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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.
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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.
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The generic 1-bond â 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.
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DL-glutamic acid monohydrate crystal was synthesized from an aqueous solution by slow evaporation technique. The crystal was submitted to high-pressure (1 atm-14.3 GPa) to investigate its vibrational behavior and the occurrence of phase transitions. We performed Raman spectroscopy as probe and through the analysis of the spectra we discovered three structural phase transitions. The first one occurs around 0.9 GPa. In this phase transition, glutamic acid molecules suffer modifications in their conformations while water molecules are less affected. The second phase transition at 4.8 GPa involves conformational changes related to CO2-, NH3+ units and the water molecules, while the third one, between 10.9 and 12.4 GPa, involves motions of several parts of the glutamic acid as well as the water molecules. Considering the dynamic of high pressure, the second phase of DL-glutamic acid monohydrate crystal presented a better stability compared with the second phase of its polymorphs α and ß L-glutamic acid. In addition, water molecules seem to play important role on this structural stability. All changes are reversible.
Asunto(s)
Ácido Glutámico/química , Conformación Molecular , Transición de Fase , Presión , Cristalografía por Rayos X , Enlace de Hidrógeno , Modelos Moleculares , Espectrometría RamanRESUMEN
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.
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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.
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DLisoleucine single crystals were grown by the slow evaporation method at ambient temperature. Their vibrational properties were studied at ambient temperature as a function of pressure by Raman scattering. At ambient conditions the mode assignment was done in terms of the Potential Energy Distribution (PED) through density functional theory calculations. Both nitrogen and neon were used as pressure transmitting media. The pressure-dependent investigation shows modifications in the Raman spectra recorded between 30 and 3200â¯cm-1 that were interpreted as phase transitions undergone by the crystal between 1.3 and 1.9â¯GPa and between 3.6 and 5.1â¯GPa. Finally, stress was simulated on the unit cell of the crystal from ambient up to 5.0â¯GPa.
Asunto(s)
Isoleucina/química , Modelos Moleculares , Teoría Funcional de la Densidad , Presión , Espectroscopía Infrarroja por Transformada de Fourier/métodos , Espectrometría Raman/métodosRESUMEN
Near-forward Raman scattering combined with ab initio phonon and bond length calculations is used to study the 'phonon-polariton' transverse optical modes (with mixed electrical-mechanical character) of the II-VI ZnSe1-x S x mixed crystal under pressure. The goal of the study is to determine the pressure dependence of the poorly-resolved percolation-type Zn-S Raman doublet of the three oscillator [1 × (Zn-Se), 2 × (Zn-S)] ZnSe0.68S0.32 mixed crystal, which exhibits a phase transition at approximately the same pressure as its two end compounds (~14 GPa, zincblende â rocksalt), as determined by high-pressure x-ray diffraction. We find that the intensity of the lower Zn-S sub-mode of ZnSe0.68S0.32, due to Zn-S bonds vibrating in their own (S-like) environment, decreases under pressure (Raman scattering), whereas its frequency progressively converges onto that of the upper Zn-S sub-mode, due to Zn-S vibrations in the foreign (Se-like) environment (ab initio calculations). Ultimately, only the latter sub-mode survives. A similar 'phonon freezing' was earlier evidenced with the well-resolved percolation-type Be-Se doublet of Zn1-x Be x Se (Pradhan et al 2010 Phys. Rev. B 81 115207), that exhibits a large contrast in the pressure-induced structural transitions of its end compounds. We deduce that the above collapse/convergence process is intrinsic to the percolation doublet of a short bond under pressure, at least in a ZnSe-based mixed crystal, and not due to any pressure-induced structural transition.
