Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-nYn (n=0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds

Autores
Maldonado, Alejandro Fabian; Aucar, Gustavo Adolfo; Melo, Juan Ignacio
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The nuclear magnetic shieldings of Si, Ge, and Sn in MH 4−n Y n (M = Si, Ge, Sn; Y = F, Cl, Br, I and n=1-4)molecular systems are highly influenced by the substitution of one or more hydrogens by heavy-halogen atoms. We applied the linear response elimination of small components (LRESC) formalism to calculate those shieldings and learn whether including only a few of the leading relativistic correction terms is sufficient to be able to quantitatively reproduce the full relativistic value. It was observed that the nuclear magnetic shieldings change as the number of heavy halogen substituents and their weights vary, and the pattern of σ(M) generally does not exhibit the normal halogen dependence (NHD) behavior that can be seen in similar molecular systems containing carbon atoms. We also analyzed each relativistic correction afforded by the LRESC method and split them in two: core-dependent and ligand-dependent contributions; we then looked for the electronic mechanisms involved in the different relativistic effects and in the total relativistic value. Based on this analysis, we were able to study the electronic mechanism involved in a recently proposed relativistic effect, the "heavy atom effect on vicinal heavy atom" (HAVHA), in more detail. We found that the main electronic mechanism is the spin-orbit or σ T(3) correction, although other corrections p such as σ S(1) and σ S(3) are also important. Finally, we analyzed p p proton magnetic shieldings and found that, for molecules containing Sn as the central atom, σ(H) decreases as the number of heavy halogen substituents (of the same type: either F, Cl, or Br) increases, albeit at different rates for different halogens. σ(H) only increase as the number of halogen substituents increases if the halogen is iodine.
Fil: Maldonado, Alejandro Fabian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado E Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Cs.exactas Naturales y Agrimensura. Instituto de Modelado E Innovación Tecnologica; 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 Cs.exactas Naturales y Agrimensura. Instituto de Modelado E Innovación Tecnologica; Argentina
Fil: Melo, Juan Ignacio. 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
Materia
Nmr
Relativistic Effects
Lresc
Core Effects
Polarization Propagators
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:11336/16485
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/16485
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-nYn (n=0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compoundsMaldonado, Alejandro FabianAucar, Gustavo AdolfoMelo, Juan IgnacioNmrRelativistic EffectsLrescCore EffectsPolarization Propagatorshttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1The nuclear magnetic shieldings of Si, Ge, and Sn in MH 4−n Y n (M = Si, Ge, Sn; Y = F, Cl, Br, I and n=1-4)molecular systems are highly influenced by the substitution of one or more hydrogens by heavy-halogen atoms. We applied the linear response elimination of small components (LRESC) formalism to calculate those shieldings and learn whether including only a few of the leading relativistic correction terms is sufficient to be able to quantitatively reproduce the full relativistic value. It was observed that the nuclear magnetic shieldings change as the number of heavy halogen substituents and their weights vary, and the pattern of σ(M) generally does not exhibit the normal halogen dependence (NHD) behavior that can be seen in similar molecular systems containing carbon atoms. We also analyzed each relativistic correction afforded by the LRESC method and split them in two: core-dependent and ligand-dependent contributions; we then looked for the electronic mechanisms involved in the different relativistic effects and in the total relativistic value. Based on this analysis, we were able to study the electronic mechanism involved in a recently proposed relativistic effect, the "heavy atom effect on vicinal heavy atom" (HAVHA), in more detail. We found that the main electronic mechanism is the spin-orbit or σ T(3) correction, although other corrections p such as σ S(1) and σ S(3) are also important. Finally, we analyzed p p proton magnetic shieldings and found that, for molecules containing Sn as the central atom, σ(H) decreases as the number of heavy halogen substituents (of the same type: either F, Cl, or Br) increases, albeit at different rates for different halogens. σ(H) only increase as the number of halogen substituents increases if the halogen is iodine.Fil: Maldonado, Alejandro Fabian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado E Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Cs.exactas Naturales y Agrimensura. Instituto de Modelado E Innovación Tecnologica; 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 Cs.exactas Naturales y Agrimensura. Instituto de Modelado E Innovación Tecnologica; ArgentinaFil: Melo, Juan Ignacio. 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; ArgentinaSpringer Verlag Berlín2014-09info: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/11336/16485Maldonado, Alejandro Fabian; Aucar, Gustavo Adolfo; Melo, Juan Ignacio; Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-nYn (n=0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds; Springer Verlag Berlín; Journal Of Molecular Modeling - (online); 20; 9-2014; 2417-24321610-29400948-5023enginfo:eu-repo/semantics/altIdentifier/url/https://link.springer.com/article/10.1007/s00894-014-2417-zinfo:eu-repo/semantics/altIdentifier/doi/10.1007/s00894-014-2417-zinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:36:07Zoai:ri.conicet.gov.ar:11336/16485instacron: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 09:36:07.683CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-nYn (n=0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds
title Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-nYn (n=0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds
spellingShingle Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-nYn (n=0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds
Maldonado, Alejandro Fabian
Nmr
Relativistic Effects
Lresc
