Structural Analysis of the Complexation of Uranyl, Neptunyl, Plutonyl, and Americyl with Cyclic Imide Dioximes
Structural Analysis of the Complexation of Uranyl, Neptunyl, Plutonyl, and Americyl with Cyclic Imide Dioximes
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DOI：
10.1021/acsomega.8b02068
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发表时间：
2018-10-01
期刊：
影响因子：
4.1
通讯作者：
Hall, Howard L.
中科院分区：
文献类型：
--
作者：
Penchoff, Deborah A.;Peterson, Charles C.;Hall, Howard L.
基于知识的萃取剂的选择性结合锕系元素的设计是必不可少的库存堆管理，环境修复分离，和核燃料处置。稳健的计算方法对于深入理解结构性质和进一步推进选择性配体的设计至关重要。特别是，快速放射化学分离需要预测能力的结合在气相中。本文研究了环酰亚胺二肟与铀酰、镎酰、钚酰和americyl的气相键合选择性，用自然键级布居分析研究了环酰亚胺二肟的结构性质、吸电子效应及其对键合选择性的影响。发现芳香族酰胺肟比脂肪族酰胺肟具有更大的供电子效应。它也被发现，plutonyl是更多的吸电子比铀酰，neptunyl，americyl结合到环酰亚胺二肟研究时。
Knowledge-based design of extracting agents for selective binding of actinides is essential in stock-pile stewardship, environmental remediation separations, and nuclear fuel disposal. Robust computational protocols are critical for in depth understanding of structural properties land to further advance the design of selective ligands. In particular, rapid radiochemical separations require predictive capabilities for binding in the gas phase. This study focuses on gas phase binding preferences of cyclic imide dioximes to uranyl, neptunyl, plutonyl, and americyl Structural properties, electron withdrawing effects, and their effects on binding preferences are studied with natural bond-order population analysis. The aromatic amidoximes are found to have a larger electron-donation effect than the aliphatic amidoximes. It is also found that plutonyl is more electron withdrawing than uranyl, neptunyl, and americyl when bound to the cyclic imide dioximes studied.