Gas-phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3)

Autores
Defonsi Lestard, Maria Eliana; Tuttolomondo, María Eugenia; Varetti, Eduardo Lelio; Wann, Derek A.; Robertson, Heather E.; Rankin, David W. H.; Ben Altabef, Aída
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The molecular structure of methyl trifluoroacetate (CF3C(O)OCH3) has been determined in the gas phase from electrondiffraction data supplemented by abinitio (MP2) and DFT calculations using different basis sets. Experimental data revealed an anti conformation with a dihedral angle θ (CCOC) = 180°. Quantum mechanical calculations indicate the possible existence of two conformers, differing by a rotation about the C(O)-O bond. The global minimum represents a Cs-symmetric structure in which the CF3 group has the anti orientation with respect to the CH3 group,but there is another potential minimum, much higher in energy, representing a Cs-symmetric structure with a cis conformation. The preference for the anti conformation was studied using the total energy scheme and the natural bond orbital (NBO) partition scheme. Additionally, the total potential energy has been deconvoluted using a six-fold decomposition in terms of a Fourier-type expansion, showing that the electrostatic and steric contributions are dominant in stabilizing the anti conformer. Infrared spectra of CF3C(O)OCH3 were obtained for the gaseous and liquid phases, while the Raman spectrum was recorded for the liquid phase. Harmonic vibrational frequencies and a scaled force field have been calculated, leading to a final root mean-square deviation of 9cm-1 when comparing experimental and calculated frequencies. © 2009 John Wiley & Sons, Ltd.
Fil: Defonsi Lestard, Maria Eliana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Tuttolomondo, María Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Varetti, Eduardo Lelio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Wann, Derek A.. University of Edinburgh; Reino Unido
Fil: Robertson, Heather E.. University of Edinburgh; Reino Unido
Fil: Rankin, David W. H.. University of Edinburgh; Reino Unido
Fil: Ben Altabef, Aída. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Materia
Ab Initio Calculations
Dft Calculations
Gas Electron Diffraction
Infrared Spectra
Methyl Trifluoroacetate
Raman Spectra
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/54502
Acceder
id CONICETDig_288511a44683dd19438841360c31e206
oai_identifier_str oai:ri.conicet.gov.ar:11336/54502
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Gas-phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3)Defonsi Lestard, Maria ElianaTuttolomondo, María EugeniaVaretti, Eduardo LelioWann, Derek A.Robertson, Heather E.Rankin, David W. H.Ben Altabef, AídaAb Initio CalculationsDft CalculationsGas Electron DiffractionInfrared SpectraMethyl TrifluoroacetateRaman Spectrahttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The molecular structure of methyl trifluoroacetate (CF3C(O)OCH3) has been determined in the gas phase from electrondiffraction data supplemented by abinitio (MP2) and DFT calculations using different basis sets. Experimental data revealed an anti conformation with a dihedral angle θ (CCOC) = 180°. Quantum mechanical calculations indicate the possible existence of two conformers, differing by a rotation about the C(O)-O bond. The global minimum represents a Cs-symmetric structure in which the CF3 group has the anti orientation with respect to the CH3 group,but there is another potential minimum, much higher in energy, representing a Cs-symmetric structure with a cis conformation. The preference for the anti conformation was studied using the total energy scheme and the natural bond orbital (NBO) partition scheme. Additionally, the total potential energy has been deconvoluted using a six-fold decomposition in terms of a Fourier-type expansion, showing that the electrostatic and steric contributions are dominant in stabilizing the anti conformer. Infrared spectra of CF3C(O)OCH3 were obtained for the gaseous and liquid phases, while the Raman spectrum was recorded for the liquid phase. Harmonic vibrational frequencies and a scaled force field have been calculated, leading to a final root mean-square deviation of 9cm-1 when comparing experimental and calculated frequencies. © 2009 John Wiley & Sons, Ltd.Fil: Defonsi Lestard, Maria Eliana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Tuttolomondo, María Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Varetti, Eduardo Lelio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Wann, Derek A.. University of Edinburgh; Reino UnidoFil: Robertson, Heather E.. University of Edinburgh; Reino UnidoFil: Rankin, David W. H.. University of Edinburgh; Reino UnidoFil: Ben Altabef, Aída. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaJohn Wiley & Sons Ltd2009-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/54502Defonsi Lestard, Maria Eliana; Tuttolomondo, María Eugenia; Varetti, Eduardo Lelio; Wann, Derek A.; Robertson, Heather E.; et al.; Gas-phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3); John Wiley & Sons Ltd; Journal Of Raman Spectroscopy; 40; 12; 12-2009; 2053-20620377-0486CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1002/jrs.2371info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/jrs.2371info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:30:58Zoai:ri.conicet.gov.ar:11336/54502instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:30:58.789CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Gas-phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3)
title Gas-phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3)
spellingShingle Gas-phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3)
Defonsi Lestard, Maria Eliana
Ab Initio Calculations
Dft Calculations
Gas Electron Diffraction
Infrared Spectra
Methyl Trifluoroacetate
Raman Spectra
title_short Gas-phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3)
title_full Gas-phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3)
title_fullStr Gas-phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3)
title_full_unstemmed Gas-phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3)
title_sort Gas-phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3)
dc.creator.none.fl_str_mv Defonsi Lestard, Maria Eliana
Tuttolomondo, María Eugenia
Varetti, Eduardo Lelio
Wann, Derek A.
