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The reaction pathway in photoexcited hemeproteins (ligand dissociation, energy redistribution and structural dynamics) has been unraveled by Femtosecond Stimulated Raman Scattering. The possible existence of short living intermediates as opposed to vibrational relaxation is discussed.

Despite that the thermodynamic distinction between a liquid and the corresponding gas ceases to exist at the critical point, it has been recently shown that reminiscence of gaslike and liquidlike behavior can be identified in the supercritical fluid region, encoded in the behavior of hypersonic waves dispersion. By using a combination of molecular dynamics simulations and calculations within the approach of generalized collective modes, we provide an accurate determination of the dispersion of longitudinal and transverse collective excitations in soft-sphere fluids. Specifically, we address the decreasing rigidity upon density reduction along an isothermal line, showing that the positive sound dispersion, an excess of sound velocity over the hydrodynamic limit typical for dense liquids, displays a nonmonotonic density dependence strictly correlated to that of thermal diffusivity and kinematic viscosity. This allows rationalizing recent observation parting the supercritical state based on the Widom line, i.e., the extension of the coexistence line. Remarkably, we show here that the extremals of transport properties such as thermal diffusivity and kinematic viscosity provide a robust definition for the boundary between liquidlike and gaslike regions, even in those systems without a liquid-gas binodal line. Finally, we discuss these findings in comparison with recent results for Lennard-Jones model fluid and with the notion of the "rigid-nonrigid" fluid separation lines.

This paper describes the scientific aims and potentials as well as the preliminary technical design of RUDE, an innovative tool for multi-disciplinary investigations in a wide field of scientific, technological and industrial applications. IRIDE will be a high intensity "particles factory", based on a combination of high duty cycle radio-frequency superconducting electron linacs and of high energy lasers. Conceived to provide unique research possibilities for particle physics, for condensed matter physics, chemistry and material science, for structural biology and industrial applications, IRIDE will open completely new research possibilities and advance our knowledge in many branches of science and technology. [RIDE is also supposed to be realized in subsequent stages of development depending on the assigned priorities. (C) 2013 Elsevier B.V. All rights reserved.

New inelastic X-ray scattering experiments have been performed on liquid lithium in a wide wavevector range. With respect to the previous measurements, the instrumental resolution, improved up to 1.5 meV, allows to accurately investigate the dynamical processes determining the observed shape of the the dynamic structure factor, $S(Q,\omega)$. A detailed analysis of the lineshapes shows the co-existence of relaxation processes with both a slow and a fast characteristic timescales, and therefore that pictures of the relaxation mechanisms based on a simple viscoelastic model must be abandoned., Comment: 5 pages, 4 .PS figures

The sound attenuation in the THz region is studied down to T 16 K in glassy glycerol by inelastic x-ray scattering. At striking variance with the decrease found below 100 K in the GHz data, the attenuation in the THz range does not show any T dependence. This result (i) indicates the presence of two different attenuation mechanisms, active, respectively, in the high- and low-frequency limits, (ii) demonstrates the nondynamic origin of the attenuation of THz sound waves, and confirms a similar conclusion obtained in SiO2 glass by molecular dynamics, and (iii) supports the low-frequency attenuation mechanism proposed by Fabian and Allen [ Phys. Rev. Lett. 82, 1478 (1999)].

We present new inelastic X-ray scattering data for the dynamic structure factor S(Q, ω) of liquid lithium collected at two different temperatures (T = 475K and T = 600K) and in a wide range of exchanged wave-vectors (Q = 1 nm−1 to Q=110nm−1). The analysed Q range covers the transition from collective to single-particle regimes. The spectra have been put on an absolute scale using its first sum rules, and the result obtained has been tested on diffraction data and novel molecular dynamie results. A relaxation fingerprint is observed at low wave-vectors (the so-called positive dispersion of the apparent sound speed), while at higher Q the single particle behaviour gradually emerges.

Spectral compression of femtosecond pulses by second harmonic generation in the presence of substantial group velocity dispersion provides a convenient source of narrowband Raman pump pulses for femtosecond stimulated Raman spectroscopy (FSRS). We discuss here a simple and efficient modification that dramatically increases the versatility of the second harmonic spectral compression technique. Adding a spectral filter following second harmonic generation produces narrowband pulses with a superior temporal profile. This simple modification i) increases the Raman gain for a given pulse energy, ii) improves the spectral resolution, iii) suppresses coherent oscillations associated with slowly dephasing vibrations, and iv) extends the useful tunable range to at least 330-750 nm.

