Influence of anisotropic ion shape, asymmetric valency, and electrolyte concentration on structural and thermodynamic properties of an electric double layer
M. Kaja, S. Lamperski, W. Silvestre-Alcantara, L. B. Bhuiyan, D. Henderson
Grand canonical Monte Carlo simulation results are reported for an electric double layer modelled by a planar charged hard wall, anisotropic shape cations, and spherical anions at different electrolyte concentrations and asymmetric valencies. The cations consist of two tangentially tethered hard spheres of the same diameter, $d$. One sphere is charged while the other is neutral. Spherical anions are charged hard spheres of diameter $d$. The ion valency asymmetry 1:2 and 2:1 is considered, with the ions being immersed in a solvent mimicked by a continuum dielectric medium at standard temperature. The simulations are carried out for the following electrolyte concentrations: 0.1, 1.0 and 2.0 M. Profiles of the electrode-ion, electrode-neutral sphere singlet distributions, the average orientation of dimers, and the mean electrostatic potential are calculated for a given electrode surface charge, $σ$, while the contact electrode potential and the differential capacitance are presented for varying electrode charge. With an increasing electrolyte concentration, the shape of differential capacitance curve changes from that with a minimum surrounded by maxima into that of a distorted single maximum. For a 2:1 electrolyte, the maximum is located at a small negative $σ$ value while for 1:2, at a small positive value.
We study the ionic equilibria and interactions of neutral semi-permeable spherical shells immersed in electrolyte solutions, including polyions. Although the shells are uncharged, only one type of ions of the electrolyte can permeate them, thus leading to a steric charge separation in the system. This gives rise to a charge accumulation inside the shell and a build up of concentration- dependent shell potential, which converts into a disjoining pressure between the neighboring shells. These are quantified by using the Poisson-Boltzmann and integral equations theory. In particular, we show that…
Grand canonical simulations designed to resolve critical universality classes are reported for $z$:1 hard-core electrolyte models with diameter ratios $λ{=} a_+/a_- {\lesssim} 6$. For $z {=} 1$ Ising-type behavior prevails. Unbiased estimates of $T_c(λ)$ are within 1% of previous (biased) estimates but the critical densities are $\sim $5 % lower. Ising character is also established for the 2:1 and 3:1 equisized models, along with critical amplitudes and improved $T_c$ estimates. For $z {=} 3$, however, strong finite-size effects reduce the confidence level although classical and O$(n {\geq} 3)…
We study electrostatic mechanisms of destabilization of highly asymmetric electrolytes. For this purpose, we perform primitive model Monte Carlo simulations of charged macroions immersed in multivalent salt solution. At low salt concentration, the macroion effective charge is reduced due to multivalent counterion adsorption. At high salt concentrations, the macroions become overcharged so that their apparent charge has the opposite sign to the stoichiometric one. The inverted charge is growing up to a saturation value upon further increasing the salinity. The system remains stable at low as we…
The pair-correlation functions for fluid ionic mixtures in arbitrary spatial dimensions are computed in hypernetted chain (HNC) approximation. In the primitive model, all ions are approximated as non-overlapping hyperspheres with Coulomb interactions. Our spectral HNC solver is based on a Fourier-Bessel transform introduced by Talman [J. Comput. Phys., 29, 35 (1978)], with logarithmically spaced computational grids. Numeric efficiency for arbitrary spatial dimensions is a commonly exploited virtue of this transform method. Here, we highlight another advantage of logarithmic grids, consisting i…
The Poisson-Boltzmann equation for a strongly charged plate inside a generic charge-asymmetric electrolyte is solved using the method of asymptotic matching. Both near field and far field asymptotic behaviors of the potential are systematically analyzed. Using these expansions, the renormalized surface charge density is obtained as an asymptotic series in terms of the bare surface charge density.
