溶液の非平衡過程の分子論的アプローチ

1992 Fiscal Year Annual Research Report

• Project/Area Number: 04215104
• Research Institution: Okazaki National Research Institutes
• Principal Investigator: 大瀧 仁志 岡崎国立共同研究機構, 分子科学研究所, 教授 (80022549)
• Co-Investigator(Kenkyū-buntansha): 山寺 秀雄 大同工業大学, 化学教室, 教授 (70022499) ; 斎藤 一夫 国際基督教大学, 理学研究科, 教授 (70004231) ; 舟橋 重信 名古屋大学, 理学部, 教授 (30022700) ; 中原 勝 京都大学, 理学部, 助教授 (20025480) ; 野村 浩康 名古屋大学, 工学部, 教授 (50023081)
• Keywords: 溶液の非平衡過程 / ミクロ集合体のゆらぎ / 拡散過程 / 反応活性種の構造

Research Abstract

今年度は本重点領域研究の最終年度にあたり、計画研究・公募研究だけでなく共同研究の成果の取りまとめを中心として活動した。また本研究を将来へつなげるため、研究成果の一部を公表し研究者の間での溶液化学への関心を高めるよう努めた。また計画班員と公募班員に跨る共同研究の研究推進にあたって総括班は、これらの研究に研究費を配分した。その結果、共同研究や研究協力によりめざましい成果が得られた。本研究で計画した大型設備、高分解能NMR装置、高感度高分解能ラマン分光器だけでなく迅速EXAFS装置の開発に成功し大きな成果を挙げた。
総括班の今年度の活動は次の通りである。第1班、第2班はそれぞれWorkshop「液体中の分子の非平衡ー振動・回転の緩和過程」、「溶媒和のダイナミックス」を、第3班は電気化学協会のシンポジウム一つとして「反応活性種と電気化学」を開催した。第3班のMinisymposium「Structure Aspects on Reaction Dynamics in Solution」では「平成4年度科学研究費補助金(重点領域研究(1))研究者招へいに伴う研究計画一部変更承認申請」書を文部省に提出し、J.G.Neilson教授(ブリストル大)を招へいし、講演・討論は全て英語で行い、同教授の評価・助言を受けた。同教授及び参加した数名の外国人研究者から発表内容について高い評価を得た。さらに総括班は、公開シンポジウム「溶液の非平衡の分子論的アプローチ」を開催し国内から十数名の研究者を招き公表された成果について議論し、国内での研究活動の充実を図った。さらに総括班の運営を円活に推進するために総括班会議、全体会議、班長会議を適宜開催した。特に、全体会議は2日間にわたり全員の研究成果を発表する機会をもうけた。

