Abstract
Iron hydroxide FeO2Hx (x ≤ 1) and ferrous iron chloride FeCl2 can adopt the HP-PdF2-type (space group: \(P{a_{\overline 3 }}\), Z = 4) structure in the lowermost mantle, potentially contributing to the geochemical cycles of hydrogen and chlorine within Earth’s deep interior, respectively. Here we investigate the high-pressure behavior of HP-PdF2-type FeCl2 by X-ray diffraction (XRD) and Raman measurements in laser-heated diamond anvil cells. Our results show that HP-PdF2-type FeCl2 can be formed at 60‒67 GPa and 1650‒1850 K. Upon cold decompression, the diffraction peaks at pressures above 10 GPa can be indexed to the HP-PdF2-type structure. Intriguingly, the calculated cell volumes reveal a remarkable decrease of ΔV / V = ∼ 14% between 36 and 40 GPa, which is possibly caused by a pressure-induced spin transition of Fe2+ (HS: high-spin → LS: low-spin). We also observe distinct changes in Raman spectra at 33‒35 GPa, practically coinciding with the onset pressures of isostructural phase transition in XRD results. Our observations combined with previous studies conducted at megabar pressures suggest that HP-PdF2-type FeCl2, with a wide pressure stability range, if present in subducting slabs, could facilitate the transport of chlorine from the middle lower mantle to the outer core.
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Acknowledgements
The authors acknowledge two anonymous reviewers whose detailed comments have greatly improved the quality of the manuscript. The authors are grateful for the financial support from the National Natural Science Foundation of China (Grants No.: 41902033, 42150103 and 42050203). The X-ray diffraction experiments were performed at beamline 15U1, Shanghai Synchrotron Radiation Facility.
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Yao Yao and Hongsheng Yuan contributed to the conception and design of the study. Methodology was performed by Yao Yao, Hongsheng Yuan, Xi Liu, Xueyan Du, and Lili Zhang. Formal analysis and investigation were performed by Yao Yao and Hongsheng Yuan. Data curation was performed by Yao Yao. The first draft of the manuscript was written by Yao Yao and Hongsheng Yuan. The original manuscript was subsequently reviewed and edited by Xi Liu, Xueyan Du, and Lili Zhang. Funding was acquired by Hongsheng Yuan. All authors have read and agreed to the published version of the manuscript.
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Yao, Y., Liu, X., Du, X. et al. Pressure-induced large volume collapse and possible spin transition in HP-PdF2-type FeCl2. Phys Chem Minerals 51, 11 (2024). https://doi.org/10.1007/s00269-024-01271-y
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DOI: https://doi.org/10.1007/s00269-024-01271-y