Polarizabilities of Atoms in Molecules: Choice of the Partitioning Scheme and Applications for Secondary Interactions

This paper reviews methods for partitioning the molecular polarizability into atomic terms. The advantages and disadvantages of hard space or fuzzy partitioning are critically assessed and compared. Polarizability density is proposed as a key function for the in-depth analysis and prediction of molecular recognition and chemical reactivity. Applications in the study of secondary interactions are illustrated, particularly in electron donor–acceptor complexes and other molecular adducts.