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A study of electrons in metal clusters competing between localization and delocalization

Research Project

Project/Area Number 18H03901
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Review Section Medium-sized Section 32:Physical chemistry, functional solid state chemistry, and related fields
Research InstitutionKyushu University

Principal Investigator

Terasaki Akira  九州大学, 理学研究院, 教授 (60222147)

Co-Investigator(Kenkyū-buntansha) 安池 智一  放送大学, 教養学部, 教授 (10419856)
堀尾 琢哉  九州大学, 理学研究院, 准教授 (40443022)
荒川 雅  九州大学, 理学研究院, 助教 (10610264)
Project Period (FY) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥45,630,000 (Direct Cost: ¥35,100,000、Indirect Cost: ¥10,530,000)
Fiscal Year 2020: ¥7,930,000 (Direct Cost: ¥6,100,000、Indirect Cost: ¥1,830,000)
Fiscal Year 2019: ¥9,880,000 (Direct Cost: ¥7,600,000、Indirect Cost: ¥2,280,000)
Fiscal Year 2018: ¥27,820,000 (Direct Cost: ¥21,400,000、Indirect Cost: ¥6,420,000)
Keywords金属クラスター / 電子構造 / 電子励起 / 電子局在/非局在 / s-d電子相互作用 / 光吸収分光 / 光電子イメージング / 超原子軌道 / 表面プラズモン共鳴
Outline of Final Research Achievements

This study aimed at investigation of electrons in metal clusters in terms of their competing behavior between localization and delocalization. First, we measured optical absorption spectra of silver clusters in a broad size range from dimer up to 90-mer, which revealed the change in their optical responses from molecular-like to nanoparticle-like behavior by evaluating collectivity of electrons. Second, we investigated electronic structures of silver clusters doped with a transition-metal atom by chemical reaction and photoelectron imaging experiments. We found that an electron-counting rule governs the stability of clusters, where d electrons participate through their delocalization upon encapsulation of the dopant atom. Manipulating clusters in a single-atom precision, the present study made advances in nano materials science.

Academic Significance and Societal Importance of the Research Achievements

本研究は、現状のナノテクノロジーが扱うナノ粒子よりもさらに小さな未開拓サイズ領域の微小金属粒子を研究対象とし、その電子論を展開した点に大きな学術的意義がある。研究成果を発表した論文のうち2報が物理化学分野で国際的に権威ある学術誌のHot Articleに選出されるなど、国内外で高く評価されている。これら金属クラスターは、量子材料をはじめとする次世代材料の中核に位置づけられ、今後、新規機能性材料としてナノフォトニクス、ナノエレクトロニクスなどの変革が期待される点で、社会的意義も大きい。

Report

(4 results)
  • 2021 Final Research Report ( PDF )
  • 2020 Annual Research Report
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • Research Products

    (58 results)

All 2022 2021 2020 2019 2018 Other

All Journal Article (8 results) (of which Peer Reviewed: 8 results) Presentation (49 results) (of which Int'l Joint Research: 16 results,  Invited: 10 results) Remarks (1 results)

  • [Journal Article] Electron counting in cationic and anionic silver clusters doped with a 3d transition-metal atom: endo- vs. exohedral geometry2022

    • Author(s)
      Minamikawa Kento、Sarugaku Shun、Arakawa Masashi、Terasaki Akira
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 24 Issue: 3 Pages: 1447-1455

    • DOI

      10.1039/d1cp04197e

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Reaction of nitric oxide molecules on transition-metal-doped silver cluster cations: size- and dopant-dependent reaction pathways2021

    • Author(s)
      Arakawa Masashi、Horioka Masataka、Minamikawa Kento、Kawano Tomoki、Terasaki Akira
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 23 Issue: 40 Pages: 22947-22956

    • DOI

      10.1039/d1cp02882k

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A revisit to electronic structures of cobalt-doped silver cluster anions by size-dependent reactivity measurement2020

    • Author(s)
      K. Minamikawa, M. Arakawa, K. Tono, and A. Terasaki
    • Journal Title

      Chemical Physics Letters

      Volume: 753 Pages: 137613-137613

    • DOI

      10.1016/j.cplett.2020.137613

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Preadsorption effect of carbon monoxide on reactivity of cobalt cluster cations toward hydrogen2020

    • Author(s)
      M. Arakawa, D. Okada, S. Kono, and A. Terasaki
    • Journal Title

      Journal of Physical Chemistry A

      Volume: 1242 Issue: 47 Pages: 9751-9756

    • DOI

      10.1021/acs.jpca.0c05819

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Reaction kinetics of nitric oxide on size-selected silver cluster cations2020

    • Author(s)
      M. Arakawa, M. Horioka, K. Minamikawa, T. Kawano, and A. Terasaki
    • Journal Title

      Journal of Physical Chemistry C

      Volume: 124 Issue: 49 Pages: 26881-26888

    • DOI

      10.1021/acs.jpcc.0c08890

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Improvement of reflectron time-of-flight mass spectrometer for better convergence of ion beam2020

    • Author(s)
      T. Handa, T. Horio, M. Arakawa, A. Terasaki
    • Journal Title

      Int. J. Mass Spectrom.

