Single-molecule analysis of plasmon-induced dissociation reactions

• Project/Area Number: 18H01947
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 32010:Fundamental physical chemistry-related
• Research Institution: Institute of Physical and Chemical Research
• Principal Investigator: Kazuma Emiko 国立研究開発法人理化学研究所, 開拓研究本部, 研究員 (50633864)
• Project Period (FY): 2018-04-01 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥17,810,000 (Direct Cost: ¥13,700,000、Indirect Cost: ¥4,110,000); Fiscal Year 2020: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2019: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2018: ¥11,050,000 (Direct Cost: ¥8,500,000、Indirect Cost: ¥2,550,000)
• Keywords: プラズモン / 走査型トンネル顕微鏡 / 単一分子 / 化学反応 / STM

Outline of Final Research Achievements

In this study, the plasmon-induced dissociation of a single-molecule was investigated to reveal the reaction mechanism. The main purpose of this study is to obtain fundamental understanding of the interaction between the plasmon and the molecule by considering the electronic structure of the adsorbed molecule formed by the orbital hybridization with metal. The plasmon-induced dissociation of oxygen molecules strongly chemisorbed on Ag(110) with different orientations and electronic structures was investigated using a scanning tunneling microscope combined with light irradiation. Photochemical reactions and dissociation reactions induced by injecting tunneling electrons or holes were also investigated. A combination of quantitative analysis by the experiments and density functional theory calculations revealed that the hot carriers generated through the decay of the plasmon are transferred to the molecule strongly adsorbed on the metal surface.

Academic Significance and Societal Importance of the Research Achievements

本研究は、プラズモン誘起解離反応において「金属と分子の界面における相互作用によって形成される分子の電子状態と反応素過程の関係性」についての知見を与えるものである。本研究の達成により、金属表面に強く化学吸着した分子のプラズモン誘起化学反応は、プラズモンの緩和過程で生成するホットキャリアが重要な役割を果たすことが示され、反応機構の体系化に一歩近づいた。今後、分子の電子状態と反応素過程の関係性の更なる解明によって、分子の電子状態を界面の構造制御によって積極的に制御することで、太陽光エネルギーによるグリーンプロセスが可能な全く新しい機構に基づく触媒の開拓につながると期待される。

Research Products

• [Journal Article] STM investigations of single-molecule chemical reactions (2020)
  • Author(s): KAZUMA Emiko、KIM Yousoo
  • Journal Title: Denki Kagaku Volume: 88 Issue: 3 Pages: 223-228
  • DOI: 10.5796/denkikagaku.20-FE0021
  • NAID: 130007897170
  • ISSN: 2433-3255, 2433-3263
  • Year and Date: 2020-09-05
  • Peer Reviewed
• [Journal Article] Real-Space Studies of Plasmon-Induced Dissociation Reactions with an STM (2020)
  • Author(s): Kazuma Emiko
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 93 Issue: 12 Pages: 1552-1557
  • DOI: 10.1246/bcsj.20200204
  • NAID: 130007955887
  • Peer Reviewed / Open Access
• [Journal Article] Single-molecule study of a plasmon-induced reaction for a strongly chemisorbed molecule (2020)
  • Author(s): Emiko Kazuma, Minhui Lee, Jaehoon Jung, Michael Trenary, Yousoo Kim,
  • Journal Title: Angewandte Chemie International Edition Volume: 59 Issue: 20 Pages: 7960-7966
  • DOI: 10.1002/anie.202001863
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Scanning probe microscopy for real-space observations of local chemical reactions induced by localized surface plasmon (2019)
  • Author(s): Emiko Kazuma, Yousoo Kim
  • Journal Title: Physical Chemistry Chemical Physics Volume: 21 Issue: 36 Pages: 19720-19731
  • DOI: 10.1039/c9cp02100k
  • Peer Reviewed
• [Journal Article] Mechanistic Studies of Plasmon Chemistry on Metal Catalysts (2019)
  • Author(s): Kazuma Emiko、Kim Yousoo
  • Journal Title: Angewandte Chemie International Edition Volume: 58 Issue: 15 Pages: 4800-4808
  • DOI: 10.1002/anie.201811234
  • Peer Reviewed
• [Presentation] Single-molecule plasmon chemistry－Real-space observation with STM－ (2020)
  • Author(s): Emiko Kazuma
  • Organizer: 2020 RIKEN-NCHU Joint Symposium
  • Int'l Joint Research / Invited
• [Presentation] Single-molecule study of the plasmon-induced dissociation of O2 molecules (2020)
  • Author(s): Emiko Kazuma, Minhui Lee, Jaehoon Jung, Michael Trenary, Yousoo Kim
  • Organizer: The 5th International Workshop on Advanced Nanoscience and Nanomaterials 2020
  • Int'l Joint Research
• [Presentation] 単一分子プラズモン誘起解離反応の光STM観測・解析 (2020)
  • Author(s): 数間 恵弥子
  • Organizer: ACE meeting online II
  • Invited
• [Presentation] 単一酸素分子のプラズモン誘起解離反応の実空間観測 (2020)
  • Author(s): 数間 恵弥子
  • Organizer: 分子研研究会
  • Invited
• [Presentation] 光STMによるプラズモン誘起解離反応の単一分子レベル研究 (2020)
  • Author(s): 数間 恵弥子
  • Organizer: ナノ学会合同部会シンポジウム
  • Invited
• [Presentation] Nanoscale analysis and control of chemical reactions induced by Iocalized surface plasmon (2020)
  • Author(s): Emiko Kazuma
  • Organizer: 日本化学会第100春季年会(2020)
  • Invited
• [Presentation] Single molecule study of plasmon-induced chemical reactions (2019)
  • Author(s): Emiko Kazuma
  • Organizer: The 81st Okazaki Conference
  • Invited
• [Remarks] 理化学研究所プレスリリース「ナノの光による単一酸素分子の分解」
  • URL: https://www.riken.jp/press/2020/20200323_1/index.html
• [Remarks] Kim表面界面科学研究室
  • URL: http://www.riken.jp/Kimlab/