1996 Fiscal Year Annual Research Report

分子クラスターの反応動力学

Research Project

Project/Area Number	07240101
Research Institution	Tohoku University
Principal Investigator	三上直彦東北大学, 大学院・理学研究科, 教授 (70004447)
Co-Investigator(Kenkyū-buntansha)	岩澤康裕東京大学, 理学系研究科, 教授 (40018015) 山下晃一東京大学, 工学系研究科, 助教授 (40175659) 本間健二姫路工業大学, 理学部, 助教授 (30150288) 土屋荘次日本女子大学, 理学部, 教授 (40012322) 遠藤泰樹東京大学, 教養学部, 助教授 (40106159)
Keywords	分子クラスター / クラスター分光 / クラスター構造 / クラスター反応
Research Abstract	昨年に引き続いて、これまでに開発した分光法や新しい装置を用いて、クラスター構造解析、反応ダイナミクス解析を展開した。三上は、赤外-紫外2重共鳴分光法を用いて、サイズ選別したクラスター構造解析のための振動分光法を確立し、トロポロン溶媒和クラスターのOH振動スペクトル解析から分子内・分子間水素結合の競合過程と酸解離過程との関連を研究した。また、クラスターアニオンの分光計測を目標としたレーザー誘起光電子付着法の開発改良を行い、(H_2O)_n^-の光電子脱離スペクトル測定から溶媒和電子の性質に関わる余剰電子の局材性の検討を行った。遠藤は、ミリ波領域の光源を利用したフーリエ変換分光法あるいは紫外レーザーと結合した光分解能二重共鳴分光法を用いて、NaCl-(H_2O)_3における配向構造、Ar-HCO^+およびKr-HCO^+の分子間相互作用、C4H,C3N,CCSなどの精密構造を決定した。本間は、O_2,NO,N_2Oなどと遷移金属原子クラスターを生成して、レーザー励起による反応性の高い励起電子状態からの反応生成を調べた。特に、Co,Niなどの3d軌道の占有数が大きい金属原子の種々の電子配置の励起状態の反応速度を測定した。山下は、ヘリウムクラスターの量子液体性に注目し、量子クラスターのシミュレーションに必要なモンテカルロ経路積分法を新たに開発した。その方法を理研の笠井、高見らによって行われたナフタレン-ヘリウム系の実験解析に適用した。岩澤は、表面におけるクラスター反応特性を新しい触媒作用との関連を調べた。特に、[PtAu_6]バイメタルクラスターにおいて、Au_6骨格内のPt原子が特異な水素交換活性を持つこと、およびCO吸着にともなう骨格構造変化を見出した。更に、世界最高の酸素活性のあるAu_9クラスター固定化触媒を開発した。

Research Products

(42 results)

All Other

All Publications (42 results)

