Variation of the electrophilicity index along the reaction path

Abstract

Some exact conditions for the extremals of the electrophilicity index, ω = μ²/2η (Parr, R. G.; von Szentply, L.; Liu, S. J. Am. Chem. Soc. 1999, 121, 1922), along an arbitrary reaction coordinate, have been carefully examined. Implications within the widely used finite difference approximation for the density-functional based reactivity descriptors, their relationship with the maximum hardness principle, and the reliability of the general relationships have been tested in the framework of computational evidence for some simple systems of chemical interest.