Nonlinear screening and effective electrostatic interactions in charge-stabilized colloidal suspensions.

A nonlinear response theory is developed and applied to electrostatic interactions between spherical macroions, screened by surrounding microions, in charge-stabilized colloidal suspensions. The theory describes leading-order nonlinear response of the microions (counterions, salt ions) to the electrostatic potential of the macroions and predicts microion-induced effective many-body interactions between macroions. A linear response approximation [A.R. Denton, Phys. Rev. E 62, 3855 (2000)] yields an effective pair potential of screened-Coulomb (Yukawa) form, as well as a one-body volume energy, which contributes to the free energy. Nonlinear response generates effective many-body interactions and essential corrections to both the effective pair potential and the volume energy. By adopting a random-phase approximation (RPA) for the response functions, and thus neglecting microion correlations, practical expressions are derived for the effective pair and triplet potentials and for the volume energy. Nonlinear screening is found to weaken repulsive pair interactions, induce attractive triplet interactions, and modify the volume energy. Numerical results for monovalent microions are in good agreement with available ab initio simulation data and demonstrate that nonlinear effects grow with increasing macroion charge and concentration and with decreasing salt concentration. In the dilute limit of zero macroion concentration, leading-order nonlinear corrections vanish. Finally, it is shown that nonlinear response theory, when combined with the RPA, is formally equivalent to the mean-field Poisson-Boltzmann theory and that the linear response approximation corresponds, within integral-equation theory, to a linearized hypernetted-chain closure.

• Publication year

  2004

• Venue

  Physical review. E, Statistical, nonlinear, and soft matter physics

• Publication date

  2004-05-06

• Fields of study

  Medicine, Physics, Chemistry

• Identifiers
  DOI 10.1103/PhysRevE.70.031404arXiv cond-mat/0405126PMID 15524523
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Integral Equation Prediction of Reversible Coagulation in Charged Colloidal Suspensions

  2003cited by this paper
• Many-body interactions in colloidal suspensions

  2003cited by this paper
• Phase diagrams of hard-core repulsive Yukawa particles.

  2003cited by this paper
• Crystallization of weakly charged colloidal spheres: a numerical study

  2002cited by this paper
• The phase behavior of charged colloidal systems in the mean spherical approximation

  2002cited by this paper
• Self-consistent effective interactions in charged colloidal suspensions

  2002cited by this paper
• Where the linearized Poisson–Boltzmann cell model fails: Spurious phase separation in charged colloidal suspensions

  2002cited by this paper
• Effective attractions between like-charged colloidal particles

  2002cited by this paper
• Effective Macroion Charge and Stability of Highly Asymmetric Electrolytes at Various Salt Conditions

  2002cited by this paper
• Effect of many-body interactions on the solid-liquid phase behavior of charge-stabilized colloidal suspensions

  2002cited by this paper
• Electrostatic correlations: from plasma to biology

  2002cited by this paper
• Thermodynamics and phase separation of a de-ionized colloidal system in the symmetric Poisson–Boltzmann and mean spherical approximation theories

  2002cited by this paper
• Macroion shielding and state-dependent pair potentials in colloidal suspensions

  2002cited by this paper
• Three-body forces between charged colloidal particles.

  2002cited by this paper
• Osmotic pressure of charged colloidal suspensions: a unified approach to linearized Poisson-Boltzmann theory.

  2002cited by this paper
• Phase separation in deionized colloidal systems: extended Debye-Huckel theory

  2001cited by this paper
• Polarization effects in liquid metals and charge stabilized colloidal dispersions

  2001cited by this paper
• Gas-liquid phase coexistence in colloidal suspensions?

  2001cited by this paper
• Simple simulations of DNA condensation.

  2001cited by this paper
• Effective macroion-macroion potentials in asymmetric electrolytes.

