The global minimal structures of terbium‐doped Si clusters and their anions TbSi _n^0/− (n = 6‐18) are confirmed by employing the ABCluster unbiased global search technique combined with a B2PLYP double‐hybrid density functional and comparing consistency of simulated and experimental photoelectron spectroscopy (PES). The results demonstrated that structural evolution patterns for neutral clusters prefer Tb‐substitutional to Tb‐encapsulated configuration starting from n = 16. While for the corresponding anionic clusters, the growth pattern adopts Tb‐linked structures to encapsulated motif. The Natural Population Analysis revealed that the 4f electrons of Tb atom in TbSi _n^0/− (n = 6‐18) clusters participate in bonding. The way to participate in bonding is one 4f electron transition to 5d orbital ([Xe]6s²4f⁹ → [Xe]6s²4f⁸5d¹), which significantly affects the cluster's magnetism and appearance of PES. The total magnetic moments of neutral TbSi _n and the corresponding anions maintain at 7 μB and 6 μB, respectively, which are larger than that of an isolated Tb atom. The HOMO‐LUMO energy gap, relative stability, and chemical bonding analysis demonstrated that superatomic TbSi₁₆⁻ cluster is a magic cluster with fine thermodynamic and moderate chemical stability.

中文翻译：

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b掺杂硅团簇的结构稳定性和演化以及4f→5d电子跃迁机制对TbSin0 /-（n = 6-18）团簇的磁性和光电子能谱的影响

employing掺杂硅团簇及其阴离子TbSi _n ^{0 /-}（n = 6-18）的全局最小结构是通过采用ABCluster无偏全局搜索技术结合B2PLYP双杂化密度函数并比较模拟和模拟的一致性来确定的实验光电子能谱（PES）。结果表明，从n = 16开始，中性簇的结构演化模式更倾向于用Tb取代而不是Tb封装。而对于相应的阴离子簇，其生长模式采用Tb连接的结构来封装主题。自然种群分析表明，4个˚F在TBSI铽原子的电子_ñ ^{0 / -} （ n = 6-18）集群参与绑定。参与键合的方式是一个4 f电子跃迁到5 d轨道（[Xe] 6 s ² 4 f ⁹  →[Xe] 6 s ² 4 f ⁸ 5 d ¹），这显着影响了团簇的磁性和PES。中性TbSi _n和相应阴离子的总磁矩分别保持在7μB和6μB ，这比孤立的Tb原子的总磁矩大。的HOMO-LUMO能隙，相对稳定性，和化学粘合分析表明，superatomic TBSI ₁₆ ^- 团簇是具有良好的热力学和中等化学稳定性的魔术团簇。