Anomalous isotopic predissociation in the F³Πu(v=1) state of O₂

Abstract

Using a tunable, narrow-bandwidth vacuum-ultraviolet source based on third-harmonic generation from excimer-pumped dye-laser radiation, the F³Πu←X³Σg-(1,0)photoabsorption cross sections of ¹⁶O₂ and ¹⁸O₂ have been recorded in high resolution. Rotational analyses have been performed and the resultant F(v=1) term values fitted to the ³Π Hamiltonian of Brown and Merer [J. Mol. Spectrosc. 74, 488 (1979)]. A large rotationless isotope effect is observed in the F(v=1)predissociation, wherein the Lorentzian linewidth component for ¹⁸O₂ is a factor of ∼50 smaller than the corresponding ¹⁶O₂linewidth. This effect, a consequence of the nonadiabatic rotationless predissociation mechanism, is described using a coupled-channel treatment of the strongly Rydberg-valence-mixed 3Πu states. Significant J, e/f-parity, and sublevel dependencies observed in the isotopic F(v=1) rotational widths are found to derive from an indirect predissociation mechanism involving an accidental degeneracy with the E³Σ−u(v=3) level, itself strongly predissociated by ³Σ−u Rydberg-valence interactions, together with L-uncoupling (rotational) interactions between the Rydberg components of the F and E states. Transitions into the E(v=3) level are observed directly for the first time, specifically in the ¹⁸O₂ spectrum