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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REBn-(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REBn-(RE=La,Sc;n=6)的基态结构具有C2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LaB8-的基态结构类似于三维的“筝形”结构,而ScB8-的基态结构则是Sc原子位于“伞柄”处形成的具有C7V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.LaB6-和ScB6-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REBn-(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ScB8-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 REBn- (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 REBn- (RE = La, Sc; n = 6, 8) are all C2 symmetry, 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 LaB8- is a “zither-like” three-dimensional structure, and the ground state structure of ScB8- is an “umbrella” structure with C7V symmetry 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 LaB6- and ScB6- are σ-π double aromatic clusters, and the structures exhibit aromaticity. The density of states of low-energy isomers shows that the open shell ScB8- 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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[1] Zhang C J, Xu H G, Xu X L, Zheng W J 2021 Acta Phys. Sin. 70 023601 (in Chinese) [张超江, 许洪光, 徐西玲, 郑卫军 2021 物理学报 70 023601]
[2] Boustani I 1997 Phys. Rev. B 5 16426-16438
[3] Kiran B, Bulusu S, Zhai H J, Yoo S, Zeng X C, Wang L S 2005 Proc. Natl. Acad. Sci. 102 961-964
[4] Li S X, Zhang Z P, Long Z W, Qin S J 2017 Acta Phys. Sin. 6 103102 (in Chinese) [李世雄, 张正平, 隆正文, 秦水介 2017 物理学报 66 103102]
[5] Sergeeva A P, Popov I A, Piazza Z A, Li W L, Romanescu C, Wang L S, Boldyrev A I 2014 Acc. Chem. Res. 47 1349-1358
[6] Jian T, Chen X, Li S D, Boldyrev A I, Li J, Wang L S 2019 Chem. Soc. Rev. 48 3550-3591
[7] Wang L S 2016 Int. Rev. Phys. Chem. 35 69-142
[8] Bai H, Chen T T, Chen Q, Zhao X Y, Zhang Y Y, Chen W J, Li W L, Cheng L F, Bai B, Cavanagh J, Huang W, Li S D, Li J, Wang L S 2019 Nanoscale. 11 23286-23295
[9] Liu L R, Lei X L, Chen H, Zhu H J 2009 Acta Phys. Sin. 58 355-5361 (in Chinese) [刘立仁, 雷雪玲, 陈杭, 祝恒江 2009 物理学报 58 5355-5361]
[10] Pham H T, Duong L V, Pham B Q, Nguyen M T 2013 Chem. Phys. Lett. 577 32-37
[11] Zhai H J, Alexandrova A N, Birch K A, Boldyrev A I, Wang L S 2003 Angew. Chem. Int. Ed. 42 6004-6008
[12] Zhai H J, Zhao Y F, Li W L, Chen Q, Bai H, Hu H S, Piazza Z A, Tian W J, Lu H G, Wu Y B, Mu Y W, Wei G F, Liu Z P, Li J, Li S D, Wang L S 2014 Nature Chem. 6 727
[13] Islas R, Heine T, Ito K, Schleyer P V, Merino G 2007 J. Am. Chem. Soc. 129 14767-14774
[14] Romanescu C, Galeev T R, Li W L, Boldyrev A I, Wang L S 2013 Acc. Chem. Res. 46 350-358
