Wang Juan, Wang Cong-Zhi, Wu Qun-Yan, Lan Jian-Hui, Chai Zhi-Fang, Nie Chang-Ming, Shi Wei-Qun
School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China.
Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China.
J Phys Chem A. 2022 Jun 9;126(22):3445-3451. doi: 10.1021/acs.jpca.2c00563. Epub 2022 May 25.
Metal doping has been considered to be an effective approach to stabilize various boron clusters. In this work, we constructed a series of largest metal-centered double-ring tubular boron clusters An@B (An = Th, Pa, Pu, and Am). Extensive global minimum structural searches combined with density functional theory predicted that the global minima of An@B (An = Th, Pu, and Am) are double-ring tubular structures. Formation energy analysis indicates that these boron clusters are highly stable, especially for Th@B and Pa@B. Detailed bonding analysis shows that the significant stability of An@B is determined by the covalent character of the An-B bonding, which stems from the interactions of An 5f and 6d orbitals and B 2p orbitals. These results show that actinide metal doping is a feasible route to construct stable large metal-centered double-ring tubular boron clusters, offering the possibility to design boron nanomaterials with special physiochemical properties.
金属掺杂被认为是稳定各种硼簇的有效方法。在这项工作中，我们构建了一系列以最大金属为中心的双环管状硼簇An@B（An = 钍、镤、钚和镅）。结合密度泛函理论的广泛全局极小值结构搜索预测，An@B（An = 钍、钚和镅）的全局极小值是双环管状结构。形成能分析表明，这些硼簇非常稳定，特别是对于Th@B和Pa@B。详细的键合分析表明，An@B的显著稳定性由An-B键的共价特性决定，这源于An 5f和6d轨道与B 2p轨道的相互作用。这些结果表明，锕系金属掺杂是构建稳定的以大金属为中心的双环管状硼簇的可行途径，为设计具有特殊物理化学性质的硼纳米材料提供了可能性。
