Topaz and Kyanite Luminescence Under High Pressure

Monday, 15 December 2014
Earl F O'Bannon III and Quentin C Williams, University of California Santa Cruz, Santa Cruz, CA, United States
The luminescence spectra of Cr3+ in heat-treated topaz Al2SiO4(OH,F)2 and natural kyanite Al2SiO5  were measured from 650 - 800 nm in a hydrostatic environment up to pressures of 15 GPa. The R1 and R2 peaks of topaz shift at average rates of 0.30 nm/GPa and 0.22 nm/GPa, respectively, implying that the deformation of the Cr3+ octahedra increases with pressure. Three peaks are fit under each R line of topaz at both room and high pressure, and these peaks are associated with different Al sites into which the Cr substitutes. The shift of the R lines in topaz under pressure is remarkably linear, which appears to be a general feature of many Cr3+-bearing oxides: the underlying cause of this linearity may lie in anharmonic coupling with lattice vibrations. In this context, we also characterize the frequency shifts of two vibronic peaks within topaz. The R1 and R2 peaks of kyanite shift at 0.37 nm/GPa and 0.88 nm/GPa respectively. Two peaks are fit under R1 and three peaks are fit under R2 of kyanite at both room and high pressure; this result is also consistent with three different Cr3+ sites in this material. The R lines in kyanite are notably optically anisotropic, depending strongly on crystallographic orientation: this is most strongly manifested in the R2 peak. The Cr3+ luminescence in these materials provides a sensitive probe of pressure-dependent shifts in the local geometry of the Al-sites in these materials, which are analyzed in the context of previous single-crystal x-ray diffraction measurements.