Robertson, Heather E.
Rankin, David W. H.
Ben Altabef, Aída
author Defonsi Lestard, Maria Eliana
author_facet Defonsi Lestard, Maria Eliana
Tuttolomondo, María Eugenia
Varetti, Eduardo Lelio
Wann, Derek A.
Robertson, Heather E.
Rankin, David W. H.
Ben Altabef, Aída
author_role author
author2 Tuttolomondo, María Eugenia
Varetti, Eduardo Lelio
Wann, Derek A.
Robertson, Heather E.
Rankin, David W. H.
Ben Altabef, Aída
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Ab Initio Calculations
Dft Calculations
Gas Electron Diffraction
Infrared Spectra
Methyl Trifluoroacetate
Raman Spectra
topic Ab Initio Calculations
Dft Calculations
Gas Electron Diffraction
Infrared Spectra
Methyl Trifluoroacetate
Raman Spectra
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The molecular structure of methyl trifluoroacetate (CF3C(O)OCH3) has been determined in the gas phase from electrondiffraction data supplemented by abinitio (MP2) and DFT calculations using different basis sets. Experimental data revealed an anti conformation with a dihedral angle θ (CCOC) = 180°. Quantum mechanical calculations indicate the possible existence of two conformers, differing by a rotation about the C(O)-O bond. The global minimum represents a Cs-symmetric structure in which the CF3 group has the anti orientation with respect to the CH3 group,but there is another potential minimum, much higher in energy, representing a Cs-symmetric structure with a cis conformation. The preference for the anti conformation was studied using the total energy scheme and the natural bond orbital (NBO) partition scheme. Additionally, the total potential energy has been deconvoluted using a six-fold decomposition in terms of a Fourier-type expansion, showing that the electrostatic and steric contributions are dominant in stabilizing the anti conformer. Infrared spectra of CF3C(O)OCH3 were obtained for the gaseous and liquid phases, while the Raman spectrum was recorded for the liquid phase. Harmonic vibrational frequencies and a scaled force field have been calculated, leading to a final root mean-square deviation of 9cm-1 when comparing experimental and calculated frequencies. © 2009 John Wiley & Sons, Ltd.
Fil: Defonsi Lestard, Maria Eliana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Tuttolomondo, María Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Varetti, Eduardo Lelio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Wann, Derek A.. University of Edinburgh; Reino Unido
Fil: Robertson, Heather E.. University of Edinburgh; Reino Unido
Fil: Rankin, David W. H.. University of Edinburgh; Reino Unido
Fil: Ben Altabef, Aída. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
description The molecular structure of methyl trifluoroacetate (CF3C(O)OCH3) has been determined in the gas phase from electrondiffraction data supplemented by abinitio (MP2) and DFT calculations using different basis sets. Experimental data revealed an anti conformation with a dihedral angle θ (CCOC) = 180°. Quantum mechanical calculations indicate the possible existence of two conformers, differing by a rotation about the C(O)-O bond. The global minimum represents a Cs-symmetric structure in which the CF3 group has the anti orientation with respect to the CH3 group,but there is another potential minimum, much higher in energy, representing a Cs-symmetric structure with a cis conformation. The preference for the anti conformation was studied using the total energy scheme and the natural bond orbital (NBO) partition scheme. Additionally, the total potential energy has been deconvoluted using a six-fold decomposition in terms of a Fourier-type expansion, showing that the electrostatic and steric contributions are dominant in stabilizing the anti conformer. Infrared spectra of CF3C(O)OCH3 were obtained for the gaseous and liquid phases, while the Raman spectrum was recorded for the liquid phase. Harmonic vibrational frequencies and a scaled force field have been calculated, leading to a final root mean-square deviation of 9cm-1 when comparing experimental and calculated frequencies. © 2009 John Wiley & Sons, Ltd.
publishDate 2009
dc.date.none.fl_str_mv 2009-12
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/54502
Defonsi Lestard, Maria Eliana; Tuttolomondo, María Eugenia; Varetti, Eduardo Lelio; Wann, Derek A.; Robertson, Heather E.; et al.; Gas-phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3); John Wiley & Sons Ltd; Journal Of Raman Spectroscopy; 40; 12; 12-2009; 2053-2062
0377-0486
CONICET Digital
CONICET
url http://hdl.handle.net/11336/54502
identifier_str_mv Defonsi Lestard, Maria Eliana; Tuttolomondo, María Eugenia; Varetti, Eduardo Lelio; Wann, Derek A.; Robertson, Heather E.; et al.; Gas-phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3); John Wiley & Sons Ltd; Journal Of Raman Spectroscopy; 40; 12; 12-2009; 2053-2062
0377-0486
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/jrs.2371
info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/jrs.2371
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv John Wiley & Sons Ltd
publisher.none.fl_str_mv John Wiley & Sons Ltd
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1844614319175630848
score 13.070432

Publicaciones similares