  2001cited by this paper
• EFFECTIVE INTERACTIONS IN SOFT CONDENSED MATTER PHYSICS

  2001cited by this paper
• Gas–liquid phase separation in charged colloidal systems

  2001cited by this paper
• Effective interactions between electric double layers.

  2000cited by this paper
• Effective interactions between like-charged macromolecules

  2000cited by this paper
• Screening of a charged particle by multivalent counterions in salty water: Strong charge inversion

  2000cited by this paper
• Long-range electrostatic attractions between identically charged particles in confined geometries and the Poisson-Boltzmann theory

  2000cited by this paper
• DNA‐Inspired Electrostatics

  2000cited by this paper
• REVIEW ARTICLE: Colloidal interactions

  2000cited by this paper
• Effective interactions and volume energies in charged colloids: linear response theory

  2000cited by this paper
• Structure, phase stability, and thermodynamics in charged colloidal solutions

  2000cited by this paper
• Effect of three-body forces on the phase behavior of charged colloids

  2000cited by this paper
• Phase behavior of a model of colloidal particles with a fluctuating internal state

  2000cited by this paper
• Surprisingly short-ranged interactions in highly charged colloidal suspensions.

  2000cited by this paper
• Strong attraction between charged spheres due to metastable ionized states

  2000cited by this paper
• Effect of colloidal charge discretization in the primitive model

  2000cited by this paper
• Intermolecular structure of spherical polyelectrolyte microgels in salt-free solution. 1. Quantification of the attraction between equally charged polyelectrolytes.

  2000cited by this paper
• A theory of void formation in charge-stabilized colloidal suspensions at low ionic strength

  1999cited by this paper
• Colloidal particles: Origin of anomalous multibody interactions

  1999cited by this paper
• Effective interactions and volume energies in charge-stabilized colloidal suspensions

  1999cited by this paper
• Reentrant condensation of DNA induced by multivalent counterions

  1999cited by this paper
• Screening of a macroion by multivalent ions: correlation-induced inversion of charge.

  1999cited by this paper
• Negative electrostatic contribution to the bending rigidity of charged membranes and polyelectrolytes screened by multivalent counterions.

  1999cited by this paper
• Long-Range Electrostatic Attractions between Identically Charged Particles in Confined Geometries: An Unresolved Problem.

  1999cited by this paper
• Long-range electrostatic interactions between like-charged colloids: steric and confinement effects.

  1999cited by this paper
• Bundle Binding in Polyelectrolyte Solutions

  1999cited by this paper
• Phase diagram of charge-stabilized colloidal suspensions: van der Waals instability without attractive forces

  1999cited by this paper
• An Exact Evaluation of Salt Concentration Dependence of Interparticle Distance in Colloidal Crystals by Ultra-Small-Angle X-ray Scattering. 3. Confirmation of Solid−Liquid Transition by Three-Dimensional Paracrystal Analysis

  1999cited by this paper
• Many-bodied effects and the structure of colloidal crystals

  1999cited by this paper
• Simulation of an asymmetric electrolyte with charge asymmetry 60:1 using hard-sphere and soft-sphere models

  1999cited by this paper
• Electrostatic attraction and phase separation in solutions of like-charged colloidal particles

  1999cited by this paper
• On the convergence of simulation of asymmetric electrolytes with charge asymmetry 60:1

  1999cited by this paper
• Absence of many-body effects in interactions between charged colloidal particles

  1999cited by this paper
• Wall-Mediated Forces between Like-Charged Bodies in an Electrolyte

  1999cited by this paper
• EXTENDING LINEAR RESPONSE : INFERENCES FROM ELECTRON-ION STRUCTURE FACTORS

  1998cited by this paper
• CHARGE OSCILLATIONS AND MANY-BODY EFFECTS IN BUNDLES OF LIKE-CHARGED RODS

  1998cited by this paper
• Long-range electrostatic attraction between like-charge spheres in a charged pore

  1998cited by this paper
• Attraction between Like-Charged Macroions by Coulomb Depletion

