Direct observation of the steric effect in chemical reactions by controlling the orientation at transition state

• Project/Area Number: 20350006
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Physical chemistry
• Research Institution: Osaka University
• Principal Investigator: KASAI Toshio Osaka University, 名誉教授 (20152613)
• Co-Investigator(Kenkyū-buntansha): CHE DockーChil 大阪大学, 大学院・理学研究科, 助教 (20273732)
• Project Period (FY): 2008 – 2010
• Project Status: Completed (Fiscal Year 2010)
• Budget Amount: ¥19,630,000 (Direct Cost: ¥15,100,000、Indirect Cost: ¥4,530,000); Fiscal Year 2010: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2009: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000); Fiscal Year 2008: ¥12,740,000 (Direct Cost: ¥9,800,000、Indirect Cost: ¥2,940,000)
• Keywords: 化学反応 / 立体ダイナミクス / 分子配向 / 反応遷移状態 / 配向OH分子ビーム / 反応分岐 / 衝突錯合体 / 準安定CO分子ビーム / アライメント選別 / 偏光レーザー / 配向分子線 / OHラジカル / 分子の電子密度 / 分子のアライメント状態選別 / 反応制御 / 立体効果の直接観測 / 単一量子状態

Research Abstract

Direct observation of the steric effect in the OH + HBr chemical reaction was made by controlling the OH radical orientation in order to clarify mechanisms for stereo-anisotropy. We find that the HBr collision at the O-end of OH radical is more favorable than that at the H-end. The theoretical analysis suggested that there are at least two mechanisms play roles to give the observed steric effect. One is the H atom abstraction at the O-end of OH and another is the H atom migration at the H-end of OH. Alignment of CO(a) was performed using a linearly polarized laser at 206nm. This success will allow us to control molecular orientation at transition state in a novel way.

Research Products

• [Journal Article] Orientation dependence for Br formation in the reaction of oriented OHradical with HBr molecule (2011)
  • Author(s): P.-Y.Tsai, D.-C.Che, M.Nakamura, K.-C.Kin, T.Kasai
  • Journal Title: Phys.Chem.Chem Phys. vol.13 Pages: 1419-1423
  • Peer Reviewed
• [Journal Article] Orientation dependence for Br formation in the reaction of oriented OH radical with HBr molecule (2011)
  • Author(s): Po-Yu Tsai, et.al.
  • Journal Title: Phys.Chem.Chem.Phys. Volume: 13 Pages: 1419-1423
  • Peer Reviewed
• [Journal Article] Orientation dependence in the four-atom reaction of OH+HBr using the single-state oriented OH radical beam (2010)
  • Author(s): P.-Y.Tsai, D.-C.Che, M.Nakamura, K.-C.Lin, T.Kasai
  • Journal Title: Phys.Chem.Chem.Phys.,(Communications) vol.12 Pages: 2532-2534
  • Peer Reviewed
• [Journal Article] Electrostatic Hexapole State-Selection of the Asymmetric-Top Molecule Propylene Oxide (2010)
  • Author(s): D.-C.Che, F.Palazzetti, Y.Okuno, V.Aquilanti, T.Kasai
  • Journal Title: J.Phys.Chem.A. vol.114 Pages: 3280-3286
