Simulating CO₂ diffusivity in rigid and flexible Mg-MOF-74 with machine-learning force fields

Abstract

The flexibility of metal–organic frameworks (MOFs) affects their gas adsorption and diffusion properties. However, reliable force fields for simulating flexible MOFs are lacking. As a result, most atomistic simulations so far have been carried out assuming rigid MOFs, which inevitably overestimates the gas adsorption energy. Here, we show that this issue can be addressed by applying a machine-learning potential, trained on quantum chemistry data, to atomistic simulations. We find that inclusion of flexibility is particularly important for simulating $CO_2$ chemisorption in MOFs with coordinatively unsaturated metal sites. Specifically, we demonstrate that the diffusion of $CO_2$ in a flexible Mg-MOF-74 structure is about one order of magnitude faster than in a rigid one, challenging the rigid-MOF assumption in previous simulations.