Water at Positive and Negative Pressures

Abstract

We review recent results of molecular dynamics simulations of two models of liquid water, the extended simple point charge (SPC/E) and the Mahoney-Jorgensen transferable intermolecular potential with five points (TIP5P), which is closer to real water than previously-proposed classical pairwise additive potentials. Simulations of the TIP5P model for a wide range of deeply supercooled states, including both positive and negative pressures, reveal (i) the existence of a non-monotonic ``nose-shaped'' temperature of maximum density (TMD) line and a non-reentrant spinodal, (ii) the presence of a low temperature phase transition. The TMD that changes slope from negative to positive as P decreases and, notably, the point of crossover between the two behaviors is located at ambient pressure (temperature approx 4 C, and density approx 1 g/cm^3). Simulations on the dynamics of the SPC/E model reveal (iii) the dynamics at negative pressure shows a minimum in the diffusion constant $D$ when the density is decreased at constant temperature, complementary to the known maximum of D at higher pressures, and (iv) the loci of minima of D relative to the spinodal shows that they are inside the thermodynamically metastable regions of the phase-diagram. These dynamical results reflect the initial enhancement and subsequent breakdown of the tetrahedral structure and of the hydrogen bond network as the density decreases.