量子化学計算による多核金属錯体の物性発現機構の解明と分子素子設計への展開

• Project Area: Coordination Programming - Science of Molecular Superstructures for Chemical Devices
• Project/Area Number: 22108515
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Osaka University
• Principal Investigator: 北河 康隆 大阪大学, 理学研究科, 助教 (60362612)
• Project Period (FY): 2010 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥5,980,000 (Direct Cost: ¥4,600,000、Indirect Cost: ¥1,380,000); Fiscal Year 2011: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000); Fiscal Year 2010: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
• Keywords: 量子化学 / 第一原理計算 / 磁性 / 多核遷移金属錯体 / スピン射影(AP)エネルギー微分法 / 光物性 / 電気伝導性 / 電子状態理論 / DNA-metal錯体

Research Abstract

本年度は、(1)多核錯体の磁性パラメータ(J)値の第一原理計算、(2)一次元多核錯体の電気伝導度計算、(3)π共役配位子を有する多核錯体の光吸収スペクトルの第一原理計算、(4)巨大ビラジカル分子の構造最適化のための二階層QM/QM法の開発、を行った。まず(1)の、J値の定量的計算に関しては、大塩グループによって合成されたFe_2Co_24核錯体に関して、金属イオン間に働くJ値を量子化学計算により求めた。本研究は大塩グループとの共同研究にて遂行された。続いて(2)では、PengらによるNi一次元錯体に着目し、電気伝導計算を行った。計算結果は実験と良く一致し、また、伝導性に寄与する軌道を明らかにする事に成功した。これらの結果は招待講演などで発表した。(3)では(1)で計算したFe_2Co_24核錯体の光吸収による電荷移動(IVCT)のメカニズムを時間依存密度汎関数(TD-DFT)計算により検討した。励起スペクトルを計算し、遷移に関与する分子軌道の解析を行った結果、電荷移動に関与する軌道を明らかにする事に成功した。加えて、棚瀬グループにより合成されたPd8核錯体における電子状態および光吸収スペクトルをDFTおよびTD-DFT計算により解析した。本錯体は、σ軌道が分子内に大きく非局在している事から、ナノワイヤの有力な候補となることが考えられる。また、光吸収にともなう遷移に関与する軌道を明らかにした。本研究は棚瀬グループとの共同研究である。最後に(4)では、巨大配位子を有する二核錯体などの、巨大ビラジカル分子の構造最適化を精度よく行うために、本研究グループで開発したAP法とスピン制限法をONIOM法に基づいて融合するAP/R法を提案した。得られた結果は、全体をAP法で最適化した座標とほぼ一致しながら、計算機コストを大幅に削減させる事に成功した。