[Publications] T. Macyama: "Photodctachment of small water cluster anions in the near-infrared through the visible region" Chem. Phys. Lett.264. 292-296 (1997)
[Publications] H. Ishikawa: "Observation of the “Isomerization states" of HCP by stimulated emission pumping spectroscopy Comparison between theory and experiment" J. Chem. Phys.106. 1-4 (1997)
[Publications] T. Ebata: "Structures of size selected hydrogen-bonded phenol-(H_2O)_n clusters in S_0, S_1 and ion" Int. J. Mass. Spect. Ion Proc.(in press). (1996)
[Publications] A. Fujii: "Infrared Spectroscopy of (Phenol)_n^+ (n = 2-4), and (Phenol-Benzene)^+ Cluster Ions" J. Phys. Chem.(in press). (1996)
[Publications] A. Iwasaki: "Infrared Spectroscopy of Hydrogen-Bonded Phenol-Amine Cluster in Supersonic Jets" J. Phys. Chem.100. 16053-16057 (1996)
[Publications] A. Fujii: "Infrared spectroscopy of precursor for nucleophilic substitution reactions : fluorobenzene-(CH_3OH)_n (n = 1 and 2)" Chem. Phys. Lett.256. 1-7 (1996)
[Publications] A. Mitsuzuka: "Infrared spectroscopy of OH stretching vibrations of hydrogen-bonded tropolone-(H_2O)_n (n = 1-3) and tropolone-(CH_3OH)_n (n = 1 and 2) clusters" J. Chem. Phys.105. 2618-2627 (1996)
[Publications] S. Ishikawa: "Hole-Burning and Stimulated Raman-UV Double Resonance Spectroscopies of Jet-Cooled Toluene Dimer" J. Chem. Phys.100. 10531-10535 (1996)
[Publications] T. Sawamura: "Characterization of the Hydrogen-bonded Cluster Ions. [Phenol-(H_2O)_n]^+ (n = 1-4), (Phenol)_2^+ and (Phenol-methanol)^+ as Studied by Trapped Ion Infrared Multiphoton Dissociation Spectroscopy of Their OH Stretching Vibrations" J. Phys. Chem.100. 10055-10058 (1996)
[Publications] T. Watanabe: "Size-selected Vibrational Spectra of Phenol-(H_2O)_n (n = 1-4) Clusters Observed by IR-UV Double Resonance and Stimulated Raman-UV Double Resonance Spectroscopies" J. Chem. Phys.105. 408-419 (1996)
[Publications] S. Sato: "Size Dependence of Intracluster Proton Transfer of Phenol-(H_2O)_n (n = 1-4) Cations" J. Phys. Chem.100. 4765-4769 (1996)
[Publications] T. Ebata: "OH Stretching Vibrations of Phenol-(H_2O)_1 and Phenol-(H_2O)_3 in the S_1 State" J. Phys. Chem.100. 546-550 (1996)
[Publications] Y. Kasai: "Laboratory detection of the C_5N radical by Fourier-transiform microwave spectroscopy" Astrophys. J. in press. (1997)
[Publications] Y. Ohshima: "Rotational spectrum of the Ar-HCO^+ ionic complex" J. Chem. Phys.(in press). (1997)
[Publications] H. Kohguchi: "Laser-induced fluorescence spectroscopy of the C^2Σ^+-X^2Π_<1/2> band system of jet-cooled CCN radical" J. Chem. Phys.(in press). (1997)
[Publications] Y. Ohshima: "Rotational spectroscopy of jet-cooled molecular ions and ion complexes" Chem. Phys. Lett.256. 635-640 (1996)
[Publications] H. Kohguchi: "Laser-induced fluorescence spectra and observation of quantum beats in the Λ^2Π_i-Χ^2Π_i transition of the HCCS radical" Chem. Phys. Lett.101. 397-402 (1996)
[Publications] R. Matsui: "Kinetics of Co (a^4F, b^4F, a^2F) and Ni (a^3F,a^3D,a^1D) Depletion by O_2, N0, and N_2O" J. Phys. Chem.101. 179-186 (1997)
[Publications] R. Matsui: "Kinetics of depletion of Co (b^4F) and Co (a^2F) atoms by O_2" Chem. Phys. Lett.250. 560-566 (1996)
[Publications] M. Furubayashi: "Laser Induced Fluorescence of the CH_2CFO Radical" J. Chem. Phys. in press. (1997)
[Publications] A. Hishikawa: "Femtosecond Transition-State Dynamics of Dissociating OCS on the Excited 1Σ^+ Potential Energy Surface" J. Phys. Chem. in press. (1997)
