Halogen bonds and σ-holes

Abstract

The models behind simple bonding theory and the origins of some components often proposed to be involved in weak intermolecular bonds are described with special reference to σ-hole bonding, of which halogen bonds are a subset. A protocol for the analysis of weak intermolecular interactions is proposed on the basis of sound physical principles. This protocol uses three different levels of interaction; “permanent” Coulomb interactions between unperturbed monomers, relaxed Coulomb interactions and dispersion. Of the three, only dispersion is not a real, measurable quantity. It is, however, included in order to describe interactions that cannot be treated entirely by the first two levels.