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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/24666
Ver los metadatos del registro completo
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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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1844613834364420096 |
score |
13.070432 |