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Abstract Sub-Neptune exoplanets may have thick hydrogen envelopes and therefore develop a high-pressure interface between hydrogen and the underlying silicates/metals. Some sub-Neptunes may convert to super-Earths via massive gas loss. If hydrogen chemically reacts with oxides and metals at high pressures and temperatures (P−T), it could impact the structure and composition of the cores and atmospheres of sub-Neptunes and super-Earths. While H2gas is a strong reducing agent at low pressures, the behavior of hydrogen is unknown at theP−Texpected for sub-Neptunes’ interiors, where hydrogen is a dense supercritical fluid. Here we report experimental results of reactions between ferrous/ferric oxides and hydrogen at 20–40 GPa and 1000–4000 K utilizing the pulsed laser-heated diamond-anvil cell combined with synchrotron X-ray diffraction. Under these conditions, hydrogen spontaneously strips iron off the oxides, forming Fe-H alloys and releasing oxygen to the hydrogen medium. In a planetary context where this reaction may occur, the Fe-H alloy may sink to the metallic part of the core, while released oxygen may stabilize as water in the silicate layer, providing a mechanism to ingas hydrogen to the deep interiors of sub-Neptunes. Water produced from the redox reaction can also partition to the atmosphere of sub-Neptunes, which has important implications for understanding the composition of their atmospheres. In addition, super-Earths converted from sub-Neptunes may contain a large amount of hydrogen and water in their interiors (at least a few wt% H2O). This is distinct from smaller rocky planets, which were formed relatively dry (likely a few hundredths wt% H2O).more » « less
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Abstract H2O transforms to two forms of superionic (SI) ice at high pressures and temperatures, which contain highly mobile protons within a solid oxygen sublattice. Yet the stability field of both phases remains debated. Here, we present the results of an ultrafast X-ray heating study utilizing MHz pulse trains produced by the European X-ray Free Electron Laser to create high temperature states of H2O, which were probed using X-ray diffraction during dynamic cooling. We confirm an isostructural transition during heating in the 26-69 GPa range, consistent with the formation of SI-bcc. In contrast to prior work, SI-fcc was observed exclusively above ~50 GPa, despite evidence of melting at lower pressures. The absence of SI-fcc in lower pressure runs is attributed to short heating timescales and the pressure-temperature path induced by the pump-probe heating scheme in which H2O was heated above its melting temperature before the observation of quenched crystalline states, based on the earlier theoretical prediction that SI-bcc nucleates more readily from the fluid than SI-fcc. Our results may have implications for the stability of SI phases in ice-rich planets, for example during dynamic freezing, where the preferential crystallization of SI-bcc may result in distinct physical properties across mantle ice layers.more » « less
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null (Ed.)X-ray diffraction indicates that the structure of the recently discovered carbonaceous sulfur hydride (C-S-H) room temperature superconductor is derived from previously established van der Waals compounds found in the H2S-H2 and CH4-H2 systems. Crystals of the superconducting phase were produced by a photochemical synthesis technique leading to the superconducting critical temperature Tc of 288 K at 267 GPa. X-ray diffraction patterns measured from 124 to 178 GPa, within the pressure range of the superconducting phase, are consistent with an orthorhombic structure derived from the Al2Cu-type determined for (H2S)2H2 and (CH4)2H2 that differs from those predicted and observed for the S-H system to these pressures. The formation and stability of the C-S-H compound can be understood in terms of the close similarity in effective volumes of the H2S and CH4 components, and denser carbon-bearing S-H phases may form at higher pressures. The results are crucial for understanding the very high superconducting Tc found in the C-S-H system at megabar pressures.more » « less
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Experiments accessing extreme conditions at x-ray free electron lasers (XFELs) involve rapidly evolving conditions of temperature. Here, we report time-resolved, direct measurements of temperature using spectral streaked optical pyrometry of x-ray and optical laser-heated states at the High Energy Density instrument of the European XFEL. This collection of typical experiments, coupled with numerical models, outlines the reliability, precision, and meaning of time dependent temperature measurements using optical emission at XFEL sources. Dynamic temperatures above 1500 K are measured continuously from spectrally- and temporally-resolved thermal emission at 450–850 nm, with time resolution down to 10–100 ns for 1–200 μs streak camera windows, using single shot and integrated modes. Targets include zero-pressure foils free-standing in air and in vacuo, and high-pressure samples compressed in diamond anvil cell multi-layer targets. Radiation sources used are 20-fs hard x-ray laser pulses at 17.8 keV, in single pulses or 2.26 MHz pulse trains of up to 30 pulses, and 250-ns infrared laser single pulses. A range of further possibilities for optical measurements of visible light in x-ray laser experiments using streak optical spectroscopy are also explored, including for the study of x-ray induced optical fluorescence, which often appears as background in thermal radiation measurements. We establish several scenarios where combined emissions from multiple sources are observed and discuss their interpretation. Challenges posed by using x-ray lasers as non-invasive probes of the sample state are addressed.more » « less
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