Phase Transition and vibration properties of MnCO3 at high pressure and high-temperature by Raman spectroscopy

The high pressure and high-temperature behavior of MnCO₃ was investigated up to 55?GPa at ambient temperature and up to 573?K at ambient pressure by Raman spectroscopy, respectively. Some new modes were detected at ～16 and ～32?GPa, which were assigned to MnCO₃-I below 16?GPa and to MnCO₃-II above 32?GPa, and to a coexisting phase of them in between. The high pressure vibration properties of all Raman modes, especially high frequency modes, were systematically reported. The coexisting phase of MnCO₃-I and MnCO₃-II had much easier compressibility than the MnCO₃-II phase. The thermal stability of MnCO₃ was at least to 573?K and its thermal expansion along the c axis was easier than a and b axes.     

Crystal structure and compressibility of FePt nanoparticles under high pressures and high temperatures

FePt nanoparticles with an average grain size of 4 nm and equiatomic composition of Fe and Pt was studied under high pressures in a diamond anvil cell to investigate its structural stability and compressibility under high compression. The ambient pressure disordered face-centered-cubic (fcc) phase was found to be stable to the highest pressure of 61 GPa (compression of 15%) at room temperature. The compression of Fe₅₀Pt₅₀ nanoparticles is closer to the compression curve for pure Pt and shows lower compressibility than what would be expected for a bulk Fe₅₀Pt₅₀ alloy. The nanoparticle character of Fe₅₀Pt₅₀ sample is maintained to the highest pressure without any observable grain coarsening effects at ambient temperature. Laser heating of disordered fcc phase at 32 GPa to a temperature of 2000 K resulted in a phase transformation to a microcrystalline phase with the distorted fcc structure.     

In situ observations of temperature- and pressure-induced phase transitions in TiH2: Angle-dispersive and synchrotron energy-dispersive X-ray diffraction studies

We investigated the behavior of the structure of titanium hydride (TiH₂), an important compound in hydrogen storage research, at elevated temperatures (0-120 °C) and high pressures (1 bar-34 GPa). Temperature-induced changes of TiH₂ as indicated in the alteration of the ambient X-ray demonstrated a cubic to tetragonal phase transition occurring at about 17 °C. The main focus of this study was to identify any pressure-induced structural transformations, including possible phase transitions, in TiH₂. Synchrotron X-ray diffraction studies were carried out in situ (diamond anvil cell) in a compression sequence up to 34 GPa and in subsequent decompression to ambient pressure. The pressure evolution of the diffraction patterns revealed a cubic (Fm-3m) to tetragonal (I4/mmm) phase transition at 2.2 GPa. The high-pressure phase persisted up to 34 GPa. After decompression to ambient conditions the observed phase transition was completely reversible. A Birch-Murnaghan fit of the unit cell volume as a function of pressure yielded a zero-pressure bulk modulus K₀=146(14) GPa, and its pressure derivative K′₀=6(1) for the high-pressure tetragonal phase of TiH₂.     

Pressure-induced phase transitions in gypsum

Abstract

We report high-pressure Raman scattering spectroscopy and energy dispersive X-ray diffraction investigations on gypsum, CaSO₄ · 2H₂O, at room temperature in a diamond cell. With increasing pressure, measurements indicate that CaSO₄ · 2H₂O undergoes two stages of crystalline-state phase transitions at 5 and 9 GPa, and then converts to a disordered phase above 11 GPa. The structures of the three high-pressure phases of gypsum have not been determined yet. These phases are tentatively named as “post-gypsum-I” (PG-I), “post-gypsum-II” (PG-II) and “disordered” according to the sequence of their appearance with pressure.

Gypsum shows anisotropic compressibility along three crystallographic axes with b > c > a below 5 GPa. The difference in the behavior of the two OH stretching modes in gypsum is attributed to the different reduction rate in the hydrogen bonding distances by the anisotropic axial compressibility.     

Structural phase stability,electronic structure and mechanical properties of alkali metal hydrides AMH4 (A=Li,Na; M=B,AL)

The structural stability of Alkali metal hydrides AMH₄ (A=Li, Na; M=B, Al) is analyzed among the various crystal structures, namely hexagonal (P6₃mc), tetragonal (P4₂/nmc), tetragonal (P-42₁c), tetragonal (I4₁/a), orthorhombic (Pnma) and monoclinic (P2₁/c). It is observed that, orthorhombic (Pnma) phase is the most stable structure for LiBH₄, monoclinic (P2₁/c) for LiAlH₄, tetragonal (P4₂/nmc) for NaBH₄ and tetragonal (I4₁/a) for NaAlH₄ at normal pressure. Pressure induced structural phase transitions are observed in LiBH₄, LiAlH₄, NaBH₄ and NaAlH₄ at the pressures of 4 GPa, 36.1 GPa, 26.5 GPa and 46 GPa respectively. The electronic structure reveals that these metal hydrides are wide band gap insulators. The calculated elastic constants indicate that these metal hydrides are mechanically stable at normal pressure.     

