Home Intervalence charge transfer in aluminum oxide and aluminosilicate minerals at elevated temperatures
Article
Licensed
Unlicensed Requires Authentication

Intervalence charge transfer in aluminum oxide and aluminosilicate minerals at elevated temperatures

  • Helen V. Evans and George R. Rossman ORCID logo EMAIL logo
Published/Copyright: November 29, 2024
Become an author with De Gruyter Brill

Abstract

Single-crystal optical spectra of corundum (Al2O3) and the Al2SiO5 polymorphs andalusite, kyanite, and sillimanite, containing both Fe2+-Fe3+ and Fe2+-Ti4+ intervalence charge transfer (IVCT) absorption bands were measured at temperatures up to 1000 °C. Upon heating, thermally equilibrated IVCT bands significantly decreased in intensity and recovered fully on cooling. These trends contrast with the behavior of crystal field bands at temperature for Fe, Cr, and V in corundum, kyanite, and spinel. The effects of cation diffusion and aggregation, as well as the redistribution of band intensity at temperature, are also discussed. The loss of absorption intensity in the visible and near-infrared regions of the spectrum of these phases may point to a more general behavior of IVCT in minerals at temperatures within the Earth with implications for radiative conductivity within the Earth.

Acknowledgments and Funding

Samples used in the study were obtained from Ed Grew, Paul Brian Moore, The American Museum of Natural History, Art Boettcher, William F. Larson, Ed Swobota, Richard Hughes, and John Emmett who is also thanked for several helpful discussions regarding corundum. This research was supported by grant EAR-2148727 from the National Science Foundation and by the White Rose Foundation.

References cited

Agui, A., Uozumi, T., Mizumaki, M., and Käämbre, T. (2009) Intermetallic charge transfer in FeTiO3 probed by resonant inelastic soft X-ray scattering. Physical Review B: Covering Condensed Matter and Materials Physics, 79, 092402, https://doi.org/10.1103/PhysRevB.79.092402.Search in Google Scholar

Agui, A., Mizumaki, M., and Uozumi, T. (2015) Intermetallic charge transfer in MTiO3 (M=Mn, Fe, Co, and Ni) by Ti 2p edge resonant inelastic X-ray scattering. Journal of Electron Spectroscopy and Related Phenomena, 205, 106–110, https://doi.org/10.1016/j.elspec.2015.08.017.Search in Google Scholar

Allen, G.C. and Hush, N.S. (1967) Intervalence-transfer absorption. Part 1. Qualitative evidence for intervalence-transfer absorption in inorganic systems in solution and in the solid state. Progress in Inorganic Chemistry, 8, 357–444, https://doi.org/10.1002/9780470166093.ch6.Search in Google Scholar

Amthauer, G. and Rossman, G.R. (1984) Mixed valence of iron in minerals with cation clusters. Physics and Chemistry of Minerals, 11, 37–51, https://doi.org/10.1007/BF00309374.Search in Google Scholar

Blasse, G. (1991) Optical electron transfer between metal ions and its consequences. Complex Chemistry, 153–187.Search in Google Scholar

Bristow, J.K., Tiana, D., Parker, S.C., and Walsh, A. (2014) Defect chemistry of Ti and Fe impurities and aggregates in Al2O3. Journal of Materials Chemistry A, 2, 6198–6208, https://doi.org/10.1039/C3TA15322C.Search in Google Scholar

Burnham, C.W. (1963) Refinement of the crystal structure of kyanite. Zeitschrift für Kristallographie, 118, 337–360, https://doi.org/10.1524/zkri.1963.118.5-6.337.Search in Google Scholar

Burns, R.G. (1993) Mineralogical Applications of Crystal Field Theory (2nd ed.), 576 p. Cambridge University Press.Search in Google Scholar

Dubinsky, E.V., Stone-Sundberg, J., and Emmett, J.L. (2020) A quantitative description of the causes of color in corundum. Gems & Gemology, 56, 1–27, https://doi.org/10.5741/GEMS.56.1.2.Search in Google Scholar

Emmett, J.L. and Douthit, T.R. (1993) Heat treating the sapphires of Rock Creek, Montana. Gems & Gemology, 29, 250–272, https://doi.org/10.5741/GEMS.29.4.250.Search in Google Scholar

Ferguson, J. and Fielding, P.E. (1971) The origins of the colours of yellow, green and blue sapphires. Chemical Physics Letters, 10, 262–265, https://doi.org/10.1016/0009-2614(71)80282-8.Search in Google Scholar

Ferguson, J. and Fielding, P.E. (1972) The origins of the colours of natural yellow, blue, and green sapphires. Australian Journal of Chemistry, 25, 1371–1385, https://doi.org/10.1071/CH9721371.Search in Google Scholar

