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精密な相対論的電子状態理論の開発:分子物性と励起状態への展開

Research Project

Project/Area Number 20038040
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionTokyo Metropolitan University

Principal Investigator

波田 雅彦  Tokyo Metropolitan University, 理工学研究科, 教授 (20228480)

Project Period (FY) 2008 – 2009
Project Status Completed (Fiscal Year 2009)
Budget Amount *help
¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 2009: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2008: ¥800,000 (Direct Cost: ¥800,000)
Keywords磁気物性 / 相対論 / 計算科学 / 量子化学 / NMR / 相対論的量子化学 / 無限次Douglas-Kroll変換 / 2電子項 / スピン-軌道相互作用 / Dirac-Fock-Coulomb / エネルギー勾配法 / 2成分ハミルトニアン / 分子物性
Research Abstract

相対論補正項と電子相関を適切に含めて電子状態計算を実施することは近年の量子化学では日常的になりつつあります。実験との不一致は電子状態理論の誤差ではなく、殆どは化学系のモデル化等によって生じる外的要因に帰すると考えられます。大規模計算はこのモデル化の自由度を高める上で計算精度向上と相補的に必要と云えます。一方、我々が本研究課題において目的とする事は相対論補正を中心とした電子状態理論の精密化です。日常的な化学反応解析などには不要かもしれませんが、精密な実験計画を支援したり、波動関数の精度に敏感な分子物性の計算、超重原子を含む化合物の計算などに具することを目指します。このためには上述の理由から大規模計算に適応する理論であることも必須となります。
本研究課題では1電子系では理論上Dirac方程式と等価な無限次Douglas-Kroll (IODK)変換を用いて、(a)多電子系分子の種々の2電子相対論補正を導出し、(b)計算プログラムを作成し、(c)計算精度を確認し、(d)各種の分子物性の計算を実施し、(d)電子相関との関係を検討します。
具体的な成果は以下の通りです。重原子や超重原子を含む化合物のエネルギーや分子物性の高精度計算を低コストで実現することが可能な多電子系10DK法を提案し、分子構造最適化や磁気的分子物性を含めた計算プログラムを開発した。この方法を利用して核磁気遮蔽定数やNMR化学シフトの計算を実施し、従来の高次相対論的では精度が不十分であった極めて重い原子でも、良好な精度で計算が可能であることを示した。

Report

(2 results)
  • 2009 Annual Research Report
  • 2008 Annual Research Report
  • Research Products

    (33 results)

All 2010 2009 2008 Other

All Journal Article (21 results) (of which Peer Reviewed: 19 results) Presentation (12 results)

  • [Journal Article] Dilithioplumbole : A Lead-Bearing Aromatic Cyclopentadienyl Analog2010

    • Author(s)
      M.Saito, et al.
    • Journal Title

      Science 328

      Pages: 339-342

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Calculations and Electronic Analyses of ^<55>Mn and ^<13>C Nuclear Magnetic Shielding Constants for Mn(CO)_5X (X=H, F, Cl, Br, I, and CH_3) and M(CO)(NH_3)_3 (M=Cr^<2+>, Fe^<2+>, Cu^<+>, and Zn^<2+>)2010

    • Author(s)
      H.Tanimura, et al.
    • Journal Title

      Bull.Chem.Soc.Japan (印刷中)

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Relativistic and Electron-Correlation Effects on Magnetizabilities Investigated by the Douglas-Kroll-Hess Method and the Second-Order Moller-Plesset Perturbation Theory2009

    • Author(s)
      T.Yoshizawa, M.Hada
    • Journal Title

      J.Comp.Chem. 30(15)

      Pages: 2550-2566

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Critical Role of Extermal Axial Ligands in Chirality Amplification of trans-Cyclo-hexane-1,2-diamine in Salen Complexes2009

    • Author(s)
      T.Kurahashi, et al.
    • Journal Title

      J.Am.Chem.Soc. 131(34)

      Pages: 12394-12405

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Magnetic Shielding in Carbon Nanotube2009

    • Author(s)
      N.Miyake, et al.
    • Journal Title

      AIP Conf.Proc (印刷中)

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 13C NMR Shifts of Iron-bound Cyanide Ions in Heme-Protein Environments2009

    • Author(s)
      D.Yamaki, M.Hada
    • Journal Title

      AIP Conf.Proc (印刷中)

