By: Anna Oleksy
At: Instituto de Investigação Interdisciplinar, Anfiteatro
Classical density functional theory (DFT) of inhomogeneous fluids is applied to an explicit solvent â€˜semi-primitiveâ€™ model (SPM) of ionic solutions to investigate the influence of ionic solutes on the wetting behaviour of a solvent in contact with a neutral or charged planar substrate. The SPM is made up of three species of hard sphere particles with different diameters, interacting via an attractive Yukawa potential to model excluded volume and cohesion. The solvent particles are neutral, while the monovalent anions and cations are oppositely charged. The polar nature of the solvent is modelled by a continuum dielectric permittivity linked to the local solvent density. All three species interact with the impenetrable substrate via an attractive external potential. While excluded volume effects are accurately described by a Rosenfeld â€˜fundamental measureâ€™ free energy functional, the short range Yukawa attraction and Coulombic interactions are treated within the mean-field approximation. The ionic solutes are found to have a significant impact on the wetting behaviour of the solvent, in particular on the wetting temperature. Strong electric fields, or long-ranged (weakly screened) Coulombic forces are shown to have the propensity to change the wetting transition from second to first order. The relative size of anions and cations is shown to have a crucial influence on interfacial properties, as observed experimentally. A novel drying scenario is predicted near a charged wall.