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dc.contributor.author
Maldonado, Alejandro Fabian
dc.contributor.author
Aucar, Gustavo Adolfo
dc.contributor.author
Melo, Juan Ignacio
dc.date.available
2017-05-15T17:50:39Z
dc.date.issued
2014-09
dc.identifier.citation
Maldonado, Alejandro Fabian; Aucar, Gustavo Adolfo; Melo, Juan Ignacio; Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-nYn (n=0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds; Springer Verlag Berlín; Journal Of Molecular Modeling - (online); 20; 9-2014; 2417-2432
dc.identifier.issn
1610-2940
dc.identifier.uri
http://hdl.handle.net/11336/16485
dc.description.abstract
The nuclear magnetic shieldings of Si, Ge, and Sn in MH 4−n Y n (M = Si, Ge, Sn; Y = F, Cl, Br, I and n=1-4)molecular systems are highly influenced by the substitution of one or more hydrogens by heavy-halogen atoms. We applied the linear response elimination of small components (LRESC) formalism to calculate those shieldings and learn whether including only a few of the leading relativistic correction terms is sufficient to be able to quantitatively reproduce the full relativistic value. It was observed that the nuclear magnetic shieldings change as the number of heavy halogen substituents and their weights vary, and the pattern of σ(M) generally does not exhibit the normal halogen dependence (NHD) behavior that can be seen in similar molecular systems containing carbon atoms. We also analyzed each relativistic correction afforded by the LRESC method and split them in two: core-dependent and ligand-dependent contributions; we then looked for the electronic mechanisms involved in the different relativistic effects and in the total relativistic value. Based on this analysis, we were able to study the electronic mechanism involved in a recently proposed relativistic effect, the "heavy atom effect on vicinal heavy atom" (HAVHA), in more detail. We found that the main electronic mechanism is the spin-orbit or σ T(3) correction, although other corrections p such as σ S(1) and σ S(3) are also important. Finally, we analyzed p p proton magnetic shieldings and found that, for molecules containing Sn as the central atom, σ(H) decreases as the number of heavy halogen substituents (of the same type: either F, Cl, or Br) increases, albeit at different rates for different halogens. σ(H) only increase as the number of halogen substituents increases if the halogen is iodine.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Springer Verlag Berlín
dc.rights
info:eu-repo/semantics/restrictedAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Nmr
dc.subject
Relativistic Effects
dc.subject
Lresc
dc.subject
Core Effects
dc.subject
Polarization Propagators
dc.subject.classification
Física Atómica, Molecular y Química
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Ciencias Físicas
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CIENCIAS NATURALES Y EXACTAS
dc.title
Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-nYn (n=0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2017-05-02T18:17:42Z
dc.identifier.eissn
0948-5023
dc.journal.volume
20
dc.journal.pagination
2417-2432
dc.journal.pais
Alemania
dc.journal.ciudad
Berlín
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 Cs.exactas Naturales y Agrimensura. Instituto de Modelado E Innovación Tecnologica; Argentina
dc.description.fil
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
dc.journal.title
Journal Of Molecular Modeling - (online)
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://link.springer.com/article/10.1007/s00894-014-2417-z
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1007/s00894-014-2417-z