Comparative Study of the Compressibility of M3V2O8 (M = Cd, Zn, Mg, Ni) Orthovanadates

We report herein a theoretical study of the high-pressure compressibility of Cd3V2O8, Zn3V2O8, Mg3V2O8, and Ni3V2O8. For Cd3V2O8, we also present a study of its structural stability. Computer simulations were performed by means of first-principles methods using the CRYSTAL program. In Cd3V2O8, we found a previously unreported polymorph which is thermodynamically more stable than the already known polymorph. We also determined the compressibility of all compounds and evaluated the different contributions of polyhedral units to compressibility. We found that the studied vanadates have an anisotropic response to compression and that the change in volume is basically determined by the compressibility of the divalent-cation coordination polyhedra. A systematic discussion of the bulk modulus of M3V2O8 orthovanadates will also be included

Stability of FeVO4-II under Pressure: A First-Principles Study

In this work, we report first-principles calculations to study FeVO4 in the CrVO4 -type (phase II) structure under pressure. Total-energy calculations were performed in order to analyze the structural parameters, the electronic, elastic, mechanical, and vibrational properties of FeVO4 -II up to 9.6 GPa for the first time. We found a good agreement in the structural parameters with the experimental results available in the literature. The electronic structure analysis was complemented with results obtained from the Laplacian of the charge density at the bond critical points within the Quantum Theory of Atoms in Molecules methodology. Our findings from the elastic, mechanic, and vibrational properties were correlated to determine the elastic and dynamic stability of FeVO4 -II under pressure. Calculations suggest that beyond the maximum pressure covered by our study, this phase could undergo a phase transition to a wolframite-type structure, such as in CrVO4 and InVO4. Keywords: FeVO4 under pressure; CrVO4-type structure; first-principles; mechanical properties; vibrational properties; electronic propertie

Evolution of structural and electronic properties of TiSe2 under high pressure

A pressure-induced structural phase transition and its intimate link with the superconducting transition was studied for the first time in TiSe2 up to 40 GPa at room temperature using X-ray diffraction, transport measurement, and first-principles calculations. We demonstrate the occurrence of a first-order structural phase transition at 4 GPa from the standard trigonal structure (S.G.P3¯m1) to another trigonal structure (S-G-P3¯c1). Additionally, at 16 GPa, the P3¯c1 phase spontaneously transforms into a monoclinic C2/m phase, and above 24 GPa, the C2/m phase returns to the initial P3¯m1 phase. Electrical transport results show that metallization occurs above 6 GPa. The charge density wave observed at ambient pressure is suppressed upon compression up to 2 GPa with the emergence of superconductivity at 2.5 GPa, with a critical temperature (Tc) of 2 K. A structural transition accompanies the emergence of superconductivity that persists up to 4 GPa. The results demonstrate that the pressure-induced phase transitions explored by the experiments along with the theoretical predictions may open the door to a new path for searching and controlling the phase diagrams of transition metal dichalcogenides.C.C. acknowledges support from the Spanish Ministry of Science, Innovation, and Universities under the “Ramon y Cajal” fellowship RYC2018-024947-I.Peer ReviewedPostprint (author's final draft

Ab Initio Phase Diagram of Chromium to 2.5 TPa

Chromium possesses remarkable physical properties such as hardness and corrosion resistance. Chromium is also a very important geophysical material as it is assumed that lighter Cr isotopes were dissolved in the Earth's molten core during the planet's formation, which makes Cr one of the main constituents of the Earth's core. Unfortunately, Cr has remained one of the least studied 3d transition metals. In a very recent combined experimental and theoretical study (Anzellini et al., Scientific Reports, 2022), the equation of state and melting curve of chromium were studied to 150 GPa, and it was determined that the ambient body-centered cubic (bcc) phase of crystalline Cr remains stable in the whole pressure range considered. However, the importance of the knowledge of the physical properties of Cr, specifically its phase diagram, necessitates further study of Cr to higher pressure. In this work, using a suite of ab initio quantum molecular dynamics (QMD) simulations based on the Z methodology which combines both direct Z method for the simulation of melting curves and inverse Z method for the calculation of solid-solid phase transition boundaries, we obtain the theoretical phase diagram of Cr to 2.5 TPa. We calculate the melting curves of the two solid phases that are present on its phase diagram, namely, the lower-pressure bcc and the higher-pressure hexagonal close-packed (hcp) ones, and obtain the equation for the bcc-hcp solid-solid phase transition boundary. We also obtain the thermal equations of state of both bcc-Cr and hcp-Cr, which are in excellent agreement with both experimental data and QMD simulations. We argue that 2180 K as the value of the ambient melting point of Cr which is offered by several public web resources ("Wikipedia," "WebElements," "It's Elemental," etc.) is most likely incorrect and should be replaced with 2135 K, found in most experimental studies as well as in the present theoretical work

