O(2) adsorption in proton, sodium and copper exchanged chabazite has been studied using periodic and cluster approaches by means of density functional theory. The Grimme's correction has been used to include the dispersion contribution to B3LYP. Two cation locations have been considered: one with the cation at the six-membered ring (MCHA(I)) and the other with the cation at the 8-membered ring (MCHA(IV)). The O(2)-HCHA and O(2)-NaCHA adsorption complexes present a eta(1)-O(2) bent coordination. The adsorption energies, which are due to dispersion, are between -15 and -19 kJ mol(-1), in agreement with the experimental values. On the other hand, the O(2) coordination to CuCHA is through a eta(2)-side-on mode with a square planar coordination around the metal center. This structure favors the Cu d -->pi* O(2) charge transfer which becomes the predominant stabilizing factor. The adsorption of singlet states of O(2) in HCHA and NaCHA, modeled with an ONIOM M12T:48T, is of the same nature as that of the ground state, and only the highest in energy (1)Sigma is significantly more stabilized in MCHA than the triplet state by 14 to 24 kJ mol(-1). The adsorption of singlet O(2) in Cu exchanged zeolites presents a higher electron transfer from Cu(+) to O(2) than that calculated for the triplet species and thus both singlet states are stabilized with respect to the ground state O(2). Generally, singlet oxygen appears more attractive to active zeolite models than those calculated with triplet oxygen, indicating a source of oxidative efficiency for designed structures.

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The influence of molecular water on the structure and formation of silica clusters is modeled with the use of the MMH (multiple minima hypersurfaces) approach. It combines quantum chemical Hamiltonians for the calculation of the internal energy with statistical modeling and formulas for the calculation of thermodynamic functions of association. The structures of the most probable clusters of hydration and some properties of the association with water are proposed. Different simple structures are calculated to consider the entropy of association in place of the simpler approach of a single "global minimum". Ab initio, DFT, and semiempirical calculations of the structures and relevant reactions of silica fragments are also reported, confirming the reliability of the results on very different grounded quantum mechanical methods. Particularly, it has been shown that semiempirical PM3 Hamiltonian is reliable for silica cluster calculations of this kind, in comparison with accurate ab initio SCF and other DFT calculations. Apparently, the well-known systematic failures of this Hamiltonian are absent in this kind of structures and interactions. The increasing hydrophobic character of neutral silica clusters appears as a result of the free energies of association, and therefore, it originates on entropy. It is remarkable that the simple global minimum approach currently used in works of molecular modeling on this kind of compounds, where several hydrogen bridges have a place to exist with several different conformations, must be taken with caution given the remarkable entropy of association of such systems.

Hydrothermal zeolite synthesis is a complex process that is difficult toanalyze experimentally. In this work, the role of water as solvent on the formation of aluminate and aluminosilicate clusters is described by quantum chemical calculations. The multiple minima hypersurfaces approach was used. It combines quantum chemical Hamiltonians for the calculation of the internal energy with statistical modeling and formulae for the calculation of thermodynamic functions of association. The structures of most probable hydration clusters are proposed and some of their association properties are calculated. Ab initio and semiempirical calculations of the structures and relevant reactions of aluminate and aluminosilicate fragments were reported. The results could be employed for an interpretation of the aluminosilicate synthesis. Calculations demonstrate the importance of considering other than the deepest minimum structures, giving a significant role to consider entropy of association.

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