for a full description of the electronic state of the system at the quantum chemical level, and still represent the most reliable atomistic description of ZIF-4 glasses published to date in the literature. Due to the significant computational cost of ab initio MD, a faster melt-quenching procedure was used: only the quenching from a 1500 K liquid was simulated, with a faster cooling rate (50 K/ps), on a smaller system (unit cell) and with a shorter equilibration (∼ 100 ps). To limit the impact of finite size effects, 10 quenched glasses were generated and their properties averaged. Due to the difficulty of performing (N, P, T ) ab initio simulations of such flexible frameworks, all ab initio simulations were performed in the (N, V, T ) ensemble. Although the influence of the density on the crystal and liquid properties was evaluated in a previous work, the inability to capture changes in density remains an important limitation of this ab initio methodology. The ab initio simulation of a crystal at 300 K reported here comes from the same work. Local order: interatomic distances and bond angles