arXiv subjects

Alexandre Diehl

Publications and source records attributed to Alexandre Diehl.

14 recordsLinked to original sources

arXiv2019

Charge Regulation of Colloidal Particles: Theory and Simulations

To explore charge regulation (CR) in physicochemical and biophysical systems, we present a model of colloidal particles with sticky adsorption sites which account for the formation of covalent bonds between the hydronium ions and the surface functional groups. Using this model and Monte Carlo simulations, we find that the standard Ninham and Parsegian (NP) theory of CR leads to results which deviate significantly from computer simulations. The problem of NP approach is traced back to the use of bulk equilibrium constant to account for surface chemical reactions. To resolve this difficulty we present a new theory of CR. The fundamental ingredient of the new approach is the sticky length, which is non-trivially related with the bulk equilibrium constant. The theory is found to be in excellent agreement with computer simulations, without any adjustable parameters. As an application of the theory we calculate the effective charge of colloidal particles containing carboxyl groups, as a function of pH and salt concentration.

cond-mat.soft↗

arXiv2018

Adsorption isotherms of charged nanoparticles

We present theory and simulations which allow us to quantitatively calculate the amount of surface adsorption excess of charged nanoparticles onto a charged surface. The theory is very accurate for weakly charged nanoparticles and can be used at physiological concentrations of salt. We have also developed an efficient simulation algorithm which can be used for dilute suspensions of nanoparticles of any charge, even at very large salt concentrations. With the help of the new simulation method, we are able to efficiently calculate the adsorption isotherms of highly charged nanoparticles in suspensions containing multivalent ions, for which there are no accurate theoretical methods available.

cond-mat.soft↗

arXiv2015

Interaction between random heterogeneously charged surfaces in an electrolyte solution

We study, using Monte Carlo simulations, the interaction between infinite heterogeneously charged surfaces inside an electrolyte solution. The surfaces are overall neutral with quenched charged domains. An average over the quenched disorder is performed to obtain the net force. We find that the interaction between the surfaces is repulsive at short distances and is attractive for larger separations.

cond-mat.soft↗

arXiv2012

Diffusion Enhancement in Core-softened fluid confined in nanotubes

We study the effect of confinement in the dynamical behavior of a core-softened fluid. The fluid is modeled as a two length scales potential. This potential in the bulk reproduces the anomalous behavior observed in the density and in the diffusion of liquid water. A series of $NpT$ Molecular Dynamics simulations for this two length scales fluid confined in a nanotube were performed. We obtain that the diffusion coefficient increases with the increase of the nanotube radius for wide channels as expected for normal fluids. However, for narrow channels, the confinement shows an enhancement in the diffusion coefficient when the nanotube radius decreases. This behavior, observed for water, is explained in the framework of the two length scales potential.

cond-mat.soft↗

arXiv2012

Ion fluxes through nano-pores and transmembrane channels

We introduce an implicit solvent Molecular Dynamics approach for calculating ionic fluxes through narrow nano-pores and transmembrane channels. The method relies on a dual-control- volume grand-canonical molecular dynamics (DCV-GCMD) simulation and the analytical solution for the electrostatic potential inside a cylindrical nano-pore recently obtained by Levin [Europhys. Lett., 76, 163 (2006)]. The theory is used to calculate the ionic fluxes through an artificial trans-membrane c hannel which mimics the antibacterial gramicidin A channel. Both current-voltage and current-concentration relations are calculated under various experimental conditions. We show that our results are comparable to the characteristics associated to the gramicidin A pore, specially the existence of two binding sites inside the pore and the observed saturation in the current-concentration profiles.

cond-mat.soft↗

arXiv2010

Surface tensions, surface potentials and the Hofmeister series of electrolyte solutions

A theory is presented which allows us to accurately calculate the surface tensions and the surface potentials of electrolyte solutions. Both the ionic hydration and the polarizability are taken into account. We find a good correlation between the Jones-Dole viscosity $B$-coefficient and the ionic hydration near the air-water interface. The kosmotropic anions such as fluoride, iodate, sulfate and carbonate, are found to be strongly hydrated and are repelled from the interface. The chaotropic anions such as perchlorate, iodide, chlorate and bromide are found to be significantly adsorbed to the interface. Chloride and bromate anions become weakly hydrated in the interfacial region. The sequence of surface tensions and surface potentials is found to follow the Hofmeister ordering. The theory, with only one adjustable parameter, quantitatively accounts for the surface tensions of 10 sodium salts for which there is experimental data.

cond-mat.soft↗

arXiv2009

Ions at the air-water interface: An end to one hundred year old mystery?

