The analysis of NMR J-couplings of saturated and unsaturated compounds by the localized second order polarization propagator approach method

Autores
Zarycz, Maria Natalia Cristina; Aucar, Gustavo Adolfo
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Calculations of NMR J-coupling with polarization propagators are not invariant under unitary transformations at second order level of approach, second order polarization propagator approach (SOPPA). They are only invariant at first order or random phase level of approach (RPA). We performed “localized” SOPPA (Loc-SOPPA), calculations of J-couplings applying two different schemes for the localization of molecular orbitals(LMO): Foster-Boys and Pipek-Mezey. We show here that results of such Loc-SOPPA calculations are different though not much: they are less than 6% different in the worst case. Therefore it is possible to apply them with confidence in the analysis of the transmission of different coupling mechanisms within the molecule. We are able now to get reliable information on what LMOs are the most important (and so which are not important) for a given J-coupling in a molecule. This information can then be used for selecting which are the paths that should be described with the highest possible accuracy for that J-coupling calculation. A few unsaturated compounds are analyzed: ethene, trans-difluoroethene or DiF-ethene, and imine. It is shown that different lone pairs (of pz or px/y type) are responsible for the vicinal F-F J-coupling in DiF-ethene; and also the fact that the main LP contributor is not the same for the fermi contact and the spin-dipolar mechanisms.We also studied phosphorous containing compounds such as phosphine and cis-propylene phosphine. In both cases the analysis of the main LMO contributing to one-bond P-H coupling and through-space P-C coupling were performed. The above mentioned unsaturated molecular systems have quasiinstability problems that arise at RPA level of approach. We show here that they are mostly originated in the antibonding π* LMO, corresponding to the C=C or C=N double bonds. We performed the analysis of the origin of quasiinstabilities for the SD mechanism. The contribution of each kind of excitation terms to SOPPA calculations were considered, meaning the main contributions by single and double excitations. It is shown that one can get more than 97% of the total electron correlation contribution when including terms that mainly contain single excitations (though double-excitation matrix elements should still be calculated).
Fil: Zarycz, Maria Natalia Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; Argentina
Fil: Aucar, Gustavo Adolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; Argentina
Materia
NMR
POLARIZATION PROPAGATOR
LOC-SOPPA
LOCALIZED ORBITALS
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:11336/78379

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spelling The analysis of NMR J-couplings of saturated and unsaturated compounds by the localized second order polarization propagator approach methodZarycz, Maria Natalia CristinaAucar, Gustavo AdolfoNMRPOLARIZATION PROPAGATORLOC-SOPPALOCALIZED ORBITALShttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Calculations of NMR J-coupling with polarization propagators are not invariant under unitary transformations at second order level of approach, second order polarization propagator approach (SOPPA). They are only invariant at first order or random phase level of approach (RPA). We performed “localized” SOPPA (Loc-SOPPA), calculations of J-couplings applying two different schemes for the localization of molecular orbitals(LMO): Foster-Boys and Pipek-Mezey. We show here that results of such Loc-SOPPA calculations are different though not much: they are less than 6% different in the worst case. Therefore it is possible to apply them with confidence in the analysis of the transmission of different coupling mechanisms within the molecule. We are able now to get reliable information on what LMOs are the most important (and so which are not important) for a given J-coupling in a molecule. This information can then be used for selecting which are the paths that should be described with the highest possible accuracy for that J-coupling calculation. A few unsaturated compounds are analyzed: ethene, trans-difluoroethene or DiF-ethene, and imine. It is shown that different lone pairs (of pz or px/y type) are responsible for the vicinal F-F J-coupling in DiF-ethene; and also the fact that the main LP contributor is not the same for the fermi contact and the spin-dipolar mechanisms.We also studied phosphorous containing compounds such as phosphine and cis-propylene phosphine. In both cases the analysis of the main LMO contributing to one-bond P-H coupling and through-space P-C coupling were performed. The above mentioned unsaturated molecular systems have quasiinstability problems that arise at RPA level of approach. We show here that they are mostly originated in the antibonding π* LMO, corresponding to the C=C or C=N double bonds. We performed the analysis of the origin of quasiinstabilities for the SD mechanism. The contribution of each kind of excitation terms to SOPPA calculations were considered, meaning the main