18 September 1995 Dynamics of electron ejection: Fermi resonance and mode specificity in the vibrational autoionization of NO2
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Abstract
Ionization-detected absorption spectra of autoionizing Rydberg series converging to (100), (010), (0200), and 0220) vibrational states of NO2+ have been recorded in three-color triple resonant excitation. Resonances associated with decay by relaxation in symmetric stretch are found to be much broader than those observed for the core excited in one quantum of the bending vibration, consistent with earlier findings on mode- specificity of vibrational autoionization in this system. Series excited in (0200), on the other hand, are found to behave much more like (100) than (010), indicating that the bending specificity that characterizes the fundamental is lost in the overtone. This loss of mode specificity with increasing vibrational energy is ascribed to (100) - (0200) Fermi resonance in the NO2+ core, exemplifying how even small vibrational coupling can redirect mode-specific fragmentation pathways in polyatomic molecules.
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Hiroshi Matsui, Edward R. Grant, "Dynamics of electron ejection: Fermi resonance and mode specificity in the vibrational autoionization of NO2", Proc. SPIE 2548, Laser Techniques for State-Selected and State-to-State Chemistry III, (18 September 1995); doi: 10.1117/12.220851; https://doi.org/10.1117/12.220851
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