High-pressure X-ray Diffraction Research Articles

High-Pressure Structural and Optical Studies of Pure Low-Dimensional Cesium Lead Chlorides CsPb2Cl5 and Cs4PbCl6.

We report high-pressure single-crystal X-ray diffraction, optical absorption, and photoluminescence investigations of all-inorganic perovskite-related materials CsPb2Cl5 and Cs4PbCl6. The crystal structure of CsPb2Cl5, composed of alternate layers of Cs+ cations and Pb-Cl frameworks, is stable under pressure up to at least 4.2 GPa. Because external stress is mainly absorbed by the Cs+ layers, the optical absorption edge of the crystal only slightly red-shifts with increasing pressure, which correlates well with a moderate shortening of the Pb-Cl bonds. A quite different response to pressure shows Cs4PbCl6, the crystal built of isolated PbCl64- octahedra and Cs+ cations. During the compression at around 3.4 GPa, the trigonal phase I, space group R3̅c, transforms to the orthorhombic phase II, space group Cmce, which at around 4 GPa transforms into phase III. On decompression, phase II is not restored, but phase III converts through a diffuse phase transition into another high-pressure phase IV, which is stable in a wide pressure range and transforms to the initial phase I only around atmospheric pressure. The red shift of the absorption edge and the profound modification of the absorption spectrum in phase II were ascribed to the deformation of the PbCl64- octahedra. The transition to phase III induces a blue shift of the absorption edge, while the transition to phase IV is associated with a large red shift. Photoluminescence was detected in phases I and II with the intensity quenched with increasing pressure.

High-pressure high-temperature synthesis of NdRe2.

In this study, we report the synthesis of a new cubic neodymium-rhenium metallic alloy NdRe2 through the utilization of high pressure and laser heating in a diamond anvil cell. NdRe2 crystallizes in the space group with a lattice parameter equal to 7.486 (2) Å and Z = 8at 24 (1) GPa and 2,200 (100) K. It was studied using high-pressure single-crystal X-ray diffraction. The compound crystallizes in the cubic MgCu2 structure type. Its successful synthesis further proves that high-pressure high-temperature conditions can be used to obtain alloys holding a Laves phase structure. Ab initio calculations were done to predict the mechanical properties of the material. We also discuss the usage of extreme conditions to synthesize and study materials present in the nuclear waste.

Pressure-Induced Structural, Optical and Magnetic Modifications in Lanthanide Single-Molecule Magnets.

Lanthanide Single-Molecule Magnets are fascinating objects that break magnetic performance records with observable magnetic bistability at the boiling temperature of liquid nitrogen, paving the way for potential applications in high-density data storage. The switching of lanthanide SMM has been successfully achieved using several external stimuli such as redox reaction, pH titration, light irradiation or solvation/desolvation thanks to the high sensitivity of the magnetic anisotropy to any structural change in the lanthanide surrounding. Nevertheless, the use of applied high pressure as an external stimulus is largely underused, especially considering that it can be combined with high pressure X-ray diffraction to establish a complementary structure-property relationship. This Concept article summarizes the few relevant examples of investigations of lanthanide SMMs under applied high pressure, provides conclusions on the effect of such stimulus on molecular structures and magnetic anisotropy, and finally draws perspective on the future development of magnetic measurements under applied pressure.

Phase comparison and equation of state for Ta2O5

Tantalum pentoxide (Ta2O5) is among the most technologically useful heavy transition metal oxides. Unfortunately, its crystal structure is the subject of long-standing and unresolved disagreement. Among other consequences, this uncertainty has made it impossible to formulate a robust high pressure equation of state for Ta2O5. Here, we report the results of high pressure x-ray diffraction experiments indexed against a comprehensive list of proposed Ta2O5 phases. Five of the proposed phases produce good matches to experimental observations, and the compressibility parameters for these phases are all consistent within uncertainty. This means that regardless of the particular phase chosen, the Ta2O5 equation of state can be described with bulk modulus K0=138±3.68  GPa and pressure derivative K0′=1.82±0.45 . Combining these experimental results with new density-functional theory calculations allows us to identify the λ phase as the best structural model of Ta2O5 at ambient conditions.

