1,095 research outputs found
Interfacial Tension of Electrolyte Solutions
A theory is presented to account for the increase in surface tension of water
in the presence of electrolyte. Unlike the original ``grand-canonical''
calculation of Onsager and Samaras, which relied on the Gibbs adsorption
isotherm and lead to a result which could only be expressed as an infinite
series, our approach is ``canonical'' and produces an analytic formula for the
excess surface tension. For small concentrations of electrolyte, our result
reduces to the Onsager-Samaras limiting law.Comment: contains two figures. Journal of Chemical Physics, in pres
All-Electron Path Integral Monte Carlo Simulations of Warm Dense Matter: Application to Water and Carbon Plasmas
We develop an all-electron path integral Monte Carlo (PIMC) method with
free-particle nodes for warm dense matter and apply it to water and carbon
plasmas. We thereby extend PIMC studies beyond hydrogen and helium to elements
with core electrons. PIMC pressures, internal energies, and pair-correlation
functions compare well with density functional theory molecular dynamics
(DFT-MD) at temperatures of (2.5-7.5) K and both methods together
form a coherent equation of state (EOS) over a density-temperature range of
3--12 g/cm and 10--10 K
Nonlinear dielectric effect of dipolar fluids
The nonlinear dielectric effect for dipolar fluids is studied within the
framework of the mean spherical approximation (MSA) of hard core dipolar Yukawa
fluids. Based on earlier results for the electric field dependence of the
polarization our analytical results show so-called normal saturation effects
which are in good agreement with corresponding NVT ensemble Monte Carlo
simulation data. The linear and the nonlinear dielectric permittivities
obtained from MC simulations are determined from the fluctuations of the total
dipole moment of the system in the absence of an applied electric field. We
compare the MSA based theoretical results with the corresponding Langevin and
Debye-Weiss behaviors.Comment: 10 pages including 4 figure
Ionic profiles close to dielectric discontinuities: Specific ion-surface interactions
We study, by incorporating short-range ion-surface interactions, ionic
profiles of electrolyte solutions close to a non-charged interface between two
dielectric media. In order to account for important correlation effects close
to the interface, the ionic profiles are calculated beyond mean-field theory,
using the loop expansion of the free energy. We show how it is possible to
overcome the well-known deficiency of the regular loop expansion close to the
dielectric jump, and treat the non-linear boundary conditions within the
framework of field theory. The ionic profiles are obtained analytically to
one-loop order in the free energy, and their dependence on different
ion-surface interactions is investigated. The Gibbs adsorption isotherm, as
well as the ionic profiles are used to calculate the surface tension, in
agreement with the reverse Hofmeister series. Consequently, from the
experimentally-measured surface tension, one can extract a single adhesivity
parameter, which can be used within our model to quantitatively predict hard to
measure ionic profiles.Comment: 14 pages, 6 figure
Lattice Models of Ionic Systems
A theoretical analysis of Coulomb systems on lattices in general dimensions
is presented. The thermodynamics is developed using Debye-Huckel theory with
ion-pairing and dipole-ion solvation, specific calculations being performed for
3D lattices. As for continuum electrolytes, low-density results for sc, bcc and
fcc lattices indicate the existence of gas-liquid phase separation. The
predicted critical densities have values comparable to those of continuum ionic
systems, while the critical temperatures are 60-70% higher. However, when the
possibility of sublattice ordering as well as Debye screening is taken into
account systematically, order-disorder transitions and a tricritical point are
found on sc and bcc lattices, and gas-liquid coexistence is suppressed. Our
results agree with recent Monte Carlo simulations of lattice electrolytes.Comment: 25 pages, 3 figures, ReVTeX 4, Submitted to J. Chem. Phy
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
Crossover Scales at the Critical Points of Fluids with Electrostatic Interactions
Criticality in a fluid of dielectric constant D that exhibits Ising-type
behavior is studied as additional electrostatic (i.e., ionic) interactions are
turned on. An exploratory perturbative calculation is performed for small
ionicity as measured by the ratio of the electrostatic energy to the strength
of the short-range nonionic (i.e., van der Waals) interactions in the uncharged
fluid.
With the aid of distinct transformations for the short-range and for the
Coulombic interactions, an effective Hamiltonian with coefficients depending on
the ionicity is derived at the Debye-Hueckel limiting-law level for a fully
symmetric model. The crossover between classical (mean-field) and Ising
behavior is then estimated using a Ginzburg criterion. This indicates that the
reduced crossover temperature depends only weakly on the ionicity (and on the
range of the nonionic potentials); however, the trends do correlate with the,
much stronger, dependence observed experimentally.Comment: 25 pages, 4 figure; submitted to J. Chem. Phy
Field theory fo charged fluids and colloids
A systematic field theory is presented for charged systems. The one-loop
level corresponds to the classical Debye-H\"uckel (DH) theory, and exhibits the
full hierarchy of multi-body correlations determined by pair-distribution
functions given by the screened DH potential. Higher-loop corrections can lead
to attractive pair interactions between colloids in asymmetric ionic
environments. The free energy follows as a loop-wise expansion in half-integer
powers of the density; the resulting two-phase demixing region shows pronounced
deviations from DH theory for strongly charged colloids.Comment: 4 pages, 2 ps figs; new version corrects some minor typo
Where the linearized Poisson-Boltzmann cell model fails: (I) spurious phase separation in charged colloidal suspensions
We perform a linearization of the Poisson-Boltzmann (PB) density functional
for spherical Wigner-Seitz cells that yields Debye-H\"uckel-like equations
agreeing asymptotically with the PB results in the weak-coupling
(high-temperature) limit. Both the canonical (fixed number of microions) as
well as the semi-grand-canonical (in contact with an infinite salt reservoir)
cases are considered and discussed in a unified linearized framework. In the
canonical case, for sufficiently large colloidal charges the linearized theory
predicts the occurrence of a thermodynamical instability with an associated
phase separation of the homogeneous suspension into dilute (gas) and dense
(liquid) phases. In the semi-grand-canonical case it is predicted that the
isothermal compressibility and the osmotic-pressure difference between the
colloidal suspension and the salt reservoir become negative in the
low-temperature, high-surface charge or infinite-dilution (of polyions) limits.
As already pointed out in the literature for the latter case, these features
are in disagreement with the exact nonlinear PB solution inside a Wigner-Seitz
cell and are thus artifacts of the linearization. By using explicitly
gauge-invariant forms of the electrostatic potential we show that these
artifacts, although thermodynamically consistent with quadratic expansions of
the nonlinear functional and osmotic pressure, may be traced back to the
non-fulfillment of the underlying assumptions of the linearization.Comment: 32 pages, 3 PostScript figures, submitted to J. Chem. Phy
The Nonlinear Debye-Onsager Relaxation Effect in Weakly Ionized Plasmas
A weakly ionized plasma under the influence of a strong electric field is
considered. Supposing a local Maxwellian distribution for the electron momenta
the plasma is described by hydrodynamic equations for the pair distribution
functions. These equations are solved and the relaxation field is calculated
for an arbitrary field strength. It is found that the relaxation effect becomes
lower with increasing strength of the electrical field.Comment: 4 pages, 1 figur
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