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Probing Transition States of Chemical Reactions Utilizing Neutralization of Molecular Ions

Research Project

Project/Area Number 03403003
Research Category

Grant-in-Aid for General Scientific Research (A)

Allocation TypeSingle-year Grants
Research Field 物理化学一般
Research InstitutionHimeji Institute of Technology

Principal Investigator

KOYANO Inosuke  Himeji Institute of Technology Professor, 理学部, 教授 (80016089)

Co-Investigator(Kenkyū-buntansha) FUKUZUMI Takahiro  Himeji Institute of Technology Research Associate, 理学部, 助手 (20244684)
SHIMA Nobuyuki  Himeji Institute of Technology Associate Professor, 理学部, 助教授 (90167445)
HONMA Kenji  Himeji Institute of Technology Associate Professor, 理学部, 助教授 (30150288)
今村 隆史  国立環境研究所, 主任研究員 (60184826)
Project Period (FY) 1991 – 1994
Project Status Completed (Fiscal Year 1994)
Budget Amount *help
¥33,900,000 (Direct Cost: ¥33,900,000)
Fiscal Year 1994: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1993: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1992: ¥11,700,000 (Direct Cost: ¥11,700,000)
Fiscal Year 1991: ¥19,200,000 (Direct Cost: ¥19,200,000)
KeywordsIon-Molecule Reactions / Transition States / Vibronically Excited Ions / Transition-Metal Atom / Ion-Ion Recombination / イオンーイオン再結合 / イオンー分子反応
Research Abstract

In this project, we intended to probe intermediate or transition state of chemical reactions as directly as possible, by taking four different approaches. The main objective is to establish the technique that utilizes the recombination processes of polyatomic ions to produce temporarily the intermadiate states of neutral rections. In the first approach, we studied the reverse processes to this, that is, the ion pair formation from neutral excited molecules. For this purpose we utilized photoexcitation by synchrotron radiation. The systems we studied include, for example, CH_3X *X^-+CH_3^+, where X is either a halogen atom, H,or D,SO_2*O_-+SO_+, O_-+S_+O.We could successfully obtain a body of important information on the potential energy surfaces leading to ion pair formation, which in turn is relevant to the positive ion-negative ion recombination. In the second approach, a flowing afterglow technique has been used to investigate collisional deactivation of vibronically excited molecul … More ar ions and electronically excited transition metal atoms. Valuable information on the mechanisms, intermediate states, and the relevant rate constants have been obtained for the collisional processes of, for example, CO_+ (A^2II,v), N_2O^+ (A^2SIGMA, v), Ti (a^3F,a^5F), and V (a^4F,a^6D). In the third and fourth approarch, we started with designing and constructing a beam-chamber/cressed beams apparatus with three types of ion sources for generating high intensity positive and negative ion beams. These are duoplasmatron type, Colutron type, and ordinary electron impact type ion sources. We have succeeded in obtaining as high an intensity of positive ion beam, such as of N_2+, as that close to the space-charge limit, i.e., <approximately equal> 10_5 cm^<-3>, after mass selection and deceleration down to a few eV.In addition, we developed a cooled version of the duoplasmatron type ion source to produce cluster ions, with which we studied the photodissociation and collisional dissociation of the cluster ions. Photodissociation of cluster ions (N_2) _2^+, (N_2) _3^+, (CO_2) _2_+, and (N_2O) _2^+has been stuided using a copper vapor laser. It has been found that the only product obtained in the photodissociation of, for example, (CO_2) _2^+is CO_2_+, indicating that the excited states of the dimer ion probed here cannot be an intermediate state of the reaction CO_2^++CO_2*CO_3^++CO. Less

Report

(5 results)
  • 1994 Annual Research Report   Final Research Report Summary
  • 1993 Annual Research Report
  • 1992 Annual Research Report
  • 1991 Annual Research Report
  • Research Products

    (62 results)

All Other

All Publications (62 results)

