NMR espectroscopic parameters of HX and Si (Sn)X4 (X = H, F, Cl, Br and I) and SnBr4-nIn model compounds

Autores
Maldonado, Alejandro Fabián; Giménez, Carlos Ariel; Aucar, Gustavo Adolfo
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The NMR spectroscopic parameters are largely influenced by relativistic effects. They are highly dependent on the electronic behavior inside the spatial regions occupied by nuclei. Full relativistic calculations of indirect nuclear spin-spin couplings at random phase level of approach (RPA) in the title compounds with reoptimized Dyall cVTZ basis sets are given. A comparison with the results of calculations with other basis sets that are mostly used within the non-relativistic (NR) domain is presented. We analyzed the dependence of that couplings with the speed of light over the whole range of values, from the full relativistic to the NR regimes. Within this last regime, calculations at the second-order level of approach (SOPPA) indicated that electron correlation effects may not be as important for nuclear magnetic shieldings, but they must be included with care for J-coupling calculations. From these calculations, we determined that relativity enlarges the electron correlation effects of the J-couplings of HBr and HI. Because the results of nuclear magnetic shielding calculations within polarization propagators at the RPA level were reliable, we were able to show a new and easy procedure to obtain absolute nuclear magnetic shieldings on reference compounds for both Si and Sn nuclei: σ[Si (CH 3) 4] = 421.28 ± 29.33 ppm and σ[Sn (CH 3) 4] = 3814.96 ± 79.12 ppm. They were obtained from experimental chemical shifts and accurate nuclear magnetic shielding calculations on different molecular systems.
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: 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
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
Relativistic Effects
Polarization Propagators
Shielding Si
Shielding Sn
Nmr
Σref(Si)
Σref(Sn)
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:11336/78436
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/78436
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling NMR espectroscopic parameters of HX and Si (Sn)X4 (X = H, F, Cl, Br and I) and SnBr4-nIn model compoundsMaldonado, Alejandro FabiánGiménez, Carlos ArielAucar, Gustavo AdolfoRelativistic EffectsPolarization PropagatorsShielding SiShielding SnNmrΣref(Si)Σref(Sn)https://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1The NMR spectroscopic parameters are largely influenced by relativistic effects. They are highly dependent on the electronic behavior inside the spatial regions occupied by nuclei. Full relativistic calculations of indirect nuclear spin-spin couplings at random phase level of approach (RPA) in the title compounds with reoptimized Dyall cVTZ basis sets are given. A comparison with the results of calculations with other basis sets that are mostly used within the non-relativistic (NR) domain is presented. We analyzed the dependence of that couplings with the speed of light over the whole range of values, from the full relativistic to the NR regimes. Within this last regime, calculations at the second-order level of approach (SOPPA) indicated that electron correlation effects may not be as important for nuclear magnetic shieldings, but they must be included with care for J-coupling calculations. From these calculations, we determined that relativity enlarges the electron correlation effects of the J-couplings of HBr and HI. Because the results of nuclear magnetic shielding calculations within polarization propagators at the RPA level were reliable, we were able to show a new and easy procedure to obtain absolute nuclear magnetic shieldings on reference compounds for both Si and Sn nuclei: σ[Si (CH 3) 4] = 421.28 ± 29.33 ppm and σ[Sn (CH 3) 4] = 3814.96 ± 79.12 ppm. They were obtained from experimental chemical shifts and accurate nuclear magnetic shielding calculations on different molecular systems.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: 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; 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; ArgentinaElsevier Science2012-02info: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/11336/78436Maldonado, Alejandro Fabián; Giménez, Carlos Ariel; Aucar, Gustavo Adolfo; NMR espectroscopic parameters of HX and Si (Sn)X4 (X = H, F, Cl, Br and I) and SnBr4-nIn model compounds; Elsevier Science; Chemical Physics; 395; 1; 2-2012; 75-810301-0104CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0301010411003764info:eu-repo/semantics/altIdentifier/doi/10.1016/j.chemphys.2011.08.020info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:47:05Zoai:ri.conicet.gov.ar:11336/78436instacron: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:34982025-10-22 11:47:05.888CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv NMR espectroscopic parameters of HX and Si (Sn)X4 (X = H, F, Cl, Br and I) and SnBr4-nIn model compounds
title NMR espectroscopic parameters of HX and Si (Sn)X4 (X = H, F, Cl, Br and I) and SnBr4-nIn model compounds
spellingShingle NMR espectroscopic parameters of HX and Si (Sn)X4 (X = H, F, Cl, Br and I) and SnBr4-nIn model compounds
Maldonado, Alejandro Fabián
Relativistic Effects
Polarization Propagators
Shielding Si
Shielding Sn
Nmr
Σref(Si)
