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

doi:10.1016/j.molstruc.2008.08.012

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

Chemistry

Research output: Contribution to journal › Article › peer-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 language	Undefined/Unknown
Pages (from-to)	183-192
Number of pages	10
Journal	JOURNAL OF MOLECULAR STRUCTURE
Volume	917
Issue number	2-3
DOIs	https://doi.org/10.1016/j.molstruc.2008.08.012
Publication status	Published - 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: [email protected]

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

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10.1016/j.molstruc.2008.08.012

http://www.scopus.com/inward/record.url?eid=2-s2.0-58149180190&partnerID=40&md5=77db9c7ec039ea5357707eb1f7fbab40

Cite this

@article{ca3395f3bcb84f848a3ec35848383e09,

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

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. {\textcopyright} 2008 Elsevier B.V. All rights reserved.",

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",

author = "{Defonsi Lestard}, M.E. and M.E. Tuttolomondo and E.L. Varetti and D.A. Wann and H.E. Robertson and D.W.H. Rankin and {Ben Altabef}, A.",

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 Qu{\'i}mica F{\'i}sica, Facultad de Bioqu{\'i}mica, Qu{\'i}mica y Farmacia, Universidad Nacional de Tucum{\'a}n, San Lorenzo 456, T4000CAN Tucum{\'a}n, Argentina; email: [email protected] 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., Fern{\'a}ndez, L.E., Navarro, A., Varetti, E.L., Ben Altabef, A., (2004) Spectrochim. Acta A Inglaterra, 60, p. 611; Tuttolomondo, M.E., Argara{\~n}az, 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, 2004M{\o}ller, 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 V{\'e}dova, 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",

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TY - JOUR

T1 - Experimental and theoretical studies of the vibrations and structure of 2,2,2-trifluoroethyl trifluoroacetate, CF3CO2CH2CF3

AU - Defonsi Lestard, M.E.

AU - Tuttolomondo, M.E.

AU - Varetti, E.L.

AU - Wann, D.A.

AU - Robertson, H.E.

AU - Rankin, D.W.H.

AU - Ben Altabef, A.

N1 - 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: [email protected] 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

PY - 2009/1/15

Y1 - 2009/1/15

N2 - 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.

AB - 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.

KW - 2,2,2-Trifluoroethyl trifluoroacetate

KW - Ab initio calculations

KW - DFT calculations

KW - Gas-phase electron diffraction

KW - Infrared and Raman spectroscopy

KW - Internal barrier to rotation

KW - Auger electron spectroscopy

KW - Carbon dioxide

KW - Conformations

KW - Data structures

KW - Density functional theory

KW - Diffraction

KW - Electron diffraction

KW - Experiments

KW - Probability density function

KW - Quantum chemistry

KW - Raman scattering

KW - Raman spectroscopy

KW - Rotation

KW - Spectrum analysis

KW - Sulfur compounds

KW - Infrared spectroscopy

U2 - 10.1016/j.molstruc.2008.08.012

DO - 10.1016/j.molstruc.2008.08.012

M3 - Article

SN - 0022-2860

VL - 917

SP - 183

EP - 192

JO - JOURNAL OF MOLECULAR STRUCTURE

JF - JOURNAL OF MOLECULAR STRUCTURE

IS - 2-3

ER -