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dc.contributor.author Provasi, Patricio Federico
dc.contributor.author Aucar, Gustavo Adolfo
dc.contributor.author Sauer, Stephan P. A.
dc.date.available 2017-09-20T15:04:56Z
dc.date.issued 2000-03
dc.identifier.citation Provasi, Patricio Federico; Aucar, Gustavo Adolfo; Sauer, Stephan P. A.; The use of locally dense basis sets in the calculation of indirect nuclear spin–spin coupling constants: The vicinal coupling constants in H3C–CH2X (X=H, F, Cl, Br, I); American Institute of Physics; Journal of Chemical Physics; 112; 14; 3-2000; 6201-6208
dc.identifier.issn 0021-9606
dc.identifier.uri http://hdl.handle.net/11336/24665
dc.description.abstract We have calculated the vicinal indirect nuclear spin-spin coupling constants 3J1H1H3J1H1H  in the series of molecules H3C–CH2XH3C–CH2X with X=H, F, Cl, Br, and I at the self-consistent field level and using the second order polarization propagator approximation (SOPPA). We have studied the effect of electron correlation and of the substituents (X=F, Cl, Br, and I) on all four contributions to the coupling constants. But in particular we have investigated the possibility of using locally dense basis sets, i.e., we have carried out calculations with basis sets, where the basis functions on the hydrogen atoms were optimized for the calculation of spin–spin coupling constants whereas on the other atoms smaller, contracted sets of basis functions were used. This changes the results for the couplings by ∼0.3 Hz or 3%. However, the change is almost entirely due to the orbital paramagnetic term and is independent of electron correlation, which enables one to estimate the SOPPA results in the full basis sets. Furthermore we find that the Fermi contact term is the dominant contribution to the vicinal coupling constants, because it is about an order of magnitude larger than the other contributions and because the two orbital angular moment terms almost cancel each other completely. Also the changes in the calculated couplings due to electron correlation are solely due to the Fermi contact term. However, the shifts in the coupling constants caused by the different substituents arise in equal amounts from the Fermi contact and the orbital diamagnetic term, whereas the changes in the orbital paramagnetic term are smaller and are in the opposite direction. In comparison with the experimental data we find very good agreement for C2H6C2H6 and C2H5F.C2H5F. However, the agreement becomes less good with increasing nuclear charge of the substituent X.
dc.format application/pdf
dc.language.iso eng
dc.publisher American Institute of Physics
dc.rights info:eu-repo/semantics/openAccess
dc.rights Atribución-NoComercial-CompartirIgual 2.5 Argentina (CC BY-NC-SA 2.5 AR)
dc.rights.uri https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject BASIS SETS
dc.subject NMR PARAMETERS
dc.subject SPIN-SPIN COUPLING CONSTANT
dc.subject SUBSTITUENT EFFECT
dc.subject ELECTRON CORRELATION CALCULATIONS
dc.subject PARAMAGNETISM
dc.subject DIAMAGNETISM
dc.subject POLARIZATION
dc.subject.classification Otras Ciencias Físicas
dc.subject.classification Ciencias Físicas
dc.subject.classification CIENCIAS NATURALES Y EXACTAS
dc.title The use of locally dense basis sets in the calculation of indirect nuclear spin–spin coupling constants: The vicinal coupling constants in H3C–CH2X (X=H, F, Cl, Br, I)
dc.type info:eu-repo/semantics/article
dc.type info:ar-repo/semantics/artículo
dc.type info:eu-repo/semantics/publishedVersion
dc.date.updated 2017-08-04T15:41:04Z
dc.identifier.eissn 1089-7690
dc.journal.volume 112
dc.journal.number 14
dc.journal.pagination 6201-6208
dc.journal.pais Estados Unidos
dc.journal.ciudad Nueva York
dc.description.fil Fil: Provasi, Patricio Federico. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
dc.description.fil Fil: Aucar, Gustavo Adolfo. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
dc.description.fil Fil: Sauer, Stephan P. A.. Universidad de Copenhagen; Dinamarca
dc.journal.title Journal of Chemical Physics
dc.relation.alternativeid info:eu-repo/semantics/altIdentifier/url/http://aip.scitation.org/doi/abs/10.1063/1.481219
dc.relation.alternativeid info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1063/1.481219


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