材料機能の理論的研究

1991 Fiscal Year Annual Research Report

• Project/Area Number: 03204006
• Research Institution: The University of Tokyo
• Principal Investigator: 寺倉 清之 東京大学, 物性研究所, 教授 (40028212)
• Co-Investigator(Kenkyū-buntansha): 能勢 修一 慶応義塾大学, 理工学部, 助教授 (30172795) ; 山口 兆 北海道大学, 理学部, 教授 (80029537) ; 那須 奎一郎 岡崎国立共同研究機構, 分子科学研究所, 助教授 (90114595) ; 細矢 治夫 お茶の水女子大学, 理学部, 教授 (10017204) ; 中辻 博 京都大学, 工学部, 教授 (90026211)
• Keywords: 第一原理分子動力学法 / 化学吸着 / 表面反応機構 / 高温超伝導体 / 格子振動の非調和性 / 同位元素効果 / 有機強磁性体 / グラファイト

Research Abstract

材料機能の発現は原子の組み合わせとそれらの構造に強く依存する。現実の材料は完全結晶であることは稀であり、何らかの非周期性を持っている。そのような場合には、実験的に原子配列を正確に決めることは困難であることが多く、理論計算が重要な役割を演じる。原子配列が求まったうえで材料の性質を微視的に知るには電子状態を知られなければならない。また、外部の刺激に対する応答として電子状態が変化すると、それが原子配列を変えることもある。種々の興味深い系に対して、以上のような観点から理論研究を行うための手法の開発、整備および具体的な理論解析が行われた。
寺倉と能勢は、電子状態計算を出発点として原子の運動を追いかけることのできる第一原理分子動力学法のプログラム開発を行った。この方法は固体表面での化学吸着のメカニズムの解明に適用された。それと平行して、この方法の適用範囲を広げるために、定圧力で定温度の計算を可能とする作業が進行中である。中辻は量子化学的手法で表面ー分子相互作用系を調べた。特に、固体表面をクラスタ-で近似する方法について詳しくテストを行い、Li表面での水素分子の化学吸着の機構を調べた。また、中辻の開発したSACーC1法により、過マンガン酸イオンが分解して酸素分子を放出する反応の機構を明らかにした。那須は、酸化物高温超伝導体やK_3C_<60>の超伝導について、強い電子格子相互作用と格子振動の非調和性に注目した研究を行い、同位元素効果や高い超伝導転位温度に対する興味深い結果を得ている。細矢は、グラファイトの電子構造に出来るだけ速やかに収束する炭素の平面クラスタ-の幾何学を詳しく調べた。山口は有機化合物の磁気的性質を量子化学的計算によって調べた。ハイゼンベルグ模型での交換相互作用のパラメタを第一原理計算から導いたことは、現実の系とモデルとの対応をとるという本班の目標の一つに沿ったものである。

