The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atoms

Autores
Maldonado, Alejandro Fabián; Aucar, Gustavo Adolfo
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Fully relativistic calculations of NMR magnetic shielding on XYHȝ (X = C, Si, Ge and Sn; Y = Br, I), XHn (n = 1–4) molecular systems and noble gases performed with a fully relativistic polarization propagator formalism at the RPA level of approach are presented. The rate of convergence (size of basis set and time involved) for calculations with both kinetic balance prescriptions, RKB and UKB, were investigated. Calculations with UKB makes it feasible to obtain reliable results for two or more heavy-atom-containing molecules. For such XYHȝ systems, the influence of heavy vicinal halogen atoms on σ(X) is such that heavy atom effects on heavy atoms (vicinal plus their own effects or HAVHA + HAHA effects) amount to 30.50% for X = Sn and Y = I; being the HAHA effect of the order of 25%. So the vicinal effect alone is of the order of 5.5%. The vicinal heavy atom effect on light atoms (HALA effect) is of the order of 28% for X = C and Y = I. A similar behaviour, but of opposite sign, is observed for σ(Y) for which σᴿ¯ᴺᴿ(I; X = C) (HAHA effect) is around 27% and σᴿ¯ᴺᴿ(I; X = Sn) (HAVHA + HAHA effects) is close to 21%. Its electronic origin is paramagnetic for halogen atoms but both dia- and paramagnetic for central atoms. The effect on two bond distant hydrogen atoms is such that the largest variation of σ(H) within the same family of XYHȝ molecules appears for X = Si and Y = I: around 20%. In this case σ(H; X = Sn, Y = I) = 33.45 ppm and σ(H; X = Sn, Y = H) = 27.82 ppm.
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: 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
Materia
Heavy Atom
Ukb
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:11336/24666

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spelling The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atomsMaldonado, Alejandro FabiánAucar, Gustavo AdolfoHeavy AtomUkbhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Fully relativistic calculations of NMR magnetic shielding on XYHȝ (X = C, Si, Ge and Sn; Y = Br, I), XHn (n = 1–4) molecular systems and noble gases performed with a fully relativistic polarization propagator formalism at the RPA level of approach are presented. The rate of convergence (size of basis set and time involved) for calculations with both kinetic balance prescriptions, RKB and UKB, were investigated. Calculations with UKB makes it feasible to obtain reliable results for two or more heavy-atom-containing molecules. For such XYHȝ systems, the influence of heavy vicinal halogen atoms on σ(X) is such that heavy atom effects on heavy atoms (vicinal plus their own effects or HAVHA + HAHA effects) amount to 30.50% for X = Sn and Y = I; being the HAHA effect of the order of 25%. So the vicinal effect alone is of the order of 5.5%. The vicinal heavy atom effect on light atoms (HALA effect) is of the order of 28% for X = C and Y = I. A similar behaviour, but of opposite sign, is observed for σ(Y) for which σᴿ¯ᴺᴿ(I; X = C) (HAHA effect) is around 27% and σᴿ¯ᴺᴿ(I; X = Sn) (HAVHA + HAHA effects) is close to 21%. Its electronic origin is paramagnetic for halogen atoms but both dia- and paramagnetic for central atoms. The effect on two bond distant hydrogen atoms is such that the largest variation of σ(H) within the same family of XYHȝ molecules appears for X = Si and Y = I: around 20%. In this case σ(H; X = Sn, Y = I) = 33.45 ppm and σ(H; X = Sn, Y = H) = 27.82 ppm.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; 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; ArgentinaRoyal Society of Chemistry2009-04info: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/11336/24666Maldonado, Alejandro Fabián; Aucar, Gustavo Adolfo; The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atoms; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 11; 27; 4-2009; 5615-56271463-90761463-9084CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2009/CP/b820609kinfo:eu-repo/semantics/altIdentifier/doi/10.1039/b820609kinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:02:40Zoai:ri.conicet.gov.ar:11336/24666instacron: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 10:02:41.289CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atoms
title The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atoms
spellingShingle The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atoms
Maldonado, Alejandro Fabián
Heavy Atom
Ukb
title_short The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atoms
