Abstract
Quantum defects of lλ-Rydberg states (l=s,p,d, λ=σ,π,δ) of NO were calculated by SCF and CI methods at various internuclear distances. Employing the multichannel quantum defect theory (MQDT), the recently observed resonantly enhanced multiphoton ionization (REMPI) photoelectron spectra were analyzed with use of the calculated quantum defects. Analysis was made particularly to the autoionization of vibrationally excited Rydberg states of σ and δ symmetry. It is concluded that the autoionization is dominated by the two-step electronic mechanism in which dissociative superexcited state plays a role of intermediate state. Potential curves and electronic coupling strengths of the relevant dissociative states (B′ 2Δ and I 2∑) were estimated from this analysis. This provides us with useful information to investigate various dynamic processes involving these superexcited states. Importance of dissociative superexcited state is emphasized in reference to the various dynamic processes.
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