Microscopic mechanism of thermal amorphization of ZIF-4 and melting of ZIF-zni revealed via molecular dynamics and machine learning techniques

We investigate the microscopic mechanism of the thermally induced ambient pressure ordered-disordered phase transitions of two zeolitic imidazolate frameworks of formula Zn(C3H3N2)(2): a porous (ZIF-4) and a dense, non-porous (ZIF-zni) polymorph via a combination of data science and computer simulation approaches. Molecular dynamics simulations are carried out at the atomistic level through the nb-ZIF-FF force field that incorporates ligand-metal reactivity and relies on dummy atoms to reproduce the correct tetrahedral topology around Zn2+ centres. The force field is capable of reproducing the structure of ZIF-4, ZIF-zni and the amorphous (ZIF_a) and liquid (ZIF_liq) phases that respectively result when these crystalline materials are heated. Symmetry functions computed over a database of structures of the four phases are used as inputs to train a neural network that predicts the probabilities of belonging to each of the four phases at the local Zn2+ level with 90% accuracy. We apply this methodology to follow the time-evolution of the amorphization of ZIF-4 and the melting of ZIF-zni along a series of molecular dynamics trajectories. We first computed the transition temperature and determined the associated thermodynamic state functions. Subsequently, we studied the mechanisms. Both processes consist of two steps: (i) for ZIF-4, a low-density amorphous phase is first formed, followed by the final ZIF_a phase while (ii) for ZIF-zni, a ZIF_a-like phase precedes the formation of the liquid phase. These processes involve connectivity changes in the first neighbour ligands around the central Zn2+ cations. We find that the amorphization of ZIF-4 is a non-isotropic process, and we trace back the origins of this anisotropic behaviour to the density and lability of coordination bonds.