Vibrational Relaxation of Ground-State Oxygen Molecules With Atomic Oxygen and Carbon Dioxide

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0340 Middle Atmosphere: Composition And Chemistry, 0341 Middle Atmosphere: Constituent Transport And Chemistry (3334), 0342 Middle Atmosphere: Energy Deposition (3334), 3332 Mesospheric Dynamics, 3334 Middle Atmosphere Dynamics (0341, 0342)

Scientific paper

Vertical water vapor profiles are key to understanding the composition and energy budget in the mesosphere and lower thermosphere (MLT). The SABER instrument onboard NASA's TIMED satellite measures such profiles by detecting H2O(ν2) emission in the 6.8 μm region. Collisional deactivation of vibrationally excited O2, O2(X3Σ-g, υ = 1) + H2O ↔ O2(X3Σ-g, υ = 0) + H2O(ν2), is an important source of H2O(ν2). A recent study has identified two other processes involving excited O2 that control H2O(ν2) population in the MLT: (1) the vibrational-translational (V-T) relaxation of O2(X3Σ-g, υ = 1) level by atomic oxygen and (2) the V-V exchange between CO2 and excited O2 molecules [1]. Over the past few years SRI researchers have measured the atomic oxygen removal process mentioned above at room temperature [2] and 240 K [3]. These measurements have been incorporated into the models for H2O(ν2) emission [1]. Here we report laboratory studies of the collisional removal of O2(X3Σ-g, υ = 1) by O(3P) at room temperature and below, reaching temperatures relevant to mesopause and polar summer MLT (~150 K). Instead of directly detecting the O2(X3Σ-g, υ = 1) population, a technically simpler approach is used in which the υ = 1 level of the O2(a1Δg) state is monitored. A two-laser method is employed, in which the pulsed output of the first laser near 285 nm photodissociates ozone to produce atomic oxygen and O2(a1Δg, υ = 1), and the pulsed output of the second laser detects O2(a1Δg, υ = 1) via resonance-enhanced multiphoton ionization. With ground-state O2 present, owing to the rapid equilibration of the O2(X3Σ-g, υ = 1) and O2(a1Δg, υ = 1) populations via the processes O2(a1Δg, υ = 1) + O2(X3Σ-g, υ = 0) ↔ O2(a1Δg, υ = 0) + O2(X3Σ-g, υ = 1), the information on the O2(X3Σ-g, υ = 1) kinetics is extracted from the O2(a1Δg, υ = 1) temporal evolution. In addition, measurements of the removal of O2(X3Σ-g, υ = 1) by CO2 at room temperature will also be presented. This work is supported by the Johns Hopkins University, Applied Physics Laboratory, under grant 939991 (under NASA grant NAG5-13002). [1] Feofilov, A., Kutepov, A. A., Garcí­a-Comas, M., López-Puertas, M., Marshall, B. T., Gordley, L. L., Manuilova, R. O., Yankovsky, V. A., Pesnell, W. D., Goldberg, R. A., Petelina, S. V., and Russell III., J. M. 'SABER/TIMED Observations of Water Vapor in the Mesosphere: Retrieval Methodology and First Results'. Submitted to J. of Atmos. and Terrest. Phys., (2008). [2] Kalogerakis, K. S., Copeland, R. A., and Slanger, T. G., J. of Chem. Phys., 123, 194303, (2005). [3] Pejakovic, D. A., Campbell, Z., Kalogerakis, K. S., Copeland, R. A., and Slanger, T. G., Eos. Trans. AGU 85(47), Fall Meet. Suppl., Abstract SA41A-1032, (2004).

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