Fritsch, E. and Rossman, G.R. (1988) An update on color in gems. Part 2: Colors involving multiple atoms and color centers. Gems & Gemology, 24, 3–15, https://doi.org/10.5741/GEMS.24.1.3.Search in Google Scholar

Geiger, C.A. and Taran, M.N. (2023) Single-crystal UV/Vis absorption spectroscopy of aluminosilicate garnet: Part III. {Fe2+} + [Fe3+] → {Fe3+} + [Fe2+] intervalence charge transfer. American Mineralogist, 108, 1171–1181, https://doi.org/10.2138/am-2022-8756.Search in Google Scholar

Grose, C.J. and Afonso, J.C. (2019) New constraints on the thermal conductivity of the upper mantle from numerical models of radiation transport. Geochemistry, Geophysics, Geosystems, 20, 2378–2394, https://doi.org/10.1029/2019GC008187.Search in Google Scholar

Hammarström, L. (2015) Accumulative charge separation for solar fuels production: Coupling light-induced single electron transfer to multielectron catalysis. Accounts of Chemical Research, 48, 840–850, https://doi.org/10.1021/ar500386x.Search in Google Scholar

Hofmeister, A.M. (2005) Dependence of diffusive radiative transfer on grain-size, temperature, and Fe-content: Implications for mantle processes. Journal of Geodynamics, 40, 51–72, https://doi.org/10.1016/j.jog.2005.06.001.Search in Google Scholar

Hunault, M.O.J.Y., Khan, W., Minár, J., Kroll, T., Sokaras, D., Zimmermann, P., Delgado-Jaime, M.U., and de Groot, F.M.F. (2017) Local vs Nonlocal States in FeTiO3 Probed with 1s2pRIXS: Implications for Photochemistry. Inorganic Chemistry, 56, 10882–10892, https://doi.org/10.1021/acs.inorgchem.7b00938.Search in Google Scholar

Hush, N.S. (1967) Intervalence-transfer absorption. Part 2. Theoretical considerations and spectroscopic data. In F.A. Cotton, Ed., Progress in Inorganic Chemistry, 8, 391–444. WileySearch in Google Scholar

Hush, N.S. (1968) Homogeneous and heterogeneous optical and thermal electron transfer. Electrochimica Acta, 13, 1005–1023, https://doi.org/10.1016/0013-4686(68)80032-5.Search in Google Scholar

Keppler, H. and Smyth, J.R. (2005) Optical and near infrared spectra of ringwoodite to 21.5 GPa: Implications for radiative heat transport in the mantle. American Mineralogist, 90, 1209–1212, https://doi.org/10.2138/am.2005.1908.Search in Google Scholar

Keppler, H., Dubrovinsky, L.S., Narygina, O., and Kantor, I. (2008) Optical absorption and radiative thermal conductivity of silicate perovskite to 125 gigapascals. Science, 322, 1529–1532, https://doi.org/10.1126/science.1164609.Search in Google Scholar

Lin, J., Speziale, S., Mao, Z., and Marquardt, H. (2013) Effects of the electronic spin transitions of iron in lower mantle minerals: Implications for deep mantle geophysics and geochemistry. Reviews of Geophysics, 51, 244–275, https://doi.org/10.1002/rog.20010.Search in Google Scholar

Livshits, M.Y., Turlington, M.D., Trindle, C.O., Wang, L., Altun, Z., Wagenknecht, P.S., and Rack, J.J. (2019) Picosecond to nanosecond manipulation of excited-state lifetimes in complexes with an FeII to TiIV metal-to-metal charge transfer: The role of ferrocene centered excited states. Inorganic Chemistry, 58, 15320–15329, https://doi.org/10.1021/acs.inorgchem.9b02316.Search in Google Scholar

Mattson, S.M. and Rossman, G.R. (1987a) Fe2+-Fe3+ interactions in tourmaline. Physics and Chemistry of Minerals, 14, 163–171, https://doi.org/10.1007/BF00308220.Search in Google Scholar

Mattson, S.M. and Rossman, G.R. (1987b) Identifying characteristics of charge transfer transitions in minerals. Physics and Chemistry of Minerals, 14, 94–99, https://doi.org/10.1007/BF00311152.Search in Google Scholar

Mattson, S.M. and Rossman, G.R. (1988) Fe2+-Ti4+ charge transfer in stoichiometric Fe2+,Ti4+-minerals. Physics and Chemistry of Minerals, 16, 78–82, https://doi.org/10.1007/BF00201333.Search in Google Scholar

McClure, D.S. (1962) Optical spectra of transition metal ions in corundum. The Journal of Chemical Physics, 36, 2757–2779, https://doi.org/10.1063/1.1732364.Search in Google Scholar

