DFT-Based Multireference Diagnostics in the Solid State: Application to Metal-Organic Frameworks

When a many-body wave function of a system cannot be captured by a single determinant, high-level multireference (MR) methods are required to properly explain its electronic structure. MR diagnostics to estimate the magnitude of such static correlation have been primarily developed for molecular systems and range from low in computational cost to as costly as the full MR calculation itself. We report the first application of low-cost MR diagnostics based on the fractional occupation number calculated with finite-temperature DFT to solid-state systems. To compare the behavior of the diagnostics on solids and molecules, we select metal- organic frameworks (MOFs) as model materials because their reticular nature provides an intuitive way to identify molecular derivatives. On a series of closed-shell MOFs, we demonstrate that the DFT-based MR diagnostics are equally applicable to solids as to their molecular derivatives. The magnitude and spatial distribution of the MR character of a MOF are found to have a good correlation with those of its molecular derivatives, which can be calculated much more affordably in comparison to those of the full MOF. The additivity of MR character discussed here suggests the set of molecular derivatives to be a good representation of a MOF for both MR detection and ultimately for MR corrections, facilitating accurate and efficient high-throughput screening of MOFs and other porous solids.

Automated summary

High-level multireference (MR) methods are necessary for systems with complex wave functions that cannot be described by a single determinant. This study applies low-cost MR diagnostics, based on fractional occupation numbers calculated with finite-temperature DFT, to solid-state systems for the first time. The results demonstrate that the DFT-based MR diagnostics are equally applicable to solids as to their molecular derivatives, providing a more affordable alternative for characterizing the electronic structure of solids.