Abstract
The np (n=3–10) and nf (n=4–9) Rydberg states of O2 converging on O2+ X 2Π1/2,g and X 2Π3/2g have been studied between 75 000 and 99 900 cm−1 using optical–optical double resonance with multiphoton ionization. Three-photon excitation from single rotational levels of the initially excited b 1Σ0g+ valence state was used to access these states. The nf states show a strong tendency towards (Ω,ω) coupling for all values of n, whereas the np states appear to be best described by (Λ,S) coupling for n⩽8. The intensities of some of the 5f bands are anomalously high due to accidental resonances with the 3s d 1Π1g Rydberg state at the two-photon level.
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