125 research outputs found
Overcharging: The Crucial Role of Excluded Volume
In this Letter we investigate the mechanism for overcharging of a single
spherical colloid in the presence of aqueous salts within the framework of the
primitive model by molecular dynamics (MD) simulations as well as
integral-equation theory. We find that the occurrence and strength of
overcharging strongly depends on the salt-ion size, and the available volume in
the fluid. To understand the role of the excluded volume of the microions, we
first consider an uncharged system. For a fixed bulk concentration we find that
upon increasing the fluid particle size one strongly increases the local
concentration nearby the colloidal surface and that the particles become
laterally ordered. For a charged system the first surface layer is built up
predominantly by strongly correlated counterions. We argue that this a key
mechanism to produce overcharging with a low electrostatic coupling, and as a
more practical consequence, to account for charge inversion with monovalent
aqueous salt ions.Comment: 7 pages, 3 figs (4 EPS files). To appear in Europhysics Letter
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
DNA-condensation, redissolution and mesocrystals induced by tetravalent counterions
The distance-resolved effective interaction potential between two parallel
DNA molecules is calculated by computer simulations with explicit tetravalent
counterions and monovalent salt. Adding counterions first yields an attractive
minimum in the potential at short distances which then disappears in favor of a
shallower minimum at larger separations. The resulting phase diagram includes a
DNA-condensation and redissolution transition and a stable mesocrystal with an
intermediate lattice constant for high counterion concentration.Comment: 4 pages, 4 figure
Effective forces in colloidal mixtures: from depletion attraction to accumulation repulsion
Computer simulations and theory are used to systematically investigate how
the effective force between two big colloidal spheres in a sea of small spheres
depends on the basic (big-small and small-small) interactions. The latter are
modeled as hard-core pair potentials with a Yukawa tail which can be both
repulsive or attractive. For a repulsive small-small interaction, the effective
force follows the trends as predicted by a mapping onto an effective
non-additive hard-core mixture: both a depletion attraction and an accumulation
repulsion caused by small spheres adsorbing onto the big ones can be obtained
depending on the sign of the big-small interaction. For repulsive big-small
interactions, the effect of adding a small-small attraction also follows the
trends predicted by the mapping. But a more subtle ``repulsion through
attraction'' effect arises when both big-small and small-small attractions
occur: upon increasing the strength of the small-small interaction, the
effective potential becomes more repulsive. We have further tested several
theoretical methods against our computer simulations: The superposition
approximation works best for an added big-small repulsion, and breaks down for
a strong big-small attraction, while density functional theory is very accurate
for any big-small interaction when the small particles are pure hard-spheres.
The theoretical methods perform most poorly for small-small attractions.Comment: submitted to PRE; New version includes an important quantitative
correction to several of the simulations. The main conclusions remain
unchanged thoug
Strong Attraction between Charged Spheres due to Metastable Ionized States
We report a mechanism which can lead to long range attractions between
like-charged spherical macroions, stemming from the existence of metastable
ionized states. We show that the ground state of a single highly charged
colloid plus a few excess counterions is overcharged. For the case of two
highly charged macroions in their neutralizing divalent counterion solution we
demonstrate that, in the regime of strong Coulomb coupling, the counterion
clouds are very likely to be unevenly distributed, leading to one overcharged
and one undercharged macroion. This long-living metastable configuration in
turn leads to a long range Coulomb attraction.Comment: REVTEX-published versio
DNA condensation and redissolution: Interaction between overcharged DNA molecules
The effective DNA-DNA interaction force is calculated by computer simulations
with explicit tetravalent counterions and monovalent salt. For overcharged DNA
molecules, the interaction force shows a double-minimum structure. The
positions and depths of these minima are regulated by the counterion density in
the bulk. Using two-dimensional lattice sum and free energy perturbation
theories, the coexisting phases for DNA bundles are calculated. A
DNA-condensation and redissolution transition and a stable mesocrystal with an
intermediate lattice constant for high counterion concentration are obtained.Comment: 26 pages, 10 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
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