Comparative very-high-resolution VUV spectroscopy: Laser spectroscopy of O₂

Despite their importance to the photochemistry of the terrestrial atmosphere, and many experimental studies, previous characterization of the Schumann-Runge (SR) bands of O₂, B³∑_ū ← X ³∑_ḡ (υ, 0) (1750-2050 Å) has been limited by poor experimental resolution. In addition, our understanding of the SR spectrum is incomplete, many rovibrational transitions in the perturbed region of the spectrum [B(υ > 15)] remaining unassigned. We review new very-high-resolution measurements of the O₂ photoabsorption cross section in the SR bands. Tunable, narrow-bandwidth background vacuum-ultraviolet (VUV) radiation for the measurements (∼ 7 × 10⁵ resolving power) was generated by the two-photon-resonant difference-frequency four-wave mixing in Xe of excimer-pumped dye-laser radiation. With the aid of these cross-section measurements, rovibrational and line-shape analyses have led to new insights into the molecular structure and predissociation dynamics of O₂. The current VUV laser-spectroscopic measurements are shown to compare favourably with results from two other very-high-resolution experimental techniques, namely laser-induced fluorescence spectroscopy and VUV Fourier-transform spectroscopy, the latter performed using a synchrotron source.