Phenomenological chemical reactivity theory for mobile electrons

Abstract

We present herein a model to deal with the chemical reactivity, selectivity and site activation concepts of p electron systems derived by merging the classical Coulson–Longuet-Higgins response function theory based on the Hu¨ckel molecular orbital (HMO) theory and the conceptual density functional theory. HMO-like expressions for the electronic chemical potential, chemical hardness and softness, including their local counterparts, atomic and bond Fukui functions and non-local response functions are derived. It is shown that sophisticated nonlocal concepts as site activation may be cast into deeper physical grounds by introducing a simplified version of static response functions. In this way, useful quantities such as self and mutual polarizabilities originally defined through the HMO parameters can be redefined as self and mutual softnesses. The model is illustrated by discussing the classical Hammett free energy relationship describing inductive substituent effects on the reactivity of benzoic acids.