Assessment of First‐Principles and Semiempirical Methodologies for Absorption and Emission Energies of Ce3+‐Doped Luminescent Materials

In search of a reliable methodology for the prediction of light absorption and emission of Ce3+-doped luminescent materials, 13 representative materials are studied with first-principles and semiempirical approaches. In the first-principles approach, that combines constrained density-functional theory and ∆SCF, the atomic positions are obtained for both ground and excited states of the Ce3+ ion. The structural information is fed into Dorenbos' semiempirical model. Absorption and emission energies are calculated with both methods and compared with experiment. The first-principles approach matches experiment within 0.3 eV, with two exceptions at 0.5 eV. In contrast, the semiempirical approach does not perform as well (usually more than 0.5 eV error). The general applicability of the present first-principles scheme, with an encouraging predictive power, opens a novel avenue for crystal site engineering and high-throughput search for new phosphors and scintillators.