  • [Publications] Kazushige Inaoka: "Low-energy,high-intensity ion beam apparatus for the study of intermediate states of ion-molecule collisions" Reports of Toyota Physical and Chemical Research Institute. 49. 39-49 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Yusuke Tamenori: "Dissociative photoionization of tungsten hexacarbonyl in the range 30-120eV" Journal of Electron Spectroscopy and Related phenomena. (in press). (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takashi Imamura: "State selected charge transfer reaction of CO^+(X,v;A,v')" International Journal of Mass Spectrometry and Ion Processes. 149/150. 161-166 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takashi Imamura: "Collisional quenching of N_2O^+ A-X emission by He,Ne,Ar,Kr,N_2,CO,CO_2,and N_2O" Journal of Physical Chemistry. 99. 15465-15469 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Kenji Honma: "The importance of electron transfer mechanism in reaction of neutral transition metal atoms" Laser Chemistry. 15. 209-220 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Shin-ichi Nagaoka: "Site-specific fragmentation following SI : 2p core-level phptoexcitation of F_3SiCH_2Si(CH_3)_3 in the vapor phase" Journal of Chemical Physics. 102. 6078-6086 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Kazushige Inaoka: "Low-energy, high-intensity ion beam apparatus for the study of intermediate states of ion-molecule collisions" Rept.Toyota Phys.Chem.Res.Inst. 49. 39-49 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Yusuke Tamenori: "Dissociative photoionization oftungsten hexacarbonyl in the range 30-120 eV" J.Electron Spectrosc.Relat.Phenom. (in press). (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Shin-ichi Magaoka: "Si : 2p core-level photoexcitation and photoionization of organosilicon molecules" J.Electron Spectrosc.Relat.Phenom. (in press). (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Bong-Hyun Boo: "Dissociative multiple ionization following valence and Si : 2p core level photoexcitation of HSi (CH_3) _3 in the range 38-133 eV" J.Phys.Chem. 100. 523-531 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takashi Imamura: "State selected charge transfer reaction of CO^+ (X,v ; A,v' ) with Ar" Int.J.Mass Spectrom.Ion Process. 149/150. 161-166 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takashi Imamura: "Collisional quenching of N_2O^+ A-X emission by He, Ne, Ar, Kr, N_2, CO,CO_2, and N_2O" J.Phys.Chem. 99. 15465-15469 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Seun-Ming Park: "Dissociative photoionization of bis (dimethyl-isopropylamido-aluminum) and bis (dimethyl-m-t-butyl amido-aluminum) in the region hgamma=65-133eV by mass spectrometry" JPn.J.Appl.Phys. 34. 933-936 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Bong-Hyun Boo: "Dissociative double ionization following valence and Si : 2p core level photoexcitation of SiCl_4 in the range 38-133 eV" J.Phys.Chem. 99. 13352-13367 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Shin-ichi Nagaoka: "Site-specific fragmentation following Si : 2p core-level phptoexcitation of F_3SiCH_2Si (CH_3)_3 in the vapor phase" J.Chem.Phys. 102. 6078-6086 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Kenji Honma: "The importance of electron transfer mechanism in reaction of neutral transition metal atoms" Laser Chem. 15. 209-220 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Kenji Honma: "Kinetics of depletion of electronically excited Ti atom by CH_4, C_2H_2, C_2H_4, and C_2H_6" J.Chinese Chem.Soc. 42. 371-379 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Kenji Honma: "Kinetics of Ti (a^3F,a^5F) and V (a^4F,a^6D) depletion by NH_3 and H_2S" J.Phys.Chem. 98. 13286-13293 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takashi Imajo: "Collision-induced transition between two spin-orbit states of CO^+ A^2P (v=1) with He" Chem.Phys.Lett. 223. 99-103 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] David E.Clemmer: "Kinetics of excited state Ti (a^5F) depletion by NO,O_2, N_2O,and N_2" J.Phys.Chem. 97. 11480-11488 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Shin-ichi Nagaoka: "Ionic fragmentation processes following Si : 2p core level photoexcitation of 1,1,1-trimethyltrichlorodisilane (Me_3SiSiCl_3)" J.Phys.Chem. 97. 1488-1405 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Koichiro Mitsuke: "Negative-ion mass spectrometric study of ion-pair formation in the vacuum ultraviolet. VII.SO_2*O_-+SO^+, O^-+S^++O" Org.Mass Spectrom. 28. 335-339 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takashi Imamura: "Mechanisms and rate constants for the collisional deactivtion of CO^+ (A^2II,gamma) by He and Ar" J.Chem.Phys. 98. 6248-6256 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Toshio Ibuki: "Dissociation of doubly charged CH_2=CD_2 and CH_2=CF_2 ethylenes in the valence shell photoexcitation" J.Chem.Phys. 98. 2908-2915 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Takashi Imamura: "Collisional quenching of N_2O^+A‐X emission by He,Ne,Ar,Kr,N_2,CO,CO_2,and N_2O." Journal of Physical Cnemistry. 99(in press). (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] Shin‐ichi Nagaoka: "Site‐specific fragmentation following Si:2p core‐level photoexcitation of F_3SiCH_2Si(CH_3)_3 in the vapor phase." Journal of Chemical Physics. 102(in press). (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] Kenji Honma: "Kinetics of Ti(a^3F,a^5F)and v(a^4F,a^6F).depletion by NH_3 and H_2S." Journal of Physical Chemistry. 98. 13286-13293 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Takashi Imajo: "Collision‐induced transitions between two spin‐orbit states of CO^+A^2II(v=1) with He." Chemical Physics Letters. 223. 99-103 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] David E.Clemmer: "Kinetics of excited state Ti(a^5F) depletion by NO,O_2,H_2O,and N_2." Journal of Physical Chemistry. 97. 11480-11488 (1993)

