873 research outputs found
Macroion adsorption: The crucial role of excluded volume and coions
The adsorption of charged colloids (macroions) onto an oppositely charged
planar substrate is investigated theoretically. Taking properly into account
the finite size of the macroions, unusual behaviors are reported. It is found
that the role of the coions (the little salt-ions carrying the same sign of
charge as that of the substrate) is crucial to understand the mechanisms
involved in the process of macroion adsorption. In particular, the coions can
accumulate near the substrate's surface and lead to a counter-intuitive {\it
surface charge amplification}.Comment: 11 pages - 4 figures. To appear in JC
Extended Feynman Formula for the Harmonic Oscillator by the Discrete Time Method
We calculate the Feynman formula for the harmonic oscillator beyond and at
caustics by the discrete formulation of path integral. The extension has been
made by some authors, however, it is not obtained by the method which we
consider the most reliable regularization of path integral. It is shown that
this method leads to the result with, especially at caustics, more rigorous
derivation than previous.Comment: 9 page
Discrete aqueous solvent effects and possible attractive forces
We study discrete solvent effects on the interaction of two parallel charged
surfaces in ionic aqueous solution. These effects are taken into account by
adding a bilinear non-local term to the free energy of Poisson-Boltzmann
theory. We study numerically the density profile of ions between the two
plates, and the resulting inter-plate pressure. At large plate separations the
two plates are decoupled and the ion distribution can be characterized by an
effective Poisson-Boltzmann charge that is smaller than the nominal charge. The
pressure is thus reduced relative to Poisson-Boltzmann predictions. At plate
separations below ~2 nm the pressure is modified considerably, due to the
solvent mediated short-range attraction between ions in the the system. For
high surface charges this contribution can overcome the mean-field repulsion
giving rise to a net attraction between the plates.Comment: 12 figures in 16 files. 19 pages. Submitted to J. Chem. Phys., July
200
Nonlinear screening of charged macromolecules
We present several aspects of the screening of charged macromolecules in an
electrolyte. After a review of the basic mean field approach, based on the
linear Debye-Huckel theory, we consider the case of highly charged
macromolecules, where the linear approximation breaks down and the system is
described by full nonlinear Poisson-Boltzmann equation. Some analytical results
for this nonlinear equation give some interesting insight on physical phenomena
like the charge renormalization and the Manning counterion condensation
Non-linear screening of spherical and cylindrical colloids: the case of 1:2 and 2:1 electrolytes
From a multiple scale analysis, we find an analytic solution of spherical and
cylindrical Poisson-Boltzmann theory for both a 1:2 (monovalent co-ions,
divalent counter-ions) and a 2:1 (reversed situation) electrolyte. Our approach
consists in an expansion in powers of rescaled curvature , where
is the colloidal radius and the Debye length of the electrolytic
solution. A systematic comparison with the full numerical solution of the
problem shows that for cylinders and spheres, our results are accurate as soon
as . We also report an unusual overshooting effect where the
colloidal effective charge is larger than the bare one.Comment: 9 pages, 11 figure
Ion condensation on charged patterned surfaces
We study ion condensation onto a patterned surface of alternating charges.
The competition between self-energy and ion-surface interactions leads to the
formation of ionic crystalline structures at low temperatures. We consider
different arrangements of underlying ionic crystals, including single ion
adsorption, as well as the formation of dipoles at the interface between
charged domains. Molecular dynamic simulation illustrates existence of single
and mixed phases. Our results contribute to understanding pattern recognition,
and molecular separation and synthesis near patterned surfaces.Comment: 3 figure
The Role of the Gouy Phase in the Coherent Phase Control of the Photoionization and Photodissociation of Vinyl Chloride
We demonstrate theoretically and experimentally that the Gouy phase of a
focused laser beam may be used to control the photo-induced reactions of a
polyatomic molecule. Quantum mechanical interference between one- and
three-photon excitation of vinyl chloride produces a small phase lag between
the dissociation and ionization channels on the axis of the molecular beam.
Away from the axis, the Gouy phase introduces a much larger phase lag that
agrees quantitatively with theory without any adjustable parameters.Comment: 4 pages, 4 figure
Theory and simulations of rigid polyelectrolytes
We present theoretical and numerical studies on stiff, linear
polyelectrolytes within the framework of the cell model. We first review
analytical results obtained on a mean-field Poisson-Boltzmann level, and then
use molecular dynamics simulations to show, under which circumstances these
fail quantitatively and qualitatively. For the hexagonally packed nematic phase
of the polyelectrolytes we compute the osmotic coefficient as a function of
density. In the presence of multivalent counterions it can become negative,
leading to effective attractions. We show that this results from a reduced
contribution of the virial part to the pressure. We compute the osmotic
coefficient and ionic distribution functions from Poisson-Boltzmann theory with
and without a recently proposed correlation correction, and also simulation
results for the case of poly(para-phenylene) and compare it to recently
obtained experimental data on this stiff polyelectrolyte. We also investigate
ion-ion correlations in the strong coupling regime, and compare them to
predictions of the recently advocated Wigner crystal theories.Comment: 32 pages, 15 figures, proceedings of the ASTATPHYS-MEX-2001, to be
published in Mol. Phy
Effects of image charges, interfacial charge discreteness, and surface roughness on the zeta potential of spherical electric double layers
We investigate the effects of image charges, interfacial charge discreteness,
and surface roughness on spherical electric double layers in electrolyte
solutions with divalent counter-ions in the setting of the primitive model. By
using Monte Carlo simulations and the image charge method, the zeta potential
profile and the integrated charge distribution function are computed for
varying surface charge strengths and salt concentrations. Systematic
comparisons were carried out between three distinct models for interfacial
charges: 1) SURF1 with uniform surface charges, 2) SURF2 with discrete point
charges on the interface, and 3) SURF3 with discrete interfacial charges and
finite excluded volume. By comparing the integrated charge distribution
function (ICDF) and potential profile, we argue that the potential at the
distance of one ion diameter from the macroion surface is a suitable location
to define the zeta potential. In SURF2 model, we find that image charge effects
strongly enhance charge inversion for monovalent interfacial charges, and
strongly suppress charge inversion for multivalent interfacial charges. For
SURF3, the image charge effect becomes much smaller. Finally, with image
charges in action, we find that excluded volumes (in SURF3) suppress charge
inversion for monovalent interfacial charges and enhance charge inversion for
multivalent interfacial charges. Overall, our results demonstrate that all
these aspects, i.e., image charges, interfacial charge discreteness, their
excluding volumes have significant impacts on the zeta potential, and thus the
structure of electric double layers.Comment: 11 pages, 10 figures, some errors are change
Ion-Size Effect at the Surface of a Silica Hydrosol
The author used synchrotron x-ray reflectivity to study the ion-size effect
for alkali ions (Na, K, Rb, and Cs), with densities as high as
m, suspended above the surface of a
colloidal solution of silica nanoparticles in the field generated by the
surface electric-double layer. According to the data, large alkali ions
preferentially accumulate at the sol's surface replacing smaller ions, a
finding that qualitatively agrees with the dependence of the Kharkats-Ulstrup
single-ion electrostatic free energy on the ion's radius.Comment: 17 pages, 4 figure
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