Hard and soft acids and bases: small molecules

The operational chemical hardness has been determined for the hydride, chloride, and fluoride derivatives of the anionic atomic bases of the second period. Of interest is the identification of the structure and associated processes that give rise to hard-soft behavior in small molecules. The Pearson Principle of Hard and Soft Acids and Bases has been taken to be the defining statement about hard-soft behavior and as a definition of chemical hardness. Similar to the case for atoms, the molecule's responding electrons have been identified as the structure giving rise to hard-soft behavior, and a relaxation described by a modified Slater model has been identified as the associated process. The responding electrons are the molecule's valence electrons that are not undergoing electron transfer in an acid-base interaction. However, it has been demonstrated that chemical hardness is a local property, and only those responding electrons that are associated with the base's binding atom directly impact chemical hardness.