Exact relation for contributions to heat capacity of liquids is obtained from hydrodynamic theory. It is shown from analysis of the long-wavelength limit of heat density autocorrelation functions that the heat capacity of simple liquids is represented as a sum of two contributions due to “phonon-like” collective excitations and heat relaxation. The ratio of both contributions being the analogy of Landau-Placzek ratio for heat processes depends on the specific heats ratio. The theory of heat density autocorrelation functions in liquids is verified by computer simulations. Molecular dynamics simulations for six liquids having the ratio of specific heats γ in the range 1.1–2.3, were used for evaluation of the heat density autocorrelation functions and predicted Landau-Placzek ratio for heat processes. The dependence of contributions from collective excitations and heat relaxation process to specific heat on γ is shown to be in excellent agreement with the theory.

The lack of long-range structural order in amorphous solids induces well known thermodynamic anomalies, which are the manifestation of distinct peculiarities in the vibrational spectrum. Although the impact of such anomalies vanishes in the long wavelength, elastic continuum limit, it dominates at length scales comparable to interatomic distances, implying an intermediate transition regime still poorly understood. Here we report a study of such mesoscopic domains by means of a broadband version of picosecond photo-acoustics, developed to coherently generate and detect hypersonic sound waves in the sub-THz region with unprecedented sampling efficiency. We identify a temperature-dependent fractal v3/2 frequency behaviour of the sound attenuation, pointing to the presence of marginally stable regions and a transition between the two above mentioned limits. The essential features of this behaviour are captured by a theoretical approach based on random spatial variation of the shear modulus, including anharmonic interactions., Characterizing the acoustic dynamics of glasses at mesoscopic wavelengths is challenging. Here, Ferrante et al. use the broadband picosecond acoustics technique to study attenuation at such length scales, where they find temperature-dependent, fractal frequency behaviour.

International audience; Sudden changes in the dynamical properties of a supercritical fluid model have been found as a function of pressure and temperature (T/Tc52-5 and P/Pc510-103), striving with the notion of a single phase beyond the critical point established by thermodynamics. The sound propagation in the Terahertz frequency region reveals a sharp dynamic crossover between the gas like and the liquid like regimes along several isotherms, which involves, at sufficiently low densities, the interplay between purely acoustic waves and heat waves. Such a crossover allows one to determine a dynamic line in the phase diagram which exhibits a very tight correlation with a number of thermodynamic observables, showing that the supercritical state is remarkably more complex than thought so far

Density-driven phase transformations are a known phenomenon in liquids. Pressure-driven transitions from an open low-density to a higher-density close-packed structure were observed for a number of systems. Here, we show a less intuitive, inverse behavior. We investigated the electronic, atomic, and dynamic structures of liquid Rb along an isothermal line at 573 K, at 1.2-27.4 GPa, by means of ab initio molecular dynamics simulations and inelastic x-ray scattering experiments. The excellent agreement of the simulations with experimental data performed up to 6.6 GPa validates the overall approach. Above 12.5 GPa, the breakdown of the nearly-free-electron model drives a transition of the pure liquid metal towards a less metallic, denser liquid, whose first coordination shell is less compact. Our study unveils the interplay between electronic, structural, and dynamic degrees of freedom along this liquid-liquid phase transition. In view of its electronic nature, we believe that this behavior is general for the first group elements, thus shedding new light into the high-pressure properties of alkali metals.

The high frequency dynamics of Indomethacin and Celecoxib glasses has been investigated by inelastic x-ray scattering, accessing a momentum-energy region still unexplored in amorphous pharmaceuticals. We find evidence of phonon-like acoustic dynamics and determine the THz behavior of sound velocity and acoustic attenuation. Connections with ordinary sound propagation are discussed, along with the relation between fast and slow degrees of freedom as represented by non-ergodicity factor and kinetic fragility, respectively.

