Nucleophilicity index from perturbed electrostatic potentials

Abstract

We introduce and test a nucleophilicity index as a new descriptor of chemical reactivity. The index is derived from a perturbation model for the interaction between the nucleophile and a positive test charge. The computational implementation of the model uses an isoelectronic process involving the minimum values of the electronic part of the perturbed molecular electrostatic potential. The working expression defining the nucleophilicity index encompasses both the electrostatic contributions and the second-order polarization effects in a form which is consistent with the empirical scales previously proposed. The index is validated for a series of neutral nucleophiles in the gas phase for which the nucleophilicity pattern has been experimentally established within a spectroscopic scale.