Abstract
We examined the crystal structure of FeHX (X~1) (FeH hereafter) at high pressure and temperature by X‑ray diffraction up to 137 GPa. Results show that FeH adopts a face-centered cubic (fcc) structure at pressures of 43 to 137 GPa and temperatures of ~1000 to 2000 K. Our study revises a phase diagram of stoichiometric FeH in which fcc has a wider-than-expected stability field at high pressure and temperature. Based on our findings, the FeH end-member of the Fe-FeH system is expected to be stable in the fcc structure at the P-T conditions of the Earth’s core, rather than in the double-hexagonal close packed (dhcp) structure as previously reported. We compared the experimentally determined unit-cell volumes of FeH with those from ab initio calculations. Additionally, we observed a change in compressibility at ~60 GPa, which could be attributed to a magnetic transition—an interpretation supported by our ab initio computations.
Acknowledgments and funding
We thank two anonymous reviewers for their constructive comments that improved the quality of the manuscript. In situ XRD measurements were performed at BL10XU, SPring-8 (proposal no. 2014A0080, 2014B0080, 2015A0080, 2015B0080, and 2016B0080). Calculations were performed at ELSI and supported by JSPS Kakenhi (Grant number: 17K05627).
References cited
Antonov, V., Cornell, K., Fedotov, V., Kolesnikov, A., Ponyatovsky, E., Shiryaev, V., and Wipf, H. (1998) Neutron diffraction investigation of the dhcp and hcp iron hydrides and deuterides. Journal of Alloys and Compounds, 264, 214–222.10.1016/S0925-8388(97)00298-3Search in Google Scholar
Badding, J.V., Hemley, R.J., and Mao, H.K. (1991) High-pressure chemistry of hydrogen in metals: in situ study of iron hydride. Science, 253, 421–424.10.1126/science.253.5018.421Search in Google Scholar PubMed
Baroni, S., de Gironcoli, S., Dal Corso, A., and Giannozzi, P. (2001) Phonons and related crystal properties from density-functional perturbation theory. Reviews of Modern Physics, 73, 515–558.10.1103/RevModPhys.73.515Search in Google Scholar
Bazhanova, Z., Oganov, A., and Gianola, O. (2012) Fe–C and Fe–H systems at pressures of the Earth’s inner core. Physics-Uspekhi, 55, 489–497.10.3367/UFNe.0182.201205c.0521Search in Google Scholar
Boehler, R., von Bargen, N., and Chopelas, A. (1990) Melting, thermal expansion, and phase transitions of iron at high pressures. Journal of Geophysical Research, 95, 21731–21736.10.1029/JB095iB13p21731Search in Google Scholar
Caillabet, L., Mazevet, S., and Loubeyre, P. (2011) Multiphase equation of state of hydrogen from ab initio calculations in the range 0.2 to 5 g/cc up to 10 eV. Physical Review B, 83, 094101.10.1103/PhysRevB.83.094101Search in Google Scholar
Chi, Z., Nguyen, H., Matsuoka, T., Kagayama, T., Hirao, N., Ohishi, Y., and Shimizu, K. (2011) Cryogenic implementation of charging diamond anvil cells with H2 and D2. The Review of Scientific Instruments, 82, 105109.10.1063/1.3652981Search in Google Scholar PubMed
Dewaele, A., Belonoshko, A., Garbarino, G., Occelli, F., Bouvier, P., Hanfland, M., and Mezouar, M. (2012) High-pressure–high-temperature equation of state of KCl and KBr. Physical Review B, 85, 214105.10.1103/PhysRevB.85.214105Search in Google Scholar
Dorogokupets, P.I., and Oganov, A.R. (2007) Ruby, metals, and MgO as alternative pressure scales: A semiempirical description of shock-wave, ultrasonic, X‑ray, and thermochemical data at high temperatures. Physical Review B, 75, 024115.10.1103/PhysRevB.75.024115Search in Google Scholar
Elsässer, C., Zhu, J., Louie, S.G., and Meyer, B. (1998) Ab initio study of iron and iron hydride: II. Structural and magnetic properties of close-packed Fe and FeH. Journal of Physics: Condensed Matter, 10, 5113–5129.Search in Google Scholar
Fukai, Y. (1992) Some properties of the Fe-H system at high pressures and temperatures, and their implications for the Earth’s core. In Y. Syono and M.H. Manghnani, Eds., High Pressure Research: Application to Earth and Planetary Sciences, p. 373–385. Terrapub, Washington, D.C.10.1029/GM067p0373Search in Google Scholar
