30 research outputs found
Non-linear Poisson-Boltzmann Theory for Swollen Clays
The non-linear Poisson-Boltzmann equation for a circular, uniformly charged
platelet, confined together with co- and counter-ions to a cylindrical cell, is
solved semi-analytically by transforming it into an integral equation and
solving the latter iteratively. This method proves efficient, robust, and can
be readily generalized to other problems based on cell models, treated within
non-linear Poisson-like theory. The solution to the PB equation is computed
over a wide range of physical conditions, and the resulting osmotic equation of
state is shown to be in fair agreement with recent experimental data for
Laponite clay suspensions, in the concentrated gel phase.Comment: 13 pages, 4 postscript figure
Correlation functions in ionic liquid at coexistence with ionic crystal. Results of the Brazovskii-type field theory
Correlation functions in the restricted primitive model are calculated within
a field-theoretic approach in the one-loop self-consistent Hartree
approximation. The correlation functions exhibit damped oscillatory behavior as
found before in the Gaussian approximation [Ciach at. al., J. Chem. Phys. {\bf
118}, 3702 (2003)]. The fluctuation contribution leads to a renormalization of
both the amplitude and the decay length of the correlation functions. The
renormalized quantities show qualitatively different behavior than their
mean-field (MF) counterparts. While the amplitude and the decay length both
diverge in MF when the -line is approached, the renormalized
quantities remain of order of unity in the same dimensionless units down to the
coexistence with the ionic crystal. Along the line of the phase transition the
decay length and the period of oscillations are independent of density, and
their values in units of the diameter of the ions are
and respectively.Comment: 21 pages including 9 figure
Charge Oscillations in Debye-Hueckel Theory
The recent generalized Debye-Hueckel (GDH) theory is applied to the
calculation of the charge-charge correlation function G_{ZZ}(r). The resulting
expression satisfies both (i) the charge neutrality condition and (ii) the
Stillinger-Lovett second-moment condition for all T and rho_N, the overall ion
density, and (iii) exhibits charge oscillations for densities above a "Kirkwood
line" in the (rho_N,T) plane. This corrects the normally assumed DH
correlations, and, when combined with the GDH analysis of the density
correlations, leaves the GDH theory as the only complete description of ionic
correlation functions, as judged by (i)-(iii), (iv) exact low-density (rho_N,T)
variation, and (v) reasonable behavior near criticality.Comment: 6 pages, EuroPhys.sty (now available on archive), 1 eps figur
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
Ginzburg Criterion for Coulombic Criticality
To understand the range of close-to-classical critical behavior seen in
various electrolytes, generalized Debye-Hueckel theories (that yield density
correlation functions) are applied to the restricted primitive model of
equisized hard spheres. The results yield a Landau-Ginzburg free-energy
functional for which the Ginzburg criterion can be explicitly evaluated. The
predicted scale of crossover from classical to Ising character is found to be
similar in magnitude to that derived for simple fluids in comparable fashion.
The consequences in relation to experiments are discussed briefly.Comment: 4 pages, revtex, 2 tables (latex2.09 required due to revtex's
incompatibility with latex2e tables
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
The osmotic pressure of charged colloidal suspensions: A unified approach to linearized Poisson-Boltzmann theory
We study theoretically the osmotic pressure of a suspension of charged
objects (e.g., colloids, polyelectrolytes, clay platelets, etc.) dialyzed
against an electrolyte solution using the cell model and linear
Poisson-Boltzmann (PB) theory. From the volume derivative of the grand
potential functional of linear theory we obtain two novel expressions for the
osmotic pressure in terms of the potential- or ion-profiles, neither of which
coincides with the expression known from nonlinear PB theory, namely, the
density of microions at the cell boundary. We show that the range of validity
of linearization depends strongly on the linearization point and proof that
expansion about the selfconsistently determined average potential is optimal in
several respects. For instance, screening inside the suspension is
automatically described by the actual ionic strength, resulting in the correct
asymptotics at high colloid concentration. Together with the analytical
solution of the linear PB equation for cell models of arbitrary dimension and
electrolyte composition explicit and very general formulas for the osmotic
pressure ensue. A comparison with nonlinear PB theory is provided. Our analysis
also shows that whether or not linear theory predicts a phase separation
depends crucially on the precise definition of the pressure, showing that an
improper choice could predict an artificial phase separation in systems as
important as DNA in physiological salt solution.Comment: 16 pages, 5 figures, REVTeX4 styl