Bryantsev Vyacheslav S, Hay Benjamin P
Oak Ridge National Laboratory, Chemical Sciences Division, 1 Bethel Valley Rd., Oak Ridge, Tennessee, 37831-6119 USA.
Dalton Trans. 2015 May 7;44(17):7935-42. doi: 10.1039/c4dt03275f.
Selective extraction of minor actinides from lanthanides is a critical step in the reduction of radiotoxicity of spent nuclear fuels. However, the design of suitable ligands for separating chemically similar 4f- and 5f-block trivalent metal ions poses a significant challenge. First-principles calculations should play an important role in the design of new separation agents, but their ability to predict metal ion selectivity has not been systematically evaluated. In this work, we examine the ability of several density functional theory methods to predict selectivity of Am(iii) and Eu(iii) with oxygen, mixed oxygen-nitrogen, and sulfur donor ligands. The results establish a computational method capable of predicting the correct order of selectivities obtained from liquid-liquid extraction and aqueous phase complexation studies. To allow reasonably accurate predictions, it was critical to employ sufficiently flexible basis sets and provide proper account of solvation effects. The approach is utilized to estimate the selectivity of novel amide-functionalized diazine and 1,2,3-triazole ligands.
从镧系元素中选择性萃取次锕系元素是降低乏核燃料放射性毒性的关键步骤。然而，设计用于分离化学性质相似的4f和5f族三价金属离子的合适配体是一项重大挑战。第一性原理计算在新型分离剂的设计中应发挥重要作用，但其预测金属离子选择性的能力尚未得到系统评估。在这项工作中，我们研究了几种密度泛函理论方法预测镅（III）和铕（III）与氧、氧氮混合以及硫供体配体选择性的能力。结果建立了一种能够预测液 - 液萃取和水相络合研究中获得的正确选择性顺序的计算方法。为了进行合理准确的预测，采用足够灵活的基组并适当考虑溶剂化效应至关重要。该方法用于估计新型酰胺官能化二嗪和1,2,3 - 三唑配体的选择性。
