Time dependence of the velocity autocorrelation function of a fluid: An eigenmode analysis of dynamical processes.

ABSTRACT

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.