Structural evolution and bonding characteristics of neutral Cs2Bn clusters. (2nd December 2022)

• Record Type: Journal Article
• Authors: Yang, Hang; Hu, Yan-Fei; Ding, Jun-Jie; Yuan, Yu-Quan; Zhao, Yu
• Is Part Of: Molecular physics. Volume 120:Number 23(2022)
• Publication Date: 2022-12-02
• Subjects: Diatomic doped clusters -- π-aromaticity -- AdNDP -- density of states; Molecules -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Molécules -- Périodiques; Chimie physique et théorique -- Périodiques; 539.6.05
• DOI: 10.1080/00268976.2022.2133753
• Languages: English
• ISSNs: 0026-8976

Abstract

Abstract : 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 Cs2 B n ( n = 1–12) clusters, as well as the corresponding global minimum of the potential energy surface were determined. The ground-state structures of the Cs2 B n ( 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 Cs2 B8 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-2 s and 2 p atomic orbitals of Cs2 B8 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 Cs2 B8 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 Cs2 B n clusters and enrich the chemical bonding properties of boron-based clusters. GRAPHICAL ABSTRACT: UF0001