Statistical Spectroscopy of Quantum Chaos State in Vibrationally Highly Excited polyatomic Molecules

高振动激发多原子分子中量子混沌态的统计光谱

• 批准号: 02044038
• 负责人: TSUCHIYA Soji
• 金额: $ 3.46万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for international Scientific Research
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02044038/
• 关键词: Chaos; Molecular Vibration; Laser spectroscopy; Unimolecular Reaction; van der Waals complex; カオス; 振動高励起分子

This project aims at cooperative experimental and theoretical studies on intramolecular vibrational dynamics of highly excited polyatomic molecules which have been carried out in four laboratories of Tokyo, Cambridge, Grenoble and Paris.1. Vibrational dynamics of highly excited acetylene(1) MIT group proposed a chaotic vibrational dynamics by means of a statistical analysis of level energies of vibrationally highly excited acetylene.(2) Grenoble group claimed an incomplete chaotic dynamics of excited acetylene based on the Fourier analysis of the spectral data obtained by MIT group.(3) Tokyo group observed a dispersed fluorescence spectrum of acetylene in a single rovibronic level to obtain a global feature of the vibrational level structure. They could analyze it in terms of an anharmonic expansion function assuming five normal modes in an energy region up to around 14, 000 cm^<-1>. Beyond this energy, two CH bending, modes (trans and cis) couple each other, so that a local chaotic dy … More namics is realized within these modes. Couplings to other modes occur in another stage approaching a final full chaotic dynamics.(4) Following the above proposal, MIT group confirmed an anharmonic coupling scheme between two CH stretching modes based on the high-resolution SEP spectrum of acetylene.2. Unimolecular dissociation reaction of NO_2(1) Tokyo group succeeded to take a state-selected photofragment (O or NO) excitation spectrum of NO_2. The observed spectrum showed a line structure which indicated the dissociation reaction via highly excited vibrational states of N0_2.(2) The vibrational level structure of excited N0_2 was discussed by Grenoble group, who predicted a chaotic level structure even in the region below the dissociation threshold.3. Structure and dynamics of electronically excited van der Waals complexes(1) Tokyo group predicted the structure of HgAr_2 complex by means of LIF spectroscopy and optical-optical double resonance method.(2) Orsay group discussed the structure of HgAr_2 based on a semi-empirical calculation of the potential surface as well as resonantly enhanced multiple photon ionization method. Less

该项目旨在对高度激发的多原子分子的分子内振动动力学进行合作实验和理论研究，这些研究已在东京、剑桥、格勒诺布尔和巴黎的四个实验室进行。高激发态乙炔的振动动力学（1）MIT小组通过对乙炔振动高激发态能级能量的统计分析，提出了一种混沌振动动力学。(2)Grenoble小组基于MIT小组获得的光谱数据的傅立叶分析，声称激发态乙炔存在不完全混沌动力学。(3)东京研究组在单振子能级上观测到乙炔的色散荧光光谱，得到了乙炔振动能级结构的整体特征。他们可以用非谐展开函数来分析它，假设在大约14000 cm ↑ [3]的能量范围内有五个简正模<-1>。超过这个能量，两个CH弯曲模（反式和顺式）相互耦合，从而产生局部混沌模。 ...更多信息 在这些模式中实现了动力学。耦合到其他模式发生在另一个阶段接近最终的完全混沌动力学。(4)MIT研究组根据乙炔的高分辨SEP谱，证实了两个CH伸缩模之间的非谐耦合方案. NO_2的单分子解离反应（1）东京群成功地得到了NO_2的选态光碎片（O或NO）激发谱。所观察到的光谱显示了一个线结构，这表明通过NO_2的高激发振动态的解离反应。(2)格勒诺布尔小组对激发态NO_2的振动能级结构进行了讨论，预测在低于解离阈值的区域也存在混沌能级结构.电子激发态货车德瓦耳斯配合物的结构和动力学（1）东京小组用激光诱导荧光光谱和光-光双共振方法预测了HgAr_2配合物的结构。(2)奥赛小组基于势面的半经验计算和共振增强多光子电离方法讨论了HgAr_2的结构。少

项目成果

D.J.Jonas et al.: "Intramolecular vibrational relaxation and forbidden transitions in the SEP spectrum of acetylene" J.Chem.Phys.

D.J.Jonas 等人：“乙炔 SEP 光谱中的分子内振动弛豫和禁戒跃迁”J.Chem.Phys。

J.Miyawaki et al.: "Photofragment excitation spectrum of NO_2 observed through O( ^3P_J) detection" Chem.Phys.Lett.180. 287-292 (1991)

J.Miyawaki等人：“通过O(^3P_J)检测观察到的NO_2的光碎片激发光谱”Chem.Phys.Lett.180。

K.Yamanouchi et al.: "Vibrationally highly excited acetylene as studied by dispersed fluorescence and stimulated emission pumping spectroscopy:Vibrational assignment of feature states" J.Chem.Phys.95. 6330-6342 (1991)

K.Yamanouchi 等人：“通过分散荧光和受激发射泵浦光谱研究振动高度激发的乙炔：特征态的振动分配”J.Chem.Phys.95。

N. Ochi et al.: "Rovibronic level structure of electronically excited acetylene (A ^1A_u) in a supersonic jet" Chem. Phys.152. 319-336 (1991)

N. Ochi 等人：“超音速射流中电子激发乙炔 (A ^1A_u) 的 Rovibronic 能级结构” Chem。

N.Ochi et al.: "Rovibronic level structure of electronically excited acetylene (A^lA_u) in a supersonic jet" Chem.Phys.). 02%33 (1991)

N.Ochi 等人：“超音速射流中电子激发乙炔 (A^lA_u) 的 Rovibronic 能级结构”Chem.Phys.）。