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Abstract Accurate knowledge of the phase transitions and thermoelastic properties of candidate iron alloys, such as Fe‐Si alloys, is essential for understanding the nature and dynamics of planetary cores. The phase diagrams of some Fe‐Si alloys between 1 atm and 16 GPa have been back‐extrapolated from higher pressures, but the resulting phase diagram of Fe83.6Si16.4(9 wt.% Si) is inconsistent with temperature‐induced changes in its electrical resistivity between 6 and 8 GPa. This study reports in situ synchrotron X‐ray diffraction (XRD) measurements on pre‐melted and powder Fe83.6Si16.4samples from ambient conditions to 60 GPa and 900 K using an externally heated diamond‐anvil cell. Upon compression at 300 K, thebccphase persisted up to ∼38 GPa. Thehcpphase appeared near 8 GPa in the pre‐melted sample, and near 17 GPa in the powder sample. The appearance of thehcpphase in the pre‐melted sample reconciles the reported changes in electrical resistivity of a similar sample, thus resolving the low‐pressure region of the phase diagram. The resulting high‐temperature Birch‐Murnaghan equation of state (EoS) and thermal EoS based on the Mie‐Gruneisen‐Debye model of thebccandhcpstructures are consistent with, and complement the literature data at higher pressures. The calculated densities based on the thermal EoS of Fe‐9wt.%Si indicate that bothbccandhcpphases agree with the reported core density estimates for the Moon and Mercury.
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Theoretical predictions suggest carbon dioxide phases III and VII are identical
Solid carbon dioxide exhibits a rich phase diagram at high pressures. Metastable phase III is formed by compressing dry ice above ∼10–12 GPa. Phase VII occurs at similar pressures but higher temperatures, and its stability region is disconnected from III on the phase diagram. Comparison of large-basis-set quasi-harmonic second-order Møller–Plesset perturbation theory calculations and experiment suggests that the long-accepted structure of phase III is problematic. The experimental phase III and VII structures both relax to the same phase VII structure. Furthermore, Raman spectra predicted for phase VII are in good agreement with those observed experimentally for both phase III and VII, while those for the purported phase III structure agree poorly with experimental observations. Crystal structure prediction is employed to search for other potential structures which might account for phase III, but none are found. Together, these results suggest that phases III and VII are likely identical.
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- PAR ID:
- 10062124
- Date Published:
- Journal Name:
- Chem. Sci.
- Volume:
- 8
- Issue:
- 11
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 7374 to 7382
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C7SC03267F
