Hybrid solvation models for bulk, interface, and membrane: Reference interaction site methods coupled with density functional theory

Abstract

We present two hybrid solvation models for the calculation of the solvation structure with model 1 in a confined nanospace in bulk materials and model 2 at solid/liquid interfaces where an electrode is in contact with an electrolyte and a membrane is immersed into a solution. The hybrid theory is based on the reference interaction site method (RISM) for the solvent region. The electronic structure of a bulk material, an electrode, and a membrane is treated by density functional theory with the plane-wave basis and pseudopotentials technique. For model 1, we use the three-dimensional RISM (3D-RISM) by imposing a 3D periodic boundary condition on the system. However, for model 2, we reformulate the RISM by means of a two-dimensional boundary condition parallel to the surface and an open boundary condition normal to the surface. Four benchmark calculations are performed for the formaldehyde-water system, water packed into a zeolite framework, a NaCl solution in contact with an Al electrode, and an Al thin film immersed in a NaCl solution with different concentrations. The calculations are shown to be efficient and stable. Because of the flexibility of the RISM theory, the models are considered to be applicable to a wide range of solid/liquid interfaces.