High-Pressure and Temperature Effects on the Clustering Ability of Monohydroxy Alcohols.

This study examined the clustering behavior of monohydroxy alcohols, where hydrogen-bonded clusters of up to a hundred molecules on the nanoscale can form. By performing X-ray diffraction experiments at different temperatures and under high pressure, we investigated how these conditions affect the ability of alcohols to form clusters. The pioneering high-pressure experiment performed on liquid alcohols contributes to the emerging knowledge in this field. Implementation of molecular dynamics simulations yielded excellent agreement with the experimental results, enabling the analysis of theoretical models. Here we show that at the same global density achieved either by alteration of pressure or temperature, the local aggregation of molecules at the nanoscale may significantly differ. Surprisingly, high pressure not only promotes the formation of hydrogen-bonded clusters but also induces the serious reorganization of molecules. This research represents a milestone in understanding association under extreme thermodynamic conditions in other hydrogen bonding systems such as water.

Stable and metastable structures of tin (IV) oxide at high pressure.

We have analysed [Formula: see text] with a combination of synchrotron X-ray diffraction and X-ray absorption spectroscopy across a pressure range of [Formula: see text] GPa with thermal annealing by a [Formula: see text] laser allowing access to all of the known high-density polymorphs of [Formula: see text], and here report their crystallographic information. The metastability of the post-rutile [Formula: see text]-[Formula: see text] and [Formula: see text] structures in [Formula: see text] are investigated by experiment and PW-DFT simulations, revealing a complex energetic landscape and suggesting a significant dependence of the observed phases on the pressure-temperature pathway taken in experiment. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.

Experimental demonstration of necessary conditions for X-ray induced synthesis of cesium superoxide.

Absorption of sufficiently energetic X-ray photons by a molecular system results in a cascade of ultrafast electronic relaxation processes which leads to a distortion and dissociation of its molecular structure. Here, we demonstrate that only decomposition of powdered cesium oxalate monohydrate induced by monochromatic X-ray irradiation under high pressure leads to the formation of cesium superoxide. Whereas, for an unhydrated form of cesium oxalate subjected to the same extreme conditions, only degradation of the electron density distribution is observed. Moreover, the corresponding model of X-ray induced electronic relaxation cascades with an emphasis on water molecules' critical role is proposed. Our experimental results suggest that the presence of water molecules in initially solid-state systems (i.e. additional electronic relaxation channels) together with applied high pressure (reduced interatomic/intermolecular distance) could potentially be a universal criteria for chemical and structural synthesis of novel compounds via X-ray induced photochemistry.

CO2 laser heating system for in situ radial x-ray absorption at 16-BM-D at the Advanced Photon Source.

We present a portable CO2 laser heating system for in situ x-ray absorption spectroscopy (XAS) studies at 16-BM-D (High Pressure Collaborative Access Team, Advanced Photon Source, Argonne National Laboratory). Back scattering optical measurements are made possible by the implementation of a Ge beamsplitter. Optical pyrometry is conducted in the near-infrared, and our temperature measurements are free of chromatic aberration due to the implementation of the peak-scaling method [A. Kavner and W. R. Panero, Phys. Earth Planet. Inter. 143-144, 527-539 (2004) and A. Kavner and C. Nugent, Rev. Sci. Instrum. 79, 024902 (2008)] and mode scrambling of the input signal. Laser power stabilization is established using electronic feedback, providing a steady power over second timescales [Childs et al., Rev. Sci. Instrum. 91, 103003 (2020)]-crucial for longer XAS collections. Examples of in situ high pressure-temperature extended x-ray absorption fine structure measurements of ZrO2 are presented to demonstrate this new capability.

Overview of HPCAT and capabilities for studying minerals and various other materials at high-pressure conditions.

High-Pressure Collaborative Access Team (HPCAT) is a synchrotron-based facility located at the Advanced Photon Source (APS). With four online experimental stations and various offline capabilities, HPCAT is focused on providing synchrotron x-ray capabilities for high pressure and temperature research and supporting a broad user community. Overall, the array of online/offline capabilities is described, including some of the recent developments for remote user support and the concomitant impact of the current pandemic. General overview of work done at HPCAT and with a focus on some of the minerals relevant work and supporting capabilities is also discussed. With the impending APS-Upgrade (APS-U), there is a considerable effort within HPCAT to improve and add capabilities. These are summarized briefly for each of the end-stations.

Electron Density Changes across the Pressure-Induced Iron Spin Transition.

