A semiempirical correlation between the optical band gap of binary oxides and the difference of electronegativity between the oxygen and metallic elements (Pauling's extraionic energy) is proposed. In the frame of the proposed correlation an estimate of the repulsive term in the total lattice energy of ionic oxides is obtained in very good agreement with the existing data. An extension of the correlation to the ternary oxides and hydroxides is proposed by using the concept of average cationic or anionic group electronegativity. The usefulness of the proposed correlation for the in situ characterization of passive films on metals and alloys by photocurrent spectroscopy is illustrated by reporting some preliminary experimental results on Sn and AlTi alloy.

A detailed investigation of the initial film grown on mechanically polished Mg electrodes has been carried out by ex situ X-ray Photoelectron Spectroscopy (XPS) and in situ Photocurrent Spectroscopy (PCS), allowing to reach a detailed picture of the passive layer structure. The XPS data show that the films formed soon after mechanical treatment and immersion in aqueous electrolyte have a bilayer structure, consisting of an ultra-thin MgO inner layer (∼2.5 nm) and a Mg(OH) 2 external layer. The thickness of the Mg(OH) 2 layer is a function of immersion time and solution temperature. After mechanical treatment and immersion in aqueous solution at room temperature, the MgO/Mg(OH) 2 layer in some area of electrodes is so thin to allow an electron photoemission process from the Mg Fermi level to the electrolyte conduction band. Only internal photoemission processes are evidenced for Mg electrodes aged in NaOH at 80 • C, due the formation of a thicker Mg(OH) 2 layer. From anodic photocurrent spectra an optical band gap of ∼4.25 eV has been estimated for Mg(OH) 2 , lower with respect to the optical gap of the corresponding anhydrous counterpart.

An analysis of the electronic properties of amorphous semiconductor-electrolyte junction is reported for thin (D ox < 20 nm) passive film grown on Nb in acidic electrolyte. It will be shown that the theory of amorphous semiconductor-electrolyte junction (a-SC/El) both in the low band-bending and high band-bending regime is able to explain the admittance data of a-Nb 2 O 5 /El interface in a large range (10 Hz-10 kHz) of frequency and electrode potential values.A modelling of experimental EIS data at different potentials and in the frequency range of 0.1 Hz-100 kHz is presented based on the theory of amorphous semiconductor and compared with the results of the fitting of the admittance data obtained in a different experiment. Some preliminary insights on the possible dependence of the density of state (DOS) distribution on the mobile defects concentration and mechanism of growth of anodic film on valve metals are suggested.

A detailed photoelectrochemical study was c~rried out in order to identify the nature and the properties of the passive layers on chromium under different experimental conditions. Different compositions of the films, related to various hydration degrees of the Cr(III) oxides, have been inferred on the basis of the bandgap values measured at changing pH, electrode potential, and polarization time. By comparison with air-grown films, it has been concluded that anhydrous Cr203 is never formed in acidic solution. The water content in the passive film increases at decreasing potentials and for long polarization times. In some cases, especially at neutral pH values, passive films possess a duplex structure, consisting of two layers with different hydration degrees. The photoelectrochemical study suggests an insulating or a slightly p-type behavior of the passive layers.

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