Viewpoint 8 : polarization propagator analysis of spin-spin coupling constants

Abstract

The analysis of electronic mechanisms that define indirect NMR spin-spin coupling constants can be efficiently carried out by combining the polarization propagator formalism with the use of localized molecular orbitals. This approach is applied to study several trends of one-bond couplings along the Periodic Table when one of the coupled nuclei bears a lone pair. This analysis is preceded by a revision of the fundamentals of the method in which its approximations, shortcomings and capabilities are commented on. A brief overview of results already pub- lished in the literature is also given. The relationship between the classical approach of Pople and Santry and the polarization propagator 249 calculation of the Fermi contact term is discussed. zy