A thermally conductive Martian core and implications for its dynamo cessation.

Mars experienced a dynamo process that generated a global magnetic field ~4.3 (or earlier) to 3.6 billion years ago (Ga). The cessation of this dynamo strongly affected Mars' history and is expected to be linked to thermochemical evolution of Mars' iron-rich liquid core, which is strongly influenced by its thermal conductivity. Here, we directly measured thermal conductivities of solid iron-sulfur alloys to pressures relevant to the Martian core and temperatures to 1023 Kelvin. Our results show that a Martian core with 16 weight % sulfur has a thermal conductivity of ~19 to 32 Watt meter-1 Kelvin-1 from its top to the center, much higher than previously inferred from electrical resistivity measurements. Our modeled thermal conductivity profile throughout the Martian deep-mantle and core indicates a ~4- to 6-fold discontinuity across the core-mantle boundary. The core's efficient cooling resulting from the depth-dependent, high conductivity diminishes thermal convection and forms thermal stratification, substantially contributing to cessation of Martian dynamo.

Collective motion in hcp-Fe at Earth's inner core conditions.

Earth's inner core is predominantly composed of solid iron (Fe) and displays intriguing properties such as strong shear softening and an ultrahigh Poisson's ratio. Insofar, physical mechanisms to explain these features coherently remain highly debated. Here, we have studied longitudinal and shear wave velocities of hcp-Fe (hexagonal close-packed iron) at relevant pressure-temperature conditions of the inner core using in situ shock experiments and machine learning molecular dynamics (MLMD) simulations. Our results demonstrate that the shear wave velocity of hcp-Fe along the Hugoniot in the premelting condition, defined as T/Tm (Tm: melting temperature of iron) above 0.96, is significantly reduced by ~30%, while Poisson's ratio jumps to approximately 0.44. MLMD simulations at 230 to 330 GPa indicate that collective motion with fast diffusive atomic migration occurs in premelting hcp-Fe primarily along [100] or [010] crystallographic direction, contributing to its elastic softening and enhanced Poisson's ratio. Our study reveals that hcp-Fe atoms can diffusively migrate to neighboring positions, forming open-loop and close-loop clusters in the inner core conditions. Hcp-Fe with collective motion at the inner core conditions is thus not an ideal solid previously believed. The premelting hcp-Fe with collective motion behaves like an extremely soft solid with an ultralow shear modulus and an ultrahigh Poisson's ratio that are consistent with seismic observations of the region. Our findings indicate that premelting hcp-Fe with fast diffusive motion represents the underlying physical mechanism to help explain the unique seismic and geodynamic features of the inner core.

Lack of Association between YEASTONE Antifungal Susceptibility Tests and Clinical Outcomes of Cryptococcus Meningitis.

The relation between antifungal susceptibility and treatment outcomes is not well-characterized. There is paucity of surveillance data for cerebrospinal fluid (CSF) isolates of cryptococcus investigated with YEASTONE colorimetric broth microdilution susceptibility testing. A retrospective study of laboratory-confirmed cryptococcus meningitis (CM) patients was conducted. The antifungal susceptibility of CSF isolates was determined using YEASTONE colorimetric broth microdilution. Clinical parameters, CSF laboratory indices, and antifungal susceptibility results were analyzed to identify risk factors for mortality. High rates of resistance to fluconazole and flucytosine were observed in this cohort. Voriconazole had the lowest MIC (0.06 µg/mL) and lowest rate of resistance (3.8%). In a univariate analysis, hematological malignancy, concurrent cryptococcemia, high Sequential Organ Failure Assessment (SOFA) score, low Glasgow coma scale (GCS) score, low CSF glucose level, high CSF cryptococcal antigen titer, and high serum cryptococcal antigen burden were associated with mortality. In a multivariate analysis, meningitis with concurrent cryptococcemia, GCS score, and high CSF cryptococcus burden, were independent predictors of poor prognosis. Both early and late mortality rates were not significantly different between CM wild type and non-wild type species.

Strain-Modulated Interlayer Charge and Energy Transfers in MoS2/WS2 Heterobilayer.

