An ESR and optical study of V4+ in zircon-type crystals

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Abstract
The electron spin resonance and polarized optical absorption spectra of V4+ have been studied in single crystals of ZrSiO4, HfSiO4, ThSiO4, and ThGeO4, each having the zircon structure. The principal values of g and A in ZrSiO4 and HfSiO4 are found to be anomalous and significantly different from those of ThSiO4 and ThGeO4. The optical spectra suggest that V4+ enters the tetrahedral rather than the dodecahedral site. The spectra are all similar except for the observation of strong D2d‐ forbidden transitions in ZrSiO4 and HfSiO4. We show that the optical and ESR data in these two crystals cannot be accounted for by conventional crystal field theory. We show that, while the dynamic Jahn–Teller effect can give a good account of the ESR data, the optical data are not consistent with this interpretation. We tentatively attribute the anomalies to dynamic local distortions of unknown origin.

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