Nuclear magnetic resonance shielding constants and chemical shifts in linear 199Hg compounds: A comparison of three relativistic computational methods
- Autores
- Arcisauskaite, Vaida; Melo, Juan Ignacio; Hemmingsen, Lars; Sauer, Stephan P.A.
- Año de publicación
- 2011
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- We investigate the importance of relativistic effects on NMR shielding constants and chemical shifts of linear HgL2 (L = Cl, Br, I, CH 3) compounds using three different relativistic methods: the fully relativistic four-component approach and the two-component approximations, linear response elimination of small component (LR-ESC) and zeroth-order regular approximation (ZORA). LR-ESC reproduces successfully the four-component results for the C shielding constant in Hg(CH3)2 within 6 ppm, but fails to reproduce the Hg shielding constants and chemical shifts. The latter is mainly due to an underestimation of the change in spin-orbit contribution. Even though ZORA underestimates the absolute Hg NMR shielding constants by ∼2100 ppm, the differences between Hg chemical shift values obtained using ZORA and the four-component approach without spin-density contribution to the exchange-correlation (XC) kernel are less than 60 ppm for all compounds using three different functionals, BP86, B3LYP, and PBE0. However, larger deviations (up to 366 ppm) occur for Hg chemical shifts in HgBr 2 and HgI2 when ZORA results are compared with four-component calculations with non-collinear spin-density contribution to the XC kernel. For the ZORA calculations it is necessary to use large basis sets (QZ4P) and the TZ2P basis set may give errors of ∼500 ppm for the Hg chemical shifts, despite deceivingly good agreement with experimental data. A Gaussian nucleus model for the Coulomb potential reduces the Hg shielding constants by ∼100-500 ppm and the Hg chemical shifts by 1-143 ppm compared to the point nucleus model depending on the atomic number Z of the coordinating atom and the level of theory. The effect on the shielding constants of the lighter nuclei (C, Cl, Br, I) is, however, negligible. © 2011 American Institute of Physics.
Fil: Arcisauskaite, Vaida. University Of Copenhagen, Faculty Of Life Sciences;
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
Fil: Hemmingsen, Lars. University Of Copenhagen, Faculty Of Life Sciences;
Fil: Sauer, Stephan P.A.. Universidad de Copenhagen; Dinamarca - Materia
-
Shielding Tensor
computational methods
Mercury compunds
NMR - 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:11336/57001
Ver los metadatos del registro completo
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Nuclear magnetic resonance shielding constants and chemical shifts in linear 199Hg compounds: A comparison of three relativistic computational methodsArcisauskaite, VaidaMelo, Juan IgnacioHemmingsen, LarsSauer, Stephan P.A.Shielding Tensorcomputational methodsMercury compundsNMRhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1We investigate the importance of relativistic effects on NMR shielding constants and chemical shifts of linear HgL2 (L = Cl, Br, I, CH 3) compounds using three different relativistic methods: the fully relativistic four-component approach and the two-component approximations, linear response elimination of small component (LR-ESC) and zeroth-order regular approximation (ZORA). LR-ESC reproduces successfully the four-component results for the C shielding constant in Hg(CH3)2 within 6 ppm, but fails to reproduce the Hg shielding constants and chemical shifts. The latter is mainly due to an underestimation of the change in spin-orbit contribution. Even though ZORA underestimates the absolute Hg NMR shielding constants by ∼2100 ppm, the differences between Hg chemical shift values obtained using ZORA and the four-component approach without spin-density contribution to the exchange-correlation (XC) kernel are less than 60 ppm for all compounds using three different functionals, BP86, B3LYP, and PBE0. However, larger deviations (up to 366 ppm) occur for Hg chemical shifts in HgBr 2 and HgI2 when ZORA results are compared with four-component calculations with non-collinear spin-density contribution to the XC kernel. For the ZORA calculations it is necessary to use large basis sets (QZ4P) and the TZ2P basis set may give errors of ∼500 ppm for the Hg chemical shifts, despite