Probing the Structural Evolution, Stabilities and Properties of LiBn (n = 2–12) Clusters.

In this paper, we used CALYPSO program which is conjuncted with DFT to investigate Li doped small-sized neutral B_n 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 LiB_n are formed by replacing the terminal boron atom of the B_n+1 clusters in the same size with a Li atom or by adding a Li atom to the B_n clusters. The transition point from 2 to 3D configuration of LiB_n clusters appears at n = 5. The stability of LiB_n 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]