      Volume: 451 Pages: 116311-116311

    • DOI

      10.1016/j.ijms.2020.116311

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Electronic and geometric effects on chemical reactivity of 3d-transition-metal-doped silver cluster cations toward oxygen molecules2019

    • Author(s)
      S. Sarugaku, M. Arakawa, T. Kawano, and A. Terasaki
    • Journal Title

      J. Phys. Chem. C

      Volume: 123 Issue: 42 Pages: 25890-25897

    • DOI

      10.1021/acs.jpcc.9b05117

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Analysis of cluster growth in magnetron-sputtering metal-cluster source by optical emission spectroscopy2019

    • Author(s)
      S. Kono, M. Arakawa, and A. Terasaki
    • Journal Title

      Chem. Lett.

      Volume: 48 Issue: 12 Pages: 1537-1540

    • DOI

      10.1246/cl.190727

    • NAID

      130007757565

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Presentation] CWレーザー光電子画像観測法による超原子軌道イメージング2022

    • Author(s)
      堀尾琢哉、南川賢人、西里 将、荒川 雅、寺嵜 亨
    • Organizer
      レーザー学会 第42回年次大会
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] 光電子イメージングによる銀クラスター負イオンの超原子軌道の探究2022

    • Author(s)
      西里 将、南川賢人、橋本治暉、松本一陽、荒川 雅、堀尾琢哉、寺嵜 亨
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] セリウム添加銀クラスター正イオンの電子構造・幾何構造:酸素との反応性を介したサイズ効果の探究2021

    • Author(s)
      林 奈穂、南川賢人、荒川 雅、寺嵜 亨
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 光解離および光吸収分光による銀クラスター正イオンの構造成長の探索2021

    • Author(s)
      河野 聖、河村 駿、森下健介、荒川 雅、堀尾琢哉、寺嵜 亨
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] イオン軌道シミュレーションを用いた線形イオントラップ内のイオン密度分布の解析2021

    • Author(s)
      飯田岳史、寺嵜 亨
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 酸素との反応性を介した遷移金属添加銀クラスター正・負イオンの3d電子の局在/非局在性探究:電子数と幾何構造の効果2021

    • Author(s)
      南川賢人、荒川 雅、寺嵜 亨
    • Organizer
      ナノ学会第19回大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Photoelectron imaging of metal cluster anions using a continuous wave laser source2021

    • Author(s)
      T. Horio, K. Minamikawa, T. Nishizato, M. Arakawa, and A. Terasaki
    • Organizer
      第36回化学反応討論会
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Formation of metal cluster ion beams investigated by mass spectrometry and optical emission spectroscopy2021

    • Author(s)
      S. Kono, M. Arakawa, and A. Terasaki
    • Organizer
      The 29th (XXIX) International Symposium on Molecular Beams (ISMB2021)
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Reflectron time-of-flight mass spectrometer with improved convergence of an ion beam2021

    • Author(s)
      T. Handa, T. Horio, M. Arakawa, and A. Terasaki
    • Organizer
      The 29th (XXIX) International Symposium on Molecular Beams (ISMB2021)
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] CWレーザーダイオードを用いた金属クラスター負イオンの光電子画像観測2021

    • Author(s)
      堀尾琢哉、南川賢人、西里 将、荒川 雅、寺嵜 亨
    • Organizer
      第15回分子科学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 銀クラスター正イオン上での一酸化窒素分子の逐次反応:サイズに依存した反応経路2021

    • Author(s)
      荒川 雅、堀岡正崇、南川賢人、河野知生、寺嵜 亨
    • Organizer
      第15回分子科学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 飛跡シミュレーションを用いた線形イオントラップ内のイオン分布解析2021

    • Author(s)
      飯田岳史、寺嵜 亨
    • Organizer
      第15回分子科学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] サイズ選別銀クラスター正イオンの多光子解離分光:幾何構造の推移に応じたスペクトルの形状変化2021

    • Author(s)
      河村 駿、河野 聖、荒川 雅、堀尾琢哉、寺嵜 亨
    • Organizer
      第15回分子科学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Electronic properties of silver and doped-silver clusters studied by laser spectroscopy and chemical reaction2021

    • Author(s)
      A. Terasaki
    • Organizer
      Pacifichem: Advanced Functional Clusters and Nanostructured Materials (Symposium #416)
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Cluster-growth analysis by optical emission spectroscopy in a magnetron-sputtering metal-cluster source2021