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Evaluation of Electron Population Term for <rse^<-3>>4p, <rrs^<-3>>3p, and <ro^<-3>>2p How do HOMO and LUMO Shrink or Spread Depending on Nuclear Charges?2008

    • Author(s)
      W. Nakanishi et.al.
    • Journal Title

      Chemistry A European J 14

      Pages: 7278-7284

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Contributions from atomic p(Se), d(Se), and f(Se)Orbitals to Absolute Paramagnetic Shielding Tensors in Neutral and Charged SeHn and Some Oxides, together with the Effect of Methyl and Halogen Substitutions on σ^P (Se)2008

    • Author(s)
      W. Nakanishi et.al.
    • Journal Title

      Chemistry A European J. 14

      Pages: 9467-9655

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] An ab initio study based on a finite nucleus model for isotope fractionation in the U(III)-U(TV) exchange reaction system2008

    • Author(s)
      M. Abe et.al.
    • Journal Title

      J. Chem. Phys. 128

      Pages: 1443091-1443096

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] An ab initio molecular orbital study of the nuclear volume effects in uranium isotope fractionations2008

    • Author(s)
      M. Abe et.al.
    • Journal Title

      J. Chem. Phys 129

      Pages: 1643091-1643097

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Examination of accuracy of electron-electron Coulomb inter-actions in two-component relativistic methods2008

    • Author(s)
      J. Seino and M. Hada
    • Journal Title

      Chem. Phys. Letters 461

      Pages: 327-331

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Relativistic quantum-chemical calculations of magnetizabilities of noble gas atoms using the Douglas-Kroll-Hess method2008

    • Author(s)
      T. Yoshizawa and M. Hada
    • Journal Title

      Chem. Phys. Letters 458

      Pages: 223-226

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Effect of Tridentate Ligand on Structure, Electronic Structure, and Reactivity of Copper(I) Nitrite Complex : Role of Conserved Three-Histidines Ligand Environment of Type-2 Copper Site in Copper Containing Nitrite Reducatse2008

    • Author(s)
      M. Kujime et.al.
    • Journal Title

      J. A. C. S. 130(19)

      Pages: 6088-6098

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Natural Orbital Analysis of Difference Density Matrix of Cyanide Fe(III) Porphyrins2008

    • Author(s)
      D. Yamaki et.al.
    • Journal Title

      AIP Conf. Proc. 1046

      Pages: 68-71

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Excitation and Circular Dichroism Spectra of (-)-(3aS, 7aS)-2-chalcogena-trans-hvdrindans(Ch=S, Se, Te) : SAC and SAC-CI Calculations2008

    • Author(s)
      Y Honda et.al.
    • Journal Title

      J. Comp. Chem 29

      Pages: 612-621

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Erratum : An ab initio molecular orbital study of the nuclear volume effects in Uranium isotope fractionations [J.Chem.Phys.129,164309,2008]

    • Author(s)
      M.Abe, et al.
    • Journal Title

      J.Chem.Phys. (印刷中)

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Expectation values in two-component relativistic theories

    • Author(s)
      J.Seino, et al.
    • Journal Title

      J.Chem.Phys. (印刷中)

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Magnetic shielding constants calculated by the infinite-order Douglas-Kroll-Hess Method with electron-electron relativistic corrections

    • Author(s)
      J.Seino, M.Hada
    • Journal Title

      J.Chem.Phys. (印刷中)

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Excitation and Circular Dichroism Spectra of (+)-(S,S)-bis(2-methylbutyl) chalcogenides

    • Author(s)
      Y.Honda, et al.
    • Journal Title

      Molecules (印刷中)

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Relativistic and Electron-Correlation Effects on Magnetizabilities Investigated by the Douglas Kroll Hess Method and the Second-Order Moller-Plesset Perturba-tion Theory

    • Author(s)
      T. Yoshizawa and M. Hada
    • Journal Title

      J. Comp. Chem (in press)

    • Related Report
      2008 Annual Research Report
  • [Journal Article] Quantum-Chemical Calculations of Natural Circular Dichroism

    • Author(s)
      Y. Honda and M. Hada
    • Journal Title

      Computing Letters (in press)

