基于卡里普索结构预测方法和密度泛函理论,研究了Ni原子掺杂 B20-团簇的结构、电子和光谱特性。首先在PBE0/6-311+G(d)标准下优化得到了 B20-和Ni B20-团簇的基态结构, B20-的基态结构同实验结果符合得很好,Ni B20-的基态为一个Ni原子被两个B10环包裹在中间的管状结构;然后基于该基态结构分析了团簇的自然布局分布和自然电子组态、分子轨道等电子特性。结果表明,电荷从Ni原子向B原子转移,Ni和B原子之间存在强烈的spd轨道杂化。最后利用Multiwfn程序拟合出了团簇的光电子能谱、红外和拉曼光谱,并分析了主要特征峰的归属,希望为Ni原子掺杂硼纳米材料的制备和表征提供重要参考。

In this study, we employed the CALYPSO structure searching method and density functional theory to systematically investigate the structural, electronic and spectral properties of a Ni-doped B20- cluster. The lowest energy structures of B20- and Ni B20- were obtained with the PBE0/6-311+G(d) level. The obtained structure of B20- is consistent with previous experimental and theoretical research reports. The Ni B20- cluster is composed of a nickel atom sandwiched by two B₁₀ monocyclic rings. Furthermore, the natural population analysis, the natural electron configuration and molecular orbitals were studied based on the lowest energy structures. The results show that charges are transferred from Ni to B atoms and strong spd hybridization occurs in the Ni and B atoms. Finally, we simulated the photoelectron spectroscopy, IR, and Raman spectra, and assigned the main vibrational peaks for further experimental investigation. This research presents a powerful reference for future experimental synthesis and characterization of nickel-doped boron-based nanomaterials.