Influence of the nuclear charge distribution and electron correlation effects on magnetic shieldings and spin-rotation tensors of linear molecules

Autores
Aucar, Ignacio Agustín; Giménez, Carlos Ariel; Aucar, Gustavo Adolfo
Año de publicación
2018
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The nuclear charge distribution effects (NChDE) on two response properties, the NMR magnetic shielding (σ) and the nuclear spin-rotation (SR) constants (M), are analyzed. We do it employing point-like and Gaussian-like models for describing the nuclear charge density of three linear molecules: HBr, HI and HAt. According to our results, both properties are sensitive to the NChDE. We show that the NChDE are almost completely relativistic, i.e., they nearly vanish in the non-relativistic limit of both properties. We calculated the NChDE on σ and M, and analyzed the differences between them in terms of a relativistic relation between these two properties. Using that relation we found that the electronic core mechanisms are the main ones for the NChDE on the shielding of nuclei of both, molecules and free atoms. The NChDE are smaller on SR constants than on shieldings. Nevertheless, within the relativistic polarization propagator formalism at the RPA level of approach they are very important for SR constants of nuclei in heavy-atom-containing compounds. Astatine in HAt has the largest influence: MAt = -9.95 kHz for a point-like model and -50.10 kHz for a Gaussian-like model. Correlation effects must be included and we do it using different DFT schemes. The PBE0 functional gives results that are closest to experiments for Br and I, though the LDA gives the closest for hydrogen. The value of the SR constant of At is reduced among 350 kHz and 500 kHz from its RPA value, when different and usual functionals are applied. Given that the NChDE on M and σ are mostly relativistic in their origin, these effects are also dependent on electron correlation. They have also a nonvanishing dependence with the Gaunt electron-electron interactions.
Fil: Aucar, Ignacio Agustín. 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: 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: 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
NMR SHIELDING
NUCLEAR SPIN-ROTATION CONSTANT
RELATIVISTIC EFFECTS
NUCLEAR CHARGE DISTRIBUTION EFFECTS
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/90565

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spelling Influence of the nuclear charge distribution and electron correlation effects on magnetic shieldings and spin-rotation tensors of linear moleculesAucar, Ignacio AgustínGiménez, Carlos ArielAucar, Gustavo AdolfoNMR SHIELDINGNUCLEAR SPIN-ROTATION CONSTANTRELATIVISTIC EFFECTSNUCLEAR CHARGE DISTRIBUTION EFFECTShttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1The nuclear charge distribution effects (NChDE) on two response properties, the NMR magnetic shielding (σ) and the nuclear spin-rotation (SR) constants (M), are analyzed. We do it employing point-like and Gaussian-like models for describing the nuclear charge density of three linear molecules: HBr, HI and HAt. According to our results, both properties are sensitive to the NChDE. We show that the NChDE are almost completely relativistic, i.e., they nearly vanish in the non-relativistic limit of both properties. We calculated the NChDE on σ and M, and analyzed the differences between them in terms of a relativistic relation between these two properties. Using that relation we found that the electronic core mechanisms are the main ones for the NChDE on the shielding of nuclei of both, molecules and free atoms. The NChDE are smaller on SR constants than on shieldings. Nevertheless, within the relativistic polarization propagator formalism at the RPA level of approach they are very important for SR constants of nuclei in heavy-atom-containing compounds. Astatine in HAt has the largest influence: MAt = -9.95 kHz for a point-like model and -50.10 kHz for a Gaussian-like model. Correlation effects must be included and we do it using different DFT schemes. The PBE0 functional gives results that are closest to experiments for Br and I, though the LDA gives the closest for hydrogen. The value of the SR constant of At is reduced among 350 kHz and 500 kHz from its RPA value, when different and usual functionals are applied. Given that the NChDE on M and σ are mostly relativistic in their origin, these effects are also dependent on electron correlation. They have also a nonvanishing dependence with the Gaunt electron-electron interactions.Fil: Aucar, Ignacio Agustín. 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: 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: 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; ArgentinaRoyal Society of Chemistry2018-06info: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/11336/90565Aucar, Ignacio Agustín; Giménez, Carlos Ariel; Aucar, Gustavo Adolfo; Influence of the nuclear charge distribution and electron correlation effects on magnetic shieldings and spin-rotation tensors of linear molecules; Royal Society of Chemistry; RSC Advances; 8; 36; 6-2018; 20234-202492046-20692046-2069CONICET DigitalCONICETengInformación suplementaria http://www.rsc.org/suppdata/c8/ra/c8ra03948h/c8ra03948h1.pdfinfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2018/RA/C8RA03948H#!divAbstractinfo:eu-repo/semantics/altIdentifier/doi/10.1039/C8RA03948Hinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:33:26Zoai:ri.conicet.gov.ar:11336/90565instacron: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 10:33:26.554CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Influence of the nuclear charge distribution and electron correlation effects on magnetic shieldings and spin-rotation tensors of linear molecules
title Influence of the nuclear charge distribution and electron correlation effects on magnetic shieldings and spin-rotation tensors of linear molecules
spellingShingle Influence of the nuclear charge distribution and electron correlation effects on magnetic shieldings and spin-rotation tensors of linear molecules
Aucar, Ignacio Agustín
NMR SHIELDING
NUCLEAR SPIN-ROTATION CONSTANT
RELATIVISTIC EFFECTS
NUCLEAR CHARGE DISTRIBUTION EFFECTS
title_short Influence of the nuclear charge distribution and electron correlation effects on magnetic shieldings and spin-rotation tensors of linear molecules