Σref(Sn)
title_short NMR espectroscopic parameters of HX and Si (Sn)X4 (X = H, F, Cl, Br and I) and SnBr4-nIn model compounds
title_full NMR espectroscopic parameters of HX and Si (Sn)X4 (X = H, F, Cl, Br and I) and SnBr4-nIn model compounds
title_fullStr NMR espectroscopic parameters of HX and Si (Sn)X4 (X = H, F, Cl, Br and I) and SnBr4-nIn model compounds
title_full_unstemmed NMR espectroscopic parameters of HX and Si (Sn)X4 (X = H, F, Cl, Br and I) and SnBr4-nIn model compounds
title_sort NMR espectroscopic parameters of HX and Si (Sn)X4 (X = H, F, Cl, Br and I) and SnBr4-nIn model compounds
dc.creator.none.fl_str_mv Maldonado, Alejandro Fabián
Giménez, Carlos Ariel
Aucar, Gustavo Adolfo
author Maldonado, Alejandro Fabián
author_facet Maldonado, Alejandro Fabián
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 Relativistic Effects
Polarization Propagators
Shielding Si
Shielding Sn
Nmr
Σref(Si)
Σref(Sn)
topic Relativistic Effects
Polarization Propagators
Shielding Si
Shielding Sn
Nmr
Σref(Si)
Σref(Sn)
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 NMR spectroscopic parameters are largely influenced by relativistic effects. They are highly dependent on the electronic behavior inside the spatial regions occupied by nuclei. Full relativistic calculations of indirect nuclear spin-spin couplings at random phase level of approach (RPA) in the title compounds with reoptimized Dyall cVTZ basis sets are given. A comparison with the results of calculations with other basis sets that are mostly used within the non-relativistic (NR) domain is presented. We analyzed the dependence of that couplings with the speed of light over the whole range of values, from the full relativistic to the NR regimes. Within this last regime, calculations at the second-order level of approach (SOPPA) indicated that electron correlation effects may not be as important for nuclear magnetic shieldings, but they must be included with care for J-coupling calculations. From these calculations, we determined that relativity enlarges the electron correlation effects of the J-couplings of HBr and HI. Because the results of nuclear magnetic shielding calculations within polarization propagators at the RPA level were reliable, we were able to show a new and easy procedure to obtain absolute nuclear magnetic shieldings on reference compounds for both Si and Sn nuclei: σ[Si (CH 3) 4] = 421.28 ± 29.33 ppm and σ[Sn (CH 3) 4] = 3814.96 ± 79.12 ppm. They were obtained from experimental chemical shifts and accurate nuclear magnetic shielding calculations on different molecular systems.
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: 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
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 The NMR spectroscopic parameters are largely influenced by relativistic effects. They are highly dependent on the electronic behavior inside the spatial regions occupied by nuclei. Full relativistic calculations of indirect nuclear spin-spin couplings at random phase level of approach (RPA) in the title compounds with reoptimized Dyall cVTZ basis sets are given. A comparison with the results of calculations with other basis sets that are mostly used within the non-relativistic (NR) domain is presented. We analyzed the dependence of that couplings with the speed of light over the whole range of values, from the full relativistic to the NR regimes. Within this last regime, calculations at the second-order level of approach (SOPPA) indicated that electron correlation effects may not be as important for nuclear magnetic shieldings, but they must be included with care for J-coupling calculations. From these calculations, we determined that relativity enlarges the electron correlation effects of the J-couplings of HBr and HI. Because the results of nuclear magnetic shielding calculations within polarization propagators at the RPA level were reliable, we were able to show a new and easy procedure to obtain absolute nuclear magnetic shieldings on reference compounds for both Si and Sn nuclei: σ[Si (CH 3) 4] = 421.28 ± 29.33 ppm and σ[Sn (CH 3) 4] = 3814.96 ± 79.12 ppm. They were obtained from experimental chemical shifts and accurate nuclear magnetic shielding calculations on different molecular systems.
publishDate 2012
dc.date.none.fl_str_mv 2012-02
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/11336/78436
Maldonado, Alejandro Fabián; Giménez, Carlos Ariel; Aucar, Gustavo Adolfo; NMR espectroscopic parameters of HX and Si (Sn)X4 (X = H, F, Cl, Br and I) and SnBr4-nIn model compounds; Elsevier Science; Chemical Physics; 395; 1; 2-2012; 75-81
0301-0104
CONICET Digital
CONICET
url http://hdl.handle.net/11336/78436
identifier_str_mv Maldonado, Alejandro Fabián; Giménez, Carlos Ariel; Aucar, Gustavo Adolfo; NMR espectroscopic parameters of HX and Si (Sn)X4 (X = H, F, Cl, Br and I) and SnBr4-nIn model compounds; Elsevier Science; Chemical Physics; 395; 1; 2-2012; 75-81
0301-0104
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://www.sciencedirect.com/science/article/pii/S0301010411003764
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.chemphys.2011.08.020
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 Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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 13.144186

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