Xiang Zhiyang, Luo Zhongjie, Bi Jie, Jin Siyu, Zhang Ziqiang, Lu Cheng
School of Mathematics and Physics, China University of Geosciences (Wuhan), Wuhan 430074, People's Republic of China.
Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, People's Republic of China.
J Phys Condens Matter. 2022 Sep 5;34(44). doi: 10.1088/1361-648X/ac8b4f.
Cluster is the intermediate of individual atom and larger agglomeration. The structural evolutions of clusters are critically important to explore the physical properties of bulk solids. Here, we carry out systematic structure predictions of medium-sized vanadium-doped boron clusters by using crystal structure analysis by particle swarm optimization method combined with density function theory calculations. A great deal of low-lying isomers with attractive geometries are discovered, such as the crown-like VBcluster and the drum-like VBcluster. Interestingly, the VBcluster possesses excellently relative stability due to its higher second-order difference and larger highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gap. The molecular orbitals (MOs) and adaptive natural density partitioning (AdNDP) analysis indicate that the 3orbitals of V atom and the 2and 2orbitals of B atoms are the primary constituents of the MOs, and the interactions between V and B atoms are the main factor for the robust stabilization of the anionic VBcluster. The present findings advance the understanding of the structural evolution of transition metal doped boron clusters and offer crucial insights for future experiments.
团簇是单个原子与较大聚集体之间的中间体。团簇的结构演化对于探索块状固体的物理性质至关重要。在此，我们采用粒子群优化方法结合密度泛函理论计算的晶体结构分析，对中等尺寸的钒掺杂硼团簇进行了系统的结构预测。发现了大量具有吸引人几何形状的低能异构体，如冠状VB团簇和鼓状VB团簇。有趣的是，VB团簇由于其较高的二阶差分和较大的最高占据分子轨道（HOMO）-最低未占据分子轨道（LUMO）能隙而具有出色的相对稳定性。分子轨道（MOs）和自适应自然密度分区（AdNDP）分析表明，V原子的3个轨道以及B原子的2个和2个轨道是MOs的主要组成部分，V和B原子之间的相互作用是阴离子VB团簇稳定存在的主要因素。本研究结果推进了对过渡金属掺杂硼团簇结构演化的理解，并为未来的实验提供了关键见解。
