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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/100364
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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 |
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reponame:CONICET Digital (CONICET) instname:Consejo Nacional de Investigaciones Científicas y Técnicas |
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Consejo Nacional de Investigaciones Científicas y Técnicas |
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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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