{"title":"与 Au(111) 上绝缘烷硫酸盐层结合的咪唑基团在原子氢反应中的电子转移能力。","authors":"Hiroyuki S Kato,Mizuho Muroyama,Nano Kobayakawa,Riku Muneyasu,Yasutaka Tsuda,Natsumi Murase,Seiya Watanabe,Takashi Yamada,Yusuke Kanematsu,Masanori Tachikawa,Megumi Akai-Kasaya,Michio Okada,Akitaka Yoshigoe","doi":"10.1021/acs.jpclett.4c02306","DOIUrl":null,"url":null,"abstract":"The charge transfer capability associated with chemical reactions at metal-organic interfaces was studied via the atomic H addition reaction for an imidazole-terminated alkanethiolate self-assembled monolayer (Im-SAM) film on Au(111) at room temperature, using near-edge X-ray absorption fine structure spectroscopy, infrared reflection absorption spectroscopy, work function measurements, and density functional theory calculations. The imidazolium cation is a stable species in liquids; therefore, it is pertinent to determine whether the hydrogenation reactions of the imidazole groups produce imidazolium cations accompanied by electron transfer to the Au substrate, even in the absence of solvate and/or counterions on the insulating alkanethiolate layer. The experiments made it clear that the imidazolium moieties were formed during the irradiation of Im-SAM with atomic H. Theoretical model calculations also revealed that the total energies and molecular orbital levels satisfied the imidazolium cation formation associated with electron transfer. In a detailed analysis of the work function change depending on H irradiation, we confirmed that some of the imidazolium radicals became cations in Im-SAM.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8000,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Electron Transfer Capability in Atomic Hydrogen Reactions for Imidazole Groups Bound to the Insulating Alkanethiolate Layer on Au(111).\",\"authors\":\"Hiroyuki S Kato,Mizuho Muroyama,Nano Kobayakawa,Riku Muneyasu,Yasutaka Tsuda,Natsumi Murase,Seiya Watanabe,Takashi Yamada,Yusuke Kanematsu,Masanori Tachikawa,Megumi Akai-Kasaya,Michio Okada,Akitaka Yoshigoe\",\"doi\":\"10.1021/acs.jpclett.4c02306\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The charge transfer capability associated with chemical reactions at metal-organic interfaces was studied via the atomic H addition reaction for an imidazole-terminated alkanethiolate self-assembled monolayer (Im-SAM) film on Au(111) at room temperature, using near-edge X-ray absorption fine structure spectroscopy, infrared reflection absorption spectroscopy, work function measurements, and density functional theory calculations. The imidazolium cation is a stable species in liquids; therefore, it is pertinent to determine whether the hydrogenation reactions of the imidazole groups produce imidazolium cations accompanied by electron transfer to the Au substrate, even in the absence of solvate and/or counterions on the insulating alkanethiolate layer. The experiments made it clear that the imidazolium moieties were formed during the irradiation of Im-SAM with atomic H. Theoretical model calculations also revealed that the total energies and molecular orbital levels satisfied the imidazolium cation formation associated with electron transfer. In a detailed analysis of the work function change depending on H irradiation, we confirmed that some of the imidazolium radicals became cations in Im-SAM.\",\"PeriodicalId\":62,\"journal\":{\"name\":\"The Journal of Physical Chemistry Letters\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.8000,\"publicationDate\":\"2024-10-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry Letters\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.jpclett.4c02306\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry Letters","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpclett.4c02306","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
利用近边 X 射线吸收精细结构光谱、红外反射吸收光谱、功函数测量和密度泛函理论计算,通过原子 H 加成反应研究了室温下 Au(111)上的咪唑封端烷硫酸盐自组装单层薄膜(Im-SAM)与金属有机界面化学反应相关的电荷转移能力。咪唑阳离子是液体中的稳定物种;因此,即使在绝缘烷硫酸盐层上没有溶解物和/或反离子的情况下,确定咪唑基团的氢化反应是否会产生咪唑阳离子,并伴随着电子转移到金基底是很有意义的。实验表明,咪唑分子是在原子氢辐照 Im-SAM 的过程中形成的。理论模型计算也表明,总能量和分子轨道水平符合与电子转移相关的咪唑阳离子的形成。通过对氢辐照功函数变化的详细分析,我们证实部分咪唑自由基成为了 Im-SAM 中的阳离子。
Electron Transfer Capability in Atomic Hydrogen Reactions for Imidazole Groups Bound to the Insulating Alkanethiolate Layer on Au(111).
The charge transfer capability associated with chemical reactions at metal-organic interfaces was studied via the atomic H addition reaction for an imidazole-terminated alkanethiolate self-assembled monolayer (Im-SAM) film on Au(111) at room temperature, using near-edge X-ray absorption fine structure spectroscopy, infrared reflection absorption spectroscopy, work function measurements, and density functional theory calculations. The imidazolium cation is a stable species in liquids; therefore, it is pertinent to determine whether the hydrogenation reactions of the imidazole groups produce imidazolium cations accompanied by electron transfer to the Au substrate, even in the absence of solvate and/or counterions on the insulating alkanethiolate layer. The experiments made it clear that the imidazolium moieties were formed during the irradiation of Im-SAM with atomic H. Theoretical model calculations also revealed that the total energies and molecular orbital levels satisfied the imidazolium cation formation associated with electron transfer. In a detailed analysis of the work function change depending on H irradiation, we confirmed that some of the imidazolium radicals became cations in Im-SAM.
期刊介绍:
The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.