Abstract
Polarized low-temperature absorption spectra of V 4+ doped crystals of Mg 2SiO 4 and Ca 2GeO 4 are presented and discussed. The 2 E → 2 T 2 ligand field (LF) transition peaks in the near infrared around 12000 cm −1. The spectra are interpreted in terms of a stepwise T d → C 3v → C s symmetry reduction of VO 4 4− and analyzed within the framework of the angular overlap model (AOM). The onset to the lowest energy ligand-to-metal charge-transfer transition lies in the UV above 35000 cm −1. Upon photoexcitation in the visible, neither of the two systems exhibits luminescence even at cryogenic temperatures. From a comparison of the fine structure in the absorption spectra of VO 4 4− and the isoelectronic MnO 4 2− ion, this is shown to be due to efficient multiphonon relaxation from the 2T 2 LF state.
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