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Doping effect of rare-earth elements to metal clusters: s-f electron interactions in ultrafine metals

Research Project

Project/Area Number 19K05185
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 28010:Nanometer-scale chemistry-related
Research InstitutionKyushu University

Principal Investigator

Arakawa Masashi  九州大学, 理学研究院, 助教 (10610264)

Project Period (FY) 2019-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2021: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2020: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2019: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Keywords金属クラスター / s-f電子相互作用 / s-d電子相互作用 / 電子局在/非局在 / ランタノイド / 超原子 / 反応経路 / 反応カイネティクス / イオン-分子反応 / 幾何構造 / 電子構造 / 希土類 / 質量分析 / 希土類元素 / クラスター / 電子局在・非局在 / s-f電子間相互作用
Outline of Research at the Start

極微小金属中で量子化された状態密度を持つ有限個の伝導s電子と局在f電子との相互作用は、サブナノスケールの物質を扱う次世代のナノ物質科学にとって重要な課題である。系内の電子数を厳密に制御可能な金属クラスターに着目し、希土類原子を添加した非磁性金属クラスターのO2などの分子に対する反応性をプローブとして、極微小金属中の伝導s電子と局在 f電子との相互作用、さらには局在スピン同士の相互作用を探究する。

Outline of Final Research Achievements

This study aimed at investigation of interaction between itinerant s electrons and localized d and f electrons with quantized density of states in the finite regime. We measured reaction kinetics of size-selected gas-phase lanthanide-doped silver clusters toward oxygen to probe their electronic structures. Our results revealed that d electrons of the dopant delocalize to contribute to electronic shell closure with s electrons, whereas f electrons remain localized not to contribute to the shell closure.

Academic Significance and Societal Importance of the Research Achievements

非磁性金属に微量の磁性金属を含む希薄合金において、磁性不純物に局在したd, f電子と非磁性金属のs電子との相互作用によるスピン消失に起因した近藤効果が知られ、特に磁性金属として希土類元素を含む場合には、3d遷移金属の化合物にはない特異な性質を示す物質が数多く見出されてきた。ところが、極微小金属中で量子化された状態密度を持つ有限個の伝導s電子と局在f電子との相互作用は未解明であった。金属クラスター中の有限個の伝導電子と局在f電子との相互作用を探究した本成果は、サブナノスケールの極微小物質を扱う次世代のナノ物質科学にとって非常に有意義である。

Report

(5 results)
  • 2022 Annual Research Report   Final Research Report ( PDF )
  • 2021 Research-status Report
  • 2020 Research-status Report
  • 2019 Research-status Report
  • Research Products

    (26 results)

All 2023 2022 2021 2020 2019 Other

All Journal Article (8 results) (of which Peer Reviewed: 8 results) Presentation (17 results) (of which Int'l Joint Research: 5 results,  Invited: 5 results) Remarks (1 results)

  • [Journal Article] Exploring s-d, s-f, and d-f Electron Interactions in AgnCe+ and AgnSm+ by Chemical Reaction toward O22022

    • Author(s)
      M. Arakawa, N. Hayashi, K. Minamikawa, T. Nishizato, and A. Terasaki
    • Journal Title

      The Journal of Physical Chemistry A

      Volume: 126 Issue: 39 Pages: 6920-6926

    • DOI

      10.1021/acs.jpca.2c04941

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [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
      2021 Research-status 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 Research-status 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 Research-status 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 Research-status 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 Research-status Report
    • Peer Reviewed
  • [Journal Article] Adsorption kinetics of nitrogen molecules on size-selected silver cluster cations2019

    • Author(s)
      T. Ito, M. Arakawa, Y. Taniguchi, and A. Terasaki
    • Journal Title

      Z. Phys. Chem.

      Volume: 233 Issue: 6 Pages: 759-770

    • DOI

      10.1515/zpch-2019-1373

    • Related Report
      2019 Research-status 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 Research-status Report
    • Peer Reviewed
  • [Presentation] Reaction kinetics of NO on Agn+ and AgnM+ (M = Sc-Ni): Size- and dopant-dependent reaction pathways2023

    • Author(s)
      M. Arakawa, M. Horioka, K. Minamikawa, T. Kawano, and A. Terasaki
    • Organizer
      The Symposium on Size-Selected Clusters S3C
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Reaction kinetics of nitric oxide molecules on silver cluster cations: Size-dependent reaction pathways2022

    • Author(s)
      M. Arakawa, M. Horioka, K. Minamikawa, T. Kawano, and A. Terasaki
    • Organizer
      International Congress on Pure & Applied Chemistry Kota Kinabalu (ICPAC Kota Kinabalu 2022)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [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
      2021 Research-status 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協同効果2021

    • Author(s)
      南川賢人, 猿楽峻, 荒川雅, 寺嵜亨
    • Organizer
      ナノ学会第19回大会
    • Related Report
      2021 Research-status 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 Research-status 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 Research-status 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 Research-status Report
  • [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 Research-status Report
  • [Presentation] コバルトクラスター正イオン上での一酸化炭素-水素分子間反応2020

    • Author(s)
      荒川雅, 堀尾琢哉, 寺嵜亨
    • Organizer
      ナノ学会第18回大会
    • Related Report
      2020 Research-status Report
  • [Presentation] Electronic Structures of Cobalt-doped Silver Cluster Anions, AgNCo-, Revisited: Refined Analysis of Photoelectron Spectra in Light of Chemical Reactivity2020

    • Author(s)
      K. Minamikawa, M. Arakawa, K. Tono, A. Terasaki
    • Organizer
      The 100th CSJ Annual Meeting, Noda
    • Related Report
      2019 Research-status Report
  • [Presentation] Elementary processes in chemical evolution studied by size-selected cluster chemistry2019

    • Author(s)
      M. Arakawa and A. Terasaki
    • Organizer
      The 23rd East Asian Workshop on Chemical Dynamics (EAWCD)
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Reaction of gas-phase metal and mineral clusters with H2O, CO, and H2 molecules related to chemistry in space2019

    • Author(s)
      M. Arakawa and A. Terasaki
    • Organizer
      International Congress on Pure & Applied Chemistry Yangon (ICPAC Yangon 2019)
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [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, 第79回分析化学討論会2019

    • Author(s)
      荒川雅, 堀尾琢哉, 寺嵜亨
    • Organizer
      第79回分析化学討論会
    • Related Report
      2019 Research-status Report
    • Invited
  • [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 Research-status Report
  • [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 Research-status Report
  • [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, A. Terasaki
    • Organizer
      The 76th Fujihara Seminar: International Workshop on Designer Nanocluster Materials -From Gas Phase to Condensed Pase-
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [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 Research-status Report
  • [Remarks] Work

    • URL

      http://www.scc.kyushu-u.ac.jp/quantum/members/Arakawa/work.html

    • Related Report
      2020 Research-status Report

URL: 

Published: 2019-04-18   Modified: 2024-01-30  

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