Multiphoton ionization spectroscopy is used to characterize the (3ssgr;)3Pgr;gRydberg state of O2. It is found that the3Pgr;gRydberg state is very diffuse and has rotationally resolved structure for thevrsquo;=2 level only. The FWHM of rotational lines for both the (3ssgr;)3,1Pgr;gstates is greater than the excitation bandwidth, indicating strong radiationless decay of the two states. Interactions with the nearby3Pgr;gand1Pgr;gvalence states are invoked to explain the observed behavior.
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