ADF Highlight:能量简并驱动锕系共价成键(JACS, 2018)

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文献资料:Jing Su, Enrique R. Batista, Kevin S. Boland, Sharon E. Bone, Joseph A. Bradley, Samantha K. Cary, David L. Clark, Steven D. Conradson, Alex S. Ditter, Nikolas Kaltsoyannis, Jason M. Keith, Andrew Kerridge, Stosh A. Kozimor, Matthias W. Löble, Richard L. Martin, Stefan G. Minasian, Veronika Mocko, Henry S. La Pierre, Gerald T. Seidler, David K. Shuh, Marianne P. Wilkerson , Laura E. Wolfsberg, and Ping Yang, Energy-Degeneracy-Driven Covalency in Actinide Bonding,  J. Am. Chem. Soc.2018140 (51), pp 17977–17984

锕系元素化学键的性质,是当今锕系科学上最重要、最长期的问题之一。作者直面这一挑战性问题,并进行了Cl K-边X射线吸收光谱和相对论密度泛函理论的研究,定量地评判了AnCl62-(AnIV=Th,U,NP,Pu)中的An-Cl共价性。结果表明,Cl 3p-与AnIV 5f-和6d-轨道(t1u*/t2u*和t2g*eg*)之间存在显著混合,6d轨道的共价性成键比5f轨道更明显。从Th到U,Np和Pu,M-Cl轨道混合量显著变化:AnIV 6d-和Cl 3p-混合减少,金属5f-和Cl 3p轨道混合增加。

 
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