High-pressure single-crystal x-ray diffraction is used to experimentally map the electron-density distribution changes in (Fe,Mg)O as ferrous iron undergoes a pressure-induced transition from high- to low-spin states. As the bulk density and elasticity of magnesiowüstite-one of the dominant mineral phases of Earth's mantle-are affected by this electronic transition, our results have applications to geophysics as well as to validating first-principles calculations. The observed changes in diffraction intensities indicate a spin-transition-induced change in orbital occupancies of the Fe ion in general accord with crystal-field theory, illustrating the use of electron density measurements for characterizing high-pressure d-block chemistry and motivating further studies characterizing chemical bonding under pressure.

Pressure-induced metallization and 3d-like behavior in TcS2.

TcS2 undergoes a charge transfer insulator to metal transition above 28 GPa. Laser annealing reveals a kinetically hindered high pressure arsenopyrite phase that is recoverable to ambient. The new phase is similar to the Mn-dichalcogenides rather than the expected Re-dichalcogenides and involves the formation of S-S and Tc-Tc bonds.

The stability of subducted glaucophane with the Earth's secular cooling.

The blueschist to eclogite transition is one of the major geochemical-metamorphic processes typifying the subduction zone, which releases fluids triggering earthquakes and arc volcanism. Although glaucophane is an index hydrous mineral for the blueschist facies, its stability at mantle depths in diverse subduction regimes of contemporary and early Earth has not been experimentally determined. Here, we show that the maximum depth of glaucophane stability increases with decreasing thermal gradients of the subduction system. Along cold subduction geotherm, glaucophane remains stable down ca. 240 km depth, whereas it dehydrates and breaks down at as shallow as ca. 40 km depth under warm subduction geotherm or the Proterozoic tectonic setting. Our results imply that secular cooling of the Earth has extended the stability of glaucophane and consequently enabled the transportation of water into deeper interior of the Earth, suppressing arc magmatism, volcanism, and seismic activities along subduction zones.

Pressure Induced Assembly and Coalescence of Lead Chalcogenide Nanocrystals.

We report here pressure induced nanocrystal coalescence of ordered lead chalcogenide nanocrystal arrays into one-dimensional (1D) and 2D nanostructures. In particular, atomic crystal phase transitions and mesoscale coalescence of PbS and PbSe nanocrystals have been observed and monitored in situ respectively by wide- and small-angle synchrotron X-ray scattering techniques. At the atomic scale, both nanocrystals underwent reversible structural transformations from cubic to orthorhombic at significantly higher pressures than those for the corresponding bulk materials. At the mesoscale, PbS nanocrystal arrays displayed a superlattice transformation from face-centered cubic to lamellar structures, while no clear mesoscale lattice transformation was observed for PbSe nanocrystal arrays. Intriguingly, transmission electron microscopy showed that the applied pressure forced both spherical nanocrystals to coalesce into single crystalline 2D nanosheets and 1D nanorods. Our results confirm that pressure can be used as a straightforward approach to manipulate the interparticle spacing and engineer nanostructures with specific morphologies and, therefore, provide insights into the design and functioning of new semiconductor nanocrystal structures under high-pressure conditions.

Pressure-Induced Enhancement of Thermoelectric Figure of Merit and Structural Phase Transition in TiNiSn.

Half-Heusler thermoelectric materials are potential candidates for high thermoelectric efficiency. We report high-pressure thermoelectric and structural property measurements, density functional theory calculations on the half-Heusler material TiNiSn, and an increase of 15% in the relative dimensionless figure of merit, ZT, around 3 GPa. Thermal and electrical properties were measured utilizing a specialized sample cell assembly designed for the Paris-Edinburgh large-volume press to a maximum pressure of 3.5 GPa. High-pressure structural measurements performed up to 50 GPa in a diamond-anvil cell indicated the emergence of a new high-pressure phase around 20 GPa. A first-principles structure search performed using an ab initio random structure search approach identified the high-pressure phase as an orthorhombic type, in good agreement with the experimental results.

Long-Range Ordered Amorphous Atomic Chains as Building Blocks of a Superconducting Quasi-One-Dimensional Crystal.

