Far-Infrared Spectrum of Al2O3:V4+

Abstract

Two far‐infrared lines, 28.1 and 52.8 cm⁻¹, were observed in three different vanadium corundum samples. These lines are interpreted as transitions from the ground state to the first two excited states of Al₂O₃:V⁴⁺. Oxidation and x‐ray irradiation data support this assignment. As with the isoelectronic Ti³⁺ ion in Al₂O₃, the number of levels is as predicted by crystal‐field theory, but their spacing is much less. The far‐infrared spectrum of Al₂O₃:V⁴⁺ reported here is in substantial agreement with the results of a recent calculation of ${\text{3d}}^1$ impurity ions in Al₂O₃:V⁴⁺ in which crystal‐field theory is extended by including the dynamic Jahn–Teller effect. It also is consistent with the observation of a new spin resonance spectrum at 4.2°K in vanadium corundum attributed to Al₂O₃:V⁴⁺. The widths of these lines have been measured as a function of temperature and explained satisfactorily on the basis of lifetime broadening due to direct phonon processes. The frequency shifts of these lines as a function of temperature have also been measured, but the data are still not well understood at the present time.