Local Density Inhomogeneities and Dynamics in supercritical water: A molecular dynamics simulation Approach

Abstract

Molecular dynamics atomistic simulations in the canonical ensemble (NVT-MD) have been used to investigate the "Local Density Inhomogeneities and their Dynamics" in pure supercritical water. The simulations were carried out along a near-critical isotherm (Tr = T/Tc = 1.03) and for a wide range of densities below and above the critical one (0.2 ρc - 2.0 ρc). The results obtained reveal the existence of significant local density augmentation effects, which are found to be sufficiently larger in comparison to those reported for nonassociated fluids. The time evolution of the local density distribution around each molecule was studied in terms of the appropriate time correlation functions C Δρl(t). It is found that the shape of these functions changes significantly by increasing the density of the fluid, finally, the local density reorganization times for the first and second coordination shell derived from these correlations exhibit a decreasing behavior by increasing the density of k the system, signifying the density effect upon the dynamics of the local environment around each molecule. © 2006 American Chemical Society