We present the full diagrammatic description of non-resonant impulsive femtosecond stimulated Raman spectroscopy in a multimode model system. In this technique the pump-probe scheme is exploited to study the vibrational structure of the sample via stimulated Raman scattering. We apply closed-time-path-loop diagrams to calculate the complete response of the system at the relevant perturbation order. We show that, in presence of low-frequency modes, coherences created by the impulsive pump modify the resulting Raman signal, which oscillates from gain to loss features, depending on the time delay between the pump and probe pulses. This leads to a redistribution of photons among the fields involved in the process and, consequently, the energy flows between fields and matter. Moreover, through this formalism, we address the case of extremely short delays in which the pump and probe fields overlap in time. We find that, even in absence of photo-induced dynamics due to absorption of the pump pulse, the overlap condition can generate time dependent features, arising from additional diagrams, which offer no contribution for well separated pulses.

Molecular dynamics (MD) simulations of the glass-former 2Ca(NO(3))(2·3KNO(3), CKN, were performed as a function of temperature at pressures 0.1 MPa, 0.5 GPa, 1.0 GPa, and 2.0 GPa. Diffusion coefficient, relaxation time of the intermediate scattering function, and anion reorientational time were obtained as a function of temperature and densitiy ρ. These dynamical properties of CKN scale as ρ(γ)∕T with a common value γ = 1.8 ± 0.1. The scaling parameter γ is consistent with the exponent of the repulsive part of an effective intermolecular potential for the repulsion between the atoms at shortest distance in the equilibrium structure of liquid CKN, Ca(2+), and oxygen atoms of NO(3)(-). Correlation between potential energy and virial is obeyed for the short-range terms of the potential function, but not for the whole potential including coulombic interactions. Decoupling of diffusion coefficient and reorientational relaxation time from relaxation time take place at a given ρ(γ)∕T value, i.e., breakdown of Stokes-Einstein and Debye-Stokes-Einstein equations result from combined thermal and volume effects. The MD results agree with correlations proposed between long-time relaxation and short-time dynamics, lnτ ∝ 1∕u(2), where the mean square displacementu(2)concerns a time window of 10.0 ps. It has been found thatu(2)scales as ρ(γ)∕T above and below the glass transition temperature, so that thermodynamic scaling of liquid dynamics can be thought as a consequence of theories relating short- and long-time dynamics, and the more fundamental scaling concerns short-time dynamical properties.

Editors: T. Scopigno,1 S. De Panfilis1,2, and A. Di Cicco,3,4 1 Dipartimento di Fisica, Universita di Roma “La Sapienza”, I-00185 Roma (Italy). 2 Centro Studi e Ricerche e Museo Storico della Fisica E. Fermi, I-00184 Roma (Italy). 3 CNISM, Sezione di Fisica, Scuola di Scienze e Tecnologie, Universita di Camerino, I-62032 Camerino (MC), Italy (permanent address). 4Institut de Mineralogie et de Physique des Milieux Condenses, UMR 7590, CNRS, Universites Paris 6 et Paris 7, Paris, France.

The pressure evolution of the sound velocity in liquid water in the terahertz regime, ${c}_{\ensuremath{\infty}}$, between 0.05 and 0.88 GPa, at room temperature, has been investigated by synchrotron inelastic x-ray scattering in a diamond anvil cell. We confirm previous results showing that ${c}_{\ensuremath{\infty}}$ increases with density much less than the adiabatic sound velocity ${c}_{s}$, which is reasonably related to the known structural modifications in the hydrogen bond network. At variance with a previous study where an anomaly was found in the density evolution of ${c}_{\ensuremath{\infty}}$---most likely due to the nonisothermal character of the study---the present work reveals a smooth behavior of ${c}_{\ensuremath{\infty}}$, which could provide a useful constraint to the current theories on liquid water.

The behaviour of high-frequency acoustic excitations in disordered materials is one of the most provocative and less understood aspects of glass science. The frequency dependence of sound damping, in particular, is the result of the interplay of several physical mechanisms crucial for many theoretical models. The emerging picture suggests the existence of a frequency crossover in sound attenuation identifying a transition from a macroscopic continuum-like behavior, due to anharmonic damping effects, to a microscopic regime in which the dynamics is dominated by topological disorder, characteristic of the amorphous phase. The very nature of this hypothetic crossover, its frequency position and its relation to other anomalies of the amorphous state is highly debated.

