DFT-based MD simulations were performed using the Quickstep module 41 of the CP2K software package, 42 using parameters already fine-tuned for ZIF-4 in previous works. We used the hybrid Gaussian and plane wave method GPW, 41 the exchange-correlation energy was evaluated in the PBE approximation, and the dispersion interactions were treated at the DFT-D3 level. The multigrid system was set up with four different grids, a plane-wave cutoff for the electronic density of 600 Ry, and a relative cutoff of 40 Ry. The simulations were performed in the constant-volume (N, V, T ) ensemble with a fixed size and shape of the unit cell. A timestep of 0.5 fs was used in the MD runs; the temperature was controlled by velocity rescaling with a time constant of 1000 fs. Volumetric deformation consisted in an instantaneous and isotropic volume change by 2% from the previous volume, followed by a sufficient equilibration time of around ∼ 100-200 ps.