Structural and vibrational features of hexagonal hydroxyapatite HA [Ca(10)(PO(4))(6)(OH)(2), space group P6(3)] are computed ab initio within a periodic approach using the CRYSTAL03 program and the B3LYP hybrid functional with a Gaussian-type basis set of polarized double zeta quality. Experimental lattice parameters and internal coordinates have been fully optimized and the final structure characterized by means of its band structure, density of states and Mulliken analysis. The full B3LYP harmonic vibrational spectrum of HA at Gamma point has also been computed and compares well with the available experimental IR and Raman data. Nevertheless, the presence of one negative frequency in the computed spectrum shows that, within the hexagonal symmetry imposed by the P6(3) group, the structure is a saddle point. This is at variance with the monoclinic structure (under P2(1)/b space group), which has been computed, with the same approach, to be a minimum of 17 kJ mol(-1) (per unit cell) more stable than the corresponding hexagonal HA structure.

The joint use of microcalorimetric and computational approaches has been adopted to describe H2O interaction with cus Al(III) Lewis and Si(OH)+ Al- Brønsted acidic sites within H-BEA and H-MFI zeolites (both with approximately 6 Al/unit cell). Adsorption data obtained at 303 K were compared to experimental model systems, such as all-silica zeolites, amorphous silica, and silico-alumina, transition alumina. In parallel, ab initio molecular modeling was carried out to mimic, in a cluster approach, Lewis and Brønsted acidic sites, as well as a variety of Si-OH species either with H-bonding interacting (nests and pairs) or isolated. H-BEA and H-MFI water affinity values were found to be almost equivalent, in both quantitative and energetic terms, in that dominated by Al-containing sites population, more than by nanocavity topology or by acidic site nature. Both H-zeolites, saturated with approximately 5 Torr of H2O vapor, bind approximately 4 H2O per Al site, almost one of which is tightly bound and not eliminated by RT pumping-off. A 160 < q(diff) < 80 kJ/mol interval was measured for the adsorption up to 1H2O/Al. The zero-coverage heat of adsorption (q0 approximately 160 kJ/mol, for both H-zeolites) was assigned to H2O/Lewis complex formation, which dominates the early stage of the process, in agreement with the ab initio computed H2O/Lewis sites binding energy. The rather broad q(diff) interval was interpreted as due to the simultaneous adsorption of H2O on both structural Brønsted sites and strongly polarized H2O already adsorbed on Lewis sites. For this latter species, BE = 74 kJ/mol was computed, slightly higher than BE = 65 kJ/mol for H2O/Brønsted sites interaction, showing that H2O coordinated on cus Al(III) Lewis sites behaves as a structural Brønsted site. The investigated all-silica zeolites have been categorized as hydrophilic in that the measured heat of adsorption (100 < q(diff) < 44 kJ/mol) was larger than the heat of liquefaction of water (44 kJ/mol) in the whole coverage examined. Indeed, polar defects present in the hydrophobic Si-O-Si framework do form relatively stable H2O adducts. Crystalline versus amorphous aluminosilicate q(diff) versus n(ads) plots showed that the measured adsorption heat is lower than expected, due to the extraction work of Al atoms from the amorphous matrix to bring them in interaction with H2O. On the contrary, such an energy cost is not required for the crystalline material, in which acidic sites are already in place, as imposed by the rigidity of the framework. Modeling results supported the experimental data interpretation.

H2O adsorption on hexagonal hydroxyapatite (001) and (010) stoichiometric surfaces has been studied at B3LYP level with a localized Gaussian basis set of polarized double-zeta quality using the periodic CRYSTAL06 code. Because four Ca2+ cations are available at both surfaces, the considered H2O coverages span the 1/4