Structural, vibrational and electronic properties of α'-Ga2S3 under compression.

We report a joint experimental and theoretical study of the low-pressure phase of α'-Ga2S3 under compression. Theoretical ab initio calculations have been compared to X-ray diffraction and Raman scattering measurements under high pressure carried out up to 17.5 and 16.1 GPa, respectively. In addition, we report Raman scattering measurements of α'-Ga2S3 at high temperature that have allowed us to study its anharmonic properties. To understand better the compression of this compound, we have evaluated the topological properties of the electron density, the electron localization function, and the electronic properties as a function of pressure. As a result, we shed light on the role of the Ga-S bonds, the van der Waals interactions inside the channels of the crystalline structure, and the single and double lone electron pairs of the sulphur atoms in the anisotropic compression of α'-Ga2S3. We found that the structural channels are responsible for the anisotropic properties of α'-Ga2S3 and the A'(6) phonon, known as the breathing mode and associated with these channels, exhibits the highest anharmonic behaviour. Finally, we report calculations of the electronic band structure of α'-Ga2S3 at different pressures and find a nonlinear pressure behaviour of the direct band gap and a pressure-induced direct-to-indirect band gap crossover that is similar to the behaviour previously reported in other ordered-vacancy compounds, including ß-Ga2Se3. The importance of the single and, more specially, the double lone electron pairs of sulphur in the pressure dependence of the topmost valence band of α'-Ga2S3 is stressed.

Structural and vibrational properties of corundum-type In2O3 nanocrystals under compression.

This work reports the structural and vibrational properties of nanocrystals of corundum-type In2O3 (rh-In2O3) at high pressures by using angle-dispersive x-ray diffraction and Raman scattering measurements up to 30 GPa. The equation of state and the pressure dependence of the Raman-active modes of the corundum phase in nanocrystals are in good agreement with previous studies on bulk material and theoretical simulations on bulk rh-In2O3. Nanocrystalline rh-In2O3 showed stability under compression at least up to 20 GPa, unlike bulk rh-In2O3 which gradually transforms to the orthorhombic Pbca (Rh2O3-III-type) structure above 12-14 GPa. The different stability range found in nanocrystalline and bulk corundum-type In2O3 is discussed.

Pressure-induced amorphization of YVO4:Eu³âº nanoboxes.

A structural transformation from the zircon-type structure to an amorphous phase has been found in YVO4:Eu(3+) nanoboxes at high pressures above 12.7 GPa by means of x-ray diffraction measurements. However, the pair distribution function of the high-pressure phase shows that the local structure of the amorphous phase is similar to the scheelite-type YVO4. These results are confirmed both by Raman spectroscopy and Eu(3+) photoluminescence which detect the phase transition to a scheelite-type structure at 10.1 and 9.1 GPa, respectively. The irreversibility of the phase transition is observed with the three techniques after a maximum pressure in the upstroke of around 20 GPa. The existence of two (5)D0-->(7)F0 photoluminescence peaks confirms the existence of two local environments for Eu(3+), at least for the low-pressure phase. One environment is the expected for substituting Y(3+) and the other is likely a disordered environment possibly found at the surface of the nanoboxes.

Structural, elastic and vibrational properties of nanocrystalline lutetium gallium garnet under high pressure.

An ab initio study of the structural, elastic and vibrational properties of the lutetium gallium garnet (Lu3Ga5O12) under pressure has been performed in the framework of the density functional theory, up to 95 GPa. Pressure dependence of the elastic constants and the mechanical stability are analyzed, showing that the garnet structure is mechanically unstable above 87 GPa. Lattice-dynamics calculations in bulk at different pressures have been performed and compared with Raman scattering measurements of the nanocrystalline Tm(3+)-doped Lu3Ga5O12 up to 60 GPa. The theoretical frequencies and pressure coefficients of the Raman active modes for bulk Lu3Ga5O12 are in good agreement with the experimental data measured for the nano-crystals. The contributions of the different atoms to the vibrational modes have been analyzed based on the calculated total and partial phonon density of states. The vibrational modes have been discussed in relation to the internal and external modes of the GaO4 tetrahedron and the GaO6 octahedron. The calculated infrared modes and their pressure dependence are also reported. Our results show that with this nano-garnet size the sample has essentially bulk properties.

