The chemical versatility and modular nature of Metal–Organic Frameworks (MOFs) make them unique hybrid inorganic–organic materials for several important applications. From a computational point of view, ab initio modeling of MOFs is a challenging and demanding task, in particular, when the system reaches the size of gigantic MOFs as MIL-100 and MIL-101 (where MIL stands for Materials Institute Lavoisier) with several thousand atoms in the unit cell. Here, we show how such complex systems can be successfully tackled by a recently proposed class of composite electronic structure methods revised for solid-state calculations. These methods rely on HF/density functional theory hybrid functionals (i.e., PBEsol0 and HSEsol) combined with a double-zeta quality basis set. They are augmented with semi-classical corrections to take into account dispersive interactions (D3 scheme) and the basis set superposition error (gCP). The resulting methodologies, dubbed “sol-3c,” are cost-effective yet reach the hybrid functional accuracy. Here, sol-3c methods are effectively applied to predict the structural, vibrational, electronic, and adsorption properties of some of the most common MOFs. Calculations are feasible even on very large MOFs containing more than 2500 atoms in the unit cell as MIL-100 and MIL-101 with reasonable computing resources. We propose to use our composite methods for the routine in silico screening of MOFs targeting properties beyond plain structural features.
For instance, by starting from the B3LYP-D*/TZVP optimized geometry, the full relaxation of MIL-100(Cr) takes about 30 steps with a total wall-clock time of 3 days.