A Quasi-relativistic Density Functional Theory Study of the Actinyl(VI, V) (An = U, Np, Pu) Complexes with a Six-Membered Macrocycle Containing Pyrrole, Pyridine, and Furan Subunits
文献类型：期刊论文
| 作者 | Lan JH(蓝建慧) ; Wang CZ(王聪芝); Wu QY(吴群燕); Feng YX(冯一潇); Zhao YL(赵宇亮); Chai ZF(柴之芳); Shi WQ(石伟群); Lan, JH; Wang, CZ; Wu, QY
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| 刊名 | JOURNAL OF PHYSICAL CHEMISTRY A
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| 出版日期 | 2015 |
| 卷号 | 119期号:34页码:9178-9188 |
| 通讯作者 | 石伟群 |
| 英文摘要 | Actinyl(VI, V) (An = U, Np and Pu) complexes of the recently reported hybrid macrocycle, cyclo[1]furan[1]pyridine[4]pyrrole (denoted as H4L), have been studied using density functional theory in combination with the small-core scalar-relativistic effective core potentials and corresponding (14s13p10d8f6g)/[ 10s9p5d4f3g] basis sets in the segmented contraction scheme. On the basis of our calculations, the pyrrole nitrogen atoms that possess the shortest An-L bonds and strongest basicity are the main donor atoms that contribute to the formation of actinyl(VI, V) complexes. The natural population analysis (NPA) suggests higher ligand-to-actinyl charge transfer in the actinyl(VI) complexes than in their actinyl(V) analogues, which account for the higher decomposition energies of the former. A significant actinide-to-ligand spin density delocalization in the uranyl(V) and neptunyl(V) complexes was observed owing to the redistribution of spin density caused by complexation. A thermodynamic analysis indicates that the formation of the actinyl(VI, V) complexes are exothermic reactions in CH2Cl2 solvent, where the uranyl cations show the highest selectivity. In aqueous solution containing chloride ions, for complexing with macrocycle H4L, the plutonyl(VI) and uranyl(V) cations possess the highest selectivity among actinyl(VI) and (V) cations, respectively. This work can shed light on the design of macrocycle complexes for actinide recognition and extraction in the future. |
| 学科主题 | Chemistry; Physics |
| 类目[WOS] | Chemistry, Physical ; Physics, Atomic, Molecular & Chemical |
| 收录类别 | SCI ; EI ; CA |
| WOS记录号 | WOS:000360415400024 |
| 公开日期 | 2016-05-03 |
| 源URL | [http://ir.ihep.ac.cn/handle/311005/228641]  |
| 专题 | 高能物理研究所_院士 高能物理研究所_多学科研究中心 |
| 推荐引用方式 GB/T 7714 | Lan JH,Wang CZ,Wu QY,et al. A Quasi-relativistic Density Functional Theory Study of the Actinyl(VI, V) (An = U, Np, Pu) Complexes with a Six-Membered Macrocycle Containing Pyrrole, Pyridine, and Furan Subunits[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2015,119(34):9178-9188. |
| APA | 蓝建慧.,王聪芝.,吴群燕.,冯一潇.,赵宇亮.,...&Shi, WQ.(2015).A Quasi-relativistic Density Functional Theory Study of the Actinyl(VI, V) (An = U, Np, Pu) Complexes with a Six-Membered Macrocycle Containing Pyrrole, Pyridine, and Furan Subunits.JOURNAL OF PHYSICAL CHEMISTRY A,119(34),9178-9188. |
| MLA | 蓝建慧,et al."A Quasi-relativistic Density Functional Theory Study of the Actinyl(VI, V) (An = U, Np, Pu) Complexes with a Six-Membered Macrocycle Containing Pyrrole, Pyridine, and Furan Subunits".JOURNAL OF PHYSICAL CHEMISTRY A 119.34(2015):9178-9188. |
入库方式： OAI收割
来源：高能物理研究所
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