Simultaneous bright- and dark-field X-ray microscopy at X-ray free electron lasers.

The structures, strain fields, and defect distributions in solid materials underlie the mechanical and physical properties across numerous applications. Many modern microstructural microscopy tools characterize crystal grains, domains and defects required to map lattice distortions or deformation, but are limited to studies of the (near) surface. Generally speaking, such tools cannot probe the structural dynamics in a way that is representative of bulk behavior. Synchrotron X-ray diffraction based imaging has long mapped the deeply embedded structural elements, and with enhanced resolution, dark field X-ray microscopy (DFXM) can now map those features with the requisite nm-resolution. However, these techniques still suffer from the required integration times due to limitations from the source and optics. This work extends DFXM to X-ray free electron lasers, showing how the [Formula: see text] photons per pulse available at these sources offer structural characterization down to 100 fs resolution (orders of magnitude faster than current synchrotron images). We introduce the XFEL DFXM setup with simultaneous bright field microscopy to probe density changes within the same volume. This work presents a comprehensive guide to the multi-modal ultrafast high-resolution X-ray microscope that we constructed and tested at two XFELs, and shows initial data demonstrating two timing strategies to study associated reversible or irreversible lattice dynamics.

A MHz X-ray diffraction set-up for dynamic compression experiments in the diamond anvil cell.

An experimental platform for dynamic diamond anvil cell (dDAC) research has been developed at the High Energy Density (HED) Instrument at the European X-ray Free Electron Laser (European XFEL). Advantage was taken of the high repetition rate of the European XFEL (up to 4.5 MHz) to collect pulse-resolved MHz X-ray diffraction data from samples as they are dynamically compressed at intermediate strain rates (≤103 s-1), where up to 352 diffraction images can be collected from a single pulse train. The set-up employs piezo-driven dDACs capable of compressing samples in ≥340 µs, compatible with the maximum length of the pulse train (550 µs). Results from rapid compression experiments on a wide range of sample systems with different X-ray scattering powers are presented. A maximum compression rate of 87 TPa s-1 was observed during the fast compression of Au, while a strain rate of ∼1100 s-1 was achieved during the rapid compression of N2 at 23 TPa s-1.

Intense Reactivity in Sulfur-Hydrogen Mixtures at High Pressure under X-ray Irradiation.

Superconductivity near room temperature in the sulfur-hydrogen system arises from a sequence of reactions at high pressures, with X-ray diffraction experiments playing a central role in understanding these chemical-structural transformations and the corresponding S:H stoichiometry. Here we document X-ray irradiation acting as both a probe and as a driver of chemical reaction in this dense hydride system. We observe a reaction between molecular hydrogen (H2) and elemental sulfur (S8) under high pressure, induced directly by X-ray illumination, at photon energies of 12 keV using a free electron laser. The rapid synthesis of hydrogen sulfide (H2S) at 0.3 GPa was confirmed by optical observations, spectroscopic measurements, and microstructural changes detected by X-ray diffraction. These results document X-ray induced chemical synthesis of superconductor-forming dense hydrides, revealing an alternative production strategy and confirming the disruptive nature of X-ray exposure in studies on high-pressure hydrogen chalcogenides, from water to high-temperature superconductors.

A Spectroscopic Study of the Insulator-Metal Transition in Liquid Hydrogen and Deuterium.

The insulator-to-metal transition in dense fluid hydrogen is an essential phenomenon in the study of gas giant planetary interiors and the physical and chemical behavior of highly compressed condensed matter. Using direct fast laser spectroscopy techniques to probe hydrogen and deuterium precompressed in a diamond anvil cell and laser heated on microsecond timescales, an onset of metal-like reflectance is observed in the visible spectral range at P >150 GPa and T ≥ 3000 K. The reflectance increases rapidly with decreasing photon energy indicating free-electron metallic behavior with a plasma edge in the visible spectral range at high temperatures. The reflectance spectra also suggest much longer electronic collision time (≥1 fs) than previously inferred, implying that metallic hydrogen at the conditions studied is not in the regime of saturated conductivity (Mott-Ioffe-Regel limit). The results confirm the existence of a semiconducting intermediate fluid hydrogen state en route to metallization.