Research Products

• [Publications] H.Ohtaki: "A Structural Sturdy of Saturated Aqueours Solutions of Some Alkali Halides by X-Ray Diffraction." H.Solution Chem.21. 23-38 (1992)
• [Publications] H.Ohtaki: "An Attempt to Parameterize the Structuredness of Solvents." J.Solution Chem.21. 39-47 (1992)
• [Publications] K.Waizumi: "X-Ray Structural of FeBr_2・4H_2O,CoBr_2・4H_2O,NiCl_2・4H_2O,and CuBr_2・4H_2O.Cis/trans Selectivity in Transition Metal(II)Dihalide Tetrahydrate." Inorg.Chim.Acta.192. 173-181 (1992)
• [Publications] K.Waizumi: "Structure of 2RbCl.CuCl_2・2H_2O." Acta Crystallogr.C48. 1374-1376 (1992)
• [Publications] T.Radnai: "X-Ray Diffraction Studies on the Structure of the Tri-and Tetrathiocyanato-manganate(II)Complexes and Solvated Lithium Ion in N,N-Dimethylformamide." Bull.Chem.Soc.Jpan.65. 1445-1452 (1992)
• [Publications] K.Ozutsumi: "EXAFS and X-Ray Diffraction Studies on the Structure of the Tetrathiocyana-tocadmate(II)Complex in Dimethyl Sulfoxide." Bull.Chem.Soc.Jpn.65. 2104-2113 (1992)
• [Publications] K.Waizumi: "Density Function Calculations on the Grometries and Dissociation Energies of [M(H_2O)_6]^<2+>Ions.M^<2+>=Cr^<2+>,Mn^<2+>,Fe^<2+>,Co^<2+>,Ni^<2+>,Cu^<2+>,and Zn^<2+>." Chem.Lett.1489-1492 (1992)
• [Publications] T.Radnai: "Intramolecular and Liquid Structures of Tetramethylurea Strudied by Means of X-Ray Diffraction." Z.Naturforsch. 47a. 1003-1010 (1992)
• [Publications] H.Ohtaki: "Dissolution and Nucleation Phenomena of Salts in Water.Molecular Dynamic Approaches and Supporting Solution X-Ray Diffraction Measurements." Pure & Appl.Chem.65. 203-211 (1993)
• [Publications] S.Patnaik: "A Structural Study on AgI-Ag_2O-CrO_3 Glass." J.Phys.Soc.Jpn.62. 536-543 (1993)
• [Publications] S.PatnaiK: "An X-Ray RDF Study of the Glass 30AgI-45Ag_2O-25V_2O_5." Solid State Ionics.
• [Publications] H.Ohtaki: "Structure and Dynamics of Hydrated Ions." Chem.Rev.
• [Publications] H.Ohtaki: "Molecular Aspects on the Dissolution and Nucleation of Ionic Crystals in Water." Adv.Inorg.Chem.
• [Publications] H.Ohtaki: "Structure of Divalent Metal Complexes with Halide and Thiocyanate Ions in Solution." J.Indian Chem.Soc.
• [Publications] H.Ohtaki: "Molecular Dynamics Simulations for Dissolution and Nucleation Processes of Alkali Halide Crystals in Water." Proceedings 2nd CAMSE'92.
• [Publications] H.Ohtaki: "The First Achievement of the Direct Structural Determination of Reaction Intermediates by the Rapid EXAFS Method." Nature.
• [Publications] M.Tanaka: "A Simple Method for the Evaluation of Enthalpy of Proton Dissociation in Water" Bull.Chem.SOC.Jpn.65. 410-414 (1992)
• [Publications] M.Ohba: "Effects of Molecular Conformation on the Packing Density in the Liquid State.3.Partial Molar Volume Differences of cis and trans Conformers at Infinite Dilution" J.Phys.Chem.96. 5129-5133 (1992)
• [Publications] S.Koda: "Study on Orientational Motion of Liquid Crystals by Acoustically Induced Birefiengence." Jpn.J.Appl.Phys.31. 51-53 (1992)
• [Publications] S.Koda: "Hydrophobic Hydration of Hydroxyalkyl Cellulose" Polymer. 33. 3234-3238 (1992)
• [Publications] S.Koda: "Studies on the Interaction between Polyphosphate Ion and Sodium Ion by Sound Velocity" Rep.Prog.Polym.Phys.Jpn.35. 119-122 (1992)
• [Publications] M.Ohba: "The dielectric Constant and site-site direct correlation function of the RIMS-I theory for polar poluatomic molecular fluids." Mol.Phys.77. 689-695 (1992)
• [Publications] S.Kato: "Ultrasonic Relaxation and Volumetric Studies of the Micelle-Monomer Exchange Process in Aqueous Solutions of Sodium and Cesium Perfluorooctanoates" J.Colloid Interface Sci.150. 305-313 (1992)
• [Publications] S.Koda: "Ultrasonic Degradation of Water-Soluble Polyer" Polymer.
• [Publications] S.Koda: "Characterization of Polyvinylchloride and Polycarbonate by Means of Sound Velocity and Longitudinal Modulus Measurements" Jpn.J.Appl.Phys.
• [Publications] M.Nakahara: "Monomeric and Cluster States of Water Molecules in Organic Solvent." Chem.Lett.809-812 (1992)
• [Publications] M.Nakahara: "Inertial and Attractive Potential Effects on rotation of Solitary Water Molecules in Apolar and Polar Solvents." J.Chem.Phys.97. 4413-4420 (1992)
