In the Q range where inelastic x-ray and neutron scattering are applied to the study of acoustic collective excitations in fluids, various models of the dynamic structure factor S(Q, omega) generalize in different ways the results obtained from linearized-hydrodynamics theory in the Q-->0 limit. Here we show that the models most commonly fitted to experimental S(Q, omega) spectra can be given a unified formulation. In this way, direct comparisons among the results obtained by fitting different models become now possible to a much larger extent than ever. We also show that a consistent determination of the dispersion curve and of the propagation Q range of the excitations is possible, whichever model is used. We derive an exact formula which describes in all cases the dispersion curve and allows for the first quantitative understanding of its shape, by assigning specific and distinct roles to the various structural, thermal, and damping effects that determine the Q dependence of the mode frequencies. The emerging picture describes the acoustic modes as Q-dependent harmonic oscillators whose characteristic frequency is explicitly renormalized in an exact way by the relaxation processes, which also determine, through the widths of both the inelastic and the elastic lines, the whole shape of collective-excitation spectra.

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The velocity autocorrelation function (VAF), a key quantity in the atomic-scale dynamics of fluids, has been the first paradigmatic example of a long-time tail phenomenon, and much work has been devoted to detecting such long-lasting correlations and understanding their nature. There is, however, much more to the VAF than simply the evidence of this long-time dynamics. A unified description of the VAF from very short to long times, and of the way it changes with varying density, is still missing. Here we show that an approach based on very general principles makes such a study possible and opens the way to a detailed quantitative characterization of the dynamical processes involved at all time scales. From the analysis of molecular dynamics simulations for a slightly supercritical Lennard-Jones fluid at various densities, we are able to evidence the presence of distinct fast and slow decay channels for the velocity correlation on the time scale set by the collision rate. The density evolution of these decay processes is also highlighted. The method presented here is very general, and its application to the VAF can be considered as an important example.

When the dynamics of liquids and disordered systems at mesoscopic level is investigated by means of inelastic scattering (e.g., neutron or x ray), spectra are often characterized by a poor definition of the excitation lines and spectroscopic features in general and one important issue is to establish how many of these lines need to be included in the modeling function and to estimate their parameters. Furthermore, when strongly damped excitations are present, commonly used and widespread fitting algorithms are particularly affected by the choice of initial values of the parameters. An inadequate choice may lead to an inefficient exploration of the parameter space, resulting in the algorithm getting stuck in a local minimum. In this paper, we present a Bayesian approach to the analysis of neutron Brillouin scattering data in which the number of excitation lines is treated as unknown and estimated along with the other model parameters. We propose a joint estimation procedure based on a reversible-jump Markov chain Monte Carlo algorithm, which efficiently explores the parameter space, producing a probabilistic measure to quantify the uncertainty on the number of excitation lines as well as reliable parameter estimates. The method proposed could turn out of great importance in extracting physical information from experimental data, especially when the detection of spectral features is complicated not only because of the properties of the sample, but also because of the limited instrumental resolution and count statistics. The approach is tested on generated data set and then applied to real experimental spectra of neutron Brillouin scattering from a liquid metal, previously analyzed in a more traditional way.

We present inelastic neutron scattering measurements on liquid mercury at room temperature for wave numbers q in the range 0.3 ϽqϽ7.0 Å Ϫ1 . We find that the energy half width of the incoherent part of the dynamic structure factor S(q,E) is determined by a self-diffusion process. The half width of the coherent part of S(q,E) shows the characteristic behavior expected for a cage diffusion process. We also show that the response function at small wave numbers exhibits a quasielastic mode with a time scale characteristic of cage diffusion, however, its intensity is larger by an order of magnitude than what would be expected for cage diffusion. We speculate on a scenario in which the intensity of the cage diffusion mode at small wave numbers is amplified through a valence fluctuation mechanism.