van der Waals dispersion interactions in molecular materials: beyond pairwise additivity

Abstract

van der Waals (vdW) dispersion interactions are a key ingredient in the structure, stability, and response properties of many molecular materials and essential for us to be able to understand and design novel intricate molecular systems. Pairwise-additive models of vdW interactions are ubiquitous, but neglect their true quantum-mechanical many-body nature. In this perspective we focus on recent developments and applications of methods that can capture collective and many-body effects in vdW interactions. Highlighting a number of recent studies in this area, we demonstrate both the need for and usefulness of explicit many-body treatments for obtaining qualitative and quantitative accuracy for modelling molecular materials, with applications presented for small-molecule dimers, supramolecular host–guest complexes, and finally stability and polymorphism in molecular crystals.