Vibrational Autoionization in Polyatomic Molecules
Molecular Rydberg states converging to vibrationally excited states of a given electronic state of the ion and having total energy greater than the lowest vibrational level of that electronic state of the ion can spontaneously ionize through the conversion of vibrational energy of the ion core into electronic, and ultimately translational energy, of the Rydberg electron. This process is known as vibrational autoionization.1 Vibrationally autoionizing resonances can be thought of as vibrationally excited Feshbach resonances in the scattering of electrons off molecular ions, and the decay process is closely related to the superelastic scattering of slow electrons off vibrationally excited ions. If they are coupled to a dissociative continuum, vibrationally autoionizing resonances can also play a role in dissociative recombination.
KeywordsPhotoelectron Spectrum Orbital Energy Rydberg State Polyatomic Molecule Quantum Defect
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