Nuclear spin-spin coupling constants from regular approximate relativistic density functional calculations. II. Spin-orbit coupling effects and anisotropies

摘要

Based on our recently published two-component relativistic formulation of the nuclear spin-spin coupling hyperfine terms, we present a full implementation into the Amsterdam Density Functional program. The scalar relativistic code has been extended to include the relativistic analogue of the spin-dipole operator in the coupling calculations, which can now in addition be based on two-component spin-orbit coupled Kohn-Sham orbitals. One-bond coupling constants for some plumbanes are in good agreement with experiment, slightly improving the scalar relativistic values. Coupling constants and anisotropies for the XF (X = Cl, Br, I) and T1X (X = F, Cl, Br, I) series are compared to experimental data and for CIF additionally to recently published ab initio calculations. The spin-dipole term contributes largely to the coupling constants in XF. Spin-orbit effects are essential for the T1X couplings, where they can yield the most important contributions. In addition, data is reported for the benchmark systems ethane, ethene, and ethyne.