Related papers: Electrostatic correlation induced ion condensation…
Polyelectrolyte (PE) brushes are widely used in biomaterials and nanotechnology to regulate surface properties and interactions. Here, we apply the electrostatic correlation augmented self-consistent field theory to investigate the…
We study the reentrant condensation of polyelectrolytes in dilute solutions of small multivalent salts, whose phase-transition mechanism remains poorly understood. Motivated by recent full atomic simulation results reported by the Caltech…
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…
In this thesis we study the lateral electrostatic interaction between a pair of non-identical, moderately charged colloidal particles trapped at an electrolyte interface in the limit of short inter-particle separations. Using a simplified…
An interacting bilayer electron system provides an extended platform to study electron-electron interaction beyond single layers. We report here experiments demonstrating that the layer densities of an asymmetric bilayer electron system…
We report molecular dynamics simulation of the (overall neutral) system consisting of an immobile macroion surrounded by the electrolyte of multivalent counterions and monovalent coions. As expected theoretically, counterions adsorb on the…
New ways to treat electron correlation in electronic structure problems are discussed in the context of many-electron theory. The present work focuses primarily on static correlation. In related work, a method for including dynamical…
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…
A parallel plate capacitor containing an electrolytic solution is the simplest model of a supercapacitor, or electric double layer capacitor. Using both analytical and numerical techniques, we solve the Poisson-Nernst-Planck equations for…
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…
Recent experiments (F.H.J. Van Der Heyden et al., PRL 96, 224502 (2006)) of streaming currents in silica nanochannels with divalent ions report charge inversion, i.e. interfacial charges attracting counterions in excess of their own nominal…
The contact value of the charge profile for nonsymmetrical electrolytes is presented as the sum of three contributions. One of them is the normal component of the Maxwell electrostatic stress tensor. The second one is the surface…
We analyze the simplest problem of electrochemical relaxation in more than one dimension - the response of an uncharged, ideally polarizable metallic sphere (or cylinder) in a symmetric, binary electrolyte to a uniform electric field. In…
We explore the effect of steric interaction on the ionic density distribution near a charged hard wall. For weakly charged walls, small particles, and monovalent ions the mean-field Poisson-Boltzmann equation provides an excellent…
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 $g = 4 \pi b/\ell_{\rm {\scriptscriptstyle DB}}$, where $b,…
Electric double layer (EDL) formation underlies the functioning of supercapacitors and several other electrochemical technologies. Here, we study how the EDL formation near two flat blocking electrodes separated by $2L$ is affected by…
We revisit the popular notion of effective or renormalized charge, which is a concept of central importance in the field of highly charged colloidal or polyelectrolyte solutions. Working at the level of a linear Debye-H\"uckel like theory…
A new modified Poisson-Boltzmann equation accounting for the finite size of the ions valid for realistic salt-free concentrated suspensions has been derived, extending the formalism developed for pure salt-free suspensions [Roa et al.,…
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…
The classical treatment of the electrical double-layer (EDL) structure at a planar metal/electrolyte junction via the Gouy-Chapman-Stern (GCS) approach is based on the Poisson equation relating the electrostatic potential to the net mean…