Development of New Materials by Molecular Orbital Engineering

2012 Fiscal Year Final Research Report

• Project Area: New Frontier in Materials Science Opened by Molecular Degrees of Freedom
• Project/Area Number: 20110003
• 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: Nihon University
• Principal Investigator: KOBAYASHI Akiko 日本大学, 文理学部, 教授 (50011705)
• Co-Investigator(Kenkyū-buntansha): KATO Reizo 独立行政法人理化学研究所, 加藤分子物性研究室, 主任研究員 (80169531) ; HORIUCHI Sachio 独立行政法人産業技術総合研究所, フレキシブルエレクトロニクス研究センター, チーム長 (30371074) ; ISHIBASHI Shoji 独立行政法人産業技術総合研究所, ナノシステム研究部門, 研究グループ長 (30356448) ; NISHIBORI Eiji 独立行政法人理化学研究所, 放射光科学総合研究センター, 連携センター長 (10293672) ; SAWA Hiroshi 名古屋大学, 大学院・工学研究科, 教授 (50215901)
• Co-Investigator(Renkei-kenkyūsha): TERAKURA Kiyoyuki 北陸先端科学技術大学院大学, 特別招聘教授 (40028212) ; KUMAI Reiji 独立行政法人産業技術総合研究所, フレキシブルエレクトロニクス研究センター, 主任研究員 (00356924) ; ZHOU Biao 日本大学, 文理学部, 助教 (80434067) ; YUSHIMI Kazuyoshi 東京大学, 大学院・理学系研究科, 特任研究員 (10586910)
• Project Period (FY): 2008 – 2012
• Keywords: 分子性固体 / 有機導体 / 誘電体物性 / 第一原理電子状態計算 / 粉末 X線回折 / 電子密度解析 / 分子性量子スピン液体 / 単一分子性伝導体

Research Abstract

Three groups, participating in design of new materials, calculation of the electronic structures and determination of accurate electron densities proceeded the development of new molecular materials based on molecular orbital engineering. The field of investigations covers a wide field, such as conductivity, magnetism and dielectricity.
We developed a molecular quantum spin liquid in a molecular triangular-lattice antiferromagnet and a molecular Kondo system. We also developed many molecular ferroelectric systems by using the freedom of MO and hydrogen bonds. Theoretical group preceded the first-principles theoretical calculations on single-component molecular conductors and organic ferroelectric materials. We succeeded in accurate electron density studies of key molecular crystals and X-ray powder diffraction studies of unknown crystals by using the synchrotron radiation.