[15] Saha R, Kar S, Pan S, Martínez-Guajardo G, Merino G, Chattaraj P K 2017 J. Phys. Chem. A 121 2971-2979
[16] Li S X, Chen D L, Zhang Z P, Long Z W 2020 Acta Phys. Sin. 69 193101 (in Chinese) [李世雄, 陈德良, 张正平, 隆正文 2020 物理学报 69 193101]
[17] Li H F, Wang H Q, Zhang J M, Qin L X, Zheng H, Zhang Y H 2024 Molecules 29 1692
[18] Jiang X M, Wang H Q, Cao Y, Sun Z H, Cao Y F, Wu W B 2018 Chemical Journal of Chinese Universities 39 1976-1984 (in Chinese) [蒋贤明, 王怀谦, 曹宇, 孙之惠, 曹玉芳, 吴伟宾 2018 高等学校化学学报 39 1976-1984]
[19] Zheng H, Wang H Q, Li H F, Zhang J M, Zhang Y H, Qin L X, Mei X J, Jiang K L, Zeng J K, Zhang B, Wu W H 2024 Chem.Phys. 583 112321
[20] Wen S H, Zhou J J, Zheng K Z, Bednarkiewicz A, Liu X G, Jin D Y 2018 Nat. Commun. 9 2415
[21] Jiang L Y, Wang H Q, Li H F, Xie B, Zhang J M, Ji J Y 2023 Chem. Phys. 567 111819
[22] Wang H Q, Li H F 2014 RSC advances 4 29782-29793
[23] Yi Z G, Luo Z C, Qin X, Chen Q S, Liu X G 2020 Acc. Chem. Res. 53 2692
[24] Qin L X, Li H F, Xiao B W, Zhang J M, Zeng J K, Mei X J, Zhang Y H, Zheng H, Wang H Q 2023 Chem.Phys. 575 112064
[25] Li W L, Chen T T, Xing D H, Chen X, Li J, Wang L S 2018 Proc. Natl Acad. Sci. 115 E6972-E6977
[26] Robinson P. J, Zhang X X, McQueen T, Bowen K H, Alexandrova A N 2017 J. Phys. Chem. A 121 1849-1854
[27] Chen T T, Li W L, Li J, Wang L S 2019 Chem. Sci. 10 2534-2542
[28] Zuo J N, Zhang L L, Chen B L, He K H, Dai W, Ding K W, Lu C 2024 J. Phys.: Condens. Matter 36 015302
[29] Xiang Z Y, Luo Z J, Bi J, Jin S Y, Zhang Z Q, Lu C 2022 J. Phys.: Condens. Matter 34 445302
[30] Jin S Y, Sun W G, Chen B L, Kuang X Y, Lu H Y, Lu C 2021 J. Phys. Chem. A 125 4126-4132
[31] Lu C, Gong W, Li Q, Chen C 2020 J. Phys. Chem. Lett. 11 9165-9170
[32] Li W L, Chen T T, Chen W J, Li J, Wang L S, 2021 Nat. Commun. 12 6467
[33] Zhang J, Dolg M 2015 Phys. Chem. Chem. Phys. 17 24173-24181
[34] Frisch M J, Trucks G W, Schlegel H B, et al. 2016 Gaussian 09 (Revision Ed. 01) (Wallingford, CT: Gaussian, Inc.)
[35] Lu T, Chen F W 2012 J. Comput. Chem. 33 580-592
[36] Humphrey W, Dalke A, Schulten K 1996 J. Mol. Graph. 14 33-38
[37] Dolg M, Stoll H, Savin A, Preuss H 1989 Theor. Chim. Acta. 75 173-194
[38] Peterson A, Kirk F, Detlev G, Erich S H, Michael D 2003 J. Chem.Phys. 119 11113-11123
[39] Binkley, Stephen J, Pople, John A, Hehre, Warren J 1980 J. Am. Chem. Soc 102 939-947
[40] Adamo C, Barone V 1999 J. Chem. Phys. 110 6158-6170
[41] Wadt W R, Hay P J 1985 J. Chem. Phys. 82 284-298
[42] Krishnan R, Binkley J S, Seeger R, Pople J A 1980 J. Chem. Phys. 72 650-654
[43] Tozer D J, Handy N C 1998 J. Chem. Phys. 109 10180
[44] Alexandrova A N, Boldyrev A I, Zhai H J, Wang L S, Steiner E, Fowler P W 2003 J. Phys. Chem. A 107 1362
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