高位電子励起状態の高精度計算に向けた電子論の開発と光化学分子への応用

• Project Area: Application of Cooperative-Excitation into Innovative Molecular Systems with High-Order Photo-functions
• Project/Area Number: 15H01097
• 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: Institute for Molecular Science
• Principal Investigator: 柳井 毅 分子科学研究所, 理論・計算分子科学研究領域, 准教授 (00462200)
• Project Period (FY): 2015-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2016: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000); Fiscal Year 2015: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
• Keywords: 理論化学 / 電子相関 / 光化学 / フォトクロミズム / 励起状態 / ラジカル

Outline of Annual Research Achievements

研究実績は主に２つにある。（１）密度行列繰り込み群（ＤＭＲＧ）と呼ばれる電子状態理論を基盤として、高位励起状態に対する高精度な理論的記述を可能とする方法論および計算法の開発を行い、高性能プログラムを完成させた。（２）その手法を用いて、領域内研究者と協力して、種々のフォトクロミック化合物（ジアリールエテン誘導体等）の励起状態に対する計算を行った。
（１）では、電子励起状態の波動関数を高精度に求める理論のフレームワークとして、多参照理論に基づく電子状態理論DMRG-XMS-CASPT2法を開発した。多参照理論では、波動関数は複数の電子配置の量子的重ね合わせとして記述される。ＣＡＳＰＴ２法は広く用いられている高精度多参照理論であり、計算効率もよく大きな系への適用が期待される。本研究では、このＣＡＳＰＴ２法を複数の励起状態を効率よく数値的安定に求めることが可能な拡張理論ＸＭＳ－ＣＡＳＰＴ２法の実装を行い、ＤＭＲＧ波動関数を参照関数とする組み合わせを実現した。
（２）本手法を用いて、種々のフォトクロミック化合物（ジアリールエテン誘導体等）の励起状態に対する応用計算を行った。応用計算では、領域内の研究者と共同研究を実施した。Ａ０３グループの阿部教授らは近年フェノキシル-イミダゾールラジカル化合物(PIC)およびペンタアリルビイミダゾール（ＰＡＢＩ）のフォトクロミック分子の開発報告した。本研究では、ＰＩＣおよびＰＡＢＩのフォトクロミック分子の機構に関する理論研究を行った。高速分光により反応機構の解明に関する研究は行われてきたが、フォトクロミックの開環反応の具体的反応機構、電子論的理解は不十分であった。そこで本研究では、阿部グループ（Ａ０３）および重田グループ（Ａ０１）との共同で、高精度電子状態理論に基づく理論解析を行った。

