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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/21973
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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 Técnicas2025-09-29T09:49:10Zoai: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:34982025-09-29 09:49:10.311CONICET 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 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 |
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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13.070432 |