{"title":"观察氟化双金属 CoAuF1-2- 和 CuAuF1-2- 簇中金的卤素样行为:阴离子光电子能谱和密度泛函理论。","authors":"Zhen-Chao Long, Aaron Shah, Huta Banjade, Kai-Wen Liu, Hong-Guang Xu, Weijun Zheng, Puru Jena","doi":"10.1063/5.0224002","DOIUrl":null,"url":null,"abstract":"<p><p>Using size-selected anion photoelectron spectroscopy and density functional theory, we investigated the structures and properties of fluorinated bimetallic clusters CoAuF1-2- and CuAuF1-2- and their neutrals. Both experimental and theoretical results show that in these cluster anions, Au behaves like a halogen atom. For example, the measured vertical detachment energies (VDEs) of CoAuF- (2.00 ± 0.08 eV) and CuAuF- (3.8 ± 0.1 eV) are close to those of CoF2- (2.12 ± 0.08 eV) and CuF2- (3.58 ± 0.08 eV), respectively. The theoretical results show that the geometries and electronic structures of CoAuF- and CuAuF- are similar to those of CoF2- and CuF2-. The natural population analysis and natural electron configuration analyses further confirm that the electronic properties of Au in MAuF- (M = Co, Cu) mimic those of MF2-. In addition, the electron localization function analyses show that the M-Au chemical bonds are similar to the corresponding M-F chemical bonds, providing evidence for the ionic nature of the interactions. When a second F atom is attached to the CoAuF- and CuAuF- clusters, the VDEs of the resulting CoAuF2- and CuAuF2- are 4.38 ± 0.08 eV and 3.71 ± 0.08 eV, respectively, indicating their superhalogen character as these values are higher than those of halogen anions. The results may be useful for understanding the properties of gold at the nanoscale that play an important role in catalysis and nanotechnology.</p>","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.1000,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Observation of halogen-like behavior of gold in fluorinated bimetallic CoAuF1-2- and CuAuF1-2- clusters: Anion photoelectron spectroscopy and density functional theory.\",\"authors\":\"Zhen-Chao Long, Aaron Shah, Huta Banjade, Kai-Wen Liu, Hong-Guang Xu, Weijun Zheng, Puru Jena\",\"doi\":\"10.1063/5.0224002\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Using size-selected anion photoelectron spectroscopy and density functional theory, we investigated the structures and properties of fluorinated bimetallic clusters CoAuF1-2- and CuAuF1-2- and their neutrals. Both experimental and theoretical results show that in these cluster anions, Au behaves like a halogen atom. For example, the measured vertical detachment energies (VDEs) of CoAuF- (2.00 ± 0.08 eV) and CuAuF- (3.8 ± 0.1 eV) are close to those of CoF2- (2.12 ± 0.08 eV) and CuF2- (3.58 ± 0.08 eV), respectively. The theoretical results show that the geometries and electronic structures of CoAuF- and CuAuF- are similar to those of CoF2- and CuF2-. The natural population analysis and natural electron configuration analyses further confirm that the electronic properties of Au in MAuF- (M = Co, Cu) mimic those of MF2-. In addition, the electron localization function analyses show that the M-Au chemical bonds are similar to the corresponding M-F chemical bonds, providing evidence for the ionic nature of the interactions. When a second F atom is attached to the CoAuF- and CuAuF- clusters, the VDEs of the resulting CoAuF2- and CuAuF2- are 4.38 ± 0.08 eV and 3.71 ± 0.08 eV, respectively, indicating their superhalogen character as these values are higher than those of halogen anions. The results may be useful for understanding the properties of gold at the nanoscale that play an important role in catalysis and nanotechnology.</p>\",\"PeriodicalId\":15313,\"journal\":{\"name\":\"Journal of Chemical Physics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.1000,\"publicationDate\":\"2024-09-28\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Chemical Physics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1063/5.0224002\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1063/5.0224002","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Observation of halogen-like behavior of gold in fluorinated bimetallic CoAuF1-2- and CuAuF1-2- clusters: Anion photoelectron spectroscopy and density functional theory.
Using size-selected anion photoelectron spectroscopy and density functional theory, we investigated the structures and properties of fluorinated bimetallic clusters CoAuF1-2- and CuAuF1-2- and their neutrals. Both experimental and theoretical results show that in these cluster anions, Au behaves like a halogen atom. For example, the measured vertical detachment energies (VDEs) of CoAuF- (2.00 ± 0.08 eV) and CuAuF- (3.8 ± 0.1 eV) are close to those of CoF2- (2.12 ± 0.08 eV) and CuF2- (3.58 ± 0.08 eV), respectively. The theoretical results show that the geometries and electronic structures of CoAuF- and CuAuF- are similar to those of CoF2- and CuF2-. The natural population analysis and natural electron configuration analyses further confirm that the electronic properties of Au in MAuF- (M = Co, Cu) mimic those of MF2-. In addition, the electron localization function analyses show that the M-Au chemical bonds are similar to the corresponding M-F chemical bonds, providing evidence for the ionic nature of the interactions. When a second F atom is attached to the CoAuF- and CuAuF- clusters, the VDEs of the resulting CoAuF2- and CuAuF2- are 4.38 ± 0.08 eV and 3.71 ± 0.08 eV, respectively, indicating their superhalogen character as these values are higher than those of halogen anions. The results may be useful for understanding the properties of gold at the nanoscale that play an important role in catalysis and nanotechnology.
期刊介绍:
The Journal of Chemical Physics publishes quantitative and rigorous science of long-lasting value in methods and applications of chemical physics. The Journal also publishes brief Communications of significant new findings, Perspectives on the latest advances in the field, and Special Topic issues. The Journal focuses on innovative research in experimental and theoretical areas of chemical physics, including spectroscopy, dynamics, kinetics, statistical mechanics, and quantum mechanics. In addition, topical areas such as polymers, soft matter, materials, surfaces/interfaces, and systems of biological relevance are of increasing importance.
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Atoms, Molecules, and Clusters
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