The d 1 Π g (v=1) Rydberg State of O 2 : Optical-optical Double-resonance and Huggins-band Ozone-photolysis, Resonance-enhanced Multiphoton-ionization Studies with a b 1 Σ + g (v=0)-state Platform

Resonance-enhanced multiphoton-ionization spectra are presented of the d 1Πg←←b 1Σg+(1,0) transition of O2, the b(v=0) state generated both by photolysis of O3 in the Huggins bands and also by direct excitation of single J levels in an optical-optical double-resonance (OODR) experiment. The ozone-photolysis-derived spectra reveal a preferential formation of b(v=0) fragments with high J, the rotational distributions exhibiting significant dependence on the photolysis wavelength. Rotational analyses of the OODR and ozone-photolysis-derived spectra indicate that the d(v=1) Rydberg state is multiply perturbed by successive vibrational levels of the II 1Πg valence state. The OODR technique allows the first full resolution of the low-J levels of d(v=1) and the high-J levels favored by the ozone-photolysis technique are reported here for the first time.

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