Journal of Chemical Physics, Vol.113, No.6, 2182-2187, 2000
An optical-optical double resonance study of the perturbed O-2 d3s sigma(g)((1)Pi(g)) Rydberg state excited via single rotational levels of the b((1)Sigma(+)(g)) valence state
The perturbed v=3 level of the d3s sigma(g)((1)Pi(g)) Rydberg state of O-2 has been excited in an optical-optical double resonance (OODR) experiment via J=0-16 of v=0 of the b((1)Sigma(g)(+)) state. The d((1)Pi(g)) state resonances were detected by ionization with one further probe photon near 340 nm. The range of J levels of the d((1)Pi(g)) state now accessed reveals a lack of variation in line widths that is not predicted by previous models of state-dependent predissociation. Instead, intensities of rotational lines in the ionization spectrum appear to be controlled by a J-dependent mixing of the d((1)Pi(g)) state with a nearby valence state that has a much lower ionization cross section at the probe wavelengths used.