Vibrational contributions to vicinal proton-proton coupling constants3JHH

Autores
Esteban, Angel L.; Díez, Ernesto; Galache, Maria P.; San Fabián, Jesus; Casanueva, Jorge; Contreras, Ruben Horacio
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Vibrational contributions to the 3JHH couplings of six mono- and five 1,1-di-substituted ethanes, three mono-substituted cyclohexanes, three norbornane-type molecules, and 11 three-membered rings have been calculated at the DFT/B3LYP level for the Fermi contact term using a moderate sized basis set. When, for a data set of 70 couplings, the sums of the values for the equilibrium configurations Je and the respective vibrational contributions J300vib at 300K are multiplied by a factor of 0.8485, the corresponding predicted couplings Jpre are in good agreement with the experimental couplings Jexp with a standard deviation σ of 0.18 Hz. The same σ results when J pre values are obtained by multiplying the Je values by 0.9016. However, the vibrational contributions must be taken into account, together with the Je values, in order to achieve a procedure for a reliable and accurate prediction of 3JHH couplings since, globally, J300vib contributions amount to about 7% of the Je values and the correlation coefficient between J 300vib and Je is only 0.68 with a σ deviation of 0.20. The first and diagonal second derivatives of J with respect to each normal coordinate Qk, required to estimate the vibrational contributions, have been obtained from six Jk values computed for molecular geometries positively (+δQk) and negatively (-δQk) displaced from the equilibrium geometry along the normal coordinate Qk and using for δ the values 0.01, 0.05 and 0.10. The computational precision of the results obtained when using one, two and three δ values is analysed. © 2010 Taylor & Francis.
Fil: Esteban, Angel L.. Universidad de Alicante; España
Fil: Díez, Ernesto. Universidad de Alicante; España
Fil: Galache, Maria P.. Universidad de Alicante; España
Fil: San Fabián, Jesus. Universidad Autónoma de Madrid; España
Fil: Casanueva, Jorge. Universidad Autónoma de Madrid; España
Fil: Contreras, Ruben Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina
Materia
Dft/B3lyp
Numerical Precision
Vibrational Contributions
Vicinal Coupling Constants
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:11336/59063
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/59063
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Vibrational contributions to vicinal proton-proton coupling constants3JHHEsteban, Angel L.Díez, ErnestoGalache, Maria P.San Fabián, JesusCasanueva, JorgeContreras, Ruben HoracioDft/B3lypNumerical PrecisionVibrational ContributionsVicinal Coupling Constantshttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Vibrational contributions to the 3JHH couplings of six mono- and five 1,1-di-substituted ethanes, three mono-substituted cyclohexanes, three norbornane-type molecules, and 11 three-membered rings have been calculated at the DFT/B3LYP level for the Fermi contact term using a moderate sized basis set. When, for a data set of 70 couplings, the sums of the values for the equilibrium configurations Je and the respective vibrational contributions J300vib at 300K are multiplied by a factor of 0.8485, the corresponding predicted couplings Jpre are in good agreement with the experimental couplings Jexp with a standard deviation σ of 0.18 Hz. The same σ results when J pre values are obtained by multiplying the Je values by 0.9016. However, the vibrational contributions must be taken into account, together with the Je values, in order to achieve a procedure for a reliable and accurate prediction of 3JHH couplings since, globally, J300vib contributions amount to about 7% of the Je values and the correlation coefficient between J 300vib and Je is only 0.68 with a σ deviation of 0.20. The first and diagonal second derivatives of J with respect to each normal coordinate Qk, required to estimate the vibrational contributions, have been obtained from six Jk values computed for molecular geometries positively (+δQk) and negatively (-δQk) displaced from the equilibrium geometry along the normal coordinate Qk and using for δ the values 0.01, 0.05 and 0.10. The computational precision of the results obtained when using one, two and three δ values is analysed. © 2010 Taylor & Francis.Fil: Esteban, Angel L.. Universidad de Alicante; EspañaFil: Díez, Ernesto. Universidad de Alicante; EspañaFil: Galache, Maria P.. Universidad de Alicante; EspañaFil: San Fabián, Jesus. Universidad Autónoma de Madrid; EspañaFil: Casanueva, Jorge. Universidad Autónoma de Madrid; EspañaFil: Contreras, Ruben Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; ArgentinaTaylor & Francis Ltd2010-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/59063Esteban, Angel L.; Díez, Ernesto; Galache, Maria P.; San Fabián, Jesus; Casanueva, Jorge; et al.; Vibrational contributions to vicinal proton-proton coupling constants3JHH; Taylor & Francis Ltd; Molecular Physics; 108; 5; 3-2010; 583-5950026-8976CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1080/00268971003630687info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:58:28Zoai:ri.conicet.gov.ar:11336/59063instacron: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:34982025-10-22 11:58:28.903CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Vibrational contributions to vicinal proton-proton coupling constants3JHH
title Vibrational contributions to vicinal proton-proton coupling constants3JHH
spellingShingle Vibrational contributions to vicinal proton-proton coupling constants3JHH
Esteban, Angel L.
