258 research outputs found
Hard Spheres: Crystallization and Glass Formation
Motivated by old experiments on colloidal suspensions, we report molecular
dynamics simulations of assemblies of hard spheres, addressing crystallization
and glass formation. The simulations cover wide ranges of polydispersity s
(standard deviation of the particle size distribution divided by its mean) and
particle concentration. No crystallization is observed for s > 0.07. For 0.02 <
s < 0.07, we find that increasing the polydispersity at a given concentration
slows down crystal nucleation. The main effect here is that polydispersity
reduces the supersaturation since it tends to stabilise the fluid but to
destabilise the crystal. At a given polydispersity (< 0.07) we find three
regimes of nucleation: standard nucleation and growth at concentrations in and
slightly above the coexistence region; "spinodal nucleation", where the free
energy barrier to nucleation appears to be negligible, at intermediate
concentrations; and, at the highest concentrations, a new mechanism, still to
be fully understood, which only requires small re-arrangement of the particle
positions. The cross-over between the second and third regimes occurs at a
concentration, around 58% by volume, where the colloid experiments show a
marked change in the nature of the crystals formed and the particle dynamics
indicate an "ideal" glass transition
Crystal Nucleation of Colloidal Suspensions under Shear
We use Brownian Dynamics simulations in combination with the umbrella
sampling technique to study the effect of shear flow on homogeneous crystal
nucleation. We find that a homogeneous shear rate leads to a significant
suppression of the crystal nucleation rate and to an increase of the size of
the critical nucleus. A simple, phenomenological extension of classical
nucleation theory accounts for these observations. The orientation of the
crystal nucleus is tilted with respect to the shear direction.Comment: 4 pages, 3 figures, Submitted to Phys. Rev. Let
Depletion forces in non-equilibrium
The concept of effective depletion forces between two fixed big colloidal
particles in a bath of small particles is generalized to a non-equilibrium
situation where the bath of small Brownian particles is flowing around the big
particles with a prescribed velocity. In striking contrast to the equilibrium
case, the non-equilibrium forces violate Newton's third law, are
non-conservative and strongly anisotropic, featuring both strong attractive and
repulsive domains.Comment: 4 pages, 3 figure
Static and dynamic heterogeneities in a model for irreversible gelation
We study the structure and the dynamics in the formation of irreversible gels
by means of molecular dynamics simulation of a model system where the gelation
transition is due to the random percolation of permanent bonds between
neighboring particles. We analyze the heterogeneities of the dynamics in terms
of the fluctuations of the intermediate scattering functions: In the sol phase
close to the percolation threshold, we find that this dynamical susceptibility
increases with the time until it reaches a plateau. At the gelation threshold
this plateau scales as a function of the wave vector as , with
being related to the decay of the percolation pair connectedness
function. At the lowest wave vector, approaching the gelation threshold it
diverges with the same exponent as the mean cluster size. These
findings suggest an alternative way of measuring critical exponents in a system
undergoing chemical gelation.Comment: 4 pages, 4 figure
Simulating Hard Rigid Bodies
Several physical systems in condensed matter have been modeled approximating
their constituent particles as hard objects. The hard spheres model has been
indeed one of the cornerstones of the computational and theoretical description
in condensed matter. The next level of description is to consider particles as
rigid objects of generic shape, which would enrich the possible phenomenology
enormously. This kind of modeling will prove to be interesting in all those
situations in which steric effects play a relevant role. These include biology,
soft matter, granular materials and molecular systems. With a view to
developing a general recipe for event-driven Molecular Dynamics simulations of
hard rigid bodies, two algorithms for calculating the distance between two
convex hard rigid bodies and the contact time of two colliding hard rigid
bodies solving a non-linear set of equations will be described. Building on
these two methods, an event-driven molecular dynamics algorithm for simulating
systems of convex hard rigid bodies will be developed and illustrated in
details. In order to optimize the collision detection between very elongated
hard rigid bodies, a novel nearest-neighbor list method based on an oriented
bounding box will be introduced and fully explained. Efficiency and performance
of the new algorithm proposed will be extensively tested for uniaxial hard
ellipsoids and superquadrics. Finally applications in various scientific fields
will be reported and discussed.Comment: 36 pages, 17 figure
Columnar and lamellar phases in attractive colloidal systems
In colloidal suspensions, the competition between attractive and repulsive
interactions gives rise to a rich and complex phenomenology. Here, we study the
equilibrium phase diagram of a model system using a DLVO interaction potential
by means of molecular dynamics simulations and a thermodynamical approach. As a
result, we find tubular and lamellar phases at low volume fraction. Such
phases, extremely relevant for designing new materials, may be not easily
observed in the experiments because of the long relaxation times and the
presence of defects.Comment: 5 pages, 5 figure
Homogeneous nucleation of colloidal melts under the influence of shearing fields
We study the effect of shear flow on homogeneous crystal nucleation, using
Brownian Dynamics simulations in combination with an umbrella sampling like
technique. The symmetry breaking due to shear results in anisotropic radial
distribution functions. The homogeneous shear rate suppresses crystal
nucleation and leads to an increase of the size of the critical nucleus. These
observations can be described by a simple, phenomenological extension of
classical nucleation theory. In addition, we find that nuclei have a
preferential orientation with respect to the direction of shear. On average the
longest dimension of a nucleus is along the vorticity direction, while the
shortest dimension is preferably perpendicular to that and slightly tilted with
respect to the gradient direction.Comment: 10 pages, 8 figures, Submitted to J. Phys.: Condens. Matte
Lattice-switch Monte Carlo
We present a Monte Carlo method for the direct evaluation of the difference
between the free energies of two crystal structures. The method is built on a
lattice-switch transformation that maps a configuration of one structure onto a
candidate configuration of the other by `switching' one set of lattice vectors
for the other, while keeping the displacements with respect to the lattice
sites constant. The sampling of the displacement configurations is biased,
multicanonically, to favor paths leading to `gateway' arrangements for which
the Monte Carlo switch to the candidate configuration will be accepted. The
configurations of both structures can then be efficiently sampled in a single
process, and the difference between their free energies evaluated from their
measured probabilities. We explore and exploit the method in the context of
extensive studies of systems of hard spheres. We show that the efficiency of
the method is controlled by the extent to which the switch conserves correlated
microstructure. We also show how, microscopically, the procedure works: the
system finds gateway arrangements which fulfill the sampling bias
intelligently. We establish, with high precision, the differences between the
free energies of the two close packed structures (fcc and hcp) in both the
constant density and the constant pressure ensembles.Comment: 34 pages, 9 figures, RevTeX. To appear in Phys. Rev.
Simple Fluids with Complex Phase Behavior
We find that a system of particles interacting through a simple isotropic
potential with a softened core is able to exhibit a rich phase behavior
including: a liquid-liquid phase transition in the supercooled phase, as has
been suggested for water; a gas-liquid-liquid triple point; a freezing line
with anomalous reentrant behavior. The essential ingredient leading to these
features resides in that the potential investigated gives origin to two
effective core radii.Comment: 7 pages including 3 eps figures + 1 jpeg figur
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