Excitonic properties in 2D heterobilayers are closely governed by charge transfer (CT) and excitonic energy transfer (ET) at van der Waals interfaces. Various means have been employed to modulate the interlayer CT and ET, including electrical gating and modifying interlayer spacing, but with limited extent in their controllability. Here, we report a novel method to modulate these transfers in the MoS2/WS2 heterobilayer by applying compressive strain under hydrostatic pressure. Raman and photoluminescence measurements, combined with density functional theory calculations, show pressure-enhanced interlayer interaction of the heterobilayer. Heterobilayer-to-monolayer photoluminescence intensity ratio (η) of WS2 decreases by five times up to ≈4 GPa, suggesting enhanced ET, whereas it increases by an order of magnitude at higher pressures and reaches almost unity. Theoretical calculations show that orbital switching and charge transfers in the heterobilayer's hybridized conduction band are responsible for the non-monotonic modulation of the transfers. Our findings provide a compelling approach toward effective mechanical control of CT and ET in 2D excitonic devices.

Hot dense silica glass with ultrahigh elastic moduli.

Silicate and oxide glasses are often chemically doped with a variety of cations to tune for desirable properties in technological applications, but their performances are often limited by relatively lower mechanical and elastic properties. Finding a new route to synthesize silica-based glasses with high elastic and mechanical properties needs to be explored. Here, we report a dense SiO2-glass with ultra-high elastic moduli using sound velocity measurements by Brillouin scattering up to 72 GPa at 300 K. High-temperature measurements were performed up to 63 GPa at 750 K and 59 GPa at 1000 K. Compared to compression at 300 K, elevated temperature helps compressed SiO2-glass effectively overcome the kinetic barrier to undergo permanent densification with enhanced coordination number and connectivity. This hot compressed SiO2-glass exhibits a substantially high bulk modulus of 361-429 GPa which is at least 2-3 times greater than the metallic, oxide, and silicate glasses at ambient conditions. Its Poisson's ratio, an indicator for the packing efficiency, is comparable to the metallic glasses. Even after temperature quench and decompression to ambient conditions, the SiO2-glass retains some of its unique properties at compression and possesses a Poisson's ratio of 0.248(11). In addition to chemical alternatives in glass syntheses, coupled compression and heating treatments can be an effective means to enhance mechanical and elastic properties in high-performance glasses.

Molten iron in Earth-like exoplanet cores.

Iron crystallization in super-Earth interiors plays a key role in their habitability.

Thermal conductivity of Fe-Si alloys and thermal stratification in Earth's core.

Light elements in Earth's core play a key role in driving convection and influencing geodynamics, both of which are crucial to the geodynamo. However, the thermal transport properties of iron alloys at high-pressure and -temperature conditions remain uncertain. Here we investigate the transport properties of solid hexagonal close-packed and liquid Fe-Si alloys with 4.3 and 9.0 wt % Si at high pressure and temperature using laser-heated diamond anvil cell experiments and first-principles molecular dynamics and dynamical mean field theory calculations. In contrast to the case of Fe, Si impurity scattering gradually dominates the total scattering in Fe-Si alloys with increasing Si concentration, leading to temperature independence of the resistivity and less electron-electron contribution to the conductivity in Fe-9Si. Our results show a thermal conductivity of ∼100 to 110 W⋅m-1⋅K-1 for liquid Fe-9Si near the topmost outer core. If Earth's core consists of a large amount of silicon (e.g., > 4.3 wt %) with such a high thermal conductivity, a subadiabatic heat flow across the core-mantle boundary is likely, leaving a 400- to 500-km-deep thermally stratified layer below the core-mantle boundary, and challenges proposed thermal convection in Fe-Si liquid outer core.

Electronic and crystal structures ofLnFeAsO1-xHx(Ln= La, Sm) studied by x-ray absorption spectroscopy, x-ray emission spectroscopy, and x-ray diffraction: II pressure dependence.

We examine electronic and crystal structures of iron-based superconductorsLnFeAsO1-xHx(Ln= La, Sm) under pressure by means of x-ray absorption spectroscopy (XAS), x-ray emission spectroscopy (XES), and x-ray diffraction. In LaFeAsO the pre-edge peak on high-resolution XAS at the Fe-Kabsorption edge gains in intensity on the application of pressure up to 5.7 GPa and it saturates in the higher pressure region. We found integrated-absolute difference values on XES forLn= La, corresponding to a spin state, decline on the application of pressure, and then it is minimized when theTcapproaches the maximum at around 5 GPa. In contrast, such the optimum value was not detected forLn= Sm. We reveal that the superconductivity is closely related to the lower spin state forLn= La unlike Sm case. We observed that As height from the Fe basal plane and As-Fe-As angle on the FeAs4tetrahedron forLn= La deviate from the optimum values of the regular tetrahedron in superconducting (SC) phase, which has been widely accepted structural guide to SC thus far. In contrast, the structural parameters were held near the optimum values up to ∼15 GPa forLn= Sm.