title_full Influence of the nuclear charge distribution and electron correlation effects on magnetic shieldings and spin-rotation tensors of linear molecules
title_fullStr Influence of the nuclear charge distribution and electron correlation effects on magnetic shieldings and spin-rotation tensors of linear molecules
title_full_unstemmed Influence of the nuclear charge distribution and electron correlation effects on magnetic shieldings and spin-rotation tensors of linear molecules
title_sort Influence of the nuclear charge distribution and electron correlation effects on magnetic shieldings and spin-rotation tensors of linear molecules
dc.creator.none.fl_str_mv Aucar, Ignacio Agustín
Giménez, Carlos Ariel
Aucar, Gustavo Adolfo
author Aucar, Ignacio Agustín
author_facet Aucar, Ignacio Agustín
Giménez, Carlos Ariel
Aucar, Gustavo Adolfo
author_role author
author2 Giménez, Carlos Ariel
Aucar, Gustavo Adolfo
author2_role author
author
dc.subject.none.fl_str_mv NMR SHIELDING
NUCLEAR SPIN-ROTATION CONSTANT
RELATIVISTIC EFFECTS
NUCLEAR CHARGE DISTRIBUTION EFFECTS
topic NMR SHIELDING
NUCLEAR SPIN-ROTATION CONSTANT
RELATIVISTIC EFFECTS
NUCLEAR CHARGE DISTRIBUTION 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 nuclear charge distribution effects (NChDE) on two response properties, the NMR magnetic shielding (σ) and the nuclear spin-rotation (SR) constants (M), are analyzed. We do it employing point-like and Gaussian-like models for describing the nuclear charge density of three linear molecules: HBr, HI and HAt. According to our results, both properties are sensitive to the NChDE. We show that the NChDE are almost completely relativistic, i.e., they nearly vanish in the non-relativistic limit of both properties. We calculated the NChDE on σ and M, and analyzed the differences between them in terms of a relativistic relation between these two properties. Using that relation we found that the electronic core mechanisms are the main ones for the NChDE on the shielding of nuclei of both, molecules and free atoms. The NChDE are smaller on SR constants than on shieldings. Nevertheless, within the relativistic polarization propagator formalism at the RPA level of approach they are very important for SR constants of nuclei in heavy-atom-containing compounds. Astatine in HAt has the largest influence: MAt = -9.95 kHz for a point-like model and -50.10 kHz for a Gaussian-like model. Correlation effects must be included and we do it using different DFT schemes. The PBE0 functional gives results that are closest to experiments for Br and I, though the LDA gives the closest for hydrogen. The value of the SR constant of At is reduced among 350 kHz and 500 kHz from its RPA value, when different and usual functionals are applied. Given that the NChDE on M and σ are mostly relativistic in their origin, these effects are also dependent on electron correlation. They have also a nonvanishing dependence with the Gaunt electron-electron interactions.
Fil: Aucar, Ignacio Agustín. 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: 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: 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 The nuclear charge distribution effects (NChDE) on two response properties, the NMR magnetic shielding (σ) and the nuclear spin-rotation (SR) constants (M), are analyzed. We do it employing point-like and Gaussian-like models for describing the nuclear charge density of three linear molecules: HBr, HI and HAt. According to our results, both properties are sensitive to the NChDE. We show that the NChDE are almost completely relativistic, i.e., they nearly vanish in the non-relativistic limit of both properties. We calculated the NChDE on σ and M, and analyzed the differences between them in terms of a relativistic relation between these two properties. Using that relation we found that the electronic core mechanisms are the main ones for the NChDE on the shielding of nuclei of both, molecules and free atoms. The NChDE are smaller on SR constants than on shieldings. Nevertheless, within the relativistic polarization propagator formalism at the RPA level of approach they are very important for SR constants of nuclei in heavy-atom-containing compounds. Astatine in HAt has the largest influence: MAt = -9.95 kHz for a point-like model and -50.10 kHz for a Gaussian-like model. Correlation effects must be included and we do it using different DFT schemes. The PBE0 functional gives results that are closest to experiments for Br and I, though the LDA gives the closest for hydrogen. The value of the SR constant of At is reduced among 350 kHz and 500 kHz from its RPA value, when different and usual functionals are applied. Given that the NChDE on M and σ are mostly relativistic in their origin, these effects are also dependent on electron correlation. They have also a nonvanishing dependence with the Gaunt electron-electron interactions.
publishDate 2018
dc.date.none.fl_str_mv 2018-06
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/11336/90565
Aucar, Ignacio Agustín; Giménez, Carlos Ariel; Aucar, Gustavo Adolfo; Influence of the nuclear charge distribution and electron correlation effects on magnetic shieldings and spin-rotation tensors of linear molecules; Royal Society of Chemistry; RSC Advances; 8; 36; 6-2018; 20234-20249
2046-2069
2046-2069
CONICET Digital
CONICET
url http://hdl.handle.net/11336/90565
identifier_str_mv Aucar, Ignacio Agustín; Giménez, Carlos Ariel; Aucar, Gustavo Adolfo; Influence of the nuclear charge distribution and electron correlation effects on magnetic shieldings and spin-rotation tensors of linear molecules; Royal Society of Chemistry; RSC Advances; 8; 36; 6-2018; 20234-20249
2046-2069
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv Información suplementaria http://www.rsc.org/suppdata/c8/ra/c8ra03948h/c8ra03948h1.pdf
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2018/RA/C8RA03948H#!divAbstract
info:eu-repo/semantics/altIdentifier/doi/10.1039/C8RA03948H
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc/2.5/ar/
eu_rights_str_mv openAccess
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dc.format.none.fl_str_mv application/pdf
application/pdf
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dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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reponame_str CONICET Digital (CONICET)
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repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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