Density functional study of uranyl （VI） amidoxime complexes  

作　　者：匙芳廷 李鹏 熊洁 胡胜 高涛 夏修龙 汪小琳 

机构地区：[1]Institute of Nuclear Physics and Chemistry,China Academy of Engineering Physics,Mianyang 621900,China [2]College of Chemistry,Siehuan University,Chengdu 610064,China [3]Institute of Atomic and Molecular Physics,Sichuan University,Chengdu 610065,China

出　　处：《Chinese Physics B》2012年第9期179-186,共8页中国物理B（英文版）

基　　金：Project supported by the Science and Technology Development Foundation of China Academy of Engineering Physics （Grant No. 2011A0301003）.

摘　　要：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 （[UO2（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 [UO2（CH3AO）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.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 （[UO2（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 [UO2（CH3AO）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.

关 键 词：uranyl amidoxime complexes intra-molecular hydrogen bonds bond order Mullikenpopulations 

分 类 号：O621.1[理学—有机化学]