Studies on the production of O2(a1Δg, υ = 0) and O2(b1Σg+, υ = 0) from collisional removal of O2(A3Σu+, υ' = 6-10)

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Atmospheric Composition And Structure: Airglow And Aurora, Atmospheric Composition And Structure: Chemical Kinetic And Photochemical Properties, Atmospheric Composition And Structure: Constituent Sources And Sinks, Atmospheric Composition And Structure: Middle Atmosphere: Composition And Chemistry

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Production of two metastable O2 species, O2(a 1Δ g , υ = 0) and O2(b 1Σ g +, υ = 0), from collisional removal of O2(A 3Σ u +) by O2 and N2 is investigated at a temperature of 240 K. A state-selective two-laser technique is used, in which the output of the first laser excites ground-state O2 molecules to a specific vibrational level (6 <= υ' <= 10) in the A 3Σ u + state, and the output of the second laser subsequently probes the O2(a 1Δ g , υ = 0) and O2(b 1Σ g +, υ = 0) populations by resonance-enhanced multiphoton ionization via the intermediate d 1Π g Rydberg state. For the relatively short timescales of our experiment (~10-4 Torr.s), we find that the O2(a 1Δ g , υ = 0) quantum yield from collisional removal of O2(A 3Σ u +, υ') by O2 is approximately constant for υ' = 7-9, and decreases by 30-40% for υ' = 6 and 10. The O2(b 1Σ g +, υ = 0) yield is nearly constant for υ' = 8-10, and decreases by about 50% for υ' = 6 and 7. The eventual O2(a 1Δ g , υ = 0) and O2(b 1Σ g +, υ = 0) yields from O2(A 3Σ u +, υ' = 8) measured in synthetic air are nearly equal to those measured in pure O2, suggesting that N2 collider does not significantly affect the relaxation pathways leading to the production of the two metastable species. However, at short experimental times the buildup of the O2(a 1Δ g , υ = 0) population is considerably slower in synthetic air than in O2.

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