Response to Comment on "Insulator-metal transition in dense fluid deuterium".

In their comment, Desjarlais et al claim that a small temperature drop occurs after isentropic compression of fluid deuterium through the first-order insulator-metal transition. We show that their calculations do not correspond to the experimental thermodynamic path, and that thermodynamic integrations with parameters from first-principles calculations produce results in agreement with our original estimate of the temperature drop.

Insulator-metal transition in dense fluid deuterium.

Dense fluid metallic hydrogen occupies the interiors of Jupiter, Saturn, and many extrasolar planets, where pressures reach millions of atmospheres. Planetary structure models must describe accurately the transition from the outer molecular envelopes to the interior metallic regions. We report optical measurements of dynamically compressed fluid deuterium to 600 gigapascals (GPa) that reveal an increasing refractive index, the onset of absorption of visible light near 150 GPa, and a transition to metal-like reflectivity (exceeding 30%) near 200 GPa, all at temperatures below 2000 kelvin. Our measurements and analysis address existing discrepancies between static and dynamic experiments for the insulator-metal transition in dense fluid hydrogen isotopes. They also provide new benchmarks for the theoretical calculations used to construct planetary models.

Metallization and molecular dissociation of dense fluid nitrogen.

Diatomic nitrogen is an archetypal molecular system known for its exceptional stability and complex behavior at high pressures and temperatures, including rich solid polymorphism, formation of energetic states, and an insulator-to-metal transformation coupled to a change in chemical bonding. However, the thermobaric conditions of the fluid molecular-polymer phase boundary and associated metallization have not been experimentally established. Here, by applying dynamic laser heating of compressed nitrogen and using fast optical spectroscopy to study electronic properties, we observe a transformation from insulating (molecular) to conducting dense fluid nitrogen at temperatures that decrease with pressure and establish that metallization, and presumably fluid polymerization, occurs above 125 GPa at 2500 K. Our observations create a better understanding of the interplay between molecular dissociation, melting, and metallization revealing features that are common in simple molecular systems.

Optical Properties of Fluid Hydrogen at the Transition to a Conducting State.

We use fast transient transmission and emission spectroscopies in the pulse laser heated diamond anvil cell to probe the energy-dependent optical properties of hydrogen at pressures of 10-150 GPa and temperatures up to 6000 K. Hydrogen is absorptive at visible to near-infrared wavelengths above a threshold temperature that decreases from 3000 K at 18 GPa to 1700 K at 110 GPa. Transmission spectra at 2400 K and 141 GPa indicate that the absorptive hydrogen is semiconducting or semimetallic in character, definitively ruling out a first-order insulator-metal transition in the studied pressure range.

Direct measurement of thermal conductivity in solid iron at planetary core conditions.

The conduction of heat through minerals and melts at extreme pressures and temperatures is of central importance to the evolution and dynamics of planets. In the cooling Earth's core, the thermal conductivity of iron alloys defines the adiabatic heat flux and therefore the thermal and compositional energy available to support the production of Earth's magnetic field via dynamo action. Attempts to describe thermal transport in Earth's core have been problematic, with predictions of high thermal conductivity at odds with traditional geophysical models and direct evidence for a primordial magnetic field in the rock record. Measurements of core heat transport are needed to resolve this difference. Here we present direct measurements of the thermal conductivity of solid iron at pressure and temperature conditions relevant to the cores of Mercury-sized to Earth-sized planets, using a dynamically laser-heated diamond-anvil cell. Our measurements place the thermal conductivity of Earth's core near the low end of previous estimates, at 18-44 watts per metre per kelvin. The result is in agreement with palaeomagnetic measurements indicating that Earth's geodynamo has persisted since the beginning of Earth's history, and allows for a solid inner core as old as the dynamo.

Opacity and conductivity measurements in noble gases at conditions of planetary and stellar interiors.

