Statistical Spectroscopy of Quantum Chaotic Level Structure in Vibrational Highly Excited Molecules and Molecular Complexes

振动高激发分子和分子复合物中量子混沌能级结构的统计光谱

• 批准号: 02403006
• 负责人: TSUCHIYA Soji
• 金额: $ 16万
• 依托单位: THE UNIVERSITY OF TOKYO
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (A)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02403006/
• 关键词: Molecular Vibration; Highly Excited Molecules; Normal Vibration; Local Vibration; Unimolecular Reaction; Chaos; Photodissociation

Stimulated emission pumping(SEP),dispersed fluorescence(DF),and photofragment excitation(PHOFEX)spectroscopy have been applied to elucidate the vibrational dynamics of highly excited molecules. 1.Vibrational assignment was performed for more than 500 levels identified in the observed DF spectra up to 24,000 cm^<-1>. The bending vibration is very hamonic while two stretching modes couple with each other in the region above 20,000 cm^<-1>.2.Hierarchical structure is identified in the vibrational level structure of acetylene. A spectral peak called a feature state is formed by a Darling Dennision anharmonic resonance of two CH bending modes. In the higher energies,the feature is evolved to include couplings of other vibrational modes. 3.The photodissociation rate constant of the state-selected NO_2 is observed to show that the constant fluctuates around the value which is predicted by the phase-space theory. The fluctuation reflects quantum fluctuations associated with individual quasibound eigenstates. This conclusion is supported by the statistical analysis of the vironic levels of NO_2 just below the dissociation threshold.

受激发射泵浦（SEP）、色散荧光（DF）和光碎片激发（PHOFEX）光谱已被应用于阐明高度激发分子的振动动力学。 1.对在高达24,000cm^-1的观察到的DF光谱中识别的500多个水平进行振动分配。弯曲振动是非常谐波的，而两个伸缩模式在20,000 cm^-1>以上的区域中相互耦合。2.乙炔的振动能级结构中发现了层次结构。称为特征状态的谱峰是由两个 CH 弯曲模式的 Darling Dennision 非简谐振动形成的。在更高的能量中，该特征演变为包括其他振动模式的耦合。 3.对状态选择NO_2的光解离速率常数进行观察发现，该常数在相空间理论预测值附近波动。该涨落反映了与单个准束缚本征态相关的量子涨落。对略低于解离阈值的 NO_2 病毒水平的统计分析支持了这一结论。