Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Anisotropy of the Electrical Conductivity of the Fayalite, Fe2SiO4, Investigated by Spin Dimer Analysis

  • Lee, Kee Hag (Department of Materials Science and Engineering, Bard Hall, Cornell University) ;
  • Lee, Jeeyoung (Department of Chemistry, Nanoscale Science and Technology Institute, Wonkwang University) ;
  • Dieckmann, Rudiger (Department of Materials Science and Engineering, Bard Hall, Cornell University)
  • Received : 2012.12.11
  • Accepted : 2013.01.04
  • Published : 2013.02.20
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Abstract

Many properties of inorganic compounds are sensitive to changes in the point-defect concentrations. In minerals, such changes are influenced by temperature, pressure, and chemical impurities. Olivines form an important class of minerals and are magnesium-rich solid solutions consisting of the orthosilicates forsterite $Mg_2SiO_4$ and the fayalite $Fe_2SiO_4$. Orthosilicates have an orthorhombic crystal structure and exhibit anisotropic electronic and ionic transport properties. We examined the anisotropy of the electrical conductivity of $Fe_2SiO_4$ under the assumption that the electronic conduction in $Fe_2SiO_4$ occurs via a small polaron hopping mechanism. The anisotropic electrical conductivity is well explained by the electron transfer integrals obtained from the spin dimer analysis based on tight-binding calculations. The latter analysis is expected to provide insight into the anisotropic electrical conductivities of other magnetic insulators of transition metal oxides.

