Different Melting Behavior in Pentane and Heptane Monolayers on Graphite; Molecular Dynamics Simulations

Molecular dynamics simulations are utilized to study the melting transition in pentane (C5H12) and heptane (C7H16), physisorbed onto the basal plane of graphite at near-monolayer coverages. Through use of the newest, optimized version of the anisotropic united-atom model (AUA4) to simulate both systems at two separate coverages, this study provides evidence that the melting transition for pentane and heptane monolayers are significantly different. Specifically, this study proposes a very rapid transition from the solid crystalline rectangular-centered (RC) phase to a fluid phase in pentane monolayers, whereas heptane monolayers exhibit a slower transition that involves a more gradual loss of RC order in the solid-fluid phase transition. Through a study of the melting behavior, encompassing variations where the formation of gauche defects in the alkyl chains are eliminated, this study proposes that this gradual melting behavior for heptane monolayers is a result of less orientational mobility of the heptane molecules in the solid RC phase, as compared to the pentane molecules. This idea is supported through a study of a nonane monolayer, which gives the gradual melting signature that heptane monolayers also seem to indicate. The results of this work are compared to previous experiment over pentane and heptane monolayers, and are found to be in good agreement

Spin dynamics for the Lebwohl-Lasher model

A spin dynamics algorithm, combining checkerboard updating and a rotation algorithm based on the local second-rank ordering field, is developed for the Lebwohl-Lasher model of liquid crystals. The method is shown to conserve energy well and to generate simulation averages that are consistent with those obtained by Monte Carlo simulation. However, care must be taken to avoid the undesirable effects of director rotation, and a method for doing this is proposed

Effect of Image Forces on Polyelectrolyte Adsorption at a Charged Surface

The adsorption of flexible and highly charged polyelectrolytes onto oppositely charged planar surfaces is investigated by means of Monte Carlo simulations. The effect of image forces stemming from the dielectric discontinuity at the substrate interface is considered. The influence, at fixed polyelectrolyte volume fraction, of chain length and surface-charge density is also considered. A detailed structural study, including monomer and fluid charge distributions, is provided. It is demonstrated that image forces can considerably reduce the degree of polyelectrolyte adsorption and concomitantly inhibit the charge inversion of the substrate by polyelectrolytes.Comment: 19 pages - 7 eps figs - RevTex 4 - submitted for publicatio

Ab initio mass tensor molecular dynamics

Mass tensor molecular dynamics was first introduced by Bennett [J. Comput. Phys. 19, 267 (1975)] for efficient sampling of phase space through the use of generalized atomic masses. Here, we show how to apply this method to ab initio molecular dynamics simulations with minimal computational overhead. Test calculations on liquid water show a threefold reduction in computational effort without making the fixed geometry approximation. We also present a simple recipe for estimating the optimal atomic masses using only the first derivatives of the potential energy.Comment: 19 pages, 5 figure

Well-defined silica-supported olefin metathesis catalysts

Two triethoxysilyl-functionalized N-heterocyclic carbene ligands have been synthesized and used to prepare the corresponding second-generation ruthenium olefin metathesis catalysts. These complexes were then grafted onto silica gel, and the resulting materials were efficient heterogeneous catalysts for a number of metathesis reactions. The solid-supported catalysts were shown to be recyclable over a number of reaction cycles, and no detectable levels of ruthenium were observed in reaction filtrates (ruthenium concentration of filtrate <5 ppb)

Theory and simulation of the nematic zenithal anchoring coefficient

Combining molecular simulation, Onsager theory and the elastic description of nematic liquid crystals, we study the dependence of the nematic liquid crystal elastic constants and the zenithal surface anchoring coefficient on the value of the bulk order parameter

New Green-Kubo formulas for transport coefficients in hard sphere-, Langevin fluids and the likes

We present generalized Green-Kubo expressions for thermal transport coefficients $\mu$ in non-conservative fluid-type systems, of the generic form, $\mu$ $= \mu_\infty$ +\int^\infty_0 dt V^{-1} \av{I_\epsilon \exp(t {\cal L}) I}_0 where $\exp(t{\cal L})$ is a pseudo-streaming operator. It consists of a sum of an instantaneous transport coefficient $\mu_\infty$, and a time integral over a time correlation function in a state of thermal equilibrium between a current $I$ and its conjugate current $I_\epsilon$. This formula with $\mu_\infty \neq 0$ and $I_\epsilon \neq I$ covers vastly different systems, such as strongly repulsive elastic interactions in hard sphere fluids, weakly interacting Langevin fluids with dissipative and stochastic interactions satisfying detailed balance conditions, and "the likes", defined in the text. For conservative systems the results reduce to the standard formulas.Comment: 7 pages, no figures. Version 2: changes in the text and references adde

Collective motion of binary self-propelled particle mixtures

In this study, we investigate the phenomenon of collective motion in binary mixtures of self-propelled particles. We consider two particle species, each of which consisting of pointlike objects that propel with a velocity of constant magnitude. Within each species, the particles try to achieve polar alignment of their velocity vectors, whereas we analyze the cases of preferred polar, antiparallel, as well as perpendicular alignment between particles of different species. Our focus is on the effect that the interplay between the two species has on the threshold densities for the onset of collective motion and on the nature of the solutions above onset. For this purpose, we start from suitable Langevin equations in the particle picture, from which we derive mean field equations of the Fokker-Planck type and finally macroscopic continuum field equations. We perform particle simulations of the Langevin equations, linear stability analyses of the Fokker-Planck and macroscopic continuum equations, and we numerically solve the Fokker-Planck equations. Both, spatially homogeneous and inhomogeneous solutions are investigated, where the latter correspond to stripe-like flocks of collectively moving particles. In general, the interaction between the two species reduces the threshold density for the onset of collective motion of each species. However, this interaction also reduces the spatial organization in the stripe-like flocks. The most interesting behavior is found for the case of preferred perpendicular alignment between different species. There, a competition between polar and truly nematic orientational ordering of the velocity vectors takes place within each particle species. Finally, depending on the alignment rule for particles of different species and within certain ranges of particle densities, identical and inverted spatial density profiles can be found for the two particle species.Comment: 16 pages, 10 figure