Microsolvation of methylmercury: structures, energies, bonding and NMR constants (199Hg, 13C and 17O)

Autores
Flórez, Edison; Maldonado, Alejandro Fabian; Aucar, Gustavo Adolfo; David, Jorge; Restrepo, Albeiro
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Hartree–Fock (HF) and second order perturbation theory (MP2) calculations within the scalar and full relativistic frames were carried out in order to determine the equilibrium geometries and interaction energies between cationic methylmercury (CH3Hg+) and up to three water molecules. A total of nine structures were obtained. Bonding properties were analyzed using the Quantum Theory of Atoms In Molecules (QTAIM). The analyses of the topology of electron densities reveal that all structures exhibit a partially covalent Hg⋯O interaction between methylmercury and one water molecule. Consideration of additional water molecules suggests that they solvate the (CH3Hg⋯OH2)+ unit. Nuclear magnetic shielding constants σ(199Hg), σ(13C) and σ(17O), as well as indirect spin–spin coupling constants J(199Hg–13C), J(199Hg–17O) and J(13C–17O), were calculated for each one of the geometries. Thermodynamic stability and the values of NMR constants correlate with the ability of the system to directly coordinate oxygen atoms of water molecules to the mercury atom in methylmercury and with the formation of hydrogen bonds among solvating water molecules. Relativistic effects account for 11% on σ(13C) and 14% on σ(17O), which is due to the presence of Hg (heavy atom on light atom, HALA effect), while the relativistic effects on σ(199Hg) are close to 50% (heavy atom on heavy atom itself, HAHA effect). J-coupling constants are highly influenced by relativity when mercury is involved as in J(199Hg–13C) and J(199Hg–17O). On the other hand, our results show that the values of NMR constants for carbon and oxygen, atoms which are connected through mercury (C–Hg⋯O), are highly correlated and are greatly influenced by the presence of water molecules. Water molecules introduce additional electronic effects to the relativistic effects due to the mercury atom.
Fil: Flórez, Edison. Universidad de Antioquia; Colombia
Fil: Maldonado, Alejandro Fabian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado E Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Cs.exactas Naturales y Agrimensura. Instituto de Modelado E Innovación Tecnologica; 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 Tecnologica; Argentina
Fil: David, Jorge. Universidad Eafit; Colombia
Fil: Restrepo, Albeiro. Universidad de Antioquia; Colombia
Materia
Microsolvation
Methylmercury
Relativistic Effects
Nmr
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:11336/16195

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oai_identifier_str oai:ri.conicet.gov.ar:11336/16195
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network_name_str CONICET Digital (CONICET)
spelling Microsolvation of methylmercury: structures, energies, bonding and NMR constants (199Hg, 13C and 17O)Flórez, EdisonMaldonado, Alejandro FabianAucar, Gustavo AdolfoDavid, JorgeRestrepo, AlbeiroMicrosolvationMethylmercuryRelativistic EffectsNmrhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Hartree–Fock (HF) and second order perturbation theory (MP2) calculations within the scalar and full relativistic frames were carried out in order to determine the equilibrium geometries and interaction energies between cationic methylmercury (CH3Hg+) and up to three water molecules. A total of nine structures were obtained. Bonding properties were analyzed using the Quantum Theory of Atoms In Molecules (QTAIM). The analyses of the topology of electron densities reveal that all structures exhibit a partially covalent Hg⋯O interaction between methylmercury and one water molecule. Consideration of additional water molecules suggests that they solvate the (CH3Hg⋯OH2)+ unit. Nuclear magnetic shielding constants σ(199Hg), σ(13C) and σ(17O), as well as indirect spin–spin coupling constants J(199Hg–13C), J(199Hg–17O) and J(13C–17O), were calculated for each one of the geometries. Thermodynamic stability and the values of NMR constants correlate with the ability of the system to directly coordinate oxygen atoms of water molecules to the mercury atom in methylmercury and with the formation of hydrogen bonds among solvating water molecules. Relativistic effects account for 11% on σ(13C) and 14% on σ(17O), which is due to the presence of Hg (heavy atom on light atom, HALA effect), while the relativistic effects on σ(199Hg) are close to 50% (heavy atom on heavy atom itself, HAHA effect). J-coupling constants are highly influenced by relativity when mercury is involved as in J(199Hg–13C) and J(199Hg–17O). On the other hand, our results show that the values of NMR constants for carbon and oxygen, atoms which are connected through mercury (C–Hg⋯O), are