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Infrared signatures of OH-defects in wadsleyite: A first-principles study

  • Marc Blanchard EMAIL logo , Mathilde Roberge , Etienne Balan , Guillaume Fiquet and Hélène Bureau
Published/Copyright: March 7, 2015
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American Mineralogist
From the journal American Mineralogist Volume 98 Issue 11-12

Abstract

The structure and the polarized infrared absorption spectrum of OH-defects in wadsleyite (β-Mg2SiO4) are studied, at 0 and 15 GPa, by first-principles calculations based on density functional theory (DFT). Four types of OH-defects are considered: fully protonated magnesium vacancies, fully protonated silicon vacancies, silicon vacancies compensated by a magnesium cation and two protons, and OH-defects associated with the migration of a silicon cation to a normally vacant site, as reported by Kudoh and Inoue (1999). The results suggest that the main absorption band constituted by a doublet (3326 and 3360 cm-1) corresponds to at least two types of OH-defects involving M3 vacancies with protonation of the O1-type O atoms along the O1...O4 edges. The main contribution of the less intense band at 3581 cm-1 is likely related to the partial protonation of a silicon vacancy (protonation of the O3-type oxygen) associated with the migration of the silicon cation to the Si2 site. This assignment is consistent with several experimental constraints: wavenumber and pleochroism of infrared OH-stretching bands, pressure-dependence of the band wavenumber, evidence from X‑ray diffraction of magnesium vacancies in M3 site, and increase of the b/a axial ratio with water content. The integrated absorption coefficients of the corresponding OH-defects are also calculated and thus complement the set of data obtained previously for forsterite and ringwoodite. Absorption coefficients of wadsleyite computed at 0 and 15 GPa indicate that for a precise quantification of the hydrogen content in in situ experiments, one must consider higher absorption coefficients than those determined at 0 GPa after quench. It is also shown that a single theoretical relation can account for the three Mg2SiO4 polymorphs at 0 GPa: Kint = 278.7 ± 18.1 (3810 ± 465 - x), where Kint is the integrated molar absorption coefficient of the OH stretching modes and x is the average wavenumber in cm-1. Absorption coefficients are significantly lower than the general calibrations, the use of which would lead to an underestimation of the water concentrations

Keywords : Wadsleyite; OH-defect; IR spectroscopy; ab initio calculations; DFT
Received: 2013-1-15
Accepted: 2013-7-1
Published Online: 2015-3-7
Published in Print: 2013-11-1

© 2015 by Walter de Gruyter Berlin/Boston

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  3. Amorphous Materials: Properties, structure, and durability. North American microtektites are more oxidized than tektites
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  26. Melting and subsolidus phase relations in the system Na2CO3-MgCO3±H2O at 6 GPa and the stability of Na2Mg(CO3)2 in the upper mantle
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https://doi.org/10.2138/am.2013.4468
Keywords for this article
Wadsleyite; OH-defect; IR spectroscopy; ab initio calculations; DFT

Articles in the same Issue

  1. Highlights and Breakthroughs. Lessons from a lost technology: The secrets of Roman concrete
  2. Crossroads in Earth and Planetary Materials. H-D interdiffusion in brucite at pressures up to 15 GPa
  3. Amorphous Materials: Properties, structure, and durability. North American microtektites are more oxidized than tektites
  4. Actinides in Geology, Energy, and the Environment. Vorlanite, (CaU6+)O4, from Jabel Harmun, Palestinian Autonomy, Israel
  5. What Lurks in the Martian Rocks and Soil? Investigations of Sulfates, Phosphates, and Perchlorates. Mössbauer parameters of iron in sulfate minerals
  6. What Lurks in the Martian Rocks and Soil? Investigations of Sulfates, Phosphates, and Perchlorates. Looking for jarosite on Mars: The low-temperature crystal structure of jarosite
  7. Compressibility and structural stability of two variably hydrated olivine samples. (FO97Fa3) to 34 GPa by X-ray diffraction and Raman spectroscopy
  8. Interaction between composition and temperature effects on non-bridging oxygen and high-coordinated aluminum in calcium aluminosilicate glasses
  9. Topotactic transformation and dehydration of the zeolite gismondine to a novel Ca feldspar structure
  10. The origin of melanophlogite, a clathrate mineral, in natrocarbonatite lava at Oldoinyo Lengai, Tanzania
  11. Clay mineral evolution
  12. Experimental determination of solubilities of sodium tetraborate (borax) in NaCl solutions, and a thermodynamic model for the Na-B(OH)3-Cl-SO4 system to high-ionic strengths at 25 °C
  13. Thermodynamic basis for evolution of apatite in calcified tissues
  14. A first-principles calculation of the elastic and vibrational anomalies of lizardite under pressure
  15. Acoustic velocity measurements for stishovite across the post-stishovite phase transition under deviatoric stress: Implications for the seismic features of subducting slabs in the mid-mantle
  16. A new framework topology in the dehydrated form of zeolite levyne
  17. Mid- and far-infrared spectra of synthetic CaMg2(Al4–xGax)(Si1–yGey)O10(OH,OD)2- clintonite: Characterization and assignment of the Ca-Oinner and Ca-Oouter stretching bands
  18. Mechanism of mineral transformations in krennerite, Au3AgTe8, under hydrothermal conditions
  19. Cubic perovskite polymorph of strontium metasilicate at high pressures
  20. Size distributions of nanoparticles from magnetotactic bacteria as signatures of biologically controlled mineralization
  21. Medium-range order in disordered K-feldspars by multinuclear NMR
  22. Infrared signatures of OH-defects in wadsleyite: A first-principles study
  23. K-Ar dating and δ18O-δD characterization of nanometric illite from Ordovician. K-bentonites of the Appalachians: Illitization and the Acadian-Alleghenian tectonic activity
  24. New morphological, chemical, and structural data of woolly erionite-Na from Durkee, Oregon, U.S.A.
  25. New experimental data on phase relations for the system Na2CO3-CaCO3 at 6 GPa and 900–1400 ºC
  26. Melting and subsolidus phase relations in the system Na2CO3-MgCO3±H2O at 6 GPa and the stability of Na2Mg(CO3)2 in the upper mantle
  27. A critical comment on Ertl et al. (2012): “Limitations of Fe2+ and Mn2+ site occupancy in tourmaline: Evidence from Fe2+- and Mn2+-rich tourmaline”
  28. Letter. Developing vanadium valence state oxybarometers (spinel-melt, olivine-melt, spinel-olivine) and V/(Cr+Al) partitioning (spinel-melt) for martian olivine-phyric basalts
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