Related papers: Charge neutrality breakdown in confined aqueous el…
We investigate the possibility of electrostatic potential saturation, which may lead to the phenomenon of effective charge saturation. The system under study is a uniformly charged infinite plane immersed in an arbitrary electrolyte made up…
Near-critical binary mixtures containing ions and confined between two charged and selective surfaces are studied within a Landau-Ginzburg theory extended to include electrostatic interactions. Charge density profiles and the effective…
A model system is proposed to investigate the chemical equilibrium and mechanical stability of biological spherical-like nanoshells in contact with an aqueous solution with added dissociated electrolyte of a given concentration. The ionic…
Due to efficient scaling with electron number N, density functional theory (DFT) is widely used for studies of large molecules and solids. Restriction of an exact mean-field theory to local potential functions has recently been questioned.…
We derive an exact representation of the exchange-correlation energy within density functional theory (DFT) which spawns a class of approximations leading to correct long-range asymptotic behavior. In what amounts to be the simplest…
Quantum-chemical processes in liquid environments impact broad areas of science, from molecular biology to geology to electrochemistry. While density-functional theory (DFT) has enabled efficient quantum-mechanical calculations which…
Standard flavors of density-functional theory (DFT) calculations are known to fail in describing anions, due to large self-interaction errors. The problem may be circumvented by using localized basis sets of reduced size, leaving no…
We propose an approach that links density functional theory (DFT) and molecular dynamics (MD) simulation to study fluid behavior in nanopores in contact with bulk (macropores). It consists of two principal steps. First, the theoretical…
The wetting of a charged wedge-like wall by an electrolyte solution is investigated by means of classical density functional theory. As in other studies on wedge wetting, this geometry is considered as the most simple deviation from a…
Linear scaling density functional theory approaches to electronic structure are often based on the tendency of electrons to localize even in large atomic and molecular systems. However, in many cases of actual interest, for example in…
In recent years, the theoretical description of electrical noise and fluctuation-induced effects in electrolytes has gained a renewed interest, enabled by stochastic field theories like stochastic density functional theory (SDFT). Such…
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…
Determining the solvation free energies of single ions in water is one of the most fundamental problems in physical chemistry and yet many unresolved questions remain. In particular, the ability to decompose the solvation free energy into…
Standard density functional approximations often give questionable results for odd-electron radical complexes, with the error typically attributed to self-interaction. In density corrected density functional theory (DC-DFT), certain classes…
Using classical density functional theory (DFT) the effect of bringing a liquid crystal (LC) into contact with a porous substrate or matrix is investigated. The DFT used is a combination of the Onsager approximation to evaluate the excess…
In the exact Kohn-Sham density-functional theory (DFT), the total energy versus the number of electrons is a series of linear segments between integer points. However, commonly used approximate density functionals produce total energies…
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,…
We study the distribution of multivalent counterions next to a dielectric slab, bearing a quenched, random distribution of charges on one of its solution interfaces, with a given mean and variance, both in the absence and in the presence of…
We examine electrolyte systems confined between two parallel, grounded metal plates using a field-theoretic approach truncated at one-loop order. For symmetric electrolytes, the density distribution of the ions is non-uniform, with a…
The study of the electrical double layer lies at the heart of colloidal and interfacial science. The standard mean-field Poisson-Boltzmann (PB) theory is incapable of modeling many phenomena originated from ion correlation. An important…