Illumination of the effect of the overlap of lone-pairs on indirect nuclear spin-spin coupling constants

The effect of electron lone-pairs on the Fermi-contact (FC) contribution to indirect nuclear spin-spin coupling constants is analyzed using new tools for their interpretation. In particular, visualization of spin-spin coupling pathways using the coupling deformation density (CDD) has been employed. Furthermore, the recently developed perturbation-stable localization procedure has been applied for decomposition of CDD and the calculated value of couplings into contributions from localized molecular orbitals (LMOs). Correlation between the overlap of densities of LMOs representing lone-pairs and the Fermi-contact contribution to spin-spin coupling constants has been demonstrated. A new way for analyzing spin-spin couplings using the expansion of CDD as a linear combination of the products of molecular orbitals has been suggested. The considered examples include two-and three-bond phosphor-phosphor couplings. Significance of the obtained insight is not restricted to spin-spin couplings of nuclei possessing lone-pairs, as demonstrated in the example of vicinal hydrogen-hydrogen coupling in ethane.