Li Shi-Xiong, Yang Yue-Ju, Chen De-Liang, Long Zheng-Wen
School of Physics and Electronic Science, Guizhou Education University Guiyang 550018 Guizhou People's Republic of China
College of Physics, Guizhou University Guiyang 550025 Guizhou People's Republic of China.
RSC Adv. 2022 Jun 6;12(26):16706-16716. doi: 10.1039/d2ra02500k. eCollection 2022 Jun 1.
A theoretical study of geometrical structures, electronic properties, and spectral properties of single-atom transition metal-doped boron clusters MB (M = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) is performed using the CALYPSO approach for the global minimum search, followed by density functional theory calculations. The global minima obtained for the MB (M = Sc, Ti, V, and Cr) clusters correspond to cage structures, and the MB (M = Mn, Fe, and Co) clusters have similar distorted four-ring tubes with six boron atoms each. Interestingly, the global minima obtained for the NiB cluster tend to a quasi-planar structure. Charge population analyses and valence electron density analyses reveal that almost one electron on the transition-metal atoms transfers to the boron atoms. The electron localization function (ELF) of MB (M = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) indicates that the local delocalization of MB (M = Sc, Ti, V, Cr, and Ni) is weaker than that of MB (M = Mn, Fe, and Co), and there is no obvious covalent bond between doped metal and B atoms. The spin density and spin population analyses reveal that open-shell MB (M = Ti, Cr, Fe, and Ni) has different spin characteristics which are expected to lead to interesting magnetic properties and potential applications in molecular devices. The polarizability of MB (M = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) shows that MB (M = Mn, Fe, and Co) has larger first hyperpolarizability, indicating that MB (M = Mn, Fe, and Co) has a strong nonlinear optical response. Hence, MB (M = Mn, Fe, and Co) might be considered as a promising nonlinear optical boron-based nanomaterial. The calculated spectra indicate that MB (M = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) has different and meaningful characteristic peaks that can be compared with future experimental values and provide a theoretical basis for the identification and confirmation of these single-atom transition metal-doped boron clusters. Our work enriches the database of geometrical structures of doped boron clusters and can provide an insight into new doped boron clusters.
采用CALYPSO方法进行全局最小值搜索，随后进行密度泛函理论计算，对单原子过渡金属掺杂硼簇MB （M = Sc、Ti、V、Cr、Mn、Fe、Co和Ni）的几何结构、电子性质和光谱性质进行了理论研究。对于MB （M = Sc、Ti、V和Cr）簇获得的全局最小值对应于笼状结构，而MB （M = Mn、Fe和Co）簇具有类似的扭曲四环管，每个管中有六个硼原子。有趣的是，对于NiB 簇获得的全局最小值趋向于准平面结构。电荷布居分析和价电子密度分析表明，过渡金属原子上几乎有一个电子转移到硼原子上。MB （M = Sc、Ti、V、Cr、Mn、Fe、Co和Ni）的电子定域函数（ELF）表明，MB （M = Sc、Ti、V、Cr和Ni）的局域离域比MB （M = Mn、Fe和Co）弱，并且掺杂金属与B原子之间没有明显的共价键。自旋密度和自旋布居分析表明，开壳层MB （M = Ti、Cr、Fe和Ni）具有不同的自旋特征，预计会导致有趣的磁性以及在分子器件中的潜在应用。MB （M = Sc、Ti、V、Cr、Mn、Fe、Co和Ni）的极化率表明，MB （M = Mn、Fe和Co）具有较大的第一超极化率，表明MB （M = Mn、Fe和Co）具有强烈的非线性光学响应。因此，MB （M = Mn、Fe和Co）可能被认为是一种有前途的基于硼的非线性光学纳米材料。计算得到的光谱表明，MB （M = Sc、Ti、V、Cr、Mn、Fe、Co和Ni）具有不同且有意义的特征峰，可与未来的实验值进行比较，并为这些单原子过渡金属掺杂硼簇的鉴定和确认提供理论依据。我们的工作丰富了掺杂硼簇几何结构的数据库，并能为新型掺杂硼簇提供深入了解。