International audience; Liquid and amorphous metals are an outstanding example of systems combining great relevance in both industrial applications and basic science. They find broad technological application, ranging from the production of industrial coatings (walls of refinery cokers, drill pipes for oil drilling) to medical equipment (reconstructive devices, surgical blades) or high-performance sporting goods. Most metallic materials, indeed, need to be refined in the molten state before being manufactured. Liquid metals, in particular the monoatomic ones, have long been recognized as the prototype of simple liquids, in the sense that they encompass most of the physical properties of real fluids without the complications which may be present in a particular system. Until the sixties the understanding of the physical properties of liquid metals proceeded rather slowly. It was John Ziman, indeed, who first developed a theory for the electron transport in liquid metals in 1961, and subsequently several experimental and theoretical studies were presented at the first Liquid Metals International Conference held in Brookhaven in 1966 (see, for example, refs. [1-3]). From the experimental point of view, the 1950s saw major efforts related to the development of neutron scattering facilities, which constitute a unique probe in accessing the microscopic structure and dynamics in condensed matter and, in particular, in the liquid and amorphous state. A further experimental breakthrough, however, has happened in the last twenty years when X-rays generated by synchrotron radiation facilities could be used as a probe for structure and dynamics in frequency and wavelength regions similar to those explored by neutrons. Concerning the nature of the dynamical structure in liquid and amorphous metals, in the last two decades many theoretical and experimental groups have switched their studies to researching effects due to non-hydrodynamic processes in liquids, i.e. collective processes which cannot be predicted by ordinary hydrodynamics. Examples of such non-hydrodynamic propagating excitations are shear waves, the famous "fast sound" [4] in binary liquids with disparate masses, or charge waves in ionic melts [5], while the most obvious non-hydrodynamic relaxation process is structural

In contrast to crystalline solids in which structural order governs dynamics and thermodynamics, the lack of long-range periodicity in amorphous materials is responsible for several anomalies. Although the relation between these anomalies and the 'bulk structure' is generally understood, the surface structure and the corresponding vibrational spectrum of amorphous solids is practically an unexplored theme. In this study, we resolve the differences in vibrational dynamics and atomic structure between bulk and surface (top 5 nm) atoms of amorphous selenium. We combine experimental (grazing incidence inelastic X-ray scattering) and computational (ab initio and semiempirical molecular orbital theoretical calculations) methods to scrutinize a variety of possible structural models. We find that a high concentration of particular types of 'coordination defects' in the surface layer is responsible for the observed differences. Resolving the structure of amorphous surfaces is, for example, important for understanding nanoparticles' properties where the surface-to-bulk ratio has a crucial role.

4 páginas, 3 figuras.-- PACS number(s): 64.70.kj, 61.05.C-, 63.50.-x, 64.70.Q-.-- et al., The connection between viscous flow and vibrational properties in glass-forming materials is scrutinized examining the fragility of a wide set of liquids and the nonergodicity factor of the corresponding glasses. Building on the same line of reasoning which allows us to extend the connection between viscosity and thermodynamics in complex systems, we show here how the two quantities are strongly correlated once the effect of those secondary relaxation processes due to internal degrees of freedom is correctly accounted for. This result provides a missing thermodynamic rationale for the recently debated universality of the correlation between fast and slow degrees of freedom., T.S. acknowledges support from the European Research Council under the European Community Seventh Framework Program (FP7/2007-2013)/ERC IDEAS Grant No. 207916.

According to textbook definitions1, there exists no physical observable able to distinguish a liquid from a gas beyond the critical point, and hence only a single fluid phase is defined. There are, however, some thermophysical quantities, having maxima that define a line emanating from the critical point, named 'the Widom line'2 in the case of the constant-pressure specific heat. We determined the velocity of nanometric acoustic waves in supercritical fluid argon at high pressures by inelastic X-ray scattering and molecular dynamics simulations. Our study reveals a sharp transition on crossing the Widom line demonstrating how the supercritical region is actually divided into two regions that, although not connected by a first-order singularity, can be identified by different dynamical regimes: gas-like and liquid-like, reminiscent of the subcritical domains. These findings will pave the way to a deeper understanding of hot dense fluids, which are of paramount importance in fundamental and applied sciences.

The approach of generalized collective modes is applied to the study of dispersion curves of collective excitations along isothermal lines of supercritical pure Lennard-Jones fluid. An effect of structural relaxation and other nonhydrodynamic relaxation processes on the dispersion law is discussed. A simple analytical expression for the dispersion law in the long-wavelength region of acoustic excitations is obtained within a three-variable viscoelastic model of generalized hydrodynamics. It is shown that the deviation from the linear dependence in the long-wavelength region can be either "positive" or "negative" depending on the ratio between the high-frequency (elastic) and isothermal speed of sound. An effect of thermal fluctuations on positive and negative dispersion is estimated from the analytical solution of a five-variable thermoviscoelastic model that generalizes the results of the viscoelastic treatment. Numerical results are reported for a Lennard-Jones supercritical fluid along two isothermal lines T(*)=1.71,4.78 with different densities and discussed along the theoretical expressions derived.