highly correlated and are greatly influenced by the presence of water molecules. Water molecules introduce additional electronic effects to the relativistic effects due to the mercury atom.Fil: Flórez, Edison. Universidad de Antioquia; ColombiaFil: Maldonado, Alejandro Fabian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado E Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Cs.exactas Naturales y Agrimensura. Instituto de Modelado E Innovación Tecnologica; 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 Tecnologica; ArgentinaFil: David, Jorge. Universidad Eafit; ColombiaFil: Restrepo, Albeiro. Universidad de Antioquia; ColombiaRoyal Society Of Chemistry2015-11info: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/11336/16195Flórez, Edison; Maldonado, Alejandro Fabian; Aucar, Gustavo Adolfo; David, Jorge; Restrepo, Albeiro; Microsolvation of methylmercury: structures, energies, bonding and NMR constants (199Hg, 13C and 17O); Royal Society Of Chemistry; Physical Chemistry Chemical Physics; 18; 3; 11-2015; 1537-15501463-90761463-9084enginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/content/articlelanding/2015/cp/c5cp04826einfo:eu-repo/semantics/altIdentifier/doi/10.1039/c5cp04826einfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:34:08Zoai:ri.conicet.gov.ar:11336/16195instacron: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 09:34:08.986CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Microsolvation of methylmercury: structures, energies, bonding and NMR constants (199Hg, 13C and 17O)
title Microsolvation of methylmercury: structures, energies, bonding and NMR constants (199Hg, 13C and 17O)
spellingShingle Microsolvation of methylmercury: structures, energies, bonding and NMR constants (199Hg, 13C and 17O)
Flórez, Edison
Microsolvation
Methylmercury
Relativistic Effects
Nmr
title_short Microsolvation of methylmercury: structures, energies, bonding and NMR constants (199Hg, 13C and 17O)
title_full Microsolvation of methylmercury: structures, energies, bonding and NMR constants (199Hg, 13C and 17O)
title_fullStr Microsolvation of methylmercury: structures, energies, bonding and NMR constants (199Hg, 13C and 17O)
title_full_unstemmed Microsolvation of methylmercury: structures, energies, bonding and NMR constants (199Hg, 13C and 17O)
title_sort Microsolvation of methylmercury: structures, energies, bonding and NMR constants (199Hg, 13C and 17O)
dc.creator.none.fl_str_mv Flórez, Edison
Maldonado, Alejandro Fabian
Aucar, Gustavo Adolfo
David, Jorge
Restrepo, Albeiro
author Flórez, Edison
author_facet Flórez, Edison
Maldonado, Alejandro Fabian
Aucar, Gustavo Adolfo
David, Jorge
Restrepo, Albeiro
author_role author
author2 Maldonado, Alejandro Fabian
Aucar, Gustavo Adolfo
David, Jorge
Restrepo, Albeiro
author2_role author
author
author
author
dc.subject.none.fl_str_mv Microsolvation
Methylmercury
Relativistic Effects
Nmr
topic Microsolvation
Methylmercury
Relativistic Effects
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 Hartree–Fock (HF) and second order perturbation theory (MP2) calculations within the scalar and full relativistic frames were carried out in order to determine the equilibrium geometries and interaction energies between cationic methylmercury (CH3Hg+) and up to three water molecules. A total of nine structures were obtained. Bonding properties were analyzed using the Quantum Theory of Atoms In Molecules (QTAIM). The analyses of the topology of electron densities reveal that all structures exhibit a partially covalent Hg⋯O interaction between methylmercury and one water molecule. Consideration of additional water molecules suggests that they solvate the (CH3Hg⋯OH2)+ unit. Nuclear magnetic shielding constants σ(199Hg), σ(13C) and σ(17O), as well as indirect spin–spin coupling constants J(199Hg–13C), J(199Hg–17O) and J(13C–17O), were calculated for each one of the geometries. Thermodynamic stability and the values of NMR constants correlate with the ability of the system to directly coordinate oxygen atoms of water molecules to the mercury atom in methylmercury and with the formation of hydrogen bonds among solvating water molecules. Relativistic effects account for 11% on σ(13C) and 14% on σ(17O), which is due to the presence of Hg (heavy atom on light atom, HALA effect), while the relativistic effects on σ(199Hg) are close to 50% (heavy atom on heavy atom itself, HAHA effect). J-coupling constants are highly influenced by relativity when mercury is involved as in J(199Hg–13C) and J(199Hg–17O). On the other hand, our results show that the values of NMR constants for carbon and oxygen, atoms which are connected through mercury (C–Hg⋯O), are highly correlated and are greatly influenced by the presence of water molecules. Water molecules introduce additional electronic effects to the relativistic effects due to the mercury atom.
