Investigations of the optical and EPR spectra for (NiX6)4− (X=Cl, Br, I) clusters

Abstract In this paper, the formulae of optical spectral levels and electron paramagnetic resonance (EPR) spectra in trigonal symmetry of 3d 8 ions are established on the basis of strong field mechanism and a two spin-coupling (SO) parameters model. Unlike the classical crystal-field approach which has only taken the SO coupling of the central metal ions into account, the contribution of the SO coupling of the ligand ions to the optical and EPR spectra has been included in these formulae. When the optical and EPR spectra of the strong covalent crystals are calculated, the reasonable results can be obtained if the two SO parameters model has been put into action. As an application, the optical and EPR spectra of the (NiX 6 ) 4− clusters in CsMgX 3 :Ni 2+ (X=Cl, Br, I) crystals have been studied by the complete diagonalization (of energy matrix) method (CDM). The calculated results agree well with experimental findings. From the investigations, a more valid method to calculate the optical and EPR spectra for 3d 8 ions clusters is provided.