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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]

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]