双金属Au_(n)Cu^(0∕-)(n=1~9)团簇结构、稳定性、电子及光学性能研究  

Study on structures,stabilities,electronic and spectral properties of gold⁃copper bimetallic Au_(n)Cu^(0∕-)(n=1-9)clusters

作　　者：韩思蕊 张慧源 郭雅雯 丁雅妮 李成刚 崔颍琦 HAN Sirui;ZHANG Huiyuan;GUO Yawen;DING Yani;LI Chenggang;CUI Yingqi(School of Physics and Electronic Engineering,Zhengzhou Normal University,Zhengzhou 450044,China;School of Chemical Engineering,Zhengzhou University,Zhengzhou 450001,China)

机构地区：[1]郑州师范学院物理与电子工程学院,郑州450044 [2]郑州大学化工学院,郑州450001

出　　处：《材料科学与工艺》2024年第1期42-53,共12页Materials Science and Technology

基　　金：国家自然科学基金资助项目(11904328,12104416);河南省大学生创新创业训练计划项目(S202212949003);郑州师范学院青年骨干教师培养计划(QNGG-211361);郑州师范学院本科教学改革研究项目(JXGG--221910).

摘　　要：为了探究铜掺杂金团簇的结构及特性,依据密度泛函理论对Au_(n) Cu^(0/-)(n=1~9)团簇的结构、稳定性、电子及光学性能进行了系统分析。基于卡利普索结构预测程序,在B3LYP/Lanl2dz水平下优化得到了不同尺寸的基态结构。研究表明,除Au7 Cu和Au8 Cu-呈现三维结构外,其它尺寸下的基态均呈现二维平面结构。而且,Au_(n) Cu^(0/-)的基态可通过在Au_(n)-1 Cu^(0/-)基态基础上添加一个Au原子得到。稳定性分析确定了Au_(5) Cu和Au_(2) Cu-团簇在各自体系中拥有相对强的稳定性。磁性分析发现,闭壳层电子结构体系的总自旋磁矩为零;开壳层电子结构体系分别具有1μB的总磁矩。分析极化率表明,Au_(9) Cu和Au_(9) Cu-团簇对外场的各向异性响应最强,AuCu和Au_(3) Cu-团簇对外场的各向异性响应最弱。AdNDP分析发现,众多σ键连通了整个分子骨架,促进了整个团簇的稳定。基于Multiwfn程序,拟合的光电子能谱、红外谱、拉曼谱和紫外可见光谱可为实验上鉴别Au_(n) Cu^(0/-)团簇的结构提供帮助。In order to explore the structures and properties of copper⁃doped gold clusters,the structures,stabilities,electronic and spectral properties of bimetallic Au_(n) Cu^(0/-)(n=1-9)clusters were systematically analyzed according to the density functional theory.The lowest energy structrues were obtained at the B3LYP/Lanl2dz level based on the CALYPSO searching method.The results show that except for the three⁃dimensional structures for Au7Cu and Au8Cu-,the lowest energy structures favor two⁃dimensional structures.Moreover,Au_(n) Cu^(0/-)clusters can be obtained by adding one Au atom on the lowest energy structures of Au_(n)⁃1Cu^(0/-).The stability studies indicated that Au_(5)Cu and Au_(2)Cu-have relatively strong stability in neutral and anionic serises,respectively.Magnetic properties analyses revealed the total magnetic moments of the closed shell systems are zero;the total magnetic moments keep a constant 1μB for opened shell systems.The analyses of polarisability revealed that Au_(9)Cu and Au_(9)Cu-clusters have relativley stronger anisotropic response to the external field,while AuCu and Au_(3)Cu-clusters have relativley weaker anisotropic response to the external field.According to AdNDP analysis,the molecular shape is connected byσ⁃bonds,which contribute to the stability of doped systems.Based on the Multiwfn program,the photoelectron spectra,infrared spectra,Raman specta and UV⁃vis spectra were simulated and could help to identify the structures of Au_(n) Cu^(0/-)clusters in experiments.

关 键 词：密度泛函理论 卡利普索 双金属 电子特性 光学特性 

分 类 号：O641.1[理学—物理化学]