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

Research output: Contribution to journalArticlepeer-review

Abstract

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
JournalJOURNAL OF MOLECULAR STRUCTURE
Volume917
Issue number2-3
DOIs
Publication statusPublished - 15 Jan 2009

Bibliographical note

Cited By (since 1996):6

Export Date: 1 October 2013

Source: Scopus

CODEN: JMOSB

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

References: Fujishige, M., Shiraishi, Y., Sekiguchi, O., Tajima, S.J., (1998) Mass Spectrom. Soc. Jpn., 46, p. 448; Crowder, G.A., (1971) J. Fluorine Chem., 1, p. 219; Pulay, P., Fogarasi, G., Pongor, G., Boggs, J.E., Braga, A., (1983) J. Am. Chem. Soc., 105, p. 7037; Tuttolomondo, M.E., Fernández, L.E., Navarro, A., Varetti, E.L., Ben Altabef, A., (2004) Spectrochim. Acta A Inglaterra, 60, p. 611; Tuttolomondo, M.E., Argarañaz, P.E., Varetti, E.L., Hayes, S.A., Wann, D.A., Robertson, H.E., Rankin, D.W.H., Ben Altabef, A., (2007) Eur. J. Inorg. Chem., p. 1381; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J. Chem. Soc. Dalton Trans., p. 954; Fleischer, H., Wann, D.A., Hinchley, S.L., Borisenko, K.B., Lewis, J.R., Mawhorter, R.J., Robertson, H.E., Rankin, D.W.H., (2005) Dalton Trans., p. 3221; Hinchley, S.L., Robertson, H.E., Borisenko, K.B., Turner, A.R., Johnston, B.F., Rankin, D.W.H., Ahmadian, M., Cowley, A.H., (2004) Dalton Trans., p. 2469; A.W. Ross, M. Fink, R. Hilderbrandt, International tables for crystallography, in: A.J.C. Wilson, (Ed.), vol. C, Kluwer Academic Publishers, Dordrecht Netherlands, 1992, p. 245National Service for Computational Chemistry Software (NSCCS). URL http://www.nsccs.ac.ukM.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, Gaussian 03, revision C.02; Gaussian, Inc., Wallingford, CT, 2004Møller, C., Plesset, M.S., (1934) Phys. Rev., 46, p. 618; Krishnan, R., Binkley, J.S., Seeger, R., Pople, J.A., (1980) J. Chem. Phys., 72, p. 650; McLean, A.D., Chandler, G.S., (1980) J. Chem. Phys., 72, p. 5639; Hehre, W.J., Schleyer, P.v.R., Pople, J.A., (1986) Ab initio Molecular Orbital Theory, , Wiley, New York; Becke, A.D., (1993) J. Chem. Phys., 98, p. 5648; Lee, C., Yang, W., Parr, R.G., (1988) Phys. Rev. B, 37, p. 785; Perdew, J.P., Burke, K., Ernzerhof, M., (1996) Phys. Rev. Lett., 77, p. 3865; Perdew, J.P., Burke, K., Ernzerhof, M., (1997) Erratum Phys. Rev. Lett., 78, p. 1396; Alamo, C., Barone, V., (1998) J. Chem. Phys., 108, p. 664; Sipachev, V.A., (1985) J. Mol. Struct. (THEOCHEM), 121, p. 143; Sipachev, V.A., (2001) J. Mol. Struct., 567, p. 67; McCaffrey, P.D., Mawhorter, R.J., Turner, A.R., Brain, P.T., Rankin, D.W.H., (2007) J. Phys. Chem. A, 111, p. 6103; Glendening, E.D., Badenhoop, J.K., Reed, A.D., Carpenter, J.E., Weinhold, F.F., (1996) Theoretical Chemistry Institute, , University of Wisconsin, Madison WI; Fogarasi, G., Zhou, X., Taylor, P.W., Pulay, P., (1992) J. Am. Chem. Soc., 114, p. 8191; Wilson, E.B., Decius, J.C., Cross, P.C., (1955) Molecular Vibrations, , McGraw-Hill, New York; W.B. Collier, Program FCARTP (QCPE #631); Department of Chemistry, Oral Roberts University, Tulsa, OK, 1992A.B. Nielsen, A.J. Holder, GaussView, User's Reference; GAUSSIAN Inc., Pittsburgh, PA, 1997-1998Duncan, J.L., (1974) Mol. Phys., 28, p. 1177; Millefiori, S., Alparone, A., (1998) J. Chem. Soc. Faraday Trans., 94, p. 25; Radom, L., Hehre, W.J., Pople, J.A., (1972) J. Am. Chem. Soc., 94, p. 2371; Radom, L., Pople, J.A., (1970) J. Am. Chem. Soc., 92, p. 4786; Bond, D., Schleyer, P.v.R., (1990) J. Org. Chem., 55, p. 1003; Blake, A.J., Brain, P.T., McNab, H., Miller, J., Morrison, C.A., Parsons, S., Rankin, D.W.H., Smart, B.A., (1996) J. Phys. Chem., 100, p. 12280; Brain, P.T., Morrison, C.A., Parsons, S., Rankin, D.W.H., (1996) J. Chem. Soc. Dalton Trans., p. 4589; Mitzel, N.W., Rankin, D.W.H., (2003) Dalton Trans., p. 3650; Hamilton, W.C., (1965) Acta Crystallogr., 18, p. 502; Erben, M.F., Della Védova, C.O., Boese, R., Willner, H., Leibold, C., Oberhammer, H., (2003) Inorg. Chem., 42, p. 7297; Berney, C.V., (1973) J. Am. Chem. Soc., 95, p. 708; Tuttolomondo, M.E., Navarro, A., Varetti, E.L., BenAltabef, A., (2005) J. Raman Spectrosc., 36, p. 427

Keywords

  • 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

Cite this