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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, we used CALYPSO program which is conjuncted with DFT to investigate Li doped small-sized neutral Bn clusters. From ground-state and low energy structures, the properties and geometric significance of Li-doped boron clusters are greatly affected. Except for LiB9, which adds a B atom on preceding LiB8 boron wheel, the ground-state clusters of LiBn are formed by replacing the terminal boron atom of the Bn+1 clusters in the same size with a Li atom or by adding a Li atom to the Bn clusters. The transition point from 2 to 3D configuration of LiBn clusters appears at n = 5. The stability of LiBn clusters was analyzed by calculating the average binding energy, Gibbs free energy, first-order differential energy, second-order differential energy, HOMO–LUMO gap (the energy gap between the highest occupied and lowest unoccupied molecular orbital) and charge transfer. The results show that the LiB11 cluster with excellent symmetry and planar structure is the relative most stable structure. Molecular orbital and chemical bonding analysis indicated that the main reason for the stability of the LiB11 cluster is mainly due to the strong s-p bonding of B–B. [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]

In this study, the unbiased crystal structure analysis by particle swarm optimisation (CALYPSO) combined with the density functional theory (DFT) method were used to perform a structure search for neutral Cs2Bn (n = 1–12) clusters, as well as the corresponding global minimum of the potential energy surface were determined. The ground-state structures of the Cs2Bn (n = 1–12) clusters have four types of geometries: planar, arch bridge, double pyramid, and shield shape. Subsequently, the relative stability of the ground-state structures was systematically analysed based on three effective rules, which indicates that the C7V Cs2B8 with a double pyramid structure has unusual stability. The results of the molecular orbitals (MOs) and density of states analysis (DOS) show that the B-2s and 2p atomic orbitals of Cs2B8 are the main components of MOs. In addition, from the results of adaptive natural density partitioning (AdNDP) and localised orbital locator (LOL), it can be seen that the excellent stability of Cs2B8 originates from the delocalised large π bonds with aromaticity and the s–p bonding of B–B. Our results reveal the structural growth mode of Cs2Bn clusters and enrich the chemical bonding properties of boron-based clusters. [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]

To understand the effects of Cs on pure boron clusters, the growth mode, electronic properties, and bonding characteristics of CsB n 0/− (n = 2–12) clusters were discussed by CALYPSO combined with DFT method. Photoelectron spectra of the ground-state structures are reliable and efficient based on the accurate structure search method, which can provide theoretical information for future related studies. Through the study of the three valid criteria, we conclude that the CsB 8 and CsB 8 − with point group symmetry C 7V have outstanding stability and electronic properties. The orbital composition analysis indicates that the molecular orbitals of these two clusters are mainly composed of B-2 s and B-2 p atomic orbitals (AOs), and there is a strong interaction between these two AOs. Furthermore, we also found that the high stability of CsB 8 and CsB 8 − clusters mainly originates from the s - p bonding, σ and π bonds of B–B, especially the CsB 8 − cluster has (σ+π) double aromaticity. • The evolution of the structures for CsB n (n = 2-12) clusters has be elucidated. • The corresponding ground state structures are determined. • It is found that the most stable isomer is a double pyramid structure with double aromaticity. • The molecular orbitals and bonding characteristics of the most stable structure are discussed by various methods. [ABSTRACT FROM AUTHOR]

[Display omitted] • The evolution of the structures for Ba 2 Mg n (n = 1–10) clusters has be elucidated. • The corresponding ground state structures are determined. • A pagoda-like most-stable structure are found. • The properties of electrons and bonds of the most stable isomers are discussed. This paper reports systematic studies of small sized magnesium clusters doped with two barium atoms in both neutral and anionic species. The search, geometric optimization, and energy correction of stable and low-energy structures were completed using CALYPSO software package and DFT calculations. The structural evolution of Ba 2 Mg n 0/– clusters (n = 1–10) with increasing size were elucidated, and we found that most of the ground-state isomers of them inherit that of the corresponding pure Mg clusters well in terms of structure. After verifying the NBO (natural bond orbital) charge of the low-lying Ba 2 Mg n 0/– clusters (n = 1–10), a new fact was exposed: that all the doped Ba atoms in the structures are positively charged except in Ba 2 Mg–. A pagoda-like most-stable cluster Ba 2 Mg 8 with a HOMO-LUMO gap of 1.59 eV was found by relative stability analysis within the scope of our study. Further analyses of the molecular orbitals and bonding of Ba 2 Mg 8 clusters also revealed a strong interaction between Ba-6 s and Mg-3 p AOs, which may be the main reason for the high stability of Ba 2 Mg 8. We hope our studies will provide guidance for the synthesis and application of doped Mg-based nanomaterials in the future. [ABSTRACT FROM AUTHOR]

[Display omitted] • The evolution of the structures for Sr 2 Mg n (n =1–12) clusters has be elucidated. • The corresponding ground state structures are determined. • Several stable structural units are found. • The properties of electrons and bonds of the most stable isomers are discussed. Alkali earth metal clusters have been the subject of intense interest due to the wide range of applications and unique characteristics of transition from nonmetallic to metallic bond. In this work, the structural evolution and electronic properties of neutral and anionic strontium-doped magnesium clusters have been studied by structural search code of CALYPSO and subsequent calculation of DFT at B3PW91 level. The results reveled that most of the Sr 2 Mg n 0/– clusters are viewed as the substituted structures of corresponding pure magnesium clusters, in which the Sr atoms prefer to occupy the convex capped sites. Analysis of the natural population show that the Sr atoms always play the role of electron donor in the charge transfer process except for Sr 2 Mg 1-3 –. In the range of studied size, the neutral Sr 2 Mg 8 cluster with a tower-like structure and outstanding stability is uncovered. The molecular orbital and chemical bonding analysis indicate that the stronger Sr-Mg interaction lead to s-p hybridization between Sr and Mg atoms can stabilize the Sr 2 Mg 8 cluster. [ABSTRACT FROM AUTHOR]