Moon, A.R. and Phillips, M.R. (1994) Defect clustering and color in Fe, Ti: α-Al2O3. Journal of the American Ceramic Society, 77, 356–367, https://doi.org/10.1111/j.1151-2916.1994.tb07003.x.Search in Google Scholar

Parkin, K.M., Loeffler, B.M., and Burns, R.G. (1977) Mössbauer spectra of kyanite, aquamarine, and cordierite showing intervalence charge transfer. Physics and Chemistry of Minerals, 1, 301–311, https://doi.org/10.1007/BF00307569.Search in Google Scholar

Platonov, A.N., Tarashchan, A.N., Langer, K., Andrut, M., Partzsch, G., and Matsyuk, S.S. (1998) Electronic absorption and luminescence spectroscopic studies of kyanite single crystals: Differentiation between excitation of FeTi charge transfer and Cr3+ dd transitions. Physics and Chemistry of Minerals, 25, 203–212, https://doi.org/10.1007/s002690050104.Search in Google Scholar

Rossman, G.R. (2024) Mineral Spectroscopy Server (dataset). California Institute of Technology, Pasadena, https://doi.org/10.7907/jywr-qq57.Search in Google Scholar

Rossman, G.R. and Taran, M.N. (2001) Spectroscopic standards for four- and fivefold-coordinated Fe2+ in oxygen-based minerals. American Mineralogist, 86, 896–903, https://doi.org/10.2138/am-2001-0713.Search in Google Scholar

Rossman, G.R., Grew, E.S., and Dollase, W.A. (1982) The colors of sillimanite. American Mineralogist, 67, 749–761.Search in Google Scholar

Rüscher, C.H. (2012) Temperature-dependent absorption of biotite: Small-polaron hopping and other fundamental electronic excitations. European Journal of Mineralogy, 24, 815–820, https://doi.org/10.1127/0935-1221/2012/0024-2200.Search in Google Scholar

Sherman, D.M. (1987a) Molecular orbital (SCF-Xα-SW) theory of metal-metal charge transfer processes in minerals: I. Application to Fe2+→Fe3+ charge transfer and “electron delocalization” in mixed-valence iron oxides and silicates. Physics and Chemistry of Minerals, 14, 355–363.Search in Google Scholar

Sherman, D.M. (1987b) Molecular orbital (SCF-Xα-SW) theory of metal-metal charge transfer processes in minerals: II. Application to Fe2+ → Ti4+ charge transfer transitions in oxides and silicates. Physics and Chemistry of Minerals, 14, 364–367, https://doi.org/10.1007/BF00309811.Search in Google Scholar

Smith, G. (1977) Low-temperature optical studies of metal-metal charge-transfer transitions in various minerals. Canadian Mineralogist, 15, 500–507. https://rruff.info/doclib/cm/vol15/CM15_500.pdf.Search in Google Scholar

Smith, G. (1978) Evidence for absorption by exchange-coupled Fe2+-Fe3+ pairs in the near infra-red spectra of minerals. Physics and Chemistry of Minerals, 3, 375–383, https://doi.org/10.1007/BF00311848.Search in Google Scholar

Smith, G. and Strens, R.G.J. (1976) Intervalence-transfer absorption in some silicate, oxide and phosphate minerals. In R.G.J. Strens, Ed., The Physical Chemistry of Rocks and Minerals, p. 584–612. WileySearch in Google Scholar

Taran, M.N. (2019) Electronic intervalence Fe2+ + Ti4+ → Fe3+ + Ti3+ charge-transfer transition in ilmenite. Physics and Chemistry of Minerals, 46, 839–843, https://doi.org/10.1007/s00269-019-01044-y.Search in Google Scholar

Taran, M.N. and Koch-Müller, M. (2011) Optical absorption of electronic Fe-Ti charge-transfer transition in natural andalusite: The thermal stability of the charge-transfer band. Physics and Chemistry of Minerals, 38, 215–222, https://doi.org/10.1007/s00269-010-0397-9.Search in Google Scholar

Taran, M.N. (2013) FTIR spectroscopic study of natural andalusite showing electronic Fe-Ti charge-transfer processes: Zoning and thermal evolution of OH-vibration bands. Physics and Chemistry of Minerals, 40, 63–71, https://doi.org/10.1007/s00269-012-0547-3.Search in Google Scholar

Taran, M.N. and Langer, K. (1998) Temperature and pressure dependence of intervalence charge transfer bands in spectra of some Fe- and Fe,Ti-bearing oxygen-based minerals. Neues Jahrbuch für Mineralogie Abhandlungen, 172, 325–346, https://doi.org/10.1127/njma/172/1998/325.Search in Google Scholar

Taran, M.N. and Langer, K. (2001) Electronic absorption spectra of Fe2+ ions in oxygen-based rockforming minerals at temperatures between 297 and 600 K. Physics and Chemistry of Minerals, 28, 199–210, https://doi.org/10.1007/s002690000148.Search in Google Scholar

