In this paper, geometric bulk parameters, bulk moduli, energy gaps and relative stabilities of the TiO 2 anatase and rutile phases were determined from periodic DFT calculations. Then, for the rutile phase, structures, relaxations and surface energies of the (110), (100), (101) and (001) faces were computed. The calculated surface energies are consistent with the natural rutile powder composition, even if a dependence on the number of layers of the slab used to model the surface was identified. Internal constraints, consisting in freezing some internal 2 layers of the slab to atomic bulk positions, were thus added to mimic the bulk hardness in order to stabilize the computed surface energies for thinner systems. In parallel, the influence of pseudopotentials was studied and it appears that four valence electrons for titanium atoms are sufficient. The aim of this study was to optimise accurate rutile TiO 2 surfaces models that will be used in further calculations to investigate water and uranyl ion sorption mechanisms.

XPS and periodic DFT calculations have been used to investigate water sorption on the TiO 2 rutile (110) face. Two sets of XPS spectra were collected on the TiO 2 (110) single crystal 2 clean and previously exposed to water: the first set with photoelectrons collected in a direction parallel to the normal to the surface; and the second set with the sample tilted by 70°, respectively. This tilting procedure promotes the signals from surface species and reveals that the first hydration layer is strongly coordinated to the surface and also that, despite the fact that the spectra were recorded under ultra-high vacuum, water molecules subsist in upper hydration layers. In addition, periodic DFT calculations were performed to investigate the water adsorption process to determine if molecular and/or dissociative adsorption takes place.The first step of the theoretical part was the optimisation of a dry surface model and then the investigation of water adsorption. The calculated molecular water adsorption energies are consistent with previously published experimental data and it appears that even though it is slightly less stable, the dissociative water sorption can also take place. This assumption was considered, in a second step, on a larger surface model where molecular and dissociated water molecules were adsorbed together with different ratio. It was found that, due to hydrogen bonding stabilisation, molecular and dissociated water molecules can coexist on the surface if the ratio of dissociated water molecules is less than ≈ 33 %. These results are consistent with previous experimental works giving a 10-25 % range.

Periodic density functional theory (DFT) calculations using plane-wave basis sets were performed in order to study the bulk of nickel ferrite NiFe2O4. The local spin density approximation (LSDA) and the generalized gradient approximation (GGA) formalism were used, and it appeared that the LSDA failed to describe the magnetic structure of this compound. However, the GGA formalism gave reliable results in good agreement with experimental data for the lattice parameters, the electronic properties and the bulk modulus. In addition, the calculated density of states of the metallic species d block as well as their local magnetic moments were correlated to the crystal-field theory. Then, a charge deformation map was computed and, as expected from the electronegativity scale, the electron excess is localized around oxygen atoms along the bond axes. The formation energies of metallic vacancies are in good agreement with the inverse spinel structure experimentally observed.