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Temperature dependence of Raman shifts and line widths for Q0 and Q2 crystals of silicates, phosphates, and sulfates

  • H. Wayne Nesbitt EMAIL logo , G. Michael Bancroft and Grant S. Henderson
Published/Copyright: May 28, 2018
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American Mineralogist
From the journal American Mineralogist Volume 103 Issue 6

Abstract

The temperature dependence of Raman shifts and line widths (full-width at half maxima or FWHM) for the A1 symmetric stretch of TO4 (T = Si, P, S) have been analyzed for nine alkali and alkaline earth silicates, phosphates, and sulfates. In crystalline silicates, the Q0 and Q2 species Raman shifts decrease with temperature, whereas FWHM increase. The strikingly similar behavior of Q0 and Q2 in silicates and Q0 in phosphates makes it possible to estimate to within ±4 cm−1 Raman shifts up to ~1000 K. Similarly systematic increases in FWHM with temperature can be estimated to within ±5 cm−1 up to ~1400 K. The type of element centering TO4 (i.e., Si, P, or S) has no appreciable effect on the temperature dependence of Raman shifts or line widths; the local environment of the Q0 and Q2 tetrahedra is the primary determinant of the temperature dependence. The type of cation in the first coordination sphere of the tetrahedron may have a secondary effect by affecting Heisenberg lifetimes of Raman virtual states.

Previous theoretical considerations have been modified to include the effect of the Heisenberg (or natural) lifetime on Raman FWHM. This contribution is required to explain the anomalous FWHM of Li2SiO3 relative to the FWHM of isostructural Na2SiO3 and the large Li2SO4 and Li3PO4 FWHM (relative to Ba and Sr phosphates). The theoretically based expressions dictate a necessary, simple relationship among temperature, Raman shift, and FWHM. The relationship is developed and it allows, with one measurement of Raman shift and FWHM (e.g., measured at 298 K), prediction of Raman shifts and FWHM of Q0 and Q2 crystals to within 5 cm−1 up to ~1500 K. The properties of the TO4 moiety (T = Si, P, S) are mostly responsible for the striking regularity of Raman shifts and FWHM, although alkali and alkaline earth cations affect to varying extent Heisenberg lifetimes, hence FWHM.

Keywords: Raman shifts in crystals; Raman line widths in crystals; temperature dependence of Raman shifts; temperature dependence of Raman line widths

Acknowledgments

The authors acknowledge logistical support provided by their associated universities. We thank Yang Song for sending us papers on phosphates by Zhai and associates. The authors are especially thankful to the managing editor, Sergio Speziale, Charles LeLosq, and another reviewer for their detailed editing of the manuscript. The manuscript has been improved greatly due primarily to their efforts.

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Received: 2017-9-26
Accepted: 2018-2-19
Published Online: 2018-5-28
Published in Print: 2018-6-26

© 2018 Walter de Gruyter GmbH, Berlin/Boston

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https://doi.org/10.2138/am-2018-6314
Keywords for this article
Raman shifts in crystals; Raman line widths in crystals; temperature dependence of Raman shifts; temperature dependence of Raman line widths

Articles in the same Issue

  2. Crystallography on Mars: Curiosity’s Bragging right
  4. Al diffusion in quartz
  6. Relationships between unit-cell parameters and composition for rock-forming minerals on Earth, Mars, and other extraterrestrial bodies
  8. Crystal chemistry of martian minerals from Bradbury Landing through Naukluft Plateau, Gale crater, Mars
  10. Petrogenesis of martian sulfides in the Chassigny meteorite
  12. Immiscible sulfide melts in primitive oceanic magmas: Evidence and implications from picrite lavas (Eastern Kamchatka, Russia)
  14. Snapshots of primitive arc magma evolution recorded by clinopyroxene textural and compositional variations: The case of hybrid crystal-rich enclaves from Capo Marargiu Volcanic District (Sardinia, Italy)
  16. Three-dimensional distribution of primary melt inclusions in garnets by X-ray microtomography
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  20. Determination of Al/Si order in sillimanite by high angular resolution electron channeling X-ray spectroscopy, and implications for determining peak temperatures of sillimanite
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