Dynamics of electron ejection: Fermi resonance and mode specificity in the vibrational autoionization of NO2

Hiroshi Matsui; Edward R. Grant

doi:10.1117/12.220851

18 September 1995 Dynamics of electron ejection: Fermi resonance and mode specificity in the vibrational autoionization of NO₂

Hiroshi Matsui, Edward R. Grant

Author Affiliations +

Proceedings Volume 2548, Laser Techniques for State-Selected and State-to-State Chemistry III; (1995) https://doi.org/10.1117/12.220851
Event: SPIE's 1995 International Symposium on Optical Science, Engineering, and Instrumentation, 1995, San Diego, CA, United States

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.

Citation Download Citation

Hiroshi Matsui and 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); https://doi.org/10.1117/12.220851

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