324 research outputs found
McMillan–Mayer theory for solvent effects in inhomogeneous systems: Calculation of interaction pressure in aqueous electrical double layers
We demonstrate how to use the McMillan–Mayer theory to include solvent effects in effective solute–solute interactions for inhomogeneous systems, extending a recent derivation [S. Marčelja, Langmuir 16, 6081 (2000)] for symmetric planar double layers to the general case. In the exact treatment, the many-body potential of mean force between the solute molecules can be evaluated for an inhomogeneous reference system in equilibrium with pure bulk solvent. The reference system contains only solvent and a finite number, n, of fixed solute molecules and it has an external potential that in some cases is different from that of the original system. It is discussed how the n-body potential of mean force between the ions for the relevant cases of large n values can be approximated by a sum of effective singlet and pair interactions evaluated in the presence of, on average, all n ions, i.e., at finite concentration. In examples considered in this work we use effective interionic pair potentials evaluated from bulk electrolyte calculations at finite electrolyte concentrations. We calculate the contribution to the double layer interaction pressure arising from the interaction between ions dissolved in aqueous electrolyte. In cases of moderate or high surface charge, calculations show several new effects. At small surface separations one finds attractive and then strongly repulsive contributions. For surface charge density around one negative charge per 70 Å2 the full results for pressures resemble “secondary hydration force” measured in classical experiments in 1980s. When there is a tendency for ions to adsorb at the surfaces there is a marked change in behavior. The force is then oscillatory, reminiscent of results obtained with the surface force apparatus at low electrolyte concentration
Steric Effects in Electrolytes: A Modified Poisson-Boltzmann Equation
The adsorption of large ions from solution to a charged surface is
investigated theoretically. A generalized Poisson--Boltzmann equation, which
takes into account the finite size of the ions is presented. We obtain
analytical expressions for the electrostatic potential and ion concentrations
at the surface, leading to a modified Grahame equation. At high surface charge
densities the ionic concentration saturates to its maximum value. Our results
are in agreement with recent experiments.Comment: 4 pages, 2 figure
Hydration interactions: aqueous solvent effects in electric double layers
A model for ionic solutions with an attractive short-range pair interaction
between the ions is presented. The short-range interaction is accounted for by
adding a quadratic non-local term to the Poisson-Boltzmann free energy. The
model is used to study solvent effects in a planar electric double layer. The
counter-ion density is found to increase near the charged surface, as compared
with the Poisson-Boltzmann theory, and to decrease at larger distances. The ion
density profile is studied analytically in the case where the ion distribution
near the plate is dominated only by counter-ions. Further away from the plate
the density distribution can be described using a Poisson-Boltzmann theory with
an effective surface charge that is smaller than the actual one.Comment: 11 Figures in 13 files + LaTex file. 20 pages. Accepted to Phys. Rev.
E. Corrected typos and reference
Charge-Reversal Instability in Mixed Bilayer Vesicles
Bilayer vesicles form readily from mixtures of charged and neutral
surfactants. When such a mixed vesicle binds an oppositely-charged object, its
membrane partially demixes: the adhesion zone recruits more charged surfactants
from the rest of the membrane. Given an unlimited supply of adhering objects
one might expect the vesicle to remain attractive until it was completely
covered. Contrary to this expectation, we show that a vesicle can instead
exhibit {\it adhesion saturation,} partitioning spontaneously into an
attractive zone with definite area fraction, and a repulsive zone. The latter
zone rejects additional incoming objects because counterions on the interior of
the vesicle migrate there, effectively reversing the membrane's charge. The
effect is strongest at high surface charge densities, low ionic strength, and
with thin, impermeable membranes. Adhesion saturation in such a situation has
recently been observed experimentally [H. Aranda-Espinoza {\it et al.}, {\sl
Science} {\bf285} 394--397 (1999)]
Counterion Condensation and Fluctuation-Induced Attraction
We consider an overall neutral system consisting of two similarly charged
plates and their oppositely charged counterions and analyze the electrostatic
interaction between the two surfaces beyond the mean-field Poisson-Boltzmann
approximation. Our physical picture is based on the fluctuation-driven
counterion condensation model, in which a fraction of the counterions is
allowed to ``condense'' onto the charged plates. In addition, an expression for
the pressure is derived, which includes fluctuation contributions of the whole
system. We find that for sufficiently high surface charges, the distance at
which the attraction, arising from charge fluctuations, starts to dominate can
be large compared to the Gouy-Chapmann length. We also demonstrate that
depending on the valency, the system may exhibit a novel first-order binding
transition at short distances.Comment: 15 pages, 8 figures, to appear in PR
Negative electrostatic contribution to the bending rigidity of charged membranes and polyelectrolytes screened by multivalent counterions
Bending rigidity of a charged membrane or a charged polyelectrolyte screened
by monovalent counterions is known to be enhanced by electrostatic effects. We
show that in the case of screening by multivalent counterions the electrostatic
effects reduce the bending rigidity. This inversion of the sign of the
electrostatic contribution is related to the formation of two-dimensional
strongly correlated liquids (SCL) of counterions at the charged surface due to
strong lateral repulsion between them. When a membrane or a polyelectrolyte is
bent, SCL is compressed on one side and stretched on the other so that
thermodynamic properties of SCL contribute to the bending rigidity.
