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Physics and Chemistry of Minerals

, Volume 39, Issue 2, pp 131–141 | Cite as

The influence of the Jahn–Teller effect at Fe2+ on the structure of chromite at high pressure

  • Atsushi Kyono
  • Stephen A. Gramsch
  • Takamitsu Yamanaka
  • Daijo Ikuta
  • Muhtar Ahart
  • Bjørn O. Mysen
  • Ho-kwang Mao
  • Russell J. Hemley
Original Paper

Abstract

The crystal structure of chromite FeCr2O4 was investigated to 13.7 GPa and ambient temperature with single-crystal X-ray diffraction techniques. The unit-cell parameter decreases continuously from 8.3832 (5) to 8.2398 (11) Å up to 11.8 GPa. A fit to the Birch–Murnaghan equation of state (EoS) based on the P–V data gives: K 0 = 209 (13) GPa, K′ = 4.0 (fixed), and V 0 = 588 (1) Å3. The FeO4 tetrahedra and CrO6 octahedra are compressed isotropically with pressure with their Fe–O and Cr–O bond distances decreasing from 1.996 (6) to 1.949 (7) Å and from 1.997 (3) to 1.969 (7) Å, respectively. The tetrahedral site occupied by the Fe2+ cation is more compressible than the octahedral site occupied by the Cr3+ cation. The resulting EoS parameters for the tetrahedral and the octahedral sites are K 0 = 147 (9) GPa, K′ = 4.0 (fixed), V 0 = 4.07 (1) Å3 and K 0 = 275 (24) GPa, K′ = 4.0 (fixed), V 0 = 10.42 (2) Å3, respectively. A discontinuous volume change is observed between 11.8 and 12.6 GPa. This change indicates a phase transition from a cubic (space group Fd-\({\overline{3}}\) m) to a tetragonal structure (space group I41 /amd). At the phase transition boundary, the two Cr–O bonds parallel to the c-axis shorten from 1.969 (7) to 1.922 (17) Å and the other four Cr–O bonds parallel to the ab plane elongate from 1.969 (7) to 1.987 (9) Å. This anisotropic deformation of the octahedra leads to tetragonal compression of the unit cell along the c-axis. The angular distortion in the octahedron decreases continuously up to 13.7 GPa, whereas the distortion in the tetrahedron rises dramatically after the phase transition. At the pressure of the phase transition, the tetrahedral bond angles along the c-axis direction of the unit cell begin decreasing from 109.5° to 106.6 (7)°, which generates a “stretched” tetrahedral geometry. It is proposed that the Jahn–Teller effect at the tetrahedrally coordinated Fe2+ cation becomes active with compression and gives rise to the tetrahedral angular distortion, which in turn induces the cubic-to-tetragonal transition. A qualitative molecular orbital model is proposed to explain the origin and nature of the Jahn–Teller effect observed in this structure and its role in the pressure-induced phase transition.

Keywords

Chromite Spinel structure High pressure Phase transition Jahn–Teller effect Diamond anvil cell 

Notes

Acknowledgments

The authors would like to thank Dr. Michail Taran and an anonymous reviewer for their helpful comments and suggestions. This work was performed at HPCAT (Sector 16), Advanced Photon Source, Argonne National Laboratory. HPCAT is supported by CIW, CDAC, UNLV, and LLNL through funding from DOE-NNSA, DOE-BES, and NSF. APS is supported by DOE-BES, under Contract No. DE-AC02-06CH11357.

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Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Atsushi Kyono
    • 1
    • 2
  • Stephen A. Gramsch
    • 2
  • Takamitsu Yamanaka
    • 2
  • Daijo Ikuta
    • 3
  • Muhtar Ahart
    • 2
  • Bjørn O. Mysen
    • 2
  • Ho-kwang Mao
    • 2
  • Russell J. Hemley
    • 2
  1. 1.Division of Earth Evolution Sciences, Graduate School of Life and Environmental SciencesUniversity of TsukubaIbarakiJapan
  2. 2.Geophysical Laboratory, Carnegie Institution of WashingtonWashingtonUSA
  3. 3.HPCAT, Geophysical LaboratoryCarnegie Institution of WashingtonArgonneUSA

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