    • Related Report
      1994 Annual Research Report
  • [Publications] Koichiro Mitsuke: "Negative‐ion mass spectrometric study of ion‐pair formation in the vacuum ultraviolet.VII.SO_2→O^-+SO^=,O^-+S^++O." Organic Mass Spectrometry. 28. 335-339 (1993)

    • Related Report
      1994 Annual Research Report
  • [Publications] Takashi Imajo: "Collision-induced transitions between two spin-orbit states of CO^+2A^2II(v=1) with He." Chemical Physics Letters. xx(in press). (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] David E. Clemmer: "Kinetics of excited state Ti(a^5F) depletion by NO,O_2,N_2O,and N_2." Journal of Physical Chemistry. 97. 11480-11488 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Koichiro Mitsuke: "Negative-ion mass spectrometric atudy of ion-pair formation in the vacuum ultraviolet. VII. SO_2 O^-+SO^=, O^- + S^+ +O.21GC03:Organic Mass Spectrometry" 28. 335-339 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Takashi Imamura: "Mechanism and rate constants of the collisional deactivation of CO^+(A^2II,v) by He and Ar." Journal of Chemical Physics. 98. 6248-6256 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Shin-ichi Nagaoka: "Ionic fragmentation processes following Si:2P core level photo-excitation of 1,1,1-trimethyltrichlorodisila21GC05:Journal of Physical Chemistry" 97. 1488-1495 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Toshio Ibuki: "Dissociation of doubly charged CH_2=CD_2 and CH_2=CF_2 ethylenes in the valence shell photoexcitation." Journal of Chemical Physics. 98. 2908-2915 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Inosuke Koyano: "Dynamics of Excited Molecules" Elsevier Publishing Company, Amsterdam, 53 (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Inosuke Koyano: "化学ハンドブック" 朝倉書店, 8 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Koichiro mitsuke: "Negative-mass spectrometric study of ion-pair formation in the vacuum ultraviolet.VII.SO_2→O^-+SO^+,O^-+S^++O." Organic Mass Spectrometry. 28. (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Takashi Imamura: "Mechaisms and rate constants of the collisional deactivation of CO^+(A^<2π>,V)by He and Ar." Journal of Chemical Physics. 98. (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Shin-ichi Nagaoka: "Ionic fragmantation processes following si:2p core levelphotoexcitation and photoionization of 1,1,1-trimethyltrichlorodisilane." Journal of physucal Chemistry. 97. 1488-1495 (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Toshio Ibuki: "Dissociation of doubly charaged CH_2=CD_2 and CH_2=CF_2 ethylenes in the valence shell photoexcitation." Journal of Chemical Physics. 98. 2908-2915 (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Toshio Masuoka: "Kinetic enerqy release in dissociative double photo-ionization of OCS." Journal of Chemical Physics. 97. 2392-2399 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Shinzo Suzuki: "Negative-ion mass spectrometric study of ion-pair formation in the vacuum ultraviolet.VI.CH_3X→X^++CH^+_3(X=F,C1,Br)." Journal of Chemical Physics. 96. 7500-7505 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Takashi Imamura: "Collisionl deaccivation of CO^+A^2π(V=0-2)by He,Ne,Ar,N_2,and CO." Chemical Physics Letters. 178. 399-404 (1991)

