Vibrational-mechanical properties of the highly-mismatched Cd1-xBexTe semiconductor alloy: experiment and ab initio calculations.

The emerging CdTe-BeTe semiconductor alloy that exhibits a dramatic mismatch in bond covalency and bond stiffness clarifying its vibrational-mechanical properties is used as a benchmark to test the limits of the percolation model (PM) worked out to explain the complex Raman spectra of the related but less contrasted Zn1-xBex-chalcogenides. The test is done by way of experiment ([Formula: see text]), combining Raman scattering with X-ray diffraction at high pressure, and ab initio calculations ([Formula: see text] ~ 0-0.5; [Formula: see text]~1). The (macroscopic) bulk modulus [Formula: see text] drops below the CdTe value on minor Be incorporation, at variance with a linear [Formula: see text] versus [Formula: see text] increase predicted ab initio, thus hinting at large anharmonic effects in the real crystal. Yet, no anomaly occurs at the (microscopic) bond scale as the regular bimodal PM-type Raman signal predicted ab initio for Be-Te in minority ([Formula: see text]~0, 0.5) is barely detected experimentally. At large Be content ([Formula: see text]~1), the same bimodal signal relaxes all the way down to inversion, an unprecedented case. However, specific pressure dependencies of the regular ([Formula: see text]~0, 0.5) and inverted ([Formula: see text]~1) Be-Te Raman doublets are in line with the predictions of the PM. Hence, the PM applies as such to Cd1-xBexTe without further refinement, albeit in a "relaxed" form. This enhances the model's validity as a generic descriptor of phonons in alloys.

Exceptional phonon point versus free phonon coupling in Zn1-xBexTe under pressure: an experimental and ab initio Raman study.

Raman scattering and ab initio Raman/phonon calculations, supported by X-ray diffraction, are combined to study the vibrational properties of Zn1-xBexTe under pressure. The dependence of the Be-Te (distinct) and Zn-Te (compact) Raman doublets that distinguish between Be- and Zn-like environments is examined within the percolation model with special attention to x ~ (0,1). The Be-like environment hardens faster than the Zn-like one under pressure, resulting in the two sub-modes per doublet getting closer and mechanically coupled. When a bond is so dominant that it forms a matrix-like continuum, its two submodes freely couple on crossing at the resonance, with an effective transfer of oscillator strength. Post resonance the two submodes stabilize into an inverted doublet shifted in block under pressure. When a bond achieves lower content and merely self-connects via (finite/infinite) treelike chains, the coupling is undermined by overdamping of the in-chain stretching until a «phonon exceptional point¼ is reached at the resonance. Only the out-of-chain vibrations «survive¼ the resonance, the in-chain ones are «killed¼. This picture is not bond-related, and hence presumably generic to mixed crystals of the closing-type under pressure (dominant over the opening-type), indicating a key role of the mesostructure in the pressure dependence of phonons in mixed crystals.

Phonon-based partition of (ZnSe-like) semiconductor mixed crystals on approach to their pressure-induced structural transition.

The generic 1-bond → 2-mode "percolation-type" Raman signal inherent to the short bond of common A1-xBxC semiconductor mixed crystals with zincblende (cubic) structure is exploited as a sensitive "mesoscope" to explore how various ZnSe-based systems engage their pressure-induced structural transition (to rock-salt) at the sub-macroscopic scale-with a focus on Zn1-xCdxSe. The Raman doublet, that distinguishes between the AC- and BC-like environments of the short bond, is reactive to pressure: either it closes (Zn1-xBexSe, ZnSe1-xSx) or it opens (Zn1-xCdxSe), depending on the hardening rates of the two environments under pressure. A partition of II-VI and III-V mixed crystals is accordingly outlined. Of special interest is the "closure" case, in which the system resonantly stabilizes ante transition at its "exceptional point" corresponding to a virtual decoupling, by overdamping, of the two oscillators forming the Raman doublet. At this limit, the chain-connected bonds of the short species (taken as the minor one) freeze along the chain into a rigid backbone. This reveals a capacity behind alloying to reduce the thermal conductivity as well as the thermalization rate of photo-generated electrons.

Melting Curve and Isostructural Solid Transition in Superionic Ice.

