Wilson Richard E, De Sio Stephanie, Vallet Valérie
Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL, 60439, USA.
Université de Lille, CNRS, UMR 8523 - PhLAM - Physique des Lasers Atomes et Molécules, F-59000, Lille, France.
Nat Commun. 2018 Feb 12;9(1):622. doi: 10.1038/s41467-018-02972-z.
The role of the 5f and 6d orbitals in the chemistry of the actinide elements has been of considerable interest since their discovery and synthesis. Relativistic effects cause the energetics of the 5f and 6d orbitals to change as the actinide series is traversed left to right imparting a rich and complex chemistry. The 5f and 6d atomic states cross in energy at protactinium (Pa), making it a potential intersection between transition metal and actinide chemistries. Herein, we report the synthesis of a Pa-peroxo cluster, A(PaO(O)F) [A = Rb, Cs, (CH)N], formed in pursuit of an actinide polyoxometalate. Quantum chemical calculations at the density functional theory level demonstrate equal 5f and 6d orbital participation in the chemistry of Pa and increasing 5f orbital participation for the heavier actinides. Periodic changes in orbital character to the bonding in the early actinides highlights the influence of the 5f orbitals in their reactivity and chemical structure.
自锕系元素被发现和合成以来，5f和6d轨道在其化学性质中的作用一直备受关注。相对论效应导致随着从左到右遍历锕系元素，5f和6d轨道的能量发生变化，赋予其丰富而复杂的化学性质。5f和6d原子态在镤（Pa）处能量交叉，使其成为过渡金属化学和锕系元素化学之间的一个潜在交叉点。在此，我们报告了一种为了追求锕系多金属氧酸盐而合成的镤过氧簇合物A(PaO(O)F) [A = Rb、Cs、(CH)N]。密度泛函理论水平的量子化学计算表明，在镤的化学性质中5f和6d轨道参与程度相同，而对于较重的锕系元素，5f轨道的参与程度增加。早期锕系元素键合中轨道特征的周期性变化突出了5f轨道对其反应性和化学结构的影响。
