Spectroscopic Studies of Unimolecular Reaction Dynamics of Vibronically State-selected Molecules

振动状态选择分子的单分子反应动力学的光谱研究

• 批准号: 11640515
• 负责人: TSUCHIYA Soji
• 金额: $ 2.37万
• 依托单位: JAPAN WOMEN'S UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640515/
• 关键词: Acetylene; Vibrational Dynamics; Excited State Dynamics; Photodissociation Dynamics

In order to investigate vibrational dynamics of vibronically state-selected acetylene, various spectroscopic techniques have been applied.(1) The rovibronic level system of the ungerade nv_3'+v_4'/v_6' (n=0,1,2,3) vibrational states in the A^1A_u state of acetylene which are accessible from the selected rotational level J" of the v_3" state in the X^1Σ_g^+ state. The nv_3'+v_6' and nv_3'+v_4' state are found to couple with each other by the a-and b-axis Coriolis interactions.(2) Most of rotational levels of the 3v_3'+v_6' state split into two or more levels, while those of the 3v_3'+v_4' state are single. The fluorescence decay from the spilit levels shows a quantum beat under a weak magnetic field. This indicates that the level splitting is attributable to the S-T interaction. Since the v_6' mode is in-plane while the v_4'is out-of-plane, the S-T interaction occurs in the planar geometry of the excited acetylene.(3) The H-atom action spectroscopy has been applied to investigate the predissociation efficiency of acetylene excited in the gerade vibrational states in the region of 47000〜50600 cm^<-1>. The predissociation is enhanced in the states exceeding the inversion barrier of the bending vibration which is located around 48000 cm^<-1>.

为了研究振动选态乙炔的振动动力学，各种光谱技术已被应用。(1)乙炔的A^1A_u态的nv_3 '+ v_4'/v_6'（n= 0，1，2，3）转动振动能级系统可从X^1A_g ^+态的v_3”态的选择转动能级J”得到。发现nv_3 '+ v_6'和nv_3 '+ v_4'态通过a轴和b轴Coriolis相互作用相互耦合。(2)3v_3 '+ v_6'态的转动能级大多分裂为两个或多个能级，而3v_3 '+ v_4'态的转动能级为单能级。从分裂能级的荧光衰减表明在弱磁场下的量子拍。这表明能级分裂是由S-T相互作用引起的。由于v_6'模是面内模，而v_4'模是面外模，所以S-T相互作用发生在激发态乙炔的平面几何结构中。(3)本文用氢原子作用谱研究了乙炔在47000 ~ 50600 cm ~ 2范围内的激发态预解离效率<-1>。在超过位于48000 cm-3附近的弯曲振动的反转势垒的状态下，预解离增强<-1>。

项目成果

K.Tsuji et al.: "Trans-cis isomerization of acetylene in the A^1A_u state as studied by dispersed fluorescence Spectroscopy"Chem.Phys.Lett.. 306. 41-47 (1999)

K.Tsuji 等人：“通过分散荧光光谱研究 A^1A_u 态乙炔的反式异构化”Chem.Phys.Lett.. 306. 41-47 (1999)

S.Iwamoto et al.: "Detection of hydrogen atoms by 2-photon resonance-enhanced 3-photon ionization method"J.Jpn.Women's Univ.Fac.Sci.. 9. 59-64 (2001)

S.Iwamoto等：“通过2-光子共振增强3-光子电离法检测氢原子”J.Jpn.Womens Univ.Fac.Sci.. 9. 59-64 (2001)

M.Mizoguchi et al.: "IR-UV double resonance spectroscoopy of acetylene in the A^1A_unv_3'+v_4' and nv_3'+v_6' (n=2,3) ungerade vibrational state"J.Phys.Chem.. 104. 10212-10219 (2000)

M.Mizoguchi 等人：“乙炔在 A^1A_unv_3 v_4 和 nv_3 v_6 (n=2,3) ungerade 振动状态下的红外-紫外双共振光谱”J.Phys.Chem.. 104. 10212

M.Mizoguchi 他: "IR-UV Double Resonance Spectroscopy of Acetylene in the A^^〜 ^1A_u nυ_3'+υ_4' and nυ_3'+υ_6' (n=2,3) Ungerade Vibrational State"J.Phys.Chem.. 104(45). 10212-10219 (2000)

M. Mizoguchi 等人：“A^^~ ^1A_u nυ_3+υ_4 和 nυ_3+υ_6 (n=2,3) Ungerade 振动状态下乙炔的红外-紫外双共振光谱”J.Phys。化学104(45)。

K.Tsuji 他: "Trans-cis isomerization of acetylene in the ^1A_u state as studied by dispersed fluorescence spectroscopy"Chem.Phys.Lett.. 306(1-2). 41-47 (1999)

K. Tsuji 等人：“通过分散荧光光谱研究^1A_u 态乙炔的反式-顺式异构化”Chem.Phys.Lett.. 306(1-2) (1999)。