17 research outputs found
Fundamental measure theory for mixtures of parallel hard cubes. II. Phase behavior of the one-component fluid and of the binary mixture
A previously developed fundamental measure fucntional [J. Chem. Phys.
vol.107, 6379 (1997)] is used to study the phase behavior of a system of
parallel hard cubes. The single-component fluid exhibits a continuous
transition to a solid with an anomalously large density of vacancies. The
binary mixture has a demixing transition for edge-length ratios below 0.1.
Freezing in this mixture reveals that at least the phase rich in large cubes
lies in the region where the uniform fluid is unstable, hence suggesting a
fluid-solid phase separation. A method is develop to study very asymmetric
binary mixtures by taking the limit of zero size ratio (scaling the density and
fugacity of the solvent as appropriate) in the semi-grand ensemble where the
chemical potential of the solvent is fixed. With this procedure the mixture is
exactly mapped onto a one-component fluid of parallel adhesive hard cubes. At
any density and solvent fugacity the large cubes are shown to collapse into a
close-packed solid. Nevertheless the phase diagram contains a large
metastability region with fluid and solid phases. Upon introduction of a slight
polydispersity in the large cubes the system shows the typical phase diagram of
a fluid with an isostructural solid-solid transition (with the exception of a
continuous freezing). Consequences about the phase behavior of binary mixtures
of hard core particles are then drawn.Comment: 14 pages, 6 eps figures, uses revtex, amstex, epsfig, and multicol
style file
Surface phase transitions in polydisperse hard rod fluids
I study the effect of length polydispersity in the surface phase diagram of
hard rods interacting with a hard wall. The properly extended interface
Gibbs-Duhem equation for a polydisperse system allows us to predict the
behaviour of the surface tension as a function of the bulk density at the the
wall-isotropic interface. Two groups of qualitative different bulk and surface
phase diagrams are calculated from two families of parametrized length
distribution functions . This parameterization controls the law of decay
at large . I also study the segregation due to polydispersity at the
isotropic-nematic interface and the capillary nematization phenomena as a
function of polydispersity.Comment: 20 pages, 27 figure
Theory and simulation of the confined Lebwohl-Lasher model
We discuss the Lebwohl-Lasher model of nematic liquid crystals in a confined
geometry, using Monte Carlo simulation and mean-field theory. A film of
material is sandwiched between two planar, parallel plates that couple to the
adjacent spins via a surface strength . We consider the cases where
the favoured alignments at the two walls are the same (symmetric cell) or
different (asymmetric or hybrid cell). In the latter case, we demonstrate the
existence of a {\it single} phase transition in the slab for all values of the
cell thickness. This transition has been observed before in the regime of
narrow cells, where the two structures involved correspond to different
arrangements of the nematic director. By studying wider cells, we show that the
transition is in fact the usual isotropic-to-nematic (capillary) transition
under confinement in the case of antagonistic surface forces. We show results
for a wide range of values of film thickness, and discuss the phenomenology
using a mean-field model.Comment: 40 pages 19 figures (preprint format). Part of the text and some
figures were modified. New figure was include
Isotropic-nematic transition in hard-rod fluids: relation between continuous and restricted-orientation models
We explore models of hard-rod fluids with a finite number of allowed
orientations, and construct their bulk phase diagrams within Onsager's second
virial theory. For a one-component fluid, we show that the discretization of
the orientations leads to the existence of an artificial (almost) perfectly
aligned nematic phase, which coexists with the (physical) nematic phase if the
number of orientations is sufficiently large, or with the isotropic phase if
the number of orientations is small. Its appearance correlates with the
accuracy of sampling the nematic orientation distribution within its typical
opening angle. For a binary mixture this artificial phase also exists, and a
much larger number of orientations is required to shift it to such high
densities that it does not interfere with the physical part of the phase
diagram.Comment: 4 pages, 2 figures, submitted to PR
Dislocation loops in overheated free-standing smectic films
Static and dynamic phenomena in overheated free-standing smectic-A films are
studied using a generalization of de Gennes' theory for a confined presmectic
liquid. A static application is to determine the profile of the film meniscus
and the meniscus contact angle, the results being compared with those of a
recent study employing de Gennes' original theory. The dynamical generalization
of the theory is based on on a time-dependent Ginzburg-Landau approach. This is
used to compare two modes for layer-thinning transitions in overheated films,
namely "uniform thinning" vs. nucleation of dislocation loops. Properties such
as the line tension and velocity of a moving dislocation line are evaluated
self-consistently by the theory.Comment: 16 pages, 8 figure
Density Functional for Anisotropic Fluids
We propose a density functional for anisotropic fluids of hard body
particles. It interpolates between the well-established geometrically based
Rosenfeld functional for hard spheres and the Onsager functional for elongated
rods. We test the new approach by calculating the location of the the
nematic-isotropic transition in systems of hard spherocylinders and hard
ellipsoids. The results are compared with existing simulation data. Our
functional predicts the location of the transition much more accurately than
the Onsager functional, and almost as good as the theory by Parsons and Lee. We
argue that it might be suited to study inhomogeneous systems.Comment: To appear in J. Physics: Condensed Matte
Predicting phase equilibria in polydisperse systems
Many materials containing colloids or polymers are polydisperse: They
comprise particles with properties (such as particle diameter, charge, or
polymer chain length) that depend continuously on one or several parameters.
This review focusses on the theoretical prediction of phase equilibria in
polydisperse systems; the presence of an effectively infinite number of
distinguishable particle species makes this a highly nontrivial task. I first
describe qualitatively some of the novel features of polydisperse phase
behaviour, and outline a theoretical framework within which they can be
explored. Current techniques for predicting polydisperse phase equilibria are
then reviewed. I also discuss applications to some simple model systems
including homopolymers and random copolymers, spherical colloids and
colloid-polymer mixtures, and liquid crystals formed from rod- and plate-like
colloidal particles; the results surveyed give an idea of the rich
phenomenology of polydisperse phase behaviour. Extensions to the study of
polydispersity effects on interfacial behaviour and phase separation kinetics
are outlined briefly.Comment: 48 pages, invited topical review for Journal of Physics: Condensed
Matter; uses Institute of Physics style file iopart.cls (included