Vibrational and electronic spectra of alkali halides doped with CrO42− ions

The i.r. spectra of alkali halides doped with FrO₄^2? ions are very sensitive to the concentration of background divalent impurities. Highly pure crystals containing CrO₄^2? ions show a 5 line i.r. spectrum in the v₃ stretch frequency region. One of these lines is attributed to CrO₄^2? ions in perfect crystal surroundings having T_d symmetry and the other 4 lines are attributed to C_s symmetry produced by a charge compensating anion vacancy in the nearest neighbour position. If the crystal contains a concentration of divalent cation impurity which is equal to or more than that of CrO₄^2? ions, a different spectrum characteristic of C_2x symmetry as well as the line corresponding to T_d symmetry are obtained. The crystals of ordinary purity contain all the three (C_s, C_2x and T_d symmetry) species and show eight line spectra. The changes in force constants calculated from the observed splitting of the energy levels agree with those evaluated from the known polarizability of the chromate ions.At 600°C, the vibration spectra of the highly pure crystals doped with CrO₄^2? ions show an increase in intensity of the line characteristic of T_d symmetry and the other lines practically disappear, because the anion vacancies move away from the neighbourhood of the CrO₄^2? ions at high temperatures. The energy of association of the vacancy with CrO₄^2? ions and the energy of migration of the vacancy are derived from the spectra obtained at different temperatures and with different heat treatments.The electronic spectra of the crystals show 3 bands (at 345, 270 and 240 nm for KCI). The lowest energy band has a fine structure with a spacing of about 800 cm^?1 at LAT. Since the transition involved is from a non-bonding to an antibonding state, the Condon parabola is shifted in the excited state and therefore the fine structure is attributed to a vibrational progression involving a totally symmetric frequency 800 cm^?1 in the excited state.