ELECTROCHEMISTRY, A TOOL FOR PILOTING LEW IS ACID-BASE INTERACTIONS -THEORETICAL ASPECT

A theoretical model of Lewis acid-base interactions, designed within t he Density Functional Theory (DFT) formalism, is used to interpret som e of the results obtained in the grafting of vinylic molecules (methac rylonitrile...) on metallic surfaces (Ni, pt) via electropolymerizatio n. Global (electronic chemical potential, electronic softness) and loc al (Fukui functions) parameters can be computed which allow a tentativ e description of the long- to medium-range zone of the reaction profil e, through which reactivities can be compared in the tron-crossing ass umption. It is proposed that a direct, linear, relationship exists bet ween DFT's chemical potential and the electrode potential, which is im posed with respect to a reference electrode. A theoretical framework w hich permits a continous monitoring of DFT's chemical potential is all uded to. The correspondance thus obtained between the two - experiment al and theoretical - potentials opens a way to describing how long- to medium-range interactions are modified upon electrode polarization, a nd how the chemical reactivity of metallic surfaces ran be monitored v ia electrochemistry.