Theoretical investigations of the local structures and the g factors for 3d9 ions in CdS

The local structures and the g factors g _// and g _⊥ for the isoelectronic 3d⁹ ions Cu²⁺ and Ni⁺ in CdS are theoretically investigated from the perturbation formulas of these parameters for a 3d⁹ ion under trigonally distorted tetrahedral environments. In consideration of significant covalency of the [MS₄] combinations (M = Cu and Ni), the ligand orbital and spin–orbit coupling contributions are taken into account using the cluster approach. Based on the studies, the substitutional impurity Cu²⁺ (or Ni⁺) on Cd²⁺ site is found to undergo a small inward displacement 0.026 Å (or a slight outward shift 0.017 Å) towards (or away from) the ligand triangle along C ₃ axis. The theoretical g factors for both ions based on the above impurity displacements are in good agreement with the experimental data.