Theoretical, ab initio and DFT, study of the structure and vibrational analysis of Raman, IR and INS spectra of (CH3)3SiNCO

Autores
Fernández Liencres, M.P.; Navarro, A.; Ben Altabef, Aida; López González, J. J.; Fernández Gómez, M.; Kearley, G.J.
Año de publicación
2006
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The molecular geometry for trimethylsilylisocyanate ((CH3)3SiNCO) has been calculated at MP2 and DFT/B3LYP and DFT/B3PW91 methods, and using the 6-31G*, 6-311G**, 6-311++G**, cc-pVDZ and cc-pVTZ basis sets. The equilibrium structure of the molecule, linear or bent as concerns the -SiNCO moiety, was found to rely on the method employed. The potential energy surface of -SiNC bending has been investigated by quantum mechanical ab initio calculations at MPn (n = 2-4) and QCISD(T) levels of theory with the cc-pVTZ basis set. This large amplitude bending motion (the υ24 mode) was determined to be very anharmonic, with a low barrier to linearity of the SiNCO skeleton of ∼4-25 cm-1. New vapour and liquid IR, liquid Raman spectra and, for first time, INS spectrum have been recorded, and a complete vibrational assignment has been performed. INS data have allowed to assign two modes at 674 cm-1 and 141 cm-1 which, so far, have been considered as silent, i.e. A2, since previous authors have used a frame of C3v symmetry for this system. The intermolecular interactions show to have little effect on the torsional region (below 250 cm-1 in INS spectrum) and the isolated-molecule approximation works well in that region. A normal coordinate analysis has been carried out by scaling the force fields calculated at MP2/6-311++G** and B3LYP/cc-pVDZ levels of theory using the scaled quantum mechanical force field (SQMFF) methodology. In order to get the best possible agreement between calculated and observed vibrational wavenumbers, the scale factors were refined by least squares yielding a final r.m.s. of ≈7 cm-1. © 2006 Elsevier B.V. All rights reserved.
Fil: Fernández Liencres, M.P.. Universidad de Jaén; España
Fil: Navarro, A.. Universidad de Jaén; España
Fil: Ben Altabef, Aida. 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. Universidad Nacional de Tucumán; Argentina
Fil: López González, J. J.. Universidad de Jaén; España
Fil: Fernández Gómez, M.. Universidad de Jaén; España
Fil: Kearley, G.J.. Delft University of Technology; Países Bajos
Materia
AB INITIO
DFT
INFRARED
INS
RAMAN
STRUCTURE
TRIMETHYLSILYLISOCYANATE
VIBRATIONAL ANALYSIS
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:11336/100364

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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Theoretical, ab initio and DFT, study of the structure and vibrational analysis of Raman, IR and INS spectra of (CH3)3SiNCOFernández Liencres, M.P.Navarro, A.Ben Altabef, AidaLópez González, J. J.Fernández Gómez, M.Kearley, G.J.AB INITIODFTINFRAREDINSRAMANSTRUCTURETRIMETHYLSILYLISOCYANATEVIBRATIONAL ANALYSIShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The molecular geometry for trimethylsilylisocyanate ((CH3)3SiNCO) has been calculated at MP2 and DFT/B3LYP and DFT/B3PW91 methods, and using the 6-31G*, 6-311G**, 6-311++G**, cc-pVDZ and cc-pVTZ basis sets. The equilibrium structure of the molecule, linear or bent as concerns the -SiNCO moiety, was found to rely on the method employed. The potential energy surface of -SiNC bending has been investigated by quantum mechanical ab initio calculations at MPn (n = 2-4) and QCISD(T) levels of theory with the cc-pVTZ basis set. This large amplitude bending motion (the υ24 mode) was determined to be very anharmonic, with a low barrier to linearity of the SiNCO skeleton of ∼4-25 cm-1. New vapour and liquid