Translational and Rotational Diffusion in Stretched Water

Abstract

We perform molecular dynamics simulations using the extended simple point charge SPC/E water model in order to investigate the dynamical behavior of supercooled-stretched water. We focus on the behavior of the translational diffusion coefficient, the orientational relaxation time, and the local hydrogen bond network. Decreasing density or pressure along an isothermal path, there is a mininum in the diffusion coefficient and a maximum in the orientational relaxation time, suggesting an initial enhancement and subsequent breakdown of the tetrahedral structure and of the hydrogen bond network as the density decreases. The analysis of the tetrahedral structure of the nearest neighbors help to clarify the relationship between the local structural changes and the system dynamics. We also find that the product of diffusion coefficient and relaxation time is nearly constant, indicating that the anomalous behavior observed in the rotational and translational diffusion arise from the same microscopic mechanism.