Electronic and vibrational spectra of MnO2?4 in KBr crystals

Two new features have been observed in the electronic spectrum of KBr crystals doped heavily with MnO^2?₄ ions. The band at 870 nm is assigned to the crystal field transition e → t₂. The band at 600 nm shows a series of vibrational sub-bands at an interval of 740cm^?1 and is ascribed to the coupling between electronic transition and totally symmetric mode of the ion.A line at 830cm^?1, ascribed to totally symmetric mode v₁(A₁), has been observed for the first time in the Raman spectrum. I.R. spectrum of KBr: MnO^2?₄ shows four lines—one due to MnO^2?₄ in Td symmetry and the other three to the split components of v₃(T₂) for MnO^2?₄ in Cs symmetry. I.R. spectrum of KBr: MnO^2?₄: Ca²⁺ shows another s of four lines—one due to MnO^2?₄ in Td symmetry and the other three to the v₃(T₂) mode of the ion in C_2v symmetry. The v₁(A₁) line could not be observed in the i.r. spectra.