Theoretical studies of the spin Hamiltonian parameters and local structures for Cs3CoX5 (X = Cl, Br)

The spin Hamiltonian (SH) parameters (zero-field splitting D and anisotropic g factors g|| and g⊥) and local structures for Cs3CoX5 (X = Cl, Br) are theoretically studied from the perturbation formulas of the SH parameters for a 3d7 ion in tetragonally distorted tetrahedra based on the cluster approach. In these formulas, both the contributions from the crystal-field (CF) mechanism and those from the charge-transfer (CT) mechanism are taken into account. It is found that the [CoX4]2− clusters are slightly elongated and the tetragonal distortion angles Δθ(=θ − θ0, where θ0 ≈ 54.74 ° is the bonding angle related to the C4-axis in regular tetrahedra) are about −1.68° and −1.71° for X = Cl and Br, respectively. The calculated SH parameters as well as the effective magnetic moments based on the above angles are in reasonable agreement with the observed values. From the studies, the importance of the contributions to the SH parameters from the CT mechanism increases with increasing the spin–orbit coupling coefficient of the ligand, i.e., Cl− < Br−. The results are compared with those obtained from the conventional crystal-field model in the previous works.