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

受激发射泵浦(SEP)、分散荧光(DF)和光碎片激发(PHOFEX)光谱被用来解释高激发态分子的振动动力学。1.对观察到的df谱中的500多个能级进行了振动归属，最高可达24,000 cm^-1&gt；在20,000 cm~(-1)~(-1)&g~(-1)范围内，弯曲振动十分简谐，而两个伸缩模式相互耦合。2.乙炔的振动能级结构中存在层次型结构。两个CH弯曲模的Darling-Dennision非谐共振形成了一个称为特征态的光谱峰值。在更高的能量中，该特征被演化为包括其他振动模式的耦合。3.观测了态选择NO_2的光解离速率常数，结果表明，光解速率常数在相空间理论预测值附近波动。这种涨落反映了与单个准束缚本征态相关的量子涨落。这一结论得到了环境NO_2浓度低于离解阈值的统计分析的支持。

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.