Electronic and crystal structures ofLnFeAsO1-xHx(Ln= La, Sm) studied by x-ray absorption spectroscopy, x-ray emission spectroscopy, and x-ray diffraction (part I: carrier-doping dependence).

A carrier doping by a hydrogen substitution in LaFeAsO1-xHxis known to cause two superconducting (SC) domes with the magnetic order at both end sides of the doping. In contrast, SmFeAsO1-xHxhas a similar phase diagram but shows single SC dome. Here, we investigated the electronic and crystal structures for iron oxynitrideLnFeAsO1-xHx(Ln= La, Sm) with the range ofx= 0-0.5 by using x-ray absorption spectroscopy, x-ray emission spectroscopy, and x-ray diffraction. For both compounds, we observed that the pre-edge peaks of x-ray absorption spectra near the Fe-Kedge were reduced in intensity on doping. The character arises from the weaker As-Fe hybridization with the longer As-Fe distance in the higher doped region. We can reproduce the spectra near the Fe-Kedge according to the Anderson impurity model with realistic valence structures using the local-density approximation (LDA) plus dynamical mean-field theory (DMFT). ForLn= Sm, the integrated-absolute difference (IAD) analysis from x-ray Fe-Kßemission spectra increases significantly. This is attributed to the enhancement of magnetic moment of Fe 3delectrons stemming from the localized picture in the higher doped region. A theoretical simulation implementing the self-consistent vertex-correction method reveals that the single dome superconducting phase forLn= Sm arises from a better nesting condition in comparison withLn= La.

Tungsten Hexanitride with Single-Bonded Armchairlike Hexazine Structure at High Pressure.

WN_{6} phase discovered at 126-165 GPa after heating of W in nitrogen. XRD refinements reveal a unit cell in space group R3[over ¯]m which is consistent with the WN_{6} structure with armchairlike hexazine (N_{6}) rings, while strong A_{1g} Raman mode confirms its N─N single bonds. Density functional theory (DFT) calculations reveal balanced contributions of attractive interactions between W and covalent N_{6} rings, and repulsions between N_{6} rings that make WN_{6} ultrastiff and tough. The WN_{6} phase displays long bond lengths in the nearest N-N and pressure-enhanced electronic band gap, which pave the way for finding novel nitrides.

Elasticity of a Pseudoproper Ferroelastic Transition from Stishovite to Post-Stishovite at High Pressure.

Elastic moduli (C_{ij}) of single-crystal stishovite and post-stishovite are determined using Brillouin light scattering, impulsive stimulated light scattering, and x-ray diffraction up to 70 GPa. The C_{12} of stishovite converges with the C_{11} at ∼55 GPa, where the transverse wave V_{S1} propagating along [110] also vanishes. Landau modeling of the C_{ij}, B_{1g} optic mode, and lattice parameters reveals a pseudoproper type ferroelastic post-stishovite transition. The transition would cause peculiar anomalies in V_{S} and Poisson's ratio in silica-bearing subducting slabs in the mid-lower mantle.

Pressure-Dependent Behavior of Defect-Modulated Band Structure in Boron Arsenide.

The recent observation of unusually high thermal conductivity exceeding 1000 W m-1 K-1 in single-crystal boron arsenide (BAs) has led to interest in the potential application of this semiconductor for thermal management. Although both the electron/hole high mobilities have been calculated for BAs, there is a lack of experimental investigation of its electronic properties. Here, a photoluminescence (PL) measurement of single-crystal BAs at different temperatures and pressures is reported. The measurements reveal an indirect bandgap and two donor-acceptor pair (DAP) recombination transitions. Based on first-principles calculations and time-of-flight secondary-ion mass spectrometry results, the two DAP transitions are confirmed to originate from Si and C impurities occupying shallow energy levels in the bandgap. High-pressure PL spectra show that the donor level with respect to the conduction band minimum shrinks with increasing pressure, which affects the release of free carriers from defect states. These findings suggest the possibility of strain engineering of the transport properties of BAs for application in electronic devices.

Reconciliation of Experiments and Theory on Transport Properties of Iron and the Geodynamo.