The hypernetted chain/mean spherical approximation (HNC/MSA) integral equation is obtained and solved numerically for a totally asymmetric primitive model electrolyte around a spherical macroparticle. The ensuing radial distribution functions show a very good agreement when compared to our Monte Carlo and molecular dynamics simulations for spherical geometry and with respect to previous anisotropic reference HNC calculations in the planar limit. We report an analysis of the potential vs charge relationship, radial distribution functions, mean electrostatic potential and cumulative reduced char…
A variational theory is developed to study electrolyte solutions, composed of interacting point-like ions in a solvent, in the presence of dielectric discontinuities and charges at the boundaries. Three important and non-linear electrostatic effects induced by these interfaces are taken into account: surface charge induced electrostatic field, solvation energies due to the ionic cloud, and image charge repulsion. Our variational equations thus go beyond the mean-field theory. The influence of salt concentration, ion valency, dielectric jumps, and surface charge is studied in two geometries. i)…
Within the Poisson-Boltzmann (PB) framework useful for a wealth of charged soft matter problems, we work out the Coulombic grand potential of a long cylindrical charged polyion in a binary electrolyte solution of arbitrary valency and for low salt concentration. We obtain the exact analytical low-salt asymptotic expression for the grand potential, derived from known properties of the exact solutions to the cylindrical PB equation. These results are relevant for understanding nucleic acid processes. In practice, our expressions are accurate for arbitrary polyion charges, provided their radius i…
The ion distribution of electrolytes near interfaces with dielectric contrast has important consequences for electrochemical processes and many other applications. To date, most studies of such systems have focused on geometrically simple interfaces, for which dielectric effects are analytically solvable or computationally tractable. However, all real surfaces display nontrivial structure at the nanoscale and have, in particular, nonuniform local curvature. Using a recently developed, highly efficient computational method, we investigate the effect of surface geometry on ion distribution and i…
The self-consistent field theory (SCFT) is used to study the mean potential near a charged plate inside a $m:-n$ electrolyte. A perturbation series is developed in terms of $g = 4 πb/\ell_{\rm {\scriptscriptstyle DB}}$, where $b, \ell_{\rm{\scriptscriptstyle DB}}$ are Bjerrum length and {\em bare} Debye length respectively. To the zeroth order, we obtain nonlinear Poisson-Boltzmann theory. For asymmetric electrolytes ($m \neq n$), the first order (one-loop) correction to mean potential contains a {\em secular term}, which indicates the breakdown of regular perturbation method. Using a renormal…
Monte Carlo simulations of a spherical macroion, surrounded by a size-asymmetric electrolyte in the primitive model, were performed. We considered 1:1 and 2:2 salts with a size ratio of 2 (i.e., with coions twice the size of counterions), for several surface charge densities of the macrosphere. The radial distribution functions, electrostatic potential at the Helmholtz surfaces, and integrated charge are reported. We compare these simulational data with original results obtained from the Ornstein-Zernike integral equation, supplemented by the hypernetted chain/hypernetted chain (HNC/HNC) and h…
The Debye charging method is generalized to study the linear response properties of the asymmetric primitive model for electrolytes. Analytic results are obtained for the effective charge distributions of constituent ions inside the electrolyte, from which all static linear response properties of system follow. It is found that, as the ion density increases, both the screening length and the dielectric constant receive substantial renormalization due to ionic correlations. Furthermore, the valence of larger ion is substantially renormalized upwards by ionic correlations, whilst that of smaller…
We calculate phase diagrams of charged colloidal spheres (valency $Z$ and radius $a$) in a 1:1 electrolyte from multi-centered nonlinear Poisson-Boltzmann theory. Our theory takes into account charge-renormalization of the colloidal interactions and volume terms due to many-body effects. For valencies as small as Z=1 and as large as $10^4$ we find a gas--liquid spinodal instability in the colloid-salt phase diagram provided $Z\lB/a\gtrsim24\pm1$, where $\lB$ is the Bjerrum length.
