A density functional theory study of the competitive complexation of   pyridine against H2O and Cl- to Cm3+ and Ce4+

doi:10.1515/ract-2014-2114

CORC > 北京大学 > 化学与分子工程学院

	A density functional theory study of the competitive complexation of pyridine against H2O and Cl- to Cm3+ and Ce4+
	Wang, Zhuxiang ; Chu, Taiwei ; Chai, Zhifang ; Wang, Dongqi
刊名	radiochimica acta
	2014
关键词	Trivalent lanthanide and actinide Tertiary pyridine resin Ligand exchange Density functional theory SOFT ACIDS BASES HSAB APPROXIMATION EXCHANGE ENERGY RESIN HARD GEOMETRY ION
DOI	10.1515/ract-2014-2114
英文摘要	Density functional theory was used to study the coordination of Cm3+ and Ce4+ with pridine (Py), water (H2O) and chloride anion (Cl-). The competitive coordination of Cl- and Py was investigated to simulate the ligand exchange between Cl(-)and Py at high concentration of hydrochloric acid (HCl), where Cm3+ and Ce4+ may exist in the form of [CmCl6](3-) and [CeCl6](2-), while that of water and Py to simulate the process at low concentration or without the presence of Cl-. The calculations show that Ce4+ has higher affinity to Py than Cm3+ in the absence of Cl-, while it binds much more weakly at high concentration of HCl. This is consistent with experimental data that at high concentration of HCl, Ce4+ has much shorter retention time than Cm3+ using tertiary pyridine resin (TPR). In view of the strengthening of M-Cl and the weakening of M-OW at bonds upon the coordination of Py, we conclude that the distinct coordination abilities of the three ligands to Ce4+ and Cm3+ are due to different strengths of the inner-shell electrostatic interaction between the ligands and the central metal ions.; Chemistry, Inorganic & Nuclear; Nuclear Science & Technology; SCI(E); 0; ARTICLE; dwang@ihep.ac.cn; 1-2; 101-109; 102
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/390061]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Wang, Zhuxiang,Chu, Taiwei,Chai, Zhifang,et al. A density functional theory study of the competitive complexation of pyridine against H2O and Cl- to Cm3+ and Ce4+[J]. radiochimica acta,2014.
APA	Wang, Zhuxiang,Chu, Taiwei,Chai, Zhifang,&Wang, Dongqi.(2014).A density functional theory study of the competitive complexation of pyridine against H2O and Cl- to Cm3+ and Ce4+.radiochimica acta.
MLA	Wang, Zhuxiang,et al."A density functional theory study of the competitive complexation of pyridine against H2O and Cl- to Cm3+ and Ce4+".radiochimica acta (2014).