Understanding the Structure and Formation of Uranyl Peroxide Nanoclusters by Quantum Chemical Calculations

作者：Vlaisavljevich Bess; Gagliardi Laura^*; Burns Peter C

来源：Journal of the American Chemical Society, 2010, 132(41): 14503-14508.

DOI：10.1021/ja104964x

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.

• 出版日期2010-10-20