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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/78437
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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 Técnicas2025-09-29T09:55:00Zoai: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:34982025-09-29 09:55:01.01CONICET 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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13.070432 |