title_full The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atoms
title_fullStr The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atoms
title_full_unstemmed The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atoms
title_sort The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atoms
dc.creator.none.fl_str_mv Maldonado, Alejandro Fabián
Aucar, Gustavo Adolfo
author Maldonado, Alejandro Fabián
author_facet Maldonado, Alejandro Fabián
Aucar, Gustavo Adolfo
author_role author
author2 Aucar, Gustavo Adolfo
author2_role author
dc.subject.none.fl_str_mv Heavy Atom
Ukb
topic Heavy Atom
Ukb
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Fully relativistic calculations of NMR magnetic shielding on XYHȝ (X = C, Si, Ge and Sn; Y = Br, I), XHn (n = 1–4) molecular systems and noble gases performed with a fully relativistic polarization propagator formalism at the RPA level of approach are presented. The rate of convergence (size of basis set and time involved) for calculations with both kinetic balance prescriptions, RKB and UKB, were investigated. Calculations with UKB makes it feasible to obtain reliable results for two or more heavy-atom-containing molecules. For such XYHȝ systems, the influence of heavy vicinal halogen atoms on σ(X) is such that heavy atom effects on heavy atoms (vicinal plus their own effects or HAVHA + HAHA effects) amount to 30.50% for X = Sn and Y = I; being the HAHA effect of the order of 25%. So the vicinal effect alone is of the order of 5.5%. The vicinal heavy atom effect on light atoms (HALA effect) is of the order of 28% for X = C and Y = I. A similar behaviour, but of opposite sign, is observed for σ(Y) for which σᴿ¯ᴺᴿ(I; X = C) (HAHA effect) is around 27% and σᴿ¯ᴺᴿ(I; X = Sn) (HAVHA + HAHA effects) is close to 21%. Its electronic origin is paramagnetic for halogen atoms but both dia- and paramagnetic for central atoms. The effect on two bond distant hydrogen atoms is such that the largest variation of σ(H) within the same family of XYHȝ molecules appears for X = Si and Y = I: around 20%. In this case σ(H; X = Sn, Y = I) = 33.45 ppm and σ(H; X = Sn, Y = H) = 27.82 ppm.
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: 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
description Fully relativistic calculations of NMR magnetic shielding on XYHȝ (X = C, Si, Ge and Sn; Y = Br, I), XHn (n = 1–4) molecular systems and noble gases performed with a fully relativistic polarization propagator formalism at the RPA level of approach are presented. The rate of convergence (size of basis set and time involved) for calculations with both kinetic balance prescriptions, RKB and UKB, were investigated. Calculations with UKB makes it feasible to obtain reliable results for two or more heavy-atom-containing molecules. For such XYHȝ systems, the influence of heavy vicinal halogen atoms on σ(X) is such that heavy atom effects on heavy atoms (vicinal plus their own effects or HAVHA + HAHA effects) amount to 30.50% for X = Sn and Y = I; being the HAHA effect of the order of 25%. So the vicinal effect alone is of the order of 5.5%. The vicinal heavy atom effect on light atoms (HALA effect) is of the order of 28% for X = C and Y = I. A similar behaviour, but of opposite sign, is observed for σ(Y) for which σᴿ¯ᴺᴿ(I; X = C) (HAHA effect) is around 27% and σᴿ¯ᴺᴿ(I; X = Sn) (HAVHA + HAHA effects) is close to 21%. Its electronic origin is paramagnetic for halogen atoms but both dia- and paramagnetic for central atoms. The effect on two bond distant hydrogen atoms is such that the largest variation of σ(H) within the same family of XYHȝ molecules appears for X = Si and Y = I: around 20%. In this case σ(H; X = Sn, Y = I) = 33.45 ppm and σ(H; X = Sn, Y = H) = 27.82 ppm.
publishDate 2009
dc.date.none.fl_str_mv 2009-04
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/11336/24666
Maldonado, Alejandro Fabián; Aucar, Gustavo Adolfo; The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atoms; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 11; 27; 4-2009; 5615-5627
1463-9076
1463-9084
CONICET Digital
CONICET
url http://hdl.handle.net/11336/24666
identifier_str_mv Maldonado, Alejandro Fabián; Aucar, Gustavo Adolfo; The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atoms; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 11; 27; 4-2009; 5615-5627
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/2009/CP/b820609k
info:eu-repo/semantics/altIdentifier/doi/10.1039/b820609k
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 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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