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Alkali metal‐doped boron clusters have captured much attention because of their novel electronic properties and structural evolution. In the study of RbBn0/− (n = 2–12) clusters, the minimum global search of the potential energy surface and structure optimization at the level of PBE1PBE by using the CALYPSO method and Gaussian package coupled with DFT calculation; the geometrical structures and electronic properties are systematically investigated. At n = 8, the ground‐state structures are composed of an Rb atom above B atoms, forming a structurally stable pagoda cone. By stability analysis and charge transfer calculation, the RbB8− cluster shows more stability. It found that s‐p hybridization between Rb atom and B atoms as well as s‐p hybridization between B atoms is one of the reasons for the outstanding stability exhibited in the RbB80/− clusters by using DOS and HOMO–LUMO orbital contour maps. The chemical bonding of the RbB80/− groups was analyzed by using the AdNDP method, and B atoms with larger numbers readily form multi‐center chemical bonds with the Rb atom. From the results of the bonding analysis, the interaction between the Rb atom and B atoms strengthens the stability of the RbB80/− clusters. It is hoped that this work provides a direction for experimental manipulation. [ABSTRACT FROM AUTHOR]

In this paper, the geometric structure and physicochemical properties of Li2Bn0/− (n = 1–12) clusters were investigated using CALYPSO structure prediction software in combination with density functional theory at B3LYP/6-311G level. The results suggest that the doping of Li atoms has a significant effect on the ground state geometry of the Bn clusters. The stability changes with the increase in the number of boron atoms. Then two stable ground state structures, Li2B8 and Li2B9−, are selected for further analyzing their molecular orbitals and bonding properties. It is demonstrated that the stability of the Li2Bn0/− (n = 1–12) clusters originates from the s–p hybridization between B–B and Li–B. It is expected that this work can provide some references for future research on boron-based nanomaterials. [ABSTRACT FROM AUTHOR]

• The evolution of the structures for Mg 2 Bn0/– (n = 1–12) clusters has be elucidated. • The corresponding ground state structures are determined. • The local stable ground state structure is found. • The properties of electrons and bonds of the most stable isomers are discussed. In this paper, a global search for the lowest energy structure of Mg 2 B n 0/- (n = 1–12) clusters is performed based on Density functional theory combined with the particle swarm optimization algorithm program CALYPSO. The geometry, stability, charge transfer, and bonding properties of the clusters were analyzed at the B3LYP/def2-tzvp level. Then Mg 2 B 8 with high symmetry D 4h was found to be the magic numbers cluster among them. The doped clusters Mg 2 B n 0/− were compared with the pure boron clusters B n+2 0/− (n = 1–12) at the same level. The following results are obtained: as the number of boron atoms increases, the boron clusters doped with Mg atoms change from a two-dimensional planar or quasi-plane structure to a three-dimensional structure. The doped magnesium atoms are always positively charged in the convex capped position. And the doping of Mg atoms drives the overall stabilization of the boron clusters and makes the clusters more compact. There is a large amount of charge transfer between the Mg atom and the B atom, and the main orbitals involved are the S and p orbitals. There are strong interactions between the two atoms of boron and magnesium. Through the analysis of the bonding properties, it was found that the s-p hybridization mode between Mg B is the main reason for the enhanced cluster stability. [Display omitted] [ABSTRACT FROM AUTHOR]

• The evolution of the structures for Ca 2 Mg n – (n=1-15) clusters has be elucidated. • The corresponding ground state structures are determined. • One of the most stable structural units are found. • The properties of electrons and bonds of the most stable isomers are discussed. In recent years, the structure and properties of alkaline earth metal-doped Mg clusters have attracted much attention. Here, we investigated the structural properties, stability analysis, chemical bonding properties and charge transfer properties of Ca 2 Mg n ˉ (n=1-15) nanoclusters by using the efficient CALYPSO structure search software and the DFT full domain search method based on B3PW91 level calculation. It is found that most of their ground state structures can inherit pure Mg n+2 ˉ (n=1-15) clusters with high symmetry. We further compare the experimental and theoretical PES spectral data using pure Mg n+2 ˉ (n=1-15) and find a high agreement, which also indicating the validity of my calculated all-domain most stable structure. We found the outstanding stability of the pentagonal Ca 2 Mg 7 ˉ by stability analysis. Charge transfer occurred in all Ca 2 Mg n ˉ clusters, and this transfer was from Ca to Mg. The chemical bonding properties and molecular orbital revealed that the contribution of Mg- s and Mg- p to the molecular orbitals led to the formation of strong Mg-Mg bonds in the Ca 2 Mg 7 ˉ cluster, the s-p hybridization between Ca and Mg atoms and between Mg and Mg atoms also led to more powerful Mg-Mg bonds and Ca-Mg bonds, which is strong evidence for the stability of the Ca 2 Mg 7 ˉ clusters. [ABSTRACT FROM AUTHOR]