Alessandro Cunsolo

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.

Revealing the mechanism of passive transport in lipid bilayers via phonon-mediated nanometre-scale density fluctuations

The passive transport of molecules through a cell membrane relies on thermal motions of the lipids. However, the nature of transmembrane transport and the precise mechanism remain elusive and call for a comprehensive study of phonon excitations. Here we report a high resolution inelastic X-ray scattering study of the in-plane phonon excitations in 1,2-dipalmitoyl-sn-glycero-3-phosphocholine above and below the main transition temperature. In the gel phase, for the first time, we observe low-frequency transverse modes, which exhibit a phonon gap when the lipid transitions into the fluid phase. We argue that the phonon gap signifies the formation of short-lived nanometre-scale lipid clusters and transient pores, which facilitate the passive molecular transport across the bilayer plane. Our findings suggest that the phononic motion of the hydrocarbon tails provides an effective mechanism of passive transport, and illustrate the importance of the collective dynamics of biomembranes.

Revealing the Mechanism of the Viscous-to-Elastic Crossover in Liquids.

In this work, we report on inelastic X-ray scattering experiments combined with the molecular dynamics simulations on deeply supercritical Ar. The presented results unveil the mechanism and regimes of sound propagation in the liquid matter and provide compelling evidence for the adiabatic-to-isothermal longitudinal sound propagation transition. We introduce a Hamiltonian predicting low-frequency transverse sound propagation gaps, which is confirmed by experimental findings and molecular dynamics calculations. As a result, a universal link is established between the positive sound dispersion (PSD) phenomenon and the origin of transverse sound propagation revealing the viscous-to-elastic crossover in liquids. The PSD and transverse phononic excitations evolve consistently with theoretical predictions. Both can be considered as a universal fingerprint of the dynamic response of a liquid, which is also observable in a subdomain of supercritical phase. The simultaneous disappearance of both these effects at elevated temperatures is a manifestation of the Frenkel line. We expect that these findings will advance the current understanding of fluids under extreme thermodynamic conditions.

Quasielastic neutron scattering investigation of the pressure dependence of molecular motions in liquid water

We report on a high-resolution, high-statistics, quasielastic neutron scattering (QENS) experiment on liquid water, aimed at accurately measuring the pressure dependence of the single-particle dynamic response function at low wave vector transfers, namely, from 0.26 to 1.32 A(-1). High-pressure QENS data were collected along the T = 268 K isothermal path over the rather extended pressure range of 80 up to 350 MPa, a thermodynamic region so far unexplored by this microscopic technique. The analysis of the measured line shapes enabled us to draw a consistent picture of the wave vector and pressure dependences of the diffusion mechanisms in liquid water, against which the most recent models for water dynamics can be checked. In close similarity with the case of supercooled water, the relaxing-cage model was found to provide a quantitatively more accurate description of the molecular motions and their pressure evolution in liquid water.

The Frenkel Line: a direct experimental evidence for the new thermodynamic boundary

Supercritical fluids play a significant role in elucidating fundamental aspects of liquid matter under extreme conditions. They have been extensively studied at pressures and temperatures relevant to various industrial applications. However, much less is known about the structural behaviour of supercritical fluids and no structural crossovers have been observed in static compression experiments in any temperature and pressure ranges beyond the critical point. The structure of supercritical state is currently perceived to be uniform everywhere on the pressure-temperature phase diagram, and to change only in a monotonic way even moving around the critical point, not only along isotherms or isobars. Conversely, we observe structural crossovers for the first time in a deeply supercritical sample through diffraction measurements in a diamond anvil cell and discover a new thermodynamic boundary on the pressure-temperature diagram. We explain the existence of these crossovers in the framework of the phonon theory of liquids using molecular dynamics simulations. The obtained results are of prime importance since they imply a global reconsideration of the mere essence of the supercritical phase. Furthermore, this discovery may pave the way to new unexpected applications and to the exploration of exotic behaviour of confined fluids relevant to geo- and planetary sciences.

