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dc.contributor.author
Maldonado, Alejandro Fabián
dc.contributor.author
Aucar, Gustavo Adolfo
dc.date.available
2017-09-20T15:15:28Z
dc.date.issued
2009-04
dc.identifier.citation
Maldonado, Alejandro Fabián; Aucar, Gustavo Adolfo; The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atoms; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 11; 27; 4-2009; 5615-5627
dc.identifier.issn
1463-9076
dc.identifier.uri
http://hdl.handle.net/11336/24666
dc.description.abstract
Fully relativistic calculations of NMR magnetic shielding on XYHȝ (X = C, Si, Ge and Sn; Y = Br, I), XHn (n = 1–4) molecular systems and noble gases performed with a fully relativistic polarization propagator formalism at the RPA level of approach are presented. The rate of convergence (size of basis set and time involved) for calculations with both kinetic balance prescriptions, RKB and UKB, were investigated. Calculations with UKB makes it feasible to obtain reliable results for two or more heavy-atom-containing molecules. For such XYHȝ systems, the influence of heavy vicinal halogen atoms on σ(X) is such that heavy atom effects on heavy atoms (vicinal plus their own effects or HAVHA + HAHA effects) amount to 30.50% for X = Sn and Y = I; being the HAHA effect of the order of 25%. So the vicinal effect alone is of the order of 5.5%. The vicinal heavy atom effect on light atoms (HALA effect) is of the order of 28% for X = C and Y = I. A similar behaviour, but of opposite sign, is observed for σ(Y) for which σᴿ¯ᴺᴿ(I; X = C) (HAHA effect) is around 27% and σᴿ¯ᴺᴿ(I; X = Sn) (HAVHA + HAHA effects) is close to 21%. Its electronic origin is paramagnetic for halogen atoms but both dia- and paramagnetic for central atoms. The effect on two bond distant hydrogen atoms is such that the largest variation of σ(H) within the same family of XYHȝ molecules appears for X = Si and Y = I: around 20%. In this case σ(H; X = Sn, Y = I) = 33.45 ppm and σ(H; X = Sn, Y = H) = 27.82 ppm.
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
Heavy Atom
dc.subject
Ukb
dc.subject.classification
Otras Ciencias Físicas
dc.subject.classification
Ciencias Físicas
dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
dc.title
The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atoms
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2017-08-04T15:41:14Z
dc.identifier.eissn
1463-9084
dc.journal.volume
11
dc.journal.number
27
dc.journal.pagination
5615-5627
dc.journal.pais
Reino Unido
dc.journal.ciudad
Londres
dc.description.fil
Fil: Maldonado, Alejandro Fabián. 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 Tecnológica; 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 Tecnológica; Argentina
dc.journal.title
Physical Chemistry Chemical Physics
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2009/CP/b820609k
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1039/b820609k
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