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

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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.