Potential energy landscape-based extended van der Waals equation

The inherent structures ({\it IS}) are the local minima of the potential energy surface or landscape, $U({\bf r})$, of an {\it N} atom system. Stillinger has given an exact {\it IS} formulation of thermodynamics. Here the implications for the equation of state are investigated. It is shown that the van der Waals ({\it vdW}) equation, with density-dependent $a$ and $b$ coefficients, holds on the high-temperature plateau of the averaged {\it IS} energy. However, an additional ``landscape'' contribution to the pressure is found at lower $T$. The resulting extended {\it vdW} equation, unlike the original, is capable of yielding a water-like density anomaly, flat isotherms in the coexistence region {\it vs} {\it vdW} loops, and several other desirable features. The plateau energy, the width of the distribution of {\it IS}, and the ``top of the landscape'' temperature are simulated over a broad reduced density range, $2.0 \ge \rho \ge 0.20$, in the Lennard-Jones fluid. Fits to the data yield an explicit equation of state, which is argued to be useful at high density; it nevertheless reproduces the known values of $a$ and $b$ at the critical point

An exploding glass ?

We propose a connection between self-similar, focusing dynamics in nonlinear partial differential equations (PDEs) and macroscopic dynamic features of the glass transition. In particular, we explore the divergence of the appropriate relaxation times in the case of hard spheres as the limit of random close packing is approached. We illustrate the analogy in the critical case, and suggest a ``normal form'' that can capture the onset of dynamic self-similarity in both phenomena.Comment: 8 pages, 2 figure

A test of non-equilibrium thermodynamics in glassy systems: the soft-sphere case

The scaling properties of the soft-sphere potential allow the derivation of an exact expression for the pressure of a frozen liquid, i.e., the pressure corresponding to configurations which are local minima in its multidimensional potential energy landscape. The existence of such a relation offers the unique possibility for testing the recently proposed extension of the liquid free energy to glassy out-of-equilibrium conditions and the associated expression for the temperature of the configurational degrees of freedom. We demonstrate that the non-equilibrium free energy provides an exact description of the soft-sphere pressure in glass states

Thermodynamic Comparison and the Ideal Glass Transition of A Monatomic Systems Modeled as an Antiferromagnetic Ising Model on Husimi and Cubic Recursive Lattices of the Same Coordination Number

Two kinds of recursive lattices with the same coordination number but different unit cells (2-D square and 3-D cube) are constructed and the antiferromagnetic Ising model is solved exactly on them to study the stable and metastable states. The Ising model with multi-particle interactions is designed to represent a monatomic system or an alloy. Two solutions of the model exhibit the crystallization of liquid, and the ideal glass transition of supercooled liquid respectively. Based on the solutions, the thermodynamics on both lattices was examined. In particular, the free energy, energy, and entropy of the ideal glass, supercooled liquid, crystal, and liquid state of the model on each lattice were calculated and compared with each other. Interactions between particles farther away than the nearest neighbor distance are taken into consideration. The two lattices show comparable properties on the transition temperatures and the thermodynamic behaviors, which proves that both of them are practical to describe the regular 3-D case, while the different effects of the unit types are still obvious.Comment: 27 pages, 13 figure

The distance between Inherent Structures and the influence of saddles on approaching the mode coupling transition in a simple glass former

We analyze through molecular dynamics simulations of a Lennard-Jones binary mixture the statistics of the distances between inherent structures (IS) sampled at temperatures above the mode coupling transition temperature T_MCT. We take equilibrated configurations and randomly perturb the coordinates of a given number of particles. After that we take the nearest IS of both the original configuration and the perturbed one and evaluate the distance between them. This distance presents an inflection point near T~1 with a strong decrease below this temperature and goes to a small but nonzero value on approaching T_MCT. In the low temperature region we study the statistics of events which give zero distance, i.e. dominated by minima, and find evidence that the number of saddles decreases exponentially near T_MCT. This implies that saddles continue to exist even for T<=T_MCT. As at T_MCT the extrapolated diffusivity goes to zero our results imply that there are saddles associated with nondiffusional events at T<T_MCT.Comment: 5 pages, 5 ps figure

Water-like anomalies for core-softened models of fluids: One dimension

We use a one-dimensional (1d) core-softened potential to develop a physical picture for some of the anomalies present in liquid water. The core-softened potential mimics the effect of hydrogen bonding. The interest in the 1d system stems from the facts that closed-form results are possible and that the qualitative behavior in 1d is reproduced in the liquid phase for higher dimensions. We discuss the relation between the shape of the potential and the density anomaly, and we study the entropy anomaly resulting from the density anomaly. We find that certain forms of the two-step square well potential lead to the existence at T=0 of a low-density phase favored at low pressures and of a high-density phase favored at high pressures, and to the appearance of a point $C'$ at a positive pressure, which is the analog of the T=0 ``critical point'' in the $1d$ Ising model. The existence of point $C'$ leads to anomalous behavior of the isothermal compressibility $K_T$ and the isobaric specific heat $C_P$.Comment: 22 pages, 7 figure

Homogeneous nucleation of a non-critical phase near a continuous phase transition

Homogeneous nucleation of a new phase near a second, continuous, transition, is considered. The continuous transition is in the metastable region associated with the first-order phase transition, one of whose coexisting phases is nucleating. Mean-field calculations show that as the continuous transition is approached, the size of the nucleus varies as the response function of the order parameter of the continuous transition. This response function diverges at the continuous transition, as does the temperature derivative of the free energy barrier to nucleation. This rapid drop of the barrier as the continuous transition is approached means that the continuous transition acts to reduce the barrier to nucleation at the first-order transition. This may be useful in the crystallisation of globular proteins.Comment: 6 pages, 1 figur

Evidence for "fragile" glass-forming behavior in the relaxation of Coulomb frustrated three-dimensional systems

We show by means of a Monte Carlo simulation study that three-dimensional models with long-range frustration display the generic phenomena seen in fragile glassforming liquids. Due to their properties (absence of quenched disorder, physical motivation in terms of structural frustration, and tunable fragility), these systems appear as promising minimal theoretical models for describing the glass transition of supercooled liquids.Comment: 4 pages, 4 figure

Simple Fluids with Complex Phase Behavior

We find that a system of particles interacting through a simple isotropic potential with a softened core is able to exhibit a rich phase behavior including: a liquid-liquid phase transition in the supercooled phase, as has been suggested for water; a gas-liquid-liquid triple point; a freezing line with anomalous reentrant behavior. The essential ingredient leading to these features resides in that the potential investigated gives origin to two effective core radii.Comment: 7 pages including 3 eps figures + 1 jpeg figur

Space-time Phase Transitions in Driven Kinetically Constrained Lattice Models

Kinetically constrained models (KCMs) have been used to study and understand the origin of glassy dynamics. Despite having trivial thermodynamic properties, their dynamics slows down dramatically at low temperatures while displaying dynamical heterogeneity as seen in glass forming supercooled liquids. This dynamics has its origin in an ergodic-nonergodic first-order phase transition between phases of distinct dynamical "activity". This is a "space-time" transition as it corresponds to a singular change in ensembles of trajectories of the dynamics rather than ensembles of configurations. Here we extend these ideas to driven glassy systems by considering KCMs driven into non-equilibrium steady states through non-conservative forces. By classifying trajectories through their entropy production we prove that driven KCMs also display an analogous first-order space-time transition between dynamical phases of finite and vanishing entropy production. We also discuss how trajectories with rare values of entropy production can be realized as typical trajectories of a mapped system with modified forces