contributions by single and double excitations. It is shown that one can get more than 97% of the total electron correlation contribution when including terms that mainly contain single excitations (though double-excitation matrix elements should still be calculated).Fil: Zarycz, Maria Natalia Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; ArgentinaFil: Aucar, Gustavo Adolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; ArgentinaAmerican Institute of Physics2012-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/78379Zarycz, Maria Natalia Cristina; Aucar, Gustavo Adolfo; The analysis of NMR J-couplings of saturated and unsaturated compounds by the localized second order polarization propagator approach method; American Institute of Physics; Journal of Chemical Physics; 136; 17; 5-2012; 1-10; 1741150021-9606CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1063/1.3697844info:eu-repo/semantics/altIdentifier/url/https://aip.scitation.org/doi/10.1063/1.3697844info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:04:48Zoai:ri.conicet.gov.ar:11336/78379instacron: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 10:04:48.416CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv The analysis of NMR J-couplings of saturated and unsaturated compounds by the localized second order polarization propagator approach method
title The analysis of NMR J-couplings of saturated and unsaturated compounds by the localized second order polarization propagator approach method
spellingShingle The analysis of NMR J-couplings of saturated and unsaturated compounds by the localized second order polarization propagator approach method
Zarycz, Maria Natalia Cristina
NMR
POLARIZATION PROPAGATOR
LOC-SOPPA
LOCALIZED ORBITALS
title_short The analysis of NMR J-couplings of saturated and unsaturated compounds by the localized second order polarization propagator approach method
title_full The analysis of NMR J-couplings of saturated and unsaturated compounds by the localized second order polarization propagator approach method
title_fullStr The analysis of NMR J-couplings of saturated and unsaturated compounds by the localized second order polarization propagator approach method
title_full_unstemmed The analysis of NMR J-couplings of saturated and unsaturated compounds by the localized second order polarization propagator approach method
title_sort The analysis of NMR J-couplings of saturated and unsaturated compounds by the localized second order polarization propagator approach method
dc.creator.none.fl_str_mv Zarycz, Maria Natalia Cristina
Aucar, Gustavo Adolfo
author Zarycz, Maria Natalia Cristina
author_facet Zarycz, Maria Natalia Cristina
Aucar, Gustavo Adolfo
author_role author
author2 Aucar, Gustavo Adolfo
author2_role author
dc.subject.none.fl_str_mv NMR
POLARIZATION PROPAGATOR
LOC-SOPPA
LOCALIZED ORBITALS
topic NMR
POLARIZATION PROPAGATOR
LOC-SOPPA
LOCALIZED ORBITALS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Calculations of NMR J-coupling with polarization propagators are not invariant under unitary transformations at second order level of approach, second order polarization propagator approach (SOPPA). They are only invariant at first order or random phase level of approach (RPA). We performed “localized” SOPPA (Loc-SOPPA), calculations of J-couplings applying two different schemes for the localization of molecular orbitals(LMO): Foster-Boys and Pipek-Mezey. We show here that results of such Loc-SOPPA calculations are different though not much: they are less than 6% different in the worst case. Therefore it is possible to apply them with confidence in the analysis of the transmission of different coupling mechanisms within the molecule. We are able now to get reliable information on what LMOs are the most important (and so which are not important) for a given J-coupling in a molecule. This information can then be used for selecting which are the paths that should be described with the highest possible accuracy for that J-coupling calculation. A few unsaturated compounds are analyzed: ethene, trans-difluoroethene or DiF-ethene, and imine. It is shown that different lone pairs (of pz or px/y type) are responsible for the vicinal F-F J-coupling in DiF-ethene; and also the fact that the main LP contributor is not the same for the fermi contact and the spin-dipolar mechanisms.We also studied phosphorous containing compounds such as phosphine and cis-propylene phosphine. In both cases the analysis of the main LMO contributing to one-bond P-H coupling and through-space P-C coupling were performed. The above mentioned unsaturated molecular systems have quasiinstability problems that arise at RPA level of approach. We show here that they are mostly originated in the antibonding π* LMO, corresponding to the C=C or C=N double bonds. We performed the analysis of the origin of quasiinstabilities for the SD mechanism. The contribution of each kind of excitation terms to SOPPA calculations were considered, meaning the main contributions by single and double excitations. It is shown that one can get more than 97% of the total electron correlation contribution when including terms that mainly contain single excitations (though double-excitation matrix elements should still be calculated).