Role of GdO addition in the structural stability of cubic Gd2O3 at high pressures: Determination of the equation of states of GdO and Gd2O3

We report a high-pressure X-ray diffraction study on bixbyite-type Gd2O3 showing that the addition of 4.3 mol% of GdO increases the pressure stability of Gd2O3. In our experiments the onset of the phase transition to the previously reported high-pressure trigonal polymorph was detected upon compression at 15.1(1) GPa, with the low- and high-pressure phases coexisting up to 20 GPa. The observed transition is reversible upon decompression. Our finding extends the high-pressure stability of the low-pressure phase, which in previous studies was reported to undergo phase transitions from 2.6 to 13.4 GPa. This is important for many of the technological applications of Gd2O3 including gas turbine engines, light water reactors, and nuclear waste immobilization. Additionally, we find that GdO undergoes an irreversible amorphization beyond 15.1(1) GPa. Finally, accurate equations of state were determined from experiments and density-functional theory calculations. These calculations also provided information on elastic constants and moduli. A systematic discussion of the bulk modulus and its pressure derivative is also presented.

Stabilization of N6 and N8 anionic units and 2D polynitrogen layers in high-pressure scandium polynitrides

Nitrogen catenation under high pressure leads to the formation of polynitrogen compounds with potentially unique properties. The exploration of the entire spectrum of poly- and oligo-nitrogen moieties is still in its earliest stages. Here, we report on four novel scandium nitrides, Sc2N6, Sc2N8, ScN5, and Sc4N3, synthesized by direct reaction between yttrium and nitrogen at 78-125 GPa and 2500 K in laser-heated diamond anvil cells. High-pressure synchrotron single-crystal X-ray diffraction reveals that in the crystal structures of the nitrogen-rich Sc2N6, Sc2N8, and ScN5 phases nitrogen is catenated forming previously unknown N66− and N86− units and ∞2(N53−)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\!\\,}_{\\infty }{\\!\\,}^{2}({{{{{\\rm{N}}}}}}_{5}^{3-})$$\\end{document} anionic corrugated 2D-polynitrogen layers consisting of fused N12 rings. Density functional theory calculations, confirming the dynamical stability of the synthesized compounds, show that Sc2N6 and Sc2N8 possess an anion-driven metallicity, while ScN5 is an indirect semiconductor. Sc2N6, Sc2N8, and ScN5 solids are promising high-energy-density materials with calculated volumetric energy density, detonation velocity, and detonation pressure higher than those of TNT.

Mechanical properties and high-pressure behavior of high entropy carbide (Mo, Nb, Ta, V, W)C

High-entropy carbides (HECs) often exhibit superior mechanical properties compared to single-component carbides. In this work, the (Mo0.2Nb0.2Ta0.2V0.2W0.2)C0.9 (named as Mo-HEC) was synthesized using the spark plasma sintering (SPS) method. The mechanical properties of Mo-HEC were evaluated using Vickers hardness and nanoindentation tests. The results indicate that Mo-HEC exhibits relatively high toughness, with hardness value surpassing the average hardness of constituent monocarbides. Nanoindentation tests on grains with different orientations revealed an isotropic mechanical behavior of Mo-HEC. Furthermore, the structural stability of Mo-HEC under extreme compression was explored by in situ high-pressure X-ray diffraction. Its cubic structure can be retained up to 58 GPa, and a bulk modulus of 334 GPa was obtained, which is among the highest reported values for HECs. The favorable mechanical properties, structural stability, and high bulk modulus suggest the significant potential of Mo-HEC for applications under extreme conditions.

Structure Responsible for the Superconducting State in La3Ni2O7 at High-Pressure and Low-Temperature Conditions.