  1998cited by this paper
• DENSITY JUMPS ACROSS PHASE TRANSITIONS IN SOFT-MATTER SYSTEMS

  1998cited by this paper
• The role of effective triplet interactions in charged colloidal suspensions

  1998cited by this paper
• Attraction between like-charged colloidal particles induced by a surface: A density-functional analysis

  1998cited by this paper
• Like-charge attractions in metastable colloidal crystallites

  1997cited by this paper
• VAN DER WAALS-LIKE INSTABILITY IN SUSPENSIONS OF MUTUALLY REPELLING CHARGED COLLOIDS

  1997cited by this paper
• Counterion-Mediated Attraction between Two Like-Charged Rods

  1997cited by this paper
• Melting of metastable crystallites in charge-stabilized colloidal suspensions.

  1996cited by this paper
• Macroion Attraction Due to Electrostatic Correlation between Screening Counterions. 1. Mobile Surface-Adsorbed Ions and Diffuse Ion Cloud

  1996cited by this paper
• Interactions between charged spherical macroions

  1996cited by this paper
• When Like Charges Attract: The Effects of Geometrical Confinement on Long-Range Colloidal Interactions.

  1996cited by this paper
• Exact evaluation of the salt concentration dependence of interparticle distance in colloidal crystals by ultra-small-angle X-ray scattering. 2. The universality of the maximum in the interparticle distance-salt concentration relationship

  1996cited by this paper
• Overscreening in colloidal systems: the attractive branch of pair macroion interaction

  1995cited by this paper
• CHARGED DIELECTRIC SPHERES IN ELECTROLYTE SOLUTIONS : INDUCED DIPOLE AND COUNTERION EXCLUSION EFFECTS

  1995cited by this paper
• Void Structure in Colloidal Dispersions

  1994cited by this paper
• Cavity Forces and Criticality in Electrolytes

  1994cited by this paper
• An Exact Evaluation of Salt Concentration Dependence of Interparticle Distance in Colloidal Crystals by Ultra-Small-Angle X-ray Scattering

  1994cited by this paper
• The story of coulombic critiality

  1994cited by this paper
• The interaction of ions in an ionic medium

  1994cited by this paper
• Attractive potential between confined colloids at low ionic strength.

  1994cited by this paper
• Nonlinear counterion screening in colloidal suspensions

  1993cited by this paper
• Optimal Effective Pair Potential for Charged Colloids

  1993cited by this paper
• Macroions in solution and colloidal suspension

  1993cited by this paper
• Ab initio description of counterion screening in colloidal suspensions.

  1992cited by this paper
• Vapor-liquid condensation in charged colloidal suspensions.

  1992cited by this paper
• Melting line of Yukawa system by computer simulation

  1991cited by this paper
• A self-consistent theory of the effective interactions in charge-stabilized colloidal dispersions

  1991cited by this paper
• Phase diagram and dynamics of Yukawa systems

  1988cited by this paper
• Static correlations in macro-ionic suspensions: Analytic and numerical results in a hypernetted-chain-mean-spherical approximation.

  1987cited by this paper
• A variational approach to static correlations in dilute macro-ion suspensions

  1987cited by this paper
• Foundations of Colloid Science

  1987cited by this paper
• Spinodal curve in highly asymmetrical polyelectrolytes.

  1986cited by this paper
• From Hamiltonians to Phase Diagrams

  1985cited by this paper
• Charge renormalization, osmotic pressure, and bulk modulus of colloidal crystals: Theory

  1984cited by this paper
• Intermolecular potentials that are functions of thermodynamic variables

  1984cited by this paper
• The interaction of two spherical colloidal particles in electrolyte solution. An application of the hypernetted‐chain approximation

  1980cited by this paper
• Theory of the Thermodynamics of Simple Liquid Metals

  1978cited by this paper
• Charge densities and interionic potentials in simple metals: Nonlinear effects. I

  1975cited by this paper
• Bulk moduli and pseudopotential perturbation theory

  1973cited by this paper
• Role of three-body forces in the dynamical properties of white tin

  1970cited by this paper
• Electron-Ion Interactions and Many-Body Effects in Simple Metals

  1970cited by this paper
• Electron-ion pseudopotentials in metals☆

  1966cited by this paper
• A and V

  1962cited by this paper
• Theory of the stability of lyophobic colloids.