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References

  1. Brown, G. E., Jr. Olivines and Silicate Spinels; In Reviews in Mineralogy, Ribbe, P. H., Ed.; Mineralogical Soc. Amer.: Washington, D. C., 1980; Vol. 5, Chap. 11.
  2. Smyth, J. R. Am. Mineral. 1975, 60, 1092.
  3. Lottermoser, W.; Steiner, K.; Grodzicki, M.; Jiang, K.; Scharfetter, G.; Bats, J. W.; Redhammer, G.; Treutmam, W.; Hosoya, S.; Amthauer, G. Phys. Chem. Minerals 2002, 29, 112. https://doi.org/10.1007/s00269-001-0226-2
  4. Mao, H. K.; Bell, P. M. Science 1972, 176, 403. https://doi.org/10.1126/science.176.4033.403
  5. Williams, Q.; Knittle, E.; Reichlin, R.; Martin, S.; Jeanloz, R. J. Geophys. Res. B 1990, 95(13), 21549. https://doi.org/10.1029/JB095iB13p21549
  6. Fuess, H.; Ballet, O.; Lottermoser, W. Structural and Magnetic Phase Transitions in Minerals. In Advances in Physical Geochemistry, Ghose, S., Coey, J. M. D., Salje, E., Eds.; Springer- Verlag: Berlin, 1988; Vol. 7, p 185.
  7. Tsai, T.-L.; Dieckmann, R. Materials Science Forum 1997, 239, 399
  8. Schock, R. N.; Duba, A. G.; Shankland, T. J. J. Geophys. Res. 1989, 94, 5829. https://doi.org/10.1029/JB094iB05p05829
  9. Sockel, H. G. Defect Structure and Electrical Conductivity of Crystalline Ferrous Silicate; In Defects and Transport in Oxide; Seltzer, M. S.; Jaffee, R. I., Eds.; Prenum Press: New York, 1974; pp 341-356.
  10. Schock, R. N.; Duba, A. C. In Point Defects and the Mechanisms of Electrical Conduction in Olivine; Shock, R. N., Ed.; Amer. Geophys. Union: Washington, D. C., 1985; pp 88-96.
  11. Hirsch, L. M.; Shankland, T. J.; Duba, A. G. Geophys. J. Int. 1993, 114, 36. https://doi.org/10.1111/j.1365-246X.1993.tb01464.x
  12. Constable, S.; Roberts, J. J. Phys. Chem. Minerals 1997, 24, 319. https://doi.org/10.1007/s002690050044
  13. Brodholt, J. P.; Voèadlo, L. MRS Bulletin 2006, 31, 675. https://doi.org/10.1557/mrs2006.176
  14. Hafner, J.; Wolverton, C.; Ceder, G. MRS Bulletin 2006, 31, 659. https://doi.org/10.1557/mrs2006.174
  15. Cococcioni, M.; Corso, A. D.; de Gironcoli, S. Phys. Rev. B 2003, 67, 094106. https://doi.org/10.1103/PhysRevB.67.094106
  16. Mott, N. F. Metal-Insulator Transitions; Taylor and Frances: London, 1974.
  17. Mott, N. F. Metal-Insulator Transitions, 2nd ed.; Taylor & Francis: New York, 1990.
  18. Anisimov, V. I.; Zaanen, J.; Andersen, O. K. Phys. Rev. B 1991, 44, 943. https://doi.org/10.1103/PhysRevB.44.943
  19. Jiang, X.; Guo, G. Y. Phys. Rev. B 2004, 69, 155108. https://doi.org/10.1103/PhysRevB.69.155108
  20. Whangbo, M.-H.; Koo, H.-J.; Dai, D. J. Solid State Chem. 2003, 176, 417. https://doi.org/10.1016/S0022-4596(03)00273-1
  21. Kroger, F. A. The Chemistry of Imperfect Crystals; North-Holland Pub. Co.: Amsterdam, 1974.
  22. Tyburczy, J. A.; Fisler, D. K. Electrical Properties of Minerals and Melts; In Mineral Physics and Crystallography, A Handbook of Physical Constants; Amer. Geophys. Union: Washington, D. C., 1995; pp 185-208.
  23. Coropceanu, V.; André, J. M.; Malagori, M.; Brédas, J. L. Theo. Chem. Acc. 2003, 110, 59. https://doi.org/10.1007/s00214-003-0445-3
  24. Newton, M. D. Electron Transfer: Theoretical Models and Computational Implementation, In Electron Transfer in Chemistry; Balzani, V., Ed.; Wiley-VCH: New York, 2001; Chap. 1.
  25. Marcus, R. A. Rev. Mod. Phys. 1993, 65, 599. https://doi.org/10.1103/RevModPhys.65.599
  26. Albright, T. A.; Burdett, J. K.; Whangbo, M.-H. Orbital Interactions in Chemistry; Wiley: New York, 198; Chapter 2.
  27. Koo, H.-J.; Whangbo, M.-H.; Coste, S.; Jobic, S. J. Solid State Chem. 2001, 156, 464. https://doi.org/10.1006/jssc.2000.9025
  28. Dai, D.; Koo, H.-J.; Whangbo, M.-H. In MRS Symposium Proceedings, Vol. 658; Geselbracht, M. J., Greedan, J. E., Johnson, D. C., Subramanian, M. A., Eds.; Materials Research Society: Warrendale, PA, 2001; GG5.3.1-5.3.11.
  29. Whangbo, M.-H.; Koo, H.-J.; Dai, D.; Jung, D. Inorg. Chem. 2002, 41, 5575. https://doi.org/10.1021/ic0202458
  30. Whangbo, M.-H.; Koo, H.-J.; Dumas, J.; Continentino, M. A. Inorg. Chem. 2002, 41, 2193. https://doi.org/10.1021/ic010956q
  31. Clementi, E.; Roetti, C. Atomic Data Nuclear Data Tables 1974, 14, 177. https://doi.org/10.1016/S0092-640X(74)80016-1
  32. Dai, D.; Ren, J.; Liang, W.; Whangbo, M.-H. http://chvamw.chem.ncsu.edu/, 2002.
  33. Ammeter, J.; Bürgi, H.-B.; Thibeault, J.; Hoffmann, R. J. Am. Chem. Soc. 1978, 100, 3686. https://doi.org/10.1021/ja00480a005
  34. Lee, K. H.; Dieckmann, R.; Lee, C.; Whangbo, M.-H. Chem. Mater. 2007, 19, 4393. https://doi.org/10.1021/cm071481p