Polarization propagator analysis of the through space transmission of spin—spin coupling constants by overlap of lone pairs

Abstract

Abstract The inner projections of the polarization propagator (IPPP) technique together with the decomposition into contributions from localized orbitals within the polarization propagator approach (CLOPPA) are applied to study different features of the spin—spin coupling constants between atoms bearing lone pairs which overlap to a considerable extent. Model compounds are chosen to study 4 J (FN), 2 J (FN), 2 J (PP) and 2 J (SeSe) couplings. Calculations are performed at the INDO level. Total calculated couplings are in reasonable agreement with experimental values. Through space transmitted components as well as total couplings are analyzed yielding insight into factors affecting both the polarization propagator and the perturbations. It is found that only the F and Se lone pairs with the largest s character make significant contributions to the through space transmission of the Fermi contact interaction.