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Artículo

Communication: Localized molecular orbital analysis of the effect of electron correlation on the anomalous isotope effect in the NMR spin-spin coupling constant in methane

Zarycz, Maria Natalia CristinaIcon ; Sauer, Stephan P. A.; Provasi, Patricio FedericoIcon
Fecha de publicación: 15/10/2014
Editorial: American Institute of Physics
Revista: Journal of Chemical Physics
ISSN: 0021-9606
e-ISSN: 1089-7690
Idioma: Inglés
Tipo de recurso: Artículo publicado
Clasificación temática:
Física Atómica, Molecular y Química

Resumen

We discuss the effect of electron correlation on the unexpected differential sensitivity (UDS) in the 1J(C-H) coupling constant of CH4 using a decomposition into contributions from localized molecular orbitals and compare with the 1J(N-H) coupling constant in NH3. In particular, we discuss the well known fact that uncorrelated coupled Hartree-Fock (CHF) calculations are not able to reproduce the UDS in methane. For this purpose we have implemented for the first time a localized molecular orbital analysis for the second order polarization propagator approximation with coupled cluster singles and doubles amplitudes - SOPPA(CCSD) in the DALTON program. Comparing the changes in the localized orbital contributions at the correlated SOPPA and SOPPA(CCSD) levels and at the uncorrelated CHF level, we find that the latter overestimates the effect of stretching the bond between the coupled atoms on the contribution to the coupling from the localized bonding orbital between these atoms. This disturbs the subtle balance between the molecular orbital contributions, which lead to the UDS in methane.
Palabras clave: Nmr , Spin-Spin Couplig Constant , Anomalous Isotope Effect , Localized Molecular Orbital
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info:eu-repo/semantics/openAccess Excepto donde se diga explícitamente, este item se publica bajo la siguiente descripción: Creative Commons Attribution-NonCommercial-ShareAlike 2.5 Unported (CC BY-NC-SA 2.5)
Identificadores
URI: http://hdl.handle.net/11336/15154
DOI: http://dx.doi.org/10.1063/1.4897625
URL: http://aip.scitation.org/doi/10.1063/1.4897625
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Articulos(CCT - NORDESTE)
Articulos de CTRO.CIENTIFICO TECNOL.CONICET - NORDESTE
Citación
Zarycz, Maria Natalia Cristina; Sauer, Stephan P. A.; Provasi, Patricio Federico; Communication: Localized molecular orbital analysis of the effect of electron correlation on the anomalous isotope effect in the NMR spin-spin coupling constant in methane; American Institute of Physics; Journal of Chemical Physics; 141; 15; 15-10-2014; 1-7
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