LiB13: A New Member of Tetrahedral-Typed B13 Ligand Half-Surround Cluster

Hongxiao Shi,Cheng Lu,Xiaoyu Kuang

doi:10.1038/s41598-020-57769-2

Abstract

It will get entirely unusual derivatives with gratifying chemical bonding schemes for boron clusters by doping with lithium, the lightest alkalis. The geometric structures and electronic properties of the LiBn0/− (n = 10−20) clusters have been studied through Crystal structure AnaLYsis by Particle Swarm Optimization (CALYPSO) structural search approach along with the density functional theory (DFT) calculations. The low-lying candidates of LiBn0/− (n = 10–20) are reoptimized at the B3LYP functional in conjunction with 6–311 + G(d) basis set. Three forms of geometric configurations are identified for the ground-state structures of LiBn0/− clusters: half-sandwich-type, quasi-planar and drum-type structures. The photoelectron spectra (PES) of the LiBn− clusters have been calculated through time-dependent density functional theory (TD-DFT). A promising LiB13 with tetrahedral-typed B13 ligand half-surround cluster and robust stability is uncovered. The molecular orbital and adaptive natural density partitioning (AdNDP) analysis show that B-B bonds in the B13 moiety combined with the interaction between the B13 shell and Li atom stabilize the C2v LiB13 cluster. Our results advance the fundamental understanding about the alkali metal doped boron clusters.

Highlights

It will get entirely unusual derivatives with gratifying chemical bonding schemes for boron clusters by doping with lithium, the lightest alkalis
It is of crucial importance for us to have a systematical study of middle-sized Li-doped boron clusters
It should be noteworthy that the B13 ligand of the 13a/a− is no longer planar or quasi-planar but a tetrahedral-typed structure, which is in stark contrast to that of pure B13 cluster[36] through doping of a Li atom

Summary

Introduction

It will get entirely unusual derivatives with gratifying chemical bonding schemes for boron clusters by doping with lithium, the lightest alkalis. The MnBn−/0/+ (n = 10−20) clusters have been systematically studied to reveal the geometric constructions of middle-sized boron clusters after doping of a manganese atom[28]. The lowest-energy structures of the LiBn0/− (10 ≤ n ≤ 15) clusters present in forms of half-sandwich type, while for n ≥ 16 turn out to be quasi-planar and drum-type structures.

Results

Conclusion