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

该项目旨在对东京、剑桥、格勒诺布尔和巴黎的四个实验室进行的关于高激发态多原子分子分子内振动动力学的合作实验和理论研究。高激发乙炔的振动动力学(1)MIT小组通过对振动高激发乙炔的能级能量进行统计分析，提出了一个混沌振动动力学。(2)格勒诺布尔小组基于对MIT小组获得的光谱数据的傅立叶分析，提出了一个不完全的激发乙炔混沌动力学。(3)东京小组在单个振动能级观测到了乙炔的色散荧光光谱，从而获得了该振动能级结构的整体特征。他们可以用非调和展开函数来分析它，假设在大约14,000 cm^-1&gt；的能量范围内有五个简正波。在这个能量之外，两个CH弯曲模(反模和顺模)相互耦合，使得局部混沌的dy…在这些模式中实现了更多的名称。在接近最终完全混沌动力学的另一个阶段发生耦合到其他模。(4)遵循上述建议，麻省理工学院研究小组基于乙炔的高分辨率SEP谱证实了两个CH伸缩模之间的非简谐耦合方案。NO2(1)东京基团的单分子解离反应成功地获得了NO2的态选择光碎片(O或NO)激发谱，观察到的谱线结构表明NO2是通过高激发振动态发生解离反应的。(2)格勒诺布尔小组讨论了激发态NO2的振动能级结构，他预言即使在解离阈值以下的区域也存在混沌能级结构。电子激发范德华络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学-光学双共振方法预测了HgAr_2络合物的结构。(2)Orsay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。较少

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