Understanding the structure and formation of uranyl peroxide nanoclusters by quantum chemical calculations

Quantum chemical calculations were performed to understand the formation of nanoscale cage clusters based on uranyl ions. We investigated the uranyl-peroxide-uranyl interaction and compared the geometries of clusters with and without such interactions. We show that a covalent interaction along the U-O_peroxo bonds causes the U-O₂-U dihedral angle to be bent, and it is this inherent bending of the configuration that encourages curvature and cage cluster formation. The U-O₂-U dihedral angle of the peroxo bridge is tuned by the size or electronegativity of the counterion present.