186 research outputs found
Fluid-fluid demixing transitions in colloid--polyelectrolyte star mixtures
We derive effective interaction potentials between hard, spherical colloidal
particles and star-branched polyelectrolytes of various functionalities and
smaller size than the colloids. The effective interactions are based on a
Derjaguin-like approximation, which is based on previously derived potentials
acting between polyelectrolyte stars and planar walls. On the basis of these
interactions we subsequently calculate the demixing binodals of the binary
colloid--polyelectrolyte star mixture, employing standard tools from
liquid-state theory. We find that the mixture is indeed unstable at moderately
high overall concentrations. The system becomes more unstable with respect to
demixing as the star functionality and the size ratio grow.Comment: 24 pages, 9 figures, submitted to Journal of Physics: Condensed
Matte
Mean-field dynamical density functional theory
We examine the out-of-equilibrium dynamical evolution of density profiles of
ultrasoft particles under time-varying external confining potentials in three
spatial dimensions. The theoretical formalism employed is the dynamical density
functional theory (DDFT) of Marini Bettolo Marconi and Tarazona [J. Chem. Phys.
{\bf 110}, 8032 (1999)], supplied by an equilibrium excess free energy
functional that is essentially exact. We complement our theoretical analysis by
carrying out extensive Brownian Dynamics simulations. We find excellent
agreement between theory and simulations for the whole time evolution of
density profiles, demonstrating thereby the validity of the DDFT when an
accurate equilibrium free energy functional is employed.Comment: 8 pagers, 4 figure
Generation of defects and disorder from deeply quenching a liquid to form a solid
We show how deeply quenching a liquid to temperatures where it is linearly
unstable and the crystal is the equilibrium phase often produces crystalline
structures with defects and disorder. As the solid phase advances into the
liquid phase, the modulations in the density distribution created behind the
advancing solidification front do not necessarily have a wavelength that is the
same as the equilibrium crystal lattice spacing. This is because in a deep
enough quench the front propagation is governed by linear processes, but the
crystal lattice spacing is determined by nonlinear terms. The wavelength
mismatch can result in significant disorder behind the front that may or may
not persist in the latter stage dynamics. We support these observations by
presenting results from dynamical density functional theory calculations for
simple one- and two-component two-dimensional systems of soft core particles.Comment: 25 pages, 11 figure
Why do ultrasoft repulsive particles cluster and crystallize? Analytical results from density functional theory
We demonstrate the accuracy of the hypernetted chain closure and of the
mean-field approximation for the calculation of the fluid-state properties of
systems interacting by means of bounded and positive-definite pair potentials
with oscillating Fourier transforms. Subsequently, we prove the validity of a
bilinear, random-phase density functional for arbitrary inhomogeneous phases of
the same systems. On the basis of this functional, we calculate analytically
the freezing parameters of the latter. We demonstrate explicitly that the
stable crystals feature a lattice constant that is independent of density and
whose value is dictated by the position of the negative minimum of the Fourier
transform of the pair potential. This property is equivalent with the existence
of clusters, whose population scales proportionally to the density. We
establish that regardless of the form of the interaction potential and of the
location on the freezing line, all cluster crystals have a universal Lindemann
ratio L = 0.189 at freezing. We further make an explicit link between the
aforementioned density functional and the harmonic theory of crystals. This
allows us to establish an equivalence between the emergence of clusters and the
existence of negative Fourier components of the interaction potential. Finally,
we make a connection between the class of models at hand and the system of
infinite-dimensional hard spheres, when the limits of interaction steepness and
space dimension are both taken to infinity in a particularly described fashion.Comment: 19 pages, 5 figures, submitted to J. Chem. Phys; new version: minor
changes in structure of pape
Multi-interaction mean-field renormalization group
We present an extension of the previously proposed mean-field renormalization
method to model Hamiltonians which are characterized by more than just one type
of interaction. The method rests on scaling assumptions about the magnetization
of different sublattices of the given lattice and it generates as many flow
equations as coupling constants without arbitrary truncations on the
renormalized Hamiltonian. We obtain good results for the test case of Ising
systems with an additional second-neighbor coupling in two and three
dimensions. An application of the method is also done to a morphological model
of interacting surfaces introduced recenlty by Likos, Mecke and Wagner [J.
