Journal of Chemical Physics, Vol.106, No.6, 2239-2247, 1997
Rotationally Resolved Photoelectron-Spectra from Vibrational Autoionization of No Rydberg Levels
Rotationally resolved photoelectron spectra from vibrational autoionization of individual rotational levels of the nl(R) (v=1, 11 less than or equal to n less than or equal to 15, 0 less than or equal to l(R) less than or equal to 3) Rydberg states of NO are measured by combining two-color double-resonance excitation via the NO A(2) Sigma(+) (upsilon(i)=1, N-i=19) state with time-of-flight photoelectron spectroscopy. The photoelectron spectra show that both even-l and odd-l continuum partial waves are generated by the autoionization events, and thus provide evidence for angular momentum exchange between the outgoing electron and the molecular-ion core. We interpret these observations as caused by the multipolar interactions between the outgoing electron and the vibrating nuclear core, which appear to be brought about both by the dependence on internuclear distance of the electron-ion-core electronic interaction and by Rydberg-valence state couplings.
Keywords:RESONANCE MULTIPHOTON IONIZATION;QUANTUM DEFECT ANALYSIS;SUPERSONIC FREE JET;ANGULAR-DISTRIBUTIONS;DIATOMIC-MOLECULES;NITRIC-OXIDE;THRESHOLD PHOTOIONIZATION;STATE DISTRIBUTIONS;BRANCHING RATIOS;SELECTION-RULES