Research Products

• [Journal Article] Singlet-Triplet Energy Gap for Trimethylenemethane, Oxyallyl Diradical and Related Species : Single and Multi-reference Computational Results (2011)
  • Author(s): Toru Saito
  • Journal Title: Theoretical Chemistry Accounts Volume: 130 Issue: 4-6 Pages: 739-748
  • DOI: 10.1007/s00214-011-0914-z
  • Peer Reviewed
• [Journal Article] Symmetry and Broken Symmetry in Molecular Orbital Description of Unstable Molecules IV. Comparison between Single- and Multi-reference Computational Results for Antiaromtic Molecules (2011)
  • Author(s): Toru Saito
  • Journal Title: Theoretical Chemistry Accounts Volume: 130 Issue: 4-6 Pages: 749-763
  • DOI: 10.1007/s00214-011-0941-9
  • Peer Reviewed
• [Journal Article] Theoretical study of intra- and inter-chain magnetic interactions in [Ni(chxn)_2Br]Br_2 (2011)
  • Author(s): Y.Kitagawa, et al
  • Journal Title: POLYHEDRON Volume: 30 Issue: 18 Pages: 3116-3120
  • DOI: 10.1016/j.poly.2011.03.006
  • Peer Reviewed
• [Journal Article] Potential Energy Curve for Ring-Opening Reactions : Comparison Between Broken-Symmetry and Multireference Coupled Cluster Methods (2011)
  • Author(s): Toru Saito
  • Journal Title: Journal of Physical Chemistry A Volume: 115 Issue: 22 Pages: 5625-5631
  • DOI: 10.1021/jp201463h
  • Peer Reviewed
• [Journal Article] Electron Conductivity in Modified Models of Artificial Metal-DNA Using Green's Function-Based Elastic Scattering Theory (Selected Paper) (2011)
  • Author(s): Y.Nakanishi, Y.Kitagawa, et al
  • Journal Title: BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN Volume: 84 Issue: 4 Pages: 366-375
  • DOI: 10.1246/bcsj.20100207
  • NAID: 130004152889
  • Peer Reviewed
• [Journal Article] Broken-symmetry Natural Orbital (BSNO)-Mk-MRCC Study on the Exchange Coupling in the Binuclear Copper (II) Compounds (2011)
  • Author(s): T.Saito, M.Okumura, K.Yamaguchi, et al
  • Journal Title: Chem.Phys.Lett. Volume: 505 Issue: 1-3 Pages: 11-15
  • DOI: 10.1016/j.cplett.2011.02.018
  • Peer Reviewed
• [Journal Article] Theoretical Studies on the Structural and Magnetic Property of Arginase Active Site (2011)
  • Author(s): Y.Kitagawa, M.Okumura, K.Yamaguchi, et al
  • Journal Title: Suplamol.Chem. Volume: 23 Issue: 1-2 Pages: 22-29
  • DOI: 10.1080/10610278.2010.506552
  • Peer Reviewed
• [Journal Article] Theoretical Studies on the Electronic Structure of the Synthetic Complex of Soluble Methanemonooxygenase Intermediate Q (2011)
  • Author(s): T.Saito, M.Okumura, K.Yamaguchi, et al
  • Journal Title: Suplamol.Chem. Volume: 23 Issue: 1-2 Pages: 83-87
  • DOI: 10.1080/10610278.2010.510560
  • Peer Reviewed
• [Journal Article] Theoretical Study of Absorption Spectrum of Dirhodium Tetracarboxylate Complex [Rh_2(CH_3COO)_4(H_2O)_2] in Aqueous Solution Revisited (2011)
  • Author(s): 片岡祐介
  • Journal Title: Supramolecuar Chemistry Volume: 23 Issue: 3-4 Pages: 329-336
  • DOI: 10.1080/10610278.2010.534553
  • Peer Reviewed
• [Journal Article] Which hybrid GGA DFT is suitable for Cu_2O_2 systems if the spin contamination error is removed? (Cover figure article) (2010)
  • Author(s): T.Saito, Y.Kitagawa, et al.
  • Journal Title: Chemical Physics Volume: 368 Pages: 1-6
  • Peer Reviewed
• [Journal Article] Reinvestigation of the Reaction of Ethylene and Singlet Oxygen by the Approximate Spin Projection Method. Comparison with Multireference Coupled-Cluster Calculations, (2010)
  • Author(s): T.Saito, Y.Kitagawa, et al.
  • Journal Title: Journal of Physical Chemistry A Volume: 114 Pages: 7967-7974
  • Peer Reviewed
• [Journal Article] Sequence-Dependent Proton-Transfer Reaction in Stacked GC Pair III : The Influence of Proton Transfer to Conductivity (2010)
  • Author(s): Y.Nakanishi, Y.Kitagawa, et al
  • Journal Title: International Journal of Quantum Chemistry Volume: 110 Pages: 2221-2230
  • Peer Reviewed
• [Journal Article] Theoretical studies of the effect of orientation of ligands and spin contamination error on the chemical bonding in the FeO_2 core in oxymyoglobin (2010)
  • Author(s): T.Saito, Y.Kitagawa, et al.
  • Journal Title: Journal of Molecular Structure (Theochem) Volume: 954 Pages: 98-104
  • Peer Reviewed
• [Journal Article] A broken-symmetry study on the automerization of cyclobutadiene. Comparison with UNO-and DNO-MRCC methods (2010)
  • Author(s): T.Saito, Y.Kitagawa, et al.
  • Journal Title: Chemical Physics Letters Volume: 498 Pages: 253-258
  • Peer Reviewed
• [Journal Article] Theoretical Study on the Electronic Configurations and Nature of Chemical Bonds of Dirhodium Tetraacetato Complexes[Rh_2(CH_3COO)_4(L)_2](L=H_2O, Free): Broken Symmetry Approach (2010)
  • Author(s): Y.Kataoka, Y.Kitagawa, et al.
