（n = 4-12）团簇的结构演化和键合性质：尺寸选择的负离子光电子能谱和理论计算。

Structural evolution and bonding properties of (n = 4-12) clusters: Size-selected anion photoelectron spectroscopy and theoretical calculations.

机构信息

Department of Chemistry and Chemical Engineering, Heze University, Heze, Shandong 274015, China.

Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.

出版信息

J Chem Phys. 2018 Nov 7;149(17):174314. doi: 10.1063/1.5052559.

DOI:10.1063/1.5052559

PMID:30408980

Abstract

Size-selected anion photoelectron spectroscopy and theoretical calculations were used to investigate the structural evolution and bonding properties of BSi (n = 4-12) clusters. The results showed that the B atom in BSi prefers to occupy the high coordination sites to form more B-Si bonds. The lowest-lying isomers of BSi primarily adopt bowl-shaped based geometries, while those of BSi are mainly dominated by prismatic based geometries. For anionic clusters, BSi is the critical size of the endohedral structure, whereas BSi neutrals form the B-endohedral structure at n = 9. Interestingly, both anionic and neutral BSi have a symmetric tricapped tetragonal antiprism structure with the B atom at the center and exhibit 3D aromaticity. The BSi anion possesses σ plus π doubly delocalized bonding characters. The natural population analysis charge distributions on the B atom are related with the structural evolution of BSi and the B-Si interactions.

摘要

采用尺寸选择的负离子光电子能谱和理论计算研究了 BSi(n=4-12)团簇的结构演化和键合性质。结果表明，BSi 中的 B 原子倾向于占据高配位位点，形成更多的 B-Si 键。BSi 的低能异构体主要采用碗状基几何构型，而 BSi 的低能异构体主要由棱柱形基几何构型主导。对于负离子团簇，BSi 是内壳层结构的临界点，而 BSi 中性体在 n=9 时形成 B-内壳层结构。有趣的是，负离子和中性 BSi 均具有中心 B 原子的对称三帽四方反棱柱结构，表现出 3D 芳香性。BSi 负离子具有 σ 加 π 双重离域键合特征。B 原子上的自然布居分析电荷分布与 BSi 的结构演化和 B-Si 相互作用有关。