Dft/B3lyp
Numerical Precision
Vibrational Contributions
Vicinal Coupling Constants
title_short Vibrational contributions to vicinal proton-proton coupling constants3JHH
title_full Vibrational contributions to vicinal proton-proton coupling constants3JHH
title_fullStr Vibrational contributions to vicinal proton-proton coupling constants3JHH
title_full_unstemmed Vibrational contributions to vicinal proton-proton coupling constants3JHH
title_sort Vibrational contributions to vicinal proton-proton coupling constants3JHH
dc.creator.none.fl_str_mv Esteban, Angel L.
Díez, Ernesto
Galache, Maria P.
San Fabián, Jesus
Casanueva, Jorge
Contreras, Ruben Horacio
author Esteban, Angel L.
author_facet Esteban, Angel L.
Díez, Ernesto
Galache, Maria P.
San Fabián, Jesus
Casanueva, Jorge
Contreras, Ruben Horacio
author_role author
author2 Díez, Ernesto
Galache, Maria P.
San Fabián, Jesus
Casanueva, Jorge
Contreras, Ruben Horacio
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Dft/B3lyp
Numerical Precision
Vibrational Contributions
Vicinal Coupling Constants
topic Dft/B3lyp
Numerical Precision
Vibrational Contributions
Vicinal Coupling Constants
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Vibrational contributions to the 3JHH couplings of six mono- and five 1,1-di-substituted ethanes, three mono-substituted cyclohexanes, three norbornane-type molecules, and 11 three-membered rings have been calculated at the DFT/B3LYP level for the Fermi contact term using a moderate sized basis set. When, for a data set of 70 couplings, the sums of the values for the equilibrium configurations Je and the respective vibrational contributions J300vib at 300K are multiplied by a factor of 0.8485, the corresponding predicted couplings Jpre are in good agreement with the experimental couplings Jexp with a standard deviation σ of 0.18 Hz. The same σ results when J pre values are obtained by multiplying the Je values by 0.9016. However, the vibrational contributions must be taken into account, together with the Je values, in order to achieve a procedure for a reliable and accurate prediction of 3JHH couplings since, globally, J300vib contributions amount to about 7% of the Je values and the correlation coefficient between J 300vib and Je is only 0.68 with a σ deviation of 0.20. The first and diagonal second derivatives of J with respect to each normal coordinate Qk, required to estimate the vibrational contributions, have been obtained from six Jk values computed for molecular geometries positively (+δQk) and negatively (-δQk) displaced from the equilibrium geometry along the normal coordinate Qk and using for δ the values 0.01, 0.05 and 0.10. The computational precision of the results obtained when using one, two and three δ values is analysed. © 2010 Taylor & Francis.
Fil: Esteban, Angel L.. Universidad de Alicante; España
Fil: Díez, Ernesto. Universidad de Alicante; España
Fil: Galache, Maria P.. Universidad de Alicante; España
Fil: San Fabián, Jesus. Universidad Autónoma de Madrid; España
Fil: Casanueva, Jorge. Universidad Autónoma de Madrid; España
Fil: Contreras, Ruben Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina
description Vibrational contributions to the 3JHH couplings of six mono- and five 1,1-di-substituted ethanes, three mono-substituted cyclohexanes, three norbornane-type molecules, and 11 three-membered rings have been calculated at the DFT/B3LYP level for the Fermi contact term using a moderate sized basis set. When, for a data set of 70 couplings, the sums of the values for the equilibrium configurations Je and the respective vibrational contributions J300vib at 300K are multiplied by a factor of 0.8485, the corresponding predicted couplings Jpre are in good agreement with the experimental couplings Jexp with a standard deviation σ of 0.18 Hz. The same σ results when J pre values are obtained by multiplying the Je values by 0.9016. However, the vibrational contributions must be taken into account, together with the Je values, in order to achieve a procedure for a reliable and accurate prediction of 3JHH couplings since, globally, J300vib contributions amount to about 7% of the Je values and the correlation coefficient between J 300vib and Je is only 0.68 with a σ deviation of 0.20. The first and diagonal second derivatives of J with respect to each normal coordinate Qk, required to estimate the vibrational contributions, have been obtained from six Jk values computed for molecular geometries positively (+δQk) and negatively (-δQk) displaced from the equilibrium geometry along the normal coordinate Qk and using for δ the values 0.01, 0.05 and 0.10. The computational precision of the results obtained when using one, two and three δ values is analysed. © 2010 Taylor & Francis.
publishDate 2010
dc.date.none.fl_str_mv 2010-03
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/11336/59063
Esteban, Angel L.; Díez, Ernesto; Galache, Maria P.; San Fabián, Jesus; Casanueva, Jorge; et al.; Vibrational contributions to vicinal proton-proton coupling constants3JHH; Taylor & Francis Ltd; Molecular Physics; 108; 5; 3-2010; 583-595
0026-8976
CONICET Digital
CONICET
url http://hdl.handle.net/11336/59063
identifier_str_mv Esteban, Angel L.; Díez, Ernesto; Galache, Maria P.; San Fabián, Jesus; Casanueva, Jorge; et al.; Vibrational contributions to vicinal proton-proton coupling constants3JHH; Taylor & Francis Ltd; Molecular Physics; 108; 5; 3-2010; 583-595
0026-8976
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1080/00268971003630687
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 Taylor & Francis Ltd
publisher.none.fl_str_mv Taylor & Francis 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
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score 12.982451

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