Collective dynamics near fluid phase transitions.

By means of molecular dynamics simulations, we calculate the intermediate scattering function F(k(axially),t) where k(||) is the wave number and t is the time. We focus on thermodynamic states in the vicinity of a fluid phase transition in bulk and confined systems which we locate in parallel Monte Carlo simulations in the grand canonical ensemble. As one approaches the limit of stability of the fluid (i.e., its spinodal) from either low- or high-density branches of a subcritical isotherm, F(k(axially),t) becomes increasingly long-range. The apparent lack of decorrelation in the metastable regime can be understood within the framework of a simple mean-field theory that links the long-range nature of F(k(axially),t) to a divergence of the ratio of isostress and isochoric heat capacities gamma. Our results suggest that as one approaches the spinodal the dynamic structure factor S(k(axially),omega) (omega frequency), which is related to F(k(axially),t) through a Laplace transformation, should undergo a qualitative change from the usual triplet of Brillouin and Rayleigh lines to a singlet (delta-function-like peak) centered at omega=0 for states directly at the spinodal. This qualitative change in S(k(axially),omega) should be measurable in scattering experiments thereby promoting more detailed insight into the phase behavior and thermodynamic stability of confined and bulk fluids.