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The study of the effect of ligand and modifier ions on the spectroscopic properties of dn or fn elements in vitreous materials is important for the development of controllable lasers and amplifiers. The spectroscopic characteristics of inorganic compounds of transition elements and their solutions are well understood theoretically in the spectrochemistry of complexes, but developments for vitreous materials in these conditions are often well-documented. This work offers to fill the gap by applying the ligand field theory of solid materials to the vitreous state, and presenting the data obtained from luminescence, electron absorption spectra and electron paramagnetic resonance.