山西大学学报（自然科学版）2022，Vol.45Issue(5)：1281-1291,11.DOI:10.13451/j.sxu.ns.2020170
硼基B6Al2-/0/+合金团簇结构和成键理论研究
Al-B Substitution in Boron-based Alloy Clusters is Not Completely Isoelectronic:Structures and Bonding of B6Al2-/O/+Clusters
摘要
Abstract
Elemental boron and aluminum clusters show unique structures and chemical bonding.Consequently,binary B-Al clus-ters are normally studied following the idea of isoelectronic Al-B substitution.However,the concept is purely an assumption.We report on the structures,bonding,and aromaticity of a series of binary B6Al2-/0/+clusters in their different charge states,using com-putational global-minimum(GM)searches and electronic structure calculations.Relative energies of top low-lying structures are systematically assessed at the PBEO and single-point CCSD(T)levels of theory,offering useful methodological information for this and relevant systems.The key cluster structures(1-4)have two distinct motifs:inverse sandwich versus heteroatomic molecular wheel.Neutral GM cluster I slightly favors the inverse sandwich,with molecular wheel structure 2 being a low-lying isomer.An-ionic GM cluster 3 is also a molecular wheel,whereas cationic GM cluster 4 strongly favors the inverse sandwich.Upon the se-quential reduction from cation,neutral,to anion,the molecular wheel monotonically gains a relative advantage,and a structural transition from inverse sandwich to molecular wheel takes place in the anion.In terms of bonding,clusters 1/2 feature the 6π/4σconflicting aromaticity,leading to elongated structural shapes.The cationic cluster 4 and anionic cluster 3 have the 3a/5a frame-works,which deviate from strict 4σ antiaromaticity.Thus,clusters 3/4 are relatively circular.The doping Al sites fall into three dis-tinct categories,being chemically valence threee/two/one,respectively.Only one out of three categories conforms to the isoelectron-ic B-Al substitution.关键词
硼基B-Al合金团簇/等电子取代/反三明治团簇/分子轮团簇/冲突π/σ芳香性Key words
boron-based B-Al alloy clusters/isoelectronic substitution/inverse sandwich clusters/molecular wheel clusters/con-flicting π/σ aromaticity分类
化学化工引用本文复制引用
张洁琼,王康,翟华金..硼基B6Al2-/0/+合金团簇结构和成键理论研究[J].山西大学学报（自然科学版）,2022,45(5):1281-1291,11.基金项目
国家自然科学基金(21873058 （）
21573138) （）