  • Peer Reviewed
• [Journal Article] Temperature dependence of chemical and biophysical rate processes : Phenomenological approach to deviations from Arrhenius law (2010)
  • Author(s): V.Aquilanti, K, C.Mundim, M.Elango, S.Kleijn, T.Kasai
  • Journal Title: Chem.Phys.Lett. vol.498 Pages: 209-213
  • Peer Reviewed
• [Journal Article] 配向分子線と化学反応 (2010)
  • Author(s): 笠井俊夫
  • Journal Title: J.Vacuum Sci.Jpn No.11
  • NAID: 10027498650
  • Peer Reviewed
• [Journal Article] TiAl表面酸化のシンクロトロン放射光を用いた光電子分光研究 (2010)
  • Author(s): 橋之口道宏, 角本雄一, 戸出真由美, James Harries, 岡田美智雄, 寺岡有殿, 笠井俊夫
  • Journal Title: 電気学会誌C 130 Pages: 1723-1729
  • NAID: 10026693977
  • Peer Reviewed
• [Journal Article] Molecular Orientation Effects in Gas-Surface Dynamical Processes (2010)
  • Author(s): 岡田美智雄, 笠井俊夫
  • Journal Title: Euro.Phys.J.B vol.75 Pages: 71-79
  • Peer Reviewed
• [Journal Article] Steric effects in the scattering of oriented CH_3Cl molecular beam from a Si(111) surface (2010)
  • Author(s): H.Ito, M.Okada, D.Yamazaki, T.Kasai
  • Journal Title: J.Phys.Chem.A vol.114 Pages: 3080-3086
  • Peer Reviewed
• [Journal Article] Multi-Dimensional Steric Effect for the XeBr* (B, C) Formation in the Oriented Xe* (3P2,MJ=2)+Oriented CF3Br Reaction (2010)
  • Author(s): H.Ohoyama, R.Oda, T.Kasai
  • Journal Title: J.Chem.Phys. vol.132
  • Peer Reviewed
• [Journal Article] Multi-dimensional Steric Effect for the XeI*(B) Formation in the Oriented Xe^*(3P2, MJ=2)+Oriented CH3I Reaction (2010)
  • Author(s): H.Ohoyama, T.Kasai
  • Journal Title: Phys.Chem.Chem.Phys. vol.12 Pages: 6949-6954
  • Peer Reviewed
• [Journal Article] Orientation dependence in the four-atom reaction of OH + HBr using the single-state oriented OH radical beam (2010)
  • Author(s): Po-Yu Tsai, et.al.
  • Journal Title: Phys.Chem.Chem.Phys.(Communications) Volume: 12 Pages: 2532-2534
  • Peer Reviewed
• [Journal Article] 配向分子線と化学反応 (2010)
  • Author(s): 笠井俊夫
  • Journal Title: Journal of the Vacuum Society of Japan Volume: 11 Pages: 629-634
  • NAID: 10027498650
  • Peer Reviewed
• [Journal Article] Steric effects in the scattering of oriented CH_3Cl molecular beam from a Si(111) surface (2010)
  • Author(s): H.Ito, et.al.
  • Journal Title: Journal of Physical Chemistry A Volume: 114 Pages: 3080-3086
  • Peer Reviewed
• [Journal Article] Orientation dependence in the four-atom reaction of OH+HBr using the single-state oriented OH radical beam (2010)
  • Author(s): P, -Y.Tsai, et al.
  • Journal Title: Phys.Chem.Chem.Phys.(communications) 12 Pages: 2532-2534
  • Peer Reviewed
• [Journal Article] Electrostatic Hexapole State-Selection of the Asymmetric-Top Molecule Propylene Oxide (2010)
  • Author(s): D.-C.CHE, et al.
