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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/16195
Ver los metadatos del registro completo
id |
CONICETDig_b03ddfc317469ce5456142bdb0365818 |
---|---|
oai_identifier_str |
oai:ri.conicet.gov.ar:11336/16195 |
network_acronym_str |
CONICETDig |
repository_id_str |
3498 |
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 |
_version_ |
1844613055056445440 |
score |
13.070432 |