Mixed-Valence Lanthanide-Activated Phosphors: Invariance of the Intervalence Charge Transfer (IVCT) Absorption Onset across the Series

Abstract

Recently, direct evidence was given for the existence of intervalence charge transfer (IVCT) states of Eu2+/Eu3+ pairs in Eu-doped fluorite hosts and their signature in absorption spectra was characterized [J. Phys. Chem. Lett. 2019, 10, 1851]. Here we show, by means of multiconfigurational ab initio calculations, that the IVCT absorptions of all 2+/3+ mixed valence lanthanides doped in CaF2 start basically at the same energy. This is rationalized with a simplified model of IVCT absorptions. Emissions above that energy are expected to be partly or totally quenched when 2+/3+ pairs are formed. On the basis of this finding and existing calculations, we report expected IVCT absorptions of mixed valence lanthanides doped in several fluoride, oxide, and sulfide hosts.