Giannozzi, P., Gironcoli, S., Pavone, P., and Baroni, S. (1990) Ab initio calculation of phonon dispersions in semiconductors. Physical Review B, 43, 7231–7242.10.1103/PhysRevB.43.7231Search in Google Scholar
Giannozzi, P., Baroni, S., Bonini, N., Calandra, M., Car, R., Cavazzoni, C., Ceresoli, D., Chiarotti, G., Cococcioni, M., Dabo, I., and others (2009) Quantum Espresso: a modular and open-source software project for quantum simulations of materials. Journal of Physics: Condensed Matter, 21, 395502.10.1088/0953-8984/21/39/395502Search in Google Scholar PubMed
Gomi, H., Fei, Y., and Yoshino, T. (2018) The effects of ferromagnetism and interstitial hydrogen on the equation of states of hcp and dhcp FeHX: Implications for the Earth’s inner core age. American Mineralogist, 103, 1271–1281.10.2138/am-2018-6295Search in Google Scholar
Hirao, N., Kondo, T., Ohtani, E., Takemura, K., and Kikegawa, T. (2004) Compression of iron hydride to 80 GPa and hydrogen in the Earth’s inner core. Geophysical Research Letters, 31, L06616.10.1029/2003GL019380Search in Google Scholar
Hirose, K., Tagawa, S., Kuwayama, Y., Sinmyo, R., Morard, G., Ohishi, Y., and Genda, Y. (2019) Hydrogen limits carbon in liquid iron. Geophysical Research Letters, 46, https://doi.org/10.1029/2019GL082591.10.1029/2019GL082591Search in Google Scholar
Ikuta, D., Ohtani, E., Sano-Furukawa, A., Shibazaki, Y., Terasaki, H., Yuan, L., and Hattori, T. (2019) Interstitial hydrogen atoms in face-centered cubic iron in the Earth’s core. Scientific Reports, 9, 7108.10.1038/s41598-019-43601-zSearch in Google Scholar PubMed PubMed Central
Isaev, E., Skorodumova, N., Ahuja, R., Vekilov, Y., and Johansson, B. (2007) Dynamical stability of Fe-H in the Earth’s mantle and core regions. Proceedings of the National Academy of Sciences, 104, 9168–9171.10.1073/pnas.0609701104Search in Google Scholar PubMed PubMed Central
Kvashnin, A., Kruglov, I., Semenok, D., and Oganov, A. (2018) Iron superhydrides FeH5 and FeH6: Stability, electronic properties and superconductivity. The Journal of Physical Chemistry C, 122, 4731–4736.10.1021/acs.jpcc.8b01270Search in Google Scholar
Machida, A., Saitoh, H., Hattori, T., Sano-Furukawa, A., Funakoshi, K., Sato, T., Orimo, S., and Aoki, K. (2019) Hexagonal close-packed iron hydride behind the conventional phase diagram. Scientific Reports, 9, 12290.10.1038/s41598-019-48817-7Search in Google Scholar PubMed PubMed Central
Methfessel, M., and Paxton, A. (1989) High-precision sampling for Brillouin-zone integration in metals. Physical Review B, 40, 3616–3621.10.1103/PhysRevB.40.3616Search in Google Scholar
Narygina, O., Dubrovinsky, L., McCammon, C., Kurnosov, A., Kantor, I., Prakapenka, V., and Dubrovinskaia, N. (2011) X‑ray diffraction and Mössbauer spectroscopy study of fcc iron hydride FeH at high pressures and implications for the composition of the Earth’s core. Earth and Planetary Science Letters, 307, 409–414.10.1016/j.epsl.2011.05.015Search in Google Scholar
Nishi, M., Kuwayama, Y., Tsuchiya, J., and Tsuchiya, T. (2017) The pyrite-type high-pressure form of FeOOH. Nature, 547, 205–208.10.1038/nature22823Search in Google Scholar
Ohishi, Y., Hirao, N., Sata, N., Hirose, K., and Takata, M. (2008) Highly intense monochromatic X‑ray diffraction facility for high-pressure research at SPring-8. High Pressure Research, 28, 163–173.10.1080/08957950802208910Search in Google Scholar
Ohta, K., Ichimaru, K., Einaga, M., Kawaguchi, S., Shimizu, K., Matsuoka, T., Hirao, N., and Ohishi, Y. (2015) Phase boundary of hot dense fluid hydrogen. Scientific Reports, 5, 16560.10.1038/srep16560Search in Google Scholar
Ohta, K., Suehiro, S., Hirose, K., and Ohishi, Y. (2019) Electrical resistivity of fcc phase iron hydrides at high pressures and temperatures. Comptes Rendus Geoscience, 351, 147–153.10.1016/j.crte.2018.05.004Search in Google Scholar
Pépin, C., Dewaele, A., Geneste, G., Loubeyre, P., and Mezouar, M. (2014) New iron hydrides under high pressure. Physical Review Letters, 113, 265504.10.1103/PhysRevLett.113.265504Search in Google Scholar
Pépin, C.M., Geneste, G., Dewaele, A., and Mezouar, M. (2017) Synthesis of FeH5: A layered structure with atomic hydrogen slabs. Science, 357, 382–385.10.1126/science.aan0961Search in Google Scholar
