Role of Spin-Dependent Terms in the Relationship among Nuclear Spin-Rotation and NMR Magnetic Shielding Tensors

Autores
Aucar, Ignacio Agustín; Gomez, Sergio Santiago; Giribet, Claudia Gloria; Aucar, Gustavo Adolfo
Año de publicación
2016
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The broadly accepted procedure to obtain the experimental absolute scale of NMR magnetic shieldings, σ, is well-known for nonheavy atom-containing molecules. It was uncovered more than 40 years ago by the works of Ramsey and Flygare. They found a quite accurate relationship among σ and the nuclear spin-rotation constants. Its relativistic extension was very recently proposed, although it has an intrinsic weakness because a new SO-S two-component term needs to be considered. We show how to overcome this problem. We found that (νYS – νYatom,S) generalizes the SO-S term, where νYS = ⟨⟨[((r – rY) × α)/(|r – rY|3)]; S(4)⟩⟩, r – rY is the electron position with respect to the position of nucleus Y, and S(4) is the four-component total electron spin. When including this new term, one finds that the best of our relativistic Flygare-like models fits quite well with the results of the most accurate method available at the moment. We also show that the difference among the parallel component of σ(Xe) in XeF2 and σ(Xe) of the free atom is almost completely described by that new term.
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: Gomez, Sergio Santiago. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina. 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: Giribet, Claudia Gloria. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; 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 Rotation Tensor
Relativistic Quantum Chemistry
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:11336/21986
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Role of Spin-Dependent Terms in the Relationship among Nuclear Spin-Rotation and NMR Magnetic Shielding TensorsAucar, Ignacio AgustínGomez, Sergio SantiagoGiribet, Claudia GloriaAucar, Gustavo AdolfoSpin Rotation TensorRelativistic Quantum Chemistryhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1The broadly accepted procedure to obtain the experimental absolute scale of NMR magnetic shieldings, σ, is well-known for nonheavy atom-containing molecules. It was uncovered more than 40 years ago by the works of Ramsey and Flygare. They found a quite accurate relationship among σ and the nuclear spin-rotation constants. Its relativistic extension was very recently proposed, although it has an intrinsic weakness because a new SO-S two-component term needs to be considered. We show how to overcome this problem. We found that (νYS – νYatom,S) generalizes the SO-S term, where νYS = ⟨⟨[((r – rY) × α)/(|r – rY|3)]; S(4)⟩⟩, r – rY is the electron position with respect to the position of nucleus Y, and S(4) is the four-component total electron spin. When including this new term, one finds that the best of our relativistic Flygare-like models fits quite well with the results of the most accurate method available at the moment. We also show that the difference among the parallel component of σ(Xe) in XeF2 and σ(Xe) of the free atom is almost completely described by that new term.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: Gomez, Sergio Santiago. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina. 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: Giribet, Claudia Gloria. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; 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; ArgentinaAmerican Chemical Society2016-11info: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/11336/21986Aucar, Ignacio Agustín; Gomez, Sergio Santiago; Giribet, Claudia Gloria; Aucar, Gustavo Adolfo; Role of Spin-Dependent Terms in the Relationship among Nuclear Spin-Rotation and NMR Magnetic Shielding Tensors; American Chemical Society; The Journal of Physical Chemistry Letters; 7; 24; 11-2016; 5188-51921948-7185CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpclett.6b02361info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.jpclett.6b02361info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:34:18Zoai:ri.conicet.gov.ar:11336/21986instacron: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 10:34:18.97CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Role of Spin-Dependent Terms in the Relationship among Nuclear Spin-Rotation and NMR Magnetic Shielding Tensors
title Role of Spin-Dependent Terms in the Relationship among Nuclear Spin-Rotation and NMR Magnetic Shielding Tensors
spellingShingle Role of Spin-Dependent Terms in the Relationship among Nuclear Spin-Rotation and NMR Magnetic Shielding Tensors
Aucar, Ignacio Agustín
Spin Rotation Tensor
Relativistic Quantum Chemistry
