Antiferromagnetism in Pressure-Amorphized Fe2SiO4.

Amorphous Fe(2)SiO(4) synthesized at elevated pressures exhibits a Néel transition at a temperature identical to that observed in the crystalline form, T(N) = 65 (+/-2) kelvin at zero pressure. This behavior contrasts sharply with observations on other disordered systems, such as spin glasses, which characteristically exhibit strong "frustration" of the spins and consequent marked suppression of the Néel transition.

High pressure ellipsometry: a novel method for measuring the optical properties and electronic structure of materials in diamond anvil cells.

High pressure ellipsometry (HPE) method was developed for determining the index of refraction of opaque materials in a diamond anvil cell (DAC). A main difficulty in DAC-based HPE, namely, the pressure-induced birefringence developed in the diamond, was overcome enabling the extraction of the ellipsometric parameters of the sample. The method used was based on the fact that an unpolarized light is unaffected by a retarding optical element and thus reduces the number of unknown parameters in the problem. Because of technical difficulties in using unpolarized light, a linear combination of orthogonal polarizations was applied. In the experimental procedure, multiangle measurements of the ellipsometric parameter ψ are collected at each pressure and the data is fitted together with a measurement of the near normal reflectivity, in order to extract the complex index of refraction. As a test case, this procedure was used to measure the high pressure index of refraction of iron up to 30 GPa for light with wavelengths of 532 and 633 nm. From the index of refraction as a function of pressure the diamond-iron interface emissivity for different pressures was derived and from which the phase transition α → ε could be identified and characterized. The emissivity increases with pressure both at the α (0-9 GPa) and the ε phase (21-30 GPa) however decreases at the mixed α - ε (9-21 GPa) range. From the imaginary part of the index of refraction the pressure dependence of the energy skin depth of iron was extracted. It was found that the energy skin depth increases by an order of magnitude at 30 GPa relative to ambient conditions.

Determination of iron sites and the amount of amorphization in radiation-damaged titanite (CaSiTiO5).

Iron is a ubiquitous impurity in metamict (radiation-damaged and partially amorphized) materials such as titanite (CaSiTiO(5)). Using (57)Fe Mössbauer spectroscopy we find that iron in metamict titanite is partitioned between amorphous and crystalline regions based on valence. Trivalent iron exists in the crystalline titanite matrix whereas divalent iron exists almost exclusively in radiation-amorphized regions. We find that the relative abundances of the oxidation states correlate with the volume fraction of amorphous and crystalline regions. Our data also show that oxidation of iron proceeds along with the recrystallization of the amorphized regions. Recrystallization is confirmed to occur over the range 700 °C < T < 925 °C, and no further structural changes are observed at higher temperatures. It is surprising that our Mössbauer measurements show divalent iron to be surrounded by titanite with a high degree of short-range structural order in the amorphized regions. This observation is fundamentally different from other metamict materials such as zircon (ZrSiO(4)), where amorphized regions show no short-range order.

Origin of the Verwey transition in magnetite.

Comprehensive x-ray powder diffraction studies were carried out in magnetite in the 80-150 K and 0-12 GPa ranges with a membrane-driven diamond anvil cell and helium as a pressure medium. Careful data analyses have shown that a reversible, cubic to a distorted-cubic, structural transition takes place with increasing pressure, within the (P,T) regime below the Verwey temperature TV(P). The experimental documentation that TV(P)=Tdist(P) implies that the pressure-temperature-driven metal-insulator Verwey transition is caused by a gap opening in the electronic band structure due to the crystal-structural transformation to a lower-symmetry phase. The distorted-cubic insulating phase comprises a relatively small pressure-temperature range of the stability field of the cubic metallic phase that extends to 25 GPa.

Iron spin transition in Earth's mantle.

High-pressure Mössbauer spectroscopy on several compositions across the (Mg,Fe)O magnesiowüstite solid solution confirms that ferrous iron (Fe(2+)) undergoes a high-spin to low-spin transition at pressures and for compositions relevant to the bulk of the Earth's mantle. High-resolution x-ray diffraction measurements document a volume change of 4-5% across the pressure-induced spin transition, which is thus expected to cause seismological anomalies in the lower mantle. The spin transition can lead to dissociation of Fe-bearing phases such as magnesiowüstite, and it reveals an unexpected richness in mineral properties and phase equilibria for the Earth's deep interior.

Pressure induced self-oxidation of Fe(OH)2.

Mössbauer spectroscopy, x-ray diffraction, and electrical resistance [R(P,T)] studies in Fe(OH)(2) to 40 GPa revealed an unforeseen process by which a gradual Fe2+ oxidation takes place, starting at approximately 8 GPa reaching 70% Fe3+ abundance at 40 GPa. The nonreversible process Fe2+-->Fe3++e(-) occurs with no structural transition. The "ejected" electrons form a deep band within the high-pressure electronic manifold becoming weakly localized at P>50 GPa. This process is attributed to an effective ionization potential created by the pressure induced orientationally deformed (OH) dipoles and the unusual small binding energy of the valence electron in Fe2+(OH)(2).

Pressure-induced quenching of the Jahn-Teller distortion and insulator-to-metal transition in LaMnO(3).

LaMnO(3) was studied by synchrotron x-ray diffraction, optical spectroscopies, and transport measurements under pressures up to 40 GPa. The cooperative Jahn-Teller (JT) distortion is continuously reduced with increasing pressure. There is strong indication that the JT effect and the concomitant orbital order are completely suppressed above 18 GPa. The system, however, retains its insulating state to approximately 32 GPa, where it undergoes a bandwidth-driven insulator-metal transition. Delocalization of electron states, which suppresses the JT effect but is insufficient to make the system metallic, appears to be a key feature of LaMnO(3) at 20-30 GPa.