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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/78436
Ver los metadatos del registro completo
id |
CONICETDig_adda6495e252d6158c9303eedf6e08c4 |
---|---|
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 Técnicas2025-09-29T10:16:55Zoai: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:34982025-09-29 10:16:56.189CONICET 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 |
_version_ |
1844614118280003584 |
score |
13.070432 |