Research Products

• [Publications] K.Kobayashi: "Atomic Arrangemet of Alkali Adatoms on the Si(001)-2×1 Surface" Surf.Sci.242. 349-353 (1991)
• [Publications] T.Mohri: "First-Prinsiples Study of Short Range Order and Instabilities in Au-Cu,Au-Ag and Au-Pd Alloys" Acta Matall.Mater.39. 493-501 (1991)
• [Publications] Y.Morikawa: "Theoretical Support to the Double-Layer Model for Potassium Adsorption on the Si(001) Surface" Phys.Rev.B. 44. 3459-3462 (1991)
• [Publications] M.Ikeda: "Alternating Change of Allowed and Forbidden Optical Transition in Si_<2m>/Ge_<10-2m> Superlattices with (001) Stacking" Phys.Rev.B. 45. 1496-1499 (1992)
• [Publications] K.Kobayashi: "Optimized Structures and Electronic Properties of Alkali Metal (Na,K) Adsorbed Si (001) Surfaces" Phys.Rev.B. 45(2月15日号). (1992)
• [Publications] T.Miyazaki: "Self-Interaction-Corrected Local-Spin Density-Functional Theory for strongly Correlated Electron Systems" Prog.Theor.Phys.Suppl.
• [Publications] H.Nakatsuji: ""Exponentially Generated Configuration Interaction Theory.Descriptions of Excited,Ionized,and Electron Attached States"" J.Chem.Phys.94. 6716-6727 (1991)
• [Publications] H.Nakatsuji: ""Mixed-Exponentially Generated Wave Function Method for Ground,Excited,Ionized,and Electron Attached States of a Molecule"" J.Chem.Phys.95. 4296-4305 (1991)
• [Publications] H.Nakatsuji: ""Description of Two-and Many-Electron Processes by the SAC-CI Method"" Chem.Phys.Letters. 177. 331-337 (1991)
• [Publications] H.Nakatsuji: ""Dipped Adcluster Model for Chemisorptions and Catalytic Reactions on a Metal Surface:Image Force Correction and Applications to Pd-O_2 Adclusters"" J.Chem.Phys.95. 640-647 (1991)
• [Publications] H.Nakatsuji: ""Theoretical Study on the Ground and Excited States of MnO^-_4"" J.Chem.Phys.95. 8287-8291 (1991)
• [Publications] H.Nakatsuji: ""Theoretical Study on the Dissociative Chemisoption of Hydrogen Molecule on a ZnO Surface"" Intern.J.Quantum Chem.
• [Publications] H.Nakatsuji: ""Dipped Adcluster Model Study for the End-on Chemisoption of O_2 on an Ag Surface"" Can.J.Chem.
• [Publications] H.Nakatsuji: ""SAC-CI and Full-CI calculations for the Singlet and Triplet Excited States of H_2O"" Chem.Phys.Letters. 179. 555-558 (1991)
• [Publications] H.Nakatsuji: ""Excited and Ionized States of RuO_4 and Oso_4 Studied by SAC and SAC-CI Theories"" Intern.J.Quantum Chem.39. 93-113 (1991)
• [Publications] Y.Mizukami: ""Potential Energy Curves of the Ground,Excited and Ionized States of Kr_2 Studied by the SAC-CI Theory"" J.Molec.Struct.(THEOCHEM). 234. 469-481 (1991)
• [Publications] Y.Mizukami: ""Ab inition MO Calculations of Model Molecules for Ribozyme Reaction Including an Mg^<2+> Ion"" Chem.Letters. 2119-2122 (1991)
• [Publications] H.Nakatsuji: ""Electronic Structures of Dative Metal-Metal Bonds;Ab initio Molecular Orbital Calculations of (OC)_5Os-M(CO)_5(M=W,Cr) in Comparison with (OC)_5M-M(CO)_5(M=Re,Mn)"" Inorg.Chem.
• [Publications] M.Sugimoto: ""Theoretical Study on Metal NMR Chemical Shifts.Niobium Complexes"" J.Phys.Chem.
• [Publications] H.Nakatsuji: ""Dipped Adcluster Model Study for Molecular and Dissociative Chemisorptions of O_2 on an Ag Surface"" J.Chem.Phys.
• [Publications] H.Nakatsuji: ""Theoretical Study on the Photochemical Reaction of Permanganate Ion"" J.Chem.Phys.
• [Publications] H.Nakatsuji: ""Theoretical Study on the Excited and Ionized States of Titanium Tetrachloride"" J.Chem.Phys.
• [Publications] S.Nos^^´: "Contstant Temperature Molecular Dynamics Methods" Prog.Theor.Phys.Suppl.103. 1-46 (1991)
• [Publications] H.Hosoya: "Factorization and Recursion Relations of the Matching and Cheracteristic Polynomials of Periodic Polymer Networks" J.Mathematical Chemistry. 7. 289-305 (1991)
• [Publications] H.Narumi: "Generalized Expression for the Number of Perfect Matching of Cylindrical mxn Graphs" J.Mathematical Physics. 32. 1885-1889 (1991)
• [Publications] Y.-D.Gao: "Analysis of the π-Electronic Structure of Infinitely Large Networks.IV.Polycylic Aromatics with Bond Alternation" Theoretica Chimica Acta. 81. 105-123 (1991)
• [Publications] S.J.Cyvin: "Kekule^^´ Structure Counts:General Formulations for Primitive Coronoid Hydrocarbons" Monatscheft fur Chemie. 122. 435-444 (1991)
