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

Vista sencilla de ítem
dc.citation.journalTitlePHYSICAL CHEMISTRY CHEMICAL PHYSICS
dc.contributor.authorFlórez, E.
dc.contributor.authorMaldonado, A.F.
dc.contributor.authorAucar, G.A.
dc.contributor.authorDavid, J.
dc.contributor.authorRestrepo, A.
dc.contributor.departmentUniversidad EAFIT. Departamento de Ciencias Básicas
dc.contributor.researchgroupElectromagnetismo Aplicado (Gema)spa
dc.date.accessioned2021-03-23T21:39:01Z
dc.date.available2021-03-23T21:39:01Z
dc.date.issued2016-01-21
dc.description.abstractHartree-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 center dot center dot center dot O interaction between methylmercury and one water molecule. Consideration of additional water molecules suggests that they solvate the (CH3Hg center dot center dot center dot OH2)(+) unit. Nuclear magnetic shielding constants sigma(Hg-199), sigma(C-13) and sigma(O-17), as well as indirect spin-spin coupling constants J(Hg-199-C-13), J(Hg-199-O-17) and J(C-13-O-17), 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 sigma(C-13) and 14% on sigma(O-17), which is due to the presence of Hg (heavy atom on light atom, HALA effect), while the relativistic effects on sigma(Hg-199) 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(Hg-199-C-13) and J(Hg-199-O-17). 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 center dot center dot center dot 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.eng
dc.identifierhttps://eafit.fundanetsuite.com/Publicaciones/ProdCientif/PublicacionFrw.aspx?id=1681
dc.identifier.doi10.1039/c5cp04826e
dc.identifier.issn14639076spa
dc.identifier.issn14639084spa
dc.identifier.otherWOS;000369482100020
dc.identifier.otherPUBMED;26670708
dc.identifier.otherSCOPUS;2-s2.0-84954148984
dc.identifier.urihttp://hdl.handle.net/10784/27132
dc.language.isoengeng
dc.publisherROYAL SOC CHEMISTRY
dc.relation.urihttps://www.scopus.com/inward/record.uri?eid=2-s2.0-84954148984&doi=10.1039%2fc5cp04826e&partnerID=40&md5=2cfb5982c630bbb8079003ab90131526
dc.rightshttps://v2.sherpa.ac.uk/id/publication/issn/1463-9076
dc.sourcePHYSICAL CHEMISTRY CHEMICAL PHYSICS
dc.subject.keywordNUCLEAR-MAGNETIC-RESONANCEeng
dc.subject.keywordELECTRON-DENSITY ANALYSISeng
dc.subject.keywordTAPAJOS RIVER REGIONeng
dc.subject.keywordR-ALPHA-STRUCTUREeng
dc.subject.keywordAQUEOUS MICROSOLVATIONeng
dc.subject.keywordMOLECULAR-PROPERTIESeng
dc.subject.keywordPERTURBATION-THEORYeng
dc.subject.keywordMERCURY(II) IODIDEeng
dc.subject.keywordSHIELDING TENSOReng
dc.subject.keywordDFT CALCULATIONSeng
dc.titleMicrosolvation of methylmercury: structures, energies, bonding and NMR constants (Hg-199, C-13 and O-17)eng
dc.typearticleeng
dc.typeinfo:eu-repo/semantics/articleeng
dc.typeinfo:eu-repo/semantics/publishedVersioneng
dc.typepublishedVersioneng
dc.type.localArtículospa

Archivos

Bloque original
Mostrando 1 - 1 de 1
No hay miniatura disponible
Nombre:
CONICET_Digital_Nro.19461.W.pdf
Tamaño:
1.95 MB
Formato:
Adobe Portable Document Format
Descripción:
Descargar

Colecciones

Artículos (Gema)