    • Related Report
      1992 Annual Research Report
  • [Publications] Toshio Masuoka: "Anisotropic angular distribution of fragment ions in dissociative double photoionization of OCS." Physical Review A. 44. 4309-4315 (1991)

    • Related Report
      1992 Annual Research Report
  • [Publications] Shin-ichi Nagaoka: "Dissociative photoionization of Al_2(CH_3)_6 and Al_2(CH_3)_3Cl_3 in the range 40-100e^2V." Applied Oranometallic Chemistry. 5. 269-276 (1991)

    • Related Report
      1992 Annual Research Report
  • [Publications] Toshio Masuoka: "Dissociative single and double photoionination of CH_3F in the region 20-110 ev studied by mass spectrometry and the photoion-photoion coincidence method." Journal of Chemical Physics. 95. 1619-1627 (1991)

    • Related Report
      1992 Annual Research Report
  • [Publications] Koichiro Mitsuke: "Negative-ion mass spectrometric study of ion-pair formation in the vacuum ultraviolet.IV.CH_4→H+CH^+_3 and CD_4→D^-+CD^+_3." Jornal of Chemical Physics. 94. 6003-6006 (1991)

    • Related Report
      1992 Annual Research Report
  • [Publications] Koichiro Mitsuke: "Negative-ion mass spectrometric study of ion-pair formation in the vacuum ultraviolet.V.CF_4→F+CF^+_." Joirnal of Chemical Physics. 95. 2398-2406 (1991)

    • Related Report
      1992 Annual Research Report
  • [Publications] 小谷野 猪之助: "実験化学講座8巻「分光III」" 丸善株式会社, 21 (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] 小谷野 猪之助: "化学ハンドブック" 朝倉書店, 8 (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] 小谷野 猪之助: "Advances in Chemical Physics,vo1.LXXXII,part1" Wiley-Interscience Publishing Company, 45 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] 小谷野 猪之助: "シンクロトロン放射光-化学への基礎的応用" 学会出版センター, 37 (1991)

    • Related Report
      1992 Annual Research Report
  • [Publications] 今村 隆史,今城 尚志,小谷野 猪之助: "Collisional deactivation of co^+A^2II(v=u-2)by He,Ne,Ar,N_2,and Co." Chemical physics Letters. 178. 399-404 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 増岡 俊夫,小谷野 猪之助,斎藤 則生: "Anisotropic angular distribution of fragment ions in dissociative double photoinization of OCS." Physical Review A. 44. 4309-4315 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 長岡 伸一,小谷野 猪之助,今村 隆史,増岡 俊夫: "Dissociative photoionization of Al_2(CH_3)_6 and Al_2(CH_3)_3Cl_3 in the range 40ー100eV." Applied Organometallic Chemistry. 5. 269-276 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 増岡 俊夫,小谷野 猪之助: "Dissociative single and double photoionizaton of CH_3F in the region 20ー110 eV studied by mass spectrometry and the photoionーphotoion coincidence method." Journal of Chemical Physics. 95. 1619-1627 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 見附 孝一郎,鈴木 信三,今村 隆史,小谷野 猪之助: "Negativeーion mass spectrometric study of ionーpair formation in the vacuum ultraviolet.IV.CH_4→H+CH_3^+ and CD_4→D^-+CD_3^+." Journal of Chemical Physics. 94. 6003-6006 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 見附 孝一郎,鈴木 信三,今村 隆史,小谷野 猪之助: "Negativeーion mass spectrometric study of ionーpair formation in the vacuum ultraviolet.V.CF_4→F+CF_3^+." Journal of Chemical Physics. 95. 2398-2406 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 小谷野 猪之助,田中 健一郎: "Advances in Chemical Physics,Vo1.LXXXII,Part 1" WileyーInterscience Publishing Company, 45 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] 小谷野 猪之助: "シンクロトロン放射光ー化学への基礎的応用" 学会出版センタ-, 37 (1991)

    • Related Report
      1991 Annual Research Report

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Published: 1991-04-01   Modified: 2016-04-21  

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