IR, liquid Raman spectra and, for first time, INS spectrum have been recorded, and a complete vibrational assignment has been performed. INS data have allowed to assign two modes at 674 cm-1 and 141 cm-1 which, so far, have been considered as silent, i.e. A2, since previous authors have used a frame of C3v symmetry for this system. The intermolecular interactions show to have little effect on the torsional region (below 250 cm-1 in INS spectrum) and the isolated-molecule approximation works well in that region. A normal coordinate analysis has been carried out by scaling the force fields calculated at MP2/6-311++G** and B3LYP/cc-pVDZ levels of theory using the scaled quantum mechanical force field (SQMFF) methodology. In order to get the best possible agreement between calculated and observed vibrational wavenumbers, the scale factors were refined by least squares yielding a final r.m.s. of ≈7 cm-1. © 2006 Elsevier B.V. All rights reserved.Fil: Fernández Liencres, M.P.. Universidad de Jaén; EspañaFil: Navarro, A.. Universidad de Jaén; EspañaFil: Ben Altabef, Aida. 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. Universidad Nacional de Tucumán; ArgentinaFil: López González, J. J.. Universidad de Jaén; EspañaFil: Fernández Gómez, M.. Universidad de Jaén; EspañaFil: Kearley, G.J.. Delft University of Technology; Países BajosElsevier Science2006-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/100364Fernández Liencres, M.P.; Navarro, A.; Ben Altabef, Aida; López González, J. J.; Fernández Gómez, M.; et al.; Theoretical, ab initio and DFT, study of the structure and vibrational analysis of Raman, IR and INS spectra of (CH3)3SiNCO; Elsevier Science; Chemical Physics; 330; 1-2; 11-2006; 26-420301-0104CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.chemphys.2006.07.033info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0301010406004198?via%3Dihubinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:02:59Zoai:ri.conicet.gov.ar:11336/100364instacron: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:34982025-10-15 15:02:59.996CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Theoretical, ab initio and DFT, study of the structure and vibrational analysis of Raman, IR and INS spectra of (CH3)3SiNCO
title Theoretical, ab initio and DFT, study of the structure and vibrational analysis of Raman, IR and INS spectra of (CH3)3SiNCO
spellingShingle Theoretical, ab initio and DFT, study of the structure and vibrational analysis of Raman, IR and INS spectra of (CH3)3SiNCO
Fernández Liencres, M.P.
AB INITIO
DFT
INFRARED
INS
RAMAN
STRUCTURE
TRIMETHYLSILYLISOCYANATE
VIBRATIONAL ANALYSIS
title_short Theoretical, ab initio and DFT, study of the structure and vibrational analysis of Raman, IR and INS spectra of (CH3)3SiNCO
title_full Theoretical, ab initio and DFT, study of the structure and vibrational analysis of Raman, IR and INS spectra of (CH3)3SiNCO
title_fullStr Theoretical, ab initio and DFT, study of the structure and vibrational analysis of Raman, IR and INS spectra of (CH3)3SiNCO
title_full_unstemmed Theoretical, ab initio and DFT, study of the structure and vibrational analysis of Raman, IR and INS spectra of (CH3)3SiNCO
title_sort Theoretical, ab initio and DFT, study of the structure and vibrational analysis of Raman, IR and INS spectra of (CH3)3SiNCO
dc.creator.none.fl_str_mv Fernández Liencres, M.P.
Navarro, A.
Ben Altabef, Aida
López González, J. J.
Fernández Gómez, M.
Kearley, G.J.
author Fernández Liencres, M.P.
author_facet Fernández Liencres, M.P.
Navarro, A.
Ben Altabef, Aida
López González, J. J.
Fernández Gómez, M.
Kearley, G.J.
author_role author
author2 Navarro, A.
Ben Altabef, Aida
López González, J. J.
Fernández Gómez, M.
Kearley, G.J.