Research Products

• [Journal Article] Molecular Ionics in Supramolecular Assemblies with Channel Structures Containing Lithium Ions (2012)
  • Author(s): M. Moriya, H. Kitaguchi, E. Nishibori, H. Sawa, W. Sakamoto, T. Yogo
  • Journal Title: Chemistry-a European Journal Volume: 18 Pages: 15305-15309
  • Peer Reviewed
• [Journal Article] Electronic Structure of Cu(tmdt)_2 Studied with First-Principles Calculations (2012)
  • Author(s): S. Ishibashi, K. Terakura
  • Journal Title: Crystals Volume: 2 Pages: 1210-1221
  • Peer Reviewed
• [Journal Article] Molecular Alloy with Diluted Magnetic Moments-Molecular Kondo System (2012)
  • Author(s): Y. Idobata, B. Zhou, A. Kobayashi, H. Kobayashi
  • Journal Title: Journal of the American Chemical Society Volume: 134 Pages: 871-874
  • Peer Reviewed
• [Journal Article] Above-room-temperature ferroelectricity and antiferroelectricity in benzimidazoles (2012)
  • Author(s): S. Horiuchi, F. Kagawa, K. Hatahara, K. Kobayashi, R. Kumai, Y. Murakami, Y. Tokura
  • Journal Title: Nature Communications Volume: 3 Pages: 1308
  • Peer Reviewed
• [Journal Article] A novel phosphor for glareless white light-emitting diodes (2012)
  • Author(s): H. Daicho, T. Iwasaki, K. Enomoto, Y. Sasaki, Y. Maeno, Y. Shinomiya, S. Aoyagi, E. Nishibori, M. Sakata, H. Sawa, S. Matsuishi, H. Hosono
  • Journal Title: Nature Communications Volume: 3 Pages: 1132
  • Peer Reviewed
• [Journal Article] First-principles calculations of spontaneous polarization for TTF-QBrCl_3 (2012)
  • Author(s): S. Ishibashi, S. Horiuchi, R. Kumai, K. Terakura
  • Journal Title: Physica Status Solidi B-Basic Solid State Physics Volume: 249 Pages: 1008-1011
  • Peer Reviewed
• [Journal Article] Electronic Ferroelectricity in a Molecular Crystal with Large Polarization Directing Antiparallel to Ionic Displacement (2012)
  • Author(s): K. Kobayashi, S. Horiuchi, R. Kumai, F. Kagawa, Y. Murakami, Y. Tokura
  • Journal Title: Physical Review Letters Volume: 108 Pages: 237601
  • Peer Reviewed
• [Journal Article] Spin-Orbital Short-Range Order on a Honeycomb-Based Lattice (2012)
  • Author(s): S. Nakatsuji, K. Kuga, K. Kimura, R. Satake, N. Katayama, E. Nishibori, H. Sawa, R. Ishii, M. Hagiwara, F. Bridges, T. U. Ito, W. Higemoto, Y. Karaki, M. Halim, A. A. Nugroho, J. A. Rodriguez-Rivera, M. A. Green, C. Broholm
  • Journal Title: Science Volume: 336 Pages: 559-563
  • Peer Reviewed
• [Journal Article] Giant Dielectric Anomaly of a Metal-Organic Perovskite with Four-Membered Ring Ammonium Cations (2011)
  • Author(s): B. Zhou, Y. Imai, A. Kobayashi, Z. M. Wang, H. Kobayashi
  • Journal Title: Angewandte Chemie-International Edition Volume: 50 Pages: 11441-11445
  • Peer Reviewed
• [Journal Article] Above-room-temperature ferroelectricity in a single-component molecular crystal (2010)
  • Author(s): S. Horiuchi, Y. Tokunaga, G. Giovannetti, S. Picozzi, H. Itoh, R. Shimano, R. Kumai, Y. Tokura
  • Journal Title: Nature Volume: 463 Pages: 789-792
  • Peer Reviewed
• [Journal Article] A layered ionic crystal of polar Li@C_<60> superatoms (2010)
  • Author(s): S. Aoyagi, E. Nishibori, H. Sawa, K. Sugimoto, M. Takata, Y. Miyata, R. Kitaura, H. Shinohara, H. Okada, T. Sakai, Y. Ono, K. Kawachi, K. Yokoo, S. Ono, K. Omote, Y. Kasama, S. Ishikawa, T. Komuro, H. Tobita
  • Journal Title: Nature Chemistry Volume: 2 Pages: 678-683
  • Peer Reviewed
• [Journal Article] Ferroelectricity in a one-dimensional organic quantum magnet (2010)
  • Author(s): F. Kagawa, S. Horiuchi, M. Tokunaga, J. Fujioka, Y. Tokura
  • Journal Title: Nature Physics Volume: 6 Pages: 169-172
  • Peer Reviewed
