Unprecedented neptunyl(V) cation-directed structural variations in Np2Ox compounds,Nanoscale

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Unprecedented neptunyl(V) cation-directed structural variations in Np2Ox compounds
Nanoscale ( IF 5.8 ) Pub Date : 2021-08-30 , DOI: 10.1039/d1nr03408a
Zhong-Fei Xu _{1,

2} , Wen-Jing Zhang _{1,

2} , Ping Zhang ₂ , Shu-Xian Hu _{1,

2}

Affiliation

Studies on transuranic oxides provide a particularly valuable insight into chemical bonding in actinide compounds, in which subtle differences between metal ions and oxygen atoms are of fundamental importance for the stability of these compounds as well as their existence. In the case of neptunium, it is still mainly limited to specific Np oxide compounds without periodicity in the formation of stable structures or different oxidation states. Here, we report a systematic global minimum search of Np₂O_x (x = 1–7) clusters and the computational study of their electronic structures and chemical bonding. These studies suggest that Np(V) ion could play the structure-directing role, and thus the mixed-valent Np(III/V) in Np₂O₄ is predicted accessible. In comparison with lower oxidation state Np analogues, significant 5f-orbital covalent interactions with Np(V) [double bond, length as m-dash]

O bonding are observed, which shows that these model neptunium oxides can provide new understandings into the behavior of 5f-electrons in chemical bonding and structural design.

中文翻译：

Np2Ox 化合物中前所未有的 neptunyl(V) 阳离子导向结构变化

对超铀氧化物的研究提供了对锕系化合物中化学键合的特别有价值的见解，其中金属离子和氧原子之间的细微差异对于这些化合物的稳定性及其存在至关重要。就镎而言，在稳定结构的形成或不同氧化态的形成方面，仍主要限于特定的Np氧化物化合物。在这里，我们报告了对 Np ₂ O _x ( x = 1–7) 簇的系统全局最小搜索及其电子结构和化学键合的计算研究。这些研究表明 Np( V ) 离子可以起到结构导向作用，因此混合价 Np( III/ V ) 在 Np ₂ O _{4 中}被预测为可访问的。与较低氧化态的 Np 类似物相比，观察到显着的 5f-轨道共价相互作用与 Np( V ) [双键，长度为 m-dash]