581 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
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
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
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
Radius of a Photon Beam with Orbital Angular Momentum
We analyze the transverse structure of the Gouy phase shift in light beams
carrying orbital angular momentum and show that the Gouy radius
characterizing the transverse structure grows as with the
nodal number and photon angular momentum number . The Gouy radius is
shown to be closely related to the root-mean-square radius of the beam, and the
divergence of the radius away from the focal plane is determined. Finally, we
analyze the rotation of the Poynting vector in the context of the Gouy radius.Comment: 11 page
Incorporation of excluded volume correlations into Poisson-Boltzmann theory
We investigate the effect of excluded volume interactions on the electrolyte
distribution around a charged macroion. First, we introduce a criterion for
determining when hard-core effects should be taken into account beyond standard
mean field Poisson-Boltzmann (PB) theory. Next, we demonstrate that several
commonly proposed local density functional approaches for excluded volume
interactions cannot be used for this purpose. Instead, we employ a non-local
excess free energy by using a simple constant weight approach. We compare the
ion distribution and osmotic pressure predicted by this theory with Monte Carlo
simulations. They agree very well for weakly developed correlations and give
the correct layering effect for stronger ones. In all investigated cases our
simple weighted density theory yields more realistic results than the standard
PB approach, whereas all local density theories do not improve on the PB
density profiles but on the contrary, deviate even more from the simulation
results.Comment: 23 pages, 7 figures, 1 tabl
Non-mean-field theory of anomalously large double-layer capacitance
Mean-field theories claim that the capacitance of the double-layer formed at
a metal/ionic conductor interface cannot be larger than that of the Helmholtz
capacitor, whose width is equal to the radius of an ion. However, in some
experiments the apparent width of the double-layer capacitor is substantially
smaller. We propose an alternate, non-mean-field theory of the ionic
double-layer to explain such large capacitance values. Our theory allows for
the binding of discrete ions to their image charges in the metal, which results
in the formation of interface dipoles. We focus primarily on the case where
only small cations are mobile and other ions form an oppositely-charged
background. In this case, at small temperature and zero applied voltage dipoles
form a correlated liquid on both contacts. We show that at small voltages the
capacitance of the double-layer is determined by the transfer of dipoles from
one electrode to the other and is therefore limited only by the weak
dipole-dipole repulsion between bound ions, so that the capacitance is very
large. At large voltages the depletion of bound ions from one of the capacitor
electrodes triggers a collapse of the capacitance to the much smaller
mean-field value, as seen in experimental data. We test our analytical
predictions with a Monte Carlo simulation and find good agreement. We further
argue that our ``one-component plasma" model should work well for strongly
asymmetric ion liquids. We believe that this work also suggests an improved
theory of pseudo-capacitance.Comment: 19 pages, 14 figures; some Monte Carlo results and a section about
aqueous solutions adde
Description beyond the mean field approximation of an electrolyte confined between two planar metallic electrodes
We study an electrolyte confined in a slab of width composed of two
grounded metallic parallel electrodes. We develop a description of this system
in a low coupling regime beyond the mean field (Poisson--Boltzmann)
approximation. There are two ways to model the metallic boundaries: as ideal
conductors in which the electric potential is zero and it does not fluctuate,
or as good conductors in which the average electric potential is zero but the
thermal fluctuations of the potential are not zero. This latter model is more
realistic. For the ideal conductor model we find that the disjoining pressure
is positive behaves as for large separations with a prefactor that is
universal, i.e. independent of the microscopic constitution of the system. For
the good conductor boundaries the disjoining pressure is negative and it has an
exponential decay for large . We also compute the density and electric
potential profiles inside the electrolyte. These are the same in both models.
If the electrolyte is charge asymmetric we find that the system is not locally
neutral and that a non-zero potential difference builds up between any
electrode and the interior of the system although both electrodes are grounded.Comment: 16 pages, 5 figures, added a new appendix B and a discussion on ideal
conductors vs. good conductor
Experimental proposal for measuring the Gouy phase of matter waves
The Schr\"odinger equation for an atomic beam predicts that it must have a
phase anomaly near the beam waist analogous to the Gouy phase of an
electromagnetic beam. We propose here a feasible experiment which allows for
the direct determination of this anomalous phase using Ramsey interferometry
with Rydberg atoms. Possible experimental limitations are discussed and shown
to be completely under control within the present day technology. We also
discuss how this finding can open the possibility to use the spatial mode
wavefunctions of atoms as q-dits, since the Gouy phase is an essential
ingredient for making rotations in the quantum states.Comment: 9 pages and 3 figure
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