An efficient computational approach for the evaluation of substituent constants

Density functional theory (DFT) computations are carried out for a series of 15 monosubstituted benzene derivatives in order to study dependencies between electronic structure parameters and experimental reactivity constants. The results have emphasized the reliability of electrostatic potential values (EPN) as a local reactivity descriptor and have indicated that the relative values of the [sigma.sup.D] constants are predominantly determined by intramolecular influences.