Optical Spectrum of Re4+ in Single Crystals of K2PtCl6 and Cs2ZrCl6 at 4.2°K

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Abstract
The optical spectrum of Re4+(5d3) has been studied at 4.2°K in single crystals of K2PtCl6 and Cs2ZrCl6. The spectrum is characterized by extremely narrow lines in the region from 8500 to 36 000 cm−1. Vibrational structure is observed which is assigned to the odd modes of the ReCl62− complex. A crystal‐field analysis of the 0–0 transitions fits the observed eight electronic transitions with an rms deviation of 209 cm−1 for the parameters A = 0, B = 327 cm−1, C = 1818 cm−1, V = 30 347 cm−1, and λ5d=2392 cm−1. Magnetic‐field measurements of the excited states give g values which are compared with theory. A discussion of the intensities of the transitions is presented which demonstrates that some absorptions observed are magnetic‐dipole transitions. Finally, several conclusions about the study of optical spectra of dn systems are presented.