  • Journal Title: J.Phys.Chem.A. 114 Pages: 3280-3286
  • Peer Reviewed
• [Journal Article] His Arrows and His Targets : A Tribute to Vincenzo Aquilanti (2009)
  • Author(s): P.Casavecchia, F.Vecchiocattivi, R.W.Anderson, T.Kasai
  • Journal Title: J.Phys.Chem.A Enzo Special Issue vol.113 Pages: 14181-14183
• [Journal Article] Collision energy dependence for the Br formation in the reaction of OD+HBr (2009)
  • Author(s): D.-C.Che, A.Doi, Y.Yamamoto, Y.Okuno, T.Kasai
  • Journal Title: Phys.Scr. vol.80 Pages: 48110-48114
  • Peer Reviewed
• [Journal Article] Kinetics of Oxygen Adsorption and Initial Oxidation on Cu(110) by Hyperthermal Oxygen Molecular Beams (2009)
  • Author(s): K.Moritani, M.Okada, Y.Teraoka, A.Yoshigoe, T.Kasai
  • Journal Title: J.Phys.Chem.A 113 Pages: 15217-15220
  • Peer Reviewed
• [Journal Article] Steric effects in the scattering of oriented CH_3Cl molecular beam from a graphite surface : weak interaction of physisorption (2009)
  • Author(s): T.Fukuyama, M.Okada, T.Kasai
  • Journal Title: J.Phys.Chem.A 113 Pages: 14749-14755
  • Peer Reviewed
• [Journal Article] Cu3Au表面自然酸化のシンクロトロン放射光を用いた光電子分光研究 (2009)
  • Author(s): 宗和誠, 山崎大地, 岡田美智雄, 吉越章隆, 寺岡有殿, 笠井俊夫
  • Journal Title: 電気学会誌C 129-C Pages: 229-232
  • Peer Reviewed
• [Journal Article] Collision Energy Dependence of the Rotational-State-Resolved Cross Section in the CH(v=0,J)+O_2→OH(A)+CO Reaction (2009)
  • Author(s): H.Ohoyama, Y.Nagamachi, K.Yamakawa, T.Kasai
  • Journal Title: Phys.Chem.Chem.Phys. vol.11 Pages: 10281-10285
  • Peer Reviewed
• [Journal Article] Collision energy dependence for the Br formation in the reaction of OD+HBr (2009)
  • Author(s): D.-C.CHE, et al.
  • Journal Title: Physica Scripta 80
  • Peer Reviewed
• [Journal Article] Negative collision energy dependence of the Br formation in the OH+HBr four-atom reaction (2008)
  • Author(s): D.-C.Che, T.Matsuo, Y.Yano, L.Bonnet, T.Kasai
  • Journal Title: Phys.Chem.Chem.Phys. vol.10 Pages: 1419-1423
  • Peer Reviewed
• [Journal Article] Steric Effects in Dissociative Adsorption of Low Energy CH_3Cl on Si(100): Orientation and Steering Effects (2008)
  • Author(s): M.Okada, S. Goto, T.Kasai
  • Journal Title: J.Phys.Chem.C 112 Pages: 19612-19616
  • Peer Reviewed
• [Presentation] Embedded Sign of Stereodynamics in Overall Chemical Reaction (2010)
  • Author(s): 笠井俊夫
  • Organizer: Stereodynamics Santa Cruz
  • Place of Presentation: 米国
  • Year and Date: 2010-11-05
• [Presentation] Stereodynamics : Generic Meaning in Chemical Reactions (2010)
  • Author(s): 笠井俊夫
  • Organizer: III SEEDMOL, Brasilia-DF
  • Place of Presentation: Brasil
  • Year and Date: 2010-10-25
• [Presentation] Stereodynamics : Generic Meaning in Chemical Reactions (2010)
  • Author(s): Toshio Kasai
  • Organizer: III SEEDMOL
  • Place of Presentation: Brasil, Brasilia
  • Year and Date: 2010-10-21
• [Presentation] OHの配向制御によるOH+HBrの反応機構の解明 (2010)
  • Author(s): 中村雅明、蔡徳七、P.-Y. Tsai, K.-C. Lin, 笠井俊夫
  • Organizer: 分子科学討論会2010
  • Place of Presentation: 大阪
  • Year and Date: 2010-09-17
• [Presentation] Chemical Reaction Rates Beyond Arrhenius (2010)
  • Author(s): V.Aquilanti, K.C.Mundim, T.Kasai
  • Organizer: MOLEC Curia-Anadia
  • Place of Presentation: Portugal
  • Year and Date: 2010-09-07
• [Presentation] OH orientation dependence of the OH+HBr reaction (2010)
  • Author(s): M.Nakamura, D.-C.Che, P.-Y.Tsai, K.-C.Lin T.Kasai
  • Organizer: 第4回化学反応討論会
  • Place of Presentation: 広島
  • Year and Date: 2010-06-03
• [Presentation] OH orientation dependence of the OH + HBr reaction (2010)
  • Author(s): M.Nakamura, et.al.