In this work, the Quasi-Random Lattice (QRL) model is summarized and critically discussed, in order to outline its potentialities and limitations, in perspective of future developments. QRL primarily focuses on the mean activity coefficient of ionic solutions, the model having first been developed in order to provide practical equations, able to involve a minimal number of unknown or unpredictable quantities. QRL at present depends on one adjustable parameter (at given pressure and temperature), experimentally known for many common salts either symmetric or asymmetric, and corresponding to a w…
Machine-Learned Many-Body Potentials for Charged Colloids reveal Gas-Liquid Spinodal Instabilities only in the strong-coupling regime of Primitive Models
We present a simulation method to study electrolyte solutions in a dielectric slab geometry using a modified 3D Ewald summation. The method is fast and easy to implement, allowing us to rapidly resum an infinite series of image charges. In the weak coupling limit, we also develop a mean-field theory which allows us to predict the ionic distribution between the dielectric charged plates. The agreement between both approaches, theoretical and simulational, is very good, validating both methods. Examples of ionic density profiles in the strong electrostatic coupling limit are also presented. Fina…
We present a theoretical description of the effect of polyvalent ions on the interaction between titratable macro-ions. The model system consists of two point-like macro-ions with dissociable sites, immersed in an asymmetric ionic mixture of monovalent and polyvalent salts. We formulate a {\em dressed ion strong coupling theory}, based on the decomposition of the asymmetric ionic mixture into a weakly electrostatically coupled monovalent salt, and into polyvalent ions that are strongly electrostatically coupled to the titratable macro-ions. The charge of the macroions is not considered as fixe…
We consider the non-linear Poisson-Boltzmann theory for a single cylindrical or spherical macro-ion in symmetric 1:1, together with asymmetric 1:2 and 2:1 electrolytes. We focus on the regime where $κa $, the ratio of the macro-ion radius $a$ over the inverse Debye length in the bulk electrolyte, is large. Analyzing the structure of the analytical expansion emerging from a multiple scale analysis, we uncover a hidden structure for the electrostatic potential. This structure, which appears after a heuristic resummation, suggests a new and convenient expansion scheme that we present and work out…
A recently proposed local second contact value theorem [Henderson D., Boda D., J. Electroanal. Chem., 2005, 582, 16] for the charge profile of an electric double layer is used in conjunction with the existing Monte Carlo data from the literature to assess the contact behavior of the electrode-ion distributions predicted by the density functional theory. The results for the contact values of the co- and counterion distributions and their product are obtained for the symmetric valency, restricted primitive model planar double layer for a range of electrolyte concentrations and temperatures. Over…
Mean-field electrostatics is used to calculate the bending moduli of an electric double layer for fixed surface charge density of a macroion in a symmetric 1:1 electrolyte. The resulting expressions for bending stiffness, Gaussian modulus, and spontaneous curvature refer to a general underlying equation of state of the electrolyte, subject to a local density approximation and the absence of dipole and higher-order fields. We present results for selected applications: the lattice-gas Poisson-Fermi model with and without asymmetric ion sizes, and the Poisson-Carnahan-Starling model.