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv AB INITIO
DFT
INFRARED
INS
RAMAN
STRUCTURE
TRIMETHYLSILYLISOCYANATE
VIBRATIONAL ANALYSIS
topic AB INITIO
DFT
INFRARED
INS
RAMAN
STRUCTURE
TRIMETHYLSILYLISOCYANATE
VIBRATIONAL ANALYSIS
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 geometry for trimethylsilylisocyanate ((CH3)3SiNCO) has been calculated at MP2 and DFT/B3LYP and DFT/B3PW91 methods, and using the 6-31G*, 6-311G**, 6-311++G**, cc-pVDZ and cc-pVTZ basis sets. The equilibrium structure of the molecule, linear or bent as concerns the -SiNCO moiety, was found to rely on the method employed. The potential energy surface of -SiNC bending has been investigated by quantum mechanical ab initio calculations at MPn (n = 2-4) and QCISD(T) levels of theory with the cc-pVTZ basis set. This large amplitude bending motion (the υ24 mode) was determined to be very anharmonic, with a low barrier to linearity of the SiNCO skeleton of ∼4-25 cm-1. New vapour and liquid IR, liquid Raman spectra and, for first time, INS spectrum have been recorded, and a complete vibrational assignment has been performed. INS data have allowed to assign two modes at 674 cm-1 and 141 cm-1 which, so far, have been considered as silent, i.e. A2, since previous authors have used a frame of C3v symmetry for this system. The intermolecular interactions show to have little effect on the torsional region (below 250 cm-1 in INS spectrum) and the isolated-molecule approximation works well in that region. A normal coordinate analysis has been carried out by scaling the force fields calculated at MP2/6-311++G** and B3LYP/cc-pVDZ levels of theory using the scaled quantum mechanical force field (SQMFF) methodology. In order to get the best possible agreement between calculated and observed vibrational wavenumbers, the scale factors were refined by least squares yielding a final r.m.s. of ≈7 cm-1. © 2006 Elsevier B.V. All rights reserved.
Fil: Fernández Liencres, M.P.. Universidad de Jaén; España
Fil: Navarro, A.. Universidad de Jaén; España
Fil: Ben Altabef, Aida. 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. Universidad Nacional de Tucumán; Argentina
Fil: López González, J. J.. Universidad de Jaén; España
Fil: Fernández Gómez, M.. Universidad de Jaén; España
Fil: Kearley, G.J.. Delft University of Technology; Países Bajos
description The molecular geometry for trimethylsilylisocyanate ((CH3)3SiNCO) has been calculated at MP2 and DFT/B3LYP and DFT/B3PW91 methods, and using the 6-31G*, 6-311G**, 6-311++G**, cc-pVDZ and cc-pVTZ basis sets. The equilibrium structure of the molecule, linear or bent as concerns the -SiNCO moiety, was found to rely on the method employed. The potential energy surface of -SiNC bending has been investigated by quantum mechanical ab initio calculations at MPn (n = 2-4) and QCISD(T) levels of theory with the cc-pVTZ basis set. This large amplitude bending motion (the υ24 mode) was determined to be very anharmonic, with a low barrier to linearity of the SiNCO skeleton of ∼4-25 cm-1. New vapour and liquid IR, liquid Raman spectra and, for first time, INS spectrum have been recorded, and a complete vibrational assignment has been performed. INS data have allowed to assign two modes at 674 cm-1 and 141 cm-1 which, so far, have been considered as silent, i.e. A2, since previous authors have used a frame of C3v symmetry for this system. The intermolecular interactions show to have little effect on the torsional region (below 250 cm-1 in INS spectrum) and the isolated-molecule approximation works well in that region. A normal coordinate analysis has been carried out by scaling the force fields calculated at MP2/6-311++G** and B3LYP/cc-pVDZ levels of theory using the scaled quantum mechanical force field (SQMFF) methodology. In order to get the best possible agreement between calculated and observed vibrational wavenumbers, the scale factors were refined by least squares yielding a final r.m.s. of ≈7 cm-1. © 2006 Elsevier B.V. All rights reserved.
publishDate 2006
dc.date.none.fl_str_mv 2006-11
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/11336/100364
Fernández Liencres, M.P.; Navarro, A.; Ben Altabef, Aida; López González, J. J.; Fernández Gómez, M.; et al.; Theoretical, ab initio and DFT, study of the structure and vibrational analysis of Raman, IR and INS spectra of (CH3)3SiNCO; Elsevier Science; Chemical Physics; 330; 1-2; 11-2006; 26-42
0301-0104
CONICET Digital
CONICET
url http://hdl.handle.net/11336/100364
identifier_str_mv Fernández Liencres, M.P.; Navarro, A.; Ben Altabef, Aida; López González, J. J.; Fernández Gómez, M.; et al.; Theoretical, ab initio and DFT, study of the structure and vibrational analysis of Raman, IR and INS spectra of (CH3)3SiNCO; Elsevier Science; Chemical Physics; 330; 1-2; 11-2006; 26-42
0301-0104
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.chemphys.2006.07.033
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0301010406004198?via%3Dihub
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
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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
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