Comparison of thermodynamic properties of coarse-grained and atomic-level simulation models.

Thermodynamic data are often used to calibrate or test amomic-level (AL) force fields for molecular dynamics (MD) simulations. In contrast, the majority of coarse-grained (CG) force fields do not rely extensively on thermodynamic quantities. Recently, a CG force field for lipids, hydrocarbons, ions, and water, in which approximately four non-hydrogen atoms are mapped onto one interaction site, has been proposed and applied to study various aspects of lipid systems. To date, no extensive investigation of its capability to describe salvation thermodynamics has been undertaken. In the present study, a detailed picture of vaporization, solvation, and phase-partitioning thermodynamics for liquid hydrocarbons and water was obtained at CG and AL resolutions, in order to compare the two types or models and evaluate their ability to describe thermodynamic properties in the temperature range between 263 and 343 K. Both CG and AL models capture the experimental dependence of the thermodynamic properties on the temperature, albeit a systematically weaker dependence is found for the CG model. Moreover, deviations are found for solvation thermodynamics and for the corresponding enthalpy-entropy compensation for the CG model. Particularly water/oil repulsion seems to be overestimated. However, the results suggest that the thermodynamic properties considered should be reproducible by a CG model provided it is reparametrized on the basis of these liquid-phase properties.     

The third law of thermodynamics and the degeneracy of the ground state for lattice systems

The third law of thermodynamics, in the sense that the entropy per unit volume goes to zero as the temperature goes to zero, is investigated within the framework of statistical mechanics for quantum and classical lattice models. We present two main results: (i) For all models the question of whether the third law is satisfied can be decided completely in terms of ground-state degeneracies alone, provided these are computed for all possible boundary conditions. In principle, there is no need to investigate possible entropy contributions from low-lying excited states, (ii) The third law is shown to hold for ferromagnetic models by an analysis of the ground states.Dedicated to Pierre Résibois. Work supported in part by NSF grant PHY-7825390 A01.     

A Singular Limit Problem for Conservation Laws Related to the Camassa–Holm Shallow Water Equation

We consider a shallow water equation of the Camassa–Holm type, which contains nonlinear dispersive effects as well as fourth order dissipative effects. We prove that as the diffusion and dispersion parameters tend to zero, with a condition on the relative balance between these two parameters, smooth solutions of the shallow water equation converge to discontinuous weak solutions of a scalar conservation law. The proof relies on deriving suitable a priori estimates together with an application of the compensated compactness method in the L ^p setting.     

Optimal error estimates of a decoupled scheme based on two-grid finite element for mixed Stokes–Darcy model

Although the numerical results suggest the optimal convergence order of the two-grid finite element decoupled scheme for mixed Stokes–Darcy model with Beavers–Joseph–Saffman interface condition in literatures, the numerical analysis only gets the optimal error order for porous media flow and a non-optimal error order that is half order lower than the optimal one in fluid flow. The purpose of this paper is to fill in the gap between the numerical results and the theoretical analysis.     

Shock waves for the hyperbolic balance laws with discontinuous sources

In this paper, we are concerned with the behavior of shock waves in a 2 × 2 balance law with discontinuous source terms. We obtain the existence of a local shock wave solution of this problem and deduce that the discontinuous source terms create a weak discontinuity in this solution. Copyright © 2013 John Wiley & Sons, Ltd.     

A simultaneous canonical form of a pair of matrices and applications involving the weighted Moore–Penrose inverse

In this paper, a simultaneous canonical form of a pair of rectangular complex matrices is developed. Using this new tool we give a necessary and sufficient condition to assure that the reverse order law is valid for the weighted Moore–Penrose inverse. Additionally, we characterize matrices ordered by the weighted star partial order and adjacent matrices as applications.     

Role of self-assembled surfactant structure on the spreading of oil on flat solid surfaces

Uniform spreading of oil on solid surfaces is important in many processes where proper lubrication is required and this can be controlled using surfactants. The role of oil–solid interfacial self-assembled surfactant structure (SASS) in oil spreading is examined in this study for the case of hexadecane-surfactant droplet spreading on a flat horizontal copper surface, with triphenyl phosphorothionate surfactants having varying chain lengths (0 to 9). It is shown that the frictional forces (F_SASS) as determined by the SASS regulate droplet spreading rate according to surfactant chain length; surfactants with longer chains led to higher reduction in the spreading rate. The extent of such forces, F_SASS, depends on the surfactant density of the evolving SASS, and specific configuration the evolving SASS exhibit as per the orientations of the surfactant chains therein. Thus, F_SASS = [k₁ + k_2(t)] Γ_δ(t), where Γ_δ(t) is the surfactant adsorption density of SASS at time ‘t’ during evolution, and, k₁ and k_2(t) are the force coefficients for Γ_δ(t) and orientations (as a function of spreading time) of the surfactant chains respectively. As a SASS evolves/grows along with adsorption of surfactants at the spreading induced fresh interface, the k₁Γ_δ(t) component of F_SASS increases and contributes to reduction in the net spreading force (S). With a decrease in the net spreading force, the existence of a cross-over period, during which the transition of the spatial dynamics of the chains from disordered to realignment/packing induced ordered orientation occurs, has been inferred from the F_SASS vs. chain length relationships. Such relationships also suggested that the rate of realignment/packing is increased progressively particularly due the realignment/packing induced decrease in the net spreading force. Therefore, the realignment process is a self-induced process, which spans a measurable period of time (several minutes), the cross-over period, during which the net spreading force decreases essentially due to such self-induced process.