Electronic structures and magnetism of Zr-, Th-, and U-based metal-organic frameworks (MOFs) by density functional theory

Metal-organic frameworks (MOFs) have recently gained wide interest as candidate materials for nuclear waste immobilization. While the fundamental thermodynamic properties, such as the substitution energies, determine the favorability of radionuclide sequestration in a MOF matrix, studies of MOF electronic structure reveal the role of d-, and/or f-electrons on changes in physical properties of actinide-containing materials. We use density functional theory (DFT) calculations to investigate the electronic structures of Zr-, Th-, and U-MOFs, including their electronic band structures and, where appropriate, their magnetic properties. We employ various DFT methods including DFT + U, collinear spin-polarization, spin-orbit coupling, and various flavors of exchange-correlation functionals to assess the robustness to the specific exchange-correlation functional. Unlike the Zr-, and Th-MOFs, the U-MOF is found to be sensitive to electron localization and spin; hence we explore the magnetic structure of the U-MOF in further detail.