144 research outputs found
Origin of attraction between likely charged hydrophobic and hydrophilic walls confining near-critical binary aquaeous mixture with ions
Effect of ionic solute on a near-critical binary aqueous mixture confined
between charged walls with different adsorption preferences is considered
within a simple density functional theory. For the near-critical system
containing small amount of ions a Landau-type functional is derived based on
the assumption that the correlation, , and the Debye screening length,
, are both much larger than the molecular size. The corresponding
approximate Euler-Lagrange equations aresolved analytically for ions insoluble
in the organic solvent. Nontrivial concentration profile of the solvent is
found near the charged hydrophobic wall as a result of the competition between
the short-range attraction of the organic solvent and the electrostatic
attraction of the hydrated ions. Excess of water may be present near the
hydrophobic surface for some range of the surface charge and . As a
result, the effective potential between the hydrophilic and the hydrophobic
surface can be repulsive far from the critical point, then attractive and again
repulsive when the critical temperature is approached, in agreement with the
recent experiment [Nellen at.al., Soft Matter {\bf 7}, 5360 (2011)]
Field-theoretic description of ionic crystallization in the restricted primitive model
Effects of charge-density fluctuations on a phase behavior of the restricted
primitive model (RPM) are studied within a field-theoretic formalism. We focus
on a -line of continuous transitions between charge-ordered and
charge-disordered phases that is observed in several mean-field (MF) theories,
but is absent in simulation results. In our study the RPM is reduced to a
theory, and a fluctuation contribution to a grand thermodynamic
potential is obtained by generalizing the Brazovskii approach. We find that in
a presence of fluctuations the -line disappears. Instead, a
fluctuation-induced first-order transition to a charge-ordered phase appears in
the same region of a phase diagram, where the liquid -- ionic-crystal
transition is obtained in simulations. Our results indicate that the
charge-ordered phase should be identified with an ionic crystal.Comment: 31 pages, 10 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
Phase diagrams in the lattice RPM model: from order-disorder to gas-liquid phase transition
The phase behavior of the lattice restricted primitive model (RPM) for ionic
systems with additional short-range nearest neighbor (nn) repulsive
interactions has been studied by grand canonical Monte Carlo simulations. We
obtain a rich phase behavior as the nn strength is varied. In particular, the
phase diagram is very similar to the continuum RPM model for high nn strength.
Specifically, we have found both gas-liquid phase separation, with associated
Ising critical point, and first-order liquid-solid transition. We discuss how
the line of continuous order-disorder transitions present for the low nn
strength changes into the continuum-space behavior as one increases the nn
strength and compare our findings with recent theoretical results by Ciach and
Stell [Phys. Rev. Lett. {\bf 91}, 060601 (2003)].Comment: 7 pages, 10 figure
Partial integration and local mean-field approach for a vector lattice model of microemulsions
A vector model on the simple cubic lattice, describing a mixture of water, oil, and amphiphile, is considered. An integration over the amphiphile orientational degrees of freedom is performed exactly in order to obtain an effective Hamiltonian for the system. The resulting model is a three-state (spin-1) system and contains many-site interaction terms. The analysis of the ground state reveals the presence of the water-oil-rich phase as well as the amphiphile-rich and the cubic phases. The temperature phase diagram of the system is analyzed in a local mean-field approach, and a triple line of water-rich, oil-rich, and microemulsion coexistence is obtained. For some values of the model parameters, lamellar phases also appear in the system, but only at finite temperature. The Lifshitz line is determined in a semianalytical way in order to locate the microemulsion region of the disordered phase
Mesoscopic theory for size- and charge- asymmetric ionic systems. I. Case of extreme asymmetry
A mesoscopic theory for the primitive model of ionic systems is developed for
arbitrary size, , and charge, ,
asymmetry. Our theory is an extension of the theory we developed earlier for
the restricted primitive model. The case of extreme asymmetries
and is studied in some detail in a mean-field
approximation. The phase diagram and correlation functions are obtained in the
asymptotic regime and , and for infinite
dilution of the larger ions (volume fraction or less). We find a
coexistence between a very dilute 'gas' phase and a crystalline phase in which
the macroions form a bcc structure with the lattice constant . Such coexistence was observed experimentally in deionized aqueous
solutions of highly charged colloidal particles
Universality class of the critical point in the restricted primitive model of ionic systems
A coarse-grained description of the restricted primitive model is considered
in terms of the local charge- and number-density fields. Exact reduction to a
one-field theory is derived, and exact expressions for the number-density
correlation functions in terms of higher-order correlation functions for the
charge-density are given. It is shown that in continuum space the singularity
of the charge-density correlation function associated with short-wavelength
charge-ordering disappears when charge-density fluctuations are included by
following the Brazovskii approach. The related singularity of the individual
Feynman diagrams contributing to the number-density correlation functions is
cured when all the diagrams are segregated ito disjoint sets according to their
topological structure. By performing a resummation of all diagrams belonging to
each set a regular expression represented by a secondary diagram is obtained.
The secondary diagrams are again segregated into disjoint sets, and the series
of all the secondary diagrams belonging to a given set is represented by a
hyperdiagram. A one-to-one correspondence between the hyperdiagrams
contributing to the number-density vertex functions, and diagrams contributing
to the order-parameter vertex functions in a certain model system belonging to
the Ising universality class is demonstrated. Corrections to scaling associated
with irrelevant operators that are present in the model-system Hamiltonian, and
other corrections specific to the RPM are also discussed
Spatial inhomogeneities in ionic liquids, charged proteins and charge stabilized colloids from collective variables theory
Effects of size and charge asymmetry between oppositely charged ions or
particles on spatial inhomogeneities are studied for a large range of charge
and size ratios. We perform a stability analysis of the primitive model (PM) of
ionic systems with respect to periodic ordering using the collective variables
based theory. We extend previous studies [A. Ciach et al., Phys. Rev.E
\textbf{75}, 051505 (2007)] in several ways. First, we employ a non-local
approximation for the reference hard-sphere fluid which leads to the
Percus-Yevick pair direct correlation functions for the uniform case. Second,
we use the Weeks-Chandler-Anderson regularization scheme for the Coulomb
potential inside the hard core. We determine the relevant order parameter
connected with the periodic ordering and analyze the character of the dominant
fluctuations along the -lines. We show that the above-mentioned
modifications produce large quantitative and partly qualitative changes in the
phase diagrams obtained previously. We discuss possible scenarios of the
periodic ordering for the whole range of size- and charge ratios of the two
ionic species, covering electrolytes, ionic liquids, charged globular proteins
or nanoparticles in aqueous solutions and charge-stabilized colloids
Field theory for size- and charge asymmetric primitive model of electrolytes. Mean-field stability analysis and pretransitional effects
The primitive model of ionic systems is investigated within a field-theoretic
description for the whole range of size-, \lambda, and charge, Z, ratios of the
two ionic species. Two order parameters (OP) are identified, and their
relations to physically relevant quantities are described for various values of
\lambda and Z. Instabilities of the disordered phase associated with the two
OP's are determined in the mean-field approximation.
A gas-liquid separation occurs for any Z and \lambda different from 1. In
addition, an instability with respect to various types of periodic ordering of
the two kinds of ions is found
- …