Very recently, a new superconductor with Tc = 80 K has been reported in nickelate (La3Ni2O7) at around 15-40 GPa conditions (Nature, 621, 493, 2023), which is the second type of unconventional superconductor, besides cuprates, with Tc above liquid nitrogen temperature. However, the phase diagram plotted in this report was mostly based on the transport measurement under low-temperature and high-pressure conditions, and the assumed corresponding X-ray diffraction (XRD) results were carried out at room temperature. This encouraged us to carry out in situ high-pressure and low-temperature synchrotron XRD experiments to determine which phase is responsible for the high Tc state. In addition to the phase transition from the orthorhombic Amam structure to the orthorhombic Fmmm structure, a tetragonal phase with the space group of I4/mmm was discovered when the sample was compressed to around 19 GPa at 40 K where the superconductivity takes place in La3Ni2O7. The calculations based on this tetragonal structure reveal that the electronic states that approached the Fermi energy were mainly dominated by the eg orbitals (3dz2 and 3dx2-y2) of Ni atoms, which are located in the oxygen octahedral crystal field. The correlation between Tc and this structural evolution, especially Ni-O octahedra regularity and the in-plane Ni-O-Ni bonding angles, is analyzed. This work sheds new light to identify what is the most likely phase responsible for superconductivity in double-layered nickelate.

Structural evolvement of 1-methyl-3,4,5-trinitropyrazole at high pressure

Explosives, a type of energetic material (EM), face a high-pressure environment in the detonation process or under shock conditions. Determining their high-pressure behavior is critical to their explosion and safety. 1-Methyl-3,4,5-trinitropyrazole (MTNP), a carrier of melt-cast explosives, exhibits the potential for replacing trinitrotoluene (TNT). However, there is limited knowledge about its structural evolvement at high pressure. Using a diamond anvil cell (DAC), this study investigated the structural variation of MTNP through in situ high-pressure synchrotron angle-dispersive X-ray diffraction (ADXRD) experiments and Raman measurements. As evidenced by the results, MTNP underwent phase transition at 8.7 GPa and amorphization at 15.3 GPa due to high pressure. Through the analysis of first-principles calculations and Raman spectra, this study proposed the mechanisms behind the changes in MTNP at high pressure. Furthermore, this study systematically explored the structural evolvement of MTNP and the evolution of its weak intermolecular interactions at high pressure, gaining further understanding of MTNP's detonation and safety.

Pressure-induced superconductivity in SnSb2Te4

Owing to their unique compositional and structural characteristics, layered van der Waals solids in binary and ternary chalcogenide families provide a fertile testbed for exploring novel exotic structures and states, e.g., topological insulators and superconductors. Herein, a comprehensive study on the structural variations and correlated electrical transport behavior of SnSb2Te4, a ternary member, has been carried out considering elevated pressures. Under 45.6 GPa, three distinct structural phase transitions have been observed, with strong evidence from the variations of high-pressure X-ray diffraction patterns. The onsets of phase II (monoclinic, C2/m ) at 6.3 GPa, phase III (monoclinic, C2/c ) at 15.5 GPa, and phase IV (body-centered cubic with substitutional disorder, Im-3m ) at 17.2 GPa have been observed owing to the emergence of new diffractions. Based on electrical measurements at low temperature and high pressure conditions, two pressure-induced superconducting states have been distinguished in SnSb2Te4. The first state occurs in the range of 12.3-17.1 GPa. The positive pressure dependence on Tc indicates that the aforementioned state is related to the monoclinic C2/m phase. At > 17.1 GPa, the second superconducting state emerges, with the negative pressure dependence on Tc . It relates to the body-centered cubic solid solution phase, which is characteristic of a substitutional disordered crystal structure. The discovery that the pressure-induced superconductivity in SnSb2Te4 is affected by structural phase transitions under pressure may help understand the universal relationship between the ambient condition topological insulating state and derived superconductivity. Ab initio theoretical calculations reveal that an electronic topological transition takes place at approximately 2.0 GPa, which is featured by the obvious changes in the distribution of electronic density of states near the Fermi level.

