团簇ConMoS(n=1-5)原子间作用力及前线轨道成分密度泛函理论分析  

Density Functional Theory Analysis of Interatomic Force and Frontier Orbital Composition of Cluster ConMoS(n=1-5)

作　　者：王智瑶 方志刚[1] 王洁 刘立娥 毛智龙 吴庭慧 宋嘉 WANG Zhiyao;FANG Zhigang;WANG Jie;LIU Li’e;MAO Zhilong;WU Tinghui;SONG Jia(School of Chemical Engineering,University of Science and Technology Liaoning,Anshan 114051,China)

机构地区：[1]辽宁科技大学化学工程学院,辽宁鞍山114051

出　　处：《太原理工大学学报》2024年第3期513-521,共9页Journal of Taiyuan University of Technology

基　　金：国家自然科学基金重点资助项目(51634004);国家级大学生创新创业训练计划(202110146027,202010146009,202010146016)。

摘　　要：【目的】为得到团簇ConMoS(n=1-5)更多微观结构信息,同时为后续电子性质、催化性能等研究提供理论基础,探究了该团簇的原子间作用力关系及前线轨道成分。【方法】依据密度泛函理论,采用B3LYP泛函和def2-TZVP基组,在多个自旋多重度下运用Gaussian09软件包对该团簇进行构型优化和理论分析。【结果】结果表明:该团簇含有21种稳定构型;通过对AIM理论、电子定域化函数和变形密度分析,得到了该团簇内部相互作用程度及电子密度转移趋势,其中该团簇内原子相互作用时,Co、Mo和S原子间成键共价作用较强,S原子定域性较高,域内电子不易逃逸出去,Co和Mo原子离域性较强,域内电子易于外界交换;通过Hirshfeld方法原子贡献率分析,得出金属原子是HOMO、LUMO轨道成份主要贡献来源,其中Mo和Co原子对前线轨道贡献率占据优势。最终得出该团簇内部原子间主要以共价键作用结合,但作用力强弱并不一致,Mo和Co原子在化学反应中应重点关注。【Purposes】In order to obtain additional microstructural information on the ConMoS(n=1-5)cluster and establish a theoretical foundation for subsequent investigations of its electronic properties and catalytic performance,the atomic interaction relationships and frontier orbital compositions of the cluster are investigated.【Methods】To accomplish this,density functional theory with the B3LYP functional and def2-TZVP basis set is adopted to optimize the cluster configuration and perform theoretical analysis under various spin multiplicities with the Gaussian09 software package.【Findings】The results demonstrate the existence of 21 stable configurations.AIM theory,electron localization function,and deformation density are analyzed to obtain information on the degree of internal interaction and electron density transfer trends of the cluster.The findings indicate that covalent bonding interactions between Co,Mo,and S atoms are strong in the internal atom interactions of the cluster,with S atoms exhibiting high localization and low probability of electron escape from the domain.In contrast,Co and Mo atoms exhibit strong delocalization and are likely to exchange electrons with the outside electrons.Through Hirshfeld analysis of atomic contribution rates,it can be observed that metal atoms are the primary contributors to the HOMO and LUMO orbitals,with Mo and Co atoms dominating the frontier orbitals.Overall,covalent bonding is the primary atomic interaction within the cluster,but the strength of these interactions varies.Mo and Co atoms should be the focus in chemical reactions of the cluster.

关 键 词：团簇ConMoS 密度泛函理论 AIM理论 电子定域化函数 

分 类 号：O641.12[理学—物理化学]