An FTIR emission study of the products of NO A2Σ+ (v = 0, 1) + O2 collisions

Abstract

Collisional quenching of NO A²Σ⁺ (v = 0, 1) by O₂ has been studied through the detection of vibrationally excited products by time-resolved Fourier transform infrared emission spectroscopy. Non-reactive quenching of NO A²Σ⁺ (v = 0) produces a vibrational distribution in NO X²Π which has been quantified for v = 2–22, and is found to be bimodal. The results are consistent with two quenching channels. The first forms the ground X³Σ⁻_g or low-lying a ¹Δ_g electronic state of O₂ with a distribution including high vibrational levels of NO X²Π which is slightly hotter than statistical. Two possibilities are identified for the second channel. The first, with a similar quantum yield to that producing higher vibrational levels, forms a highly electronically excited state, such as O₂ c¹Σ⁻_u, with low vibrational levels in NO X²Π which are inverted with a distribution resembling that resulting from a sudden or harpoon mechanism. The second is that ground state oxygen is formed with low vibrational energy partitioned into NO X²Π. In addition, vibrationally excited NO₂ is observed, but at intensities which indicate that it is formed in low quantum yield. Quantitatively unobservable processes (defined as those which do not form ground state NO (v ≥ 2)) are found to have a branching ratio of at most 25 ± 5%. The results are compared with those of previous studies and the most consistent interpretation suggests that dissociation of O₂ to form ground state O(³P) atoms and ground vibrational state NO X²Π (v = 0) is the main reactive process rather than NO₂ formation. Qualitatively similar results are seen for the quenching of NO A²Σ⁺ (v = 1).