Transferable Classical Force Field for Pure and Mixed Metal Halide Perovskites Parameterized from First-Principles.

Many key features in photovoltaic perovskites occur in relatively long time scales and involve mixed compositions. This requires realistic but also numerically simple models. In this work we present a transferable classical force field to describe the mixed hybrid perovskite MAxFA1-xPb(BryI1-y)3 for variable composition (∀x, y ∈ [0, 1]). The model includes Lennard-Jones and Buckingham potentials to describe the interactions between the atoms of the inorganic lattice and the organic molecule, and the AMBER model to describe intramolecular atomic interactions. Most of the parameters of the force field have been obtained by means of a genetic algorithm previously developed to parametrize the CsPb(BrxI1-x)3 perovskite (Balestra et al. J. Mater. Chem. A. 2020, DOI: 10.1039/d0ta03200j). The algorithm finds the best parameter set that simultaneously fits the DFT energies obtained for several crystalline structures with moderate degrees of distortion with respect to the equilibrium configuration. The resulting model reproduces correctly the XRD patterns, the expansion of the lattice upon I/Br substitution, and the thermal expansion coefficients. We use the model to run classical molecular dynamics simulations with up to 8600 atoms and simulation times of up to 40 ns. From the simulations we have extracted the ion diffusion coefficient of the pure and mixed perovskites, presenting for the first time these values obtained by a fully dynamical method using a transferable model fitted to first-principles calculations. The values here reported can be considered as the theoretical upper limit, that is, without grain boundaries or other defects, for ion migration dynamics induced by halide vacancies in photovoltaic perovskite devices under operational conditions.

Effect of diol isomer/water mixtures on the stability of Zn-MOF-74.

The stability of metal-organic frameworks is a key factor in many applications in some fields that require working under harsh conditions. It is known that a large number of MOFs are vulnerable to humid air. It means that when they are exposed to water, a structural collapse of the crystal happens. In this work, Molecular Dynamics simulations using a reactive force field have been performed to study the stability of MOF-74 against the adsorption of catechol, resorcinol and hydroquinone in the presence of water. We reproduced the water instability of Zn-MOF-74 and we studied the resistance of the structure. Our simulations showed that the three isomers generate a volume change in the framework but the structural collapse does not happen. In contrast, for water-isomer mixtures, there is structural collapse. Not only do catechol, resorcinol and hydroquinone not behave as stabilizing agents but they do enhance the hydration effect on the structure.