We measure the electrical resistivity of hcp iron up to ∼170 GPa and ∼3000 K using a four-probe van der Pauw method coupled with homogeneous flattop laser heating in a DAC, and compute its electrical and thermal conductivity by first-principles molecular dynamics including electron-phonon and electron-electron scattering. We find that the measured resistivity of hcp iron increases almost linearly with temperature, and is consistent with our computations. The results constrain the resistivity and thermal conductivity of hcp iron to ∼80±5 µΩ cm and ∼100±10 W m^{-1} K^{-1}, respectively, at conditions near the core-mantle boundary. Our results indicate an adiabatic heat flow of ∼10±1 TW out of the core, supporting a present-day geodynamo driven by thermal and compositional convection.

Low thermal conductivity of iron-silicon alloys at Earth's core conditions with implications for the geodynamo.

Earth's core is composed of iron (Fe) alloyed with light elements, e.g., silicon (Si). Its thermal conductivity critically affects Earth's thermal structure, evolution, and dynamics, as it controls the magnitude of thermal and compositional sources required to sustain a geodynamo over Earth's history. Here we directly measured thermal conductivities of solid Fe and Fe-Si alloys up to 144 GPa and 3300 K. 15 at% Si alloyed in Fe substantially reduces its conductivity by about 2 folds at 132 GPa and 3000 K. An outer core with 15 at% Si would have a conductivity of about 20 W m-1 K-1, lower than pure Fe at similar pressure-temperature conditions. This suggests a lower minimum heat flow, around 3 TW, across the core-mantle boundary than previously expected, and thus less thermal energy needed to operate the geodynamo. Our results provide key constraints on inner core age that could be older than two billion-years.

Stacking-Order-Driven Optical Properties and Carrier Dynamics in ReS2.

Two distinct stacking orders in ReS2 are identified without ambiguity and their influence on vibrational, optical properties and carrier dynamics are investigated. With atomic resolution scanning transmission electron microscopy (STEM), two stacking orders are determined as AA stacking with negligible displacement across layers, and AB stacking with about a one-unit cell displacement along the a axis. First-principles calculations confirm that these two stacking orders correspond to two local energy minima. Raman spectra inform a consistent difference of modes I & III, about 13 cm-1 for AA stacking, and 20 cm-1 for AB stacking, making a simple tool for determining the stacking orders in ReS2 . Polarized photoluminescence (PL) reveals that AB stacking possesses blueshifted PL peak positions, and broader peak widths, compared with AA stacking, indicating stronger interlayer interaction. Transient transmission measured with femtosecond pump-probe spectroscopy suggests exciton dynamics being more anisotropic in AB stacking, where excited state absorption related to Exc. III mode disappears when probe polarization aligns perpendicular to b axis. The findings underscore the stacking-order driven optical properties and carrier dynamics of ReS2 , mediate many seemingly contradictory results in the literature, and open up an opportunity to engineer electronic devices with new functionalities by manipulating the stacking order.

Prediction and Synthesis of Dysprosium Hydride Phases at High Pressure.

Crystal structure prediction (CSP) methods recently proposed a series of new rare-earth (RE) hydrides at high pressures with novel crystal structures, unusual stoichiometries, and intriguing features such as high-Tc superconductivity. RE trihydrides (REH3) generally undergo a phase transition from ambient P63/mmc or P3̅c1 to Fm3̅m at high pressure. This cubic REH3 (Fm3̅m) was considered to be a precursor to further synthesize RE polyhydrides such as YH4, YH6, YH9, and CeH9 with higher hydrogen contents at higher pressures. However, the structural stability and equation of state (EOS) of any of the REH3 have not been fully investigated at sufficiently high pressures. This work presents high-pressure X-ray diffraction (XRD) measurements in a laser-heated diamond anvil cell up to 100 GPa and ab initio evolutionary CSP of stable phases of DyH3 up to 220 GPa. Experiments observed the Fm3̅m phase of DyH3 to be stable at pressures from 17 to 100 GPa and temperatures up to ∼2000 K. After complete decompression, the P3̅c1 and Fm3̅m phases of DyH3 recovered under ambient conditions. Our calculations predicted a series of phases for DyH3 at high pressures with the structural phase transition sequence P3̅c1 → Imm2 → Fm3̅m → Pnma → P63/mmc at 11, 35, 135, and 194 GPa, respectively. The predicted P3̅c1 and Fm3̅m phases are consistent with experimental observations. Furthermore, electronic band structure calculations were carried out for the predicted phases of DyH3, including the 4f states, within the DFT+U approach. The inclusion of 4f states shows significant changes in electronic properties, as more Dy d states cross the Fermi level and overlap with H 1s states. The structural phase transition from P3̅c1 to Fm3̅m observed in DyH3 is systematically compared with other REH3 compounds at high pressures. The phase transition pressure in REH3 shows an inverse relation with the ionic radius of RE atoms.