Chem. Phys. {\bf{102}}, 9350 (1995)].
PACS: 64.60.Ak, 64.60.Fr, 05.70.JkComment: Tex file and three macros appended at the end. Five figures available
upon request to: [email protected], Fax: [+]39-40-224-60
Polyelectrolyte stars in planar confinement
We employ monomer-resolved Molecular Dynamics simulations and theoretical
considerations to analyze the conformations of multiarm polyelectrolyte stars
close to planar, uncharged walls. We identify three mechanisms that contribute
to the emergence of a repulsive star-wall force, namely: the confinement of the
counterions that are trapped in the star interior, the increase in
electrostatic energy due to confinement as well as a novel mechanism arising
from the compression of the stiff polyelectrolyte rods approaching the wall.
The latter is not present in the case of interaction between two
polyelectrolyte stars and is a direct consequence of the impenetrable character
of the planar wall.Comment: 34 pages, 8 figures. Revised version of the manuscript. To appear in
J. Chem. Phys. May, 200
Ground state at high density
Weak limits as the density tends to infinity of classical ground states of
integrable pair potentials are shown to minimize the mean-field energy
functional. By studying the latter we derive global properties of high-density
ground state configurations in bounded domains and in infinite space. Our main
result is a theorem stating that for interactions having a strictly positive
Fourier transform the distribution of particles tends to be uniform as the
density increases, while high-density ground states show some pattern if the
Fourier transform is partially negative. The latter confirms the conclusion of
earlier studies by Vlasov (1945), Kirzhnits and Nepomnyashchii (1971), and
Likos et al. (2007). Other results include the proof that there is no Bravais
lattice among high-density ground states of interactions whose Fourier
transform has a negative part and the potential diverges or has a cusp at zero.
We also show that in the ground state configurations of the penetrable sphere
model particles are superposed on the sites of a close-packed lattice.Comment: Note adde
Tailoring the flow of soft glasses by soft additives
We examine the vitrification and melting of asymmetric star polymers mixtures
by combining rheological measurements with mode coupling theory. We identify
two types of glassy states, a {\it single} glass, in which the small component
is fluid in the glassy matrix of the big one and a {\it double} glass, in which
both components are vitrified. Addition of small star polymers leads to melting
of {\it both} glasses and the melting curve has a non-monotonic dependence on
the star-star size ratio. The phenomenon opens new ways for externally steering
the rheological behavior of soft matter systems.Comment: 4 pages, 4 figures, accepted in Phys. Rev. Let
Is there a reentrant glass in binary mixtures?
By employing computer simulations for a model binary mixture, we show that a
reentrant glass transition upon adding a second component only occurs if the
ratio of the short-time mobilities between the glass-forming component
and the additive is sufficiently small. For , there is no
reentrant glass, even if the size asymmetry between the two components is
large, in accordance with two-component mode coupling theory. For , on the other hand, the reentrant glass is observed and reproduced only by
an effective one-component mode coupling theory.Comment: 4 pages, 3 figure
Multiple glass transitions in star polymer mixtures: Insights from theory and simulations
The glass transition in binary mixtures of star polymers is studied by mode
coupling theory and extensive molecular dynamics computer simulations. In
particular, we have explored vitrification in the parameter space of size
asymmetry and concentration of the small star polymers at
fixed concentration of the large ones. Depending on the choice of parameters,
three different glassy states are identified: a single glass of big polymers at
low and low , a double glass at high and low
, and a novel double glass at high and high which is
characterized by a strong localization of the small particles. At low
and high there is a competition between vitrification and phase
separation. Centered in the -plane, a liquid lake shows up
revealing reentrant glass formation. We compare the behavior of the dynamical
density correlators with the predictions of the theory and find remarkable
agreement between the two.Comment: 15 figures, to be published in Macromolecule
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