• [Journal Article] Instability of a quantum spin liquid in an organic triangular-lattice antiferromagnet (2010)
  • Author(s): T. Itou, A. Oyamada, S. Maegawa, R. Kato
  • Journal Title: Nature Physics Volume: 6 Pages: 673-676
  • Peer Reviewed
• [Journal Article] Highly Mobile Gapless Excitations in a Two-Dimensional Candidate Quantum Spin Liquid (2010)
  • Author(s): M. Yamashita, N. Nakata, Y. Senshu, M. Nagata, H. M. Yamamoto, R. Kato, T. Shibauchi, Y. Matsuda
  • Journal Title: Science Volume: 328 Pages: 1246-1248
  • Peer Reviewed
• [Journal Article] Variety of valence bond states formed of frustrated spins on triangular lattices based on a two-level system Pd(dmit)_2 (2009)
  • Author(s): M. Tamura, R. Kato
  • Journal Title: Science and Technology of Advanced Materials Volume: 10 Pages: 024304
  • Peer Reviewed
• [Presentation] QMAS最局在 Wannier軌道関係を中心として (2013)
  • Author(s): 石橋章司
  • Organizer: 第一原理計算コード OpenMX, QMAS, TOMBOセミナー
  • Place of Presentation: 産業技術総合研究所関西センター、池田
  • Year and Date: 20130300
• [Presentation] Fine Tuning of Band Parameters in Strongly Correlated Systems with Geometrical Frustration based on Dimer Structure (2012)
  • Author(s): R. Kato
  • Organizer: International Conference on Science and Technology of Synthetic Metals 2012 (ICSM2012)
  • Place of Presentation: Atlanta, USA
  • Year and Date: 20120708-13
• [Presentation] Ferroelectricity in donor-acceptor molecular crystals (2012)
  • Author(s): S. Horiuchi
  • Organizer: International Conference on Science and Technology of Synthetic Metals 2012 (ICSM2012)
  • Place of Presentation: Atlanta, USA
  • Year and Date: 20120708-13
• [Presentation] Single-component Multifrontier π-d System, [Cu(dmdt)_2] with Twisted Molecular Structure and Magnetic Phase Transition around 100 K (2011)
  • Author(s): A. Kobayashi, Y. Idobata, B. Zhou, and H. Kobayashi
  • Organizer: The 9th International Symposium on Crystalline Organic Metals, Superconductors and Ferromagnets (ISCOM2011)
  • Place of Presentation: Pozna., Poland
  • Year and Date: 20110925-30
• [Presentation] Direct observation of electronic state of (TMTSF)2PF6 using synchrotron radiation X-ray analysis (2011)
  • Author(s): H. Sawa
  • Organizer: International Research School And Workshop On Electronic Crystals ECRYS 2011
  • Place of Presentation: Corsica, France
  • Year and Date: 20110815-17
• [Presentation] Ultra-high Resolution Charge Density Study from Powder Diffraction Data (2010)
  • Author(s): E. Nishibori
  • Organizer: Gordon Research Conference 2010 on Electron Distributions and Chemical Bonding
  • Place of Presentation: Massachusetts, USA
  • Year and Date: 20100711-16
• [Book] 大学院講義物理化学第 2版, ISBN 978-4-8079-0771-7 (2012)
  • Author(s): 澤博
  • Total Pages: 61-172
  • Publisher: 東京化学同人
• [Book] 物質科学の基礎, ISBN 978-4-320-03488-4 (2012)
  • Author(s): 那須奎一郎、澤博、門野良典
  • Total Pages: 175
  • Publisher: 共立出版
• [Book] Molecular Electronic and Related Materials-Control and Probe with Light 2010 (5. Study of the novel charge ordering state in molecular conductors using synchrotron radiation X-ray diffraction), ISBN 978-81-7895-460-8 (2010)
  • Author(s): H. Sawa, T. Kakiuchi, Transworld Research Network
  • Total Pages: 117-134
• [Book] Molecular Quasi-triangular Lattice Antiferromagnets. In Understanding Quantum Phase Transitions (2010)
  • Author(s): R. Kato and T. Itou,
  • Total Pages: 419-443
  • Publisher: CRC Press
• [Patent(Industrial Property Rights)] 有機強誘電体材料 (2010)
  • Inventor(s): 堀内佐智雄、熊井玲児、十倉好紀
  • Industrial Property Rights Holder: 独立行政法人産業技術総合研究所
  • Industrial Property Number: 特許、4482662号
  • Acquisition Date: 2010-04-02