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dc.contributor.author
Giménez, Carlos Ariel
dc.contributor.author
Maldonado, Alejandro Fabián
dc.contributor.author
Aucar, Gustavo Adolfo
dc.date.available
2017-08-07T19:07:36Z
dc.date.issued
2016-08
dc.identifier.citation
Giménez, Carlos Ariel; Maldonado, Alejandro Fabián; Aucar, Gustavo Adolfo; Relativistic and electron correlation effects on NMR J-coupling of Sn and Pb containing molecules; Springer Heidelberg; Theoretical Chemistry Accounts; 135; 8-2016; 201-211
dc.identifier.issn
1432-881X
dc.identifier.uri
http://hdl.handle.net/11336/21973
dc.description.abstract
We studied the influence of relativistic and electron correlation effects on NMR J-couplings in the following set of heavy-atom containing molecules: XY4 and H3XXH3 (X = Sn, Pb; Y = H, F, Cl, Br, I). We applied two formalisms, the relativistic polarization propagator approach atrandom phase level of approach (RelPPA-RPA) and density functional theory (DFT) with functionals as implemented in the DIRAC code. We have chosen four functionals that have different amount of HF exchange (PBE0, B3LYP,BLYP, BP86). For those molecular systems, results of calculationswith BLYP functional have the best performance as compared with available experimental data. As was previously found for magnetic shieldings in other molecular systems we are able to show here that DFT functionalsmust be modified in order to obtain reliable results of NMR J-coupling within the relativistic regime. We can state that there is a non-linear dependence among both, electron correlation and relativistic effects that should be introduced in the functionals. The functionals implemented in the DIRAC code are standard nonrelativistic ones which were parameterized with data taken from light-atom containing molecules. This explains why they are not able to properly introduce relativistic effects on NMR parameters, like J-coupling constant. Lastly we show that in the analysis of J-couplings for the family of compounds mentioned above, one must consider the effects of a third heavy-atom that is close to the J-coupled atoms of the same molecule, specially for nJ(H?H). This kind of effect is similar to the newest and so called heavy-atom effect on vicinal heavy atoms, HAVHA, proposed for the NMR-shielding constant. Such effects are among the most important relativistic effects in the family of compounds studied in this work.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Springer Heidelberg
dc.rights
info:eu-repo/semantics/restrictedAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Spin-Spin Coupling
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Relativistic Effects
dc.subject
Dft
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Electron Correlation
dc.subject.classification
Física Atómica, Molecular y Química
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Ciencias Físicas
dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
dc.title
Relativistic and electron correlation effects on NMR J-coupling of Sn and Pb containing molecules
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2017-07-28T15:06:58Z
dc.identifier.eissn
1432-2234
dc.journal.volume
135
dc.journal.pagination
201-211
dc.journal.pais
Alemania
dc.journal.ciudad
Heidelberg
dc.description.fil
Fil: Giménez, Carlos Ariel. 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. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina
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. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; 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. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina
dc.journal.title
Theoretical Chemistry Accounts
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/http://link.springer.com/article/10.1007/s00214-016-1952-3
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1007/s00214-016-1952-3