Perdew, J., Burke, K., and Ernzerhof, M. (1996) Generalized gradient approximation made simple. Physical Review Letters, 78, 1396.10.1103/PhysRevLett.77.3865Search in Google Scholar
Poirier, J.P. (1994) Light elements in the Earth’s outer core: a critical review. Physics of the Earth and Planetary Interiors, 85, 319–337.10.1016/0031-9201(94)90120-1Search in Google Scholar
Saitoh, H., Machida, A., Sugimoto, H., Yagi, T., and Aoki, K. (2017) P–V–T relation of the Fe–H system under hydrogen pressure of several gigapascals. Journal of Alloys and Compounds, 706, 520–525.10.1016/j.jallcom.2017.02.209Search in Google Scholar
Sakamaki, K., Takahashi, E., Nakajima, Y., Nishihara, Y., Funakoshi, K., Suzuki, T., and Fukai, Y. (2009) Melting phase relation of FeHX up to 20 GPa: Implication for the temperature of the Earth’s core. Physics of the Earth and Planetary Interiors, 174, 192–201.10.1016/j.pepi.2008.05.017Search in Google Scholar
Sakamaki, T., Ohtani, E., Fukui, H., Kamada, S., Takahashi, S., Sakairi, T., Takahata, A., Sakai, T., Tsutsui, S., Ishikawa, D., and others (2016) Constraints on Earth’s inner core composition inferred from measurements of the sound velocity of hcp-iron in extreme conditions. Science Advances, 2, e1500802.10.1126/sciadv.1500802Search in Google Scholar PubMed PubMed Central
Seto, Y., Nishio-Hamane, D., Nagai, T., and Sata, N. (2010) Development of a software suite on X‑ray diffraction experiments. The Review of High Pressure Science and Technology, 20, 269–276.10.4131/jshpreview.20.269Search in Google Scholar
Shibazaki, Y., Ohtani, E., Fukui, H., Sakai, T., Kamada, S., Ishikawa, D., Tsutsui, S., Baron, A., Nishitani, N., Hirao, N., and others (2012) Sound velocity measurements in dhcp-FeH up to 70 GPa with inelastic X‑ray scattering: Implications for the composition of the Earth’s core. Earth and Planetary Science Letters, 313–314, 79–85.10.1016/j.epsl.2011.11.002Search in Google Scholar
Shibazaki, Y., Terasaki, H., Ohtani, E., Tateyama, R., Nishida, K., Funakoshi, K., and Higo, Y. (2014) High-pressure and high-temperature phase diagram for Fe0.9Ni0.1–H alloy. Physics of the Earth and Planetary Interiors, 228, 192–201.10.1016/j.pepi.2013.12.013Search in Google Scholar
Tagawa, S., Ohta, K., Hirose, K., Kato, C., and Ohishi, Y. (2016) Compression of Fe–Si–H alloys to core pressures. Geophysical Research Letters, 43, 3686–3692.10.1002/2016GL068848Search in Google Scholar
Thompson, E.C., Davis, A.H., Bi, W., Zhao, J., Alp, E.E., Zhang, D., Greenberg, E., Prakapenka, V.B., and Campbell, A.J. (2018) High-pressure geophysical properties of fcc phase FeHX. Geochemistry, Geophysics, Geosystems, 19, 305–314.10.1002/2017GC007168Search in Google Scholar
Tsujino, N., Nishihara, Y., Nakajima, Y., Takahashi, E., Funakoshi, K., and Higo, Y. (2013) Equation of state of γ-Fe: Reference density for planetary cores. Earth and Planetary Science Letters, 375, 244–253.10.1016/j.epsl.2013.05.040Search in Google Scholar
Tsumuraya, T., Matsuura, Y., Shishidou, T., and Oguchi, T. (2012) First-principles study on the structural and magnetic properties of iron hydride. Journal of the Physical Society of Japan, 81, 064707.10.1143/JPSJ.81.064707Search in Google Scholar
Ueda, Y., Matsui, M., Yokoyama, A., Tange, Y., and Funakoshi, K. (2008) Temperature-pressure-volume equation of state of the B2 phase of sodium chloride. Journal of Applied Physics, 103, 113513.10.1063/1.2939254Search in Google Scholar
Umemoto, K., and Hirose, K. (2015) Liquid iron-hydrogen alloys at outer core conditions by first-principles calculations. Geophysical Research Letters, 42, 7513–7520.10.1002/2015GL065899Search in Google Scholar
Vanderbilt, D. (1990) Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Physical Review B, 41, 7892–7895.10.1103/PhysRevB.41.7892Search in Google Scholar
Wallace, D.C. (1972) Thermodynamics of Crystals. Wiley.10.1119/1.1987046Search in Google Scholar
Yoo, C., Cynn, H., Söderlind, P., and Iota, V. (2000) New β(fcc)-cobalt to 210 GPa. Physical Review Letters, 84, 4132–4135.10.1103/PhysRevLett.84.4132Search in Google Scholar PubMed