We report on the study of the slow dynamics of supercooled and molten Selenium by means of dynamic light scattering. To achieve this in the present case, where the opaqueness of Se prevents visible light scattering measurements, we have developed a novel experimental setup using infrared radiation as the light source. By measuring the scattered intensity autocorrelation function we have been able to extract the average size of the Se clusters in the liquid state and determine the temperature dependence of the related diffusion coefficient which was found to exhibit Arrhenius behavior.

We present an experimental setup to study terahertz dynamics in fluids under high pressure, employing inelastic x-ray scattering and diamond anvil cell techniques. The use of a carefully designed vacuum chamber and the minimization and control of sources of parasitic scattering allowed circumventing previous limitations due to important empty cell contributions to the scattering signal. The successful implementation of our setup is demonstrated in the case of supercritical fluid argon, for which a full viscoelastic analysis yields the dispersion relation of sound waves, the generalized heat capacity ratio, and longitudinal viscosity. Our results are in excellent agreement with available experimental observables and molecular dynamics simulations.

Inelastic x-ray scattering (IXS) measurements of the dynamic structure factor in liquid Na57K43, sensitive to the atomic-scale coarse graining, reveal a sound velocity value exceeding the long wavelength, continuum value and indicate the coexistence of two phonon-like modes. Applying Generalized Collective Mode (GCM) analysis scheme, we show that the positive dispersion of the sound velocity occurs in a wavelength region below the crossover from hydrodynamic to atom-type excitations and, therefore, it can not be explained as sound propagation over the light specie (Na) network. The present result experimentally proves the existence of positive dispersion in a binary mixture due to a relaxation process, as opposed to fast sound phenomena., Comment: 7 pages, 8 figures, to appear in "Physical Review B"

Within this context, the main idea of this Special issue was to bring together experimental, theoretical and simulation groups in order to present the recent developments in experimental techniques, new possibilities of experimental studies, different methods of analysing the experimental data, recently elaborated theoretical approaches and modern simulation techniques - all focused on collective processes in liquids. Fifteen research groups from Italy, Germany, France, Japan, Spain, Great Britain, United States, Korea and Ukraine report in this volume the current studies and small reviews of their experimental/theoretical methodology.

Molecular dynamics simulations of the glass-forming liquid 2Ca(NO3)2.3KNO3 (CKN) were performed from high temperature liquid states down to low temperature glassy states at six different pressures from 10(-4) to 5.0 GPa. The temperature dependence of the structural relaxation time indicates that the fragility of liquid CKN changes with pressure. In line with recent proposal [Scopigno et al., Science 302, 849 (2003)], the change on liquid fragility is followed by a proportional change of the nonergodicity factor of the corresponding glass at low temperature.

Owing to their large relatively thermal conductivity, peculiar, nonhydrodynamic features are expected to characterize the acousticlike excitations observed in liquid metals. We report here an experimental study of collective modes in molten nickel, a case of exceptional geophysical interest for its relevance in earth interior science. Our result shed light on previously reported contrasting evidences: In the explored energy-momentum region, no deviation from the generalized hydrodynamic picture describing nonconductive fluids is observed. Implications for high frequency transport properties in metallic fluids are discussed. (C) 2008 American Institute of Physics.

We investigate a $d$-dimensional model ($d$ = 2,3) for sound waves in a disordered environment, in which the local fluctuations of the elastic modulus are spatially correlated with a certain correlation length. The model is solved analytically by means of a field-theoretical effective-medium theory (self-consistent Born approximation) and numerically on a square lattice. As in the uncorrelated case the theory predicts an enhancement of the density of states over Debye's $\omega^{d-1}$ law (``boson peak'') as a result of disorder. This anomay becomes reinforced for increasing correlation length $\xi$. The theory predicts that $\xi$ times the width of the Brillouin line should be a universal function of $\xi$ times the wavenumber. Such a scaling is found in the 2d simulation data, so that they can be represented in a universal plot. In the low-wavenumber regime, where the lattice structure is irrelevant there is excellent agreement between the simulation at small disorder. At larger disorder the continuum theory deviates from the lattice simulation data. It is argued that this is due to an instability of the model with stronger disorder., Comment: 5 pages, 3 figures, to be published in physica status solidi (c) March 2008