[Publications] K. Tsuchiya: "Studies on the Reactions of Atomic Sulfur (3p) with H_2, D_2, CH_4, C_2H_6-C_3H_8, n-C_4H_<10>, and i-C_4H_<10>" J. Phys. Chem.100. 17202-17206 (1996)
[Publications] H. Shiina: "Kinetic Studies on the Pyrolysis of H_2S" J. Phys. Chem.100. 2136-2140 (1996)
[Publications] S. C. Farantos: "Normal Mode and Isomerization Bending States in HCP. Periodic Orbit Assignment and Spectroscopic Signature" J. Chem. Phys.104. 8131-8138 (1996)
[Publications] J. Takahashi: "Ab Initio Studies on the Interstellar Molecules C_3H_2 and C_3H and the mechanism for the Neutral-Neutral Reaction C(^3P)+C_2H_2" J. Chem.Phys.104. 6613-6627 (1996)
[Publications] Y. Yuan: "Structure and Calalysis of a SiO_2 -Supported Gold-Platinum Cluster [(PPh_3) Pt (PPh_3Au)_6] (NO_3)_2" Chem. Lett.129-130 (1996)
[Publications] H. Onishi: "Dynamic Visualization of a Metal-Oxide Surface/Gas-Phase Reaction : Time-Resolved Odservation by Scanning Tunneling Microscopy at 800 K" Physical Review Letters. 76. 791-794 (1996)
[Publications] T. Inoue: "Characterization of Pt-Sn/SiO_2 catalysts and the role of Sn in NO-hydrocarbon reactions" J. Chem. Soc., Faraday Trans.92. 461-467 (1996)
[Publications] H. Onishi: "Molecularly resolved observation of anisotropic intermolecular force in a formate-ion monolayer on a TiO_2 (110) surface by scanning tunneling microscopy" J. Colloid and Surfaces, A : Physicochemical ard Engineering Aspects. 109. 335-343 (1996)
[Publications] N. Ichikuni: "Surface structures and catalytic properties of supported niobium oxides" Catalysis Today. 28. 49-58 (1996)
[Publications] H. Onishi: "Atom-resolved observation of Na ensembles activating CO_2 adsorption on a TiO_2 (110)-(1×1) surface as the genesis of basic sites" Catalysis Letters. 38. 89-94 (1996)
[Publications] W. J. Chun: "PTRF X-ray absorption fine structure as a new technique for catalyst characterization" J. Mol. Catal. A : Chemical. 107. 55-65 (1996)
[Publications] Y. Iwasawa: "Characterization and chemical design of oxide surfaces" Stub. Surf. Sci. Catal.101. 21-34 (1996)
[Publications] H. Onishi: "Temperature jump STM observation of reaction intermediate on metal-oxide surfaces" J. Phys. Chem.100. 9582-9584 (1996)
[Publications] T. Kubota: "A New method for quantitative characterization of adsorbed hydrogen on Pt particles by means of Pt L-edge XANES" Chem. Phys. Lett.256. 445-448 (1996)
[Publications] K. Kitamura: "Surface structures and catalytic hydroformylation sctivities of Rh dimers attached on various inorganic oxide supports" J. Phys. Chem.100. 13636-13645 (1996)
[Publications] Y. Yuan: "Supported gold catalysts derived from gold complexes and as-precipitated metal hydroxides, highly active for low-temperature CO oxidation" Chem. Lett.254. 755-756 (1996)
[Publications] W. -J. Chun: "Surface structure analysis of dispersed metal sites on single srystal metal oxides by means of polarization-dependent total-reflection fluoresence EXAFS" Appl. surf. Sci.100/101. 143-146 (1996)
[Publications] H. Onishi: "STM observation of surface reactions on a metal oxide" surf. Sci.357/358. 773-776 (1996)
[Publications] T. Sueyoshi: "Reactive oxygen species on unreconstructed Cu (110) ; catalytic CO oxidation by reactive oxygen species at low temperature" Surf. Sci.357/358. 764-768 (1996)
[Publications] D. I. Kondarides: "Characterization and performance of a [PtM_<06>]/MgO catalyst for alkane-to-alkane conversion" J. Mol. Catal. A : Chemical. 111. 145-165 (1996)
[Publications] K. Fukui: "CO adsorption and oxidation on Pd (110)-c(2×4)-O by reflection-absorption infrared" J. Phys. Chem.100. 18795-18801 (1996)