Crystalline and amorphous structures are two of the most common solid-state phases. Crystals having orientational and periodic translation symmetries are usually both short-range and long-range ordered, while amorphous materials have no long-range order. Short-range ordered but long-range disordered materials are generally categorized into amorphous phases. In contrast to the extensively studied crystalline and amorphous phases, the combination of short-range disordered and long-range ordered structures at the atomic level is extremely rare and so far has only been reported for solvated fullerenes under compression. Here, a report on the creation and investigation of a superconducting quasi-1D material with long-range ordered amorphous building blocks is presented. Using a diamond anvil cell, monocrystalline (TaSe4 )2 I is compressed and a system is created where the TaSe4 atomic chains are in amorphous state without breaking the orientational and periodic translation symmetries of the chain lattice. Strikingly, along with the amorphization of the atomic chains, the insulating (TaSe4 )2 I becomes a superconductor. The data provide critical insight into a new phase of solid-state materials. The findings demonstrate a first ever case where superconductivity is hosted by a lattice with periodic but amorphous constituent atomic chains.

Nonclassical Behavior in Competitive Ion Adsorption at a Charged Solid-Water Interface.

Ion adsorption at solid-water interfaces is commonly described by interactions between specific surface sites and adsorbed ions in classical models. However, energetic contributions from non-site-specific ion-ion interactions have been less well understood. Here, we report nonclassical behaviors observed during competitive adsorption between Sr2+ and Na+/Rb+ at the negatively charged muscovite mica (001)-water interface, revealing apparent controls of adsorbed ion speciation over the interfacial reactivity. In the absence of competing cations, Sr2+ adsorbs in approximately equivalent proportions of inner-sphere and outer-sphere complexes, whereas it adsorbs predominantly as an outer-sphere complex in the presence of Na+/Rb+. This transformation of adsorbed Sr2+ speciation significantly decreases its adsorption strength, as indicated by the ∼15-fold shift in the Sr2+ adsorption edge concentration, compared to that calculated from a classical Langmuir isotherm model developed on the basis of site-specific interactions. These observations highlight the importance of non-site-specific interactions in controlling the energetics of chemical reactions at the charged interface.

Shape Dependence of Pressure-Induced Phase Transition in CdS Semiconductor Nanocrystals.

Understanding structural stability and phase transformation of nanoparticles under high pressure is of great scientific interest, as it is one of the crucial factors for design, synthesis, and application of materials. Even though high-pressure research on nanomaterials has been widely conducted, their shape-dependent phase transition behavior still remains unclear. Examples of phase transitions of CdS nanoparticles are very limited, despite the fact that it is one of the most studied wide band gap semiconductors. Here we have employed in situ synchrotron wide-angle X-ray scattering and transmission electron microscopy (TEM) to investigate the high-pressure behaviors of CdS nanoparticles as a function of particle shapes. We observed that CdS nanoparticles transform from wurtzite to rocksalt phase at elevated pressure in comparison to their bulk counterpart. Phase transitions also vary with particle shape: rod-shaped particles show a partially reversible phase transition and the onset of the structural phase transition pressure decreases with decreasing surface-to-volume ratios, while spherical particles undergo irreversible phase transition with relatively low phase transition pressure. Additionally, TEM images of spherical particles exhibited sintering-induced morphology change after high-pressure compression. Calculations of the bulk modulus reveal that spheres are more compressible than rods in the wurtzite phase. These results indicate that the shape of the particle plays an important role in determining their high-pressure properties. Our study provides important insights into understanding the phase-structure-property relationship, guiding future design and synthesis of nanoparticles for promising applications.

Room-temperature compression and equation of state of body-centered cubic zirconium.

Zirconium (Zr) has properties conducive to nuclear applications and exhibits complex behavior at high pressure with respect to the effects of impurities, deviatoric stress, kinetics, and grain growth which makes it scientifically interesting. Here, we present experimental results on the 300 K equation of state of ultra-high purity Zr obtained using the diamond-anvil cell coupled with synchrotron-based x-ray diffraction and electrical resistance measurements. Based on quasi-hydrostatic room-temperature compression in helium to pressure P = 69.4(2) GPa, we constrain the bulk modulus and its pressure derivative of body-centered cubic (bcc) ß-Zr to be K = 224(2) GPa and K' = 2.6(1) at P = 37.0(1) GPa. A Monte Carlo approach was developed to accurately quantify the uncertainties in K and K'. In the Monte Carlo simulations, both the unit-cell volume and pressure vary according to their experimental uncertainty. Our high-pressure studies do not indicate additional isostructural volume collapse in the bcc phase of Zr in the 56-58 GPa pressure range.

Novel Superstructure-Phase Two-Dimensional Material 1T-VSe2 at High Pressure.