Yuan, L., Ohtani, E., Ikuta, D., Kamada, S., Tsuchiya, J., Naohisa, H., Ohishi, Y., and Suzuki, A. (2018) Chemical reactions between Fe and H2O up to megabar pressures and implications for water storage in the Earth’s mantle and core. Geophysical Research Letters, 45, 1330–1338.10.1002/2017GL075720Search in Google Scholar
Zha, C., Liu, H., Tse, J., and Hemley, R. (2017) Melting and high P-T transitions of hydrogen up to 300 GPa. Physical Review Letters, 119, 075302.10.1103/PhysRevLett.119.075302Search in Google Scholar PubMed
© 2020 Walter de Gruyter GmbH, Berlin/Boston
Articles in the same Issue
- Halogens in amphibole and mica from mantle xenoliths: Implications for the halogen distribution and halogen budget of the metasomatized continental lithosphere
- New insights on Br speciation in volcanic glasses and structural controls on halogen degassing
- Decoupled water and iron enrichments in the cratonic mantle: A study on peridotite xenoliths from Tok, SE Siberian Craton
- Deconvolution of the composition of fine-grained pyrite in sedimentary matrix by regression of time-resolved LA-ICP-MS data
- A multi-method characterization of natural terrestrial birnessites
- REE redistributions during granite weathering: Implications for Ce anomaly as a proxy for paleoredox states
- The relationship of destinezite to the acid sulfate alteration at the El Laco magnetite deposit, Chile
- Crystallographic preferred orientation of talc determined by an improved EBSD procedure for sheet silicates: Implications for anisotropy at the slab–mantle interface due to Si-metasomatism
- The occurrence, origin, and fate of water in chromitites in ophiolites
- Thermoelasticity of tremolite amphibole: Geophysical implications
- Stability of fcc phase FeH to 137 GPa
- Partition coefficients of trace elements between carbonates and melt and suprasolidus phase relation of Ca-Mg-carbonates at 6 GPa
- Systematics of H2 and H2O evolved from chlorites during oxidative dehydrogenation
- Texture and geochemistry of multi-stage hydrothermal scheelite in the Tongshankou porphyry-skarn Cu-Mo(-W) deposit, eastern China: Implications for ore-forming process and fluid metasomatism
- EXCALIBR to EXCELIBR and the optical orientation of minerals: Correcting the optical orientation of clinoamphiboles
- A refined zirconium-in-rutile thermometer
- New Mineral Names
- Book Review
Articles in the same Issue
- Halogens in amphibole and mica from mantle xenoliths: Implications for the halogen distribution and halogen budget of the metasomatized continental lithosphere
- New insights on Br speciation in volcanic glasses and structural controls on halogen degassing
- Decoupled water and iron enrichments in the cratonic mantle: A study on peridotite xenoliths from Tok, SE Siberian Craton
- Deconvolution of the composition of fine-grained pyrite in sedimentary matrix by regression of time-resolved LA-ICP-MS data
- A multi-method characterization of natural terrestrial birnessites
- REE redistributions during granite weathering: Implications for Ce anomaly as a proxy for paleoredox states
- The relationship of destinezite to the acid sulfate alteration at the El Laco magnetite deposit, Chile
- Crystallographic preferred orientation of talc determined by an improved EBSD procedure for sheet silicates: Implications for anisotropy at the slab–mantle interface due to Si-metasomatism
- The occurrence, origin, and fate of water in chromitites in ophiolites
- Thermoelasticity of tremolite amphibole: Geophysical implications
- Stability of fcc phase FeH to 137 GPa
- Partition coefficients of trace elements between carbonates and melt and suprasolidus phase relation of Ca-Mg-carbonates at 6 GPa
- Systematics of H2 and H2O evolved from chlorites during oxidative dehydrogenation
- Texture and geochemistry of multi-stage hydrothermal scheelite in the Tongshankou porphyry-skarn Cu-Mo(-W) deposit, eastern China: Implications for ore-forming process and fluid metasomatism
- EXCALIBR to EXCELIBR and the optical orientation of minerals: Correcting the optical orientation of clinoamphiboles
- A refined zirconium-in-rutile thermometer
- New Mineral Names
- Book Review