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Beryl-II, a high-pressure phase of beryl: Raman and luminescence spectroscopy to 16.4 GPa

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Abstract

The Raman and Cr3+ and V2+ luminescence spectra of beryl and emerald have been characterized up to 15.0 and 16.4 GPa, respectively. The Raman spectra show that an E 1g symmetry mode at 138 cm−1 shifts negatively by −4.57 (±0.55) cm−1/GPa, and an extrapolation of the pressure dependence of this mode indicates that a soft-mode transition should occur near 12 GPa. Such a transition is in accord with prior theoretical results. Dramatic changes in Raman mode intensities and positions occur between 11.2 and 15.0 GPa. These changes are indicative of a phase transition that primarily involves tilting and mild distortion of the Si6O18 rings. New Raman modes are not observed in the high-pressure phase, which indicates that the local bonding environment is not altered dramatically across the transition (e.g., changes in coordination do not occur). Both sharp line and broadband luminescence are observed for both Cr3+ and V2+ in emerald under compression to 16.4 GPa. The R-lines of both Cr3+ and V2+ shift to lower energy (longer wavelength) under compression. Both R-lines of Cr3+ split at ~13.7 GPa, and the V2+ R1 slope changes at this pressure and shifts more rapidly up to ~16.4 GPa. The Cr3+ R-line splitting and FWHM show more complex behavior, but also shift in behavior at ~13.7 GPa. These changes in the pressure dependency of the Cr3+ and V2+ R-lines and the changes in R-line splitting and FWHM at ~13.7 GPa further demonstrate that a phase transition occurs at this pressure, in good agreement with our Raman results. The high-pressure phase of beryl appears to have two Al sites that become more regular under compression. Hysteresis is not observed in our Raman or luminescence spectra on decompression, suggesting that this transition is second order in nature: The occurrence of a second-order transition near this pressure is also in accord with prior theoretical results. We speculate that the high-pressure phase (beryl-II) might be a mildly modulated structure, and/or that extensive twinning occurs across this transition.

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Notes

  1. http://www.crystal.unito.it/vibs/beryl.

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Acknowledgments

Constructive and insightful comments from M. Prencipe and an anonymous reviewer, and helpful discussions with M. Merlini and C.M. Beavers, greatly improved the quality of this manuscript. E. O’Bannon thanks Juan Diego Prieto for the emerald sample. We thank Dan Sampson for invaluable technical assistance with the Raman spectrometer and Rob Franks for help with the trace element analysis. Work was partially supported by NSF through EAR-1215745, and COMPRES, the Consortium for Materials Properties Research in Earth Sciences under NSF Cooperative Agreement EAR 11-57758. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

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  1. Department of Earth and Planetary Sciences, University of California, Santa Cruz, 1156 High Street, Santa Cruz, CA, 95064, USA

    Earl O’Bannon III & Quentin Williams

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  1. Earl O’Bannon III
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Correspondence to Earl O’Bannon III.

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O’Bannon, E., Williams, Q. Beryl-II, a high-pressure phase of beryl: Raman and luminescence spectroscopy to 16.4 GPa. Phys Chem Minerals 43, 671–687 (2016). https://doi.org/10.1007/s00269-016-0837-2

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