High-pressure study of the aurophilic topological Dirac material AuI

We endeavour to explore the high-pressure study in the aurophilic AuI within the state-of-the-art of first principles. The impediment of expressing precise ground-state features of aurophilic compounds that had afflicted prior theoretical research has been resolved by incorporating van der Waals corrections (vdw). Mechanical and dynamical stability are ensured at ambient using the computed elastic constants and phonon dispersion curves. The dynamical instability is triggered by the application of pressure in AuI, as evidenced by the softening of an acoustic mode (Eu) at ∼7 GPa. Non-adherence of estimated elastic constants to the Born stability criterion at this pressure illustrates the system's mechanical instability. As previously demonstrated in experiments, the pressure-driven amorphization is rationalised by the phonon softening and elastic instability. Our calculations of the electronic band structure reveal an indirect bandgap (2.31 eV). Z2 invariants confirm that non-symmorphic AuI is a non-trivial Dirac material with the inclusion of spin-orbit coupling. Furthermore, a type-A hourglass dispersion with movable Dirac point is observed at the two-fold screw rotation axis (C2y). The pressure-dependent electronic structure reveal that the band topology is unaffected by pressure up to amorphous state. Our findings predict that this aurophilic class of material AuI possess exotic structural and electronic properties, encouraging further studies

High-Pressure Properties of Wolframite-Type ScNbO4

In this work, we used Raman spectroscopic and optical absorption measurements and first-principles calculations to unravel the properties of wolframite-type ScNbO4 at ambient pressure and under high pressure. We found that monoclinic wolframite-type ScNbO4 is less compressible than most wolframites and that under high pressure it undergoes two phase transitions at ∼5 and ∼11 GPa, respectively. The first transition induces a 9% collapse of volume and a 1.5 eV decrease of the band gap energy, changing the direct band gap to an indirect one. According to calculations, pressure induces symmetry changes (P2/c–Pnna–P2/c). The structural sequence is validated by the agreement between phonon calculations and Raman experiments and between band structure calculations and optical absorption experiments. We also obtained the pressure dependence of Raman modes and proposed a mode assignment based upon calculations. They also provided information on infrared modes and elastic constants. Finally, noncovalent and charge analyses were employed to analyze the bonding evolution of ScNbO4 under pressure. They show that the bonding nature of ScNbO4 does not change significantly under pressure. In particular, the ionicity of the wolframite phase is 61% and changes to 63.5% at the phase transition taking place at ∼5 GPa

Phase Transitions of BiVO4 under High Pressure and High Temperature

We have studied the occurrence of phase transitions in two polymorphs of BiVO4 under high-pressure and high-temperature conditions by means of X-ray diffraction measurements. The fergusonite polymorph undergoes a phase transition at 1.5(1) GPa and room temperature into a tetragonal scheelite-type structure. The same transition takes place at 523(1) K and ambient pressure. A second phase transition takes place at room temperature under compression at 16(1) GPa. The transition is from the tetragonal scheelite structure to a monoclinic structure (space group P21/c). All observed phase transitions are reversible. The zircon polymorph counterpart also transforms under compression into the scheelite-type structure. In this case, the transitions take place at 4.3(1) GPa and room temperature and at 653(1) K and ambient pressure. The zircon–scheelite transition is nonreversible. The experiments support that the fergusonite–scheelite transformation is a second-order transition and that the zircon–scheelite transformation is a first-order transition. Finally, we have also determined the compressibility and the thermal expansion of the fergusonite, scheelite, and zircon phases

The pressure and temperature evolution of the Ca3V2O8 crystal structure using powder X-ray diffraction

We present a comprehensive experimental study of the crystal structure of calcium vanadate (Ca3V2O8) under systematic temperature and pressure conditions. The temperature evolution (4-1173 K) of the Ca3V2O8 structural properties is investigated at ambient pressure. The pressure evolution (0-13.8 GPa) of the Ca3V2O8 structural properties is investigated at ambient temperature. Across all pressures and temperatures used in the present work, the Ca3V2O8 crystal structure was determined by Rietveld refinement of powder X-ray diffraction data. The experimental high-pressure data are also supported by density-functional theory calculations. According to the high-pressure results, Ca3V2O8 undergoes a pressure-induced structural phase transition at a pressure of 9.8(1) GPa from the ambient pressure trigonal structure (space group R3c) to a monoclinic structure (space group Cc). The experimentally determined bulk moduli of the trigonal and monoclinic phases are, respectively, B0 = 69(2) GPa and 105(12) GPa. The trigonal to monoclinic phase transition appears to be prompted by non-hydrostatic conditions. Whilst the trigonal and monoclincic space groups show a group/subgroup relationship, the discontinuity in the volume per formula unit observed at the transition indicates a first order phase transition. According to the high-temperature results, the trigonal Ca3V2O8 structure persists over the entire range of studied temperatures. The pressurevolume equation of state, axial compressibilities, Debye temperature (264(2) K), and thermal expansion coefficients are all determined for the trigonal Ca3V2O8 structure

Properties of Transition Metals and Their Compounds at Extreme Conditions

Properties of Transition Metals and Their Compounds at Extreme Condition

An Investigation of the Pressure-Induced Structural Phase Transition of Nanocrystalline alpha-CuMoO4

The structural behavior of nanocrystalline α-CuMoO4 was studied at ambient temperature up to 2 GPa using in situ synchrotron X-ray powder diffraction. We found that nanocrystalline α-CuMoO4 undergoes a structural phase transition into γ-CuMoO4 at 0.5 GPa. The structural sequence is analogous to the behavior of its bulk counterpart, but the transition pressure is doubled. A coexistence of both phases was observed till 1.2 GPa. The phase transition gives rise to a change in the copper coordination from square-pyramidal to octahedral coordination. The transition involves a volume reduction of 13% indicating a first-order nature of the phase transition. This transformation was observed to be irreversible in nature. The pressure dependence of the unit-cell parameters was obtained and is discussed, and the compressibility analyzed