P. Benassi

Acoustic nature of the boson peak in vitreous silica

New temperature-dependent inelastic X-ray scattering (IXS) and Raman scattering (RS) data are compared with each other and with existing inelastic neutron scattering (INS) data in vitreous silica, in the 300± 1775K region. The IXS data show collective propagating excitations up to Q ˆ 3:5nm i 1 . The temperature behaviour of the excitations at Q ˆ 1:6nm i 1 matches that of the boson peak found in INS and RS. This supports the fact that the acoustic origin of the excess of vibrational states gives rise to the boson peak in this glass.

Vibrations of bioionic liquids by ab initio molecular dynamics and vibrational spectroscopy.

Density functional theory and vibrational spectroscopy are used to investigate a class of bioionic liquids consisting of a choline cation and carboxylate anions. Through quantum mechanical studies of motionless ion pairs and molecular dynamics of small portions of the liquid, we have characterized important structural features of the ionic liquid. Hydrogen bonding produces stable ion pairs in the liquid and induces vibrational features of the carboxylate groups comparable with experimental results. Infrared and Raman spectra of liquids have been measured, and main bands have been assigned on the basis of theoretical spectra.

A spectrometer for high-resolution and high-contrast Brillouin spectroscopy in the ultraviolet

We present a multiple-grating spectrometer designed for high-resolution and high-contrast low-frequency scattering spectroscopy in the ultraviolet, as well as in the visible spectral regions. The instrument has a resolution better than 1 GHz and a contrast of about 1×10−10 both in the visible and in the UV range, thus doubling the highest resolution achieved by double-monochromator double-pass spectrometers such as the SOPRA DMDP2000, conceived for Raman–Brillouin spectroscopy using visible excitation. Performance tests and the Brillouin spectra obtained in the ultraviolet range are reported. Ray tracing results, aiming to give a better insight on the instrument performances are also presented. The instrument opens the possibility to study a new region of the exchanged momentum with a suitable energy resolution and to investigate the spectrum of density fluctuations in materials where the UV penetration depth could be a relevant step for the experimental study of the dynamics of disordered material.

The potential energy landscape in the Lennard-Jones binary mixture model

The potential energy landscape in the Kob-Andersen Lennard-Jones binary mixture model has been studied carefully from the liquid down to the supercooled regime, from T = 2 down to 0.46. One thousand independent configurations along the time evolution locus have been examined at each temperature investigated. From the starting configuration, we searched for the nearest saddle (or quasi-saddle) and minimum of the potential energy. The vibrational densities of states for the starting and the two derived configurations have been evaluated. Besides the number of negative eigenvalues of the saddles other quantities show some signature of the approach of the dynamical arrest temperature.

Phonon attenuation in vitreous silica and silica porous systems

The mechanisms responsible for phonon attenuation in glasses and in porous systems have been investigated. The acoustic attenuation has been measured by Brillouin light scattering using a Fabry-Pérot apparatus and a new ultraviolet spectrometer. In particular, melt-quenched vitreous silica (ρ = 2200 kg m−3), silica xerogels with different densities (ρ = 510 ± 50, 770 ± 80, 1380 ± 140 and 2190 ± 200 kg m−3), and silica aerogel (ρ = 670 ± 80 kg m−3) have been studied. The porosities of the samples have been measured by nitrogen adsorption–desorption techniques. The Brillouin linewidth is found to increase with increasing pore size, being related to the effect of the growing structural disorder. Comparison between the acoustic attenuation obtained by the two wavelengths shows the existence of a crossover length a* which identifies the wave-vector values above which the disorder induced by the pore size starts to be the dominant cause of absorption. The position of the crossover is found to be frequency dependent.

On the shape of the dynamic structure factor in glasses

Abstract The peculiar shape of the dynamie structure factor of glasses has been investigated thoroughly by light scattering and computer simulation techniques. The experimental spectra show a pronounced asymmetry with respect to their peak frequencies. Similar asymmetries have already been observed by simulation on argon glass in a range of exchanged momentum about ten times higher than that probed by light scattering. New simulation on a large sample of silica glass also shows similar features. Moreover the calculated dynamie structure factors appear as the straight continuation at higher momentum values of the experimental light scattering data. The qualitative independence of this phenomenon from the glass type together with the analysis of the eigenvector pattems in argon glass suggest that this asymmetric shape is a mark of the topological disorder.

Sound dispersion and attenuation in concentrated H2SO4 by visible and ultraviolet Brillouin spectroscopy.

The acoustic properties of highly concentrated H(2)SO(4) are investigated performing visible and ultraviolet Brillouin scattering measurements. We analyzed the isotropic and anisotropic spectra of this molecular liquid in a wide temperature and exchanged wavector range in order to study the evolution of its sound velocity and viscosity. This allows us to extract the parameters required to describe its viscoelastic relaxation behavior. We found that the behavior of the hydrodynamic parameters of this molecular liquid shares some similarities with that of water indicating a rather high increase of sound velocity if compared to that measured by ultrasonics.

Ultraviolet and visible Brillouin scattering study of viscous relaxation in 3-methylpentane down to the glass transition

Brillouin light scattering spectra from transverse and longitudinal acoustic waves in liquid and supercooled 3-methylpentane have been collected from room temperature down to 80 K, just above the glass transition. Spectra at different wave vectors have been obtained using 532 nm and 266 nm excitation. We found evidence of a shear relaxation with a characteristic time of 100 s at the glass transition which only partly accounts for the relaxation observed in the propagation and attenuation of the longitudinal modes. The inclusion of a relaxing bulk viscosity contribution with a relaxation time of the order of 10(2) ns at the glass transition is found to adequately reproduce the experimental data including transient grating data at a much lower frequency. A consistent picture of relaxed shear and bulk moduli as a function of temperature is derived. These two quantities are found to be related by a linear relation suggesting that a Cauchy-like relation holds also above the glass transition.

Study of the dynamic structure factor of strong glasses

Abstract The dynamic structure factors (DSFs) of several strong glasses (SF6, SF10, BK7, SUPRASIL) measured by Brillouin light scattering spectroscopy are reported. Spectra have been collected, at and above room temperature, at two scattering angles, θ=90° and θ=180° corresponding to exchanged wavevector q values ranging from 0.0256 to 0.0448 nm−1. In particular we find that the isotropic spectral lineshapes are in all cases well described by the simple hydrodynamic theory of an amorphous solid. The width of the Brillouin peaks are found to be consistent with the predicted q2 dependence at both investigated temperatures. This damping is however found to account only partially for the strong asymmetry of the Brillouin line clearly visible on a logarithmic intensity scale. As a matter of fact there is an excess intensity in the very low frequency plateau underlying the central component. The height of this plateau and hence the entire lineshape is well reproduced if a relaxation process is taken into account in the hydrodynamic equations. Owing to the intense elastic scattering we are able to determine unambiguously only the ratio between amplitude and characteristic time of this process which quantifies the sound dispersion to be of the order of a few percent in all samples. The temperature dependence of the parameters indicates that this relaxation cannot be attributed to thermally activated relaxation phenomena. These general findings favorably compare with molecular dynamics simulation results on similar systems.

A high resolution ultraviolet monochromator HIRESUV for the study of disordered materials in the mesoscopic regime

We present the state of the art in the realization of a new spectrometer especially designed for high resolution and high-contrast scattering experiments in the ultra-violet (UV) spectral region. Different scattering techniques, employing neutrons, X-rays or visible light are compared with each other for transferred energies and momenta. The importance of high-resolution measurements in the UV range is stressed with particular attention devoted to the study of disordered materials.