Artículos de revistas
Analysis of Canonical Molecular Orbitals to Identify Fermi Contact Coupling Pathways. 1. Through-Space Transmission by Overlap of P-31 Lone Pairs
Registro en:
Journal Of Physical Chemistry A. Amer Chemical Soc, v. 114, n. 2, n. 1044, n. 1051, 2010.
1089-5639
WOS:000273400600045
10.1021/jp908970f
Autor
Contreras, RH
Gotelli, G
Ducati, LC
Barbosa, TA
Tormena, CF
Institución
Resumen
Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) In this work, a new approach to studying Coupling pathways for the Fermi contact term of NMR spin-spin Coupling constants (SSCCs) is presented. It is based on the known form of propagating the Fermi hole through a canonical Molecular orbital (CMO). It requires having an adequate spatial description of the relevant canonical molecular orbitals, which are obtained by expanding CMOs in terms of natural bond orbitals (NBOs). For detecting the relevant contributions of CMOs to it given Fermi contact (FC) pathway, the description of the FC in terms of the triplet polarization propagator (PP) is used. To appreciate the potential of this approach, dubbed FCCP-CMO (Fermi contact coupling pathways-CMO), it is applied to analyze the through-space transmission of the FC term of J(PP) SSCCs by overlap of the P lone pairs. This method can be applied using well-known quantum chemistry software without any further modification, which makes it appealing for use as a complement to SSCC Measurements by NMR spectroscopy. 114 2 1044 1051 CONICET [5119/05] UBACYT [X-047] Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) CONICET [5119/05] UBACYT [X-047] FAPESP [06/03980-2, 08/06282-0]