Developing a novel experimental technique, we applied photon correlation spectroscopy using infrared radiation in liquid sulfur around ${T}_{\ensuremath{\lambda}}$, i.e., in the temperature range where an abrupt increase in viscosity by 4 orders of magnitude is observed upon heating within few degrees. This allowed us---overcoming photoinduced and absorption effects at visible wavelengths---to reveal a chain relaxation process with characteristic time in the millisecond range. These results do rehabilitate the validity of the Maxwell relation in sulfur from an apparent failure, allowing rationalizing of the mechanical and thermodynamic behavior of this system within a viscoelastic scenario.

A theory for the vibrational dynamics in disordered solids [W. Schirmacher, Europhys. Lett. {\bf 73}, 892 (2006)], based on the random spatial variation of the shear modulus, has been applied to determine the wavevector ($k$) dependence of the Brillouin peak position ($\Omega_k)$ and width ($\Gamma_k$), as well as the density of vibrational states ($g(\omega)$), in disordered systems. As a result, we give a firm theoretical ground to the ubiquitous $k^2$ dependence of $\Gamma_k$ observed in glasses. Moreover, we derive a quantitative relation between the excess of the density of states (the boson peak) and $\Gamma_k$, two quantities that were not considered related before. The successful comparison of this relation with the outcome of experiments and numerical simulations gives further support to the theory., Comment: To appear on PRL

A Comment on the Letter by B. Ruffl\'e et al., Phys. Rev. Lett. 96, 045502 (2006). The authors of the Letter offer a Reply.

Unlike phonons in crystals, the collective excitations in liquids cannot be treated as propagation of harmonic displacements of atoms around stable local energy minima. The viscoelasticity of liquids, reflected in transition from the adiabatic to elastic high-frequency speed of sound and in absence of the long-wavelength transverse excitations, results in dispersions of longitudinal (L) and transverse (T) collective excitations essentially different from the typical phonon ones. Practically, nothing is known about the effect of high pressure on the dispersion of collective excitations in liquids, which causes strong changes in liquid structure. Here dispersions of L and T collective excitations in liquid Li in the range of pressures up to 186 GPa were studied by ab initio simulations. Two methodologies for dispersion calculations were used: direct estimation from the peak positions of the L/T current spectral functions and simulation-based calculations of wavenumber-dependent collective eigenmodes. It is found that at ambient pressure, the longitudinal and transverse dynamics are well separated, while at high pressures, the transverse current spectral functions, density of vibrational states, and dispersions of collective excitations yield evidence of two types of propagating modes that contribute strongly to transverse dynamics. Emergence of the unusually high-frequency transverse modes gives evidence of the breakdown of a regular viscoelastic theory of transverse dynamics, which is based on coupling of a single transverse propagating mode with shear relaxation. The explanation of the observed high-frequency shift above the viscoelastic value is given by the presence of another branch of collective excitations. With the pressure increasing, coupling between the two types of collective excitations is rationalized within a proposed extended viscoelastic model of transverse dynamics.

We study autocorrelation functions of energy, heat and entropy densities obtained by molecular dynamics simulations of supercritical Ar and compare them with the predictions of the hydrodynamic theory. It is shown that the predicted by the hydrodynamic theory single-exponential shape of the entropy density autocorrelation functions is perfectly reproduced for small wave numbers by the molecular dynamics simulations and permits the calculation of the wavenumber-dependent specific heat at constant pressure. The estimated wavenumber-dependent specific heats at constant volume and pressure, $C_{v}(k)$ and $C_{p}(k)$, are shown to be in the long-wavelength limit in good agreement with the macroscopic experimental values of $C_{v}$ and $C_{p}$ for the studied thermodynamic points of supercritical Ar., 8 pages, 5 figures

The high frequency dynamics of fluid oxygen have been investigated by Inelastic X-ray Scattering. In spite of the markedly supercritical conditions ($T\approx 2 T_c$, $P>10^2 P_c$), the sound velocity exceeds the hydrodynamic value of about 20%, a feature which is the fingerprint of liquid-like dynamics. The comparison of the present results with literature data obtained in several fluids allow us to identify the extrapolation of the liquid vapor-coexistence line in the ($P/P_c$, $T/T_c$) plane as the relevant edge between liquid- and gas-like dynamics. More interestingly, this extrapolation is very close to the non metal-metal transition in hot dense fluids, at pressure and temperature values as obtained by shock wave experiments. This result points to the existence of a connection between structural modifications and transport properties in dense fluids., 4 pages, 3 figures, accepted by Phys. Rev. Lett

