Microscopic Mechanism of the Thermal Amorphization of ZIF-4 and Melting of ZIF-zni Revealed via Molecular Dynamics and Machine Learning Techniques

Abstract: We investigate the microscopic mechanism of the thermally induced ambient pressure ordered-disordered phase transitions of two zeolitic imidazolate frameworks of formula Zn(C$_3$H$_3$N$_2$)$_2$: 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 Zn$^{2+}$ 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 Zn$^{2+}$ 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 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 Zn$^{2+}$ cations. We find that the amorphization of ZIF-4 is a non-isotropic processes and we trace back the origins of this anisotropic behaviour to density and lability of coordination bonds.