High-pressure study on calcium azide (Ca(N3)2): the bending of the azide ions stabilizes the structure

Abstract The high-pressure structure and elastic properties of calcium azide (Ca(N3)2) were investigated using in-situ high-pressure X-ray diffraction and Raman scattering up to 54 GPa and 19 GPa, respectively. The compressibility of Ca(N3)2 changed as the pressure increased, and no phase transition occurred within the pressure from ambient pressure up to 54 GPa. The measured zero-pressure bulk modulus of Ca(N3)2 is higher than that of other alkali metal azides, due to differences in the ionic character of their metal-azide bonds. Using CASTEP, all vibration modes of Ca(N3)2 were accurately identified in the vibrational spectrum at ambient pressure. In the high-pressure vibration study, several external modes(ext.) and internal bending modes(ν2) of azide anions(N3 -) softened up to ~7 GPa and then hardened beyond that pressure. This evidence is consistent with the variation observed in the FE -fE data analyzed from the XRD result, where the slope of the curve changes at 7.1 GPa. The main behaviors under pressure are the alternating compression, rotation, and bending of N3 - ions. The bending behavior makes the structure of Ca(N3)2 more stable under pressure.

High-pressure study of a 3d-4f heterometallic CuEu-organic skeleton.

We prepared a 3d-4f heterobimetallic CuEu-organic framework NBU-8 with a density of 1921 kg m-3 belonging to the family of dense packing materials (dense metal-organic frameworks or MOFs). This MOF material was prepared from 4-(pyrimidin-5-yl)benzoic acid (HPBA) with a bifunctional ligand site as a tripodal ligand and Cu2+ and Eu3+ as the metal centres; the molecular formula is Cu3Eu2(PBA)6(NO3)6·H2O. This material is a very promising dimethylformamide (DMF) molecular chemical sensor. Systematic high-pressure studies of NBU-8 were carried out by powder X-ray diffraction, high-pressure X-ray diffraction and molecular dynamics simulation. The high-pressure experiment shows that the (006) diffraction peak of the crystal structure moves toward a low angle with increasing pressure, accompanied by the phenomenon that the d-spacing increases, and as the pressure increases, the (10-2) diffraction peak moves to a higher angle, the amplitude of the d-spacing is significantly reduced and finally merges with the (006) diffraction peak into one peak. The amplitude of the d-spacing is significantly reduced, indicating that NBU-8 compresses and deforms along the a-axis direction when subjected to uniform pressure. This is caused by tilting of the ligands to become more vertical along the c direction, leading to its expansion. This allows greater contraction along the a direction. We also carried out a Rietveld structure refinement and a Birch-Murnaghan solid-state equation fitting for the high-pressure experimental results. We calculated the bulk modulus of the material to be 45.68 GPa, which is consistent with the calculated results. The framework is among the most rigid MOFs reported to date, exceeding that of Cu-BTC. Molecular dynamics simulations estimated that the mechanical energy absorbed by the system when pressurized to 5.128 GPa was 249.261 kcal mol-1. The present work will provide fresh ideas for the study of mechanical energy in other materials.

High pressure raman spectroscopy and X-ray diffraction of K2Ca(CO3)2 bütschliite: multiple pressure-induced phase transitions in a double carbonate

The crystal structure and bonding environment of K2Ca(CO3)2 bütschliite were probed under isothermal compression via Raman spectroscopy to 95 GPa and single crystal and powder X-ray diffraction to 12 and 68 GPa, respectively. A second order Birch-Murnaghan equation of state fit to the X-ray data yields a bulk modulus, K0=46.9\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${K}_{0}=46.9$$\\end{document} GPa with an imposed value of K0′=4\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${K}_{0}^{\\prime}= 4$$\\end{document} for the ambient pressure phase. Compression of bütschliite is highly anisotropic, with contraction along the c-axis accounting for most of the volume change. Bütschliite undergoes a phase transition to a monoclinic C2/m structure at around 6 GPa, mirroring polymorphism within isostructural borates. A fit to the compression data of the monoclinic phase yields V0=322.2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${V}_{0}=322.2$$\\end{document} Å3,\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$,$$\\end{document}K0=24.8\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${K}_{0}=24.8$$\\end{document} GPa and K0′=4.0\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${K}_{0}^{\\prime}=4.0$$\\end{document} using a third order fit; the ability to access different compression mechanisms gives rise to a more compressible material than the low-pressure phase. In particular, compression of the C2/m phase involves interlayer displacement and twisting of the [CO3] units, and an increase in coordination number of the K+ ion. Three more phase transitions, at ~ 28, 34, and 37 GPa occur based on the Raman spectra and powder diffraction data: these give rise to new [CO3] bonding environments within the structure.

