Classical vs. quantum plasmon- induced molecular transformations at metallic nanojunctions

• 成果类型: Article
• 署名作者: Mantilla, Alexander B. C.; Wang, Chih-Feng; Krayev, Andrey; Gu, Yi; Schultz, Zachary D.; El-Khoury, Patrick Z.
• 署名单位: Washington State University; United States Department of Energy (DOE); Pacific Northwest National Laboratory; University System of Ohio; Ohio State University
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-12614
• DOI: 10.1073/pnas.2319233121
• 发表日期: 2024-04-02
• 关键词: raman; photocatalysis; closer

摘要

Chemical transformations near plasmonic metals have attracted increasing attention in the past few years. Specifically, reactions occurring within plasmonic nanojunctions that can be detected via surface and tip- enhanced Raman (SER and TER) scattering were the focus of numerous reports. In this context, even though the transition between localized and nonlocal (quantum) plasmons at nanojunctions is documented, its implications on plasmonic chemistry remain poorly understood. We explore the latter through AFM- TER- current measurements. We use two molecules: i) 4- mercaptobenzonitrile (MBN) that reports on the (non)local fields and ii) 4- nitrothiophenol (NTP) that features defined signatures of its neutral/anionic forms and dimer product, 4,4 '- dimercaptoazobenzene (DMAB). The transition from classical to quantum plasmons is established through our optical measurements: It is marked by molecular force and current measurements support our assignments. In the case of NTP, we observe the parent and DMAB product beneath the probe in the classical regime. Further reducing the gap leads to the collapse of DMAB to form NTP anions. The process is reversible: Anions subsequently recombine into DMAB. Our results have significant implications for AFM-based TER measurements and their analysis, beyond the scope of this work. In effect, when precise control over the junction is not possible (e.g., in SER and ambient TER), both classical and quantum plasmons need to be considered in the analysis of plasmonic reactions