Theoretical Elucidation of Am(III)/Cm(III) Separation Mechanism with Diamide-type Ligands Using Relativistic Density Functional Theory Calculation
Theoretical Elucidation of Am(III)/Cm(III) Separation Mechanism with Diamide-type Ligands Using Relativistic Density Functional Theory Calculation
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DOI：
10.1021/acs.inorgchem.8b01624
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发表时间：
2018-12-03
影响因子：
4.6
通讯作者：
Matsumura, Tatsuro
中科院分区：
文献类型：
--
作者：
Kaneko, Masashi;Suzuki, Hideya;Matsumura, Tatsuro
采用密度泛函理论和电子密度分析方法，研究了二甘醇酰胺（DGA）和烷基化二胺（ADAAM）两种不同类型的二胺配体对Am（III）和Cm（III）离子的分离机理。用[M(DGA)(3)]（3+）和[M(ADAAM)(NO3)(3)(H2O)]模拟了金属配体配合物的分子几何形状和形成反应。我们成功地用DGA再现了Cm（III）对Am（III）的选择性，用ADAAM再现了Am（III）对Cm（III）的选择性。此外，我们利用[M(DGA)(3)]（3+）和[M(ADAAM)(NO3)(3)(H2O)]模型配合物分析了金属离子与二胺型配体之间的键合性质，揭示了Am（III）和Cm（III）配合物在键解离能和金属5f轨道参与共价方面的差异。这些差异是了解Am(III)/Cm（III）选择性的关键因素。
We elucidated the separation mechanism between Am(III) and Cm(III) ions by using two different types of diamide ligands, diglycolamide (DGA) and alkylated diamide amine (ADAAM), by means of the density functional theory technique and electron density analysis. The molecular geometries and formation reactions of the metal ligand complexes were modeled by using [M(DGA)(3)](3+) and [M(ADAAM)(NO3)(3)(H2O)]. We successfully reproduced Cm(III) selectivity over Am(III) with DGA and Am(III) selectivity over Cm(III) with ADAAM. Furthermore, we analyzed the bonding properties between the metal ion and the diamide-type ligands by using model complexes, [M(DGA)(3)](3+) and [M(ADAAM)(NO3)(3)(H2O)], and revealed the differences in terms of the bond dissociation energy and the metal 5f orbital participation in the covalency between the Am(III) and the Cm(III) complexes. It was suggested that the differences were key factors to understand the Am(III)/Cm(III) selectivity.