Calculation of Fukui Functions Without Differentiating to the Number of Electrons. 3. Local Fukui Function and Dual Descriptor.

An alternative approach for the calculation of DFT-based reactivity descriptors involving derivatives of the energy with respect to the number of electrons and the external potential is further evaluated. Using functional derivatives with respect to the external potential, the finite difference approximation was avoided for the local calculation of the Fukui functions and the dual descriptor. A relevant set of molecules has been calculated after the optimization of computational parameters. It is shown that the new approach correctly predicts the nucleophilic attack on CH2O, the formation of CO metal complexes, the regioselectivity of monosubstituted benzenes, and the softest nucleophilic site in some ambident nucleophiles.