Experimental and theoretical studies of the vibrations and structure of 2,2,2-trifluoroethyl trifluoroacetate, CF3CO2CH2CF3

M.E. Defonsi Lestard, M.E. Tuttolomondo, E.L. Varetti, D.A. Wann, H.E. Robertson, D.W.H. Rankin, A. Ben Altabef

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The molecular structure of 2,2,2-trifluoroethyl trifluoroacetate, CF3CO2CH2CF3, has been determined in the gas-phase from electron-diffraction data supplemented by ab initio (MP2) and DFT calculations using basis sets up to 6-311++G(d,p). Both experimental and theoretical data indicate that, although both structures with anti, anti (Cs) and anti, gauche (C1) conformations exist by rotating about the O{single bond}C(H2) bond, the anti, anti structure is preferred. The difference in free energy was calculated to be 2.1 kJ mol-1 (Cs conformer lower in energy) and as the C1 conformer has a double multiplicity relative to the Cs conformer, the ratio of C1-Cs conformer was predicted to be 0.41: 0.59. This conformational preference was studied using the total energy scheme and the natural bond orbital partition scheme. Additionally, the total potential energy has been deconvoluted using six-fold decomposition in terms of a Fourier-type expansion. Infrared spectra of CF3CO2CH2CF3 have been obtained for the gaseous, liquid and solid phases and the Raman spectrum for the liquid phase. Harmonic vibrational frequencies and a scaled force field have been calculated, leading to a final root-mean-square deviation of 7.3 cm-1. © 2008 Elsevier B.V. All rights reserved.
Original languageUndefined/Unknown
Pages (from-to)183-192
Number of pages10
Issue number2-3
Publication statusPublished - 15 Jan 2009

Bibliographical note

Cited By (since 1996):6

Export Date: 1 October 2013

Source: Scopus


doi: 10.1016/j.molstruc.2008.08.012

Language of Original Document: English

Correspondence Address: Ben Altabef, A.; Instituto de Química Física, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, San Lorenzo 456, T4000CAN Tucumán, Argentina; email: altabef@fbqf.unt.edu.ar

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  • 2,2,2-Trifluoroethyl trifluoroacetate
  • Ab initio calculations
  • DFT calculations
  • Gas-phase electron diffraction
  • Infrared and Raman spectroscopy
  • Internal barrier to rotation
  • Auger electron spectroscopy
  • Carbon dioxide
  • Conformations
  • Data structures
  • Density functional theory
  • Diffraction
  • Electron diffraction
  • Experiments
  • Probability density function
  • Quantum chemistry
  • Raman scattering
  • Raman spectroscopy
  • Rotation
  • Spectrum analysis
  • Sulfur compounds
  • Infrared spectroscopy

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