Lifetimes and predissociation mechanisms of O+2 b 4Σg−(v = 5–8)

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Abstract
Predissociation linewidths (lifetimes) of the O+2 b 4Σ−g state have been measured as a function of both rotational levels N and spin‐orbit fine structure components F1, F2, F3, and F4 for vibrational levels 5 through 8. The lifetime variation is inconsistent with predissociation by either the d 4Σ+g state or the f 4Πg state alone, but can be explained by assuming both states participate in the dissociation. Analysis of the linewidth variation, using an experimentally determined f 4Πg potential curve, allows a separation of the effects of the 4Σ+g and 4Πg states on the predissociation. The experimental linewidths are compared with theoretical calculations and found to be about a factor of 3 larger than calculated. Relative transition moments from the a state to the d and f states are estimated using a single configuration interaction calculation.