arXiv subjects

Rene Messina

Publications and source records attributed to Rene Messina.

At least 19 recordsLinked to original sources

arXiv2008

Electrostatics in soft matter

Recent progress in the understanding of the effect of electrostatics in soft matter is presented. A vast amount of materials contains ions ranging from the molecular scale (e.g., electrolyte) to the meso/macroscopic one (e.g., charged colloidal particles or polyelectrolytes). Their (micro)structure and physicochemical properties are especially dictated by the famous and redoubtable long-ranged Coulomb interaction. In particular theoretical and simulational aspects, including the experimental motivations, will be discussed.

cond-mat.soft↗

arXiv2008

Binary crystals in two-dimensional two-component Yukawa mixtures

The zero-temperature phase diagram of binary mixtures of particles interacting via a screened Coulomb pair potential is calculated as a function of composition and charge ratio. The potential energy obtained by a Lekner summation is minimized among a variety of candidate two-dimensional crystals. A wealth of different stable crystal structures is identified including $A,B,AB_2, A_2B, AB_4$ structures [$A$ $(B)$ particles correspond to large (small) charge.] Their elementary cells consist of triangular, square or rhombic lattices of the $A$ particles with a basis comprising various structures of $A$ and $B$ particles. For small charge asymmetry there are no intermediate crystals besides the pure $A$ and $B$ triangular crystals.

cond-mat.soft↗

arXiv2007

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}.

cond-mat.soft↗

arXiv2006

Erratum: Effect of Image Forces on Polyelectrolyte Adsorption at a Charged Surface

See the content of the paper.

cond-mat.soft↗

arXiv2006

Behavior of block-polyampholytes near a charged surface

The behavior of polyampholytes near a charged planar surface is studied by means of Monte Carlo simulations. The investigated polyampholytes are overall electrically neutral and made up of oppositely charged units (called blocks) that are highly charged and of the the same length. The influence of block length and substrate's surface-charge-density on the adsorption behavior is addressed. A detailed structural study, including local monomer concentration, monomer mean height, transversal chain size, interface-bond orientation correlation, is provided. It is demonstrated that adsorption is favored for long enough blocks and/or high enough Coulomb interface-ion couplings. By explicitly measuring the chain size in the bulk, it is shown that the charged interface induces either a swelling or a shrinkage of the transversal dimension of the chain depending, in a non trivial manner, on the block length.

cond-mat.soft↗

arXiv2005

Behavior of rod-like polyelectrolytes near an oppositely charged surface

The behavior of highly charged short rod-like polyelectrolytes near oppositely charged planar surfaces is investigated by means of Monte Carlo simulations. A detailed microstructural study, including monomer and fluid charge distribution, and chain orientation, is provided. The influence of chain length, substrate's surface-charge-density and image forces is considered. Due to the lower chain-entropy (compared to flexible chains), our simulation data show that rod-like polyelectrolytes can, in general, better adsorb than flexible ones do. Nonetheless, at low substrate-dielectric-constant, it is found that repulsive image forces tend to significantly reduce this discrepancy.

cond-mat.soft↗

arXiv2004

Effect of Image Forces on Polyelectrolyte Adsorption at a Charged Surface

The adsorption of flexible and highly charged polyelectrolytes onto oppositely charged planar surfaces is investigated by means of Monte Carlo simulations. The effect of image forces stemming from the dielectric discontinuity at the substrate interface is considered. The influence, at fixed polyelectrolyte volume fraction, of chain length and surface-charge density is also considered. A detailed structural study, including monomer and fluid charge distributions, is provided. It is demonstrated that image forces can considerably reduce the degree of polyelectrolyte adsorption and concomitantly inhibit the charge inversion of the substrate by polyelectrolytes.

cond-mat.soft↗

arXiv2003

Screening of Spherical Colloids beyond Mean Field -- A Local Density Functional Approach

We study the counterion distribution around a spherical macroion and its osmotic pressure in the framework of the recently developed Debye-H"uckel-Hole-Cavity (DHHC) theory. This is a local density functional approach which incorporates correlations into Poisson-Boltzmann theory by adding a free energy correction based on the One Component Plasma. We compare the predictions for ion distribution and osmotic pressure obtained by the full theory and by its zero temperature limit with Monte Carlo simulations. They agree excellently for weakly developed correlations and give the correct trend for stronger ones. In all investigated cases the DHHC theory and its computationally simpler zero temperature limit yield better results than the Poisson-Boltzmann theory.

cond-mat.soft↗

arXiv2003

Polyelectrolyte Multilayering on a Charged Planar Surface

The adsorption of highly \textit{oppositely} charged flexible polyelectrolytes (PEs) on a charged planar substrate is investigated by means of Monte Carlo (MC) simulations. We study in detail the equilibrium structure of the first few PE layers. The influence of the chain length and of a (extra) non-electrostatic short range attraction between the polycations and the negatively charged substrate is considered. We show that the stability as well as the microstructure of the PE layers are especially sensitive to the strength of this latter interaction. Qualitative agreement is reached with some recent experiments.

cond-mat.soft↗

arXiv2003

Reentrant transitions in colloidal or dusty plasma bilayers

The phase diagram of crystalline bilayers of particles interacting via a Yukawa potential is calculated for arbitrary screening lengths and particle densities. Staggered rectangular, square, rhombic and triangular structures are found to be stable including a first-order transition between two different rhombic structures. For varied screening length at fixed density, one of these rhombic phases exhibits both a single and even a double reentrant transition. Our predictions can be verified experimentally in strongly confined charged colloidal suspensions or dusty plasma bilayers.

cond-mat.soft↗

arXiv2003

Ion pairing in model electrolytes: A study via three particle correlation functions

