Relativistic and electron correlation effects on NMR J-coupling of Sn and Pb containing molecules

Autores
Giménez, Carlos Ariel; Maldonado, Alejandro Fabián; Aucar, Gustavo Adolfo
Año de publicación
2016
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We studied the influence of relativistic and electron correlation effects on NMR J-couplings in the following set of heavy-atom containing molecules: XY4 and H3XXH3 (X = Sn, Pb; Y = H, F, Cl, Br, I). We applied two formalisms, the relativistic polarization propagator approach atrandom phase level of approach (RelPPA-RPA) and density functional theory (DFT) with functionals as implemented in the DIRAC code. We have chosen four functionals that have different amount of HF exchange (PBE0, B3LYP,BLYP, BP86). For those molecular systems, results of calculationswith BLYP functional have the best performance as compared with available experimental data. As was previously found for magnetic shieldings in other molecular systems we are able to show here that DFT functionalsmust be modified in order to obtain reliable results of NMR J-coupling within the relativistic regime. We can state that there is a non-linear dependence among both, electron correlation and relativistic effects that should be introduced in the functionals. The functionals implemented in the DIRAC code are standard nonrelativistic ones which were parameterized with data taken from light-atom containing molecules. This explains why they are not able to properly introduce relativistic effects on NMR parameters, like J-coupling constant. Lastly we show that in the analysis of J-couplings for the family of compounds mentioned above, one must consider the effects of a third heavy-atom that is close to the J-coupled atoms of the same molecule, specially for nJ(H?H). This kind of effect is similar to the newest and so called heavy-atom effect on vicinal heavy atoms, HAVHA, proposed for the NMR-shielding constant. Such effects are among the most important relativistic effects in the family of compounds studied in this work.
Fil: Giménez, Carlos Ariel. 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. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina
Fil: Maldonado, Alejandro Fabián. 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. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; 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. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina
Materia
Spin-Spin Coupling
Relativistic Effects
Dft
Electron Correlation
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:11336/21973
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/21973
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Relativistic and electron correlation effects on NMR J-coupling of Sn and Pb containing moleculesGiménez, Carlos ArielMaldonado, Alejandro FabiánAucar, Gustavo AdolfoSpin-Spin CouplingRelativistic EffectsDftElectron Correlationhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1We studied the influence of relativistic and electron correlation effects on NMR J-couplings in the following set of heavy-atom containing molecules: XY4 and H3XXH3 (X = Sn, Pb; Y = H, F, Cl, Br, I). We applied two formalisms, the relativistic polarization propagator approach atrandom phase level of approach (RelPPA-RPA) and density functional theory (DFT) with functionals as implemented in the DIRAC code. We have chosen four functionals that have different amount of HF exchange (PBE0, B3LYP,BLYP, BP86). For those molecular systems, results of calculationswith BLYP functional have the best performance as compared with available experimental data. As was previously found for magnetic shieldings in other molecular systems we are able to show here that DFT functionalsmust be modified in order to obtain reliable results of NMR J-coupling within the relativistic regime. We can state that there is a non-linear dependence among both, electron correlation and relativistic effects that should be introduced in the functionals. The functionals implemented in the DIRAC code are standard nonrelativistic ones which were parameterized with data taken from light-atom containing molecules. This explains why they are not able to properly introduce relativistic effects on NMR parameters, like J-coupling constant. Lastly we show that in the analysis of J-couplings for the family of compounds mentioned above, one must consider the effects of a third heavy-atom that is close to the J-coupled atoms of the same molecule, specially for nJ(H?H). This kind of effect is similar to the newest and so called heavy-atom effect on vicinal heavy atoms, HAVHA, proposed for the NMR-shielding constant. Such effects are among the most important relativistic effects in the family of compounds studied in this work.Fil: Giménez, Carlos Ariel. 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. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; ArgentinaFil: Maldonado, Alejandro Fabián. 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. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; 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; Argentina. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; ArgentinaSpringer Heidelberg2016-08info: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/11336/21973Giménez, Carlos Ariel; Maldonado, Alejandro Fabián; Aucar, Gustavo Adolfo; Relativistic and electron correlation effects on NMR J-coupling of Sn and Pb containing molecules; Springer Heidelberg; Theoretical Chemistry Accounts; 135; 8-2016; 201-2111432-881X1432-2234CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://link.springer.com/article/10.1007/s00214-016-1952-3info:eu-repo/semantics/altIdentifier/doi/10.1007/s00214-016-1952-3info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:18:36Zoai:ri.conicet.gov.ar:11336/21973instacron: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 11:18:36.929CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Relativistic and electron correlation effects on NMR J-coupling of Sn and Pb containing molecules
title Relativistic and electron correlation effects on NMR J-coupling of Sn and Pb containing molecules
spellingShingle Relativistic and electron correlation effects on NMR J-coupling of Sn and Pb containing molecules
Giménez, Carlos Ariel
Spin-Spin Coupling
Relativistic Effects
Dft
