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Abstract Hydroxylation of wadsleyite, β-(Mg,Fe)2SiO4, is associated with divalent cation defects and well known to affect its physical properties. However, an atomic-scale understanding of the defect structure and hydrogen bonding at high pressures is needed to interpret the influence of water on the behavior of wadsleyite in the mantle transition zone. We have determined the pressure evolution of the wadsleyite crystal symmetry and structure, including all O∙∙∙O interatomic distances, up to 32 GPa using single-crystal X-ray diffraction on two well-characterized, Fe-bearing (Fo90) samples containing 0.25(4) and 2.0(2) wt% H2O. Both compositions undergo a pressure-dependent monoclinic distortion from orthorhombic symmetry above 9 GPa, with the less hydrous sample showing a larger increase in distortion at increased pressures due to the difference in compressibility of the split M3 site in the monoclinic setting arising from preferred vacancy ordering at the M3B site. Although hydrogen positions cannot be modeled from the X-ray diffraction data, the pressure evolution of the longer O1∙∙∙O4 distance in the structure characterizes the primary hydrogen bond length. We observe the hydrogen-bonded O1∙∙∙O4 distance shorten gradually from 3.080(1) Å at ambient pressure to about 2.90(1) Å at 25 GPa, being still much longer than is defined as strong hydrogen bonding (2.5–2.7 Å). Above 25 GPa and up to the maximum pressure of the experiment at 32.5 GPa, the hydrogen-bonded O1∙∙∙O4 distance decreases no further, despite the fact that previous spectroscopic studies have shown that the primary O-H stretching frequencies continuously drop into the regime of strong hydrogen bonding (<3200 cm–1) above ~15 GPa. We propose that the primary O1-H∙∙∙O4 hydrogen bond in wadsleyite becomes highly nonlinear at high pressures based on its deviation from frequency-distance correlations for linear hydrogen bonds. One possible explanation is that the hydrogen position shifts from being nearly on the long O1-O4 edge of the M3 site to a position more above O1 along the c-axis.
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This content will become publicly available on December 1, 2025
Iron Bonding with Light Elements: Implications for Planetary Cores Beyond the Binary System
Light element alloying in iron is required to explain density deficit and seismic wave velocities in Earth’s core. However, the light element composition of the Earth’s core seems hard to constrain as nearly all light element alloying would reduce the density and sound velocity (elastic moduli). The alloying light elements include oxidizing elements like oxygen and sulfur and reducing elements like hydrogen and carbon, yet their chemical effects in the alloy system are less discussed. Moreover, Fe-X-ray Absorption Near Edge Structure (Fe-XANES) fingerprints have been studied for silicate materials with ferrous and ferric ions, while not many X-ray absorption spectroscopy (XAS) studies have focused on iron alloys, especially at high pressures. To investigate the bonding nature of iron alloys in planetary interiors, we presented X-ray absorption spectroscopy of iron–nitrogen and iron–carbon alloys at high pressures up to 50 GPa. Together with existing literature on iron–carbon, –hydrogen alloys, we analyzed their edge positions and found no significant difference in the degree of oxidation among these alloys. Pressure effects on edge positions were also found negligible. Our theoretical simulation of the valence state of iron, alloyed with S, C, O, N, and P also showed nearly unchanged behavior under pressures up to 300 GPa. This finding indicates that the high pressure bonding of iron alloyed with light elements closely resembles bonding at the ambient conditions. We suggest that the chemical properties of light elements constrain which ones can coexist within iron alloys.
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- PAR ID:
- 10596827
- Publisher / Repository:
- NSF-PAR
- Date Published:
- Journal Name:
- Crystals
- Volume:
- 14
- Issue:
- 12
- ISSN:
- 2073-4352
- Page Range / eLocation ID:
- 1016
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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