Using Inelastic X-ray Scattering we studied the collective dynamics of the glassy alloy Ni$_{33}$Zr$_{67}$ in the first pseudo Brillouin zone, an energy-momentum region still unexplored in metallic glasses. We determine key properties such as the momentum transfer dependence of the sound velocity and of the acoustic damping, discussing the results in the general context of recently proposed pictures for acoustic dynamics in glasses. Specifically, we demonstrate the existence in this strong glass of well defined (in the Ioffe Regel sense) acoustic-like excitations well above the Boson Peak energy., 4 pages, 4 .eps figures, accepted in Phys. Rev. Lett

The dynamic structure factor of the polycrystalline plastic crystal 1-cyanoadamantane has been measured in the THz frequency region by inelastic X-ray scattering as a function of the exchanged momentum Q in the range 1–10 nm � 1 and as a function of the temperature in the two solid disordered phases: plastic crystal and glassy crystal. We find that the dispersion of the acoustic excitations is crystal-like in the two phases and that the attenuation C(Q) shows a negligible T dependence similarly to structural glasses and a Q a behavior with 1.15 < a < 1.50 at variance with structural glasses characterized by a Q 2 dependence.

The collective dynamics of liquid Gallium close to the melting point has been studied using Inelastic X-ray Scattering to probe lengthscales smaller than the size of the first coordination shell. %(momentum transfers, $Q$, $>$15 nm$^{-1}$). Although the structural properties of this partially covalent liquid strongly deviate from a simple hard-sphere model, the dynamics, as reflected in the quasi-elastic scattering, are beautifully described within the framework of the extended heat mode approximation of Enskog's kinetic theory, analytically derived for a hard spheres system. The present work demonstrates the applicability of Enskog's theory to non hard- sphere and non simple liquids., 5 pages, 2 figures, accepted in Phys. Rev. Lett

The concept of fragility provides a possibility to rank different supercooled liquids on the basis of the temperature dependence of dynamic and/or thermodynamic quantities. We recall here the definitions of kinetic and thermodynamic fragility proposed in the last years and discuss their interrelations. At the same time we analyze some recently introduced models for the statistical properties of the potential energy landscape. Building on the Adam-Gibbs relation, which connects structural relaxation times to configurational entropy, we analyze the relation between statistical properties of the landscape and fragility. We call attention to the fact that the knowledge of number, energy depth and shape of the basins of the potential energy landscape may not be sufficient for predicting fragility. Finally, we discuss two different possibilities for generating strong behavior., 17 pages, 10 figures; accepted version, minor corrections

The high frequency collective dynamics of molten potassium has been investigated by inelastic x-ray scattering, disclosing an energy/momentum transfer region unreachable by previous neutron scattering experiments (INS). We find that a two-step relaxation scenario, similar to that found in other liquid metals, applies to liquid potassium. In particular, we show how the sound velocity determined by INS experiments, exceeding the hydrodynamic value by $\approx 30 %$, is the higher limit of a speed up, located in the momentum region $1, Comment: 7 pages, 5 .eps figures. To appear in J. Chem. Phys

The dynamic structure factor, S(Q,w), of vitreous silica, has been measured by inelastic X-ray scattering in the exchanged wavevector (Q) region Q=4-16.5 nm-1 and up to energies hw=115 meV in the Stokes side. The unprecedented statistical accuracy in such an extended energy range allows to accurately determine the longitudinal current spectra, and the energies of the vibrational excitations. The simultaneous observation of two excitations in the acoustic region, and the persistence of propagating sound waves up to Q values comparable with the (pseudo-)Brillouin zone edge, allow to observe a positive dispersion in the generalized sound velocity that, around Q=5 nm-1, varies from 6500 to 9000 m/s: this phenomenon was never experimentally observed in a glass., Comment: 5 pages, 3 figures. To appear in Phys. Rev. B