Electron Correlation
title_short Relativistic and electron correlation effects on NMR J-coupling of Sn and Pb containing molecules
title_full Relativistic and electron correlation effects on NMR J-coupling of Sn and Pb containing molecules
title_fullStr Relativistic and electron correlation effects on NMR J-coupling of Sn and Pb containing molecules
title_full_unstemmed Relativistic and electron correlation effects on NMR J-coupling of Sn and Pb containing molecules
title_sort Relativistic and electron correlation effects on NMR J-coupling of Sn and Pb containing molecules
dc.creator.none.fl_str_mv Giménez, Carlos Ariel
Maldonado, Alejandro Fabián
Aucar, Gustavo Adolfo
author Giménez, Carlos Ariel
author_facet Giménez, Carlos Ariel
Maldonado, Alejandro Fabián
Aucar, Gustavo Adolfo
author_role author
author2 Maldonado, Alejandro Fabián
Aucar, Gustavo Adolfo
author2_role author
author
dc.subject.none.fl_str_mv Spin-Spin Coupling
Relativistic Effects
Dft
Electron Correlation
topic Spin-Spin Coupling
Relativistic Effects
Dft
Electron Correlation
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We studied the influence of relativistic and electron correlation effects on NMR J-couplings in the following set of heavy-atom containing molecules: XY4 and H3XXH3 (X = Sn, Pb; Y = H, F, Cl, Br, I). We applied two formalisms, the relativistic polarization propagator approach atrandom phase level of approach (RelPPA-RPA) and density functional theory (DFT) with functionals as implemented in the DIRAC code. We have chosen four functionals that have different amount of HF exchange (PBE0, B3LYP,BLYP, BP86). For those molecular systems, results of calculationswith BLYP functional have the best performance as compared with available experimental data. As was previously found for magnetic shieldings in other molecular systems we are able to show here that DFT functionalsmust be modified in order to obtain reliable results of NMR J-coupling within the relativistic regime. We can state that there is a non-linear dependence among both, electron correlation and relativistic effects that should be introduced in the functionals. The functionals implemented in the DIRAC code are standard nonrelativistic ones which were parameterized with data taken from light-atom containing molecules. This explains why they are not able to properly introduce relativistic effects on NMR parameters, like J-coupling constant. Lastly we show that in the analysis of J-couplings for the family of compounds mentioned above, one must consider the effects of a third heavy-atom that is close to the J-coupled atoms of the same molecule, specially for nJ(H?H). This kind of effect is similar to the newest and so called heavy-atom effect on vicinal heavy atoms, HAVHA, proposed for the NMR-shielding constant. Such effects are among the most important relativistic effects in the family of compounds studied in this work.
Fil: Giménez, Carlos Ariel. 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. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina
Fil: Maldonado, Alejandro Fabián. 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. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; 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. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina
description We studied the influence of relativistic and electron correlation effects on NMR J-couplings in the following set of heavy-atom containing molecules: XY4 and H3XXH3 (X = Sn, Pb; Y = H, F, Cl, Br, I). We applied two formalisms, the relativistic polarization propagator approach atrandom phase level of approach (RelPPA-RPA) and density functional theory (DFT) with functionals as implemented in the DIRAC code. We have chosen four functionals that have different amount of HF exchange (PBE0, B3LYP,BLYP, BP86). For those molecular systems, results of calculationswith BLYP functional have the best performance as compared with available experimental data. As was previously found for magnetic shieldings in other molecular systems we are able to show here that DFT functionalsmust be modified in order to obtain reliable results of NMR J-coupling within the relativistic regime. We can state that there is a non-linear dependence among both, electron correlation and relativistic effects that should be introduced in the functionals. The functionals implemented in the DIRAC code are standard nonrelativistic ones which were parameterized with data taken from light-atom containing molecules. This explains why they are not able to properly introduce relativistic effects on NMR parameters, like J-coupling constant. Lastly we show that in the analysis of J-couplings for the family of compounds mentioned above, one must consider the effects of a third heavy-atom that is close to the J-coupled atoms of the same molecule, specially for nJ(H?H). This kind of effect is similar to the newest and so called heavy-atom effect on vicinal heavy atoms, HAVHA, proposed for the NMR-shielding constant. Such effects are among the most important relativistic effects in the family of compounds studied in this work.
publishDate 2016
dc.date.none.fl_str_mv 2016-08
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/11336/21973
Giménez, Carlos Ariel; Maldonado, Alejandro Fabián; Aucar, Gustavo Adolfo; Relativistic and electron correlation effects on NMR J-coupling of Sn and Pb containing molecules; Springer Heidelberg; Theoretical Chemistry Accounts; 135; 8-2016; 201-211
1432-881X
1432-2234
CONICET Digital
CONICET
url http://hdl.handle.net/11336/21973
identifier_str_mv Giménez, Carlos Ariel; Maldonado, Alejandro Fabián; Aucar, Gustavo Adolfo; Relativistic and electron correlation effects on NMR J-coupling of Sn and Pb containing molecules; Springer Heidelberg; Theoretical Chemistry Accounts; 135; 8-2016; 201-211
1432-881X
1432-2234
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://link.springer.com/article/10.1007/s00214-016-1952-3
info:eu-repo/semantics/altIdentifier/doi/10.1007/s00214-016-1952-3
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
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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 Springer Heidelberg
publisher.none.fl_str_mv Springer Heidelberg
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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