Fil: Zarycz, Maria Natalia Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; Argentina
Fil: Aucar, Gustavo Adolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; Argentina
description Calculations of NMR J-coupling with polarization propagators are not invariant under unitary transformations at second order level of approach, second order polarization propagator approach (SOPPA). They are only invariant at first order or random phase level of approach (RPA). We performed “localized” SOPPA (Loc-SOPPA), calculations of J-couplings applying two different schemes for the localization of molecular orbitals(LMO): Foster-Boys and Pipek-Mezey. We show here that results of such Loc-SOPPA calculations are different though not much: they are less than 6% different in the worst case. Therefore it is possible to apply them with confidence in the analysis of the transmission of different coupling mechanisms within the molecule. We are able now to get reliable information on what LMOs are the most important (and so which are not important) for a given J-coupling in a molecule. This information can then be used for selecting which are the paths that should be described with the highest possible accuracy for that J-coupling calculation. A few unsaturated compounds are analyzed: ethene, trans-difluoroethene or DiF-ethene, and imine. It is shown that different lone pairs (of pz or px/y type) are responsible for the vicinal F-F J-coupling in DiF-ethene; and also the fact that the main LP contributor is not the same for the fermi contact and the spin-dipolar mechanisms.We also studied phosphorous containing compounds such as phosphine and cis-propylene phosphine. In both cases the analysis of the main LMO contributing to one-bond P-H coupling and through-space P-C coupling were performed. The above mentioned unsaturated molecular systems have quasiinstability problems that arise at RPA level of approach. We show here that they are mostly originated in the antibonding π* LMO, corresponding to the C=C or C=N double bonds. We performed the analysis of the origin of quasiinstabilities for the SD mechanism. The contribution of each kind of excitation terms to SOPPA calculations were considered, meaning the main contributions by single and double excitations. It is shown that one can get more than 97% of the total electron correlation contribution when including terms that mainly contain single excitations (though double-excitation matrix elements should still be calculated).
publishDate 2012
dc.date.none.fl_str_mv 2012-05
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/11336/78379
Zarycz, Maria Natalia Cristina; Aucar, Gustavo Adolfo; The analysis of NMR J-couplings of saturated and unsaturated compounds by the localized second order polarization propagator approach method; American Institute of Physics; Journal of Chemical Physics; 136; 17; 5-2012; 1-10; 174115
0021-9606
CONICET Digital
CONICET
url http://hdl.handle.net/11336/78379
identifier_str_mv Zarycz, Maria Natalia Cristina; Aucar, Gustavo Adolfo; The analysis of NMR J-couplings of saturated and unsaturated compounds by the localized second order polarization propagator approach method; American Institute of Physics; Journal of Chemical Physics; 136; 17; 5-2012; 1-10; 174115
0021-9606
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1063/1.3697844
info:eu-repo/semantics/altIdentifier/url/https://aip.scitation.org/doi/10.1063/1.3697844
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
application/pdf
dc.publisher.none.fl_str_mv American Institute of Physics
publisher.none.fl_str_mv American Institute of Physics
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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