Ab initio calculations of erbium crystal field splittings in oxide hosts: role of the 4f radial wave function

Abstract

We expand here our description of a newly developed simple and effective ab initio method of calculating crystal field coefficients (CFCs) of rare-earth atoms in insulating hosts, focusing on Er in wide band gap oxide hosts MgO, ZnO, TiO$_2$, CaWO$_4$, and PbWO$_4$, which exemplify different local site symmetries. These hybrid functional calculations, which incorporate a portion of exact exchange from Hartree-Fock theory, reproduce the experimentally identified insulating band gaps of these oxides. The negative values of cohesive and formation energies confirm the structural and chemical stability of these oxides, whereas the defect formation energies indicate that Er doped ZnO, CaWO$_4$, and PbWO$_4$ are easier to form compared to Er doped MgO and TiO$_2$. Er doped in these oxide hosts exhibits a spin magnetic moment of $\sim$ 3 $\mu_B$ confirming the $3+$ valence state. The CFCs of these hosted Er are determined from charge densities and potentials obtained from non-spin-polarized calculations, involving a 4\textit{f} core approximation. These CFCs are subsequently used to solve an effective Hamiltonian and generate the crystal field splitting of Er 4f. These calculated Er 4f energy levels are in good agreement with available experiments.