    • Author(s)
      S. Kono, M. Arakawa, and A. Terasaki
    • Organizer
      Pacifichem: Advanced Functional Clusters and Nanostructured Materials (Symposium #416)
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] マグネトロンスパッタ法での金属クラスター成長:発光分光による解析2020

    • Author(s)
      河野 聖、荒川 雅、寺嵜 亨
    • Organizer
      ナノ学会第18回大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] イオン軌道シミュレーションによる線形イオントラップ内のイオン密度分布の解析2020

    • Author(s)
      飯田岳史、堀尾琢哉、荒川 雅、寺嵜 亨
    • Organizer
      ナノ学会第18回大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] コバルト添加銀クラスター負イオンの電子構造:反応性測定に基づく光電子スペクトルの再解析2020

    • Author(s)
      南川賢人、荒川 雅、登野健介、寺嵜 亨
    • Organizer
      ナノ学会第18回大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 銀クラスター正イオンの光吸収分光:2量体から40量体まで2020

    • Author(s)
      河野 聖、荒川 雅、堀尾琢哉、寺嵜 亨
    • Organizer
      分子科学会オンライン討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 酸素との反応性を介したセリウム添加銀クラスター正イオンの電子構造探究2020

    • Author(s)
      林 奈穂、南川賢人、荒川 雅、寺嵜 亨
    • Organizer
      分子科学会オンライン討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 酸素との反応性に基づくコバルト添加銀クラスター負イオンの電子構造解析:光電子分光の再解釈2020

    • Author(s)
      南川賢人、荒川 雅、登野健介、寺嵜 亨
    • Organizer
      分子科学会オンライン討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Transition-metal-doped silver clusters: Examining electron-counting effect in cations and anions2020

    • Author(s)
      A. Terasaki, K. Minamikawa, and M. Arakawa
    • Organizer
      Symposium on Size-Selected Clusters (S3C)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Electron counting in cationic and anionic silver clusters doped with a transition-metal atom2019

    • Author(s)
      A. Terasaki, K. Minamikawa, and M. Arakawa
    • Organizer
      The 10th Conference of the Asian Consortium on Computational Materials Science (ACCMS-10)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Evolution of optical responses of free silver clusters as a function of size2019

    • Author(s)
      A. Terasaki
    • Organizer
      The 76th Fujihara Seminar, International Workshop on Designer Nanocluster Materials -From Gas Phase to Condensed Phase-
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Cluster growth in the magnetron-sputtering cluster source studied by optical emission spectroscopy2019

    • Author(s)
      S. Kono, M. Arakawa, and A. Terasaki
    • Organizer
      The 76th Fujihara Seminar, International Workshop on Designer Nanocluster Materials -From Gas Phase to Condensed Phase-
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Exploring electronic and geometric structures of both cationic and anionic transition-metal-doped silver clusters via reaction with dioxygen2019

    • Author(s)
      K. Minamikawa, N. Hayashi, M. Arakawa, and A. Terasaki
    • Organizer
      The 76th Fujihara Seminar, International Workshop on Designer Nanocluster Materials -From Gas Phase to Condensed Phase-
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Size-dependent optical responses of free silver clusters studied by trapped-ion spectroscopy2019

    • Author(s)
      A. Terasaki
    • Organizer
      The 15th DAE-BRNS Biennial Trombay Symposium on Radiation & Photochemistry (TSRP-2020)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] A study on cluster growth in the magnetron-sputtering metal-cluster source by optical emission spectroscopy2019

    • Author(s)
      S. Kono, M. Arakawa, and A. Terasaki
    • Organizer
      Workshop on Advances in Cluster Beam Deposition
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Emergence of plasmonic behavior in free silver clusters, AgN+, studied by photofragmentation spectroscopy in the size range up to N = 702019

    • Author(s)
      T. Horio, S. Fujimoto, S. Kono, M. Arakawa, T. Yasuike, and A. Terasaki
    • Organizer
      Materials Research Meeting 2019 Symposium G-4 Plasmonic Materials: from Fundamentals to Applications
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 遷移金属添加銀クラスター正イオンと一酸化窒素分子との反応:サイズと添加元素に依存した反応経路の変化2019

    • Author(s)
      堀岡正崇、荒川 雅、南川賢人、西川享佑、河野知生、寺嵜 亨
    • Organizer
      ナノ学会第17回大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] イオンビーム集束性能を向上させたリフレクトロン型飛行時間質量分析計の設計と実証2019

    • Author(s)
      飯田岳史、堀尾琢哉、荒川 雅、寺嵜 亨
    • Organizer
      ナノ学会第17回大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 孤立金属化合物クラスターの生成・分析における分光測定の活用2019

