Face-Integrated Fukui Function: Understanding Wettability Anisotropy of Molecular Crystals from Density Functional Theory

Abstract

Wettability is one of the anisotropic surface properties of molecular crystals that exhibit the structural variance of chemical moieties on various growth faces. The divergence in liquid-solid interactions at different faces is thought to be related to the inherent responding capacity or sensitivity of a solid surface to the perturbation in electronic structures and atomic positions as a result of the contact by a liquid. Since the Fukui function, according to density functional theory (DFT), is a local function for describing such sensitivity to the structural perturbation and is directly related to local softness, it has been proposed and tested to use an integrated Fukui function over a crystallographic plane for describing the anisotropy of solid-liquid interactions. It is found that the contact angle of a polar solvent, such as water, on a crystal surface shows an intimate connection to the integrated Fukui functions of the surface, illustrating an extension of Pearson's HSAB (hard and soft acids and bases) to crystal systems. The concept of face-integrated Fukui function and the approach to apply the HSAB with the DFT-based concepts may provide a powerful means for describing anisotropic properties, including wettability of organic crystals.