title_short Role of Spin-Dependent Terms in the Relationship among Nuclear Spin-Rotation and NMR Magnetic Shielding Tensors
title_full Role of Spin-Dependent Terms in the Relationship among Nuclear Spin-Rotation and NMR Magnetic Shielding Tensors
title_fullStr Role of Spin-Dependent Terms in the Relationship among Nuclear Spin-Rotation and NMR Magnetic Shielding Tensors
title_full_unstemmed Role of Spin-Dependent Terms in the Relationship among Nuclear Spin-Rotation and NMR Magnetic Shielding Tensors
title_sort Role of Spin-Dependent Terms in the Relationship among Nuclear Spin-Rotation and NMR Magnetic Shielding Tensors
dc.creator.none.fl_str_mv Aucar, Ignacio Agustín
Gomez, Sergio Santiago
Giribet, Claudia Gloria
Aucar, Gustavo Adolfo
author Aucar, Ignacio Agustín
author_facet Aucar, Ignacio Agustín
Gomez, Sergio Santiago
Giribet, Claudia Gloria
Aucar, Gustavo Adolfo
author_role author
author2 Gomez, Sergio Santiago
Giribet, Claudia Gloria
Aucar, Gustavo Adolfo
author2_role author
author
author
dc.subject.none.fl_str_mv Spin Rotation Tensor
Relativistic Quantum Chemistry
topic Spin Rotation Tensor
Relativistic Quantum Chemistry
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 broadly accepted procedure to obtain the experimental absolute scale of NMR magnetic shieldings, σ, is well-known for nonheavy atom-containing molecules. It was uncovered more than 40 years ago by the works of Ramsey and Flygare. They found a quite accurate relationship among σ and the nuclear spin-rotation constants. Its relativistic extension was very recently proposed, although it has an intrinsic weakness because a new SO-S two-component term needs to be considered. We show how to overcome this problem. We found that (νYS – νYatom,S) generalizes the SO-S term, where νYS = ⟨⟨[((r – rY) × α)/(|r – rY|3)]; S(4)⟩⟩, r – rY is the electron position with respect to the position of nucleus Y, and S(4) is the four-component total electron spin. When including this new term, one finds that the best of our relativistic Flygare-like models fits quite well with the results of the most accurate method available at the moment. We also show that the difference among the parallel component of σ(Xe) in XeF2 and σ(Xe) of the free atom is almost completely described by that new term.
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: Gomez, Sergio Santiago. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina. 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: Giribet, Claudia Gloria. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; 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 broadly accepted procedure to obtain the experimental absolute scale of NMR magnetic shieldings, σ, is well-known for nonheavy atom-containing molecules. It was uncovered more than 40 years ago by the works of Ramsey and Flygare. They found a quite accurate relationship among σ and the nuclear spin-rotation constants. Its relativistic extension was very recently proposed, although it has an intrinsic weakness because a new SO-S two-component term needs to be considered. We show how to overcome this problem. We found that (νYS – νYatom,S) generalizes the SO-S term, where νYS = ⟨⟨[((r – rY) × α)/(|r – rY|3)]; S(4)⟩⟩, r – rY is the electron position with respect to the position of nucleus Y, and S(4) is the four-component total electron spin. When including this new term, one finds that the best of our relativistic Flygare-like models fits quite well with the results of the most accurate method available at the moment. We also show that the difference among the parallel component of σ(Xe) in XeF2 and σ(Xe) of the free atom is almost completely described by that new term.
publishDate 2016
dc.date.none.fl_str_mv 2016-11
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/11336/21986
Aucar, Ignacio Agustín; Gomez, Sergio Santiago; Giribet, Claudia Gloria; Aucar, Gustavo Adolfo; Role of Spin-Dependent Terms in the Relationship among Nuclear Spin-Rotation and NMR Magnetic Shielding Tensors; American Chemical Society; The Journal of Physical Chemistry Letters; 7; 24; 11-2016; 5188-5192
1948-7185
CONICET Digital
CONICET
url http://hdl.handle.net/11336/21986
identifier_str_mv Aucar, Ignacio Agustín; Gomez, Sergio Santiago; Giribet, Claudia Gloria; Aucar, Gustavo Adolfo; Role of Spin-Dependent Terms in the Relationship among Nuclear Spin-Rotation and NMR Magnetic Shielding Tensors; American Chemical Society; The Journal of Physical Chemistry Letters; 7; 24; 11-2016; 5188-5192
1948-7185
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpclett.6b02361
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.jpclett.6b02361
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 American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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 13.070432

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