The phase diagram and melting curve of water ice is investigated up to 45 GPa and 1600 K by synchrotron x-ray diffraction in the resistively and laser heated diamond anvil cell. Our melting data evidence a triple point at 14.6 GPa, 850 K. The latter is shown to be related to a first-order solid transition from the dynamically disordered form of ice VII, denoted ice VII^{'}, toward a high-temperature phase with the same bcc oxygen lattice but larger volume and higher entropy. Our experiments are compared to ab initio molecular dynamics simulations, enabling us to identify the high-temperature bcc phase with the predicted superionic ice VII^{''} phase [J.-A. Hernandez and R. Caracas, Phys. Rev. Lett. 117, 135503 (2016).PRLTAO0031-900710.1103/PhysRevLett.117.135503].

Defect-induced ultimately fast volume phonon-polaritons in the wurtzite Zn0.74Mg0.26Se mixed crystal.

Volume-phonon-polaritons (VPP's) propagating at a light-in-vacuum-like speed are identified in the wurtzite-type Zn0.74Mg0.26Se mixed crystal by near-forward Raman scattering. Their detection is selective to both the laser energy and the laser polarization, depending on whether the ordinary (n0) or extraordinary (ne) refractive index is addressed. Yet, no significant linear birefringence (n0 [Formula: see text] ne) is observed by ellipsometry. The current access to ultrafast VPP's is attributed to the quasi-resonant Raman probing of an anomalous dispersion of n0 due to impurity levels created deep in the optical band gap by oriented structural defects. The resonance conditions are evidenced by a dramatic enhancement of the Raman signals due to the polar modes. Hence, this work reveals a capacity for the lattice defects' engineering to "accelerate" the VPP's of a mixed crystal up to light-in-vacuum-like speeds. This is attractive for ultrafast signal processing in the terahertz range. On the fundamental side we provide an insight into the VPP's created by alloying ultimately close to the center of the Brillouin zone.

XAS studies of pressure-induced structural and electronic transformations in α-FeOOH.

Structural and electronic transformation taking place in α-FeOOH goethite have been studied by Fe K-edge x-ray absorption spectroscopy at pressures up to 50 GPa. These studies have shown the symmetrization of FeO6 octahedra coinciding with the Fe3+ high to low spin transition at pressure above ~45 GPa. Our data are in excellent agreement with the results of recent single crystal XRD and Mössbauer spectroscopy studies (Xu et al 2013 Phys. Rev. Lett. 111 175501), supporting the H-bonds symmetrization in iron oxyhydroxide, resulting from the Fe3+ high-to-low spin crossover at above 45 GPa. Our study shows an applicability of the x-ray absorption spectroscopy in a further study of the H-bonds symmetrization phenomenon.

Tomography and imaging at the PSICHE beam line of the SOLEIL synchrotron.

PSICHE (Pressure, Structure and Imaging by Contrast at High Energy) is the high-energy beam line of the SOLEIL synchrotron. The beam line is designed to study samples at extreme pressures, using diffraction, and to perform imaging and tomography for materials science and other diverse applications. This paper presents the tomograph and the use of the beam line for imaging, with emphasis on developments made with respect to existing instruments. Of particular note are the high load capacity rotation stage with free central aperture for installing large or complex samples and sample environments, x-ray mirror and filter optics for pink beam imaging, and multiple options for combining imaging and diffraction measurement. We describe how x-ray imaging techniques have been integrated into high-pressure experiments. The design and the specifications of the beam line are described, and several case studies drawn from the first user experiments are presented.

Pressure-induced valence crossover in superconducting CeCu2Si2.

Measurement of the Ce valence in the heavy fermion CeCu(2)Si(2) is reported for the first time under pressure and at low temperature (T=14 K) in proximity of the superconducting region. CeCu(2)Si(2) is considered as a strong candidate for a new type of pairing mechanism related to critical valence fluctuations which could set in at high pressure in the vicinity of the second superconducting dome. A quantitative estimate of the valence in this pressure region was achieved from the measurements of the Ce L(3) edge in the high-resolution partial-fluorescence yield mode and subsequent analysis of the spectra within the Anderson impurity model. While a clear increase of the Ce valence is found, the weak electron transfer and the continuous valence change under pressure suggests a crossover regime with the hypothetical valence line terminating at a critical end point T(cr) close to zero.

A microscopic view on the Mott transition in chromium-doped V(2)O(3).