High pressure studies on α-cristobalite form of Al0.5Ga0.5PO4: hydrostatic versus non-hydrostatic conditions

High pressure angle-dispersive X-ray diffraction investigations have been carried out on α-cristobalite form of Al_0.5Ga_0.5PO₄. Our investigations show that the structural stability of this phase under high pressure depends on the nature of pressure conditions in the diamond anvil cell. Under hydrostatic pressure conditions using neon as a pressure transmitting medium, ambient orthorhombic C222₁ phase transforms to orthorhombic Cmcm phase at 4.9?GPa. The high pressure Cmcm phase remains stable up to the highest pressure in the experiment, i.e. 19?GPa. The values of bulk modulus for C222₁ and Cmcm phases are 19(2) and 126(4)?GPa, respectively. In contrast to this, under non-hydrostatic pressure conditions, transformation of ambient C222₁ phase to Cmcm phase has not observed up to 17.4?GPa. Instead, a new monoclinic phase P2₁ is observed which contains layers of six coordinated Al/Ga ions separated by less dense five coordinated Al/Ga ions.     

Stable structure of metallic hydrogen at a pressure of 500 GPa

The structural, electron, phonon, and other characteristics of the metallic normal phase of hydrogen at a pressure of 500 GPa are calculated by an ab initio mathematical simulation. It is shown that metallic hydrogen having a lattice with the I41/amd symmetry is a stable phase at a high hydrostatic compression pressure. The resulting structure has the spectrum of phonons stable with respect to the decay.     

Compressibility of Fe1.087Te: a high pressure X-ray diffraction study

Fe_1.087Te exhibits three phases in the pressure range from ambient to 16.6?GPa and becomes amorphous at higher pressures. All three phases have tetragonal symmetry. The low pressure T-phase is stable in the pressure range 0≤P<4.1?GPa and is found to be relatively soft having zero pressure bulk modulus B ₀=36(1)?GPa. The intermediate cT-phase is less compressible with B ₀=88(5)?GPa and stable in the pressure range 4.1≤P<10?GPa while a more compressible phase was observed between 10 and 16.6?GPa.     

Optical properties of superhard BC5: First-principles calculations

BC₅ is a newly synthesized superhard material. We present a systematic investigation of optical properties of BC₅ in P3m1 and I-4m2 phases at ambient and high pressure in the framework of density functional theory with the generalized gradient approximation (GGA) in this paper. Optical properties such as dielectric function, refractive index, absorption, reflectivity and electron energy-loss spectrum are obtained successfully. The feature in the spectra of the optical parameters is discussed. Through calculation, we find BC₅ is optically anisotropic. Moreover, the dielectric function exhibits a large change at 70 GPa pressure for P3m1 BC₅ phase, but I-4m2 phase not, indicating the stable electronic structure that the I-4m2 phase possesses.     

High-pressure Raman and X-ray studies of barite,BaSO4

High-pressure Raman spectroscopic and X-ray diffraction experiments of barite, BaSO₄, were carried out in a diamond anvil cell up to 25?GPa at room temperature. On the basis of the changes in the diffraction patterns and the variation of lattice parameters with pressure, it is inferred that barite undergoes a phase transformation at 10?GPa. The phase transition accompanies the change in the force constant of vibrational modes in barite. Further compression beyond the phase transition causes the distortion of SO₄ tetrahedron as indicated by the splitting in the SO₄ stretching modes. Both X-ray and Raman data support that the phase transition in BaSO₄ is reversible. The compression data yield a bulk modulus of 63?±?2?GPa for barite. Barite shows anisotropic compressibility along three crystallographic axes with c being the most compressible axis.     

