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稀土掺杂硼团簇因其特殊的光学,电学和磁学性质受到广泛关注.本文采用人工蜂群算法结合密度泛函理论,在PBE0/RE/SDD//B/6-311+G *水平下研究了稀土掺杂阴离子硼团簇REB n -(RE=La,Sc;n=6,8)的几何结构,电子性质,稳定性和芳香性.计算结果表明,阴离子REB n -(RE=La,Sc;n=6)的基态结构具有C 2对称性,掺杂的镧系原子位于顶部中心形成“船形”结构.通过与实验光电子能谱的比较,证实LaB 8 -的基态结构类似于三维的“筝形”结构,而ScB 8 -的基态结构则是Sc原子位于“伞柄”处形成的具有C 7V对称性的“伞状”结构.B-B之间存在通过共享电子对的相互作用,而RE-B之间的电子定域性不如B-B之间的电子定域性.模拟得出的光电子能谱峰值位置与实验结果的吻合度较高,充分证实了研究获取的全局能量最低结构与实验观测结构的一致性.LaB 6 -和ScB 6 -的最低能量结构均为σ-π双芳香簇,表现出明显的芳香性.此外,分别计算了REB n -(RE=La,Sc;n=6,8)的总态密度,以及RE原子和硼簇的局部态密度,并对其轨道能级密度进行了评估.开壳层的ScB 8 -态密度谱呈现出自旋极化现象,这表明其作为基元可以组装成具有磁性的纳米材料.这些对稀土掺杂硼团簇的研究有助于深入理解纳米材料的结构和性质演变规律,为设计具有实际价值的纳米材料提供了重要的理论支持.Rare earth doped boron clusters have attracted much attention due to their special optical, electrical and magnetic properties. The geometric structure, stability, electronic properties and aromaticity of negative rare earth doped boron clusters REB n -(RE = La, Sc; n = 6, 8) are investigated with the artificial bee colony algorithm combined with density functional theory (DFT) calculations at the PBE0/RE/SDD//B/6-311+G *level of theory. Calculations show that the ground state structures of REB n -(RE = La, Sc; n = 6, 8) are all C 2symmetry, and the doped lanthanide atom is located in the “boat-shaped” structure with the top center. By comparing with the experimental photoelectron spectroscopy, it is confirmed that the ground state structure of LaB 8 -is a “zither-like” three-dimensional structure, and the ground state structure of ScB 8 -is an “umbrella” structure with C 7Vsymmetry formed by the scandium atom at the “umbrella handle”. The electron localization between RE-B is inferior to that between B-B. The simulated photoelectron spectra have similar spectral characteristics with the experimental results. The lowest energy structures of LaB 6 -and ScB 6 -are σ-π double aromatic clusters, and the structures exhibit aromaticity. The density of states of low-energy isomers shows that the open shell ScB 8 -density of states spectrum exhibits spin polarization phenomenon, which is expected to assemble magnetic material elements. These studies are helpful to understand the evolution of the structure and properties of nanomaterials and provide important theoretical support for the design of nanomaterials with practical value.
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Keywords:
- Density functional theory/
- Rare earth doped clusters/
- Structural optimization/
- Aromaticity
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