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We present the results of x-ray diffraction and x-ray absorption spectroscopy experiments in CuAlO(2) under high pressure. We discuss the polarization dependence of the x-ray absorption near-edge structure at the Cu K-edge. XRD under high pressure evidences anisotropic compression, the a-axis being more compressible than the c-axis. EXAFS yields the copper-oxygen bond length, from which the only internal parameter of the delafossite structure is deduced. The combination of anisotropic compression and the internal parameter decrease results in a regularization of the AlO(6) octahedra. The anisotropic compression is related to the chemical trends observed in the lattice parameters when Al is substituted by other trivalent cations. Both experiments evidence the existence of an irreversible phase transition that clearly manifests at 35 ± 2 GPa. The structure of the high-pressure polymorph could not be determined, but it implies a change of the Cu environment, which remains anisotropic. Precursor effects are observed from the lowest pressures, which are possibly related to crystal breaking at a submicroscopic scale with partial reorientation of the crystallites.
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The cerium γâα transition was investigated using high-pressure, high-temperature angle-dispersive x-ray diffraction measurements on both poly- and single-crystalline samples, explicitly addressing symmetry change and transformation paths. The isomorphic hypothesis of the transition is confirmed, with a transition line ending at a solid-solid critical point. The critical exponent is determined, showing a universal behavior that can be pictured as a liquid-gas transition. We further report an isomorphic transition between two single crystals (with more than 14% of volume difference), an unparalleled observation in solid-state matter interpreted in terms of dislocation-induced diffusionless first-order phase transformation.
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We present results of a series of experiments performed on LiBr, 6H(2)0 from room temperature down to 172 K ≈ 1.2T(g). These ultrasound, Brillouin and depolarized light scattering, and transient grating experiments show that, above 215 K, this solution behaves like supercooled water: its zero frequency sound velocity C(0) continuously decreases with decreasing temperature, and the reorientational dynamics of the water molecules can be directly detected at some temperatures of this domain. Conversely, below 215 K, a new regime sets in, where the apparent C(0) is practically temperature independent and where a ß, Arrenhius like, relaxation process coexists with the usual, Vogel-Fulcher like, α relaxation process of the supercooled liquid. These results are similar to those recently obtained in LiCl, 6H(2)O. The onset of the new regime is possibly due to an increase of the interaction of the water molecules with a neighboring Li(+) ion when lowering the temperature. We also compare our results with published dielectric data on water solutions of glass forming polyalcohols. Some of them present a low temperature splitting of their relaxation time similar to what is found in LiBr, 6H(2)O.
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This work describes x-ray absorption measurements under high pressure in ReB(2), complemented by ab initio calculations. The EXAFS analysis yields the average Re-B bond compressibility, which turns out to be χ(ReB) = 5.6(9) × 10(-4) GPa(-1). Combining this information with previous x-ray diffraction experiments we have characterized the network of covalent bonds responsible for the rigidity of the structure. The main conclusion is that the compression is anisotropic and nonhomogeneous, reflecting bonding differences between Re-B and B-B bonds and also between nonequivalent Re-B bonds. The layer defined by boron atoms tends to become flatter under high pressure. As a consequence, the structural rigidity, necessary to attain high hardness values, is compromised.
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We report the results of a series of ultrasound, Brillouin scattering, and optical heterodyne detected transient grating experiments performed on a LiCl, 6H(2)O solution from room temperature down to the vicinity of its liquid-glass transition, T(g) approximately 138 K. Down to T approximately 215 K, the supercooled liquid has a behavior similar to what is expected for supercooled water: its zero frequency sound velocity, C(0), continuously decreases while the corresponding infinite frequency velocity, C(infinity), sharply increases, reflecting the increasing importance of H bonding when temperature is lowered. Below 215 K, specific aspects of the solution, presumably related to the role of the Li(+) and Cl(-) ions, modify the thermal behavior of C(0), while a beta relaxation process also appears and couples to the sound propagation. The origin of those two effects is briefly discussed.
