Polymer Brushes in Cylindrical Pores: Simulation versus Scaling Theory

The structure of flexible polymers endgrafted in cylindrical pores of diameter D is studied as a function of chain length N and grafting density \sigma, assuming good solvent conditions. A phenomenological scaling theory, describing the variation of the linear dimensions of the chains with \sigma, is developed and tested by Molecular Dynamics simulations of a bead-spring model.Comment: 35 pages, 38 figure

Surface Transitions for Confined Associating Mixtures

Thin films of binary mixtures that interact through isotropic forces and directionally specific "hydrogen bonding" are considered through Monte Carlo simulations. We show, in good agreement with experiment, that the single phase of these mixtures can be stabilized or destabilized on confinement. These results resolve a long standing controversy, since previous theories suggest that confinement only stabilizes the single phase of fluid mixtures.Comment: LaTeX document, documentstyle[aps,preprint]{revtex}, psfig.sty, bibtex, 13 pages, 4 figure

Coarse-grained models for fluids and their mixtures: Comparison of Monte Carlo studies of their phase behavior with perturbation theory and experiment

The prediction of the equation of state and the phase behavior of simple fluids (noble gases, carbon dioxide, benzene, methane, short alkane chains) and their mixtures by Monte Carlo computer simulation and analytic approximations based on thermodynamic perturbation theory is discussed. Molecules are described by coarse grained (CG) models, where either the whole molecule (carbon dioxide, benzene, methane) or a group of a few successive CH_2 groups (in the case of alkanes) are lumped into an effective point particle. Interactions among these point particles are fitted by Lennard-Jones (LJ) potentials such that the vapor-liquid critical point of the fluid is reproduced in agreement with experiment; in the case of quadrupolar molecules a quadrupole-quadrupole interaction is included. These models are shown to provide a satisfactory description of the liquid-vapour phase diagram of these pure fluids. Investigations of mixtures, using the Lorentz-Berthelot (LB) combining rule, also produce satisfactory results if compared with experiment, while in some previous attempts (in which polar solvents were modelled without explicitly taking into account quadrupolar interaction), strong violations of the LB rules were required. For this reason, the present investigation is a step towards predictive modelling of polar mixtures at low computational cost. These very simple coarse-grained models of small molecules developed here should be useful e.g. for simulations of polymer solutions with such molecules as solvent.Comment: J. Chem. Phys., accepte

Dynamics of a stretched nonlinear polymer chain

We study the relaxation dynamics of a coarse-grained polymer chain at different degrees of stretching by both analytical means and numerical simulations. The macromolecule is modelled as a string of beads, connected by anharmonic springs, subject to a tensile force applied at the end monomer of the chain while the other end is fixed at the origin of coordinates. The impact of bond non-linearity on the relaxation dynamics of the polymer at different degrees of stretching is treated analytically within the Gaussian self-consistent approach (GSC) and then compared to simulation results derived from two different methods: Monte-Carlo (MC) and Molecular Dynamics (MD). At low and medium degrees of chain elongation we find good agreement between GSC predictions and the Monte-Carlo simulations. However, for strongly stretched chains the MD method, which takes into account inertial effects, reveals two important aspects of the nonlinear interaction between monomers: (i) a coupling and energy transfer between the damped, oscillatory normal modes of the chain, and (ii) the appearance of non-vanishing contributions of a continuum of frequencies around the characteristic modes in the power spectrum of the normal mode correlation functions.Comment: 17 pages, 9 figure

Optical identification of hybrid magnetic and electric excitations in Dy3Fe5O12 garnet

Far-infrared spectra of magneto-dielectric Dy3Fe5O12 garnet were studied between 13 and 100 cm-1 and at low temperatures between 5 and 80 K. A combination of transmission, reflectivity, and rotating analyzer ellipsometry was used to unambiguously identify the type of the dipole activity of the infrared modes. In addition to purely dielectric and magnetic modes, we observed several hybrid modes with a mixed magnetic and electric dipole activity. These modes originate from the superexchange between magnetic moments of Fe and Dy ions. Using 4x4 matrix formalism for materials with Mu=/=1, we modeled the experimental optical spectra and determined the far-infrared dielectric and magnetic permeability functions. The matching condition Mu(Wh)*Se=Eps(Wh)*Sm for the oscillator strengths Se(m) explains the observed vanishing of certain hybrid modes at Wh in reflectivity.Comment: paper and supplement appendi

Surface and capillary transitions in an associating binary mixture model

We investigate the phase diagram of a two-component associating fluid mixture in the presence of selectively adsorbing substrates. The mixture is characterized by a bulk phase diagram which displays peculiar features such as closed loops of immiscibility. The presence of the substrates may interfere the physical mechanism involved in the appearance of these phase diagrams, leading to an enhanced tendency to phase separate below the lower critical solution point. Three different cases are considered: a planar solid surface in contact with a bulk fluid, while the other two represent two models of porous systems, namely a slit and an array on infinitely long parallel cylinders. We confirm that surface transitions, as well as capillary transitions for a large area/volume ratio, are stabilized in the one-phase region. Applicability of our results to experiments reported in the literature is discussed.Comment: 12 two-column pages, 12 figures, accepted for publication in Physical Review E; corrected versio

Simulation study of the link between molecular association and reentrant miscibility for a mixture of molecules with directional interactions

The reentrant liquid-liquid miscibility of a symmetrical mixture with highly directional bonding interactions is studied by Gibbs ensemble Monte Carlo simulation. The resulting closed loop of immiscibility and the corresponding lower critical solution temperature are shown to be a direct consequence of the dramatic increase in association between unlike components as the temperature is lowered. Our exact calculations for an off-lattice system with a well-defined anisotropic potential confirm the findings of previous theoretical studies.Dirección General de Investigación Científica y Técnica PB94-144