Large-Scale Refinement of Metal-Organic Framework Structures Using Density Functional Theory

Efforts to computationally characterize large numbers of nanoporous materials often rely on databases of experimentally resolved crystal structures. The accuracy of experimental crystal structures used in such calculations has a significant impact on the reliability of the results. Here in this work, we report structures optimized using periodic density functional theory (DFT) for more than 800 experimentally synthesized metal-organic frameworks (MOFs). Many MOFs changed significantly upon structural optimization, particularly materials that were crystallographically resolved in their solvated form. For each MOF, we simulated the adsorption of CH4 and CO2 using grand canonical Monte Carlo both before and after DFT optimization. The DFT optimization has a large impact on simulated gas adsorption in some cases – for example, CO2 loading at 1 bar changed by more than 25% in over 25% of the MOFs we considered.