Taran, M.N., Langer, K., Platonov, A.N., and Indutny, V.V. (1994) Optical-absorption investigation of Cr3+ ion-bearing minerals in the temperature-range 77–797 K. Physics and Chemistry of Minerals, 21, 360–372, https://doi.org/10.1007/BF00203294.Search in Google Scholar

Taran, M.N., Langer, K., and Platonov, A.N. (1996) Pressure- and temperature-effects on exchange-coupled-pair bands in electronic spectra of some oxygenbased iron-bearing minerals. Physics and Chemistry of Minerals, 23, 230–236, https://doi.org/10.1007/BF00207754.Search in Google Scholar

Taran, M.N., Koch-Müller, M., and Langer, K. (2005) Electronic absorption spectroscopy of natural (Fe2+, Fe3+)-bearing spinels of spinel s.s.-hercynite and gahnite-hercynite solid solutions at different temperatures and high-pressures. Physics and Chemistry of Minerals, 32, 175–188, https://doi.org/10.1007/s00269-005-0461-z.Search in Google Scholar

Taran, M.N., Dyar, M.D., and Matsyuk, S.S. (2007) Optical absorption study of natural garnets of almandine-skiagite composition showing intervalence Fe2+ + Fe3+ → Fe3+ + Fe2+ charge-transfer transition. American Mineralogist, 92, 753–760, https://doi.org/10.2138/am.2007.2163.Search in Google Scholar

Turlington, M.D., Pienkos, J.A., Carlton, E.S., Wroblewski, K.N., Myers, A.R., Trindle, C.O., Altun, Z., Rack, J.J., and Wagenknecht, P.S. (2016) Complexes with tunable intramolecular ferrocene to TiIV electronic transitions: models for solid state Fe(II) to Ti(IV) charge transfer. Inorganic Chemistry, 55, 2200–2211, https://doi.org/10.1021/acs.inorgchem.5b02587.Search in Google Scholar

Ullrich, K., Langer, K., and Becker, K.D. (2002) Temperature dependence of the polarized electronic absorption spectra of olivines. Part I—Fayalite. Physics and Chemistry of Minerals, 29, 409–419, https://doi.org/10.1007/s00269-002-0248-4.Search in Google Scholar

Ullrich, K., Ott, O., Langer, K., and Becker, K.D. (2004) Temperature dependence of the polarized electronic absorption spectra of olivines. Part II—Cobaltcontaining olivines. Physics and Chemistry of Minerals, 31, 247–260, https://doi.org/10.1007/s00269-004-0393-z.Search in Google Scholar

Received: 2024-01-31
Accepted: 2024-03-28
Published Online: 2024-11-29
Published in Print: 2024-12-15

© 2024 by Mineralogical Society of America

Articles in the same Issue

  1. Fluids in the shallow mantle of southeastern Australia: Insights from phase equilibria
  2. Compositional effects on the etching of fossil confined fission tracks in apatite
  3. Evaluation of the Rietveld method for determining content and chemical composition of inorganic X-ray amorphous materials in soils
  4. High-pressure phase transition of olivine-type Mg2GeO4 to a metastable forsterite-III type structure and their equations of state
  5. The application of “transfer learning” in optical microscopy: The petrographic classification of opaque minerals
  6. Mechanisms of fluid degassing in shallow magma chambers control the formation of porphyry deposits
  7. The OH-stretching region in infrared spectra of the apatite OH-Cl binary system
  8. Thermal equation of state of Li-rich schorl up to 15.5 GPa and 673 K: Implications for lithium and boron transport in slab subduction
  9. Raman scattering of omphacite at high pressure: Toward its possible application to elastic geothermobarometry
  10. Interpreting mineral deposit genesis classification with decision maps: A case study using pyrite trace elements
  11. Geochemical characteristics of mineral inclusions in the Luobusa chromitite (Southern Tibet): Implications for an intricate geological setting
  12. Three new iron-phosphate minerals from the El Ali iron meteorite, Somalia: Elaliite Fe82+ Fe3+(PO4)O8, elkinstantonite Fe4(PO4)2O, and olsenite KFe4(PO4)3
  13. Intervalence charge transfer in aluminum oxide and aluminosilicate minerals at elevated temperatures
  14. Electron probe microanalysis of trace sulfur in experimental basaltic glasses and silicate minerals
  15. New Mineral Names
  16. Book Review
  17. Book Review: Celebrating the International Year of Mineralogy: Progress and Landmark Discoveries of the Last Decades
Downloaded on 10.9.2025 from https://www.degruyterbrill.com/document/doi/10.2138/am-2024-9343/html
Scroll to top button