V(2)O(3) is the prototype system for the Mott transition, one of the most fundamental phenomena of electronic correlation. Temperature, doping or pressure induce a metal-to-insulator transition (MIT) between a paramagnetic metal (PM) and a paramagnetic insulator. This or related MITs have a high technological potential, among others, for intelligent windows and field effect transistors. However the spatial scale on which such transitions develop is not known in spite of their importance for research and applications. Here we unveil for the first time the MIT in Cr-doped V(2)O(3) with submicron lateral resolution: with decreasing temperature, microscopic domains become metallic and coexist with an insulating background. This explains why the associated PM phase is actually a poor metal. The phase separation can be associated with a thermodynamic instability near the transition. This instability is reduced by pressure, that promotes a genuine Mott transition to an eventually homogeneous metallic state.

Inequivalent routes across the Mott transition in V2O3 explored by X-ray absorption.

The changes in the electronic structure of V2O3 across the metal-insulator transition induced by temperature, doping, and pressure are identified using high resolution x-ray absorption spectroscopy at the V pre-K edge. Contrary to what has been taken for granted so far, the metallic phase reached under pressure is shown to differ from the one obtained by changing doping or temperature. Using a novel computational scheme, we relate this effect to the role and occupancy of the a{1g} orbitals. This finding unveils the inequivalence of different routes across the Mott transition in V2O3.

Probing the transition in bulk Ce under pressure: a direct investigation by resonant inelastic X-ray scattering.

We report on the most complete investigation to date of the -electron properties at the transition in elemental Ce by resonant inelastic x-ray scattering (RIXS). The Ce 2p3d-RIXS spectra were measured directly in the bulk material as a function of pressure through the transition. The spectra were simulated within the Anderson impurity model. The occupation number n(f) and f double occupancy were derived from the calculations in both gamma and alpha phases in the ground state. We find that the electronic structure changes result mainly from band formation of 4f electrons which concurs with reduced electron correlation and increased Kondo screening at high pressure.

XMCD under pressure at the Fe K edge on the energy-dispersive beamline of the ESRF.

The present paper demonstrates the feasibility of X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) at high pressure at the Fe K edge on the ID24 energy-dispersive beamline of the ESRF. In 3d transition metals, performing experiments at the hard X-ray K edge rather than at the magnetically interesting soft X-ray L edges represents the only way to access the high-pressure regime obtainable with diamond anvil cells. The simultaneous availability of a local structure (XAS) and of a magnetic (XMCD) probe on the sample under identical thermodynamical conditions is essential for studying correlations between local structural and magnetic properties. The state-of-the-art theoretical understanding of K-edge XMCD data is briefly summarized, and the set-up of beamline ID24 for high-pressure XMCD experiments is illustrated and the conditions required to perform measurements at the K edges of 3d transition metals are underlined. Finally, two examples of recent high-pressure results at the Fe K edge in pure Fe and Fe3O4 powder are presented.

Experimental and theoretical investigation on the relative stability of the PdS2- and pyrite-type structures of PdSe2.

Under ambient condition PdSe2 has the PdS2-type structure. The crystal structure of PdSe2 under pressure (up to 30 GPa) was investigated at room temperature by X-ray diffraction in an energy-dispersive configuration using a diamond anvil cell with a mixture of water/ethanol/methanol as a pressure transmitting medium. A reversible structural transition from the PdS2-type to the pyrite-type structure occurs around 10 GPa, and the applied pressure reduces the spacing between adjacent 2/proportional to [PdSe2] layers of the PdS2-type structure to form the three-dimensional lattice of the pyrite-type structure. First principles and extended Hückel electronic band structure calculations were carried out to confirm the observed pressure-induced structural changes. We also examined why the isoelectronic analogues NiSe2 and PtSe2 adopt structures different from the PdS2-type structure on the basis of qualitative electronic structure considerations.

Ultrasonics and X-ray diffraction under pressure in the Paris-Edinburgh cell

Our objective consists in validating a new set-up which will permit us to carry out simultaneously ultrasonic and X-ray diffraction measurements under pressure. To validate the results obtained by this new set-up, the elastic properties of a single crystal of germanium were studied. Our results are in good agreement with those of Goncharova et al. and McSkimin and Andreatch. The results of the present study are compared with those of Menoni et al. and obtained by X-ray diffraction in a diamond anvil cell.