1996 Fiscal Year Annual Research Report

分子クラスターの反応動力学

Principal Investigator

三上 直彦 東北大学, 大学院・理学研究科, 教授 (70004447)

Research Products

[Publications] T. Macyama: "Photodctachment of small water cluster anions in the near-infrared through the visible region" Chem. Phys. Lett.264. 292-296 (1997)

[Publications] H. Ishikawa: "Observation of the “Isomerization states" of HCP by stimulated emission pumping spectroscopy Comparison between theory and experiment" J. Chem. Phys.106. 1-4 (1997)

[Publications] T. Ebata: "Structures of size selected hydrogen-bonded phenol-(H_2O)_n clusters in S_0, S_1 and ion" Int. J. Mass. Spect. Ion Proc.(in press). (1996)

[Publications] A. Fujii: "Infrared Spectroscopy of (Phenol)_n^+ (n = 2-4), and (Phenol-Benzene)^+ Cluster Ions" J. Phys. Chem.(in press). (1996)

[Publications] A. Iwasaki: "Infrared Spectroscopy of Hydrogen-Bonded Phenol-Amine Cluster in Supersonic Jets" J. Phys. Chem.100. 16053-16057 (1996)

[Publications] A. Fujii: "Infrared spectroscopy of precursor for nucleophilic substitution reactions : fluorobenzene-(CH_3OH)_n (n = 1 and 2)" Chem. Phys. Lett.256. 1-7 (1996)

[Publications] A. Mitsuzuka: "Infrared spectroscopy of OH stretching vibrations of hydrogen-bonded tropolone-(H_2O)_n (n = 1-3) and tropolone-(CH_3OH)_n (n = 1 and 2) clusters" J. Chem. Phys.105. 2618-2627 (1996)

[Publications] S. Ishikawa: "Hole-Burning and Stimulated Raman-UV Double Resonance Spectroscopies of Jet-Cooled Toluene Dimer" J. Chem. Phys.100. 10531-10535 (1996)

[Publications] T. Sawamura: "Characterization of the Hydrogen-bonded Cluster Ions. [Phenol-(H_2O)_n]^+ (n = 1-4), (Phenol)_2^+ and (Phenol-methanol)^+ as Studied by Trapped Ion Infrared Multiphoton Dissociation Spectroscopy of Their OH Stretching Vibrations" J. Phys. Chem.100. 10055-10058 (1996)

[Publications] T. Watanabe: "Size-selected Vibrational Spectra of Phenol-(H_2O)_n (n = 1-4) Clusters Observed by IR-UV Double Resonance and Stimulated Raman-UV Double Resonance Spectroscopies" J. Chem. Phys.105. 408-419 (1996)

[Publications] S. Sato: "Size Dependence of Intracluster Proton Transfer of Phenol-(H_2O)_n (n = 1-4) Cations" J. Phys. Chem.100. 4765-4769 (1996)

[Publications] T. Ebata: "OH Stretching Vibrations of Phenol-(H_2O)_1 and Phenol-(H_2O)_3 in the S_1 State" J. Phys. Chem.100. 546-550 (1996)

[Publications] Y. Kasai: "Laboratory detection of the C_5N radical by Fourier-transiform microwave spectroscopy" Astrophys. J. in press. (1997)

[Publications] Y. Ohshima: "Rotational spectrum of the Ar-HCO^+ ionic complex" J. Chem. Phys.(in press). (1997)

[Publications] H. Kohguchi: "Laser-induced fluorescence spectroscopy of the C^2Σ^+-X^2Π_<1/2> band system of jet-cooled CCN radical" J. Chem. Phys.(in press). (1997)

[Publications] Y. Ohshima: "Rotational spectroscopy of jet-cooled molecular ions and ion complexes" Chem. Phys. Lett.256. 635-640 (1996)

[Publications] H. Kohguchi: "Laser-induced fluorescence spectra and observation of quantum beats in the Λ^2Π_i-Χ^2Π_i transition of the HCCS radical" Chem. Phys. Lett.101. 397-402 (1996)

[Publications] R. Matsui: "Kinetics of Co (a^4F, b^4F, a^2F) and Ni (a^3F,a^3D,a^1D) Depletion by O_2, N0, and N_2O" J. Phys. Chem.101. 179-186 (1997)

[Publications] R. Matsui: "Kinetics of depletion of Co (b^4F) and Co (a^2F) atoms by O_2" Chem. Phys. Lett.250. 560-566 (1996)

[Publications] M. Furubayashi: "Laser Induced Fluorescence of the CH_2CFO Radical" J. Chem. Phys. in press. (1997)

[Publications] A. Hishikawa: "Femtosecond Transition-State Dynamics of Dissociating OCS on the Excited 1Σ^+ Potential Energy Surface" J. Phys. Chem. in press. (1997)

[Publications] K. Tsuchiya: "Studies on the Reactions of Atomic Sulfur (3p) with H_2, D_2, CH_4, C_2H_6-C_3H_8, n-C_4H_<10>, and i-C_4H_<10>" J. Phys. Chem.100. 17202-17206 (1996)