Availability of highly reactive halogen ions at the surface of aerosols has tremendous implications for the atmospheric chemistry. Yet neither simulations, experiments, nor existing theories are able to provide a fully consistent description of the electrolyte-air interface. In this paper a new theory is proposed which allows us to explicitly calculate the ionic density profiles, the surface tension, and the electrostatic potential difference across the solution-air interface. Predictions of the theory are compared to experiments and are found to be in excellent agreement. The theory also sheds new light on one of the oldest puzzles of physical chemistry -- the Hofmeister effect.

cond-mat.soft↗

arXiv2008

Colloidal charge reversal: Dependence on the ionic size and the electrolyte concentration

Extensive Monte Carlo simulations and scaling arguments are used to study the colloidal charge reversal. The critical colloidal surface charge density $σ_c$ at which the reversal first appears is found to depend strongly on the ionic size. We find that $σ_c$ has an inflection point as a function of the electrolyte concentration. The width of the plateau region in the vicinity of the inflection point depends on the temperature and the ionic radius $a$. In agreement with the theoretical predictions it is found that the critical colloidal charge above which the electrophoretic mobility becomes reversed diverges as $Z_c \sim 1/a^2$ in the limit $a \to 0$.

cond-mat.soft↗

arXiv2006

Phase behavior of the Lattice Restricted Primitive Model with nearest-neighbor exclusion

The global phase behavior of the lattice restricted primitive model with nearest neighbor exclusion has been studied by grand canonical Monte Carlo simulations. The phase diagram is dominated by a fluid (or charge-disordered solid) to charge-ordered solid transition that terminates at the maximum density, $ρ^*_{max}=\sqrt2$ and reduced temperature $T^*\approx0.29$. At that point, there is a first-order phase transition between two phases of the same density, one charge-ordered and the other charge-disordered. The liquid-vapor transition for the model is metastable, lying entirely within the fluid-solid phase envelope.

cond-mat.soft↗

arXiv2004

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)].

cond-mat.soft↗

arXiv2000

Counterion correlations and attraction between like-charged macromolecules

A simple model is presented for the appearance of attraction between two like charged polyions inside a polyelectrolyte solution. The polyions are modeled as rigid cylinders in a continuum dielectric solvent. The strong electrostatic interactions between the polyions and the counterions results in counterion condensation. If the two polyions are sufficiently close to each other their layers of condensed counterions can become correlated resulting in attraction between the macromolecules. To explore the counterion induced attraction we calculate the correlation functions for the condensed counterions. It is found that the correlations are of very short range. For the parameters specific to the double stranded DNA, the correlations and the attraction appear only when the surface-to-surface separation is less than 7 /AA.

cond-mat.soft↗

arXiv2000

Charge renormalization and phase separation in colloidal suspensions

We explore the effects of counterion condensation on fluid-fluid phase separation in charged colloidal suspensions. It is found that formation of double layers around the colloidal particles stabilizes suspensions against phase separation. Addition of salt, however, produces an instability which, in principle, can lead to a fluid-fluid separation. The instability, however, is so weak that it should be impossible to observe a fully equilibrated coexistence experimentally.

cond-mat.soft↗

arXiv1997

Sine-Gordon mean field theory of a Coulomb Gas

Sine-Gordon field theory is used to investigate the phase diagram of a neutral Coulomb gas. A variational mean field free energy is constructed and the corresponding phase diagrams in two (2d) and three dimensions (3d) are obtained. When analyzed in terms of chemical potential, the Sine-Gordon theory predicts the phase diagram topologically identical with the Monte Carlo simulations and a recently developed Debye-H\"uckel-Bjerrum (DHBj) theory. In 2d we find that the infinite order Kosterlitz-Thouless line terminates in a tricritical point, after which the metal-insulator transition becomes first order. However, when the transformation from chemical potential to the density is made the whole of the insulating phase is mapped onto zero density.

cond-mat↗

arXiv1996

A Neutral Polyampholyte in an ionic solution

The behavior of a neutral polyampholyte ($PA$) chain with $N$ monomers, in an ionic solution, is analyzed in the framework of the full Debye-H$\ddot u $ckel-Bjerrum-Flory $(DHBjF)$ theory. A $PA$ chain, that in addition to the neutral monomers, also contains an equal number of positively and negatively charged monomers, is dissolved in an ionic solution. For \underline{high} concentrations of salt and at high temperatures, the $PA$ exists in an extended state. As the temperature is decreased, the electrostatic energy becomes more relevant and at a $T=T_θ$ the system collapses into a dilute globular state, or microelectrolyte. This state contains a concentration of salt higher than the surrounding medium. As the temperature is decreased even further, association between the monomers of the polymer and the ions of the salt becomes relevant and there is a crossover from this globular state to a low temperature extended state. For \underline{low} densities of salt, the system is collapsed for almost all temperatures and exhibits a first-order phase transition to an extended state at an unphysical low temperature.

cond-mat↗