• [Publications] I.Gutman: "Two Variants of Topological Index and the Relations between Them" Bulletin of the Chemical Society of Japan. 65. 14-18 (1992)
• [Publications] Y.-D.Gao: "Topological Factors Governing the HOMO-LUMO Band Gap of the Density of States of Periodic Hydrocarbon Polymer" J.Math.Chem.8. (1992)
• [Publications] K.Iwano: "Spectral Shape of Optical Absorption in Extended Peierls-Hubbard Model" Synthetic Metals. 41-43. 2781-2784 (1991)
• [Publications] X.Sun: "Electron Interaction and Optical Gap of Conjugated Polymers" Phys.Rev.B. 44. 11042-11047 (1991)
• [Publications] K.Nasu: "Suppressed Metal-Insulator Transitions,Enhanced Super-conductivity and Reduced Isotope Effect Due to Quartic Anharmonicity of Phonons in a Peierls-Hubbard Model" Phys.Rev.B. 44. 7625-7636 (1991)
• [Publications] 田中 皓: "分子設計と人材養成" 化学工学. 55. 523-523 (1991)
• [Publications] 山口 兆: "混合原子価錯体" 季刊化学総説(無機量子化学). 13. 138-148 (1991)
• [Publications] K.Ogasawara: "Electronic Structure of Lower Singlet States of Binuclear Copperacetate Monohydrete" Can.J.Chem.
• [Publications] M.Fujiwara: "Ab Initio Study on Effective Exchange Integrals of Binuclear Metal Comlexes" Synthetic Metals. 41-43. 3267-3270 (1991)
• [Publications] M.Nakano: "New Models for Organic Magnetic Conductors or Organic Kondo and Dense Kondo Systems" Synthetic Metals. 41-43. 3631-3634 (1991)
• [Publications] M.Nakano: "A New Model of the Third-Order Nonlinear Optical Systems which Utilizes both Through-Bond and Through-Space Charge-Transfer Effects:" Synthetic Metals. 41-43. 3754-3757 (1991)
• [Publications] M.Nakano: "Coupled-Hartree-Fock Calculations of the Third-Order Hyperpolarizabilities of Substituted Polydiacetylenes" Chem.Phys.Lett.185. 550-554 (1991)
• [Publications] K.Yamaguchi: "MO Theoretical Studies of Magnetic Interactions for Clusters of Nitronyl Nitroxide and Related Species" Chem.Phys.Lett.(1992)
• [Publications] K.Yamaguchi: "Theortical Calculations of Effective Exchange Integrals between Nitronyl Nitroxides with Donor and Acceptor Groups" Chem.Phys.Lett.(1992)
• [Publications] Akitomo Tachibana: "Superconducting Vibronic Interaction in Model Organic Polymers which Contain Hetero Atoms and Triple Bonds" Journal of Molecular Structure (THEOCHEM). 235. 211-226 (1991)
• [Publications] Akitomo Tachibana: "Hu^^"ckel Framework Study on the Superconducting Vibronic Interaction in a(AB)_N Chain" Moleuclar Engineering. 1. 89-98 (1991)
• [Publications] Akitomo Tachibana: "Characteristics in Vibronic Coupling Modes of Polyene in Normal and Superconducting States" Synthetic Metals. 41-43. 3443-3448 (1991)
• [Publications] Akitomo Tachibana: "A Quantum Chemical Study of Interchain Hopping Model of Negatively Charged Solitons in Polyacetylene" International Journal of Quantum Chemistry. 41. 461-474 (1992)
• [Publications] Akitomo Tachibana: "Finite-Size Dimensional Analysis of the Superconducting Vibronic Interaction" International Journal of Quantum Chemistry. 41. 273-279 (1992)
• [Publications] Akitomo Tachibana: "Atomic Orbital-wise Characterization of the Vibronic Interaction in a Model of an Oxygen-Containing Organic Polymer" Canadian Journal of Chemistry. 70. (1992)
• [Publications] H.Nakatsuji: "Reports in Molecular Theory" CRC Press, (1992)
• [Publications] 中井 浩巳: "季刊化学総説、No.13,「無機量子化学」" 学会誌刊行センタ-, 21(158-178) (1991)
• [Publications] 福西 快文: "触媒、Vol.33,No.4" 触媒学会, 270-277(8) (1991)
• [Publications] 中辻 博: "「実験化学講座3、基本操作III」第2編" 丸善, 297-341(45) (1991)
• [Publications] H.Nakatsuji: "Metal-Ligand Interactions:From Atoms,to Clusters,to Sufraces" D.Reidel Publishing Company, (1992)
• [Publications] S.Nose^^´: "Molecular Dynamics Simulations at Constant Temperature and pressure,in"Computer Simulation in Material Science"" Eds.M.Meyer and V.Pontikis Kluwer Academic Publishers, (1991)
• [Publications] K.Yamaguchi: "An Ab Initio Approach to Molecular Magneto-Chemistry,in"Computer Aided Innovation of New Materials"" Eds.M.Doyama et.al.,Elsevier Science Pub., 984 (1991)
• [Publications] M.Nakano: "A Classification of the Third-Order Organic Nonlinear Optical Systems and Proposal of New-Type Systems,in"Computer-Aided Innovation of New Materials"" Eds.M.Doyama et.al.,Elsevier Science Pub., 984 (1991)