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We have performed XMCD and diffraction measurements on the Pt(3)Mn(x)Cr(1-x) alloy, which show that the magnetization of Pt is independently influenced by the Mn or Cr 3d orbital. We find that the magnetic moment on Pt, and its decomposition into spin and orbital components, is uniquely determined by the relative number of Mn and Cr neighbors. We then investigate the effect of pressure on the magnetization of Pt in the Pt(3)Mn(0.5)Cr(0.5) alloy. Our high pressure data enable us to conclude that at 14 GPa the spin and orbital polarization of the Pt 5d band are augmented by about 70%, with no interaction between them.
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Ga K-edge energy dispersive x-ray absorption spectroscopy and Raman spectroscopy measurements were employed to follow the pressure-induced semiconductor-metal phase transition of nanocrystalline GaSb produced by mechanical alloying up to 26 GPa. The results showed a slight increase of the phase transition pressures for both as-milled (8 GPa) and annealed (10 GPa) GaSb samples, as compared to that for the bulk one. The extended x-ray absorption fine structure analysis of the zinc blende (ZB) pressure domain (<10 GPa) showed that the microscopic compressibility of the bonds in the as-milled/annealed samples is higher/lower than the crystalline bulk modulus (56 GPa). The comparison between x-ray absorption near edge structure regions of the spectra and multiple scattering calculations suggests that the ZB structure evolves to a short-range chemically ordered ß-Sn structure for pressures as high as 8 GPa. Raman measurements confirm the semiconductor-metal phase transitions of ZB-GaSb between 8 and 11 GPa for both as-milled and annealed samples, showing that the semiconductor character was not recovered on releasing the pressure down to 3.9 and 1.8 GPa, indicating a very strong hysteresis effect (or even irreversible transitions). The well-known transverse effective charge reduction with pressure was also observed. Furthermore, resonance behaviour is clearly seen for transverse optical phonons and the resonance maxima peak occurs at about 1.2 GPa, corresponding to 2.11 eV in the E(1) scale, smaller by 0.3 eV than the incident photon energy.
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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.
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We have studied the high-pressure iron bcc to hcp phase transition by simultaneous x-ray magnetic circular dichroism and x-ray absorption spectroscopy with an x-ray energy dispersive spectrometer. The combination of the two techniques allows us to obtain simultaneously information on both the structure and the magnetic state of iron under pressure. The magnetic and structural transitions simultaneously observed are sharp. Both are of first order in agreement with the theoretical prediction. The pressure domain of the transition observed (2.4+/-0.2 GPa) is narrower than that usually cited in the literature (8 GPa). Our data indicate that the magnetic transition slightly precedes the structural one, suggesting that the origin of the instability of the bcc phase in iron with increasing pressure is to be attributed to the effect of pressure on magnetism as predicted by spin-polarized full-potential total energy calculations.
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The high-frequency dynamics of a fragile molecular glass former (dibutylphthalate) was studied through inelastic x-ray scattering (IXS), as a function of pressure and temperature. The mesoscopic structural arrest associated with the glass transition process was tracked by following upon cooling the inelastic excitations at fixed Q points in the dispersion curves, at ambient pressure and 2 kbar. The application of pressure to this system induces an offset between the macroscopic glass transition temperature T(g) and the mesoscopic glass transition temperature, as determined from IXS. The concomitant fragility decrease of dibutylphthalate under pressure unveils that the stronger the glass former is, the more its mesoscopic dynamics differ from the macroscopic regime. This trend is interpreted as the signature of a nanoscopic inhomogeneous elastic network. Further aspects of this system are obtained when studying the temperature dependence of its nonergodicity factor f(Q)(T). The chemical specificity of the molecule is suggested to be responsible for the nonobservation of a critical temperature T(c) in dibutylphthalate up to approximately 300 K.
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EXAFS (Extended X-ray Absorption Fine Structure) spectra of liquid gallium near the Ga K-edge have been collected in wide pressure and temperature ranges. Reliable short-range pair distribution functions have been determined using advanced ab-initio calculations (GNXAS) taking into account the medium and long-range structure obtained by previous neutron and x-ray-scattering studies.
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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.