Stereo-Dynamical Processes of Chemical Reactions Observed by Orienting Molecules

通过定向分子观察化学反应的立体动力学过程

• 批准号: 12440165
• 负责人: KASAI Toshio
• 金额: $ 9.41万
• 依托单位: Osaka University (2002)Okazaki National Research Institutes (2000-2001)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12440165/
• 关键词: Effect of molecular orientation; Stereodynamics; Hydrogen bonded (DCl)_2 dimer; Electrostatic hexapole method for orienting molecules; [ClDCl] transition state; Doppler-selected TOF method; Hot-hydrogen mechanism on surface reactions; Single Ω stat

1) The OH(^2P) radicals were produced by a pulsed glow DC discharge of H_2O.The focusing curve for the single quantum state |JWM_J> = |1/2 1/2 1/2 > of OH(^2P) radicals was measured using the combined method of an electrostatic hexapole state-selection with 1-m in length and a laser induced fluorescence technique for the OH(A ← X) transition at 308 nm2) Non-destructive size selection of neutral clusters was carved out using the hexapole electric field. The photodissociation of DCI dimer was studied, in which DCl dimer was preferentially selected from the DCl cluster beam using the same hexapole electrostatic field prior to the photolysis. We were able to observe the internal energy distribution of the [ClDCl] transient species resulting from the hydrogen atom elimination from (DCI)_23) We constructed a UHV compatible oriented-molecular-beam machine with six lm rods in order to elucidate the stereodynamics in surface reactions. We characterized this machine using a reagent gas of methylchloride to ensure satisfactory specification for conducting surface experiment in schedule and we confirmed that the orientational degee of the selected beam is as 86% pure as single |JKM> = |111> state4) We proposed a new hot-atom mediated mechanism in the dissociative-adsorption process of hydrogen molecule on Ir single crystal surfaces, based on the analysis of reaction kinetics

1) H_2O脉冲辉光直流放电产生OH（^2P）自由基。采用长度为1 m的静电六极态选择方法和激光诱导荧光技术对OH（a←X）在308 nm2下的跃迁进行组合，测量了OH（^2P）自由基的单量子态|JWM_J> = |1/2 / 1/2 >的聚焦曲线。研究了DCI二聚体的光解作用，在光解前使用相同的六极静电场从DCl簇束中优先选择DCl二聚体。为了研究表面反应的立体动力学，我们构建了一个具有6个lm棒的特高压兼容定向分子束机。为了保证能在规定的时间内进行表面实验，我们用甲基氯试剂气体对机器进行了表征，并确定了所选光束的取向度为86%，纯度为单一|JKM> = |111>状态。4)我们在反应动力学分析的基础上，提出了氢分子在Ir单晶表面解离吸附过程的一种新的热原子催化机理

项目成果

M.Okada, K.Monritani, S.Goto, T.Kasai, A.Yoshigoe, Y.Teraoka: "Actively-Controlled Oxidation of Cu{100} with Hyperthermal O_2 Molecular Beam"J.Chem.Phys.(Communications). 119. 6994-6997 (2003)

M.Okada、K.Monritani、S.Goto、T.Kasai、A.Yoshigoe、Y.Teraoka：“利用高温 O_2 分子束主动控制 Cu{100} 的氧化”J.Chem.Phys.（通讯）。

盛谷浩右, 岡田美智雄, 後藤征士朗, 笠井俊夫: "超高真空対応型配向分子線ビームラインの開発"J.Vac.Sac.Jpn.(真空). 46(9). 692-697 (2003)

Hiroaki Moriya、Michio Okada、Seishiro Goto、Toshio Kasai：“与超高真空兼容的定向分子束线的开发”J.Vac.Sac.Jpn（真空）46（9）。 ) )

K.Koizumi, H.Ohoyama, T.Kasai: "Collision Energy Resolved Steric Effect on the Penning Ionization Reaction of tert-Butyl Bromide and Kr(^3P)"Chem.Phys.Len.. 378. 486-492 (2003)

K.Koizumi、H.Ohoyama、T.Kasai：“碰撞能量解析空间效应对叔丁基溴和 Kr(^3P) 潘宁电离反应的影响”Chem.Phys.Len.. 378. 486-492 (2003)

S.Ukada, H.Ohojama, T.Kasai: "Stereo-selectivity in the Penning ionization reaction of CH_3X (X=Cl, Br, I)+Ar(^3P) → CH_3X^++Ar+e^-"Chem.Plays.Left.. 355. 77-81 (2002)

S.Ukada、H.Ohojama、T.Kasai：“CH_3X (X=Cl, Br, I)+Ar(^3P) → CH_3X^++Ar+e^- 彭宁电离反应中的立体选择性”Chem .左演奏.. 355. 77-81 (2002)

K.Imura, T.Kawashima, H.Ohoyama, T.Kasai: "Direct determination of the permanent dipole moments and structures of AI-CH_3CN and AI-NH_3 by using 2-meter electrostatic hexapole field"J.Am.Chem.Soc.. 123. 6367-6371 (2001)

K.Imura、T.Kawashima、H.Ohoyama、T.Kasai：“利用2米静电六极场直接测定AI-CH_3CN和AI-NH_3的永久偶极矩和结构”J.Am.Chem.Soc