Understanding the structure and formation of uranyl peroxide nanoclusters by quantum chemical calculations
Bess Vlaisavljevich1, Laura Gagliardi, Peter C Burns
1Department of Chemistry, University of Minnesota, and Supercomputing Institute, 207 Pleasant St. SE, Minneapolis, Minnesota 55455, USA.
Abstract:
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-O(2)-U dihedral angle to be bent, and it is this inherent bending of the configuration that encourages curvature and cage cluster formation. The U-O(2)-U dihedral angle of the peroxo bridge is tuned by the size or electronegativity of the counterion present.
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