    • Related Report
      2008 Annual Research Report
  • [Presentation] Quantum-Chemical Analysis of Paramagnetic 13C NMR Shifts of Iron-bound Cyanide Ions in Heme-Protein Environments2009

    • Author(s)
      山木大輔、波田雅彦
    • Organizer
      The 7^<th> International Conference of Computational Methos in Sciences and Engineering
    • Place of Presentation
      ロードス島(ギリシャ)
    • Year and Date
      2009-09-30
    • Related Report
      2009 Annual Research Report
  • [Presentation] Two-component Relativistic Calculations of Heavy-Element NMR Chemical Shifts by the Second-Order and Infinite-Order Douglas-Kroll Method s2009

    • Author(s)
      波田雅彦
    • Organizer
      The 3^<rd> Japan-Czech-Slovak Joint Symposium for Theoretical/Computational Chemistry
    • Place of Presentation
      ブラティスラバ(スロバキア)
    • Year and Date
      2009-09-10
    • Related Report
      2009 Annual Research Report
  • [Presentation] Nuclear Volume Effects in Uranium Isotope Fractionation for Molecular systems2009

    • Author(s)
      M. Abe, et.al.
    • Organizer
      The International Conference on "Simulations and Dyna-mics for nanoscale and biological systems"
    • Place of Presentation
      東京大学
    • Related Report
      2008 Annual Research Report
  • [Presentation] 2成分型相対論における2電子項の精度検討-無限次FW変換法の拡張-2008

    • Author(s)
      清野淳司、波田雅彦
    • Organizer
      第11回理論化学討論会
    • Place of Presentation
      慶応義塾大学
    • Related Report
      2008 Annual Research Report
  • [Presentation] Development of Accurate Two-Component Relativistic Methods and Calculations of Magnetic Properties of Molecules containing Heavy-Elements2008

    • Author(s)
      M. Hada, et.al.
    • Organizer
      1^<st> CMD International Symposium
    • Place of Presentation
      Seoul(Korea)
    • Related Report
      2008 Annual Research Report
  • [Presentation] Ab initio Relativistic Calculations of Isotope Fractionation in the U(III)-U(IV) Exchange Reaction2008

    • Author(s)
      M. Abe, et.al.
    • Organizer
      Odyssey 2008
    • Place of Presentation
      Edmonton(Canada)
    • Related Report
      2008 Annual Research Report
  • [Presentation] Theoretical Studies on Circular Dichroism Spectra of L-Amino Acids2008

    • Author(s)
      Y. Honda
    • Organizer
      WATOC2008
    • Place of Presentation
      Sydney (Australia)
    • Related Report
      2008 Annual Research Report
  • [Presentation] Natural Orbital Analysis of NMR Chemical Shifts of Cyanide Fe(III) Porphyrins and Cu(I) with Tridentate Ligands2008

    • Author(s)
      D. Yamaki
    • Organizer
      WATOC2008
    • Place of Presentation
      Sydney (Australia)
    • Related Report
      2008 Annual Research Report
  • [Presentation] Ab initio Relativistic Calculations of Isotope Fractionation in the U(III)-U(IV) Exchange Reaction2008

    • Author(s)
      M. Abe, et.al.
    • Organizer
      WATOC2008
    • Place of Presentation
      Sydney (Australia)
    • Related Report
      2008 Annual Research Report
  • [Presentation] Applicability of Two-Component Relativistic Theory Based on the intim-Order Foldv-Wouthuysen Transformation in Many-Electron Systems2008

    • Author(s)
      J. Seino and M. Hada
    • Organizer
      WATOC2008
    • Place of Presentation
      Sydney (Australia)
    • Related Report
      2008 Annual Research Report
  • [Presentation] An Endeavor at Constructing an Accurate Two-Component Relativistic Method for Heavy and super-Heavy Elements2008

    • Author(s)
      M. Hada and J. Seino
    • Organizer
      TACC2008
    • Place of Presentation
      Shanghai (China)
    • Related Report
      2008 Annual Research Report
  • [Presentation] 電子相関を考慮した磁気円二色性の研究2008

    • Author(s)
      本田康、中辻博、波田雅彦
    • Organizer
      第2回分子科学討論会
    • Place of Presentation
      福岡国際会議場
    • Related Report
      2008 Annual Research Report

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Published: 2008-04-01   Modified: 2018-03-28  

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