Mostrar el registro sencillo del ítem
dc.contributor.author
Fernández Liencres, M.P.
dc.contributor.author
Navarro, A.
dc.contributor.author
Ben Altabef, Aida
dc.contributor.author
López González, J. J.
dc.contributor.author
Fernández Gómez, M.
dc.contributor.author
Kearley, G.J.
dc.date.available
2020-03-19T20:24:56Z
dc.date.issued
2006-11
dc.identifier.citation
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
dc.identifier.issn
0301-0104
dc.identifier.uri
http://hdl.handle.net/11336/100364
dc.description.abstract
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.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Elsevier Science
dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
AB INITIO
dc.subject
DFT
dc.subject
INFRARED
dc.subject
INS
dc.subject
RAMAN
dc.subject
STRUCTURE
dc.subject
TRIMETHYLSILYLISOCYANATE
dc.subject
VIBRATIONAL ANALYSIS
dc.subject.classification
Química Inorgánica y Nuclear
dc.subject.classification
Ciencias Químicas
dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
dc.title
Theoretical, ab initio and DFT, study of the structure and vibrational analysis of Raman, IR and INS spectra of (CH3)3SiNCO
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2020-03-11T18:34:32Z
dc.journal.volume
330
dc.journal.number
1-2
dc.journal.pagination
26-42
dc.journal.pais
Países Bajos
dc.journal.ciudad
Amsterdam
dc.description.fil
Fil: Fernández Liencres, M.P.. Universidad de Jaén; España
dc.description.fil
Fil: Navarro, A.. Universidad de Jaén; España
dc.description.fil
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
dc.description.fil
Fil: López González, J. J.. Universidad de Jaén; España
dc.description.fil
Fil: Fernández Gómez, M.. Universidad de Jaén; España
dc.description.fil
Fil: Kearley, G.J.. Delft University of Technology; Países Bajos
dc.journal.title
Chemical Physics
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/https://dx.doi.org/10.1016/j.chemphys.2006.07.033
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0301010406004198?via%3Dihub
Archivos asociados