A superstructure can elicit versatile new properties in materials by breaking their original geometrical symmetries. It is an important topic in the layered graphene-like two-dimensional transition metal dichalcogenides, but its origin remains unclear. Using diamond-anvil cell techniques, synchrotron X-ray diffraction, X-ray absorption, and first-principles calculations, we show that the evolution from weak van der Waals bonding to Heisenberg covalent bonding between layers induces an isostructural transition in quasi-two-dimensional 1T-type VSe2 at high pressure. Furthermore, our results show that high pressure induces a novel superstructure at 15.5 GPa rather than suppresses it as it would normally, which is unexpected. It is driven by Fermi-surface nesting, enhanced by pressure-induced distortion. The results suggest that the superstructure not only appears in the two-dimensional structure but also can emerge in the pressure-tuned three-dimensional structure with new symmetry and develop superconductivity.

Observation of 9-Fold Coordinated Amorphous TiO2 at High Pressure.

Knowledge of the structure in amorphous dioxides is important in many fields of science and engineering. Here we report new experimental results of high-pressure polyamorphism in amorphous TiO2 (a-TiO2). Our data show that the Ti coordination number (CN) increases from 7.2 ± 0.3 at ∼16 GPa to 8.8 ± 0.3 at ∼70 GPa and finally reaches a plateau at 8.9 ± 0.3 at ≲86 GPa. The evolution of the structural changes under pressure is rationalized by the ratio (γ) of the ionic radius of Ti to that of O. It appears that the CN ≈ 9 plateau correlates with the two 9-fold coordinated polymorphs (cotunnite, Fe2P) with different γ values. This CN-γ relationship is compared with those of a-SiO2 and a-GeO2, displaying remarkably consistent behavior between CN and γ. The unified CN-γ relationship may be generally used to predict the compression behavior of amorphous AO2 compounds under extreme conditions.

Real time study of grain enlargement in zirconium under room-temperature compression across the α to ω phase transition.

We report a synchrotron Laue diffraction study on the microstructure evolution in zirconium (Zr) as it undergoes a pressure-driven structural phase transformation, using a recently developed real time scanning x-ray microscopy technique. Time resolved characterizations of microstructure under high pressure show that Zr exhibits a grain enlargement across the α-Zr to ω-Zr structural phase transition at room-temperature, with nucleation and growth of ω-Zr crystals observed from initially a nano-crystalline aggregate of α-Zr. The observed grain enlargement is unusual since the enlargement processes typically require substantially high temperature to overcome the activation barriers for forming and moving of grain boundaries. Possible mechanisms for the grain enlargement are discussed.

Anomalous Conductivity in the Rutile Structure Driven by Local Disorder.

Many rutile-type materials are characterized by a softness in shear with pressure which is coupled to a Raman-active librational motion. Combining direct studies of anion positions in SnO2 with measurements of its electronic properties, we find a correlation between O sublattice disorder between 5 and 10 GPa and an anomalous decrease up to 4 orders of magnitude in electrical resistance. Hypotheses into the atomistic nature of the phenomenon are evaluated via ab initio calculations guided by extended X-ray absorption fine structure spectroscopy analysis, and the most likely mechanism is found to be the displacement of single anions resulting from the pressure-induced softening of the librational mode. On the basis of this mechanism, we propose that the same behavior should feature across all materials exhibiting a rutile → CaCl2 phase transition and that conductivity in other rutile-type materials could be facilitated at ambient pressure by appropriate design of devices to enhance defects of this nature.

Probing disorder in high-pressure cubic tin (IV) oxide: a combined X-ray diffraction and absorption study.

The transparent conducting oxide, SnO2, is a promising optoelectronic material with predicted tailorable properties via pressure-mediated band gap opening. While such electronic properties are typically modeled assuming perfect crystallinity, disordering of the O sublattice under pressure is qualitatively known. Here a quantitative approach is thus employed, combining extended X-ray absorption fine-structure (EXAFS) spectroscopy with X-ray diffraction, to probe the extent of Sn-O bond anharmonicities in the high-pressure cubic (Pa\bar{3}) SnO2 - formed as a single phase and annealed by CO2 laser heating to 2648 ± 41 K at 44.5 GPa. This combinational study reveals and quantifies a large degree of disordering in the O sublattice, while the Sn lattice remains ordered. Moreover, this study describes implementation of direct laser heating of non-metallic samples by CO2 laser alongside EXAFS, and the high quality of data which may be achieved at high pressures in a diamond anvil cell when appropriate thermal annealing is applied.