Part II: Quantum mechanical prediction of heats of adsorption for C2-C4 hydrocarbons in MOF-74-Mg/Zn periodic structures

Abstract Periodic boundary condition models are used to investigate the interaction of small hydrocarbons (C 2 -C 4 ) with MOF-74-Mg/Zn. In contrast to other studies where molecular cluster approaches are used, the complete chemical environment of the framework is included. This allows correcting the binding energies for basis-set superposition error, molecular lateral interaction, zero-point energy, and thermal contributions. As such, the presented results are directly comparable to experimental calorimetric values. This work discusses, for the first time, the origin of the fictitious agreement between binding energies obtained with molecular clusters and experimental heats of adsorption, identifying its origin as due to compensation of errors.