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

CLAUDIA G. GIRIBET; MARTÍN RUIZ DE AZÚA; RUBÉN H. CONTRERAS; ROSANA LOBAYAN; GUSTAVO A. AUCAR

JOURNAL OF MOLECULAR STRUCTURE

ELSEVIER SCIENCE BV

Lugar: Amsterdam; Año: 1993 vol. 300 p. 467 - 477

0022-2860

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 4J(FN), 2J(FN), 2J(PP) and´ 2J(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 propagato; 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 FC contribution