Degree of Permanent Densification in Oxide Glasses upon Extreme Compression up to 24 GPa at Room Temperature.

During the decompression of plastically deformed glasses at room temperature, some aspects of irreversible densification may be preserved. This densification has been primarily attributed to topological changes in glass networks. The changes in short-range structures like cation coordination numbers are often assumed to be relaxed upon decompression. Here the NMR results for aluminosilicate glass upon permanent densification up to 24 GPa reveal noticeable changes in the Al coordination number under pressure conditions as low as ∼6 GPa. A drastic increase in the highly coordinated Al fraction is evident over only a relatively narrow pressure range of up to ∼12 GPa, above which the coordination change becomes negligible up to 24 GPa. In contrast, Si coordination environments do not change, highlighting preferential coordination transformation during deformation. The observed trend in the coordination environment shows a remarkable similarity to the pressure-induced changes in the residual glass density, yielding a predictive relationship between the irreversible densification and the detailed structures under extreme compression. The results open a way to access the nature of plastic deformation in complex glasses at room temperature.

Synthesis of clathrate cerium superhydride CeH9 at 80-100 GPa with atomic hydrogen sublattice.

Hydrogen-rich superhydrides are believed to be very promising high-Tc superconductors. Recent experiments discovered superhydrides at very high pressures, e.g. FeH5 at 130 GPa and LaH10 at 170 GPa. With the motivation of discovering new hydrogen-rich high-Tc superconductors at lowest possible pressure, here we report the prediction and experimental synthesis of cerium superhydride CeH9 at 80-100 GPa in the laser-heated diamond anvil cell coupled with synchrotron X-ray diffraction. Ab initio calculations were carried out to evaluate the detailed chemistry of the Ce-H system and to understand the structure, stability and superconductivity of CeH9. CeH9 crystallizes in a P63/mmc clathrate structure with a very dense 3-dimensional atomic hydrogen sublattice at 100 GPa. These findings shed a significant light on the search for superhydrides in close similarity with atomic hydrogen within a feasible pressure range. Discovery of superhydride CeH9 provides a practical platform to further investigate and understand conventional superconductivity in hydrogen rich superhydrides.

Thermal Conductivity Enhancement in MoS_{2} under Extreme Strain.

Because of their weak interlayer bonding, van der Waals (vdW) solids are very sensitive to external stimuli such as strain. Experimental studies of strain tuning of thermal properties in vdW solids have not yet been reported. Under ∼9% cross-plane compressive strain created by hydrostatic pressure in a diamond anvil cell, we observed an increase of cross-plane thermal conductivity in bulk MoS_{2} from 3.5 to about 25 W m^{-1} K^{-1}, measured with a picosecond transient thermoreflectance technique. First-principles calculations and coherent phonon spectroscopy experiments reveal that this drastic change arises from the strain-enhanced interlayer interaction, heavily modified phonon dispersions, and decrease in phonon lifetimes due to the unbundling effect along the cross-plane direction. The contribution from the change of electronic thermal conductivity is negligible. Our results suggest possible parallel tuning of structural, thermal, and electrical properties of vdW solids with strain in multiphysics devices.

The effect of substrate and surface plasmons on symmetry breaking at the substrate interface of the topological insulator Bi2Te3.

A pressing challenge in engineering devices with topological insulators (TIs) is that electron transport is dominated by the bulk conductance, and so dissipationless surface states account for only a small fraction of the conductance. Enhancing the surface-to-volume ratio is a common method to enhance the relative contribution of such states. In thin films with reduced thickness, the confinement results in symmetry-breaking and is critical for the experimental observation of topologically protected surface states. We employ micro-Raman and tip-enhanced Raman spectroscopy to examine three different mechanisms of symmetry breaking in Bi2Te3 TI thin films: surface plasmon generation, charge transfer, and application of a periodic strain potential. These mechanisms are facilitated by semiconducting and insulating substrates that modify the electronic and mechanical conditions at the sample surface and alter the long-range interactions between Bi2Te3 and the substrate. We confirm the symmetry breaking in Bi2Te3 via the emergence of the Raman-forbidden [Formula: see text] mode. Our results suggest that topological surface states can exist at the Bi2Te3/substrate interface, which is in a good agreement with previous theoretical results predicting the tunability of the vertical location of helical surface states in TI/substrate heterostructures.