Review on distorted face-centered cubic phase in yttrium via genetic algorithm

We present two distorted face-centered cubic (dfcc) structures of yttrium under high pressure, which have been found by a first-principles genetic algorithm technique. The structures are a tetragonal P4₃ (dfcc-I) and a triclinic P1¯ (dfcc-II), formed by slight distortions from a trigonal R3¯m structure reported as the dfcc phase earlier. The enthalpy difference between the two dfcc structures is less than 0.2 mRy/atom, and dfcc-I is marginally more stable than dfcc-II in lower pressure region. The enthalpy comparison among candidate structures indicates the structural phase transitions into dfcc-I at 41 GPa, into dfcc-II at 81 GPa, and into an orthorhombic Fddd structure at 106 GPa.     

Evolution of metallization and superconductivity in solid hydrogen

Inspired by the recent experimental reports of metallic hydrogen [Science 355 (2017) 715, Nature, 577 (2020) 631], we have reexamined the metallization and superconductivity of solid hydrogen in the pressure range of interest. Based on high quality calculations with zero-point vibrations and van der Waals (vdW) corrections, hydrogen is disclosed to metallize at about 485 GPa via the phase transition from insulate molecular C2/c-24 to metallic molecular Cmca-4, then dissociate into atomic phase with increasing pressure to 600 GPa. Further analyses demonstrate that vdW interaction can reduce the H-H distances in the metallic molecular Cmca-4, thus pulling down the contributions from phonon frequencies and electronic structures to electron-phonon coupling λ, and resulting in the declining superconducting $T_{\mathrm{c}}$. Meanwhile, slightly influence on these cases can be found in metallic atomic I4₁/amd by vdW correction. Our results indicate that aspirational room-temperature superconductivity in solid hydrogen requires a high pressure beyond 600 GPa.     

High pressure phase transition in super-cell LiBH4: An ab initio prediction

LiBH₄ which have attracted considerable attention from researchers due to the crystal structure characteristics is a metal hydride that can bind four hydrogen atoms. LiBH₄ which has high gravimetric and volumetric hydrogen density shows phase transitions at high pressures. In this regard, we created and analyzed LiBH₄ structure based on the first principles calculations, and then obtained the super-cell LiBH₄ structure. We achieved the phase transitions up to 20 GPa pressure with 2 GPa regular intervals for the super-cell LiBH₄. We observed the Pnma to Pnma*, Pnma* to P2₁/c, and P2₁/c to C2/c phase transitions and calculated the volume contractions accompanying these phase transitions. According to the obtained volumetric values, one can conclude that LiBH₄ can minimize the volumetric requirements of the hydrogen storage for systems that can be used at high pressures. Thus, the hydrogen storage capacity of LiBH₄ may increase at particular phases.     

First-principles calculation of the lattice compressibility, elastic anisotropy and thermodynamic stability of V2GeC

We investigate the elastic and the thermodynamic properties of nanolaminate V₂GeC by using the ab initio pseudopotential total energy method. The axial compressibility shows that the c axis is always stiffer than the a axis. The elastic constant calculations demonstrate that the structural stability is within 0-800 GPa. The calculations of Young's and shear moduli reveal the softening behaviour at about 300 GPa. The Possion ratio makes a higher ionic or a weaker covalent contribution to intra-atomic bonding and the degree of ionicity increases with pressure. The relationship between brittleness and ductility shows that V₂GeC is brittle in ambient conditions and the brittleness decreases and ductility increases with pressure. Moveover, we find that V₂GeC is largely isotropic in compression and in shear, and the degree of isotropy decreases with pressure. The Gr黱eisen parameter, the Debye temperature and the thermal expansion coefficient are also successfully obtained for the first time.     

High pressure X-ray diffraction study of ReS2

The high-pressure behavior of rhenium disulfide (ReS₂) has been investigated to 51.0 GPa by in situ synchrotron X-ray diffraction in a diamond anvil cell at room temperature. The results demonstrate that the ReS₂ triclinic phase is stable up to 11.3 GPa, at which pressure the ReS₂ transforms to a new high-pressure phase, which is tentatively identified with a hexagonal lattice in space group P6?m2. The high-pressure phase is stable up to the highest pressure in this study (51.0 GPa) and not quenchable upon decompression to ambient pressure. The compressibility of the triclinic phase exhibits anisotropy, meaning that it is more compressive along interlayer directions than intralayer directions, which demonstrates the properties of the weak interlayer van der Waals interactions and the strong intralayer covalent bonds. The largest change in the unit cell angles with increasing pressures is the increase of β, which indicates a rotation of the sulfur atoms around the rhenium atoms during the compression. Fitting the experimental data of the triclinic phase to the third-order Birch-Murnaghan EOS yields a bulk modulus of K_OT=23±4 GPa with its pressure derivative K_OT′= 29±8, and the second-order yields K_OT=49±3 GPa.     

