EPR, Optical Absorption and Superposition Model Studies of Fe3+-Doped Diammonium Hexaaqua Magnesium Sulfate: A Case of Hyperfine Structure

Abstract

An electron paramagnetic resonance (EPR) study of Fe3+-doped diammonium hexaaqua magnesium sulphate single crystal is carried out at liquid nitrogen temperature. EPR spectrum shows two sites. The spin-Hamiltonian parameters are evaluated from angular variation of observed hyperfine lines. Fe3+ ion enters the host lattice substitutionally at site I, replacing Mg2+, whereas it enters interstitially at site II. The local site symmetry of Fe3+ ion within the host lattice is orthorhombic. An optical absorption study is performed at room temperature. Using the optical absorption spectrum the bands are assigned and the Racah parameters (B and C) and cubic crystal field splitting parameter Dq are determined. The nature of metal–ligand bonding in the crystal is determined using EPR and optical data. Crystal field parameters and zero-field splitting parameters (ZFSPs) are evaluated theoretically for both the sites using superposition model and microscopic spin Hamiltonian together with perturbation equations, respectively. The theoretically evaluated ZFSPs are in good agreement with the experimental values.