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Rare earth doped boron clusters have attracted much attention due to their special optical, electrical and magnetic properties. The geometric structures, stability, electronic properties and aromaticity of negative rare earth doped boron clusters
$ {\text{REB}}_n^ - $ (RE = La, Sc; n = 6, 8) are investigated with the artificial bee colony algorithm combined with density functional theory calculations at the PBE0/RE/SDD//B/6-311+G* level of theory. Calculations show that the ground state structures of$ {\text{REB}}_n^ - $ (RE = La, Sc; n = 6, 8) are all of C2 symmetry, and the doped lanthanide atom is located in a “boat-shaped” structure at the top center. By comparing with the experimental photoelectron spectra, it is confirmed that the ground state structure of$ {\text{LaB}}_{8}^ - $ is a “zither-like” three-dimensional structure, and the ground state structure of$ {\text{ScB}}_{8}^ - $ is an “umbrella” structure with C7V symmetry formed by the scandium atom at the “umbrella handle”. The electron localization between RE-B is not as good as that between B—B. The simulated photoelectron spectra have similar spectral characteristics to the experimental results. The lowest energy structures of$ {\text{LaB}}_{6}^ - $ and$ {\text{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$ {\text{ScB}}_{8}^ - $ density of states spectrum exhibits spin polarization phenomenon, which is expected to assemble magnetic material components. These studies contribute to understanding the evolution of structure and properties of nanomaterials, and provide important theoretical support for designing nanomaterials with practical value.
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Keywords:
- density functional theory /
- rare earth doped clusters /
- structural optimization /
- aromaticity
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图 1 在PBE0/RE/SDD//B/6-311+G*理论水平下, $ {\text{REB}}_n^ - $ (RE = La, Sc; n = 6, 8) 团簇低能异构体的结构、点群对称性、相对能
Figure 1. Structures, symmetry point group and relative energy (eV) of the lower-lying isomers for $ {\text{REB}}_n^ - $ (RE = La, Sc; n = 6, 8) clusters at the PBE0/RE/SDD//B/6-311+G* level of theory.
图 2 $ {\text{REB}}_n^ - $ (RE = La, Sc; n = 6, 8)团簇低能异构体的定域化轨道指示函数等值面图
Figure 2. $ {\text{REB}}_n^ - $ (RE = La, Sc; n = 6, 8) isosurface of localized orbital locator function of low energy isomers.
图 3 $ {\text{REB}}_n^ - $ (RE = La, Sc; n = 6, 8)团簇低能异构体的模拟光电子能谱图, $ {\text{LaB}}_{8}^ - $的实验光电子能谱来自于文献[32], 共同绘制在$ {\text{LaB}}_{8}^ - $-Ⅰ处用红色曲线表示
Figure 3. Simulated PES spectra for low-lying isomers of $ {\text{REB}}_n^ - $ (RE = La, Sc; n = 6, 8) clusters, the experimental PES spectra of the anionic ground state structure of $ {\text{LaB}}_{8}^ - $ was obtained from Ref. [32].
图 4 $ {\text{LaB}}_{6}^ - $的芳香性分析图
Figure 4. Adaptive natural density partitioning (AdNDP) bonding analyses of $ {\text{LaB}}_{6}^ - $.
图 5 $ {\text{ScB}}_{6}^ - $-Ⅰ的芳香性分析轨道图
Figure 5. Adaptive natural density partitioning (AdNDP) bonding analyses of $ {\text{ScB}}_{6}^ - $-Ⅰ.
图 6 $ {\text{ScB}}_{6}^ - $-Ⅲ的芳香性分析图
Figure 6. Adaptive natural density partitioning (AdNDP) bonding analyses of $ {\text{ScB}}_{6}^ - $-Ⅲ.
图 7 0.60 eV的半峰展宽下$ {\text{REB}}_n^ - $ (RE = La, Sc; n = 6, 8) 能量最低结构的总态密度图与局部态密度图
Figure 7. Total density of states (TDOS) and partial density of states (PDOS) plot of the lowest energy structures of $ {\text{REB}}_n^ - $ (RE = La, Sc; n = 6, 8) with a full width at half-maximum (FWHM) of 0.60 eV.
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