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dc.contributor.author
Flórez, Edison
dc.contributor.author
Maldonado, Alejandro Fabian
dc.contributor.author
Aucar, Gustavo Adolfo
dc.contributor.author
David, Jorge
dc.contributor.author
Restrepo, Albeiro
dc.date.available
2017-05-10T14:58:08Z
dc.date.issued
2015-11
dc.identifier.citation
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
dc.identifier.issn
1463-9076
dc.identifier.uri
http://hdl.handle.net/11336/16195
dc.description.abstract
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.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society Of Chemistry
dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Microsolvation
dc.subject
Methylmercury
dc.subject
Relativistic Effects
dc.subject
Nmr
dc.subject.classification
Física Atómica, Molecular y Química
dc.subject.classification
Ciencias Físicas
dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
dc.title
Microsolvation of methylmercury: structures, energies, bonding and NMR constants (199Hg, 13C and 17O)
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2017-05-02T18:02:48Z
dc.identifier.eissn
1463-9084
dc.journal.volume
18
dc.journal.number
3
dc.journal.pagination
1537-1550
dc.journal.pais
Reino Unido
dc.journal.ciudad
Cambridge
dc.description.fil
Fil: Flórez, Edison. Universidad de Antioquia; Colombia
dc.description.fil
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
dc.description.fil
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
dc.description.fil
Fil: David, Jorge. Universidad Eafit; Colombia
dc.description.fil
Fil: Restrepo, Albeiro. Universidad de Antioquia; Colombia
dc.journal.title
Physical Chemistry Chemical Physics
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/content/articlelanding/2015/cp/c5cp04826e
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1039/c5cp04826e
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