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Abstract:

A method designed to analyse transmission mechanisms of NMR indirect spin-spin coupling constants based on the use of localized molecular orbitals and inner-projections of the polarization propagator at the RPA level has been implemented within an ab initio approach. Former semi-empirical versions of this approach proved to be a valuable tool to obtain insight on transmission mechanisms of NMR parameters. The new features and difficulties found in the implementation of this method at an ab initio level are discussed. In particular, a localization procedure is proposed to deal with vacant molecular orbitals. In order to convey an idea about the potentialities of this approach, in this work a bond contribution analysis of the 1J(NH) coupling in NH3 as a function of the pyramidality at the N atom is carried out. The influence of the N lone-pair, the different N-H bonds and the N inner-shell electrons in the coupling transmission are discussed, for pyramidal and planar configurations. Trends that are expected to be of general validity are found. Results obtained are in agreement with previous theoretical studies on 1J couplings as well as with empirical trends deduced from experimentally measured values of 1J(NH) couplings in different compounds. © 1998 Elsevier Science B.V. All rights reserved.

Registro:

Documento: Artículo
Título:Ab initio IPPP-CLOPPA approach to perform bond contribution analysis of NMR coupling constants: 1J(NH) in NH3 as a function of pyramidality
Autor:Ruiz De Azúa, M.C.; Giribet, C.G.; Vizioli, C.V.; Contreras, R.H.
Filiación:Dpto. de Física, Facultad de Cs. Exactas y Naturales, Cdad. Universitaria, Pab. 1, (1428), Buenos Aires, Argentina
Palabras clave:Bond contributions; IPPP-CLOPPA; NMR coupling constants; Pyramidality
Año:1998
Volumen:433
Número:1-3
Página de inicio:141
Página de fin:150
DOI: http://dx.doi.org/10.1016/S0166-1280(98)00020-7
Título revista:Journal of Molecular Structure: THEOCHEM
Título revista abreviado:J. Mol. Struct. THEOCHEM
ISSN:01661280
CODEN:THEOD
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01661280_v433_n1-3_p141_RuizDeAzua

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Citas:

---------- APA ----------
Ruiz De Azúa, M.C., Giribet, C.G., Vizioli, C.V. & Contreras, R.H. (1998) . Ab initio IPPP-CLOPPA approach to perform bond contribution analysis of NMR coupling constants: 1J(NH) in NH3 as a function of pyramidality. Journal of Molecular Structure: THEOCHEM, 433(1-3), 141-150.
http://dx.doi.org/10.1016/S0166-1280(98)00020-7
---------- CHICAGO ----------
Ruiz De Azúa, M.C., Giribet, C.G., Vizioli, C.V., Contreras, R.H. "Ab initio IPPP-CLOPPA approach to perform bond contribution analysis of NMR coupling constants: 1J(NH) in NH3 as a function of pyramidality" . Journal of Molecular Structure: THEOCHEM 433, no. 1-3 (1998) : 141-150.
http://dx.doi.org/10.1016/S0166-1280(98)00020-7
---------- MLA ----------
Ruiz De Azúa, M.C., Giribet, C.G., Vizioli, C.V., Contreras, R.H. "Ab initio IPPP-CLOPPA approach to perform bond contribution analysis of NMR coupling constants: 1J(NH) in NH3 as a function of pyramidality" . Journal of Molecular Structure: THEOCHEM, vol. 433, no. 1-3, 1998, pp. 141-150.
http://dx.doi.org/10.1016/S0166-1280(98)00020-7
---------- VANCOUVER ----------
Ruiz De Azúa, M.C., Giribet, C.G., Vizioli, C.V., Contreras, R.H. Ab initio IPPP-CLOPPA approach to perform bond contribution analysis of NMR coupling constants: 1J(NH) in NH3 as a function of pyramidality. J. Mol. Struct. THEOCHEM. 1998;433(1-3):141-150.
http://dx.doi.org/10.1016/S0166-1280(98)00020-7