  1955cited by this paper

• Impact of mixing and configurational entropies on the entropy-driven potential of mean force

  2024cites this paper
• Probing Microscale Structuring-Induced Phase Separation with Fluorescence Recovery Diffusion Dynamics in Poly(ethylene glycol) Solutions

  2023cites this paper
• Electrostatics of charged dielectric spheres with application to biological systems. III. Rigorous ionic screening at the Debye-Hückel level.

  2020cites this paper
• Inter-surface effective electrostatic interactions in the presence of surface charge discreteness and solvent granularity

  2020cites this paper
• Effective electrostatic forces between two neutral surfaces with atomic scale strip shape surface charge separation

  2020cites this paper
• Effective electrostatic interactions in colloid-nanoparticle mixtures.

  2017cites this paper
• Effective electrostatic interactions among charged thermo-responsive microgels immersed in a simple electrolyte.

  2016cites this paper
• Effective interactions in polydisperse systems of penetrable macroions

  2015cites this paper
• Three-body critical Casimir forces.

  2014cites this paper
• Effective charge of ionic microgel particles in the swollen and collapsed states: the role of the steric microgel-ion repulsion.

  2013cites this paper
• Effective electrostatic interactions arising in core-shell charged microgel suspensions with added salt.

  2013cites this paper
• An exact method to obtain effective electrostatic interactions from computer simulations: the case of effective charge amplification.

  2013cites this paper
• Effective electrostatic interactions in mixtures of charged colloids.

  2013cites this paper
• Charge renormalization of nanoparticles immersed in a molecular electrolyte.

  2010cites this paper
• Poisson–Boltzmann theory of charged colloids: limits of the cell model for salty suspensions

  2010cites this paper
• Interactions between microgel particles

  2009cites this paper
• A self-consistent renormalized jellium approach for calculating structural and thermodynamic properties of charge stabilized colloidal suspensions.

  2009cites this paper
• Phase behavior of density-dependent pair potentials.

  2008cites this paper
• Mesoscopic simulations of multiphase flows

  2008cites this paper
• Charge renormalization, effective interactions, and thermodynamics of deionized colloidal suspensions

  2008cites this paper
• Simulation of peloids

  2007cites this paper
• Nonlinear effects in charge stabilized colloidal suspensions.

  2006cites this paper
• Nonlinear screening and gas-liquid separation in suspensions of charged colloids.

  2006cites this paper
• Phase separation in charge-stabilized colloidal suspensions: influence of nonlinear screening.

  2006cites this paper
• Colloidal electrostatic interactions near a conducting surface.

  2006cites this paper
• Nonlinear screening on the charged surfaces with trivalent and tetravalent salt ions: Monte Carlo simulations

  2006cites this paper
• A simple phenomenological fix for the dielectric constant within the reference interaction site model approach.

  2006cites this paper
• Shear viscosity of claylike colloids in computer simulations and experiments.

  2006cites this paper
• Phase separation of charge-stabilized colloids: a Gibbs ensemble Monte Carlo simulation study.

  2006cites this paper
• Electroneutrality and phase behavior of colloidal suspensions.

  2006cites this paper
• Partially converged integral equations for charged colloidal suspensions with added salt

  2005cites this paper
• Stability of macroion-decorated lipid membranes

  2005cites this paper
• Potential of mean force in confined colloids: integral equations with fundamental measure bridge functions.

  2005cites this paper