    • Author(s)
      荒川 雅、堀尾琢哉、寺嵜 亨
    • Organizer
      第79回分析化学討論会 スペクトロスコピー分析化学とその展開
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] 化学反応性を指標とした遷移金属添加銀クラスター正・負イオンの電子構造研究:s-d相互作用への電子数と幾何構造の効果2019

    • Author(s)
      南川賢人、林 奈穂、荒川 雅、寺嵜 亨
    • Organizer
      第13回分子科学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 遷移金属を添加した銀クラスター正イオンと一酸化窒素分子との反応:サイズと添加元素に依存した反応経路2019

    • Author(s)
      荒川 雅、堀岡正崇、西川享佑、南川賢人、河野知生、寺嵜 亨
    • Organizer
      第13回分子科学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] イオンビーム集束性を向上させたリフレクトロン型飛行時間質量分析計2019

    • Author(s)
      飯田岳史、堀尾琢哉、荒川 雅、寺嵜 亨
    • Organizer
      第13回分子科学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] マグネトロンスパッタ金属クラスター源の発光分析によるクラスター成長条件の解析2019

    • Author(s)
      河野 聖、荒川 雅、寺嵜 亨
    • Organizer
      第13回分子科学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 銀クラスター正イオンの光吸収・解離過程:2-40量体のサイズ依存性2019

    • Author(s)
      河野 聖、荒川 雅、堀尾琢哉、寺嵜 亨
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] リフレクトロン型飛行時間質量分析計の検出効率向上:イオンビーム集束性能の改善2019

    • Author(s)
      飯田岳史、堀尾琢哉、荒川 雅、寺嵜 亨
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Electronic structures of cobalt-doped silver cluster anions, AgNCo-, revisited: refined analysis of photoelectron spectra in light of chemical reactivity2019

    • Author(s)
      南川賢人、荒川 雅、登野健介、寺嵜 亨
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Transition-metal-doped silver clusters: cations and anions2019

    • Author(s)
      A. Terasaki
    • Organizer
      Gordon Research Conference on Gaseous Ions: Structures, Energetics and Reactions
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] レーザー・放射光とイオントラップ技術による孤立金属クラスターの分光2019

    • Author(s)
      寺嵜 亨
    • Organizer
      日本分光学会 中国四国支部 平成30年度年次講演会
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] 酸素分子との反応性を介した遷移金属添加銀クラスターイオンAgNM+/-の電子構造研究:18電子系における電子構造と幾何構造の相関2019

    • Author(s)
      南川賢人、堀岡正崇、河野知生、荒川 雅、寺嵜 亨
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 遷移金属原子を添加した銀クラスター正イオンと一酸化窒素分子との反応:サイズおよび添加元素による反応経路と生成物の変化2019

    • Author(s)
      堀岡正崇、西川享佑、南川賢人、河野知生、西浦 隼、荒川 雅、寺嵜 亨
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 光吸収による電子の集団励起:銀クラスター40-70量体2019

    • Author(s)
      藤本周平、河野 聖、荒川 雅、堀尾琢哉、安池智一、寺嵜 亨
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Finite-size effect in dilute magnetic alloy of silver in the small cluster regime2018

    • Author(s)
      A. Terasaki, K. Minamikawa, M. Horioka, and M. Arakawa
    • Organizer
      7th Interdisciplinary Symposium on Materials Chemistry (ISMC-2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Exploring electronic structures of transition-metal-doped silver clusters: Effect of electron count studied by chemical reaction of cations and anions2018

    • Author(s)
      K. Minamikawa, M. Horioka, T. Kawano, M. Arakawa, and A. Terasaki
    • Organizer
      Nineteenth International Symposium on Small Particles and Inorganic Clusters (ISSPIC 19)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 酸素との化学反応性を介した遷移金属添加銀クラスターイオンの電子構造研究2018

    • Author(s)
      南川賢人、堀岡正崇、河野知生、荒川 雅、寺嵜 亨
    • Organizer
      第12回分子科学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 遷移金属原子を添加した銀クラスター正イオンAgNM+(M = Sc-Ni)と一酸化窒素分子との反応: 添加元素による反応性・生成物の変化2018

    • Author(s)
      堀岡正崇、西川享佑、南川賢人、河野知生、西浦 隼、荒川 雅、寺嵜 亨
    • Organizer
      第12回分子科学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] TD-DFT計算による銀クラスター正イオンの電子励起における集団性の評価2018

    • Author(s)
      藤本周平、河野 聖、荒川 雅、安池智一、寺嵜 亨
    • Organizer
      第12回分子科学討論会
    • Related Report
      2018 Annual Research Report
  • [Remarks] 九州大学大学院理学研究院化学部門量子化学研究室ホームページ

    • URL

      http://www.scc.kyushu-u.ac.jp/quantum/index_j.php

    • Related Report
      2020 Annual Research Report 2019 Annual Research Report 2018 Annual Research Report

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Published: 2018-04-23   Modified: 2023-01-30  

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