Interplay Between Time-Temperature-Transformation and the Liquid-Liquid Phase Transition in Water

We study the TIP5P water model proposed by Mahoney and Jorgensen, which is closer to real water than previously-proposed classical pairwise additive potentials. We simulate the model in a wide range of deeply supercooled states and find (i) the existence of a non-monotonic ``nose-shaped'' temperature of maximum density line and a non-reentrant spinodal, (ii) the presence of a low temperature phase transition, (iii) the free evolution of bulk water to ice, and (iv) the time-temperature-transformation curves at different densities.Comment: RevTeX4, 4 pages, 4 eps figure

Lyapunov instability of fluids composed of rigid diatomic molecules

We study the Lyapunov instability of a two-dimensional fluid composed of rigid diatomic molecules, with two interaction sites each, and interacting with a WCA site-site potential. We compute full spectra of Lyapunov exponents for such a molecular system. These exponents characterize the rate at which neighboring trajectories diverge or converge exponentially in phase space. Quam. These exponents characterize the rate at which neighboring trajectories diverge or converge exponentially in phase space. Qualitative different degrees of freedom -- such as rotation and translation -- affect the Lyapunov spectrum differently. We study this phenomenon by systematically varying the molecular shape and the density. We define and evaluate ``rotation numbers'' measuring the time averaged modulus of the angular velocities for vectors connecting perturbed satellite trajectories with an unperturbed reference trajectory in phase space. For reasons of comparison, various time correlation functions for translation and rotation are computed. The relative dynamics of perturbed trajectories is also studied in certain subspaces of the phase space associated with center-of-mass and orientational molecular motion.Comment: RevTeX 14 pages, 7 PostScript figures. Accepted for publication in Phys. Rev.