A Hammett-type linear kinetic and free energy correlations pertaining to the intramolecular dissociative electron transfer in radical anions of aromatic halides have been formulated and studied using the reaction series of aromatic chlorides, bromides and iodides. The correlation evinces the higher reactivity of carbon-chlorine bond to the polar effects of the substituents in comparison to carbon-bromine and carbon-iodine bonds. The standard potentials and cleavage rate constants of radical anions of some aromatic iodides have been predicted using the Hammett-type kinetic and free energy relationships. (c) 2006 Elsevier B.V. All rights reserved.