Application of a new ensemble conserving quantum dynamics simulation algorithm to liquid para-hydrogen and ortho-deuterium

We apply the Feynman-Kleinert Quasi-Classical Wigner (FK-QCW) method developed in our previous work [Smith et al., J. Chem. Phys. 142, 244112 (2015)] for the determination of the dynamic structure factor of liquid para-hydrogen and ortho-deuterium at state points of (T = 20.0 K, n = 21.24 nm(-3)) and (T = 23.0 K, n = 24.61 nm(-3)), respectively. When applied to this challenging system, it is shown that this new FK-QCW method consistently reproduces the experimental dynamic structure factor reported by Smith et al. [J. Chem. Phys. 140, 034501 (2014)] for all momentum transfers considered. This shows that FK-QCW provides a substantial improvement over the Feynman-Kleinert linearized path-integral method, in which purely classical dynamics are used. Furthermore, for small momentum transfers, it is shown that FK-QCW provides nearly the same results as ring-polymer molecular dynamics (RPMD), thus suggesting that FK-QCW provides a potentially more appealing algorithm than RPMD since it is not formally limited to correlation functions involving linear operators.

Thermally triggered phononic gaps in liquids at THz scale.

In this paper we present inelastic X-ray scattering experiments in a diamond anvil cell and molecular dynamic simulations to investigate the behavior of phononic excitations in liquid Ar. The spectra calculated using molecular dynamics were found to be in a good agreement with the experimental data. Furthermore, we observe that, upon temperature increases, a low-frequency transverse phononic gap emerges while high-frequency propagating modes become evanescent at the THz scale. The effect of strong localization of a longitudinal phononic mode in the supercritical phase is observed for the first time. The evidence for the high-frequency transverse phononic gap due to the transition from an oscillatory to a ballistic dynamic regimes of motion is presented and supported by molecular dynamics simulations. This transition takes place across the Frenkel line thermodynamic limit which demarcates compressed liquid and non-compressed fluid domains on the phase diagram and is supported by calculations within the Green-Kubo phenomenological formalism. These results are crucial to advance the development of novel terahertz thermal devices, phononic lenses, mirrors, and other THz metamaterials.

The THz Spectrum of Density Fluctuations of Water: The Viscoelastic Regime

Relevant advances in the knowledge of the water dynamics at mesoscopic scales are reviewed, while mainly focusing on the contribution provided by high resolution inelastic X-ray scattering (IXS). In particular it is discussed how the use of IXS has improved our understanding of viscoelastic properties of water at THz frequencies. This specifically involves some solid-like features such as the onset of shear wave propagation, a sound velocity surprisingly similar to the one of ice, and an anomalously low sound absorption coefficient. All these properties can be explained by assuming the coupling of THz density fluctuations with a structural relaxation process connected to the breaking and forming of hydrogen bonds (HBs). This review also includes more recent IXS results demonstrating that, upon approaching supercritical conditions, relaxation phenomena in water gradually lose their structural character becoming essentially collisional in character. Furthermore, GHz spectroscopy results on supercooled water, suggesting the occurrence of a structural arrest, are discussed. An overview of the new opportunities offered by next generation IXS spectrometers finally concludes this review.

Refinement of the experimental dynamic structure factor for liquid para-hydrogen and ortho-deuterium using semi-classical quantum simulation

The dynamic structure factor of liquid para-hydrogen and ortho-deuterium in corresponding thermodynamic states (T = 20.0 K, n = 21.24 nm(-3)) and (T = 23.0 K, n = 24.61 nm(-3)), respectively, has been computed by both the Feynman-Kleinert linearized path-integral (FK-LPI) and Ring-Polymer Molecular Dynamics (RPMD) methods and compared with Inelastic X Ray Scattering spectra. The combined use of computational and experimental methods enabled us to reduce experimental uncertainties in the determination of the true sample spectrum. Furthermore, the refined experimental spectrum of para-hydrogen and ortho-deuterium is consistently reproduced by both FK-LPI and RPMD results at momentum transfers lower than 12.8 nm(-1). At larger momentum transfers the FK-LPI results agree with experiment much better for ortho-deuterium than for para-hydrogen. More specifically we found that for k ∼ 20.0 nm(-1) para-hydrogen provides a test case for improved approximations to quantum dynamics.

Shear propagation in the terahertz dynamics of water-glycerol mixtures

Inelastic X-ray and neutron scattering techniques were jointly used to investigate the dynamics of water-glycerol mixtures at different concentrations and temperatures. It was observed that even relatively low concentrations of glycerol increase the damping of shear modes, as a consequence of the known ability of glycerol to disrupt the hydrogen bond network of water. A similar trend was observed when increasing the temperature, which suggests the presence of a locus in the concentration-temperature plane marking a crossover in the shear modulus.