Pressure induced topological and topological crystalline insulators.

Research on topological and topological crystalline insulators (TCIs) is one of the most intense and exciting topics due to its fascinating fundamental science and potential technological applications. Pressure (strain) is one potential pathway to induce the non-trivial topological phases in some topologically trivial (normal) insulating or semiconducting materials. In the last ten years, there have been substantial theoretical and experimental efforts from condensed-matter scientists to characterize and understand pressure-induced topological quantum phase transitions (TQPTs). In particular, a promising enhancement of the thermoelectric performance through pressure-induced TQPT has been recently realized; thus evidencing the importance of this subject in society. Since the pressure effect can be mimicked by chemical doping or substitution in many cases, these results have opened a new route to develop more efficient materials for harvesting green energy at ambient conditions. Therefore, a detailed understanding of the mechanism of pressure-induced TQPTs in various classes of materials with spin-orbit interaction is crucial to improve their properties for technological implementations. Hence, this review focuses on the emerging area of pressure-induced TQPTs to provide a comprehensive understanding of this subject from both theoretical and experimental points of view. In particular, it covers the Raman signatures of detecting the topological transitions (under pressure), some of the important pressure-induced topological and TCIs of the various classes of spin-orbit coupling materials, and provide future research directions in this interesting field.

InN thin film lattice dynamics by grazing incidence inelastic x-ray scattering.

Achieving comprehensive information on thin film lattice dynamics so far has eluded well established spectroscopic techniques. We demonstrate here the novel application of grazing incidence inelastic x-ray scattering combined with ab initio calculations to determine the complete elastic stiffness tensor, the acoustic and low-energy optic phonon dispersion relations of thin wurtzite indium nitride films. Indium nitride is an especially relevant example, due to the technological interest for optoelectronic and solar cell applications in combination with other group III nitrides.

Borates or phosphates? That is the question.

Chemical nomenclature is perceived to be a closed topic. However, this work shows that the identification of polyanionic groups is still ambiguous and so is the nomenclature for some ternary compounds. Two examples, boron phosphate (BPO4) and boron arsenate (BAsO4), which were assigned to the large phosphate and arsenate families, respectively, nearly a century ago, are explored. The analyses show that these two compounds should be renamed phosphorus borate (PBO4) and arsenic borate (AsBO4). Beyond epistemology, this has pleasing consequences at several levels for the predictive character of chemistry. It paves the way for future work on the possible syntheses of SbBO4 and BiBO4, and it also renders previous structure field maps completely predictive, allowing us to foresee the structure and phase transitions of NbBO4 and TaBO4. Overall, this work demonstrates that quantum mechanics calculations can contribute to the improvement of current chemical nomenclature. Such revisitation is necessary to classify compounds and understand their properties, leading to the main final aim of a chemist: predicting new compounds, their structures and their transformations.

High-pressure characterization of multifunctional CrVO4.

The structural stability and physical properties of CrVO4 under compression were studied by x-ray diffraction, Raman spectroscopy, optical absorption, resistivity measurements, and ab initio calculations up to 10 GPa. High-pressure x-ray diffraction and Raman measurements show that CrVO4 undergoes a phase transition from the ambient pressure orthorhombic CrVO4-type structure (Cmcm space group, phase III) to the high-pressure monoclinic CrVO4-V phase, which is proposed to be isomorphic to the wolframite structure. Such a phase transition (CrVO4-type → wolframite), driven by pressure, also was previously observed in indium vanadate. The crystal structure of both phases and the pressure dependence in unit-cell parameters, Raman-active modes, resistivity, and electronic band gap, are reported. Vanadium atoms are sixth-fold coordinated in the wolframite phase, which is related to the collapse in the volume at the phase transition. Besides, we also observed drastic changes in the phonon spectrum, a drop of the band-gap, and a sharp decrease of resistivity. All the observed phenomena are explained with the help of first-principles calculations.

