5,976 research outputs found
Depletion potential in hard-sphere mixtures: theory and applications
We present a versatile density functional approach (DFT) for calculating the
depletion potential in general fluid mixtures. In contrast to brute force DFT,
our approach requires only the equilibrium density profile of the small
particles {\em before} the big (test) particle is inserted. For a big particle
near a planar wall or a cylinder or another fixed big particle the relevant
density profiles are functions of a single variable, which avoids the numerical
complications inherent in brute force DFT. We implement our approach for
additive hard-sphere mixtures. By investigating the depletion potential for
high size asymmetries we assess the regime of validity of the well-known
Derjaguin approximation for hard-sphere mixtures and argue that this fails. We
provide an accurate parametrization of the depletion potential in hard-sphere
fluids which should be useful for effective Hamiltonian studies of phase
behavior and colloid structure
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
Thermodynamic fluctuation relation for temperature and energy
The present work extends the well-known thermodynamic relation for the canonical ensemble. We start from the general
situation of the thermodynamic equilibrium between a large but finite system of
interest and a generalized thermostat, which we define in the course of the
paper. The resulting identity can account for thermodynamic states
with a negative heat capacity ; at the same time, it represents a
thermodynamic fluctuation relation that imposes some restrictions on the
determination of the microcanonical caloric curve . Finally, we comment briefly on the implications of the present
result for the development of new Monte Carlo methods and an apparent analogy
with quantum mechanics.Comment: Version accepted for publication in J. Phys. A: Math and The
Optical extinction, refractive index, and multiple scattering for suspensions of interacting colloidal particles
We provide a general microscopic theory of the scattering cross-section and
of the refractive index for a system of interacting colloidal particles, exact
at second order in the molecular polarizabilities. In particular: a) we show
that the structural features of the suspension are encoded into the forward
scattered field by multiple scattering effects, whose contribution is essential
for the so-called "optical theorem" to hold in the presence of interactions; b)
we investigate the role of radiation reaction on light extinction; c) we
discuss our results in the framework of effective medium theories, presenting a
general result for the effective refractive index valid, whatever the
structural properties of the suspension, in the limit of particles much larger
than the wavelength; d) by discussing strongly-interacting suspensions, we
unravel subtle anomalous dispersion effects for the suspension refractive
index.Comment: Submitted to Journal of Chemical Physics 37 pages, 4 figure
Density functional theory for nearest-neighbor exclusion lattice gasses in two and three dimensions
To speak about fundamental measure theory obliges to mention dimensional
crossover. This feature, inherent to the systems themselves, was incorporated
in the theory almost from the beginning. Although at first it was thought to be
a consistency check for the theory, it rapidly became its fundamental pillar,
thus becoming the only density functional theory which possesses such a
property. It is straightforward that dimensional crossover connects, for
instance, the parallel hard cube system (three-dimensional) with that of
squares (two-dimensional) and rods (one-dimensional). We show here that there
are many more connections which can be established in this way. Through them we
deduce from the functional for parallel hard (hyper)cubes in the simple
(hyper)cubic lattice the corresponding functionals for the nearest-neighbor
exclusion lattice gases in the square, triangular, simple cubic, face-centered
cubic, and body-centered cubic lattices. As an application, the bulk phase
diagram for all these systems is obtained.Comment: 13 pages, 13 figures; needs revtex
Geometrical aspects and connections of the energy-temperature fluctuation relation
Recently, we have derived a generalization of the known canonical fluctuation
relation between heat capacity and
energy fluctuations, which can account for the existence of macrostates with
negative heat capacities . In this work, we presented a panoramic overview
of direct implications and connections of this fluctuation theorem with other
developments of statistical mechanics, such as the extension of canonical Monte
Carlo methods, the geometric formulations of fluctuation theory and the
relevance of a geometric extension of the Gibbs canonical ensemble that has
been recently proposed in the literature.Comment: Version accepted for publication in J. Phys. A: Math and The
Hard-Sphere Fluids in Contact with Curved Substrates
The properties of a hard-sphere fluid in contact with hard spherical and
cylindrical walls are studied. Rosenfeld's density functional theory (DFT) is
applied to determine the density profile and surface tension for wide
ranges of radii of the curved walls and densities of the hard-sphere fluid.
Particular attention is paid to investigate the curvature dependence and the
possible existence of a contribution to that is proportional to the
logarithm of the radius of curvature. Moreover, by treating the curved wall as
a second component at infinite dilution we provide an analytical expression for
the surface tension of a hard-sphere fluid close to arbitrary hard convex
walls. The agreement between the analytical expression and DFT is good. Our
results show no signs for the existence of a logarithmic term in the curvature
dependence of .Comment: 15 pages, 6 figure
Monte Carlo simulations of the screening potential of the Yukawa one-component plasma
A Monte Carlo scheme to sample the screening potential H(r) of Yukawa plasmas
notably at short distances is presented. This scheme is based on an importance
sampling technique. Comparisons with former results for the Coulombic
one-component plasma are given. Our Monte Carlo simulations yield an accurate
estimate of H(r) as well for short range and long range interparticle
distances.Comment: to be published in Journal of Physics A: Mathematical and Genera
Lattice density-functional theory of surface melting: the effect of a square-gradient correction
I use the method of classical density-functional theory in the
weighted-density approximation of Tarazona to investigate the phase diagram and
the interface structure of a two-dimensional lattice-gas model with three
phases -- vapour, liquid, and triangular solid. While a straightforward
mean-field treatment of the interparticle attraction is unable to give a stable
liquid phase, the correct phase diagram is obtained when including a suitably
chosen square-gradient term in the system grand potential. Taken this theory
for granted, I further examine the structure of the solid-vapour interface as
the triple point is approached from low temperature. Surprisingly, a novel
phase (rather than the liquid) is found to grow at the interface, exhibiting an
unusually long modulation along the interface normal. The conventional
surface-melting behaviour is recovered only by artificially restricting the
symmetries being available to the density field.Comment: 16 pages, 6 figure
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