{"title":"二膦保护 M@Au12(M = Au、Ir)超原子纳米簇的掺杂介导激发态动力学","authors":"Wei Pei, Lei Hou, Jing Yang, Si Zhou, Jijun Zhao","doi":"10.1039/d4nr02051k","DOIUrl":null,"url":null,"abstract":"Doping heterometal atoms into ligand-protected gold superatom nanoclusters (Aun NCs) is proposed to further diversify their geometrical and electronic structures and enhance their photoluminescent properties, which are attributed to the mixing and effects between atoms. However, the fundamental principles that govern the optoelectronic properties of the doped Aun NCs remain elusive. Herein, we systematically explored the two prototypical 8-electron Aun (n = 11, 13) NCs, both with and without Ir dopant atoms, using comprehensive ab initio calculations and real-time nonadiabatic molecular dynamics simulations. These doped Aun NCs maintain their parent geometrical structures and 8-electron superatomic configuration (1S21P6). The strong core-shell (Ir-Aun) electronic coupling significantly expands the energy gap, resulting in a weak nonadiabatic coupling matrix element, which in turn increases carrier lifetime. This increase is mainly governed by the low-frequency vibration mode. We uncovered the relationship between electronic structures, electron vibration, and carrier dynamics for these doped Aun NCs. These calculated results provide crucial insights for the atomically precise design of metal NCs with superior optoelectronic properties.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":5.8000,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Doping-mediated excited states dynamics of diphosphine-protected M@Au12 (M = Au, Ir) superatoms nanocluster\",\"authors\":\"Wei Pei, Lei Hou, Jing Yang, Si Zhou, Jijun Zhao\",\"doi\":\"10.1039/d4nr02051k\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Doping heterometal atoms into ligand-protected gold superatom nanoclusters (Aun NCs) is proposed to further diversify their geometrical and electronic structures and enhance their photoluminescent properties, which are attributed to the mixing and effects between atoms. However, the fundamental principles that govern the optoelectronic properties of the doped Aun NCs remain elusive. Herein, we systematically explored the two prototypical 8-electron Aun (n = 11, 13) NCs, both with and without Ir dopant atoms, using comprehensive ab initio calculations and real-time nonadiabatic molecular dynamics simulations. These doped Aun NCs maintain their parent geometrical structures and 8-electron superatomic configuration (1S21P6). The strong core-shell (Ir-Aun) electronic coupling significantly expands the energy gap, resulting in a weak nonadiabatic coupling matrix element, which in turn increases carrier lifetime. This increase is mainly governed by the low-frequency vibration mode. We uncovered the relationship between electronic structures, electron vibration, and carrier dynamics for these doped Aun NCs. These calculated results provide crucial insights for the atomically precise design of metal NCs with superior optoelectronic properties.\",\"PeriodicalId\":92,\"journal\":{\"name\":\"Nanoscale\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.8000,\"publicationDate\":\"2024-07-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Nanoscale\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1039/d4nr02051k\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Nanoscale","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1039/d4nr02051k","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
有人提出在配体保护的金超原子纳米团簇(Aun NCs)中掺杂杂金属原子,以进一步丰富其几何和电子结构,并增强其光致发光特性。然而,支配掺杂 Aun NCs 光电特性的基本原理仍然难以捉摸。在此,我们利用全面的 ab initio 计算和实时非绝热分子动力学模拟,系统地探索了两种原型 8 电子 Aun(n = 11、13)NC,包括掺杂 Ir 原子和不掺杂 Ir 原子。这些掺杂 Aun NCs 保持了母体的几何结构和 8 电子超原子构型 (1S21P6)。强核壳(Ir-Aun)电子耦合显著扩大了能隙,从而产生了弱非绝热耦合矩阵元素,进而延长了载流子寿命。载流子寿命的增加主要受低频振动模式的影响。我们揭示了这些掺杂 Aun NCs 的电子结构、电子振动和载流子动力学之间的关系。这些计算结果为从原子上精确设计具有优异光电特性的金属 NC 提供了重要的启示。
Doping-mediated excited states dynamics of diphosphine-protected M@Au12 (M = Au, Ir) superatoms nanocluster
Doping heterometal atoms into ligand-protected gold superatom nanoclusters (Aun NCs) is proposed to further diversify their geometrical and electronic structures and enhance their photoluminescent properties, which are attributed to the mixing and effects between atoms. However, the fundamental principles that govern the optoelectronic properties of the doped Aun NCs remain elusive. Herein, we systematically explored the two prototypical 8-electron Aun (n = 11, 13) NCs, both with and without Ir dopant atoms, using comprehensive ab initio calculations and real-time nonadiabatic molecular dynamics simulations. These doped Aun NCs maintain their parent geometrical structures and 8-electron superatomic configuration (1S21P6). The strong core-shell (Ir-Aun) electronic coupling significantly expands the energy gap, resulting in a weak nonadiabatic coupling matrix element, which in turn increases carrier lifetime. This increase is mainly governed by the low-frequency vibration mode. We uncovered the relationship between electronic structures, electron vibration, and carrier dynamics for these doped Aun NCs. These calculated results provide crucial insights for the atomically precise design of metal NCs with superior optoelectronic properties.
期刊介绍:
Nanoscale is a high-impact international journal, publishing high-quality research across nanoscience and nanotechnology. Nanoscale publishes a full mix of research articles on experimental and theoretical work, including reviews, communications, and full papers.Highly interdisciplinary, this journal appeals to scientists, researchers and professionals interested in nanoscience and nanotechnology, quantum materials and quantum technology, including the areas of physics, chemistry, biology, medicine, materials, energy/environment, information technology, detection science, healthcare and drug discovery, and electronics.