Diffusion anomaly and dynamic transitions in the Bell-Lavis water model

In this paper we investigate the dynamic properties of the minimal Bell-Lavis (BL) water model and their relation to the thermodynamic anomalies. The Bell-Lavis model is defined on a triangular lattice in which water molecules are represented by particles with three symmetric bonding arms interacting through van der Waals and hydrogen bonds. We have studied the model diffusivity in different regions of the phase diagram through Monte Carlo simulations. Our results show that the model displays a region of anomalous diffusion which lies inside the region of anomalous density, englobed by the line of temperatures of maximum density (TMD). Further, we have found that the diffusivity undergoes a dynamic transition which may be classified as fragile-to-strong transition at the critical line only at low pressures. At higher densities, no dynamic transition is seen on crossing the critical line. Thus evidence from this study is that relation of dynamic transitions to criticality may be discarded

Limited-memory BFGS Systems with Diagonal Updates

In this paper, we investigate a formula to solve systems of the form (B + {\sigma}I)x = y, where B is a limited-memory BFGS quasi-Newton matrix and {\sigma} is a positive constant. These types of systems arise naturally in large-scale optimization such as trust-region methods as well as doubly-augmented Lagrangian methods. We show that provided a simple condition holds on B_0 and \sigma, the system (B + \sigma I)x = y can be solved via a recursion formula that requies only vector inner products. This formula has complexity M^2n, where M is the number of L-BFGS updates and n >> M is the dimension of x

Dynamic Transitions in a Two Dimensional Associating Lattice Gas Model

Using Monte Carlo simulations we investigate some new aspects of the phase diagram and the behavior of the diffusion coefficient in an associating lattice gas (ALG) model on different regions of the phase diagram. The ALG model combines a two dimensional lattice gas where particles interact through a soft core potential and orientational degrees of freedom. The competition between soft core potential and directional attractive forces results in a high density liquid phase, a low density liquid phase, and a gas phase. Besides anomalies in the behavior of the density with the temperature at constant pressure and of the diffusion coefficient with density at constant temperature are also found. The two liquid phases are separated by a coexistence line that ends in a bicritical point. The low density liquid phase is separated from the gas phase by a coexistence line that ends in tricritical point. The bicritical and tricritical points are linked by a critical $\lambda$-line. The high density liquid phase and the fluid phases are separated by a second $\tau$ critical line. We then investigate how the diffusion coefficient behaves on different regions of the chemical potential-temperature phase diagram. We find that diffusivity undergoes two types of dynamic transitions: a fragile-to-strong trans ition when the critical $\lambda$-line is crossed by decreasing the temperature at a constant chemical potential; and a strong-to-strong transition when the $\tau$-critical line is crossed by decreasing the temperature at a constant chemical potential.Comment: 22 page

Hydration and anomalous solubility of the Bell-Lavis model as solvent

We address the investigation of the solvation properties of the minimal orientational model for water, originally proposed by Bell and Lavis. The model presents two liquid phases separated by a critical line. The difference between the two phases is the presence of structure in the liquid of lower density, described through orientational order of particles. We have considered the effect of small inert solute on the solvent thermodynamic phases. Solute stabilizes the structure of solvent, by the organization of solvent particles around solute particles, at low temperatures. Thus, even at very high densities, the solution presents clusters of structured water particles surrounding solute inert particles, in a region in which pure solvent would be free of structure. Solute intercalates with solvent, a feature which has been suggested by experimental and atomistic simulation data. Examination of solute solubility has yielded a minimum in that property, which may be associated with the minimum found for noble gases. We have obtained a line of minimum solubility (TmS) across the phase diagram, accompanying the line of maximum in density (TMD). This coincidence is easily explained for non-interacting solute and it is in agreement with earlier results in the literature. We give a simple argument which suggests that interacting solute would dislocate TmS to higher temperatures

On Solving L-SR1 Trust-Region Subproblems

In this article, we consider solvers for large-scale trust-region subproblems when the quadratic model is defined by a limited-memory symmetric rank-one (L-SR1) quasi-Newton matrix. We propose a solver that exploits the compact representation of L-SR1 matrices. Our approach makes use of both an orthonormal basis for the eigenspace of the L-SR1 matrix and the Sherman-Morrison-Woodbury formula to compute global solutions to trust-region subproblems. To compute the optimal Lagrange multiplier for the trust-region constraint, we use Newton's method with a judicious initial guess that does not require safeguarding. A crucial property of this solver is that it is able to compute high-accuracy solutions even in the so-called hard case. Additionally, the optimal solution is determined directly by formula, not iteratively. Numerical experiments demonstrate the effectiveness of this solver.Comment: 2015-0