Ab initio simulations of water adsorbed in the microporous silicoaluminum phosphate HSAPO-34 are reported. A neutron diffraction study by L. Smith et al., Science 1996, 271, 799, showed that both H2O and H3O+ are present when this solid acid is loaded with water. The ab initio simulations support this; however, new details are revealed which are not accessible by diffraction experiments averaging over all sites. The acid−base reaction requires at least three water molecules per two nearby acidic sites in the micropores of the solid and leads to a protonated water cluster, H3O+(H2O)2.

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DFT-B3LYP calculations are performed on 4-ring models of aluminophosphates (AlPOs) and silico-aluminophosphates (SAPOs). The results are used to fit the parameters of ion pair shell model potential functions. The potentials obtained are tested in lattice energy minimizations for berlinite and the microporous materials AlPO-18, AlPO-40, AlPO-52, and VPI-5. Not only does the potential reproduce the observed structures (average error of the cell constants 1.3%), it also predicts vibrational frequencies over the whole frequency range equally well (maximum deviation 50 cm-1). The potential is used to predict the structures and properties of Bronsted acid sites in an aluminosilicate and a SAPO with the chabazite framework structure (HSSZ-13 and HSAPO-34). A new combined quantum mechanics-intermolecular potential function approach (QM-Pot) is used at the DFT level. Comparison is made with full periodic DFT calculations using plane wave basis sets. The deprotonation energies corrected for systematic errors of the methods used are 1 231-1 235 and 1 261-1 280 kJ/mol for HSSZ-13 and HSAPO-34, respectively. The same acid site has a lower acidity in a SAPO than in an aluminosilicate zeolite of the same structure.

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