Electrolyte theories enable to describe the structural and dynamical properties of simple electrolytes in solution, such as sodium chloride in water. Using these theories for aqueous solutions of charged nanoparticles is a straightforward route to extract their charge and size from experimental data. Nevertheless, for such strongly asymmetric electrolytes, the validity of the underlying approximations have never been properly challenged with exact simulation results. In the present work, well established mesoscopic numerical simulations are used to challenge the ability of advanced electrolyte…
Simulations for the density and potential profiles of the ions in the planar electrical double layer of a model electrolyte or an ionic liquid are reported. The ions of a real electrolyte or an ionic liquid are usually not spheres; in ionic liquids, the cations are molecular ions. In the past, this asymmetry has been modelled by considering spheres that are asymmetric in size and/or valence (viz., the primitive model) or by dimer cations that are formed by tangentially touching spheres. In this paper we consider spherical ions that are asymmetric in size and mimic the asymmetrical shape throug…
Ion distribution in aqueous electrolytes near the interface plays critical roles in electrochemical, biological and colloidal systems and is expected to be particularly significant inside nanoconfined regions. Electroneutrality of the total charge inside nanoconfined regions is commonly assumed a priori in solving ion distribution of aqueous electrolytes nanoconfined by uncharged hydrophobic surfaces with no direct experimental validation. Here, we use a quantitative nuclear magnetic resonance approach to investigate the properties of aqueous electrolytes nanoconfined in graphitic-like nanopor…
This paper examines the response of electrolyte-saturated polymer gels, embedded with charged spherical inclusions, to a weak gradient of electrolyte concentration. These composites present a model system to study microscale electrokinetic transport processes, and a rigorous theoretical prediction of the bulk properties will benefit novel diagnostic applications. An electrokinetic model was presented in an earlier publication, and the response of homogeneous composites to a weak electric field was calculated. In this work, the influence of the inclusions on bulk ion fluxes and the strength of …
We study an electrolyte confined in a slab of width $W$ composed of two grounded metallic parallel electrodes. We develop a description of this system in a low coupling regime beyond the mean field (Poisson--Boltzmann) approximation. There are two ways to model the metallic boundaries: as ideal conductors in which the electric potential is zero and it does not fluctuate, or as good conductors in which the average electric potential is zero but the thermal fluctuations of the potential are not zero. This latter model is more realistic. For the ideal conductor model we find that the disjoining p…
We theoretically study electrostatic properties of electric double layer using a generalized Poisson-Boltzmann approach taking into account the orientational ordering of water dipoles and the excluded volume effect of water molecules as well as those of positive and negative ions with different sizes in electrolyte solution. Our approach enables one to predict that the number densities of water molecules, counterions and coions and the permittivity of electrolyte solution close to a charged surface, asymmetrically vary depending on both of sign and magnitude of the surface charge density and t…
We investigate the effect of adsorption-desorption phenomenon of ions in an asymmetric electrolytic cell at open circuit conditions. Our approach is based on the Poisson-Nernst-Planck theory for electrolytes and the kinetic model of Langmuir for the description of adsorption-desorption phenomena on the electrodes. When the electrodes are immersed into the solution, selective ion adsorption takes place. It is shown, that the selective ion adsorption is responsible for generating an electrical potential difference between the electrodes of the cell. The analytical expressions for the potential d…
We analytically calculate the correlation potential of a test ion near a \emph{strongly} charged plate inside a dilute $m:-n$ electrolyte. We do this by calculating the electrostatic Green's function in the presence of a nonlinear background potential, the latter having been obtained using the nonlinear Poisson-Boltzmann theory. We consider the general case where the dielectric constants of the plate and the electrolyte are distinct. The following generic results emerge from our analyses: (1) If the distance to the plate $Δz$ is much larger than a Gouy-Chapman length, the plate surface will be…
We study the interaction between two neutral plane-parallel dielectric bodies in the presence of a highly asymmetric ionic fluid, containing multivalent as well as monovalent (salt) ions. Image charge interactions, due to dielectric discontinuities at the boundaries, as well as effects from ion confinement in the slit region between the surfaces are taken fully into account, leading to image-generated depletion attraction, ion correlation attraction and steric-like repulsive interactions. We investigate these effects by employing a combination of methods including explicit-ion and implicit-ion…
