184 research outputs found
Effect of many-body interactions on the solid-liquid phase-behavior of charge-stabilized colloidal suspensions
The solid-liquid phase-diagram of charge-stabilized colloidal suspensions is
calculated using a technique that combines a continuous Poisson-Boltzmann
description for the microscopic electrolyte ions with a molecular-dynamics
simulation for the macroionic colloidal spheres. While correlations between the
microions are neglected in this approach, many-body interactions between the
colloids are fully included. The solid-liquid transition is determined at a
high colloid volume fraction where many-body interactions are expected to be
strong. With a view to the Derjaguin-Landau-Verwey-Overbeek theory predicting
that colloids interact via Yukawa pair-potentials, we compare our results with
the phase diagram of a simple Yukawa liquid. Good agreement is found at high
salt conditions, while at low ionic strength considerable deviations are
observed. By calculating effective colloid-colloid pair-interactions it is
demonstrated that these differences are due to many-body interactions. We
suggest a density-dependent pair-potential in the form of a truncated Yukawa
potential, and show that it offers a considerably improved description of the
solid-liquid phase-behavior of concentrated colloidal suspensions
Field theory fo charged fluids and colloids
A systematic field theory is presented for charged systems. The one-loop
level corresponds to the classical Debye-H\"uckel (DH) theory, and exhibits the
full hierarchy of multi-body correlations determined by pair-distribution
functions given by the screened DH potential. Higher-loop corrections can lead
to attractive pair interactions between colloids in asymmetric ionic
environments. The free energy follows as a loop-wise expansion in half-integer
powers of the density; the resulting two-phase demixing region shows pronounced
deviations from DH theory for strongly charged colloids.Comment: 4 pages, 2 ps figs; new version corrects some minor typo
Attraction between like-charged colloidal particles induced by a surface a density - functional analysis
We show that the first non-linear correction to the linearised
Poisson-Boltzman n (or DLVO) theory of effective pair interactions between
charge-stabilised, co lloidal particles near a charged wall leads to an
attractive component of entro pic origin. The position and depth of the
potential compare favourably with rec ent experimental measurementsComment: 12 pages including 2 figures. submitted to physical review letter
Stability of Colloidal Quasicrystals
Freezing of charge-stabilized colloidal suspensions and relative stabilities
of crystals and quasicrystals are studied using thermodynamic perturbation
theory. Macroion interactions are modelled by effective pair potentials
combining electrostatic repulsion with polymer-depletion or van der Waals
attraction. Comparing free energies -- counterion terms included -- for
elementary crystals and rational approximants to icosahedral quasicrystals,
parameters are identified for which one-component quasicrystals are stabilized
by a compromise between packing entropy and cohesive energy.Comment: 6 pages, 4 figure
Coexistence of hexatic and isotropic phases in two-dimensional Yukawa systems
We have performed Brownian dynamics simulations on melting of two-dimensional
colloidal crystal in which particles interact with Yukawa potential. The pair
correlation function and bond-orientational correlation function was calculated
in the Yukawa system. An algebraic decay of the bond orientational correlation
function was observed. By ruling out the coexistence region, only a unstable
hexatic phase was found in the Yukawa systems. But our work shows that the
melting of the Yukawa systems is a two-stage melting not consist with the KTHNY
theory and the isotropic liquid and the hexatic phase coexistence region was
found. Also we have studied point defects in two-dimensional Yukawa systems.Comment: 9 pages, 8 figures. any comments are welcom
Discrete charge patterns, Coulomb correlations and interactions in protein solutions
The effective Coulomb interaction between globular proteins is calculated as
a function of monovalent salt concentration , by explicit Molecular
Dynamics simulations of pairs of model proteins in the presence of microscopic
co and counterions. For discrete charge patterns of monovalent sites on the
surface, the resulting osmotic virial coefficient is found to be a
strikingly non-monotonic function of . The non-monotonicity follows from a
subtle Coulomb correlation effect which is completely missed by conventional
non-linear Poisson-Boltzmann theory and explains various experimental findings.Comment: 4 twocolumn pages with 4 figure
Discrete solvent effects on the effective interaction between charged colloids
Using computer simulations of two charged colloidal spheres with their
counterions in a hard sphere solvent, we show that the granular nature of the
solvent significantly influences the effective colloidal interaction. For
divalent counterions, the total effective force can become attractive generated
by counterion hydration, while for monovalent counterions the forces are
repulsive and well-described by a solvent-induced colloidal charge
renormalization. Both effects are not contained in the traditional "primitive"
approaches but can be accounted for in a solvent-averaged primitive model.Comment: 4 pages, 3 figure
The order-disorder transition in colloidal suspensions under shear flow
We study the order-disorder transition in colloidal suspensions under shear
flow by performing Brownian dynamics simulations. We characterize the
transition in terms of a statistical property of time-dependent maximum value
of the structure factor. We find that its power spectrum exhibits the power-law
behaviour only in the ordered phase. The power-law exponent is approximately -2
at frequencies greater than the magnitude of the shear rate, while the power
spectrum exhibits the -type fluctuations in the lower frequency regime.Comment: 11 pages, 10 figures, v.2: We have made some small improvements on
presentation
Effective Interactions and Volume Energies in Charge-Stabilized Colloidal Suspensions
Charge-stabilized colloidal suspensions can be conveniently described by
formally reducing the macroion-microion mixture to an equivalent one-component
system of pseudo-particles. Within this scheme, the utility of a linear
response approximation for deriving effective interparticle interactions has
been demonstrated [M. J. Grimson and M. Silbert, Mol. Phys. 74, 397 (1991)].
Here the response approach is extended to suspensions of finite-sized macroions
and used to derive explicit expressions for (1) an effective electrostatic pair
interaction between pseudo-macroions and (2) an associated volume energy that
contributes to the total free energy. The derivation recovers precisely the
form of the DLVO screened-Coulomb effective pair interaction for spherical
macroions and makes manifest the important influence of the volume energy on
thermodynamic properties of deionized suspensions. Excluded volume corrections
are implicitly incorporated through a natural modification of the inverse
screening length. By including nonlinear response of counterions to macroions,
the theory may be generalized to systematically investigate effective many-body
interactions.Comment: 13 pages (J. Phys.: Condensed Matter, in press
Effective Interactions and Volume Energies in Charged Colloids: Linear Response Theory
Interparticle interactions in charge-stabilized colloidal suspensions, of
arbitrary salt concentration, are described at the level of effective
interactions in an equivalent one-component system. Integrating out from the
partition function the degrees of freedom of all microions, and assuming linear
response to the macroion charges, general expressions are obtained for both an
effective electrostatic pair interaction and an associated microion volume
energy. For macroions with hard-sphere cores, the effective interaction is of
the DLVO screened-Coulomb form, but with a modified screening constant that
incorporates excluded volume effects. The volume energy -- a natural
consequence of the one-component reduction -- contributes to the total free
energy and can significantly influence thermodynamic properties in the limit of
low-salt concentration. As illustrations, the osmotic pressure and bulk modulus
are computed and compared with recent experimental measurements for deionized
suspensions. For macroions of sufficient charge and concentration, it is shown
that the counterions can act to soften or destabilize colloidal crystals.Comment: 14 pages, including 3 figure
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