Barocaloric Effects in Dialkylammonium Halide Salts.

Barocaloric effects─solid-state thermal changes induced by the application and removal of hydrostatic pressure─offer the potential for energy-efficient heating and cooling without relying on volatile refrigerants. Here, we report that dialkylammonium halides─organic salts featuring bilayers of alkyl chains templated through hydrogen bonds to halide anions─display large, reversible, and tunable barocaloric effects near ambient temperature. The conformational flexibility and soft nature of the weakly confined hydrocarbons give rise to order-disorder phase transitions in the solid state that are associated with substantial entropy changes (>200 J kg-1 K-1) and high sensitivity to pressure (>24 K kbar-1), the combination of which drives strong barocaloric effects at relatively low pressures. Through high-pressure calorimetry, X-ray diffraction, and Raman spectroscopy, we investigate the structural factors that influence pressure-induced phase transitions of select dialkylammonium halides and evaluate the magnitude and reversibility of their barocaloric effects. Furthermore, we characterize the cyclability of thin-film samples under aggressive conditions (heating rate of 3500 K s-1 and over 11,000 cycles) using nanocalorimetry. Taken together, these results establish dialkylammonium halides as a promising class of pressure-responsive thermal materials.

The curious case of proton migration under pressure in the malonic acid and 4,4'-bipyridine cocrystal.

In the search for new active pharmaceutical ingredients, the precise control of the chemistry of cocrystals becomes essential. One crucial step within this chemistry is proton migration between cocrystal coformers to form a salt, usually anticipated by the empirical ΔpKa rule. Due to the effective role it plays in modifying intermolecular distances and interactions, pressure adds a new dimension to the ΔpKa rule. Still, this variable has been scarcely applied to induce proton-transfer reactions within these systems. In our study, high-pressure X-ray diffraction and Raman spectroscopy experiments, supported by DFT calculations, reveal modifications to the protonation states of the 4,4'-bipyridine (BIPY) and malonic acid (MA) cocrystal (BIPYMA) that allow the conversion of the cocrystal phase into ionic salt polymorphs. On compression, neutral BIPYMA and monoprotonated (BIPYH+MA-) species coexist up to 3.1 GPa, where a phase transition to a structure of P21/c symmetry occurs, induced by a double proton-transfer reaction forming BIPYH22+MA2-. The low-pressure C2/c phase is recovered at 2.4 GPa on decompression, leading to a 0.7 GPa hysteresis pressure range. This is one of a few studies on proton transfer in multicomponent crystals that shows how susceptible the interconversion between differently charged species is to even slight pressure changes, and how the proton transfer can be a triggering factor leading to changes in the crystal symmetry. These new data, coupled with information from previous reports on proton-transfer reactions between coformers, extend the applicability of the ΔpKa rule incorporating the pressure required to induce salt formation.

The intrinsic mechanical properties of hydromagnesite, Mg5(CO3)4(OH)2·4H2O, a key phase of reactive MgO carbonate cement

To potentially enable CO2 sequestration, reactive MgO carbonate cement is emerging as an alternative binder to Portland cement. Understanding the mechanical properties of its binding phase is critical for understanding the strength development and performing materials design for reactive MgO cement systems; however, the intrinsic mechanical properties of hydromagnesite (Mg5(CO3)4(OH)2·4H2O), a key binding phase, remain unexplored. The present study utilized synchrotron-based high-pressure X-ray diffraction to determine the unit cell-scale, intrinsic mechanical properties of hydromagnesite for the first time. Up to hydrostatic loading of 7.7 GPa, the bulk modulus of hydromagnesite was determined as 59 GPa or 71 GPa fitted using the second-order or third-order Birch-Murnaghan equation of state, which we contextualize with binding phases in various cement systems. The experiment results are applicable in materials design of low-carbon concrete and valuable for the validation and calibration of atomistic models.

Simultaneous manipulation of iron(II) spin crossover and LIESST behaviour using pressure, temperature and light.