The noble gases are elements of broad importance across science and technology and are primary constituents of planetary and stellar atmospheres, where they segregate into droplets or layers that affect the thermal, chemical, and structural evolution of their host body. We have measured the optical properties of noble gases at relevant high pressures and temperatures in the laser-heated diamond anvil cell, observing insulator-to-conductor transformations in dense helium, neon, argon, and xenon at 4,000-15,000 K and pressures of 15-52 GPa. The thermal activation and frequency dependence of conduction reveal an optical character dominated by electrons of low mobility, as in an amorphous semiconductor or poor metal, rather than free electrons as is often assumed for such wide band gap insulators at high temperatures. White dwarf stars having helium outer atmospheres cool slower and may have different color than if atmospheric opacity were controlled by free electrons. Helium rain in Jupiter and Saturn becomes conducting at conditions well correlated with its increased solubility in metallic hydrogen, whereas a deep layer of insulating neon may inhibit core erosion in Saturn.

Phase transformations and metallization of magnesium oxide at high pressure and temperature.

Magnesium oxide (MgO) is representative of the rocky materials comprising the mantles of terrestrial planets, such that its properties at high temperatures and pressures reflect the nature of planetary interiors. Shock-compression experiments on MgO to pressures of 1.4 terapascals (TPa) reveal a sequence of two phase transformations: from B1 (sodium chloride) to B2 (cesium chloride) crystal structures above 0.36 TPa, and from electrically insulating solid to metallic liquid above 0.60 TPa. The transitions exhibit large latent heats that are likely to affect the structure and evolution of super-Earths. Together with data on other oxide liquids, we conclude that magmas deep inside terrestrial planets can be electrically conductive, enabling magnetic field-producing dynamo action within oxide-rich regions and blurring the distinction between planetary mantles and cores.

Melting and dissociation of ammonia at high pressure and high temperature.

Raman spectroscopy and synchrotron x-ray diffraction measurements of ammonia (NH(3)) in laser-heated diamond anvil cells, at pressures up to 60 GPa and temperatures up to 2500 K, reveal that the melting line exhibits a maximum near 37 GPa and intermolecular proton fluctuations substantially increase in the fluid with pressure. We find that NH(3) is chemically unstable at high pressures, partially dissociating into N(2) and H(2). Ab initio calculations performed in this work show that this process is thermodynamically driven. The chemical reactivity dramatically increases at high temperature (in the fluid phase at T > 1700 K) almost independent of pressure. Quenched from these high temperature conditions, NH(3) exhibits structural differences from known solid phases. We argue that chemical reactivity of NH(3) competes with the theoretically predicted dynamic dissociation and ionization.

Structural and chemical properties of the nitrogen-rich energetic material triaminoguanidinium 1-methyl-5-nitriminotetrazolate under pressure.

The structural and chemical properties of the bi-molecular, hydrogen-bonded, nitrogen-rich energetic material triaminoguanidinium 1-methyl-5-nitriminotetrazolate C(3)H(12)N(12)O(2) (TAG-MNT) have been investigated at room pressure and under high pressure isothermal compression using powder x-ray diffraction and Raman and infrared spectroscopy. A stiffening of the equation of state and concomitant structural relaxation between 6 and 14 GPa are found to correlate with Raman mode disappearances, frequency discontinuities, and changes in the pressure dependence of modes. These observations manifest the occurrence of a reversible martensitic structural transformation to a new crystalline phase. The onset and vanishing of Fermi resonance in the nitrimine group correlate with the stiffening of the equation of state and phase transition, suggesting a possible connection between these phenomena. Beyond 15 GPa, pressure induces irreversible chemical reactions, culminating in the formation of a polymeric phase by 60 GPa.

Achieving high-density states through shock-wave loading of precompressed samples.

Materials can be experimentally characterized to terapascal pressures by sending a laser-induced shock wave through a sample that is precompressed inside a diamond-anvil cell. This combination of static and dynamic compression methods has been experimentally demonstrated and ultimately provides access to the 10- to 100-TPa (0.1-1 Gbar) pressure range that is relevant to planetary science, testing first-principles theories of condensed matter, and experimentally studying a new regime of chemical bonding.