CONICET | Buscador de Institutos y Recursos Humanos

Recently, we have proposed a unified model for electrochemical electron transfer reactions on metals, which explicitly accounts for the electronic structure of the electrode. Our approach applies the SKS-Hamiltonian [1] for concerted bond breaking and electron-transfer reactions at metal electrodes; it contains the contributions of the molecule, the metal which acts as a catalyst, the solvent and the corresponding interactions between these subsystems. First calculations had been performed within the wideband approximation for the electronic structure of the metal and the extended Hückel approximation for the molecule [1,2]. Later, we have introduced idealized band shapes [3,4]. Finally, we have performed calculations for a real system, namely the hydrogen oxidation reaction, including explicitly the band structure of different metals obtained from the Density Functional Theory (DFT) [5,6]. The results showed a good correlation between the calculated energies of activation and the exchange current densities the first such correlation based on a theory. Now, we want to follow up and we have abandoned the tight-binding approximation, by which we have previously described the hydrogen molecule and included results from DFT also for the reactant.