Spin crossover (SCO) and light-induced excited spin state trapping (LIESST) effects were studied using high pressure X-ray diffraction at cryogenic temperatures on a single crystal of the {[FeII(pyrazole)4]2[NbIV(CN)8]·4H2O}n (FeNb) coordination polymer. The studied compound does not show SCO or LIESST at ambient pressure, but these effects can be enforced by a mechanical stimulus. The obtained results demonstrate the manipulation of the spin state via the appropriate combination of multiple stimuli simultaneously.

High-pressure studies of size dependent yield strength in rhenium diboride nanocrystals.

The superhard ReB2 system is the hardest pure phase diboride synthesized to date. Previously, we have demonstrated the synthesis of nano-ReB2 and the use of this nanostructured material for texture analysis using high-pressure radial diffraction. Here, we investigate the size dependence of hardness in the nano-ReB2 system using nanocrystalline ReB2 with a range of grain sizes (20-60 nm). Using high-pressure X-ray diffraction, we characterize the mechanical properties of these materials, including bulk modulus, lattice strain, yield strength, and texture. In agreement with the Hall-Petch effect, the yield strength increases with decreasing size, with the 20 nm ReB2 exhibiting a significantly higher yield strength than any of the larger grained materials or bulk ReB2. Texture analysis on the high pressure diffraction data shows a maximum along the [0001] direction, which indicates that plastic deformation is primarily controlled by the basal slip system. At the highest pressure (55 GPa), the 20 nm ReB2 shows suppression of other slip systems observed in larger ReB2 samples, in agreement with its high yield strength. This behavior, likely arises from an increased grain boundary concentration in the smaller nanoparticles. Overall, these results highlight that even superhard materials can be made more mechanically robust using nanoscale grain size effects.

Experimental observation of two-dimensional phase in compressed FeF2

Iron difluoride (FeF2) has attracted considerable attention for its physical characteristics and practical applications, and its compression behaviors usually play a key role in the in-depth understanding of this compound. Since its high-pressure crystal structure evolution determining a more profound comprehension remains disputable, we carried out extensive experiments to focus on the pressure-induced structural phase transitions of FeF2. Through in situ high-pressure synchrotron x-ray diffraction measurements, we not only confirmed a reported high-pressure orthorhombic Pbca phase at 11 GPa but also identified an interesting two-dimensional structure with hexagonal close packed symmetry (P-3m1) that appears above 25 GPa at room temperature. Furthermore, the spontaneous strain fitting and electronic transport measurements suggest that its ambient rutile-type structure (P42/mnm) evolves into an orthorhombic structure (Pnnm) through a second-order phase transition at 5 GPa. These experimental results elaborate on the pressure-induced phase transitions of FeF2 on the order of P42/mnm → Pnnm → Pbca → P-3m1, shedding light on a rare three-dimensional to two-dimensional configuration transition in difluorides.

In situ high-pressure pair distribution function measurement of liquid and glass by using 100keV pink beam.

Understanding the pressure-induced structural changes in liquids and amorphous materials is fundamental in a wide range of scientific fields. However, experimental investigation of the structure of liquid and amorphous material under in situ high-pressure conditions is still limited due to the experimental difficulties. In particular, the range of the momentum transfer (Q) in the structure factor [S(Q)] measurement under high-pressure conditions has been limited at relatively low Q, which makes it difficult to conduct detailed structural analysis of liquid and amorphous material. Here, we show the in situ high-pressure pair distribution function measurement of liquid and glass by using the 100keV pink beam. Structures of liquids and glasses are measured under in situ high-pressure conditions in the Paris-Edinburgh press by high-energy x-ray diffraction measurement using a double-slit collimation setup with a point detector. The experiment enables us to measure S(Q) of GeO2 and SiO2 glasses and liquid Ge at a wide range of Q up to 20-29 Å-1 under in situ high-pressure and high-temperature conditions, which is almost two times larger than that of the conventional high-pressure angle-dispersive x-ray diffraction measurement. The high-pressure experimental S(Q) precisely determined at a wide range of Q opens the way to investigate detailed structural features of liquids and amorphous materials under in situ high-pressure and high-temperature conditions, as well as ambient pressure study.