title: Framework stability of nanoporous inorganic structures upon template extraction and calcination: a theoretical study of gallophosphate polymorphs.
abstract: A systematic computational study of gallophosphates was undertaken. First, lattice energy minimization calculations using a formal-charge shell model potential have been carried out on a series of hypothetical gallium phosphates derived from their metallogallophosphate, aluminophosphate, or aluminosilicate analogues through atomic substitution. The minimized structures show the typical features in terms of bond angles and distances as expected in zeolitic gallophosphates. Second, the crystal structures of several gallophosphates in their calcined forms have been predicted, using for each compound lattice energy minimization and an initial model derived from its as-synthesized templated form. All the modified structures thus have the same GaPO(4) composition. The lattice energies of all the simulated gallophosphate structures were compared to that of GaPO(4)-quartz as a reference structure. Interestingly, among all predicted calcined structures, various zeolitic topologies were found. The study of the energetics of these zeotypic structures showed a linear dependence of lattice energy upon density. Strikingly, a few simulated structures showed unrealistic structural features, such as important framework distortions, often associated with the occurrence of a hexameric unit in the original as-synthesized structures. Also, those gallophosphates with structural faults were found in the upper part of the energy/density plot. To address the validity of our force field calculations in these special cases, first principles calculations were undertaken on ULM-4, chosen as a typical representative structure. Indeed, the qualitative agreement found between our results and those obtained with the nonlocal density functional theory demonstrates the robustness of our force field. Further minimization also showed that the inclusion of polarizability is crucial for yielding results comparable with those obtained using first principles methods.
authors.affiliation: Institut Lavoisier, UMR CNRS 8637, Université de Versailles Saint-Quentin en Yvelines, 45, Avenue des Etats-Unis, 78035 Versailles Cedex, France.
authors.forename: Stéphanie
authors.initials: S
authors.lastname: Girard
authors.forename: Julian D
authors.initials: JD
authors.lastname: Gale
authors.forename: Caroline
authors.initials: C
authors.lastname: Mellot-Draznieks
authors.forename: Gérard
authors.initials: G
authors.lastname: Férey