant regions of the potential energy surface of the molecule and the detailed assignment of the infrared spectra of the two conformers in the various matrices. Noteworthly, in contrast to cis-TFA that has its trifluoromethyl group eclipsed with the [Formula presented] bond of the carboxylic moiety, trans-TFA has the trifluoromethyl group eclipsed with the [Formula presented] bond. This unusual structure of trans-TFA results from the fact that the relative orientation of the CF3 and COOH groups in this geometry facilitates the establishment of an intramolecular hydrogen-bond-like interaction between the OH group and the closely located in-plane fluorine atom of the CF3 moiety.

Original languageEnglish
Pages (from-to)288-295
Number of pages8
JournalJournal of Molecular Structure
Volume1125
DOIs
Publication statusPublished - Dec 5 2016

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Trifluoroacetic Acid
Infrared radiation
Quantum chemistry
Potential energy surfaces
Fluorine
Carboxylic Acids
Cryogenics
Hydrogen bonds
Atoms
Molecules
Geometry

Keywords

  • Matrix-isolation IR spectroscopy
  • NIR-Induced in situ generation of trans-TFA
  • Quantum chemical calculations
  • Trifluoracetic acid
  • Tunneling decay rates

ASJC Scopus subject areas

  • Spectroscopy
  • Analytical Chemistry
  • Inorganic Chemistry
  • Organic Chemistry

Cite this

The first experimental observation of the higher-energy trans conformer of trifluoroacetic acid. / Apóstolo, R. F G; Bazsó, Gábor; Bento, R. R F; Tarczay, G.; Fausto, R.

In: Journal of Molecular Structure, Vol. 1125, 05.12.2016, p. 288-295.

Research output: Contribution to journalArticle

Apóstolo, R. F G ; Bazsó, Gábor ; Bento, R. R F ; Tarczay, G. ; Fausto, R. / The first experimental observation of the higher-energy trans conformer of trifluoroacetic acid. In: Journal of Molecular Structure. 2016 ; Vol. 1125. pp. 288-295.
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AB - We report here the first experimental observation of the higher-energy conformer of trifluoroacetic acid (trans-TFA). The new conformer was generated by selective narrowband near-infrared vibrational excitation of the lower-energy cis-TFA conformer isolated in cryogenic matrices (Ar, Kr, N2) and shown to spontaneously decay to this latter form in the various matrix media, by tunneling. The decay rates in the different matrices were measured and compared with those of the trans conformers of other carboxylic acids in similar experimental conditions. The experimental studies received support from quantum chemistry calculations undertaken at various levels of approximation, which allowed a detailed characterization of the relevant regions of the potential energy surface of the molecule and the detailed assignment of the infrared spectra of the two conformers in the various matrices. Noteworthly, in contrast to cis-TFA that has its trifluoromethyl group eclipsed with the [Formula presented] bond of the carboxylic moiety, trans-TFA has the trifluoromethyl group eclipsed with the [Formula presented] bond. This unusual structure of trans-TFA results from the fact that the relative orientation of the CF3 and COOH groups in this geometry facilitates the establishment of an intramolecular hydrogen-bond-like interaction between the OH group and the closely located in-plane fluorine atom of the CF3 moiety.

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