Density functional study of uranyl (Ⅵ) amidoxime complexes

作者：Chi Fang Ting a)b) Li Peng c) Xiong Jie a) Hu Sheng a) Gao Tao c) Xia Xiu Long a) and Wang Xiao Lin a)b) a) Institute of Nuclear Physics and Chemistry China Academy of Engineering Physics Mianyang China b) College of Chemistry Sichuan University Chengdu China c) Institute of Atomic and Molecular Physics Sichuan University Chengdu China

来源：Chinese Physics B, 2012, (09): 179-186.

• uranyl amidoxime complexes
• intra-molecular hydrogen bonds
• bond order
• Mulliken populations

Uranyl (Ⅵ) amidoxime complexes are investigated using relativistic density functional theory. The equilibrium structures, bond orders, and Mulliken populations of the complexes have been systematically investigated under a generalized gradient approximation (GGA). Comparison of (acet) uranyl amidoxime complexes ([UO 2 (AO) n ] 2 n , 1≤ n ≤4) with available experimental data shows an excellent agreement. In addition, the U-O(1), U-O(3), C(1)-N(2), and C(3)-N(4) bond lengths of [UO 2 (CH 3 AO) 4 ] 2 are longer than experimental data by about 0.088, 0.05, 0.1, and 0.056 A. The angles of N(3)-O(3)-U, O(2)-N(1)-C(1), N(3)-C(3)-N(4), N(4)-C(3)-C(4), and C(4)-C(3)-N(3) are different from each other, which is due to existing interaction between oxygen in uranyl and hydrogen in amino group. This interaction is found to be intra-molecular hydrogen bond. Studies on the bond orders, Mulliken charges, and Mulliken populations demonstrate that uranyl oxo group functions as hydrogen-bond acceptors and H atoms in ligands act as hydrogen-bond donors forming hydrogen bonds within the complex.

• 出版日期2012-9-15
• 单位四川大学