Core Effects
Polarization Propagators
title_short Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-nYn (n=0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds
title_full Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-nYn (n=0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds
title_fullStr Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-nYn (n=0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds
title_full_unstemmed Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-nYn (n=0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds
title_sort Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-nYn (n=0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds
dc.creator.none.fl_str_mv Maldonado, Alejandro Fabian
Aucar, Gustavo Adolfo
Melo, Juan Ignacio
author Maldonado, Alejandro Fabian
author_facet Maldonado, Alejandro Fabian
Aucar, Gustavo Adolfo
Melo, Juan Ignacio
author_role author
author2 Aucar, Gustavo Adolfo
Melo, Juan Ignacio
author2_role author
author
dc.subject.none.fl_str_mv Nmr
Relativistic Effects
Lresc
Core Effects
Polarization Propagators
topic Nmr
Relativistic Effects
Lresc
Core Effects
Polarization Propagators
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 magnetic shieldings of Si, Ge, and Sn in MH 4−n Y n (M = Si, Ge, Sn; Y = F, Cl, Br, I and n=1-4)molecular systems are highly influenced by the substitution of one or more hydrogens by heavy-halogen atoms. We applied the linear response elimination of small components (LRESC) formalism to calculate those shieldings and learn whether including only a few of the leading relativistic correction terms is sufficient to be able to quantitatively reproduce the full relativistic value. It was observed that the nuclear magnetic shieldings change as the number of heavy halogen substituents and their weights vary, and the pattern of σ(M) generally does not exhibit the normal halogen dependence (NHD) behavior that can be seen in similar molecular systems containing carbon atoms. We also analyzed each relativistic correction afforded by the LRESC method and split them in two: core-dependent and ligand-dependent contributions; we then looked for the electronic mechanisms involved in the different relativistic effects and in the total relativistic value. Based on this analysis, we were able to study the electronic mechanism involved in a recently proposed relativistic effect, the "heavy atom effect on vicinal heavy atom" (HAVHA), in more detail. We found that the main electronic mechanism is the spin-orbit or σ T(3) correction, although other corrections p such as σ S(1) and σ S(3) are also important. Finally, we analyzed p p proton magnetic shieldings and found that, for molecules containing Sn as the central atom, σ(H) decreases as the number of heavy halogen substituents (of the same type: either F, Cl, or Br) increases, albeit at different rates for different halogens. σ(H) only increase as the number of halogen substituents increases if the halogen is iodine.
Fil: Maldonado, Alejandro Fabian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado E Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Cs.exactas Naturales y Agrimensura. Instituto de Modelado E Innovación Tecnologica; 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 Cs.exactas Naturales y Agrimensura. Instituto de Modelado E Innovación Tecnologica; Argentina
Fil: Melo, Juan Ignacio. 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
description The nuclear magnetic shieldings of Si, Ge, and Sn in MH 4−n Y n (M = Si, Ge, Sn; Y = F, Cl, Br, I and n=1-4)molecular systems are highly influenced by the substitution of one or more hydrogens by heavy-halogen atoms. We applied the linear response elimination of small components (LRESC) formalism to calculate those shieldings and learn whether including only a few of the leading relativistic correction terms is sufficient to be able to quantitatively reproduce the full relativistic value. It was observed that the nuclear magnetic shieldings change as the number of heavy halogen substituents and their weights vary, and the pattern of σ(M) generally does not exhibit the normal halogen dependence (NHD) behavior that can be seen in similar molecular systems containing carbon atoms. We also analyzed each relativistic correction afforded by the LRESC method and split them in two: core-dependent and ligand-dependent contributions; we then looked for the electronic mechanisms involved in the different relativistic effects and in the total relativistic value. Based on this analysis, we were able to study the electronic mechanism involved in a recently proposed relativistic effect, the "heavy atom effect on vicinal heavy atom" (HAVHA), in more detail. We found that the main electronic mechanism is the spin-orbit or σ T(3) correction, although other corrections p such as σ S(1) and σ S(3) are also important. Finally, we analyzed p p proton magnetic shieldings and found that, for molecules containing Sn as the central atom, σ(H) decreases as the number of heavy halogen substituents (of the same type: either F, Cl, or Br) increases, albeit at different rates for different halogens. σ(H) only increase as the number of halogen substituents increases if the halogen is iodine.
publishDate 2014
dc.date.none.fl_str_mv 2014-09
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/11336/16485
Maldonado, Alejandro Fabian; Aucar, Gustavo Adolfo; Melo, Juan Ignacio; Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-nYn (n=0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds; Springer Verlag Berlín; Journal Of Molecular Modeling - (online); 20; 9-2014; 2417-2432
1610-2940
0948-5023
url http://hdl.handle.net/11336/16485
identifier_str_mv Maldonado, Alejandro Fabian; Aucar, Gustavo Adolfo; Melo, Juan Ignacio; Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-nYn (n=0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds; Springer Verlag Berlín; Journal Of Molecular Modeling - (online); 20; 9-2014; 2417-2432
1610-2940
0948-5023
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://link.springer.com/article/10.1007/s00894-014-2417-z
info:eu-repo/semantics/altIdentifier/doi/10.1007/s00894-014-2417-z
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 Springer Verlag Berlín
publisher.none.fl_str_mv Springer Verlag Berlín
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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