Understanding Am3+/Cm3+ separation with H(4)TPAEN and its hydrophilic derivatives: a quantum chemical study
文献类型：期刊论文
| 作者 | Wang, CZ ; Wu, QY; Lan, JH; Song, G; Shi, WQ; Chai, ZF; Huang PW(黄品文); Wang CZ(王聪芝); Wu QY(吴群燕); Lan JH(蓝建慧)
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| 刊名 | PHYSICAL CHEMISTRY CHEMICAL PHYSICS
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| 出版日期 | 2018 |
| 卷号 | 20期号:20页码:14031-14039 |
| ISSN号 | 1463-9076 |
| DOI | 10.1039/c7cp08441b |
| 文献子类 | Article |
| 英文摘要 | Am3+/Cm3+ separation is an extremely hard but important task in nuclear waste treatment. In this study, Am and Cm complexes formed with a back-extraction agent N,N,N,N-tetrakis[(6-carboxypyridin-2-yl)methyl]ethylene-diamine (H(4)TPAEN) and its two derivatives with hydrophilic substituents (methoxy and morpholine groups) were investigated using the density functional theory (DFT). The optimized geometrical structures indicated that the Am3+ cation matched better with the cavities of the three studied ligands than Cm3+, and the Am3+ cations were located deeper in the cavities of the ligands. The bond order and quantum theory of atoms in molecules (QTAIM) analyses suggested that ionic interactions dominated An-N and An-O (An = Cm and Am) bonds. However, weak and different extents of partial covalency could also be found in the Am-N and Cm-N bonds. The O donor atoms in the carboxylate groups preferably coordinated with Cm3+ rather than Am3+, whereas the N atoms preferred Am3+. Therefore, the Am3+/Cm3+ selectivity of H(4)TPAEN and its two hydrophilic derivatives may be ascribed to the competition between the An-N and An-O interactions and the few dissimilarities in their geometrical structures. Based on our calculations, the methoxy and morpholine groups in the two derivatives can serve as electron-donating groups and enhance the strength of the An-N-PY bonds (N-PY denotes the nitrogen atom of pyridine ring). When compared with the Am-complex, the Cm-complex exhibited significant strength effect, resulting in the relatively lower Am3+/Cm3+ separation ability of the H(4)TPAEN's hydrophilic derivatives. |
| 电子版国际标准刊号 | 1463-9084 |
| WOS关键词 | SOLVENT-EXTRACTION ; DIGLYCOLAMIDE TODGA ; LANTHANIDE CATIONS ; MINOR ACTINIDES ; HARTREE-FOCK ; BASIS-SETS ; DENSITY ; COMPLEXATION ; ENERGY ; LIGANDS |
| WOS研究方向 | Chemistry ; Physics |
| 语种 | 英语 |
| WOS记录号 | WOS:000433262300036 |
| 源URL | [http://ir.ihep.ac.cn/handle/311005/285979]  |
| 专题 | 高能物理研究所_多学科研究中心 |
| 通讯作者 | Shi WQ(石伟群) |
| 作者单位 | 中国科学院高能物理研究所 |
| 推荐引用方式 GB/T 7714 | Wang, CZ,Wu, QY,Lan, JH,et al. Understanding Am3+/Cm3+ separation with H(4)TPAEN and its hydrophilic derivatives: a quantum chemical study[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2018,20(20):14031-14039. |
| APA | Wang, CZ.,Wu, QY.,Lan, JH.,Song, G.,Shi, WQ.,...&Huang, PW.(2018).Understanding Am3+/Cm3+ separation with H(4)TPAEN and its hydrophilic derivatives: a quantum chemical study.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,20(20),14031-14039. |
| MLA | Wang, CZ,et al."Understanding Am3+/Cm3+ separation with H(4)TPAEN and its hydrophilic derivatives: a quantum chemical study".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 20.20(2018):14031-14039. |
入库方式： OAI收割
来源：高能物理研究所
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