Mode dependent vibrational autoionization of Rydberg states of NO2.: II.: Comparing the symmetric stretching and bending vibrations

Triple-resonance excitation and high-resolution photoelectron spectroscopy are combined to characterize the mode selectivity of vibrational autoionization of the high Rydberg states of NO2. Photoelectron spectra and vibrational branching fractions are reported for autoionizing Rydberg states converging to the NO2+ X (1)Sigma(g)(+)(110) state, that is, with one quantum in the symmetric stretch, nu(1), and one quantum in the bending vibration, nu(2). These results indicate that autoionization proceeds most efficiently through the loss of one quantum from the symmetric stretch rather than from the bending vibration. The implications of this result are discussed in terms of the autoionization mechanism. (C) 2004 American Institute of Physics.