  • Organizer: 化学反応討論会
  • Place of Presentation: 広島
  • Year and Date: 2010-06-03
• [Presentation] 立体ダイナミクス:化学反応論における意義とその位置づけ (2010)
  • Author(s): 笠井俊夫
  • Organizer: 日本物理学会第65回年次大会
  • Place of Presentation: 大阪府立大学中百舌鳥キャンパス 大阪
  • Year and Date: 2010-03-29
• [Presentation] Stereodynamics aiming at ecological reaction control : a bridge to link micro-and macroscopic view of chemical reactions (2009)
  • Author(s): 笠井俊夫
  • Organizer: NTU/IAMS Joint Special Letcture
  • Place of Presentation: 台北(台湾)
  • Year and Date: 2009-10-02
• [Presentation] 六極不均一電場を用いた非対称コマ分子の回転状態選別 (2009)
  • Author(s): 蔡徳七、奥乃康弘、笠井俊夫
  • Organizer: 第3回分子科学討論会
  • Place of Presentation: 名古屋
  • Year and Date: 2009-09-22
• [Presentation] Stereodynamics : Searching for a bridge to link micro- and macroscopic concepts of chemical reactions (2009)
  • Author(s): 笠井俊夫
  • Organizer: 第25回化学反応討論会
  • Place of Presentation: 大宮
  • Year and Date: 2009-06-02
• [Presentation] Collision energy dependence of Br atom formation in the OH+HBr and the OD+HBr reactions (2009)
  • Author(s): 蔡徳七, 奥乃康弘, 笠井俊夫
  • Organizer: 第25回化学反応討論会
  • Place of Presentation: 大宮
  • Year and Date: 2009-06-02
• [Presentation] Stereodynamics : Searching for a bridge to link micro- and macroscopic concepts of chemical reactions (2009)
  • Author(s): 笠井俊井
  • Organizer: 第25回化学反応討論会
  • Place of Presentation: 大宮ソニックシティーホール(大宮)
• [Presentation] Collision energy dependence of Br atom formation in the OH+HBr and the OD+HBr reactions (2009)
  • Author(s): D.-C.CHE, (et.al.)
  • Organizer: 第25回化学反応討論会
  • Place of Presentation: 大宮ソニックシティーホール(大宮)
• [Presentation] "六極不均一電場を用いた非対称コマ分子の回転状態選別 (2009)
  • Author(s): 蔡徳七, 他
  • Organizer: 第3回分子化学討論会
  • Place of Presentation: 名古屋大学(名古屋)
• [Presentation] Stereodynamics : Searching for a bridge to link micro-and macroscopic concepts of chemical reactions (2009)
  • Author(s): 笠井俊夫
  • Organizer: 第25回化学反応討論会
  • Place of Presentation: 大宮ソニックシティ(埼玉)
• [Presentation] Collision energy dependence of Br atom formation in the OH+HBr and the OD+HBr reactions (2009)
  • Author(s): D.-C.CHE, (et.al.)
  • Organizer: 第25回化学反応討論会
  • Place of Presentation: 大宮ソニックシティ(埼玉)
• [Presentation] Stereodynamics of Chemical Reactions in Heterogeneous Systems : Dissociative Adsorption of NO on Si(111) (2008)
  • Author(s): M.Hashinokuchi, M.Okada, H.Ito, T.Kasai, K.Moritani, Y.Teraoka
  • Organizer: Stereodynamics
  • Place of Presentation: 大連China
  • Year and Date: 2008-11-03
• [Presentation] Dynamics of the OH+HBr four-atom reaction by using electrostatic hexapole state-selection and VUV-LIF product detection (2008)
  • Author(s): 蔡徳七, 笠井俊夫
  • Organizer: XVII MOLEC European Conferece on Dynamics of Molecular Systems
  • Place of Presentation: Russia, St. Petersburg
  • Year and Date: 2008-08-26
• [Presentation] Dynamics of the OH+HBr four-atom reaction by using electrostatic hexapole state-selection and VUV-LIF product detection (2008)
  • Author(s): D.-C.CHE, T.Kasai
  • Organizer: XVII MOLEC European Conferece on Dynamics of Molecular Systems
  • Place of Presentation: Russia, St.Petersburg