High-pressure phase transitions of Fe_3-xTi_xO₄ solid solution up to 60 GPa correlated with electronic spin transition

Journal Article · Wed Jun 12 00:00:00 EDT 2013 · American Mineralogist

DOI:https://doi.org/10.2138/am.2013.4182· OSTI ID:1083352

Yamanaka, Takamitsu; Kyono, Atsushi; Nakamoto, Yuki; Meng, Yue; Kharlamova, Svetlana; Struzhkin, Victor V.; Mao, Ho-kwang ^[1]

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1. CIW

The structural phase transition of the titanomagnetite (Fe_3–xTi_xO₄) solid solution under pressures up to 60 GPa has been clarified by single-crystal and powder diffraction studies using synchrotron radiation and a diamond-anvil cell. Present Rietveld structure refinements of the solid solution prove that the prefered cation distribution is based on the crystal field preference rather than the magnetic spin ordering in the solid solution. The Ti-rich phases in 0.734 ≤ x ≤1.0 undergo a phase transformation from the cubic spinel of Fd3m to the tetragonal spinel structure of I4₁/amd with c/a < 1.0. The transition is driven by a Jahn-Teller effect of ^IVFe²⁺ (3d⁶) on the tetrahedral site. The c/a < 1 ratio is induced by lifting of the degeneracy of the e orbitals by raising the d_x2-y2 orbital below the energy of the d_z2 orbital. The distortion characterized by c/a < 1 is more pronounced with increasing Ti content in the Fe_3–xTi_xO₄ solid solutions and with increasing pressure. An X-ray emission experiment of Fe₂TiO₄ at high pressures confirms the spin transition of FeKβ from high spin to intermediate spin (IS) state. The high spin (HS)-to-low spin (LS) transition starts at 14 GPa and the IS state gradually increases with compression. The ^VIFe²⁺ in the octahedral site is more prone for the HS-to-LS transition, compared with Fe²⁺ in the fourfold- or eightfold-coordinated site. The transition to the orthorhombic post-spinel structure with space group Cmcm has been confirmed in the whole compositional range of Fe_3–xTi_xO₄. The transition pressure decreases from 25 GPa (x = 0.0) to 15 GPa (x = 1.0) with increasing Ti content. There are two cation sites in the orthorhombic phase: M1 and M2 sites of eightfold and sixfold coordination, respectively. Fe²⁺ and Ti⁴⁺ are disordered on the M2 site. This structural change is accelerated at higher pressures due to the spin transition of Fe²⁺ in the octahedral site. This is because the ionic radius of ^VIFe²⁺ becomes 20% shortened by the spin transition. At 53 GPa, the structure transforms to another high-pressure polymorph with Pmma symmetry with the ordered structure of Ti and Fe atoms in the octahedral site. This structure change results from the order-disorder transition.

• Research Organization: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
• Sponsoring Organization: FOREIGNNSFDOE - BASIC ENERGY SCIENCESDOE-NNSA
• OSTI ID: 1083352
• Journal Information: American Mineralogist, Vol. 98, Issue (4) ; 04, 2013; ISSN 0003-004X
• Country of Publication: United States
• Language: ENGLISH