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 83 Pages: 1481-1488
  • NAID: 10027653603
  • Peer Reviewed
• [Journal Article] Development of approximately spin projected energy derivatives for biradical systems (2010)
  • Author(s): Y.Kitagawa, et al.
  • Journal Title: International Journal of Quantum Chemistry Volume: 110 Pages: 3053-3060
  • Peer Reviewed
• [Journal Article] Theory of Chemical Bonds in Metalloenzymes. XIV. Correspondence Between Magnetic Coupling Mode and Radical Coupling Mechanism in Hydroxylations with Methane Monooxygenase and Related Species (2010)
  • Author(s): T.Saito, Y.Kitagawa, et al.
  • Journal Title: International Journal of Quantum Chemistry Volume: 110 Pages: 2955-2981
  • Peer Reviewed
• [Journal Article] Multireference Character of 1, 3-Dipolar Cycloaddition of Ozone with Ethylene and Acrylonitrile (2010)
  • Author(s): T.Saito, Y.Kitagawa, et al.
  • Journal Title: Journal of Physical Chemistry A Volume: 114 Pages: 12116-12123
  • Peer Reviewed
• [Presentation] 量子化学計算に基づいた電子輸送機構解明への挑戦～1次元錯体の単分子電気伝導と蛋白質の電子伝達～ (2012)
  • Author(s): 北河康隆
  • Organizer: 第5回東北大学G-COE研究会
  • Place of Presentation: 東北大学理学部,宮城県(招待講演)
  • Year and Date: 2012-01-20
• [Presentation] 近似スピン射影法とスピン制限法の併用による2核錯体の構造最適化 (2011)
  • Author(s): 北河康隆
  • Organizer: 第5回分子科学討論会
  • Place of Presentation: 札幌コンベンションセンター,北海道
  • Year and Date: 2011-09-20
• [Presentation] 一次元Ni多核錯体の電気伝導性に関する理論的研究 (2011)
  • Author(s): 北河康隆
  • Organizer: 錯体化学会第61回討論会
  • Place of Presentation: 岡山理科大学,岡山県
  • Year and Date: 2011-09-17
• [Presentation] Two-layer QM/QM' calculations for a geometry optimization of large biradical systems (2011)
  • Author(s): Y.Kitagawa
  • Organizer: XVIth International Workshop on Quantum Systems in Chemistry and Physics
  • Place of Presentation: 石川県立美術館,金沢,石川県(招待講演)
  • Year and Date: 2011-09-15
• [Presentation] DFT calculations of exchange integral (J) values for (VO)6 and (VO)7 ring complexes (2011)
  • Author(s): Y.Kitagawa
  • Organizer: ICC-IMR Workshop on Development of Functionalized Molecule-based Magnetic Materials
  • Place of Presentation: 金属材料研究所国際共同研究センター,東北大学,宮城県(招待講演)
  • Year and Date: 2011-09-13
• [Presentation] Elimination of the spin contamination error from energy derivatives of the broken-symmetry method-For larger biradical systems- (2011)
  • Author(s): Y.Eitagawa
  • Organizer: 14^<th> Asian Chemical Congress 2011 (14 ACC)
  • Place of Presentation: QSNCC, Bangkok, Thailand(招待講演)
  • Year and Date: 2011-09-06
• [Presentation] Combination of spin-restricted and spin-projected calculations for a geometry optimization of large biradical systems (2011)
  • Author(s): Y.Kitagawa
  • Organizer: The 7th Congress of the International Society for Theoretical Chemical Physics (ISTCP-VII)
  • Place of Presentation: Waseda University, Tokyo, Japan
  • Year and Date: 2011-09-04
• [Presentation] 一次元Ni3核および5核錯体の磁性と伝導性 (2011)
  • Author(s): 北河康隆
  • Organizer: 第14回理論化学討論会
  • Place of Presentation: 岡山大学創立五十周年記念館,岡山県
  • Year and Date: 2011-05-14
• [Presentation] Theoretical study of magnetic interactions in ringed complexes (2010)
  • Author(s): Y.Kitagawa
  • Organizer: Pacifichem2010
  • Place of Presentation: Hawaii Convention Center, Hawaii(USA)(ポスター発表)
  • Year and Date: 2010-12-19
• [Presentation] Spin-projected energy derivatives in combination with two-layer method for large biradical systems (2010)
  • Author(s): Y.Kitagawa
  • Organizer: Pacifichem2010
  • Place of Presentation: Hawaii Convention Center, Hawaii(USA)(ポスター発表)
  • Year and Date: 2010-12-17
• [Presentation] Theoretical Study of Intra- and Inter-Chain Magnetic Interactions in [Ni(chxn)_2Br]Br_2 (2010)
  • Author(s): Y.Kitagawa
  • Organizer: International Conference on Molecule-Based Magnets
  • Place of Presentation: Beijin, China(ポスター発表)
  • Year and Date: 2010-10-10
• [Presentation] HiPIP活性中心の電子状態と水素結合の効果-量子化学計算からのアプローチ- (2010)
  • Author(s): 北河康隆
  • Organizer: 蛋白研セミナー
  • Place of Presentation: 大阪大学(招待講演)
  • Year and Date: 2010-10-06
• [Presentation] Theoretical study of electronic structures, magnetic interactions and electron conductivities of 1D-chain Ni complexes (2010)
  • Author(s): Y.Kitagawa
  • Organizer: The 60th JSCC Symposium and the 60th Anniversary Conference on Coordination Chemistry
  • Place of Presentation: 大阪国際交流センター(招待講演)
  • Year and Date: 2010-09-27
• [Presentation] 多核遷移金属錯体のためのQM/QM'法の開発 (2010)
  • Author(s): 北河康隆
  • Organizer: 分子科学討論会
  • Place of Presentation: 大阪大学(ポスター発表)
  • Year and Date: 2010-09-16
• [Presentation] HiPIP活性中心周辺の個々の水素結合が活性中心の電子状態に及ぼす影響 (2010)
  • Author(s): 北河康隆
  • Organizer: 理論化学討論会
  • Place of Presentation: 北海道大学(口頭発表)
  • Year and Date: 2010-05-24