Magnetic ordering in Fe<Subscript>1.087</Subscript>Te under pressure

The crystal and magnetic structures of Fe_1.087Te have been studied by neutron powder diffraction in the temperature range from 1.7 to 80 K at pressures of  ≈0.4 and ≈1.2 GPa. No symmetry change of the tetragonal paramagnetic ambient pressure phase (space group P4/nmm) was observed for temperatures above 60 K and pressures up to  ≈1.2 GPa. A novel pressure-induced phase of Fe_1.087Te having orthorhombic symmetry (space group Pmmn) and incommensurate antiferromagneticbicollinear order was observed in the temperature range from 50 to 60 K at  ≈1.2 GPa. The known monoclinic ambient pressure phase of Fe_1.087Te (space group P2 ₁/n) with commensurate antiferromagnetic order was found to be stable up to at least  ≈1.2 GPa at low temperature.     

Equation of state and structural characterization of Cu4I4{PPh2(CH2CH = CH2)}4 under pressure

Combined high pressure single crystal X-ray diffraction experiments and ab initio simulations based on the density functional theory have been performed on a copper(I) iodide cluster formulated [Cu₄I₄{PPh₂(CH₂CH?=?CH₂)}₄] under high pressure up to 5?GPa. An exhaustive study of compressibility has been done by means of determination of isothermal equations of state and structural changes with pressure at 298?K taking advantage of the single crystal is more precise than powder X-ray diffraction for this type of experiments. It allows us to report the evidence of the existence of an isostructural phase transition of second order at 2.3?GPa not detected so far.     

High‐pressure Raman spectroscopy study of α and γ polymorphs of AlH3

For the first time, Raman spectroscopy of α and γ polymorphs of AlH₃ has been performed in the pressure range from ambient up to 16.9 and 32.7 GPa, respectively using the diamond anvil cell (DAC) technique. An analysis of pressure response wavenumbers (ν) for α‐AlH₃ showed a change of dν_i/dP at a pressure of about 8 GPa and may indicate a monoclinic distortion from the initially hexagonal α‐AlH₃. The distortion is stable at least up to 16.9 GPa. The γ form exhibited more complex behavior transforming to the α form at a pressure of about 12 GPa. The structural phase transition was shown to be an irreversible and kinetically slow process that required at least 5 h to complete. Copyright © 2008 John Wiley & Sons, Ltd.     

Pressure-induced structural and electronic transition in KTb(MoO4)2 through Raman and optical studies

Raman and optical absorption studies under pressure have been conducted on KTb(MoO₄)₂ up to 35.5 GPa. A phase transformation occurs at 2.7 GPa when the crystal is pressurized at ambient temperature in a hydrostatic pressure medium. The sample changes to a deep yellow color at the transition and visibly contracts in theα-axis direction. The color shifts to red on further pressure increase. The Raman spectral features and the X-ray powder pattern change abruptly at the transition indicating a structural change. The pressure-induced transition appears to be a property of the layer-type alkali rare earth dimolybdates. However, the color change at the transition in KTb(MoO₄)₂ is rather unusual and is attributed to a valence change in Tb initiated by the structural transition and consequent intervalence charge transfer between Tb and Mo.In situ high pressure X-ray diffraction data suggest that phase II could be orthorhombic with a unit cell having 3 to 4% smaller volume than that of phase I.     

Study of the P-T phase diagram of pyridinium perchlorate by X-ray diffraction and Raman spectroscopy

The crystal structure and vibrational spectra of deuterated pyridinium perchlorate (d ₅PyH)ClO₄ (C₅D₅NHClO₄) are studied by means of neutron diffraction in ambient conditions, X-ray diffraction at high pressures up to 3.5 GPa in the temperature range 297–420 K, and Raman spectroscopy at high pressures up to 5.7 GPa. Deuterated pyridinium perchlorate at ambient conditions has rhombohedral structure with the R3m symmetry (paraelectric phase I). Over the pressure range of 0.5–1.2 GPa, the phase II with monoclinic symmetry Cm exists. At pressure P ～ 1.2 GPa, the phase transition to monoclinic phase III with the Pm symmetry is observed at ambient temperature. The lattice parameters, unit cell volume, and frequencies of internal vibrational modes as functions of pressure are obtained for different phases of deuterated pyridinium perchlorate. The P-T phase diagram of (d ₅PyH)ClO₄ over the extended pressure and temperature range is discussed.