The usefulness of global descriptors based on the density functional theory framework has been discussed in the context of electron transfer reactions. A simple relationship between the vertical electronic energy associated to the complete ET transfer process and the change of interaction energy associated to the D-A couple of reagents (i.e., the assorted electronic hardness), provides an immediate connection to the intrinsic electronic reorganization energy of the reaction process. Theoretical results for the recently proposed electron transfer process from substituted N,N-dimethylanilines to phthalimide N-oxyl radical, are in complete agreement with the kinetic and substituent effects experimentally available evidence. (C) 2012 Elsevier B.V. All rights reserved.