Fil: Flórez, Edison. Universidad de Antioquia; Colombia
Fil: Maldonado, Alejandro Fabian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado E Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Cs.exactas Naturales y Agrimensura. Instituto de Modelado E Innovación Tecnologica; 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 Tecnologica; Argentina
Fil: David, Jorge. Universidad Eafit; Colombia
Fil: Restrepo, Albeiro. Universidad de Antioquia; Colombia
description Hartree–Fock (HF) and second order perturbation theory (MP2) calculations within the scalar and full relativistic frames were carried out in order to determine the equilibrium geometries and interaction energies between cationic methylmercury (CH3Hg+) and up to three water molecules. A total of nine structures were obtained. Bonding properties were analyzed using the Quantum Theory of Atoms In Molecules (QTAIM). The analyses of the topology of electron densities reveal that all structures exhibit a partially covalent Hg⋯O interaction between methylmercury and one water molecule. Consideration of additional water molecules suggests that they solvate the (CH3Hg⋯OH2)+ unit. Nuclear magnetic shielding constants σ(199Hg), σ(13C) and σ(17O), as well as indirect spin–spin coupling constants J(199Hg–13C), J(199Hg–17O) and J(13C–17O), were calculated for each one of the geometries. Thermodynamic stability and the values of NMR constants correlate with the ability of the system to directly coordinate oxygen atoms of water molecules to the mercury atom in methylmercury and with the formation of hydrogen bonds among solvating water molecules. Relativistic effects account for 11% on σ(13C) and 14% on σ(17O), which is due to the presence of Hg (heavy atom on light atom, HALA effect), while the relativistic effects on σ(199Hg) are close to 50% (heavy atom on heavy atom itself, HAHA effect). J-coupling constants are highly influenced by relativity when mercury is involved as in J(199Hg–13C) and J(199Hg–17O). On the other hand, our results show that the values of NMR constants for carbon and oxygen, atoms which are connected through mercury (C–Hg⋯O), are highly correlated and are greatly influenced by the presence of water molecules. Water molecules introduce additional electronic effects to the relativistic effects due to the mercury atom.
publishDate 2015
dc.date.none.fl_str_mv 2015-11
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/11336/16195
Flórez, Edison; Maldonado, Alejandro Fabian; Aucar, Gustavo Adolfo; David, Jorge; Restrepo, Albeiro; Microsolvation of methylmercury: structures, energies, bonding and NMR constants (199Hg, 13C and 17O); Royal Society Of Chemistry; Physical Chemistry Chemical Physics; 18; 3; 11-2015; 1537-1550
1463-9076
1463-9084
url http://hdl.handle.net/11336/16195
identifier_str_mv Flórez, Edison; Maldonado, Alejandro Fabian; Aucar, Gustavo Adolfo; David, Jorge; Restrepo, Albeiro; Microsolvation of methylmercury: structures, energies, bonding and NMR constants (199Hg, 13C and 17O); Royal Society Of Chemistry; Physical Chemistry Chemical Physics; 18; 3; 11-2015; 1537-1550
1463-9076
1463-9084
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/2015/cp/c5cp04826e
info:eu-repo/semantics/altIdentifier/doi/10.1039/c5cp04826e
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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