Research Progress Status

28年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

28年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] ノースウエスタン大学(米国)
• [Int'l Joint Research] 有機化学生物化学研究所(チェコ)
• [Journal Article] Influence of the choice of projection manifolds in the CASPT2 implementation (2017)
  • Author(s): T. Yanai, Y. Kurashige, M. Saitow, J. Chalupsky, R. Lindh, P.-A. Malmqvist
  • Journal Title: Mol. Phys. Volume: 印刷中 Issue: 17-18 Pages: 2077-2085
  • DOI: 10.1080/00268976.2016.1271152
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Triplet-triplet Annihilation Process of 9,10-diphenylanthracene in solution (2017)
  • Author(s): R. Sato, H. Kioth-Nishioka, T. Yanai, Y. Shigeta
  • Journal Title: Chem. Lett. Volume: 印刷中 Issue: 6 Pages: 873-875
  • DOI: 10.1246/cl.170161
  • NAID: 130005689352
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Hyperfine Coupling Constants from Internally Contracted Multireference Perturbation Theory (2016)
  • Author(s): T. Shiozaki, and T. Yanai
  • Journal Title: J. Comp. Theo. Chem. Volume: 12 Issue: 9 Pages: 4347-4351
  • DOI: 10.1021/acs.jctc.6b00646
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Computational Evidence of Inversion of 1La and 1Lb-Derived Excited States in Naphthalene Excimer Formation from ab Initio Multireference Theory with Large Active Space: DMRG-CASPT2 Study (2016)
  • Author(s): S. Shirai, Y. Kurashige, and T. Yanai
  • Journal Title: J. Chem. Theo. Comp. Volume: - Issue: 5 Pages: 2366-2372
  • DOI: 10.1021/acs.jctc.6b00210
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] MADNESS: A Multiresolution, Adaptive Numerical Environment for Scientific Simulation (2016)
  • Author(s): R. Harrison, G. Beylkin, F. Bischoff, J. Calvin, G. Fann, J. Fosso-Tande, D. Galindo, J. Hammond, R. Hartman-Baker, J. Hill, J. Jia, J. Kottmann, M-J. Yvonne Ou, L. Ratcliff, M. Reuter, A. Richie-Halford, N. Romero, H. Sekino, W. Shelton, A. Vazquez-Mayagoitia, N. Vence, T. Yanai, Y. Yokoi
  • Journal Title: SIAM Journal on Scientific Computing Volume: 38 Issue: 5 Pages: S123-S142
  • DOI: 10.1137/15m1026171
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] A pentanuclear iron catalyst designed for water oxidation (2016)
  • Author(s): Masaya Okamura, Mio Kondo, Reiko Kuga, Yuki Kurashige, Takeshi Yanai, Shinya Hayami, Vijayendran K. K. Praneeth, Masaki Yoshida, Ko Yoneda, Satoshi Kawata, and Shigeyuki Masaoka
  • Journal Title: Nature Volume: 530 Issue: 7591 Pages: 465-468
  • DOI: 10.1038/nature16529
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Fully internally contracted multireference configuration interaction theory using density matrix renormalization group: A reduced-scaling implementation derived by computer-aided tensor factorization (2015)
  • Author(s): M. Saitow, Y. Kurashige, and T. Yanai
  • Journal Title: J. Chem. Theo. Comp. Volume: 11 Issue: 11 Pages: 5120-5131
  • DOI: 10.1021/acs.jctc.5b00270
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] 密度行列繰り込み群を用いた量子化学計算 (2017)
  • Author(s): 柳井 毅
  • Organizer: 有機固体若手の会2017
  • Place of Presentation: 神奈川, 湯河原, ホテルあかね
  • Year and Date: 2017-03-09
  • Invited
• [Presentation] Multireference theory based on density matrix renormalization group (2016)
  • Author(s): T. Yanai
  • Organizer: Theory and Applications of Computational Chemistry 2016
  • Place of Presentation: Seattle, USA
  • Year and Date: 2016-08-28
  • Int'l Joint Research / Invited
• [Presentation] CASPT2 theory with DMRG reference wavefunction (2016)
  • Author(s): T. Yanai
  • Organizer: The 8th Molecular Quantum Mechanics
  • Place of Presentation: Uppsala, Sweden
  • Year and Date: 2016-06-26
  • Int'l Joint Research / Invited
• [Presentation] Recent progress in multireference dynamic correlation methods based on density matrix renormalization group (2016)
  • Author(s): T. Yanai
  • Organizer: The 251th ACS meeting
  • Place of Presentation: San Diego, USA
  • Year and Date: 2016-03-13
  • Int'l Joint Research / Invited
• [Presentation] Computational quantum chemistry with an efficient many-electron theory: Theory and applications (2016)
  • Author(s): T. Yanai
  • Organizer: Pure and Applied Chemistry International Conference (PACCON2016)
  • Place of Presentation: Bangkok, Thailand
  • Year and Date: 2016-02-09
  • Int'l Joint Research / Invited
• [Presentation] Quantum chemistry with density matrix renormalization group (2016)
  • Author(s): T. Yanai
  • Organizer: The 75th Okazaki Conference Tensor Network States: Algorithms and Applications,
  • Place of Presentation: Okazaki, Aichi, Japan
  • Year and Date: 2016-01-11
  • Int'l Joint Research / Invited
• [Presentation] 密度行列繰り込み群に基づく拡張多状態多参照擬縮重摂動理論 (2016)
  • Author(s): 柳井 毅
  • Organizer: 第10回 革新的量子化学シンポジウム
  • Place of Presentation: 京都府京都市, キャンパスプラザ京都
  • Invited
• [Presentation] Molecular electronic structure theory based on ab initio density matrix renormalization group (2016)
  • Author(s): T. Yanai
  • Organizer: Tensor Networks and Quantum Many-Body Problems (TNQMP2016)
  • Place of Presentation: Institute for Solid State Physics, Kashiwa, Chiba
  • Int'l Joint Research / Invited
• [Presentation] 金属酵素の多参照電子状態計算および鉄五核錯体の密度汎関数計算 (2016)
  • Author(s): 柳井 毅
  • Organizer: 触媒・電池元素戦略研究拠点 第9回公開シンポジウム
  • Place of Presentation: 京都府京都市, 京大桂キャンパス
  • Invited
• [Presentation] Advanced multireference theory based on density matrix renormalization group: theory and applications (2015)
  • Author(s): T. Yanai
  • Organizer: ICIQ-FIFC Spain-Japan Joint Symposium on Theoretical and Computational Chemistry of Complex System
  • Place of Presentation: Tarragona, Spain
  • Year and Date: 2015-11-25
  • Int'l Joint Research / Invited
• [Presentation] Advanced multireference theory using ab initio density matrix renormalization group (2015)
  • Author(s): T. Yanai
  • Organizer: The 6th Japan-Czech-Slovak Symposium for Theoretical and Computational Chemistry,
  • Place of Presentation: Bratislava, Slovakia
  • Year and Date: 2015-10-11
  • Int'l Joint Research / Invited
• [Presentation] Advanced multireference theory based on density matrix renormalization group (2015)
  • Author(s): T. Yanai
  • Organizer: Recent Advances in Electronic Structure Theory
  • Place of Presentation: Nanjing, China
  • Year and Date: 2015-06-03
  • Int'l Joint Research / Invited
• [Remarks] 人工光合成の実現に向けた酸素発生触媒の開発に成功
  • URL: https://www.ims.ac.jp/news/2016/02/12_3396.html