First-principles relativistic calculation for 4f–5d transition energy of Ce3+ in various fluoride hosts

In this paper, we investigated the 4f–5d transition energy of Ce3+ in various fluoride hosts based on the first-principles discrete-variational Dirac–Slater (DV-DS) calculations using Slater's transition-state theory. Especially, we focused on the lowest energy peak (1st peak) of 4f–5d transition for Ce3+ impurities. As the host crystals, we adopted the 15 fluorides, for which the experimental data of the lowest energy peak (1st peak) in 4f–5d transitions were available from literature except for NaMgF3 and BaMgF4. A high correlation between the experimental 1st peak energies and the theoretical ones was obtained which suggests a possibility to predict the 4f–5d transition energy of Ce3+ in various fluoride hosts using the first-principles calculation.

Graphical abstractCorrelation diagram between the experimental 1st peak energy and the theoretical 1st peak energy. The left figure (A) shows the results without the lattice relaxation by correction of bond length and right one (B) shows the results with the lattice relaxation by correction of bond length. The corresponding coefficients of correlation R are 0.78 and 0.98, respectively.Figure optionsDownload full-size imageDownload as PowerPoint slide