Relativistic effects on group-12 metal nuclear shieldings

Autores
Roukala, Juho; Maldonado, Alejandro Fabián; Vaara, Juha; Aucar, Gustavo Adolfo; Lanto, Perttu
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The leading-order perturbation theory approach to relativistic effects on the nuclear magnetic shielding provides an economic method for obtaining the chemical shifts in heavy-element containing systems. The method features detailed analysis potential in terms of the different physical mechanisms affecting the shielding tensors of heavy nuclei. The perturbative nature, however, results in an increasing error with increasingly heavy elements in the system. In this work, we investigate the performance of the Breit-Pauli perturbation theory (BPPT) against fully relativistic four-component theory in computing the nuclear shielding constants as well as the chemical shifts with respect to corresponding atomic ions of group-12 metals, M = Zn, Cd, and Hg, in dimethyl M(CH3)2 and aqueous M(H2O) 62+ complexes. It is shown that five out of the total of sixteen BPPT correction terms are responsible for most of the relativistic corrections for the chemical shift of studied metals. The relativity is important already for Cd and BPPT is proven to work well up to Hg for the chemical shift, as calibrated with the fully relativistic method.
Fil: Roukala, Juho. University of Oulu; Finlandia
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
Fil: Vaara, Juha. University of Oulu; Finlandia
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
Fil: Lanto, Perttu. University of Oulu; Finlandia
Materia
Nmr
Bppt Method
Polarization Propagator
Relativistic Effects
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:11336/78437
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Relativistic effects on group-12 metal nuclear shieldingsRoukala, JuhoMaldonado, Alejandro FabiánVaara, JuhaAucar, Gustavo AdolfoLanto, PerttuNmrBppt MethodPolarization PropagatorRelativistic Effectshttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1The leading-order perturbation theory approach to relativistic effects on the nuclear magnetic shielding provides an economic method for obtaining the chemical shifts in heavy-element containing systems. The method features detailed analysis potential in terms of the different physical mechanisms affecting the shielding tensors of heavy nuclei. The perturbative nature, however, results in an increasing error with increasingly heavy elements in the system. In this work, we investigate the performance of the Breit-Pauli perturbation theory (BPPT) against fully relativistic four-component theory in computing the nuclear shielding constants as well as the chemical shifts with respect to corresponding atomic ions of group-12 metals, M = Zn, Cd, and Hg, in dimethyl M(CH3)2 and aqueous M(H2O) 62+ complexes. It is shown that five out of the total of sixteen BPPT correction terms are responsible for most of the relativistic corrections for the chemical shift of studied metals. The relativity is important already for Cd and BPPT is proven to work well up to Hg for the chemical shift, as calibrated with the fully relativistic method.Fil: Roukala, Juho. University of Oulu; FinlandiaFil: 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; ArgentinaFil: Vaara, Juha. University of Oulu; FinlandiaFil: 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; ArgentinaFil: Lanto, Perttu. University of Oulu; FinlandiaRoyal Society of Chemistry2011-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/78437Roukala, Juho; Maldonado, Alejandro Fabián; Vaara, Juha; Aucar, Gustavo Adolfo; Lanto, Perttu; Relativistic effects on group-12 metal nuclear shieldings; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 13; 47; 12-2011; 21016-210251463-90761463-9084CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/content/articlelanding/2011/cp/c1cp22043hinfo:eu-repo/semantics/altIdentifier/doi/10.1039/c1cp22043hinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:24:05Zoai:ri.conicet.gov.ar:11336/78437instacron: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 11:24:06.077CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Relativistic effects on group-12 metal nuclear shieldings
title Relativistic effects on group-12 metal nuclear shieldings
spellingShingle Relativistic effects on group-12 metal nuclear shieldings
Roukala, Juho
Nmr
Bppt Method
Polarization Propagator
Relativistic Effects
title_short Relativistic effects on group-12 metal nuclear shieldings