We present a study of the structure and differential capacitance of electric double layers of aqueous electrolytes. We consider Electric Double Layer Capacitors (EDLC) composed of spherical cations and anions in a dielectric continuum confined between a planar cathode and anode. The model system includes steric as well as Coulombic ion-ion and ion-electrode interactions. We compare results of computationally expensive, but "exact", Brownian Dynamics (BD) simulations with approximate, but cheap, calculations based on classical Density Functional Theory (DFT). Excellent overall agreement is foun…
We analyze the diffusion of charged and neutral tracers suspended in an electrolyte embedded in a channel of varying cross-section. Making use of systematic approximations, the diffusion equation governing the motion of tracers is mapped into an effective $1D$ equation describing the dynamics along the longitudinal axis of the channel where its varying-section is encoded as an effective entropic potential. This simplified approach allows us to characterize tracer diffusion under generic confinement by measuring their mean first passage time (MFPT). In particular, we show that the interplay bet…
Using computer simulations, the electrophoretic motion of a positively charged colloid (macroion) in an electrolyte solution is studied in the framework of the primitive model. Hydrodynamic interactions are fully taken into account by applying a hybrid simulation scheme, where the charged ions (i.e. macroion and electrolyte), propagated via molecular dynamics (MD), are coupled to a Lattice Boltzmann (LB) fluid. In a recent experiment it was shown that, for multivalent salt ions, the mobility $μ$ initially increases with charge density $σ$, reaches a maximum and then decreases with further incr…
We explore structural correlations of strongly asymmetric mixtures of binary charged colloids within the primitive model of electrolytes considering large charge and size ratios of 10 and higher. Using computer simulations with explicit microions, we obtain the partial pair correlation functions between the like-charged colloidal macroions. Interestingly the big-small correlation peak amplitude is smaller than that of the big-big and small-small macroion correlation peaks, which is unfamiliar for additive repulsive interactions. Extracting optimal effective microion-averaged pair interactions …
Properties of aqueous electrolyte solutions at carbon electrodes: effects of concentration and surface charge on solution structure, ion clustering and thermodynamics in the electric double layer
We investigate the possibility that electrically neutral porous spheres electrophorese in electrolyte solutions with asymmetric affinity of ions to spheres on the basis of electrohydrodynamics and the Poisson-Boltzmann and Debye-Bueche-Brinkman theories. Assuming a weak electric field and ignoring the double-layer polarization, we obtain analytical expressions for electrostatic potential, electrophoretic mobility, and flow field. In the equilibrium state, the Galvani potential forms across the interface of the spheres. Under a weak electric field, the spheres show finite mobility with the same…
We propose a Poisson-Bikerman (PBik) formula for calculating the differential capacitance (DC) of electrical double layers (EDLs) in aqueous electrolytes or ionic liquids. The PBik theory is a generalization of the classical Poisson-Boltzmann theory to include different steric energies of different-sized ions and water similar to different electrical energies for different-charged ions. Water and ions with interstitial voids in this molecular mean field theory have their physical volumes as they do in molecular dynamics simulations. The PBik formula derived from Fermi distributions of ions and…
We study the effect of solvent granularity on the effective force between two charged colloidal particles by computer simulations of the primitive model of strongly asymmetric electrolytes with an explicitly added hard sphere solvent. Apart from molecular oscillating forces for nearly touching colloids which arise from solvent and counterion layering, the counterions are attracted towards the colloidal surfaces by solvent depletion providing a simple statistical description of hydration. This, in turn, has an important influence on the effective forces for larger distances which are considerab…
The phase diagram of a water solution of DNA and oppositely charged spherical macroions is studied. DNA winds around spheres to form beads-on-a-string complexes resembling the chromatin 10 nm fiber. At small enough concentration of spheres these "artificial chromatin" complexes are negative, while at large enough concentrations of spheres the charge of DNA is inverted by the adsorbed spheres. Charges of complexes stabilize their solutions. In the plane of concentrations of DNA and spheres the phases with positive and negative complexes are separated by another phase, which contains the condens…
The ionic adsorption around a weakly charged spherical colloid, immersed in size-asymmetric 1:1 and 2:2 salts, is studied. We use the primitive model of an electrolyte to perform Monte Carlo simulations as well as theoretical calculations by means of the hypernetted chain/mean spherical approximation (HNC/MSA) and the unequal-radius modified Gouy-Chapman (URMGC) integral equations. Structural quantities such as the radial distribution functions, the integrated charge, and the mean electrostatic potential are reported. Our Monte Carlo "experiments" evidence that near the point of zero charge th…