deceivingly good agreement with experimental data. A Gaussian nucleus model for the Coulomb potential reduces the Hg shielding constants by ∼100-500 ppm and the Hg chemical shifts by 1-143 ppm compared to the point nucleus model depending on the atomic number Z of the coordinating atom and the level of theory. The effect on the shielding constants of the lighter nuclei (C, Cl, Br, I) is, however, negligible. © 2011 American Institute of Physics.Fil: Arcisauskaite, Vaida. University Of Copenhagen, Faculty Of Life Sciences;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; ArgentinaFil: Hemmingsen, Lars. University Of Copenhagen, Faculty Of Life Sciences;Fil: Sauer, Stephan P.A.. Universidad de Copenhagen; DinamarcaAmerican Institute of Physics2011-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/57001Arcisauskaite, Vaida; Melo, Juan Ignacio; Hemmingsen, Lars; Sauer, Stephan P.A.; Nuclear magnetic resonance shielding constants and chemical shifts in linear 199Hg compounds: A comparison of three relativistic computational methods; American Institute of Physics; Journal of Chemical Physics; 135; 4; 7-2011; 1-110021-9606CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1063/1.3608153info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:48:56Zoai:ri.conicet.gov.ar:11336/57001instacron: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 09:48:56.607CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Nuclear magnetic resonance shielding constants and chemical shifts in linear 199Hg compounds: A comparison of three relativistic computational methods |
title |
Nuclear magnetic resonance shielding constants and chemical shifts in linear 199Hg compounds: A comparison of three relativistic computational methods |
spellingShingle |
Nuclear magnetic resonance shielding constants and chemical shifts in linear 199Hg compounds: A comparison of three relativistic computational methods Arcisauskaite, Vaida Shielding Tensor computational methods Mercury compunds NMR |
title_short |
Nuclear magnetic resonance shielding constants and chemical shifts in linear 199Hg compounds: A comparison of three relativistic computational methods |
title_full |
Nuclear magnetic resonance shielding constants and chemical shifts in linear 199Hg compounds: A comparison of three relativistic computational methods |
title_fullStr |
Nuclear magnetic resonance shielding constants and chemical shifts in linear 199Hg compounds: A comparison of three relativistic computational methods |
title_full_unstemmed |
Nuclear magnetic resonance shielding constants and chemical shifts in linear 199Hg compounds: A comparison of three relativistic computational methods |
title_sort |
Nuclear magnetic resonance shielding constants and chemical shifts in linear 199Hg compounds: A comparison of three relativistic computational methods |
dc.creator.none.fl_str_mv |
Arcisauskaite, Vaida Melo, Juan Ignacio Hemmingsen, Lars Sauer, Stephan P.A. |
author |
Arcisauskaite, Vaida |
author_facet |
Arcisauskaite, Vaida Melo, Juan Ignacio Hemmingsen, Lars Sauer, Stephan P.A. |
author_role |
author |
author2 |
Melo, Juan Ignacio Hemmingsen, Lars Sauer, Stephan P.A. |
author2_role |
author author author |
dc.subject.none.fl_str_mv |
Shielding Tensor computational methods Mercury compunds NMR |
topic |
Shielding Tensor computational methods Mercury compunds NMR |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.3 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
We investigate the importance of relativistic effects on NMR shielding constants and chemical shifts of linear HgL2 (L = Cl, Br, I, CH 3) compounds using three different relativistic methods: the fully relativistic four-component approach and the two-component approximations, linear response elimination of small component (LR-ESC) and zeroth-order regular approximation (ZORA). LR-ESC reproduces successfully the four-component results for the C shielding constant in Hg(CH3)2 within 6 ppm, but fails to reproduce the Hg shielding constants and chemical shifts. The latter is mainly due to an underestimation of the change in spin-orbit contribution. Even though ZORA underestimates the absolute Hg NMR shielding constants by ∼2100 ppm, the differences between Hg chemical shift values obtained using ZORA and the four-component approach without spin-density contribution to the exchange-correlation (XC) kernel are less than 60 ppm for all compounds using three different functionals, BP86, B3LYP, and PBE0. However, larger deviations (up to 366 ppm) occur for Hg chemical shifts in HgBr 2 and HgI2 when ZORA results are compared with four-component calculations with non-collinear spin-density contribution to the XC kernel. For the ZORA calculations it is necessary to use large basis sets (QZ4P) and the TZ2P basis set may give errors of ∼500 ppm for the Hg chemical shifts, despite deceivingly good agreement with experimental data. A Gaussian nucleus model for the Coulomb potential reduces the Hg shielding constants by ∼100-500 ppm and the Hg chemical shifts by 1-143 ppm compared to the point nucleus model depending on the atomic number Z of the coordinating atom and the level of theory. The effect on the shielding constants of the lighter nuclei (C, Cl, Br, I) is, however, negligible. © 2011 American Institute of Physics. Fil: Arcisauskaite, Vaida. University Of Copenhagen, Faculty Of Life Sciences; 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 Fil: Hemmingsen, Lars. University Of Copenhagen, Faculty Of Life Sciences; Fil: Sauer, Stephan P.A.. Universidad de Copenhagen; Dinamarca |
description |
We investigate the importance of relativistic effects on NMR shielding constants and chemical shifts of linear HgL2 (L = Cl, Br, I, CH 3) compounds using three different relativistic methods: the fully relativistic four-component approach and the two-component approximations, linear response elimination of small component (LR-ESC) and zeroth-order regular approximation (ZORA). LR-ESC reproduces successfully the four-component results for the C shielding constant in Hg(CH3)2 within 6 ppm, but fails to reproduce the Hg shielding constants and chemical shifts. The latter is mainly due to an underestimation of the change in spin-orbit contribution. Even though ZORA underestimates the absolute Hg NMR shielding constants by ∼2100 ppm, the differences between Hg chemical shift values obtained using ZORA and the four-component approach without spin-density contribution to the exchange-correlation (XC) kernel are less than 60 ppm for all compounds using three different functionals, BP86, B3LYP, and PBE0. However, larger deviations (up to 366 ppm) occur for Hg chemical shifts in HgBr 2 and HgI2 when ZORA results are compared with four-component calculations with non-collinear spin-density contribution to the XC kernel. For the ZORA calculations it is necessary to use large basis sets (QZ4P) and the TZ2P basis set may give errors of ∼500 ppm for the Hg chemical shifts, despite deceivingly good agreement with experimental data. A Gaussian nucleus model for the Coulomb potential reduces the Hg shielding constants by ∼100-500 ppm and the Hg chemical shifts by 1-143 ppm compared to the point nucleus model depending on the atomic number Z of the coordinating atom and the level of theory. The effect on the shielding constants of the lighter nuclei (C, Cl, Br, I) is, however, negligible. © 2011 American Institute of Physics. |
publishDate |
2011 |
dc.date.none.fl_str_mv |
2011-07 |
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/11336/57001 Arcisauskaite, Vaida; Melo, Juan Ignacio; Hemmingsen, Lars; Sauer, Stephan P.A.; Nuclear magnetic resonance shielding constants and chemical shifts in linear 199Hg compounds: A comparison of three relativistic computational methods; American Institute of Physics; Journal of Chemical Physics; 135; 4; 7-2011; 1-11 0021-9606 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/57001 |
identifier_str_mv |
Arcisauskaite, Vaida; Melo, Juan Ignacio; Hemmingsen, Lars; Sauer, Stephan P.A.; Nuclear magnetic resonance shielding constants and chemical shifts in linear 199Hg compounds: A comparison of three relativistic computational methods; American Institute of Physics; Journal of Chemical Physics; 135; 4; 7-2011; 1-11 0021-9606 CONICET Digital CONICET |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/doi/10.1063/1.3608153 |
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 |
dc.publisher.none.fl_str_mv |
American Institute of Physics |
publisher.none.fl_str_mv |
American Institute of Physics |
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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1844613517762625536 |
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13.070432 |