Elucidation of lanthanides extraction pattern based on chemical bonding evaluation

• Project/Area Number: 17K14915
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Nuclear engineering
• Research Institution: Japan Atomic Energy Agency
• Principal Investigator: Kaneko Masashi 国立研究開発法人日本原子力研究開発機構, 原子力科学研究部門 原子力科学研究所 原子力基礎工学研究センター, 研究職 (50781697)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2019: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2018: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2017: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
• Keywords: ランタノイド / マイナーアクチノイド / 密度汎関数法 / 分離変換技術 / メスバウアー分光 / ランタノイドパターン / fブロック錯体 / 化学結合 / HSAB則 / 錯体化学 / ランタノイド抽出パターン

Outline of Final Research Achievements

Aiming to develop partitioning and transmutation strategy of high-level radioactive liquid waste, effective separations of minor actinides and lanthanides have been required. This study focused on lanthanides extraction pattern to discuss geometrical and electronic structures of lanthanide complexes with several extractants by using density functional theory calculations.
Chemical bonding analysis combined with Moessbauer spectroscopic parameters as well as systematic electronic state analysis using chalcogen- and pnictogen-donor ligands revealed that d- and f-orbital electrons contribute to coordination bonds with the ligands. We also discussed lanthanides pattern based on complex formation reactions between lanthanides and amide-type extractants.

Academic Significance and Societal Importance of the Research Achievements

高レベル放射性廃液からのマイナーアクチノイド及びランタノイドの分離は、有害度低減につながる重要な研究テーマであり、本研究は、その分離メカニズムを計算化学的に明らかにする一つの試みである。また、化学における基礎的な考え方の一つである化学結合とその分離メカニズムをリンクすることにより、化学結合に対する理解を深めることによる基礎科学的視点と、化学結合をコントロールすることによる新規分離材料の開発に役立てる可能性を持つ。

Research Products

• [Journal Article] Density Functional Theory (DFT)-Based Bonding Analysis Correlates Ligand Field Strength with 99Ru Moessbauer Parameters of Ruthenium-Nitrosyl Complexes (2019)
  • Author(s): Kaneko Masashi、Kato Akane、Nakashima Satoru、Kitatsuji Yoshihiro
  • Journal Title: Inorganic Chemistry Volume: 58 Issue: 20 Pages: 14024-14033
  • DOI: 10.1021/acs.inorgchem.9b02024
  • Peer Reviewed
• [Journal Article] Computational chemical analysis of Eu(iii) and Am(iii) complexes with pnictogen-donor ligands using DFT calculations (2018)
  • Author(s): Kimura Taiki、Kaneko Masashi、Watanabe Masayuki、Miyashita Sunao、Nakashima Satoru
  • Journal Title: Dalton Transactions Volume: 47 Issue: 42 Pages: 14924-14931
  • DOI: 10.1039/c8dt01973h
  • Peer Reviewed
• [Journal Article] Theoretical Elucidation of Am(III)/Cm(III) Separation Mechanism with Diamide-type Ligands Using Relativistic Density Functional Theory Calculation (2018)
  • Author(s): Kaneko Masashi、Suzuki Hideya、Matsumura Tatsuro
  • Journal Title: Inorganic Chemistry Volume: 57 Issue: 23 Pages: 14513-14523
  • DOI: 10.1021/acs.inorgchem.8b01624
  • Peer Reviewed
• [Journal Article] Benchmark study of DFT with Eu and Np Mossbauer isomer shifts using second-order Douglas-Kroll-Hess Hamiltonian (2018)
  • Author(s): Masashi Kaneko, Masayuki Watanabe, Sunao Miyashita, Satoru Nakashima
  • Journal Title: Hyperfine Interact. Volume: 239 Issue: 1
  • DOI: 10.1007/s10751-018-1495-1
  • NAID: 120007147034
  • Peer Reviewed
• [Journal Article] Correlation between Am(III)/Eu(III) selectivity and covalency in metal?chalcogen bonds using density functional calculations (2018)
  • Author(s): Masashi Kaneko, Masayuki Watanabe
  • Journal Title: J. Radioanal. Nucl. Chem. Volume: 印刷中 Issue: 3 Pages: 1129-1137
  • DOI: 10.1007/s10967-017-5683-2
  • NAID: 120007147027
  • Peer Reviewed
• [Presentation] 正八面体型ニトロシルルテニウム錯体の配位子場解析 (2019)
  • Author(s): 金子政志、加藤茜、中島覚、北辻章浩、渡邉雅之
  • Organizer: 平成31年度日本原子力学会北関東支部若手研究者発表会
• [Presentation] Ligand field analysis of ruthenium nitrosyl complexes using DFT calculation combined with 99Ru Moessbauer isomer shift (2019)
  • Author(s): Kaneko Masashi, Kato Akane, Nakashima Sastoru, Kitatsuji Yoshihiro
  • Organizer: International Conference on the Applications of the Moessbauer Effect 2017 (ICAME2019)
  • Int'l Joint Research
• [Presentation] Benchmarking of DFT with Mössbauer Isomer Shift Values for Heavy Metal Complexes (2018)
  • Author(s): Kaneko Masashi、Watanabe Masayuki
  • Organizer: The 4th Mediterranean Conference on the Applications of the Mössbauer Effect (MECAME2018)
  • Int'l Joint Research / Invited
• [Presentation] ジアミド型配位子によるAm/Cm分離メカニズムに関する計算化学研究 (2018)
  • Author(s): 金子政志、渡邉雅之、鈴木英哉、松村達郎
  • Organizer: 日本原子力学会2018年秋の大会
• [Presentation] Benchmarking of density functional theory with Mössbauer isomer shift and the application to f-block metal coordination chemistry (2018)
  • Author(s): Kaneko Masashi、Watanabe Masayuki
  • Organizer: The 9th TOYOTA RIKEN International Workshop on New Developments and Prospects for the Future of Mössbauer Spectroscopy (IWMS2018)
  • Int'l Joint Research
• [Presentation] TPEN配位子へのカルボニルドナー導入によるマイナーアクチノイド分離性能の理論的予測 (2017)
  • Author(s): 金子政志, 渡邉雅之, 松村達郎
  • Organizer: 日本原子力学会第１３回再処理・リサイクル部会セミナー
• [Presentation] Density functional study on the Am(III)/Eu(III) selectivity correlated to the covalency in metal-chalcogen bond (2017)
  • Author(s): Masashi Kaneko, Masayuki Watanabe
  • Organizer: 6th Asia-Pacific Symposium on Radiochemistry (APSORC17)
  • Int'l Joint Research / Invited
• [Presentation] Benchmark study of DFT with Eu and Np Mössbauer isomer shifts using second-order Douglas-Kroll-Hess Hamiltonian (2017)
  • Author(s): Masashi Kaneko, Masayuki Watanabe, Sunao Miyashita, Satoru Nakashima
  • Organizer: International Conference on the Applications of the Mössbauer Effect 2017 (ICAME2017)
  • Int'l Joint Research
• [Presentation] Time-dependent density functional study on tetravalent uranium halides in tetrahydrofuran solution (2017)
  • Author(s): Masashi Kaneko, Masayuki Watanabe, Noboru Aoyagi
  • Organizer: ACTINIDES2017
  • Int'l Joint Research
• [Presentation] ニトリロトリアセトアミドによるランタノイド抽出パターンに対する計算化学研究 (2017)
  • Author(s): 金子政志, 渡邉雅之, 鈴木英哉, 松村達郎
  • Organizer: 第３３回希土類討論会