The dynamic structure factor of glassy and liquid glycerol has been measured by inelastic X-ray scattering in the exchanged momentum Q region Q = 2-23 nm(-1) and in the temperature range 80-570 K. Besides the propagating longitudinal mode, at low temperatures the spectra show a second non-Q-dispersing peak at hOhm(T) approximate to 8.5 meV. This peak is the signature of the transverse dynamics which, in topologically disordered systems, acquire a small Q-dependent longitudinal symmetry component. This assignment is substantiated by a study of the temperature dependence of the intensity of the second peak. This study showed that, in the liquid, the second peak intensity vanishes when the structural relaxation time tau(alpha) approaches Ohm(T)(-1), a behaviour consistent with the condition tau(alpha)Ohm(T) much greater than1 required for the existence of a non-relaxational transverse-like dynamics in the liquid state.

We present a new experimental protocol for the spectroscopic study of the dynamics of glasses in the aging regime induced by sudden pressure jumps (crunches) across the glass transition line. The sample, initially in the liquid state, is suddenly brought in the glassy state, and therefore out of equilibrium, in a four-window optical crunch cell which is able to perform pressure jumps of 3 kbar in a time interval of ~10 ms. The main advantages of this setup with respect to previous pressure-jump systems is that the pressure jump is induced through a pressure transmitting fluid mechanically coupled to the sample stage through a deformable membrane, thus avoiding any flow of the sample itself in the pressure network and allowing to deal with highly viscous materials. The dynamics of the sample during the aging regime is investigated by Brillouin Light Scattering (BLS). For this purpose the crunch cell is used in conjunction with a high resolution double monochromator equipped with a CCD detector. This system is able to record a full spectrum of a typical glass forming material in a single 1 s shot. As an example we present the study of the evolution toward equilibrium of the infinite frequency longitudinal elastic modulus (M_infinity) of a low molecular weight polymer (Poly(bisphenol A-co-epichlorohydrin), glycidyl end capped). The observed time evolution of M_infinity, well represented by a single stretched exponential, is interpreted within the framework of the Tool-Narayanaswamy theory., 9 pages, 11 figures

In a recent paper, S. Singh and K. Tankeshwar (ST), [Phys. Rev. E \textbf{67}, 012201 (2003)], proposed a new interpretation of the collective dynamics in liquid metals, and, in particular, of the relaxation mechanisms ruling the density fluctuations propagation. At variance with both the predictions of the current literature and the results of recent Inelastic X-ray Scattering (IXS) experiments, ST associate the quasielastic component of the $S(Q,\omega)$ to the thermal relaxation, as it holds in an ordinary adiabatic hydrodynamics valid for non-conductive liquids and in the $Q \to 0$ limit. We show here that this interpretation leads to a non-physical behaviour of different thermodynamic and transport parameters., Comment: 4 pages, 1 figure, to appear in PRE (scheduled in 1 June issue)

The recently developed inelastic X-ray scattering technique opens a new kinematic region at the observation of molecular liquids vibrational dynamics over the lengthscales of the interparticle separation. We illustrate the capabilities of this powerful technique through the results obtained from liquid glycerol. A detailed analysis of the high-frequency vibrational dynamics of this system at ambient temperature is reported. New results in the study of structural relaxational dynamics in the high-temperature range (up to T = 560 K) are also discussed.

The high frequency dynamics of glassy Selenium has been studied by Inelastic X-ray Scattering at beamline BL35XU (SPring-8). The high quality of the data allows one to pinpoint the existence of a dispersing acoustic mode for wavevectors ($Q$) of $1.5, Comment: Phys. Rev. Lett. (Accepted)

The improvement in performance of the inelastic x-ray scattering technique has led to accurate determination of the dynamic structure factors of glassy and liquid glycerol, in the region of exchanged momentum Q = 2-23 nm(-1) and in the temperature range 80-570 K. Thanks to the improved statistical accuracy, it has been possible to identify, in the spectra at the lower temperatures, besides the propagating longitudinal mode, a second non-Q-dispersing peak at (h) over bar Omega(T) approximate to 8.5 meV. We interpret this peak as a signature of the transverse dynamics that, in topologically disordered systems, acquires a longitudinal symmetry component. This assignment is substantiated by the observation that this peak still survives, across the glass transition, in the liquid state, and vanishes when the structural relaxation time tau(alpha) approaches Omega(T)(-1): a behaviour consistent with the condition tau(alpha)Omega(T) >> 1 required for the existence of a non-relaxational transverse-like dynamics in the liquid state.