Computational modeling and characterization of secondary bonding in compounds of late p-block elements

Secondary bonding, the supramolecular interaction in which a heavy main-group element acts as an electrophilic center despite having its primary valences already satisfied, is generating strong interest in current literature. Recent studies have greatly expanded the variety of known examples and demonstrated applications of these interactions. Experimental work in this area is often supported by computational investigations with a wide variety of tools. The purpose of this article is to facilitate the interpretation of the information provided by each method and aid in the comparison and integration of results from dissimilar techniques. The discussion includes methods to model structure, evaluate and analyze interaction energies, and dissect the factors that contribute to the stabilization of these interactions.