• [Publications] 中原 勝: "高圧下の高分子水溶液の疎水効果" 表面. 30. 451-460 (1992)
• [Publications] 中原 勝: "溶液高圧NMR" 高圧力の科学と技術. 1. 195-203 (1992)
• [Publications] 中原 勝: "電解質溶液の現状と展望" 電気化学および工業物理化学. 61. 30-34 (1993)
• [Publications] Y.Shimizu: "Kinetic Studies of the Incorporation of the Zinc(II)Ion into Water-Soluble N-Phenyl-Substituted Porphyrins.Deformation Effect on the Metallation Rate." Bull.Chem.Soc.Jpn.65. 771-776 (1992)
• [Publications] S.Soyama: "Variable-Temperature and-Pressure Multinuclear Magnetic Resonance Study on Solvent Exchange at Tris(ethylenediamine)nickel(II)Ion in Ethylenediamine." Inorg.Chem.31. 536-538 (1992)
• [Publications] S.Funahashi: "High-Pressure Stopped-Flow Nuclear Magnetic Resonance Apparatus for the Study of Fast Reactions in Solution." Rev.Sci.Instrum.
• [Publications] S.Aizawa: "Synthesis,Structural Characterization,and Metallation of N-o-Tolyl-5,10,15,20-tetraphenylporphine:Deformation Effect due to a Bulky N-Substituent Group." Inog.Chem.
• [Publications] Y.Inada: "Structure of Copper(II)Ethylenediamine Complexes in Aqueous and Neat Ethylenediamine Solutions and Solvent Exchange Kinetics of Copper(II)Ion in Ethylenediamine As Studide by the EXAFS and NMR Methods." Inorg.Chem.
• [Publications] M.Sano: "XANES Spectra of Copper(II)Complexes:Correlation of the Intensity of the 1st→3d Transition and the Shape of the Complex." Inorg.Chem.31. 459-463 (1992)
• [Publications] M.Ebihara: "Synthesis,Structure and Properties of Oxidized Hexamolybdenum Clusters[(Mo_6X_7Y)X'_6]2-(X=X'=Cl,Br;Y=S,Se)." Inorg.Chem.31. 1644-1649 (1992)
• [Publications] K.Ishihara: "A Kinetic Study of the Borate-Boric Acid Interchange in Aquouse Solution by NMR Spectroscopy." Inorg.Chem.(1992)
• [Publications] T.Radnai: "Structures of Liquids and Solutions by X-Ray and Neutron Diffraction in "Structure and Dynamics of Solutions"" Elsevier, 10 (1992)
• [Publications] H.Ohtaki: "Structure of Solvated Ions and Metal Copmlexes in Solution Studied by the Diffraction Method.in "Structure and Dynamics of Solutions"." Elsevier, 16 (1992)
• [Publications] H.Ohtaki: "The Structure of Hydrated Ions in Aqueo1s Solutions as Studied by the Molecular Dynamics Simulation,in "Structure and Dynamics of Solutions"." Elsevier, 11 (1992)
• [Publications] S.Ishiguro: "Thermodynamic Aspects of Complex Formation Reactions Nonaqueous Solutions.in "Structure and Dynamics of Solutions"." Elsevier, 8 (1992)
• [Publications] H.Ohtaki: "Structure and Dynamics of Solutions." Elsevier, (1992)
• [Publications] 野村 浩康: "新たな展開を見せるソノケミストリー:超音波による化学作用" 日本工業出版, 4 (1992)
• [Publications] 野村 浩康: "超音波で高分子を切る" 日本工業出版, 4 (1992)
• [Publications] H.Nomura: "Chapter 4.1 Dynamic Properties of Ions in Solutions,Structure and Dynamics of Solutions." Elesevier, 14 (1992)
• [Publications] H.Nomora: "Chapter 7.2 Statistical Mechanica6 Approaches to the Structure and Thermodynamic Properties of Sol1tions,Structure and Dynamics of Solutions." Elesevier, 15 (1992)
• [Publications] 中原 勝: "高圧流体技術第12章 高圧流体反応" 丸善, 24 (1992)
• [Publications] M.Nakahara: "Chapter 5.1 pressure and Temprature Effects on Irreversible Proceses in Solution,Structure and Dynamics of Solutions." Elesevier, 23 (1992)
• [Publications] 中原 勝: "実験化学講座11 反応と速度 第2.4章"超高温高圧下の反応"" 丸善, 20 (1993)
• [Publications] S.Funahashi: "Reaction and Activation Volume for Some Reactions Involving Metal Complexes in Solution in "Structure and Dynamics in Solutions"." Elsevier, 13 (1992)
• [Publications] S.Funahashi: "High-Pressure Multinuclear Magnetic Resonance Studies of Solvent Exchange First-Row Transition Metal(II)Ions in Acetic Asid,Ethylenediamine,and Nitrites,Effects of Bound Ligand,Solvent Bulkiness,and Chelate Rings Strain in "High Pressure Liquid and Solution",CJMR Vol.13," Elsevier,
• [Publications] 関 集三: "純粋研究を育てる風土づくりが先決" 化学同人, 3 (1993)
• [Publications] Y.Masuda: "Dynamics of Ions and Molecules in Solution-Nuclear magnetic Relaxation Studies,"Structure and Dynamics of Solutions"" Elsevier, 15 (1992)
• [Publications] K.Saito: "Ion Triplets as the Precursor for Election Transfer Reactions of Coordination Compounds."Structure and Dynamics of Solutions"" Elsevier, 14 (1992)