On the short term, carbon capture is a viable solution to reduce human-induced CO₂ emissions, which requires an energy efficient separation of CO₂. Metal-organic frameworks (MOFs) may offer opportunities for carbon capture and other industrially relevant separations. Especially, MOFs with embedded open metal sites have been shown to be promising. Molecular simulation is a useful tool to predict the performance of MOFs even before the synthesis of the material. This reduces the experimental effort, and the selection process of the most suitable MOF for a particular application can be accelerated. To describe the interactions between open metal sites and guest molecules in molecular simulation is challenging. Polarizable force fields have potential to improve the description of such specific interactions. Previously, we tested the applicability of polarizable force fields for CO₂ in M-MOF-74 by verifying the ability to reproduce experimental measurements. Here, we develop a predictive polarizable force field for CO₂ in M-MOF-74 (M = Co, Fe, Mg, Mn, Ni, Zn) without the requirement of experimental data. The force field is derived from energies predicted from quantum mechanics. The procedure is easily transferable to other MOFs. To incorporate explicit polarization, the induced dipole method is applied between the framework and the guest molecule. Atomic polarizabilities are assigned according to the literature. Only the Lennard-Jones parameters of the open metal sites are parameterized to reproduce energies from quantum mechanics. The created polarizable force field for CO₂ in M-MOF-74 can describe the adsorption well and even better than that in our previous work.

The separation of light olefins from paraffins via cryogenic distillation is a very energy intensive process. Solid adsorbents and especially metal-organic frameworks with open metal sites have the potential to significantly lower the required energy. Specifically, M-MOF-74 has drawn considerable attention for application in olefin/paraffin separation. To investigate how the separation proceeds on a molecular level and to design better materials, molecular simulation can be a useful tool. Unfortunately, it is still a challenge to model the adsorption behavior of many adsorbates in metal-organic frameworks with open metal sites. Previously, the inclusion of explicit polarization has been suggested to improve the quality of classical force fields for such systems. Here, the potential of polarizable force fields for the description of olefins and paraffins in metal-organic frameworks with open metal sites is investigated. In particular, heats of adsorption, binding geometries, and adsorption isotherms are calculated for C2H4, C2H6, C3H6, and C3H8 in M-MOF-74 (with M = Co, Mn, Fe, and Ni). In this study, no force field parameters are adjusted to improve the model. The results show that including explicit polarization significantly improves the description of the adsorption in comparison to non-polarizable generic force fields which do not consider explicit polarization. The study also reveals that simulation predictions are sensitive to the assigned repulsive potential and framework charges. A fully re-parametrized polarizable force field may have the capability to improve the predictions even further.