Description beyond the mean field approximation of an electrolyte confined between two planar metallic electrodes

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 pressure is positive behaves as $1/W^3$ for large separations with a prefactor that is universal, i.e. independent of the microscopic constitution of the system. For the good conductor boundaries the disjoining pressure is negative and it has an exponential decay for large $W$. We also compute the density and electric potential profiles inside the electrolyte. These are the same in both models. If the electrolyte is charge asymmetric we find that the system is not locally neutral and that a non-zero potential difference builds up between any electrode and the interior of the system although both electrodes are grounded.Comment: 16 pages, 5 figures, added a new appendix B and a discussion on ideal conductors vs. good conductor

Non-linear screening of spherical and cylindrical colloids: the case of 1:2 and 2:1 electrolytes

From a multiple scale analysis, we find an analytic solution of spherical and cylindrical Poisson-Boltzmann theory for both a 1:2 (monovalent co-ions, divalent counter-ions) and a 2:1 (reversed situation) electrolyte. Our approach consists in an expansion in powers of rescaled curvature $1/(\kappa a)$, where $a$ is the colloidal radius and $1/\kappa$ the Debye length of the electrolytic solution. A systematic comparison with the full numerical solution of the problem shows that for cylinders and spheres, our results are accurate as soon as $\kappa a>1$. We also report an unusual overshooting effect where the colloidal effective charge is larger than the bare one.Comment: 9 pages, 11 figure

Discrete aqueous solvent effects and possible attractive forces

We study discrete solvent effects on the interaction of two parallel charged surfaces in ionic aqueous solution. These effects are taken into account by adding a bilinear non-local term to the free energy of Poisson-Boltzmann theory. We study numerically the density profile of ions between the two plates, and the resulting inter-plate pressure. At large plate separations the two plates are decoupled and the ion distribution can be characterized by an effective Poisson-Boltzmann charge that is smaller than the nominal charge. The pressure is thus reduced relative to Poisson-Boltzmann predictions. At plate separations below ~2 nm the pressure is modified considerably, due to the solvent mediated short-range attraction between ions in the the system. For high surface charges this contribution can overcome the mean-field repulsion giving rise to a net attraction between the plates.Comment: 12 figures in 16 files. 19 pages. Submitted to J. Chem. Phys., July 200

Incorporation of excluded volume correlations into Poisson-Boltzmann theory

We investigate the effect of excluded volume interactions on the electrolyte distribution around a charged macroion. First, we introduce a criterion for determining when hard-core effects should be taken into account beyond standard mean field Poisson-Boltzmann (PB) theory. Next, we demonstrate that several commonly proposed local density functional approaches for excluded volume interactions cannot be used for this purpose. Instead, we employ a non-local excess free energy by using a simple constant weight approach. We compare the ion distribution and osmotic pressure predicted by this theory with Monte Carlo simulations. They agree very well for weakly developed correlations and give the correct layering effect for stronger ones. In all investigated cases our simple weighted density theory yields more realistic results than the standard PB approach, whereas all local density theories do not improve on the PB density profiles but on the contrary, deviate even more from the simulation results.Comment: 23 pages, 7 figures, 1 tabl

Non-mean-field theory of anomalously large double-layer capacitance

Mean-field theories claim that the capacitance of the double-layer formed at a metal/ionic conductor interface cannot be larger than that of the Helmholtz capacitor, whose width is equal to the radius of an ion. However, in some experiments the apparent width of the double-layer capacitor is substantially smaller. We propose an alternate, non-mean-field theory of the ionic double-layer to explain such large capacitance values. Our theory allows for the binding of discrete ions to their image charges in the metal, which results in the formation of interface dipoles. We focus primarily on the case where only small cations are mobile and other ions form an oppositely-charged background. In this case, at small temperature and zero applied voltage dipoles form a correlated liquid on both contacts. We show that at small voltages the capacitance of the double-layer is determined by the transfer of dipoles from one electrode to the other and is therefore limited only by the weak dipole-dipole repulsion between bound ions, so that the capacitance is very large. At large voltages the depletion of bound ions from one of the capacitor electrodes triggers a collapse of the capacitance to the much smaller mean-field value, as seen in experimental data. We test our analytical predictions with a Monte Carlo simulation and find good agreement. We further argue that our ``one-component plasma" model should work well for strongly asymmetric ion liquids. We believe that this work also suggests an improved theory of pseudo-capacitance.Comment: 19 pages, 14 figures; some Monte Carlo results and a section about aqueous solutions adde

Ion-ion correlations: an improved one-component plasma correction

Based on a Debye-Hueckel approach to the one-component plasma we propose a new free energy for incorporating ionic correlations into Poisson-Boltzmann like theories. Its derivation employs the exclusion of the charged background in the vicinity of the central ion, thereby yielding a thermodynamically stable free energy density, applicable within a local density approximation. This is an improvement over the existing Debye-Hueckel plus hole theory, which in this situation suffers from a "structuring catastrophe". For the simple example of a strongly charged stiff rod surrounded by its counterions we demonstrate that the Poisson-Boltzmann free energy functional augmented by our new correction accounts for the correlations present in this system when compared to molecular dynamics simulations.Comment: 5 pages, 2 figures, revtex styl

Steric Effects in Electrolytes: A Modified Poisson-Boltzmann Equation

The adsorption of large ions from solution to a charged surface is investigated theoretically. A generalized Poisson--Boltzmann equation, which takes into account the finite size of the ions is presented. We obtain analytical expressions for the electrostatic potential and ion concentrations at the surface, leading to a modified Grahame equation. At high surface charge densities the ionic concentration saturates to its maximum value. Our results are in agreement with recent experiments.Comment: 4 pages, 2 figure

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.Comment: 10 pages, 4 figures, 2 tables, RevTeX4-styl

Bargmann invariants and off-diagonal geometric phases for multi-level quantum systems -- a unitary group approach

We investigate the geometric phases and the Bargmann invariants associated with a multi-level quantum systems. In particular, we show that a full set of `gauge-invariant' objects for an $n$-level system consists of $n$ geometric phases and ${1/2}(n-1)(n-2)$ algebraically independent 4-vertex Bargmann invariants. In the process of establishing this result we develop a canonical form for U(n) matrices which is useful in its own right. We show that the recently discovered `off-diagonal' geometric phases [N. Manini and F. Pistolesi, Phys. Rev. Lett. 8, 3067 (2000)] can be completely analysed in terms of the basic building blocks developed in this work. This result liberates the off-diagonal phases from the assumption of adiabaticity used in arriving at them.Comment: 13 pages, latex, no figure

Hydration interactions: aqueous solvent effects in electric double layers

A model for ionic solutions with an attractive short-range pair interaction between the ions is presented. The short-range interaction is accounted for by adding a quadratic non-local term to the Poisson-Boltzmann free energy. The model is used to study solvent effects in a planar electric double layer. The counter-ion density is found to increase near the charged surface, as compared with the Poisson-Boltzmann theory, and to decrease at larger distances. The ion density profile is studied analytically in the case where the ion distribution near the plate is dominated only by counter-ions. Further away from the plate the density distribution can be described using a Poisson-Boltzmann theory with an effective surface charge that is smaller than the actual one.Comment: 11 Figures in 13 files + LaTex file. 20 pages. Accepted to Phys. Rev. E. Corrected typos and reference