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Annales Geophysicae An interactive open-access journal of the European Geosciences Union
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Volume 24, issue 11
Ann. Geophys., 24, 2823–2839, 2006
https://doi.org/10.5194/angeo-24-2823-2006
© Author(s) 2006. This work is distributed under
the Creative Commons Attribution 3.0 License.
Ann. Geophys., 24, 2823–2839, 2006
https://doi.org/10.5194/angeo-24-2823-2006
© Author(s) 2006. This work is distributed under
the Creative Commons Attribution 3.0 License.

  21 Nov 2006

21 Nov 2006

Model of daytime emissions of electronically-vibrationally excited products of O3 and O2 photolysis: application to ozone retrieval

V. A. Yankovsky and R. O. Manuilova V. A. Yankovsky and R. O. Manuilova
  • Institute for Physics of St. Petersburg State University, 1 Ulaynovskaya str., Petergoff, St.-Petersburg, 198504, Russia

Abstract. The traditional kinetics of electronically excited products of O3 and O2 photolysis is supplemented with the processes of the energy transfer between electronically-vibrationally excited levels O2(a1Δg, v) and O2(b1Σ+g, v), excited atomic oxygen O(1D), and the O2 molecules in the ground electronic state O2(X3Σg, v). In contrast to the previous models of kinetics of O2(a1Δg) and O2 (b1Σ+g), our model takes into consideration the following basic facts: first, photolysis of O3 and O2 and the processes of energy exchange between the metastable products of photolysis involve generation of oxygen molecules on highly excited vibrational levels in all considered electronic states – b1Σ+g, a1Δg and X3Σg; second, the absorption of solar radiation not only leads to populating the electronic states on vibrational levels with vibrational quantum number v equal to 0 – O2(b1Σ+g, v=0) (at 762 nm) and O2(a1Δg, v=0) (at 1.27 µm), but also leads to populating the excited electronic–vibrational states O2(b1Σ+g, v=1) and O2(b1Σ+g, v=2) (at 689 nm and 629 nm). The proposed model allows one to calculate not only the vertical profiles of the O2(a1Δg, v=0) and O2(b1Σg, v=0) concentrations, but also the profiles of [O2(a1Δg, v≤5)], [O2 (b1Σ+g , v=1, 2)] and O2(X3Σg, v=1–35). In the altitude range 60–125 km, consideration of the electronic-vibrational kinetics significantly changes the calculated concentrations of the metastable oxygen molecules and reduces the discrepancy between the altitude profiles of ozone concentrations retrieved from the 762-nm and 1.27-µm emissions measured simultaneously.

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