G. Ruocco

Competing interactions in arrested states of colloidal clays

Using experiments, theory and simulations, we show that the arrested state observed in a colloidal clay at high concentrations is stabilized by screened Coulomb repulsion (Wigner glass). Dilution experiments allow us to distinguish this disconnected state, which melts upon addition of water, from a low-concentration gel state, which does not melt. Theoretical modeling and simulations at high concentrations reproduce the measured small angle x-ray scattering static structure factors and confirm the long-range electrostatic nature of the arrested structure. These findings are attributed to the different time scales controlling the competing attractive and repulsive interactions.

Microscopic relaxation in supercritical and liquid neon

The high frequency behavior of the dynamic structure factor, S(Q,ω), of liquid and supercritical neon is investigated by inelastic x-ray scattering at different temperatures and pressure. The spectral evolution is described in terms of a single-relaxation-time viscoelastic model. The occurrence of a positive dispersion in the sound velocity is clearly visible in both investigated thermodynamic phases. The anomalies in the dispersive behavior deeply reduce at the higher temperatures, probably, as a consequence of important changes in the first shell interactions. More generally, the atomic dynamics is dominated by a relaxation process whose time scale is in the range of fast microscopic degrees of freedom (≈10−13 s), and whose strength and typical time scale stay constant over all the explored liquid and supercritical regions.

Pressure-induced emergence of unusually high-frequency transverse excitations in a liquid alkali metal: Evidence of two types of collective excitations contributing to the transverse dynamics at high pressures

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.

Dual aging behaviour in a clay-polymer dispersion

Clay-polymer compounds have recently attracted increasing attention due to their intriguing physical properties in colloidal science and their rheological non-trivial behaviour in technological applications. Aqueous solutions of Laponite clay spontaneously age from a liquid up to an arrested state of different nature (gel or glass) depending on the colloidal volume fraction and ionic strength. We have investigated, through dynamic light scattering, how the aging dynamics of Laponite dispersions at fixed clay concentration (Cw = 2.0%) is modified by the addition of various amounts of poly(ethylene oxide) (PEO) (CPEO = (0.05 ÷ 0.50) %) at two different molecular weights (Mw = 100 kg mol(-1) and Mw = 200 kg mol(-1)). A surprising and intriguing phenomenon has been observed: the existence of a critical polymer concentration C that discriminates between two different aging dynamics. With respect to pure Laponite systems the aging will be assisted (faster) or hindered (slower) for PEO concentrations respectively lower (CPEO < C) or higher (CPEO > C) than the critical concentration. In this way a control on the aging dynamics of PEO-Laponite systems is obtained. A possible explanation based on the balance of competitive mechanisms related to the progressive saturation of the clay surface by polymers is proposed. This study shows how a real control on the aging speed of the PEO-Laponite system is at hand and renders possible a real control of the complex interparticle interaction potential.

Generalised hydrodynamic description of the time correlation functions of liquid metals: ab initio molecular dynamics study

A new methodology of calculation of dispersion and damping of collective excitations from ab initio molecular dynamics (AIMD) of liquid metals is proposed. It is suggested to use for the analysis of AIMD-derived time correlation functions a thermo-viscoelastic dynamic model within an approach of the generalised collective modes. The proposed scheme, in which the viscoelastic matrix elements of the generalised hydrodynamic matrix are directly calculated from AIMD and the matrix elements requiring knowledge of energy density fluctuations in the system are treated as fitting parameters, allows to recover AIMD time correlation functions in a wide range of wave numbers. The dispersion and damping of collective excitations are obtained as a complex-conjugated pair of the generalised hydrodynamic matrix. An issue of sum rules in the proposed scheme is discussed. The methodology is applied for calculations of dispersion and damping of generalised acoustic modes in molten lithium.

Phase diagram of a solution undergoing inverse melting

The phase diagram of alpha -cyclodextrin/water/4-methylpyridine solutions, a system undergoing inverse melting, has been studied by differential scanning calorimetry, rheological methods, and x-ray diffraction. Two different fluid phases separated by a solid region have been observed in the high alpha -cyclodextrin concentration range (c > or =150 mg/ml) . Decreasing c , the temperature interval where the solid phase exists decreases and eventually disappears, and a first-order phase transition is observed between the two different fluid phases.

Probing the non-Debye low-frequency excitations in glasses through random pinning

Significance Amorphous solids are continuum media. However, their mechanical and thermodynamical properties, even though universal, dramatically deviate from those in crystalline solids. Their anomalous behavior reflects peculiar and universal deviations from Debye’s law in the low-frequency sector of the density of states D(ω). Theoretical models predict a population of non-Goldstone modes following the universal power law D(ω)∼ω4 that are subdominant and therefore hard to detect. In this work, we introduce a general protocol that can be used in both numerical simulations and experiments, to probe the non-Debye portion of the spectrum. We investigate the properties of the low-frequency spectrum in the density of states D(ω) of a 3D model glass former. To magnify the non-Debye sector of the spectrum, we introduce a random pinning field that freezes a finite particle fraction to break the translational invariance and shifts all of the vibrational frequencies of the extended modes toward higher frequencies. We show that non-Debye soft localized modes progressively emerge as the fraction p of pinned particles increases. Moreover, the low-frequency tail of D(ω) goes to zero as a power law ωδ(p), with 2≤δ(p)≤4 and δ=4 above a threshold fraction pth.

Relaxation dynamics in (HF)x(H2O)1-x solutions.

The high-frequency dynamics of (HF)(x)(H(2)O)(1-x) solutions has been investigated by inelastic x-ray scattering. The measurements have been performed as a function of the concentration in the range x = 0.20-0.73 at fixed temperature T = 283 K. The results have been compared with similar data in pure water (x = 0) and pure hydrogen fluoride (x = 1). A viscoelastic analysis of the data highlights the presence of a relaxation process characterized by a relaxation time and a strength directly related to the presence of a hydrogen-bond network in the system. The comparison with the data on water and hydrogen fluoride shows that the structural relaxation time continuously decreases at increasing concentration of hydrogen fluoride passing from the value for water to the one for hydrogen fluoride tau(alphaHF), which is three times smaller. This is the consequence of a gradual decreasing number of constraints of the hydrogen-bond networks in passing from one liquid to the other.