High-pressure structural and vibrational properties of monazite-type BiPO4, LaPO4, CePO4, and PrPO4.

Monazite-type BiPO4, LaPO4, CePO4, and PrPO4 have been studied under high pressure by ab initio simulations and Raman spectroscopy measurements in the pressure range of stability of the monazite structure. A good agreement between experimental and theoretical Raman-active mode frequencies and pressure coefficients has been found which has allowed us to discuss the nature of the Raman-active modes. Besides, calculations have provided us with information on how the crystal structure is modified by pressure. This information has allowed us to determine the equation of state and the isothermal compressibility tensor of the four studied compounds. In addition, the information obtained on the polyhedral compressibility has been used to explain the anisotropic axial compressibility and the bulk compressibility of monazite phosphates. Finally, we have carried out a systematic discussion on the high-pressure behavior of the four studied phosphates in comparison to results of previous studies.

Arsenolite: a quasi-hydrostatic solid pressure-transmitting medium.

This study reports the experimental characterization of the hydrostatic properties of arsenolite (As4O6), a molecular solid which is one of the softest minerals in the absence of hydrogen bonding. The high compressibility of arsenolite and its stability up to 15 GPa have been proved by x-ray diffraction measurements, and the progressive loss of hydrostaticity with increasing pressure up to 20 GPa has been monitored by ruby photoluminescence. Arsenolite has been found to exhibit hydrostatic behavior up to 2.5 GPa and a quasi-hydrostatic behavior up to 10 GPa at room temperature. This result opens the way to explore other molecular solids as possible quasi-hydrostatic pressure-transmitting media. The validity of arsenolite as an insulating, stable, non-penetrating and quasi-hydrostatic medium is explored by the study of the x-ray diffraction of zeolite ITQ-29 at high pressure.

Experimental and theoretical study of α-Eu2(MoO4)3 under compression.

The compression process in the α-phase of europium trimolybdate was revised employing several experimental techniques. X-ray diffraction (using synchrotron and laboratory radiation sources), Raman scattering and photoluminescence experiments were performed up to a maximum pressure of 21 GPa. In addition, the crystal structure and Raman mode frequencies have been studied by means of first-principles density functional based methods. Results suggest that the compression process of α-Eu2(MoO4)3 can be described by three stages. Below 8 GPa, the α-phase suffers an isotropic contraction of the crystal structure. Between 8 and 12 GPa, the compound undergoes an anisotropic compression due to distortion and rotation of the MoO4 tetrahedra. At pressures above 12 GPa, the amorphization process starts without any previous occurrence of a crystalline-crystalline phase transition in the whole range of pressure. This behavior clearly differs from the process of compression and amorphization in trimolybdates with [Formula: see text]-phase and tritungstates with α-phase.

Pressure effects on the vibrational properties of α-Bi(2)O(3): an experimental and theoretical study.

We report an experimental and theoretical high-pressure study of the vibrational properties of synthetic monoclinic bismuth oxide (α-Bi(2)O(3): ), also known as mineral bismite. The comparison of Raman scattering measurements and theoretical lattice-dynamics ab initio calculations is key to understanding the complex vibrational properties of bismite. On one hand, calculations help in the symmetry assignment of phonons and to discover the phonon interactions taking place in this low-symmetry compound, which shows considerable phonon anticrossings; and, on the other hand, measurements help to validate the accuracy of first-principles calculations relating to this compound. We have also studied the pressure-induced amorphization (PIA) of synthetic bismite occurring around 20 GPa and showed that it is reversible below 25 GPa. Furthermore, a partial temperature-induced recrystallization (TIR) of the amorphous sample can be observed above 20 GPa upon heating to 200°C, thus evidencing that PIA at room temperature occurs because of the inability of the α phase to undergo a phase transition to a high-pressure phase. Raman scattering measurements of the TIR sample at room temperature during pressure release have been performed. The interpretation of these results in the light of ab initio calculations of the candidate phases at high pressures has allowed us to tentatively attribute the TIR phase to the recently found high-pressure hexagonal HPC phase and to discuss its lattice dynamics.