Thermodynamic properties of SCL are similar to those of Wigner crystal and are
anomalous in the sense that the pressure, compressibility and screening radius
of SCL are negative. This brings about substantial negative correction to the
bending rigidity. For the case of DNA this effect qualitatively agrees with
experiment.Comment: 8 pages, 2 figure
Ion size effects at ionic exclusion from dielectric interfaces and slit nanopores
A previously developed field-theoretic model [R.D. Coalson et al., J. Chem.
Phys. 102, 4584 (1995)] that treats core collisions and Coulomb interactions on
the same footing is investigated in order to understand ion size effects on the
partition of neutral and charged particles at planar interfaces and the ionic
selectivity of slit nanopores. We introduce a variational scheme that can go
beyond the mean-field (MF) regime and couple in a consistent way pore modified
core interactions, steric effects, electrostatic solvation and image-charge
forces, and surface charge induced electrostatic potential. We show that in the
dilute limit, the MF and the variational theories agree well with MC simulation
results, in contrast to a recent RPA method. The partition of charged Yukawa
particles at a neutral dielectric interface (e.g air-water or protein-water
interface) is investigated. It is shown that as a result of the competition
between core collisions that push the ions towards the surface, and repulsive
solvation and image forces that exclude them from the interface, a
concentration peak of finite size ions sets in close to the dielectric
interface. We also characterize the role played by the ion size on the ionic
selectivity of neutral slit nanopores. We show that the complex interplay
between electrostatic forces, excluded volume effects induced by core
collisions and steric effects leads to an unexpected reversal in the ionic
selectivity of the pore with varying pore size: while large pores exhibits a
higher conductivity for large ions, narrow pores exclude large ions more
efficiently than small ones
Density Fluctuations in an Electrolyte from Generalized Debye-Hueckel Theory
Near-critical thermodynamics in the hard-sphere (1,1) electrolyte is well
described, at a classical level, by Debye-Hueckel (DH) theory with (+,-) ion
pairing and dipolar-pair-ionic-fluid coupling. But DH-based theories do not
address density fluctuations. Here density correlations are obtained by
functional differentiation of DH theory generalized to {\it non}-uniform
densities of various species. The correlation length diverges universally
at low density as (correcting GMSA theory). When
one has as
where the amplitudes compare informatively with experimental data.Comment: 5 pages, REVTeX, 1 ps figure included with epsf. Minor changes,
references added. Accepted for publication in Phys. Rev. Let
Attraction between DNA molecules mediated by multivalent ions
The effective force between two parallel DNA molecules is calculated as a
function of their mutual separation for different valencies of counter- and
salt ions and different salt concentrations. Computer simulations of the
primitive model are used and the shape of the DNA molecules is accurately
modelled using different geometrical shapes. We find that multivalent ions
induce a significant attraction between the DNA molecules whose strength can be
tuned by the averaged valency of the ions. The physical origin of the
attraction is traced back either to electrostatics or to entropic
contributions. For multivalent counter- and monovalent salt ions, we find a
salt-induced stabilization effect: the force is first attractive but gets
repulsive for increasing salt concentration. Furthermore, we show that the
multivalent-ion-induced attraction does not necessarily correlate with DNA
overcharging.Comment: 51 pages and 13 figure
Long Range Hydration Effects in Electrolytic Free Suspended Black Films
The force law within free suspended black films made of negatively charged
Aerosol-OT (AOT) with added LiCl or CsCl is studied accurately using X-ray
reflectivity (ca. 1{\AA}). We find an electrolyte concentration threshold above
which a substantial additional repulsion is detected in the LiCl films, up to
distances of 100 {\AA}. We interpret this phenomenon as an augmentation of the
Debye screening length, due to the local screening of the condensed hydrophilic
counterions by the primary hydration shell.Comment: 4 pages, 4 figures, to be published Phys. Rev. Let
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