title_full Relativistic effects on group-12 metal nuclear shieldings
title_fullStr Relativistic effects on group-12 metal nuclear shieldings
title_full_unstemmed Relativistic effects on group-12 metal nuclear shieldings
title_sort Relativistic effects on group-12 metal nuclear shieldings
dc.creator.none.fl_str_mv Roukala, Juho
Maldonado, Alejandro Fabián
Vaara, Juha
Aucar, Gustavo Adolfo
Lanto, Perttu
author Roukala, Juho
author_facet Roukala, Juho
Maldonado, Alejandro Fabián
Vaara, Juha
Aucar, Gustavo Adolfo
Lanto, Perttu
author_role author
author2 Maldonado, Alejandro Fabián
Vaara, Juha
Aucar, Gustavo Adolfo
Lanto, Perttu
author2_role author
author
author
author
dc.subject.none.fl_str_mv Nmr
Bppt Method
Polarization Propagator
Relativistic Effects
topic Nmr
Bppt Method
Polarization Propagator
Relativistic Effects
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The leading-order perturbation theory approach to relativistic effects on the nuclear magnetic shielding provides an economic method for obtaining the chemical shifts in heavy-element containing systems. The method features detailed analysis potential in terms of the different physical mechanisms affecting the shielding tensors of heavy nuclei. The perturbative nature, however, results in an increasing error with increasingly heavy elements in the system. In this work, we investigate the performance of the Breit-Pauli perturbation theory (BPPT) against fully relativistic four-component theory in computing the nuclear shielding constants as well as the chemical shifts with respect to corresponding atomic ions of group-12 metals, M = Zn, Cd, and Hg, in dimethyl M(CH3)2 and aqueous M(H2O) 62+ complexes. It is shown that five out of the total of sixteen BPPT correction terms are responsible for most of the relativistic corrections for the chemical shift of studied metals. The relativity is important already for Cd and BPPT is proven to work well up to Hg for the chemical shift, as calibrated with the fully relativistic method.
Fil: Roukala, Juho. University of Oulu; Finlandia
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
Fil: Vaara, Juha. University of Oulu; Finlandia
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
Fil: Lanto, Perttu. University of Oulu; Finlandia
description The leading-order perturbation theory approach to relativistic effects on the nuclear magnetic shielding provides an economic method for obtaining the chemical shifts in heavy-element containing systems. The method features detailed analysis potential in terms of the different physical mechanisms affecting the shielding tensors of heavy nuclei. The perturbative nature, however, results in an increasing error with increasingly heavy elements in the system. In this work, we investigate the performance of the Breit-Pauli perturbation theory (BPPT) against fully relativistic four-component theory in computing the nuclear shielding constants as well as the chemical shifts with respect to corresponding atomic ions of group-12 metals, M = Zn, Cd, and Hg, in dimethyl M(CH3)2 and aqueous M(H2O) 62+ complexes. It is shown that five out of the total of sixteen BPPT correction terms are responsible for most of the relativistic corrections for the chemical shift of studied metals. The relativity is important already for Cd and BPPT is proven to work well up to Hg for the chemical shift, as calibrated with the fully relativistic method.
publishDate 2011
dc.date.none.fl_str_mv 2011-12
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/11336/78437
Roukala, Juho; Maldonado, Alejandro Fabián; Vaara, Juha; Aucar, Gustavo Adolfo; Lanto, Perttu; Relativistic effects on group-12 metal nuclear shieldings; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 13; 47; 12-2011; 21016-21025
1463-9076
1463-9084
CONICET Digital
CONICET
url http://hdl.handle.net/11336/78437
identifier_str_mv Roukala, Juho; Maldonado, Alejandro Fabián; Vaara, Juha; Aucar, Gustavo Adolfo; Lanto, Perttu; Relativistic effects on group-12 metal nuclear shieldings; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 13; 47; 12-2011; 21016-21025
1463-9076
1463-9084
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://pubs.rsc.org/en/content/articlelanding/2011/cp/c1cp22043h
info:eu-repo/semantics/altIdentifier/doi/10.1039/c1cp22043h
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
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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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