Generation of Emission From the v = 0 levels of the O2 Herzberg States Following the Reaction Between O(1D) and Ozone

Details Generation of Emission From the v = 0 levels of the O2 Herzberg States Following the Reaction Between O(1D) and Ozone Generation of Emission From the v = 0 levels of the O2 Herzberg States Following the Reaction Between O(1D) and Ozone

Dec 2008

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2008agufmsa31a1599s&link_type=abstract

American Geophysical Union, Fall Meeting 2008, abstract #SA31A-1599

Other

0310 Airglow And Aurora, 0317 Chemical Kinetic And Photochemical Properties, 0322 Constituent Sources And Sinks, 0340 Middle Atmosphere: Composition And Chemistry

Scientific paper

The reaction between O(1D) and ozone is highly exothermic, with a variety of possible pathways, and includes all states of O2 lying below the first dissociation limit at 5.1 eV. The three Herzberg states at 4 - 5 eV and even the 5Πg state - bound by only ~0.1 eV - are all accessible. Our interest has been to generate the lowest vibrational level of the lowest Herzberg state, O2(c1Σu-), because O2(c-X) v'=0 emission is a major nightglow feature in the visible spectral region of Venus and presumably of Mars. Although the c1Σu-(v = 0) level is known to be produced by O- atom recombination in a flowing afterglow [Lawrence, et al., 1977; Slanger, 1978; Kenner and Ogryzlo, 1983], it has not previously been generated in a pulsed experiment, where kinetics can be most easily determined. We find that photodissociation of ozone at 248 nm rapidly generates the v=0 levels of all three O2 Herzberg states - c1Σu-, A3Σu+, and A'3Δu - as observed in the Herzberg I/II/III and Chamberlain bands. These levels appear as the O(1D) disappears, each exhibiting different time histories. From earlier work, we established that the O(1D) + O3 reaction generates high vibrational levels of the O2 states [Slanger and Copeland, 2003], but here we see the lowest level. The O2(b - X) Atmospheric bands appear over a yet longer time scale. Emission from the O(1D - 3P) red lines is a prominent feature in these experiments, although the radiating efficiency is only about 10-7. This work has been supported by Grant No. NNG05GO77G from the NASA Planetary Atmospheres program. E. Byler participated as an NSF REU (Research Experience for Undergraduates) student. G.M. Lawrence, et al. Science., 195, 573, 1977. T.G. Slanger, J. Chem. Phys., 69, 4779, 1978. R.D. Kenner and E.A. Ogryzlo, Can. J. Chem., 61, 921, 1983. T.G. Slanger and R.A. Copeland, Chem. Rev. 103, 4731, 2003.

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