Thermally activated cation ordering in ZnGa2Se4 single crystals studied by Raman scattering, optical absorption, and ab initio calculations.

Order-disorder phase transitions induced by thermal annealing have been studied in the ordered-vacancy compound ZnGa2Se4 by means of Raman scattering and optical absorption measurements. The partially disordered as-grown sample with tetragonal defect stannite (DS) structure and I4¯2m space group has been subjected to controlled heating and cooling cycles. In situ Raman scattering measurements carried out during the whole annealing cycle show that annealing the sample to 400 °C results in a cation ordering in the sample, leading to the crystallization of the ordered tetragonal defect chalcopyrite (DC) structure with I4¯ space group. On decreasing temperature the ordered cation scheme of the DC phase can be retained at ambient conditions. The symmetry of the Raman-active modes in both DS and DC phases is discussed and the similarities and differences between the Raman spectra of the two phases emphasized. The ordered structure of annealed samples is confirmed by optical absorption measurements and ab initio calculations, that show that the direct bandgap of DC-ZnGa2Se4 is larger than that of DS-ZnGa2Se4.

Experimental and theoretical investigations on the polymorphism and metastability of BiPO4.

In this work we report the metastability and the energetics of the phase transitions of three different polymorphs of BiPO4, namely trigonal (Phase-I, space group P3(1)21), monoclinic monazite-type (Phase-II, space group P2(1)/n) and SbPO4-type monoclinic (Phase-III, space group P2(1)/m) from ambient and non-ambient temperature powder XRD and neutron diffraction studies as well as ab initio density functional theory (DFT) calculations. The symmetry ambiguity between P2(1) and P2(1)/m of the high temperature polymorph of BiPO4 has been resolved by a neutron diffraction study. The structure and vibrational properties of these polymorphs of the three polymorphs have also been reported in detail. Total energy calculations have been used to understand the experimentally observed metastable behavior of trigonal and monazite-type BiPO4. Interestingly, all of the three phases were found to coexist after heating a single phasic trigonal BiPO4 to 773 K. The irreversible nature of these phase transitions has been explained by the concepts of the interplay of the structural distortion, molar volume and total energy.

Structural study of α-Bi2O3 under pressure.

An experimental and theoretical study of the structural properties of monoclinic bismuth oxide (α-Bi2O3) under high pressures is here reported. Both synthetic and mineral bismite powder samples have been compressed up to 45 GPa and their equations of state have been determined with angle-dispersive x-ray diffraction measurements. Experimental results have been also compared with theoretical calculations which suggest the possibility of several phase transitions below 10 GPa. However, experiments reveal only a pressure-induced amorphization between 15 and 25 GPa, depending on sample quality and deviatoric stresses. The amorphous phase has been followed up to 45 GPa and its nature discussed.

Dispersive phonon linewidths: the E2 phonons of ZnO.

Phonon linewidths can exhibit a large variation when either pressure or isotopic masses are changed. These effects yield detailed information about the mechanisms responsible for linewidths and lifetimes, e.g., anharmonicity or isotopic disorder. We report Raman measurements of the linewidth of the upper E2 phonons of ZnO crystals with several isotopic compositions and their dependence on pressure. Changes by a factor of 12 are observed at a given temperature. Comparison with calculated densities of one-phonon states, responsible for isotope scattering, and of two-phonon states, responsible for anharmonic decay, yields a consistent picture of these phenomena. Isotopic disorder broadening by 7 cm(-1) is found in samples with mixed 16O-18O content, whereas the anharmonic processes involve decay into sums and differences of two phonons.