[Publications] H. Shiina: "Kinetic Studies on the Pyrolysis of H_2S" J. Phys. Chem.100. 2136-2140 (1996)

[Publications] S. C. Farantos: "Normal Mode and Isomerization Bending States in HCP. Periodic Orbit Assignment and Spectroscopic Signature" J. Chem. Phys.104. 8131-8138 (1996)

[Publications] J. Takahashi: "Ab Initio Studies on the Interstellar Molecules C_3H_2 and C_3H and the mechanism for the Neutral-Neutral Reaction C(^3P)+C_2H_2" J. Chem.Phys.104. 6613-6627 (1996)

[Publications] Y. Yuan: "Structure and Calalysis of a SiO_2 -Supported Gold-Platinum Cluster [(PPh_3) Pt (PPh_3Au)_6] (NO_3)_2" Chem. Lett.129-130 (1996)

[Publications] H. Onishi: "Dynamic Visualization of a Metal-Oxide Surface/Gas-Phase Reaction : Time-Resolved Odservation by Scanning Tunneling Microscopy at 800 K" Physical Review Letters. 76. 791-794 (1996)

[Publications] T. Inoue: "Characterization of Pt-Sn/SiO_2 catalysts and the role of Sn in NO-hydrocarbon reactions" J. Chem. Soc., Faraday Trans.92. 461-467 (1996)

[Publications] H. Onishi: "Molecularly resolved observation of anisotropic intermolecular force in a formate-ion monolayer on a TiO_2 (110) surface by scanning tunneling microscopy" J. Colloid and Surfaces, A : Physicochemical ard Engineering Aspects. 109. 335-343 (1996)

[Publications] N. Ichikuni: "Surface structures and catalytic properties of supported niobium oxides" Catalysis Today. 28. 49-58 (1996)

[Publications] H. Onishi: "Atom-resolved observation of Na ensembles activating CO_2 adsorption on a TiO_2 (110)-(1×1) surface as the genesis of basic sites" Catalysis Letters. 38. 89-94 (1996)

[Publications] W. J. Chun: "PTRF X-ray absorption fine structure as a new technique for catalyst characterization" J. Mol. Catal. A : Chemical. 107. 55-65 (1996)

[Publications] Y. Iwasawa: "Characterization and chemical design of oxide surfaces" Stub. Surf. Sci. Catal.101. 21-34 (1996)

[Publications] H. Onishi: "Temperature jump STM observation of reaction intermediate on metal-oxide surfaces" J. Phys. Chem.100. 9582-9584 (1996)

[Publications] T. Kubota: "A New method for quantitative characterization of adsorbed hydrogen on Pt particles by means of Pt L-edge XANES" Chem. Phys. Lett.256. 445-448 (1996)

[Publications] K. Kitamura: "Surface structures and catalytic hydroformylation sctivities of Rh dimers attached on various inorganic oxide supports" J. Phys. Chem.100. 13636-13645 (1996)

[Publications] Y. Yuan: "Supported gold catalysts derived from gold complexes and as-precipitated metal hydroxides, highly active for low-temperature CO oxidation" Chem. Lett.254. 755-756 (1996)

[Publications] W. -J. Chun: "Surface structure analysis of dispersed metal sites on single srystal metal oxides by means of polarization-dependent total-reflection fluoresence EXAFS" Appl. surf. Sci.100/101. 143-146 (1996)

[Publications] H. Onishi: "STM observation of surface reactions on a metal oxide" surf. Sci.357/358. 773-776 (1996)

[Publications] T. Sueyoshi: "Reactive oxygen species on unreconstructed Cu (110) ; catalytic CO oxidation by reactive oxygen species at low temperature" Surf. Sci.357/358. 764-768 (1996)

[Publications] D. I. Kondarides: "Characterization and performance of a [PtM_<06>]/MgO catalyst for alkane-to-alkane conversion" J. Mol. Catal. A : Chemical. 111. 145-165 (1996)

[Publications] K. Fukui: "CO adsorption and oxidation on Pd (110)-c(2×4)-O by reflection-absorption infrared" J. Phys. Chem.100. 18795-18801 (1996)

三上直彦東北大学, 大学院・理学研究科, 教授 (70004447)