A novel integral equations approach is applied for studying ion pairing in the restricted primitive model (RPM) electrolyte, i. e., the three point extension (TPE) to the Ornstein-Zernike integral equations. In the TPE approach, the three-particle correlation functions $g^{[3]}({\bf r}_{1},{\bf r}_{2},{\bf r}_{3})$ are obtained. The TPE results are compared to molecular dynamics (MD) simulations and other theories. Good agreement between TPE and MD is observed for a wide range of parameters, particularly where standard integral equations theories fail, i. e., low salt concentration and high ionic valence. Our results support the formation of ion pairs and aligned ion complexes.

cond-mat.soft↗

arXiv2003

Adsorption of Oppositely Charged Polyelectrolytes onto a Charged Rod

The adsorption of highly charged flexible polycations and polyanions on a charged cylindrical substrate is investigated by means of Monte Carlo (MC) simulations. A detailed structural study, including monomer and fluid charge distributions, is provided. The influence of a short range attraction between the polycations and the negatively charged substrate is also considered. We demonstrate that the building up of multilayer structures is highly prohibited mainly due to the high entropy penalty stemming from the low dimensionality of the substrate at strong curvature.

cond-mat.soft↗

arXiv2003

Polyelectrolyte Multilayering on a Charged Sphere

The adsorption of highly \textit{oppositely} charged flexible polyelectrolytes onto a charged spherical surface is investigated by means of Monte Carlo simulations in a fashion which resembles the layer-by-layer deposition technique introduced by Decher. Electroneutrality is insured at each step by the presence of monovalent counterions (anions and cations). We study in detail the structure of the \textit{equilibrium} complex. Our investigations of the first few layer formations strongly suggest that multilayering in spherical geometry is not possible as an equilibrium process with purely electrostatic interactions. We especially focus on the influence of specific (non-electrostatic) short range attractive interactions (e.g., Van der Waals) on the stability of the multilayers.

cond-mat.soft↗

arXiv2002

Overcharging: The Crucial Role of Excluded Volume

In this Letter we investigate the mechanism for overcharging of a single spherical colloid in the presence of aqueous salts within the framework of the primitive model by molecular dynamics (MD) simulations as well as integral-equation theory. We find that the occurrence and strength of overcharging strongly depends on the salt-ion size, and the available volume in the fluid. To understand the role of the excluded volume of the microions, we first consider an uncharged system. For a fixed bulk concentration we find that upon increasing the fluid particle size one strongly increases the local concentration nearby the colloidal surface and that the particles become laterally ordered. For a charged system the first surface layer is built up predominantly by strongly correlated counterions. We argue that this a key mechanism to produce overcharging with a low electrostatic coupling, and as a more practical consequence, to account for charge inversion with monovalent aqueous salt ions.

cond-mat.soft↗

arXiv2002

Image charges in spherical geometry: Application to colloidal systems

The effects of image charges (i.e., induced surface charges of polarization) in spherical geometry and their implication for charged colloidal systems are investigated. We study analytically and exactly a single microion interacting with a dielectric sphere and discuss the similarities and discrepancies with the case of a planar interface. By means of extensive Monte Carlo (MC) simulations, we study within the framework of the primitive model the effects of image charges on the structure of the electrical double layer. Salt-free environment as well as salty solutions are considered. A remarkable finding of this study is that the position of the maximum in the counterion density (appearing at moderately surface charge density) remains quasi-identical, regardless of the counterion valence and the salt content, to that obtained within the \textit{single}-counterion system.

cond-mat.soft↗

arXiv2002

Spherical Colloids: Effect of Discrete Macroion Charge Distribution and Counterion Valence

We report the coupled effects of macroion charge discretization and counterion valence in the primitive model for spherical colloids. Instead of considering a uniformly charged surface, as it is traditionally done, we consider a more realistic situation where \textit{discrete monovalent microscopic charges} are randomly distributed over the sphere. Monovalent or multivalent counterions ensure global electroneutrality. We use molecular dynamics simulations to study these effects at the ground state and for finite temperature. The ground state analysis concerns the counterion structure and \textit{charge inversion}. Results are discussed in terms of simple analytical models. For finite temperature, strong and weak Coulomb couplings are treated. In this situation of finite temperature, we considered and discussed the phenomena of ionic pairing (pinning) and unpairing (unpinning).

cond-mat.soft↗

arXiv2002

Like-Charge Colloid-Polyelectrolyte Complexation

We investigate the complexation of a highly charged sphere with a long flexible polyelectrolyte, \textit{both negatively charged} in salt free environment. Electroneutrality is insured by the presence of divalent counterions. Using molecular dynamics (MD) within the framework of the primitive model, we consider different Coulomb coupling regimes. At strong Coulomb coupling we find that the adsorbed chain is always confined to the colloidal surface but forms different conformations that depend on the linear charge density of the chain. A mechanism involving the polyelectrolyte \textit{overcharging} is proposed to explain these structures. At intermediate Coulomb coupling, the chain conformation starts to become three-dimensional, and we observe multilayering of the highly charged chain while for lower charge density the chain wraps around the colloid. At weak Coulomb coupling, corresponding to an aqueous solvent, we still find like-charge complexation. In this latter case the chain conformation exhibits loops.

cond-mat.soft↗

arXiv2002

Charge inversion in colloidal systems

We investigate spherical macroions in the strong Coulomb coupling regime within the primitive model in salt-free environment. Molecular dynamics (MD) simulations are used to elucidate the effect of $discrete$ macroion charge distribution on charge inversion. A systematic comparison is made with the charge inversion obtained in the conventional continuous charge distribution. Furthermore the effect of multivalent counterions is reported.

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