Theoretical Studies of the Spin Hamiltonian Parameters and Local Structures for WO3 Doped Zn3(PO4)2ZnO Nanopowders

The spin Hamiltonian parameters (SHPs) and the local structures for impurity W5+ in the Zn3(PO4)2ZnO nanopowders doped with WO3 under different concentrations are theoretically investigated using the perturbation calculations of these parameters. The exponential functions of the related quantities (cubic field parameter Dq, covalency factor N, relative tetragonal compression ratio τ and core polarisation constant κ) of concentration x with totally four adjustable coefficients a, b, c and d are adopted to fit the concentration dependences of the experimental d-d transition bands and SHPs. The impurity W5+ centres demonstrate moderate tetragonal compression ratios τ (∼3.1%) due to the Jahn–Teller effect. With the increase of WO3 concentration, Dq and N show moderately decreasing rules, while τ and κ exhibit slightly and moderately increasing tendencies with x, respectively. The mechanisms of the above concentration dependences of these quantities are analysed from the modifications of the local crystal-field strength and electron cloud density around the impurity W5+ with the variation of x. Present theoretical studies would be useful to the exploration of the structural properties and optical applications for WO3 doped Zn3(PO4)2ZnO nanopowders. GRAPHICAL ABSTRACT