Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, China.
Phys Chem Chem Phys. 2018 Dec 12;20(48):30376-30383. doi: 10.1039/c8cp05725g.
Modification of properties of boron nanoparticles by doping with transition metals presents a challenging problem because the number of isomers of both doped and un-doped nanoparticles rapidly increases with the nanoparticle size. Here, we perform a study of neutral and anionic Ru-doped boron clusters RuBn (n = 9-20) using the unbiased CALYPSO structural search method in combination with density functional theory calculations. Our results show that the neutral RuB9 cluster possesses a perfect planar wheel-like geometrical structure, whereas the RuBn clusters prefer structures of the half-sandwich type in the range of 10 ≤ n ≤ 14, drum-like type in the range of 15 ≤ n ≤ 18 and cage-like structures for larger n values. The geometrical structures of the lowest total energy states of the RuBn- anions are similar to those of the corresponding neutrals, except for RuB10-, RuB11-, RuB14-, RuB15- and RuB20-. The neutral RuB12 and RuB14 clusters are found to exhibit enhanced stability with respect to the rest of the RuBn clusters due to the delocalized bonding between the Ru atom and the boron host.
通过掺杂过渡金属来改变硼纳米粒子的性质是一个具有挑战性的问题，因为掺杂和未掺杂纳米粒子的异构体数量随着纳米粒子尺寸的增加而迅速增加。在这里，我们使用无偏 CALYPSO 结构搜索方法结合密度泛函理论计算，对中性和阴离子 Ru 掺杂硼团簇 RuBn（n = 9-20）进行了研究。我们的结果表明，中性 RuB9 团簇具有完美的平面轮状几何结构，而 RuBn 团簇在 10≤n≤14 的范围内优先采用半三明治型结构，在 15≤n≤18 的范围内采用鼓状结构，对于较大的 n 值采用笼状结构。最低总能量状态的 RuBn-阴离子的几何结构与相应的中性体相似，除了 RuB10-、RuB11-、RuB14-、RuB15-和 RuB20-。由于 Ru 原子和硼主体之间的离域键合，中性 RuB12 和 RuB14 团簇被发现相对于其余的 RuBn 团簇具有增强的稳定性。
