碱金属掺杂B180/- 团簇结构和特性研究
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作者单位:

1.郑州财经学院 智能工程学院,郑州 450045;2.郑州师范学院 物理与电子工程学院,郑州 450041;3.郑州大学 化工学院,郑州 450001

作者简介:

翟会丽(1978—),女,副教授,主要从事工程材料、智能制造研究,(E-mail)zhaihuili0304@163.com。

通讯作者:

李成刚,男,副教授,(E-mail)zznu_lcg@163.com。

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基金项目:

国家自然科学基金资助项目(11904328,12104416);河南省高等学校重点科研项目计划(21A460023);郑州师范学院本科教学改革研究项目(JXGG-20773)。


Study on structures and properties of alkali metals doped B180/- clusters
Author:
Affiliation:

1.School of Intelligent Engineering, Zhengzhou College of Finance and Economics, Zhengzhou450045, P. R. China;2.School of Physics and Electronic Engineering, Zhengzhou Normal University, Zhengzhou450044, P. R. China;3.School of Chemical Engineering, Zhengzhou University, Zhengzhou450001, P. R. China

Fund Project:

Supported by National Natural Science Foundation of China (11904328, and 12104416), the Key Scientific Research Project Plan of Henan Provincial Higher Education Institutions (21A460023), and the Undergraduate Teaching Reform Research Project of Zhengzhou Normal University (JXGG-20773).

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    摘要:

    硼基纳米材料因其独特分子结构和化学键成为团簇科学研究的重点。基于卡利普索结构预测程序和密度泛函理论,在PBE0/6-311+G(d)水平下系统分析了碱金属M2(M=Li, Na, K)原子掺杂B180/-团簇的结构和特性。结构搜索发现,所有全局极小结构均呈现管状结构。除Li2B18(C1点群对称)外,其他高对称结构(D9d点群对称)中2个掺杂碱金属原子均位居管两侧的对称轴线上。基于全局极小结构的稳定性分析表明,K2B18和Li2B18-团簇在各自体系中拥有相对高的稳定性。电荷研究发现,掺杂体系中电荷从碱金属M原子向硼原子转移。磁性分析表明,闭壳层电子结构体系(Li2B18、Na2B18和K2B18)总磁矩为0,开壳层电子结构体系(Li2B18-、Na2B18-和K2B18-)分别拥有1 μB的总磁矩。分析偶极矩和极化率发现,高对称性结构对应的偶极矩和第一超极化率为0。此外,基于Multiwfn软件,拟合出了体系的光电子能谱、红外谱和拉曼谱。最后,讨论了体系的温度和热力学参数(定容热容Cv和标准熵S)之间的关系。

    Abstract:

    Boron-based nanomaterials have attracted significant attention in cluster science due to their unique molecular structures and chemical bonding. In this study, we systematically investigated the structures and properties of M2 (M=Li, Na, K) doped B0/ ?18 clusters at the PBE0/6-311+G(d) level using the CALYPSO structure prediction program combined with density functional theory. Structure predictions found that all doped systems exhibit tubular configurations. Except for Li2B18, which has C1 point group symmetry, the global minimum structures of the other clusters adopt a D9d point group symmetry tubular shape, with the two M atoms localized along the axis of the tubular structure. Stability analyses indicated that K2B18 and Li2B?18clusters exhibit relatively strong stability in the neutral and anionic series, respectively. Charge transfer analysis revealed that electrons are transferred from the M atoms to the base boron fragment. Magnetic properties analysis indicated that the total magnetic moment is zero for the closed-shell structures of Li2B18, Na2B18 and K2B18 clusters. However, the open-shell structures of Li2B?18, Na2B?18 and K2B?18 clusters exhibit magnetic moments of 1 μB. Dipole moment and polarizability analyses showed that both the dipole moment and the first hyperpolarizability are zero for the highly symmetrical structures. Additionally, simulated photoelectron spectra, IR spectra and Raman spectra, generated using Multiwfn software, provide a theoretical basis for further experiments. At last, the relationships between thermodynamic parameters (Cv and S) and temperature were discussed.

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翟会丽,马光辉,李成刚.碱金属掺杂B180/- 团簇结构和特性研究[J].重庆大学学报,2024,47(11):120-130.

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  • 收稿日期:2023-03-14
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  • 在线发布日期: 2024-12-05
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